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Quantum Theory of Solids
"
SECOND REVISED PRINTING
JOHN WILEY & SONS
New York· Chichester· Brisbane· Toronto· Singapore
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Copyrigh t <t 1963, 1987 by John Wiley & Sons, Inc. All rights reserved. Published simultaneously in Canada. Reproduction, or translation of any part of this work beyond that permitted by Sections 107 and 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful. Requests for permission or further information should be addressed to the Perm issions Department, John Wiley & Sons.
Library of Congress Cataloging in Publication Data:
Kittel, Ch arles. Quantum theory of solids. Includes in dexes. 1. Solid state physics. 2. Quan tum theory. I. Fong, C. Y. (Ching·yao) I I. Tit le. QC176.K53 1987 530.4'1 8632478 ISBN 0471624128 (pbk. ) P rinted in t he United Stales of America 10 9 8 7 6
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5
4 3 2
1
Preface
The object of this textbook is to present the central principles of the quantum theory of solids to theoretical physicists generally and to those experimental solid state physicists who have had a one year course in quantum mechanics. The book is intended for use in a one year graduate course, to follow a year of general education in the facts of solid state physics at the level at least of my earlier book Introduc tion to Solid State Physics, second edition. Much of the physical background to the theory is developed there, and it is hoped in the next edition to develop the physical interpretation up to the level needed here. As far as possible I have tried to emphasize unifying principles. The first part of the book treats phonon, magnon, and electron fields and their interactions, culminating in the theory of superconductivity. The second part treats fermi surfaces and electron wavefunctions in metals, alloys, semiconductors, and insulators; with considerable at tention to the theory of the important types of experiments which bear on our understanding. The third part deals with correlation functions and their application to timedependent effects in solids, with a brief introduction to Green's functions. The order of the chapters, particularly within the second part, is not rigorously linear  I attempted to avoid an accumulation of material which did not challenge the imagination and participation of the reader. The first part of the book forms by itself a short course which has been observed to interest students of field theory and particle physics. A number of important theoretical calculations in solid state physics are too long, intricate, fearsome, or tedious to present in full in a course; and a summary treatment often has no pedagogical value. To give several examples, the full theory of Bloch electrons in a magnetic field, by Blount, Roth, Wannier, Kohn, and others, has been omitted,
y
p
vi
PREFACE
although a less complete treatment is included. Equally, the work of Soviet physicists and Luttinger on the Landau theory of the fermi gas is clearly beyond the scope of the book, together with a number of other manybody problems. The subject of the properties of para magnetic ions in various environments appears to me to be too specialized for a general text. While writing it became abundantly clear that there is no level at which a textbook like this could aim to be a complete treatment of all major aspects of the theory of solids; the field is simply too vast. It is natural not to report several detailed subjects which are available in existing textsthus the material on standard transport theory in the books by A. H. Wilson and J. Ziman is not repeated here; the discussion in Peierls of phonon interactions and the book by Abragam on nuclear magnetism are treatments so complete that it would be ridiculous to paraphrase them. I renounced an attempt to do everything by the method of Green's functions, for then the contents would be almost entirely inaccessible to experi mentalists at the present time. Given an opportunity, many students will choose to write a term paper on an application of Green's functions to a manybody problem. The quantum theory of transport processes is not treated here. Fortunately, for many subjects excellent monographs exist, particularly in the monumental series Solid State PhysicsAdvances in Research and Applications, edited by F. Seitz. and D. Turnbull, and in the Encyclopedia of PhysicsHandbuch der Physik series. Details far beyond the scope of this text can be found in these and other specialized works. This book contains problems and is a textbook; it is not a history of the development of the subject. I have actively tried a,.'i a matter of policy to avoid proper names, assignment Of priority, and allocation of credit. Detailed references and names are given only when it would be positively clumsy to omit them, or when the work is too recent to have been included in reviews. An adequate bibliography would be as long as the text itself. Many lists of references are readily available in the Advances and in the Handbuch series. It is increasingly clear that many active research workers cannot find time both to write a text and to give full historical credit to all their colleagues responsible for the development of a large subject. A number of very important results are developed in the problems to be found at the end of most chapters. It is urgently recommended that the problems be read over in conjunction with the text, and it would be vastly better for the reader to solve the problems. A note on notation: [,] = commutator; {,} anticommutator; the symbols c, c+ are usually reserved for fermion operators. The units
r
PREFACE
vii
I
h = 1 are employed throughout, but h is sometimes restored to the final result. A Bloch function of wavevector k is written as Ik). When convenient the volume ~ of the specimen is set equal to unity; N usually refers to the total number of particles and n to their con centration. The symbol it usually denotes a field operator, and tI> usually denotes a state vector. It is a pleasant duty to acknowledge here in part the wide as,."Iis tance I have received. M. H. Cohen, W. A. Harrison, W. Kohn, H. Suhl, J. Friedel, A. Blandin, P. Argyres, B. Cooper, S. Silverstein, B. Dreyfus, J. W. Halley, G. Mahan, D. Mills, and F. Sheard have helpfully suggested improved treatments of various demonstrations. My colleague, J. Hopfield, alertly resolved innumerable apparent paradoxes which appeared during the writing. At Stanford, M. S. Sparks and his associates, including R. M. White, R. Adler, K. Nordtvedt, K. Motozuki, and I. Ortenberger, detected many lapses in the early versions of the manuscript. R. Peierls graciously agreed to share the title of his most useful book. The typing was done with perfection by Mrs. Eleanor Thornhill, without whose help few physics books would be written in Berkeley; Mrs. Sue Limoli kindly assisted with the proofs.
C. KI'ITEL
August 1963
Preface to the Second Revised Printing
The original preface suggested that "A number of very important results are developed in the problems ...." Experience has shown that the problem solutions can be really useful both for selfstudy and as a supplement to lectures. Indeed, many of the results are too important to be left to the chance that the reader will take time off to work them out. It is fortunate that Professor C. Y. Fong offered to prepare an appendix giving the solutions to selected problems. He also made a number of typographic and algebraic corrections in the text itself. Thus the revised edition is defined by the original text, the solutions, and the corrections.
C. KITTEL
November 1986
ix
BOOKS BY CHARLES KITI'EL
Introduction to Solid State Physics. Sixth Edition Elementary Statistical Physics Elementary Solid State Physics Quantum Theory of Solids Thermal Physics, Second Edition (Freeman)
Contents
1. Mathematical Introduction, 1
2. Acoustic Phonons, 12
3.
Plasmons, Optical Phonons, and Polarization Waves, 34
Fermion Fields and the HartreeFock Approximation, 75
Polarons and the ElectronPhonon Interaction, 130
4. Magnons, 49
5.
6. ManyBody Techniques and the Electron Gas, 99
7.
8. Superconductivity,150
9. Bloch FunctionsGeneral Properties, 179
10. Brillouin Zones and Crystal Symmetry, 199
11. Dynamics of Electrons in a Magnetic Field: de Haasvan Alphen
Effect and Cyclotron Resonance, 217
12. Magnetoresistance, 237
13. Calculation of Energy Bands and Fermi Surfaces, 249
14. Semiconductor Crystals: I. Energy Bands, Cyclotron Resonance,
and Impurity States, 268
15. Semiconductor Crystals: II. Optical Absorption and Excitons,
294
16. Electrodynamics of Metals, 308
17. Acoustic Attenuation in Metals, 326
xi
338 Correlation Functions and Neutron Diffraction by Crystals. . Theory of Alloys. 20. 1119 19. 386 Green's FunctionsApplication to Solid State Physics.xu CONTENTS 18. 368 Recoilless Emission. 397 Appendix: Perturbation Theory and the Electron Gas. 21. 417 Appendix: Solutions AJA70 Index.
Low Temperature Physics. Wiley. New York. Mc GrawHill.References frequently cited QUANTUM MECHANICS BACKGROUND L. New York. 196162. ManyBody Problem. E. 47242. Academic Press. G. xiii . Schiff. Quantum Mechanics. pp. A. Benjamin. Introduction to Solid State Physics. Thirring. New York. Gordon and Breach. McGrawHill. New York. 1955. 1957 3rd edition. 1962. sixth edition. Amsterdam. Table of Integrals and Other Mathematical Data. M. de Gennes. Wiley. Macmillan. C. Brueckner. Pines. Quantum Mechanics. K. Seitz and D. edited by C. NorthHolland. 2 vols. 1958. Landau and E. This is cited as ISSP. 1959. New York. Dwight. and P. TABLES H. Turnbull. MANYBODY PROBLEMS D. De Witt. Elementary Quantum Field Theory. This is cited as Pines. L. B. Dreyfus. in Many Body Problems. SOLID STATE BACKGROUND Solid State Physics: Advances in Research and Applications. New York. Lifshitz. Quantum Mechanics. second edition. A. Kittel. 1986. edited by F. B. Integrals in here are cited by their number. This is cited as Solid state physics. edited by C. New York. AddisonWesley. 1961. De Witt. New York. This is cited as LTP. Messiah. Henley and W. 1962.
Quantum Theory of Solids SECOND REVISED PRINTING .
b*. where the direct volume D contains N primitive cells. . b.r 1 Mathe:rn..atical introduction It is convenient to gather together here a number of definitions and results which are utilized throughout the text~ RECIPROCAL LATTICE We recall several important properties of the reciprocal lattice.. b xc a· b X (2) V* _ (2. c* of the reciprocal lattice are defined in terms of the primitive basis vectors. We note that the conversion of wavevector sums to integrals involves (3) V: V' c L~ ~ k (2'1")3 fd 3k = (N/V*) fd 3k c.. a. c of the direct lattice by the equations (1) a* = 2. The basis vectors a*..)3 c  where is the volume of the primitive cell in the reciprocal lattice and V c = a • b X c is the volume of the primitive cell in the direct lattice.
Proof: Consider the series THEOREM. therefore r* is normal to one vector in the plane.2 THEOREM. ment r* is normal to the second vector and tt THEOE a b in the plane.times the reciprocal of the spacing d(hkl) of the planes (hkl) of the direct lattice. QUANTUM THEORY OF SOLIDS MATHI The vector r*(hkl) to the point hkl of the reciprocal lattice is normal to the (hkl) plane of the direct lattice. G ~ b) a By the same argu which (11) = a*·a . G ~ b) <. and thus r* is normal to the plane. (14) so that the spacing d(hkl) is (6) 1 =n . we al ~"'OUR A function f(x) which is periodic with the period of the lattice may be expanded in a fourier series in the reciprocal lattice vectors G. Now 1 h 1 l (12) unless Pr04 and is (G = (13) (5) n = r*/lr*l. We. to show that this is periodic with the period of the lattice we increase x by a lattice vector: (8) x~x+ma+nb+pc. d(hkl) and 2. Co (15) (7) f(x) = L G aGeiG'J:. =. wher. + a = kb* + le*) .. The length of the vector r*(hkl) is equal to 2. bou satis give take eikr ±(l . THEOREM.. then h1a· n is the interplanar spacing. But (4) r* .. Proof: If n is the unit normal to the plane.a = r* • a ~~ h hlr"'l Ir*1 We now go on to two important theorems about expansions of periodic functions.b*·b = 0. Proof: Note that 1 1 where (9) h a b k but (10) is a vector in the (hkl) plane of the direct lattice.. by definition of the lattice indices.
nb + pc) which is just an integer times 21r. (9) Then f(x ma nb + pc) = (ha* = = ~ aGeiG<xeiG«ma+nb+pc). shall usually determine the allowed values of k by the periodic 1. (12) Jd x f(x)eiK. If f(x) has the periodicity of the lattice. 1 3 ttice where m.LIDS MATHEMATICAL INTUOl>UCTION.+G)<x n L aG~(K G + G).1). where ~ is the kronecker symbol. we also write ~(K + G) as c)K. . where n is any integer. n. ± (iN . ± 1. < . The value n = 0 or . = f(x). so that we need take only ·~N. so that f(x + ma + nb + pc) rgu and the representation THEOREM. dic the tice . this condition is boundary condition qr+N = qr. (ma 21r(hm + kn + lp). Only N values of n give independent values of the N coordinates qr< It is convenient to take N as even and to choose the values of n as 0. 3 the ice< the unless K is a vector in the reciprocal lattice. iN. CH. and n is the volume of the specimen. l<~OURIER LATTICE SEIUES Consider the series (15) qr = N~~ L Qkeikr• 11. ± 2. whence e ikN satisfied by k = 21rn/N. p are integers. . ex We. Proof: This result is a direct consequence of the preceding theorem and is essentially a selection rule for interband (G ~ 0) and intraband (G 0) transitions< By (7) (13) f(x) = L G 3 aGeiG<x ' and (14) Jd x f(x)eiK<X 3 = LaG G Jd x ei(K.G. We note that iN and give identical values of eikr for all r.<x = 0. but the (10) G (ma < + nb + pc) + kb* + lc*) . has the required periodicity.
Given (15).:C O.k)L i(k' . (16) = NJ. If 8 = r. independent of r. . some other integer. Proof: Substitute (21) in (22): (23) Qk = L 1 '\' Qk' if JdE ei(k'k) e= L Qk'Okk' = k' (34) because except for k I = lL dE ei(k'k)E lL 2 sin t(k' .2 L a qae ika • where Pro (25) Proof: Substitute (16) in (15): (17) qr = Nl L /ca qaeik(rIJ). then the sum over k gives N qr.k) = 0. the desired result. Given (21).2 ~ where k is any integer times 211"/L. (18) If 8  r = On tal SUMl\ L n eik(f L n e i2 11'n(f/ N IN L e i2 11'M/ N + INl nl L ei2 11'M/ N n=O Nl Le i 21l'n(f/N 1_ 1 e i211'(f 0 (26) (27) (28) n=O for (I .ikE • (32) (33) Qk. THEOREM. Thus we have the orthogonality relation (19)' L /c eik(ra) = No ar • This is the analog for discrete sums of the delta function representation (20) (29) J _0000 eik % dk 211"o(x). then QIc (24) THEOREM. (30) (31) = LJ. Trans (35) k'. Consider the series defined for iL (21) q(x) < x < tL: Qkeik%. then Qk = For tl (22) L ~'J J lL dE IL q(E)e.MATH] 4 qr QUANTUM THEORY OF SOLIDS THEO} 1c = 0 is associated with what is called the uniform mode in which all are equal. (I.
Transition rate: (35) W(n ~ m) = 211"I{mIH'ln)1 2a(Em .En).C]} = Tr{[A.pz ] ' = 2~ ax pz + ox2 of o2f U.. r ~ 211" . .B].2 47r. eiq'rfl. == <P 11 1m + . 1 5 )LIDS ~h all THEOREM. Proof: Following (22) consider. for an operator F. (~ ~) a _= (0 ~} + 1) = <P i(mw/2)~(n For the harmonic oscillator. The potential1/1xl may be expanded in a fourier series as (24) where ~ \xl = 47r n Lq\ e q iq.p] = i ~ f(x). iF == [F. p • [f(x). n is the volume of the crystal. .B]C}.x . with r (25) f d 3x «r iq'·x e: = 211" f 0 = lxi. CH.MATHEMATICAL INTRODUCTION.~ A. SUMMARY OF QUANTUM EQUATIONS (Ii (26) =0 (27) (28) ~tion it/t = By. {n\pln Tr{A[B. = (~ ~} q+ = q. + l)K. 1 . (32) {nlxln (33) (34) + 1) = (2mw)~(n 1)~.00 dr (ei(q'i«)r _ = 1) q.e«r ei(q'+i«)r) r dr fl 1 dp. (x ) .iq' ~ /. principal value. Tr{ABC} = Tr{CAB}. + a2 On taking the limit a +0 we obtain (24). ax 2 = .i grad . = G ~).+oX±M x 1I"~a .= e + ~} 2 q. c (29) (30) (31) [f(x).
The unperturbed ground state is 10) and the exact ground state is 10).. The same notation is used again at the end of Chapter 6 in the identical connection. Em Ek from (47) e. J dx eix'll = 2ra(y). Even when H 0 and V are inde pendent of time.6 g (36) (37) (38) PE QUANTUM THEORY OF SOLIDS MAT Density of states per unit energy range. where V is called the perturbation. free electrons: (2m)*e~. and in particular it fails if the perturbation causes one or more bound states to appear below a continuum. then bati (45) a(g(x» f _IlOIlO 1 Ig'(xi) a(x  I where the (39) are the roots of g(x) = O. 'fHEOREM. We assume that the lowest eigen state <P of H can be derived from the unperturbed lowest eigenstate <Po of H 0 by adiabatically switching on the interaction V in the time interval 00 to O.C] + [A. The assumption is called the adiabatic hypothesis.C]B. (49) GENERAL TIMEDEPENDENT PERTURBATION THEORY We consider the hamiltonian (42) H = Ho + V. We shall use (only in this development) the notation I) to denote an eigenstate of H and I) to denote an eigenstate of H o.y) = 1~lf(y/a). and (44) f Xi dxf(x)/j(ax . (40) + LJ Ie . This assumption is not necessarily always true. important results of perturbation theory appear more from timedependent theory than from the usual time independent perturbation theory . ~. Ie = A [B. Xi).) (41) e~) + [AB. The ek (48) W. Pr (46) For nondegenerate states.C] + L' en. This is s and folIo W (50) so t with repr (52) If Eo is defined by wher form (53) (43) .
Between t = 0 and t = IX> the interaction is switched off slowly. 1 7 and IlE by (44) (H 0 + Y) 10) = (Eo + IlE) 10).D.E. Proof: The result (45) follows on subtracting (46) (olH0\0) = (olH 0 + YIO) = (01 YIO) Eo(OIO) from (47) (Eo + IlE)(OIO). We now undertake to calculate 10). a~ at Y(t)~. inde 'more time eigen 1state ~ time true. in which the interaction is switched on slowly between t = . where ~8 is in the Schrooinger representation. Q. . ~(IX» so that the timedependent Schrodinger equation has the form (51) 1. In the interaction = eiHot~8(t). We shall in the following always understand that the limit 8 ~ +0 is to be carried out.IX> and t = O.r OLIDS MATHEMATICAL INTRODUCTION. then the exact shift in the groundstate energy caused by the pertur bation is (45) IlE = (01 YIO) (010) . We work with the perturbation in the interaction representation: (50) Y(t) = eiHotYeiHotealtl. Then (48) IlE(OIO). (49) We replace Y by lim ea1tly 8++0 ' 8> o. lOund :d the j) the Istate round pter 6 This defines the process of adiabatic switching. with the boundary condition representation (52) ~(t) = ~o. CH. forming (53) We confirm (51) by i4> HoeiHot~a + ieiHot4>a = YeiHot~8' .
form.t') == P {exp [ .  = H~B(t). dtn P{V(h)V(t2) (63) V(tn) }. With U(t. (62) which may be written as (56) U(t. .. V(t n). We now define the operator U (t. Proof: If (58) is to be true. exac1 ilarl) (64) U(t. where P is a timeordering operatorthe Dyson chronological operator which orders all quantities on its right in order of decreasing time from left to right.. the exact ground state 10) is given in terms of the unperturbed ground state 10) by (58) U(O.. tells theo . J" ~ (i)n (t (t is dh • . (59) ~B(t) = eiHotU(t. and matr 1 .i h. . . from (59) and (57).8 Then (54) QUANTUM THEORY OF SOLIDS MAT] as re (58) i~B = (H 0 + V)~B' (61) E~ as required in the Schrodinger representation. (60) We One tion (65) i at ~ ~B(t) = = H O~B(t) (H 0 + eiHotV(t) U~O 00 )~o + Ve·ltl)eiHotU(t.  00) 10) = (OIU(O.oo)\O)' with all states in the interaction representation...t') (55) nO r ( i) n f. dtn V(h) V(t2) .  00 )~o should satisfy the timedependent Schrodinger equation (54).t.dh .t dt V(t) ]}. . .s h. and then (50). We may also write (57) THEOREM..t') == ~ .t') as defined above. f"t. Here V(t) is in the interaction representation.t h' . .
t (i)n 10 _eo is (tn) L (63) (II U . 8++0 X 1.(0. Eo . ilarly.. Equi1Jalence to TimeIndependent Perturbation Theory. using (62) U(O.i8 exactly as in ordinary timeindependent perturbation theory. 00) 10) = i f.:.00 dt2 (II V\p)e iCE. ~B = U(O. Interesting consequences .. Thus.Eo .LIDS ){ATREMATICAL INTRODUCTION.. the denominator in (58) follows if we normalize to make the mixed product (61) (010) = 1. From (50) and (56) we see that the lowest order term in the construction of a matrix element (fIU(O.) I. here <p denotes principal part.00)10).Eo . (Ilvlo) I E. . . f. dl" PI VOl) • • • VO.00 )~o.8 = <p! X + iro(x) tells us how to handle the poles which arise in ordinary perturbation theory.ElI i')eI(pl VIO)ei(EpEoiBH lI tIt. L (II Vlp)eHErBpia)tl(pl v\O) p Ep = ei(EpEoia)tl .00)10) = (_i)2 state Ih 1 L 0 00 dlt .2i8)(Ep . .Eo .iol" =  rator time tion.. tItl (II VIO)e'(ErB.. at t = 0. .1. p =i f.00) tn ). dl. the second order term is (64) Sim (IIU 2(0. CR. = ~ .i8) We I One advantage of the timedependent formulation is that the prescrip tion (65) lim _1_.8 L (I\vlp}(plvlo) • p (E. 1 9 as required. .
In ordinary perturbation theory the factorization is seen only at the end of the calculation.. PROBLEMS 1. one which is difficult to obtain in ordinary perturbation theory.·• = f fJ(t) = 4r ("in kpr :apr cos k.i J~oo dt eiH/JOtVlleilhOt]} Ua(O.co)Ub(O. X . (I (72) (b) (73) st H = H~ + Hg + Va + Vb. Suppose that a and b refer to different regions of space a and b with no physical connection.IKI' where XK is the projection of :x on K. +0 7r i foo 00 dx ei:r. .co) = P {exp [ . where the integral is taken over the sphere 0 2.i J~<c dt V(t)]} P {exp [ .} < k < kF..co).. Show that (70) lim 2.. An important advantage of the timedependent development makes it possible to separate immediately parts of the problem which refer to disconnected parts of the system.i J~oo dt e'iHaOleiHbOt(Va + Vb)eiHaOleiH/JOt]} = P {exp [ . vVe form.i J~<c dt eiHaOtVaeiHaOtJ exp [ . Show that (69) _ 4ri d 3xe iK·x XK ra . noting that all commutators necessarily involve Oab1 (67) U(O.. 3. Show that (68) f d·ke. This is a very useful result.10 QUANTUM THEORY OF SOLIDS MATH1 follow from a graphical analysis of the contributions to the U operator.. as discussed in Chapter 6. Let (66) where (71) 4.
x(2k • p _ k 2).ik .x.x.ikox • (b) Show that (73) [e.p] lppose lysical = ke. CH. 1 t>O t 11 lrator.p2j = eik .QLIDS MATHEMATICAL INTRODUCTION.. where (71) 8(t) makes ~fer to = 1 0 < O. ~heory 4. (a) Show that the commutator (72) [eik. } } Hnary .
Except for polarons. Phonons are associated with elastic excitationsacoustic phonons correspond to ordinary elastic waves. Landau and Lifshitz.I 2 Acoustic phonons The duality of waves and particles is the dominant concept of modern physics. The most convenient mathematical description of the particles uses the method of second quantizationthe quantization of waveparticle fields. usually in ionic crystals. Plasmons are the collec tive coulomb excitations of the electron gas in metals. but for 12 ' . plasmon.. their spectra. magnon. The Cooper pairs of electrons in the BardeenCooperSchrieffer theory of superconductivity act to a certain extent as bosons. In crystals there are many fields which combine wave and particle aspects. . and exciton describe several of the quantized fields in crystals. The method is quite easy to learn and to use: excellent introductions are given in standard textbooks on quantum mechanics. Much of the time the par ticular model employed is a matter of indifference to us. the words phonon. Excitons are neutral particles associated with the dielectric polarization field. and Henley and Thirring. The fields of interest to us can be developed for a lattice of discrete atoms or for a homogeneous continuum. the particular particles given above act as bosons. The nonrelativistic field problems we treat are good pedagogical illustrations of the more elementary content of quantum field theory. Magnons are the elementary excitations of the system of electron spins coupled together by exchange interactions. The quasiparticle composed of an electron and its interactions with the electron gas in a metal acts as a fermion. Exactly as the word photon describes the particle aspect of the electromagnetic field in a vacuum. Much of this book is concerned with these particlestheir quantiza tion. polaron. particularly those by Schiff (Chapter 13). and polarons are charged particles associated with the polarization field. Names have been given to the quantized unit of energy in these fields. and their interactions.
= NYJ ~ Qke ikr = NYJ ~ Qte.NYJ ~ These transformations are consistent: it was shown in Chapter 1 that eik (8r) No..L. The theory is quantized by the usual condition (5) [qr. Qk .qi)2]. . Let Pi denote the trans verse momentum and q. We shall later impose periodic boundary conditions. We now find the eigenfrequencies and eigenvectors of (1). 13 the discrete lattice the dispersion relations and selection rules are more general than for the continuum. qi.ACOUSTIC PHONONS. The appropriate parameters will be restored later. the transverse displacement of the mass at the point ij then for small displacements (1) H = ~ 2: [Pi 2 + (qi+l • . CH.e ike . The lattice includes the continuum as a limiting case. transform to phonon or wave coordinates Qk: (6) We qr = NYJ r k Qke ikr .ikr .q. 2 . in units with 11 = 1. after we have settled the mathematical preliminaries. We exhibit the hamiltonian of a line com posed of discrete points of unit mass at unit spacing under unit tension.i ~ (qi+l .) 2 by forming the canonical momenta (3) Pi = iJLIiJqi =. with J>~JV. ' and evaluating the hamiltonian (4) H = ~ Piqi . The coordinates qr must be hermitian variables r k in quantum mechanics.P81 = io rB ... so that qr must be equal to its hermitian adjoint: (7) qr = q. DISCRETE ELASTIC LINE The transverse motion of an elastic line under tension is a simple example of a boson field. This form is derived from the lagrangian (2) L = kinetic energy potential energy = i ~ tli 2 . "" q.
whence (11) e. ±(IN  1). qr = !N~ with Q+ the hermitian adjoint operator to Q. because we can then determine the momentum com ponent PI< canonical to QI<.cos k)QkQ_I<. .14 QUANTUM THEORY OF SOLIDS This relation is satisfied if (8) QI< = Q~. (19) Pr = N~ ~ Pl<e.ei(kH/)r = L QI<Qk.1) L QkQ_I«l k cos k). we may write (9) L (Qkeilor + Qte'I<r). . We need the relations (13) L (qrf! = Nl L L LQkQ". ±2. I< II Ib r r Further. Thus (15) L = l ~ QI<Q_I< .eikr(eik I< II r l)eiklT(eikl . which is satisfied by (12) k = 2rniNj n = 0.e ilo . k with the sum still taken over all allowed values of the wavevector k. This is not the only possible choice for k. . positive and negative. . IN. (14) L (qr+l  qr)2 = Nl = 2 L LL QI«h.kN = 1.~ (1 .. and (17) H =! ~ p"P _" + ~ (1 qse ika = .iIoT• . It is a good practice to make the coordinate transformation (6) in the lagrangian. (18) P" = N~~ ~ p. but it is the most useful choice. (16) Pk = aLIaQI< = Qk = P±k. N~~ ~ In terms of the new coordinates. .cos k)Q"Q_". ±1. The allowed values of k are usually determined as in Chapter 1 by the periodic boundary condition (10) qr+N = qr.
(kTk'8) = iOkk" T8 i T • Except for k = 0. . r p eik'8] s = Nl r [qT. here Wk is defined as (26) Wk = [2(1 . then the total wavevector is indeed rigorously conserved.ps]e. as we shall see in later chapters. 2 '15 The commutation relation becomes (20) [Qk. h. The total momentum is ~ PT. If a system is invariant under an infinitesimal translation.at] ow.P k . using the conditions (8) and (16).ikT .iP k). but this conservation law is distinct from the conservation of momentum of the centerofmass. = G. but under a translation by a multiple of the basis vectors a. a are boson creation and annihilation operators with the commutator (24) [ak. c of the primitive cell. and by (18) we see that (21) Po = N~~ ~ PT' The total momentum involves only the k = 0 mode. (22) ~ k.] = Nl [r qTe. a" = (2Wk)~(WkQk + iPk). where nk is the phonon population operator. Many interaction processes in crystals proceed as if the total wavevector ~ k were conserved for the interact ing particles. CH. The conservation law becomes.ACOUSTIC PHONONS. where G is any reciprocal lattice vector. Our object must be to get the hamiltonian into the harmonic oscillator form (23) H = ~ wk'f/'k = ~ wkatak. which is a uniform translation of the system. and for this reason k is often spoken of as the crystal momentum or as the quasimomentum. A crystal lattice is not invariant under an infinitesimal translation. and the a+. The hamiltonian (17) is not quite in the form of a set of harmonic oscillators because of the mixture of terms in k and k.cos k)]~. Let us try the linear transformation (25) at = (2Wk)~(WkQ_k . the wavevector index k refers to internal coordi nates and it has no connection with the total momentum of the system.
(33) I q. This contains the operator for the number of bosons in the state k: (30) 1l. Leibfried. A simple setl of real coordinates is provided by standing waves: (34) qr = (2/N)~ }. see especially pp. then the Schrodinger equation is (31) Hoi> = EoI> = (2: nkwk)oI>.k = atak' If a state 01> is specified by the occupancy eigenvalues nk. Now (27) [ak. with Ii and M restored..) sin kr). The modes of oscillation which we have quantized are identical with the classical modes of the system. + ateikr). Note that W is a periodic function of k.1 + iWk[Pk.16 QUANTUM THEORY OF SOLIDS The "'k are just the classical oscillation frequencies. Dispersion enters when the wavelength 21r/k approaches the interatomic separation. so that there is no dispersion.cos k)(QkQ_k + QkQk) _1 ++ a_ka_k + + a_ka_k +)• IWk (+ ak ak + a~k Thus the hamiltonian may be written as (29) IH = ~ Wk(a'tak + l). in Handb'UCh der PhY8ik. An increase of nk by one is described as the excitation of one phonon of energy Wk.D = akk'.a't'l = ( 2Wk)1( iwk[Qk. The inverse transformation to (25) is (32) P k = i(Wk/2)~(at  a k). .Pk. = 2: (1i/2MNwk)~~(akfJik. see p.Qk. 104 (1955). Qk = (2wk)~(ak + a:::k)' We insert (32) for Qk into (9) to obtain.cos k)l~. as required. Wk = [2(1 . 1 G. Let us form the sums over (28) l(PkPk ± k in the hamiltonian (17): + P kPk) + (1 .. For low k we have '" a: k. {Q~c) cos kr 1:>0 + Q~. for a discussion of the phonon polarization vector. .260. 174. 160. There are problems for which it is convenient to work only with real coordinates in the phonon expansionthe Qk above are not real because Qt :. Real Qk are particularly advantageous if we desire to exhibit the SchrOdinger eigenfunctions IQk} of the normal modes.C Qk. 165... so that the waves see the discrete nature of the lattice. VII/I..
ACOUSTIC PHONONS. nIN . P~c) = (2/N)'h 2: Pr cos kr. 2: r cos +  NI k')r <R 2: .e. This is just the hamiltonian for a collection of harmonic oscillators of frequency Wk.p~)l = iOa~okk" The hamiltonian can be written as (43) H = ~ {2~ P~"P + jMWk2Q~")2}. CH. = (2/N)~ 2: qr sin kr.17 where k assumes values (21r/N) times a positive integer up to N /2. '8 r by (37). The crossproduct terms cos k'r sin kr are always orthogonal. r Then (41) [Q~c).0 1_ eihnrlN eihn = <R 1 . r We wish to find the commutation relations of the P k. (37) Thus 2: (2/N) cos kr cos k'r = lJkk'. We note that the eigenvectors (2/N)'h cos kr and (2/N)~i sin kr are orthonormal.. For example. 2 . The momentum is (38a) Pr = (2/N)~~ k>O 2: (P~c) cos kr + P~') sin kr). r Qk8 ) r Pk 8 ) = (2/N)~ 2: pr sin kr. r and similarly (38) ~ (2/N) sin kr sin k'r = lJkk'. (35) 2: (2/N) cos kr cos k'r r = now (36) (l/N) 2: {cos (k + k')r + cos (k r k')d. (42) In general.2. in which case the sum is equal to N. Qk: (39) Q~c) = (2/N)'h (40) 2: qr cos kr. [Q~"). . where 0: runs over c and s. we assume w~c) = W~8).P~~)l = (2/N) 2: [q"P81 cos kr cos k's (2/N) L i cos kr cos k'r = ilJkk'.. = 0 unless n = 0.
n..C) 01/t I. The wavefunction t{Jm. wIth ol/.tl) = 0. Then (47) H = L . + at.).ata)....) == Q..c dt dx = a.)~(ak. The classical derivation of the lagrangian equations of motion for a field follow from the variational principle (49) o~II o. ol/t 8 ax (51) l it It a. J QUANTUM THEORY OF THE CONTINUOUS ELASTIC LINE We consider an elastic line of linear density p under tension 1'. In terms of creation and annihilation operators.. The wavefunction of the whole system may be written as the product rrIQk n . at 01/t dt [8.l.lk. The result (48) follows directly from the lagrangian (2) for the discrete line. The classical lagrangian is L dx. Thus 0... dt.c o.c aifi ol/t + ay." + i)Co.li: 2Qil IQ. Then = ay. subject to Ol/t(X.). IQiln. oy..c o. where . L .. a al/t 01/t.} satisfies the SchrOdinger equation I (44) { . at al/.2 jT ( 8l/t) ax ' 2 where l/t(x. is the amplitude of the oscillator k.n. (n./2)~(ak . on taking appropriate limits. O1/t(xh) = O. + 8(al/t/8x) 0 8x + iii ot.(Q.t) is the displacement of the string from the equilibrium position.c = = It L dt 0..}.... .c.. + j)Co. = i(MCo..c = jpy. (50) JJ o.18 QUANTUM THEORY OF SOLIDS Now Q.} = (n. from standard classical mechan ics the lagrangian density (48) .. where the first term on the right is zero because of the conditions on .c 0 al/. (45) (46) Q1a ) p1a ) = (2MCo.2M 8Q.. 0 at ax = . 2 I 0 2 1 2} +2 M Co.c]h It  ita (a 8.l..l.ol/t.c 81{t a..
'II"(x')] = io(x. at/. dx a.c and for the at/. 2 . (54) P ax 2 a wellknown wave equation.= 0./ax) a. QUANTIZATION OF TIm FIELD The particle quantum condition is [qT. CH. with t/. or.ax a(al/.c ) at/.(r) written for qT. . dx.Psl = ian..c f(a ax a(at/.e/iltj for a cell of volume dT.x') 7 o(x .(r). If the continuum is divided into cells of extension dT. where o(x. The hamiltonian density :JC is defined by (56) :Ie = 'II"{.c a f a(al/.T a:c (/JY!)2 . (59) o(x.. This is the equation of motion for the lagrangian elastic line (48) leads to 2 a21/. then the commutator becom('s. The function o(x.c 1 '11"2 2p + J. . x' are in the same cell M and zero otherwise. (57) [1/. by analogy with the definition p == aLjaq of the particle momentum. (52) Further.x') = 1/dT if X.ACOUSTIC PHONONS. .x') has the property that f j(x)o(x./ax) = o. therefore in the limit as dT 70..x') dT is equal to the average value of j for the cell in which x' is located. The extremum condition becomes (53) a a.c a a./a(i = a(dT). The definition (I).x'). in three dimensions./ax) ax ot/.') of momentum density is consistent with the limit of the discrete result (dT)'II" p aT.'II"(s) dTsl = io TS . 19 the variational principle.. =  a.x'). (58) [1/.c =.at a{. at/. . _ T . The momentum density'll" is defined by (55) 'II" ~ a.(x).
(64) J(Otfjox) Pk 2 dx = (IjL) L L kk'QkQk' k k' k Jei(k+k')z dx = L k2 QkQ_k." .20 the delta function in three dimensions.p PkP k + i Tk2 QkQ_k). In looking for suitable transformations of (61) I 3C = 11"2 2p + iT (Otf)2 ox We apply we may be guided by our experience with the discrete line. and we may wish simply to transform the quantum operators in the hamiltonian to a form solvable on inspection. periodic boundary conditions over a length L. (63) Qk = L }I. L Pke.t)} = i6(x . We define P k = P:!:k such that (65) L }I. Then where the integral is taken between . One method is to solve the quantum equation of motion directly in the Heisenberg representation. condition becomes (60) QUANTUM THEORY OF SOLIDS In this limit the quantum [tf(x.ikz . J1I"2 dx k 1I"(x) = L}1. k Qk = Q:!:k. and the hamiltonian becomes (67) H f 3C dx = L (. k Then (66) = LPkPk.22). We set (62) tf(x) = L }I. from Eq. noting that our discussion has referred only to a common time t.t).1I"(x'. It is apparent that there are two ways of dealing further with the hamiltonian of the elastic line.x'). in some problems one gains physical insight by working with the equations of motion. (1. J1I"(~)eikt d~. Jd~ tfmeik~. L Qkeib.Lj2 and Lj2. . Often it is tedious to obtain these equations.
. so that the subsequent transformation may be modeled after (25) and (32): (69) at ak i(2pCJ1k)"0. such as yttrium iron garnet.'kot) dx dx' iL 1 Jei<k'k)". axp ax. The vector R now plays the role of the scalar if.1r(x')]ei(k'". Thedeformation associated with curl R is a rotation. 1 aRp aRp +l ftl. ax. The strain energy density U in the quadratic approximation may then be written (71) U = ta(div R)2 2 1 = lf a aRp aR. Chapter 4. Cubic crystals with large primitive cells. The term in a is the square of the trace of the strain tensor.Pk'] JJ [. dx = i6kk'.x. tl are constants related to elastic moduli. 2 [SSP. There are three such invariants: (div R)2.and Icurl R12. in the pre ceding section on the elastic line. that the elastic energy associated with a given state of strain is independent of the orientation of the crystalline axes. the term in tl is the sum of the squares of the tensor components. may tend to be isotropic elastically. First we find expressions quadratic in the strain components aRpjax. It turns out that the eigensolu tions may be classified rigorously as longitudinal or transverse when the elastic energy density is isotropic.(x).¢. not a strain. where a. We are to sum over repeated indices. ax. where (70) LONG WAVELENGTH ACOUSTIC MODE PHONONS IN ISOTROPIC CRYSTALS We let R denote the vector displacement operator in a solid. and invariant under arbitrary rotation of axes. so that this term will not appear in the elastic energy.2 with R = x' .ACOUSTIC PHONONS. CH. The form (68) is similar to (20). that is. and x' is the position after deformation. where x is the initial position of an atom or of a volume element of the solid.P k i(2pWk)Jipk Wk + (T/2 wk)'hkQ_ki + (T /2Wk)~~kQk. 2 '"·21 The quantum condition is readily found: (68) [Qk. We assume the crystal is isotropic elastically. The coordinate axes xl' are assumed to be orthog onal. In [SSP the symbol g was used. IVR12.
. and we may choose the directions of the coordinate axes as we wish. k k' x IIp(x)eik' x 3 then (77) Jd3X II = 21 p k IT . Then (79) H =. y. We assume cyclic boundary conditions over a unit cube and x..:r. oR. i(2pwk. JJ (73) Q. the index has now the . 2QkQ~k' The hamiltonian was constructed to be invariant under rotation of crystal axes.. z: define the transformation to phonon variables Q:. It is convenient to choose one of the axes.Q'Q~k + if'r ja k k k. where p is the density and II. Because different k's. p~ k . oR. Rp(x) = r Qkeil&:'x. Q"Q" k k' k We define momentum components (75) (76) IIp = r Pkeik. we may choose different axes for each k. . ox...22 QUANTUM THEORY OF SOLIDS The hamiltonian density of the isotropic elastic continuum is (72) X = ~ IIJI. uXp ux. ( 74) . + ja aR.II p = Li '\' pJl. ax. !l!l = Li '\' kp k . = Jd x R!"(x)e3 with the condition Qk = ~(Q~0+. = + wk~(a&1'I + f')}2kQ~k.. are the components of the momentum density.. oR.pJl.. Now introduce the boson operators (80) at = i(2pWk.. r P'P~k + r k2(iaQLQ~k + if' r Q'Q~).. k k. I&: We have fd3 xoR.. 2p ox. are not mixed in (78). )+. + jf' aR. xl.k. ax. Pk Jd ' P: such that pp = (pJI.... k ik x ' ... parallel to k.)}2Pk akJl. k and the hamiltonian becomes (78) r P'P~ + r k. JJ In (80) repeated indices are not summed. outside the pair ± k.)}2P~k + wk~(a&"l + f')~ikQ:.
. all non degenerate. k where ekl' is a unit vector in the direction of the polarization of the phonon..akl. We consider a system of a large number of weakly interacting bosons described by the hamil tonian (85) H = L e~tak + 1 L V(kl k kl')at. With a weak and shortrange interaction most of the particles will be in the ground state..'" 23 significance of a polarization index.o)~~(ak. It will make little difference in the calculation of macroscopic quantities whether we use states with N or N + n particles. classically.~ akt.. = i L (2P"'kl)~k(akleih k aite. If V = 0. the ground state has all particles condensed because of the bose statistics in the lowest oneparticle state. "'b = [(0:8.. The dilation operator is (84) a(x) = I:JR. + (J) I plK.ik. The velocities of sound given by (81) are (82) VI' = 1:J"'I'II:Jk = [(0:8".oeik'" + ate. In liquid He" the potential is not so very weak.). relating the particle displacement to the wavevector. and a few (n « N) will be in excited states k > O.. The two transverse phonons for a given k are degenerate in an isotropic solid. and none exactly longitudinal or transverse. + {J)I plKk. a is the fractional volume change 8VIV. CH. The lattice displacement operator R is found from (73) and (SO): (83) R(x) = L ep(2pCrJk.k 1'  k 2'). + 1).") .ik.a(k1 + k2 . where l denotes the longitudinal phonon (Qk II k) and the other two choices of II. normally k = O. We verify readily that the energy is ACOUSTIC PHONONB.denote transverse phonons. PHONONS IN A CONDENSED BOSON GAS We want to show by a method of Bogoliubov how phonons may arise in a system of weakly interacting particles. 2 (81) E =b L"'k"(nk./I:Jx. but for a general direction in a cubic crystal there are three modes for each k. and it is believed from the . where the I{ronecker delta symbol a assures conservation of wave vector. but the expectation value of the total number of particles will be well defined..
Pines. We now take the expectation value of No + aitak to be the num r' k ber of particles N in the system. k Here No = atuo and the summations do not include k O. 205241. It is natural to treat . pp.. assuming V k = V k. (c) One particle not excited in the ground state: ataitakao and aitutuouk' (d) Exchange of one particle in the ground state: UitUtUkUO and utUitUOUk' (e) Both initial or both final particles in the ground state: atata~_k and aita=~oao.24 QUANTUM THEORY OF SOLIDS interpretation of neutron diffraction studies that in the ground state less than 0. The reduced hamiltonian does not commute with the opera tor for the number of particles. (86) II = r k Ekuituk + iN o2Vo + NoVo r' aitak + No r' V~itak k k + iN 0 L' V k(UkUk + aita:t"k) + terms of higher order. and P. The model we treat probably bears only a qualitative relation to real He 4• Then (85) may be written. Phys.l. But first let us consider a perturbationtheory approach. Reading from left to right. Rev. Miller. p. Nozieres. as discussed in detail in Brueckner.1 of the atoms are in the zero momentum state [see A. . the terms retained in the hamiltonian (86) are: (u) Kinetic energy: €kUitUk' (b) Interactions in the ground state: atutuoao. 127. Terms with three groundstate operators are excluded by momentum conservation. €kait~ as the unperturbed energy and i. . as the reduced hamiltonian (87) Hud We collect terms and rewrite (86) = iN2Vo + r' k (€k + NV0uit~ + iN r' V k(U~k + a=kait) + k This is a bilinear form in the boson operators and may be diagonalized exactly. 335). Vk(2uitak + a~k + a~ait) as the perturbation. The perturbation may easily be shown to lead to divergent terms in higher orders of the perturbation calculation. but for a large system this introduces no perceptible error (see Pines.l. The Green's function method discussed in Chapter 21 allows us to introduce in a natural way matrix elements connecting states with different numbers of particles. 1452 (1962)]. D.
AVk' Thus (96) + WIVk = WIUk + wOVk = WOUk . Vk UJr:llt . we want to equal .aitl 0kk" The first two relations are satisfied if in the diagonal form (89) hamiltonian can be written H = L Akatak + constant.ed .Hl = Aak. (91) wO(atak + a±Jr:llk) + wI(aka_k + a±kat). [ak. AUk. [at.H k1 = Uk( woat .H] = Aat. ak such that (88) [at.atl The commutator 2  = Uk Vk 2. WI with (92) Wo = t::k = NY k • ak Note that idk transformation (93) = wOak + wla±k Vka±k. Vk to make this equal to one. but it is best to avoid perturbation theory by diagonalizing exactly the reduced hamiltonian (87). CH." It is actually possible to sum the divergent terms to obtain a convergent result. The method is a systematic way of finding transformations such as (25). With this choice Using (91) and (93). and we can choose ak = Ukak + VkIl':±k' Uk.ACOUSTIC PHONONS. + NYk . which was produced fullblown with no derivation. [ak. 25 Bogoliubov calls the divergent terms "dangerous diagrams.vk(wOak + according to (88).wlak) . We carry out the diagonalization by a method using the equations of motion.A(UJr:llt Vkak). as we do now. [ak. k Let us write (87) as (90) H. 2 .Vkakt where (94) are real functions of k.. couples at and a±k' We make the ak = Ukak Uk.tN2yo Hk = 2:: H k . We look for new boson operators at.
p.3. .~ WI Wo WI +~1= 0. Suppose a body of mass M is moving with velocity v through a bath of liquid helium at rest at OOK. which corresponds to a repulsive potential. 1. The quasiparticle excitation spectrum of liquid helium has been determined directly by studies of inelastic neutron scattering. The frequency in (98) is a monotonically increasing function of the wavevector..26 These equations have a solution if (97) QUANTUM THEORY OF SOLIDS or (98) ~2 I = w0 2 wo . Bogoliubov.. But there is an important difference between the present phonons and those carried by a crystal lattice. Feynman and M. the result (99) is applicable only for positive V. as we saw in the discussion related to (21). The body will be slowed down if it can at a See R. P. USSR 11. Phys. In a gas. Obviously. P. ...9 AI agrees quite well with the calculations of li"eynman and Cohen. as we see immediately below. On this simplified model the dip can result from a kdependence of V k. 17 (1955). The portion of the excitation spectrum near the dip is known as the roton spectrum. R. 102. with results shown in Fig. Now Ek = k2/2M. 1. Cohen.. which is a particlelike dispersion relation. Feynman in Progress in Low Temperature Physics. and from this we can construct a criterion for superfluidity. We have assumed Vk ~ Vo for small k..  W1 2 = (Ek + NVk) 2  (NVk)2. Phys... Superjluidity. 23 (1947) i also reprinted in Pines. The dip in the dispersion relation near 1c = 1. For high k. 4 N.3 see also Problem 6 in this chapter. so that (99) ~(k ~ 0) = (NVo/M)~~k. (101) ~(k~ GO) . this limit is the dispersion relation for a phonon with velocity (100) Vs = (NVo/ M)lh. 1189 (1956)... J.4 The elementary excitation described by the operator is a collective property of the system. In a lattice. the phonons are referred to a relative coordinate system and do not carry momentum. Ek + NVk . 292 .. particularly for low k. this is shown most directly by an extension of the argument of Problem 5 to a state with one elementary excitation. the phonon excitations do carry momentum. Rev.
k + (2M)lk + "'k' 2 .2 0.27 40' 38 36 34 32 30 28 ~ Temperature 1. the parabolic curve through the origin is calculated for fret helium atoms. CH. as determined by Henshaw and Woods by inelastic neutron scatter ing. (104) o= v. we must have (102) tMv 2 = tMv.37 X 10 4 em/sec.4 1. In an event in which an elementary excitation "'k is created.6 0. (103) Mv = Mv' + k. equations.0 2.0 Momentum change Q(A 1) FIG. U lij 20 18 ~ 16 UJ 14 12 10 8 6 4 2 0.04 A 26 ~24 ~ 22 ~ ~ .8 2.2 1.0 1.12°K Neutron waveiength 4.2 + "'k. 1. The broken curve through the origin corresponds to a velocity of sound of 2.4 0. Combining these two from energy and momentum conservation.4 2.8 1.ACOUSTIC PHONONS..2 2.12°K at normal vapor pressure.8 3. Spectrum of elementary excitations in liquid helium at 1.6 2. I generate elementary excitations.6 1. 2 .&.
but have not yet been reported in crystals. We denote propagation by acoustic phonons as ordinary or first sound. we say that the fluid acts as a super fluid. that is. and we discuss only the latter. Such waves are known as second sound. where Cl is the velocity of first sound. At finite temperatures the moving body does encounter resistance. but not necessarily the number of phonons. our discussion does not apply if such umklapp processes are frequent. We are interested in the possibility that collective waves may propagate in the phonon gasmodes in which the local excitation density or phonon concentration is modulated in a wavelike way. The acoustic phonons themselves possess many of the attributes of particles. If there is an energy gap. 00.28 QUANTUM THEORY OF SOLIDS The lowest value of v for which this equation can be satisfied will occur for v k. (k "'k) 2M + k' the critical velocity is determined by the minimum of "'k > 0. The problem of second sound in liquid helium differs in important respects from the problem of second sound in crystals. 1 also leads to a positive minimum of "'k/k. this critical velocity is then II (105) Vc = mm . When M + "'k/k. The dispersion relation of the phonons at sufficiently long wavelengths is '" = clk. The situation portrayed in Fig. The acoustic phonons couple at a crystal/gas or liquid/gas interface with ordinary sound waves in the gas. They surely exist in liquid helium II. we will have Vc > O. These particles interact weakly with each other by virtue of anharmonic terms in the lattice potential. all SECOND SOUND IN CRYSTALS We have treated acoustic phonons in crystals and in liquid helium. one source of resistance comes from Raman processes in which a thermal phonon is scattered inelastically by the moving body. At higher temperatures. At low temperatures. In actual liquid helium the critical velocities observed are often two or three orders of magnitude lower than the calculated values. If the elementary excitations had a free particle dispersion relation". a: k 2then the critical velocity would be zero. the collision events among phonons conserve both energy and wavevector. " . the total wavevector of the colliding particles may change by a reciprocal lattice vector. What has been shown here is that for v < Vc the body will move at OOK without loss of energy to the fluid. probably because of the possibility of creating other lowlying excita tions of the form of vortex lines.
ax = dci. In the case of ordinary conduction of heat in a crystal there also exists a gradient in the phonon density. Now form the crystal momentum density P and energy density U: (108) P = f d k ki. For simplicity we consider only longitudinal phonons. tion is destroyed by umklapp processes. pp. C. . CH. 192196. = clk". I = iJx" 0 • 5 For a discussion of the boltzmann equation see. New York.ACOUSTIC PHONONS. Ele mentary statistical physics. 3 U f d k clki. and on multiplying by clk and integrating: (111) au at + ~ fd 3k c 2k i ax". so that (106) becomes (107) dei. Wiley. where dei denotes the rate of change of i from collisions. Thus on multiplying (107) by kJA and integrating: (110) aPJA at + ax". (109) f d k k de! = 0. We now derive an expression for the velocity of second sound in a phonon gas in a crystal. For long wavelength phonons the v component of velocity is v". 3 Because we have assumed wavevector and energy are conserved in all collisions. I{ittel. According to the boltzmann transport equation 5 (106) at ai + v.x) d 3k d 3x be the number of phonons of wavevector in d 3k at k and of position in d 3x at x. We have omitted the acceleration term ft· (ai/av) from the equation because the acceleration ft == 0 in the absence of external forces. yet no wavelike solution ordinarily results because wavevector conserva . 2 " 29 We assume that the phonon mean free path is much shorter than the wavelength of second sound. 1958. au iJt + c 2 ap". Let i(k. for example. ~ fd 3k = O' ./k. 1". f d k clk dei 3 3 = O.
but it is not evident that it should be present in crystals. FREQUENCY DISTRIBUTION FOR PHONONS The phonon frequency distribution function g(w) of a crystal is defined as the number of phonon frequencies per unit frequency range. 268 (1956). The distribution may be calculated numerically from the dispersion relation. Montroll. Chern. 43.3 ax p On combining (111) with (113). Advances in Physics 1. ' . see 7 J. This factor is present in liquid helium. and (110) may be written (113) ap" +! au = o. Ward and J. divided by the total number of frequencies. Our result for C2 2 does not include their factor [1 . 48 (1952). (112) f d3k c1k"k"j k = ~". Wilks. The above calculation is due to J. Phil. Dingle. s For a review of this area. in Solid state physics 2. (114) 2 2 a u C1 a2 u 2 =0 at 3 ax" ax" ."!" lU . An exact solution for the twodimensional square lattice has been obtained by Montroll. Phys. at . The frequency distribu tion determines an important part of the thermodynamic properties of the crystal. B. 575 (1947). In any event Pn/ P + 0 as T + 0 for phonons in liquid helium and in crys tals. E. II usually with considerable labor. which is the equation of a wave having velocity cd3~~. J. C.30 QUANTUM THEORY OF SOLIDS If j is only slightly perturbed from an isotropic distribution.. 1&. The waves of second sound are periodic variations of excitation energy associated with periodic variations of phonon concentration. The ratio cdc'}.7 who found that the distribution function has a logarith mically infinite peak." . de Launay. 112168 (1952).(Pn/ p)] in the ratio of the effective mass density Pn of the excitations to the actual density P of the medium.. but the attainable experimental accuracy is poor because second sound becomes highly damped at very low temperatures as the phonon mean free path increases relative to the wavelength of the second sound. Mag. = 3~ of the velocities of first and second sound is approximately satisfied in liquid helium as T + 0. A discussion of second sound in liquid helium is given by R.
The thickness of the shell in the direction normal to a bounding surface is given by (115) IVkWI dk n = dw. but dgldw has infinite discontinuities. PROBLEMS 1. PAY8. it/! = ['/I. This number is determined by topological considerations and depends only on the number of independent variables. g(w) = Zl JSew) IVJtw[ where Vo is the volume of the primitive cell. The theorem states that any func tion of more than one independent variable which. 2 .ACOUSTIC PHONONS. is periodic in all its variables has at least a certain number of saddle points. where all the deriva· tives in (117) vanish. A saddle point usually leads to a singularity in the distribution function. Van Hove.. In two dimensions the singularity is logarithmic. • L. in agreement with the classical equation. Z denotes the number of atoms per cell. . 1189 (1953). PAY8. and l is the dimensionality of the space. 91. We expect a singularity when (117) IVJtwl = iJw)2 [(iJk x + (iJw)2]~ iJk = ll 0. show for the elastic line (56) that '" = 11"/ p. We note that '/I and any function of '/I. so that (116) Vo [ dS. P. Rev. see also H. CH. The fact that w(k) is periodic is shown in the chapter on Bloch functions. 290 (1955). as w(k).8 who utilizes a topological theorem of M. B). written for two dimensions. The integra tion is over the surface S of constant w. Morse. The density of states g(w) dw is directly proportional to f dk. It is apparent that the singularities of g(w) originate from the critical points of w(k). in three dimensions g(w) is continuous. where the integral is over the volume in k space bounded by the constant energy surfaces at wand w + dw.·31 Such singularities are of great importance for the thermodynamic properties. Rosenstock. A general investigation of the singularities in the dis tribution function has been given by Van Hove. we have seen an example of the periodicity in (26) above. Rev. 89. From the equation " of motion for the field operator '/I in the Heisenberg representation.
so the term in T does not contribute to if. ) ~(X')] iJ1/.. averaged over the length of the line.x') . = irlp to give the wave equation in the field operator 1f: (120) p'if. ax' . 6. 469471. (a) Show that Hk in (91) is diagonal if (127) tanh 2Xk = Ek NVk NV k • + ''II .1r(r')]1r(r') dT' + J1r(r')I1f(r).x') = i ~ ~(x ax . term (118) The [1f(r). Show that for the elastic line the quantum equation of motion gives (119) :~.I ax. which may be combined with 'if.(X')] . i = T which may be reduced. see Messiah. (a) Diagonalize the hamiltonian for this problem and indicate the form of the ground state Schrodinger wave function in the Q representation.. 2.t(61r2n)~.t) = Qk(t)Uk(X). 3. pp. 4.t = hVZ. = T a1/l ax2 ' Note that (121) 1r  "2 1 1 'T J d ' X 1[1r(x. The normalization of the commutator (94) is assured if we write (126) Uk = cosh Xk. ax' ~(x . 2. with k = n1r IL. = i ~ ax' where (122) [ 1r(X) iJ1/.(x') + iJ1/. so that 1f(0) = 1f(L) = O. Show that on the Debye model the low temperature (T« 8) heat capacity per unit volume of an isotropic monatomic solid containing:n atoms per unit volume is (124) c = (121r 4nkB I5)(T18) 3. '.(x') [ ( ) ~(X')]) ax' ax' ax' 1r x. n = 1. using (60). Consider a continuous elastic line of length L with fixed ends. Vk = sinh Xk.32 QUANTUM THEORY OF SOLIDS such as iJ1/. (b) Calculate the mean square fluctuation of 1f in the ground state of the line. where L Ie (123) Uk = (2IL) H sin kx. commute. For theorems on derivatives of delta functions. Develop 1f(x. J1r(r')2 dT'l = J [1f(r).1r(r')l dT'. . 312 3 8 3 = 8Z 8 t3 ' here kB is the boltzmann constant and (125) + where k B 8Z. 3.
where the a. b are boson operators. whence show that the mixture of excitations k in the ground state is given by (130) (atak)o = (<fIolatakl«l>o) = Vk 2 = ~ (cosh 2Xk .9 and 6.ACOUSTIC PHONONS. Phys. in good agreement with the observed po~ition of the minimum in the elementary excitation dispersion relation. 9 (1960). 119. €k assuming Vk = constant.. This equation satisfies the sum rule of Problem 6.w(k)). that the dispersion relation is related to the Hquid structure factor by the Feynman relation (133) k2 w(k) = 2MS(k) The liquid structure factor measured by neutron diffraction [D. Suppose that the interactions in our condensed boson gas are such that at low k only quasiparticle excitations exist and have the dispersion relation w(k). cosh 2Xk = . Rev. Diagonalize H = wa+a + E(ab+ + ba+). 33 (b) Show that (128) atak = uk2atak + Vk 2 + vk2a~ka_k + ukvk(a:a~k + akak). Return to this problem after studying Chapter 6 and particularly Problems 6. CH. . ak<flo = 0 (c) The ground state <flo has the property (129) for all ak.1). Then at low k we approximate the dynamic structure factor S(wk) by (132) S(wk) '" NS(k)o(w . 7. 2] has a strong peak near k = 2. . Henshaw.10.9. using the sum rule of Problem 6. where S(k) is the liquid structure factor used in Chapter 6.10. Fig. Show. 2 .. + NVk 6.0 AI. G. Note Make a rough plot of (atak)O versus that (131) Ikl.
Plasrnons.. The plasma frequency in an electron gas with a positive background charge is a limiting case of this effect. . . The remaining 38 . We also discuss optical phonons in ionic crystals. and these have finite eigenfrequencies as k + O. There are then strong effects on the dispersion relations. (c) In certain circumstances the long wavelength transverse optical modes will couple strongly and be mixed with the electromagnetic radiation field.. . Our first example is the electron gas in a metal.. .E: ga~. The long range of the coulomb interaction will increase considerably the frequency of the longi tudinal optical branch with respect to the two transverse optical branches.. with a rigid . . optical phonons. with equal charges of opposite sign. (b) Consider a crystal having two ions per primitive cell. this problem will be developed in much greater detail in Chapters 5 and 6... ... fi~ed background of posftlve charge.. PLASMONS We cOl!. . Thus we are concerned in the following with fields for which electric charges of one sign are displaced relative to charges of the opposite sign. . ' ~ M ' . .. ..a continuum model of an elect!9. . . The three branches whose frequency approaches zero as the wavevector approaches zero are called the acoustical phonon branches. The continuum ~ ~ '. . and polarization waves 3 In this chapter we study simple examples of several important effects: (a) The phonon excitation spectrum will contain 38 branches if there are 8 atoms or ions in a primitive cell of a crystal.~~der.. .3 branches are called optical phonon branches.. . both without and with coupling to the electromagnetic field. ..
with electrostatic terms included and shear terms omitted: (1) JC 1 aR oR" =2 . = LQ~'"k..PLASMONS.Jax. The transverse mode eigenfrequencies are therefore zero.. ax" Using (2. k .72). but it allows us to see certain central features 6f the eigenfrequency problem in the presence of the longrange coulomb interaction. equal and opposite to the average charge density of the electrons. the dilation is aR.4'_~~u~ncies. _ .Po is given by (3) ~ ~p p = ~(x).. The volume is also filled uniformly with a rigid background of positive charge of density Po = nlel.. The longitudinal eigenfrequencies..frequeJ1~ieS. The positive background is exactly canceled by the uniform (k = 0) component of the negative charge density.po). 3" 35 an approximation. with n electrons. derived from the poisson equation (2) V 2 cp = 41r(p . ~ where nm is the mass density of the gas.  The hamiltonian density is given in analogy with (2.l  ne oR. as if the gas were uncharged. For small local dilations of the electron gas. are relatively high . The factor! in the last term on the right of (1) enters because the electrostatic term is just the selfenergy of the electron gas. ANI) POLAH.73) for longitudinal waves (Qk (5) R(x) II k).IZATION WAVES. called plasma . where (4) is the dilation. as is shown in detail in Chapter 5. The electron gas is contained in unit volume. Thus ~p = _pA _ L. Longitudinal waves in the plasma cause dilations and contractions in the electron gas. CH.x. thereby destroying neutrality and bringing into play the powerful coulomb restoring forces. a is the appropriate bulk modulus. In our approximation there is no restoring force on shear waves because such waves do not change the local charge neutrality of the system.TI"TI" + fa . the charge density fluctuation ~p = p . cp is the electrostatic potential. OPTICAL PHONONS.p nm !I uX" uX" + !(p  po) cp (X ).
q.1 1""0. (_1_ P~Pk + ak 2QkQ_k + 47rn 2e2QkQ_k)' k nm "". This is the dispersion relation for plasmons.75).81) we have (12) I = w..3 ... w.' = 41rne 2/m.·x. = .1 . Wp is usually referred to as the plasma frequency. whence Wp 10 16 secI. The frequency Wp of the uniform (k 0) mode is derived easily by a direct argument.27g..keik·x. with the momentum density components given by (2. QUANTUM THEOltY OF SOLIDS ~p = ine 2. Let the electron gas be displaced by x. after integration over the volume. the dielectric polarization is P = nex..1 1""0. and the poisson equation becomes (9) q. the term (a/nm)k 2 in (12) is still negligible in comparison with the term Wp 2. k \'" Li q. The excitation of one mode with energy Wk is described as the excitation of a plasmon. For electrons in an alkali metal n 10 23 cm. If we substitute for (a/nm)Yl the velocity of sound in a solid and take k near its probable maximum of 10 8 emI.. The electrostatic term in (1) is. . In the limit e2 ~ 0 the electrostatic effects disappear and we have left the usual dispersion relation W = (a/nm) Ylk for phonons in a gas.36 and (6) Let us write (7) so that (8) V2q. k = ~ k2q.] Jd3x 27rn02e2QkQklei(k+k/)'X(k/k') k = 2m 2e 2 2.' + (a/nm)k 2 .~ik'X.k = 47rineQJr. (11) H = i2.2 In direct analogy to the solution (2. kQkeilr. If the plasma is contained in a flat slab with the displacement normal to the slab.ik. QkQk' 'I'hen.. (10) Jd 3x !(p  po)q. the polarization P will give rise to a depolarization field Ed = 41fP = 47rnex. The 1""0. m IO.
\HIZATION W AV ES. mw ne 2 E and the dielectric constant is (16) P 4nne 2 E=I+4n=IE mw 2 I 2 7' wp When w ~ W p . E int = E . Born and K . Dynamica.4nXEint. CH. AND POL. E int = E j (1 eE  + 41rx) 2) ' = Eje from (13). LONGWAVELENGTH OPTICAL PHONONS. which is not really a plasma effect.l theory of crystal lattices. x eE mw 2 ' P= 2. (13) so that the resonance frequency is (14) W2 = 41rne m 2 = W 2 P .PLASMONS. This neglects ion core polarization. we see that e is positive and the refractive index n = e~ is real. We now consider briefly the dielectric constant associated with the uniform plasma mode. The resonance frequency of the uniform mode depends on the geo metrical form of the container.4nP = E .m (2 w Wp The free oscillations of the system parallel (transverse) to the slab are given by the poles of e. IN ISOTROPIC CRYSTALSl There are three interesting points to be made in a discussion of optical phonons. and (17) mi eE int . . Clarendon Press. thus the threshold for the transparency of metals in the ultra violet is given by w = Wp. the free oscillations normal (longitudinal) to the slab are given by the zeros of E. Huang. If the electric field E is applied normal to the slab. 3 :37 equation of motion of an electron in the plasma is mi eE d 41rne 2 x. Oxford. there is no depolarization field. 1954. Once the wavelength of the plasmon becomes small in comparison with the dimensions of the container the shape effects disappear. Then (15) mi = eE. 1 General reference : M. then (18) x = . If the electric field E of frequency w is applied parallel to the surface of the slab within which the plasma is contained.. with E int to denote the internal field. OPTICAL PHONONS.
71). they represent motions of the ions relative to one another in the same cell or rotations of the group within a cell.1) modes are the k = 0 optical modes.)wt 2. A transverse optical phonon in a crystal 2 R. Phys . In an ionic crystal having two ions per primitive cell. such branches are called optical modes. Lyddane and K. move with identical amplitudes and phases. 846 (1938). None of these 3(s . (c) The electromagnetic coupling between photons and phonons is particularly marked for longwavelength transverse optical phonons. such as NaCI. where eo is the static dielectric constant and f". is the square of the optical refractive index. The frequency difference of the longwavelength transverse and longitudinal optical modes in a cubic ionic crystal can be appreciat ed by an elementary argument. 54. . 2 The normal modes at k = 0 are simple in form : the corresponding ions in every cell. (b) The limiting frequency WI of the longitudinal branch as k 4 0 is appreciably higher because of electrostatic effects than the limiting frequency Wt of the transverse branches: the approximate theoretical connection is (19) WI 2 = (eo/e". This is the limiting frequency of the acoustic modes. The optical modes are sup pressed in the usual macroscopic analysis. F . I We now consider these points. H. Rev . the three optical branches at long wave lengths may be classified approximately into one longitudinal and two transverse branches. and there results a forbidden frequency gap between Wt and WI in which a thick crystal does not transmit energy.1) frequencies at k = 0 will in general be zero. Herzfeld. but we do not enter into the details to be found in the book by Born and Huang and in the paper by Lyd dane and Herzfeld. Three of the modes correspond to the uniform undistorted translation of the cell as a whole. and thus have zero frequency.1) branches each having a finite limiting frequency as k 40. There will be in addition 3(s . The other 3(s . two mainly transverse) of its vibrational spectrum whose frequencies approach zero as k 4 O.38 QUANTUM THEORY OF' SOLIDS (a) A crystal with s nonequivalent ions per primitive cell will have three branches (one mainly longitudinal. by definition of k = 0. There is a strong optical reflection band in the region of the frequency gap. These branches are called acoustical modes. such as we carried out in Chapter 2 following (2. There are 3s equations of motion of the s ions in a primitive cell.
u_ is the relative displacement of the positive and negative ion lattices. the equation of motion for the transverse oscillation is (21 ) Mu + MWt2U = Wt 2 0.. Optical modes of oscillation: (a) transvcrse and (b) longitudinal. Thc with two ions per cell. 3 39 o • t ~ o • 1 ~ o • ~ o • ~ o • ~ o • 0 r t 1 1 r . 1.PLASMONS. dire ctions of the displacements of individual ions are shown. where M is the reduced mass and is the transverse resonance fre . CH.'. OPT ICAL PH ON O~S.'.J) I'O LA RlZATlO . la. is pictured in Fig.~ i 1 1 ~ t o • 1 o • k (a) ~ o • +0 ~ o • +0 ~ ~ o • k (b) +0 ~ o • Basis: 0 • Anion Cation FIG ... (20) If u = u+ . A. WAVES. such as NaCI or CsCl.
The macroscopic theory of the optical modes of di. and the . e 2 ' " 25 X 10.is the relative displacement of the positive and nega tive ionic lattices..u. Note that Mn is effectively the reduced mass density. We consider the general case where the ions themselves are polarizable (nonrigid). where Ei is the internal electric field developed in the deformation. The kinetic energy densit) associated with motion of one lattice against the other is jw2.1tomic crystals which we now present was developed by Huang. then P = neu. ThE potential energy density may contain terms in w 2. Taking n = 10 22 cm. For the optical mode at k = 0 we introduce the coordinate (24) w = (u+  u)/(Mn)~. so that (23) Wl 2 = Wt 2 + 47rne 2/M.c = jw 2 . where u+ . The field satisfies D = 0 = Ei + 47rP. so that Ei = 471"P. where I'll. E2. Thus the restoring force will be . of the same order of magnitude as "'t. lb. treating them internally as rigid. The momentum density conjugate to w is hamiltonian density is (27) :JC ')'12W· n = o.3. If we neglect the induced polarization on the ions.'Y12W • E . The restoring force on an ion is not w t 2Mu.40 QUANTUM THEORY OF SOLIDS quency. . 1'22 are constants to be determined below. and n is the number of cells per unit volume. From (25) and the lagrangian equations we have the equation of motion (26) w + I'llW = jII 2 + jI'UW2  ')'12E = O. M = M+M_/(M+ + M_) is the reduced mass. we have 2 13 (47rne /M)H ~ 10 secI. where n is the number of cells per unit volume. and w· E.wt 2 M u . A longitudinal optical mode is shown in Fig. The effect on nonrigid ions is sometimes represented schematically by writing an effective charge e* for e in (23). We assume that the wavelength is much smaller than the dimensions of the specimen.c/ ow = E h22E2. M = lO22Q .h22E2). W. although long in comparison with atomic dimensions. where E is the macroscopic internal electric field. 1'12.(huW2 .47rn 2eu. The lagrangian density is (25) .20 (esu)2. but is (22) Wl 2 Mu = Wt2Mu + Bie.
it is con sistent with (23) above as derived for Eoe = 1. we have (30) P = [(1'12 /1'11) 2 + 'Y22]E = EO . and Teller. so that (26) becomes Wt + 'YllWt = O. This must be identical with w + Wt2W = 0. an applied static electric field creates a value of W given by 'YllW .'Y12E = 0. 3 _ 41 ~ The polarization P is given by (28) EO. Thus (28) gives (34) E + 41rP = (1 + 41r'Y22)E + 41r'Y12Wl 2 ) = 0. and Wt. We now solve for 'Y11. P = . Substitut ing this value w = ('Y12/'Yll)E in (28). Sachs. using the . according to (26).ax/aE = 'Y12W + 'Y22E. and the equation of motion (26) becomes (35) WI + ('Yll + 1 41r'Y12 + 4"'Y22 2 = 1'11 Wl = 0. CH. AND POLARIZATION WAVES. The transverse optical mode does not generate a depolarization field E. Under static conditions W = 0. OPTICAL PHONONS. whence (29) 'Yll 2 Wt . very high frequencies w approaches zero and (31) E 1 P = 'Y22E = ~ E. 1'22 Thus = EQ()  1 41r and (33) 1'12 = (EO  41r Eoe)~2 Wt· The longwavelength longitudinal optical modes are characterized by D = E + 41rP = 0. For NaCI. 'Y22 in terms of the accessible constants EQ(). _ Eoo This result was first derived by Lyddane.PLASMONS. for static conditions. At where we understand (32) EQ() to include the electronic polarizability. 1'12. in the absence of external fields. or (36) Wl + + 41r'Y12 2 1 41r'Y22 EO Wt 2 . where EO is the static dielectric constant.1 ~ E.
p..09 X ~013 secI."Y11 "Yl2 2 0 0 1=0. it is evident that this relation will cross at some point the dis persion relation for each optical phonon branch.3. This interaction is particularly important when the frequencies and wavevectors of the phonon and photon fields coincidenear the crossover of the dispersion relations even weak coupling of two fields can have drastic effects.ve the maxwell equations simultaneously with the lattice equations: 1 curl H = . with EO = 5. try Ez = Ez(O)ei(wtkIl). We First we look for transverse solutions E 1. ikEz = (iw/e)H II . Then the differential equations become ikHII = 2 (iw/e)(Ez + 4rP z ). H 11 = = wz(O)ei(wtkJ).k as a photon field. Our problem is to soI.".02 and Eao = 2.25. k w/e P z = "Yl2Wz + "Y22 E z. The dispersion relation for photons is W = ek. 5. one calculates WI = 4. H II. P z .42 QUANTUM THEORY OF SOLIDS observed Wt = 3. . Fig. (w + "Y12)wz = "Y12 E z.87 X 10 13 secI. P curlE = . where e is the velocity of light.(E e + 411"P). + "YllW  "Y12E = + "Y22E. W + 4rP) = "Y12W = 0. but it is not usually very strong. . The uncoupled solutions for a one dimensional problem are indicated in I SSP. H II(O)ei(w th). Wz vanishes: w/e (37) 4rw/e k "Y12 o o "Y22 1 0 0 w . div (E 0. INTERACTION OF OPTICAL PHONONS WITH PHOTONS The preceding treatment of the optical lattice mode problem at k = 0 has neglected the interaction of the optical phonons with the photons of the electromagnetic field. We do not discuss here the k~dependence of the uncoupled optical phonons.H' e ' 1 div H = 0. 111. These equations have a nontrivial solution only if the determinant of the coefficients of E z . Wz P z = Pz(O)ei(wtkJ). .
.& r / q.. where now is to be viewed as a symbol defined by (29).(..' = "'t'('o/'~) = "... W = c k /Eao.:o k FIG. There are no transverse solutions for frequencies between Wt and W Wl P~ / / / / '7 Wt .'. Eao and EO are given by (32) and (33).... 2 that the lower branch is photonlike at low k and phononlike at high k with frequency Wt... and becomes photonlike at high k.. 2.. Coupled modes of photons and transverse optical phonons in an ionic crystal.~e / ~ /. 3 43 which may be written as (38) Wt 2 w\1Q w2(Wt2EO + c2k 2 ) + Wt 2c2k 2 = [ 1 4Eao2 0. AND POLARIZATION WAVES. The solutions are (39) w 2 = 1 2Eao (Wt 2E O + c 2k 2 ) ± (Wt 2E O + c 2k 2 )2  Wt 2k2 (C2)]~2 Eao • For k (40) ~ 0 the transverse solutions are I"...=:..11'. ~o~ . (42) We see in Fig.:.. even though the phonon is transverse.:~= / ~ Phononlike / .1. OPTICAL PHONONS. The upper branch is phonon like at low k with frequency Wl....=. . PLASMONS.. The broken lines show the spectra without interaction.:=.:::. CH..:==:=.. Iw 2 and (41) = (c 2 / Eo)k 2 ·1 The twofold degeneracy in each of these solutions reflects the two independent orientations of E in the plane normal to k. For high k the solutions are 2 2 2 2 2 W = Wt .
Phys."... This is found experimentally. + at aP. _ . and P are equivalent to the maxwell equations plus the constitutive equation a a. The lagrangian equations of motion for the field vari ables A. Fano. QUANTUM THEORY OF SOLIDS further. The for bidden optical band appears as a frequency region of high reflectivity. 1202 (195G) • . There is thus a forbidden band of frequencies between Wt and Wl in which it is impossible to transmit energy through the crystal.c + .c = 1 (1 81r ~ A + grad f{J )2  81r (curl A)2 1 1 + 2x (P2  w0 2p2) P·GA+grad .44 Wl. and H = o. (44)  or. No specifically quantum effects are discussed in detail. Hopfield. We have just (35) and (36)... Thus there is no effective coupling between the photon and the longitudinal phonon fields. The lagrangian density for an electromagnetic field in an infinite classical dielectric of rigid ions may be written (43) . with E == (45) 3 !A c grad f{J.c !. a. ax. 112. there is no longitudinal mode solution in this region because the photon field is purely transverse in isotropic media.c = ! CPa + W02Pa) a. Such effects in isotr()pic or cubic crystals occur only for transverse optical phonons. Phys. f{J.a(apajax". QUANTUM THEORY OF A CLASSICAL DIELECTRIC 3 We treat the same problem by the methods of quantum field theory as an exercise in handling the quantization of coupled fields. with appropriate correction for damping. + G A+ grad . J. Pa + wo 2P a XEa. Rev.. as only these couple with an electromag netic field... Wz "" ei(wtkz). Then Ez + 41rPz = 0. exactly as in the absence of retardation.. where X is a constant which in gaussian units has the dimensions of (frequency) 2. J. which is always transverse in isotropic media. U. N ear the cross over of the dispersion relations (w versus k) of the uncoupled photon and optical phonon fields we have seen that a weak coupling has drastic effects in mixing together the mechanical and electromagnetic fields. The longitudinal solutions are found by trying E z . 1555 (1958). 103. Rev. P z .).. .) X ) _ 0 aP.
[(V'P)a C n .div (grad'P . 3 45 The equation of motion for 'P gives.. 411'c C and similarly for II: (51) ITa a.. =1 . (53) A = ~ (~cr tk>(a".eikOZ).41rP) = div (E + 41rP) = O. 1 2Aa . We now expand.aAa a. The latter is equivalent to a dielectric dispersion law appropriate to a rigidion model (that is.. OPTICAL PHONONS. The equation of motion for Aa is.1 2 (A)2 811'c . C 1 The momentum M conjugate to A is defined by (50) Ma .')p' + 4rcM· P. this completes the derivation from the lagrangian of the maxwell equation and the constitutive equation. We may drop 'Pi the lagrangian density now reduces to (49) .e 1. no electronic polarizability): (48) E We have seen in the preceding section that the longitudinal modes of the dielectric polarization field do not couple with photons and therefore do not concern us here.eilC' x..Pa.e"'·· + at... . With the definition H = curl A. . (54) P = kA 2(41I'x + X]li wo2)li £k~(~~eik'x L[ + bt.). with periodic boundary conditions over unit volume.X = The hamiltonian density is given by (52) X = MaAa + ITaPa .. Aa . 1 811' (curl A)2 1 +(p2 2X w0 2p 2)  p. in the coulomb gauge with div A = 0.. = aPa .e = .c 21I'c 2M2 + 8~ (curl A)2 + ~ 112 + (2. AND POLARIZATION WAVES. in the coulomb gauge. (46) .e _ ~Pa. CH.A. (47) V Aa 2 1.It· PLASMONS.+ .411'r a].
L {ck(atak)' + t) + wo(1 + 47rfJ)li(b0. ~ is the polarization index.  k). The first two combine to give (G1) V2H = c. (55) H = + i[1rckfJwo/(l + 41rfJ)li](at). The hamiltonian is diagonalized by the introduction of annihilation operator (56) ak X.bk). This is an interesting and striking example of coupling with the electromagnetic field. and M is the magneti zation. We have now set up the problem. = wak + xbk + ya±k + Zb±k..H] = The solution of the eigenvalue problem (57) is the dispersion relation 22 22 2 4 (58) Wk . The hamiltonian becomes.46 QUANTUM THEORY OF SOLIDS here Ek)' is a unit vector in the direction of the polarization of the wave. + a~k). identical with (38) . The details of the calculation are given in reference 3.(n c • + 47rM). b+ have the properties of boson operators.)}. M+ = J! x + iM y. a+ and b.2w2(H+ + 47rjlj+). but shall only sketch the solution.2(H + 41rM). (GO) M= ')'M X H. . (57) y.bt). with H+ = H x + iH y.wsH+).bt). Wkak' where w. where')' is the magnetomechanical ratio ge/2mc.  + t) a_k).)) = + Wo . ftf+ _wsH+ w so that (0. The linearized resonance equation may be written. The a. with fJ = x/w02.bk). INTERACTION OF MAGNETIZATION AND THE ELECTIWMAGNETIC FIELD We solve the maxwell equations and the spin resonance equations simultaneously in a infinite medium.2 = 0.Wk 2[ (1 + 47rfJ)wo + c k ] + w0 c k. z are chosen to satisfy the relation [ak.b ak). k ).. with wo = ')' H 0 and W8 = ')' M z for a static field H 0 in the z direction: (62) iwM+ = i(woM+ . k 2H+ = C. For E = I. (59) 1 curl H = E' c ' 1 TT curl E = .
Pincus [J. Roughly speak ing. . Dispersion relation for coupled photon and magnetization fields..PLASMONS.. ~q FIG. Thus the magnon branch (Fig. but arises solely from the effect of displacement currents. This result has nothing to do with demagnetizing fields. 3) comes in to the origin k = 0 at rather than at W = "(II. This effect is well known in ionic crystals and has been demonstrated by P. CH.(B.L surface) at w = . without exchange..l 'YBI / / / 'YH J~ / /  / 1/ 6 I. the displacement current shift in the resonance frequency develops when the plate contains a wavelength or more of the radiation. and not at w = "(B i . ' this has a branch at k (65) W 0 when = "(Ho = wo + 41rws + 41rllfs) = "(B. magnetic resonance is observed in flat plates (with H . However. (G4) c k = 2 2 = w ( 1 2 + W + Wo 41rws ). AND POLARIZATION WAVES. OPTICAL PHONONS. (I.. 33. Phys. 3 . Appl. The point is that in thin plates the displacement current term is not able to shift the solu tion from Hi to B i .(Hi. W = .47 Using (63) in (61). 3. 553 (1962)] for the magnetic resonance problem by solving exactly for the surface impedance of a plate as a function of the thickness. The result is the analog of the LyddaneSachsTeller rela tion (36) in ionic crystals. where Hi is the internal field corrected for surface demagnetization.
(67) WL = Wp 2L + 1 where wp 2 = 411"ne 2 jm and L is the order of the legendre polynomial in the exterior and interior potentials (68) C{Je ex r(L+1) P L m( cos 8)e im <P. Phys. using as a rough estimate for Xa the polarizability of the Ag+ ion in silver halides. Calculate for metallic silver the effect of Xa on the value of the frequency for which Ell = 0. Suppose that an electron gas has imbedded in it na atoms per unit volume. Show that in (15) (66) PII =(  mw 2 ne2 + Xa ) E. 106. each of atomic polarizability Xa.". C{Ji ex rLPLm(cOS 8)e im <P. 390 (1957).48 PROBLEMS QUANTUM THEORY OF SOLIDS 1. We assume displacemenfcurrent effects may be neglected. 2. Show that the eigenfrequencies of a plasma enclosed in a sphere are given by L 2 2 _. R. Walker. as found in the literature. . . Hint: the intrinsic dielectric constant of a plasma is (69) E = 1 wp w2 • 2 This problem is the analog of the magnetostatic mode problem treated by L. Rev.
including ferromagnetic.. We take H 0 > 0 to make the magnetic moments line up along the positive z axis when the system is in the ground state. The constants of the motion of the hamiltonian (1) include the total spin S2 = (~Sj) 2 and the z component Sz = Sjz of the total spin. The waves are called spin waves. The components are not independent. H 0 is the intensity of a static magnetic field directed along the z axis. SjYJ SjZ of each spin S j..L oH o LSjz. and the unit of energy of a spin wave is called a magnon. canted.. j L j The ground state 10) of a system of N identical atoms of spin S has (2) S210) = NS(NS + 010).7J IS the ma6etic mo.. Spin waves have been studied for all types of ordered spin arrays. jF. as shown originally by Bloch for ferromag nets. HOLSTEINPRIMAKOFF TRANSFORMATION The hamiltonian involves the three components Sjz. ferrimagnetic. the energy of a spin wave is quantized. ""0 = (g/2'). antiferromagnetic.4 Magnons The lowlying energy states of spin systems coupled by exchange interactions are wavelike. J is the exchange integral and is assumed to be posi tive. We shall study the ferromagnetic and antiferromag netic spin waves.2J. FERROMAGNETIC MAG NONS The simplest hamiltonian of interest is the sum of nearestneighbor exchange and zeeman contributions: (1) H = . but are connected 49 ./ L SjOSj+it . i where the vectors 5 connect atom j with its nearest neighbors on a bravais lattice. Sj is the spin a~r rffiomeI!tum operator of the atom at j. first with an atomic hamiltonian and later with a macroscopic hamiltonian. and spiral arrays. SzIO) = NSIO).
= s· )X (2S) Har(1 . (6) Sz2 = + 1) = S(S + 1) S(S Sx 2 . . (4).a+a/2S)Haa+(l .i(S+S + SS+) S[(l .a+a/2S)a]. Phys. SL = §~±)). in order that the S+. k Xj aj N~'J . From (3).a+a/2S)~fl a+(1 . and (5) we may calculate the transformation for SZ' Now.a+a/2S) (1  a+a/2S) (S  a+a)2. tion is then given by (10) aj The inverse transforma = NYA L eik'Xjbk.a+a] = 0 and [a+a.satisfy the correct commutation relations. .aj to the magnon variables bt. L eik'Xjb"t k The signs of the exponents ±2K· 1 have been chosen to agree with T.S[2a+a(1 .xja~ . k j J' here Xj is the position vector of the atom j.bk defined by (9) bk = NYA L eik. 1098 (1940). Rev.Sy2 = S(S + 1) .ajaj.a~a· J J ) / /2S)~~· . + 1) + + a+a/2S] SjZ = S . aj is defined by (:3) (4) I sj S7 J = Sjx + iS jy is JY · = (2S)~~(] = . It is convenient to make a transformation from the atomic at. here we require (5) rahat] = Ojl. j b+ k NIh ~ eik.a] = a. It is more convenient to work with two operat~are independent. Primakoff. The HolsteinPrimakoff transformation 1 to boson creation and annihilation operators aT. dropping the subscript j.xjaj. 68. + Using [a+a. we develop (6) to find (7) Sz 2 = S(S = whence (8) . S.50 QUANTUM THEORY OF SOLIDS by the identity Sj.ajaj/2S)~~aj. Holstein and H.
th_~_?~~~l1tor 11k. Sj = (2S/N)~~ [L eik'l[.k'...N""':l Li J i  Ukk'.ataj = S .1 Jxk' L ei(kk')'l[ibtb k ..(4SN)1 (15) L k.bk ..b " k [L k eik'l[ibk .MAGNONS.(4SN)1 (16) L k. · and st.k'. . b+] k' Je ik"l[l[ aj.w_aY~. and SZj in terms of the spinwave variables.btbk. We now wish to express Sj. We will be concerned chiefly with lowlying states of the system such that the fractional spin reversal is small: The operator bt ~l~a~~on~. destroy.1 Li ~ eik'l[. ~ and (12) [bk.a magI!on of 'waveVector k. + ._~r. .N. +] [b k. 4 ~'] those adopted by Holstein and Primakofl'.a. j j (17) £z = NS .btJ = o.bt k ..·~. . = NS L btb k k.~) (ataj)/S = (nj)/S « 1.J. the boson commutation relation: (ll) j1 The commutator satisfies .] ei(kk'k") 'l[. the eigenvalues of btbk are the positive integers nk' . We note that the total spin operator for the whole system is NS  £z = NS  L Sjz = L ajaj. so that it is pertinent to expand the square roots in (3) and (4). '" ei(kk')'l[. Thus btbk may be viewed as the occupation number operator for the magnon state k.s .k" + . The dIscrete values of k slImmed over"are those obtained from periodic boundary conditions.N.]..Nl L kk' ei(kk')·l[. CH. This is exact.btbk .] = [bt. (l.btbitb " k Sjz = S . Then (14) gj = (2S)~[aj = (2S/N)~~ (atapj/4S) + .~~_?!9l'.k" ei(k+k'k")'l[.
(20) Xo = JzS L {'Ykbkbt + 'Ykbtbk k 2btbk l + 2p. if there are z nearest neighbors.ibkbt i(kk').e J VJl:k'J X eik'·ib+b + (2p.(x o +i)J. All field amplitudes which are macroscopically observable are boson fields: the field amplitude of a fermion state is restricted severely by the occupa tion rule 0 or 1 and so cannot be measured accurately. S.52 QUANTUM THEORY OF SOLIDS We emphasize that the a's and b's act like boson amplitudes.xob+b i(kk'). Sz to spinwave variables. If there is = 'Yk. . + ei(kk'). and it may be neglected when the excitation is low. despite the fact that electrons are fermions.' i over the z nearest neighbors.e Jkk. neutrons) is a fermion. HAMILTONIAN IN SPINWAVE VARIABLES Using the transformation of S+.xibtbk" L which becomes. protons.oHolbtbk. Wk = 2JSz(1  'Yk) + 2p. jkk' where the term bilinear in spinwave variables is (19) Xo =  (JS/N) L jikk' {ei(kk'). We can write (22) as (23) Xo = L k nkwk.oHo/N) ei(kk')..oHo. the hamiltonian H = J L8 j6 j • Sj+i 2p. L {2JzS(1 k + 2p. The term Xl in (18) contains fourth and higher order terms in magnon operators. k where (21) 'Yk = zl Leik.eik.x.X. even though every fundamental particle in the system (electrons. on summing over j. a center of symmetry (22) Xo = 'Yk We note that then 'Yk) L k 'Yk = o.oH oNS + Xo + Xl. (18) H = JNzS 2  2p.+b 1 kk. This is no more surprising than having phonons act like bosons.oHo L btbk.oHo LSjz j becomes.
Acoustical and optical magnon dispersion relations in magnetite. tID Q. (24) z(1 . 1. The tenninology is borrowed from the corresponding phonon problem. as determined from inelastic neutron scattering by Brockhouse and Watanabe (IAEA Symposium. This is the dispersion relation for magnons in a spin system forming a bravais lattice.4 aq/21r 0. For Ik •61 « 1.06 '~ * >.02 00 0.6 0. 1962). so that there is one acoustic magnon branch and several optical magnon branches.08 > c ~ 0.04 0. Experimental curves for magnetite are given in Fig.8 1.2 0. the primitive spin cell in Fe304 contains several ions. (k • 6)2. Ontario. .MAGNONS.'Yk) ~! L (k • 6)2. Chalk River.0 FIG. CH. 10 1 0. 1. 4 I 53 24°C [001) 0. ~ 0. & and (25) Wk r'J 2JLoH 0 + JS L .
Keffer and R. we find. lea ~ 102 to 103. (30) Ik. .25 cm 2 . The collision cross section for two spin waves kl' k2 has been calculated by F. The leading term in :Jel is biquadratic and leads to coupling between spin waves.. so that the magnon magnon exchange scattering cross section is of the order of 10. Using (14). where a is the lattice constant. Appl. if we set 2JSa 2 = 1/2m*... Loudon. 2'YI + 2'Y3  4'Y13 .54 QUANTUM THEORY OF SOLIDS which reduces for sc. (29) :Jel = (zJ /4N) 1234: L btbtb3b4~(kl + k2  k3 . 102. or (28) m* = 1/4JSa2• For conventional ferro magnets with curie points at or above room temperature the observed dispersion relations lead to m * of the order of ten times the electronic mass. J. Phys. MAGNON INTERACTIONS The exchange hamiltonian is only diagonal in the spinwave vari ables if we neglect the interaction :Jel in (18). A physical interpretation of the Dyson result has been given by F. &1« 1. bcc.k 4 ){2'Y1 + 2'Ya For 4'Y13}. after a simple but tedious enumeration and rearrangement of tenns up to fourth order. For magnons having microwave frequencies. J. Dyson [PhY8. where ~(x) = 1 for x = 0 and ~(x) = 0 otherwise. (Supplement) 32. namely (27) Wit = 2m* _1_ k 2 . 2 (1961). which is very small for an atomic process.. Rev. and (16). 1217 (1956)] and is of the order of (kla)2(k2a)2a 2.. (15)..S(kl • &)2(k a • &)2}. 1 L2 {2(k Z i 1• &)2 + 2(k3 • &)2 . and fcc lattices of lattice constant a to (26) I Wk = 2#JoH o + 2JS(ka)2] We note that the exchange contribution to the magnon frequency is of the form of the de Broglie dispersion relation for a free particle of mass m *.
Now ret) = 3r~/4 and r(t. 4 . 2(4rD)YJ . Then the integral has the value r(t)r(ljl). or. according to the JahnkeEnde tables. 0 1 dx xYJ e~ _ l' where the upper limit may be taken as 00 if we are interested in the region T «~max. . with x = Dk2IT. and assume « 1. which are the dominant excitations at low temperatures. A discussion of the effect of magnonmagnon exchange interactions on the renormalization of magnon energies is given from Eq. D == 2SJa 2 • The internal energy of unit volume of the magnon gas in thermal equilibrium at temperature T is given by. and r(S. a plot of CT~ versus T~ will be a straight line..457% . CR. Thus the degree of diagonalization of the exchange interaction by the spinwave trans formation is extremely good for longwavelength spin waves (ka« 1). (35) IC = dUIdT = 0. (32) U = LWi[(nk)T = L k k Wi[ • ellJk/~ 1 _ = 1 (2r)3 Jd k Dk2 eDkt/~1 3 _ 1 .113k (k B B TI D)~·I If the heat capacity is composed solely of a magnon part a: T's and a phonon part a: T3. neglect magnonmagnon interactions. (33) U = :2DYJ % !. (131) on.341.l) = 1.·55 We see that a transition probability involving 1(13C[>12 will be pro portional to (ka)4.r2D~' for the heat capacity of unit volume.a) is the Riemann zeta function (see Whittaker and Watson. MAGNON HEAT CAPACITY ka We set H = 0. Chapter 13). where a is the lattice constant. Thus (34) U = 3T%r(t) ~ 0.MAGNONS. with T == kBT.~. Modern analysis. then (26) gives Wi[ {31) = Dk2. where rex) is the gamma function.
1 Therefore where the integral is equal to r(l)r(I. and taking unit volume. 2. Heat capacity of yttrium iron garnet.56 QUANTUM THEORY OF SOLIDS ..81 X 1028 ergcm 2 and 0.I). Thus for the saturation magneti zation. (36) and (37) M 8(0} . (After Shinozaki. as in Fig. with the intercept at T = 0 giving the magnon tribution and the slope giving the phonon contributions. leading to m */m MAGNETIZATION REVERSAL con Two D = ""' 6.117(JLo/a 3 )(kBT/2SJ)*.M8(T) }y[ 8 = 2JLoSz = 2JLO (NS  ~ btbk ).)% («> dx x~ z_I_.) The intercept at T = 0 measures the magnon contribution. with the same assumptions as for the heat capacity.&:! 10 200 "'0 "'e ~ ~ 100 e ~ o ~ . The number of reversed spins is given by the ensemble average of the spin wave occupancy numbers. . 2. showing magnon and phonon con tributions.117JLo(kBT/D)~2 = 0. D Jo e . J d k 3 1 At low temperatures such that Dk max 2 » (38) !:&M = JL02 27r (!. 2JLO (27r)3 == !:&M = 2JLO ~ (nk) = f T. (39) I!:&M = 0.85 X 10. specimens of yttrium iron garnet measured by Shinozaki gave 0. 00 1 2 3 4 5 6 10 'f3/2(deg 3/2) FIG.28 ergcm 2.
I. on expanding the leading term in the magnetization reversal (kBT /2SJ)%. . Akhiezer. I. Bloch.MAGNONS. Soviet PhysicsUspekhi 3.})Ma(O) for sc.l. Nauk 71. We see that magnonmagnon interactions have little effect on the temperature dependence of the saturation magnetization. bcc. a lowtemperature heat capacity a: T dominated by excitation of one electron states and a magnetization reversal a: T'2 dominated by magnon excitation.. in Low Tentperature Physics. Rev. 869 (1951)] have shown that there is no inconsistency for a metal to have. excitation by magnonphonon coupling. then for numerical significance the integral over d 3k should be taken only over the actual range of k space and not to c(). 4 .O (g/2)J. New York. is of order (kBT / J)4. Bar'yakhtar. Keffer. A. We note that 2SJ. V. including spinwave resonances in thin films. and fcc lattices. Gordon and Breach. 1230 (1956)] has considered the terms in IlM in higher orders in kB T / J. 533 (1960). and M. G. 1962. parallel pumping. as observed.j. 567 (1961). that is. if one includes the T5/1. CR. where J. Van Vleck. 286 (1962). Thus 8 . Herring and Kittel [Phys. Dyson (Phys.B is the bohr magneton. Usp. Reviews of some aspects of the literature on ferromagnetic magnons are: F.'Yk' However. Fiz. Keffer and Loudon have given a simple picture of the origin of the T4 term.. where S is the ensemble average projection of a spin on its nearest neighbor: S (Sj' 8 j +41 )/8.o/a 3 = (1.B. The first term in IlM arising from the nonideal aspect of the magnon gas.S a: T~2 from (34). Mod. 102. Revs. we get a further term in (kBT /28J)~2(kBT/2SJ)~2 a: T4. they give a dynamical argument that in (39) one should use F. for the high temperature region see M. 57 recalling that J.l. for 8. Van Kranendonk and J. C. inelastic neutron scattering. I{ittel.l. There are a considerable number of experiments in which selected magnons are excited and detected. Letters 9.l. Rev. We do not consider the effects which may arise in ferromagnetic metals because of the thermal redistribution of electron states within the bands. respectively. J. except near the curie temperature. T~2 terms. Kaganov. in Encyclopedia of Physics (Springer) (in press). Rev. and magnon pulse propagation in discs. Terms with exponents! and! arise from the use of full 'Yk rather than the leading k 2 term in the expansion of 1 . from magnon magnon exchange interactions. 1 (1958). Phys. 30. H. original in Russian. 81. Phys.
. (London) 66.aja./2S)~~aj.btbz. Proc. they are not magnon variables. W. We assume the spin structure of the crystal may be divided into two inter penetrating sublattices a and b with the property that all nearest neighbors of an atom on a lie on b. The motivation is obvious for the association of b+ with and a with We introduce the spinwave variables st st.N~ Lte l. with the property of tending for positive JJ.xiaT. = S .ajaj/2S)~. We shall see that the configuration with each sublattice saturated is not the true ground state. Anderson. which approximates the effect of the crystal anisotropy energy. Nakamura. although these may be important in real antiferromagnets.ajaj. This simple sub division is not possible in all structures. (2S) ~bt (1 . 540.z direction. l 2 Nagamiya. i l ct = N~ ~ e£k. Ziman. 97 (1955). PhY8. . Kubo. Sbi stz = = (2S)~(1 . 548 (1952). Sr. 87. Yosida.j = (2S)~at(1 . Thea. Rev. PhY8. We make the HolsteinPrimakoff transformation: (41) (42) sdi = (2S)H(1 .o to align the spins on a in the +z direction and the spins on b in the . 86. and Kubo. and vice versa. R. PhY8.btbl/2S)~bl. dt = N~ L eik'X1bt. + 2JJ. Advance8 in Physics 4. bl are creation and annihilation operators which refer to the lth atom on sub lattice b. the z axis. Prog. J. 7. We have further (43) Sj. The quantity H A is positive and is a fictitious magnetic field. J ~ ik'X1b' dk .oHA L S~. Rev. using the other choice of sign permitted by (7). We introduce H A chiefly to stabilize the spin arrays along a preferred axis.bib z/2S) ~. P. T. (44) (45) Ck = N~ L eik'xiaj. We omit every where in this section the effect of nextnearestneighbor interactions.568 (1952). S.58 ANTIFERROMAGNETIC MAGNONS2 QUANTUM THEORY OF SOLIDS We consider the hamiltonian (40) H = J L 8i • 8 + i6 j 3  2JJ. i i here J is the nearestneighbor exchange integral and with the new choice of sign is positive for an antiferromagnet. 694 (1952). Soc. Here bt. = S . 539 (1952). PhY8.oHA LSi.
k SO: JZ (48) S . {j with [ak. We neglect XI. {j+.x'ck + . + dtdk)] k where the term bilinear in magnon variables is (50) Xo = 2JzS _ L ['Yk(ctdt k + Ckdk) + (CtCk + 2p.x'ct + . st k k (46) S~ = (2S/N)Yl (2S/N)Yl (L eik. ~ c+· a+ k k' a_k ~ WI dk .. oH A . [{jk. and for dover atoms l on b. We trans form to new creation and annihilation operators a+. The leading terms in the expansion of (41) and (42) are = (2S/N)YJ (L eik. a. We now look for a transformation to diagonalize Xo.x. if there are z nearest neighbors. (49) H = 2NzJS 2  4Np.59 The sum for c is over the N atoms j on sublattice a.{jk] = 0. 'Yk Z with (51) 1" 6 '' e ik·O 'Y k' assuming a center of symmetry. The hamiltonian transformed to magnon variables is.. (2S/N)Yl {L eik. The problem becomes identical with the Bogoliubov problem discussed in Chapter 2 if in (91) there we make the identification (52) (53) ak ~ Ck. Sfz = S + N.1 kk' Lei(kk').at1 = 1.. etc. ~ a+ ~ d+· k k' Wo ~ 2JzS + 2p. 2JZS'Yk' . k st = (47) Sbi = = {L eik..). }. 4 .x'dt + .c+c • k k'.oHA L(CtCk + dtdk)..MAGNONS. .. }.x1dk + .{jt] = 1. CH.. [ak. .x1dtdk.).N. which contains higher order terms..1 kk' " '' ei(kk'). oH AS + Xo + Xl.
+ WA)' WA  w.60 QUANTUM THEORY OF SOLIDS Then the transformation is defined by (54) lXk = UkCk  vtdt. If a uniform external magnetic field H is applied parallel to the axis of magnetization. . which is the standard result.. oH A • The result is the dispersion relation for antiferromagnetic magnons. By analogy with (2. WH = (ge/2mc)H. Vk are real and satisfy Uk .'. k where each value of k is to be counted twice. nk is a positive integer. Pk = Ukdk f3t = utdt  here Uk. the resonance frequencies are easily shown to become «H) here WH ~' = Wk ± WH. There are two degenerate modes for each k. (57) Xo = N(w e + WA) + 1 Wk(atak + ptPk + 1). then {I . with (56) We == 2JzS. The bilinear hamiltonian becomes. For the uniform mode of antiferromag netic resonance 'Yo = 1 and (60) = [(2we + WA)WA]~.47rp. 2 ak += 2 UkCk  + vk dk. If we neglect WA and take ka« 1. VkCk.98) the magnon eigenfrequencies (55) Wk are given by I "'1<' = (w.1'k2} ~ ~ 3~~ka for a simple cubic lattice. and we have (59) I Wo Wk ~ 4(3)~JSka·1 This is the dispersion law for antiferromagnets in the long wavelength limit. provided Wk/WO »1.''Y. k on actually using the inverse of (54) to rewrite (50).Vk = 1. == 2p. because of the double degeneracy. is the larmor frequency corresponding to H. oH A (S +!) + 1 Wk(nk +!) + Xl. The total hamiltonian (49) is (58) H = 2NzJS(S + 1) . one associated with the a operators and one with the f3 operators. VkCt. with Wk taken to be positive.
We recall that the total number of spins in the system is 2N.{Sz) r = t L [(1 k .1) At absolute zero all (67) ASz nk = 0.. for unit volume. There is some experimental evidence from studies of nuclear magnetic resonance that the actual reduction in sublattice magnetic moment is rather less than is expected from the following calculation. = L Vk 2 = t k = Uk{jk + vkat. dk Here we have used the inverse of (54): (66) == Ukak + v~t. f d 3k (1 . From (48) and (54). 61 ZEROPOINT ENERGY In the spinwave approximation.'Yk2)~]. k now counting each value of k once. . It is usual to express Eo in terms of a constant {j defined by (63) Eo == 2NzJS(S + (jzl). counting both sublattices. (65) S~ = L Sj~ = i Ck NS  Lctck = k (Uk 2atak NS L k + Vk 2{j~t + offdiagonal terms). for WA = 0 and using the transcription of the result of Problem 5..'Yk2)~ . Using (55). 4 . counting each k once. k = NS . and.MAGNONS.58.1 L[1 k For a simple cubic lattice the value of {j is 0. neglecting H A and Xl. (64) {jZl = N.'Yk')ll. Therefore. the exchange energy of the antiferromagnetic system at absolute zero is (62) Eo = 2NzJS(S + 1) + L Wk. = jN + 2(~). CH. ZEROPOINT SUBLATTICE MAGNETIZATION A striking feature of the theory of antiferromagnetics is the depar ture of the sublattice magnetic moment at absolute zero from the value 2NSp. (68) AS. (1 .o corresponding to the elementary picture of a saturated sub lattice.1]. Chapter 2. (cosh 2Xk .
62 QUANTUM THEORY OF SOLIDS where the integral is taken over the allowed values of k. which may be written as (72) Wk ~ kBeNk/k max for the appropriate range of k. where n is the number of atoms on one sublattice per unit volume. gives the numerical constants for NaCI and CsCI type lattices.078N.1Sz = O. and counting each k once. The sublattice magnetization decreases as (T/eN)2. Rev. The temperaturedependent part (70) of the sublattice spin density is (74) 3~ 1r 2a l k '" dk·k· {e(k 1k m )(9N 1T) 1}1 0 ~ 1r 2akm 2 3~n (T)2 {<tJ eN Jo X dx eX . (70) (Sz(O) .we2'Yk2]~ will be at low temperatures essentially exponential in 1/ T until kBT > Wo. It is convenient to redefine k max as for a Debye phonon spectrum: 1 4?r 3 (73) n = (21r) 3 3 k max . 87. 1  ( n) k . Phys. There + . Heat Capacity. The heat capacity of an antiferromagnet having the dispersion relation Wk = [(We + WA)2 . here eN is a temperature of the order of the Neel temperature. Temperature Dependence of Sub lattice Magnetization. where Wo = [(2we WA)WA]~. From (65). with WA = 0.(Sz(T) = where (71) L (nk) cosh 2Xk = L (nk)(1 k k 'Yk2)~\ . Kubo.e"'k1kBT J In an appropriate temperature range Wk is given by (59). cubic lattice the integration gives (69) For a simple .l' for T« eN. At higher temperatures (but not too high) the dispersion relation will be of the form (72). after Anderson. For a simple cubic lattice kmax = ±1r/a along any cube edge. 568 (1952).
Bear in mind that and is not identical with the N eel temperature. the relation [cr .Xj) = on using the identity ~. rather than deal with individual spins 8 j • The range of usefulness of the macroscopic field theory is limited to regions of k space well away from the boundaries of the brillouin zone.x. we have for the magnon contribution to the heat capacity per unit volume (75) IC mag = (4rr4IS)(~)3(T.s1l(x')] = 2i Lcr jzo(x jl J Xj)o(x' . using [sz(x). and magnetostatic energy.Xj)o(x' . We can only use the macroscopic theory where ka « 1.4 cr jzO(X  = isz(x)o(x . The advantages of the macroscopic theory are that it is not based explicitly on a model in which each electron is attached to a particular atom. o(x .crz lI] = 2icr JZO jl: (77) We examine the commutator.Xz) Xj)O(X' . Reducing the standard Debye result for the phonon heat capacity by a factor j.MAGNONS. eN is defined by (72) FURTHER TOPICSFERROMAGNETIC MAGNONS MACROSCOPIC MAGNON THEORY For many purposes in ferromagnetic resonance and relaxation studies it is more convenient or more physical to work directly with the magnetization as a field M(x). magnetoelastic. ... CH.Xj)O(X .3. because fn d3 sex) x is the total spin in the volume O. operator sex) represents the spin moment density at x. and we can easily introduce phenomenological constants relating to anisotropy..x'). The where dj is the pauli matrix for the jth electron at position Xj. I at T « eN. but T » wolkB. We consider the vector spin density operator sex) defined by (76) sex) =i L djo(X j Xj).x'). 4 " 63 are two antiferromagnetic magnons for every value of k instead of three phonons. where a is the lattice parameter.Xj) = o(X ..
with M (82) (83) M+(x) = IM(x)l. For macro scopic purposes we may set M = M 81 a constant.Loa+(x)a(x)..Lo/M)a+(x)a(x)}~a(x). (84) it is easy for the reader to verify that the commutation relations (79) or (80) on the components of M(x) are satisfied. a+(x). k 3 or (86) bk = f d x a(x)eik. ~ Ukk'.(}.LoMz(x)c5(x . [M+(x).a+(x')]ei(k. (85) a(x) = L eik.x').64 QUANTUM THEORY OF SOLIDS We introduce the magnetization by the relation (78) M(x) = g}. (4}.LoM)~a+(x){1 .LBS(X) = 2}.xbtbk. The transformation from a+(x).M(x')] = 4}. 3 3 3 bt = f d x a+(x)eik.LoM) ~ [L eik· k x bk . assumed to satisfy the commutation relation (81) [a(x).xbt.xk'.(}. for unit volume.Los(x). a(x) to magnon field variables bt. a+(x) = L eik.LoM)~{1 .x'). If we write. bk are (88) M+(x) = (4}.f dxe 3 i(kk')·x The magnetization components (82) to (84) in terms of the bt. }. .x.a+(x')] = = c5(x .Lo = g}.(}.2}.xbk . whence.l = f d x d x' [a(x).X') .x').Lo/2M) L kk'k" ei(kk'kll).LoMz(x)c5(x ..bt.LB/2.MlI(x')] = i2}. ]. with M±(x) = Mx(x) (80) ± iMlI(x). Mz(x) = M . The commutator is (87) [bk. M(x) = (4}.bkll + . Then (79) [Mx(x).Lo/M)a+(x)a(x)}~. k x . bk is defined by. Now transform M(x) to HolsteinPrimakoff field variables a(x).
but other directions of k give a field . repeated Greek subscripts are to be summed over x. (94) e The next highest order is XC!) = 2Cp. y. (95) Xz = HoMz = 2p.J. kk' Important effects arise from the demagnetizing field of the spin waves.oHo L ei(k'k)·J:bitbk. A spin wave with k II z gives no demagnetizing field to first order in the magnon amplitude. It is shown below that in a cubic crystal the macroscopic form of the exchange energy density must contain as the leading term X ex (91) C aNI aM axp p JI ax' aMteaM _ JI where C is a constant.o/2M) (90) L kk'k" kk' eiCk+k'+k")·J:bkbitbit.Xbtbk.HoM.= 4p. for H along the z axis.2 .oM Li (k· e k k'.kIf to first order.. The zeeman energy density is.4k .o(K/M 8 ) L ei(k'k).oM)~ [I eik·)[bt k . CH. Mz(x) = Jf .2 ~ (k 2 k. To bilinear terms (92) aM+ aM'\' k') i(k'k)·J:b b+.bk"b k"" + + kIf') + of the same form as (29) derived on the localized spin or Heisenberg model.. ax p ax". 4 = 65 (89) M(x) (4p. oM kk' L ei(k'k).. z.(p..MAGNONS./) = l(KjM 8 2)(M+MMM+) x + + = 2p.. bk bk. kk' z  ax p ax p o.2p.X(bitbk + bkbit).o L ei(kk'). + . kk' dropping the constant term . For directions near an easy axis of magnetization taken as the z axis the anisotropy energy density may be written (96) XK = (K/M.. .X(bkbit + bitbk)(k • k') + k' . Therefore the exchange energy density (91) is (93) x!!) = 2Cp.2)(M 2 M. k')d( k + .
+ 2Bkb_ k .zbk' + eik/.Xo] . for which = 27r~oM tt' L (eik.2B b · = [b_ k k We look for solutions with time dependence ei"'k t • The eigenfre .X). Bk (105) Ak = A_k = 2~oMa[2Ck2 = Bk = 27r~OMa. form the equations of motion (106) tbk = [bk.1M) k2 k.1M o. (102) Xd = jHd· M. To vary the procedure slightly.1M oei("'k k. 4?r(k' .zb + eik. k + (HIMa) + (2KIMa2) + 27r]. + 3CK + Xdz) = L {Akbtbk + Btbtb~k + Bkbkbk}.zbt)(eik/.' = Akbk +.appropriate to a selfenergy. then (97) is satisfied if (99) which is equivalent to (100) Hd = _ = 4?rk· .Akbk + . The bilinear terms are (104) Xo = Jd x (X~!) + 3 3Cz where for k II i. t curl H = O. The diagonalization problem of (104) is again just the Bogoliubov problem (91) of Chapter 2.'+k tb_ +k . it is convenient to specialize this to k (103) Xdz II i. k We integrate the several energy densities over the unit volume and drop the zeropoint contributions.zb k + k+eik. with a factor j.z) M = Ma + . Hd = HdOei("'ktk. 3C O] = .zbt). k where k± = kz ± ik ll • The demagnetizing energy density is. k· Hd o .zb~")k2k. For the mag non system (101) Hd = 27r(4~oM)~ L(keik.66 H d • We look for a solution of (97) If (98) QUANTUM THEORY OF SOLIDS div H = 4?r div M.
Bk = 211"p.B[2CM sk 2 + Ho + (2K/Ms)]. of the form of the atomic result (26). Similarly. we have (108) If k is small and the anisotropy Wo = gp. H 0 is the applied external static field H a corrected for the static demagnetizing field of the specimen. 67 quencies are the roots of or (107) I Wk  Ak 2Bk 2B Wk + Ak I = 4Bk2)~.1. Wk = (Ak 2  N ow consider several special cases.1. If the terms in k 2 and Hoare 2 in agreement with the classical result. however. For (Jk = 0. (109) Wk I"J gp. For general angles (Jk between k and the z axis. We know. (91).MAGNONS.pproach than is the high mobility of the conduction electrons in the .B(H 0 + 2CMsk ). as above. oM 8 {2Ck 2 + (Ho/Ms) + (2K/Ms2) + 211" sin 2 (Jk}. In general to know this requires a detailed quantitative theory of the exchange interaction in the solid..BM sC = 4J.(41r/3)M s. the secular equation is given by (107) with (110) Ak = 2J. Thus in a sphere we are to use H 0 = Ha . We need to know the form of the exchange energy associated with nonuniform macro scopic distributions of the direction of local magnetization. Representation of the Exchange EnergyEq. we may treat magnetic deformations in terms of macroscopic exchange constants. 0.l. We note that 2JSa 2 = 2gP. subject to' the same restrictions as the elastic constants. from (26) and (31). The fact that in some ferromagnetic metals the magnetic carriers may be mobile is no more of a restriction on the validity of the macroscopic p. dominant. K = 0. exactly as a general theory of the elastic deformation of a solid requires a detailed solution of the cohesive energy problem.B[Ho(H 0 + 41rM)]~.oMs sin 2 (Jk' Here. (111) Wk = gJ.oM sC = D. 4 . CH. that we may treat many elastic problems in terms of macroscopic elastic constants if the characteristic wavelength of the deformation is long in comparison with the atomic spacing and if the relative deformation or strain is small.
so this form is manifestly invariant with respect to rota tions of the entire spin system. Just as MaM« is invariant. wise the state of uniform magnetization could not be the ground state of the system. We have left (112) Igrad MI2 = (VMx)2 + (VM lI)2 + (VM z )2. In antiferromagnets we must take into account the existence of separate sublattices. I. sity must be invariant with respect to spin rotations. noninvariant contributions to the energy are included in the magnetocrystalline anisotropy energy.. other. The desired expression must be invariant under change of sign of the magnetization deformation components. aM aM . 8' ax" aXm where 3 are sub lattice indices.. with exchange interactions within and between them. where summation over repeated indices is implied.68 QUANTUM THEORY OF SOLIDS alkali or noble metals a restriction on the applicability of elastic constants. and thus (curl M) 2 may be ruled out. The form (113) is invariant under the operations of the cubic point group. In an isotropic medium there are three quantities quadratic in the deriva tives of M and invariant under rotation of the coordinate system: (div M)2. For magnetization directed in concentric circles. and \grad M\2. div M = 0. Kaganovand V. . ax" ax. For a general crystal symmetry (114) Xes = e"" aM« aM«. (curl M)2. 73 (1958). If M is radial. Soviet 34. Kaganov and Tsukernik 3 have given the generalization of (114) to antiferromagnets (115) 88' si __ _ _~_. curl M is zero. II. The expression for the macroscopic isotropic exchange energy den. M. which is a satisfactory choice.'l Xes = Gildm 8.. We may compare (114) with the PhY8ic8~J ETP M. (113) Xes = Thus in an isotropic medium e aMa aM «. and thus the (div M) 2 form may be ruled out. We look for an expression of the lowest order in the derivatives of M compatible with the symmetry of the crystal. ax ax" p where e1''' is a tensor with the symmetry of the crystal. Tsukernik.
k each of frequency w.MyHx) = 47r. CH.). Hy = O.and the volume average of sin 2 kx 1(" = 2. 4 . The z component of the torque equation M = ')' M X H is (120) !VIz = ')'(MzHy . The process consists of the absorption of one photon of frequency 2u. (119) = 471'"ml sin kx sin wt.mlm2 sin 2 kx sin wt cos wt = 271'". ax. . and the emission of two magnons k and . The time average of sin 2 2wt is is j.)..hmlm2n sin kx sin 2wt. CopS.). Now (118) div H = aH Hz x ax = 471'" div M = 471'"m 1k cos kx sin wt.. The mean rate of power absorption by a specimen of volume U is 2 2 (121) (P = H • MO = 271'". Here H 0 is a static field..P~/I aU a au~. Two magnons of equal but opposite wavevector give a standing wave.MAGNONS. 69 elastic energy density (116) Xel Ct>. neglecting zeropoint .mlm2 sin 2 kx sin 2wt. Consider a particular standing wave mode with wavevector k along the x axis: (117) Mz = ml sin kx sin wt. We calculate the energy absorbed from the rf field h sin 2wt by a particular magnon mode and find that the net power absorption in a certain approximation increases without limit when h exceeds a threshold value he. It is convenient to express mlm2 in terms of the excitation quantum number nlc of the mode considered. We have. is a component of the EXCITATION OF FERROMAGNETIC MAGNONS BY PARALLEL PUMPING A small sphere of a ferromagnetic dielectric is placed in a magnetic field H = H 0 + h sin 2wt.). ax" here u is the particle displacement and elastic stiffness tensor. There is no resonant connection between w or 2w and the field H o.. thus (122) (p i. My = m2 sin kx cos wt. both fields parallel to the z axis.hm lm2n.
(123) nkflJ.2 + My2») ( m 2Jfs2 = MsO 1 .Mt/]~) '" MsO ( 1 so that (125) and (122) becomes (126) (P (M:r. .B = «Ms .l. In the steady state. we have (128) Wk de dnk =  Tk Wk (nk fik) + 21r'YMshYJ.Ek) The energy balance in the mode k is expressed by (127) k de =  dE + (P. Writing Ek = nkwk and using (126).M:r. (124) (Mzfl) = O([Ms2 . The problem is quite similar to .I. writing ml '" m2 '" m. = 21r'YM shyJ.B.l.l.l.2 .Bnk.4Ms2 ' 2) nk '" m 20/4gMsJ.l. where Ek is the thermal average of the energy Ek of the mode k and Tk is the relaxation time of the mode. Bnk. because in the approximation ml ::: m2 each magnon excited reduces the magnetic moment by gJ.BTk Thus a determination of he is equivalent to a measurement of T k • We have assumed that the lowest threshold he occurs for spin waves mak ing an angle Ok = 1r/2 with the z axis. The angular brackets indicate the space and time average with only the mode k excited. dnt/dt = 0. Now.70 QUANTUM THEORY OF SOLIDS motion.B. 1 Tk (Ek .Mz)O)k. so that (129) fi k this expression has a singularity at (130) h _ e  Wk • 21r'YMsYJ. TEMPERATURE DEPENDENCE OF THE EFFECTIVE EXCHANGE The problem is treated by evaluating the diagonal fouroperator terms in the exchange hamiltonian.
o We see that the energy is lowered by an amount proportional to k 2 and to ~ kb 2nb .'Yab)nanb = i L Clk. where UT is the thermal magnon energy (33) and D is the constant in . Thus the diagonal part of (131) is (132) El = (Jz/N) L('Ya + 'Yb ~ 'Yo . CH. The diagonal terms involve only two k's.4'YO)n llnb. k where (133) Clk = nk(2Jz/N) L('Yk + 'Yb b 'Yo . nk here we have collected all terms in which magnon mode k is therefore (134) Ck occurs. In fact.4'Yab)n anb. 4 11 that treated in Chapter 2 for liquid helium. N ow to O(k4) for a lattice with a center of symmetry at each spin. = ka.k 4)[2'Y1 + 2'Y3 . (135) 'Ya + 'Yb . The offdiagonal terms give rise to magnonmagnon scattering.'Ykb)nb. (137) r kb2(nb> b I'J UTI D. There are two types of diagonal terms in (131): kl kl = = k3 k4 = ka. here Wk is the energy of the mode when all other modes are in their ground state. to lowest order. (2'Ya = k3 = kb: ~ + 2'Yb . (131) Xl = (Jz/4N) 1234 L btbtb3b4~(kl + k2  k3 . which is of the form of the total spin wave energy.MAGNONS. The energy of = nk[wk + (2Jz/N) L('Yk + 'Yb b 'Yo . except there the unper turbed system was in the ground state. using the definition of the 'Y's. which we denote as kll' k o.4'Y13]. k2 k2 = k4 = kb: ~ (4'Ya .'Yo  'Yab (i'1f)k a2k b2lJ\ I'J  so that (136) Ck = nk[wk  (Jz/18N)k 2lJ4 L kb 2nb].'Ykb)nb]. the diagonal terms renormalize the energy. We have from (29).
T 2U ) ' o where Uo = JNzS 2• We have set z8 2 = 6a 2 . kB T / WIl. and the effect on the dispersion relation of No alone will be negligible..H~ + ~H1I. where No is of the order of the total number of particles in the system. = V'P. wk(eft') == wk[l . Further. ~ are determined by H 0.J. the equa where p. ( ax 2+ ay2 + az2 = 0. . In the helium problem we can treat No + 2 as nearly equal to No. and we see that we should begin to worry about the result (134) if the number of magnons is not negligible in comparison with the total number of particles. MAGNETOSTATIC MODES It follows directly from the torque equation :M = yM X H that for a static magnetic field in the z direction the rf permeability of a ferromagnet is described in the absence of exchange by the equations (141) B~ = p.82UT/6N)Jk 2. the renonnalized energy is given by (138) wk(eff) ~ [2SJa 2 .72 QU ANTUM THEORY OF SOLIDS the relation Wk = DK2 == iSJz8 2k 2 = 2SJak 2. not as the saturation moment. bcc. and M 1/' tion div B = 0 becomes (142) With H a2 'P a2'P) a2 ((J p. Thus. if we write nkwk(eft'). For the special case of a simple cubic lattice one finds (139) for all k. B1I = ~H~ + p. No is exceedingly small in comparison with the total number of spins in the system.akak must be treated on an equal footing. The result (140) demonstrates that D(T) scales as the magnon energy UT . as for sc. such as at.. w. and fcc lattices. In our present problem the number of mag nons in the uniform mode is not a very large number: No ro. 2 D(T) ~Do ( 1 . The result as obtained applies to nearest neighbor interactions within one lattice.H1I. k' (140) = U Do (1 .6N U7') D o/8 2 k EJr = Lnk'wt.at. Note that we have not considered in the partial diagonalization of (131) terms of the fonn atatakak and atataoao which were considered in the analogous problem for liquid helium.(12JNS 2)1 Using (138). and a change of 2 in this value is not obviously negligible. But actually other tenns..
. 4 2 :13 inside the specimen. 120. 2 as in [SSP. j 2 Discuss the fact that excitation of k = 0 magnons does not change S • 4. 105. which for a simple cubic lattice is (146) s = 2Ja S X V2S + 2p. assuming w = Dk 2. (4). Construct a spin function to represent a ferromagnetic spin system with one magnon excited. Show that for antiferromagnetic magnons (147) S' = NS IHA !A "j (n~ + 2H ng + 1) + terms in (n. R. Appendix O.H] and recalling that Sj X Sj = iSj. 6. Prove that [S2. Form the difference equations for Sf and ST. Phys. PROBLEMS 1. ::: (2SN) ~2bt. S. using iSj = [Sj. 308 (1961). Eshbach.MAGNONS. Derive an expression for the velocity of second sound in a magnon gas. solve for the eigenfrequency of spin waves in the limit of small amplitiide (S+/S «1). Chem. 7.2NS S2 "' (NS)2 + NS L bt~. find the quantum equation of motion for Sj.oHo LSj" . k~O observing that L S. and (5).oS X H. where H is given by (1). Kittel.. . whereas V rp = 0 outside. Solids 19. P. CR. Show that. Phys. Using the hamiltonian (145) H = J L Sj' Sj~ ja 2p. 2.] = is. Show that for long wavelengths (ka« 1) the classical difference equation reduces to a partial differential equation. for the total spin (144) S. Solutions of (142) are considered for several geometries in the following papers: L. Inter preting the spin operators as classical vectors. . R. 2004 (1960). Walker. where D is a constant. Rev. 390 (1957). Rev. Fletcher and C. Phys. The boundary condi tions are that the tangential component of H and the normal compo nent of B should be continuous across the boundary of the specimen. From (3).)'. 3.H] = 0 and that [S"H] = 0. Damon and J. show that (143) [S:I:'S.
Show from ~ j Si. + ~ S~. where c" is the coupling coefficient and a+.) \. bare magnon and phonon creation and annihilation operators. 9... a+ = A+ + B+. aj b+.sin ka). with 0 real diagonalize the hamiltonian if (151) 2cl. 10.726.ilcG) = cos ka and (1 . . Show that the transformations " (150) a" = A" cos 0" + B" sin 0.2) = sin 2 ka. tan 20" = b" = B" cos 0" . !(e"UJ + e... WB = W" + c. using (64). Show that for a linear lattice {3 = 0. l that the excitation of an antiferromagnetic magnon is accompanied by a change of ± 1 in the z component of the total spin. wf  w" Show that the nominal crossover of the dispersion relations has WA = W"  C".Isin kal) = " (4a/1r) ( 10 1I:j2(J dk(l . b+ = B+ .1'..bt + atb.. thus (148) Note that ')'1: = {3 = (2/N) ~ (1 .74 QUANTUM THEORY OF SOLIDS 8.A+. Consider the magnonphonon hamiltonian (149) H = ~ (wrata" + wfbtb" + c"(a..A" sin 0".
flexible. Next form the field operator (2) w(X) = L Cj'Pj(x) . it is tedious to indicate the subscripts distinguishing the individual indistinguishable electrons and to indi cate the permutation operators. the equation may be typically the Hartree or Hartree Fock equation with particle interactions taken into account in some average sense. such as 11 in x. where (1) H'Pj(x) = Sj'Pj(x). The theory.~IDS 'k = letic iotal Fer:rnion fields and the HartreeFock approxi:rnation 5 mon 1+. The eigenfunction label j will include the specification of the spin state. We write a solution of a oneparticle wave equation as 'Pj(x). The theory is closely analogous to that for boson fields. i w+(X) = LC]'Pj(X) . Suppose we have a set of orthonormal solutions of some oneparticle wave equation. Note that we do not label the electron with a number index. and concise representation in terms of the second quantization theory of fermion fields. There exists a more elegant. i or !. coupled by weak interactions. for example. The antisym. metrized eigenfunctions of a system of independent fermions may be written as Slater determinants of the oneelectron wavefunctions.. or a or (3. usually contemplates an assembly of moreorless independent particles.. For some purposes the Slater determinant description is convenient: it is direct and explicit. However. or the equation may be for free particles. The essential distinction between an assembly of fermi particles and an assembly of bose particles is the requirement of the pauli principle that the eigenfunctions describing the fermions must be anti symmetric under interchange of any two particles. i 75 . just as the determinantal description.
ClCm + CmCI = 0. + c.76 QUANTUM THEORY OF SOLIDS where Cj is an operator with properties to be specified below. {ct. 'Pj(x) remains' an eigenfunction and not an operator.} = aim.!. . The field operator w(x) and the fermion operators Cj operate on a state vector which we write as 4>. where the (T'S are the pauli matrices. Thus (3) .} will denote anticommutator.!.}.pvac = 1000 .!. For a system with only a single state we represent c+ and c in the following way: (7) c+ = (~ ~) = !(u. .) = Ivac) is the vacuum state in which all the occupation numbers nj of the oneelectron states are zerono particles are present in the system. The unperturbed ground state of a system of N fermions in the inde pendentparticle approximation will be written as .po. [. + C. We write these as (6) tCl. .po = 1111213 ••• I NON+I0N+2 . so that it is essentially a cnumber function of the coordinate x. where (4) . c= Thus (~ ~) = !(u. (8) c+c + cc+ = (~ ~)(~ ~)+ (~ ~) (~ = ~) (~ n· .!. . ctc. The requirements of the pauli principle are satisfied if the fermion operators c.] will continue to denote com mutator.CI = aim.t. Another common notation for anticommutator is The anticommutation relations may be satisfied uniquely by a representation in terms of 2 X 2 matrices.C. . O. + iu y).C. . We note (Problem 4) that w+(x) is an operator which adds a particle to the system at x. c+ satisfy the anticommutation relations (5) Ctc. . This state vector is in the space of the occupation numbers of the one electron states.  iu y). . the JordanWigner matrices.!. tCl. where the states are numbered in order of increasing energy. 0 .} The {. 0 .ct = O.cm} = 0.
. . respectively. ee (9) + ee = 2 (~ ~)(~ e+e+ + e+e+ = 2 (~ ~)(~ lo} = ~) (~ ~) = (~ (~} ~) ~} The 2 X 2 matrices are to be understood as operating on a two component state vector in the occupation number of the particle: (10) II} = G} corresponding to the possible fermion state occupancy numbers.FEB. 5 77 Further.. We have the property (11) e+eII} = (~ ~) G) = I (~) = Ill}. 1 and O. CH. and e is a particle annihilation operator: (15) ell} = (~ ~)G) = e+II} = (n = IO). We see that e+ is a particle creation operator: (14) = (~ ~) (n = G) II}. . A state cannot be occupied by more than one fermion: (16) (~ ~)(~) Ok . and (12) e+eIO} = (~ ~)(n = 11. It ... elO) = o.) O. o(n = DID). Thus (13) = e+e is the number operator and has the eigenvalues 1 and 0 for the eigen states 11) and 10). We construct a state <I> in which a oneparticle state k is occupied by one particle by (17) <I> = et<l>vac etIOO'" = 100 .MION FIELDS AND THE HARTREEFOCK APPROXIMATION.
The general result is (23) C) I . Ii . wher ig (35) here Pi is the number of occupied states to the left of j in the state vector 4>. ) o· . . beca (30) whereas under the operation (21) Cl4> we have ++ = CICI C2 4>vac (1  Cl c 1 C24>vac = +) + C24>vac.. the results of the opera tion cjCj are unchanged. . Ck +) 4>vao +C2 + = Cl • • • Ck + Ckp ':t'vae· +"" If there is more than one particle present. nj •.(Jil . wher Tl tion direc is (34) ) ' (24) . We can see this best from a simple exam ple. . . . + and (31) The difference in sign between (20) and (21) is the consequence of the anticommutation of cT and C2.).) .) n .. . this i that (33) n· . . +"" It is convenient in dealing with products of creation and annihilation operators to rearrange them into normal product form in which all creation operators stand to the left of any annihilation operators which may be present.) = (1 . but the results of the operations cj or Cj may alternate in sign according to the number and ordering in 4> of the other occupied states. If in a normal product there do occur one or more annihilation operators.Cl ctC2)4>vae = cT(I Cl = cT4>vao. We may omit (Ji if we redefine the matrices representing .78 QUANTUM THEORY OF SOLIDS FER1 Similarly. The statement "to the left" assumes a definite order has been adopted for the order of the oneparticle states in the state vector 4>: (22) 4> CIC2 Tl (32) ++ Cj + . Consider the state (19) 4> C2: whel (28) Cl C2 4>VI\O ++ under the operation (20) C24> We occu W (29) C2Cl C2 4>vac ++ +C2C2 +4>vac = .nj)(Jil . .. .. We must in fact put in a minus sign for every occupied state i which occurs to the left of the state j on which we operate with cj or Cj.'vae. the ground state of an unperturbed fermi sea is (18) 4>0 + ( ci' (26) (27) ( II Ikl<k.). CN't. we know at once that the result of operating on the vacuum state with the normal product is identically zero. where (25) (Ji = (I)Pi. . . .
We observe that (29) {'lr(x).cdIP.i grad. For example. this is also known as the oneparticle density matrix operator. The hamiltonian is obtained in the second quantization representa tion by the general theorem that quantum operators are obtained directly from their classical analogs.Cx)IPt(x') = LIP.Cx)IPj(x').'lr+(x')} = r fi {cj. q. T. = Tl .j ctCjIPt(x)IPix ). We include a factor T in (26).(x).. the kinetic energy is (34) H = f d'". . (27) for every state to the left of j.l T = (10 n ~) ~)..x'). The particle density operator is (32) p(x) = Jd x' 'lr+(x')o(x  x')'lr(x') = 'lr+(x)'lr(x) = r i. then (33) Notice <lp(x)l> = 2': niIPt(x)IPi(X) = 2': niPi. where Pi(X) == IPt(X)IPi(X). T i 1 (26) (27) where (28) (0 0 (~ = c.FERMION FIELDS AND THE HARTREEFOCK APPROXIMATION. ~ cjcIl"j(x) :~ I"'(x). . i and by closure (31) r i 3 IP/x)IPj(x') = o(x . where p is the momentum operator. . because (30) {'lr(x). (35) For free particles. that if I> is an eigenstate of the occupancy operator ?ti.. 'l'+(x) :~ 'l'(x) = f d'". with p = H= '1 '\"(k/) + 2m cicI' .'lr+(x')} = o(x x'). CH. occupied or not. 5 79 + Cj' Cj as cj = Tl .
[H.(I(I) ) p2(1(I') . where V(x' .J ? CjCI'Pj(X')'PI(X') = l: cici = '$ . The factor I arises because of the selfenergy.p2"{1(X') d'x' day (I+(%.) .!.) f d'x' d'y (I+(I')(I+(y) V(I' .)(I+(y) V (I' .y) (I(y) (I(I') ... .y)(I(y)(I(I'). with p operating on "(I(x'). where Ci is a fermion operator and 'Pi(x) is a oneparticle eigenfunc tion. Our object is to find approximate solutions of the equation of motion ii. .f = . The prescription for the hamiltonian in this representation is to write the mean energy in terms of individual particle wavefunctions and then replace the wavefunctions by the field operator "(I(x'). is the operator for the total number of particles.(I(I)] =  f 2~ f d'x' ((I+(%.) +} L~ p' + V(I') J(I(%.y) is the interaction energy of two particles at x' and y. For convenience we let v(x') = 0 and write (38) H = f 3 d 3x' "(I+(x') +1 where (39) f 2m . PARTICLE FIELD EQUATION OF MOTION METHOD FOR THE HARTREEFOCK EQUATION We consider a system of electrons described by the field operator (36) "(I(x) = L Cj'Pj(x). The order of terms is significant because "(I(x')"{I(y) = "(I(y)"{I(x'). The first term in the commutator [H. "(I]."{I(x)] is. Thus (37) H  f d'x' (I+(%. (40) 2~ d'~ [(I+(I')p2(1(%'). f d x' "(I+(x')"{I(x') = f d 3x' .80 QUANTUM THEORY OF SOLIDS where the factor cici automatically arranges that we count the energy of occupied states only in a representation in which the cici are diagonal.
if(x)] is (43) l = Jd x' d y [if+(x')if+(y) Vex' 3 2 y)if(y)if(x'). (29).2m p2if(x).x') if+(y) if(y) if (x') ) = ! Jd x' vex' 3 3 x)if+(x')if(x)if(x') .om(x).FERMION FIELDS AND THE HARTREEFOCK APPROXIMATION.x)if+(y)if(y)if(x) = . 1 The second term in the commutator [H. By Note the mixture of commutators and anticommutators in (40).if(x)] l J d x' d y vex' 3 3 y)(if+(x'){if(x). where ctc" is evaluated for the ground state. whence (45)  J d 3 y V(y .x)if+(y)if(y)if(x). 5 81 because the anticommutator (41) {if(x'). In the lowest or HartreeFock approximation we consider only terms in a single operator times the number operator CtCk.if(x)} O.y)if+(y)if(y)if(x) Here (44)  . where we have resumed the series for if(x) and if(y). We thus keep the terms ctCkCm and ctClC" = .x) '11+(y)if(y) if(x) I"V  J d y V(y 3 + Jd y if(y) V(y 3 x)(if+(y)if(y»if(x) x)(if+(y)if(x».ClCtCk. only terms of the form ctCk are retained within the angular brackets. The first term on the .°k(y).! y Jd 3 y vex . CH. (42) ~ f 2m d 3x' {if+(x') if(x) } p2if(x') ' ~ f 2m d 3x' o(x' .r Jd V(y 3 y CtClC m 3y x).Ol(y). that is.Jd V(y . Jd V(y . klm This expression involves products of three operators.x)p 2if(x') .if+(y) }if(y)if(x') o(x . the angular brackets indicate the expectation value in the ground state.
2~ p'  f d'y V(y .x)(q. the sum is over all states and all spin orientations.i L Cjl{)j(x) = i L € i where (49) ej<pj(x) = (:~ + f d 3y V(y . (46) [H.X)(q. In the second term on the righthand side.82 QUANTUM THEORY OF SOLIDS righthand side of (45) is the direct coulomb term.(y») <Pj(x) f d 3y <Pj(Y) V(y .x)(q.(x» 1 Suppose now that the l{)j(x) are eigenfunctions of the operator in the square brackets on the righthand side of (47). The integration is understood to include taking the spin inner product. In the usual form we see that l{)j(x) is determined by a certain averaged potential: (50) I ej<pj(x) = (:~ + f f d'y V(y .'lI(x)] = . and the second term is the exchange term.x) ~ ni<Pi(Y)<Pi(Y») <Pj(x) ~ ni<Pi(Y)<Pi(X).X)(q.+(y)q.+(y)q.(x)] f d'y q.(x) + or (47) [H. with the eigenvalues €j.(x)] ~ [ .(y») <Pj(x) f d 3y<pj(Y) V(y .+(y)q.q.x)(q.(y) V(y . Collecting (42) and (45). ~+ f t Cj [(2~ p' d 3y V(y .(x».x) where ni is the occupancy 0 or 1 of the state i.X)(q.+(y)q.(y»] q. The term i = j may be included in the two sums in (50) because for it the direct and exchange contributions cancel. d 3y <pj(y) V(y .+(y)q. . This is the HartreeFock equation. in the third term (the exchange term) on the righthand side only states i with spin parallel to j will remain because we take the spin inner product in the integration over d 3 y.+(y)q.q. then the equation of motion is (48) [H.(x».
~ n".(4)!HI4>). The work done in removing the electron from this state is the difference (4)z!H!4>z) . the <p's will be essentially identical for the problem with or without an electron in the state l.z given by (51).«lmIVllm) . with the energy referred to the ground state. KOOIJMANS'S THEOREM 5 83 rm ~)}. This important theorem states that the energy parameter EZ in the HartreeFock equation for <pz(x) is just the negative of the energy required to remove the electron in the state l from the solid. )J. and writing l for j.~ nm((lml vi 1m) .) = ~ n". N ow from (37) (52) [».(/ml Vlml»). then on taking the inner product of (50) with <Pj we have. ( m12~ p'i m) V\pm». = (112~ p'll) . If the <Pm (x) in it(x) = ~ Cm<Pm(x) are solutions of the Hartree Fock equation. Then (53) 1 (q. Because the electron charge is spread throughout the entire crystal. CH.DS FERMION FIELDS AND THE HARTREEFOCK APPROXIMATION." \ If d x it+(x) ~ 3 + (! f 2m p 2it(x)\ I d x d y i'+(x)i'+(y) V(y . This is our central assumption.(lml Vlml»). rrat (4)IHI4>). .IHIq. mp is + ! 2: nmnp(mpl Vlmp) =j md md lird pin the and the change in the energy on removing the lth particle is (li2~ p'll) . . We note that the deriva~ tion assumes invariance of the <Pm(x) under the removal of the particle from the lth state.x)i'(y)i'(x)) 3 3 where the carets on the righthand side indicate the diagonal matrix element in the state 4> in the HF representation. ~he lles where 4>l does not have an electron in the state l. thus the theorem cannot apply to small systems. in other respects 4>t is identical with 4>. Here (lm\ Vjlm) == I d 3x d 3y <pi (x) <p!(Y) V <Pl (X) <Pm(Y) and (lml Vlml) I d3x d3y <pi (X) <p! (y) V <Pm(X)<Pl(Y). (51) e. which is just the value of £:. provided that the <p's are extended functions of the Bloch type and that the electronic system is very large.
excitations which resemble oneelectron excitations. With the filled fermi sea as the vacuum we must provide separate fermion operators for processes which occur above or below the fermi level. of a freeelectron gas. We consider first a system of N free noninteracting fermions having the hamiltonian (54) Ho = L €kCtCk. in other situations the quasi particle is a wavepacket of exact eigenstates. In some situations the description of the system in terms of a sum over quasiparticles is exact. for E. 13k = C~k' for Ek EF. Thus we deal only with electrons (for states k > k p) and holes (for states k < k p). and there is a complete formal similarity between particles and holes. The quasiparticles of an ionic crystal lattice are phonons. < and the hole operators f3+. > EF. We regard the state ~o as the vacuum of the problem: it is then con venient to represent the annihilation of an electron in the fermi sea as the creation of a hole. rather than the state with no particles present. The act of taking an electron from k' within the sea to k" outside the sea involves the creation of an electronhole pair. The language of the theory has a similarity to positron theory. ak = Ck. We introduce the electron operators a +. magnons. The removal of an electron below the fermi level is described in the new scheme as the creation of a hole. In the ground state of the system ~o defined by (4) all oneparticle states are filled to the energy €p and above €p all states are empty.84 FERMION QUASIPARTICLES QUANTUM THEORY OF SOLIDS The low energy excitations of a quantummechanical system having a large number of degrees of freedom may be often approximately described in terms of a number of elementary excitations or quasi particles. k where €k is the energy of a single particle having €k = €k' We agree to measure €k from the fermi level €p. . f3 by (56) I{3t = Lk. In treating the electron system it is particularly convenient to redefine the vacuum state as the filled fermi sea. a by (55) Iat = ct. of a spin lattice. The width in energy of the eigenstates comprising the packet determines the lifetime of the packet and thus the range of validity of the quasiparticle concept.
1.FERMION FIELDS AND THE HARTREEFOCK APPROXIMATION. 5 85 The . The true vacuum state «Pvac satisfies Ck«Pvac = 0 for all k. k > kp ) L f3itf3k. CH. Excitation of an electronhole pair: the state is at" I3t <1>0. Thus "it === Ck creates a hole of momentum k.'f3. f3k«PO = 0. each within the appropriate range of k. k (k < kp). referred to «Po as a state of zero momentum.«po contains an electron hole pair. as shown in Fig.k introduced for the holes is a convention which gives correctly the net change of wavevector or momentum: the annihilation Ck of an electron at k leaves the fermi sea with a momentum k. is (57) P L k(aitak k f3itf3k)' The number operator for excited electrons is (58) and for holes (59) Ne = Nh = L aitak. 1. k:y kz FIG. The total momentum. The hamiltonian for the noninteracting fermi gas is (60) H0= k>kl' L €kaitak + L €kf'itf3k. The state a. The ground state «Po of the fermi sea has the property (61) ak«Po 0. k<k1' with €k referred to €p as zero. thus €k < 0 if k < kp. .
(x) . which minimizes the energy. The .86 ~uANTUM THEORY OF SOLIDS ELECTRON GAS IN THE HARTREE AND HARTREEFOCK APPROXIMATIONS We consider the physical properties of a free fermion gas of N electrons of charge e in a volume O. To this order the coulomb interaction term in (63) drops out and the Hartree problem is just the freeelectron problem: ~2 (66) 2m p <Pi = ej<Pi' The energy of the electron gas in the Hartree approximation is purely kinetic and hence exactly the same as for free particles.XN) = n iI N <pj(Xj). which cancels ept except for a trivial term arising from the difference between Nand N . This where p~+) describes an electron moving in the average potential of all other particles. * Ix e _ yl ~ <Pm(Y)<Pm(Y) 2 . The sum in (63) is over all occupied states except j.<p. NI ellO arises from the positive background. We show now that the set of plane waves (64) <Pk(X) = O~ik'X are selfconsistent solutions of this equation. To insure the neutrality of the system we add to the electrons a uniform background of positive charge having a charge density equal to the average charge density of the electrons. The method is said to be selfconsistent if all <p's are eigen functions of this equation. but without the exchange term [the last term on the righthand side of (50)1.l)e/O. (63) 1 p2 + [ 2m f d 3Y ". ••• .1: the associated energy is of the order of e2/O~ "' 1019 ergs for 0 "' 1 cm 3 .fd 3y p~+)lellx ~ yl] <p. In the Hartree independentparticle approximation we look for the producttype wavefunction of the form (62) <P(Xl. The Hartree solutions satisfy the same equations as the HartreeFock solutions.(x) e. The electron charge density in (63) is constant for a product (62) of plane waves: (65) e 2:' <P!<Pm m ep~) = 2:' 0m 1 • e ' 1m = (N .
CH. per particle by (69) 0= N3"ro .2' or._ 2m k F. r.52. a r.21 (eF) = . and (72) (eF) = 1na2mro = 3 It is often useful to express ro in terms of the bohr radius aH 0. = rO/aH = (me /A )ro·1 2 2 The region of actual metallic densities is 2 (74) < r. in rydbergs l(me 4/A2) = 13. This is the total energy per electron in the Hartree approximation.60 ev. a = (4/9?r)~fI 0. It turns out that the Hartree approximation does not lead to metallic cohesionthe electrons spend too much time in regions of repulsive potential energy.529 A. We note (on reflection) that in the Hartree approxi . or (71) kF 1 aro. With (73). where the factor i is from the average of k 2 over the volume of a sphere. If we define a mean radius with the factor of 2 coming from the spin.FERMION FIELDS AND THE HARTREEFOCK APPROXIMATION.5 2 2 ry I""oJ 2 ry. (75) 3 2. 2 per particle. 411"3 then (68) becomes (70) 2 (411")2 (2?r) 3 3" (k Fr o)3 = 1. < 5. 5 87 energy has the value at absolute zero (67) (eF} ="3" 1 8. 3 me 4 1 (eF) = 10 Ai a 2r. The fermi momentum k F is determined by (68) 20 411" 2 (2n)3 • 3" kF = N. as (73) I r. We introduce the dimensionless parameter r.
o 2 ro w th ze tio (8 lei. on this model. (77) e2 = e2 ( .88 QUANTUM THEORY OF SOLIDS FE mation the coulomb selfenergy of the positive background plus that of the electron gas just cancels the interaction energy of the electrons with the positive background.. The contribution of the point charge interacting with the negative charge distribution is 3 iTO 3 e2 (76) el = e 2 41rr dr = .(x) f n" ( / d'y ~~(Y)~j. w (8 is ti (8 th to (8 and the selfenergy contribution of the electron distribution with itself is 2 e 33)21TO dt l(4'n)2 4 = 3 .(y) V(x  Y)) ~.10 rO + 3 10 2 2 a mro 1.' d 3 y tfJt. The equilibrium value of rs is 2.. there is no selfenergy contribution from an electron interacting with itself.1 part of each of N electrons. on writing the spin variables 8. We have derived the HartreeFock equation (50).2 ry. 8' explicitly. We now modify the model: keeping the previous uniform electron distribution. we collect the positive charge background into point charges There is one point per atomic volume n/N. . / l. We have seen that the coulomb energy vanishes for the Hartree solutions in a uniform background of positive charge. Modified Hartree Model.80 rs 2. HartreeFock Approximation.Y)) X tfJj. so we have to decide whether or not one individual electron is localized within the cell. (78) e = el b (8 0 __ + e2 + (eF) ge 2 .(x). although this term is not present if only one electron is present in the sphere.. We make the calculation as if each electron is distributed throughout the specimen. rs p e using (72) and (75).30 Aj the equilibrium value is obtained by setting de/drs = O.t 4rro 0 5 ro so that the total energy is. (79) ejtfJjs(x) = (~ p2 2m vex) +L nz s .21 .. To a close approximation the coulomb energy of this model without exchange is obtained by calculating the energy of a point charge interacting electrostatically with a uniform negative charge distribu tion throughout the volume of the sphere of radius ro. That is..45 bohr units or 1.(Y)tfJzs'(Y) Vex . we may consider also the electrostatic interaction of the electron distribution with itself. rather than the N.
'' G(k j k· 2  k .) ' We now calculate the quantity 2:' G(k. 5 89 We have seen from the Hartree solution that if the <.) e2 = ~ 411'e 2 K2 . (S2) $. (S.. Thus the HartreeFock equa tion has plane wave eigenfunctions with the eigenvalues m I the sum is over all occupied states l excluding j.).) = he 2~' f 1 ~ k .k . etX. . with E = x . is the fourier transform of Vex .  k .). where.y. . for unit volume. f G(k.Let us now see if we can solve (79) with plane wave eigenfunc tions. ~ 1I'kj Jo [kl' + Ie.FERMION FIELDS AND THE HARTREEFOCK APPROXIMATION. for the ground state.k .l e2 (kp2 k/ log =k dk log k 11' 2k j + kF} .2:' G(k j I k')<'oj(x).x<'oI(X) l . The next problem is to calculate the G(k. the second and third terms on the righthand side of (79) add up to zero.k. Then. (S1) G(k) = f d3~ eik'~V(E) ~.) which appears in the oneelectron energy. (SO) 2:' (f d y 3 ei(kjklHYX) Vex  y» ei(kjkl). the exchange energy.)) _ ~. 2: I Now (S3) Vex . The exchange term is.y). . antiparallel pairs do not appear in the HartreeFock exchange integrals.24).  k . CH..k) 1 dp.)2 = 411'e '~1 2 = = k 2 e 211' 10 ' k 2 dk fl 22 11' 0 1 {} (211') 1 d 3k _ _ _ k<kl' (k.y) = Then G(k. (S4) = f d 3x Ie 21 x I 2 ei(kjkl)·X = (k j 411'e  k . by (1. Ik . It turns out that we can. The sum is taken only over states Ils) of spin parallel to Ijs).o's are plane waves.(Xy). = 2' .
The derivative near k == kp is given by the expansion 0.'~rr'''~rr.2r kj log kF _ k I + I + 2kF) .5 c.0 ~ C ::J e u ..3 X lO6. ~ c c aJ .5 u 4. o r  .614 == 2 log Ix . by elementary integration. Q) Q) Q) 2.. The region inside the circle is not accurat~the slope has been exaggerated for emphasis. The exchange contribution to (86) is plotted in Fig. J The average exchange energy per particle is most easily obtained by the more direct attack below.. . FIG.. 2 as a function of kj/kF.kl kF 2m . where x == k/kp.0 1.0 a!1 3. thus the slope is reduced to 20: 1 for Ix .0.. although one can sum (86) over all occupied states.90 QUANTUM THEORY OF SOLIDS 0.8 ••.. Plot of exchange energy versus wavevector for free electron gas.t:t~ ~ ~ I:: 0 2.11. 2. energy parameter is (86) ej Therefore from (82) the HartreeFock 2 e (kF2 . 1.11 == 3.!!! C Q) .5 ~ .r:: Wo 3.
5 91 EVALUATION OF THE EXCHANGE INTEGRAL FOR THE ELECTRON GAS We require the value of the G(k j .. kl<k.2k 1k 2p. l. d 3k 1 kl<k.)P. In effect we need the value of (87) hi = ff kl.k . 1 I (k2)2L+2 kl 2L + 1 1 d kl kl £.). But for the half space s (89) 2 < 1 we have a wellknown series expansion: 1 s  2 = sp. .k2 =2· kl 1 1 1 +  2sp.FERMION FIELDS AND THE HARTREEFOCK APPROXIMATION.pL(p. d'k. dk2 k!<k. 1 1 1 / 1 P L(P. t~ OO( 2L +1 2L 1 +3 )_1 ~  i~ 00 ( 1 2L 3. 1 d kl 3 3 lk! 0 < k 2.) is a legendre polynomial." 2 I ( ..(p. (90) gj = 2 Thus using (91) f. [I sLPL(P. L L. 2rk22 dk2 dp.) summed over all occupied states j. k 2)L+>. we have.)]2 = I sL+>. f.)P... (88) ~I = cos 8 and ~ = k2/kl' 1 . CH. = nT OL>'.)P>. f.A:t<k.(p. 1 12= kl . counting both the space k2 (92) gj = < kl and the space kl 8r = 8r f.2L ~ 3) = so that (94) gj = 4r 2k F 4. ks<kl I L." where PL(p. . with p. 1 Now.) dp. ~ L (2L + 1)(2L 3) GO 2 4 = 8r k F ~ (2L The sum is easily evaluated by writing it as (93) 1 + 1)(2L + 3) 1.). 1 k • k2 P L(P. d'k.(p.
The low density of states near the fermi surface on the HartreeFock model has important consequences for the thermal and magnetic properties of the electron gas. The correlation energy ec is defined as eexact .. The effect of antisymmetrization on a pair of parallel spin is treated in the next section.. the difference between the exact energy and the energy calculated in the HartreeFock approximation. 21/" arB Ta The HartreeFock energy eHF = (eF) (97) + eex is then eHF = 2  2. but none of these special consequences of the HF model is in agreement with experiment.92 QUANTUM THEORY OF SOLIDS N ow the average exchange energy is (95) eex 1 2~. 4Jre ~ ~'NLi G(kjk l ) = .916 eex= . We might expect to be able to treat the coulomb interaction as a small perturbation.. without the integral.eHF. This is a better value of the energy than the Hartree energy.. but involves a careful treatment of divergent terms. We have just calculated in the HF approximation the groundstate . One major difficulty with the HartreeFock result (86) is that the density of states at the fermi surface goes to zero because dejdk j 4 00 as k 4 kF.916 ry rs per particle.21 rs 0. Manybody corrections to the HF model lead to a screened coulomb potential.L i ( k 2 1 j  il n il k)2 1 41/"e 2 gJ  . The defect is the neglect of the correlations in the positions of the electrons introduced by their coulomb interaction. We have further 3 1 0. 2 with a (96) (4j97r)l4 as before. as discussed in the following chapter. The density of states involves (dnjdk)(dkjde). calculating the energy by pertur bation theory. Correlation is particularly important for pairs of electrons of antiparallel spin for which the antisymmetrization does not act to keep the pair apart..r y . but the binding is still too weak. the desired derivatiye is just the next to the last step of (85). and for this the density of states does not vanish at the fermi surface.(21/")3 n  2e k F 2 4  3e 41/" ar o . This can be done at high electron density (r 8 < 1)..r y = .
(2) Subtract the interaction energy E 2 of the electrons with the 2E 1 • uniform positive background. for n atoms. To take care of this in the bookkeeping we must: Subtract the selfenergy E 1 of the positive background. The terms (1) and (2) together contribute 0. As calculated. just the energy of n WignerSeitz polyhedra. the groundstate coulomb energy includes: (a) The selfenergy of the electron gas. Thus the sum of the en~rgies of the four steps we have enumerated is... sodium.6e 2 /ro or 1. but for the metal . CH. 5 93 energy of a system of electrons with a uniform rigid background of positive charge.h. (4) Add the interaction energy of the electrons E4 with the discrete lattice. The sum of the terms (3) and (4) is just the energy eigenvalue for k = 0 of the WignerSeitz boundary value problem discussed in Chapter 13. method of Wigner and Seitz developed in Chapter 13 the metal is divided up into polyhedra centered about each lattice point. In t.2/r8 to the energy of the metal. observing that E2 (3) Add the coulomb energy of the discrete lattice.FERMION FIELDS AND THE HARTREEFOCK APPROXIMATION. (77). It will require a moment's reflection by the reader to appreciate that this cancelation is implied when we say that the energy of the system is given by the number of electrons times the average HF energy (97) per electron. The polyhedra are electrically neutral and the coulomb interaction between different polyhedra is very small. for which the free electron model works best. there are four major things we must do. energy. ) + 1.2 + (correIatlOn r8 This sum will be negative for a reasonable metal. The sum of these three contributions is zero: both selfenergies are positive and enter each with a factor j. as was calculated inEq. corrected for the correlation energy. if we wish. The cohesive energy contains the sum of (HF energy) + (WS energy at k = 0) . (c) The interaction energy of the electrons with the uniform positive background. (b) The selfenergy of the positive background. In an actual metal the positive charge is collected in a discrete ionic lattice. thereby canceling the negative interaction energy (c). How do we go from this energy to the cohesive energy of an actual metal? Even for the simplest metal.
to the HF energy to give +0.l.F 2 (k F r)]. for the total term in r.tes k occupied. where we express the ionization energy as a negative number.Y)l{)(x.Y) = l{)*(x. In the following chapter we discuss for sodium the magnitudes of the several terms.l'Z»)(ei(kl'Z+ks") _ ei (k1ks )'(1Z») ei(k 1 . Note that the term 1. the probability is uniform: (98) g(x.y) = i(ei( k l'Z+k 2" ) i(2  hal ei(kC.+k:. ~ pal tra thE CO~ 1. (100) wh i= . (1 N ii ei(k.x.kj)'f) N2(211') 6 1 f f d 3k· ' J d 3k· (1  (10 • This is the probability of finding at r an electron with spin parallel to that of an electron at the origin. We may write (101) (g(r) = [1 . The difference between the ionization energy and the sum we have just written is the cohesive energy. We average (99) over the groundstate fermi sea: if there are N distinct st8.y) = ei(kl'Z+ks'7)ei(kfZ+ks'7) = (H usi (H WI an~ 8. Even for plane wave states this probability may be nonuniform.kj). the average correlation of parallel pairs is.+ks' Z») (l(J = e i (k1ks )'(1Z) _ =1 cos (k 1  k 2) • (y .r) (10 ei(k. with r = y .94 QUANTUM THEORY 011' SOLIDS FE to be stable with respect to separated neutral atoms the sum must be more negative than the first ionization energy of the neutral atom.2/r. TwoElectron Correlation Function. OF but for parallel spins the exclusion principle leads to a nonuniform correlation: (99) g(x.Y) d 3x d 3y that there is one particle in volume element d 3x at x and a second par ticle in d 3 y at y.284/r. H the spins of the two particles are antiparallel.x).. del (g(r) = = 4 }'. so' (10 where (102) F(kFr) = _1_ 3 N(2r) f If chf d 3k eik·z ' (10 . may be combined with the exchange contribution 0. We want to calculate for a fermi gas in the HartreeFock approximation the probability g(x.916/r.
. as r~ 00. the term i = j is excluded from the sum. for unit volume. N is n/2. We first rewrite the potential energy in terms of the particle density fluctuation operators PK defined as (106) (107) L PKeiK. 'l e2 _ x. The electron deficiency near the origin is known as the fermi hole. (105) 1 H = 2m ~ p/ + j~' Ix. . using (104) We note thatF(kpr) ~ 1 and (g(r»~ 0 asr~ 0.68).1 . + v(x) j ). we have PK charges. so that (108) PK = fd x j p(x)eiK.1(K K 3 K/) = PK'. 5 95 The integral in (102) was evaluated in (1. . = ~ L p/ 2m j + j. . In (104). the hamiltonian is. COULOMB INTERACTIONS AND THE FORMALISM OF SECOND QUANTIZATION With the fourier transform (83) of the coulomb interaction.Z • If p(x) is uniform and equal to n.L' L 411"~2 eiK'(Zi:l: ij K~O K where the positive background removes the term in K = 0. F(kpr) ~ 0 and (g(r» ~ 1.z p(x) = K 3 3 K = L PK. CH. We have put the 6 function in the spin projections 8. (109) p(x) = = n6KO ' For point L 6(x  Xj). 1 .z• f d x p(x)eiK":I: = f d x L PKei(KK').FERMION FIELDS AND THE HARTREEFOCK APPROXIMATION. whence (103) cos kpr) F(k pr) = 3 (sin kpr k kpr 3 3 688 p r 411" 3 3(211")3 kp = N. 8' on the z axis into (103) to emphasize that F(kpr) is zero for anti parallel spins. where n is the electron concen tration counting both spin orientations.
_ It follows that (111) and (112) PiPK = L eiK(XlX ' v i) ' Pi. Then the kinetic energy is (115) f d 3x 'i'+(x) 2m'i'(x) p2 = L EkcitckB. (116) and from (108) (117) Further.PK  L' eiK. k2 Ek = 2m' Now.96 and (110) PK QUANTUM THEORY OF SOLIDS f d x ~ ~(x 3 1  xj)e iK X . from (105) and (112). ij where n is the electron concentration.060 k ~ 211'"e 2 K2 (PKPK . by the definition (32).Xi) = L eiK(X. k fd x ei(k'kK)·x = k . (113) 1 H = 2 k Pi m j "2 + 'i'(X) K.. Thus the hamiltonian In terms of density operators is. ls) k8 in a plane wave representation.4 e1 iK Xi .n 2 The coulomb energy is (119) k ~I 211' "e K2 K 2 (PKPK  + n) ~ k Kkk' .Xi ) ij n n. (118) pi = ..8' 3 L Cit+KCk = PKo ~.+C Cks k+K.(x. = kk'.= . (~ 211'"e + + ) k K2 Ck+KCkCk'KCk'.+ PK = k Ck8 Ck's kk' p(x) = 'i'+(x)'i'(x) L Citck'8ei (k'k)"X. + It is also valuable to have H expressed in terms of fermion operators_ Let (114) = x L Ck8 eik.n). where Is) is the spin part of the one electron wavefunction.
The new solutions have the form of spin density waves there is no spatial variation of charge density. 128. i where we have used the fact that 2. We have evaluated (122) previously. but the ground state of most metals does not seem to be a spin density wave state. Phys. thus the factor involv ing the four operators has the form (121) and (122) E(diag) = + + Ck' Ck. Overhauser l has shown that both equations have solutions which give lower energies than the customary plane wave solutions. Rev.FERMION FIELDS AND THE HARTREEFOCK APPROXIMATION. The experimental situation suggests that spin density waves may occur in chromium at low temperature. nks n. The diagonal elements of the coulomb energy come from the terms for which k + K = k'. PROBLEMS 1.CkCk + (1 Ck. 5 97 so that the hamiltonian becomes (120) H = I EksCksCks + k8 + I I I ( 21re 2 K2 Ck+K.stCk'. J. This is exact. (a) Verify that the anticommutation relations (6) are satisfied by (26) and (27). 8 = 8'. W. It is not clear what happens when further correlation effects are included in the calculation.T} = 0. CH.sCksCk' . Rev. (b) Verify that (26). Kohn and S. Letters 6.Ck' + ). 1 A.n). W. 462 (1960) and Phys. The spin density wave states have a lower energy because of the increase in magnitude of the exchange energy resulting from the local augmented parallelism of the spins. but there is a spatial variation of spin density. Phys. ~ . {c.T} = O. {c+. Letters 4. To date all calculated improvements on the HF energy have been based on the normal HF state as the unperturbed state. Ovcrhauscr. . (27) are equivalent to (23). this is just the HF energy (97). Ck Ck 1 I nks Ek8  k8 kk'8 I' Ik 21re _ k'I2 2 nkRnk's.." + + Kkk' 88' . Ncttel. Rev. 1437 (1962).K. 8 (1960). (123) It will be helpful to note that T2 = 1. (24). It is important to realize we have not shown that the plane wave solutions of the Hartree and the HartreeFock equations are the lowest energy solutions.
y). a summation is implied. Find for bosons the analog to the HartreeFock equation (50). calculate the groundstate energy.gif!(x)ift(x)if. grad .98 QUANTUM THEORY OF SOLIDS 2.x') is an eigenvalue of the density matrix and if+(x') Iva.(x) ifa (x) . Hint: Let the density operator p(x) == f d3x" if+(x")8(x . when two {j's occur in the same term. Show that for boson or fermion fields (125) I if(x)N = (N + 1)if(x).. or at least as ifl plus its timereversed partner (Chapter 9).. . Show that the exact equations of motion are: (126) i'4fa (x) = 2~ p2ifa(x) + gift (x)if. 7. where g is a constant.x")if(x") operate on the state.y) = ga(x' . f Here a and {j are spin indices. Find the net electron deficiency in the fermi hole. Show that if+(x') Ivac} is a state in which there is an electron localized at x'. Show that (124) p(x)if+(x') 1vac} = f d x" 8(x 3 x") 8(x" .: A) >1<+.~ A)' (p . Let N denote the operator f d x' if+(x')if(x') 3 for the total number of particles.c} is an eigenvector. In a magnetic field described by the vector potential A. iir!(x) =  (127) 2~ if!(X)p2 . The observed cohesive energy of metallic sodium is about 26 kcal/mole.: A)' >1<. that is. grad ..(x). In (37) let vex') 0 and V(x' . We suppose that the field if may be written as if f + if 1. 3. 4. we have (128) (129) p"Jt(x) > >1<+ (x)p' > >I<+(x) (p . with F(kFr) defined by (102). thus a(x .r)if+(x")! vac} = 8(x  x')if+(x')!va. compare this value with the energy of metallic sodium referred to separated electrons and ion cores. 6. On the model leading to (78).c}. evaluate fd 3 x F2(kFr). 6.~ A)' (i > >I< > ( . referred to separated neutral sodium atoms. The results of this problem are used in the theory of superconductivity in Chapter 21.
Finally.Manybody techniques and the electron gas 6 The major defect of the HartreeFock approximation to the total energy of an electron gas lies in the failure to correlate the motion of electrons of antiparallel spin. 99 . Most of the methods lead to equivalent results. Pines.q) in the calculation of the properties of a manybody system. The simplest of the new methods is the self consistent field approach of Ehrenreich and Cohen. whereas for smaller ra the electron gas is stable. Rev. At sufficiently low density the problem is rather different: the electron gas is believed to condense into a crystalline phase of bcc structure. and Goldstone and Gottfried. It is clear physically that the coulomb repulsion will tend to separate electrons of antiparallel spin. 1437 {1961}. The direct approach to the calculation of the correlation energy is 1 W. Carr. Plys. We defined in Chapter 5 the correlation energy as the difference between the exact energy and the HartreeFock energy. The neglect of correlation is not as serious for electrons of parallel spin: we have seen with the fermi hole that the exclusion principle auto matically introduces a strong correlation for these. by D. we discuss Goldstone diagrams and the linkedcluster theorem. this includes many relevant reprints. J. We refer to the low density limit as the Wigner limit. particularly at high density (ra < 1). 122. There have been developed in recent years many powerful methods for calculating the properties of an electron gas. for r a ~ 5 it is believed 1 that the electron crystal is the stable state. This chapter is concerned with methods for the approximate calculation of the corre lation energy of the degenerate electron gas. A good general reference for this chapter is The ManyBody Problem. After developing the SCF method we show the great con venience of the frequency and wavevector dependent dielectric con stant E(W.
k2 vi = 0.' 1 + P. here 0 is measured from the direction of k2 . We develop the method of Brueckner in an appendix. In the actual physical situation we expect the coulomb interaction of a pair of electrons to appear as screened (] S v ( o t: .k 11/q. This is caused by the long range of the coulomb interaction.) • ei(ka"x+k.k 1• The integral over dO in (4) has the value 11og' 1+ K K i 1 ( 1 K '\1 The integral over dq involves II q3 and is seen to diverge at the lower limit q ~ O.o. ka + k4 .K where K = Ik2 .i(k.k2 is the momentum transfer in the inter action of kl. k 4 • Thus (3) eg) = m ( ~.2 f d'x d'y .iKO(>.ka = k4 ..») I = 411"e 2 • Qq2 Ll(kl + k2  ka k 4). and p."y) (~~~: . k2 by virtual scattering to ka. In the Brueckner method for calculating the correlation energy of an electron gas in the high density limit there are contributions from all orders of perturbation theory.') 2 ~ E 1 1 G 1 The summation can be converted into an integral: (4) L~ Q (211") 1 00 0 11" dqq4 fl 1 1 dp.100 QUANTUM THEORY OF SOLIDS to treat the coulomb interaction as a perturbation on pairs of electrons of antiparallel spin and thus to calculate the energy correction by standard perturbation theory to second and higher order. k2 i is e12 where (2) {121 (2) _ _ '"' k 34 2m{121 34){341 V112) 2 2 2 . = cos 0.o>+k. There are simpler methods of handling the correlation energy problem. The second order coulomb energy e(2) of two free electrons in the volume Q in states k11. and it turns out to be possible to sum in all orders the most important terms in the perturba tion expansion. The removal of this divergence can be accomplished by diagram matic analysis developed initially by Brueckner.kl . but the Brueckner analysis is revealing and important. Here q = kl .
SELFCONSISTENT FIELD METHOD We consider a single particle with the oneparticle ~amiltonian = H 0 + V(x. 786 (1959). The equation of motion of p = Po + op is (8) ip = [H. Ehren reich and M. such a series cannot be expected from a finiteorder perturbation calculation. Rev. Cohen. CR. The equilibrium statistical operator Po of the unperturbed system (V 0) has the property (7) polk) = fo(ek)[k).t).1 MANYBODY TECHNIQUES AND THE ELECTRON GAS.op] + * This p is not identical with the particle density operator in the second quan tization form introduced in Chapter 5. 116. We let p denote the statistical operator represented by the oneparticle density matrix.p]. but it also suggests that perturbation theory is not the natural way of handling the problem. with the expansion* H (5) 1m) == Vtm(X. m where Pm is the ensemble average probability that the state m is occupied. (9) i op r>v [H o. This screened potential is an infinite series in (e2)~. then the density matrix is defined by (6) (k'lplk) L (k'lm)Pm{mlk). where fo(e) is the statistical distribution function. if we linearize (8) by neglecting terms of order V op.t) is the selfconsistent potential arising from the interaction with all other particles of the system. or. . The clearest method is perhaps the selfconsistent field approach as described by H. We expect the unperturbed potential e2/ r to assume for the perturbed problem a form rather like (e 2/r)ef'/lIl.t) = LIk){klm) k in terms of the eigenstates Ik) of H 0. 6 101 (except at short distances) by the other electrons of the system. Phys. The calculation by GellMann and Brueck ner is a tour deforce. H. thus if Vtm is a solution of the oneparticle HartreeFock equation. where the screening length ls will be of the order of the fermi velocity vF divided by the plasma frequency: ls a: vF(m/ne2)~. where H 0 = p2j2m and V(x.
The potential V is composed of an external potential V O plus a screening potential VB related to the induced change on in electron density.!O(Sk)] FiJ to + 41r:2 [!O(Sk+q) q L (k'lopjk' + q). k' (2~ This equation is essentially the same as that obtained in the random phase approximation of Bohm and Pines.Sk+q)(k\oplk where (11) eJ( re (1 v q(t) = (kl Vlk + q) = Jd 3x V(x. m m kk' q (21 kk' k" q wI The screening potential is related to on(x) by the poisson equation (13) V 2 V8 = 41re 2 on. . 2 It is generally helpful to express the prop~rties of the interacting electron gas in terms of the longitudinal dielectric constant E(W.poJlk + q) + q) + (fO(Sk+q) X W (Sk .t).2 q E(' co de L (k'lop\k' + q). Thus.102 QUANTUM THEORY OF SOLIDS M.Xonq. The usual definition relates the polarization component P q to the longi a For a review ijee D. In this section other fourier components are defined similarly.Sk+q)(k\op\k + q) . so that (14) 41re 2 V:(t) = . tu (1 :t (kloplk + q) = (kJrHo. . on taking matrix elements between \k) and (10) i Ik + q). k' (2 so On combining (10) and (14) we have the equation of motion in the absence of an external perturbation: (15) (2: i ~ (kloplk + q) iJt = (Sk .t)e iq• is the qth fourier component of V(x.!O(Sk)] Vq(t) .q).op]ik + q) + (kl[V. Thus V O might be the potential of a charged impurity and V8 the potential of the screening charges in the electron gas as induced by Vo. Pines in Solid ~tate Th tie ex] an ele th~ physic8 1 (1955). q 2 V:(t) = 41re 2(klonlk + q). N ow the induced change in electron density is (12) on (x) be eh (1 th (1 so LIm)Pm(ml = L L Ik')(k'\m)Pm(mlk)(kl = L Ik')(kl(k'lp\k) = Leiq·x L(k'\oplk' + q) = Leiq. We may define the dielectric constant in various equivalent ways.
+0 q k k € +q .47r 2"JT' e20nq q q where w is the frequency associated with Vq • The definition (16) of E(W. q)V q . k k € +q . (19) Further.): (23) ESCF(W . the ratio of the applied potential to the effective potential. q) = V~/Vq.c.MANYBODY TECHNIQUES AND THE ELECTRON GAS..k € + w + ~s Finally we have the longitudinal dielectric constant (we shou1d add to this the c. where E: is derived from the potential V:.q)Eq D q. and not a manyparticle.k € + w + is V q' V q' so that (22) onq = L(kloplk + q) = L fO(€k+q) k 2 . The approximation takes the electron to respond as a free particle to the average potential V(x. hamiltonian.fO(€k) k € +q .t) in the system.q) = 1 1 . q) = 1 _ lim 47re '\' fO(€k+q) . CH. 6 103 tudinal electric field Eq by (16) Eq + 47rPq = O E(w. Thus (18) E(W.k € + w + is This is an important result.E:/47r. The relation (16) is equivalent to (17) Vq  V: = E(W. from which we may calculate many proper ties of the system.fO(€k). The result is equivalent to that of the random phase . The particular expression (23) is approximate because we started with a oneparticle. where VO is the external potential and VB the potential of the induced charge. Now if Vq(t) acts as a timedependent driving force in (10). because the longitudinal polarization P q gives rise to the induced electric field . we have (21) (kloplk + q) = fO(€k+q) .q) is also used in (40) below. including the correlation energy. but there it is found convenient to consider an expression (42) for the dielectric constant in terms of the density of test and induced charges. We recall that V V + V" is the net potential. iqPq = e onq.fO(€k) 2 ~ • . div P = eon. P q) + 47r ( E q eEq = iqVql so that (20) E(W.
3. 1 1m . Thus there are collective excitations as well as quasiparticle excitations. with wp2 4rne 2/m. af _0 0 ( w ak .. PhY8. The imaginary term'in (24) gives rise to a damping of plasma oscillations called Landau damping. Sawada.'L . which is the energy needed to create an electronhole pair by taking an electron from k in the fermi sea to k + q outside the sea.) "" q .+ ~8 X 1 1. () 1/lrO X . In the limit w» kFq/m the result (23) reduces to.ek. at absolute zero. These special particles ride in phase with the excitation and extract energy from it. (24) W 2 E(W q) "" 1 . we say this is the plasmon region.q) in (23). 372 (1957).fo(e. already familiar from Chapter 3. = <P . a here <P denotes principal part. The equations of motion (15) of the undriven system may be solved to give the approximate eigenfrequencies as functions of q. and the plasmons then are not good normal modes. w "" ek+q . The real part of E in (24) was obtained by writing (26) e o g' fO(ek+q) . . w2 s v q e+i 2Jrq2 2 f d3 k q . The other type of eigenvalue appears for small q and is w 2 "" 4rne 2/ m. the eigenfrequencies are just the roots of E(W. the magnitude of the damping involves the number of particles whose velocity component kq / m in the direction q of the collective excitation is equal to the phase velocity w/q of the excitation. At absolute zero the absorption given by d {E} vanishes if w > k Fq/ m. For w < kFq/m the imaginary part of E is 2m 2e2w/q3. but the total number of degrees of freedom is 3n. The transverse dielectric con stant of an electron gas is the subject of Problem 16. The equations of motion are equivalent to those considered by K.104 QUANTUM THEORY OF SOLIDS approximation of N ozieres and Pines. In a degenerate fermi gas the maximum electron velocity is vF. ak' afo and (27) w + k· q/m  1 !:::::! w 1 (1 _ k· mw q). +k m q) v n where we have used the relation (25) ~+o x ( . T fi ( p p The real part of E agrees with the result for the dielectric constant of a plasma at q = 0. Rev. This damping is important at large values of q. 106. for q d' T in tr ti B . The eigenvalues are of two types: for one type.
470 (1960). We summarize: at low q the normal modes of the system are pi as mons.0 5. as is expected.018r8 .73). Li Weal o Na K 3. The dependence of this radiation on the angle of observation and on film thickness was predicted by R. Rev. A.71) and (5. P. 1214 (1958). then the ratio of the number of plasmon modes n' to the total number of degrees of freedom 3n is (28) n' 3n 1 3 % 2 . 111.4 5.9 ev flE Wopt 8. 6 105 such that wp/q > VF there are no particles in the plasma that travel with the phase velocity. PhY8.8 ev 3.7 5. at high q the normal modes are essentially individual particle excitations.9 ThomasFermi Dielectric Constant. LeUer8 6.9 ev 3. and 14 percent of the degrees of freedom are plasmon modes. The ThomasFermi approxima tion to the dielectric constant of the electron gas is a quasistatic a W.96. 3 (0. R. Rev. Brown. Phys. W. % where the 2 in the denominator is from the spin.0 9. More detailed evidence of the existence of plasmons is given by the observation 3 of photon radiation by excited plasmons. Steinman. Ferrell. A comparison of the observed energyloss peaks with the calculated plasma frequencies for the assumed valences are given in the accom panying table. PhY8. Rev. CH.5 8.472 (1960).48r8~' If we consider all modes having q > qc to be indi vidual particle modes. Trounson.92 (1961).48) r8 0. and E. . 163.MANYBODY TECHNIQUES AND THE ELECTRON GAS. In sodium r8 = 3. and consequently the imaginary part of E(W. Plasmons in metals have been observed as discrete peaks in plots of energy loss versus voltage for fast electrons transmitted through thin metal films.q) vanishes for q < qc = Wp/VF' Using (5. Lettera 6. we have qc/kF = 0. Z. The plasma frequencies given are corrected for the dielectric constant of the ion cores. P. Wessel. PhY8. Be Valence Wealc B C 4 Mg Al 3 16 15 Si 4 Ge 4 16 ev 17 ev 2 19 19 flEobs 3 24 19 2 11 10 25 22 17 17 The comparison for the alkali metals is also striking because the inelasticloss peaks are in close agreement with the threshold of optical transparency.
This is identical with (34). In this limit (36) ESCF(O.)3 c.V: is the external potential. We expect the ThomasFermi dielectric constant (34) to be a special case of the selfconsistent field dielectric constant (23) for w = 0 and for q/kp «1.V: = 1 _ (47Ie onJq2) . We note that Vq . .V. The basic assumption (Schiff. From the definition (18) of the dielectric constant. C == &nne 2/eF.(2'J1') 3 2m fdk 3 q' q •k afo/ak a + (47Ie 2) 8'JI'nk F • _q2 (2. t s c t VI (31) onq~ 3n .(x)]%. as in (13).2 Vq {j rl eF But the poisson equation requires that a variation onq give rise to a potential V:: q2 8 (32) onq = 471e 2 V q.106 QUANTUM THEORY OF SOLIDS 1\ (w + 0) approximation applicable at long wavelengths (q/kF« 1).. p. for the fourier components.:. (. """"" (47Ie 2 ) . (. 282) is that the local electron density n(x) satisfies (29) I t c n(x) a: reF .q) = 1 = 1 '1 v (. (33) Vq (2eF onq/3n) or (34) where (35) ks 2 (. and (Vq .V:) + V: V q is the effective potential.k .". I h (: (: s~ ( ETF(q) = q + q. the ThomasFermi dielectric constant is 2 ETF(q) = Vq . for a weak potential on ~ _ 3n (30) 2eF V. because m = k F 2/2ep and kp3 = 3n'Jl'2. or. Thus where V(x) is the potential energy and ep is the fermi energy. s 2 2 (.
the response of the system to the test charge. We recall from (5. we wish to solve for this induced particle density component. Nozieres and D. We write the test charge density as erq[eHCllt+q.113). 4nerqeiCllt . P.q) as the appropriate dielectric constant. Pines. 470 (1958). and H' is the coulomb interaction between the system and the test charge: (44) C H' = 4ne . In the absence of the test charge the expectation value (Pq) of all particle density fluctuation operators Pq will be zero. The hamiltonian is H = H 0 + H'.t q 2 + ee. Let us imagine that we introduce into the system a test charge distribution of wavevector q and frequency w. (43) ~ 1 2 H 0 = k 2 Pi i m ~ 27re +k q 2 (Pq Pq  + n). Nuovo cimento 9. CH. from (5. We calculate now a more general expression for the dielectric constant in terms of matrix elements between exact eigenstates of the manybody system. 6 107 DIELECTRIC RESPONSE ANALYSIS4 The selfconsistent field calculation of the dielectric constant is based on an independent particle model and is only approximate. . (42) 1 E(W.MANYBODY TECHNIQUES AND THE ELECTRON GAS.2 . so that.p_qrqeiwH. (test charge density + induced charge density).q)q' Eq iq • Eq = 47re(rqeiwt + (pq»). with r q real. = total charge. by the definition of D and E.118) that (37) Pq = L k Ct"_qCk' In the presence of the test charge (p± q) ~ 0. test charge On dividing (40) by (41). iq • Dq = i€ ( w. where for a specimen of unit volume we have.q) 1 + (pq~ rqetMt We now calculate (Pq). (38) (39) (40) (41) div E = 4ndiv D = 4n(test charge density).X) + ecl. with E(W. Now.
108 QUANTUM THEORY OF SOLIDS where for adiabatic switching s is small and positive. = 1 _ 4re q2 2 a L 11.+ ~ro X .q) . q n q2 q . ' + WnO ~8 = I(n\p_q!O)12. as for the roots the mode response is singular according to (42). we have for the imaginary part (49) $I ( () E w. + ~8 w g k 1(njpqI0)2 n " (1 + W WnO where we have used the symmetry property l(nlpqI0)\2 From (42) we have the exact result (47) 1 E(W.. in the presence of the test charge <1>0 ~ <l>o(rq). + Then to terms of first order in rq (46) ei c. tl The eigenfrequencies of the system are given by the roots of E(W. We assume the test charge is sufficiently small that the response of the system is linear. () .(0) in the ground state <1>0. <l>n.4r e 2 L I(nlpqIO)] 2 = 2 2 4r e 2 2 q (Olptpq\O). (P 1 . Wno)  o w n eJ On integrating over all positive frequencies w. . rqe~Wt+8t (<I>o(rq)lpql<l>o(r q»  4re 7 2 .W WnO .q) = 0.lt+8t. L x 1 (d~no J (. dwfJ () o E w. 11. 1) a e e T '] (. The expectation value of the coulomb interaction energy in the (f a1 .~8 '\ L + .EO = WnO. l4re 2 (nlp_qI0)ewt+8t (n\pq\0)e wt+8t ) <l>o(r ) <1>0 r . (50) f.q oo (1) = . We suppose the system is initially (t = . SI Recall that the states used as bases in this development are the true eigenstates of the problem including internal interactions.is W WnO . 1m 1 8++0 ± ~s 1 . x o o(W wno)]. Using (48) (J iE .q 1 ) 2 2 4r e =2 q L l(n\pqI0)12[0(w 11. where by firstorder timedependent perturbation theory in the Schrodinger picture with En .
according to (5. (51) E int = (OiL' 21r:2 (p. obtain the exact groundstate energy simply by adding Eint to the unperturbed groundstate energy.Eint(g) 1 d I + Eo(g) dg (cI»o(g) cI»o(g». Here Eo(g) is the exact eigenvalue and cI»o(g) the exact eigenfunction. g = coupling constant. Proof: From (54) and (55). on integrating. of course. Given the hamiltonian (53) H = H0 + gHint .q) This expression gives formally the coulomb energy of the exact ground state in terms of the imaginary part of the dielectric response. That is. because the kinetic energy of the ground state is modified by the coulomb interaction. Pq q q  n)IO). we utilize the theorem which follows. we have (56). We do not. and. where the second term on the righthand side is zero because the normalization is independent of the value of g. I then the exact value of the total groundstate energy (55) Eo(g) = (cI»o(g)IHo gHintlcI»o(g» is given by (56) Eo(g) = Eo(O) + lo(J g1Eint (g) dg. H0 = kinetic energy. (57) dE o dg g. . 6 109 ground state is.~( +7 . THEOREM. Thus we have a special case of Feynman's theorem: (58) dEo 1 dg = g Eint(g) . which may now be written as (52) Eint 2 100 (1) 21rne ) I = .113). and the value of (54) Eint(g) = (cI»o(g) gHintl cI»o(g» . CH. cI»o is a function of e2• To obtain the total energy of the exact ground state. 21r 0 dw S E(W.MANYBODY TECHNIQUES AND THE ELECTRON GAS.
t). 95. (6 b That is. so that given E int from (52) or in some other way.q) by calculating (47) with matrix elements taken in a plane wave representation. \1 Jd x' ~[x 3 T Xi(O) + x'] ~[x' = N1 (L ~[x ij Xj(t)] Xi(O) + Xj(t)]). in ze .xi(t». Rev. we can find the total energy in the presence of the coulomb interaction from (56). for example.10). We note that with the integral representation of the delta function we may rewrite (49) as (60) e b a c d(_1_) = r 21r 1f E(W. and (6. H.q) describes the scattering properties of the system in the first Born appro~im&tion. Now Van Hove [Phys. see also Problems (2. the groundstate energy is just the sum of the fermi energy plus E int • We get a much better value of the energy using the selfconsistent dielectric constant (23). if where the Xi are in the Heisenberg picture.q) 2 41re dt (e iwt  eiwt)(eiq·Xi(O)eiq·Xj(t».110 QUANTUM THEORY OF SOLIDS In the electrongas problem the groundstate energy without the coulomb interaction is.t) ( = NliJ. (6. per unit volume.q) = ~ f d'x dt e"q·''lG(x. we find an approxi mate result for I/E(w.q) (61) = r1f ij i b o p sc OA dt eiwt(eiq·Xi(O)eiq. (63) S(w. 2r ' w S has the property that it is the fourier transform of the pair distribu tion function (62) G(x. (6 We shall see later in connection with neutron diffraction that S(w. The coupling constant is g = e2.249 (1954)] discusses a function called the dynamic structure factor which may be defined as S(w.9). then we get just the usual Hartree Fock exchange for the interaction energy E int• As ~o in this approxi mation does not involve e2. ( (59) Eo(O) = !n€F.6).
This establishes the connection between the dielectric constant and the correlation function S.q) is indeed a structure factor which describes the elementary excitation spectrum of the density fluctuations of the system.~ fd 3 411'" iq'x x.e~q·x r (211")3 q2 becomes. (64) S(""q) = ~ f dt e. We have also an . for the linear response region. The screening of charged impurities has many consequences for the theory of alloys. The screening of the coulomb potential by the electron gas is an important effect.MANYBODY TECHNIQUES AND THE ELECTRON GAS. From (60) and (61). we have (65) g e(w.110). It is because of screening of the electronelectron interaction that the free electron or quasi particle model works as well as it does for transport processes. 6 111 We may also write.q) e in the medium.)' Thus S(w. (68) V( ) . with appropriate oper ators in the expansion of the Pq.  "'n. It may be used equally for boson or fermion systems.(211")3 q q2E(w. d q.q)]. because the impurity is stationary.q) ( 1) = 7 41I'"e 2 [s( w. DIELECTRIC SCREENING OF A POINT CHARGED IMPURITY An interesting application of the dielectric formulation of the manybody problem is to the problem of screening of a point charged impurity in an electron gas. We are usually concerned with the potential V (x) at zero frequency. CH.S(w. the charge density may:be written (66) p(x) = Z o(x) =~ (211")3 f d 3q eiq•x • The potential of the bare charge (67) Vo(x) = Z = 1.f3411'". using (5.q) . Let the charge of the impurity be Z.w ."(pq(t)pt(O» = ~ I(nlptloll' $(".
e"q':I' . 0:: nJ. = 11k.'0) . and (69) Using (68) with ~ = 0 V2y = 41r[Ap + Z o(x)].. The dielectric constant in this approximation is given by (34) and (35): 2 2 k8 ks 2 = &nne = 3k F • (72) ETF(O.55 X 108 cm.112 QUANTUM THEORY OF SOLIDS interest in the charge Ap(x) induced by Z o(x).i. = . If 11E(O. .(. Thus the screened potential is.q) has poles.. In copper k. there will be oscillations in space of the screening charge density. The total displaced charge A involved in screening is (71) a = f d'x ap(x) = = (2!)' f f ('(. is roughly double that for copper.)3 Zf d q 3 Z corresponding to a screening length (74) l.O) is sometimes not welldefined. The screening charge around an impurity is largely concentrated in the impurity sphere itself and the interaction between impurity atoms is small.q) 1+2 . ..q) . Screening is a very impor tant feature of the electron gas.ek •r 02 + k. From (71) the total screening charge is Z. from (68). eF 1faH' q here aH is the bohr radius. l=:::: 0.1) e. E(O. In potas sium l.I} The value of E(O. but may depend on the order in which ~ and q are allowed to approach zero. (a) ThomasFermi. We now consider the screening in several approximations. 2 r ' (73) Y(x) = .1 e we have (70) ) Ap (X Z (2r)3 f q (1 d2 ) iq'x .I . or l. 4.(2.q·· d'q d'x Zfd 3q o(q) (_1_ .1) E(O. l=:::: 1.'q) . The induced charge .8 X 10 8 cm.q) =Z (.
411"r 2 ~ This is singular at r = 0. Kohn has made the interesting observation that the sudden drop in the dielectric constant as q increases through 2k p should lead to a small sudden increase in the eigenfrequency w(q) of a lattice vibrrtion at the point q = 2k p as q is increased. 1. Woll. 126. 1693 (1962). There is a singularity in the dielectric constant at zero frequency of the type (q . There is an infinite screening charge. . J. thus the energy denom. It is not yet clear why the effect should persist in the presence of electron collisions with phonons and with impurities.3 cos 2kpr. the stiffer will be the response of the elecltrons to the ion motion and the higher will be the lattice frequency. The dielectric constant is given in Problem 1. q k 2 In m ~) . eH = 1 + 2 82 g(q). and the magnitude decreases monotonically as r increases. because coulomb interactions between electrons are not included. 251.. ). Kohn. The result (23) for the dielectric constant ESCF in the SCF or RPA approxi mation is seen by comparison to be simply related to the dielectric constant eH in the Hartree approximation given' in Problem 1: 1 (76) ESCF 2 . Jr. 6 113 density is (75) 1 . (c) SelfCon8i8tent Field or Random Pha8e Approximation. see Pines. The infinite electronic density on the nucleus is in disagreement with the finite lifetime of positrons in metals and with the finite Knight shift of solute atoms. Rev. PhY8.he ~ge written for zero frequency. p. :t.2k p l. For a general argument connecting ESCF and EH. (b) H artree A pproximation. What happens at q = 2kp? For q < 2k p one can draw a vector q such that both ends lie on the fermi surface. and W. We see that the total screening charge is equal to ... The lower the dielectric con stant (as a function of q)..V2V = 411" 8 Z k k r e ·. But for q > 2k p it is not possible to take an electron from a filled state k to an empty state k + q with approximate conservation of energy. CH.s )r an . as shown in Fig. so that the charge density contains oscillatory terms at large distances of the form r.MANYBODY TECHNIQUES AND THE ELECTRON GAS.Z. see E.1p(x) = . inator in the expression (23) for the dielectric constant can be small and there is a corresponding large contribution to the dielectric constant. For a discussion of the detailed theory of fermi surface effects on phonon spectra. Here the energy denominator is always large and the contri bution of all processes to the dielectric constant is smalL W.2k p ) log Iq .
0005 0 0. Distribution of screening charge density around a point charge for an electron gas with r.04 0.08 . 1. using (5. J..114 0 0.+ S c ry (Ts2 Ts ' where the first two terms on the righthand side give the HartreeFock energy. S.a 0. H..0015 0. and Sc is the correlation energy. = 3. Rev.10 . 196 (1960).02 0 0 2 kFr 3 4 5 0..12 0. Chem.0010 2 4 6 kFr . In the range of actual metallic densities Nozieres and Pines [PhY8.916 ) .. (77) So= 2.06 0.0020 0. CORRELATION ENERGYNUMERICAL We write the groundstate energy per electron as. QUANTUM THEORY OF SOLIDS ~b.... 442 (1958)] . ~ 0. 0. 111.. Bolid8 12.97)..0005 0.0010 C!\)1t.. Langer and S. Vosko.a 8 10 12 FIG..21 0. as calculated on manybody theory by J. Phys.
Note that e2 tends to cancel the exchange and correlation contributions.13 ev. if the positive charge is gathered together as positive ions. according to calcula tions described in the references cited in Chapter 13. Their paper should be consulted for details. The mean free path of an electron near the fermi surface is actually quite long.0. as we emphasized in Chapter 5. This energy is to be compared with e1 = 0. where the terms are ordered as in (77). The solution for k = 0 of the oneelectron periodic potential problem for sodium gives e(k = 0) "' 0.07) ry.30 0.16 = 0. Thus the cohesive energy of metallic sodium referred to neutral atoms is (80) ecoh = e1 + e(k = 0) + eo + e2 = + 0.77). CH.031 log rs) ry.60 .2/rs ry is the selfenergy of a uniform distribution of electrons within the 8 sphere. is a statistical factor which expresses the requirement that the target electron must have an energy within kBT of the fermi surface if the final state of this electron is to be reasonably .38 . I t is instructive to use (77) and (78) to estimate the cohesive energy of a simple metal referred to separated neutral atoms. and for sodium has the value 0. we should add to eo the term we denoted by e2 in (5. 6 115 recommend the interpolation result (78) ec "' ( 0.38 ry. where 0'0 is the scattering cross section of the screened coulomb potential and (kBT/eF)'J.MANYBODY TECHNIQUES AND THE ELECTRON GAS.23 .0. which is rather too close to the observed value 1. the ionization energy of a neutral sodium atom. With rs = 3. The cross section for scattering of an electron at the fermi level of an electron gas at temperature T is of the order of (81) q~qo·e::y.0.14 .1 ev. But. ELECTRONELECTRON LIFETIME Because of the offdiagonal parts of the electronelectron interaction. an electron put into a quasiparticle state k will eventually be scattered out of this initial state.30 ry.08 ry = 1. eo was calculated for a uniform background of positive charge.96 we have (79) eo = (0.0.60 ry.115 + 0. Sodium is a convenient example because it has an effective electronic mass close to the free electron mass: here we neglect differences between m and m*. e2 = 1.
812 (1958)]. We consider the scattering caused by an external potential v(w.. They calculate for an electron gas at absolute zero the mean free path of an electron added in a state k outside the fermi surface (k > k F). .L Jd x ei(kk'+q). the final state of the incident electron must be avail able for occupancy. We see that an electron is not strongly scattered by the other electrons in a metalthis remarkable effect makes it possible to use the quasiparticle approximation to the lowlying excited states of an electron gas.q) through the perturbation hamiltonian (84) H'(w. at 3000 K it is 4.q) of the fermi sea at absolute zero. Numerically.q)eiwteiq·. Another pertinent result is that of J. (83) I"'V kF r/~ in the limit of high electron density. equally. For sodium with l8 as estimated by Pines.116 QUANTUM THEORY OF SOLIDS empty. We take the unperturbed system H 0 to be the free electron gas. Rev. Abrahams [Phys. 112. in Na at 4°K the mean free path for electronelectron scattering of an electron at the fermi surface is 2. )0 GRAPHICAL ANALYSIS OF DIELECTRIC RESPONSE It is instructive to carry out a graphical analysis of the most impor tant terms in a perturbation series which contribute to the dielectric constant ~(w.5 cm. The diag~ams we use are called Goldstone diagrams and are related to Feynman dia grams.Xw(x) + cc v(w. Ferrell [Phys. For high electron density the mean free pa\th A is \ AkF = (k . the result is 0"0 171raH 2 . A. 839 (1954)] by calculating phase shiftsthe Born approximation is not accurate. Rev.q)e. J. The factor (k kF)2/kF2 is a phase space factor analogous to the factor (k B T / ~ F ) 2 in the thermal kF the mean free path increases indefinitelythis is problem.q) = = Jd x w+(x)v(w. where aH is the bohr radius.5 X 104 cm.kF)2 3.q) eiwt Li k + CC. 96.98. the states at k F are indeed welldefined. Quinn and R. The fraction of states thus available is (k B T / ~ F ) 2. As k one reason why we may speak of a sharp fermi surface in a metal. The scattering cross section for the screened potential (82) V(r) erJl• r e2 has been calculated by E.x + cc k'k 3 iwt CitCk 3 ~ Ck ++qCk v( w.
We recall that the term involves a product of four operators.k. It is as if v(w.55) and (5.q) and the coulomb interactions V (q) among the electrons. We use the convention (5.Pq q n) between the electrons of the system. [J. The other perturbation is the coulomb interaction (85) V = L' V(q)(p. thus combinations such as at+qak. this interaction will tend to screen v(w. 13kq/f~. The perturbation terms in the hamiltonian are v(w. In the following development we consider only terms linear in the external perturbation v(w.q) represented the interaction with an ultrasonic phonon. is indicated by an arrow directed downward. reprinted in Pines.56) P. such as Cit+qCk/Ct_qCk. We retain only terms linear in the external potential. and the fourth as the annihilation of a holeelectron pair. Hole creation (k <kF) Hole annihilation (k <kF) Electron annihilation (k >kF ) FIG. a hole state (within the fermi sea) is indicated by an upward arrow. 2.q) with time dependence eilllt and spatial dependence eiq ·][. c may be written as in Chapter 5 in terms of electron and hole operators. Soc. the third as the creation of a holeelectron pair. Proc. The creation and annihilation operators c+. but we are interested in all Pq orders of the coulomb interaction. Goldstone. 2. the second pair as hole scattering. In constructing the graphs which represent the terms of the perturbation series we use the hole and electron con ventions shown in Fig. in terms of the a and 13 there are 16 possible combinations. An electron state outside the fermi sea. The operation of the first pair will be spoken of as electron scattering. 268 (1957).] . (London) A239. but only that part of the interaction which causes absorption of a phonon of wavevector q and energy w. Lines for Goldstone diagrams. 6 117 In what follows we concern ourselves for the sake of brevity with a discussion of the terms shown explicitly and not with the hermitian conjugate terms. at+q13~. Roy.q). Electron creation (k>k F . We consider then the scattering caused by the external potential v(w.q).MANYBODY TECHNIQUES AND THE ELECTRON GAS. CH. and 13kqak may occur.
We consider as unpe outside the fille outside the fill have Ii) of the (87) (11 U 1 (0. 4.q). and (b) holehole.. The dashed line represents an interaction.) 1\ (6) tI_k_qO!k A convenien of the U operat (86) U(O. We take the screening into account by going to higher orders of a perturbation calculation in calculating the response of the electron gas to the external potentiaL We still stay at first order in v(w.q).118 O!k + qtlk QUANTUM THEORY OF SOLIDS MANYBODY TE + + y (0. FIG. Electron electron and holehole scattering processes in lowest order are shown in Fig.) and annihilation (b) of a holeelectron pair. the scattering of an electron with k < kp to a state outside the fermi sea is represented as the creation of a holeelectron pair.64). Schematically (88) Ule for the electron the subscript ee. q q These are the c cated in (86) tl imposed by COlli to discuss. electronelectron. 4. but consider all orders of the interelectronic coulomb potential V(q).) tlk+qtlk + (6) (0. 3. Scattering in lowest order: the external potential v(""q). Creation (0. The (89) (11 U 2ce li) [L (11 n . As in Fig. of the fermion quasiparticle discussion in Chapter 5. In the actual electron gas problem we know that screening plays an important part in reducing the effect of v(~. Consider fi the special case exist. We next stud in (1. 3. The broken line ending at the vertex represents schematically the interaction responsible for the process shown in the graph.) I. 00 FIG. We electron of wave at+ q ak (0. by ~ . but for a then two possib: with II)this CI operators assogi.
k i . we have (/Iv(w.. We have not indi cated in (86) the restrictions on the intermediate and final states imposed by conservation of wavevector. This part is represented graphically by Fig. k at. Vet. but for a more general interaction it may exist...wia)t. rs of the for the electronelectron scattering part of the process.. v(w. as denoted by the subscript ee. CH. ..  00 )  ~ L.130): olehole. (87) (II U 1(0.s". following (1. f ~"~1 dt" V(t l ) V(t2) . 0 t (. I. The restrictions are simple to discuss.(0).q) Ii) .). 4a. . (II V(q/) Im)ei(s. as above.55): (86) U (0.. and a state Ij) containing one electron in k f outside the filled fermi sea..i  Fig. ..f C. In lowest order.is)tl(ml v(w. ..ia)t. that in the state Ii) there is a single electron of wavevector k i outside the filled fermi sea. 6 119 A convenient question to ask is the value of the matrix element of the U operator defined by (1.f~ f~11» i)" I» dh dt2 . Consider first in the coulomb interaction the term q' = 0: for the special case of the electron gas YeO) = 0 and this term does not exist.. We suppose.fjJrftt.f  w  ~8 • ak+qak + plays an screening .ia)tl(n1 V(q')li)ei(e. 'he dashed We consider as an example the matrix element taken between a state of the unperturbed system containing one electron in a state k i outside the filled fermi sea. of the form given in (1.q) involve (89) (II U 2ee li) = (_i)2 f~I» dtl f~ll» dt2 [}.q) C.q)1n)e i (I. . tside the ire The ally the Electronre shown n w  ~8 Schematically we may write (88) U lee (0.(0) = " ...lculation potential.].64).63).SOLIDS MANYBODY TECHNIQUES AND THE ELECTRON GAS. There are then two possibilities: for YeO) the state In) in (89) may be identical with I~}this corresponds in the second quantization formalism to operators associated with YeO) of the form (see 5. We next study the secondorder term U2ee(O. (/Iv(w. 3.q) Ii)ei(sme. ~(kf . ak• . m These are the crossproduct terms in (V + V)2. by ~ L.00 = C. . . The terms linear in v(w.I. " + }.i  k C.q).
5. accompanied by the creation of an electronhole pair: ~ + R+ + k ak_q'I'_kak.q). II. But we must annihilate the same pair we create.q). there is no momentum exchange. as shown in Fig. two holes k and k' are created and then annihilated..+q. (= k i + q'). here. although (a) alters the energy of an added electron in k. The total process is ~ + R+ + k akq(jkak ql'_kak i+qaki' k If we denote this process as V(tl) V(t2) in the timeordered sequence. The annihilation is represented by the operators akq(jk. a hole is created in the fermi sea at some k. For q' ¢ 0 the coulomb interaction can scatter the incident electron from k i to k. where the presence of q is forced by the q dependence eiq·:r.. neither process affects the scattering. Scattering processes with zero wavevector transfer. This term is represented graphically by Fig. Another possibility for V(O) arises from operators of the form kk' L (jk/(jt(jk(jit. 6a just as for the direct process of Fig. I ~k + O~~O k k' (b) ak I (a) FIG. 5a. so that q' above must equal q. 6a. 4a. and (b) enters into the energy of the fermi sea. I i ~(~O ~k k.' k This process is represented in Fig. 5b. ~ . but it is annihilated in the same process. The creation of the electron hole pair is followed by its annihilation by interaction with the external perturbation v(w.120 QUANTUM THEORY OF SOLIDS a+ k.ak. of the potential v(w. Thus the scattering process is k i ~ k i + q for the indirect process of Fig.
The process of Fig.IJkak+qIJ_kak +q.fo(Sk+q)] Sk+q Sk W  Sk+q Sk Sk.~_O'\ la' (b. 6. 6b is "\' a + R R+ + . where fo denotes the occupancy in the unperturbed ground state. Now because k is a dummy index we may replace it in (92) ". ..+q  Sk. k k. k in the timeordered sequence it is V(t l )V(t2).MANYBODY TECHNIQUES AND THE ELECTRON GAS.+qak.'!!o~~~ ki V(q) ~(~.k a hole by writing (91) as (92) fO(S_k)[1 . FIG.fo(Skq)] Skq Sk +w is . CH.q be an electron and . Electron scattering involving an electronhole pair in the intermediate state: (a) ak_ql3_ka~_ql3~kat+qakii and (b) at+qakil3_kakHI3~ka~iq. Sk  w  is is . and thus (90) may be written tion: w Sk+q l l (91) 1 Sk_q S_k +w  is We can indicate the requirement that k .i"!!. so that the denominator from the t2 integration is (93) ~ 1 fo(Sk)[1 .  is But the subsequent integral over tl assures overall energy conserva Sk. 6 121 then the integral over t2 as in (89) gives the denominator (90) Skq Sk 1 + Sk.
8. Exchange graphs. Two of the 3! sequences for polarization loops in third order.ek  w {fo(ek)[l .q) = 1 L k ek+q . from (93) and (94). vertices the momentum changes must be equal.fo(ek+q)[l .is With s = 0 the result of the integration over t2 for the sum of the two processes in Fig. as (95) M(w.fo(ek+q)] .ek+q w . At all . by k (94) + q and rewrite (92) as + fo(ek+q)[l .fo(ek)] ek . 7.122 QUANTUM THEORY OF SOLIDS t I v v E0 (a) (b) FIG. 6 may be written.fo(ek)]}·1 ____ov v uv (a)  _~_DL~y_ (b) FIG.
. Two further types of scattering processes are shown in Fig. with exchange. representing the scattering of an electron in state kJ by interaction with an electron within the fermi sea.MANYBODY TECHNIQUES AND THE ELECTRON GAS. 6 123 ~o ___0 v (a) v ___9 v (b) v V_V"J (c) ~ v V FIG. 9. second in V) the analogous graphltto Fig. In (a) the coulomb interaction contains operators a~r. 8. Several other thirdorder scattering processes are shown in Fig. 9. we expect such diagr. Both involve electron exchange.tfltak/. In third order (first in v. Several other scattering processes in third order. 6 are given in Fig. III. these are not pure polarization loop processes. CH. The process in Fig. 7. and. by the same argument given in the appendix for the effect of ring diagrams on the energy.1ms to dominate the scattering process at high elec tron density. In (b) the coulomb interaction creates an electronhole pair at one vertex and annihilates it at the other vertex. We say that such graphs contain polarization loops. 6 is of particular interest because all momentum changes in the graph are equal.
4a. 8. Thus linked graphs include Figs. may be written as (96) v(w. A careful extension of this analysis shows that the polarization loop series. a broken line represents the bare or unscreened interaction.]. Let L . we use the timedependent perturbation approach discussed at the end of Chapter 1. i a ! .q) .q) = Veff(W. A graph containing no unlinked parts is called a linked graph. The effective or screened inter action is usually represented by a double wavy line connecting two vertices. 4. We now derive the famous linkedcluster perturbation theorem.VM t ti Ii 8 t + (VM)2 .q)at +qak[1 . The relative positions in time of the unlinked and linked parts of a graph affect the range of integration in U4>0. effective potential is (97) On summing the series we see that the 1 t ( Vcff(W. 5a.q) v(w. For electronelectron scattering the first term of the series is shown in Fig. The second term is shown in Fig. Consider all those graphs containing unlinked parts which differ among themselves only in that the interactions in the unlinked part are in different positions relative to the rest of the graph.q) 1 + V(q)M(w.q). the relative order of the interactions is fixed. 9. 7a. however.124 QUANTUM THEORY OF SOLIDS ~ The subset of graphs in all orders which contain only polarization loops may be written as a series.q) so that (99) E(W. unlinked parts are found in Figs. 6. The dielectric constant is defined as (98) E(W. 8. LINKEDCLUSTER THEOREM Any part of a graph which is disconnected from the rest of the graph and has no external lines going in or out is called an unlinked part. E where M(w. We see that the SCF method is (like the random phase approximation) equiv alent as far as the dielectric response is concerned to counting only those interaction terms in the Umatrix expansion which may be represented by polarization loops. in exact agreement with the result (23) of the SCF method. 3.q) = v(w.q) 1 + V(q)M(w. Within the linked and unlinked parts. 5b and 7b. and the third term is shown in Fig. including signs and numerical factors.q) is given by (95).(VM)3 + . 6.
t" (0 > tl > t2 > . = (Eo ._1 ei(HoB )t._l f '·_1 _ co dt" e iHot .. This permits the terms for unlinked parts to be taken out as a factor.lI'. . Thus. CH. Then UIO} = (2'. We now carry out the time integration: (100) 10) UIO} = ~ (<1" f. V 1 . The sum over all these graphs or over all the different relative positions of the linked and unlinked parts is obtained by carrying out the time integrations where the only restriction is that 0 > tl > t2 .Ho 1 . But the normaliz ing denominator (01 UIO) = (2'. .. co EoHo+~s VIO). because an external line gives zero for the diagonal element._. .. = I..' . t"' dt. . + + 0 0 + t8 ..l e.. dlJ t.._.. VIO) + ~s) . .. unlinked parts). (linked parts). > tm').)t. terms from unlinked parts) X (2'._1 co .. > t" and 0 > h' > t2' > . > t..) and the times of the interactions in the linked part be tI" t2'._1+ 8t ._1 eiHot "_1 V eiHot . t2. ... exact result: (102) 10) = Then we Inay write the f (Eo ~ Ho v)" 10}. V Ho tns Eo .. dtl .Ho t(n . . where the sum L .+.t.r MANYBODY TECHNIQUES AND THE ELECTRON GAS._IV .~)"l " f ..is over linked graphs only.VeiHot"e8t. . VIO} ei(H.l " hence (101) 10) f f .. 6 125 the times of the interactions in an unlinked part be tI.+8t. tm ' • The sum is therefore the product of the expressions obtained separately from the two parts.8)t.. lim . linked parts)..l)s 1 ••• E H VIO}.. +0 L L Eo  1.. = ~ (i)" ~ f. 10) = 2'. L(i). tm ' (0 > t I' > t2' > ....10) _ co dt" ei (H oBo)t. = L (.(HoB o+2t... f (1" f . . f t"' dt.. . ..
Bloch. 10. 10. Graph (a) and (b) are each connected graphs. Show first that ( 106) _1_ _ _ _ 32re m EH(O. Using (47). 1 in which a boson is created and then destroyed.:r( J d1k d k'\(k\ eiqJ:\k')\2 <P k'2 1 _ k2' 3 k<k1' k'>k1' l .126 QUANTUM THEORY OF SOLIDS )a ~~O~~D (a) \l (: VI (b) FIG. (a) or (b). The normalization denominator (010) is equal to unity. (105) Thus ilE = _fJ2/ e is the exact shift in the groundstate energy_ PROBLEMS 1. 451 (1958). for an alternate derivation see C. where H 0 = ea+a. A connected graph i8 a graph with no external line8 but with the property that the entire graph may be traced out continuou8ly. consider the boson hamiltonian H = ea+a + '1(a + a+). (1.q) 1 (2r)6 q2 2 .E = t (01 V (Eo ~ Ho V riO). As a trivial example. The only connected graph in the expansion is from (104) (01'1 a I 1)(11 _ H 0 11)(11'1a +10).45): (103) !!. The exact energy shift ilE is given by Eq. Nuclear Physic8 7. where now contributions to the sum come only from connected graphs with no external lines. calculate the dielectric constant of the electron gas in the Hartree approximation. as in Fig. Equations (102) and (103) are linkedcluster perturbation equations.
2 On comparison with (49). CH.  ~. A. < Hint: In evaluating the integral show first that the related integral (109) II k<b !r.MANYBODY TECHNIQUES AND THE ELECTRON GAS. if the potential energy term in the hamiltonian is of the form ~ V.2 g(q) q2) Iq+ 2k.. using lowest order timedependent p.. that the rate at which the test charges do work on the electron gas is (112) dW di = 2rw (4re2) 7 rq21(n\pqIO)12[8(wn o . the value of a2E(Jla~2 is negative.q) 2 q 4. Rev. where ~ is the coupling constant.• 1 •• ~ O.erturbation theory. This result has been used by R. 3.. this is easily evaluated. ( 1 .  .116 2 where k. Ferrell [Phys...w) .O) = = m' w 116 2 + i1Jw 1 . Thus. Letters 1.1+log q 4k. d'kd'k' 8(k' +q  k)1l' .'<k. show. < . On evaluating the integrals.. 444 (1958)] as a criterion for the extrapolation of expressions for the correlation energy of an electron gas. is the groundstate energy.& eElm. Consider the equation of motion of a free electron gas having relaxation frequency 1J: (114) f + 1Ji = E 116:. For the test charge density (111) erq(eiCwHq·x) + cc).q) . (a) Show that the secondorder perturbation energy of the ground state of a system is always negative..2q2 &.. (113) at  dW __ 8re wr 2d (_1_). 6 127 where (107) (» denotes principal value. 2. 2 (108) Ie" = and k. EH(O. < kF. but over all k'. Here E.8(wno + w»). 2 Show that the polarizability (115) a(w. .. (b) Show further that a(V)/a~ ~ 0. show that 1 k2 1• g(q).. Thus the desired integral is equal to the integral over k with the use of the 8 function we have (110) I k<b d'k . q2 E(W.
show that ) J(00 0 dw O'I(W. Pkys.n q • (c) In the representation with H 0 diagonal.128 where. E.  Note the contribution of the zeropoint plasmon modes to the groundstate energy.q = jWp . show that (a) (119) (b) (120) [Ho. This is an important sum rule. III.(Xi)].pq] =  ~ ~ q. for a discussion of the application to the superconducting transition see R. Show that (117) ~+o lim d (!) = W1r~(W E If we use only this pole in evaluating (52). Usually. [[H o. From (47) in the limit W» WnO. A. when is this true? 6. . using the result of Problem 5. The proof is simple. 109. 00 dwwd . 1398 (1958). Pkys. 6. 109. that (122) E(W. =~ G 7'} w. Ferrell and R.331 (1959). show. (p + iq)eiN. Rev. and Ho =L i [f m Pi 2 + V.. for (116) W QUANTUM THEORY OF SOLIDS near Wp. Rev. using the NozieresPines sum rule.W2.. show that (118) Ein. Recalling that (124) E J. m This is the NozieresPines longitudinalJsum rule: Pkys. 2 47rw/ w. Show. Rev.741 (1958). M.q) "" 1 _ 47rne 2 • mw 2 7.Pq].q) (1) = 1 7rW 2 p. Ferrell. 2 where 0' = 0'1 .O) = 2' W  Wp + i'q + ii'q' . 1(0Ipqlm)12 = 1(0Ip_q\m)12. Now from (47) we see that on the real axis WEI is an odd function of wand WE2 is an even . If in unit volume pq = i=1 t eiq'%i. Causality requires that E be analytic with respect to w in the upper half w plane. 1 "" 1 W E(W.( o E w. that (123) 8.wp ). (121) L wmol 1(0Ipqlm)12 + 1(0Ip_qlm)12} =!~ q2.Pq] n 2 = . Tinkham and R. Letters 2. Glover. A.
ai'+q ak+q . In ring graphs (see the appendix) we are concerned with coupled events described by the operators (129) Ai(q) = ai+qI3~k.q) = sew. 13+ are hole operators.Ai. a+ are electron operators and the Show that (130) 13. 11.q) == NS(q).P:!:. We note that in this approximation the A. We have assumed that S(w.8qq " because in the unperturbed vacuum state the electron and hole occupancies are zero.k'+q.q) = Nq2/2m. p(x) Nl{Olp+(O)p(x) 10).(q')] Ch+q. show that (128) 10'" dw wS(w.lC • 10.00 to 00 on the real axis and completed by a semicircle at 00 in the upper half plane. where the a. Here Seq) is known as the liquid structure factor and is the fourier transform of the pair correlation function (126) (127) seq) = Nl{OlpqptIO) 1d x 3 p(x)eiq .MANYBODY TECHNIQUES AND THE ELECTRON GAS. show that (125) 10'" dw S(w. 9.k. . CH. . Using the result of part c of Problem 5. and that (131) [Ak(q). where m is the particle mass. Ak(q) == Pkak+q.Pk :::::: 8kk.8k k. Consider a contour integral from . [Ai(q).8k+q. for N particles. With the dynamic structure factor S(w.8 kk .Ai. using the result of Problem 6 for the asymptotic form of E.(q')] = 0. 6 129 function. A+ have the same commutation rules as boson operatorsan electronhole pair acts as a boson.q) as given by (64). q).k'+q.
THE DEFORMATIONPOTENTIAL INTERACTION (5' wi In covalent crystals the electronphonon interaction is often rela tively weak. is called a polaron. Suppose that in an unstrained cubic covalent crystal the electron 130 (6 or (7 T' . to ] low uns of t we (3) wh4 be thif Br< if' (4) a tl wh Ic~ edl th4 pe In this chapter we discuss several central aspects of the electron phonon interaction. The chief effects of the coupling of electrons and phonons are: (a) To scatter electrons from one state k to another k'. (b) To cause the absorption (or creation) of phonons: the interaction of conduction electrons and phonons is an important source of attenua tion of ultrasonic waves in metals. (d) The electron will always carry with it a lattice polarization field. The composite particle. and when in semiconductors the concentration of charge carriers is low it will be valid to neglect screening effects of the carriers on each other. with emphasis on features which may be presented without lengthy and detailed calculation. electron plus phonon field. it has a larger effective mass than the electron in the unper turbed lattice. In this situation the deformationpotential method of Bardeen and Shockley may be applied for phonons of long wavelength.Polarons and the electronphonon interaction 7 herl L the calc (2) Conduction electrons sense in various ways any deformation of the ideal periodic lattice of positive ion cores. leading to electrical resistivity. Even the zeropoint motion of phonons has its effect on the conduction electrons. this interaction is important for superconductivity and results from the virtual emission and absorption of a phonon. (c) To cause an attractive interaction between two electrons.
k2 here m * is the effective mass of the conduction electron. . 7 131 energy band of interest is nondegenerate.l""ep. to leading terms. The kinetic energy per electron is.. it is not possible for e(k) to be an odd function of the shear strain: we must therefore have CI''' = 0 for p.. Thus ae eF 2an 3Q = jd. in Electronics 7.. where d is the dilation.k"ep. For a spherical energy surface in the unstrained crystal."kp. spherical. This result assumes that the charges move to keep each part of the .POLARONS AND THE ELECTRONPHONON INTERACTION." .}d). It is easily shown that for a free electron gas the constant C1 has the value jeF' where eF is the fermi energy. 2m n (31r N)% 2 with N electrons in volume (6) n. CH. Thus we write for low k (3) e(k) '" eo(k) + Cld. The extension of this result to nonspherical energy surfaces has been considered by Brooks [Adv. Values of ICll and are of the order of magnitude of 10 ev for the conduction band edges of Si and Ge. Here Cl = ae(O)/ad is a constant which may be determined in part by pressure measurements. ~ v. or (7) e(k F) = eo(k F) . (5) eF = 1 . It is found that if it is the unit vector in the direction of k." + .teO(kF)Ll. the'shear strains add to (3) a term of the form (4) C2 (k. Let us now make a small uniform static deformation described by the strain components ell'"~ The perturbed energy surface may be calculated in principle.. at the fermi surface. 85 (1955)] and others. IC21 where C~ vanishes for a spherical energy surface. and we set C~" aside. it will be of the form (2) e(k) = eo(k) CI'"ep''' C. In a semiconductor the k's of interest are usually low. and given by (1) eo(k) = 2m*.
a+ q Jd x 3 eiCkk'+q). for one thing. For acoustic phonons of long wavelength we assume that (3) may be generalized to read (8) c(k. I Iattlce. In semiconductors at low temperatures the possibility zero may be the only process allowed energetically. where Uk(X) has the periodicity of the lattice (Chapter 9). In the Born approximation we are concerned with the matrix ele ments of C 1~(X) between the unperturbed oneelectron Bloch states Ik) and Ik'). product U. with Ik) = eik. k k and the at. thus the integrals in (9) vanish unless (11) we . with a similar generalization applying to (4).132 QUANTUM THEORY OF SOLIDS POL crystal electrically neutralthis is well satisfied for quasistatic pertur bations of wavelength long in comparison with the screening length as defined in Chapter 6. 0. .k' ±q= CJ. It is quite apparent that optical phonons are not covered by such a treatment.x) = coCk) + CI~(X). (13) If The B stre: elec· elec· witl but elec· is Cl ' optic It . vector 111 For plane waves only the possibility zero exists. the expansion of the dilation in phonon operators. (9) H' = J d x 'I'+(X)Cl~(X)'I'(x) = k/k L ctck(k'ICl~lk) 3 = iC 1 k'k L CtCk ~ '\' (2PWq)~~ lql (a f d x q k' 3 U*U . Using. . we have not included longrange electrostatic potentials which would arise from longitudinal optical phonon deformations. .84).'(X)Uk(X) involves the periodic parts of the Bloch functions and is itself periodic in the lattice.x) k' k . t h e reClproca . the scattering process is said to be a normal or N process. If (12) k . from (2.k' + q= I 0 . as here each Uk(X) is constant. a The q refer to longitudinal phonons of wavevector q. the dilation is only related to acoustic phonons. for another. where (10) wh sal' as "ve two L ven pot (14 'I'(X) = L Ck<Pk(X) = L Ckeik.k' ± = G.xuk(X). (15) k .x k U*U eiCkk'q).xUk(X).
Before going further we should see what the limitations are on the strength of the coupling parameter C1 in order that our separation of electron and phonon energies should make sense. we may equally write this as (15) H' = iC 1 r (2pWq)~2Iql (aq kq a~q)cit+qCk' The field operators describe the scattering processes shown in Fig. the scattering process is said to be an umklapp or U process. where G is a vector in the reciprocal lattice. The classification of processes as normal or umklapp depends on the choice of Brillouin zone. Electronphonon scattering processes in first order. and for con venience we approximate f d 3 x U:. 1.I FIG. CH. is called a polaron. 1. Let us limit ourselves for the present to N processes. By "vector in the reciprocal lattice" we always mean a vector connecting two lattice points of the reciprocal lattice. . 7 133 k+q aqck+qck + a q Ck_qCk + + Phonon absorption Phonon emission L. * The phonon cloud changes the energy of the . The term polaron is most often used for an electron plus the cloud of virtulilll optical phonous in ionic crrstal~. The existence of the electronphonon coupling H' (14) means that an electron in a state k with no phonons excited cannot be an exact eigenstate of the system. The composite particle... but there will always be a cloud of virtual phonons accompanying the electron.POLARONS AND THE ELECTRONPHONON INTERACTION. Then the deformation potential perturbation is (14) H' = iC 1 r kq (2pw q ) Hi lql (aqcit+qCk at CitqCk) .Uk by unity. electron plus lattice deformation.
2pc. Phonon Cloud. Let us calculate by perturbation theory the number of virtual acoustic phonons accompanying a slow electron.ekq . This is not a trivial question: for heavy particles such as protons moving in the crystal the number of virtual phonons is very large (see Problem 1). (19) ek . Nor can we then have much confidence in the validity of crystal wavefunctions written as a product of separate electronic and vibronic functions. squares of the admixture coefficients we have Ta X ata dit eX] (17) (N) = L I(k  q.lq!H'lkO)12.q ) . Thus we write the unperturbed state of the total system as IkO). In these circumstances the proton may become trapped locally in the crystal.lq) (k . 2 2m*2C 1 q 3 (20) (N) = (27r)3 pcs d q.l IH'lkO)12 q = C121ql. (2~ where H' is the electronphonon interaction. the firstorder perturbed state denoted by IkO)(l) is given by (16) IOD as eql (2] wh ele est int (2~ Be int IkO)(l) = IkO) + LIk q q. th bt co wi in pI (2 f where the integral should be carried over the first Brillouin zone of thE .ekq .ekq .q. (18) I(k . the unperturbed state of the electronic system is taken as a Bloch state.134 QUANTUM' THEORY OF SOLIDS POl electron. is the longitudinal velocity of sound.wq) ele co: (2. q (ek .Wq.csq· 1 For a very slow electron we neglect k in comp~rison with q and then write the sum in (17) as an integral. with m* as the 2 where c. For the deformation potential interaction (14). effective mass of the conduction electron. we can no longer trust the result of a firstorder perturbation calculation. If the number of virtual phonons accompanying the electron is of the order of unity or larger. We take as the unperturbed state of the phonon system the ground state in which no phonons are excited.Wq = 2m * (2k' q .l qIH'lkO). Now. (q2 + 2 c. The total number of phonons (N) accompanying the electron is given by taking the expecta tion value of ~ On summing over the q over the state IkO)(l). ek .m *q)2' gi.q.
The numerical estimate was made using m* = m and c. (qm/ qc) ditions. (23) (N) ~"2 1i 3 1(' 1 m*2C 2 1 pCs t""V log (qm/qc)' t""V t""V Taking C1 5 X 10. Cs 5 10 2. If we do not neglect k in comparison with q. how long will it stay in the same state? We calculate first the probability w per unit time that the electron in k will absorb a phonon q. If nq is the initial population of the phonon state. = 5 X 10 5 em/sec. we have (N) 0. we obtain the more complete result t""V t""V (24) (N) = /n 2 . pCs 0 dq ( + )2' q qc q where. The integral is standard: (22) l t""V q ". We shall for convenience take the integral over a sphere in q space out to a qm chosen to enclose a number of modes equal to the number of atoms: (21) (N) = "2 1(' 1 m*2c121Q".nq) = 27r1(k + q. o dq (q + qc) q 2 q m .11 ergs.nq>.m*2C 1 J .2k) log qm 1 I +2k I qc _ 2k + (q. with Ii restored. we have qm/qc» 1 and the value of the integral is approximately log (qm/qc). qc = 2m*cs/1i ~ 10 6 cm. but the sum of the wavevectors of the electron and virtual phonon is conserved.POLARONS AND THE ELECTRONPHONON INTERACTION. We see from the form of the wavefunction IkO)(1) given by (16) that in the presence of the electronphonon interaction the wavevector k is not a constant of the motion for the electron alone. Now. Suppose an electron is initially in the state Ik).nq  1Ik.1 2o(€k + Wq  k € +q)' . the expectation value of the number of virtual phonons around each electron is yery much smaller than unity.2 X 1027 gm.nq  1IH'lk.02. p 5. with Ii restored. m* 0. Because qm ~ 10 8 emI.1 is essentially the electron compton wavevector in the phonon field. CH. 7 135 longitudinal phonons. which are perhaps typical for covalent semiconductors. + 2k) log I qm : ~ ~ 2k I}' Relaxation Time.2 ~!h (qc . In these con X 10 5 em/sec. = log (1 + ) qc  qm qm + qc. (25) w(k + q.
. W (~ = 2s{e}. On comparison with (28).nq 1IH'lk.qm dq 0 q3 0(Ck  Ckq  Wq).csq 2m 2 1 m * (2k . this requirement resembles the Cerenkov threshold for the emission of photons in crystals by • There is a simple connection between the fust. where the limit 8 + +0 is to be taken. m *c s • which for q (31) = 0 reduces to k min = lqc so For this value of k the electron group velocity Vg = kminlm * is equal to cs .QUANTUM 136 For the deformation potential interaction THEORY OF SOLIDS POl fas n q. ekq  L q m tl. Thus the threshold for the emission of phonons by electrons in a crystal is that the electron group velocity should exceed the acoustic velocity. .34). The renormalized energy is (3 El 10 til e=~ 2m • + L I<k q ell:  Qi 1 qIH'lkjOq>!2.nq hal in (3~ + 1IH'lk. Cdq i8 ell:_q  fr tr el Cdq). (3: N ow the argument of the delta function is (29) no q .nq }12 =C 12q thI eVE 2 pCs The probability per unit time that an electron in k will emit a phonon q involves the matrix element through (27) I(k . (28) an W _1_ 41rpc s C 2/1 1 d(cos 6q) /. The total collision rate W of an electron * in the state Ik} against a phonon system at absolute zero is. ~ .q. 10· (26) I(k + q. q  db IS where qc = 2m *c s as before.order renormalization of the electron energy and the relaxation rate (28). 2 1 * (2k . argument can be zero is (30) The minimum value of k for which the trl gr (3 k min = l(q + qc). siel =: 11" By (1. q .qqc). the velocity of sound. from (27) with nq = 0.q2) .nq}12 = 2 C 21 q (nq pCS + 1).
1 and the emission rate is (33) 2C 1 2m*k 2 3rpcs note that this is directly proportional to the electron energy Sk. k 2iJ. q . Then the integrals in (28) become (32) I~1 diJ. The fractional rate of loss of k is given by the transition rate integral with the extra factor (q/k) cos 0 in the inte grand. An electron of energy below this threshold will not be slowed down in a perfect crystal at absolute zero.tudinal optical phonons is approximately (36) Ho = wl2: btbq. Instead of (32). we have (34) 80 2m* k fr~ctional (I Jo dl' 8k'l" = 16m*k' 5 that the rate of decrease of k. the hamiltonian of the longi . The interaction with transverse optical phonons will be less strong because of their smaller 'electric field. except at very low q where the electromagnetic coupling may be strong. at least in the harmonic approximation for the phonons. W(emission) q) = 8m* 10 diJ.POLARONS AND THE ELECTRONPHONON INTERACTION. The electron energy at the threshold is jm *C s 2 ~ 1027 • lOll ~ 10. even by higher order electron~phonon interactions. This is a longrange coulomb interaction and is different from the deformation potential interaction.2 = 8m*k2j3. I dq q3(2m*/q)o(2kiJ. Neglecting dispersion. 7 137 fast electrons. CH. The loss of the component of wavevector parallel to the original direction of the electron when a phonon is emitted at an angle 0 to k is given by q cos 0.e is W(k z ) (35) = 4C 1 m*k 5rpc s 2 2 • ELECTRON INTERACTION WITH LONGITUDINAL OPTICAL PHONONS We expect electrons in ionic crystals to interact strongly with longitudinal optical phonons through the electric field of the polariza tion wave. For k» qc we may neglect the qqc term in (29).16 ergs ~ 10 K.
X+ CPteiq·X). q WI p. =i but w (44) whence (39) E = grad cp L q(cpqeiq.Xs .X2) = ecp(xI) + ecp(x2) q i4?rFe 1 ql(bqeiq.x q CPte. We now want to evaluate the constant F in terms of the'interaction energy e2/ Er between two electrons in a medium of dielectric constant E.iq.NTUM THEORY OF SOLIDS POLAR where b+. But div D = 0.83) tells us that the dielectric polarization field is proportional to the optical phonon amplitude and will have the form (37) P = F 1 tq(bqeiq.138 QUA.X ). Consider electrons at Xl and X2 which interact directly through the vacuum coulomb field and indirectly through the secondorder pertur bation of the optical phonon field. (47) where we have dropped products in Xl alone or X2 alone.124): (41) Th actio] contr betwi elect] contI have (46) H'(XI. the V2: phon() that t in the inters Iti (43) where tq is a unit vector in the direction of q and F is a constant to be determined. In st only shou inte] left dist~ Now at absolute zero the secondorder energy perturbation caused by (41) is (42) H"(XI. nurr. Here the state 10) denotes . That is.X1 + bqeiq.X ). so that E (40) + 4?rP = 0. We expand the electrostatic potential in the form (38) cp(X) = 1 (cpqeiq.X + bteq iq. The factor 2 arises from the interchange of Xl and X2 in the expression for the perturbation.X2 ). b are boson operators. as these are selfenergy terms.Xl  bte. according to an extension of (5. The desired form of the effective perturbation hamiltonian in first order is obtained as the expectation value of the potential energy operator e J d 3x p(x)cp(x) over the state Y+(XI)y+(x2)lvac) which represents electrons localized at Xl and X2.X2) = 21 (Olecp(XI) 1 q)(qlecp(x2) 1o). we have N modes of differ ent q.iq. but with the identical frequency WI. or CPq so thl (45) = i4?rFb q/q. Reference to (2.bteiq.
It is easy to evaluate H" from (41) and (42): (43) H "( XI.POLARONS AND THE ELECTRONPHONON INTERACTION.. and !q) denotes the state with one optical phonon q excited virtually with energy wz. From (16) (47) (N) = L I(k q (Ek  q. where qm is on the zone boundary.. Ekq Wi)?' . actually the sum should only be r'over q's in the first Brillouin zone.Oq)12.X2) . We now solve in the weak coupling limit for the number of optical phonons which clothe an electron. Polaron Cloud. and EoJ) includes only the electronic contribution. without recoil. _ e tq q2 . ·(J: 1 J:2). 7 139 the vacuum phonon state. I~l  811"F 2 e2 X2! This interaction is thus of the form of an attractive coulomb inter action between the charges e at Xl and X2: it gives exactly the ionic contribution to the interaction. We have (46) 1 EO 1 EoJ) 811"F 2 Wz In step (44) the sum was carried out over all q. where the dielectric constant EO includes electronic and ionic polarizabilities. The ionic term lowers the energy of the system.l q l!!'lk. but flatter at distances within 1/qm.X2 )  2e2(411"F) Wz 2 L1 q . It thus accounts for the difference between e2/EoT and e2/EoJ)r.. On subtracting from 11r a screened interaction we are left with a potential essentially 11r at long distances. The part of q space we should have excluded may be seen to give by itself a screened coulomb interaction. CH. This problem is almost identical with the interaction problem in neutral scalar meson theory. but we have seen that when summed over all q (44) L 411" q2 q eiq·J: 1 so that in the ground state (45) H"(XI. It is supposed in using (42) that the electrons are localized and that their state does not change in the interaction process.
(50) 2 (N) = 8e F2(2m*)2 where qp 2 = 2m *Wl..25 2. The value of the integral in (50) is 7r/4qp 3.1 3. Mag. 41. however. Phil. Zienau.l qJH'Jk.Oq)J2 = (47reF)2jq2. with h restored (51) 1 00 0 dq (q2 + qp2)2' after (56) so tl phoIJ (57) (.4 3. obtain an impression of the actual situation. we have taken the upper limit as 00 in the integra tion.l qJH'Jk.62 5. the dimensionless coupling constant commonly employed in polaron theory.2m* L I(k q 1 q. so that the perturbation theory cannot be trusted to give valid quantitative results and more powerful methods are needed. thus qp times the lattice constant is of the order of i. q + qp Here we have used (49) and qp 2 2m*Wl. we do. Then (49) J(k . For NaCI qp ~ 10 7 cm. With m* taken as the mass oLthe free electron.2 niqu see ~ GrOt Thus for the alkali halides our estimate leads to (N) > 1.(N) = . The Pek2 Sovil conc the] Tl of tl ticu] Bur] Mot 1200 . q + qp2 or. neglecting k .q. typical values of a calculated from the observed dielectric properties and infrared absorption of alkali halide crystals are: LiF a Fori (58) in Ot F{ NaCI NaI KCI KI RbCI (N) 5. H.1 if m* is taken as the electronic mass. Pelzer.e (2m*wl)~ 4hwl h Eco EO 2 1 1) a =. Frohlich.9 2.4 5. q2 _ 2k .1 6. The selfenergy of a polaron for weak coupling is given in secondorder perturbation theory as (52) T. ek = e~ . Polaron Effective Mass.  e~ = 8e F m* 2 2 11 d(cos 9) = Jo roo 1 dq q2 _ 2k. R. using (38) and (40) for <p(x).Oq)J2. F. q in comparison with q2.9 6. after H . using the interaction (48) appropriate to the ionic crystal problem. 2 this defines a. and S.5 2. 221 (1950).8 2.8 4. 1 and.140 QUANTUM THEORY OF SOLIDS but now instead of the deformation potential (14) we have (48) H' = J d x e'l1+(x)<p(x)'l1(x) 3 = i47rFe Lql(bqct+qCk kq btCt_qCk) . (53) e.
S. JJ = cos 0. Pines. For a good review of the numerous literature and of the elegant tech niques which have been applied to the polaron problem when a» 1.. . 883 (1953). Par ticularly thorough results are available for AgBr. 97. . Further references include: T.2 JJ 2X 2 + x2) 2 + . Lee and D. The Soviet literature is reviewed by Schuitz. Rev. between 40 and 1200 K the mobility is dominated by scattering by optical nhonons. . 98. Pines. m:Ol rv m*(1 + ia). Low and D. .. ) = q/qp. 119. 7 141 The integral can be evaluated exactly. Feynman. Mobilities up to 50.POLARONS AND THE ELECTRONPHONON INTERACTION. . Knox. P. 660 (1955). Report 9. the mass of the polaron is l."JJx (1 4. 1560 (1960). and R. F. E. Phys. The polaron was first studied by Landau. Rev. C. Phys.) 2 ) after integrating over x from 0 to (56) ( Wl we have. SolidState and Molecular Theory Group. Burnham. + 12m so that the groundstate energy is depressed by aWl by the electron phonon interaction. Phys. 1956. 1 *k + . Tech. Rev. see T. using Dwight (122. but for slow electrons (k «qp) we might as well expand the integrand as 1 ( (54) with x as (55) 1 + 1 + 1 + x2 + k/qp. 92.ek o a (1 : ' 00 +. . C. F. Phys.3).. and by other workers in the USSR. 2.. :s in our weak coupling approximation." = The integral over dJJ leaves (54) (2 +h' ek . D. as reported by D.. The coupling constant a can be determined from measurements of the mobility of polarons in pure specimens of ionic crystals. CH. R. D.LT. . 414 (1955). For a (58) « 1. M. and then extensively by Pekar and his school. much of this literature is concerned implicitly with the limit of very strong coupling in which the lattice deformation follows the electron adiabatically.2 til • i ~. Brown. Schultz. and the total polaron kinetic energy is (57) ekin 2m* 1 _1_ ( sa 1 )1. as e 'e n k 1.000 cm 2 / volt sec were observed. Rev.
but in the ground state crystallize into a bcc' array. The number of optical phonons of energy e is proportional to the Bose factor (e 9 / T . we see that the model is the Wigner limit (Chapter 6) for high T8 of the correlation energy problemthe positive ions do not form a gas. The high T8 limit is applicable because the appropriate bohr radius for the unit of length is not h 2 / e2m. 1004 (1962)]. m: = 0.78) we found an approximate value for the average energy per electron on this model in the ground state: (60) e~ (65) and (66) with N~ (5.7] (67) Fins (68)  9 e 3 + ' 10 T 10~2mr2 2 . m:. when analyzed in terms of the calculations of Feynman.27m for the electron polaron mass. with a functional dependence determined by the details of the theoretical approximation employed. (64) usin~ m:. and Platz man [Phys. thus in excellent agreement with the value inferred from the mobility experiments. ELECTRONPHONON INTERACTION IN METALS We consider first some aspects of a very simple model of a metal based on point positive ion cores imbedded in a uniform distribution of electrons. will be observed in a cyclotron resonance experiment as long as the cyclotron frequency is much lower than the optical phonon frequency. give a = 1. F(a) is a function of the coupling constant. whe rou Wit wer sph coul T bul (61) whe (62) at e (63) wit Li. The form of the temperature dependence (59) can be understood simply: for T « e the relaxation rate of polarons is dominated by the absorptive collisions with optical phonons. but is h 2/ e2M.142 QUANTUM THEORY OF SOLIDS POL indicated by a temperature variation of the form (59) JL = F(a)(e 9 / T  1). = 0.1). The value of m* is related to a by the definition (51). with e = 195°K in excellent agreement with optical data. The electron mobility experiments on AgBr. In (5.60 for the coupling constant and m* = 0.20m. respectively. Rev. and for this value of a we can use the approxi mation (57) to obtain Cyclotron resonance experiments by Ascarelli and Brown give m. This model metal is sometimes called jellium. If we think of the electron cloud as fixed and of the positive ions as forming a fermion (or boson) gas. where M is the mass of the ion. so that the relaxation time and the mobility are proportional to (e 9 / T . 127.27m for the bare electron and the polaron effective mass. Hellwarth.1)1. Iddings. Note that the polaron mass rather than the bare mass m *.
i L '"' ei Q eiq·XjO q q. The same result is found in another way in (91). We assume the metal is monoatomic with n ions per unit volume.543)~ = 4. where na is the atomic volume.7).1 X 1010/0. following l . we would have (69) cs 1 m 2 __  3M VF 2. the value at OaK calculated from (69) with the fermi velocity 1.X~ J (njJf)J. and H eoul is the electronelectron coulomb interaction of the valence electrons. as their frequencies are determined chiefly by the shortrange interaction Hionion' The phonon hamiltonian exclusive of the electronphonon interaction may be written. we do not consider here the transverse waves. the experimental value of (B/ p)~2 at 25°C is (12. and the value calculated from (68) is 3 X 10 5 cm/sec.J Xj) + Hion.ion + Heouh where i is summed over the valence electrons and j over the ions. v is the electronion interaction. We have also supposed that the mass which enters the fermi energy is the freeelectron mass. so that the fermi energy is a more complicated function of roo For Li.31 X 10 8 em/sec as for the freeelectron mass is 6. ElectronIon Hamiltonian in Metals. We expand the departure of an ion from its equilibrium position as. In real metals m * will enter. X1 (71) oX· J = X· J . We write the hamiltonian in the form (70) H = 2~ ~ Pi 2 + ~ V(Xi • t. We have assumed implicitly in deriving (68) that the electrons follow along with the nuclei during the compression and during the passage of a longitudinal acoustic phonon. corresponding to B lmv F2 Ina. and m * will be a function of ro.8 X 10 5 cm/sec. following (2. Hion~ion describes the ionion interaction.144 QUANTUM THEORY OF SOLIDS If we had counted in the compressibility only the contribution from the fermi gas and neglected the coulomb contribution.7 X 10 5 cm/sec. The energy terms from K = 0 charge components sum to zero. and we suppose that such terms have been eliminated. q where Eq is the longitudinal polarization vector.
vex 1 X. q The coulomb term in (70) is. for free electrons. CH.(nM)~ iq L Qq[tq • Vv(x  XJ)eiq.POLARONS AND THE ELECTRONPHONON INTERACTION. where the first term on the righthand side may be combined with the electron kinetic energy to give the Bloch hamiltonian (74) Hel = L (Pi L V(Xi .LJ \" Ck+qCk. 7 145 (2.ph L QqVqP_q. where Oq is an ionic plasma frequency. k where (76) Vq =  (nllf)~\k + ql ~ ciq. coordinates are contained in (80) The phonon i ~ {PqP_q + Oq2QqQ_q + 2v q QqP_q}.17) and (2. . Using the density fluctuation operator (77) Pq  Note that (v_ q)* vq • . (72) Hionion = i L (P q qP_q + O~QqQ_q).) = ~ vex .X~) 1 . Now the q component of the second term of (73) may be written in second quantization as (75)  f d 3x i'+(x)i'(x)(nM)~Qqtq • V ~ vex 1 X~)eiq. (79) Heaul = 27re L 2PqPq· q q 2 ElectronLattice Interaction: SelfConsistent Calculation.26). The electronion interaction may be expanded as (73) 2.XjO = Lcit+qCkQqVq.xltq • Vv(x 1 XJ)lk) = will be assumed to be independent of k.X~)) = L ckCtCk' 2m i k 2 i with the spin included in k. + k the electronphonon interaction term is (78) H el .XjO].
where for longitudinal modes Oq is essentially the plasma frequency of the ions and is nearly independent of q. By (6. le s 2' k s 2 611"ne 2 (94 e. + [2 . The ions move slowly. Let p~ denote the component of the ionic density. ThE: Thus (81) becomes (85) Qq .ETF(q) ETF(q) 88:1 . whence (83) Pq T itly e2/1: 1 . so that we may treat the ionic motion as a quasistatic test charge density in the sense of (6. q M 2 1.(M n )HI 1 . (95: .. the quantity Vq is the pro portionality constant connecting the interaction energy of the electron distribution and the phonon amplitude Qq. We now use as an approximation the ThomasFerlni result (6.42) we have (82) P~ If 0.E(q) i E(q) Pq· (92: The ionic density is related to the phonon coordinate Qq in (71) by (84) P~ i(n/M)~$. (93' O.38) to (6. whence (86) 1 .Hph + H e1.42). [2 x:r 47re n Qq + nq 2 2 q2 ins toni the for Qq + k82 ] k8 O. with (I.F PR~ We show in the following that for the free electron gas: (87) v q 411"e i (n)~ .146 QUANTUM THEORY OF SOLIDS POL. so that the equation of motion becomes (88) .E(q) ] nq + q E(q) V_q Qq 1.ph]. where Pq is the electronic density fluctuation and E(q) is the static dielectric constant. The equation of motion of Qq is . on calculating [P _q.34) for the dielectric constant. 2Q (81) Qq + Oq q V_qPq. (89) thm (90) whe (91) = E(q)(Pq + p!).qQq.) ~ O.
!' k.' WI' C.') Oqq/k. now written explic itly for free electrons and for a phonon in the z direction. Q. 2 3M m 2 • The result (87) follows from the definition (76).ZJ xe iq'x Ixl3' Z The integral has the value (93) f= / 21r dp.VF e.3A . Suggestion: Note that now q.q. with v(x) = 2 e /lxl: (92) Vq = .xl' lOX 21r = .I' 1) = ~ . + 0. show that (N»> 1.x".). which suggests that the separation of pro tonic and lattice modes is poor.z.» q"" so that the denominator of the integrand in (21) may be replaced by qc 2• The result for (N) is C12q". /. • 3 . for (tq) /1. Wq ' " o ic a h where the longitudinal phonon velocity c. 7 147 If Oq2 1 '" 41rne /M. dp.. 1. for q ~ 0. (95) (N) ~ 81r2 pc. M PROBLEMS 1. qXm m as Xm~ 00 (94) Vi q = 41re i q 2 (. the equation of motion becomes 2 f (89) Q. = 0. CH.!:)3i.q.. Estimate the number of virtual phonons accompanying a proton moving in a crystal.(ni1/)34e2 Jy =  (.2. 41r ( 1 q sinqX . is given by (91) . dx • x 2 • xp...POLARONS AND THE ELECTRONPHONON INTERACTION. et.!:) M 1 34 e2 f f d 3x d3 L j eiq'(Xx/> Ix  x~13 ' z .. c. thus the eigenfrequency (90) is given by. 1 (eI<l.
: show that (96) (104) In (105) . If H' and thus 8 'arePinde pendent of time in the Schrodinger picture.6. 4. can be solved exactly.s H eS .: to the electron energy for an electron of wavevector k such that k m » Ikl »k.S) + ' . show that the solution leads to (43) for the interaction coupling the particles at Xl. In the weak coupling limit find an expression for the mobility of a polaron in an ionic crystal.H.?(x) given by (41). so that (95) is only a rough estimate. • We can write this method in an instructive way.148 QUANTUM THEORY OF SOLIDS POLA We must remember that (16) is inadequate for strong coupling. Rev. X2. (a) Consider the hamiltonian H and the canonical transformation defined by e. The result is of the same form (in fact. At a finite tempera ture T satisfying kBT » hCsk show that the integrated phonon emission rate is. SO.E I""o. Then (107) becomes (lO3) 111 (0) = Ho +2 ~.(t'). formed hamiltonian vanish if S is chosen * to make (b) Thus if H + AH'. This is an explicit expression for 8I as an operator. 6.(O)] 00 + . ..6. 72 (1950)] for the relaxation rate for electrical conductivity in semiconductors.J C 1 2 m*km 2 = 101 ev .. by expanding in a power series and collecting terms show that (99) wher Note polar (d) state bOBo 7.S] + t[[H. then in the interaction picture (100) iS1 == [8J. (97) fV(emission) 1""0.. elasti elect (a) longi tion (b) iI == esHe s = H H0 + [H.1 C1 m*kkBT 2 so th: (107) (c) (108) For electrons in thermal equilibrium at not too low temperatures the required inequality is easily satisfied for the rms value of k.Ho]i eiHot8eiHot. with q.?(x2).?(xl) + eq. The hamiltonian (98) show (109) H WI}. it happens to be identical) with the BardeenShockley result [Phys.. . with h restored. The results (33) and (34) apply to absolute zero. considering only interaction processes with optical phonons of constant frequency WI. Examine the electronphonon energy correction . X2 JO dt' [H. provi Usi (106) 3.. 2. 8I(t) == iX J ~" dt' H~(t').. btbq + eq. 6.S]. in c phon we see this directly from 81 == (101) (102) Then the condition (104) gives iSI = XH. show that the terms linear in A in the trans in a defor Phys 8.
where Cp is a piezo electric constant. Suppose. (105) provided En :F Em. Using this solution for S. 7 149 (104) XH' + [H o. ex: T%. ex: T~. y (nIHln) = nw .1 n w s e where n is the expectation value of a+a in the unperturbed boson system. for example. .POLARONS AND THE ELECTRONPHONON INTERACTION. ii = Ho + H = wa+a d e 'Vith (108) show that (109) .S]. (a) Find an expression for the interaction energy of an electron with a longitudinal phonon having q II noting that here H' ex: For deforma tion potential coupling H' ex: q~. CH.(X2/W ). Phys. and compare with the deformation potential result [ISSP (13.17)] iJ. that P z = Cpezz . but that the state <1>0 bosons. [See W.S] + ![[H o. e ii = esHe s = H 0 + [XH'. In a piezoelectric crystal the polarization P is a linear function of the elastic strain.t + X(a+ + a).S] + (106) as ii has no offdiagonal terms of O(X). We can rewrite + 0(X3). 101. In a representation in which H 0 is diagonal. using the deformation potential form of the electron z. Discuss the form of the electronelectron interaction via virtual pnonons in covalent crvstals. 903 8. (b) Derive an expression for the temperature dependence of the mobility in a piezoelectric semiconductor. there are no bosons present in the ground eS<t>o contains virtual state cj. Note that this result is consistent with our calculation in the text of the polaron interaction. Harrison. (106) so that (nIH'lm) (nISlm) = X .S] = O. (d) Show that. ls a 1.o of ii as given by (108). 7. show that iJ. and for optical phonon coupling H' ex: ql. A. Rev. at least to 0(X2).
In elements which exhibit an isotope effect it is believed that the interaction responsible for superconductiv ity is the attractive interaction between two electrons near the fermi surface caused by their interaction with the zeropoint phonons. Cooper. Cooper. and J. The isotope effect is explained in a fairly natural way. GENERAL REFERENCES herE a Cl In j tivi1 bet' thrc elec T (3) We the (4) 11= To to 1 the sys1 ph(J phc (5) L. way for the essential effects associated with superconductivity. In the transition group elements the polarization of the d band provides an additional coupling mechanism. are involved in superconductivity. zero point or thermal. N.1 (2) M'ATc = constant. for a given element. it is difficult to see how else the atomic mass could enter the problem. 1 (6) 150 . Phys. Schrieffer. Phys. We shall not enter into the phenomenology of superconductors or into the technology of high critical field materials. Rev. excellent detailed agreement with experiment exists in a number of areas. This chapter is devoted to a thorough explanation of the BCS theory. 1175 (1957). 104. although not trivial. The BCS theory accounts in a fairly simple. with the exception of several transition group elements including Ru and Os. 1189 (1956).SUPi I' oj 81 . 6 phy~ 8 expE Superconductivity revi on E IND] In superconducting elements in which the dependence of the critical temperature T c on the isotopic mass ltf has been studied it is found that (1) L (7. R. Bardeen. one which does not involve an isotope effect. 2 J. The result (1) suggested to Frohlich that the properties of the lattice phonons. 108. Rev. The BardeenCooperSchrieffer theory of superconductivity is a striking success of the quantum theory of solids. L. and the discovery of flux quantization in units of onehalf the natural unit chie is a striking confirmation of the central role of the paired electron states predicted by the theory.
1959. New York.wq' 1 75 (6) ~ Cit+qCk' ek' + Wq . the other electron interacts with the polarization.15).102) of problem~~A"~~~~ ~ y.al nt is n of 11 = esHe s (4) We now make a canonical transformation to a new hamiltonian which has no offdiagonal terms of OeD). A new method in the theory of superconductivity. and for convenience we take it equal to D. phonollS. Consultants Bureau. A thorough review of the position before the BCS theory. Following the result (7. 6 M. Dq is a cnumber.aq + r ekctck + iD r kq ct+qck(aq . 6 J. 4 J. A simple account with emphasis on electrodynamics. In firstorder H' leads to electron scattering and to electrical resis tivity. to To obtain the effective electronelectron coupling it is convenient to take the matrix element over the phonon operators. 170287 (1961). R. but to leave the fermion operators explicitly displayed. 274368.v i n here c+. 8 151 3 Bogoliubov. c are fermion operators and a+. a real constant. in Progress in low temperature physics 3.a~). Then (5) (lqI810) = iD (01811q) = iD t 1 . An excellent review of the theoretical and experimental position. Tinkham. 149230. (2) H' = i r Dqct+qck(aq kq a~q) r k Hk' P h re ic e .ekq . Tolmachev. LTP. Bardeen. a are boson operators. a ry '.SUPERCONDUCTIVITY. INDIRECT ELECTRONELECTRON INTERACTION VIA PHONONS :al d Let us write the firstorder electronphonon interaction as. We consider the phonon system at absolute zero. following (7. Schrieffer.Et'+q . Ct_qCk ek . Encyclopedia of Physics 16. pp. The coupling is an indirect interaction through the phonon field. so that either n or m refers to the vacuum phonon state. in secondorder H' leads to a selfenergy and also to coupling between two electrons. One electron polarizes the lattice. The final result (9) is actually independent of the phonon excitation. CR. Bardeen and J. The total hamiltonian of electrons. and their interaction is (3) H = Ho H' es n = r q wqa. and Shirkov.
the phonon interaction is domi nant. wheI be a ham esser task ferm inter ~+ + LJ Ck' _qCk.q is iD2 Tl ertie actic who with LL q kk' 2 + 4w q ek_q)2  pair~ 2' Wq prov so that the electronelectron interaction may be written as (9) byE H" D LJ LJ ( q kk' ~ ~ Wq ek ekq )2  2 Ck'+qCk'Ck_qCk· Wq + + The graph for H" is shown in Fig. The lowil imp( duct morl appr W The (12) WD < ek. with Wq W_ q. Even in the attractive region the interac tion is opposed by the screened cou lomb repulsion.Ekl < wq . but for sufficiently large values of the interaction constant D . Electronelectron in direct interaction through the lattice phonons. 1. it is repulsive otherwise.q in the inter mediate state. The electronelectron interactioJ). FIG.q give a contribution of the form. and reorder the operators: the sum of the terms in q and . The repulsive re gion of (9) is of little consequence or Intr4 (13) (14) . We assume for simplicity that in superconductors the attraction is dominant when (10) eF  mus1 latio duct a th hanc is m . where WD is the Debye energymost of the zeropoint phonons are near the Debye limit. The terms in . 1. inter (9) il (11) whence to 0(D2) (8) Ho + jD2 L L Ct+qCk'Ct_qCk q kk' X ( 1 ekq Wq ek' ek  + Wq  1 ). ek±q < eF + WD. N ext interchange k and k'.107) that (7) i1 = Ho + ![H'. (9) is attractive (negative) for excitation energies IEk±q . ek'+q We proceed to group the terms with phonons in q and .Ck+qCk kk' (1 ek ek+q Wq ek' Ct+qCk'Ck_qCk· (ek _ + Wq  1) ek'q BOU~ .152 ~aANTUM THEORY OF SOLIDS SUPE We saw in (7.S] i1 = + 0(D 3 ).
Ck_qCk. 2) only over q's which satisfy (10).ost ear re i or Introduce the centerofmass and relativemotion coordinates (13) x K = !(XI = + X2). This important result (which we FIG. The density of supercon ~ 4T c about the fermi ducting electrons is such that ". The simplified hamiltonian (11) is believed to contain the essential features of the problem. We consider two free electrons. The region a theory might take. but plays no active is more complex than the pair problem. 4). The first suggestion that unusual prop erties would result from attractive inter actions in a fermi gas was made by Cooperl. k = !(k l k 2).. but it suggests the lines such bye energy. The unperturbed eigenfunction of the pair is. more Cooper pairs would have to overlap appreciably. X Xl  X2.W D is entirely handles the manyelectron problem. The states The BCS matrix element argument fol most involved actually lie lowing (34) below shows why the pairs are in a shell of thickness important. Ck'+qCk.tly ~nt mi hat l is . The thickness of lation is not in itself a theory of supercon the shell is twice the De ductivity. 8 153 interest. V is taken to be a positive constant. with an antisymmetric spin state. . which filled. BOUND ELECTRON PAIRS IN A FERMI GAS he for Ten 'ac ou .} Jr th where we sum (Fig..S SUPERCONDUCTIVITY. ~ + + . Our task now is to study the properties of a fermi gas under an attractive twobody interaction with the cutoff (10).XIX2) = ei(kl'Xl+k2'X2). . It area) in k space used in must be emphasized that Cooper's calcu forming the BCS ground state.)D. 2. Range of one prove below) led directly to the analysis electron states (shaded by BCS of the superconducting state.V L. q kk' . (12) qJ(k l k 2. in unit volume. CR. so we drop the repulsive parts from the hamiltonian and write (9) in the simplified form (11) H" \""' L.10 3 or surface (Fig. part in the superconduct ing properties. The BOS theory below e: F . who proved that the fermi sea is unstable with respect to the formation of bound pairs.  (14) kl + k2.
the secular equation becomes (21) (E . k wherE one n so thl (27) using (13). (28) (ek . k + q and + . Let us suppose the packet (17) is made up of oneelectron states above the top of the fermi sea. (15) on substitution.X)Yk +~ Yk'(k. outside this range we take the interaction as zero. We now examine for convenience only states having K = 0. between eF and eF + WD.q.kIH"lk'. wher~ or. with V positive. Then (29) where (20) or (30) k = k' If p(e) is the density of twoelectron states k. k per unit energy range. k L Ykeik. with ek (19) k 2/m.k') = 0. (H . The kinetic energy of the state (15) is (l/m)(lK 2 + k 2 ).(P1 2 2m + P2 2) + H" x = = 1 .X+k.(XIX2) k = 0.k = . the oneelectron states are involved in pairs ±k. we take.154 QUANTUM THEORY OF SOLIDS SUPER then (12) takes the form <p(Kk.Xx) = ei(K.k' . k2 = k.Xleik.p2 m + H" of the form (17) x(x) = L Yteik.(X1X2)(H .eF = W D· of t l " .X) ~ Yk/eik/. Now if X is the eigenvalue. or between kF and km. We look for an eigenfunction of (16) Then (24) a com Thus (25) Usi (26) H = 1 . =  In agreement with (11). Next include the electronelectron interaction (11) in the hamil tonian of the problem. (22) (eIH"le') V for an energy range ± WD of one electron relative to the other. where km is defined by (23) 1 2 2m (k m  This We : lowe the j mod of p takil 0' fore the SUP] kF 2 ) = em . so that on taking a matrix element we have the secular equation (18) f = dx eik .X)y(e) f de' p(e')y(e')(eIH"le') = o.X)x(x) = 0.X) . so that kl = k. That is.X2.
X)g(e) = V 2•• /: 2. so that on 27 ( ) = PFV 1 /. ined This is the binding energy of the pair with respect to the fermi level. 8 155 Then the secular equation (21) becomes (24) so d il (e . CH. dc' p(e')g(e') = C... We write the complete hamiltonian with the . Thus (25) gee) = e C x· Using this solution in the secular equation.2. There fore a perturbation calculation summed to all orders could not give the present result. the value at the fermi level. or rgy (30) A= 2WD side ~ket sea.. dc' =og 2. .. (24) becomes (26) 1. dc' e'pee') =0 2./ 1 ppv . taking account of the exclusion principle.. Over the small energy range involved one may replace pee') by the constant pp. therefore the fermi sea is unstable. where we have written the lowest eigenvalue Xo as (28) Xo = 2eF . Observe that (30) may not be written as a power series in V. a constant independent of c. We have thus found that for V positive (attractive interaction) we lower the energy of the system by exciting a pair of electrons above the fermi level.S SUPERCONDUCTIVITY. __ A 2em _ 2S Then (29) F + A = e. . This instability modifies the fermi sea in an important wayactually a high density of pairs are formed and we must study the fermi surface carefully. SUPERCONDUCTING GROUND STATE We now consider the ground state of a fermi gas in the presence of the interaction (11).2.A. e'  X X =og A + A.X ' I 2em 2e F X I 2em 2e p where the limits refer to a pair.V /.
The result for the Cooper pair suggests how this selection may be made. just as for the Cooper pair.I .. .nj. We can generate a coherent state of low energy by working with a subset of configurations between which the matrix elements of the interaction are always negative. fermion operators satisfy (32) c.nj. . Con sider first ctc4~(00111) = ct~(OOIOI) = ~(10101). We can see the alternation in sign for a simple example. The interaction term in the hamiltonian connects together a large number of nearly degenerate configurations or sets of occupation numbers.) . If all the terms in H" are negative.. . But because of the sign alternation.00).00.11) or ~(II .~(nh" We recall from (5. ~(OO. . .I . according to the evenness or oddness of the number of occupied states which precede the state j in the ordering of states which has been adopted.).11). (33) cj ~(nh . = (1)1'. here the ordering of indices is arranged in pairs by the semicolons. . If one member of the wh of st BI su sh ve ju ti reI SO h as (3 . etc. . . = 9j(1 belj sha) com  ni)~(nh where (34) 9. on rearranging (II) we have (31) Then pair OCCt H = ~ et. if" whi (If (35" Th the (3 Thus the sign of the matrix element (10101\ctc4100111) is opposite to that of (IOOlllctcaIOOIII). etc. ctc3~(00111) = ct~(OOOII) = ~(10011). writ We F That is. This property is assured for V positive in the hamiltonian (31) if the Bloch states are always occupied only in pairs. there are for configurations picked at random about as many positive as negative matrix elements of V. The alternation of sign in these operations is of critical importance to the ground state of superconductors.156 QUANTUM THEORY OF SOLIDS SUP] oneelectron Bloch energy ek referred to the fermi level as zero.nj.. .nj.II . cj there occurs multiplication by ± I.CtCk  V ~ ct+qctqCkCk" with spin indices omitted. further. .10. . .10.23) and (5. . This effect must be controlled by a special selection of configurations to avoid reduction of the average matrix element and reduction of the net effect of the interaction.) = 9jnj~(nh .24) that the will sam zero ~ .). . . but not ~(10.00). in operations with cj. Thus in our subspace we allow ~(II .1 Vi = pl L np. . . . . we can obtain a state of low energy.
In the same way a Bloch wall in ferromagnetic domain theory is not usually described in such a way that the total spin is a constant of the motion. Anderson. cit (37) 1 H red = . 112. where <l>vac is the true vacuum. . . Rev. The inte~action itself conserves wavevector. The ground state <1>0 contains only pairs.k. W.SUPERCONDUCTIVITY. In this connec tion see Problem 3. then the other member is also occupied. whereas one written as k has spin !. it operates only within the pair subspace.}. 7 We rearrange the hamiltonian (135) as. and so we use <1>0 just as in the spirit of the grand canonical ensemble. €k(1  ?tk  ?tk )  V}. CtC~k'CkCk' This is known as the BCS reduced hamiltonian. Uk. so that we will be most concerned with configurations for which all pairs have the same total momentum k + k' = K. We adopt below the convention that a state written explicitly as k has spin j. 8 157 pair is occupied in any configuration.c. 1900 (1958). CH. We shall work with antiparallel spins. where K is usually O. BCS have shown for a macroscopic system the probable number of pairs in <1>0 is very strongly peaked about the most probable value. The total number of electrons is a constant of the motipn of the hamiltonian. Vk are constants. Pkys.Vk' because the c+ anticommute. SOLUTION OF THE BCS EQUATIONSPINANALOG METHOD The most physical method for studying the properties of the reduced hamiltonian is due to Anderson. The relation (36) implies Vk .' CitC~k'CkCk' P. We have not discussed the spin. with ?tk = Ck. If K is zero. The exchange energy will usually be lower for an antiparallel ! j pair than for a pair of parallel spin. €k(Ct Ck + C~kCk)  V}. We suppose always that €k €k' For the reasons just enumerated it is sufficient for the ground state if we work in the pair subspace using the truncated hamiltonian in which the interaction terms contain only a part of the interaction in (11) : (35) H red = }. The approximate groundstate <1>0 is shown below to be of the form (36) <1>0 = n + (Uk k Vkct C~k)<I>va. The spin will hereafter not be considered explicitly. the pair is k. but our state <1>0 is not diagonal in the number of electrons.
11_k): (39) (1 .L ekUkz  L' Uktuit tV L' tV kk' Su int bu sp: lik do to pr av (Uk'xUkx + Uk'yUkY). (3 here are the usual spin functions for spin up and spin down.nk = (~ _~)=u" WbE if the pair state is represented in the subspace by the column matrix (~) = pair empty ++ oI>(OkOk) ++ ak ++ "spin up" (n = (42) pair occupied ++ oI>(1k L k) ++ p& ++ "spin down" ThE mol bes1 sho' fiel< invi vec I where ex. (46) H red =  L ekUkz .11k . and (43) for em] occ dirl 1 at u=ux'tu y = . in terms of pauli operators. (0 1 2 ~} Ikl (4~ so that (44) ++ CkC_k CkCk ~Uk' The hermitian conjugate is (45) ~Uk' 1 + The hamiltonian becomes.cf»(l k 1_k) . The combinations of operators in the potential energy term may be represented by other pauli matrices. according to (10).11_k)cf»(1k1k) = .11_k)cf»(OkOk) = cf»(OkOk)' on 1 ove] barr. CtC~kcf»(OkOk) = cf»(1k 1k). (1 . We consider first only the subspace of states defined by (38) nk nk. bere ord for tion solv V (47) Uz Thus this operator may be represented by the pauli matrix (40) 1 : nk . . Consider the operator (1 .11k . We know that ctc~kcf»(lk1_k) = wb~ 0. respectively. this is the subspace in which both states k.11k .158 QUANTUM THEORY OF SOLIDS SUP] setting ~ ek = 0 or a constant for states symmetrical about the fermi level in the range of energy ±WD. k of a Cooper pair are occupied or both are empty.
We rotate the spin vectors Uk into the best possible classical arrangement. Now consider an attractive interaction. But we may use all the methods developed for the theory of ferromagnetism to find accurate approximate solu tions of (46). The situation is quite like the Bloch wall in ferromagnets. In the unperturbed fermi sea (V = 0). where i. Because of the interaction the spin will tend to make nearby spins line up along X.SUPERCONDUCTIVITY. V positive. The stable spin state has the spins up (pairs empty) for energies above the fermi surface. which means that each spin k should be parallel to the pseudofield 3Ck acting on it. In the molecular field approximation to the ground state in the presence of the interaction we quantize each spin parallel to the average field which it sees. The molecular field approximation is very good here because the number of spins involved in 3Ck is very large. 8 159 on taking account of the automatic symmetrization when summing over all k' and k. CR. the effective field is SkZ. in the present problem we have a domain wall in k space. so that the only field acting on a spin Ikl = k F arises from the interaction term in the effective field = (48) tV 2:' k' (Ukix X + Uk'YY)' Suppose the spin at k F is horizontal and along x. (46) is an exact hamiltonian. with states rotating smoothly from occupied to empty. It is essential to remember that we are using the u's here not as operators on actual spins. where Sk is positive for energies above the fermi surface and negative for energies below. Within the subspace of pair states. Z are unit vectors in the directions of the coordinate axes. and the spins down (pairs occupied) for energies below the fermi surface. In Problem 3 we show that the hamiltonian can be solved exactly in the strong coupling limit where all Sk = O. that is. but as we go away from kF the kineticenergy terms Ek. y. The form of the BCS hamiltonian suggests the application of the molecular field approximation. so that it may be treated as a classical vector. . but as operators which create or destroy pair states ± k. we treat the field itself as a classical vector. We define a fictitious magnetic field 3Ck acting on Uk by (47) 3Ck = SkZ + tv 2:' (Uk'XX k' Uk' flY) .Z will pull the spins more and more into the ± Z directions. Exactly at the fermi surface Sk = 0. The spins reverse direction precisely at the fermi energy.
Then. " (5 The molecular field is given by (47) with all Uk'y = 0 if. d 2 ) ~. / CTk / . Sl 01 k' Ek = tan 8k . Then the fundamental equation becomes (54) 1 = jVPF fWD ( 2 ~e "'D d 2)" = VPF sinh.. 3. W D is of the order of the Debye energy./ Jek H«: spi (5~ (5 ~ i if w~ as FIG.· tl fi .1 (WD/I1). (53) d = jV t (d 2 + ck' ~. as in Fig.. Ukz Now (50) Uk'x = sin 8k " giving the BeS integral equation tan 8k = (V12c k) l' sin 8 k' k . by trigonometry (52) e Ck ( sin 8k = cos 8k = Using this expression for sin 8k . We replace the summation by an integral. The limits are determined by the region W D to . 3. Molecular field method of solution of the spinanalog BCS hamiltonian. a e: el ti ti To solve (50) we set (51) d S I = jV l' sin 8k " k' i1 n so that (50) gives tan 8k = dick. in (51).W D within which V is attractive.V 1'Uk'X (49) 3ekx 3ekz Ukx w e. C . for con venience. the axes are chosen such that the spins lie in the xz plane. j.160 QUANTUM THEORY OF SOLIDS su z .
we see that . The first approximation to the excitation spectrum is obtained as the energy Ek required to reverse a fictitious spin in the field 3Ck • We have. "'D de e . (50). Other excitations not included in our subspace are possible for which the two electrons in the excited state have different k's.1.1 is positive if V is positive.SUPERCONDUCTIVITY. and on the tunneling of electrons through barriers..1.. ~ 21:re. and (54).1 2 V' . This is the BCS solution for the energygap parameter . Ickl term takes account of the energy 21 ckl per electron pair up to the fermi level in the normal state. 8 161 Here PF is the density of states at the fermi level. If P F is the density of states at the fermi level.1 = sinh (1/ PF V) . The minimum excitation energy is 2. apart from the uniform mode. Lowlying excitations like magnons do not exist for the special hamiltonian (46) because of the long range of the interactions. (57) Eg = =  L Ck cos Ok .(e' { + d')l' c 2 I . but taken for one spin direction. on the transmission of far infrared radiation through thin films. From (54) (55) . The fictitious spinreversal corresponds to the excitation of a pair ± k into a state orthogonal to the ground state of the same pair. Thus there is an energy gap in the excitation spectrum of a superconductor.. (58) Eg ~ 2PF f..1 ~ 2(e.1 for such excita tions. it is not a question of summing nearest over neighbors only.. The expectation value of the groundstate energy of the supercon ducting state referred to the normal state is. using (47). (56) I E.. then there are no low energy excitations. (51). The evaluation of the integral is elementary. from (46)./V PF. 1 if PF V «1. CR.i V L' CTk'zCTkx + L ICkl L Ck(COS Ok + i sin Ok tan Ok) + L ICkl· k kk' k k The 2. If in the magnon problem one couples all spins equally. we study these excita tions later and will see that the energy gap is also 2. The gap has been detected in work on heat capacity.. I where we are concerned only with the positive root. WD 2wDe.' + d')l'.
in units with the boltzmann constant absorbed in the temperature. ~ = The transition T = Tc occurs on this model when (64) 1 = V '" . as in ISSP Eq. p. (62) and (63). as in (102).162 where we have used the relation (59) QUANTUM THEORY OF SOLIDS sn eX L Sk sin Ok tan Ok = ~ L (Sk 2 + ~ 2)~ = V.. exactly as in the theory of . (63) 'JCk = {Sk2 + ~ 2(T)}~. which is exactly equivalent in the free energy to doubling the temperature. with Sk unchanged: (62) tan Ok f v o = (V/2sk ) L' tanh ('JCk. because two single particle excitations have the same energy as one real pair . from (56). At a finite temperature T. on eliminating V with (54) we have (60) Eg = PFWD 2J \1  [ 1 + ( WD ~ )2]~) 2 w 1 =  9/. Doubling the number of excitations doubles the entropy. p. The critical magnetic field at absolute zero is obtained by equating Eg to Hc2/87r for a specimen of unit volume.168. Hence Tc in (64) is to be replaced by 2Tc. The transition temperature Tc may be determined by the molecular field method._V 2PFWD f"'oJ  ~PF~2.. 2 1 2~2 th (6 The integral in (58) is elementary. 169.tanh . This result is correct 'for the spin analog model which.1 Sk' 0.ferromagnetism. If we extend the space to allow single particle excitations. works entirely in the pair subspacethe allowed excited states are only the real pair excitations as in (103). p. (9. The BCS integral equation (49) is modified accordingly at a finite temperature to take account of this decrease in Uk. the ensemble average spin is directed along the effec tive field 3Ck and has the magnitude./T) sin Ok' = ~/Sk' It' t e t r with. 2sk . we double the number of possible excitations. Thus as long as V is positive the coherent state is lower in energy than the normal state: the criterion for superconductivity is simply that V > O. The energy contribution to the free energy is not affected by doubling the excitations. 168 and (110). of v 10 (6 c E C (61) (Uk) = tanh (xt/T). we recall. or using (52).19). Tc ~.
125. Pb. both transition elements. p.4. 4. Anderson.IS SUPERCONDUCTIVITY.= VPF 2 fWD WD de. below which it is =x. we operate with the spin rotation operator U (Messiah. More closely. The known exceptions to this rule include Ru and Os. The frequency of an oscillator of a given force constant is proportional to MYJ. but + on the vacuum gives zero and jUk = state is (69) <1»0 u ctC~k. tanhe. down to x = 1. d x tanh x . Morel and P. 1263 (1962). 2). e. Phys. we suppose that V is independent of M.1/ Pl'V .5Te. . P. 8 163 On rewriting according to (167) and (168). To generate a state with the spin in the xz plane and quantized at an angle 8k with the z axis. excitation of the same the modified result as an integral. see. CH. we may replace tanh x by unity over most of the range of integration. for example. because WD is related directly to the frequency of lattice vibrations. te d: og he 68. The spinanalog ground state we have described may be generated by spinrotation operations from the true vacuum state in which all pairs are empty (spin up). (66) I Te = 1. and thus TeMYJ = constant. Even in simple metals V is expected to depend somewhat on M. p. 1 ar te combined with (55) for (67) PF V The energy gap is c 2d = 3. 534) for a rotation 8k about the y axis: (68) U = cos j8k  iUkY sin j8k = cos j8k  j(ut . and Cd. which should spoil the agreement of observation with the simple theory. k Thus the ground = n (cos j8 + ctC~k sin j8 )<I»vllo. it is likely that dshell polarization effects are responsible. 14wDe. for isotopic variations of a given chemical element. . respectively (reference 4.1. Rev. W. AI.3 for Sn. The isotope effectthe constancy of the product TeMYJ observed when the isotopic mass M is varied in a given elementfollows directly from (66). 3. the approximate value of the integral is 1 + log (wD/2Te).5. is reo ion use air Experimental values of 2d/Te are 3.uk) sin j8k . we have (65) re 2 Ikl. «1. 2Te =2 lwD12T. If Te « W D. 3. 0 x 7Y at >y which is the BCS result for T e . ns. e. k II. 243). on graphical integration.
These matrix ~lements are similar to those we handled in Chapter 2 in connection with the phonon spectrum of a condensed boson gas.V~' CtC~k'CkCk. 505 (1958)] as described in Chapter 21.B_ k . Note that for k « kF we have i8k = p. (Sf .we h ave CkCk (71) == 0 and ThE iCk = ckCk . (79) Then.NIckCklo.. and (107). on (S3 = V r' B k' k . The ground state (69) is only an approximation to the exact ground state.Ck V~' ++ ZC_k ~ Ck. There now exist a variety of proofs that the BCS solution is exact to 0(1/ N) for the reduced hamiltonian. and finds the agreement between the exact and the semiclassical energies is good and improves as the number of spins increases. and cJ>o in this region is entirely filled with electrons. Phys. Orbach s has made similar calculations for a ferromagnetic Bloch wall. on evaluating commutators with the use of CkCk ++= . the final wave function contains a mixture of states with a small spread in the num bers of particles. We form the equations of motion for Ck and C~k from the reduced hamiltonian (35): (70) H red = ~ Ck(CtCk whe T + C~kCk) . B: = (OICtC~kIO). Orbach. SOLUTION OF THE Bes EQUATION EQUATIONOFTHEMOTION METHOD Thel (75) (76) This proc solu1 (77) or (7S) It is useful to consider another approach to the solution of the BCS equation. Ll: V r' B:" k' and.N + 2). as discussed in (88).C_k'· (80: We define (72) Bk = (OICkCkI O) = . We set. The result of Problem 3 suggests that (69) is excellent. Rev.0 . He] We understand (OIckCkIO) to mean (O. for ICkl > (74) 8 (S4 Llk = Llt ~ O~ usi R. Phys. they are handled quite naturally in supercon ductivity in the Green's function method of Gorkov [Sov. JETP 7. .ckC_k + .+ = . (73) Llk WD. for ICkl < WD. 116. (92). 1181 (1959).164 QUANTUM THEORY OF SOLIDS SUPE This is just the BCS ground state. ver (81 FUl (S2 If. because we have assumed a product form for (69) and the true eigenstate is bound to be much more complicated.C~k V ~' Ck'Ck'.
1 2(T) } ~. 2~ 1 k ek sm Ok tan Ok =. 2ek' Tc using (52). (9. Doubling the number of excitations doubles the entropy. works entirely in the pair subspacethe allowed excited states are only the real pair excitations as in (103).1 k (2 ek +. The transition T = Tc occurs on this model when . p. If we extend the space to allow single particle excitations. the ensemble average spin is directed along the effec tive field 3Ck and has the magnitude./T) sin Ok' = .168. The transition temperature Tc may be determined by the molecular field method. 168 and (110). because two single particle excitations have the same energy as one real pair Exp Cd. in units with the boltzmann constant absorbed in the temperature. as in ISSP Eq. T by pai xz the the (68. on eliminating V with (54) we have (60) Eg = PFWD . This result is correct 'for the spin analog model which. 169. T whe fro vibr of a thu ele tran resp on • the 126. Hence Tc in (64) is to be replaced by 2Tc. (63) Xk = {ek 2 + . we double the number of possible excitations.19). p.1 • Thus as long as V is positive the coherent state is lower in energy than the normal state: the criterion for superconductivity is simply that V > O.. whic If of in valu inte (66) com (67) (61) (Uk) = tanh (xkiT). The critical magnetic field at absolute zero is obtained by equating Eg to He 2/8rr for a specimen of unit volume. but sta1 (69 ' . from (56). with ek unchanged: (62) tan Ok = (V / 2ek) L' tanh (Xk. p. (62) and (63).1 ek' 1 = V k tanh.162 where we have used the relation (59) QUANTUM THEORY OF SOLIDS 8UPE ~ . as in (102). or (64) ~. The BCS integral equation (49) is modified accordingly at a finite temperature to take account of this decrease in Uk.12 2) ~ = V.1/ek. I". excit the (65) The integral in (58) is elementary. which is exactly equivalent in the free energy to doubling the temperature. exactly as in the theory of ferromagnetism. The energy contribution to the free energy is not affected by doubling the excitations. we recall.1 2. k' with. I [ +( 2 1 1 .1 )2]~) WD = 9/::: 2 D 2 .1 = 0. At a finite temperature T.J 2 fPF.
SUPERCONDUCTIVITY, CH.
8
163 On rewriting
excitation of the same Ikl, according to (167) and (168). the modified result as an integral, we have (65)
 =
2
fWD
V PF
dE E lwD/2TO tanh oX tanh = 2 dx, WD E 2Tc 0 oX
which is the BCS result for T c • If Tc «WD, we may replace tanh oX by unity over most of the range of integration, down to x ~ 1, below which it is ~x; the approximate value of the integral is 1 + log (wD/2Tc). More closely, on graphical integration, (66)
ITc
=
1.1~:~~=u:TJ
The energy gap is
combined with (55) for PF V «1. (67)
2a = 3.5Tc •
Experimental values of 2a/Tc are 3.5, 3.4, 4.1, 3.3 for Sn, AI, Pb, and Cd, respectively (reference 4, p. 243). The isotope effectthe constancy of the product TcM~ observed when the isotopic mass M is varied in a given elementfollows directly from (66), because W D is related directly to the frequency of lattice vibrations; we suppose that V is independent of M. The frequency of an oscillator of a given force constant is proportional to M~, and thus TcM~ = constant, for isotopic variations of a given chemical element. The known exceptions to this rule include Ru and Os, both transition elements; it is likely that dshell polarization effects are responsible. Even in simple metals V is expected to depend somewhat on M, which should spoil the agreement of observation with the simple theory; see, for example, P. Morel and P. W. Anderson, Phys. Rev. 126, 1263 (1962). The spinanalog ground state we have described may be generated by spinrotation operations from the true vacuum state in which all pairs are empty (spin up). To generate a state with the spin in the xz plane and quantized at an angle 8k with the z axis, we operate with the spin rotation operator U (Messiah, p. 534) for a rotation 8k about the yaxis:
(68) U = cos j.8k

iUk71
sin j.8k
cos j.8k
=

j.(ut  uk) sin j.8k ,
but u+ on the vacuum gives zero and j.uk state is (69)
tPo =
CtC:!:k'
Thus the ground
n(cos j.8 + ct
k
k
C:!:k
sin i8k )tPv,1O'
164
QUANTUM THEORY OF SOLIDS
au
Tl
(7 (7
This is just the BCS ground state, as discussed in (88), (92), and (107). Note that for k « k p we have i8k = j.,r, and 4>0 in this region is entirely filled with electrons. The ground state (69) is only an approximation to the exact ground state, because we have assumed a product form for (69) and the true eigenstate is bound to be much more complicated. The result of Problem 3 suggests that (69) is excellent. Orbach 8 has made similar calculations for a ferromagnetic Bloch wall, and finds the agreement between the exact and the semiclassical energies is good and improves as the number of spins increases. There now exist a variety of proofs that the BCS solution is exact to 0(1/ N) for the reduced hamiltonian.
SOLUTION OF THE BCS EQUATION EQUATIONOFTHEMOTION METHOD
Tl
pr
so
(7
o
(
It is useful to consider another approach to the solution of the BCS equation. We form the equations of motion for Ck and C~k from the reduced hamiltonian (35):
w
(70)
H red
= ~ Ck(CtCk + C~kCk)
V~' ctc~k'CkCk'
Then, on evaluating commutators with the use of CkCk ++=  0 ,we h ave CkCk (71) We define
(72)
iCk CkCk  C~k V ~' Ck'Ck';
== 0 and
..+ 'tC_k
Bk
+  Ck V "'" ..... , Ck'C_k" ++ ckC_k
B:
(OICkCkIO) = B_ k ;
= (OlctC~kIO).
We understand (OIckCkIO) to mean (0 ;NIckcklo;N 2); the final wave function contains a mixture of states with a small spread in the num bers of particles. These matrix tllements are similar to those we handled in Chapter 2 in connection with the phonon spectrum of a condensed boson gas; they are handled quite naturally in supercon ductivity in the Green's function method of Gorkov [Sov. Phys. JETP 7, 505 (1958)] as described in Chapter 21. We set, for ICkl < WD,
(73)
~k
V
L' B
k'
k ,;
* ~k
~t ~ O~
V~' *" L, B k
k'
and, for ICkl
(74)
8
> WD,
~k
R. Orbach, Phys. Rev. 115, 1181 (1959).
SUPERCONDUCTIVITY, CH.
8
4kC~k;
'"'kCk'
165
Then the linearized equations of motion are (75) (76)
iCk
=
ekck 
'. + tCk
+ ekc_k
A*
This linearization is simply a generalization of the HartreeFock procedure to include terms such as CJr.lCk', These equations have a solution of the form eiM if
ct
(77) or
(78)
I 4:
Xk
x
ek
X
4k I + ek
0,
=
(ek
2
+ 42)Y.l,
where l1 2 = 4k4:; we now neglect the kdependence of l1. The eigenvectors of the equations (75) and (76) are of the form
ak
(79)
=
UkCk 
VkC~k;
VkCk;
a_k 

UkCk
at UkCt Ck = Ukak
a~k =
+ VkCk +• UkC~k + VkCk'
+
The inverse relations are
(80)
ct
{ak,aitJ
+ vka~k; = ukat + Vkak;
Ck
Ukak 
Vkak' Vkak'
c~
=
uka~k

Here Uk, Vk are real; Uk is even and Vk is odd: Uk = Uk; Vk = verify that the a's satisfy fermion commutation rules if Uk 2 (SI)
= UkUk/{Ck,C:'J
Vk'
+ VkVk/{c~k,Ck'J

=
+ Vk 2 = ~kk'(Uk2 + Vk2).
VkUk =
We 1:
Further,
(82)
{ak,akJ
= U~k{Ck,ctJ
XUk
VkUk{C~k,Ck} =
UkVk 
O.
If we substitute (SO) in (75), we have, for
(S3)
ak a: e'lAt,
=
ekuk
+ l1Vk;
on squaring
(S4)
X2Uk2
=
ek2uk2
+ 42Vk2 + 2ek 4UkVk = (ek 2 + 42)Uk2,
2 (Uk 2 Vk2)
using (7S).
(85)
Thus
4
=
2ek 4UkVk'
166 Let us represent u, v by (86) then (85) becomes
(87)
QUANTUM THEORY OF SOLIDS
Uk = COS}Ok;
Vk
sin }Ok;
a cos Ok
= ck
sin Ok;
tan Ok
=
.1/Ck,
so that, from (52), Ok has the identical meaning as in the spinanalog method. GroundState Wave/unction. We show now that the ground state of the system in terms of the quasiparticle operator ak is (88) or
(89)
4>0
naka k4>vae,
k
4>0 =
n(Vk)(Uk + vkctC~k)4>vae.
k
We may normalize 4>0 by omitting the factors (Vk), for then
(90)
(4)014>0) = (4)vacl n (Uk + VkCkCk)(Uk = n(Uk 2 + Vk 2) (4)vael 4>vac).
+ VkCt c~k)l4>vac)
We verify that (88) is the ground state: we have for the quasiparticle annihilation operator
(91)
ak,4>o = ak,ak,ak'
n' akak4>vaa = 0,
k
because ak,ak' == 0 for a fermion operator. ground state is
(92)
4>0 =
Thus the normalized
n(Uk + VkCtC~)4>vae
k
in the quasiparticle approximation. by (52) and (86): (93) (94)
The values of Uk, Vk are given
I Uk 2
2
=
COS }Ok
2
2
=
HI + cos Ok) =
l[l
+
(Ck/Ak)];
Vk = sin lOk = l(l  cos Ok) = l[1  (Ck/Ak)].
The functional dependence is shown in Fig. 4. It is instructive to confirm the groundstate energy (60) calculated on the spinanalog model by a direct calculation using the wavefunc
SUPERCONDUCTIVITY, CH.
8
2 uk
167
1
FIG. 4. Dependence of coefficients Uk, Vk in the BeS state on Ek/Xk, where Ek is the free particle kinetic energy referred to the fermi surface and Xk  (Ek 2 + a2)~ is the quasiparticle energy parameter.
tion (88) or (92).
(95)
The expectation value of the kinetic energy involves The expectation value of the potential
(~OICtCk'l~o) = (~olvk'2a_k,a~k'l~o) = Vk,2,
plus terms whose value is zero. energy involves
(96)  (~olctC~k'Ck"Ck"l~o) = (~OIUk'Vk,uk"vk"a_k,a~k,a_kfla~k"l~o)
Uk,Vk,Uk"Vk",
plus terms whose value is zero. Then, with account taken in the kinetic energy of the two spin orientations,
(97)
(~oIHredl~o) = 2 ~ CkVk2  V~' UkvkUk'Vk'
= ~ ck(l 
cos Ok)  iV~' sin Ok sin Ok"
The last term on the righthand side can be summed by applying (51) twice, giving a 2/v. The term ~ Ck is zero. Thus (98)
(~oIHredl~o) =  ~ Ck cos Ok  (a 2/V),
and the change of the groundstate energy in the superconducting state with respect to the vacuum is (99)
Eg =  ~ ck cos Ok  (a 2/V)
+ ~ ICkl,
exactly as found earlier in (57) and (58); the expectation value of the energy in the state ~o is identical with that given by the spinanalog method.
EXCITED STATES
With
(100)
~o
IIakak~vac,
168 the products (101)
cf!kl ... k
j
QUANTUM THEORY OF SOLIDS
SU
fOJ
a+ 1 . . . a+cf! j 0
are easily seen to form a complete orthogonal set. The operation at on cf!o creates an elementary excitation or quasiparticle with the proper ties of a fermion: (102)
to to' N
le~
cs
(1
aitcf!o = (Uk'cit  Vk,C_k,)(Uk' +n' ... C k'
.
+ vk,citc~k,)n'
wl
p~
Here we have picked out of the product the term in k'. The state atcf!o is known as a state with a single particle excited. The state has one particle in the state k and is missing a virtual pair from cf!o. The general twoparticle excitation is aitait,; when k" = k' we have the special state (103)
aita~k'cf!o (Uk'Ctc~k'  Vk,)n' . . . ,
(1
a
E
which is said to have a real pair excited, with a virtual pair missing from cf!o. The number operator in the state k is, from (79), (104)
nk
is e e o
n
E
= ctCk = (Ukat
+ Vkak) (Ukak + Vka~).
The expectation value of nk in the ground state cf!o results only from the ordered term in aka±k, so that (105)
(nk)O
t
= Vk 2 = hk = sin 2 tOk.
Here hk is the symbol originally used by BOS to denote the expectation value of finding a pair k, k in the ground state cf!o; the relation (105) establishes the connection with the expressions of BOS: (106) (107)
hklA
d t
=
sin tOk = Vk;
cf!o
(1  hk)1A = cos tOk = Uk;
hk)1A
=
n [(1 k
hklActc~k]cf!vac.
s
In our approximation, the quasiparticle hamiltonian is
(108) H
~ Akatak'
The energies of the excited states are given directly as the sum of the roots Ak of the equations of motion for the quasiparticle creation operators, (75) to (79): (109)
E 1 ••• j
=
i=l
2:
j
Ak.,
Ak = (ek 2
+ ~2)1A,
SUPERCONDUCTIVITY, CR.
8
169
for j excited quasiparticles. In the actual problem we must be careful to compare energies only for excited states having the same average total number of particles as the ground state. If the ground state has N pairs, we can work with an excited state having 2p excitations, leaving (N  p) pairs. Thus the lowest allowed excitation of the type called singleparticle excitation must have two particles excited:
(110)
tIls atat,tIl o ctct, n' (Uk + VkctC~k)tIlvac,
=
k
where the product over k is to be understood to include (N  1) pairs without using our discretionary power it would include only (N  2) pairs. The real pair excitation
(111)
'¥p
'"
++ o ak,a_k,tIl
E
automatically has (N  1) unexcited pairs. For this excitation = 2Ak', The calculation of the energy for the states (110) and (111) is left to Problem 6. It is found that the contribution of the potential energy vanishes for the excited particles; the increase of potential energy on excitation comes about from the reduction of the number of bonds among the unexcited pairs, because of the reduction of the number of unexcited pairs.
ELECTRODYNAMICS OF SUPERCONDUCTORS
The first objective of a theory of superconductivity is to explain the Meissner effect, the exclusion of magnetic flux from a supercon ductor. The l\1eissner effect follows directly [ISSP, Eq. (16.22)] if the London equation
(112)
j(x)

1 A(x), cA
A
m
ne 2
411"AL2
~'
is satisfied. Here j is the current density; A is the vector potential; AL is the London penetration depth. We assume that A(x) varies only slowly in space; otherwise the London equation is replaced by an integral form due to Pippard. The integral form in effect determines j(x) by a weighted average of A over a distance of the order of a correlation length ~o defined below. We treat the electrodynamics only in the ground state (T = OOK). We consider
(113)
A(x)
= aqe iq. X ;
it is easier to treat an oscillatory potential than one linear in the coordinates. For the London equation we are concerned with the limit
170
QUANTUM' THEORY OF SOLIDS
SUPE
q  4 O. The complex conjugate part of (113) need not be treated explicitly, because the following argument will apply equally to it. The current density operator in the secondquantized form is
(114) .&j(x)
whic the t para
=  . (++ grad 'lr  'lr grad 'lr+)
2m~
e
  'lr+A'lr mc
e2
(123:
whet
= .&jp(x)
+ .&jD(X),
in terms of the paramagnetic and diamagnetic parts. The expression for .&j(x) follows as the symmetrized form of the velocity operator [p  (e/c)A]/m. We expand 'lr as, in unit volume,
(115)
(12{
W
'lr(x) =
L Ckeik.%,
k
ture cent] proc
(125
whence (116) (117)
.&jp(X) .&jD(X)
2
e
L Ct+qCke iq'%(2k + q); mkq
e2
Exa]
(126
 ct+qcke~q·%A(x). mCkq
L
•
We suppose that the current vanishes in the absence of the field. We write the manyparticle state ~ of the system as
(118)
~ = ~o
This
+ ~1 (A) + . . . ,
~1
in tl
where
(119)
~o
is independent of A and
is linear in A:
(liH 110 ). Eo  E,
=
~1
=
L' Il)
,
(127
but 0, for
Here to O(A), in the coulomb gauge with div A
(120)
HI = 
f
d 3x 'lr+(x)
3
~ A • p'lr(x) mc
(128
~ L fd
mCkq (121)
x ct+qCkA(x).keiq.% = 
~ Lct+qck(k. a q).
mc k
Not: l is
(129
In the coulomb gauge we have
q • aq
=l
O.
The theory can be shown to be gaugeinvariant, as discussed below. To O(A) the expectation value of the diamagnetic current operator is, letting q 4 0,
(122)
whic dene
(13C
jD(X) =
= 

2 e
mc
A(x)
L
k
CtCk
=
ne 2
mc
and
(13]
A(x),
SUPERCONDUCTIVITY, CH.
8
171
which would be the London equation if jp = O. The quantity n is the total electron concentration. The expectation value jp(x) of the paramagnetic current operator over the state ~ is, to O(A),
(123)
jp(x) = (Olsp\l)
+ (1ISpIO),
(OISpll)(l\H110).
where 11) is defined by (119), so that
(124)
(OISpll) =
2;'
z
T;I
1
L"f
We consider the matrix element (ll H 110); this has an unusual struc ture for the BCS ground and excited states. The structure is of central importance for the Meissner effect and for various other processes in superconductors. We have
(125)
(liH 110) =  (e/mc)(ll
2; (k· aq)c:+qckI O). k
Examine the contributions from a particular excited state l defined by
(126)
~, 
+ + ak'+qa_k'~O
+ + Ck'+qC_k'
n' (Uk + VkCk + C_k + )
k
~vac.
This state is connected with the ground state by the entry
(k' • aq)ct+qCk'
in the sum in (125), for, using (80),
(127)
ct+qCk'~O = Uk'+qVk'~l
[( k'  q) • aq]c~c_k'_q,
but there is a second entry which contributes, for
(128)
C:!:k'Ck'q~O
Uk'Vk'+q~"
Noting that (q • aq ) = 0, the total matrix element to a particular state l is
(129)
(liH 110) =  (e/mc)(k' • aq)(Uk'+qVk'  Uk,Vk'+q) d: sin i(8k

8k +q ) ,
which ~ 0 as q ~ 0, using (93) and (94). denominator
(130)
In this limit the energy
Eo  E, ~ 2(€k 2
+ ,:12)Y.r,
and thus
(131)
(O\Sp\l) ~ 0
172 as q + O. (132) in this limit.
ne 2
mc
QUANTUM THEORY OF SOLIDS
We are left with the London equation
j(x)
=  
A(x),
In the normal state the paramagnetic current approximately cancels the diamagnetic, as discussed by Bardeen. 9 The energy gap is zero in the normal state. For a normal insulator the virtual excited state is reached by a oneelectron transition, and no cancellation as in (129) is found. The gauge invariance of the theory has been demonstrated from several approaches. Schrieffer10 gives a summary of the argument based on plasmon properties. A gauge transformation from the cou lomb gauge means that one adds to our vector potential a longitudinal part iq~(q). Such a term in the potential is coupled strongly to plasmon excitations and in fact shifts the plasmon coordinate. This shift does not change the plasmon frequency and thus does not change the physical properties of the system. Another approach to the gauge question is to note that a gauge transformation is equivalent to a transformation 'It + 'lte iK.X (133) on the state operator. fined, for A quantity such as Bk in (72) must be rede
(134) (OI'lt(y)'It(x)IO) + (OI'lt(y)'It(x)IO)e~x,(x+y) = (01 Ckei(k+K)·Yck,ei(k'+K),xIO).
L
kk'
The pair states are now such that (135)
k = k' 2K,
so that the pair part of (134) which we want to keep in the hamiltonian, by analogy with (72), is (136)
(01 'It(y)'It (x) 10)
L eik·(YX)(Olc_k_KCk_x::O).
k
With these new pairs the calculation goes through unchanged. brought out below in the discussion of flux quantization.
II 10
This is
J. Bardeen, Hand. Phys. 15, 274 (1956), p. 303 et 8eq.
J. R. Schrieffer, The manybody problem, Wiley, 1959, pp. 573575.
D.q e:k) ::: 4mA' This term is small if (141) q 4mA 4A « qo == . its behavior in strong magnetic fields is changed drastically. Theoret. recall that we obtained the London relation for q + 0 from (129). 1064 (1950). where r = x y. involves. kF VF we see that qo defined in this way is equal to 1/ to apart from a factor . The coherence distance to is a fundamental prop erty of the material and is of the order of 104 cm in a pure metal. this equation for small q and for k near k. In impure material the to in the argument of the exponential is to be replaced by t. L. the superconductor is said to be a hard or Type II super.SUPERCONDUCTIVITY. with A as defined there. Expa. (USSR) 20. Soviet Phys. Ginzburg and L. conductor. COHERENCE LENGTH 8 173 Pip pard proposed on empirical grounds a modification of the London equation in which the current density at a point is given by an integral of the vector potential over a region surrounding the point: (137) . If ~ < "'L. (140) 1 4A (e:k+q k. Abrikosov.= . 3 CA 47T to f d 3y r(r • A(y))e. the derivation is given in the original paper. Landau J.rlto r4 . A form similar to the Pippard equation is obtained on the BCS theory. Phys. A. as in certain alloy super conductors. For slowly varying A the Pippard expression (137) reduces to the London form (112). JETP 6. from (93) and (94). 1174 (1957). CH. J(x) = . see in particular A. BCS make the identification (139) ~ ~ Uk+qVk Ukvk+q ' " To understand this. which is based on the work of V. The ~o outside the integral remains unchanged. where (138) 1 1 ~ = to 1 al Here a is an empirical constant of the order of unity and l is the conductivity mean free path in the normal state.
!1 ) 1+ XX • k k+q SkSk+q surf the This is the result for photon absorption and for nuclear spin relaxation in a superconductor. Thus the effective part of (142) Ct+qCk  We (14! (143) ct+qCk  C±kCkq = Uk+qUka4qak = (Uk+qUk Vkvk+qakat+q + . For photon energies less than the gap the only inelastic photon process which can occur is the scattering of a quasiparticle in an excited state. but the term in a4qak which corresponds to the scatter ing of a quasiparticle from k to k + q. ~ ma~ The transition rate for the scattering process k (144) (Uk+qUk k + q involves prOl + VkVk+q) = 2 1 { T 2 + . There are other types of scattering processes which lead to a different type of result. This is called a coherence effect.!1... The penetration depth XL at low temperatures is of the order of 106 to 105 cm.. The result (139) is quantitatively in quite good agreement with experiment. their explanation is a remarkable and cogent argument for the physical reality of the BCS wavefunction. Coherence effects are a striking feature of superconductivity. MATRIX ELEMENT COHERENCE EFFECTS ThE to 1 (141 WhE ind~ In treating the matrix elements in the Meissner effect we saw that two terms contributed to the excitation of a single virtual state. We consider the absorption of ultrasonic waves by quasiparticles. the contribution of the crossproduct of the two terms will depend on their relative sign. The process described by (143) vanishes at absolute zero because ak on the ground state gives zero.. . but increases as T ~ Te. For some processes the terms add to the result and for others terms subtract. whe V nel + Vkvk+q)a4qa k + . In a secondorder calculation the square of the matrix element enters. Values of ~o are of the order of 104 cm. . which is the sum of the terms involved in (127) and (128).. in hard superconducting alloys ~ may be of the order of 107 cm. not the previous term in a4qa::!:k which connected the ground state with an excited state. We now want to pick out of tol fror (14: (14~ Ad (14L QUA 11 duc (14: C~Ckt. with the deformation potential interaction hamiltonian (2): (15( wh€ pho regi 11 n . The coupling with a photon field of wavevector q involves the square of the matrix element worked out in (125) to (129).174 QUANTUM THEORY OF SOLIDS SUP (14~ 4/. Our sketchy argument (140) to (141) is essentially an argument about the minimum extent 1/qo of a wavepacket if the excess energy of the packet is to be of the order of .
That is. Deaver. Rev. from (143) with the appropriate change of sign. where we have a plus sign. More generally. Fairbank. 51 (1961).. QUANTIZED MAGNETIC FLUX IN SUPERCONDUCTORS It has been observed 11.1A(x. Thus the scattering term is. The terms in H' which cause the scattering of a quasiparticle from k to k + q. magnetic flux through the ring.= 2. (147) (Uk+qUk VkVk+q) 2 = T 1 I+ 1 SkSk+q  AA 6 2 } • k k+q A discussion of experiments involving coherence effects of the type of (144) and (147) is given in reference 4. and W. M. because D is independent of k for the deformation potential coupling which leads to H'. Phys. we assume the Meissner effect. 5. Jr.07 X 107 gauss/cm 2 • 2 e We note that the unit may be written as (149) ! 2dc = 21r eli mc = 21r/oLB. unlike the photon problem.SUPERCONDUCTIVITY. as in Fig. if we neglect a microscopic region near the surfaces. + (146) Ck+qCk + C_kCkq. Phys. where we may let V include the electronphonon interaction and the phonon energy. R. Letters 1.)]2 + V} ft = Eft. 2 e 2mc e2 ae 2 where ae is the classical radius of the electron. 11 12 B. . Doll and M. are proportional to +. Letter8 1. The wave equation of the particles in the ring is (150) It 2~ [Pi + ec. Rev. Nabauer. 8 kq 175 (145) H' = iD L ct+qck(aq  a~q). with the absorption of a phonon q. CH. We consider a circular ring R with a tun FIG. 5. 12 that the magnetic flux through a supercon ducting ring or toroid is quantized in units of 1 ch (148) . the symmetry of the phonon interaction differs from that of the photon interaction. Let 4> denote the net ducting ring. the flux is produced by external sources of field and by surface currents on the ring. Inside R we have H = 0. Supercon nelO. S.. 43 (1961).
on carrying one electron once around the ring. + ec1A(x.y must always be singlevalued. In cylindrical polar coordinates we take X = (f'/2r)lI>. i by the cylindrical symmetry. We now make the transformation. Thus. j (J t v with the property that (153) pit' = {exp Li(e/c)x(x.(2l1'e/C)+("l+"I) . (152) it'(x) = .l • We now consider a twoelectron state: (158) it' e.y.). Thus the angular dependence of it' is (157) it' '" exp c p [i n In.)} j {L [~V. Ii (J T even if the path of the line integral is taken only through points where H = O.y(x) exp (: OJ Li(e/c)x(x. is an integer.y '" exp (i L n. . j The wavefunction it' satisfies (154) t p E'It. is determined by the flux 11>. ell = ~ A . n2 are integers. However.n1"le. positive or negative. noting that in this section it' is a oneelectron wavefunction and not a field operator.).176 QUANTUM THEORY OF SOLIDS s' Then curl A = 0 and A = grad x.f'. where f' is the angle. from (151) and (152). and carrying that one around the ring. s C r.)]} .. here n. The angular dependence of . relative coordinates (159) fJ = 1(f'1 + f'2). dS = 11>. fl n {2~ p/ + v} 'It = t which is identical with the equation (150) for A == O. + (2retl>/c) }f'. dl = J JH . where X cannot be a constant because it must ensure that on going once around (151) '1 (: ~x = ~ grad x . (155) it'(x) ~ c s ( t it'(x) exp (iell>/c).y is (156) . t 8 where nl.ntt'le. whereas the change in it on fixing all coordinates except one.f'2. Transform this to centerofmass and f' = f'l .
particularly of the factor j. subject to (10).. ein1'Pl'. and so this special quantum condition on the flux is not energetically advantageous in the normal state. taking L1 :. CH......: : : kBTc. where To is the critical temperature for a superconductor. WI .. We can do the arithmetic another way. ei( n l+e4J/hc)'P2. which does not contain A. PROBLEMS 1.. ei (n 1+2e4J/hc)'P2'. SUPERCONDUCTIVITY. we have just the Cooper pair (161) The term in (162) (J W ei~(nln2)'PleiH(nln2)'P2.. 3. W2 are a Cooper pair.. (a) Discuss the form in relative coordinate space of the groundstate Cooperpair wavefunction... for a Debye energy of 1014 ergs.. Estimate in a onedimensional metal the range of the interaction (11)... but W2 satisfies periodic boundary conditions only if 2e<l>/hc is integral.. (b) Estimate the range of the function for a representative superconductor.. which is the fermi surface. W2 .. with Ii restored.. For a normal conductor we do not need to restrict ourselves to pair states. is strong evidence of the importance of BCS pairing in the ground state... In the strong coupling limit all ek are set equal to 0. The equivalent spinor hamiltonian (if V is constant for N' states . 1/12 . but the pairing condition on W is only compatible with the periodic boundary condition on 1/1 if the flux is quantized in the units hc/2e.. The point is that we definitely need pairs to carry out the BCS procedure with the wave equation on w. 8 177 Then (160) W ei~(nln2)'Peil(nl+n2)+(4 .. 2.. or. ei (nl+e4J/hc)'Pl'. these go over into (165) Now WI.. The experimental verification of this. is zero when 47re<l>/c = (ni + n2) integer..... Thus when the flux satisfies (163) we may form pairs and deal with the equation for w...e4J/cH8 • If the factor multiplying (J is zero. If we take the states (164) 1/11 . (163) <I> = integer X (hc/2e)..
nkt .2 +V. iN~ 1.. [bt. 8. (4) Th .II' The allowed values of S are iN'.)8u:.nkJ. I fun rna N' where S is the total spin quantum number and M is the quantum number of S.(1 .bt. Discuss the theory of tunneling with reference to experiments on super conductors. Show that the b.Okk').178 and zero otherwise) is (166) QUANTUM THEORY OF SOLIDS H = tv L' (O'kzO"k'z + O'kUO'k'U). kk' where k. pro 1 poi gro irrE ( using the hamiltonian (70).bt.] = (1 . 4. show that H may be written as (167) H = _VS2 N' + VS. 6. Discuss the density of states in a superconductor near the energy gap.· " according to 0 that the number of reversed spins n. BL TH per (1) are bt = Ck l Ck t . the so that here the energy gap E(l) . 7.E(O) is exactly N'V. Verify by direct calculation that the expectation value of the excitation energy in the state (110) is given by (172) (173) E = Xk' E + Xk".} = eleJ 2btb k . (b) Show for the state M (169) E(n) = Eo + nVN' . jN' . 2 g' which has the exact eigenvalues (168) E = V{S(S + 1) .M21 +"2 V. b+ satisfy the mixed commutation relations (171) [bklbt.] = 0. Confirm that the equations of motion (71) conserve the total number of particles. The BCS creation and annihilation operators for pairs are defined as (170) bt = ct t C~k l . 6. (a) If S refers to the total spin S = i Ld k k of these states. c+ are oneparticle fermion operators. k' run over the N' states. (c) What are the states with different M values? (d) Show that the groundstate and firstpair excitedstate energies calculated in the molecular field (BCS) approximation agree with the strong coupling result to O(l/N'). {bk.2. (2) wh where the c. show that (3) wh = 2Xk' for the real pair excitation (111).1). This fur nishes an excellent and important check on the accuracy of the usual methods of finding the eigenvalues of the BCS reduced hamiltonian.Vn(n .
All operations of an abelian group commute.xuk(X). The discussion is presented largely in the form of theorems. n. BLOCH THEOREM THEOREM 1.(x) are of the form (2) where Uk(X) is periodic with the periodicity of the direct lattice. the translation group is abelian. If all operations of a group commute. The Bloch theorem states that if V(x) is periodic with the periodicity of the lattice. then (4) T mnpCPk(X) \ <PJt(x + ma + nb + pc). where m.(x) = C~ p' + V(X») ". 179 The operations T form a cyclic group. Proof: With periodic boundary conditions over a volume of N 3 lattice points.Bloch functions general properties 9 In this chapter we discuss a number of general properties of eigen functions in infinite periodic lattices and in applied electric and magnetic fields.(x) <PJt(x) = eik. Consider the lattice translation operator T defined by (3) Tx = x + tmnp = = x + ma +_ nb + pc. The most direct and elegant proof utilizes a little group theory. p are integers. then all the irreducible representations of the group are onedimensional. Analytical proofs of this central theorem are found in the standard elementary texts on solid state theory. then the solutions cp(x) of the wave equation (1) H". because the representations are . = E".
(9) thus CIOO must be one of the N roots of unity: (10) CIOO " c = e2TrifIN.2'1'(mE+n t +pt>IN fPk(x). fPk(x) ~ = 1. eik. (13) For a lattice translation t. as required by (5) and (10). fPk(x) is an eigenvector of T D' THEOREM 2. (l where emnp is a constant. (l we must have in particular for a lattice having N lattice points on a side (7) TNOOfPk(X) = fPk(x al + Na) = = (Cloo)NfPk(x).tfPk(x) t fPk(x + t) = eik'(l£+t)Uk(X s = e. .teik. if Uk(X) has the period of the lattice and (12) Nk = ~a* + '1b* + sc*. 3. where t.zuk(X) = eik. (6) Because T = TloofPk(x) = fPk(x + a) CIOOfPk(X). F t) = s integral) ( is a vector of the reciprocal lattice. . In other language. ~ This condition is satisfied generally by the function (11) (: a = eik'l£uk(X). ( that (CIOO)N = 1. '1. The function Uk(X) of the Bloch function fPk(x) = eik·l£uk(X) satisfies the equation (15) (2~ (p + k)2 + V(J:») Uk(J:) = E&Ut (J:).180 QUANTUM THEORY OF SOLIDS B1 only onedimensional. This is equivalent to a gauge transformation. (5) T mnpfPk(X) emnpfPk(X) . 2. . N. eik.to is the eigenvalue of the lattice translation operator T D: (14) T DfPk(X) = eik. is a lattice translation vector.tofPk(X). (~. (J But with periodic boundary conditions (8) 80 fl fPk(X + Na) fPk(x). .
using p = iV. with the components ". and (22) Ck  . and (18) from which (15) follows directly. simply (23) (  At the point k = 0 the equation for uo(x) is 2~ '(72 + V (x) ) uo(x) ~ eouo(X).2m ~k2. == 0.X(p + k). a solution of (19) is = 0. SpinOrbit Interaction. CH. p. 9 181 Proof: Note that. which is the symmetry of the crystal space group. ~ (~ ~) '" = The hamiltonian (24) is invariant under lattice translations T if V(x) G n . The hamiltonian with spinorbit interaction has the form (Schiff. thus the equation for uo(x) has the symmetry of V(x). We may rewrite (15) as (19) with (20) Ak Ck ( 2~ ('(72 + 2ik· '(7) + V(X») u. 'Pk(X) = eik•x.(x) ~ = Ck AkUk(X).X :x eik. Uk(X) = constant. the usual plane wave. 2m If V(x) Ak where (21) is the eigenvalue of (15). we have the operator equation pe ik.X(p p 2'Pk(X) = eik. + k)2 Uk (X). _~k2.BLOCH FUNCTIONSGENERAL PROPERTIES. where (25) is the pauli spin operator. 333) (24) H d =  1 p2 2m + V(x) + 22 d 1 4m c X grad V(x) • p.X(p + k)Uk(X). ~ (~ ~} ". (16) Thus (17) P'Pk(X) = eik.
thus [H. The quantity 1 (29) 1C == P 4~(T X grad V THE( + so tl Pl that (35) me has many of the properties for the problem with spinorbit interaction which p has for the problem without spinorbit interaction. enel the poil THE Further. (33) = Xkl (x)a + 'Ykl (x){3 = eik. THEOREM An i] madE show defin pairs THEO 3. Section 18) for the time reversal operator is .xukl (x).K] = O. (28) The terms ~ (p + _1_ d X m 4me 2 grad V). For a system of a single electron the result of Kramers (Messiah. TIME REVERSAL SYMMETRY apaI tion. but they will not in general correspond to the pure spin states a or {3 for which uza = a. where the arrow i on the Bloch function <Pkl (x) denotes a state with the spin generally up in the sense that (<Pkl . The time reversal transformation K takes x into x.Kocp). The eigenfunctions of (24) will be of the Bloch form.Kcp) = (Ko1/l.UzCPkl) is positive. u z{3 = {3. In general (26) CPkl (x) also. (K1/I. The arrows on Xkl and 'Ykl are labels to indicate their association with <Pkl. Chapter 15.d. With spinorbit interaction the function Uk(X) satisfies (27) L~ (p + k)2 + V(x) + 4~2C2 d X grad V(x) • (p + k)] Uk(X) = EkUk(X). k = H' so tl are often treated as perturbations for small k or small changes in k from a special wavevector k o. and cP l only (3.1/I).182 QUANTUM THEORY OF SOLIDS BLOC'] is invariant under T. (32) the] (37: . usin (36) (30) K = iu1/K o. In the absence of spinorbit interaction CPl involves only a.u1/ 2K Ocp) = (cp. d into The hamiltonian (24) is invariant under time reversal.1/I) = (Ko1/l. eigeIJ magI theo] Pr eiger by (: (34) This follows directly from (16) and (18). Thus Ko has the property for any two states cP and 1/1 that (31) (cp. pinto p. The ocm where Ko in the Schrodinger representation is the operation of taking the complex conjugate. with U1/2 = 1.
W. We recall that u"..K~) =  (~. ~t<x) ~kt< x). (36) From (35) and Theorem 4 we have ekt = ekJ.~kJ)' using u". The states K~t and K~J belong to wavevector k. K~ is orthogonal to~.K~r> = (~kJ.E. Proof: The hamiltonian commutes with K.u.K~) = 0. He shows that in very impure superconductors we must consider pairs defined by the time reversal operation. so that (35) K~t = ~kJ. with the inversion operation J the energy surface will be double at every point in k space. reverses the spin direc tion. This is the Kramers theorem. Q. then K ~ is also an eigenstate with the same energy eigenvalue in the absence of external magnetic fields. = u.D. A double degeneracy at the same energy and k occurs only if other symmetry elements are present.~t) = (Ku. but not at the same k. 26 (1959)]. then (37) .~t. THEOREM 5. and the eigenvalues are the same.U.u". Anderson [J. The bands have a twofold degeneracy in the sense that each energy occurs twice. 183 also. rather than Bloch function pairs.BLOCH FUNOTIONsGENERAL PROPERTIES. CH. If ~ is a oneelectron eigenstate of H.D. therefore K~ must be an eigenstate if ~ is an eigenstate.E.)( iu". so that ekt = ekJ and ekJ = ekt· Proof: KfPk:t = iu".K~) ~ = _(K2~. Now by (32) and (33) (34) (~.)~ = An important application of timereversed pairs of states has been made by P. (33) K2~ = (w". If the hamiltonian is invariant under space inversion. Phys. Chem.Ko~t = eik' x X (periodic function of x) J. 9 ~. THEOREM 4. THEOREM 6. so that and K~ are linearly independent.u. apart from a phase factor. Solids 11. We assign opposite spin arrows to ~ and K~ because (~t. ekJ = ekt· Q. Further.
k. But (39) JlPki (x) wh inti (47 == eik·:a:uki (x) wh for (4~ is a Bloch function belonging to . pinto p. THEOREM wl (5 7. so that the expectation value of O'z over ct'ki and ct'ki is the same. Therefore. (5( where (43) ct'k! = KJ lPki' is (5 apart from a phase factor. The reason d does not change sign is that it is an angular momentum and transforms as an axial vector. and (38) €ki = €ki' (4e Proof: The space inversion operator J sends x into x. because the eigenvalue of J ct'k i under a lattice translation operator Tis e. ] and (41) €ki = €ki' Q. The product operation (44) C == KJ = iO'yKoJ = JK TH will be called conjugation. hf frl . whence (40) ct'ki (x) = tal of J lPki (x). and d into d. with G a reciprocal lattice vector.D. Conjugation reverses the spin of a Bloch state. Then JlPki (x) is degenerate with lPki (x). then the hamiltonian including spinorbit interaction is invariant under J.184 QUANTUM THEORY OF SOLIDS BL( apart from a phase factor. Thus if JV(x) = V(x). A number of theorems involving the opera tions K and C are given as exercises at the end of the chapter. that Uki (x) satisfies the same differential equation as uki (x). (4{ It is simple to show directly.ik•tn • We may call Uki (x) = Uki (x). In the momentum representation. the com bined symmetry elements K and J have the consequence that tio (42) €ki = €k!. We recall that J commutes with 0' z. if one wishes. but does not reverse its wavevector: (45) ClPki = lPk b (5 (5 apart from a phase factor.E. using (36).
ij = ~(Oi' m :J Sk Sk Cf'k ~ G. The energy is periodic in the reciprocal lattice . IfG(k)12} Sk+G' Sk. CH. where g is a reciprocal lattice vector and V(G) is the fourier trans form of V(x) between plane wave states: (48) V(G) f d 3x eiG. from Cf'k.XV(x). that is. An alternate deriva tion is given as Theorem 11.xeiG.xuk(X) has the periodicity of the lattice. a~. The result (47) follows on operating on (46) with H = T + V and taking the scalar product with eik. = eik. G where the fG(k) are cnumbers. (52) = Proof: Consider a state (53) Cf'k of energy we may write Cf'k+G.x LfG(k)e iG. it follows that Sk = Sk+G' Thus <Pk+G may be constructed .1 L (k + G)lfG(k)12 G = gradk s(k). the wave equation without spinorbit interaction is (47) 1 (k 2m + G)2fG(k) + L V(G g g)fg(k) = sJG(k).BLOCH FUNCTIONSGENERAL PROPERTIES.X.xUk+G(x) = Uk+G(X) where (54) == eiG.X . 9 185 (46) <Pk(x) = eik. The proof of the last step is left to the reader. lt also follows that the effective mass tensor defined by (50) 1) ( m* lAP iJ iJ s(k) = iJk" iJk" is equal to (Problem 8): (51) THEOREM ~) (m* 8. lt follows from the representation (46) that the expectation value of the velocity v satisfies (49) (klvlk) = (klp/mlk) = m.xuk(X) = ei(k+G).
6 CYO C60 w~ (6 where 0. The spin indices are not shown in our present notation. r 7 X rv = r 6 + r 8. dE by Exercise 5.186 QUANTUM THEORY OF SOLIDS BI We now develop an important theorem related to the effective mass tensor (l/m)"" defined by (50). say k o. with the hamiltonian for k = 0 treated as the unperturbed hamiltonian. The result (56) is referred to also as the fsum rule for k = o. further (59) ('Yol~lc'Y) = 0. which is equivalent to (55) Ck ta ne Tl (1 = __ 1 2m m* "" k"k" ( 171. 580 (1955). with Ic'Y) denoting the conjugate state to 10'1'). ) + Vfl k· P PERTURBATION THEORY THEOREM 9. If the state lPk at k = 0 in the band '1' is nondegenerate. and usually it is sufficiently accurate to write p for~. where r v is the vector representation. ('Yol~lo'Y) = 0 If er bf of bf or dE o·. along with the character .k =  m 1· ~ k (6 as a perturbation. Without spinorbit interaction p replaces~. Rev. Dresselhaus. 100. we must consider the matrix elements for the particular symmetry involved. '1' are band indices and the zeros stand for k = O. Thus at the point r in the zincblende structure the twofold representations r 6 and r7 of the double group satisfy the selection rules (see Chapter 10) (60) Sll er Ie: X th m r6 X rv = r7 + r 8. These rules are given by G. Proof: In the equation (27) for Uk(X) we treat (57) B: th ti4 H' =  1(1 p + m 4mc 2 d X grad V ) . the effective mass tensor at this point is given by (56) m*) = 0"" m "" (6 wl as ( +2 m L' ('Yol1r"IOo)(oOI1r"l o'Y). Phys. If the crystal does not have a center of symmetry. We could equally expand about any other wavevector. Let us consider first the diagonal matrix elements of H'. then (58) by parity. If the crystal has a center of symmetry. except for the time reversal degeneracy.
(k) = s'Y(O) nerate. as in Schiff. The valence band edge in important semiconductor crystals is degenerate. p perturba tion theory. Rev.86 0. Phys. the form of the band 'Y near k = 0 will be determined largely by the matrix elements connecting it with the band 0.Sao If the The rystal atrix oint r nd r7 If further degeneracy exists at the point k 0. we have a situation in which the firstorder energy does not vanish. we must apply degen erate perturbation theory. m II s'Yo .73 . the effective masses at k = 0 in the conduction bands of the alkali metals have the following values: Metal Li 2s Na K 4s Rb Os 6s n by Band index 3s 5s racter m*/m 1. According to calculations by F. if the energy denominator is very small.. S.4). but an example will be given below.1 ('Y ol1f'"k"IOo)(oOI1f' k"l o 'Y) Jl a s 'YO s ao ' where on the righthand side we have included the kinetic energy associated with the eik •z modulation. Further.. The eigenfunction to first order in k is (63) s the other Ik'Y) eik. We can draw some immediate conclusions from the form of (61). the effective mass ratio m*/m will be very small..33 0.2. By going to higher orders in the perturbation theory we may construct the entire energy surface.. Ham.136) is less than 0. z (IO'Y) + .SOLIDS BLOCH FUNCTIONSGENERAL PROPERTIES. 0 will be determined by 'Y. 82 (1962). the form of the energy surfaces is considered in a later chapter on semiconductor bands.006 ev.965 0. The energy to second order is (61) e. lsor at + 2 m k2 2 1 m ~ \. pp. vice versa. and. The result (56) is obtained if we write (61) in the form (62) ithout curate rule s')'(k) = s')'(O) 1 2 (m*) k"kJl m m IH + . In Problem (14. and the experiments suggest also that m*/m ~ 4 X 104 at the bottom of the conduction band. The method is referred to as k . Thus the firstorder energy correction from H' vanishes.!.' 100) (oOlk • 1C\0'Y»).78 0. 128. CR. An extreme example may be cited: It is believed that the energy gap in the semiconductor crystal CdxHg1_xTe (x 0.. the rules tell us that 1C does not have diagonal matrix elements within the twofold representations. Because 1C transforms as a vector. 156158. 9 187 'e mass table. If one S')'o sao is very small.
by parity. 1 (65) (66) Further. by the 2p levels below and the 3p levels above 3s in energy. ply) m g = =  !~kEY (xIPxls)(slpyly)· m g = x or y. The symmetry axis is along the z direction. pls)(slk. j Akikj. for Li Eso . We note that the firstorder energy correction vanishes from the perturbation (l/m)k . The state which is zlike at k = 0 will be neglected implicitly: we assume that the crystal potential splits z off from the other states by an energy large in com parison with Eg. as there is no Ip level. (iIH"jj) = A = m 2 Eg l(xIPxl s)12. y. The simplest example of k· p perturbation theory for degenerate bands occurs in uniaxial crystals with a center of symmetry. The secondorder energy involves the matrix elements (64) (6 thi sta th (7 hel (7] or (7~ T~ sec (sIH"lx) = m. p. g tho m th ab xz all (7 wl (xIH"lx) = ~E (xlk. As we go further along in the alkali series. For Na the 3s conduction band is perturbed about equally. the perturbations from below increase in effect relative to those from above. Degenerate k· P Perturbation Theory. Ak y2 . By symmetry (slpyly) (67) (sIPxlx). but in opposite directions.Epo < 0. 1 th in (7 The secular equation for the three states is (68) I Eg + A(kx + k y 2 2 )  A o Akx 2 . p/j)ul k . and thus m* ::: m.188 QUANTUM THEORY OF SOLIDS BL Su. pix) =  m g (xIH"ly) = ~E (xlk· pls)(slk.E 4(slk . here j = x. also by parity. k 2 . Suppose we have a band of slike symmetry at k = 0 lying above by an energy Eg a pair of bands degenerate at k = 0 and transforming at this point like x and y. Then in Li all the perturbations on the 2s conduction band will come from p levels higher in energy than 28. pix) g J (7: = 0. thus we may write.E l(xIPxl s)12. for i. so that m < m*.A Akykx o Akxky 1=0. and m * < m.A w (~ 0 o . We neglect spinorbit interaction in this example.ppose that the order of the bands near k = 0 in an alkali metal is the same as the order of the states in a free atom.
. in general. ~like =m +m* m 2Eg 112 2. (73) €a(k) 2 . 1 this shows that to second order in k the energy band structure of the 8 state near the band edge is spheroidal. plxz)(xzlk. 1 the olves = 0. Suppose that somewhere above the 8 state there lie two degenerate d states which transform as xz and yz. ~k = . ply). 0 are. to 'Y stal or (72) ~ cornIe. (k) = 2m k2 +~ = Eg + 2m k 2 + A(kz 2 + k. here m* < m. (75) 1 Akz2 + Bkz 2 + ~ Akykz Ak/ + Bk z 2 + ~ .. The contributions of the d states to the offdiagonal elements vanish. ..J. Akzky 1_ 0 which has the eigenvalues o.l). 9 189 tal is [1 the igher that lally. with the free electron mass m in the z direction and with the effective mass in the xy plane given by (70) Ie of laxial ld of lands ld y. Then the diagonal elements of the secular equation will also involve (74) (xlk. The energies of the degenerate bands involve the solutions of (71) 1 Akz2 + ~ Akykz Ak1. evels n the ative One solution is (69) € .Bk/. 2m k .kg Ak y 2 + ~ 1_ 0 . . pix) 2 or y. (76) ~k = . plyz)(yzlk.)LIDS BLOCH FUNCTIONSGENERAL PROPERTIES. which is also the value of (ylk. and (kz 2 Therefore the energies of the two bands degenerate at k second order in k.Bk z 2 A(kz 2 + k/). Thus (71) becomes. etl(k) = 2~ k 2  A(kz 2 + k y2). CH.. The form of the secular equation (68) is not the most general form: the coefficients of the offdiagonal elements are usually not equal to the coefficients of the diagonal elements. + k g 2 ).
the nonboundedness of x causes some mathematical difficulty. It is useful to become familiar with the classical motion of free electrons in the vector field A = .1 ( P .H) = 0. The oneelectron hamiltonian is (S6) (SO) e)2 If == .. where ko is the eigenvalue of p. it = [x.~at = whe viev expl of a in t: tion enel wit} for ' (S5) so t if (~ will in k " A = eEt.' + eEt)/m.eEt : Tha hav the stat will E (SI) H =  1 2m (p + eEt) 2. . The simplest approach to the problem is to establish the electric field by a vector potential which increases linearly with time. 1 aA E == grad". We suppose that the band is nondegenerate. One surface (that with the + sign) describes heavy holes. First proof: If the electric field is included in the hamiltonian in the usual way as a scalar potential". which is a constant of the motion. E. t = aH/ap = (p (S7 : On quantum theory for a free electron (S3) ip = [P.H) = i(k o + eEt)/m. = eE· x. In a steady applied electric field E the acceleration of an electron in a periodic lattice is described by (77) k = eE. ACCELERATION THEOREMS THEOREM: o whe the (S4) 10.190 QUANTUM THEORY OF SOLIDS BLO The surfaces of constant energy are figures of revolution about the z axis. OUI Th« ove .A 2m e == 2m (p 1 + V(x) + eEt)2 + V(x). We set (7S) thus (79) as required. and the electron remains within the same band. the hamiltonian equations are (S2) not ban adh and peri p = aH/ax = 0. the other surface describes light holes.
We see that bands can be defined rigorously in the electric field and k is a good quantum number: in this formula tion k is not changed by the electric field! We now treat the time t as a parameter and compare the kinetic energy term (p + eEt + k) 212m in the effective hamiltonian for uk(E.E. Therefore the solutions are precisely of the Bloch form: (84) <P:k(x.eEt. We must still show that an electron at k in band 'Y will at time t still be in the same band. it will not cause k to change. where uk(x. but in different bands. Thus an electron which stays in a given state k will appear to change its properties in terms of the states classified in k at t = as if ° (86) I k = eE·1 That is. an electron in <P:k at t = will at a later time t be in a state having the original k. whether or not E is present. the current will tend to increase linearly with time because A ex t.t) . The two hamiltonians will be identical if (85) eEt +k = eEt' + k'.t) for band 'Y can be expanded as a linear combination of uak(x.E. but with all the other properties (including the energy) of the state originally at k . The argument of the present . so that the state and the energy at k. The functions u'Yk(x.BLOCH FUNCTIONSGENERAL PROPERTIES. The current in the state k is related to the expectation value of p . That is. here the time t is viewed as a parameter. at Wa'Y Wa'Y Our states a and 'Yare states of the same k. CH. Because eE(t .(E.t) has the periodicity of the lattice. _1 «1. t' if (85) is satisfied.E. The condition (87) is very easily satisfiedit is difficult to violate over an extended volume of a crystal. 9 191 Observe that the hamiltonian (80) has the periodicity of the lattice.t').t') is invariant under spatial translation. which states that a transition between states a and 'Y is unlikely to occur if the change in the hamiltonian during the period l/wa'Y is small in comparison with the energy difference Wa'Y: (87) ° aH _1_ . we need the adiabatic theorem.E.(elc)A.t are identical with those at k'.O)the eigenfunctions of all bands for E = 0.t) = eik'XUk(X.t) with the kinetic energy term (p + eEt' + k') 212m in the hamiltonian for uk.
here the time t is viewed as a parameter.t') is invariant under spatial translation. Thus an electron which stays in a given state k will appear to change its properties in terms of the states classified in k at t = 0 as if (86) Ik = eE·1 That is.E. The condition (87) is very easily satisfiedit is difficult to violate over an extended volume of a crystal. where uk(x. we need the adiabatic theorem.t) for band l' can be expanded as a linear combination 6f uak(x.E. Because eE(t .O)the eigenfunctions of all bands for E = O.t). whether or not E is present.BLOCH FUNCTIONSGENERAL PROPERTIES. Wa')' Wa')' Our states a and l' are states of the same k. it will not cause k to change.t) with the kinetic energy term (p + eEt' + k') 212m in the hamiltonian for uk. but in different bands. The current in the state k is related to the expectation value of p .t) has the periodicity of the lattice. but with all the other properties (including the energy) of the state originally at k .(E. Therefore the solutions are precisely of the Bloch form: (84) ~(x. _1 «1. the current will tend to increase linearly with time because Acct.t').eEt. 9 191 Observe that the hamiltonian (80) has the periodicity of the lattice. an electron in <Pk at t = 0 will at a later time t be in a state having the original k. so that the state and the energy at k. That is.E.E. We see that bands can be defined rigorously in the electric field and k is a good quantum number: in this formula tion k is not changed by the electric field! We now treat the time t as a parameter and compare the kinetic energy term (p + eEt + k)2/2m in the effective hamiltonian for uk(E. The two hamiltonians will be identical if (85) eEt +k eEt' + k'. We must still show that an electron at k in band l' will at time t still be in the same band. The functions u')'k(x. t' if (85) is satisfied.(elc)A.t) = eik'XUk(X.t are identical with those at k'. which states that a transition between states a and l' is unlikely to occur if the change in the hamiltonian during the period IIWa')' is small in comparison with the energy difference wa')': (87) Tt oH _1_ . CH. The argument of the present .
x U:'iF • gradk 3 Uk'Y' which vanishes except for k = k' because the term U:'8 gradk Uk'y is invariant under a lattice translation. note that (89) Then (90) Now gradk ~'Y(x) = H ix~'Y(x) + e ik . unlike the earlier one with a timedependent vector potential. Consider the problem of a free electron (93) in an electric field.dk •x dt ~ ' . with F = eE as the force on an electron in the electric field. (94) ~k = eik..xF .x acts as invariant under a lattice translation because the term in F does not mix states of different k. But. The vector potential A = .ik. k is not a constant of the motion. from (93). Second proof: We write H = H 0 + H'. Notice that in the present formulation. gradk in the hamiltonian (90) can cause a change of k. gradk e.da ( z dt ) + z.. gradk eik.xeia(t) .xlky) = i f d x ei(kk'). H' F· x. t ~ :{ lt) The timedependent Schrodinger equation is i ~~ = C~ p'  F. If ~k'Y(X) are the eigenstates of H 0. (95) dt d~ a~ dk +·gradk~= at dt .192 QUANTUM THEORY OF SOLIDS theorem is due to Kohn and to Shockley. then (92) i(ok'leik'xF .% gradk e~'k·x~'Y(x). but only of the same k of different bands.~u. but only the term z'F . x) q>. It follows that HF gives interband mixing. = HF + z'F· gradk. where (91) HF = H 0  ieik. where (88) 1 Ho = 2m p2 + V(x).cEt can be established in a ringshaped crystal by changing magnetic flux at a uniform rate through an infinite solenoid running through the inside of the ring..
for example. 2m dk =F.. Jt= ddt f1{((.x]) = gradk €ky.F • X. thereby enabling us to us~ the accelera tion theorem to connect the change of velocity and the applied force.1 k 2 . gradk)Xk. Thus the acceleration theorem is valid in the basis XIn of Bloch states for which the polarization effect of the electric field has been taken into account by the hamiltonian Hp. E. . Rev. or. 9 193 so that (96) or (97) d dt  a dk • X _ dt = . For very short time intervals it can be shown that the motion of an electron in a crystal is governed by the free electron mass and not by theeffective mass.BLOCH FUNCTIONSGENERAL PROPERTIES. (102) (JVVJJ. see also (49).dXk dt = (da dt + i dk dt .rn. 605 (1956). N. We give now a theorem which connects the expectation value of the velocity with the wavevector. If (v) is the expectation valueof the velocity in a state Ik'Y).JL 1... Argyres. on comparing (99) with (101). . Xk = eik·][e. tions Xk'Y(X) as the eigenfunctions of (98) HpXk'Y We define a set of func = €InXIn· The timedependent equation is (99) i dXk dt = (Hp + iF . The same argument applies in a crystal. We try a solution with Xk confined to one band: (100) the derivative is (101) 1. in the absence of magnetic fields. see.  . z.ia (t)Uk'Y (x) . THEOREM 11. then (103) (v) = i([H.dol _ . grad k) dk =F dt . CH. dt ~ . Phys. Xk.. N. 102. Adams and P.
Rev. Phys.~ F" rn* . (l = gradk k €.x]lk) = i Jd x u:(x)(gradk eik. Blount in Solid state physics 13.x. ( 1) c If k € (112) = k2j2m*.X))Uk(X). He 1!:'X)uk(X) i Jd x u:(x)(gradk H(p + k.x]eik..D.xxlleik'J: + ieik. Wannier. (111) 0: dt d (x~) = de dk" ( 1 ) rn* . For electrons in nondegenerate bands h . 3 x 1 aI 3 (1 Now use the Feynman theorem. Tl or.xllxeik.xuk(X). fu la fiE w (kl[ll. For a general discussion and further references. and (109) (i:) Thus (107) becomes Q.x)e ik. Tl ax / \\ where X is a parameter in the hamiltonian.E. 645 (1962) and E.xll(p Thus (107) k.194 QUANTUM THEORY OF SOLIDS ')'= Bl Proof: We consider the matrix element in the band (104) (kl[ll. namely (108) w ~ (killik) ax \ / kl all Ik\.xHe'K'X) ieik. then d m* dt (i:) = F..i gradk k € . as (i:) is a function of k alone. (110) (l d dt (i:) dk dt : gradk grad k k €. we have seen in (15) that (106) H(p. H.~.x]lk) = J d 3x u:(x)e1K'X[H.x = ieik'X[ll.x). J. Afod.x]eik. 306. c I t is more difficult to treat rigorously the motion of a lattice electron in a magnetic field. Further. Particular problems are treated at several points in the text. 34. see G. . ar tic Now (105) (1 grad k (eik.x = eik. further. by (55).
W ANNIER FUNCTIONS Let 1Ok.(X) be a Bloch function in the band "Y. The Bloch functions may be expanded in terms of Wannier functions as (115) fPk(X) = NYl Le ik.(x) = Nl THEOREM L e (kk'). (117) J 3x w*(x)w(x d xn) = 0.(X  xn) = Nl2 L eik. that is. (116) fPk(X) = NYJ Le n ik' Xll NYJ i Lek' ik '.xll fPh(X). The Wannier functions tend to be peaked around the individual lattice sites X n • We examine this under the special assumption that (119) 10k eik.xllw(x n xn). Proof: From the definition of w. 12. k where N is the number of atoms and THEOREM Xn is a lattice point.XllfPk. Proof: (118) J 3x w*(x)w(x d Xn) = NI ~. the Wannier functions are defined by (114) W.n 13.(x) = fPk(X). O. We now give several theorems concerning special functionsWannier functionswhich are sometimes used in discussions of the motion of lattice electrons in perturbed potentials and in electric and magnetic fields. k'. = Nl J 3x eik'Xll~(X)1Ok'(X) d L k ~On. 9 195 and nottoostrong magnetic fields the result of the detailed calcula tions is that the equation of motion (111) may be generalized to (113) F = e(E + ~ v X H)...x llfPk. Wannier functions about different lattice points are orthogonal. CH.BLOCH FUNCTIONSGENERAL PROPERTIES. .Xuo(X) . Xn .t..
(120) w(x Xn) = NYluo(x) QUANTUM THEORY OF SOLIDS B Then L k eik.xn)/a}. (1. Then L eiH = L e Ie i (211' m V Na ) ~ sin (r~/a). (1 Proof: A clear proof is given by J. Thus the Wannier function assumes its largest value within the lattice cell about X n . In a magnetic field (124) becomes (1 he (127) [e (p .  m (r~/Na) (1 » 1. and it tails off as we go out from the central cell. C. Phys. ml he where x(x) is the solution of the Schrodinger equation (126) [H 0 + H'(x)Jx(x) = Ax(X). the method given there is the one most often used in practice when quantitative calculations are carried out. al eJ p: oj In one dimension with lattice constant a. of . THEOREM 14. (121) in p 211" k=m. then the eigenvalues with a slowly varying perturbation H'(x) are given by the eigenvalues A of the equation (124) [e(p) (1 sh (1: K.. A treatment of a similar problem for weakly bound donor and acceptor states in semiconductors is given in Chapter 14. where e(p) is the operator obtained on SUbstituting p or .).196 where uo(x) is independent of k. 76. {rex .2 UO (X) sin {rex . Slater. + H'(x)]U(x) = AU(X). and w(x _ xn) = N. If e(k) is the solution of the unperturbed oneparticle periodic potential problem for a nondegenerate energy band.~ A) + H'(X)] U(x) = AU(x) .i grad for kin e(k) in the band 1'. U(x) has the property that (125) x(x) = un L U(xn)w(x n x n).xn)/a} sh (1 (123) F( co (1 In three dimensions we have the product of three similar functions.(XX. Na where m is an integer between (122) for N ±IN. Rev. 1592 (1949).
If O2 has the property (131) K0 2 Kl = 0 2 +. (cpIOlIKcp) = 0. show that (130) (cpIOllcp) = (KcpIOlIKcp). or any function of x. For '0 1 as defined in the first problem. Phys. show that (135) here ° = might be L or d.0+. show that (132) (CPI02Icp) =  (KcpI02IKcp). 6.BLOCH FUNCTIONSGENERAL PROPERTIES. An example of effects arising from the noncommutativity of the components of k in a magnetic field is given in Chapter 14. Evaluate the effective mass tensor (56). 2. (ikIOlkj) = (lkIOlkl)· (ikI01ki) (lkIOlkl). PROBLEMS 1. show that (133) here might be p. Prove (49). 2. show that (129) For 0 1 we may have a symmetrized product of an even number of momentum components. 3. 84. or the spinorbit interaction. 6. 3 hold if everywhere C == KJ is written for K. If COCl = 0+. In the expansion of s(k) any product of k's is to be written as a symmetrized product before making the substitution k ~ p . If COCl = . Luttinger. M. 9. CH. 4.e/ cA. with p written for ?C. The wavefunctions may be written in the tight binding . use (47) and the normalization condition grad k = L IfG(k)12 G O. in the limit of separated atoms. . 7. show further that (134) ° (ikIOlkl) = 0. Show that the results of 1. 8. Rev. Prove (51) . the states are now assumed to be eigenstates of a hamiltonian invariant under C. If (128) ° 1 has the property K0 1Kl = 0 1+.814 (1951). a symmetrized product of an even number of linear momenta. 9 197 as demonstrated by J.
.ik) ~ k.using tt'k(X) as an expansion of tt'o(x) to first order in k • p. Show that (136) satisfies the trans· lational symmetry requirement (14). (:. L p 0: 81 to first order in k.e(ko). from conservation of energy.xjv'Y(X i Xi).('YlpI6) m == (ell .198 form as (136) QUANTUM THEORY OF SOLIDS tt'k'Y(X) = NJA Leik. It is assumed that v's centered on different lattice sites do not overlap. where ae is the width of the band. b it c fl V o i: i ~ . Consider a Bloch state which is nondegenerate at k = O. 11. where V'Y and Va are different states of the same atom. show by direct calculation that (140) tl pi c] C~ (kip. on application of the atomic isum rule. Now (137) i . ] c so that (138) m. We find that ('Yk lplk6) = (v'Ylplva).) (m zz = [1  2m L' (ell i e'Y)I('Yl x I6}12] = 0. (c) Estimate the frequency of the motion. (a) Show that an electron in a crystal in an electric field & will oscillate according to (139) pl e(x  %0) • & e(k o + eSt) .e'Y)('YlxI6). The amplitude ax of oscillation is ax '" aelel&l. where v is an atomic function in the state 'Y. 10. (b) Estimate ax for a reasonable electric field.
Unless otherwise specified. ~ . The Brillouin zone of the linear lattice is shown in Fig. The symmetry properties are first discussed without spin. 7. and the fcc lattice in Fig. our k's are under stood to be reduced to this zone. or first Brillouin zone. 3. the sc It.l. of the square lattice in Fig. There are certain useful symmetry properties of the hamiltonian for the periodic crystal potential which are most easily discussed with the help of elementary group theory. ic = ek. This cell is called the Brillouin zone. and later the spin is added. but the standard convention is to bound the cell by the planes which bisect the lines joining k = 0 to the nearest points of the reciprocal lattice. the bcc lattice in Fig. The construction of the zones is described i~ [SSP. Chapter 12.e We have seen that the energy eigenvalues of the periodic potential problem are periodic in the reciprocal lattice: ek+G :1. We also sum marize in tabular form results which are frequently used. 1. The primitive cell may be chosen in various ways. 10 Brillo*in zones and crystalsyDa~etry \ \. In a crystal the group G of the hamiltonian is the space group of the crystal structure plus the operation of time reversal. We recall that the lattice and thus the hamiltonian is invariant under all trans 199 .~ :l ~ . 5. 19 m thus to label the eigenvalues uniquely it is necessary to restrict k to a primitive cell of the reciprocal lattice. The reader without benefit of group theory may acquire the needed elements from Chapter 12 in Landau and Lifshitz.ttice in Fig. 2. The modest object of this chapter is to make it possible for a reader equipped with a knowledge of point symmetry groups and their representations to extend his knowledge to the important symmetry properties of the Brillouin zone.
We now study the effect of the operations of the point group R. 1 For full details of these space groups.(X) . Now Uk(X) is a solution of (6) {2~ (p2 + 2k· P + k 2) + V(X») Uk(X) = >'. and a. the <Pk belong to onedimensional representations of the translation group T and have the eigenvalue eik. London.U. where R is a real orthogonal transformation. The result of operating on a function f(x) with R is defined to be (4) PRf(x) = f(RIx). NorthHolland. l. Proof: We have (5) <Pk(R1x) = eik. If <Pk(R1x) is a solution of the wave equation. n = integers. Jones. THEOREM. F. 1960. Let P R be an operator of the point group. where R is an element of the group of the Schrodinger equation. This result is intuitively obvious on observing that k· R1x = X· Rk. Koster. where t is a vector in the direct lattice: (2) t = la + mb + nc. . Pergamon. Group theory in quantum mechanics. Heine. <Pk. Thus for a Bloch function (3) T <Pk eik·t<Pk .200 QUANTUM THEORY OF SOLIDS lations of the form (1) Tx = x + t. 1960. b. Solid state physics 6. V. 174256. m. Theory of Brillouin zones and electronic states in crystals. Chapter 1. see H.xUk(RIx). G.t • We restrict our discussion at the beginning to crystal structures which are themselves bravais lattices. where k' is derived from k by a rotation R applied in k space. c are the primitive basis vectors. Amsterdam. we defer discussion of space groups which contain screw axes or glide planes. That is. then <PR(k] (x) is a solution with the same energy. The rotation R transforms a Bloch function <Pk(X) = eik'Xuk(X) into a new function <Pk'(X). 1 Crystallographic nomenclature is sum marized in ISSP.RIXUk(RIx) = eiR(k).
I operate on x in real space. RIp = p2. the degenerate lPk form (for a non special k) an ndimelfsional representation of the group of the Schro dinger equation. BRILLOUIN ZONES AND CRYSTAL SYMMETRY.. 1. We can therefore generate a representation of R by letting R operate on k in k space or by letting R...s n elements. we may replace (4) by (12) PRlPk(X) = lPR[k) (x).(R1x). Note that lPR[k) (x) is an eigenfunction of the lattice translation operator T. so that lPR[k) (x) is ~ solution of the same equation as lPk(RIx) and has the same energy..t. these symmetry elements form a group which is called the group of the wavevector. where G is a vector in the reciprocal lattice.. That is. If the point group h. The representation is known as the small representation..(R1x) VCRIX) = Xku. RI[p].. these operations form the group of ko. and (9) RIp. if there are symmetry elements which leave special wave vectors invariant. The first zone is .. and (11) R[k] . Suppose that the states lPkl' of given k are degenerate in energy: the operations of the group of k transform lPkl' into a lPkA with the same k. R[k] = k 2. But observe that (10) R[k] • p = k . with the eigenvalue eiR [k].. where we have used the relations (8) = Vex). of lattice constant a. 10 201 and uk(RIx) is a solution of (7) {2~ (p2 + 2k· R1p + k 2) + V(X)} u. If a certain ko is invariant with ko = R'k o under certain operations R' forming a subgroup of R. This statement is consistent with the correct enumeration of states (Chap ter 1). CH. If there is only a single lPk for each k.. Because of the periodicity of the reciprocal lattice we treat k and k + G as identical (not merely equiv alent) wavevectors. and the lP'S are said to form a representation of the group of k. the Brillouin zone is shown in Fig. We consider first the trivial example of a linear lattice.. .
(211"la) is identical with kl because the points differ only by a vector in the reciprocal lattice. Brillouin zone of linear lattice.a) a lim e ( h +0 11"  a a) = lim e ( h +0 !: + a). they differ by the reciprocal lattice vector 211"1a and are therefore identical points in every respect.representations and thus to differ ent energies. Recall that ± kl are degenerate in energy./a = sin (1I"xla)u. and either (14) or (15) f{).oints in k space in this example are ria and ria... so that (17) lim e h +0 (!: .../a f{). tlIus the point ria is invariant under mz • The operations E and mz . If the potential V(x) is even with V( x) then the group of the hamiltonian includes the reflection operation in a plane through the origin. because the f{)'S belong to different . [~] = ..202 QUANTUM THEORY OF SOLIDS ./ix). are the group of the wavevector ria. = cos (1I"xla)u. so that f{)r/a = ± f{)r/a./a(x).~ o=~.. and kl and kl are degenerate in energy. 1. We see that the Bloch functions at the boundaries of this zone are standing waves. we see that k2 approaches ria. The point k2 = kl . ~ I ~ · k . bounded by and ria. We notice another feature of the zone boundary. The u's in (14) and (15) need not be identical. a . Thus the energies satisfy (16) e(kl) e(k 2 ) = e( k 1). The representations of this group are one dimensional and are trivial. We denote the reflection operation normal to the x axis by mz • The special p. they are either even or odd under mz . if we let kl approach ria. where E is the identity. I t follows that (13) m. G ~ FIG.
2. Z. The corners are connected to each other by vectors in the reciprocal lattice. and the lines.~. There are six special types of points or lines in the Brillouin zone of the square latticethe points r. M. CR. 2. The point r which lies at k = 0 transforms into itself under all the opera tions of the point group. Under the same operations M transforms directly into itself or into the other corners of the square. mdl. The special lines ~. . and therefore the four corners represent only a single point. SQUARE LATTICE The Brillouin zone of the square lattice is shown in Fig. Trans forming one corner into another is equivalent to taking a corner M into itself. The point group symmetry of the lattice is denoted by the symbol 4mm. there is a fourfold axis containing two sets of mirror planes. see I SSP. Chapter 1..BRILLOUIN ZONES AND CRYSTAL SYMMETRY. one set made up of m:z and my. the point group symmetry is 4mm. whence ak e(k) a =0 at the points ±rla. 10 203 This implies that the energy is even about (18) ±rla. and m:z.1.1. my.!!: a Ii 11' r F V a Ii" 11' x G k% FIG. m:z. For a discussion of crystal symmetry elements. the invariance of Z under m:z follows ky 11" Ii" M Z . where the reflection m:z and the twofold rotation 2z carries ria into the identical point ria. and Z are invariant respectively under the mirror operations md. X. my. and the other made up of two diagonal planes designated md. Brillouin zone of the square lattice. The point X is invariant under the operations 2z .
so that gradk E = on the zone boundary. for example. the property does not hold. ~l.M rl. ~2.1. at the (Ill) faces in the fcc problem (Fig.4: 1 1 1 1 m x. COMP ATIBILITY RELATIONS Within a single energy band the representations at the special points and lines are not entirely independent. The representations . Ma r4. Ms X Xl X2 Xa X4 E 1 1 1 1 2" 1 1 1 1 4 z . For the square lattice we see that the argument of (l7) applies to every point on the zone boundary. 7) because there is no mirror plane normal to the r1111 direction. ° TABLE 1 CHARACTER TABLES OF THE SMALL REPRESENTATIONS OF THE SPECIAL POINTS AND LINES OF THE SQUARE LATTICE r. Thus the points labeled G and F are related by mx and differ by the reciprocal lattice vector (21r/a.204 QU ANTUM THEORY OF SOLIDS because the operation takes Z into a point connected to Z by a recip rocallattice vector. d2. my md. M2 r a. Ml r2.0). Zl Z2 1 1 1 1 The character tables for the special points and lines of the square lattice are given in Table 1. thus a band might be labeled as r Sd 1X 4Z 2 M 51. M4 r s.0. md' 1 1 1 1 1 1 1 1 " 2 E 1 1 1 1 2 2" 1 1 1 1 0 0 0 mz 1 1 1 1 m ll 1 1 1 1 d ~ Z E E E my md mx dl. This property of the energy is inseparable from the presence of the mirror plane. We can usefully label a band by the set of labels of its irreducible representations at special points.
r4. Ms X 2.. r a. Xa. CH. M 2 . FIG. T. M 4 . kz k:x. Ms Xl. r 4. M l . but M b is reducible under the group E. with special poip. M 4. There are four special points R. Xl. MI. rs. Ms The full cubic point group is 4/m'3 21m. X. TABLE 2 COMPATIBILITY RELATIONS FOR THE SQUARE LATTICE Representation ill il2 2::1 2::2 Compatible with Zl Z2 SIMPLE CUBIC LATTICE r l. The complete compatibility relations for the square lattice are simple to work out and are given in Table 2. Z2 is not compatible with M 1 and M 3. Ma. Z. M2l M a.ts Ittbeled. . which are even under m x . so that M b is compatible with either Z 1 or Z 2. rs. Brillouin zone of the simple cubic lattice. S. M.BRILLOUIN ZONES AND CRYSTAL SYMMETRY. 10 205 must be compatible. because these representations are even under m x • The question of M b requires attention. r and five special lines il. X 2l Xa r l . 2. as shown in Fig. Suppose that the band has the representation Z2 at Z. 3. further. rs. X 4 r 2 . rs. so that the state is odd under the mirror operation m x • This representation is not compatible at the point X on the line Z with the representations Xl and X 3 . 3. Ms r2. X 4 . mx into Z I and Z2. r a.
p. 99 and 104. as given in Table 3.!l.206 QUANTUM THEORY OF SOLIDS 1'. T.y} . Character tables may be found in Jones. M.!l2' xy . k z. pp. For x. There are three points equivalent to M. . H E 1'1 1'2 1'12 I'lS' I'2S' 1'1' 1'2' 1'12' I'lS I'2S 42 4 2 3 J J4 2 J4 J2 J3 1 1 2 3 3 1 1 2 1 1 1 1 2 1 1 0 1 1 1 1 0 1 1 1 1 0 1 1 1 1 0 1 1 1 1 1 0 0 1 1 1 0 0 1 1 2 3 3 1 1 2 1 1 1 1 2 1 1 0 1 1 1 1 0 1 1 1 1 0 1 1 1 1 0 1 1 1 1 1 0 0 1 1 1 0 0 1 1 2 3 3 1 1 2 3 3 1 1 1 1 In. The point T is equivalent to three points on the other vertical edges. Smoluchow ski and Wigner. which is given in every textbook on group theory.!l1' xy(x2 _ y2) . The point equivalent to X lies at the intersection of the kz axis with the lower face of the cube. at the intersections of the kxk y plane with the vertical edges. R. The basis functions below are referred to the z axis: . 64 . thus R and I' have the same representations.!l2 x2 _ y2 . The point I' at the center of the zone obviously transforms into itself under all the operations of the cubic group. Bouckaert. R.!ls {x. The eight corners transform into each other under the cubic group. TABLE 3 CHARACTER 'l'ABLE OF THE SMALL REPRESENTATIONS OF 1'. y.!l1 1 . The point R at the corner is connected to the other corners by reciprocal lattice vectors. X. and give the lowestorder basis functions which transform according to these representations. k y. The representations and symmetry types are given in Table 5. The point H is included for use with the bcc lattice. the points X and M have the same symmetry elements. the point . 4/mmm. so that all eight corners are a single point. z we could equally well write kx. The point group is 4mm. Basis functions of higher orders are given in Table II of the paper by Von der Lage and Bethe.!l has the same point group. Table 4 we compare three of the common notations used for the representations of the cubic group.
Ma X 4 . Rev. 71. Pkys. Y(Z2 . .l(x 2 y2)]. xyz(x 2 _ y2)} {x. (y .y2). SYMMETRY TYPES OF POINTS TABLE 5 X. CH.z} {z(x 2 . M 2 ' X a'. and Wigner. Ml X 5'.x 2)} {xy. x(y2 _ Z2). Chem == used by most chemists. 58(1936). reference 1. Rev.BRILLOUIN ZONES AND CRYSTAL SYMMETRY. Pkys.yz. ZX(Z2 . 10 207 SYMMETRY TYPES AT POINTS TABLE 4 r. 50. M OF CUBIC LATTICES (REFERRED TO THE Z AXIS) Representation Xl. M5 Xl" Ml' X 2'. Ma' Xl.z). YZ(y2 .zx} xYZ[X 4(y2 _ Z2) y4(Z2 _ x 2) Z4(x 2 _ y2)] xyz {xYZ[Z2 .x 2)} r1 a r2 W r12 'Y r15' 0' r 2o ' e r l' a' r2' {3 ru' 'Y' rIo 0 r 26 e' 1 + + + + + + Note: BSW == Bouckaert. M2 Basis Functions 1 x2 y2 xy xy(x2 y2) {yz.y} A. H OF CUBIC LATTICES Notation BSW LB Chern Alg A2C/ EC/ Tlg T2C/ A lu A 2u Eu T lu T 2u Basis Functions X4(y2 _ Z2) y4(Z2 _ x 2) z4(x2 _ y2) {Z2 _ l(x 2 y2). R. LB == Von der Lage and Bethe. Ml X 2 . M4 X 5. Smoluchowski. 612(1947). [111] axis: Al 1 A2 The basis functions are referred to the Aa {(x . (x2 _ y2) } {xy(x 2 y2). The point group is 3m.zx} xyz(x2 _ y2) xyz z(x2 _ y2) Z X a. also in the text by Heine.z)} ~~0+~~~+a~~ The representations of F are identical with that of A.y.M 5' {x.Z2).
208 QUANTUM THEORY OF SOLIDS ~. The groups are holomorphic to 2mm. One gains a very powerful insight into band structure by considering the perturbed plane waves. TABLE 6 COMPATIBILITY RELATIONS FOR THE SIMPLE CUBIC LATTICE 1\ ~1 r 2 r 12 ~2 ~1~2 ru' ~l'~S r 2 s' ~2'~S r l' ~l' r 2' ~2' r 12' ~1'~2' r15 ~l~S r2S ~2~S Al 2':1 A2 2':4 Aa 2':12':4 A2 Aa 2': 22': a2': 4 AlAa 2': 12': 22': a A2 2':2 Al ~a Aa 2': 22': a AlAa 2':12':a2':4 A2Aa 2':12':22':4 Xl ~1 X2 ~2 Xa ~2' X4 ~l' Xs Xl' X 2' ~2' Xa' ~2 X4' Xs' Lls Z2 Z a Ll l ' Z2 82 Lll Lls Zl Z 4 Zl 81 Zl 84 Z4 81 Z4 84 M4 2':4 8 28 a Ms 2': 22': a Z2 8a Za 82 Za 8a 8 18 4 M1 2':1 M2 Ma 2':4 2':1 Ml' ~2 Ma' 2": a 2':2 Ml 2': a 2':12':4 Zl T1 Zl T2 Za T 2' Za Tl' Z2Z 4 T5 Z2 Tl' Z2 T 2' Z4 T2 Z4 Tl ZlZa Ts CLASSIFICATION OF PLANE WAVE STATES IN THE EMPTY LATTICE In Chapter 13 on the calculation of energy bands we shall discover reasons why the sequence of bands in a crystal often has a strong resemblance to the sequence of plane wave states. The point Z has two mirror planes and a twofold axis. The compatibility relations for the sc lattice are given in Table 6. with the crystal field considered as a potential which lifts certain accidental degeneracies which occur for plane waves. the basis functions are: referred to kx = ky and kz ~l 2':2 1 z(x . with basis functions referred to the z axis: Zl 1 Z2 yz Za y Z4 Z The representations of G.y) Ea z ~4 xy Z. D are identical with those of Z. S. K. For operations 0. . U.
The unperturbed wavefunctions at r may be written as e (25) CPI = CP4 = e2rix . and eBlc drops as we go out in the [100] direction to make contact with band A at the point X (k = 7rOO). as required.G Then we define CPk' We can always find a lies in the first Brillouin zone. (21) with (22) Uk(X) = eiG'J: _ CPk = = eik'J:Uk (x) . There is in the empty lattice a sixfold degeneracy at r for G = 27r(100) and equivalent G's. (001). We consider the effect of a weak cubic crystal potential in lifting the accidental parts of the degeneracies evident in the band scheme of Fig. 4. • CP2 CPs = e. ek G)2 = ek" Here eiG'J: has the periodicity of the direct lattice. LaUice. 1 2m (k . E. • e2riz .2rix . F. The lowest energy occurs for G = 0 and gives us the band A sketched in Fig. • CPa = e2riy . (001). • e. according to (22) 1 = 2m {(k:c 27r)2 + k y 2 + k z 2 }. eBO = (1/2m)(27r)2.BRILLOUIN ZONES AND CRYSTAL SYMMETRY. (010). for G = 27r(110) and equivalent G's.2m _ 1 k 2• = 27r(IOO).2riz • . At k = 0. The band is defined for G = 27r(100). CR. The next set contains 12 bands. Energy versus k in Reduced Zone. G are defined for G/27r (010). for an empty sc lattice of unit lattice constant (a = 1) and V(x) == O. reciprocal lattice vector G such that (20) k = k' . 4: se (23) Define band B for G (24) eBk eAk .2riy . We consider now the behavior and degeneracies of the energy bands in the reduced zone. • CP6 = e. ek' = 1 k'2 2m ' so that it appears in the reduced zone scheme. The bands D. 10 209 We wish to rewrite a plane wave of general wavevector k' : (19) CPk' eik"J: .
j 1 .(271")2X 2.2riz  We emphasize that the elements R' of the group of the wavevector are elements which operate on the coordinates. Thus. by expanding the f{)i in series for small arguments and then using ingenuity. Representative values of for a the extended wavevectors are given for several boundary points. 4. f". At r the group of the wavevector is that of the full cubic point group.j (271")2X 2. (271") 2Z 2. We may form several .2rix . 1 . Degeneracies are indicated in parentheses. to quadratic terms in the coordinates.j f{)6 "' 1 . (26) + 271"ix f{)3 1 + 271"iy f{)5::: 1 + 271"iz f{)1 ::: 1 f". guided by Table 4. We can construct irreducible representations of this group from the f{)i by determining the characters of the f{)i and then reducing the represen tation or. perhaps more easily. (271")2y2. (271")2 Z 2. f{)2 f{)4 f".(271")2y2.271"iy .210 Ek ·(2m/7r 2) E QUANTUM THEORY OF SOLIDS k·(2m/11"2) 15 15 71"(311) 10 10 5 71"(200) 11" (120) 5 71"(111) 71"(100) 71"(000)0 71" r kin {100] direction X r o R k in {Ill] direction FIG. Reduced zone scheme for free electrons in empty simple cubic lattice 1.
BRILLOUIN ZONES AND CRYSTAL SYMMETRY. A. 4\02 e7rix • sin 1I"X. two. . cos 1I"X. At the lowest point X the states are (31) 4\01 e ix . 5. 5. The sixfold degeneracy splits into one. by analogy with atomic orbitals. d. it is likely that X I will lie lower in energy than X 4'. CR. and threefold states. are identical with those of the ky FIG. 4\03 4\03 4\04 4\04 rv X2  y. the form of the zone is derived in I SSP. From these we may form the combinations (32) Xl rv X 4' rv If the ioncore potential is attractive. 10 211 representations from (26): (27) (28) (29) rl: 4\01 + 4\02 + 4\03 + 4\04 4\02 rv 4\00 + 4\06 rv rIo: 4\01 r X. The Brillouin zone of the bodycentered cubic lattice showing the sym metry points and axes. Chapter 12. 24\05  4\00  4\06 rv z 12 : 4\01 + 4\02 4\01 + 4\02 + 4\03 + 4\04 r1 y2. 24\06 rv X2 +  2Z2. because the cosine piles up more charge on an ion core centered at x = 0 than does the sine. }. BODYCENTERED CUBIC LATTICE The Brillouin zone of the bcc lattice is the rhombic dodecahedron shown in Fig. Thus for G = 211"(100) we reduce the sixfold degenerate r to (30) r + rIo + r12 rv 8 + p + d"(. . The symmetry operations for r.
We note that there is no mirror plane normal to the [111] direction in the fcc lattice. Special points of unusual interest are L at the center of each hexagonal face. the zone is a truncated octahedron. The point H has the full cubic sym metry. a r o 0. and W at each corner formed by two hexagons and one square. The classification of the representations of the energy bands in the empty lattice is given in Fig. a FIG. The classification of the represen tatiqnsof the energy bands is given in Fig. Their coordinates in terms of the side a of the unit cube of the direct lattice are 2 (33) HI HI2 { HI5 )( = 27r (001). a a 27r (1 1 1) L=vvv. 7. thus there is no need for gradk € to be zero across the hexagonal faces. The irreducible representations of wave vectors lying within the zone are not radically changed by the new operations. 47. 8. HEXAGONAL CLOSEPACKED AND DIAMOND STRUCTURES The space groups of these structures contain glide planes or screw axes which are not inherent in the primitive translational lattice. FACECENTERED CUBIC LATTICE riu r'25 r25 rI5 rI2 The form of the Brillouin zone is given in Fig. Because of the new opera tions it can happen that at a special point. Free particle energy bands for a bodycentered cubic lattice. p. but there is a serious change at the surface points of the zone. W = 27r (! 0 1). or on a .0 H K = 27r (t l 0). )( at the center of each square face. along a whole line. 6. The characters and symmetry types of Nand Pare given by Jones. 6. as for r.212 QUANTUM THEORY OF SOLIDS same points in the sc lattice.2 1. For details of the behavior on the hexagonal faces. see Jones.
BRILLOUIN ZONES AND CRYSTAL SYMMETRY, CR.
E
10
213
LI L'2
kz
J
[
L3 L'3
f .. f
)10
ky
LI ( L'2
rl'
o
r
C=:!
!
!
0.1
0.2 0.3 0.4 0.5
L
FIG. 7. The Brillouin zone of the facecentered cubic lattice showing the symmetry points and axes.
FIG. 8. Free particle energy bands for.a facecentered cubic lattice.
whole zone face the irreducible representations are only two dimen sionaL One says that the glide planes and screw axes cause the bands to stick together on the special surface lines and planes. We emphasize that our discussion of zone symmetry is still worded as if electron spin did not exist. We illustrate the effect by a simple example in two dimensions. Consider the rectangular Brillouin zone shown in Fig. 9; let the space group of the direct crystal have mirror planes m normal to the a axis at x = ia and la, and a glide plane g parallel to the a axis. The space group is p2mg. Suppose that X(x,y) is a solution of the wave equation at k = r/a(lO), which we denote by X. The glide operation implies
(34)
gX(x,y) = X(x
+ ja;y).
This space group necessarily contains the inversion J, so that
(35)
JX(x,y)
=
X( x;y).
214
QUANTUM THEORY OF SOLIDS
The mirror plane at x =
(36)
ia implies
mX(x,Y) = X( x
+ ia;y).
Then we see that
(37)
J 2X(x,y) m 2X(x,y) (37) (38) gX(x,y)
=
mJX(x,y).
Suppose that the representation were onedimensional: then because = X(x,y), we would have JX(x,y) ±X(x,y). Because = X(x,y), it would follow that mX(x,y) ±X(x,y). From
g2X(X,y) = mJmJX(x,y) = (± 1)2(± 1)2X(x,y) X(x,y).
However,
(39) g2X(X,y)
=
gX(x
+ ja,y) =
X(x
+ a,y)
=
X(x,y),
= eik..,ax(x,y)
eirX(x,y)
which contradicts (38). Therefore the representation in this space group at X cannot be onedimensional. The bands must stick at X. By using time reversal invariance we show that the bands stick on the boundary line through XZ. Let K be the time reversal oper ator; we know from the preceding chapter that in the absence of spin
(40)
KCPk(X,y)
= CP_k(X,y).
But on the boundary k
(41)
=
(7f/a,ky) we have
k
= (
~, k.) == (~, k.).
ky
z
p
L
H
CY __
Ht<=:::::: ' " _
::;3>J
x
k"
K .... __ T
H
H
FIG. 9. Brillouin zone for a simple
FIG. 10. Brillouin zone of the hexag onal closepacked structure.
rectangular lattice.
BRILLOUIN ZONES AND CRYSTAL SYMMETRY, CH.
10
215
Thus, from (37) and assuming the state k to be nondegenerate,
(42)
gK({)k(X,y) = mJ({)_k(X,y) = m({)k(x,y) = ({)k(X,y) ,
where in the last step we have used the relation
m. 1 [(~, Ic.)] =
However,
(~, Ic.), instead of letting m. act on the coordinates.
gKgK({)k(X,y) = g2({)k(X,y);
and by the argument of (39) (43)
g2({)k(X,y) =
({)k(X
+ a,y)
 ({)k(X,y),
which is inconsistent with (42). Thus the ({)k and gK({)k must be independent functions; their energy must be the same because the hamiltonian is invariant under the operations g and K. The bands stick on the boundary line through X Z; there can be no energy gap between these two bands. A similar argument applied to the hexagonal closepacked structure [C. Herring, Phys. Rev. 52, 361 (1937); J. Franklin Institute 233, 525 (1942)] shows that only doublydegenerate states exist on the hexag onal faces of the Brillouin zone, Fig. 10. This result is important because it implies that no energy gap exists across the hexagonal face. It has been shown, however, [M. H. Cohen and L. M. Falicov, Phys. Rev. Letters 5, 544 (1960)] that the degeneracy is lifted by the spin orbit interaction. For the diamond structure, see the paper by Elliott cited in footnote 2; for the zinc blende structure, the paper by Dresselhaus.
SPINORBIT COUPLING 2
We now add the electron spin to the Brillouin zone problem. Adding the spin without turning on the spinorbit coupling simply doubles the degeneracy of every state. But the spinorbit interaction will lift some of the degeneracynot, however, at k values for which the states are only doublydegenerate in the presence of spin, because the Kramer theorem on time reversal symmetry requires at least two fold degeneracy. A plike state (such as r iS in a cubic crystal, according to Table 4) is threefold degenerate without spin; sixfold degenerate with spin; and with spinorbit interaction the state behaves as a P%, p~ set in atomic spectroscopy: the sixfold level splits into one fourfold level like P~i and one twofold level like Pli'
2 R. J. Elliott, PhY8. Rev. 96, 280 (1954); O. Dresselhaus, Phys. Rev. 100, 580 (1955).
216
QUANTUM THEORY OF SOLIDS
The small representations are changed by spinorbit coupling. For the group r of Table 4, the representations with spin are given in terms of the representations without spin.
ri ri
rl
X D~2
r2
r7
The representations respectively. Character tables for special points are given in the paper by Elliott; results for the point r are given in Table 7.
TABLE 7
CHARACTER TABLE OF THE EXTRA REPRESENTATIONS IN THE DOUBLE
GROUP OF
rs r6 + rs r7 + rs r6' r7' r6 , r7 , rs are two, two, and fourdimensional,
r 12
r 15'
r25'
r 1'
r2'
r
(The operations with bars overhead are isomorphous to those without them)
E
E
2 2
4 2 :12
0 0 0 0 0 0
4
2~2
_2~2
4"
2~
2~'2
2
0 0 0
"2
0 0 0
3 1 1
1
3
1 1 1
JXZ ±x(Z) ±x(Z) ±x(Z)
r6 , r6' r7, r7' r s, ra'
2 2
4
4
0
0
Further effects of spinorbit coupling on band structure are best discussed by important specific examples. Several of these are given in the chapter on the band structure of semiconductors.
PHONONS
The symmetry properties of phonons in crystals may be described in the same way as we have described the symmetry properties of electrons. For a discussion of selection rules in processes involving both phonons and electrons, see R .•1. Elliott and R. Loudon, Phys. Chem. Solids 16, 146 (1960); M. Lax and J. J. Hopfield, Phys. Rev. 124, 115 (1961).
PROBLEl\1:S
ZI + Z2. 2. Show that the bands D, E, F, G in Fig. 4 on a line ..1 reduce into the representations ..1 1, ..1 2, ..1 5• 3. Show that without spin only doublydegenerate states exist at general points of the hexagonal faces of the Brillouin zone of the hcp structure. 4. Confirm the labeling of all the bands shown in Fig. 8 for the fcc lattice.
~1
1. Show for the square lattice that r5
+ ~2; 1115 =
..11
+ ..1 2; r6
~1
+ ~2; M 5
11 Dyna:rnics of electrons
in a :magnetic field: de Haasvan Alphen effect and cyclotron resonance
In a crystal the behavior of electrons in a magnetic field is vastly more interesting than their behavior in an electric field. In a mag netic field the orbits are usually closed and quantized; occasionally the orbits are open, with unique consequences. Observations on the orbits provide quite direct information on the fermi surface. The more interesting and revealing observations include cyclotron resonance, the de Haasvan Alphen effect, magnetoacoustic attenuation, and mag netoresistance. I t is unfortunate, but probably not generally serious, that the theoretical basis of the motion of electrons in crystals in a magnetic field has not yet been developed in a clean and closed form as concise as the earlier theorem on the motion of electrons in an electric field. One or two magnetic problems have been solved exactly, and a wide family of problems have been solved in a semiclassical approximation. Other solutions have been obtained in the form of a series expansion in the magnetic field, with several terms in the series calculated. The semiclassical analysis of the motion of an electron on a fermi surface in a magnetic field appears to be sufficiently accurate for most purposes.
FREE ELECTRON IN A MAGNETIC FIELD
We first consider the motion of a free particle of mass m and charge e in a uniform magnetic field H directed parallel to the z axis. The vector potential in the Landau gauge is A = H(O,x,O). The hamil tonian is
(1) H
2m p  c A
1 (
e)2
=
2m [Px2
1
+ pz2 + (Pu + mWcx)2],
217
218
QUANTUM THEORY OF SOLIDS
DYNAMIC
where the cyclotron frequency is defined for an electron as (2)
which ha (12) where).
(13)
We
== eH/mc.
We first examine the classical equations of motion in order to gain familiarity with their form in this gauge. We have ; (3) t
j
= fJH/fJpx = px/m;
iI = fJH/fJpy = (py
+ mWex)/m;
i = pz/m;
pz = O.
'P(:
(4)
Px
=
fJH/fJx =  (py
+
mWex)we;
py = 0;
Thus P'll, pz are constants of the motion, which we may denote by k'll' kz, respectively. From the equations for :t and Px, we have
(5)
Them ment th,; gas is in
(14)
mx
kywe  mWe2x
=
mwe2 (x
+ _1_ ky),
mWe
then (15) The nun
which is the equation of a linear harmonic oscillator of frequency We with origin at 1  k • (6) Xo =  mWe y Note too that iI is not a constant of the motion, although py is constant. A typical solution is
(7)
(16)
x
= 
1
mWe
. ky
negiectill energy ( A), 1 i
+ P cos wet;
Y = Yo
+ P sin wet,
mLxL'Ii2 The d
field is
(17)
where Yo is disposable, as is ky.
The quantum equations of motion are:
(8) it = [x,HJ = ipx/m;
iii = [y,HJ
=
i(py
+ mwcx)/m;
ii
=
ipz/m;
0,
(9)
ipx
=
[Px,HJ
=
i(py
mwex)we;
py = 0;
pz
in agreement with the classical equations (3) and (4). substitutions (10) P'll = k'll;
If we make the
pz
= kz ;
x=ky mWe
1
q=xo+q,
with e = the magJ of states Atabf all state; ~kll at kJ of allowl degenerf (18)
the hamiltonian (1) takes the form
(11)
H = 2m (Px
1
2
22) + m2 We q +
lk 2m z,
2
We defi
DYNAMICS OF ELECTRONS IN A MAGNETIC FIELD, CH. 11
219
which has the eigenvalues
(12)
e=
(X
i)we
+ 2~ kz 2,
where X is a positive integer. (13) <p(x)
= ei(kll ll+ k.,z>
The eigenfunctions are of the form
X harmonic oscillator function of (x  xo).
The maximum value of kll is determined through (6) by the require ment that Xo fall within the specimen. We suppose that the electron gas is in a rectangular parallelepiped of sides L:r" L lI , L z. If
(14)
iL:r,
< Xo < iL:r" < kll < imuJeL:r,.
eH
then
(15)
 imuJeL:r,
The number of allowed values of kll in this range in kll space is (16)
LlI
21r mWcL:r, = L:r,LlI 211"c
neglecting spin. This is the degeneracy of a state of fixed kz and energy quantum number X. The separation in energy of states .:1X = 1 is We, so that the number of states per unit energy range is mL:r,LlI /211", for fixed k z. The density of states of a twodimensional gas in zero magnetic field is
(17)
L:r,LlI 211"k dk (211")2 de
L:r,LlIm, 211"
with e = k 2/2m. Thus the average density of states is unaffected by the magnetic field; what the field does is to pull together a large number of states into a single level. At absolute zero all states are filled up to the fermi level eF; above, all states are empty. Consider a plane slab in k space, of thickness akz at kz , with the z axis parallel to the magnetic field. The number of allowed values of kz in the range 8kz is (Lz/211")lJk z , so that the total degeneracy of the state X in the slice 8kz is, from (16),
(18)
eHL:r,L lI Lz ~kz e8kz H  L :r, L 11L z A_2 :1I"C 211" ":I:1r C
 {J
== L:r,LlILz~H.
We define the degeneracy parameter
~
as the degeneracy per unit
220
QUANTUM THEORY OF SOLIDS
magnetic field per unit volume of the specimen:
(19)
~
eok z = , 2
411" c
apart from spin.
DE HAASVAN ALPHEN EFFECTl, 2,
3
Many of the electronic properties of pure metals at low temperatures are periodic functions of l/H. The Schubnikowde Haas effect is the periodic variation of electric resistivity with l/H. The de Haasvan Alphen effect is the periodic variation of the magnetic susceptibility; it is a spectacular and important effect. It provides one of the best tools for the investigation of the fermi surfaces of metals. We treat first the de Haasvan Alphen effect in a freeelectron gas at absolute zero. The fermi level eF can be shown to be approximately constant as H is varied; for the periodic effects in l/H in which we are interested the variation in the fermi level may be neglected entirely. At absolute zero all levels A in the slice ok z defined above will be com pletely filled (Fig. 1) for which
(20) (A
+
j)w e
<
eF
2~ kz 2 e~,
and above this all orbits are empty. If the highest filled level is A', then the total number of electrons n in the slice of thickness ok z is
(21)
n
=
(A'
+ 1HH,
using (18) and recalling that A = 0 is a filled level. The number n increases linearly with H until A' coincides with the fermi level eF. An infinitesimal further increase of H will raise A' above eF, and all the electrons in A' will empty out into orbits in other slices of the fermi surface; that is, slices with other values of kz and e~. The discontinuous evacuation occurs whenever an integer A' satisfies
(22) (A'
+ j)
=
e~
We
mce~ , 1
e
H
so that the population on is approximately a periodic function of 1/H, with period e/mce~. The population of the slice oscillates with ampliA. B. Pippard, LTP. D. Shoenberg, in Progress in low temperature physics 2, 226 (1957) i this contains a full review of the experimental situation up to 1957. 3 A. H. Kahn and H. P. R. Frederikse, Solid state physics 9, 257 (1959).
I
2
DYNAMICS OF ELECTRONS IN A MAGNETIC FIELD, CR.
E
11
221
10 9 8 7
6
5
4
I I f
I
I
I
/
(F fermi level of slab
2
;\=0
........
H
FIG. 1. Spectrum of Landau levels versus H; as H is increased, states of lower and lower}" burst up through the fermi level fF'.
tude i~H about the value no, which is the total number of electrons in the slice ~kz in zero magnetic field. The variation is shown in Fig. 2. The energy of the electrons in the slice ~kz in a magnetic field such that the population is no is
(23) U o = ~Hwe
kz kz L (A + !) + no 2 = j~Hwe(A' + 1)2 + no 2 o m m
~
2
2
=
1
We
2~H
nO
2
kz + no, 2m
2
using no = (A' IHH from (21) for this value of H. with the same value of A' for the topmost filled state,
(24)
For nearby H
U
=
2 ~Hn
1
We
2
+
kz n2m
2
+
 n)sF.
222
n
QUANTUM THEORY OF SOLIDS
~
I Uo
v+3
v+2
v+l
VOCJj
1
H increasing
FIG. 2. Variation of population n, energy U, and magnetic moment 8M of slice flk z , as the magnetic field is increased. The successive values of X' are denoted by JI + 3, JI + 2, JI + 1, JI, • • • • The horizontal scale is linear in liB, which decreases to the right.
The first two terms on the righthand side are the energy of the' elec trons in the slice ~kz; the term (no  n)eF is the change in energy of the rest of the fermi sea arising from the transfer of n  no electrons at the fermi level. By including the transfer, we have in U  U 0 the entire energy change of the whole fermi surface, provided eF remains exactly constant. We may write we/2~H = p./~, with
(25)
2
/J
~u = U 
== e/2mc.
Thus, with e~ == eF  k z /2m,
(26)
U o = (/J/~)(n2  no 2)
~U
+ (no 
n)e~.
Now e~ = (no/~H)we = 2/Jno/~, so that
(27)
=
(/J/~)(n  no)2.
This is always positive. The magnetization of the slice at absolute zero is
(28)
~M=
au
aH
dn  (2/J/ ~)(n  no) dH;
by (21) and (22),
(29)
dn , dH = (X
+ 1)~
ro.J
' /we) = eF(~/2p.H), ' eF(~
: (34) M = e [pr( L(I)Pj'" . 4pr3 We sum over all k. Now. The value of the integral in (34) to high accuracy is (35) eF . function of k. (pre F p sm JJ. r pl 1 Ap sin px. we have to sum the contributions from slices at all k.no varies cycli cally with extrema ± t~H as the population of the level A' varies between ~H and O. for (32) < X < r. 2 here we have used (36) 10 (00 dx cos ~ x 2 2 = 1 00 0 dx sin ~ x 2 = i. e/mce~.p .H« eF. after using the trigonometric formula for the sine of the difference of two angles.2 1)] • Now in metals and semimetals JJ. :::::: O. The magnetization varies between +t~e~. To determine the variation of the total magnetization with H. 11 223 so that (30) oM e' "I .no). 8M = . 6. ee~ A =eF(I)P pr 8k. 00 • using the Smithsonian Mathematical Formulae.H.H eF  2m k.H)~ r) 4. as we have seen. 1 = r 00 x = re~/JJ.H (mJJ. We analyze oM in a fourier series: (31) 8M = 8k. .810. CR. except for k. and the intezrand oscillates very rapidly as a. we are left with Fresnel integrals... (33) P Thus C 1. We have seen that as H is increased the quantity n . DYN AMICS OF ELECTRONS IN A MAGNETIC FIELD.2 Ee~x r 1 Ee~ p=l 1 (I)P smppx. This cyclic variation of magnetization as a periodic function of 1/H is the de Haasvan Alphen effect. (n . The period in I/H is. Thus we may replace e~ by eF in the integrand. for each slice on and e~ are different. ( .E ) = (I)P._kI'dk•.. e~ sin JJ.
the factor L1 ~ 0. For a general fermi surface the period of the de Haasvan Alphen effect may be expressed in terms of the area S in k space of the sta tionary section of the fermi surface. As the temperature is increased from absolute zero.LH 4 It is important to note that this result refers only to the properties of a stationary section of the fermi surface. Thus at a finite temperature the oscillations are more sinusoidal than sawtooth in form.LH)YJ ~ (. Thus measurements of the de Haasvan Alphen effect usually relate to the characteristics only of the stationary sections of the fermi surface. 41r 3c ': p~ J. it is found from the full analysis that the pth term in the sum in (37) is multiplied by the factor (38) L = p Xp . further. L3 ~ 0.71 at 10K.224 QUANTUM THEORY OF SOLIDS Then (37) M = eFem~~(J.LH pcS eH .L4 ~ 0. The relevant parameter is the ratio of k B T to the magnetic splitting We. that is. In any event. the de Haas van Alphen effect is limited to low temperatures: at 4°K we have L1 ~ 0. At absolute zero a section may enclose either all filled states or all empty states. more precisely. As in many other fermisurface problems. ]hreF J. For a given orientation of the magnetic field 'relative to the crystal axes there may be several stationary sections.30. we are involved with the properties of that section of the surface for which the integrand is stationary.03. surfaces for which as/ak H = O. sinh xp where xp = 21r2pk B T /w e • With H = 10 5 oersteds and We as for the freeelectron mass. With the general quantization condition given in (61) below. the orbital states near the fermi level will be partly populated. in this instance the section with kz = O. It is also necessary that the specimen be quite pure in order that collisions do not blur the quantization. taken normal to the direction of the magnetic field. L2 ~ 0. instead of being either filled or empty.10. On a simple model the effect of a relaxation frequency l/T is to replace kBT by kBT + l/1rT in (38). where kH is the projection of k on the direction of the magnetic field.~)p sin (]hre F _ ~).03 in the foregoing conditions. The distribution of population tends to average out the oscillations in the magnetic moment. Here S is the area of the section of the surface at k 1I = constant. it is apparent that in (37) we should make the replacement (39) ').
In recent years the range of experimental work has been extended to include a number of alkali and noble metals. The de Haasvan Alphen effect is a powerful tool for the investiga tion of fermi surfaces. so that after multiplying (44) by 2 we have (45) X 2EF This is the Landau diamagnetic susceptibility of an electron gas. au (41) (aU) = !(p. Phil. CH. 43. This result is valid even for nonquadratic fermi surfaces.. Pippard.247r 2c okz.H. as well as transitiongroup metals. ox = ~ (oM) / H = . For the whole fermi surface the average diamagnetic susceptibility is (44) X = 2 247r c (2k F) = kF =  2 The total electron concentration. 1006 (1952). Onsager.H2../~)(i~H)2 = T\. because low values of EF or of S make for less difficult experiments in terms of the values of T and H required Landau Diamagnetism. at the extremal section. Mag.~p. 2 p. in a magnetic field is given by (27). Now (42) and (43) (oM) = dH = i~p. earlier it referred to the slice okz. DYNAMICS OF ELECTRONS IN A MAGNETIC FIELD. counting both spin orientations. LTP. The earlier work was largely con cerned with semimetals or with small pockets of the Brillouin zone. Note that n now refers to the whole fermi sea.m H (2mEF) • 67r ep. is given by 37r 2n = (2mEF)7I!. we have... SEMICLASSICAL DYNAMICS OF AN ELECTRON IN A MAGNETIC FIELD4 If the fermi surface is itself independent of the magnetic field H. The change of energy aU of the slice okz. When is averaged over a cycle between the extrema n . For free electrons (40) S 7rk F2 = 27rmEF. from (27).. 11 225 apart from phase.m 2 p. . we believe following Chapter 9 that we are justified except at special 4 L. A.no ±!~H.
L is the velocity in the plane . 3. FIG.226 kfJ QUANTUM THEORY OF SOLIDS ka.. points in k space in describing the motion of an electron in the mag netic field by (46) k = (e/c)v X H. We rewrite (48) as (49) it = (e/c)vJ. therefore the velocity is always normal to the constantenergy surface (Fig. where V..k{J plane.. Cyclotron Resonance FrequencyGeometrical Interpretation. The transformation K ~ 9 is independent of the shape of the energy surface. The lorentz force causes k to change only along the curve of constant energy formed by the intersection of the constant energy surface with a plane . the wavevector component parallel to H. From (48) we see that 9(t) is derived from K(t) by multiplying K(t) by c/eH and rotating by r/2. Thus in k space the electron moves in a plane normal to H. is constant and is determined by the initial conditions. the value of kH.H. where the righthand side is just the lorentz force. The magnetic field is normal to the ka. Let K be the twodimensional wavevector in the section and let 9 be the components in real space of x in a plane normal to H. We have seen that (47) Vk = gradk e(k). sider two orbits in the same plane section in K ~pace.LH. where e(k) is the energy as calculated in the absence of the magnetic field. it also describes a similar orbit in real space. 3). Con one orbit of . as the electron describes an orbit in k space.LH. Then (46) may be written (48) It (e/c)e X H. Motion of an electron in k space around an orbit of constant energy.
where See:) is the area in K space of the orbit of energy e:. the rate at which it may be said to sweep out the area (Fig. 11 227 energy e: and the other of energy e: of these orbits is (50) ~e: ~K + ~e:. c dS eH de: or. Let T denote the period of the orbit. Geometrical representation of the cyclotron frequency. ~e: . the effective mass of the orbit for cyclotron resonance. 2r de: which relates the cyclotron frequency and the effective mass to the ktJ E + OE II ka FIG. then T(eH/c) ~e: is equal to the area of the annulus (dS/de:) ~e:. which is constant at constant ~e:.DYNAMICS OF ELECTRONS IN A MAGNETIC FIELD. Thus (52) T = .Vx: . 4) between the two orbits is (51) K ~K (e/c)pH ~E/p (eH/c) ~E. (53) We = . are~ in ~ .Ivx:e:\ . for the cyclotron frequency. 4.P Imagine an electron moving on one orbit because of a magnetic field. CR. Thus (54) me = 1 dS .= . ~e: The separation in K space .= 2r T 2reH 1 cdS/de: eH mec This equation defines me. the space of the orbit at energy e is denoted by S(e).
(58) T p' dq = The quantum condition is (59) Tp . Thus by the stokes theorem. (72). Thus. where the pairing condition makes the effective charge 2e. dq <f. dp = Jcurl A . with orbits in k space separated in energy by We. we have directly for the area of allowed orbits (61) s= 211"eH (>. Lifshitz and to Onsager. dq = Tee1(p T p X X H + A) . dp. (55) Tp . where>.. T p X dp = 2<f. is the flux contained within the orbit in real space. in usual units.. where <f. is an integer and 'Y is a phase factor having the value! for a free electron in a magnetic field. apart from sign. (60) (211"e/e)(>. This result. + 'Y). do = JH . Now (56) H . Quantization of the Orbits. due to L M. 211"(>' + 'Y). where we have integrated (3) to give k = ee1(p X H) apart from an additive constant which vanishes on integration. c + 'Y). The periodic character of the motion leads us to expect that the energy levels are quantized. The vector potential is A. We have assumed that the effective hamil tonian in a magnetic field is obtained by the substitution k~p ec1A in the energy e(k). may be contrasted with the quantum of flux he/2e observed in superconductors. The result (60) is translated into k space by multiplying by (eH/e)2. dp = H ..228 QUANTUM THEORY OF SOLIDS geometry of the fermi surface. the different orbits differ by integral multiples of the unit of flux 211"e/e.. . We may show this by the Bohr Sommerfeld method. he/e. here do is the area element in real space. Another form for me is given in Eq. or. further (57) TA ... dq T(k + ec1A) . do = <f.
It is essential to recall from the chapter on Bloch functions that the energy is periodic in the reciprocal lattice. the surface will be closed and all orbits in a magnetic field will also be closed. The cyclotron resonance frequency gives us dB/dE. CH.s We have seen from (48) that as an electron describes an orbit in k space it also describes an orbit in real space. 1960. the righthand side is pcSjehH. Chambers. Kaganov. The existence of open orbits comes as a surprise at first sight. The surfaces are not confined within one Brillouin zone. (London) A270. In strong enough magnetic fields the semiclassical quantization procedure failsas the field is increased the energy levels are broadened and eventually reform into a different set of levels. At a station ary section iJS/iJk H = O. Some orbits are not closed curves in k space. 61. Roy. A simple analysis of the situation is given in a paper by A. 1. Pippard. The helix is periodic in the sense that every turn is a repetition of the last turn. Proc. the electron will describe a helix in real space. If the section of the constantenergy surface in k space is a closed curve. taken normal to H. where S is the area of a stationary section of the fermi surface. With h. Wiley. the magnetic breakthrough failure is likely to occur when we» E~/eF' where Eg is the energy gap between bands. We consider several different situations: (a) If the fermi surface lies entirely within the zone boundaries. • R. When an electron meets the boundary of a zone it simply passes into the next zone. M. B.. which is related to the velocity at the fermi surface.H eF * eH = 27r(X + "Y). thus the constantenergy surfaces in each band extend periodically through the whole of k space. 1 (1962). Soviet PhysicsUspekhi 2. the argu ment of the pth oscillatory term in the expression (34) for the magneti zation is replaced as follows: (62) p7r pcB p. G. TOPOLOGICAL PROPERTIES OF ORBITS IN A MAGNETIC FIELDs. 831 (1959). Lifshitz and M. The de Haasvan Alphen effect thus gives us the area of the fermi surface at a stationary plane . Apart from phase.LH. in The fermi 8'Urface. 11 229 Thus in the discussion of the de Haasvan Alphen effect we should replace the quantum condition (20) on the frequency by the condition (61) on the area of the orbit in k space. Soc. .DYNAMICS OF ELECTRONS IN A MAGNETIC FIELD.
. and thus an electron in a hole orbit acts as if positively charged. An elec tron in a magnetic field traverses a hole orbit in the opposite sense to an electron orbit. When the 2 lorentz force brings an electron to the zone boundary. (a) First and second space. One r L. the velocity vector v = gradk e points outward from an electron orbit. In Fig.230 QUANTUM THEORY OF SOLIDS (b) If the fermi surface consists of sections attached to separate zone faces or around separate corners. (d) If the fermi surface extends aeross one cell. these sections may be combined in the periodic zone scheme to form simple closed surfaces. 5. from one face to another or from one corner to an 0' o other. on the almostfree electron model. The simplest example of an zones. v points inward. A hole orbit is o 0' defined as enclosing states of high energy. (b) First zone on extended open orbit occurs in the rectangular zone scheme. according to the direction of H. Fermi surface in a simple multiplyconnected surface extend rectangular lattice in two dimen ing continuously throughout k sions. Sometimes it Gc is possible for a given point on the fermi surface to be part of either an electron or hole orbit. 5. For a sc lattice a possible fermi surface containing open orbits is shown in Figs. 6 and 7. as in Fig. (c) The closed orbits may be either electron orbits or hole orbits. An electron orbit encloses states of lower energy. it will continue into the adjacent cell of the ex tended zone scheme. 8 are shown schemati cally two types of sections at constant kz of such an open surface. Such a closed surface will consist of pieces from more than one cell in the extended zone scheme. almost free electron model when the fermi surface cuts into the second zone. then in the extended zone scheme the fermi surface will be a FIG. The open orbits are lattice in two dimensions on the marked 00 and 0'0'.
surface. 11 231 z y FIG. Bethe. 6. 6 continued in k space. (After Sommerfeld and x FIG. 7. The fermi surface of Fig.) Possible fermi surface in a simple cubic lattice.) This is an open fermi . CH.DYNAMICS OF ELECTRONS IN A MAGNETIC FIELD. (After Sommerfeld and Bethe.
(e) The open orbits become clearer if we tilt H slightly in the kxkz plane. (After R. FIG. Electron orbits above and below. here open orbits occur which run throughout k space. as in Fig. Left: electron orbits. Between the closed electron orbits there are open orbits unbounded in k space.) cut contains electron orbits. G. G. right: hole orbits. For a particular value of kz (intermediate between the two shown) there is a transition between electron and hole orbits. showing two sections of constant k". For such an orbit dS/de + 00. 9. showing the periodic open orbits bounding the central shaded strip. the other contains hole orbits.232 QUANTUM THEORY OF SOLIDS FIG.) . The shaded regions denote filled states. One possible type of open fermi surface for a cubic metal. for H along [100]. the boundary of the shaded regions is the fermi surface. Chambers. 9. 8. Chambers. Section of fermi surface for H in (010) plane. (After R.
as shown in Fig.DYNAMICS OF ELECTRONS IN A MAGNETIC FIELD. Chambers. {open orbit (open orbit '~( 0 ). in front of and behind the value for the section shown.U  CO 0 0 O~)/ \ ( .. As in :Fig. CH. Slice through extended BZ scheme of fcc crystal. 9. 10. separated by an aperiodic open orbit 00'. with H tilted in yz plane slightly from z direction.) . (After R. 10. (After Pippard. ) \. Regions of electron orbits (top left) and hole orbits (bottom right). The open orbits shown exist for a range of values of kH. \"'n~  1 J t • u FIG. from (53) and (54) the cyclotron fre quency We ~ 0 and the cyclotron mass me ~ 00. but with H tilted slightly away from [100] in an arbitrary direction. 11 233 x 0' o FIG..U"U . Direction of open orbit taken as x axis. G.. Open orbits also exist when H is tilted slightly away in a general direction from the normal to a principal plane.) t where S is the area of the orbit.. Periodic open orbits. 11...
They have a striking effect on magnetoresistance. The importance of the open orbits is that they act as twodimen sional conductors. \ ... ...\"" open orbit ~. '.J I \ 1"" ... ( ... neglecting spin and the spinorbit interaction.. .) (f) The situation of Fig.'\ D ... 9 is shown again in Fig. (h) An extended orbit is a closed orbit which cannot be contained within a single cell.. CYCLOTRON RESONANCE ON SPHEROIDAL ENERGY SURFACES The neighborhood of the conductionband edge in germanium and silicon consists of a set of spheroidal energy surfaces located in equiv alent positions in k space.. ..... but for a fcc lattice in real space."...J ( . .o.::. ...234 QUANTUM THEORY OF SOLIDS l~ ) O.. __ '\ I '. successive elements of the open orbit are identical. \ " "'.. Such open orbits are not in general replicated exactly as we move along the orbit.....\<"....>c. . (After Pippard.. The effect of these is considered in Chapter 14.... ... Aperiodic open orbit.. M __ M~ __ FIG. . 0 [ L __ 0[ M M~ . however the origin of the Brillouin zone is chosen. Open orbit\ t r _} 1 . . they carry current only in the plane containing the magnetic field and the general line of the orbit.. J j I. We now discuss the semiclassical theory of cyclotron resonance for surfaces of this character.. ' .~ ~ \ /~ ~. t ~) ~o~ ( End of same ... \ 0 c.... Because H lies in a plane of high symm~try....~\... but for a fcc crystal. (g) The situation of Fig.. 12. Alternate periodic open orbits are traversed in opposite senses. . ... 12.... 10 is shown again in Fig... 11... . as we shall see in the following chapter.._ .. ) I ..... 1 ~ .. This is called a periodic open orbit.. and they are called aperiodic open orbits..A:::.. '1.
.2.2 cos 2 fJp~ + """'t sin 8 cos 8p.ec1A). there are roots at '" = 0 for the analogue of motio:q parallel to the field.HJ = i".. 1 (k~2 + k'll2) + 2 m. sin 8 cos 8 1_ 0 sin 2 8 .c The equations of motion of the momenta are. with and "" = eH/m..)2 = COS 2 8 + sin 8..2 cos 2 8 + "'.(x cos 8 + z sin 8) cos 8.. m.w. = 0..DYNAMICS OF ELECTRONS IN A MAGNETIC FIELD. We have further (68) + z sin 8) sin 8. = ". 11 235 We make the replacement (63). (67) ip~ = [p~. sin 2 8. ".m.". me me m.(x cos 8 = ip" = 0.2 cos 2 8 1 ".fJ~ p. CD.2 sin 8 cos 8p~ + """'t sin 2 8p~.. ip.!. the mass for motion in the xy plane. m. in addition..iw " this set of equations has a solution if (69) ".2 "'e"" "..2 sin 8 cos 8 ". where e(k) is the energy in the absence of the magnetic field: (64) 1 e(k) = 2 m.c. With time dependence e. A" = H(x cos 8 + z sin 8) describes a uniform magnetic field H in the xz plane at an angle 8 with the z axis. Cyclotron resonance in metals is considered in Chapter 16. From (70) we see that the effective mass me de~rmining the cyclotron frequency is (71) 2 2 (. is the longitudinal effective massthe mass for motion parallel to the z or figure axis. "'e = eH/m... The vector potential (65) A~ A. = u".2 _ "'e"" or (70) = ".2 . . Then the transcription (63) gives (66) H = 21 p~2 me + 21 [p" me ec1H(x cos 8 + z sin 8)]2 + 21 p.. e(k) ~ H(p . where me is the transverse effective mass of the spheroid. k~2. . that is.
Pz) JJdpx dpll J TeaS de t :~.(. '1. 4. Show that (77) is the cyclotron energy. 3. Show further that if '110 is an eigenstate of H having energy Eo. Find and solve the quantum equations of motion of a free particle in a uniform magnetic field. 2.dl. here dl is the element of length in k space.236 QUANTUM THEORY OF SOLIDS PROBLEMS 1. k Xk = _ ieH ~. Consider the hamiltonian of a manybody system: (75) H = 2~ 4P.. then (P x iPlI )vo = '111 is an exact eigenstate of the manybody system with energy + El Eo + We.2 + . For the magnetic field H parallel to the x axis of the spheroidal energy surface (55).ec1A.L' . .. may be written as (73) Show that the area of the surface S(€. compare this result with that deduced from (71). using the gauge A = (jHYiiHxiO).1 Xj). where 6. so that (74) eH ae' in agreement with (52). Show that the period of an electron on an energy surface in a magnetic field is (72) T= c . show that (76) Form P We (e/mc)P X H. evaluate the area S of the orbit in k space and calculate me. where Pi = Pi .~ ~~ c . with A for a uniform magnetic field H. 'fV.4 V(Xi . P ~ Pi.
but somewhat complicated. thus normal to the axis of the wire. Pioneer papers dealing with the quantum theory of charge transport in metals include those by J. A uniform magnetic field Hz is applied along the z axis. The analysis of the experimental results bears directly on the shape and connectivity of the fermi surface. In Chapters 16 and 17 we treat several interesting. which we shall refer to as the standard geometry.12 Magnetoresistance In this chapter we consider an important transport problem the electrical conductivity of metals in a magnetic field. Kohn. In these conditions the details of the collision processes are suppressed and the details of the fermi surface enhanced. But the startling highlights of the observed magnetoresistive phenomena in solids can be elucidated qualitatively by relatively elementary methods. The classical theory of magnetore sistance is developed rather fully in the books by Wilson and by Ziman. 1227 (1957). in gases._/ iF which is usually studied in the following geometrical arrangemen : a ~ long thin wire is directed along the x axis. A large effort of theoretical physicists in recent years has gone into the deriva tion of improved solutions to transport problems. ~ The effect of greatest interest is the ~JUagnetoresista~e!. problems by classical methods. M.JETP 6. Lifshitz. plasmas. Rev. 109. In the geometry described. The most interesting experiments are those carried out at low temperatures on very pure specimens in strong magnetic fields. z By magnetoresistance we mean the increase in the electrical resistance of a metal or semiconductor when placed in a magnetic field. Phys. and metals. Luttinger and W. and a dc electric field Ex is established in the wire by means of an external power supply. M./' 237 . the effect of a weak magnetic field (Iwelr « 1) is to increase /7\ . Soviet Phys. as here the product Iwelr of the cyclotron frequency and the relaxation time may be »1. 1892 (1958) and by 1.
ZO: In very strong fields. AUt Mg. There are geometrical situations possible for which open fermi surfaces do not contain open orbits. (a) The resistance m~y saturate. and Mo. thus T is lengthened by 10 3 and in the same magnetic fie~. Ga. N a. (c) The resistance may saturate)n so~~ry~1~L<!~_~~tj. this category is known to include C!lJ. for m* = m and H = 30 koe we have lWei ~ 8 X 1011 . On dimensional grounds we could not expect much else. Many interesting features can be explained by an elementary drift velocity treatment or by simple extensions thereof. bearing in mind that a term __linear i~. so that IwelT ~ 0.4g. and Li. We note (I SSP. 238) that in copper at room temperatureihe ~eIaxation t. Cd. and Pt.ime is ~2 X 1014 sec. Saturation occurs for all orientations of the crystal axes relative to the measurement axes. W. Sb. The value of mag iletoresistance as atool is that· it tells us whether the fermi surface is closed or contains open orbits.__ ~~~_. (b) The resistance may continue to increase up to the highest fields studied for all crystal orientations.Q_Q. p. as illustrated _~ 1. Crystals are known in three categ~.02. We shall see that the first category comprises cry'Stals wl~~egaiSllrf~._such as In. the transverse magneto resistance of a crystal may generally do one of three quite different things.g!le~tc_tield. Pb. perhaps at a resIstance of several tImes the zero' fielO value. The third category comprises crystals with fermi surfaces having ?J!~ o~Jor some directions of the magnetic field. The second category comprises crystals with equal numbers of electrons and holes.. that is. may become ~epend~nt of H./~jIl~onsistent_~ith the Q~'"}Jllt~~e~~gt jhE. This behavior is exhibited as an extraordinary anisotropy of the resistance in a magnetic field. not saturate in other. Zn.esl. Sn.ljmiJ'jIem wifuesp~ct_to the sign Qft~ ll!3. At 4°K the conductivity of a fairly pure crystal of copper may be higher than at room temperature by 10 3 or more.238 QUANTUM THEORY OF SOLIDS the resistance by an additive term proportional to H2. AI. that is.. term may be of the order of magnitude of (WeT) 2 : (1) ~ The additive (WeT) 2. TI. We give this /~ an ~ .§I. such as Bi. for IwelT » 1. and in which directions the open orbits lie. often very ~ erystal djrectiQ!!~.
1 Single CarrierType I sotUipfCiijjective ~f ass and Constant Relaxation Time.. according to ISSP. 12 239 A 1\1 ~~I~ :. where 'T is the relaxation time of the charge carriers. We take H . (3) m*(t+ fVJ » = e(E+~VXH). t t :~ 1000 \~ ~ ~ [001] +100 0 9 [110] 500 [111] +500 t o FIG.MAGNETORESISTANCE. The drift velocity v is defined as the average carrier velocity: (2) v = N~Vi' . Chapter 10. for a single crystal Au specimen with current II [110]. (From Gaidukov. 1959. 1.. The relaxation time is approximately related to the mean free path A by A "" where is the mean magnitude of the particle velocity.5 kG. The equation of motion of the drift velocity of a gas of carriers having isotropic mass m* is. CH.) treatment first as a preliminary to the application of more detailed transport theory. I~ II 6 ) ~ j 4 ~ \~1 2 . Variation of transverse magnetoresistance with field direction in a field of 23.
~ If we set (5) {p.~Ex)./ ~ p. for H z.tVx.Ex.~~~ jy = jz = O.~theory of the thermodynamics of irreversible processes. v p.Ey . where n is the carrier concentra tion. Jx = fie~!!. Vy = p. I 1 . o 1 e The components satisfy the condition as a general consequence "~f ti1.. thus (12) (l1)J':(~)::..'' Ez = O.. . or (8) Vx = 1 + (Ex + tEy).. so that ) m*~E+~VXH._'"'"_..H/e:. = WeT. In our standard geometry the boundary conditions permit current flow only in the x direction. Vz = Thus.. From (8) we see that the boundary conditions can be satisfied only if (13) Ey = tEx~' ~. + ~2 (Ex + ~Ey) = nep. 1 nep. v = O'}..~. .= eHT/m*c Vy = p. (7) Vx = p.t2vx..Ey . The current density component j" is obtained from the velocity component v" by multiplying by ne. The conductivity tensor component (T"II is defined by (9) From (8) we have. From (10) and (13).. then (4) oecoroes (6) Vx = p.. ~~...tEy ./"..E z. ~ eT/~'*'j .. (4) QUANTUM THEORY OF SOLI[ In the steady state v eT v= 0.~Ex . p.240 in the z direction. The field (14) is known as the hall .t2Vy.p.1 + ~2 (E y .~.. on solving for Vx and Vy.E~"/ t 1 iJ = ~ t 1 + t2 ( 0 1 o o ). y .Ex p.. .Ex + tVy.
But usually the relaxation time depends on the speed Vi of an individual carrier.~. ne~ Hz.!lard ___..Jx = ~ x. so that we cannot expect to describe the motion of the carriers in terms of a single drift velocity. s electrons and d electrons. The resistivity tensor p is the inverse of the conductivity tensor. With two carrier types the identical hall electric field cannot rectify the orbits of both carrier types at once. the standard geometry with jy = 0 we have from (17) that (18) · f p= . etc.heJllagnetic fi~l<i. In any field the steady state drift velocity equations are. A simple and important alteration of the drift velocity model is to introduce a second carrier type. or nearly always.. There is a special value in treating the problem of two carrier types in the high field limit. Then the ~~~." ~~TsUf~lt of the"h1). even though the conductivity tensor components (10) do involve the magnetic field..e stan. our model gives zero for the transverse magnetoresistance. tlXII is the Xvth minor. That is.: I }' (15) PXII = tl XII / tl.l!~~~The experimental situation is that a transverse magneto resistance is always.J.. Jz. open orbits and closed orbits. E E'Y = . whic}!just balang_~sthe lor~ntz force of). CH. ne~ nec 'onTY·for in agreement with (13) and (14). O.. and tl = . pxv!~. 0 '''' J  '. Ex = Jx.. ' . This is an important practical situationthe two carrier types may be electrons and holes. The absence of magnetoresistance on this____ l!todell!!.e'kl~~~alicalquantity v included in the equations of motion. where tl is the determinant of (16) ff. Two Carrier TypesHigh Field Limit. 12 241 ~./r ~ thus in this geometry the effective conductivity in the x direction as calculated on our model is independent of the magnetic field in the z direction. by analogy ..h.lt'eleCfticfieTa E y .. (ne~)3 1 + e 1 Thus for ff given by (10) the resistivity tensor is (17) This is consistent ~lth' (6)~from which p is most easily found.MAGNETORESISTANCE. For 1 . The components are given by so tha~ Ex. = . observed. The balance can be maIntained tlieori.L ne~ (1~ 0 f ~ 0) .
(19) (20) VI V2 = (erIlmt)E + (ert!m!C)Vl X H.nQL s~~ are equa. But if Uy:t. (21) E:t.nl)ec E:t. C E:t.:t. where the fermi surface has been constructed with parts in two zones.242 QUANTUM THEORY OF SOLIDS with (4). . Equality of electron and hole concentrations can also occur in metals of odd valence if the primitive cell contains an even number of atoms. and concentration nl. =  (er2/m:)E . Without Ey the effec tive resistivity becomes simply l/uu. there is no hall voltage E y.l ~U!!lbers of h~_!!'~_~~~trons. as jy = 0 without benefit of an Ey. = 0. where U:t. Thus (22) jy == nleVl y . 7"F whence (23) I uy:t.(er2/m:C)V2 X H. Fig. see. Under these conditions it is observed that the transverse magneto resistance does not saturate.. for example. is given by (10) and in this limit (24) U u '" nlel ( = H2 11'11 1 + 11'21 ' 1 ) where n = nl = n2. The topology of the equality of electrons and holes is easily understood in two dimensions. We now consider fields such that IwcIITI » 1 and IW c2IT2» 1. but with the total filled area just equal to the area of one zone.n2 eV 2y = (n2 . whence for the x compo nents of these equations we have mt.nl)ec/ H·I This is a crucial result. The carriers of mass type 2 are taken to be holes. ~ the trQ!lsverse magnetore8i8ta1tee d668. There is one point in k space in each Brillouin zone for each primitive cell in the crystal. provided there are no open orbits. H +V2y C = O. = O. Then we can neglect VI. ~ DIvalent metals navIng one atom (and two valence electrons) per primitive cell will necessarily have equal numbers of holes and electrons (n_ = n+). = (n2 . H +Vl y = 0. because it shows that for equal numbers of holes and electrons Uy:t. V2 when they appear on the leftband side of (19) and (20). 2. where the carriers of type 1 are taken to be electrons of effective relaxation time TI.
integrating over the surface of the section.. if we may neglect collisions. bounded by planes normal to H.MAGNETORESISTANCE. = aec(Ex/H. 12 243 (b) Holes in o first zone (c) Electrons in second zone (a) General zone FIG.) fdk x dk. The integral on the righthand side is just the area of the section. ec (28) Jy = H (n+ . This result (23) holds also for a general fermi surface.. (c) One electron orbit as connected. of the fermi surface from equilibrium is given by (26) ~e = ckyEx/H.(e/c)vxH. at least in the semiclassical approximation developed in the preceding chapter for the dynamics of an electron in a magnetic field. Thus the shift because ky = . so that J y is the number of states in the section times ecEx/ H. with a states per unit area of the section. . recalling that a f dk x dky dkz gives the number of states in the volume. For the whole fermi surface we integrate over dk z. 2. The resultant current in the y direction is. (b) Hole orbit as connected. We consider a thin section of an electron fermi surface. (27) J.n_)Ex. (a) Fermi surface in two dimensions enclosing an area equal to the area of one Brillouin zone. CH. In constant fields Hz and Ex the energy e of an electron in the section changes according to (25) e= eVxEx = ckyEx/H. = ae fdk x dk. within an additive constant. :. Thus the total current density is .
. this is not the most general situation. In strong magnetic fields an open orbit carries current essentially only in a single direction in the plane normal to the magnetic field. thus the open orbit cannot be saturated by the field. The absence of saturation in certain directions may be explained in terms of open orbits. LTP. With (30) we obtain 111 = 0 when (31) _ Ex ~ + sEy = 0. Ex . the field strength only affects the rate kx at which the open orbit is traversed in k space. as enumer ated earlier. The strength of the magnetic field does not affect the average carrier velocity Vy on the orbit. ~ a: not considering the contribution of open orbits. (lxx. in agreement with experiment. pp. Suppose that for a given crystal orientation there are open orbits parallel to in real space these orbits carry current parallel to the y axis. this defines s. _ We recall that With the contribution of the open orbits we have ~l H. etc. The applicability of (29) and (30) as high field limits is demonstrated by Pippard. and by the above argument the magnetoresistance does not saturate. For n_ = n+ we have (lyx = 0.~l o ~). let us write the op~norbit conductivity as equal to snep.0 S o ~) Here we have dropped ~2 in comparison with s in the term U yy • We have assumed for convenience that U xz = 0 = (lzx. We note that an open orbit parallel to kx has an average velocity component only in the y direction and does not contribute to U xy . We can associate a conductivity U yy with the open orbits. 9395. in agreement with (23). or Ey ~.244 QUANTUM THEOHY OF SOLIDS where n+ is the hole concentration and n_ the electron concentration. (30) a '" ne" ( . The high field limit of the conductivity tensor (10) is ~2 ~l ~2 (29) If ~ nep' ( . INFLUENCE OF OPEN ORBITS I t is a remarkable experimental fact that in some crystals the magnetoresistance saturates except for certain special crystal orien tations. This result is independent of crystal orientation and explains the second variety of magnetoresistive behavior.
+ rIE. For this orientation the magnetoresistance saturates.MAGNETORESISTANCE. Suppose the crystal is oriented so that the open orbit carries current in the x direction.l.) nell (1 + D ~2E. + l)neJ.Ez. By the geometrical rules discussed in Chapter 11 this requirement is that the orbit in k space must run in the kz direction. except when there are open orbits in the kx direction. If the open orbit runs in a general direction in the xy plane. again in the limit ~ » 1. (s ~l ~2 o ~). and jy = 0 if Ey_ = (35) ~Ez.l. "" nell(~2E.l. but increases as H2. = neJ.neJ.l. S1 ~1 (36) a : : :. We have thus accounted for the third variety of magnetoresistive behavior. The circumstance that the magnetoresistance saturates in suffi ciently strong magnetic fields.ISl + ~) S2~ Thus the magnetoresistance saturates except when the open orbit carries current almost precisely parallel to the y direction. Crystal dis tributions tend to reduce the exponent towards 1.~I so that jx :::::. whence the effective resistivity is (33) ~2 s p:::::. CR. ( _~1 o Ez/~S2. S2 ~). the conductivity tensor has the form. s +1 The resistivity does not saturate.. as illustrated for gold in . explains the extraordinary anisotropy of the transverse magnetoresistance observed in single crystals.sIEz.' neJ. namely nonsaturation only in special crystal orientations.l. Then (34) 5 ~ nell ( . neJ. The anisotropy is a striking feature of the experimental results. This givesjy = 0 when Ey = (37) jz we have Ez 4. 12 245 thus (32) j.
ThE ~e = f. (4 if the relaxation time T is a constant. Then (39) ~e = e J ~ co dt E . Soc. then the electric current density is (38) •= 2e 1  (2~)3 J d 3kvh 2e = (2~)3 J dlo d 3kv~e de' where ~e is the mean energy gained by the electron from the electric field E in the time between collisions. except in special directions in which the metal may simulate a twoband metal with equal numbers of electrons and holes.246 QUANTUM 'I'HEORY OF SOLIDS Fig.t dt" F . It is a simple matter to generalize (39) to problems in which T is known as a function of k. Here e1tl!T is the probability that the last collision took place at least a time ItI from the next collision. taken at t = O. A proof is given by H. v(t)et / T . 1. Budd. If the distribu tion is f = 10 + h. We first work with a version of the theory linearized in E. In directions in which open orbits exist the resistance does not saturate. in which magnetic effects appear only in second order. I t is assumed that immediately after a collision the electron is in the equilibrium distribution. The general nonlinearized result of Chambers [Proc. Thus highfield studies of the angular dependence of the transverse magnetoresistance in single crystals can provide information on the presence of open orbits and on the connectivity of the fermi surface. TRANSPORT EQUATIONS FOR MAGNETO RESISTANCE The Chambers or kinetic formulation of the transport equation is rather more revealing for the magnetoresistance problem with a general fermi surface than is the usual iterative formulation of the boltzmann method. Phys. Rev. v(t") for (48) is the energy gain from the force F between times t' and t in the absence of collisions. T is the relaxation time. f. (London) AGo.~e(t'» exp  dt' ( it t' As (47 ds ) T(k(s» . 458 (1952)] for the distribution function is (40) Tl (4{ 1= where (41) i t 00 T(k(t'» lo(e . and lois the equilibrium distribution function. An electron in a high magnetic field will traverse a closed orbit 1 Thu (49) . Phys. in other directions it does. 127. that (40) satisfies the boltzmann equation. where 10 is the equilibrium distribution.4 (1962).
Thus there is a longitudinal magnetoresistance. We expand vp(t) = vp(o) + tvp(O) + jt 2iip(0) + + The integrals are trivial and we have (46) f~GO dt vp(t)e t / T"= TVP(O) + T2zjP(0) + T3iiP(0) 2 As an example. We are concerned with ° f~ for constant relaxation time T. it I .. then (v x ) = 0. which always saturates.~f  = ~yy = ~yx = 0. for a freeelectron gas is obtained by using e n 4 (48) The term in Vy mvy e . consider (47) ~xy = (271")3 2e f o d 3k Vx dl ds (TV y + T2· Vy ·· + T3Vy + . If open orbits are present in the kx direction. by symmetry.~ """:1'" (43) ~zz .. Then O'YV ~ in the highfield limit.247 and tp. The term in Vy vanishes on integration.vxH. (45) GO dt vp(t)e t / T ..e integral (39) will approach zero in the plane normal to the magnetic field to H (= II z) may be replaced by the average orbit at collstant k H • Thus if the magnetic ~zx = ~xy ~ . Thus to O(H) (49 ) 2e2 2 ~xy = (271")3 WeT f ) 3 2 dlo d k Vx ds = WeT~xx(O . (27r)3T o d 3k v/v z ) dl ds· This value of ~zz for H = (44) 00 is in general lower than the value 2e 2 ~zz(o) (27r)3T f 3 2 dl o d k Vz ds for zero magnetic field by an amount depending on the anisotropy of Vz around the orbit. just as found in (30). c fly WcVx. Let us apply the kinetic method to transverse magnetoresistance in weak magnetic fields such that IwelT «1.). but (v y ) ~ 0.
.. next (39) Soc.l0) + + T2V. + T 2'Vy + T 3Vy + . . then (v x) = 0. just as found in (30).. The term in Vy (48) mvy 2 . 12 247 \ " the Ltion ermi does iions . . (45) 00 dt v. which always saturates. Then O'yy ~ in the highfield limit. '). consider (47) (fxy 2e = (21\")3 2 f 3 di0 d k Vx de The term in Vy vanishes on integration.lt)e t / T .. by symmetry. 4 Thus to O(H) )rbit 1 . We expand ~ility VI£(t) = VI£(O) + tvl£(O) + it 2ii.lO) T As an example.vxH. If open orbits are present in the kx direction.lt)e t / = TV. d k vz(v z ) dio de' )n is leral lann We 'ibu . but (v y ) ~ 0. (49) (fxy 2e 2 = (21\")3 WeT f 3 2 dio d k Vx de = WeT(fxx(O). We are concerned with ° f~ for constant relaxation time T. the This value of (f zz for H = (44) 00 is in general lower than the value 2e 2 (fzz(O) (21\")3 T f 3 2 dio d k V z de Vz ctric Ltely rhen for zero magnetic field by an amount depending on the anisotropy of around the orbit. Let us apply the kinetic method to transverse magnetoresistance in weak magnetic fields such that IwelT «1.l0) + T3iil£(0) + (TV y . the component parallel to H (= Hz) may be replaced by the average (vH(k H » taken over the orbit at constant kH' Thus if the magnetic field is in the z direction.. for a freeelectron gas is obtained by using the ~ium ~7. (42) (fxx (fxy (f yy 2 (43) (fzz = (21\")3 2e T f (f yx 3 °. The integrals are trivial and we have (46) f~ 00 dt v.LIDS MAGNETORESISTANCE. Thus there is a longitudinal magnetoresistance.bers many times between collisions and the integral (39) will approach zero for the velocity components in the plane normal to the magnetic field H. c e Vy WeVx. CH.
Tl = T2. For example. but assuming ml = m2. We have (50) Vy weVx We 2Vy . Wiley.n 2) 2 2] + n2)eIJ.  . 3. _ (nl 1 [ (n 1 .248 QUANTUM THEORY OF SOLIDS The term of O(H2) in Uxx or Uyy is obtained by evaluating vy. 2. so that (51) Uyy = Uyy(O) . r ae d 3k ae (ae .(W eT)2u yy (0). 1 + ~2 1 + (nl + n2)2 ~ E. Discuss the magnetoresistive properties of a conductor with a fermi sur face in the form of an infinite circular cylinder.c.r. These results for the freeelectron gas agree to the appropriate order with the driftvelocity treatment given earlier. for example. Consider the magneto resistance of the twocarriertype problem for all values of the magnetic field. but the present formulation can be applied to general energy surfaces. I . Show that the transverse magnetoresistance vanishes for a conductor with an isotropic relaxation time and an ellipsoidal mass surface. The quantum oscillations in transport properties have the same origin as the susceptibility oscillations in the de Haasvan Alphen effect considered in Chapter 11. 7/ = kll . to evaluate U xy we need (52) v. An elegant derivation of this result is quoted by Chambers in The fermi surface. ae ak ll ak y 2 =  eH (ae a e c aky akx ak y 2   ae a e) 2 ' akx aky 2 2 whence to O(H) we have a wellknown result: (53) U xy = 3' 2e (27r) 2 eHT2 c. Show that for the standard geometry (54) J. PROBLEMS 1.ak x aky ak x ak y 2 2 • ak x aky ae a e) For We > kBT and WeT » 1 an oscillatory behavior is observed in the conductivity components.
Brooks. Our confidence in our ability to calculate the electronic proper ties of transition metals is low. Solid state physics 1. Woodruff. Ham. 165 (1958). 82. R. Nuovo cimento supplement 7. S. among which are: 1 There are a number of useful F. 4 J. 127 (1955). Reitz. Solid state physics 7. Phys. 128. 3 T. In perhaps five years time the situation for the simpler metals will have stabilized somewhat. The monograph would also develop in detail computational aids and instructions. 100 (1958). Ham. Solid state physics 4. O. 2524 (1962).13 Calculation of energy bands and FerITli surfaces The title of this chapter could more appropriately be used as the title of a substantial monograph which would derive and evaluate the principal terms and corrections which contribute to the one electron energy band structure of a crystal. Callaway. Such a monograph would be extremely useful. and pertinent experimental data are being acquired at a substantial rate. S. ( c) The calculations on other metals are improving rapidly because of improvements in modified plane wave methods. and it would contain a careful comparison of the theoretical calculations by various methods with the experimental observations. 2 249 . Solid state physics 1. I) H. 1 (1955). 367 (1957). reviews. Rev. J. F. but if compiled at the present time even by a committee of the experts learned in the field. There is now no such monograph. it would have several defects: (a) The relevance of manybody corrections to the band struc ture and to the interpretation of the experiments is known quite incompletely.
Those which we are going to discuss in detail are the WignerSeitz method applicable to the alkali metals. 1002 (1934). 46.: E. Inside the ion core where the potential is large it is approximately spherical.71A. Rev. and various modified plane wave nlethods applicable over an extraordinarily wide range of crystals. Phys. 355 (1959) and the unpub lished reports of the group associated with Slater at the Massachusetts Institute of Technology. 4'1. Harrison.1 the variational method of Kohn has been applied widely by Ham. 1190 (1960). Physics 23. Each polyhedron con tains one lattice point and is a possible choice for the primitive cell. the ionic radius is given as 0. is discussed by Ham. The first realistic band calculations were carried out by Wigner and Seitz 8 for lithium and sodium.95A or 0. Thus to a good approximation the potential V(x:) may be taken to be spherical within each polyhedron.28A. as extended by Brooks. We can also give a good idea of the accuracy of the methods. 804 (1933). 509 (1934). Na. Bardeen. 46. Phys. A. THE WIGNERSEITZ METHOD We consider first the state k = 0 of the 3s conduction band of metallic sodium. Rev. 6. 7 But what we can do in one chapter is to develop the principles of those methods which give a deep physical insight into the nature of the wavefunctions in the crystals to which the methods apply. Phys.. Wig ner. Seitz. . Thus the potential energy is small over most of the volume of an atomic polyhedron. 43.6A. The point k = 0 is the special point r. At room temperature the crystal structure is body centered cubic and the lattice constant is 4. Chern. 1. J.367 (1938). Rev.(r(fQrbcc) ne~arest neigh~The atomic polyhedra thus obtained are shown in Fig. group. J. An ion core is found at the center of each polyhedron. The distance between nearestneighbor atoms is 3. if the state lPo (at r) is 8 Li: F. This modest program does not by any means exhaust the methods which are used in practice and which give excellent results: the method of Kuhn and Van Vleck. In the bcc and fcc lattices it is possible to fill the whole space with q'Uasispherical 01 hedra 1)_ constructing planes Ise' e mes w IC Join each atom to its ~~~~. Repts. Pincherle. In sodium the halfdistance is 1.LT. Phys. 118.5 an augmented plane wave method has been used extensively by the M. E. Phys. The ion core is often small in comparison with the halfdistance to nearest neighbors.85A. Seitz. but the core potential is only strong over less than 0.250 6 QUANTUM THEORY OF SOLIDS W. Wigner and F. 400 (1935). Rev. Prag. L.98A.
...) / . The boundary condition (1) is replaced by (2) \ ~ aT (acpo) = r. Uo is the sollltl(Jlll [1 Thus :r (r2 :r) + V(r)] uo(r) eouo(r).1// I II 1/ ________________ y 1/ L / (b) I I (a) FIG. The spheres are known as ~~s. The state is also periodic with the period of the lattice. acp_~ = an o... ~.. 0.' .49a.....::'/ / //" I ". ~ ... 3 ia 3 ../: I ~~ I II I II I I < I .::. for the bcc lattice of cube edge a the radius Ts of an 8 sphere is determine~ ~ . ___+__ __ 'V I I I . 1... CH. 13 251 / ///jjI I f': ~I/ . . In the actual calculation Wigner and Seitz replaced the polyhedra by spheres of equal volume. : I I I I I I I fI I I I I I i / /: I I I I I I I I I I I I I I I I I 1. there are two lattice points in a unit cube of the bcc lattice. or Ts rJ 0. Atomic polyhedra surrounding an atom for structure and <iJL bodycentered cubic structure.J /// I I/ [ I _______.. it will transform into itself under the operations of the full cubic group. 4.~.:>f r.. consequently the normal derivative ofopo must vanish on the polyhedral surfaces: /.. (~faCecentered cubic nondegenerate and derived from a 38 atomic function..CALCULATION OF ENERGY BANDS AND FERMI SURFACES. The boundary planes of the polyhedral cells are related by reflection in a mirror plane through the center.
l . The potential V(r) was calculated on the assumption that screening by the fermi sea of the interaction between one conduction electron and on~core was negIlgiblewhe~th were within the same cell and was complete otherwise. C. Phys. but the model does not work at all badly. That is. This function is tabulated as a cubic harmonic by F. It is quite reasonable to neglect the possible mixture of 5g in 38 in the crystal. 612 (1947). the effect of these was approximated simply by constructing a potential V(r) which reproduced empirically to high accuracy the spectroscopic term values of the free atom. Von der Lage and H. This is a crude model of correlation effects among the conduction electrons. The function is quite constant over 90 percent of the 12 8 1J. A. 2. t 4 0 4 8 12 0 2 r (bohr units)'. about 5 ev higher in energy than 38. We assumed in writing (4) that the lowest energy solution at k = 0 is an s function. The lowest wavefunction of metallic sodium. The 3p states transform as 1'15 and are about 2 ev in the free atom. Rev. 71. The next possible solution which transforms as 1'1 is the g function (l = 4) with angular dependence described by (5) (X 2y2 + y2z2 + Z2X2) _ l(x 4 + y4 + Z4). 2. The groundstate wavefunction is shown in Fig. Bethe. it is assumed that only one conduction electron exists within each cell. The actual freeion potential contains exchange terms. Note that the boundary con dition differs from that for the free atom where u(r) must vanish at r = 00. so there is no reason why in the crystal at k = 0 the p state should be lowered relative to the s state. The potential within each 8 sphere is then just the potential of the free ion. In the free Na atom the lowest possible g state is 5g.loo 3 4 FIG. Their energy is not split in first order in a cubic field.252 QUANTUM THEORY OF SOLIDS subject to the boundary condition (2).
This effect can be seen easily by an explicit example..353. Thus ". however. Let (7) u(~) = L cn~n. we have 0 at (11) 1 + iA2 ". for example. The term in C6 gives a negligible correction for ~o 1. The electronic energy of the state Uo is generally lowered with respect to the free atom because of the change in the boundary condi tions.. For ~o = 1. .. ~o If we require du/d~ given..." 0. We now look for the ground state with thewlgiierSeiti boundary condition du/d~ = 0 at ~ = ± ~o...== e=~!2.r.. in the ground state with the usual boundary condition ~i~ I~I+ 00 the eigenvalue is A = 1 and u(~)..rul::state ~r~~~ tf) be lowered substantially. the eigenvalue is A ".. The potential in the outer regions of the 8 sphere is itself not constant. CR. n=O co The differential equation is satisfied if (8) + l)(n + 2)Cn +2 ~.!. 13 253 atomic volume. C4 = hA2 + Thus (10) ua) = 1 ." ~02. the boundary condition (2) forces the solution to look rather flat. but is e 2 /. AC n Cn 2 = O.CALCULATION OF ENERGY BANDS AND FERMI SURFACES. which is much lower than the eigenvalue A = 1 for the unbounded harmonic oscillator. Consider the harmonic oscillator wave equation d 2u d~2 + (A  e)u = 0. We set Co = 1 for a solution even in have C2 then from n = 0 and n = 2 we iA.the· ~i~nerSeitz boundary condition ~m.A ~2 2 du/d~ + 12(1 + iA 2)~4 + and cut off the series (10) at the terms 3A = A~ + t(1 + iA 2)e + .
as we saw in (6. V. Roy. The difference.8_.. 85 (1958). The theoretical calculations account moderately well for the cohesive energies and other properties. Ts2 aH m* or 2. The corrections are all large. The net binding energy is 8. but are quite anisotropic in Li and in Cs. 1.1 ev in the metal than in the atom.80).254 QUANTUM THEORY OF SOLIDS The groundstate energy calculated for sodium with ~ar = 0 at ~ about=. V.3_~s compared with tlieeiPeri mental atomic groundstate energy~. the mean fermi energy per electron is Ts (12) {eF) ~ _1_ kF2 52m* !J~ ~ (~). r. Soc. (London) A261. Phil. ALMOSTFREE ELECTRON APPROXIMATION GENERALIZED OPW METHOD ~ It has been realized for a long time that even in_~ the overall width in energy of the filled bands is not greatly different from the width 0 e ex ects from a free electron as of the s~~G~r~t!. but a fairly good value of the effec tive mass may be calculated by the k· p perturbation theory discussed in the chapter on Bloch functions. as compared with 5. exchange. This result must ollow if t e l e lC ener 0 the fermi gas is comparable with or larger than the differences in potential energy of the individual electrons. although the experimental situation is not yet as clear as in less reactive metals. Gold.3 + 2. as we expect it to. The fermi surfaces are believed to be nearly spherical in N a and K.0 ev in Na with m* taken as m. our present calculation builds in a great deal of electron correlation by taking one electron per cell. the sum of all other corrections should not be very large.1 ev. But the conduction electrons at finite k in the metal have extra kinetic energy. and correlation correc tions.13 ev.3 ev. Tram. In 1958 A. This is not entirely surprising. but nearly cancel among them selves. thus the 3s energy at k = 0 is lower by 3.0 = 6. If this model corresponds fairly well to reality. For the other alkali metals it is not a good approximation to take m = m*. A review of calculations on the alkali metals is given by Ham. Gold 9 made the remarkable observation for lead that his de Haasvan Alphen 9 A. is in good agreement with the observed cohesive energy 1. . The physical properties of the alkalis relative to one another appear to be fairly well understood.16 ev in the free atom. These estimates omit all coulomb.9n.
Phys.". the fermi surface is complicated. This circumstance is of tremendous value to the theory of metals. Lead would appear at first sight to be a complicated non transition metal. Our program in this section is to describe how the fermi surfaces are determined by this method and then to explain the theoretical basis of the method. . We find the energy at the zone boundary 1r/ a by degenerate pertur 16 J. where G1 = 21r/a is the first or shortest vector in the reciprocal lattice. Harri son. and here the perturbation will have its maximum effect on the energy. Phillips and L. the lattice constant in the direct lattice is a. W. he assumed the conduction electrons behave as if free. C. We consider first in one dimension the perturbation of nearly free electrons by the real periodic potential (13) v= Vl(eiGlx + e. Away from the boundary the perturbation will not change the energy seriously as long as the potential Viis small compared with the kinetic energy difference.CALCULATION OF ENERGY BANDS AND FERMI SURFACES. thus it is less useful in the noble metals where the cores touch.P~/ Lead has four valence electrons outside the filled 5d lo shell. Such states are degenerate in energy at the Brillouin zone boundary k = ±1r/a. using a model of free electrons weakly perturbed by the crystal lattice. 13 255 data could be explained on a nearly free electron approximation. a. Rev. Thus the perturbation mixes states differing by the reciprocal lattice vector GI. yet it appears that a simple model of nearly free electrons will account closely for the form of the fermi surface. The method applies best to crystals whose ion cores are not in contact. 118. 1190 (1960).w~~_periodic . as measured typically by G I 2/2m.iG1X ). A.880 (1959). It is becoming increasingly evident 10 that many features of the band structure of polyvalent metals may be calculated in a simple way. 116. CH. The result does not imply that the actual wavefunctions resemble plane waves.287. Kleinman. Ret. the nuclear charge is 82 and there are 78 electrons in the ion core..iG1X ) + GI ) + a(k k' V l[a(k . That is. Phys. The matrix elements of V in a plane wave representation are (14) (k'f Vfk) = VI fol dx ei(kkl)X(eiGlX + e.k' G1)J. but subject at zone boundaries to Bragg reflectio!l~JrotQ.
e (k .G 1• (15) The secular determinant is  (kIH/k) . (4) the eigenfunctions at the gap are either even or odd with respect to x.~a2m 7('2 )2 7('2 V 1 . e =~ (k . . (2) near the zone boundaries the energy is perturbed.G1 /H/k) . 3). Band structure of a linear lattice as calculated on the nearly free electron approximation.G1) (k  . 2. e= ± VI..1 related to the single matrix element ~ .e For k exactly at the boundary k 2 = (k . The features of the result are: (1) the dependence of e on k over most of the zone is close to that of a free electron with m * m.256 Ek QUANTUM THEORY OF SOLIDS TrIa \ . 3.G1 ) 2m  e = O. (3) the magnitude of the energy gap is simply 1"'.GIl VI~) V 1 of the crystal potential.G1 )2 and the equation reduces to (16) . bation theory on the states k and k .r 7('la I k First Brillouin zone FIG. with effective masses m* = (a 2 ejak 2 )1 markedly different from m and possibly much smaller than m. An energy gap of magnitude Eg = 2V 1 exists at the zone boundary (Fig.( e .G 1 )2 2m .
three. The fermi surface is made to intersect the zone boundaries at right angles. all segments can be moved to the first zone by a translation by a reciprocal lattice vector. Reciprocal lattice points are shown as dots. the boundaries are drawn. (b) Same as Fig. 4a. 4(a). which is not shown. where two waves are necessary. . The numbers denote the zone in order of increasing energy (as measured by k 2) to which the segment belongs. four. CH. All electrons on the fermi surface have the same energy. and fourth zones. A circle is drawn about the central reciprocallattice point as origin. The circle represents a constantenergy surface for a free electron gas. near a zone edge. the fermi surface will have segments in the second. gives good results except near a zone face. near a zone corner. an elec tron moving on a constantenergy surface will remain within one zone. In an actual crystal there may be energy gaps across all zone boundaries. If this particular energy is the fermi energy.CALCULATION OF ENERGY BANDS AND FERMI SURFACES. CONSTRUCTION OF FERMI SURFACES We observe that in two and three dimensions the fermi surface can appear to be quite complicated even if the energy varies every where exactly as k 2• In Fig. and also in zone 4. First three Brillouin zones of a simple square lattice. Zone boundaries are defined as the bisectors of lines joining reciprocal lattice points. suitably orthogonalized to the core. The first zone lies entirely within surface and at absolute zero will be filled entirely. third. It is interesting to look at the several portions of the fermi surface (a) (b) FIG. 4a we show the first three Brillouin zones of a simple square lattice in two dimensions. The circle drawn might represent a fermi surface with area in zones 2 and 3. 13 257 In three dimensions a single plane wave. but showing distortion of fermi surface by a weak crystal potential.
Looking at anyone of the surfaces by itself. Harrison has given a simpler construction for fermi surfaces on the freeelectron model. The surfaces give the appearance of being profoundly modified by the crystal structure. 5 and 6. Any point in k space which lies within at lea. 6. 4 in the reduced zone scheme as in Figs. The reciprocal lattice is con structed and a freeelectron sphere is drawn around each lattice point. as in Fig. Points FIG. The orbits form rosettes when com bined with adjacent third zonesj the orbits are electron orbits. . 4J shown in the re duced zone. 4 by the appropriate reciprocal lattice vectors. 7.258 QUANTUM THEORY OF SOLIDS FIG. Fermi surface in the second Brillouin zone of Fig.st one of the spheres corresponds to an occupied state in the first zone. The orbit is a hole orbit. 5 and 6 were constructed by translating the several portions of Fig. The freeelectron surfaces in Figs. Fermi surface in the third zone. of Fig. 5. we might not guess that they result from free electrons.
CALCULATION OF ENERGY BANDS AND FERMI SURFACES. lying within at least two spheres correspond to occupied states in the second zone. 4. in another square. CH. and fourth zones for the problem of Fig. 8. in another square. four or more. These are the fermi surfaces in the second. third. 13 259 FIG. 7 we have drawn the circles equivalent to the circle of Fig. three or more. In one square. It is evident immediately that the introduction of the slightest amount of a periodic potential will change the surfaces near the boundaries. thus compare Figs. . 4a and 4b. In a square lattice the FIG. One corner of the third zone of Fig. etc. and fourth zones. we have enclosed within a heavy line the regions which lie within two or more circles. 7. The line of constant energy intersects the boundary at norma1 incidence. In Fig. Harrison construction of the fermi surfaces in the second. in the freeelectron approximation. third. 6 as it might be affected by a weak crystal potential. 4.
.I y ~ I +X I .' " . '' / . and 7 must come in at normal incidence to the boundary._~II ) / t o a h s h " Y I I / // / / _~ ~"'l"' Third zoneelectrons Fourth zoneelectrons re A z FIG..""" ... K " // ( I I I I I I·L . .w I I L I I  \... / • " r...x./ / //~. u II I I .w ~ / .~ / w ( / / / . 4. Freeelectron fermi surface of aluminum in the reduced zone scheme. . We note that the perturbation of the freeelectron fermi surface / / / ~::::.. .....my forces the condition (16a) a€ an 0 at each zone boundary.. "._ I I I I V .260 QUANTUM THEORY OF SOLIDS c existence of the mirror planes m. '/ //  '>._ I _. (After Harrison.. ...) p . 1 First zonefull 'Y / / ) / / Second zoneholes F h w Ji<:::. <.. There fore in an actual crystal the lines of constant energy in Figs.:. A possible form of a corner of the third zone is shown in Fig. " •r . 9..__ // < ... // '... // L • " '...... I> I I I s l. where n is the normal to the boundary. 8.I I I I ... b s h ) I f.t..// . / / .....A /A /'.~:::. .. 6.l..
... I I I I ....... .... .. . 10. M ... I I I ~~ ~~ .. There are two similar monsters in this zone related by symmetry to the one shown. ..A l e .. r I I r<:: ..... The crystal structure of aluminum is the fcc structure.CALCULATION OF ENERGY BANDS AND FERMI SURFACES... after Harrison... In the fourth zone only little electron pockets exist....". the radius of the freeelectron sphere is chosen to enclose three electrons per atomic volume........ because the potential . " _ _ _ _ _ _ _ _ . L __________ 1 I I I I I I I I I I A : : Fourth band FIG... I _ .  M " ............. 9......... (After Harrison. with little effect on the average energy at the fermi surface...... The second zone contains hole states with a large area of fermi surface.l ....J.. by the crystal lattice acts to reduce the exposed area of the fermi surface..... " I I Third band I I I_J . H I I I I I I I~ I I I I I ~H I I I I I I I I I : I 1 . .. ..... r_... .... The section of the fermi surface shown in the third zone is known as the monster........ I...... r K •• .... These are empty when the periodic potential is included in the calculation....... Spinorbit splittings are included with their consequent reduction of the double zone.. 13 261 .....K_.......... the monster has eight tentacles... .. 1@'~IH • ....... A relatively weak perturbation can reduce the area by one half.......... There are three valence electrons. The data on the de Haasvan Alphen effect are compatible with this fermi surface.. ............ The first zone is full..>! I r ......... CH..........) c.. hexagonal closepacked metal of ideal cia ratio. ) Second band First band f... The freeelectron construction of the fermi surface of aluminum is shown in Fig...:....e r _... The oneOPW or nearly freeelectron fermi surface for a divalent..
127.09 1. Heine.89 1. A series of developments due to Herring. the assumptions on which the calculation (13) to (16) rest are unfounded.09 1. the region outside the core and the region inside the core. M. PhY8. PhY8. inside the core the wavefunction oscillates rapidly to gain kinetic energy to cancel approximately the strong potential of the core. Heine. 122. 126. (J k T THEORETICAL BASIS OF THE NEARLY FREEELECTRON MODEL It is not immediately obvious that the nearly freeelectron model is justified theoretically. Herring observed that the wavefunction of a conduction electron in a solid is nearly a plane wave in the region between the ion cores and that the oscillations of the wavefunction near the nuclei can be represented by subtracting C. However.421 (1962).69 0.276 (1962).11 0. H. Rev.81 1.12 have shown that one can transform the hamiltonian into a modified hamiltonian whose solutions vary smoothly and resemble plane waves.93 1.89 1. acts to raise considerably the energy of the pockets. but the core potential is a great complication in finding a solution. Cohen and V.09 h Heine 1. TABLE 1 ENERGIES IN RYDBERGS IN ALUMINUM RELATIVE TO THE BAND MINIMUM FOR SEVERAL POINTS OF HIGH SYMMETRY fi p '1 '1 s« el (After Harrison) Free Electron Fermi level First zone: 1.10 and to Cohen and Heine.11 to Phillips and Klein man. there are two essentially different regions within the unit cell. 11 12 (l w e( (2 W VE tl: (2 T .72 0. Rev. PhY8.01 1.09 0.01 0. The core potential has little real connection with the solution of the eigenvalue problem.09 0. Austin. Brown. if VI in (13) is not small. Outside the core the potential energy is weak and the wavefunction is smooth. The expectation value of the potential energy of a conduction electron in a solid is usually not small in comparison with the fermi energy. PhY8. Rev. Rev. 67.. see also E. and Sham. Table 1 compares the freeelectron energies with the results of the band calculations for aluminum by Heine. Herring. 1821 (1961).262 QUANTUM THEORY OF SOLIDS C.06 1. The extent of the agreement is quite remarkable. 1169 (1940).18 (: X W Second zone: L X iE T tl Third zone: Fourth zone: W W W 1/.
we have (20) Hy. or OPW. 13 263 filledcore orbitals from the plane wave. The solution ¥topw(k) of (17) can be improved by adding terms in k + G.lcpc') = O. The core states are usually taken in the tightbinding approximation.. The secular equation is obtained by taking the scalar product of this equation with one plane wave. + vlG) ~ e.( .L (CPclei(k+G).. then (17) ¥topw(k) = eik.) l .xiCPc(x . n 1 where H CPo = ecCPc. and 2p contributions.. and we assume that eo is independent of k.L (CPcl k + G)(k G c G'I .\Ve note that L j . where G is a reciprocal lattice vector.x (CPcleik.)] A Ig n.. derived from the 3s level.le ik'X ) .. with Ik + G) = ei(k+G)'X. method.lk + G)(k + G'I .. say k + G': (21) m 'y Ie Ie IS ~ CG [ (k + G)2 n 5GG . . Let CPc denote the states in the filled core. The eigenvalues are the roots A of this set of equations. ¥topw is orthogonal to any core state CPc': (18) (CPc'!¥topw) = (cpc.Xj). is repre sented by a plane wave minus Is.opw = is n Le ~ eG Wk ~mG)2 + V(X)] Ik + G) L + G)ecCPc(x) I.CALCULATION OF ENERGY BANDS AND FERMI SURFACES.X)cpc(x) L is an orthogonalized plane wave. thus CPc(x) is a condensed notation eik. 2s.leik'X)(cpc. CR. Now. We emphasize that the true eigenfunctions do not resemble plane waves.x . L CG[ei(k+G). ~) L CG [5 GG ' . The method is called the orthogonalized plane wave. . thus (19) ¥topw = lS y n n le ~. Thus a conduction state in sodium. but the eigenvalues are close to the freeelectron energies.X)cpc(x)}.(cpc. G where CG is a constant to be determined by the solution of a secular equation. The subtraction makes it possible for the alnended function to he orthogonal to the core states. as for a very narrow core band. where the sum runs over core states CPc.
and (26) V R(X. within about 5 percent. wave equation for Xk: (23) H otfk = ektfk H OXk  Lec({)c«({)cIXk) ekXk  Lek({)c«({)clxk).X') = L(e k  ec)({)d(x')({)c(x). (24) Now define an operator VRXk such that L(ek= Thus V R is an integral operator or nonlocal potential such that (25) V Rf(x) f c d 3x' V R(x. Proc.264 QUANTUM THEORY OF SOLIDS It is useful to summarize the actual procedure by which a band cal culation is carried out in the OPW method. or we may often approximate the secular equations by considering only two or three G values appropriate for a specific region in k space. p. Heine. where f(x) is any function. 13 We can V. d. 354. . this potential is repulsive at x' near x. We then suppose that the exact wavefunction is expanded in a series of orthogonalized plane waves as in (19). We want to write tfk as the sum of some smoothly varying function Xk and of a linear combination of filledcore states ({)c. The exact tfk cannot be written as a single plane wa ve. and we form the secular equa tion (21). Because ek > ee. Heine 13 has carried out a careful calculation for aluminum and finds that the cancellation is remarkably complete. . We write (22) tfk = Xk  L We look at the which is automatically orthogonal to the core states. We take for the potential of the ion core at each ion site a Hartree or HartreeFock potential. Roy. . We may work with a reasonably large secular equation and for easier computation reduce it at a symmetry point. Soc. separate V R into the sum of 8. with H O({)c = ee({)e.x')f(x'). . 361 (1957). The core terms actually tend to subtract in (21) from the plane wave matrix elements of the crystal potential. contributions. Let tfk be an exact eigenstate of H otfk = ektfk in the band of interest. One can express the method in terms of an effective wave equation. (London) A240.
The this criterion may be said to make Xk as smooth as possible. the quantity ~ 1(<Pclxk>12.J V Xk  L (<Pel vi Xk)<PC' n We show below that if the <Pc formed a complete set of functions. which turns out to be of the order of 0. The <Pc for the filledcore states alone are. demand that Xk be chosen to minimize the expectation value of the kinetic energy (28) s n 's '1' = (xkl TI Xk)I (xkl Xk).'l'(<Pclx) o.1.T)x that (<Pel V + V R!X) = (e: .'l')(<Pclx). . thus the cancelation in practice is quite good. however. We can add to Xk any linear combination of core states without changing 1fk: whatever we add to 1fk from the core is cancelled exactly by the change in ~ <PC(<PCIXk)' Thus we are at liberty to impose an additional constraint on Xk. the scalar product of any <Pc with the righthand side would give zero. 126. For actual calculations a modified treatment of (22) has been recommended 14 W. 13 265 With (27) f defined by (24). It appears then (34) (V + V R)Xk r. This close cancellation is the basis of the applicability of the almost freeelectron approximation. the wave equation for Xk is (Ho + V R)Xk e:kXk. We could. Phys. = [VXk  with (24). here the repulsive V R cancels part of the attractive crystal potential.c<Pc. as = k k (30) OX ~ CY. variation equation is (29) If we write the variation in X o. then (31) (<PcITlx) .497 (1962).CALCULATION OF ENERGY BANDS AND FERMI SURFACES. A. Rev. a complete cancellation of V and V R. after taking the scalar product with X. It follows from (V e (32) + V R)X = (e: . for example. CH. that is. we have (33) (V + V R)Xk L + 'l')L The terms in the second bracket on the righthand side involve. Harrison. quite a good set for the representation of V over the extent of the ion core.
PROBLEMS 1. Prokofjew. Rev. ~ . We hope that oV can be made small in compari son with V.266 N OW suppose that we can write (35) QUANTUM THEORY OF SOLIDS V(x)eik'J: = LIck L eik·:r.Xi). 2. 807 (1933). Use the potential given by W. Wigner and F. or else by pro gramming a modern computer. 43. When this is true. Seitz. i where the <Pc(x . calculate uo(r) and eo for metallic sodium at r. when viewed by an electron. L. acts as an effective potential for the band or scattering problem. Phys."k·:r <pc(X i Xj) = provided that (38) eket. The message is that imperfect condensed phases are often much less disordered. Consider the 0 PW solution (39) irk = n~2eik'l:  L<Pc(clk). even if we are dealing with a mixed crystal or a liquid.Xj) i + L ecdck L e1. This residue.:r + LIck L c eik·:ri<pc(x . which is not unique.<pc(x . = 4 atomic units.ec ). We can always choose the <Pc appropriate to the par ticular local environment. of course. the scattering cross section of impuri ties in insulating crystals will be much smaller than the geometric cross section. By crude numerical integration using a desk calculator... solution of the wave equation of the form (36) 2 Then we can find a irk(X) = eik·:r + L d Ck L eik·:ri<pc(X . there are no energy gaps! Actually. (37) For Hirk = e~ik. than one might guess.x). ekU'ck rl " c c i Xj ) . eik·:r·'<Pc (X L. the <Pc are not a complete set and there will always be a residue oV(x) after an attempted expansion. i dCk = ICk/(ek . i with ek = k /2m. as corrected by E.:r +" . Thus if V(x) can be expanded in the form (35).'k.Xi) are atomic core functions.
. in Phys.. Now puo(x) is small over the outer part of the cellwhy? (c) Show that pi' N is approximately zero over the interior of the cell. ill . In what respects does the color scheme violate the crystal symmetry requirements? ht ~o at ed . Define a function i'k(X) such that the Bloch function <Pk(X) = UO(X)i'k(X). . Suppose that all core functions c vanish outside a core volume Il..aI ~n (P. z + c 2 ie . z + ~.iXIII~o2) [)r  (1 .' . and thus that (43) ~y eN""'" eo + 2~ kN 2 . 3 d d ~r where the hypergeometric function F (a[ cl z) 1 a a(a + 1) a(a + l)(a + 2) +z + ~. . . Farber) 6. 4.. CH. j) where uo(x) is the eigenfunction for k = O.  eN) ] i'N(X) = ~ (pu.tXlil~o2) = 0. a e This result shows that the core admixtures are small when the cores occupy only a small fraction of the volume of the cell.x normalized in the cell volume n. (a) Find the wave equation satisfied by i'k(X). This result is due to Cohen and Heine.. The jacket on this book is an example of artistic license. 13 267 where Ik) denotes n~~eik. Fig. (Pi'N). Show that at N the function WN(X) satisfies the equation (42) u. 10.) . (b) Consider an sstate at the point N in the Brillouin zone of the bcc lattice.X)F(t ..395 (1958).. 7.)S CALCULATION OF ENERGY BANDS AND FERMI SURFACES.. .. Then show that L l(clk)12 ~ Il/n.e. Show that the exact eigenvalue equation for the harmonic oscillator with the WignerSeitz boundary condition at ~o is (44) F(t . 3.5.(x) [~ p' + (e. Adv.
1 1 1. Using the language of chemistry. The diamond structure is based on a fcc bravais lattice (1 SSP. s + pz . and we then treat phenomena which involve the structure at the band edge: cyclotron resonance.py Il l. Si. and Ge. . with the spinorbit interaction we shall see that this 3 X 2 sixfold degenerate band edge splits into fourfold (P%like) and twofold (p~like) levels. ENERGY BANDS F OJ P d E ~ The most important semiconductor crystals have the diamond struc ture or structures closely related to diamond. and impurity states In this and the following chapter we discuss the band structures of several important semiconductors. impurity states. pz. oscillatory mag netoabsorption. Si. 3.s 14 Selll. 4 for diamond.py S  Pz. The valence electrons in the ground state of the free atoms have 2. cyclotron resonance. 1. as shown in Fig. pp. The structures of the valence bands are similar in diamond. and excitons. Energy bands. The valence band edge for these crystals would be threefold degenerate (plike) in the absence of spin and of spinorbit interaction. the configuration ns 2np2.pz + py  pz . 3637) with a basis of two atoms at 000. we say that the valence electrons form directed Sp3 tetrahedral bonding orbitals of the form s 268 jl '1 h rl Ie fl p Ie I t ~ t + pz py + Pz. In the crystal the ground state is formed from the configuration nsnp3. optical transitions. with the point of maximum energy at k = O. and Ge. spin resonance. The point of maximum energy is called the band edge. Pz. s c b a s . with n respectively.iconductor crystals: I.
. fractions denote height above base in units of a cube edge. The representation r 1 is believed to occur at the bottom of the valence band (Fig. lId lId ve ie. The points at 0 and t are on the fcc lattice. // "" of la :e. Each of the two atoms in the primitive cell of the diamond structure furnishes one electron to the lowest band. / / 'tIt" 'rr{ /" / / 'rrf" /" "" .'~/ / " . CH. yz.7 ev above r~5' It is useful to consider the form of the wavefunctions at the points r in terms of a tightbinding model. The four orbitals just enumerated have lobes pointing in the tetrahedral directions. 2) at the center of the zone. g FIG. r 1 is like an s state and is formed from the sum of the Sp3 orbitals above. This band turns out to be slike at the points r. X. [c . The valence band edge lies at the center of the zone and has the threefold representation r~5' transforming as xy. the representation may be reduced into the identical representation r 1 and the vector representation r 15. 1. xz about the center of the line joining the two atoms in the primitive cell. These orbitals form the basis of a reducible representation of the tetra hedral point group 43m.re ce lm iVO nd lId ill. and L. 14 269 "" / / /" 'rr{ / / "" / . The representa tion may be formed from p orbitals on the individual atoms. taken to be symmetrical with respect to inversion about the center of the line connecting the two atoms. Atomic positions in the unit cell of the diamond structure projected on a cube face. with the nearestneighbor atoms at the vertices. those at t and ! are on a similar lattice displaced among the body diagonal by onefourth of its length. also called a linear combination of . The antibonding combination forms the representation r15 and in diamond lies about 5. the symmetrical combination is said to be bonding. he he he Each atom in the diamond structure is at the center of a tetrahedron.SEMICONDUCTOR CRYSTALS: I.
in the crystal the eight fold degeneracy will be lifted and we will have the threefold levels r. There is no other plausible way of forming the lowlying state rl. the tightbinding functions have the form (2) 'l!f (x) = (2N)~i 0 L[9'. 'l!... bands quite low in energy. We expect r.8 is formed in the tightbinding approximation by taking 28 functions on each lattice. and the nondegenerate levels r l and r.t)]. P'II' or P" The ± sign indicates the two independent ways in which the atomic functions may be combined on the two lattices.l. We can understand qualitatively some of the features of the band structure of diamond by reference to the freeelectron energy bands in an fcc bravais lattice.. as illustrated in Fig. where Xn runs over all the lattice points of one fcc lattice. The states belong to four different representations of the cubic group. but they form an easy pictorial representation of the symmetry properties of the exact solutions. 10. We omit from the treatment the electrons of the 18 2 core.of r. with a positive choice of the sign in (2): (3) 'l!(r l ) (2N)YA L [9'8(X n xn) + 9'8(X  Xn t)].5 and r u . 1.(x n Xn) ± 9'.Xn . ± 1. of ru.l). pz. Tightbinding functions are not a good approximation to the actual wavefunctions. 'l!. Next in energy at r on the freeelectron model are eight degenerate states having G = (211"/ a)( ± 1. and 'l!t'll. are atomic or Wannier functions with j = 8. The lowest point (r l ) shown in Fig.''II.8. The rl com ponent will require 38 orbitals and is therefore expected to lie quite high in energy. The two interpenetrating fcc lattices of diamond are displaced from the other by the vector (1) t = la(l. 10. This combination is called bonding. the 9'.. because these go into narrow r l and r. The arrangement of p orbitals . ± 1). whereIn runs over all lattice points of an fcc lattice. I) to lie below r 15. One may readily show by examining the transformation properties that 'l!t forms a representation of rl.270 QUANTUM THEORY OF SOLIDS atomic orbitals.' of r~5. At k = referred to the edges of the unit cube shown in Fig.(X .
1 12.006 0. with spin the degeneracy is sixfold.33* * Room temperature. CH.98 m.23 Vertical gap at k = 0 (ev) 0./m at conduction band edge 0.y a sy ct on of d III Antibonding p orbitals but this contains fourier components at twice the wavevector as for Our rough argument suggests that r~5 lies lower than r 15 .14 0.19 0.0 13.::l is estimated to be 0.2310.64 0.::l: valence band spinorbit splitting (ev) 0.082 0. In diamond and silicon C(r 15 ) < c(r~). which is very much less than the band TABLE 1 ENERGYBAND DATA OF SEVERAL SEMICONDUCTOR CRYSTALS (At helium temperature unless specified) on he te ur ht els m Diamond Si Ge InSb ite als 1. in fact. The spinorbit interaction lifts some of the degeneracy by splitting the plike states into p% and P~2 states.29 (0. this arrangement is even under inversion at the center of the line.to 1) by gn The valence band edge in diamondtype crystals has a threefold orbital degeneracy.5) (20) Valence band width (ev) 17 7. In diamond (Table 1) the spinorbit splitting .4 (2. in all crystals of the diamond and zinc blende structures that is believed to be realized.0 .898 0. r~5' STRUCTURE OF VALANCE BAND EDGE m . probably because the stronger core potentials lower s relative to p.S SEMICONDUCTOR CRYSTALS: I.5 Eg: minimum energy gap (ev) 5. We cannot order the r~ antibonding s level by the same argument.014 2mA/h2 4.1 8.1 Valence band edge parameters 2m[B[ /h 2 1.744 0. . For r 15 the arrangement must be odd under inversion: re n .006 ev.9) mz/m at conduction band edge 1.04 0. 14 271 re along the shortest line joining two atoms is schematically as o Bonding p orbitals for r~5.3 { 2m C /h2 4. the order is inverted in the heavier elements.014 0.
The secular equation is then of the form (8) I Lk x2 + M(k y2 + k z2 ) lVkxky lVkxkz  A Lky2 + lVkxky M(k x2 + k z2) lVkykz A Lk z2 + JVkxkz lVkykz M(k x 2 + ky2 )  I = AI O..~ ... in heavy elements the splitting is one of the important factors deter mining the gap. the spinorbit splitting increases markedly and the energy gap may decrease... Expressions for L. The energy eigenvalue is given by e:(k) = e:(0) + (1/2m)k2 + A. As we advance along the periodic table. Even in diamond the splitting is important for experiments on holes if their effective temperature is less than about 50o K. In InSb the spinorbit splitting is 0. 2...3 ev. m [. e:.272 QUANTUM THEORY OF SOLIDS gap.e:~ where r.. 5. lV. yz. a mathematical convenience in first setting up the k· p perturbation theory for the valence band edge with the neglect of spinorbit interaction.. e:~.23 ev.9 ev and the band gap is 0. however. 156158) has the form (5) (e:. M. There is. p) 2/ S). Thus the spinorbit splitting may be larger than the band gap.. or 3 above and the sum is over all states at k = 0 except those in the valence band edge level under consideration. and later including it.. xy.) = \ L' (rlk . on examining the derivatives. pi 0)( o/k • pIs). s denote 1. Then by the completeness relation (6) (r/H"ls) ex: (rl (k .]H"Ie:. We make an arbitrary choice of a basis for the representation r~5 at k = 0. The cubic symmetry of the crystal enables us to express the coefficients in terms of the three constants L. and similarly for the other matrix elements. J. The dependence of (r/H"ls) on the components of k is found by con sidering the form of the sum if all energy denominators were equal. e:. taking the three degenerate orbital states to transform as (4) e:~ . pp. (7) (1IH"12) = 2k xky(llpyPxj2). zx.. ... as ~.l.. The secondorder perturbation matrix (Schiff.. lV. with (4) we have.
given by (10) and (11). atomic functions on each atom. 1 ·25 .i) and Ii. each root is double. The band at r7 is called the splitoff band and lies lower in energy than r s. it may be viewed as built up from atomic p~~ functions.~. where a. e~l3. that is.it [n . The solutions (11) converge at k 0 to a twofold degenerate state which belongs to the r7 representation. e~l3. Herman. C. Representative theoretical calculations of the band structure of diamond are given by F. To include spinorbit effects. Phys. p. Phys. Chem. as required by the time reversal and inversion invariance of the hamil tonian.. the 1 Solutions valid over a wider range of k have been given by E. e~a.33 ev. The valence band edge is r~5' The conduction band edge is believed to lie along the Ll axis. If we restrict ourselves to energies k2/2mLl « 1.mJ are diagonal. The results are shown in Fig. one along each 100 axis. Diamond. 2. the electron energy surfa. Phys. we take as the basis the six functions e~ a. Solids 1. where J is the operator for the total angular momentum.ces are six equivalent spheroids. . Phillips and L. mts e is . on tal. the representation may be built up from p~1. 1214 (1954). Suppose that we transform from the basis just given to a basis in which the quantum numbers J. 82 (1956). are given in Table 1. Kip. 368 (1955). The calculated band gap of 5.. 14 273 . The presence of r 7 was first deduced from the analysis of experiments on optical absorption in pGe. Kleinman. Kane. Values of A. The form (10) is established at the end of this chapter. CR. The solutions (10) converge at k 0 to a fourfold degenerate state which belongs to the rs representation of the cubic group. Rev. the 6 X 6 secular equation has the approximate eigenvalues 1 (10) (11) e(k) Ak2 ± [B2k4 at on. Rev. are given by Dresselhaus. O.he and neglect the corresponding term having k written for p.287 (1959). and J. 93.4 ev agrees well with the observed 5. 98. 13 are the spin functions. It is known experimentally that the band edges are indirect. Then in the new 6 X 6 secular equation the spinorbit interaction simply subtracts the splitting Ll from the two diagonal terms involving the states I!. B.. Rev..Pi ~r simplified by the use of symmetry.DS SEMICONDUCTOR CRYSTALS: I. C. e~a. as There are three roots. + C 2(k:1?ky2 + k y2k/' + e(k) = Ll + Ak 2 • 2kz2)f. and Kittel.' as . We include in the perturbation the spinorbit interaction 'or ut ng he = 4m 2c2 (d X grad V) . e~l3. 116. Phys. as determined by cyclotron resonance.
Energy bands of diamond along (100) and (111) axes of the Brillouin zone. (111) FIG..0 ~ ~ . tlll o~ I rg r6 r+g r+7 L4 + Ls L6 L6 L+6 Xi) c: Q3 I.0 .0 1' 1. 2.6 FIG. Elliott. (After Phillips and Kleinman.) FI va inl . ~ g. r7 00 L\+L+5 L+6 ~l ~~ X". The valence band edge is at k = 0 and has the representation 1"25.0 Q) s s t ~ Ll a a 2. < L3 QUANTUM THEORY OF SOLIDS s v 0. 1.. the conduction band edge should lie along A. 3.5 0. (Based on Herman's calculations.61 k =~ (111) 1 k = (000) k = 2: (100) 12. J.274 0.) +1.0 rl 2.0 Al r'25 a Q) ~ . Schematic representation of the energy bands of diamond including spinorbit coupling effects. after R.J Xs 2 3 2'/1'" a (100) (000) (000) Reduced wavevector k :.I.0.
0. The transverse and longitudinal effective masses are r"V mt = 0.0).06 for the band split off by the spinorbit interaction. Energy band structure of silicon.2 2.) The valence band edge is at r' 25..6 "'0 ~ 1. 4 1.8 2.4 ~:.) k=~(1l1) r' Xl 2 ~ AJ Ir.. cn. 0. the conduction band edge is along dl. Silicon.. uin the ml = 0.S SEMICONDUCTOR CRYSTALS: I.:= ding ott. Spinorbit interaction has not been considered in this figure..86..6.2 for the light and heavy hole bands at the band edge and m*1m 1.2 1. 4. k=O k = ~(100) FIG.0 5 2.19m.7 and 2. 3. (After Kleinman and Phillips. Cyclotron resonance experiments on ptype diamond give m*1m 0.98m. one along each cube edge. .4 5 ~ ~Xl iO ~ ri73 . < .al at a general point along the axis between rand X. 4 without spinorbit interaction..IX . The energy bands of silicon are shown in Fig. there are six equivalent minima. LO 1. The splitting caused by spinorbit interaction is shown in Fig.: I <t ~ 7' ::::> 7 . 14 r"V 275 ~ valence and conduction band edges are connected by a nonzero k.. There is a good deal of evidence that one minimum is at (2rla) (0. The band structure is similar to that of dia mond: the valence band edge belongs to the representation r~5 and the conduction band edge belongs to .
mtlm state r. Energy bands in germanium along the [100] and [111] axes according to the experimental information and the calculations of Herman.64.082. that is. The valenceband edge is r~5' with a spinorbit splitting of 0. the conductionband edge occurs at the point L and is presumed to have the representation L 1• The effective masses of the prolate spheroidal surfaces are highly 0.036.14 ev. Callaway. Germanium. The effective mass in the anisotropic: mzlm = 1.L'2 X4 +4 ~ (5 +2 g u Q) > c: ~ » Q) 0 ~ ::.29 ev. Values of the valenceband constants A. B. Levels determined by experiment are circled. it does not occur vertically in an energyband diagram in k space. 5.0 1X4 afi 2 4 6 FIG. but the splitting of the optical absorption +6 1 .5 ev. Rev.5 is believed to be about 2. Spinorbit cou pling is neglected.) t . C calculated by Kleinman and Phillips [Phys.276 QUANTUM THEORY OF SOLIDS The minimum energy gap is 1. 5. 1153 (1960)] are in excellent agreement with the values determined by cyclotron resonance. at k = 0 is isotropic and has the value m* 1m = 0. The minimum of the conduction band occurs in the 111 directions at the edge of the zone. this state is normally vacant. (Mter J. 118. without spin orbit interaction. The gap at the center of the zone between r15 and r. The band structure is shown in Fig.
23 ev in InSb. as for a plane wave model. but no longer has an inversion center.9 ev.580 (1955).07 ev in grey tin to 0. In this situation it makes no sense to treat the representations of the problem without spin. A number of changes in the band structure occur with respect to the correspond ing 44 crystals because of the loss of the inversion J as a symmetry element. 3 The spinorbit splitting . 14 277 ln ne he ps les in Jit in nd on lly ihe his lon in a magnetic field gives the mass. In InSb and grey tin the conduction band at k = 0 is r~. and E. they were degen erate. . it will act to increase the splitting. The conductionband edge is at k = 0 in both crystals. C. of the valenceband edge in InSb is estimated to be 0.460 (1960). both ing to r 7 twofold. The gap at k 0 in BN is calculated 2 to be about 10 ev. I ndiufn A ntimonide. The diamond structure is composed of two identical interpenetrating fcc lattices. O. 249 (1956).0 ev. The crystal symmetry resembles that of diamond. beyond Ge. Phys. Kleinman and J. so that ek 1 is degenerate with ek! .s of the original valenceband edge and the representation riS. the valenceband edge belongs to the fourfold cubic representation rg. with the splitoff band belong . Phys. CH. see G. The chemical valences are 3 and 5. The time reversal operation K still commutes with the hamiltonian. the antisymmetric potential increases the gap from 0. or about four times as large as the band gap.6. Chem. The conductionband edge may belong to r6 or r 7 . it is believed that r~ remains lower than r I 5. One major change which occurs in going from Si to Ge is that the lowest conductionband state at k = 0 changes from rl5 in Si to the nondegenerate r~ in Ge. Solids 1. 100. Phillips. which differs from the diamond structure in an important respect. compared with 1.DS SEMICONDUCTOR CRYSTALS: I.1 ev in Si. L. 117. \ about twice as large as in diamond. With spin. In grey Sn. Thus we can no longer say that the energy levels at fixed k have the twofold conju gation invariance. this introduces a component of the crystal potential anti symmetric with respect to a point midway between the two atoms in a cell. Rev. The crystal InSb has the zinc bien de struc ture. but in InSb one of the lattices contains In atoms and the other lattice contains Sb atoms. 2 3 g to cou r J. Dresselhaus. InSb is an example of 35 compound. Kane. Phys. if the representations are already split. For a detailed theoretical treatment of the bandedge structure of InSb. We note that the gap observed in AlP is 3. The antisymmetric potential by itself will split these representations if. In 35 crystals in which the lowest conductionband state at k = 0 belongs to r15 it is expected that the antisymmetric potential will mix the representation r. Rev.
The circled numbers indicate the dimension of the representation. This follows because p transforms as the vector representation rv. (Mter Dresselhaus. ~ ~4 r7 I CD CD ~3 ~4 k [110] L15 (000) do sh wi of ab th CY co cr.) bu . de r7 ® In L15 (1 (000) k [1001 T m A6 wh r7 ® As m (000) k [1111 po (1 FIG. and rv X r6 does not contain r6. ge rs ~3 T ~4 ~3 T~. but the degeneracy is not lifted in this order. and k· (r7Iplr7) == o. [11 0].278 QUANTUM THEORY OF SOLIDS SE The k· P perturbation does not give a term in the energy first order in k for either of the twofold representations. To third order for f6 or r7 the energy is Energy sp (1 It in y. Plot of energy versus wavevector in InSb showing the firstorder energy for the spinorbit split r' 25 level in [100]. 6. There are secondorder contributions to the energy. similarly rv ~ r7 does not contain r 7 . and [111] directions. Thus firstorder matrix elements k· (r6Iplr6) == 0.
14 279 'st split in all but the 100 and 111 directions: (12) e(k) COk 2 WS r6 us ± Cdk 2(k x2k/ + k y2k z2 + k/k x2)  9kx2ky2kz2J~~. to first order in k. 6..Afj] . we have written the spin magnetic moment operator as /JBd.s) = e".~ A~) . + + (13) e(k) ±C{k2 ± [3(k x2 k/ + ku + kz kx 2 }~ The four signs are independent. (3 x. WITH SPINORBIT COUPLING We consider a conductionband edge at k = 0 in an orthorhombic crystal and suppose the band has only the twofold time reversal degeneracy. CYCLOTRON AND SPIN RESONANCE IN SEMI CONDUCTORS.DS SEMICONDUCTOR CRYSTALS: I.014m.: o. O. In the absence of a magnetic field the energy to second order in k is (14) e(k) = ~ D afjkakp. Thus there will be firstorder matrix elements k . The twocomponent Wannier effective wave equation (Chap.(x.(e/c)A as an operator: (15) [L Da~ (Va ~ Aa) (V~ . 9) in a magnetic field is written by viewing k = p . The constant C is very small. and the linear region of (13) is soon dominated by the normal quadratic terms as in (10). In using form (15) it is usually assumed implicitly that the com ponent. CH. The C terms shift the band edge slightly from k 0.s of k commute. z). The fourfold representation rs gives contributions to the energy in first order in k. The crystal is assumed to have a center of inversion. cy is It is known from cyclotron resonance that m* = 1/2Co 0.(X. but in a magnetic field the commutator of the k's includes [Pa. which contains rg. because rv X rs = r6 r7 2rs.kfj] = [Pa.003 of the way out to the zone boundary. The splitting is shown in Fig. For hole energies» 104 ev the valence band of InSb will resemble that of Ge./lBd' H ] ". (a.Pfj] = 0. <rg\p\rs) . In the absence of a magnetic field they do: (16) ergy 'cled {ka. the expectation is that there will be a nest of band edges in InSb along 111 directions about 0. Very close to k = 0 the four bands at the valenceband edge have the general form. with an energy at the maximum about 104 ev above the energy at k = O. where 8 is a spin coordinate.s). y.
fJa e'Y  In our gauge and with the coordinate axes along the crystal axes. A A ie Dzll [k z .d~~L~)(oIPah) = ea _ DA . D: iii .(. respectively. c We now want to write in terms of the angular momentum com lI ponent L. to write (14) in a form which will permit the possibility of a contribution from the antisymmetric form [k z .280 QUANTUM THEORY OF SOLIDS which is not necessarily zero. Here (20) {ka. In the absence of a magnetic field only the symmetrical term of (19) will contribute. therefore. _1_ ~I ~lPal~)(~lp"I'Y) 2m 2 D~ = i(Da" . 't .kllJ = DxyH. = D aa~a".. (22) (23) DA all I 1 \ H 0 p"I'YI' Then D~1l = = i(Da" + D"a).]). where in the summation each pair a(3 is to be taken only once.kll ] =  (18) eH c . that is.. (26) Thus e(k) = Daakaka + iD:y ~ H . The coefficient D is given by k • p perturbation theory: a" (21) Da = ~ " 2m ~a + ~ ~I ('YIPalo)(olp"I'Y) 2 " m 't ~ ~a 2m" 1 e'Y  ell + m 2 \ 'YIPa e'Y where'Y denotes the state under consideration at k = O.k" 1 = kak" DB and DA denote the symmetrical and antisymmetrical coefficients.x. (17) For the gauge A = H(O.k.k z] = 0.k. [kx.O) we have [ky.] = O.] = 0. (3a is not counted if a(3 is counted. and the total antisymmetric contribution to e(k) is (25) c using (18).iJBd· H.Dlla).eH c We need...k. as then [ka. [k z. + k"ka.kll]: (19) e(k) = ~ (D!..{ka.Pz] = ~ .k"l + D~[ka. [x. we have (24) D!..
is.29). as in (9. according to (9.DS SEMICONDUCTOR CRYSTALS: I. we have (32) iD1y =  2m  1 ('YILzl'Y)' Now if Ic'Y) is the state conjugate to I'Y) in the sense introduced in (9. 14 281 e The equation of motion of x in zero magnetic field is (27) ix = [x. (3 y. If a == x.H] = i (~ Px + m 1 (0 X grad V)x) i 7rx. CIL z = Lz. for zero magnetic field: (30) i m Y)' 0) = o)eo . then (33) Im (C'YILz\ C'Y) ('Y\ CILzC\'Y) .e. The ':I:'S have essen tially the properties with spinorbit interaction which the p's have without it. then L z is the component of the orbital angular momentum L in (31).('Y\LzcIcl'Y) =  ('Y\Lzl'Y). Therefore because CLz = Lz. cal 4 2 2 (0 X grad V)x.H so] Lts. which follows by parity for k = 0 if the crystal has a center of inversion. where V(x) is the periodic crystal potential. the commutator (29) [x. Now write (27) in a representation in which H is diagonal. If we neglect the difference between p and then (31) we 2:' ('Y\Pa\0)(0\p~YL:Jl1ppJO)_(OlPa\'Y) o ey eo = im 2:' «'Y\xalo)(olptJ['Y) . for most purposes the term in 0 X grad V is a small correction to p. ':1:. With (23) and (31).44). here we have made use of (OlxIO) = 0. me 't The operator ':I: is defined by (27). p. (0 X grad V) . CR. .135).y(y\x\ 0). m ihe The term following Px arises from the spinorbit term in the hamil tonian: (28) Hso 1 22 4m c .('YlxtJlo)(oIPal'Y» o im('YILaxtJl'Y).
mJ) = IJ.282 we may write (34) €(k) I' = QUANTUM THEORY OF SOLIDS DOtakaka  2mc e 6'iLzl'Y)u zH . split off by the spinorbit interaction. In the absence of spinorbit interaction .iy)a]. the term p. 8 €')'  €a where S signifies "the imaginary part of". We assume that there are interactions only among these bands.('Ylp1{lo)(olPz h). '" fc (~ I!.i) li.iy){1).* because (35) and C'Y have opposite spins.i) = 6~~[2za + (x + iy){11. 3~~[za .B = «'YILzl'Y) 1 + 1) .mJ).i) 2. To see this. fl h (. p.m (L' ('Ylpxlo)(~I1Jyh'»). iuyKo is the Kramers time reversal operator.i) = 3~[z{1 + (x .m 0 ( t (37) p:* P. also at k = 0.(x iy)a]. here we have used the fact that p is hermitian.(x + iy){1].kOtka p. The state lies an energy Eg above a P~ valenceband edge.i) = 6~[2z{1 . z. at an energy . The terms DOtakaka in (35) gives the splitting observed in cyclotron resonance. li. The phases of these states satisfy KIJ. In the model we are concerned with the g value and magnetic moment of the state 101') which we suppose is an slike state at the conductionband edge with spin i.* I c where the anomalous magnetic moment (36) is defined by c P. (. We may represent schematically the states IJ. Thus p:*d • H. let 0 = x.6 below this there lies the level P~~.mJ) by (38) t f rc (.*d· H gives the splitting observed in spin resonance.P. We now consider the anomalous magnetic moment for a specific model which is quite typical of many semiconductors. li. = 2~(x . I €(k) = DOto. Note that these are ~" .B = 1+ ~S 2'l. y.6 is zero and then (OILzIO) vanishes because the representa tion can then be chosen so that either ('YIPxlo) = 0 or hlpylo) = 0 for any state 0 in the representation. where K = li.i) li.BuzH.H(x + iy)a. €8 €')'  + ~ L' 6'IPxlo)(ojpyl'Y) 'l.
l) i3~a.. Now Pxl!.J ! m L 1{'YIPzl~ €.r2 a'.!) = Pxl!.. = 21L*/ILB~  2~ m ( m* 3Eo + 2~ ) +2 ~ 50 .y Py Is. (42) m .{3 represen tation of the valenceband edge. m* 3E + 2~ o r.. 1 1 Pyy. for InSb.. The g value in conductionelectron spin resonance is defined as g )~] . so that In Ge and Si the orbital moments are much smaller. €o (j 2 2 m + 3(Eg 1 + w£ 1(0IPzIX)12.J (OILzIO) ~ 25. The effectivemass tensor for the conductionband edge is given by. lific )del iate dge !tnd Pr2' where X denotes symbolically the state xa in the x.IDS SEMICONDUCTOR CRYSTALS: I.a._3)= yy. 3 ..!) i6r2~. )a]. ~·_3) X2.. hamiltonian is (45) Here the effective H 1 are 2m* (p ..y 1 • ) = Px\l.. in good agreement with experiment.lower ing operator. 1) y.9 ev.r2 a.2 ev.. py\l. For InSb. ~:::::: 0.·. (44) for m* «m. p. 2 pl pIS.~) [(O[Pz[X)['. Eo 0.y. i2HR._ 1 ) p y 1y. relation (43) Thus have the Roth are rbit (OiL 10) z lta for  ~ r. 14 283 not the phases obtained from successive applications of the J. . y On taking the appropriate matrix elements with (yl we see that the contribution to (..J ~ (~). = 6. y 6. ". CR.z.l) = 3. 'act ing iing 3~ ~ d . The contribution from the states with J = ! is found using = (40) i3~R' p. = 2~~a. with the matrix elements used for (41). m/m* 70. 2 Px 1 ~·_I) pyl!.r2 .r2R p. for m*« m.~ r. Thus the contribution is jm(Eg + ~).A e)2 c IL *d • H. = (39) 2. = i6.ILzl'Y) from the states with J = ! is 2/3mEg.
ValenceBand Edge with SpinOrbit Interaction.ky} {Jx. e Here J is a 4 X 4 matrix which satisfies the angular momentum commutation relation J X J = iJ. C.J x }). Phys.Jx }) + f34HaJa + f35HaJaJaJa.0004 and g ~ 2500 at the bottom of the conduction band.kz}{Jy. We now give a procedure due to Hopfield for the reduction of (47) to a 2 X 2 matrix for the two independent roots. the study of magnetic effects on the P:.J a + 4f33({kx.kxl{Jz. u t. Amer.. In the absence of a magnetic field the second order hamiltonian has the form (46) of the 4 X 4 matrix (. Luttinger. with x 0. according to k· p perturbation theory. I ~ 4 T.2 band edge of a diamondtype semiconductor../J z2) + 4f33({kx. M. Solid state physics 14. In the basis IJmJ) for J = i as given by (38) th~ time reversal operator is represented by ~ '] v (48) J( (J 0 0 1 0 0 1 0 0 DK.kx}{Jz. m* 1m ~ 0. l~ (. Harman et aI. 7. as usual. The expression (47) contains all the forms quadratic in the k's and J's which are invariant under the operations of the cubic point groups.Jy} + {ky. 1030 (1956).J z } + {kz. further. so that every root of the eigenvalue problem is double. Rev.kzl{Jy. The method which led to (35) was developed by J.J y } + {ky. In (46) the { } denote anticommutator.. the energy gap between conduction and valence bands is believed to be ~0. He found that the hamiltonian in a magnetic field to terms quadratic in k may be written as \\ if (.J z } + {kz. where J x.284 QUANTUM THEORY OF SOLIDS S The crystal having the narrowest band gap known at present'" is CdxHg1_xTe. Soc. . A careful detailed study of the g values of conduction electrons is given by Y. Jz are 4 X 4 matrices which satisfy J X J iJ. 102.006 ev. 203 (1962). The low mass and high g value are direct consequences of the low value of the energy gap. Bull. We want to derive the form (10) of the energy near the rg valenceband edge of a crystal with diamond structure. for a more difficult problem.ky} {Jx. (46) H = f31kaka + f32kakJ. Phys. The dimensionality of the matrix representing J is 4 X 4 because the rg state is fourfold degenerateo We know that H is invariant under the conjugation operation. (47) H f3 1k 2 + f32(k x2J x2 + k y2J/ k. Yafet. J y.136. 1 (1963).
)8 SEMICONDUCTOR CRYSTALS: I.~1:) ( _%41 • • H43 a' a Z::b)=A(} . say d. SUbstitute this for c' and we have the redundant 3 X 3 equation Hl1 H 21 H31 H12 (56) ( . But the states cp and Kcp are independent: . We write all ier of (53) :lId Then. 14 is ld )4 ss 285 This is easily demonstrated: where Ko denotes complex conjugation. 6) is an eigenvector having the same energy. because (54) we have (55) H 41 a' ~'=e) H p"CP" so ea . equal to zero: D· (52) where + peia K)cp. but with one coefficient.. CR. 1m and a are constants. Its at be is an eigenvector of H. c'  H41 H43 a' _ H42 H43 b'.ve tal (51) ~(D=o. if (49) nr ns )d ~ (D (=fD 12.rix ACP". because K commutes with the hamiltonian. 'sal + lI 42 b' + H 43C' 0. then (50) K~ K(D To. cp' = (1 p tdWe may then combine cp and Kcp to form a state having the same energy.
each along a [100] axis. particu larly trivalent and pentavalent impurities in germanium and silicon.286 QU ANTUM THEORY OF SOLlpS SEM The first two components of this equation are sufficient. The impurity states will in a sense be hydrogenlike. The rydberg constant involves 1/E2.. H42 H13*. . \~.H 23 H43 H4l II" _~H 23 H43 ]{ H l?~H _ 13 ) H4? H 43 of t the que C) a = X a (h)· tot With the representation (39) of the J's we have that (58) H 41 thal to ~ bin( opti = H 23 = 0..2 ml Er 2 Bec. Such energies are much less tha~ the energy gap.04 ev in Si and 0. UnlE (69) in the absence of a magnetic field. conduction or valence. written They may be ~ (57) ( Hu . = EF(x) . thus it is reasonable to expect the impurity states to be formed from oneparticle states of the appropriate band.H22)2 + H 22 ) ± [i(H ll + IH1212 + IHl:l12]~\ latt (62) which is equivalent to the standard form (10). The Wannier equation associated with (60) is (61) 1 2 [ 2 (Px mt + py2) + e ] F(x) 1 py2 . largely because the dielectric constant E of the medium is high. we consider for the conduction band the single spheroidal energy surface (60) e(k) (63) whe (64) is assu turl (65) ~ seal (66) We (67) = 1 2m t (k x 2 +k + 2 y ) 1 2 2 kz • ml whe (68) In the actual crystal there are six equivalent spheroids. The ionization energies of these impurities are of the order of 0. When m* < m there is a further reduction of the binding energy. IMPURITY STATES AND LANDAU LEVELS IN SEMICONDUCTORS whe is jl unp l iJ\ We are now concerned with the theory of the shallow donor and acceptor states associated with impurities in semiconductors. ) The Wannier theorem gives us the effective hamiltonian for the problem. H21 H43. We treat first a simplified model of a pentavalent impurity in silicon.. but loosely bound.01 ev in Ge. for E = 15 the binding energy will be reduced from that of hydrogen by the factor rts. ~ so that (57) has the solutions (59) A = !(H ll The .H13 H43 H41 H21 ..
<Pkl where (64) vin ~ap. E(lkl). where H 0 refers to the perfect lattice and V to the impurity. We now consider the validity of the effective mass approach itself. We assume the band is not degenerate. CH. The ionic polarizability will contribute only if the binding energy of the impurity level is small in comparison with the optical phonon frequency near k = O. so that the electronic polarizability will contribute to feW) in full. the integral vanishes unless (69) k = k' + K+ G. K whence Ig a (68) (lkl Vlk'l') = L VK Jd x ei(k'k+K)':W: 3 K U : l Uk' 1'0 Because Ukl(X) is periodic in the direct lattice. == Ikl) = eiko:W:ukl(X) rom nce. In situations of interest to us this energy is smaller than the band gap. Consider the solution of the unperturbed problem (63) and icu ~onO H O<Pkl = ey(k) <Pkl. First. 14 287 be We now examine the validity of (61). We substitute (65) in the Schrodinger equation (62) and take the scalar product with (lkl. finding directly the secular equation (66) ez(k)(lk[) the rity idal + ~ (lkl Vlk'l'I)(l'k'l) = V = We next expand the perturbation V in a fourier series: (67) L VKeiKo:w:. f(W. there is the question of the dielectric constant.q) as measured at the fre quency w corresponding to the energy E of the impurity level referred to the band edge. better. Here'lr is just a oneelectron wavefunction. . The solutions 'lr(x) of the per turbed problem may be written (65) 'lr(X) = k/l' L [k'l')(l'k'[). md.IpS SEMICONDUCTOR CRYSTALS: I. The Schrodinger equation of one electron in the perturbed periodic lattice is (62) (H 0 + V)'lr = E'lr. It is fairly obvious that we should use the dielectric constant feW) or. The I be (m is the Bloch function with wavevector k and band index l.
where (75) Fl(X) L eik·J:(lkl>· k e 2 /e (61 We suppose we have solved (74) for Fl(x).k KI> E(lkl>.+K.r.r. Eq.\k+K. In this limit the secular equation reduces to (73) l € (k)(lkl> + LV K(l. 3 upp by elm (81) so that the solutions 'ltl(X) of our original problem are (77) 'ltl(X) L 'Pkl(X) Jd3~ Fl(~)eik'f.\~~K. and K. The secular equation may be written (70) bec (79 z € (k)(lkl> + Kit L VK. k'.r. then (78) F (83) 'ltz(X) "' UOl(X) J d3~ Fz(~) Leik'(J:f.k(l'. We note that for the coulomb potential V K a: 1/K2.\~~K. For slowly varying perturbations only a small range of k will enter the solution for lowlying states in a given band.) k uOl(x)Fz(x). (74). (72) .k+ Oll'.l(X)Uklt(X). T Th€ . 3 Thi repl im mix tio Kit (80 As IKI+ 0.k = J llt d x U. k We resu F (82) where Fl is an eigenfunction of the Wannier problem.. where the function (71) . so that G = 0 for the matrix elements of interest. If we make the approximation that UkZ may be replaced by uoz(x) in (77).k + KI> = E(lkl>· K whi dea ate and imp phy ml The use of (72) is our central approximation. The secular equation (73) is precisely the Schrodinger equation in the momentum represen tation of the following Wannier problem in a coordinate representation: (74) [€z(p) + V(x)]Fl(x) = EFl(x).288 QUANTUM THEORY OF SOLIDS SE We are concerned only with small k. In this approximation the different bands are entirely independent. volume (76) In a specimen of unit (lkl> = J d x Fz(x)eik'J:.
258 (1957). PhY8.6. 1488 (1954). We go on to the solution of (61). show for l . CR.082. With ml = alm. mt atm. Rev. For nSi with (83) = 1. where one deals with coupled Wannier equations connecting the several degener ate components. For a spherical energy surface ml = mt = m*. e = 12: b2 = 0. a2 0.. the reader should consult the review by W. a2 0.IDS SEMICONDUCTOR CRYSTALS: I. 96. Kohn. a2 = 0. For a discussion of the .216. 0. The Wannier equation (74) is seen to be rigorous in an approxima tion which can be stated precisely. The anisotropic hamiltonian (61) is not exactly solvable in closed form. The theory may be generalized directly for degenerate band edges. The replacement of Ukl(X) by UOl(X) introduces no approximation more important than we have made already in neglecting the interband mixing terms in (72).0729. and To = E/me 2. we try a variational function of the form (81) F(x) = (ab2/1rTo3)~ exp {_[a 2z 2 + b2(X 2 + y2)f.1 for Si and perhaps less for Ge.'2/TO l.0174. The method is easily extended to degenerate bands.tcceptor levels in Si and Ge.0298 ev. We find on carrying out the variational calculation the following results: For nGe with will ake al = 1. e = 10: (82) Eo 0. and for a treatment of shortrange effects within the atomic core of the impurity.00905 ev. al a2 0.58. Solid 8tate physic8 5.. namely that (73) should hold. The Wannier equation becomes an equation for a multicomponent . If that (80) /1l'l ~ ion ion enIOn: nit which may be of the order of 0. I f d k eik'(X~) = c5(x 3 ~).135.2. . 1)2 = 0. Kittel and Mitchell. We may determine an upper bound to the groundstate energy relative to the band edge by a variational calculation. . and we have exactly the hydrogenatom problem with e2/ E written for e2 and m * written for m. 14 289 the tial because (79) f eik'(X~) . This displays the role of Fl(x) as a slow modulation on uo(x).
mt ml in the absence of the magnetic field. If we write (87) s = e.290 QUANTUM THEORY OF SOLIDS wave function (84) F: (H(p) SEM ele + V)F(x) = EF(x). We (95: the hamiltonian is (88) H = Ho .. LANDAU LEVELS in t regl (90 By Landau levels we mean the quantized orbits of a free particle in a crystal in a magnetic field. and we considered the semiclassical theory of magnetic orbits on general fermi surfaces. In the chapter on electron dynamics in a magnetic field we gave the Landau solution for a free particle in a vacuum in a magnetic field.1C/c.Xx.xp + . the vector potential for a uniform magnetic field JC in the z direction in the Landau gauge is (86) A = (O. In 1 (97 . p perturbation theory and F(x) is a column matrix. (89 where H(p) is the square matrix from secondorder k .x 2 • m y 2m 8 8 2 wit] ~ The eigenfunctions of Hoare the Bloch functions Ik. At present we consider only the qu~ntization of a spinless electron near the non degenerate conduction band edge of a semiconductor having the spheroidal energy surface (84a) We per (91 the (92 e(k) = 2~ (k x 2 + k y 2) + 2~ k z 2. The hamiltonian with the magnetic field is (85) the ate (93 for to s (94 H=1 . Because of the presence of terms in x and x 2 it is a difficult and lengthy problem to analyze the validity of the effective mass equation in a uniform magnetic field.O). the eigenvalues are el(k). In order to avoid singular matrix (96.( pA 2m c e)2 +V(x).l).
k2q .k2q .k2q 2ok'.kq) me e2 2 * 2IAqI2(2ok'k .2iq·x  2Ik'l).2me 2 m* .k).(k).(k') ~ ~.lkl) to first order in k.. antisy betwe so that Fl(X) satisfies the Wannier equation (104) 1 (p . 2m* . (98) ~ k.Aq • k(Ok'.k+2q + 0k'.. Similarly (101) and sh in a m 2. (:. IAq . ( of a h sentat We need also (99) (lkl U 2 Ik'l) e2 2 2 IAql2 (lkle 2iq.0kf.°k'.k+2q). using the isum rule. 0k'.1 IA qI2(Ok'..el.k+2q + Ok'.k+ 2q + 0k'.292 but we have seen in Chapter 9 that QUANTUM THEORY OF SOLIDS SEMI< (lklp.~ e)2 A Fl(x) = EFl(X). 1r/2. k where are plane siderin filled a 6. 4.X me + e.k2q  20k'k) and tl absenc S. me ie 0'11 and (95) is identical with the effective mass equation in the plane wave representation (103) Fl(X) = L eik'X(lkl).) . (lklplkl')12 m2e2 Li el(k) el.20k'k).Ok'. (102) Thus e (m 2 ) using i directi.kq . 11 (lklcplk'l) = .k+q . with in the limit q ~ 0 (100) (lkl U 2Ik'l) :::::  e2 Aq(Ok'. Th tion ~ limiti Thus for a spherical energy surface PRO! (lkl U llk'l) '"  ie * k· Aq(Ok'. S levels 1 L' (lkl U llk'l')(l'k'i U llk"l) el(k') .k+q me ) 1.(Ok'. (c = .
p.&. 869 (1955)] avoids the limiting process q + 0 at the price of treating singular matrix elements. LIDS 14 293 The above derivation is due to Argyres (unpublished). for the band with spin parallel to the positive y axis. Ok ~ lA(k.rTy  k. This is an exercise in a method of handling matrix elements of the coordinates.~ G ~) + C(k. to 0(k 2 ). Verify the statement made in connection with 35 crystals that the anti symmetric crystal potential component will act to increase the splitting between r~6 and r 16 states. with (k'ix 2ik) = ::2 o(k . with coordinate axes along the cube edge directions.SEMICONDUCTOR CRYSTALS: I. . PROBLEMS 1.). does this band carry a net current when filled at OaK to a level CF? 5. Show that states which transform as J = i are split into two twofold levels by an axial crystal field. and the spinorbit splitting A between the J = absence of the crystal field. 4. Evaluate the splitting for the crystal potential v = a(x2 + y2  Z2). Plot a section of a constant energy surface in the plane ky = 0. CH. Con sidering only this spin orientation. k'k). are pauli matrices. the (/'. and show that one obtains the correct energy eigenvalues. 97. 3.k'). Hint: Consider the effect on D~y of rotating about the z axis by 7r/2.' + k y ') + Bk. Consider the hamiltonian H = p2 + X2 of a harmonic oscillator. (a) Show for a cubic crystal at k = 0 that D~y ! and J = ~ levels in the = 0. Rev. ave (/'y where the z direction is parallel to the symmetry axis of the crystal. 0. 2q). In CdS the conduction band edge may be written in the form. the deriva tion of Luttinger and Kohn [Phys. solve for the eigenvalues using a plane wave repre sentation: 'l1 = J  dx eikx(ki).t. (b) Show that in the absence of spinorbit coupling D1y = O. 2. D1y =. using the definitions (21) and (22).
The conserva tion of wavevector in the absorption process requires (1) kel FIG. 294 If the inks absor . if the fourier components of the radiation field A are at low wavevector.k ho1e • This is simply interpreted: the total wavevector of the valence band when filled is zero. Optical absorption and excitons DIRECT OPTICAL TRANSITIONS In the process of direct photon absorption a photon of energy w and wavevector K is absorbed by the crystal with the creation of an electron at kel in a conduction band and a hole at k ho1e in the valence band. 1a and b. where G is a vector in the reciprocal lattice. 1 is indiri + k ho1e I"'V G. 10 8 emI. particularly for excitons. In the reduced zone scheme G = 0. as in Fig. the total wavevector 1 electrons left in the valence band is equal but opposite of the N to the wavevector of the electron which was taken away. so that if we remove an electron from the valence band. The matrix element for electric dipole allowed transitions is (3) the v band allow optic But a Place (4) (6k' I ~ A • p Ik~). In some connections.1 and may almost always be neglected in comparison with the scale of wavevectors in the Brillouin zone. the fact that the photon wavevector is not exactly zero is of considerable importance. The scale of wavevectors of optical photons is of the order of 10 4 cm. It is customary to call a transition in which I"'V we m intens intera tenso alway tion 0 INDIR (2) kel + k ho1e :::: 0 So a vertical or direct transition because the electron is raised vertically on an energyband diagram.SEMIC 15 Semiconductor crystals: II. so that kel .
INDIRECT OPTICAL TRANSITIONS lally ons. this same quantity determines the mutual interaction of the two bands "Y. But at energies slightly above the energy gap a weak absorption takes place with the emission or absorption of a phonon of wavevector q: (4) kel + khole ± q r. the threshold of strong optical absorption will lie at a higher energy than the energy gap.SEMICONDUCTOR CRYSTALS: II. <5 in the reciprocal effective mass tensors. If this is true. :tor. zone : the at if ~ctor )site :t is we may usually replace k' by k. CH. as in Si and Ge. the absorption process (c) is indirect and takes place with the emission or absorption of a phonon. The energy balance . Direct absorption processes in (a) and (b). We see that bands which perturb each other strongly are always connected by allowed optical transitions for the direct absorp tion or emission of a photon. 1. but the band minima fall at different k values and cannot be connected by an allowed optical transition. Thus 1{<5klplky)12 determines the intensity of the transition.J O. the indirect or nonvertical process will dominate the optical absorption over the appropriate energy interval. If the conduction and valence band edges do not lie at the same point in k space. the minimum energy difference between the valence and conduction bands does not occur for ilk = 0. not Sometimes. E 15 295 ns (c) I(a) (b) ~y w )f an ence ~r of lthe ~rva o k FIG.
Blatt.1Ictckqaqlnq.nq . and photon absorption may take place at an energy lower by 2W p honon . Secondorder matrix elements for processes in which a phonon is absorbed involve (oklp • Alk'Y)('Y. The form of the electronphonon interaction was discussed in Chapter 7.1: The corresponding matrix element for emission of a phonon is written down by using the terms Ct_qCka"t of the electronphonon interaction. provided tha" the phonon spectrum itself is known. p.k . In the final state the electron is at k in the conduction band 0 and the phonon occupation is nq .1!ctck_qaq q. n (kz = in whic tion magn nonde (6) where magn band functi (7) In the presence of a strong static magnetic field the optical absorp tion near the threshold of the direct transition in semiconductors is observed to exhibit oscillations.nq . Actually there will be a number of threshold energies because in principle every branch of the phonon spectrum will participate at the same wavevector. where the phonon has a wavevector of magnitude close to the difference Ike . but at different frequencies.k .q. and Hall. Here the c's are electron operators and the a's are phonon operators. Atlantic City. as from inelastic neutron scatter· ing studies. 1956). at fixed H the absorption coefficient is periodic in the photon energy. at absolute zero no phonon is available to be absorbed in the process and here the positive sign must be taken on the righthand side.q in the valence band l' and the phonon occupation number is nq for wavevector q. 2.q. In a magnetic field the interband transitions (Fig. 1 in the nier e nth ex The (8) (1 . 2) take place between the Landau magnetic levels in the valence band and the corresponding levels in the conduc See Bardeen. Proc.kvl at the band edges. The intensity of the indirect transition 1 is determined by second order matrix elements of the electronphonon and electronphoton interactions.q.qfp • Alk . 146. In the process described the electron is initially at k . on Photoconductivity. At higher temperatures there are thermal phonons available to be absorbed.o)(o.k. 1954 (Wiley. Optical measurements have been able in this way to determine directly the difference in thl wavevectors of the conduction and valence band edges.k.'Y). That is.296 QUANTUM THEORY OF SOLIDS SE?lHC at the indirect threshold will be (5) W = c(ke)  c(kv ) ± wq . of Conf. and ln (o. OSCILLATORY MAGNETO ABSORPTIONLANDAU TRANSITIONS Fig.k .'Y).
where We. from Eq. (nck~k~lplnvk~k=) rv J d3x u! (x)puov(x) J d 3x F!c(x)Fnv(X). tha" tter· tion band. Wv are the cyclotron frequencies and Pc. (7) sorp ctors tion the netic lduc ~ Fn(x) = .kz) Eg + i)wc 2me kz ± PcH. where uo(x) is the Bloch function in the appropriate band for k = 0 and. 2. The possible transitions are shown for the case in which the direct transition is allowed by parity. pter the ctor and ent Ckat Fig.13). 15 297 cess ide. be wer lose nd ton ha I ~tl~ 2 3 4 tors. Pv are the anomalous magnetic moments. are 1 2 ec(n. Here F n is the solution of the appropriate Wan nier equation and <(In is the harmonic oscillator wavefunction for the nth excited state. if nondegenera te.IDS SEMICONDUCTOR CRYSTALS: II. Such transitions are called Landau transitions. CH. The spatial parts of the wavefunctions in each band are of the form "'(x) = uo(x)F(x). e in the lents th. The matrix element for optical absorption is proportional to (8) City.cky/eH) in the Landau gauge. Schematic showing the magnetic levels for kz = 0 as labeled n (kz = 0) for two simple bands. In a magnetic field parallel to the z axis the energies in the two bands.(n + i)wv  1 kz 2 2mv ± PvH . (11. cell crystal .kz) . (6) ev(n.
as indicated in Fig. 90 (1959). usually a nonmagnetic insulator.'/)H. and nc n'/). of radii large in comparison with a lattice constant. k~ = k~. This is analogous to the selection rules conserving k in the absence of a magnetic field. After integrating the transition probability over the density of states for kg and k z . Lax. there is no sharp division between the two types. the experiments involve the anomalous magnetic moments or g factors. The integral involving the F's will vanish unless k~ = k~. The equality of the n's follows by the orthogonality property of harmonic oscillator wavefunctions. The theory of oscillatory magnetoabsorption for degenerate bands and also for indirect transitions has been given by Roth. Rev. because it is not the band edge. noting that these do not depend on the effective mass. Mott excitons are found in semiconductor crystals having small energy gaps and high dielectric constants. we limit ourselves here to the discussion of weakly bound excitons. (w If nonde wavef above tive a (10)  UJ n ) ~~' where in a c (11) where (9) Wn = + (n + ±  J. and Zwerdling. It is usual to speak of two types of excitons: a tightly bound or Frenkel exciton and a weakly bound or Mott exciton. We note that magnetoabsorp tion experiments are particularly valuable in determining the param eters of a direct conductionband energy surface which. cannot be kept populated sufficiently to permit a cyclotron resonance experiment to be made. For this reason.I. and because their experimental picture is richer. and impu (14) where <Pv(Xh) propa Th (15) refen and t ~epar the e (16) . 114. Phys. The machinery we developed for the inpuritystate problem may be taken over directly to the discussion of weakly bound excitons. EXCITONS Thep in the (12) is the (13) An exciton is defined as a nonconducting excited electronic state in a perfect insulator. In a Frenkel exciton there is a high probability of finding the electron and hole on the same atom in the crystal. Frenkel excitons are realized in alkali halide crystals and in many crystals of aromatic molecules. in a Mott exciton the wavefunction in the relative coordinate extends over many atoms. Both types of excitons may be thought of as bound states of an electron and a hole.298 QUANTUM THEORY OF SOLIDS SEMIC where we have broken up the integral by treating the F's as essentially constant over a cell. it is found that the absorption coefficient is proportional to 1 \"' £. further. 2. The allowed transitions have ~n = 0.
and are located at k =. For bound states En is negative and the total exciton energy at low K is negative with respect to a ~eparated holeelectron pair. (16) En =  2f2/i2 n 2 ' p. The energy of the state (14) is (15) E Kn = En + 2(me 1 + mh) K2. fter s for al to If both the conduction and valence band edges are spherical.~. nondegenerate.r F n(x) = EnF n(x) is the hydrogenic wave equation with the reduced mass (13) =+. p2 . Elxl ands and sorp ram it is it a ents The part of the wavefunction in X must contain a factor e iK.X) = eiK.. referred to the conduction band edge. 0.e 4 ~. + mh) + 2p. CH. the exciton spectrum and wavefunctions are obtained readily by an extension of the result found above for electrons bound in impurity states.X . The effective hamiltonian in a cubic crystal is e2 p2 p2 e2 (11) H = 2me + 2mh . where <Pc(xe) is the Bloch function at k = 0 in the conduction band and <Pv(Xh) is the valence band function at k O. We introduce the rela tive and centerofmass coordinates X Xe  Xh. . with It restored. In direct analogy to the treatment of impurity states in Chapter 14.LIDS SEMICONDUCTOR CRYSTALS: II. The excitation is propagated in the crystal as a wave of momentum K.Elxl 2 = 2(me . the total exciton wavefunction is (14) VtKn(X. shere and dielectric constant E.xFn(x)<Pc(xe)<Pv(Xh). where (12) e ) 1 ( 2p. the part in the relative coordinates contains a factor F n(x). 1 p. of ason. 1 me 1 mh state usual citon ay be sharp L high n the inate lkali Mott nergy ay be ns. x= mexe me + mhXh + mh where both me and mh are usually positive. For the hydrogenic hamiltonian (12) the energy is. 15 299 ially less tion lity ator ass.
in agre The (18) to of the r.p2 21' . + 1 ( 1 2 me  1 ) mh n· e. rather than with the transformation (10).Xh. to dege using band e practic confron We in whi from a + 1 p 2 2p. It is somewhat unusual to find a crystal in which there are two spherical band edges at k = 0. = 8/l Kn K' The hamiltonian at K = 0 has the eigenvalues (23) this is band at state fo (2~) En = .e 4 1 . 2 p.p. This it is bet We den (E __) Fn(x). 2e 2 n 2 p.n(~.. Excitons created by photon absorption from the ground state of the crystal are created near K = 0.5m the ionization energy (n = 1) of the exciton is about i ev.X) = eiK·'lFn(x). 2 elxl k=O K = O· (27) If we look for a wavefunction of the form (21) tf. ax2 2 Thus._ . therefore the direct exciton absorption spectrum is a series of sharp lines below the optical absorption edge of the crystal. x. It is instructive to reexam ine the problem we have just solved.2e2/i . we have for the special case of spherical surfaces (20) H = 1 II 2 8p.Ixl Fn(x) and in unity. for which the exciton spectrum is closely hydrogenic. if n. the equation for F n(x) is (22) [ 1 . We note that the minimum energy required to create an exciton starting from the ground state of the crystal is (17) The pertur (24) b' = b'g .e 4 But by (25) where Eg is the energy gap. For general energy surfaces the exciton problem is best formulated using the coordinate transformation (18) ~ whence (26) = ~(xe + Xh) . p are the momenta conjugate to~. The hamiltonian (11) is trans formed with the use of (19) a2 aXe2 = "4 a~2 1 a2 + a~ax + a2 a2 ax 2. p .300 QUANTUM THEORY OF SOLIDS SEMICO for e = 5 and p. x = Xe . but this is apparently the situation in Cu 20. = 0. K 2 (me mh 1 + ~ 1) _ 2 ] ~ .. a2 1 a2 a2 =2 aXh 4 a~2 a~ ax a +.
This is not the clearest way to treat a manyelectron problem.enic. 'n(x). 4 me . __ k En . and in this scheme the wavefunction of the initial state is simply unity..on is ~e an I SEMICONDUCTOR CRYSTALS: II.x")lf!c(xe)lf!v(x. + 2(me + ffl. The further extension to degenerate band edges is complicated in practice. The extension of the present treatment in the coordinate system (18) to ellipsoidal band edges follows directly on using the components of the reciprocal mass tensors in (19) and (20). Solids 1. +t:l+""'. k k . We denoted the filled valence band by CI>o. CH. .)LIDS . whence (24) becomes (26) the . it is better to use the formalism of second quantization. then we define "'" '*'k = akl'_k':l:"O. Dresselhaus.>tion edge ~here ~ ~.ecial in agreement with (15). leaving a hole in the valence band at . n.). From (14) the exciton wavefunction at K = 0 is (27) 1/Ion(x) = Fn(xe . 14 (1956).) xam rans ~2 'x 2 ' .!.Ez But by the atomic isum rule on the hydrogenic states l. m" z En .)2 L' (niK • pll)(lIK·pln). In practice various approximate dodges are often employed to avoid confronting the complexity of the multicomponent equations. 15 301 The ei~envalue of (12) to second order in K is found by K· p perturbatIOn theory: (24) E Kn '" En + ~ K2 + ! (~ 8p. We take the bands to be spherical about k = 0 and nondegenerate. Phys.. lated r E Kn = En 1 K2. (25) If the .. see O. The nth exciton state for K = 0 may be written (2~) CI>n = L CI>k(kln) = L att3!kCI>o(kjn). as in Chapter 5.EZ ~JI'" P.k. but follows by using matrix operators for the multicomponent state functions at each band edge. I this is a state in which an electron has been raised to the conduction band at k. We now discuss the intensity of optical absorption for a process in which an allowed (electric dipole) transition creates an exciton from a filled valence band. Chern.(nlpJlll)(llppln>.
Thi~ and (3 associa exciton In u andap directio .(X)P<PkZ(X). (30) P~ LatP~(cklplkv).302 QUANTUM THEORY OF SOLIDS SEMICO The electric dipole absorption is determined by the matrix element (cklplkv) of the momentum p between the state k in the valence band and the state k in the conduction band. which is nonzero only for p states. but the n = 1 exciton will be absent. k k' if (cklplkv) ~ (clplv) over the range of k involved. In second quantization the momentum operator is (29) p appeari seen ve sugges = LCtz. with F n(O) = 0. 3 Long or.ak. k that th and tr.. with l denoting the valence band v and l' the conduction band c. if n is the principal quantum number. we may still observe excitons because (cklplkv) ~ 0.3 . polariz by the depend the qu of longi assump dispers same ti the d' We con vector of the parison Phot transve 8condu couple xoryb term in and co (36) Fn(O) = L(kin). k Then t and thus the transition probability involves (35) l(tI>nlpltl>o)12 "'oj l(clplv)12IF n(0)12. for hydrog~nic 8 states IFn(0)12 0:: n. k Then the matrix element of P between the vacuum and the nth exciton state is (31) (tI>nlpltl>o) = L(nlk')(tI>oll3k.CkZ k ll' f d x <P:. (37) For spherical masses F n(O) is nonzero only for 8 states. There are no pstates for n = 1. such that in (32) (33) whence (34) But the (kin) are Fn(x) = Leik'J:(kln). "First forbidden" electric dipole transitions arise when the transition probability is proportional to laF n (0)/axI 2 .atP~kltl>o)(cklplkv) = L(nlk)(cklplkv). k'k k The transition probability is proportional to (32) I(tI>nlpltl>o)1 2 ~ l(clplv)12 (L (nlk») (L (k'ln»). Thus when electric dipole transitions are forbidden.
Photons are transverse and in cubic crystals couple only with transverse excitons. To see this we work in the gauge div A 0 and consider the electromagnetic wave (36) A = YeHwtkz). 124. the crystal is supposed to be la~ge in com parison with a wavelength. (37) . y. Then the wave is polarized in the y direction: H = curl A = _ikiei(wtl. CH. 108. Rev. We have seen in Chapter 3 that the dielectric polarization field of a cubic crystal has longitudinal and transverse modes. dton > are appears to be the picture in Cu 20. An exciton is in fact the quantum unit of the polarization field. Elliott [Phys. In uniaxial crystals the dielectric polarizability is anisotropic and a purely longitudinal exciton mode exists only in special symmetry directions of k.340 (1961). Longitudinal and Transverse Excitons. the polarizability depends on the nature of the exciton states. The n = 1 line can actually be seen very faintly. there is no Azpz term in the interaction.z). The polarization splitting of longitudinal and transverse excitons was derived in Chapter 3 on the assumption that the wavevector of the excitation was small so that the dispersion of the uncoupled polarization could be neglected. The polariza\ion associated with these excitons is purely transverse for k II z.and the ld c. so that shape effects could be neglected.LIDS SEMICONDUCTOR CRYSTALS: II. 1384 (1957)] suggests the weak transition is by electric quadrupole radiation. a photon with k II z in a crystal with an s conduction band edge and an x. We continue here to make the same approximation. with a frequency splitting determined by the polarizability. At the same time we supposed the wavelength was small in comparison with the dimensions of the crystal. only sz' excitons have a longitudinal polarization for this direction of k.~nic E 1 aA = i c at W yei(wtkz) c ' :ition y for with tthe This and (36) has A • p coupling only with sy excitons. 15 303 (lent . although the wave vector of the incident photon is very small compared with the extent of the first Brillouin zone.. z degenerate valence band edge will couple with the exciton bands made up from hole wavefunctions in the x or y bands and electron wavefunctions in the s band. We must consider depolarization effects on the exciton . that is. In a covalent crystal the polarizability is determined by the excited electronic states of the crystal. That is.
P II denote polarization components normal and parallel.53 degen and r ductio (45) as in term almos va]enc The el 2Zwe . We find E.1 2 2W.3 ture.1 effecti bindi hydro II.1 = (3. The projection of P. 276 (1960). Now (38) Ger inger tion 0 band The e 0. but increases sharply as Ok is varied from this orientation. respectively. Solids 12. These results are due to J.1. ass (43) where E.1 E . The mixed mode is purely longitudinal for Ok = 1r/2 and it is asymptotically transverse for Ok = 0 on our assumption {3n = O. mixed mode. Let k be the unit vector in the direction of k. This has two solutions: (41) k. Thomas. W = w.1. {3n are the static polarizabilities and W. E.1) sm Ok· " .1 at + P. The photon coupling to the longitudinal or mixed mode therefore vanishes for Ok = 1r/2.1 and the depolarization field is (39) The c (44) E = 41rk· P. we consider an exciton of frequency near W.1 sin 2 Ok).1.037 1 W. Hopfield and D. W. 122.1 = .41r(k • P. otherwise 41r would be replaced by 41r/E.1 component of the depolarization field of a polariza tion wave.1 and neglect the contribution to the polarizability of the oscillators at WI!. simila 2.304 QUANTUM THEORY OF SOLIDS SEMIC spectrum. (42) k· P.1.1 on the wave normal is k.P. P. We now discuss observations of excitons in several crystals which have been studied in detail. C.1 2. J. We are particularly interested in the special case {3n « {3. . to the c axis in a uniaxial crystal.1(k· P.1 is the .1 sin Ok.1..1 2(1 + 41r{3.1) sin Ok. This effect has been observed in ZnO. exactly as in Chapter 4 we found the demagnetization field of a magnon. Then w here Ok is the angle between k and the c axis. that is.12 iJi2 + P. (40) 1 a2P. Phys. Chem.1.1=O.1 = W 2 2 %(3. (1960) We have neglected E. WII are the resonance frequencies for transverse waves. G. the contribution to the dielectric properties from other modes.1 = P. a2P. transverse mode. Let P.1 from div D = 0. {3. using Th emissi energ Cad fine st fully. t R. The observation of an energy difference between transverse and longitudinal excitons is evidence that the exciton is mobile in the sense that there is a wavevector k associated with the exciton.
be m* 1m 0. 122.ass IJ. The effective mass of the spherical r~ band edge is known to. the energy of the direct gap is 0. Phys.4. including fine structure and magnetooptic effects. The electronic g value is 1. J. CdSe. 371 (1960).ILIDS SEMICONDUCTOR CRYSTALS: II.8 and is very nearly isotropic.20 0. the band edge is ellipsoidal. Cadmium Sulfide. from ~su1ts ls 12. the energy band structure of wurtzitetype crystals is discussed by R.0017 ev. Thomas. The hole masses for the top valence band are m. and ZnO are similar and lie at or very near to k = O. The indirect excitons are excited across the indirect gap with the emission of a phonon of energy 0. 0.016 ev. is given by (43) m ~ . .031 1 the 1 the ·P. For r7 the energy has the form (45) E(k) A(k x 2 +k y ) 2 + Bk.2 ± C(k x 2 + as in Problem 14. The valence band is split at k = 0 into three twofold degenerate states. it is The lishes ttion. Rev. 114.20m. The crystal is hexagonal and has the wurtzite struc ture.7m and mil ~ 5m. Phys. It is believed that the band edges in CdS.057 and 0. the holes 2 Zwerdling.037 from experiments on Landau transitions. with m * = 0.002(5) ev. Lax.0025 ev. for example.53 ev. Casella. Xote that the third term is linear in k. 2 15 305 and are s for case and t wn. Germanium. The observed value is 0. has been investigated rather see. lergy :lence tor k vhich using E = 16.898 ev. The energy gap in CdS is 2.riza IJ. (lode. C.L = 0. and r9. but this term has never been detected..037 1 1 + . Letters 5.J:2 n = 0. 35 (1961). respectively. G. r7. 80 (1959). Both direct and indirect excitons have been studied in germanium. and Button. In CdS the conduction band edge is almost isotropic. transforming in order of increasing energy as r7. 114.  1 0. band.e 4 2E 2. Roth. CR. The con duction band edge transforms as r 7 . An approximate effective hole mass can be defined as the mass which reproduces the binding energy of the lowest acceptor state when calculated from the hydrogenic relation.20m. with separations of 0. Rev. Rev. J. The exciton spectrum of this crystal. Hopfield and D. Rev. Phys.L The calculated groundstate exciton energy referred to the (44) edge is El  lJ. this mass is 0. The direct excitons are formed at k = 0 by the absorp tion of one photon.. Phys. 1514 (1959). The observed binding energy of the indirect excit~m is 0. The direct band gap is between the rs valence band edge and the r. Thus the exciton effective IT.0276 ev.
particularly by E. everything else remaining unchanged. see D. Such an effect is impossible for a free electron.306 QUANTUM THEORY OF SOLIDS (r 9) have gil = . Perhaps the most interesting feature of the exciton spectrum in CdS is its dependence on the sense of a magnetic field perpendicular to the e axis.. but the absence of a center of symmetry in the crystal allows it to occur. M1. Cuprous Oxide. F. where q is the photon wavevector. There are three series of exciton lines. 1518. 2637 (1961).1. In the reference system of the exciton wavepacket the magnetic field appears as an electric field. 353.. but some strong inferences can be made from the exciton results. . as discussed previously.e. Show that in a uniaxial crystal with nondegenerate band edges at k = C the exciton wave equation may be written as I where 3 1 2 . 245286 (1958). 1. It would not occur for impurity absorption lines. 2. 3 It is unfortunate that the structure of the band edges are not yet known from cyclotron resonance or other independent studies.21'0 v  1 2y (1 (J2 21'0"3 2 (Jx 2 + 2 (Jy2  1 (J2 (J2) (JZ2  e2 ) EoT if. if. The observations are analyzed in the paper by Hopfield and Thomas cited previously. This cubic crystal exhibits beautiful hydrogenic excitons. y = y.H and i. PROBLEMS 1.. Nuovo eimento supplemento 7. Only a moving exciton could experience such an effect.Yh. That is.15 and g = O. Gross and his school.  Zh). for example. For a discussion of excitons in ionic crystals. Z = E1.~ (kz2 + kl + kz2)) 2 M1. each series associated with one of the three valence bands at k = O. L. with the photon wavevector i. U" . the effect depends on the sign of q X H. See. A striking feature of the exciton spectrum is that the optical transition from the ground state of the crystal to the Is exciton state is very weak. IE. . Soviet PhysicsSolid State Physics 2. Dexter. Discuss for a direct optical transition the dependence of the absorption coefficien t on the energy difference of the photon energy from the threshold energy. Mil x = Xe  Xh.)~ ( Ell  (Z. It is found that the intensities of the exciton lines vary markedly when H is reversed in sign. which have been extensively studied.
F. EO = (EnEol)/~. Treat the term in 'Y in Problem 2 as a small perturbation. Mu = mel! + mhll' 3.lE I (1 Eq + r\'Y). 1961). lEI(l + x\'Y). 1 1'11 Mol 1 +_1_. 15 E 307 iton s at in r to that rsed fleet ueh nter tern etrie and enee enie . 4. CH. 5. It. estimate the magnitude of the quasielectric field for a magnetic field of 30 kilooersteds. 1'11 Ell = m. 2P o: 2P±I: Eq. the ther the t the iton xter. 18: 28. me II 'Y = _1 __ ~ Eol. r=O ption shold =c )1 ~. Show that the transition probability for a "first forbidden" electric dipole process creating an exciton is proportional to I(oF n/ox)z=0!2. 1 1'0 2 1 3 I'ol mhll 1 1 +3 1'11 1 I'ol I'ol = 1 meol 1 + mhol . with E I as the effective rydberg.ol + mhol. In the magnetostark effect as discussed above for CdS. Show that to first order in 'Y the energies of the n = 1 and n = 2 states are.LIDS SEMICONDUCTOR CRYSTALS: II.Eli Eq Eq . .
and spin diffusion. We note that 41rU == Wp 2r . where Wp is the plasma freq uency and r the carrier relaxation time. In this chapter we treat the anomalous skin effect.ILH (1) c c ' or (2) curl curl H = . (7) B We consider first the normal skin effect. 2 ei(k. magnetoplasma resonance.J k 2H = i4?rulLw cH. In a good conductor at room temperature u :::::: 10 18 secI. cyclotron resonance. Th descri (9) u The wavevector has equal real and imaginary is real and equal to u 0 : k = (1 +i)(21rILUOW/C2)~2 = (1 +i)/oo. ANOMALOUS SKIN EFFECT rf c (6) for resul equa micr.V2 H = . .47rulL 2 c H.ELE A 00 :::::: 10. where u is the conductivity in esu. The effects often give important detailed information about the fermi surface. Then the maxwell equations are 4?r 1 curl H = uE. The imaginary part of k is the reciprocal of the classical skin depth (5) 308 WherE the Sl resist: 00 = (c 2/21rlLuow/~.. curl E = .6 U IS 16 Electrodyna:mics of :metals Diverse and subtle phenomena are observed when a metal is coupled to an electromagnetic field. if (4) t'o. the dielectric anomaly. muc 10.5 j(x) electr The r long: acteri SURFl whence we have the eddy current equation (3) for H parts.xwt). The displacement current valid mea dept the f (8) D in a metal may usually be neglected at frequencies w «u.
6 cm given by (5) or 0 ~ 10. . The region A > 0 is called the region of the anomalous skin effect. 9 1 ~ . In pure specimens at helium temperature and microwave frequencies it is possible to have WT » 1. The . in this limit (7) k2 "' 411"pw(lo (i . which means that WT «1. The results (4) and (5) are written on the supposition that (I is real.2 cm. Typically T might be 1010 sec. SURFACE IMPEDANCE The observable electrodynamic properties of a metal surface are described completely by the surface impedance Z(w) defined as ~inary (9) Z = R 'X 't t 411" E. much larger than the skin depth 00 ::::: 10. The elementary result for the r~f conductivity is ELECTRODYNAMICS OF METALS. R determines the power absorption by the metal. CR.iWT' 1pled iailed t the naly. in a very pure specimen at helium temperature 00 ~ 106 cm. so that for an electron on the fermi surface the mean free path is (8) A V FT ~ (10 8)(10.5 cm given by (7).WT). The real part R of Z is called the surface resistance.OOWT lrrent ~e (I is 'ature lasma ~xwell But with either (5) or (7) for 0 there is a serious question of the validity of the calculation at low temperatures because the carrier mean free path A at helium temperature may be larger than the skin depth. 16 (6) (I ne 2T m(l iWT) (10 • 1 . 309 10 At room temperature in a good conductor at 3 X 10 cps we have 00 ~ 104 cm. When A/o :> 1 the electric current density j(x) can no longer be determined only by the local value E(x) of the electric field. and our use of (IE in the maxwell equation is invalid. A long mean free path has a profound effect on the propagation char acteristics of the medium.10) ~ 10. (WT)2 . The result (6) follows immediately from a drift velocity or transport equation treatment..c Ht ~pth where E t . H t are the tangential components of E and H evaluated at the surface of the metal. for WT « 1 this reduces to the usual static value (10 = ne 2T/m.
.411"wIJ. = kc 2 (1 _ i) 27rwooIJ. fd Fora invol dz Hy(z)jJ..( E . C ~ where ~ = c/w. 2 (20) when the fields are evaluated at z part is (14) = +0.Ht/c Then = aEt/az. it determines the frequency shift of a resonant cavity bounded by the metal.(Z).}. For fund be s (18) t ) 47riwIJ. Then the inductance per unit length is (15) This Th is in( meas' direc1 (22) 'Y :::::: : L = (J\ {fiux/91 = (J\ U fd d dz H . we have (16) 2Ex(d) =  'tw C . so that (12) z = 47rwIJ. (21) where H is the amplitude of H y at the surface. • 00 . The rate of energy loss per unit area normal to the z direction is given by the time average of the real part of the poynting vector S of magnitude (13) S = T quali Only the e We s Thus is a c (19) c IE X HI 411" =  c HY = ( 411" E JX 411" C)2 ZH If we Y .310 QUANTUM THEORY OF SOLIDS ELEC imaginary part X is called the surface reactance.Hy/c. For the normal skin effect k = (1 + i)/oo. Z . We now examine the contribution of the surface to the inductance of a magnetizing circuit: consider a flat solenoid with inside it a flat slab of conductor of thickness 2d. Because aEx/az = iWIJ. Let gJ be the current per unit length in the solenoid.. (11) with (17) iWIJ. c2 = (1 _ i) 211"IJ.c2 aEt/az +0 kc 2 with z normal to the surface and directed inward. Thus the ratio of the skin depth to the wavelength determines the magnitude of Z. The time average of the real and «(J\{SI) =! (:J H2(J\{Z\. p(k ll ) const . . From the equation for curl E we have (10) for permeability IJ. ..
I. 16 311 the the with H(d) (17) = 41rJJ/c.. Thus the concentration of effective electrons is neff = 'Yno/ A. where "I is a constant of the order of unity. 27r'Yuow c2A and the surface resistivity <R {Z} is (21) R = 27rW c2 (~)Y. we find (20) real 03 = . 27r'Yuow This indeed is of the form of the correct answer derived below. CH.. W For a specimen forming one end surface of a rectangular cavity in the fundamental TE mode the effective change in length of the cavity can be shown to be (18) ol =  47r Xf/ { Z }.. where p(ky) is the radius of curvature of the slice of the fermi surface at constant ky. because Uo a: A. We suppose that the effective electrons are those in an angle '""0/ A. 1. Thus a measurement of R determines the momentum at the fermi level in the direction of the electric field: (22) U xx ne 2 = m:xVF A ne 2 = kF • For a general fermi surface the surface resistance tensor component Rxx involves the form of the fermi surface through Ip(ky)1 dky. The most important property of (21) is that the surface resistance is independent of the mean free path A. The effective f . from the definition (9).IDS ELECTRODYNAMICS OF METALS. with ce of flat ngth "I ~ 10. Thus the effective conductivity is (19) U S of err n e rre . L = <R I Thus. Only those electrons traveling nearly parallel to the surface remain in the electric field long enough to absorb a significant amount of energy. c gth n is The extreme anomalous skin effect (A/o» 1) can be understood qualitatively in terms of the ineffectiveness concept of Pippard. 2 T "I A ° U o· If we use U cff for Uo in (5) and solve for the effective skin depth.... (2C/iw)E x(d)) (c/47r)Hy(d) = 2c <R{ iZ} W = 2c f/{Z}. This result is seen directly from Fig.
Here p is the radius of curvature in the slice. 2c4 e2 f dky Ip(ky)1 . 325 (1957)J on copper demonstrated the power of the anomalous skin effect in the determination of fermi surfaces.. B.. If the surface is polycrystalline with crystallites oriented randomly. Slice of a fermi surface at constant k". the volume in k space which contributes to the current is Oeff (28) It iE (29) = J 1 dky e8 xTlp(ky)I(')'oj A). (London) A250. "Dynamics of Conduction Electrons" in LTP. The work of Pippard [Trans. ThE (26: wh{ (27J FIG. We fun( If tl ordE current involves only the electrons in the sectors shown as lying in the appropriate angular range. Soc. In a relaxation time the electrons in the sectors advance by llkx = e8 xT. showing the effective electrons whose velocities lie within the angle 'rfJ/ A of the surface. We COlle so that (23) Jx = eVF47r30cff = 4. 1. (31) We i (32) T: .312 ky QUANTUM THEORY OF SOLIDS ELF 11 sen intE (25 . Pippard. Roy.3 ')'0 e 8x 2 J dkylp(ky)l· This defines the effective conductivity for a general fermi surface. For further details see A. the anomalous skin effect leads to a determination of the total area of the fermi surface. Then for diffuse scattering (24) '( of tl as if elec1 a cu (30) Thi~ Rxx = 3~~w2 )~~ 64.
afo ae. The surface of a semiinfinite metal is in the xy plane.iwr T II = . 16 313 Mathematical Theory of the A nomalous Skin Effect. We must only provide the proper electric field at z = O.2 j c + 2 (dE)  dz +0 o(z). the electrons in each half will have the same history as if the reflection were specular. J(q) = (21r)~ f _«)«) dz jeiqz . with z directed towards the interior. C We treat the electrons as isotropic with mass m. (27) trons ius of We eliminate H: + C2 w2 E _  41riw. The distribution function is f = fo + lI(v. If we consider the remaining half of space (z < 0) filled with another piece of the same metal.z).E(z) e afo m avx = evxE(z).iwt . rface.(4?riw/c 2)J(q) + (2/1r)~(dE/dz)+0. The transport equation gives us another relation between Sand J. ce is alous fermi (31) 2 E = 4?riw .LIDS ELECTRODYNAMICS OF METALS. If the relaxation time is T. 2 J. H(z) = H yo(z)e. (25) Then the maxwell equations are (26) dH dz iw 41r . We express each term as a fourier integral and find (32) q 2S(q) + (w/C)2S(q) = . because the field is damped in both ± z directions: (30) e~t~e~L' d2E .2 dz w +2 c This condition can be incorporated into (27) by adding a delta function: 7)] on n the pard. . the boltzmann transport equation in lowest order for f 1 is (28) g in ns In hich alI vz dz + 1 . CH. It is convenient to work with the fourier transforms defined by: (29) Seq) = (21r)~ f _«)«) dz Eeiqz . We write E(z) = Exo(z)eiwt. c c d 2E 2 dZ dE = iw H . where fo is the unperturbed distribution. We assume specular reflection of the electrons at the surface. E+J. dz c where now j(z) is the current density. The gradient of this artificial field will have a cusp at z = 0.
1 . Reuter and E.t 0 the result (38) becomes (39) O"xx(O) t ne T 1 = m 1 . H.1 .iWT /1 dx' 1 1 1 .iWT + iqvZT)if.>I(q)  aloTev x8(q) ae rv O(e  eF)TeVx8(q).() 1 'l.qrv cos .>l (q) = 8(q) 3 3 e 411"3 m T 2 f  w in iqrv z We define the conductivity tensor component O"xx(q) by J(q) = O"xx(q)8(q). 'l.iWT 2 in as th th to in agreement with our earlier result.314 QUANTUM THEORY OF SOLIDS EL We define the transform (33) <I> 1 (q) = (2'1J)~~ f on _0000 dz !lC iqz • Then (28) becomes (34) (1 .qvzT q. for a fermi gas at kBT «eF. Proc. We evaluate (38) in the extreme anomalous region Aq » Let (40) A' .WT . A195. Sondheimer.eF )evxT f. H. The general solution is given in detail by G. 336 (1948). 11" Alql th fu au (1'.1A 'tWT 11  iWTI. then (38) us 3 em T O"xx(q) = . ZWT 'l. Soc. au p C . on co tu st re The electric current density (36) j(z) = e f so d k v.x2 + iA'qx  C:::! 2 tan 1  Aq C:::!. +.iWT' then the integral over d(cos 8) is (41) 1 1 .4 2 11" 2 f dv v4 13(e ~ eF) /1 d(cos 8) 1 1 +./1 3 (4 has the fourier components (37) e J(q) = 41r 3 f d k vxif. . (3t» cI> ( ) lq The solution is 13(e . E. The reader may verify that for q . Roy.iWT . sin 8 2 fo (4 The whole problem now revolves on the evaluation of the integral over d(cos 8).
.= t(3 J. The static field Ho lies in the plane of the sample. 412 (1958). Bardeen. the integral in (44) at z = 0 has the value (45) 2i(2A02/3 )J3 (OO 7r }0 1 d~ + ie = _ 2(2 g 7r 2A02/3)~3(1 + i3~~) .27rW 2A/e 4lTo) ~ (1 . The quantum theory of the anomalous skin effect in normal and superconducting metals is treated by D. neglecting the displacement cur rent term in (w/e)2: (43) so that 8(q)( _q2 + 47rilT xx we. The most suitable geometry was suggested by M. e dE/dz +0 'wrl· in agreement ·with result of Reuter and Sondheimer.6. Kaner [Soviet Phys.2) = (2/7r)~~(dE/dz)+0. Phys.. and (45): (46) IS IS (J Iver Iter .JETP 3. Note that this is a transverse conductivity (x 1. 1~ Zoo = 2..: . but we have not assumed wr «1. C. (44). Using (42) and setting ~ = q(2A02/37r)~3. (44) 2 1 (dE) E(z) = 7r dz +0 1 00 00 iqz dq e 2 ' q + 2i(lT xx /0 lTo) 2 where 0 = e2/27rwlTo. A.23' ). Because lTo ex: A. CH. 856. Azbel and E. Mattis and J. 772 (1956)].q) and therefore is not identical with the longi tudinal conductivity associated with the longitudinal dielectric con stant of the electron gas of Chapter 6. CYCLOTRON RESONANCE IN METALS The observation of cyclotron resonance in metals naturally requires that the surface impedance should show a resonance behavior as a function of the static magnetic field.. 4Alql = lTo . 111. using Dwight.der 47riw ( E ) . 4Alq\' on using the relation 2mCF = (37r 2n)%. Rev. For diffuse surface reflection it turns out that the factor! is absent from Zoo' It is believed that reflection is likely to be diffuse except under special surface conditions. the rf . 1. The surface impedance Zoo in the extreme anomalous region found from (11). 16 Thus 315 on neglecting terms of higher order in (A'q)l. We combine this result with (32). we see that Zoo is independent of the mean free path.IDS ~LECTRODYNAMICS Ol<' ME'rALS. (42) ne 2r 37r 37r lTxxCq) "' .
316
QUANTUM THEORY OF SOLIDS
ELl
electric field also lies in the plane of the surface and may be either parallel (longitudinal) or at right angles (transverse) to Ho. If the relaxation time is sufficiently long, we may think of the carriers as spiraling about H o, dipping once each cycle in and out of the rf field localized in the skin depth. Resonant absorption of energy will occur if a carrier sees an electric field in the same phase every time the carrier is in the skin depth: thus at resonance
(47)
=p; We W
(51
Wf spi refl
27r
27r
p = integer,
(5~
or We = w/p~. where p is the index of the subharmonic. Recall that in cyclotron resonance in semiconductors only the possibility p = 1 occurred because the rf field was assumed to penetrate the specimen uniformly. A qualitative argument given below suggests that in the presence of the magnetic field
(48)
Z~(H)
r.J
so
(5::
27r  i 27rW)]~ Zoo(O) [ 1  exp (  . WeT We
(5~
This is indeed periodic in w/we. To understand (48), consider the contribution to the current and thus to the conductivity of a single carrier having an orbital radius large in comparison with the skin depth. The change in phase of the rf field in the period 27r/ We is 27rw/w e ; with collisions W ~ W  i/T, so that on each revolution the current is multiplied by the phase factor
(49)
wh
(5f
an~
eW == exp (_ 27r _ i 27rW).
WeT We
as
del
The phase factor of the total current arising from all cycles is
(50)
(5f
1
+ e + e + . . .
w 2w
=
1 . 1  eW '
this quantity is involved in the effective conductivity, as is clear from Chamber's formulation of the transport equation. From (21) or (46) we know that Zoo cc (1/O"eff)~' whence (48) follows. A result closely similar to (48) follows from the solution of the transport equation in the extreme anomalous limit in the presence of a static magnetic field parallel to the surface. We shall see that the treatment is exactly the same as without the field, but now a term We afI/acp is added to the lefthand side of the transport equation (28), where We = eH /meC is the cyclotron frequency and cp is the azimuthal angle about Ho as polar axis.
Tl Rf
Te
(5'
wI lin
sp
(5:
~j
DS
ELECTRODYNAMICS OF METALS, CR.
16
317
ler he as ld mr ler
In a static magnetic field (51)
Ho the linearized transport equation is
m av x me
dV
. 1,wlI
eE af0 alI + Vz alI +  + e v x Ho . az
=

II .
T
We consider specifically the arrangement with HollEllx. Introduce spherical polar coordinates in velocity space so that v == (v,O,cp), referred to i as the polar axis. Then
(52)

eH 0 afI alI x •v X = WeX . curl v f 1 = We  , me av acp
A A
in 1 en of
so that the transport equation is
(53)
(1  1,WT)1I
.
.. alI alI + VT sm 0 sm cp  + WeT az acp
= eTV COS 0  '
afo ae
In terms of the fourier transforms,
(54)
(1 +
ivfq sin 0 sin",
+ w/f :"') <p.(q)
 0(0  of)efv cos Oe(q),
he .gle in is he
where f == T/(1  iWT). and has the solution
This is a simple linear differential equation
(55) <I>l(q) = o(e  eF)ev cos Of,(q)w e
.
j'"
d ' cp
~p
I
1
 co
(cp'  cp)  ivfq sin O(cos cp'  cos cp) ' WeT
I
as may be verified by differentiation. density is
3
The q component of the current
(56)
J(q) = em 47r 3 v 3 dv cos 0 sin 0 dO dcp . <I>l(q).
f
ar
1)
The integration is not trivial; for full details see S. Rodriguez, Phys. Rev. 112, 80 (1958). In the limit vFq/W e » 1, which is equivalent to Te » 0, where Te is the cyclotron radius, it is found that
(57)
he fa he rm 8), hal
37r ne f,(q) h q =    cot J() 4 mVFq
2
(1 
iWT 7r ) , WeT
which shows periodic oscillations provided WeT, WT »1. In the same limit the surface impedance in the extreme anomalous region with specular reflection is (58)
Zoo(H) = Zoo(O) tanh~ [7r(1  iWT)/WeT],
318
QUANTUM THEORY OF SOLIDS
ELEC'
according to D. C. Mattis and G. Dresselhaus, Phys. Rev. 111, 403 (1958), and S. Rodriguez, Phys. Rev. 112, 1016 (1958). The perio dicity of (58) is the same as the approximate form (48), because sinh 2x  i sin 2y. (59) tanh (x  iy) = cosh 2x + cos 2y In the extreme anomalous limit the result (58) applies to both the longitudinal and transverse geometries. The boundary condition in a magnetic field is more complicated than realized by these authors: see Azbel and Kaner, JETP 39, 80 (1963). An experimental cyclotron resonance curve for copper, together with a theoretical calculation for adjusted values of me and 1', is shown in Fig. 2. The mass involved is given in terms of the area S of the fermi surface by the relation 1 dS , (60) me = 2w d€ from (11.54). Stationary values of dSjd€ with respect to kH define
~ .~
)(
::t: ~ "tS E
3

~
the s' resol In reso skin buti the equa the ferm· to S T as in cyclo mass effec invol ferm T field Haer cond
DIE
W havi The
(61)
so th
::t: ~~
~Q)
(62)
_0
"tS§.
Thu
WT
= 10
(63) wher, Qthe writ N
o
0.25 H/Hc
0.50
FIG. 2. Cyclotron resonance absorption in copper; comparison of calculations of the magnetic field dependence of the derivative of the surface resistivity with experimental results at 24 kMc/sec. (Mter Kip, Langenberg, and Moore.)
.IDS
ELECTRODYNAMICS OF METALS, CR.
16
319
403 rio
the na rs: ith in rmi
1
ne
the sections of the fermi surface which contribute to the central and resolved portions of the cyclotron lines. In the cyclotron resonance experiment in metals, we observe the resonance of a few selected electrons with orbits passing through the skin depth. These electrons do not necessarily have the same contri bution to their effective mass from electronelectron interactions as in the de Haasvan Alphen effect where all the electrons participate equally. One must not expect the cyclotron experiments to reproduce the masses obtained from the de Haasvan Alphen effect, even if the fermi surface is such that dS/de in (60) can be related unambiguously to S itself, the quantity involved in the de Haasvan Alphen effect. The effective mass is altered also by the electronphonon interaction, as in the polaron problem, but we expect this effect to be the same in cyclotron resonance as in other experiments involving the effective mass at the fermi surface. Optical experiments, however, may see the effective mass of the electron unclothed by the phonon; the electrons involved in an optical transition will not, however, lie only on the fermi surface. The theory of cyclotron resonance in metals when the magnetic field is normal to the surface is discussed by P. B. Miller and R. R. Haering, Phys. Rev. 128, 126 (1962); in this geometry the resonance condition contains a doppler shift.
DIELECTRIC ANOMALY
We consider now the dielectric properties of a free electron gas having n carriers per unit volume of effective mass m* and charge e. The acceler~tion equation is, assuming WT » 1, (61)
m*i = eE;
w 2m*x
eE,
so that the free carrier contribution to the dielectric polarization is (62)
P = nex =
~E. m*w 2
2
Thus the dielectric constant is given by (63)
E
=
1  ;2 mw
47rne 2
+ 47rXa,
ions ith
where Xa is the dielectric susceptibility per unit volume of whatever other material is present. The carrier contribution to E may also be written as wp 2 /w 2 , where Wp is equal to the plasma frequency. Now at low frequencies wp 2/wJ}. will dominate E and make it nega
320
QUANTUM THEORY OF SOLIDS
E
tive.
(64)
The dispersion relation for electromagnetic waves is, with,.,. = 1,
w = ck
2 2 2 /E;
w
It fr th
r'
if
E
f'"OooJ
_w p2/w 2, we have _w p2 k
= c2k 2,
=
or
(65)
iwp/c.
Thus the wave is damped in a metal in a distance of the order of the Debye length, 10 6 cm, independent of frequency provided that WT » 1 and Wp » w. This result neglects the anomalous skin effect. For W higher than a root Wo of
(66)
di co in fie
(6
E(WO) = 0,
the dielectric constant becomes positive, the wavevector is real, and a wave may propagate in the medium. This theory accounts for the onset of transmission in the alkali metals in the ultraviolet. The change in the reflectivity of the crystal when W passes through Wo is known as the dielectric anomaly_ If the carrier concentration n is known, a determination of Wo gives us a value of m*. The usefulness of the value naturally depends on the simplicity of the band edge structure. The treatment above assumes that we are not in the region of the anomalous skin effect. It is quite possible in the visible region of the spectrum to have WT » 1 without having A > 5. The situation in the visible region of the spectrum is discussed by Reuter and Sond heimer, as previously cited, and by T. Holstein, Phys. Rev. 88, 1427
(1952).
or
(6
In su
(7
be al
With values of the electron effective masses for the alkali metals calculated by Brooks, the transparency limit should occur at the optical wavelength 1840, 2070, 2720, and 3000 A for Li, N a, K, and Rb, respectively. The values observed are 1550, 2100, 3150, and 3400 A. No correction for ion core polarizability was made; the cores should have an observable effect. We see from (49) that the transparency limit in the presence of Xa is
(67) Wo 2
2 Wp
(7
TI of
(7~
1
+ 47rXa
In metallic silver the value of (1 + 47rXa) ~2 is about 2, from reflectivity experiments. This is consistent with estimates of Xa from the refrac tive indices of silver halides compared with alkali halides.
MAGNETOPLASMA PROPAGATION
A striking propagation effect was observed by Bowers, Legendy, and Rose [Phys. Rev. Letters 7, 339 (1961)] in high purity sodium at 4°K
in4 th al1 eh: ca n
IDS
ELECTRODYNAMICS OF METALS, CR.
16
4
321
1,
when placed in a static magnetic field of the order of 10 oersteds.
It is observed that real electromagnetic waves propagate in metal at a
the at
t.
frequency of the order of 10 cycles per second and at wavelengths of the order of 1 cm. That is, the phase velocity of light is reduced to 1"110 cm/sec, which corresponds to a refractive index "'3 X 10 9 and a dielectric constant "'10 19. The electromagnetic modes under these conditions are called helicon modes and were predicted by Aigrain. We consider the equations of motion of a free electron of mass m * in a static magnetic field H parallel to the z axis and in an rf electric field with components Ex, Ey:
(68)
m*x = eEx
We =
2
da the ge wn ,a lue he of
III
e +yH; c
m*y··
eE  xH
y
e c
'
or, with
(69)
eH/m*c,
;
w X
e E x m
?,wweY,
.
.
 W Y = ;
2
e Ey m
+
?'WWe X •
.
In the conditions of the experiment W« We, so that the dielectric susceptibility tensor is given by, with wp 2 = 41rne 2/m*,
(70)
41rx =
="J
d 27
(
?,W p
•
2
t
0
iw p /ww e
2
WWe
o o
W p
o ) 2 2
/w
"J
=
=E,
because »1. For a wave propagating with wavevector k along the z axis the maxwell equations reduce to
kHy =  (ExxEx c
W
2 wp / WWe
,als cal lb,
+
ExyEy);
W
kHx =   (EyXEx
W
A.
~Ild
lCY
(71)
c
+
EyyEy);
kEy =  Hx; c
kEx = H y. c
W
Then on forming the equation for Ex of ~.zx and Eyy,
(72)
+
iEy we have, with the neglect k 2Hc , = 41rne
k2
2 WWp
ity
!tc
~; We
or
W
nd
:lK
independent of the particle mass; the experiment is therefore suited to the determination of the effective charge of a carrier in a metal, although it appears fairly well established theoretically that the electronelectron interaction does not make the effective charge on a carrier differ from e. In (72) let k = 10 cm I ; H = 10 4 oersteds, and n = 10 23 cm 3 ; then W "' 60 secI.
322
QUANTUM THEORY OF SOLIDS
ELEC
For a general energy surface we can discuss the problem in the limit WeT» 1 with WT «1. Pippard has given the general limiting form of the static magnetoconductivity tensor. \Vith H II z and with no open orbits,
field:
CTO/W,
AH2
(73)
5
=
( CHI
GH
I
GH 1 DH 2 EH 1
CH ) EH 1 F
1
wheI lost. the (
,
spa
Tl mag]
(81)
where A, C, D, E, F, G are independent of H.
(74)
E/,v
In general
= i 
41r
CT/,v
W
+
O/'V;
for
W
«we «wp as above, the secular equation is, approximately,
Now
(82)
(75) provided G
(76)
~
c2k,2 I i47rGw/H
i47rGw/H I = 0, 2 2 c k
wheI then
(83)
0; the solution of (75) is
W
= ±k2c2H/47rG,
whm
(84)
of the form of (72). We emphasize that all magneto resistive effects are included in (75). If there are open orbits in a general direction in the crystal, the static (WT« 1) magnetoconductivity tensor in the xy plane has the form 1 AI GH ) (77) 5 = ( GH 1 A2 ' where AI, A2 are independent of H.
(78)
If cA 1, cA 2 » w, then
t '"" i41r5/w.
Tl ma minE: The the 1 In to t: relat
(85)
The general secular equation is, from (71),
c 2k 2
W2 Exx Exy
If
(79)
Exy
c2k 2
w2
Eyy
= O.
(86)
then
(87)
If Al = A2 = A, then for
(80)
W
WT«
1
k 2c2H = ± 41r(G + iAH)'
Am
skin
D:
reSO]
N ow A is the fraction of the static conductivity (in zero magnetic
,IDS
ELECTRODYNAMICS OF METALS, CR.
16
323
the iing V'ith
(fO/WeT.
field) which is carried by open orbits and G/ H is some average of Thus in magnetic fields sufficiently strong that WeT» 1/1], where 1] is the openorbit fraction, the lowfrequency resonance is lost. If H is not this large, the resonance will merely be damped by the conductivity associated with the open orbits.
SPIN RESONANCE IN THE NORMAL SKIN EFFECT
The surface impedance in the normal skin effect involves the magnetic permeability: from (12)
(81) Z
• (27rWJ.1.)~ = (1  1,) C2(f
ex:
• ~2 (1  1,)J.1. •
Now write
(82)
J.1.
= 1 + 47r(XI
+ iX2),
where Xl = <R {x} and X2 = !J {x}. If, as in nuclear resonance, then we may expand J.1.Yl. to obtain
(83)
Z
ex:
Ixl «
1,
(1  i)(1
+ 27rXI + 27rix2), + 27r(XI + X2).
whence
(84)
ects the the
<R{Z}
ex:
1
This shows that the actual power absorption near nuclear resonance in a metal specimen thick in comparison with the skin depth is deter mined by Xl + X2, and not by the absorptive component X2 alone. The skip. depth itself varies as we pass through resonance and therefore the power absorbed involves Xl as well as X2. In ferromagnetic resonance in these conditions it is not possible to take as small. We define real quantities J.1.R and J.1.L by the relation
Ixi
(85)
Z
ex:
(1 
1,)J.1.
.!/.!
=
J.1.R " 
~(,.
WL ' ".
1 (,
If
(86)
J.1. = J.1.1
+ iJ.1.2,
J.1.L
then
(87)
J.1.R = (J.1.1
2
+ J.1.22)~ + J.1.2;
=
(J.1.1
2
+ J.1.22)~2 
J.1.2.
letic
A measurement of losses gives J.1.R; of inductance, J.1.L. Dysonian Line Shape. An interesting result is found in electron spin resonance in paramagnetic metals if the spins diffuse in and out of the skin depth many times in the relaxation time for spin relaxation.
324
QUANTUM THEORY OF SOLIDS
ELECTRC
This is not necessarily the same situation as the anomalous skin effect, because the translational or conductivity relaxation time for electrons in the alkali metals is very much shorter than the electron spin relaxa tion time. In our derivation we assume we are in the region of the normal skin effect with respect to the electrical conductivity. The Bloch equation with diffusion and a single relaxation time Tl is
(88)
of an elec
in the lir Hint: cal
aM M = ",M x H  at' Tl
+
D V2M
'
for the transverse components of magnetization. simultaneously with the eddy current equation
(89)
V2H =
We solve this
to terms bation
~u (H +
c
4nM).
Note tha"
These equations lead to a 2 X 2 secular equation formed from the coefficients of M+ = Mx + iMy; H+ = Hx + iHy. The roots of the secular equation give the dispersion relation k(w); there are two differ ent roots. The two solutions at given w must be combined in order to satisfy the surface boundary condition on the magnetization diffusion. If we suppose that the spins are not relaxed at the surface, then at the surface k· grad M = 0, where k is normal to the surface. The shape of the magnetic absorp tion line under these conditions looks rather like a dispersion curve. The solution is discussed in detail by F. J. Dyson, Phys. Rev. 98, 349 (1955).
PROBLEMS
1. Let Ho and k be liz, and let there be an undamped periodic open orbit parallel to the k:r; axis. Show that the dispersion relation of electromagnetic wa ves in the metal is 2 W f"V kcwcw*/w p , where w*2 = 47rnopene2/m is the effective plasma frequency for open orbits. 2. Consider a film of thickness D; show that D > c/uo (rather than D > a o) is the criterion for the film to reflect most of the radiation incident normally upon it. We assume c/uo « a o; this problem is a straightforward exercise in the use of maxwell equations, although it is best solved by physical reasoning. The result means that the reflectivity in a very thin film is mainly a question of impedance mismatch, rather than power absorption in the film. 3. Show by the methods of Chapter 6 that the transverse dielectric constant
,IDS
~ct,
ELECTRODYNAMICS OF METALS, CH.
16
41ri 31rne 2 W 4mvFQ
325
of an electron gas at absolute zero is
( ) EW,q 41ri
=(j
ons xa
the
1
W
q
=,
This result is in agreement with (42).
f'I
is
in the limit wT » 1 and (kq/m) Hint: calculate
»w.
(jq)x = Tr eiq.xpv x = ~
m
L kx(kJ opJk + q) k
2
mc
ne A q,
ihis
to terms of O(A), where the density fluctuation op results from the pertur bation I e 'A xPx; Ax Aqe,qZeiwt + cc. H  mc Note that
(jq
is real even when there are no collisions (T  ? 00).
the the
~
fer
to
on.
at
'rp 'Ye.
349
rbit etic
3.
00)
tHy
~
in ng. lof
3.nt
326 The probability per unit time . V. a good illustration of the application of ultrasonic measurements to the determination of fermi surface dimensions is given in the paper by H. although this applies with less force to the subharmonics in cyclotron resonance. We shall not enter into a discussion of the experimental data. R ev. 128. the perturbation is (2) H' = From (7.::l is the dilation and co(k F) is the fermi energy CF. see also the references cited there. J. prol T where p is the density of the crystal.::l(x).14) llleB jicF L (1 / 2 pWq)~4 Iql (aqct+qCk kq atCt_qCk).fco(kF). We have seen in the chapter on the electronphonon interaction that for a free electron gas (1) (8) Thl (9) C(kF. I t is equally true that theoretical formulation of the general attenuation problem in metals is unusually subtle and the area is littered with traps. The standard transition probability calculation assumes implicitly that the electron mean free path A from all causes is long in comparison with the phonon wavelength A. Easterling. Bohm and V.X) = co(k F) . LONGITUDIN AL PHONON FREEELECTRON GAS (6) wh (7) wit ter rna We consider first the attenuation of a longitudinal phonon in a free electron gas in the absence of a static magnetic field. The essential experimental virtue of the ultrasonic method for study ing fermi surfaces is that at a given value of magnetic field intensity the frequency needed for resonance is much less than for cyclotron resonance. Phys. (3 Acoustic attenuation in :metals 17 o (4 w so (5 Ultrasonic phonon attenuation studies in metals in static magnetic fields are a powerful tool for the study of fermi surfaces.A t fr. 1021 (1962). otherwise the electron states cannot be treated as plane waves or as Bloch functions. Thi where.
ekq)' etic ally lem ps.ii q ) . Vkfo(k)]o (k.0 (qkp. We have neglected the term in q2 in the delta function.~ ek+q) .fo(k PC s 41reF 2q + q)]o(ek + Wq C. where the phonon relaxation time Tq is given from (4) and (5) by (7) T "" q 1 161reF q ~ fo(k)[q .Wq 91r pC s m 2cs /81r2.~. for phonon emission (5) w(+) is the velocity of = 47reF2q 9. Thus the energy attenuation coefficient a q is given by (9) a q == . dy sity ron 's in the OllIC We form. The electrons which are chiefly responsible for the absorption of energy from the phonon are those with velocity component along the phonon direction equal to the phonon velocity. ) Iven 021 with allowance for the two spin orientations. CH. ae m m eF) = _(21r)2mcs J dk kfoo(e 2 eF 2m 2 .Wq .= T qC s 1 (Aq» 1).. k q PC s m . Similarly..fiq) dt 1 .T q (nq . k = = (21r)3 Jdk 21rk2 f 0 1 afo qkp. The statement of .ACOUSTIC ATTENUATION IN METALS.. using (4) and (5). Here A is the mean free path of the conduction electrons as limited by all relevant processes.Wq .fo .n q fo(k)[1 . .(nq PC s + l)fo(k)[1 .14) time This is the correct standard result for the model.fo(k .q)]o(ek . dp. (4) w(_) = 9. The sum over k may be rewritten as (8) free dard tron mon .Wq ) .lane the ~ L.2 .. (6) d(nq .nq  IIH'lk. because q/m «c.nq)1 2 o(ek + Wq  ek+q)' On averaging over an electron ensemble in thermal equilibrium. 2 9 L. 17 327 that a phonon in a state q will be absorbed in scattering an electron from k to k + q is (3) w(_) = 21rI(k + q. where fo is the fermi distribution function and sound. 7.
This result is of the order of Aq times the result (9). aj 1.q)2 . 205 (1948).q m = vqq. with the usual neglect of the term in q2. Kittel. then it 1 2 See. Proy. on the assumption of a constant electron relaxation time. Transport TreatmentLongitudinal Phonon. 2 where the viscosity coefficient 11 of a fermi gas is given by2 (11) 11 = trcnEF. so that a q 0: 0"0. aj = _ j .fo.v. The boltzmann equa tion enables us to give a unified treatment of the above problem for arbitrary values of Aq. Elementary statistical physics. where Vq is the electron velocity component in the direction of q.3 3 pc s Wq . the electrical conductivity is (13) ne2Tc 0"0 We recall that whe (18) m N (19) on the same model. In the absence of magnetic fields the transport equation in the relaxation time approximation is (14) whe (20) aj 1. Rpts. In the other limit of short electron free path Aq = 27rA/'A « 1. 206. for example. Wiley. the problem is that of the damping of phonons by the viscosity of the electron gas. 1958. Wq fun Thi Phy If (15) = csq rv  1 k . Physics 11. C. have the result (12) aq  Thus we usin f= (17)  8 nEFTc 3 15 pcs Wq 2 (Aq« 1). C. Kittel.eE .ACO energy conservation is app k2 12m W q (k 1. It is well known from acoustics l that the energy attenu a tion of gas in this limit is (10) aq  the con pho flue foll elee (16)  4 11 .328 QUANTUM THEORY OF SOLIDS . p. This proportionality is confirmed by experiment. at ax m av T We suppose that the electron scattering is by impurities. . 2m whence.
ac aio Equation (19) is the constitutive equation of the medium. CH.r3 2 f d 3k v".iWT + iq .OF SOLIDS ACOUSTIC ATTENUATION IN METALS..611'3 nOC8 ~ f d 3k 1 .f" '/. VT . Holstein. and CF O ex: n*. ac ah and the conductivity tensor is (21) (J' iesj then it = . VT ac d: Now the electric current density je is given by (19) is confirmed je = . [E + (mu/eT)] + fCFO(ndno)] aio. 113.iWT . We write n = no I:. VT . viI + eE· v  ac t'oJ  iI    T T aio mv· U + fC F 0 n1) .t» j . If u(x. then (16) Jo t'oJ io(v. + iq . with 1( Thus we using aio/ac i == io + i1.t) jCF(X.v" 1 .iWT .n1(x. no Thus (14) becomes.u(x. then (15) Jo(XjVjt) = io(v . 479 (1959).WJ 1 = iJiO/acF. 17 329 appears reasonable to take Jo as the equilibrium electron distribution function in the local coordinate system moving with the local lattice. . Phys.. . no ac recall that whence (18) iI = _ [Tev.t) is the local lattice velocity. aio + '/. + iq . where the diffusion vector R is defined from (18) by (20) R  . 1 . The strong tendency of conduction electrons to screen Huctuations in the positive ion density means that the electrons will follow closely the lattice dilation. the 3ity of the 'gyattenu the fermi energy is modified by the phonon because the local electron concentration is modified by the dilation accompanying a longitudinal phonon.e T "'" 4. (17) .no)  U . This important point has been considered in detail by T. av aio + n1 (Jio (In aio ( mv· U = io .2e 3 mann equa problem for le transport (211') f d3 kiIv = (mu) + eT + n1 E v ecs R . of q. X« 1. Rev.t) for the electron concentration. ac + fCF 0 n1) .q.
wn Ie + q • je = = O. 3 4CF2 7r nocs 2 (1  'l.iWT a ~  . wh( (37 When we study the attenuation of transverse phonons. The electron current density satisfies the continuity equation (27) for ma1 (33 : ape+divje=O.neu z). we will need an equation connecting j. for c = p.1 a .tan a).L' tim (38 where is the acoustic velocity and c the velocity of light.tan. = 'I.WT 1 1 . hert equ (3{ where j is the total current density and is composed of the electronic current density je and the ionic current density (e)nu. for q parallel to the z axis.iWT): (22) T (31) 0' 2Z = 0'0 1 .' 3 2 3 [(1 + a 2 ) tan. (35: The maxwell equation needed to relate jz and Ez is (28) div E = 47rp. (32J a whe (33. = 1. . ) . The result (23) was considered previously in connection with the anomalous skin effect.L' The maxwell equations for curl E and curl H may be combined to give. 33 (a . In the limit a ~ 0 the diagonal components ~ 0'0/(1 ..1 a)' 0'0 . 2 (a . so that (25) jez = U zz ( Ez + muz _ eT iamv F 3eT • no nl). We write (2G) j = je .a].L and E.:. The nonvanishing component of R is (24) The oth4 virt scat imp F wav Rz . a and the nondiagonal terms are zero in the absence of a static magnetic field.iWT).neu. 'I dra so that (29) (36: wE z 47rijz 47ri(jez .330 QUANTUM THEORY OF SOLIDS ACO We may integrate (21) directly to find. (30) 47ri E. with a = qA/(l . or div E 47r div j. (23) U xx = U yy = 'l.L Cs (c s / c) 2 • '] = .WT . 1 _ (cs/C)2J. at . The electric field E arises from the small local charge imbalance.
,IDS
ACOUSTIC ATTENUATION IN METALS, CH.
17
331
.xis,
The power absorption per unit volume is given by
(31)
<P = !<R
.etic WT). the
The term in E is the ohmic loss of the electrons. We see that the other term is the power absorbed by the lattice from the electrons by virtue of the fact that the electrons have a mean velocity (v) before scattering and u just after scattering. This collision drag term is important chiefly at high frequencies or high magnetic fields. From the equation of continuity (27) we have for a longitudinal wave
(32)
j: .
· IJ:.
) E  nomu*  T  «v)  u) .
nl
qjez/we = jez/cse,
whence (25) becomes, dropping the subscript z on j, E, and u,
(33)
. Je
=
1
+ i(u zz /uO)(avF/3c s)
uzz
( u) Em + eT == , u (E
mu) , +eT
nce.
hereby defining u'. This relation must be consistent with the maxwell equation (29); on eliminating E with the use of (29) we have (34)
.
Je
=
(411"u'neui/w) + (u'mu/eT) 1 + (47riu' /w) ::::: neu,
onic tron
for w «u' and w «W0 2T. In this limit the total current j approxi mately vanishes. We obtain the electric field by substituting (34) in
(33) : (35)
E~U(;~ ;}
The power density dissipation is given by, with the neglect of collision drag in this order,
(36)
<P~!u*u<R
I
o ne  nm) = nmu*u    <R (u  1 ) , u' T 2T u'
2 2
need HIE
whence, using the definition of u' and taking a to be real (WT
(37)
<P~ 
«
1),
nmu*u [ a tan 1 a  1 ] . 2T 3(a  tan 1 a)
2
The attenuation coefficient a is equal to the power density dissipa tion per unit energy flux:
(38)
a
<P/~pu*ucs,
332
2 1
QUANTUM THEORY OF SOLIDS
ACO MA
where p is the density; thus for the longitudinal wave (39)
nm (
a tan a
I"'o.J
a = PCsT 3(a _ tan 1 a) 
) 1 ,
which is the Pippard result, with a Aq. This agrees with (9) in the limit Aq » 1 and with (12) in the limit Aq « 1. Transverse Wave Attenuation. For transverse waves the local lattice velocity u is perpendicular to the wavevector q of the phonon. We take u in the x direction and q in the z direction. The density fluctua tion nl is zero for a transverse wave. We have for the current density in the x direction
(40)
v.
wit ma. of t trea refe Phy. trea
j, = u" ( E
+ ::}
stu ne
which must be consistent with the maxwell equation (30):
(41)
E
I"'o.J

;;
411"i (cs)2 (Je .  neu).
;
On eliminating E,
(42)
Je =
.
1
+ (411"iu xx /w)(C s/c)2
Uxxu
(m eT
2)' + 47rinecs Wc 2
where the tenn in m/er is usually negligible. Now 411"iuxxcs2/wC2 is essentially (}../ 0) 2, where }.. is the acoustic wavelength and 0 is the classical skin depth. Below the microwave frequency range }.. is usually» 0, so that 2 . . mwuc . wneu (C)2 , (43) Je ~ neu  1,    2 + 1,   47rerc s 47ru xx Cs and E mu + neu, (44) er U xx whence nmu*u Uo  , (p1"'o.J_(R (45) 2T U xx
I"'o.J
1
1)
and, using (23) in the limit WT
(46)
«
1, the attenuation of a shear wave is
a = nm(1  pC 8 T
t
1) ,
where
(47)
FIG.
props
IleattE
t
=
2a 3 [(1 + a 2) tan l a  aJ.
3
than 1
IDS
ACOUSTIC ATTENUATION IN METALS, CH,
17
333
MAGNETIC FIELD EFFECTS ON ATTENUATION
the
tice We ;ua sity
Much valuable work in ultrasonic attenuation in metals is concerned with the study of fermi surfaces by means of periodicity effects in magnetic fields under conditions WeT» 1 and Aq» 1. The theory of the attenuation follows by an obvious but lengthy extension of the treatment we have given above: for the freeelectron theory one may refer to the paper by M. H. Cohen, M. J. Harrison, and W. A. Harrison, Phys. Rev. 117, 937 (1960); the problem for a general fermi surface is treated by A. B. Pippard, Proc. Roy. Soc. A257, 165 (1960), and V. L. Gurevich, J. Exp. Th. Phys. USSR 37, 71 (1959). Ultrasonic studies may be done at relatively low frequencies, as compared to those needed in cyclotron resonance.
24i~''''''
20
Ic 2 is
16
:0:
; the A is
o
c: c:
It!
::s
~
It!
~
>
CI>
12
Q)
It!
a::
8
4
1ve is
0'
o
<":'
4
8
12
qR
The fielddependent factor in the attenuation of a transverse wave ting perpendicular to the field, when the classical skin depth is much less wavelength and the cyclotron frequency is much greater than the electron ~nerin2 frequency. (After Cohen, Harrison, and Harrison,)
334
QUANTUM THEORY OF SOLIDS
AC
The resonance attenuation effects which are most studied are the geometrical resonances for which the diameter of the cyclotron orbit is an integral multiple of the half wavelength of the phonon, with H, q, and u mutually perpendicular. The geometrical resonances have to do with the strength of the interaction between particular orbits and the electric field in the metal. The attenuation involves the inverse of the effective conductivity, as we have seen in the results (36) and (45):
(48)
ex
of reE
OP
nm < R0  l '
pesT
17e ff
117
I
fiel thE ele
(5C
Because of the screening we have to do with a constant current system, rather than a constant voltage system. The conductivity is reasonably expected to be a periodic function of the number of phonon wavelengths encompassed in a cyclotron orbit, for an extremal orbit. Thus 2r c = nA or qr c = n7r is the periodicity condition, where rc = VF/W c ; and n is an integer; this may be rewritten as
(49)
wh thE sto
~
in fre ass
'qJ~ =
eH
nA,
(5]
mVF. We see from the calculated curve in Fig. 1 that the with p differences in qR values at the absorption maxima are closely multiples
=
Th
(5~
2.5 2.0
~
Q)
wh fre rec
(5~
c:
wh
(54
IV
::I
c: 1.5
:t::
IV
:0:;
>
Q)
Qj
IV
1.0 0.5
Nc
(5t
c:::
Th
0.5 1.0 1.5 2.0 2.5 3.0
(56
w/wc
FIG. 2. The ratio of the attenuation of longitudinal waves as a function of magnetic field to that at zero field as a function of the ratio of phonon frequency to cyclotron frequency. The product of the phonon frequency and the electron scattering time W7' is taken equal to ten. (After Cohen, Harrison, and Harrison.)
H,
JE B. I
IDS
ACOUSTIC ATTENUATION IN METALS, CH.
17
335
the it is
, q,
of 11". Calculations for longitudinal waves under AzbelKaner type resonance conditions are shown in Fig. 2.
OPENORBIT MAGNETOACOUSTlC RESONANCE
do the of
45) :
A striking resonance property of periodic open orbits in a magnetic field is observed in one aspect of ultrasonic absorption in metals. 3 If the magnetic field is perpendicular to the line of an open orbit, the electron wa vevector increases as
(50)
k= 
e c
Vl.
X H,
eIll,
tion bit, city tten
where Vl. = grad K E(K,kH) lies in the plane normal to H and through the line of the open orbit. The openorbit absorption may be under stood by an argument due to W. A. Harrison. Consider an electron on an open orbit and moving in the x direction in the crystal. We send into the crystal a longitudinal phonon of frequency wand wavevector q also in the x direction. There will be associated with the phonon an effective electric field
(51)
Ex = Eo cos (qx  wt).
The velocity of the electron is of the form the pIes
(52)
x=
Vo
+
VI
cos Ot,
where Vo is of the order of the fermi velocity, and 0 is the angular frequency associated with the motion of the electron through a reciprocal lattice vector in k space. That is, if VI « Vo, (53) 0 = 211"k/G c : : 211"evoH/c Gc , where Gc is the spatial period of the open orbit in k space. The rate at which the phonon does work on the electron is
(54) eExx = eEo cos (qx  wt)(vo
+ VI cos Ot). +
VI
Now x = vot
(55)
+
(vI/O) sin Ot, so that
eExx = eEo[cos {(qvo  w)t
+
(qvdO) sin Ot} ][vo
cos Ot].
The first cosine factor may be rewritten as (56)
n of
cos {. . . }
==
cos (qvo  w)t cos [(qvdO) sin Ot]  sin (qvo  w)t sin [(qvdO) sin Ot].
If qui/O
«
1 we may expand (56) as a power series in this quantity.
cy to ctron son.)
• Theory: E. A. Kaner, V. G. Peschanskii, and I. A. Privorotskii, Soviet Physics
J BTP 13, 147 (1961); experimental observation on cadmium: J. V. Gavenda and
B. C. Deaton, Phys. Rev. Letters 8, 208 (1962).
336 From (55), to zero order,
(57)
QUANTUM THEORY OF SOLIDS
(eExx)o
=
eEovo cos (qvo  w)t,
=
which averages to zero unless qvo magnetic field. In first order
w, a condition independent of the
(58)
(eExxh
=
eEo(qvda) [ Vo sin (qvo  w)t sin at + (a/q) cos (qvo  w)t cos at].
On averaging over the time this gives a contribution only if qvo w = a, or q(vo  vs) = a, where Vs is the phonon velocity. Because Vs «vo, the resonance condition is (59)
qvo
~
a=
27rev oH/c Gc,
using (53); or, for the acoustic wavelength Aq , (60)
c A =.
cG
q
eH
This relation is satisfied quite well by the observations on cadmium in reference 3. We notice that (60) involves e, and not e/m*; the resonance reported is very sharp and may provide a good method for the investigation of the question of whether electronelectron interac tions cause the effective carrier charge e* to differ slightly from the electronic charge e. Theoretical arguments against the possibility that e* ~ e are given by W. Kohn, Phys. Rev. 116, 1460 (1959), and J. M. Luttinger, Phys. Rev. 121, 1251 (1961).
PHONON AMPLIFICATION BY ELECTRONPHONON INTERACTIONS 4
Let the electron density everywhere be equal to the hole density, thereby allowing the neglect of coulomb effects accompanying charge bunching. The situation in the absence of charge neutrality is con sidered by Weinreich, Sanders, and White in reference 4. Write n(x,t) as the deviation of the particle density from the static equi librium value. If V is the difference of the electron and hole deforma tion potential constants, then Ve xx is the shift in relative energy of electron and hole states under a deformation exx . The equilibrium particle density is shifted by VexxN F; here N F is the density of states at the fermi surface. Thus the transport equation for drift velocity v is (61)
an an +v=at ax n(x,t)
+ N F V(au/ax) ,
Teh
4 G. Weinreich, Phys. Rev. 104, 32 (1956); G. Weinreich, T. M. Sanders, and H. G. White, Phys. Rev. 114, 33 (1959); J. Hopfield, Phys. Rev. Letters 8, 311 (1962); A. R. Hutson, Phys. Rev. Letters 7, 237 (1961). In piezoelectric crystals the cou
[,.
IDS
ACOUSTIC ATTENUATION IN METALS, CR.
17
337
the
where reh is the electronhole recombination time. The drift velocity enters because we have in (61) already integrated the distribution function over the velocity. We assume that the drift velocity is maintained by an external source. The elastic equation of motion is
(62)
pu =
clI2
gt].
a 2u ax
an + V· ax

This follows from the lagrangian density
(63)
use
.c = !pu 
2
~CII ( ax
1
_
a u)2
au Vn(x,t) ax'
where the last term on the righthand side is the classical transcrip tion of the deformation potential. We look for solutions of (61) and (62) of the form
(64)
n, u
(iwn
I""o.J
ei(kxwt).
1
in the for ·ac the
hat M.
Then
(65)
+ vikn)r
= n  N v Viku,
pw 2u = k 2cllu
+ ikVn.
o.
The secular equation is
(66)
I (1

lkV
i~
+ ikvr)
iN FVk 21 = k 2cII  pw
ity, ,rge on rite lui na of urn sat v is
r
If kv > w, the waves increase in amplitudethe drift velocity, if maintained, puts energy into both systems. This is essentially a traveling wave amplifier for phonons. The condition kv > w is equivalent to v > Cs , where Cs is the acoustic velocity. The approximate solution of (66) is
(67)
k
I""o.J 
Cs
wiN V [1 + l(W 1 + 2 F .
2cn
kv)r]
I
~
for (w  kv)r
«
1.
PROBLEM
and
62);
~ou
1. The longitudinal velocity of sound in Cd perpendicular to the hexagonal axis is 3.8 X 10 6 cm/sec. At what acoustic frequency will the lowest open orbit magnetoacoustic resonance occur for a magnetic field of 1 kilooersted?
Piing is much stronger than that of the deformation potential at the frequencies of interest in experiments.
THEon
18 Theory of alloys
Many interesting practical and intellectual problems arise when a of one element in another is prepared. We can ask a number of questions about the alloy, including solubility limits, energy of solution, lattice dilation, electrical resistivity, magnetic moment, magnetic coupling, Knight shift, nuclear quadrupole broadening, and supereonducting properties (energy gap, transition temperature, crit ical field). We do not have space to treat all of these, but we shall discuss several of the central aspects of dilute alloys with particular reference to the effect of the impurity atoms on the electronic structure of the host or solvent metal. We assume the impurities are substitu tional for atoms of the host lattice unless otherwise specified. In principle even a minute concentration of impurities destroys the translational periodicity of the crystal. Formally, the lattice is either periodic or it is not periodic. In the alloy the wavevector is no longer a constant of the motion and the true electronic eigenstates do not carry momentum. The actual consequences of small concentra tions of impurities are often much less serious than might be imagined· from this formal statement, particularly if the impurity atom has the same valence as the atoms of the host crystal. Thus in an experiment with 5 percent Si in Ge the mean free path of electrons in the conduc tion band at 4OK was found to be ,,,10 5 cm, about 400 interatomic spacings. is also known that solid solutions or mixed crystals are often formed over very wide composition ranges without destroying the insulating or metallic nature of the materials, as the case may be. On the nearly free electron model the presence of a band gap at a zone boundary is related to an appropriate fourier component of the periodic crystalline potential; the "partial" destruction of the periodicity by the admixture of a weak spectrum of other fourier components associ ated with a low concentration of impurity atoms does not destroy the
338
gap. Phys. We alloys sever mode
1 J. 2.J.
3A.
LAUE
Thi energ, at dis wavel scree note
'!O~(x)
think subst was s Pr
(1)
Weir
(2)
wher
(3)
Now
(4)
(5)
Furt
(6)
THEOHY OF ALLOYS,
elf. 18
339
gap. On this particular point the reader may consult n. D. Mattuck, Phys. Rev. 127 t 738 (1962) and references cited therein. We first discuss two results of wide application in the theory of alloys, the Laue theorem and the Friedel sum rule. We then treat several representative alloy prohlems. Some general references on the modern theory of alloys include:
2
J. Friedel, Phil. Mag. Supplement 3t 446507 J. Priedel, Nuovo cimento supplemento 7t 287311 (1958). 3 A. Blandin, Thesis, Paris, 1961.
1
LADE THEOREM
This important theorem states that the particle density per unit energy range is approximately independent of the form of the boundary, at distances from the boundary greater than a characteristic particle wavelength at the energy considered. This result is not caused by screening, but obtains even for a noninteracting electron gas. We note that we are concerned with the product of probability density CPk(X)CPE(X) and the density of states geE). In using the theorem we think of the boundary perturbation as caused by the insertion or substitution of an impurity atom in the crystal. The following proof was suggested by Dyson, unpublished. Proof: We treat free electrons with the eigenvalue equation
2m V 'PI!:
1
2
= EkCPk'
We introduce the function
(2)
u(xt)
2: CP:(X)CPk(O)eekl, II: 2: cp:(x)CPII:(O) = II:
au at
= Dv 2u
where
(3)
u(xO)
o(x).
Now u(xt) satisfies the diffusion equation
(4)
'
with
(5)
1 D=·
2m
Further, at tne orIgIn,
(6)
u(Ot) =
2: CP:(O)cpk(O)eekt = J dEli: cp:(O)'PI!:(O)g(Ek)eekl
It
340
QUANTUM THEORY OF SOLIDS
is the laplace transform of the probability density
1t'~(Oh~k(O)g(Ck)
per unit energy range per unit volume. We know from the theory of diffusion that u(Ot) is influenced by the presence of a boundary at a distance ~ from the origin after a time t such that
(8)
t>
tc:::::: ~2/D
2m~2.
Thus in the laplace transform (6) the presence of the boundary will be felt at time te. The components which contribute to (6) at time te are principally those for which cktc < 1, or, using (8),
(9)
ck
< 2m~2' <~
1
1
But ck
(10)
k2/2m, so that if
k
the boundary will have an influence on the problem. wavelength A, if the distance from the origin
(11)
~
In terms of the
< 71./271",
then the boundary will have an influence. We view an impurity atom as equivalent to a new boundary. Thus the electron density per unit energy range at the fermi surface of a metal will usually be only weakly perturbed by an impurity at dis tances greater than l/kF, or about a lattice constant, from the point of observation. We consider as a simple illustration of the Laue theorem the particle density on a onedimensional line with impenetrable boundaries at x = 0 and x L. The eigenfunctions are
(12)
It'n(x)
2)lii n (L sin; x,
2m
and the energy eigenvalues are
(13)
C =
n
~ (n7l")2.
L
Thus
(14)
1t':(X)lt'n(X) =
(~) sin
2
7
x;
(15) p(x) = (i) . Here 1JL(k) is the phase shift produced by the scattering potential. and therefore is subject to a correction for changes in the wavefunction near the scattering potential. (Schiff. Here (16) ) p( x.P L(COS LO ~ ~L(r) r 8). 104) (19) We know that ~L(r) 1 2rrR ~ 0 as r 0 and also that ~L(r) ~ ( )H' sin (kr + 1/L(k)  jlnr) as r ~ 00. ~ here U(r) = 2m VCr). to assume that V has no bound states and is localized within one atomic cell.Y = nF 2 { L2 1 _ sin 2kFX} {I _ sin 2kFY}. In one dimension dp/dn or dp/dE does not settle down to a steady value as we leave the boundary: this is because only one mode at a time is counted in the derivative. 18 341 if states up to nF are filled with one particle each. (17) u(r. with kF = nF'7r/L. apart from oscillatory terms exhibited in (27). 2k F x 2k F y FRIEDEL SUM RULE We consider a freeelectron gas and a spherical scattering potential It is convenient.THEORY OF ALLOYS. L 2k F x so that the density increases from zero at x = 0 to a value close to nF/L in a distance of the order of l/k F. but not necessary. This result is written for 1JL(k) = 0. CH. . The numerical factor in (19) is chosen to normalize ~dr a sphere of large radius R: (20) 41r Jo (R ~L2(r) dr = R 2 Jo (R dr·j 1.sin 2kFX} . In two dimensions the situation is improved and both p and dp/dE can be shown to have the expected behavior. the particle density is.8) = '" . p.8) of the wave equation may be written as VCr).. where P L is a legendre polynomial and (18) ~L(r) satisfies ~L d2~L + dr 2 lk 2 _ = 0. 2 dnsm (m1"x) = L nF { 1 . From standard collision theory we know that the solution u(r.
dk .IDS We find the desired correction: (a) Multiply (18) by 'fiL'(r).k.k sm 'Y/L cos (2kR + 'Y/L  L?r) .2 . If 'fi~ is the wavefunction in the absence of the potential. + .2k sin 2(kR .k. (24) 'fiL' = 'fiL + (k _ k') d'fiL.t/I") • Using the asymptotic form (19) for large R. [ 'fiL' _L dr dro If 'fiL is a continuous function of k. dk' 2 d'fiL' = d'fiL dr dr + 2 d 'fiL .O)2] = 11 Ii [d'Y/L 1. (c) Integrate (21) over dr from 0 to R: (22) tEl Jo dr ( 'fiL' 'fi ') .tL?r) J. (b) Form the similar product of 'PL(r) multiplied by the differential equation for 'fiL'(r).k 2 ) r dr 'fiL''fiL.'fiL d 'fiL 2 . for small k' .'fi L dk dr 0 = 2k J0 r dr 'fi L . d 'fiL 2 .342 t~UANTUM THEORY OF SOI.'fiL d'fi'lR . Jo R On integration by parts the lefthand side becomes (23) d'fi .'fiL ddr~ 2 = (k. ] The density of states of angular momentum L per unit wavenumber . (26) Jo r dr 'fiL + 41TR 2 1 [ R + drlL die  2k sm 2(kR 1.L) inside the sphere of radius R is (28) 41T!oR dr ['fiL 2  ('fil. Subtract this from the above result: (21) 'fiL . + 'Y/L ] jJ. we may write. (27) 1 2 !oR dr ('fiLO) + 4:R [ R .2)'fiI/'fiL O. Thus the change in the number of particles in the state (k.k') dk dr' 2 so that (25) d'fiL d'fiL d 'fiL]R [ dk dr . which is the solution of (18) for a wavevector k'.
1'/1. CH. It is an important selfconsistency condition on the potential. if we neglect the oscillatory term. giving R/7r different radial solutions per unit range of k. chosen to satisfy (30). For many alloy problems it is not neces sary to know the detailed form of the potentialwe need only the first few phase shifts 1'/0.cos (1'/L  Lr». so that the total change in the . the total number of particles IlN displaced by the potential into the sphere of radius 'R is (29) IlN = 2 7rL L (2L + 1) r' dk [d1'/L Jo d:k 1)1'/L(k F) 1. Ie sm 1'/L cos (2kR + 1'/L  Lr) ] = 71' ~ L (2L L + oscillatory term. 2r2R3 L (2L + l)(sin 1'/L)(COS (2kFR + 1'/L L Lr) . and for fixed L and mL the allowed values of k differ asymptotically by Ilk = 71'/ R. Often the phase shifts are negligible for L > 3 or 4. counting both spin orientations. using (28). Thus (29) becomes. we know that a selfconsistent potential VCr) will ensure that the displaced charge (IlN)e will cancel ZJel exactly in order that the impurity potential be screened at large distances. Then. (30) Z = r ~ L (2L + l)1'/L(k F)i L this is the Friedel sum rule. • • . We note that the oscillatory term gives rise to an oscillatory variation in the local charge density: (29') IIp(R) = 1 oR o(IlN) 1 =. If the impurity has valency Z relative to that of the host lattice. for 1'/L independent of k. 1'/2. 18 343 range inside a large sphere of radius R is 2(2L + 1)R/7r. This follows because there are (2L 1) values of the azimuthal quantum number mL for each value of L. Note that (30) may be checked by an elementary argument: for phase shift 1'/ L(kF) the quantized values of k near k F in a sphere of radius R are shifted by Ilk = 1'/L(k F)/Rj but there are 2(2L + l)R/r states of given L for a unit range of k.THEORY OF ALLOYS. .
1. The kinetic energy away from the poten tial has a contribution proportional to k 2. Outside the region of the localized potential the wave equation is unchanged by the perturbation. and the shift in the eigen value is (34) ~Sk = . This statement appears to contradict (31). . 167) f dr r 2jx.:(x). Suppose the impurity is at the center of a large empty sphere of radius R.2km « 1 we have (Schiff. RIGID BAND THEOREM (: According to the rigid band theorem. the boundary condition will be satisfied by a wavevector le' such that (33) k'R + 71L = kR. not for Bloch electrons. and thus the energy eigen value as a function of k must be unchanged.1 (k 2m . where the Bloch function is written II'k(X) not depend strongly on k. then (32) If Uk(X) does ~ek '" fd 3 $ uti (x) V p(x)uo(x). However.k 2 ) = 2m 1 [(k . We give a discussion only for free electrons. . 2J ::=. Any extra electrons added with the impurity atom will simply fill up the band. the electron is free within the sphere except for the impurity potential. p. where 71L is the phase shift. 1 which must equal Z if the excess charge is to be screened. That is. as given by the firstorder perturbation result: (31) v t ( ~ek = (kl V plk) = fd 3 $ U:(x) V p (x) u.k71L . = et"k·%uk(X). the allowed values of k are changed: it is essential to consider the effect of the overall boundary conditions.k R 711.71L)2 . the whole energy band is shifted without change of shape. the effect of a localized per turbation V p(x) in first order is to shift every energy level of the host crystal by nearly the same amount. The validity of the result (31) is not as obvious as it may seem at first sight.2 . If the boundary condition on the value of the wavefunction at R is satisfied by a partiCUlar k before the introduction of the impur ity. mR In the Born approximation for (35) 71L '" .344 QUANTUM: THEORY OF SOLIDS T: number of states below the fermi level is just (2/11') L (2£ + l)71L(kF).2(kr) V(r).
from (34). the electrical resistivity is concerned with the change on scattering of the projection of the wavevector along the axis of current flow.THEORY OF ALLOYS. from Schiff (15. As we have seen in Chapter 7. Q. A more general derivation is given in the thesis of Blandin.cos 8). reference 3. 1 Ti where the last factor on the righthand side weights the average accord ing to the change of k t • The associated relaxation frequency (40) VF A ni where A is the mean free path. 345 The unperturbed wavefunction is. the concentration of scatterers. ELECTRICAL RESISTIVITY Let 0'(8) be the cross section per unit solid angle for scattering of a conduction electron by an impurity atom. and vF the fermi velocity.8). Thus the effective average cross section for resistivity is (39) (0') = 27r f:. . 18 1 )~" k ( 27rR i£(kr) YL'(8. It must be noted for impurities of valency different from that of the host lattice the Friedel sum rule tells us that V p cannot really be a weak interaction. d8sin80'(8)(1.E. and.D. The contribution ~p of the scattering centers to the electrical resistivity is m* n~F (41) ~ =~~ 2 m~ u . The result holds only to first order in V p. so that (38) mR '1L '"  k (kl V plk). the radial normalization in (36) is only approximate and follows from the asymptotic form (19). (36) UL ::::: where the spherical harmonics are normalized to give 47r on integrating their square over the surface of a sphere..'P) . Thus (37) f 2 dr r i£2(kr) V per) = 2~2 (kl V plk). ~ek = (kl V plk). CH.
2( 1l"Z ) + 1) sm L ' 4 +2 from the sum rule (:30). 105) (42) Now in terms of phase shifts 0'(8) = 1 . 3 ok"'": eu Zn Ga Ge As Se FIG. Closed circles: experimental values.. (Schiff..ne 2k p 2: (T. 121 2: ICp (2L LO + l)ei~r...... sin 7]LP L(COS 8)1 2.41l"n i dp ./t)0'(8) = 2 + 1) sin 2 (11£  l1L+1).. computed values by Friedel. .... and then (46) dp = ~k (2L 41l"ni ne 'F ." ~ c: <V <V 0 l2 ~ 5 ~E u c: <l <:l.. and de Faget de Casteljau and Friedel. we have (45) l1L If only one = 1l"Z/(4TJ + 2) . . Residual resistivity 6..... phase shift l1L is lal'ge. Blatt...:346 10 QUANTUM THEORY OF SOLIDS r . I) sin 2 l1L Here the phase shifts are to be taken at the fermi surface. . p.... .. L~O (L "" whence (4~) and (44) f l 1 d/t (1 .. .. .lflcm per percent of polyvalent impurities in copper.. where n is the electron concentration.p in J........ 1.
1 gk(x)eik. we have ikr C (GO) (. L The agreement is seen to be excellent and is rather insensitive to the form of the potential.c.ilcr 'k " .X + cc + 2. We achieve this result by integrating (49) by parts twice. are com pared with experiment in Fig.3 cos 2kpr. We write the wavefunction describing the scattering of an electron of wa vevector k as (47) ""k(X) eik . According to the optical theorem (Schiff. provided that the value of some parameter determining the potential is chosen to make the phase shifts satisfy the sum rule. (/. with allowance for the cell volume changes at the impurity.rC '1.H 4rr '/. LONGRANGE OSCILLATIONS OF ELECTRON DENSITY We saw in Chapter 6 that the selfconsistent field solution for the screening charge density around a charged impurity contains oscilla tory terms at large distances of the form r.THEORY OF ALLOYS. The results of detailed calculations of phase shifts. outside the central charge (49) eikr gk(X) :::: !k(IJ) _. which is essentially an upper limit to the effect observed for nonmag netic impurities.1Pk(X) '" 4 7r [27r'fk(7r)eilcr 'k 2 t r + cc  27r!k(0)e. 10fi). . p. the result (29') above indicates that such terms are present also in this approximation. but keeping only the dominant terms for large r.x + gk(X). 11 l. 18 2 347 15 2 For Z = 1 and L = 0 we have (0') = 4rr/k p ~ 10. CH. Then the variation of electron density is (48) .1Pk(X) = "":""k .c t r + r~ f dU iJk(lJ) I2]. We reexamine the density varia tion here. It is instruc tive to exhibit directly the longrange oscillations on the independent particle model.cm and the resistivity is seen to be of the order of 4 Io'Ocm per percent impurity. r On averaging (48) over the surface of the sphere at k.
Rev.1Pk(X» = fk(1r)e 2ikr 2kr 2i + ce. 119. The diminution of peak intensity arises because the resonance line is broadened by the strong electric field gradients associated with the screening charge. We see that even on the independent particle model there are longrange oscillatory density variations . 6. The actual effect depends strongly on the atomic p and d character of the wavefunction at the fermi surface. Voski. Phys. particularly the difference of • W.1p(x) 2 f d 3k (. both immediately adjacent to the impurity atom and also in the long range tail. show a strong attenuation of the central intensity of the nuclear resonance lines of eu and AI. for a small impurity atom concentration in eubase and AIbase alloys.1Pk(x» = where GF and I{'F are constants. the amplitude falls off as variation is closely similar to that shown in Fig. We can rewrite (52) as (53) _ sin (2kr? + I{') 'f ( )1 (.1p(x) in electron density is obtained by weight ing (53) by the density of states and integrating over the fermi sea. and others. The total variation . The density around an impurity atom. The electric field gradients interact with the quadrupole moments of the eu and Al nuclei and broaden the resonance. H. Thus the charge density depends only on the backward scattering amplitude. They are in good agreement with the experimental results. I where I{' is a constant.1. according to the particular situation. For nonmagnetic impurity atoms perhaps the strongest experimental evidence for longrange variations in the electron density among impurities is found in the quadrupolar effects in the nuclear magnetic resonance of dilute alloys.912 (1960). .1Pk (x » I k 7T . The asymptotic form at large r is .4 The quantitative calcu lations will not be reproduced here. 3. Experiments by Bloembergen and Row land. Kohn and S. which is determined by the phase shifts lIL. The sensitivity of the experimental method is such that resonance line shape effects are seen if there is one impurity among the first 20 to 90 atoms around a given atom.348 QUANTUM THEORY OF SOLIDS whence (50) simplifies to (52) (.
. rather than Z. 398) that a potential well with an energy level nearly at zero will exhibit a reso nance in the lowenergy scattering of particles with the same L value as the energy level. Messiah. we replace Z by Z . then in effect the impurity atom acts as if possessed of an excess valency Z . p. If one electron is bound. t. The energy of this bound state must be below the minimum band edge of the conduc tion band of the metal. To be consistent. The effects increase with the difference in valence and with the atomic number of the matrix: the difference in valence increases the perturbation and the atomic number increases the amplitude of the Bloch functions. 18 349 valency. If we choose to do the bookkeeping to delete the oneelectron bound state from (55).. The bound state is thereby increased in energy and eventually merges into the continuum of conduction band states. It is known from scattering theory (Schiff. This pro duces a large distortion in the wavefunction and thus a large amount of scattering. 105) that the total scattering cross section is (56) (f = 411' 2: (2L + 1) sin L 2 'l/L.1. Let Z be positive. The second special situation arises if the attractive impurity poten tial is reduced.1 on the lefthand side and we must then delete the contribution '1//11' of the single bound state from the righthand side. p. that is. 113. the value of '1/ for the bound state must be 11'. CH. VIRTUAL STATES Let us consider the sum rule (30): (55) 2 Z =  1I'L 2: (2L + l)'l/L(kF). at resonance for a particular L we must have I'l/LI = i1I'. now with positive energy relative to the conduction band minimum. An incident particle with nearly the right energy to be bound by the potential tends to concentrate there. the valency of the impurity is higher than that of the host metal. It is useful to think of the state as still existing as a virtual state. p. We recall (Schiff. There are several special situations of interest..THEORY OF ALLOYS.r. . One special situation is that one of the extra electrons of the impur ity remains bound in the metal to the impurity atom. because a true bound state cannot exist any where in the same energy region as a continuous energy spectrum. Somewhat below the resonance energy the phase shift is approxi .
A small change in average electron concentration. can sweep the fermi level through the virtual level. Quantum mechanics. In Fig. If the fermi level is well above the virtual level. 1961. If the fermi level is well below virtual level for a given L.350 QUANTUM THEORY OF SOl. The resonance energy may be defined as the energy for which 1/L j)1r. the wavevector dependence of partial scattering cross section is also shown. Phase shift 111 and partial cross section 0'1 for pwave scattering from square well of radius a and depth Vo such that (2m Yo) \'a = 6. then the phase shift 1/L will be large and a major part of the screening charge may arise 40 30 cl~ 'll 20 " 10 1 ka 3 4 5 FIG. say £I.2. 2. Wiley.) .IDS mately mr. then the screening charge is made up of various L components as necessary to satisfy the sum rule (55). 2 we show the phase shift for pwave scattering from a particular square well. and somewhat above the shift is approximately (n + 1)1r. as might be produced by the addition of a third component to the alloy. (After Mcrz bacher. The resonance aspect is quite marked and deter~nines the position of the virtual level. The rapid variation of phase shift with electron energy near the virtual level makes the properties of an alloy having its fermi level in this region highly sensitive to the electron concentration.
Phys. Rev. 114. Suhl and B. F. 541 (1962). Rev. may be expanded in terms of Wannier functions from a single band: (58) if. A. = N'. Clogston et aL. If V is localized at Xo and of such short range that it does not overlap appreciably the Wannier functions centered on nearby I> G.1208 (1954). Slater. The exact solution if. Phys. 3 = N"~ 1 mn Jd x w~(x 3 xm)eik"Xm VU(Xn)W'Y(X  Xn). specifically. n Our neglect of interband terms may not be too serious if both the impurity and the band states are derived chiefly from the same atomic states. 1030 (1961). Let V be the impurity potential and H 0 the oneelectron unperturbed hamiltonian of the host lattice. and H. Anderson. Rev. Rev. we assume that if.xn) W for band 'Y is defined in terms of the = N'. M. 233259. P.439 (1962).' 2: U(xn)w'Y(x n x n). 96.li4. Chap ter 19. 125. C.' 2: eik. We now make the fairly drastic assumption that V does not mix states from different bands. The mathematical treatment 5 of virtual states in a metal has been considered by a number of authors. as in Messiah.·11 CWOl). A. We note that the matrix element (60) Jd x irO~''Y(X) Vif. .1i4. Matthias.. P. Phys. Phys. LTP. Phys. = irOk'Y +€ _ H0 1 + is Vif. but related. where the Wannier function Bloch functions irOln(X) by (59) W'Y(X . Suhl. Clogston. T. For nonmagnetic impurities it is convenient to use the Wannier functions defined by (9. Koster and J. We give separate. For the of impurity scattering effects in superconductors.THEORY OF ALLOYS. bound and may be thought of as localized. 18 351 from electrons in the virtual level L'such electrons act as quasi. This follows from the formal theory of scattering.114). CR. and we cite only several of the early papers. Wolff. pp.xll'Pk'Y(x). of the wave equation in the perturbed lattice may be written in the limit s + +0 as (57) if. W. Hev. Phys. Rev. see H. treatments best suited for nonmagnetic impurities (Wolff) and for magnetic impurities (Ander son). 125.977 (1959).
Thus (57) may be written as (62) '" = 'Pk1' + .ek''Y 28 eik' XA or.L' eik'·(x. If eo lies within the band.xoN~~ ''+. gr(CO) is finite and U(xo) has its resonance maximum at eo.E' so that (64) may be written as (67) eik 'xo U(xo) = 1 .L [e . .xn) = VnOOnOOm. eik·xo U(XO) = 1 . the root then represents a real bound state.Vn F1'(eo) = OJ this is the definition on this model of the position of the virtual level.1' + is = f dE "'''' e .L' 'Pk''YU(xo)eik'. (63) U(X n ) Xn . then g1'(co) = 0 and U(xo) + 00. using (58).VnFr(e) + The amplitude U(xo) of the wavefunction on the impurity atom will be large at the roots eo of (68) 1 .Vn.Xo) k' e .ck'1' k' + is] l' The summation may be written as (65) 1 f d 3k' 1 e . For (64) = xo. Here gee) is the density of states in the band under consideration.E + is = iP f dE e _ E i1rg(e).352 we may make the approximation (61) QUANTUM THEORY OF SOLIDS Jd x w~(x 3 xm )VW1'(x . We denote the principal value integral by (66) F1'(e) == iPfdE g1'(E) c .ek'1' + is VnU(xo). If a root eo lies outside the band.. k' e .ek. and iP denotes principal value.
o denote the ground state in the HartreeFock approximation of the system with the hamiltonian written above. With this effect and the associated broadening of the d states. and V dk is the interaction energy between a d state and a Wannier function on a nearestneighbor atom to the dstate impurity. the degenerate situation is considered in an appendix to the original paper.E' + U lies above the fermi level. The coupling of sand d states raises the energy of the spinup state and lowers that of the spindown state. A covalent mixture of free electron states with the d state will reduce the number of electrons in the spinup state and increase the number in the spindown state. We write the hamiltonian for the Anderson model as (69) H = L kor €knkor + E(ndt + ndl) + Undtndl + L Vdk(ctCd<7 + CtCkor)' kor Here €k is the energy of a freeelectron state. CH. also. with two possible spin orientations. the persistence of a localized moment beeomes a cooperative phenomenon. 18 353 LOCALIZED MAGNETIC STATES IN METALS The treatment by Anderson of localized magnetic states in metals is particularly applicable when the impurity atom has an unfilled or partly filled d shell and the conduction band states of the matrix are not dlike. If the unperturbed energy of the spinup state lies a distance E' below the fermi level. According to the argu . If a localized magnetic moment exists around the impurity atom.THEORY OF ALLOYS. U is the coulomb repulsive energy between electrons in di and dl. one of the two spin states (say the up state) will be filled or partly filled.. We suppose there is a single orbital dshell state <Pd.E' + U. nkor "'" CtCka. We assume a single nondegenerate d level. the energy of the spindown localized state will be . Let (70) ipo '<'F n c~ipv . where U is the repulsive dd interaction. E is the unperturbed energy of the d state on an impurity atom. but it is shown in an appendix to the paper by Anderson not to be of major consequence. A localized moment will exist if . We assume that <Pd is orthogonal to all Wannier functions of the conduction band. the virtual state can contain any nonintegral number of spins. Then an electron with spin down will feel the coulomb repulsion of the spinup electron. say slike or an sp mixture. This is a nontrivial assumption.
t"u [c. 29 IG~n I  ] 'If' .Hl av ekct = (E  + Vkdcti U(nd. k Now substitute (72) in (71) and utilize the results (73) and (74).en).n(e + 91G':. which is the mean density in energy of the admixture l(nld)ui 2 of the state du in the continuum levels n of energy e._u»ct + LV dkct.Hl. We examine the Green's function (78) G(e + is) 1 = e + is _ which is diagonal in the representation n of the exact eigenstates: (70) ~.!.!.eltU Now 'If'8(e .). (nik)uct) + (nld)uct.»)(nld)u What we want to calculate in this problem is (77) Pdu(e) == L 11. so that (81) pt!u(e) !L 'If' 11.nl 1 (nulnlnu) e+ £s . on equating the coefficients of ct and of Cd. ." we find the relations (75) enu{nlk)u = ek(nlk)u enu{nld)u = (E + Vkd{nld)u. k where the operators cit. Now write (72) c. k (7G) U{nd..v [ct. this means that (71) QUANTUM THEORY OF SOLIDS it.354 ment of Chapter 5. The quantity Pdu(e) may be calculated very neatly.en. = 0..t. .ll].'i{(dgiGldu»)..vJ where the subscript av means that the three fermion terms in the commutator are to be reduced to single fermion terms times average values over the state <Po. + L V dk(nlk)u. = enuc." ct refer to the unperturbed states and satisfy (13) (74) [ct...._.
~d{TrG~I. = e + is.) = . IS 355 We note that the total density of states (S2) p.ek ir 2: IVdkI2~(e k ek) . eH..ill! with Il defined by (91).\l state &t (92) ~ = E" .G..)Gdk (~  L Vdk. . ek. The equations for the matrix elements of G are (S3) 2: (e + is E" E H)I".en.THEORY OF ALLOYS..)Gdd  2: VdkGkd = 1. ~ we can find the matrix elements of (e Thus we obtain (S5) (S6) + is  (~ .E.). the righthand side of (90) may be written as (91) ir(Vdk 2)avp(e) == ill. where p(e) denotes the density of states. according to the definition (7S) of G.(e) = ~ ~(e n .Gh = k' 0. If we write (S4) + U(nd. (S7) (S8) (~ .>. = e~. = CV 2: IVdkl  k e . H) from (75) and (76). r From (SI) we see that our problem is reduced to the determination of the matrix elements Gdd . Thus._.)Gh  Vk'P'dt = ~k'k' We solve for Gdd from (S5) and (86): (S9) Gdda) = [~  EIT  2: 2 k ~ The sum over k in this result may be evaluated: (00) lim • > +0 k e 2: ek + 2S 2 . k (~ . Gdd behaves exactly as if there were a virtul. apart from the energy shift.E.ek)Gkd  VkaGdd = 0... Neglecting this. The first term on the righthand side is an energy shift which may be absorbed in E".
The point is considered by Clogston· and by Blandin3 and FriedeL We now discuss several examples of virtual levels. which shows a large broad peak around Cr. 4.vp(e) .cot . with the results for the ground state shown in Fig. . for the s band of copper p(e) may be of the order of 0... at the beginning of the first transition group.(E) = 11" ~ coc 1 E _ ::=..5.: (e _ ~ + The total number of d electrons of spin IT is given by (94) (ndg) f"' de _.. this is a defect which should be remedied. Transition Element Impurities in Aluminum. The peak is believed to be caused by resonance scattering of electrons at the fermi level of Al when this level crosses the broadened dshellievels of the impurity. In the iron group U may be about 10 ev. according to the definition (84). If (ndT) = (nd!).6 to 1. The residual resistivity of these impurities in Al are plotted in Fig.. Pd. When going continuously from Ti to Ni added to AI... which covers the transition between magnetic and non magnetic behavior. For rare earth solutes the sf interaction V will be much smaller.1 (ev)1. so that ~ 1I"(V 2 ) . as is observed. 2 to 5 ev and 1I"~/U falls in the range 0. When Ti.2 to 3 ev. From binding energy considerations Vav may be estimated roughly as. the solution is nonmagnetic.. 11" The solutions of these equations are considered in detail by Anderson. the dshell states of the impurity should descend and cross the fermi level of Al and give rise to virtual bound d states.. 3. ff ~ But Ell involves (nd. is dissolved in AI.: cot We must  eF + U(nd!) ~ ~ j 1 _1EEp+U(ndt} (nd! ) = .. we may write (81) as 1 11" I Pda(e) = d { e_ Eg 1 1 + i~ } =._g).356 QUANTUM THEORY OF SOLIDS If we assume (93) ~ to be independent of Ell. so that for the smaller ~ we expect magnetic behavior to occur frequently.. We note that the theory does not automatically give solutions which satisfy the Friedel sum rule. we expect its d shell to be relatively unstable compared with the d shell of Ni at the end of the group.. make the values of ndt and nd! selfconsistent: (95) (96) (ndt ) 1 1 E =.
in conformity with Hund's rule. . (After Anderson.5 0. The numerical criterion is discussed in detail by Anderson.0 1r/Y= 1rt:.0 0.1 0' ~J ! o 0. reference 5.THEORY OF ALLOYS. Here z Regions of magnetic and nonmagnetic behavior. CH.E)/U and y "" Y/A. Not all transition element impurities are magnetic in copper.9 0. 3. The exchange and par ticularly the coulomb interactions within a d shell tend to split it into two halves of opposite spin directions.6 0.3 0. In the alloy this spin splitting is maintained if the associated energy is larger than the width of the virtual level and larger than the distance from the fermi level to the virtual level.2 0.6 x 0. In the free atom the first five d electrons have parallel spins. 18 357 1.4 0.8 1.4 0. (eF . the sixth and subsequent d electrons have their spin antiparallel to the direction of the spins of the first five electrons.2 0.8 0./U FIG.) Transition Element Impurities in Copper.7 0.
Residual resistivities of transitional impurities ill copper. (After Friedel. c. then ~ ~ ~ 10 ~ i. ~ <l c:t . 5..em per percent for transition element and other impurities in aluminum. 4. peak B to the lower half B with opposite spin direction. Residual resistivity tip in JLU.358 10 QUANTUM THEORY OF SOLIDS ~ '" ~ c: ~ lv Q. .p in the series from Ti to Ni dissolved in Cu. Peak A corresponds to the emptying of the upper half A of the d shell. 5) of the residual resistivity !:.. Magnetic measurements provide a useful criterion for a localized magnetic moment: if the impurity contributes a Curie Weiss temperaturedependent term to the magnetic susceptibility.) The exchange splitting explains the double peak (Fig.'3' 01 K I )! E Ca Sc Ti V Cr Mn Fe Co Ni Cu FIG. or Au. 6. as shown in Fig.. E I 5 0 Ti Cr Mn Co Cu Zn Ga InG. Ag..
) . 18 359 Cu Mn Cu FIG. (Mter Clogston et 11.n iron atom dissolved tn various second row transition metals and alloys as a function of electron concentration. 7. there is no localized moment. A local moment is developed when the fermi level is close to a virtual level and the virtual level is sufficiently narrow. 7 we exhibit the local magnetic moment of Fe in various solvents as a function of the electron concentration of the solvent. Magnetic moment in bohr magnetons of a..s ~ E ~ E o 4 ~ 2 ~ OLb__&DC~~~o~__~__~__~~ 3 4 5 6 7 8 9 10 11 N Y Electron concentration FIG. In Fig..8 . but not in AI. If there is no temperature dependent contribution. there is a localized magnetic moment.l:: '" : ~ 8 . c:: ~ 10 . d shell of a transitional impurity such as Mn in Cu. 14 irrrrrr!~1 OIl :::l I '"i 12 . split into two virtual bound levels of opposite spin directions. Varying the electron concentration varies the width of the virtual level and the position of the fermi level.1. 6. CH.THEORY OF ALLOYS.:: 6 . It is a question of relative width which makes Fe magnetic in Cu.
9 A. 7. phys. 160 (J956). 8. Ruderman and C. II and 12 • The electrons are described by Bloch functions (97) ~k. 99 (1954). k. S of the hyperfine coupling scatters a conduction electron having a given state of the spin S differently according to the state of the nuclear spin II. two closely related problems in metals: the indirect interaction of two nuclei via their hyperfine interaction with the conduction electron sea. normalized in unit volume. In. Rev. 96.~:8(X). ~+(x) = L Ct. where A(x. Mod.. Blandin and J. Rev. but it is useful to see the detailed calculation. where Xj is the position of electronj.(X) = ~(X)18). BJ. we also assume that the oneelectron energy is ex: k 2• The essential results of our calculation below can be understood easily from (29') or (54). 106. Our treatment neglects correlation effects. 681 (1962). ~ 7 In this representation we obtain M. Friedel. H. The ionic interaction is of considerable importance in the study of metals with magnetic order. . 34. The spin of one nucleus in a metal senses the spin direction of another nucleus in the following way. where c. The contact interaction is in metals often the dominant part of the hyperfine coupling. Phys. First we treat the nuclear problem. Kittel. Rev. Tad. i Rn)S. J.(:x:) eik. S.360 INDIRECT EXCHANGE INTERACTION VIA CONDUCTION ELECTRONS 6.~s(X). A. For the contact interaction the hamiltonian has the form (98) II = L A(x.xuk. In the language of second quantization the electron field operator is (99) ~(x) L Ck. k. Phys.63). PhY8. The contact part II . according to (19.893 (1957). A second nuclear spin 12 sees the density of the scattered electron through the interaction 12 . Van Vleck. and the indirect interaction of two ions via the exchange interaction of their inner shells (d or f) with the conduc tion electrons. 9 QUANTUM THEORY OF SOLIDS There are. and thereby senses the state of II. c+ are fermion operators. This process effectively couples together the two nuclear spins. 20. K Yosida. here 8 is the spin index and denotes i or ! for We calculate first the perturbation in electron density created by the hyperfine interaction of the electron with the nucleus at Rn. Rn) is proportional to a deltafunction.
a constant with the dimensions energy X volume. In the Born approximation the wavefunctions to first order in .'2 (I. and (107) r' _Am*J k' . independent of k and k'.(x) = where S operates on the spin part of 'PIt.. Ck'tCk! j~(ctiCki  ct!ckd. electron expectation value Thus.Rn)S. thus (104) J(k'. get directly: 'PIt(x)!s). we 1 ~ i(kk')·R""l(k' k) (j+ + H ="!". length and phase shift (105) We may view JB(x) as the pseudopotential associated with the swave scattering b = mJ/27r.k) by setting AI (103) A (x) .k) is constant.t'lk' !)o + I~[k't>o)..1. In'Plts(x)] Ct.k) .o' kk' r [/ kk' d 3x ~'8(x)A(x . where (102) J(k'.e . with Rn = 0. We note that we may simulate a constant J(k'.THEORY OF ALLOYS.J B(x) . we obtain (100) H = . CH.. 18 361 the hamiltonian by the usual prescription. With 'PIt. Ck'!Ckt + 1+ .k) = / d 3x ~(x)A(x)'PIt(x). guided by the one / d 3x cp*(x)A(x . 'I/o = kb. (106) Ikt) = Ikt)o + r' Ik's)o (k'sIHlkt> k's e:k e:k' = [kt>o + r' 1_2m*~..'Cks. k' for the wavefunction with the electron spin mainly up. as is discussed in Chapter 19.I are. We shall assume that J(k'.Rn)S ·InCP(x).
the semicircle gives no contribution to the integral because the exponential is vanishingly small on this segment. Thus the value of the first integral is (111) t2ri(te'" + lei") = ri cos tT. 8 If the Uk part of the Bloch function is independent of k.'2 u. where the t on the extreme lefthand side arises because of the principal value in (110). P 2 peip 2  tT oc P  2 pe iP 2 tT } with p k'r and tT = kr. for details of why the principal value gives the full answer in the end for this problem. The prime in ~' means that the state k's = kj is to be excluded from the summation.:.. The residue at the pole p = tT is le'" and at the pole p = tT the residue is te. and the integral has the value ri cos tT.. Thus (109) assumes the value (112) (J> f = (21r2/r) cos kr. because the adiabaticswitching form of perturbation theory tells us to exclude the energy shell ak = at' in the sense of taking the principal value of the integral formed from the summation above.362 QUANTUM THEORY OF SOLIDS for the wavefunction with electron spin mainly down. The integrands are even functions of p when this is real.. . see Yosida7 and Van Vleck. This is a delicate point.a f (J> d k' 3 1. so we may write (110) (J> f (r) 7" ~r (J> {f" dp _ '" p 2 peip _ 2 tT f'" _ '" dp P pe2 _ iP tT 2} • The first integral may be evaluated by completing the contour with an infinite semicircle in the upper halfplane../'' ' ':.!"I!) + 1~1j»· The integral in (108) has the value (109) (J> f = 21r(J> = 2r(ir)1(J> f~l dJj 10" dk' (k +e~:~~~'~ k') f'" dp {f "dp _. at this point we have not carried out any operations on the nuclear spin. The arrows refer to the electron spin. we may write (106) as (108) Ikj) = Ikj)o + (. The contour of the second integral in (110) is com pleted by an infinite semicircle in the lower halfplane.
or (117) where (118) F(x) = x cos x . 8.23) in the paper by Y08idajT the difference is merely a matter of definition.m*J. of which n are of each spin.1). CH. to O(J). (114) also (115) p(kt) = 1 .:\t) + 1~\j))..4 10 } F(2k]i'r) .. we may summarize (117) and the corresponding result for p(!) by* (119) P:l. m*JI· (2kl'r dx x sin:v.ft (k ]i'T)3 4e]i' Now suppose a second nuclear moment 1m is added at a lattice point m a distance r from n.S kr cos kx p(kj) = 1 I~ I~ It is interesting to sum p(kj) over the ground state fermi sea: (116) 1 p(j) = (211')3 f k]i'3 3 d kp(kj) = 611'2 + 4(2r)3. The net polarization has at k]i'r» 1 the asymptotic form (120) Pi + Pf 91I'n 2 J18 cos 2k]i'r • . cos kr + m*J21I'r cos kx The electron density corresponding to (113) is.8 is seen on examining his Eq. The nucleus at m will be perturbed by the spin • The second term here differs by a factor of 2 from Eq.. = ..THEORY OF ALLOYS. (3. 18 363 whence (113) \kj} = Ikj)o + m*~~~s kr (l..(x) = n [1 + ~ 1I'JF(2kFT)I~ r We see that the nuclear moment perturbs the electron spin polariza tion in an oscillatory fashion.. . (2.sin x X 4 • p(n = 611'2 k]i'3 {3m*Jl~k]i' 1 11' If the electron concentration is 2n..
364 QUANTUM THEORY OF SOLIDS '1'B polarization due to the nucleus at n.' (k8!Hlk's')(k'8'IHlk8). (122) s. to c m Now the trace of any component of (124) 8 vanishes.2_k'''"'"2 + cc. F(x) ~ 1/6x. (8 • In)(8 • 1m) = fIn' 1m. and vice ver8a. In)(d • 1m) = In' 1m d + id • In X 1m. p Thus the indirect interaction resulting from the isotropic hyperfine coupling has the form of an isotropic exchange interaction between the two nuclear spins. via the conduction electrons. Sk Sk' ' using (101) for H.. Now the operator I It e m o J (1 .h de< thl of Fr lar H"(x) = 2. arc thl The sum over electron spin states is carried out with the help of a standard relation (Schiff. p. The final form of (122) is (125) H"(x) = In' 1m 4J2m*k '''' . The first zero occurs at x magnitude of the interaction (125) is supported by experimental results on nuclear resonance line widths in pure metals. with the assumption (104). thereby leading to an effective indirect interaction between the two moments. so that 2. so that the oscillatory interaction (125) for x less than the first 4.49. (8· In)(8· Im)m*J 2 (211")6p • Jkr roo Jo r'd 3k d 3k' ei(kk')'x k:. The integrations are similar to those we have already carried out.H 4f 68 sp in fa T t ti 4 F F(2k F r). The zero of F(x) is ferromagnetic. we have. The evaluation of J is discussed in reference 6. t (1 where the range function F(x) is given by (118). The exclusion principle actually plays no part in the k' integration the value of the total integral is not changed by carrying the integra tion at the lower limit down to k' = O. 333) between pauli operators: (123) (d. The secondorder interaction between the two nuclear spins is given by (121) H"(x) = is 1 an thl stt M: Fr fOI ~ 2. For small x. It is tempting to extend the use of the result (125) to the indirect exchange coupling of paramagnetic ions in metals.
THEORY OF ALLOYS. The ion cores are too far apart in relation to their radii for direct exchange to be significant. The magnetic properties of these metals can be understood in detail in terms of an indirect exchange interaction between the magnetic cores via the conduction electrons.1 of the interatomic spacings. The results have been analyzed in detail by Blandin and Friedel. • 8 m F(2k p r). whereas the Friedel rule for d states and Z = 1 demands '12 = '11"/10. Donath. 128. The prototype system much studied experimentally is the CuMn system at low concentration of Mn in Cu. the coupling J between I and a conduction electron spin 8 is the exchange interaction. the core diameters are about 0. see D. It is an experimental fact that the coupling rs is roughly constant for (126) H"(X) = most of the rare earth metals. Phys. The indirect exchange interaction will have the form (125). The metals of the rare earth (lanthanide) group have very small 41" magnetic cores immersed in a sea of conduction electrons from the 6s6p bands. 1618 (1962). The oscillatory character of the indirect exchange interaction leads to a large variety of possible ordered spin structures in magnetic crystals. which is much larger. CH. and papers cited there. 9 They find that all the alloy properties may be accounted for by an interaction of the form of (125) but they require a consider ably stronger interaction than is provided by values of the coupling deduced from atomic spectroscopy. They go on to show that a selfconsistent spin polarization around the Mn ion will lead to an interaction considerably stronger than from a bound d shell. including spirals. The nature of the spin structure is deter mined by the value of k p and thus by the electron concentration. Mattis and W. The fact that the curie temperatures are much higher in the metals than in the oxides is consistent with the role we ascribe to the conduc tion electrons. Rev. but with the ionic spins 8 written for I: rs 811. . In the limit of strong spin orbit coupling the results are more naturally analyzed in terms of a In' 1m interaction: (127) H"(X) = r 1 In' Im F(2k p r). instead of the contact hyperfine interaction. E. This is not surprising because the phase shift (105) from the deltafunction potential is seen to be of the order of 0. 18 365 is the electronic spin of the paramagnetic ion.1 (atomic exchange energy/fermi energy). this is compatible with the indirect exchange model and is quite encouraging.
in Physics 11. T. and the result following (28) for the density of states. On a molecular field model the ferromagnetic curie temperature is proportional to J(J + l)rS2(g . Show. 114. A.(exp) Tc(theo) Gd 300 300 Tb Dy 154 237 200 135 Ho 85 85 Er 41 48 Tm 20 25 Yb 0 0 Lu 0 0 degK degK The agreement is quite satisfying. 977 (1959)]. Rocher. The theoretical values of the curie temperature in the following table were calculated by Rocher using the value rs= 5. using (30). is very well satisfied. T. We recall that g for free atoms or ions is defined so that (128) gPBJ = PB(L + 28). (34).366 QUANTUM THEORY OF SOLIDS but now it is found that a constant rJ does not fit the various experi mental data. = L + 28.1)2. experiments on the reduction in the 8uperconducting transition temperature of lanthanum caused by the solution of various rare earth elements are compatible with the value rs '" 5. due to de Gennes. Matthias. For example.(kIVplk). 8. A review of the theory of the structural and magnetic properties of the rare earth metals is given by Y.1)2 = r J• This relation.1 evA 3 [H. that in the Born approximation the screening charge (133) z = p. . 233 (1963). Rev. Phys. PROBLEMS 1. so that (131) 1)J = whence (132) rs(g .7 evA3 which fits the observed curie tempera ture of Gd. Adv. in the sense that a constant rs will reproduce well the rJ deduced from experiment. Suhl and B. L or (129) gJ But (130) J= (g  + 8.
(. 2.Ek)2(t . CH. P' . although they cause the bottom of the band to be shifted.THEORY OF ALLOYS. From this result it follows that the fermi level is not changed by the presence of isolated impurities.g (19.Po + dpo IVdkl (E . According to the discussion followin.. Now assume that only the phase shifts flo and ''h are important: write down equations for op and I{Jp in terms of the residual resistance and the valence difference between solute and solvent.. 4..) dEk (E . keeping only lowest order terms in 1/r.electron density..1rYJ d 3kS{Gh(E)1 . 6. Note that if is independent of Ek..E. Find from (67) the positions of the virtual levels for V positive and for V negative. Solve these equations for small flo and 1h. Evaluate I1p(R) for large R from (29) for a deltafunction potential with flL = 0 except for flo.E" + ia)' (b) Show that the freeelectron dell8ity in energy (131) PYr•• (E) ..E IT )2 a 2' 2 + where PO(Ek) is the density of states in the unperturbed problem. This is known as the compensation theorem.19) we have flo = kb. (a) Show for the localized magnetic state problcm that (134) Gh = _ 1 Ek + IVdkl 2 (t . in this situation there will be no set polarization of the free electrons. Express the coefficients Op and I{Jp of (54) in terms of fk by carrying out the integration over k. 3. Suppose that the density of states geE) in a band is equal to a constant go for 0 < E < El and is zero elsewhere. (f(E) . the virtual d state does not change the free. 18 367 where PF is the unperturbed density of states per unit energy range. which is described by the scattering length b given by (105).. Note that tan I{Jk = S I!k(1r)j/<Rl!k(1r) I and integrate by parts..
Here x is the position of the incident particle..19 correlation functions and neutron diffraction by crystals We consider a crystalline system bombarded by an incident particle which interacts weakly with the crystal. where H' describes the interaction of the particle with the target. to II} of energy a. and the state of the crystal is changed from Ii) of energy a. M is the reduced mass of the particle j n here denotes solid angle and not volume. The incident particles of most interest to us are xray photons and slow neutrons. w is the energy transfer to the target. Suppose that in a single scattering event the incident particle is scattered from a state Ik) to a state \k'). per unit volume of specimen. This relation is derived in the standard texts on quantum mechanics. where (3) 368 K=kk' .. Then (2) (k'/IH'I~k) = (II f d3x eiK'%Wli). In the first Born approximation without spin the state Ik) eik '% and Ik') = eik'·%.). We are particularly interested in the excitation of phonons or magnons in the crystal as a means of studying the dispersion relations over the entire Brillouin zone. (1) dw dn = k ~ k'(M)2 211" \(k'/\ H' 2~(W + a.. BORN APPROXIMATION According to the Born approximation the inelastic differential scattering cross section per unit solid angle per unit energy range is.  a.
12 ~ p. j = 1 . we arrive at an important form due to Van Hove: d2 (8) 0 k' (M)21 VK. using (2). We have also used (11) L (ileiK''''j(O)If)UleiK''''I(t)li) = I (ileiK·"'i(O)eiK·"'t(t)li).'''. (ii.k 2< if" . 19 369 is the change in wavevector of the incident particle.. ')T denotes quantum and ensemble average over a canonical ensemble at temperature T. f"" _ dt ei(. With the integral representation of the delta function.. (5) (k'fIH'lik) = VK L Ule iK''''tIi). we have 2 (7) d 0de dn k' k 2r (M)21 V KI2 L ilil • o(w e.''if)(fk''''ii).t.. In the last step we have transformed XI(t) to the Heisenberg repre sentation: (10) ei(e. (4) H' L V(x i xi)... If the inter action H' is the sum of twoparticle interactions between the incident particle and the particles of the target. ..2.)tUleiK·"'lli) == UleiHoteiK''''I(O)eiHotli) U!eiK·"'I(t)ji)..  e/). where (. " N' and.V(x). Both exponentials are quantum operators and commute only at iden ..)t • de dO . j with (6) VK = J d 3x eiK·".. Using (5) and assuming a statistical distribution of initial target states with the probability Pi of finding the target initially in Ii}..+. or (9) d dn 0k' 2r de = 2rk 2 (M)2 IvKI2 f '" dt ewt _00 L (eiX''''/(OleiK''''I(t» jl T.CORRELATION FUNCTIONS AND NEUTRON DIFFRACTION. CH...
This is not a particularly handy form for actual computation.K) in terms of the spacetime fourier transform of a density correlation function: (17) S(w. In solid state physics there is as much interest in inelastic scattering processes. but it exhibits clearly the dependence of the differential scattering cross section on the density correlation function (p(x'O)P(Xt)}T.370 QUANTUM THEORY OF SOLIDS tical times. The statistical average in (9) is defined as (12) }.!.ltj(Oleilt·:Ij(t)T.K) = . but we shall develop the neutron theory. I so that we have S(w. and (15) S(w. II in conformity with (6. dt eM L (eilt. is the time fourier transform of a correlation function describing the system_ It is revealing to introduce the par ticle density operator (16) p(X. p. 6[x . where (14) k' Alt = k (M)2 2r Iv l lt 2 depends essentially only on the twobody potential.(ltlt') f dt ei''''(p(x'O)P(Xt»T.ltj(O)eiltltl(t»T. • in thermal eqUilibrium. we cannot in general write the product of the two exponen tials as a single exponential.xi(t)]. with the excitation of phonons and magnons. with emphasis on the determination of phonon and magnon dispersion relation by inelastic neutron scattering.(ileiltltj(Oleilt·:Ij(tlli) == (eilt.K).t) = }.. f" 2r .. The result (9) is conveniently written as (13) d2 (J' dO de = AltS(w.K) = 2~ f d 3x d 3x' eilt. NEUTRON DIFFRACTION The theory of xray scattering by crystals is closely similar to the theory of neutron scattering. Both subjects are important in solid state physics.64).. as there is in the classical applications of .
S. 8oc. :ii' U Co 0 '0 C u lIJ :J 0 q 1. . 9~.0. Phys. Ph1l8. 2.0 0 q ~. 4 L. a. W. Repts. In the conditions assumed the regular solution of the wave equation in the interior of the well is insensitive to small changes in the energy of the incident particle. March. CH. Marshall and R. 249. [100) I ~o ~ . [110j. Shull and E.~. Rev. 2.~. and Bowers. 79. Lowde. 137 (1956). The dispersion curves of sodium in the [001]. 109 (1959). 4. pt. D. Solid state physics 8. hog. G. Kothari and K.CORRELATION FUNCTIONS AND NEUTRON DIFFRACTION. o Transverse q %. 1968. 1. 31. pt. 1374 (1954. Solid state physics 2. Van Hove. Proc.nd [1111 directions at 900 K as determined by inelastic scattering of neutrons by Woods. S. I C. Wollan. ~ •e oe • (110) • 0 • 0 0 • 0 • 0 •• 00 0 21 I ·0 0 ·0 0 0 0 o . Singwi. O.. 440 (1962).. 19 371 elastic scattering to the determination of crystal and magnetic struc tures. Phys. Brockhouse. Several general references are: 2 L.o » c: ! l 2~ t 01 0 (1111 • • • • • 0 0 • • 0  I • Longitudinal.) 1 The concept of the scattering length is useful for the description of 8wave scattering of lowenergy incident neutrons which interact with a deep and narrow potential well. .~ FIG..
eat.lt~(x) 21Tb = . But the standard result for the 8wave elastic scattering cross section in terms of '10 is (20) dodO =k2! do.lt. Here b is called the scattering length or 8Cdttering amplitude.. the wavefunction lI'(x) just outside the well has the form (18) rll' = B sin (kr + '10) ~ B(kr + '10). (25) d 2(J' dw dO b o(w). not a field operator.b). 2 dodO b2• . Thus B = C/k and '10 = . We consider the fictitious potential klbl «1. Thus. The cross section in (21) in the scattering length approximation may be simulated in the Born approximation by a suitable choice of an effective potential or pseudopotential. This is a very useful property. dt ei<I'(e. M independent of K. In terms of the 8wave phase shift '10.= b2. for elastic scattering A = b2• Now for elastic scattering from a single nucleus the form factor (15) is (24) £(w. in (14).kb. so that.lt(O»T = ~(w). it is the in tercept shown in the figure. as long as Note that b here is a length."JC·lt(O)e. thus the logarithmic derivative at the edge of the well is insensitive to the incident energy. according to our argument above. (14).372 QUANTUM THEORY OF SOLIDS the energy of the incident particle. which may be written in terms of quantities C and b which are approx imately constant with energy at low energies (19) rll' = C(r . from (13) with k = k' for elastic scattering.K) = ~I . and (24). sin2 '10 so that in our approximation (21) dO approximately independent of scattering angle and energy. (22) V(x) = (21T/M)M(x)j then (23) 21Tb V It = M I d3r. (23).
zi. The coherent scattering cross section per atom is defined from (31) as (32) Ucoh = 4r (L Pibj) 2 == 4r1(b}12.K). (27) VK = (21rIM) L bjeiK. i vK I2 = (21rIM) 2 L bibmeiK'(Z. so that per atom (33) Utota\ '!1r Lp b j j 2 == 4r(IW>· i .ASTIC NUCLEAR SCATTERING 19 373 We suppose that the target contains N particles.CORRELATION FUNCTIONS AND NEUTRON DIFFRACTION. the ensemble average for lrfmis (29) (bib m ) = 2 or. 1m Here we have included for convenience the exponential factors in V K rather than in the form factor S(w.Zj). where for elastic scattering from a macroscopic target we may take M as the mass of the neutron. If the values bl. COHERENT AND INCOHERENT E[.. Thus from an ensemble of scattering centers (31) dc:r dO l(bW\ Le I iK XI ' N«IW)  l(b}12). CH. j where Pi is the probability that an atom will have the scattering amplitude bi' The total scattering must be the sum of the contribu tions to the scattered intensity from all sources. it arises from the presence of different nuclear isotopes of the scattering atoms. From (23) and (26). more generally. The jth particle is located at Xi and is characterized by the scattering amplitude bi' The pseudo potential of the target system is (26) VeX) = (21rIM) Lbjli(x j xi). 1m for scattering with the scattering vector K.. bm are uncorrelated. incoherent The incoherent scattering term is seen to be isotropic.. and also from different directions of the nuclear spin relative to the spin direction of the incident particle. . ____ coherent .zj 12 L bibmeiK'(ZmZI\ j. Thus (28) dc:r dO IL bjeiK.. (30) (bib m ) l(b)12 + lilm«lbI2) 12 2).
cos Ka ~i~22t~Ka "" 2'11"N 2: o(K sm 1fKa a G G). where we have implicitly restricted K to lie near G. we have also used . ( where a*. and calculate f. that is. We evaluate the lattice sum in (31) for a onedimensional crystal of lattice constant a. Tf SIn 1f'1a 2 f'" . m. where Tf is a small quantity. VI (... We thus have the Bragg condition that coherent scattering occurs when the scattering vector K is equal to a vector G in the reciprocal lattice. C are v s where n. If the Xl are at lattice points (3!l) Xl v = Ula + vzb + WIC.__ = cos tNGa cos 211'.:. where l is an integer between 0 and N . Nil e l=O ilKa 12 = 1 . b. then coherent K = la * + mb * + nc * == G.'" '1 d s_i_n_2~c::' (. = 2'11"(ul + vm wn) = 2'11" X integer. The sum vanishes unless K . n are integers. ware integers and a. v. For a crystal of N atoms. q o ( _. scattering occurs when (36) the crystal axes./ i!"Va 2 f'" d sin tNTfa ~ '21 _ . 4'11"« IbiZ)  The coherent scattering from a target involves 12: I eiK'%j r as we ol . b*. NI \' u e 2: ei1Ka 10 1 1 e iNKa s e \1 and (37) (. To obtain the normalization we let K = G + Tf.cos NKa 1 .1. c* are the basis vectors of the reciprocal lattice and l. Thus the lefthand side represents a periodic delta function. when tKa n'll" or K = 2'11"n/a == G. = 2'11"N = 2:N a f d'1 0('1). v ( We notice that the lefthand side is large when the denominator sin 2 tKa is small. For then K· Xl 1.374 QUANTUM THEORY OF SOLIDS c The incoherent scattering cross section per atom is (34) O"incoh 0" total 0" coh t 2). lHUlVlfJlC see in (31). and then write down the result for three dimen sions. Xl is an integral 2'11" for all sites l. with Xl = la.
In (42) we expand the displacement in phonon modes.(xlXi)(eiK. q where (44) are phonon operators. Uj(t))).53). CH.wqt) .(O)]eiK'IXj(O)+ul(t)I)T L jt eiK.t) = = = eoh Nv:l(b)12 Lo(K G G). G By extension to three dimensions G) = NV: IL l eiK'J:j \2 = (211")3(N IV e ) Lo(K L o(K G G). Xi' The phonon operators enter through the expansion of the u's in phonon coordinates.iK ' Uj (0) eiK. (41) where where (42) Qlj(t) lK2«l Uj(t) . which is assumed to be real. for the present we take over the results (20. following (2. Ul.33). Thus (e.UI(O) }2)T [uz(O). Uj(t) . q Then e iq . uj (t)T eQ1j (I).!xj(O)+u. for simplicity it is assumed that all phonon modes of given wavevector q are degenerate and we arrange always to take the polarization of one of the modes q along K.51) and (20. (43) Uj(t) = a q . The form factor (15) involves L jl (eiK.uz(O) L (2N M wq)~(aq(ei(q·xrwqt)  + at(ei(q'J:. where V c is the volume a . INELAS'£IC LATTICE SCATTERING We supposc that all atoms in the crystal have the identical scattering length b. The seeond factor on the righthand side of (40) is quite famous.CORRELATION FUNCTIONS AND NEUTRON DII!'FRACTION. we shall discuss it in detail for l = j in the following chapter on recoilless emission. Xj are now the coordinates of the undisplaced atoms and are the displacements referred to Xl. ail" L (2N M wq)~(aqeHq'%i".uj(O)eiK'UI(t)T. b X c of a primitive cell and V: is the cell volume in the reciprocal lattice. Uj Xl. 19 375 the fact that ¥fa (38) = 11" X integer. with the appropriate modifications for l ¢ j.xl ) _ eiq'J:I». Thus the coherent scattering cross section of the crystal is (du) dfJ (40) F(K.qt) + atei(q·xiWqt).
from (42)."ql L (K + q . We may rewrite this as.i sin 81i)' Qli(t) = 2~~ L wq. cc whence.aq]ei.. (48) co . G q FIe for soli net nel .t)/e.G) q G + (nq)ei. We write the first factor on the righthand side of (49) as e.. (51) F(K. (Xl 1 q Xi)' fre wi tr4 eth (47) [ul(O).2W .ei.cos 81i) .{[aq.376 (45) (ui(t) . exhibiting only terms diagonal in the phonon occupancy.91j1 = (i/NM) L w sin 81i' l.91j)(ataq + aqat) q Tl ar in pi + nondiagonal terms.Ui(t)] = (1/2NM) L wq.2W ~(K .t) = NV:e. (1/2NM) L wq. Sl( q 1 SOl q atl Thus.Ul(O) 12 = QUANTUM THEORY OF SOLIDf.(t) = exp {(K 2/2NM) LWql(2(nq) + l)} .J[·(:a'J:a'I) +L q 11 (K 2/2NMw q)«nq + l)ewqt ei. we have (49) eQ.1«2(nq) + 1)(1 q If we split Qli(t) up into timedependent and timeindependent terms. . Each term in the exponential is small by order Nl.9. then F(K.1(2 .ei.X j) + (nq)eioIqlei(q+lt)·(:a'IXj»}.at]ei. using (38).l + [at. = Wqt where (46) Also 81i + q.(qlt)'(XI.2W = L {ei. so the second factor on the righthand side may be expanded in a power series as (50) exp ( 1 = 1 + L (K 2/2NMwq)[(2(nq) + I) cos 81i q + i sin 81i] + The neglected terms represent multiple phonon effects.G) {L G + L (K 2/2NMw q) (n + l)e iwqt L ~(K q . exp {(K2/2NM) Lw q q q 1 [(2(n q) + 1) cos 81i + i sin 81i ]}.G»}.
we will observe only those phonons for which energy is conserved for the whole system.q. 1. The energy changes in the inelastic scattering processes are found from the time factors. in the last term a phonon q is absorbed by the neutron. CH. • • . with K G .na CORRELATION FUNCTIONS AND NEu'rRON DIFFRAC'fION. • • Units of energy gain by neutrons • • • • ») }. 19 377 ns. The requirements of energy and ms. . )1 G ond . and the energy of the scattered neutrons has been increased by "'q over the energy of the incident neutrons. • " 110 010 ". l!9  " " . phonons q on the scattering surface (shown as a solid curve) are absorbed by the neutrons. On the scattering surface the scattered neutrons have wavevector k + G(210) + q. The first term on the righthand side represents elastic scattering at any G. The inelastic scattering surface near the point 210 in reciprocal space for neutrons k incident on a target. the second term represents inelastic scattering K = G + q in which a phonon q is emitted by the neutron. 2.s _. Of the values G + q which we can'enumer ate for given G. The time integrand in (15) for the form factor will involve for phonon emission the factor e''''te''''qt. • _ " " '\. \. in first order of the expan sion (50). " • \. "' '\. 'a 100 \ \ \ \ 000 \ \ 200 • \ \ \ \ \ • • • o ~ \\ \ +2 \ \ \ \. Experimental results for W versus k for phonons in metallic sodium are given in Fig. so that the neu tron must lose energy Wq • For phonon absorption the integrand is e''''tei'''qt. +1 +3 I)} . and the neutron energy is increased by Wq • This argument tells us that inelastic neutron scattering occurs with the emission or absorption of one phonon. • the • "'\. FIG. ~ 020 • • • . \ '\. • Units of energy loss by phonon annihilation • i]} .
It is often convenient to work with very slow neutrons. This is at present the only known general method for determining the dispersion relations. the neutron cannot emit phonons. but can absorb them. . If the incident neutron energy can be neglected.q + G. the slow neutrons cannot be scattered elastically. Scattering surfaces generally similar to that shown will be found centered about every reciprocal lattice point. Thus the entire scattered spectrum in the onephonon approximation may arise from neutrons for which K = . 3. Further. In Fig. 2 we show schematically the energy balance for processes in which a phonon is absorbed.q and (52) 2M q = 1 2 Wq• I t is possible with high stiffness constants for K to be given by . It is equally possible to q FIG. 3. By inelastic neutron scattering experiments it is possible ~o deter mine the dispersion relations of all branches of the acoustic and optical phonon spectrum. for given k. Solutions of (52) are shown in one dimension in Fig.378 QUANTUM THEORY OF SOLIDS wavevector conservation restrict severely the energies and directions of the inelastically scattered neutrons. The solid circles indicate the possible scattered energies in one dimension for neutrons with k + 0 scattered with absorption of a phonon from a crystal with one acoustic phonon branch and one optical phonon branch.
It is shown in the following chapter that for a Debye phonon spectrum (56) iK2(U· 2) = J 3K 4Mk B O 2{ 1 ('P)2 +. The DebyeWaller factor arose originally in connection with xray diffraction. then (!l5) 2W i(K 2/2NM) ~ wq. Further. from the integrated effects at absolute zero of phonon emission by the incident neutron. Optical principles of the diffraction of xrays. where here the sum is over 3N normal modes.1(2(nq) + 1) i[(2(Uj 2). that is. If we redefine the sum in (53) to refer to all 3N modes. for convenience. Weinstock.+. A full discussion of the experimental situation concerning the DebyeWaller factor in xray diffraction is given by R.2W . } 3 0 21l"2 2W. CH. Taking Xi 'rhe factor e. see R. but the peak height decreases as the factor e. Thus W is proportional to the mean square oscillation amplitude (u 2) of an atom in thermal equilibrium at temperature T. 66. 1950. W. We note that at ahsolute zero W is approximately the ratio of the neutron recoil energy l(~/2lvI to the Debye energy knO.. Chapter 5. 1 (1944). Phys. For a detailed discussion of inelastic neutron scattering. we note from (43) that (54) (Uj2) = = ° (1/2NM) 2: w q q 1 (2(n q ) + 1).CORRELATION FUNCTIONS AND NEUTRON DIFFRACTION. Bell. e. We can see from (51) that the width of the peaks of elastic scattering do not broaden as the temperature increases. 19 379 determine the dispersion relations of magnons.2W ? 1.. The factor is a measure of the effect of thermal motion in reducing the apparent periodicity of the lattice. The term 1 in the curly brackets arises from zeropoint motion. where (53) 2W = (K 2/2NM) 2: w q q 1 (2(nq} + 1). Rev. whereas the sum in (53) refers to the N modes which may be chosen with the polarization vector parallel to K. James.2W is known as the DebyeWaller factor. from the thickness of the observed scattering surfaces one may estimate the relaxation times of the phonons and magnons. ELECTRONIC MAGNETIC SCATTERING OF NEUTRONS The magnetic interaction of the electronic magnetic moment of a paramagnetic atom with the magnetic moment of a slow neutron . London. DebyeWaller Factor. For K ? 0.
The scattering cross sections for bound nuclei are given in the following table: Nucleus Mn s5 Fe56 Ni 58 C0 59 Paramagnetic Magnetic Coherent Nuclear Ion Cross Section (barns) Cross Section (barns) 2 I bet k ele4 the 13 26 6 Mn++ Fe+t+ Ni++ Co++ 21 21 It' cell wri (64 5 9 The magnetic values refer to forward scattering. V)V  ] r + t'n V2 1 r (6 w (6 Now (60) V2 1 r 41rIl(r). F n This is usually written as the sum of (62) H .3 r t'n X r =  curl t'n X V~.= r (t'n . We now treat the magnetic scattering. (7 . where Hn is the magnetic field caused by the magnetic moment t'n of the neutron. (58) Hn wh de by (6 curl . We neglect the magnetic field of the orbital motion of the electron. so that (61) H= t'e·V(t'n'VD41rt'e. Thus if r = Xn Xc. 1 r but by standard vector algebra (59) 1 curl t'n X V . H n . The hamiltonian is (57) wh is t (65 wh (66 H = t'•.t'no(r). this is a good approximation for the elements of the iron group. first calculating the matrix elements of the neutronelectron magnetic interaction in the Born approximation. _ t'e' t'n 3 3(t'e • r)(t'n .. r) dIpole  r rO w. and (63) Hcolltact =  3 &r t'e • t'nll(r).380 QUANTUM THEORY OF SOLIDS COl leads to scattering lengths of the same order of magnitude as the purely nuclear scattering we considered above.
The part of (all . For transitions in which the spatial state is unchanged note that then F(O) 1. The final state is (65) if) eik"X"'I'/(X e) [al).'e· 1.r = (K· 1. The initial state of the system may be written as (64) eik'X"'I'i(Xe) Iai). (67) f r d 3r eiK.X. It is convenient to choose the origin of the coordinate system at the centerofmass of the atom.91. V' (1.'1l .rHlai) f d3xe 'l'j(Xe)'I'i(Xe)CiK. band hetween the spatial states k and k' k K. mnc le\ g = 1. 1. • K)K.'•.. Thus (68) • 1. (66) Then n Ull/li) = (all f d 3x d 3xe 'l'j(Xe)'I'i(Xe)CiK. Here r = x" .'e (K· 1.'n = gS".'n (1. the other part of (61) gives.2Iai)F(K). V' ~ (f'r ~ eiK. . where the !'S denote final.'6 we me C Se.x•• '1'1 = 'l'i.'n after integration. With 1.'n)(4rjK2). 3 where we have made a coordinate transformation having a functional determinant of value unity. 19 381 In the Born approximation we require the matrix elements of l/ hetween the spin states a.(Se' K)(Sn' K)K2iai)F(K).'. lai) in oCr) gives 4rr1.Xc is the difference between the nuclear and electron positions. CR. we may write (70) (iIHli) 4rrg e2 (a/ls e • Sn . V'D = iK· 1. 1. where ai contains the electron and neutron spin coordinates and 'l'i(Xe) is the initial spatial electronic wavefunction.'e· K) the maanetic form factor F(K) is defined by F(K) f d :ce 'l'j(Xe)'I'i(Xe)ciK. We want to separate the spatial and spin parts of the matrix element in order to exhibit the spin function explicitly. .''' . on integration by parts.xnHlai) (all f d r ciK.'n) f 3 f r d 3r eiK.CORRELATION FUNCTIONS AND NEUTRON DIFFRACTION. .)(K· 1. 1.'e)(K . 1.
and (71) to give (7. . If we write P. k \F(KW f dte'wt(P. Thus the quan equal.L as the vector of length Se.. where (72) p is the spin density matrix for the initial state.' !IS 2: (qsIS:P1Iq's')(q's'ls~p~. We now consider several applications of For elastic scattering by an isolated paramagnetic ion of spin B.8./l(slpls) = jaa. (sls:s~ls)(slpls) = jaa.P. "s' q./l(qlp1P We suppose below that the neutrons are unpolarized.i) dQ ~ d u 2 d~ k' . where ro e2/mc 2 2. tity in (71) becomes. The scattering cross section is proportional to. Now 2: (sI8:ls')(S'IS~ls)<slpls) = ' • .L(t»T 1 (g r O)2 k' 2. the function of the spins in (70) may be written as S" • [t X [S8 X K]. q' the electron spin quantum numbers.382 QUANTUM THEORY OF SOLIDS Note that if :K: is a unit vector in the direction of K.13 cm is the classical radius of the electron. normal to K.Iq)(qslplqs). To include inelastic processes we must follow the timedependent generalization introduced earlier for neutronphonon scattering.L(O).k 27r (mn)2 ( e2 m e m n c2 )2 (41rg)2 . with s. (70).L and in the direction K X [So X Kj.8(slpls) .. then the matrix element involves S.. all (slpls) (73) !..82 X 10. so that the scattering matrix element is proportional to the component of S. = If the neutron beam is unpolarized.lqs)<qslplqs) = 2: (sls:ls')(s'IS~ls)(qlp1Iq')(q'lp~.1q) = j(qlp1P1Iq).L(t»r. s' as the neutron spin quantum numbers and q. (71) ". ja.L.· P. and 2: ja. for elastic processes with aU (74) 1. We combine (13).F(K) 2 4(27r) I I f dtei·.L(O)'P. Paramagnetic Scattering.t(P.
For elastic scattering we may replace the trace in (80) by its time average: (81) time average of [Sj(O)S~(t»T = (S)T 2li ./ I Then (80) (Plo(O) • Plo(t)}T = L ciJC'(X/lIOjl(Sloj(O). because all component pairs Sa. Paramagnetic scattering is often used to determine the magnetic form factor. The magnetic cross section is somewhat larger than the square of the classical radius of the electron. an where for random electronic spin orientation (77) (Pi)T = !S(S + 1). NV:<S)2{1  (t. For an antiferro . contribute equally except the com ponent parallel to K.Ii/l" a where (S) is a function of temperature. 19 383 in the absence of a magnetic field. 6)2}Ii(K  G). 11 if the lattice is rigid. F(K). (82) : = (gro)2NV:(S)T2 ~ 2fl  ct.!(gro)2IF(K)j2S(S + 1). Slol(t»7'. This gives magnetic Bragg scattering for a ferromagnet at exactly the same reciprocal lattice points as nuclear scattering. using (38) and the result of Problem 4. CH. Then (80) becomes. and. (78) dcr dO . Elastic Ferromagnetic Scattering. The only dependence on scattering angle enters from the form factor.Sa. 6)2\ L Ii(K G G). we may define (79) Plo(K) = LciJC. 6 is defined as a unit vector along the axis of magnetic orientation. In a ferromagnetic crystal with spins Sl at lattice points XI.lIO/Sl. Thus . from (75). (76) dO = (gro)2IF(K)12(Pi)T.CORRELATION FUNCTIONS AND NEUTRON DIFFRACTION.
Show that (87) I+l I} (b)= { 2I. Magnetic scattering involves a form factor F(K). . (89) the I 5.t. (86) a = Ie e'~o sIn 110 1 . Show that as usual in scattering problems. VVe note from (82) that because of the factor (S)T 2 the coherent magnetic elastic scattering will fall off rapidly with temperature near the curie temperature. . The theory of inelastic ferromagnetic scattering is quite similar to that for inelastic lattice scattering. thus the Bragg reflections are different for magnetic and for nuclear scattering. where b is the scattering length. in the form (85) 'P. iden uncc two 4. the magnetic scattering vanishes for K parallel to the magnetization.ib++2rt=lL. The high alm( entiI 3.ks + (. . sin (krkr+ 11 0 ). (88) (IW> = {I + 1 Ib+12 + I 21 + 1 1 Ib 12}. The theory follows on develop ing (80) in magnon operators. a +r e. and let L be the scattering length in the state I . further. Suppose that the state is represented by an incident wave e. 2. whereas the corresponding nuclear form factor is unity apart from the effect of lattice vibrations. here 110 is the awave phase shift. e'~'b. = ei~. The results of the experiments can be used to determine the dispersion relations and relaxation times of magnons in a wavevector region at present entirely inaccessible by other methods.f.k" 'Ve can express 'P. then (90) Forl corr' PROBLEMS 1. Suppose that the scattering nuclei consist of a single isotope with spin Ii let b+ be the scattering length in the state I + ! of nucleus plus neutron.l! eik'.k. = kr sm kr 1. ing r ' by a\'eraging over a sphere show that the swave part of 'P is (84) 'P. and an isotropic scattered wave (a/r)e ik '. (83) 'P e.384 QUANTUM THEORY OF SOLIDS COR magnet the definitions of G are different for the magnetic and the atomic primitive nuclear cells.
Thus in a strict sense there is no elastic scatter ing from a 11 Lt f. per ion. 3. The scattering from hydrogen also is almost entirely incoherent. Show that (89) r PiPi = (6"iJ K"i(fJ)S"sfJ. to a paramagnetic crystal if the that is. 4.CORRELATION FUNCTIONS AND NEUTRON DIFFRACTION. but not from deuterons. f the righthand side gives the form employed by Van Hove and others. show that the identical result applies. d . 5. <SfS~) = Oij<SrS~). The result (79) was derived for a single paramagnetic ion. Show that if n(x) is the concentration of nuclei of scattering length b. where i and j are the two ion sites in the lattice. CH. so that the cross section involves o(K). but this corresponds to no scattering. 19 385 The scattering from natural iron is almost entirely coherent because of the high abundance of an isotope of zero spin. The scattering from vanadium is almost entirely incoherent. then the differential elastic scattering cross section is given by 2 (90) d dQ (T de = b2 o(e) If d3x elK x n(x) [2• For a liquid n(x) = constant. 1 .
23 g.. A shift of this magnitude may sometimes be greater than the natural radiative width of the 'Yray line.. .. From 0).. of the order of thermal velocities.. the final velocity of the atom of mass M is obtained directly from the principle of conservation of momentum: (1) 0= Mv+ K..7 erg emitted by an atom of mass 10. where K is the wavevector of the 'Y ray.23 )(3 X 1010) ....20 Recoilless e:rn. (2) y = w/Mc.... we have y. In the present example R r. where Eo is the energy of the 'Y ray. the atom recoils and the energy of the emitted 'Y ray is reduced by the amount of the recoil energy. for a 'Y ray of energy .. which corresponds to a f1'c quency shift of the 'Y ray .... If the atom is initially at rest.. 3 X 10 6 em/sec. One may alter natively simply say that the wavevector of the recoiling atom is K.100 kev or 10.....6..ission When a lowenergy 'Y ray is emitted by the nucleus of an isolatl'd atom. IKI w/c. 10 15 secI. Thus because of recoil the emitted 'Y ray may not have the frequency needed to be reabsorbed by a nucleus of the same kind.12 ergs. 107/(10.... The recoil energy R is (3) R = K2/2M = Eo2/2Mc 2... 5 X 10...w R/Ii.I 1014/2(1023)(1021) . some 'Yray lines of interest have widths as narrow as 10 7 secI....... From a free atom in thermal equilibrium the 'Yray line will be 386 . The recoil may therefore quench the 'Yray resO nance fluorescence.
essentially unshifted in frequency (as distinguished by the cross sec tion for reabsorption) and a broad shifted background.2 (p2) = 2M{v 2 ) c 2M ' or (7) A2 ~ R .HECOILLESS EMISSION. the portions with recoil. kB'l'. arise when the emission of the 'Y ray is accompanied by the emission or absorption of phonons in the crystal. Thus ~he fraction of elastic events may be the same in a diffraction experiment with 20 kev x rays as in the emission of a 20 kev 'Y ray. When the radiating atoms are embedded in a crystal a fraction of the emission of 'Y rays take place with no perceptible recoil energy. Indeed. the width A is of the order of the shift R. the usual energies of x rays uti lized in diffraction work are of the same order as the energies of interest in the study of the recoilless emission of 'Y rays. In a solid one may find both a sharp 'Yray line. The inelastic diffuse reHections of x rays are entirely analogous to that portion of the 'Yray spectrum which is accompanied by the emission or absorption of phonons. where R is the recoil energy and kB is the boltzmann constant. For the numerical values above. The doppler width may therefore be much greater than the natural line width of a 'Y emitter having a long lifetime. the Bragg reHections are recoilless or elastic in the same sense. This is known as the Mossbauer effect. the proportion of the un shifted radiation increasing as the temperature is lowered. The mean square doppler width «Aw)2) is given approxi mately by ~ where (p2) is the mean square thermal velocity of the atom. The shifted portions of the 'Yray spectrum. We have seen in the . The energy of the phonons now plays the part of the translation recoil energy in the free atom. ()H. define A2 = «Aw)2). but never becoming unity. The width of the sharp line is independent of temperature. then from (5). after all. The rela tive proportions are temperaturedependent. (6) If we A2 ~ w2 K2 . From our experience with xray diffraction by crystals we should not be entirely surprised at the existence of 'Yray transitions in a crystal not accompanied by the excitation of phonons. 20 387 broadened by the doppler effect as a result of the thermal distribution of velocities. The natural width is usually dominant. and with a width close to the natural width.
dipole. magnetic. The operator A depends upon the coordinates.). etc.i)K2{u Sl r . where the operator a(q) depends only upon the relative variables and spins of the particles and has an explicit form depending upon the nature of the transition (electric.388 QUANTUM THEORY OF SOLIDS REC last chapter that the intensity of a Braggreflected xray line is pro. quadrupole.za(q). momenta. Benjamin. that is. For the emission of a ')' ray of momentum K.qi)ii). Frauenfelder: The M ossbauer effect. The explicit form of a(q) is of no interest for our present purposes. portional to e(). The factor eiK·z allows nonvanishing matrix elements with a ')'ray wave function having a spatial variation eiK·z. and spins of the particles in the nucleus. New York. The DebyeWaller factor describes the temperaturedepend ence of the elastic reflections. We now consider the emission or absorption of a ')' ray by a nucleus bound in a crystal. A review of the applications of recoilless emission of ')' rays to solid state problems is given by A. The same factor determines the pro portion of recoilless events in ')'ray emission of absorption in a crystal. The dependence of A upon the centerofmass coordinate x is determined completely by the requirements of trans lational and Galilean invariance. here K is the wavevector of the x ray. The operator describing the transition is the same operator A. Let us now express A in terms of the centerofmass coordinate of the nucleus x and the relative coordinates q which include spins. TRANSITION MATRIX ELEMENT fina can the whc spe( berf Ii) t (10) We first consider the emission or absorption of a gamma ray by a free nucleus not bound in a lattice. 1962. This transition is described by a matrix element M of an appropriate operator A between the initial state Ii) and the final state if) of the nucleus: (8) 'I dep inte 'I elen ber latt the (11 M = UIA(xi. and (U 2)T is the mean square displacement of an atom under both thermal motion and zeropoint motion. the above requirements are satisfied only if the operator A has the form (9) A bec (12 Thi of = eiK.pi. but we must take the matrix element between initial and ave vid\ giv I of ha kin res (13 Fu (14 . Abragam in LTPj see also the reprint collection edited by H. by the requirements that momentum should be conserved and that the transition probability for a moving nonrelativistic observer should not depend upon the velocity of the observer.
in which the state of the lattice is unchanged.ni) !(n/leiK.RECOILLESS EMISSION.xeiK. If the binding forces of the crystal depend only on the positions of the atoms and not on their velocities.ei!:'X] = 2~ eiK. Further (14) [[II. while the lattice goes from a state specified by quantum numbers ni to a state specified by quantum num bers nj. namely p2/2M.x(K 2 + 2K· p). We are interested mainly in the fraction of the total num ber of transitions which are recoilless.x]. The matrix element thus separates into the product of a factor depending only upon the lattice and a factor depending only upon the internal structure of the nucleus. The transition probability depends upon the square of the matrix element. rather than of the free nucleus. from any initial state ni of the lattice. There is a powerful sum rule due to Lipkin which states that the average energy transferred to the lattice is just the energy the indi vidual nucleus would have if it recoiled freely. <J!a(q)li). (13) [H. the total probability of anything happening or not happening is unity. Then from the result of Problem 1.eiK'Xj .r!n/)(n/leiK.ni) = L (nileiK. We can now write down an expression for the matrix element describing the transition in which a l' ray of momentum K is emitted by a nucleus whose centerofmass coordinate is x. This matrix element is (10) M L = (n/!exp (iK· x)ln.x !ni)!2. 20 389 final states of the whole lattice. (12) L P(nj. _ K2/ M. then the only term in the hamiltonian II of the crystal which does not commute with X is the kinetic energy of the same nucleus. CH. that is. The probability P(n/. because.eiK.) .xlni) nf nf = (nileiK.) of a transition in which the phonon quantum numbers change from ni to n/ is just (11) P(nj.n.4. The sum rule also gives a quick way of seeing at least that recoilless emission can occur. This confirms the normalization of (11).zlni) = (nilni) = 1. that is. and the internal state of the emitting nucleus changes from Ii} to If).
where eqj is a unit vector for the jth polarization component of the mode q. from the phonon N'h k.ni). We assume that the crystal binding is purely har monic.ni) = w{l P(ni. Note that (15) [[H. Now write the ii diagonal matrix element of (15) in the representation in which the phonon populations are diagonal: (16) (n.¢i L P(n"ni) P(ni.L {(nileiK·l:ln/)(n. expansion of Chapter 2. RECOILLESS EMISSION IN A CRYSTAL LATTICE.I[[H.lei1.!Hln/) . according to (3). It is convenient to simplify the notation by setting Xo = 0 .(R/w). If Xo is the equilibrium position of a radioactive nucleus. then we may write (19) x = Xo + u. ~ (1/2Mw q}·)'he q}·(a q]·eiq·l:0ei"'qjl + a+eiq'l:0ei"'qjt) qj .e i 1. (20) U QJ Then.t·l:ln/)(n/le i1. this inequality demonstrates the necessity for recoilless emission. the lefthand side of (17) is larger than w . using the result (17) Thus.iK·l:Hi1.i1. For a single harmonic oscillator of frequency w.ni) is essentially equivalent to the DebyeWaller factor..t·l:.t'l:j. We introduce normal coordinates for a bravais lattice of N identical atoms of mass M. {€(n/)  R.) . The ensemble average of P(ni.ni)l.390 QUANTUM THEORY OF SOLlO::. so that (18) > 1 . with €(ni)jP(n"ni) K2/2M L .eiK'l:j.(nil e. ABSOLUTE ZERO The simplest problem is that of emission in a crystal lattice at absolute zero.t·l:lni)(n.)P(n"ni. The probability of recoilless emission is given by P(ni.eiK'l:j 2H . where R is exactly the free atom recoil energy. with u as the displacement from equilibrium. eiK'l:j!ni) / 2(ni!Hlni) .) j 2 L(€i / €. at least when w > R.t·l:l ni)(n/IHln.eiK'l:HeiK'l: _ e.
RECOILLESS EMISSION.(1/2Mw.) = l 2: {M w" 2Q.t .dQ.ate.O) = I {(a.. The hamiltonian for the normal modes is (24) II (xlo. The normalized groundstate wavefunction in the coordinate repre sentation for the mode 8 is just the harmonic oscillator result: (25) =a .. Using (25)./1I'~) e. 2• If we assume that (Qq/) = (Qq2). Q.) = 1/2a.H Thus u L (1/211fw.IQ. as the amplitude of the normal mode momentum is (23) p.e.)2(Q.O) = 1<0IeiK. We note that the quantity within the curly brackets has the value exp (13.N~lo. CH.2) eL(K'e.2)/ N.2Io. = i1lfw..e.. a. ~~1I'~e..·2Q. 1 where 13.""t).2)/N = K2(Qq2)/N.)12. independent of the polarization j. with Q.ei"'.)N~.)~(a. 2 (27) P(O.. 20 391 and by using (21) 8 to denote the pair of indices qj.1 1\ 2 }.(a"ei""t + atl)""t). so that (28) P(O.lei(K. 2 ).·eill. ° I n(O. + 2 . The probability of recoilless emission from the ground state is (26) P(O. 2/4a. where we have used the result for the ground state that (29) (Q.} .)2(Q.2/2 . The associated = MQ.. u which may be expressed as (22) N~~ 2: Q..u IO)12 where signifies that all lattice oscillators are in their ground states. N. i .1 12 • • = ne• II•I (Q. = (K· e. 8.)~e.O) = I neII•I / 4.)Q. • n • f"'". 2) = (0. then (30) L (K' e.Q. 2 Mw•.
2) = 3N12: (Qq2). = and we are concerned with ° For a Debye solid w = vq. = 2kB S' and N (43) 2: (37) P(O. Glauber. " 1 ~w • • so that. (31). (32) P(O. the identical result follows for a harmonic system not in the ground state of all phonons. 2(Q. where v is the velocity of sound and q is the wavevector. The same result obtains even for anharmonic lattice oscillators. provided that the total number of atoms »1.392 QUANTUM THEORY OF BOLms RE( Now (31) (u 2) = Nl 2: (Q. 2: C We in a the 2M 3N. where R = K2/2M is the freeatom recoil energy. 449451). according to a theorem due to R. combining (28).O) = e3R/2kB9. of 1/q over the 3N phonon modes. At absolute zero n. 2R (n. (30). 395 For a harmonic oscillator (34) (39: incl TIM Mw. We note that (1/3N) (l/q. Rev.) is just the mean value • wh€ int 2: • E" 1 (41.~ = 2 qm ~.2) = (ns + !)liw.. Phys. Thus the probability f of recoilless emission with phonons distributed according to the canonical distribution at temperature Tis (33) whi (38: ThE f = P(nr. + !). J. l! n. By the properties of hermite polynomials or otherwise (see Messiah.O) = e. pp. (35) il{2(U2) = l{2 • 2 2: (no + !) = w. (40. 2k B S Ifp and coo: (42) the standard definition of the Debye temperature S = wmlkB' Therefore R 1 3R 3N w.K2 (u')/3. 3N.nr) = e.. but with the phonons in a canonical distribution. (36) _1 Thus 3v 2w m 2:! = q. 84. q Thl lesE mu so that.K2 (U 2)T/3. . w. from (31). 3N q dq q2 dq = ~ .
for T (38) « e. lK2( 2) = ~ u T 2kBe {1 + 3"8)' (!V} including the absolute zero contribution.. If the lattice is initially in the state i of energy ei and after emission is in the state f of energy e" the line shape function is (41) I(E) r2 4 (E . dt exp {%(E  Ei)t} r + e. has the value kB T2 3 4v 2 2. (E .Eo + e/ 1 If p(i) is the probability that the system is initially in the state i. We assume that the shape of the line when emitted from a nucleus held at rest is described by (40) I(E) = "4 (E _ r2 1 EO)2 + !r2' where r is the lifetime. which. TIME CORRELATIONS IN RECOILLESS EFFECTS AND THE LINE SHAPE Our object now is to calculate the shape of the emitted yray line. CH< 20 393 Thus the fraction of emission events at absolute zero which are recoil less is substantial if the freeatom recoil energy is less than the maxi mum possible phonon energy.Eo Now (43) f:. for T (39) 11" « e. frN  (7' )2. then the shape function is given by i<IieiK<uliW (42) I(E) = r2 L p(i) 4 ''/ Eo)t  i<JjeiK<uli)i 2 .  Ei)2 +Jr 2' . At a nonzero temperature we must include the equilibrium value of ns. e 211"2 The total exponent is. We consider the emission of a y ray by a nucleus bound harmonically in a lattice of N atoms each of mass M. and P(fi) = is the probability that the phonon state will change from i to I. it is easily seen that we need the quantity 3kB2T2 211" 2V 3 JOlT X 0 ~dx. note that I(Eo) 1.RECOILLESS EMISSION.iCE.
so that (49) [u(O).t..i Ilt'lI(tl. in terms of creation and annihilation operators a+.t = L... A timl The commutator is therefore a cnumber. whe 382 (53) U We assume p is the canonical distribution. We now recall the theorem (Messiah. w.uli) = J K.BlI2.. we may without further assumption arrange to take one of the three polarization directions j always along ordt The rep] .u(O)] ¢ 0 for t ¢ O.. L (1/2Mw.atle.a. I(E) = f J:. In the Heisenberg representation u(t) = eiHlu(O)eiHI. • i ~ sin w.' whE the term in the curly brackets has the value 2i sin w. (55) dt '\I We observe that [u(t). and we introduce the notation for thermal average: (45) (eiE'U(I) eiltu (O»T = sot (M) L p(i)(i[eiJt'U(1)e. This follows because. where H is the hamiltonian of the phonons.ueiHleiJt..ilrltl(eilt'U(C)eiJt'U(Ol}T.Bl commutes with A and with B. It follows that (51) (eiE'U(t)eiJt'U(Ol)T The exp: all t = (eiE. and the right side of (44) becomes (il e iJt' lI (1) e iJt' lI (O) Ii). from (42) and (43). then (50) (59) eAe B = eA+BeIA. (46) whe eHEEoll().lewet }.• + [at.(u(t)U(O) ')TeJ. 442) that if [A.i (56. If we make the assumption that all phonon polarization modes of given wavevector q are degenerate. p. • 1 t ) •.ew" + ate.uli). i Then.. The (57) Then (48) [u(O).ie.u(t)] (58) NM. a (47) u(t) = NJ. (52) (ileiHleiJt.)J.Jt'U(Ol Ii).(a.394 QUANTUM THEORY OF SOLIDS BEe We may rearrange some of the factors in (42): (44) L eiail(i!eiE'lIlf)eil/l(fleiE.u(t)] = (1/2NM) L w.Jt·U(O)].1{[a.
(tu(t) .qt ). The timedependent factor contains N terms each of order liN.. one K2j2M.. With R (59) eQ(t) = exp [. we have (53) (eiK1u(Ou(O»))T = e(~)K2([n(t)n(O)J2)T. coswqt).RECOILLESS EMISSION. we have. timedependent and one timeindependent.(RIN) L wq. Therefore for the timeindependent parts of a large system we may replace exp { I by unity. pp.. CU. elt ei(EEo)tni)rltlQ(t) .1(2(nq) + 1] exp q {(RIN) r q wq 1 . 1are timedependent.. The timedependent parts do not con 12 + .K. Then we may rewrite the right siue of (51) as (52) (eiJ['U(Oe.U(O)I~T + I· i .ta. 382383.i " qt )2 + a.taq )(l + 1)(1 cos wqt) l.C'''qt)2 2(a qa. of which only N terms are independent of the time.u(O)I~T (l/NM) LWql(2(nq) As in the last chapter. from (56) L (1j2Mwq)~(aqewqt + a. Using the exact harmonic oscillator result given in Messiah.e. we separate eQ(t) into two factors. we expand this exponential as all the terms in { order IIN 2 .t + a.u(O»T where u denotes the component of u along K. where (55) Q(t) = iK2{( .t(l whence (58) .te q Then (57) {u(t) .n (0) J K. [(2(nq) + 1) cos Wqt i sin wqtll. so that (54) I(E) 4 r J" . in { 12 there are N 2 terms of 1 i{ .. With one of the polarization directions along K. 20 = (ciKtu(OU(O) 395 .u(O) 12 (1/2NM) L wql{a qa q(l q + q .
the system must forget at long times the value of u(O). [u(t).U) = itMI.u(O) 12)1' = 2Dt. Elementary statistical physics. PROBLEMS 1. whereas in (59) only the N modes q appear. « where . The usual argument leading to the same result is that. in the limit T» 2. which is just the recoil energy R of Eq. Thus = !K2{ (V 2)t 2 e + so that the line is shifted by an energy !K2 MI. For Brownian motion of a free particle we have the wellknown result (I u(t) . which may therefore be set equal to zero. Study the line width and recoil shift of 'Y rays from a free thermalized atom in a gas. Neglecting collisions. The intensity at the peak E = Eo is. pp.tl 2 = RkeT 4rp. we have ({ u(t) .Eo is equal to some wq . using the method of Eqs. (3). Find an approximate relation for the proportion of recoilless emissions for a Debye solid. Ws in exact agreement with our earlier result (33) and (35).u(O) 12)1' = (V 2)1't2. Thus for rapid relaxation the doppler broaden . 153156. where the diffusivity D = keT/pM. (54) and (55). The line shape J(E) off the peak will have a contribution whenever E . for the derivation. from (54). given essentially by the timeindependent terms of Q(t): J(Eo) '" exp {  3N 7' 2R'V }. or . thus there will be a broad continuous background in addition to the sharp central peak of width r. further.tl is the doppler width. ing is suppressed.396 QUANTUM THEORY OF SOLIDS tribute significantly to J(Eo). the factor i in arises because the sum is written over the 3N modes s. Go on to estimate the 3.u(O)] MI[tP. see Kittel. with a finite collision time for the phonons. The result tells us that the line width is r if K2D« r/2. Study the line width of 'Y rays from atoms in a gas when the collision frequency p of the atoms is much greater than the line width r.
Abrikosov. and an impression of their direct relevance to manybody problems. Nozieres. P. particularly those by Beliaev. occasionally. Galitskii. We say that the Green's function is a thermodynamic or thermal Green's function if the system is in a grand canonical ensemble at a nonzero temperature. Dzyaloshinsky. New York. L. A oneparticle Green's function describes the motion of one particle added to a manyparticle system. Gorkov. General references include the following. PrenticeHall. P. an idea of how they are used. Le problCme d N corps. New Jersey. The Green's function method is in principle merely a particular unified formulation of the quantum mechanical problem. E. Our object here is to give the reader some familiarity with the properties of Green's functions. Methods of the quantum theory of fields in statistical physics. Dunod. 1962. 1963. Kadanoff and G. Various reprints in the collection cited as Pines. It does allow us to introduce in a natural way matrix elements connecting states differing in the number of particles. 1963. i 21 Green's functions application to solid state physics There has been a rapid growth in the use of Green's functions in published work in theoretical solid state physics. Benjamin. it has the dis advantage of concealing the physical nature of approximations which may be made in using the method. Englewood Cliffs. and Migdal. as we were led to handle in connection with superfluidity in Chapter 2 and superconductivity in Chapter 8. P. L. Quantum statistical mechanics. 397 . Paris. A twoparticle Green's function describes the motion of two added particles. Baym. A. particularly in connection with manybody problems. as in some spin problems. A.r . It has often the advantage of great directness and flexibility.
x") Ivac). The operator '1' (x't') at another point x' and a later time t' > t measures the probability amplitude that the added particle has moved from x at t to x' at t'. It is convenient to work with the expectation value (4) (I qr(x't')qr+(xt) I). 1 == xt. The quantity in (4) or (5) is essentially a correlation function. k > kp. The notation qr+(xt) for the operator in the Heisenberg . we consider as the state of the system the unperturbed ground state of a fermi gas. Important aspects of the dynamical behavior of an added particle in a state of the system thus are described by. or with the average of this quantity over a grand canonical ensemble: (5) where p is the appropriate statistical operator. We decompose '1'+ into two parts: '1'+ = qrt + qrh.(I')qrt(l) + 'l1(l')qrh(l) + qre(1')qrh(l) + qrt(l')qrt(I). 'There is some motivation for working with a generalization of (4) or (5). We give the proof here. (3) Then p(x')qr+(x)lvac) = o(x . To exhibit one aspect. Then (6) '1'(1')'1'+(1) = W.x')qr+(x)lvac).4) that the operator qr+(x) adds a particle at x to the vacuum state on which it operates. . for t' > t. The operator qr(xt) applied to the state qr+(xt)lvac) will remove the added particle. The particle density operator is (1) p(x') = J d x" qr+(x")o(x' 3 x")qr(x").representa tion tell us that the added particle is at x at time t. (qr(x't')qr+(xt» = Tr pqr(x't')qr+(xt). '1' (x't')qr+ (xt) \). where qrt is defined for electron states. where l' == x't'. and qrh is the hole annihilation operator defined for k < kp. and it is well suited to the description of a quasiparticle. The only term which contributes to the expectation value of (6) in the unperturbed ground state is it e(1')qrt(l).398 QUANTUM 'fHEORY OF SOLIDS We have seen (Problem 5. 3 because qr(x")lvac) = O. thus (2) p(x')qr+(x)lvac) = Jd x" qr+(x")o(x' Jd x" qr+(x")o(x' 3 x")qr(x")qr+(x)lvac} x")o(x . which is the desired result.
but not to the motion of an added hole. . provided t > t'. and (18). The twoparticle Green's function is similarly defined by (12) K(l234) = (T(+(1)+(2}++(3)++(4))). With our factor . because +h(1)+t(l') has a nonvanishing expectation value. (7) '11+(1)'11(1') +t(1)+eCl') + +h(l)+t(l') + +h(1)+e(1') + '1ft (I )+t(1') is adapted to the study of the motion of an added hole. (17).xt} = i{OIT(+(x't'}++(xt»IO}. &(x)&(t).i in the definition of the oneparticle Green's function. where 1 denotes X1t 1. We have seen that we get more information by using the entire time domain than by restricting t' to be >t. ift > t'. etc .GREEN'S FUNCTIONSSOLID STATE PHYSICS.i the Green's function for a freeelectron gas satisfies. using (14). 1 at) a + 2 Go(xt} . For boson fields T is identical with P. The field operators are in the Heisenberg representation. For fermion fields it is more satisfactory to take account· of the equal time anticommutation relation by using the "Vick chrono logical operator T defined to give (9) T(+(x't')++(xt» ={ . Now note that (8) 'II (x't')++ (:xt) if t' if t P(+(x't'}++(xt» = { ++(xt)+(x't') >t > t'. .++(xt)+(x't') +(x't')++(xt) ift' > t. The oneparticle Green's function is defined* over the whole time domain by (10) G(x't'. If 'II and '11+ anticommute we have always that T(+(x't')++(xt» = +(x't')++(xt). However. in the ground state (11) G(x't'. Some workers use i in place of . (i at max 2 which shows that Go is like a Green's function for the SchrMinger equation. where P is the Dyson chronological operator which orders earlier times to the right. 21 399 so that the product '11(1')'11+(1) is adapted to the study of the motion of an added electron...xt) = i{T(+(x't')++(xt))).. CH.
.400 QUANTUM THEORY OF SOLIDS If the system has galilean invariance and also rotational invariance the Green's functions may be written in terms of relative coordinates.+O) =  . 2'1r x (18) Go(x.kF] dk eikz  ~ [2'1rO(X) . thus (10) becomes (13) \ G(xt) = i(T('lt(xt)'lt+(OO))). _ i [2d(X) _ 2 sin kpx]."'tt. (14) L k L k where Wk = k j2m. +0) i for t > 0 and zero otherwise. for t > O. We observe that G1)(x.\ As a trivial example. We note here merely that for this problem (17) Go(x. Green's function is 2 Then for the vacuum state the oneparticle (15) Gv(xt) = i(vacl'lt(xt)'lt+(OO)!vac) = i(vac! T i k (L ckctei"'kteikz) !vac) kk' L eikze.f~~dk eikz ] fkF k.O) i 2'1r dk eikx i 8m kpx. dk exp [i (kX . The natural expansion for 'It(xt) is in terms of the free particle eigenfunctions: 'It(xt) = ck(t)e ilcz = Ckei(Olteikz. On replacing the summation by an integral. 'lrX . consider a onedimensional system of non interacting fermions in the true vacuum state !vac).'Ir [1: + f_". Gv(xt) = i (16) f"'". The evaluation of G(xt) for the ground state \0) of a noninteracting fermi gas in one dimension is the subject of Problem 1.2~ k 2t)] e. Note that this is a solution of the timedependent Schrod inger equation.i31r / 4 (2'1rmj t) l11eimz2/2t. L k = io(x).
i(OlctckIO)e''''k'.+O) . We define (19) G(kt) = f d 3x eik·XO(xt). (21) G(kw) = f dt ei""G(kt). 3 Further.O) = i. 211" NONINTERACTING FERMION GAS The oneparticle Green's function Go(kt) in the ground state of a noninteracting fermion gas is (23) Go{kt) = i(O! T (~ ck'citei"'k't f d x e'i(k'k). with the inverse (22) G(kt) = ~ fdw ei""G(kw). here 1/l'k is the lifetime for the decay of a quasiparticle excitation into other excitations_ . .r GREEN'S FUNCTIONSSOLID STATE PHYSICS.Go(k.nk). CH. (24) Go(kt) = { ~i~i"'kt(1 w''''ktnk. 21 401 Observe the difference between (15) and these results. over a limited interval of time.X) 10) 3 = { i(OlckCtIO)~i"'k'. (15) was for the vacuum_ FOURIER TRANSFORMS The theory makes abundant use of the transforms G(kt) and G(kw). 0 is the population of the state k in the ground state. < 0. For a quasiparticle excitation in a real (interacting) fermion gas we expect the time dependence of G(kt) for t > 0 to be of the form ei"'ktefk t . thus Go(k. the inverse transformation is (20) G(xt) = (2:)3 f d k eikXO{kt). t > OJ t < O. t > OJ t If nk = 1.
w  .. . For t < 0 the contour in (28) must be completed by a semicircle in the upper halfplane: (31) (f' 'J j . We see that (28) further. + 't8k u n positive for k negative for > kF . t < 0.wt (f' Wk . dw eiwto(w GoCkt) = Wk) = £1Te.. k < k F• s1 We show that this expression for Go(kw) is consistent with the result (24) for Go(kt).402 We now establish that QUANTUM THEORY OF SOLIDS GJ ill (25) where 8k 8k GoCkw) = lim 81C"0 W  1. (~ I .. Go(kt) = . . Consider the situation for k > k F ."'kt ."'kt .' l t1Te"'k t . k = 0. > kF.ie(26) t < O. Wk t > 0. for this region (24) tells us that wkt t > 0. f Now from (25) (27) Sl Go(kt) 1 JOO . . '" dw e. . .. dwewtGo(kw) (: = 1 21T j'" _00 dwe. :E p £1T f. thus (32) Go(kt) . ( and we have the result (30) iei"'k /. wI dw _e__ wWk i1Te.£1TO(W Wk)' _ J I b written for k > le F • For t > 0 a contour integral may be completed by an infinite semicircle in the lower halfplane. WI!. (29) (P j _."'1 (. k > kF. t < 0. = 21T _ . ( t > 0.
Nl :10 E~+l) ~o E~) ::::: w. We may arrange (36) as (37) G(kt) = l li = L (O!ckeiHtln)(nlcitIO)eiEoNt. N.. Let the excited states of the systems of (N + 1) or ( N . N i(Olcite. Here H is the exact hamiltonian.+l . > 0. i t > 0. CH. L l(nlckI0)12ei(EnNlEoNlt. < k F• INTERACTING FERMION GAS We exhibit the form of the Green's function in the exact ground state 10) of a fermion gas with interactions: (34) G(kt) = i(0111(Ck(t)C~(0»10) = { i(Ole. . i~ I(nl ctlO) I'. Let EoN denote the exact ground state energy of the N particle system. i(OI cite. n The exponents in (37) may be rearranged: (38) R.Nl) + (}.HtckIO)e. . < O._E.l~o + It.E o' t.+l l1Nl  EN (EN1 ~o = ~n + (E~+l E.1) particles be denoted by the index n. < O.. { .E~ 1'!i n (E. i(OlckeiHtcitIO)eiEoNt.I. Then (35) may be rewritten as (36) G(kt) For t > 0 the states n are excited states of a system of (N + 1) particles.GREEX'S FUNCTIONSSOLID STATE PHYSICS. t t > 0. iWk! le t .Htcke..N". i ~ ~OlciteiHtln)(nlckIO)eiEoNt.iHtcke~fltcitIO).HtIO). t t > 0. J.1) particles. for t < 0 the states n refer to excited states of a system of (N . t < O.HE. 21 403 For k < k F we change the sign of Sk in (25) j this changes the sign in front of the delta function in (27) aud we have (33) (lo(kt) 0. Then (35) G(kt) = { .. pN) == "' Wn where (39) Wn :::: 1 _ E~±l . t < O. t > 0. < OJ k lc t < kF ...
Then (37) becomes G(kt) = (41) SPECTRAL DENSITY AND THE LEHMANN REPRESENTATION l i 2: i(n!citi O)i e2 n i (w.I') t ' We introduced the spectral density functions defined by (42) (43) p+(kw) 2: \(nicitI0)i 0(w " p(kw) == 2: \(nick\0)\2 0(w == 2 n wn ). + Wk).404 QUANTUM THEORY OF SOLIDS is the excitation energy referred to the ground state of the system of (N ± 1) particles. < 0. < o. we do not need to add superscripts to Wn or J1.nk)o(w . i fo" dw p(kw)ei(wl'lI.... + J1. i t > OJ t < O. > 0. in agreement with (24)...+I')t J t t > 0. to distinguish N ± 1 from N. For noninteracting fermions the spectral densities reduce to single delta functions: (45) (46) l fo" dwp+(kw)ei(w+l'lt. and (40) J1.).. EN+1 aN = 0  EN "'" EN 0 = "0  EN1 0 is the chemical potential. wn ).J1. Then (44) reduces to (47) Go(kt) I ~i~i"kt(I  nk).  _ aE . If the system is large (N)> 1). p+(kw) = (1 . (44) G(kt) = The integral over dw need include only positive w because Wn is always positive. 0 is the groundstate occupancy and Wk = k 2/2m. 1e'''kt nk. .Wk p(kw) = nk o(w . t t where nk 1. We also encounter the notation A(kw) With our notation (41) becomes == p+(kw)j B(kw) == p(kw).. i 2: \(nlckI 0 )12eH n w.
We see from their definitions (42) and (43) that p+ and p.I ) +w 1 I £s Combining (50) and DISPERSION RELATIONS with (49).J... dt ei(wi.405 We now exhibit an important result known as the Lehmann repre sentation: (48) G(kw) = lim .are real. 21 10 r dW' [ p+(kw').J..)I = _ J.. w < J.f o '" .w'!'+i8)t 10 (w ...)t 10'" dW' p(kwl)ei(W'!')t]. (w .I) .I.w). we can separate the real and imaginary parts of G(kw). Thus (53) g {G(kw) I 11' 10" dW' [p+(kW')~(W J.w 1I'P (k..Wi)  p(kW')~(W . p(kw') (w .I. CH. J.I) + w' .is J..dleiwtG(kt) 8>+0 lim [i Jo r" dt ei (w+i8)t Jo r'" dW' p+(kw')ei(w'+!<)t + i J~ . Using (52) .I + Wi)] = \:P+(k. The separation occurs because the integral is only over positive values .. We verify this result by taking the transform of (44): (49) G(kw) = J_oo".J. I1m . we obtain the result (48)..J.. dt ei(w+". 1 The first integral involves (50) .'p. +0 GREEN'S FUNCTIONSSOLID STATE PHYSICS. e + 211'~ () e in the Lehmann representation.J.I . 1 e ± zs = (p . +0 ..w + zs + .I) w' + is' _ .i {'" dt ei(". w> J.I).I . the second integral involves ([)1) 2 .
the groundstate energy is determined by the oneparticle Green's function. . (w . (54) <R(G(kw) J  CP o dw . thus (56) <R(G(kw)} ~ 7r p. .f~.)} + dIG(k.406 QUANTUM THEORY OF SOLIDS of w'.1 7r~ dw G(kw). c where c is a contour consisting of the real axis and a semicircle at infinity in the upper halfplane..1" . w We make the substitutions w" = w' + p.) . (fig) nk 21. Proof: We note from (34) that the expectation value nit of the occu pancy of the state k is given by (58) nk = (OlctckIO) iG(k. cit II 1 = ~ V(kl. ) + w' .O). .k 4 )ct1 2 Ck Ck • LJ 34 . ) wI p(kw' ) ]. using (22). with Ho = (li 1) 2: wkctCk. The result is the analog of the Kramers Kronig relation. p. + . ll" .w' in the +~ 7r rJI' ao (_dw")d(G(kw")I.) fao dwII d (G(kw") I " I' ww WI»)]. with (53). . (55) <R(G(kw)} = Jo r" dw' [_ fI(G(k. thus 9 (Gl changes sign at w p. . because t = 0. We now calculate the real part of G(kw) and express the result in terms of the imaginary part.w" (57) I <R(G(kw) I = . Further.w' + p.are nonnegative. We write H = Ho + HI.p. and w" appropriate parts of the integrand.(wp. We note from their definitions that p+.w (w . GROUNDSTATE ENERGY If the system has only twoparticle interactions..p.p. Using (52). w . Cp 7r [p+(kw') (wp.J dw" if ~~~': J.
(Olct[H.y (65) Eo = (OIHo may be written = + IllIO) i L (Wk 1£ We note now that. 2: (Olct[ll.D. This result is exact. {J l/k81'. The groundstate energ.2: 1£ 1 c dw (W1£ + w)G(kw).II 0 1£ and (63) so that (64) 2: ct[H 1. THERMAL AVERAGES The Green's function method has directed attention to several neat tricks in taking ensemble averages. 21 407 Now we see readily that (62) 2>t[ II o.cklIO) 1£ (OIHo + 2[[110). and a+..c1£lIO».l1a+a = 1. We calculate the thermal average occupancy (69) Tr eflfia+a n (a+a) = T refliI ' where n relation (70) II . dw p(kw)(w and. consider the following exact and concise derivation of the boson and fermion distribution laws. (65) may be written as (68) Eo = 1 4 1T2 .) (kt)]  [dO tit 1=0 i 21T 1 c dw wG(kw).p. As a simple example.Ckll o) = .ckl = . CH.N.Ckl 1£ 2Ih. (66) (Olct[H. from (42). from (44) and {22). . a satisfy the commutation 00+ . Q.p.GREEN'S FUNCTIONSSOLID S'l'ATE PHYSICS.E. (67) 1"' o dw p(kw)(w .
(71) N ow by the invariance Tr efJlia+a = Tr aefJlia+ = Tr efJliae{Jlia+eflli . L nm .. or (75) 1 n = efJ(wl'l . < O...Em. so that (73) Tr e fJ Ii + fJ(wl'l Tr efJli aa+ a a = e = e.fJ (wl'l Tr e.fJli (1 + 77a + a). we obtain G(kt) = i efJ (O+I'N".t. But on any eigenstate 4> of the system of noninteracting particles (72) efJli a+efJli 4> = efJ (wl' l a+4>. Thus (74) n = efJ (wl'l(1 + 77n).nt.. nm t t > 0. of the trace under cyclic permutations. with Wnm (79) G(kt) En . then our previous result (37) may be written.Enll(mlckln)12eiw.77 which is the standard result.ll(nlckl m)12eiw n. In the same way it is a trivial matter to show that the average over a canonical ensemble of two arbitrary operators A and B satisfies the relation (76) (A(t)B(O) = (B(O)A(t + i(3).408 QUANTUM THEORY OF SOLIDS with 77 = 1 for bosons and 1 for fermions. i L efJ(O+I'NnEnll(nlcklm)12ewnmt. with the introduction of the statistical operator p = efJ (O+I'NHl (78) as. We first note that (77) l(mjctln)12 = l(nlcklm)12. with n the grand potential. It is instructive to rederive the dispersion relation (57) now with averages taken over a grand canonical ensemble.E. nm Now in the result for t < 0 we interchange the indices nand m. = { i L efJ(O+I'N. (80) t < O.
. = 1I"o(a) = (83) ..00 to 0 and from 0 to 00. this is equal. +0 lim Thus (84) f o dx et(aisl..n»..l)]...GREEN'S FUNCTIONSSOLID STATE PHYSICS.ft l ) + (S> Wmn W (1 + cfJ(II"'". dw' coth jcf1(w' t p.e/l(II"'". This agrees in limit T 0 with (57). n~ = coth if1(wmn  p.) g {~(kw')} .t... and form (88) . with separate regions of integration from . . 21 409 t Because N n = N m (81) G(kt) = i nm  1... We employ the identities (82) lim 8 .) g ~~(~w~ I . Thus we have the dispersion relation (90) m{G(kw)} = : f"'". + e/l(I'"'''''» We may separate the real and imaginary parts: (85) mIG(kw)} =  L cfJ(!!+I'N"E. + i ~.p.E"li(n!ckim>i 2. 1I"o(a) _ i '" a G(kw)  L cll (!!+IIN... Note now that (87) 1+ ~~II"' .. dw' coth if1(w' . +0 h ('" dx c'(a+i 8 l. ClI.. We now take the time fourier transform..Enl(1 + e/l(IIw" ')i(ni ckim)i 2 n mil 1 Wmn W . to (89) (S> L C8(1l+IIN.+lIli(nickim)i2cw""... nm [ i1l"O(W wmn)(l  e/l(II"... a (S> < O.).. f'"'". this may be written as L e8(1l+IINnE"le/l("'". by (86)..li(nickim)i2 nm (S> Wmn W (1 (86) g{G(kw)} 11" L e/l(!!+IINftEftli(nickim)i2o(w nm wmn )(1 .
Now (94) a~' (T('li(x't')'li+(xt»)  (T (a~' 'li(X't')'li+(xt»)) oCt' .xt). (. where we have used the may rewrite (93) as (95) time commutation relations.5.)2)G(X't'.i \T i i / (a at' f (p')2) 'li(x't')'li+(xt)/ \ 2m d 3 y V(y . From (91) we form (93) .x't'. It is revealing to study the meaning of the HartreeFock approxi mation in terms of Green's functions.yt~.yt~.43) we have the exact equations of motion (91) (02) i!.i f d y V(y 3 x')K(yt'.x) 'li+ (yt)'li (yt)'li (xt) . Thus we (i~.xt).x)'li+ (xt)'li+ (yt)'li(yt).42).~ at . In the Hartree approximation we solve (95) under the assumptIOn that the two added particles in the twoparticle Green's function propagate through the system entirely independently of each other.. with the twoparticle Green's function K defined by (12).x) .x')(T('li+(yt')'li(yt')'li(x't')'li+(xt» = f d~y V(y x')K(yt'. at  (. This is an exact equation which relates the singleparticle Green's function to the twoparticle Green's function.t)o(x' .xt) ~m = oCt' .x).x't'.38).i!. Here t~ is infinitesimally larger than t'.. and (5. ~ 2m 'li+(xt) .) (i ~ at 2m 'li(xt) = f d 3 y V(y . so that the basic assumption of the Hartree approximation is .t)o(x' .) ( ..410 EQUATION OF MOTION QUA NTUM TH1WRY OF SOLIDS From (5. and is used to maintain the order of the factors.
repeated indices ~re to be summed. for fermions. The relative signs on the righthand side are fixed by the property [(1234) K(2134) for fermions.G(14)G(23).t(xt)'lrt(yt)o(x . reprinted in Pinesl. Thus in the HartreeFock approxi mation the assumption is made that.i at  2m p2) 'lra(x) + V'lrt(x)'lrg(x)'lra(x) = + l''lr.31) may be written as " s e (U8) H = f £l3 X 'lr. 2m 'lr. where V is positive for an attractive interaction. however.t(x) p2) . Q. we cannot in principle dis tinguish processes in which the particle added at 4 appears at 2 from processes in which it appears at 1. P. SUPERCONDUCTIVITY It is instructive to develop the BCS theory of superconductivity using the Green's function approach as developed by L.t(xt) :~ 'lr a(xt) tV f d 3x d~y 'lr. The effective hamiltonian (8. e Here a. 21 411 (96) K(1234) ~ G(13)G(24). (3 are spin indicesit is important'to display them explicitly. The oneparticle Green's function is defined as (99) Gag(xt) i(T('lr a (xt)'lrt (00))).SOLIIJ s'rATE PHYSICS. We adopt. Gorkov [Soviet PhysicsJETP 34. ). (97) K(1234) ""' G(13)G(24) .GREEN'S FUNC'l'IONS. 's The equations of motion are obtained in the familiar way: (100) (101) . 505 (1958). The treat ment is closely similar to the equationofmotion method given in Chapter 8. CH. the convention that V is zero except in an energy shell of thickness 2w D.n on r.y) 'lrg(yt) '1' a(xt). Note that the potential term in (98) automatically vanishes for parallel spins (a = (3).t(x)'lrt(x)'lrg(x) 0. ). But this does not take into account the identity of the particles. We observe that an interaction independent of k may be represented by a delta function potential. centered about the fermi surface. provided the spin indices 81 = 83 and S2 = 84. a ( i at a ( .
(XI)'lr/l(X2) )IN (: We may write the factors in (104) in the form (105) (106) (NIT('lr. This is a very natural addition to (103).(NIO(t)IN + 2).. . so is IN + 2}.:~) in Ga(j(x. hi (l o (l But the ground state of the superconducting system is characterized by bound pairs of electrons..t/l. Here p..iVF".x') .(T ('lr a(Xl)'lr:. On operating from the left with T nt 'lrt(x') and forming the thermal average.(x)'lra(x)'lrt(x ' ») = o(x x')Oa(j..(x)'lr.412 We have used the notation x QUANTUM THEORY OF SOLIDS OJ == xt. so that we should add to the righthand side of (103) the term " (J s( w + 2}{N + 21 T('lr:. = &E/iJN...l'tF"/l(x  x'). We have assumed galilean invariance.(xa» )(T ('lr /l(X2)>¥t(X4»).. 2i + 2IT('lr.(Xa») .y( +O)F~(x  I x') = o(x .(Xa)'lrt(X4») (T('lra(Xl)'lrt (X4» )(1'('lr /l(X2)'lr:. The number of such pairs is a variable of the problem. v using the definition p.. If IN) is in the ground state.:~)Ga(j(x .H]IN + 2)  b t EN)(NIO(t)IN (E N+2 + 2) ( .x') . The following equation follows directly from the equation of motion (102) and the definitions of F and G: (108) (i :t . for an arbitrary operator O(t)..(x)'lr/l(x'nIN (N + 2) = e.(x)'lrt(x'»IN) v ( = e2il't~(x x'). The states IN). 2p. IN + 2) are corresponding states for Nand N + 2 particles..(Xa)'lrt(X4) )IN).x')o(. (107) i :t (NIO(OIN + 2) (NI[O. (1 Now in the HartreeFock approximation we made the following assumption for the twoparticle Green's function: (103) (T('lr a(XI)'lr(j(X2)'lr:.iV(T('lr:. (104) T('lr . we have (102) (i :t . is the chemical poten tial and enters the problem because.
lU~). = J( ~ 6) = JA. we obtain the equation (117) i.(+O). F"/J(x .O). here (110) F a"( +0) == lim XtX' F. P = AF(x . ) P+(x .x') = AF+(x x'). (F+(x .x) oalJ(X .x') = o(x .x') = e2il't('It. 1+/'+0 On inserting (109) into . where 1 is the unit matrix.(x)'It"(x».x'... we have (116) (i at a_ ( a 2m p2) G(x  x') + iVF( +O)F+(x  x') = o(x . thus with (115) I G"/J(x . by (104) with the neglect of the ordinary HartreeFock terms which may be included in p" (109) (T('It~(x)'It"(x)'It a(X) 'Itt (x') » ::::: .('It a(x)'It"()(T('It~(x)'ltt(x'») Fa"( +O)F~a(x .O»* = F(x  x'.x'). 21 413 This follows because the potential term in (102) is.x'. We may write (108) in matrix form: (114) (i iat  2m p2) G(x  x') .x'.iVP( +O)P+(x ."(x .:e 1'. We record that A2 = 1.x'). from (106).x') = o."(+O) = F"(. By operating on (101) from the right with 'Itt..GREEN'S FUNCTIONSSOLID STATE PHYSICS.O»* so that we may write (113) /H(x . we that F..x')l ' but it is readily verified that the offdiagonal components of Gare zero. .x'). where J is a c number.at 2m p2 + 2p. because of We may write the matrix (111) JI\+O) pairing a . (112) (F~(x .. CR. further.X') .O).
(126) 0 p+( +0) = vp+( +3 ) f d 3k 1 2(211') Ak = l Vp+( +0) 1 (Ck + a p or (127) 1 =jV2: k 1 .: : ) G(kw) + iVP( +O)P+(kw) = 1.t . Ak w as L m where we have replaced Ak by lim (Ak . Ck = (k2j2m) . then wh of' wh 1m: + Ck P+(kw) = i V~+(~O~. te m H ap to or. To investigate this we form (123) P+(x) = _1_ fd 3k dwei(k'''wt)P+(kw) (211')4 .2J. P+(Ot) iVP+( +0) fd 3k dw w. (12 We analyze (116) and (118) in fourier components G(kw) andP+(kw): (119) (120) (w .is) to represent the effect of collisions.78).is 1) = 2: k ilr .L. (1 w' 8++0 _0) Ak + is  w' + Ak . (125) st+O 1 f'" · r2Ak 1 1m Thus dwe·". . The solution (121) for P+(kw) must be consistent with the value of p+( +0). thE PE which is the quasiparticle energy of (8.53). ( w + : : .L.L) P+(kw) iVP+( +O)G(kw) = O. for t 7 +0. A2 and (120) have the solutions (121) with (122) Ak 2 = ck 2 G(kw) = w' V 2p( +O)p+( +0).414 QUANTUM THEORY OF SOLIDS GRI which reduces to (118) .L) P+(x 2m x') + iVP+(+O)G(x  x') = o. = wh (12 (13 Write w' w .H' (I This is just the fundamental BCS equation.J. W k + A 2. as in (8. (i at a _ p2 + 2J.: ':"t _ Ak ' (211')4 2 (1.J. for x (124) 0. The integral over dw is.
2 . The Vet) in (13I) are in the illteraction representation. where T is the Wick timeordering operator. .~k2)F+(kw) which leads to the second part of of the form we may B(k)o(W'2 .Z8 .. We make the adiabatic hypothesis.)}. + 'I\k . 00). The unitary operator U(t. so that 8<1>0 can differ from <1>0 only by a phase factor. (129) 2 Uk w . this part was determined by Gorkov by using the dispersion relation. as (132) The 8 matrix is defined 8 == U(oo. CH. (<1>0181<1>0) .i (<1>01 T(clr:(t)cit(0)8) 1<1>0>. Let <1>0 denote the ground state of H 0. .93) and (8.94). as in (8. 21 415 We may rewrite G(kw) from (121) as (128) where.~1r:2).56) may be written as (131) U(t. • V(t. if V is bilinear in the fermion opera tors '11. 1: = 1: (1 + ~:) 2 Vk (1 . '11+. PERTURBATION EXPANSION FOR GREEN'S FUNCTIONS At this point the theory becomes intricate except for students with a technical knowledge of quantum field theory. and choose II 0 so that the oneparticle Green's function appropriate to H 0 can be found explicitly. denoted by 10) in Chapter 1. I' . dt" T{V(tl)V(t2) . We write 11 = H 0 + V. then (1. This is equivalent to adding an arbitrary imaginary part to G(kw).t') = ( I)" 11 L = " n! t' . We shall only sum marize the central results for fermion systems. it dh . where B(k) is arbitrary. .GREEN'S FUNCTIONSSOLID STATE PHYSICS.t') was defined in Chapter 1. The first result (which we do not derive here) is that the exact one particle Green's function is given by G(kt) = .~:} to p+ (kw) a term We observe in the equation (130) (w.
bsence of a magnetic field may be written as.'" (cf>O!T(ClI. cited at the beginning of this chapter. A full discussion is given in the book by Abrikosov et al. The result may be expressed in terms of the fresnel integrals. Find the expressions for G(xt} for a fermi gas in one dimension for the ground state with all oneelectron states filled up to kF and zero for k > k F• Consider both t > 0 and t < O. Show that the particle current density in the a. xt}.. 1 bet' traI an the gen ene ove cou we lb (1) Note that the particle density is (136) n(xt) = . f" A: The evaluation of the nth order term in the perturbation expansion of G is usually accomplished with the help of Wick's theorem which gives a systematic reduction procedure to products of expectation values involving one c and one c+. to combine (131) and (133): (134) G(kt) It is useful .gradz)G(x't'j xt).416 QUANTUM THEORY OF SOLIDS where all quantities are in the interaction representation. V(tn»!cf>o}.. .. (135) j(xt} ! m fx+x' 1>1'+0 lim (grad z' . dt n (cf>oISIcf>o) n n .f'" . on taking account of the two spin orientations. PEl PROBLEMS 1. 2. L=. . '" ( l)n 'l dtl .. x+r 1>1'+0 Th Ik2 pr oc No (2) wh th th (3) . ..(t)ct(O)V(tl) .i lim '2I}(x't'.
on summing the secondorder energy Eg> over all pairs of electrons ij in the fermi sea. The sum is.4) between two electrons diverged at low values of the momentum transfer q. We first show that the diver gence is weakened.2k 1 • q = k 12 + q2 + 2qkl~1. but not removed. for simplicity we shall omit further reference to the spin.~because we want to examine the convergence here. We are concerned with the behavior of the integrand for small q. We calculate here only the direct coulomb terms for electron pairs of antiparallel spin. k2 < kp.<kF ka. In this appendix we examine the situation in some detail and discuss the Brueckner technique for summing the perturbation theory series in the high density limit. Ikl .l«>kF (121 VI34)(341 v112) k2 k 42 I k2 2 .Appendix PERTURBATION THEORY AND THE ELECTRON GAS In Chapter 6 we saw that the secondorder coulomb energy (6.ql > k p . 417 . where the limits imply that ~l. ~2 are positive. kl = qkl~l. Ik2 + ql > k p • In applying perturbation theory to a manybody problem it is clear from the secondquantized formulation that occupied states are not to be counted among the intermediate states. Now let (2) q . The limits on the integrals in (1) are kl. q • k2 = qk2~2.k2 3 d q 3 3 m (~)2 C2~)3y f f f d k1 d k2 3 1 x 2q4[q2 + q. (k2  k 1)] . with a factor t because of double counting. Now (3) k p2 < k 12 q2 . E2 m ~ k ~ k k ••k. We sum only over unoccupied virtual states.
(8) Let 1 = 1 . to express the limits on the integrations over kl and k 2_ For a part of (1) evaluated at small q. it becomes possible to sum an important class of contributions to obtain a nondivergent result.2) + 0 1 kFq~1 dk 1 lkl' kPq~..418 QUANTUM THEORY OF SOLIDS APP so that for small q (4) 2qk 1h > (k p . which diverges logarithmically_ Thus the perturbation calculation breaks down even in second order. ~2 are positive. recalling that h.k1)(k p +k 1 ) "'" 2k p (k p . 1  dk2 .qkph qkp~2 as i (2~)2 kp aq all 11 dh 0 III ( db h~2 h + ~2 prir k2' The integrals over h. h are definite. b Eo . (1OJ dk 1 = (2~)2 10o d~l 101 d~2 0 i'" d~2 kpq~l ~ 4. valid for small q. con per1 (9) and similarly for h We use these relations. 1959. A. Wiley. We write H = Ho + V. Brueckner in The manybody problem. BRUECKNER METHOD 1 'I (11. k22 dk2 + qklh + qk 2!.. wh{ (fro stat or (5) kp V > kl > k p  q~l.c . whc of t firsi (12: We need an abridged notation for the terms in RayleighSchrOdinger perturbation expansion. so that the integral in (1) over d 3 q for small q involves f ql dq.Po . We now show that if the perturbation calculation is carried out to infinite order.k p 4 (2~)2 q 11 11 dh 0 0 lkF l kP kPq~. New York. (6) f f:l d 3k1 1 wh€ sec( 1 d k2 .k 1 ). where V is the coulomb interaction: (7) V = t L Vim 1m over all pairs of electrons treated as spinless. des' vah .Ho Thi F are (12: 1 For full details see the review by K.
We consider. 12 34 This term can couple more than two electrons.k 2• In the most genera.APPENDiX 419 where Po is the projection operator arranged as 1 . we drop the electron indices from V. that the state kl' = k 1 . in states kl' k 2 • The firstorder perturbation energy is (9) e(1) = (V) = (12IVd12) = (12IVI12). secondorder perturbation energy is (10) S(2) = (V ~ V) 1'2' 111211 L 1/12") /1"2/1 11 \ E12 '2') 1 E12 1  P1211'21\ Ho / 12) 1'2' L' E l'2' VI12). The first term on the righthand side may be written out as (12) /V!V 1 V\ \ b b / = L' (12IVI56) E 34 56 1 E 56 (56Ivj34) E ' 12  1 E (34IvI12). Here we have used primes to denote intermediate states in order to save numbers for use later with other electrons. as in (6.k1' or by k2' . First we consider the form of (12) when only two electrons k1. as denoted here by the subscript zero. where the second term on the righthand side represents the effect of the normalization correction to the firstorder wavefunction.\ V b2 V / (V). for convenience.Po to eliminate (from the summation over intermediate states) terms in the original state. The thirdorder energy correction is given in standard texts: (11) S(3) \ /11\ /1\ V b V b V / . an unperturbed system containing only two electrons. k2' = k2 is to be omitted from the summation. as we shall see. There are three matrix elements in each contribution to (12). The prime on the summation indicates. For the coulomb interaction the value of each matrix element is described completely by the momentum transfer q. The where. k2 are present.l .1). In (1'2'1 V112) the value of q is given by kl . to illustrate the notation. as before.
2 has the structure (15) 1'3') T.kl") dr: tra wo + (k I " k 1) = q + q' + q" = 0 in order to carry \12) back to (121 after the three scattering events contained in (121V 1"2")(1"2"1 vi 1'2')(1'2'1 vi 12). 1. In other words.1 (3'2IV23 132') T. Consider the terms with the three electrons 1. we must have (13) (ki . other types of graphs are possible. 1. Note that the solid lines on the graph are not shown as bent in the collision regionno attempt is made to simulate the scattering angles.420 1 ~ QUANTUM THEORY OF SOLIDS AI IH I l' J 1 Iq I I I I q" I I I Iq' I I I 2 2" 2' 2 FIG. labeled with the momentum transfer in the collision. . as in Fig. There are a number of ways of drawing graphs to illustrate perturbation theory: the diagrams used in this appendix are different from the Goldstone diagrams used in Chapter 6. Graph for It thirdorder energy correction involving two electrons. 2.l 1 '" (l'2'IV 12 II2). q'. The interactions are represented by dashes. 3. 2 involves three electrons in initial states 1. For the present we show all electrons as solid lines directed on the graph from right to left with interactions following the order of the terms in (12) or similar perturbation expansions. but we must have zero total momentum transfer between the initial state ki and the final state k i . \ V ~ V ~ V) is now more complicated. We represent the structure of this contribution to the thirdorder energy correction by a diagram. The graph in Fig.kd (kIf . q". We label the intermediate states as 1'. 3. 1 involves co co: by gives the three twoparticle interactions. 2. When more than two electrons are present. 2'. The term in the energy corresponding to the graph of Fig. FI Tb term of (12) for two electrons the three matrix elements will each involve a different momentum transfer. say q. 3. two electrons in the initial states 1 and 2. then (14) TI tw A di: pa In th In tel as fOJ V 12 + V13 + V23 The development 01 The graph of Fig.1 1 T.
3. except at the initial and final vertices. terms such as 1'2') L:J .. For a general interaction this term does contribute.12  E 1'2' (32'1 V 23132') 1. In the coulomb interaction there is no term for q 0. This particular diagram is a special case of a linked graph known as a ring graph. l' I I q' Ii is :S I 2' 2' e h 0( 2 I I I I q=O I 1" Iq' I 2 3 . the scattering of 2' by 3 is described as forward scattering by an unexcited particle. 3. drawn in a slightly different way to emphasize the ring structure. In third order we have.e ~ .e n It This term is linked in the sense that the diagram may not be split into two parts with no interaction lines between the parts. The momentum transfer at all vertiees must be equal in a ring graph. besides the terms corresponding to Figs. IS n as represented in Fig. therefore (32'1 V 23132') = 0. This particular graph is called a ring graph. . it is equivalent to the graph (b). one new particle enters and one old particle leaves at each vertex.S ir If IS d is . (a) Graph for a thirdorder energy correction involving three electrons. .'5) APPENDIxj 421 l' I 1 2' 'i" 3 0( Iq I ! nnni Iq 3' I 2 i Iq 2 3 I ( 2 (b) (a) h e LI FIG. 3' FIG. and this process does not contribute to the energy. 2. if 3 lies within the fermi sea. E 1'2' Vuj12). In a ring graph the momentum changes are equal at all vertices..e . otherwise all the electrons would not be carried back to their initial states. 1 and 2. Forward scattering by an unexcited particle. A ring graph is a graph in which.. The structure of perturbation theory requires that all terms in the energy be constructed to get particles back to their initial states..
But. and this is the most important feature. of (1 11\ = (12IV 12 !I'2') IT.4 is not connected to the part 1. but the contribution (17) vanishes also for a more general reason: the term d o 12 n pi pi to . We may thus restrict our calculation to linked graphs.422 QUANTUM THEORY OF SOLIDS A In third order there are terms of the structure (17) iJ c (1'2'! 12).J (34!V 34 !34) '" 1 '" involving four electrons. 6. but approximate. as illustrated by Fig. By carrying out the summation we obtain the correlation energy in the highdensity limit.:6.(V b\ V) (V) on the righthand side of the expression (11) for the . simplification at high densities (ra < 1) in the electron gas problem. n V12 !I'2') '" 1 T.\V b2 VI (V) thirdorder energy exactly cancels the unlinked term (17).2. For the coulomb interaction (341 V 34134) vanishes. An unlinked graph: the part 3. 4. The graph is called an unlinked graph because it can be separated into two noninteracting parts. they are also divergent in each order at low q. . Goldstone has shown in general that the cancellation of unlinked graphs always occurs exactly in every order. the proof is given in Chapter 1. We note that the kinetic (fermi) energy is dom \ ti tw (2 wh 10 en (21 whO l' ~ 2 ( 2 ______________~__ 3 ______________~______________ 4 mi hav infi indi SU FIG. There is a further. 4. as we saw explicitly for the secondorder energy correction. which corresponds to a ring graph. the ring graphs may be summed to all orders to give a convergent sum even at low q. At high densities ring graphs are dominant. for we may write (18) r.' 1 " ' ) 2 (1'2'!V 12 !12>(34!V 34 !23).
both for a system of N electrons in volume Q. (6). (k2 .. In Fig.k 1) where kl < k p and [k l + ql > k p . Thus (20) E3 = 4m 2(~e2y C2~)3r f 3 f 3l f 32f 3 d q dk dk d ka' :6 1 1 • q·7""2 / +q'(kk3 1 + q. Thus the ratio of the number of terms for Fig. 106.3'>kF (k 1 2 + k3 2  (131 VllI3'L~3'2IXI32')(1'2'IYI12)_ k1'2 . 364 (1957)1 have deter mined the form of the nthorder ring diagram contribution B n . but q and q' are independent and may be picked in Q2 ways. The reason for the dominance of the ring graphs at high densities may be understood from an example. 1 there are N 2 ways of picking the incident particles.2)(k l 2 + k22  k 1. Rev. in the small q limit the integral over q ends up as \21) E:l~ f ~ f which diverges quadratically for small q.2  1. In Fig. and they shown that the ring diagram contributions can be summed to ULll111~e order. The thirdorder ring graph contribution to the correlation energy of the fermi gas E3 = 2: 2: 2m 2 l.2. 2 is Q/ N a: .2) times the number of possible sequences or equivalent graphs.APPENDIX 423 inant as rs jo 0. because the kinetic energy increases faster than the coulomb energy as the density is increased. but we shall indicate schematically how an infinite series of divergent terms can be summed to give a convergent result. We shall not repeat their calculation here. 2 the incident particles can be chosen in N 3 ways and q in a number of ways proportional to Q.2'. :Fig.k 3. which is two in third order. Let us compare the density dependence of all thirdorder terms of the structure of Fig.2. and similarly for k2 and k a• Fol lowing the argument of Eq. . so that the ring graphs dominate as rs70.3<kF l'. 1 to those for Fig. 1 with those of the ring structure. GellMann and Brueckner [Phys. 2.
q q Ts () + T. A detailed analysis of all other integrals..) . + ~.)" . because no other graph gives the same factor at every vertex.. so that the ring graphs are dominant as T. direct contribution to the correlation energy Ee would be (23) Then the Ee = n=2 i En = {'" dq 1 1'" o 10 .424 QUANTUM THEORY OF SOLIDS En Suppose that (22) were given by the divergent integral En (_l) nT sn2 n f. ~ O.. q T. recall that lim xm log x = 0. There are also exchange contributions to the correlation energy. for m > O. ~ O. The reason is simple: a ring graph has a contribution 1/q2 from every vertex V.0 is composed of two parts. We have shown that the ring graphs may be summed. where (24) n=2 . (T. At small q this divergence is stronger than that from any other graph of the same order. f dq q is convergent at the lower limit.2 The integral (25) T. so that in the nth order the vertices give 1/q2n.) = f dq . 0 which is correct with respect to the important exponents. but we must show why the ring graphs are in every order the most important graphs for a coulomb interaction at T.2' (q + q'l 1 which ~ 00 only as q2 when q ~ 0 independent of q'. log q .. q..:~=:nq dq q3 n=2 L . q3 .. further. . each convergent as q ~ 0. shows that T 8 appears as a factor for all graphs except the ring graphs.. q3 log (q2 f dq' q3 . including the exchange integrals. the ring graph has a corresponding contribution 1/q6. L "2 log 1 +"2 . log (1 f dq .2 n i . Thus the graph of Fig. 1 has contributions to the integrand of ~(3) of the form 1 1 .
zei(kl+q)·yV(x .APPENDIX 425 When an exchange interaction appears. instead of a direct interaction. then 1/q2 is replaced by 1 (q + k1  k 2) 2' which is regular as q lo O.zeik2'Y = ~2 f V(xye ) i(klkz+q)'{xy) ex: ( q+ k 1 . with the exchange matrix element (27) (2'1'1 V112) = ~2 f d 3x d 3 y ei(k2q).k 2)2' 1 . direct matrix element (26) (1'2'\ V!12) We see the substitution on comparing the d 3x day V(x .y) X eikl.(Xy) = 1 f ex: l/q2.y)eiq.
The orientation of integration variable k with respect to P. o ikr = 2'71' lk}<.kFrcos kFr) .Appendix Solutions CHAPTER 1 1..ikr 2'71'lkFk2 d k . o FIG.kdk(e're· 'k 'k r ) =. A·I .. J d 3ke ik 'r= J:Fk2dkdfJeikrCOSIl e ikr _ e. zr r 0 4'71' { k coskr IkF + I1kF coskrdk } = r 0 r 0 = 4'71' { r .1.cos k Fr + 2" sin k Fr kF r 1 r } 4'71'{ sin kFr . 1.
r k 2 drsinfJdfJ cosO = 27T1OCJdr fl dp. 1 . 1= .dr.eikrp. .f le .A2 A QUANTUM THEORY OF SOLIDS S( k A r o r'IG.=cosfJ 1 . OCJ coskr 2 0 0 = 47T( .krp.sin + k lo cos = 27T OCJ OCJ OCJ 1 OCJ 0 00 1 OCJ o r 1=  lo d rikr 1 cos kr 1 IOO} . The orientation of integration variable r with respect to k. 1. 3..i::r)' expansion of sin kr with small kr is used. 2. ] lo dr [p.2. 11 .krp. zkr ) zkrl {2COSkr 2 } 27T l dr 'k ..lo ikr ik2 sinkr r2 dr kr r.dr + :k sin kr z r tr ex:. o p...p. 47Ti k ._e. xr3 = 27T f r f d 3xe'k.=22" sin kr o zr zk r cos kr l dr } =47T{ d r . 1 sin kr = . dp..'k 1 . .
I.SOLUTIONS: CHAPI'ER 1 ZPLANE A3 s FIG.. e.z+is t> 0. t z + is dz s. 1.l 80' 2'11" foo e dx . dz= c z + ts f oo dx 00 eixt e. The contour of c.:e. + . dz 1. dO 1 O.izt .rt ) + t < 0..izt . c is the closed contour with the great circle in the lower half plane (Fig.e.ixt 00 X+lS 1 +!nZ+ts .dz 1.1. • i::c:t 3.. 12{'/2 e . O(t) = lim . 2r_ 00 ( 2rt . eiztdz=O.3. I  fo" e '11" rtsin 11 dO Is. 1.izt . we have to close the contour in the upper half plane..rt2ilj. .z+ts 1 foo dx.. ~ where .3). dz x+ts uz+ts f 2'11"ie st 8+0+ 2 '11"i ... 00 x+ts Consider: e.
4. 1 . so.ik "p1fi + hkeik~ . CHAPTER 2 1.p] = hke.ik "p1fi = hkeik~. p _ h 2k 2). 1fi is arbitrary. (a) [eik". [eik". I 2>'dx'] = J[1fi' n 2~7T]7Tdx'+ 2~J7T[1fi'7T]dx' ih ih ih = 7T{X) + 7T{X) = 7T{X). t < O.ik ".ik "._p2] 1fi = e.ik "p 21fi .ik "p 21fi _ p2( eik~) = e. 1fi )2] 1 2 1 H = J [ 2p 7T + 2T dx dx. HJ ~ [~.dz + izt nZ lS + 0.ik ". p2] = e.ik "{2hk· p .2hke.ik "p 21fi} = [e. p1fi + e. e.p]1fi=eik"p1fi_p(eik~) = e. I[ 2>'+ ~T( :: dx'] ~ [~.e.A4 QUANTUM THEORY OF SOLIDS It is easy to show ef . 2p 2p p 1fi = 7T. O{t)=l = 0 t>O.H]. P .p' (hkeik~ + e.ik "(2hk. (d [~.ik "p1fi) =e.ik ". (b) [e. ih~=[1fi.(h 2 k 2 ) }1fi.ik "p 21fi_ {{ hk)· {hk)eik~ .
i h =iliT. T f {21p 17 + ~ T( : :' f} dx'l = 2 al/J] al/J T f [17. I/J] dx' 21/J 21/J 2 T T 1/J = iii + . E= E hwq fill.. H] = [17. 10 3 3 (xJ) x dx eX 1 . ax' ax' dx' + "2 { a fax' ::' ) a ~]dx' ax' T 2 ax' ) a:' [ 17.n. 1 Vtz(1)4XDX 3 dx = 2172 V vr 1i/3 fo V21i(1)4 + 2'172 v. dx eX . so V E = (217)3 ·417 vr 1 f liw dw 3 V 2 eflllw _ 1 + (2'17)3 ·4'17' v. p 17 we get ~ = p ax 1 T a21/J 2 ' 4. ih17 [ 17 . and X D = 2172 (kBT) 4{ 1 2} li vr + li v. 3 . q e q1 = 3 V (2'17) f q2dqdrJ. 2 2 2 ax ax 2 a a 17= a 1/J 2 From ~= . liwq f liw dw 3 There ate three acoustical modes.SOLUTIONS: CHAPTER 2 A·5 2 2.1 1i/3 1 liwD /3 x = liw/3.
1 kB 46 2 3 T 'IT n3 0 3 Xl) X dx 00 LX 0 4 J) x:ldx 3 03 = 1 03 / 2 eX l' + 03 ' t 3 X dx 'IT fo eX 1 T«()Dfo 7l:" e= 15' kIlD=hwD' 3nkB'IT T4 4 ae Cv = aT = 5.k .2'IT2 kBT k~Ol + 10 eX .H1 = uk(woaLwlak) vk(wOak+w1aL) u k{ w o( ukaL + Vkak) . (a) We need to show [at. ak = Ukak + Vka~k' at ukaL + Vka .wj ( Ukak + V kat) } V k{ W o( ukak + Vkat) + W 1 ( ukaL + Vk a . e E __ 1_( 4){6'IT2n 6'IT2nX2} rXDX3dx V .A6 QUANTUM THEORY OF SOLIDS Use: k1/J l = hV/(6'IT2n) 1/3 and kilt hVt (6'IT2n)1/3. (95). = haL and [ak' H] = hak' From [al. H] Eq. Hk = wo( at ak + a~ka_k) + w1( aka_k + at kat).k )} W o( U~ + vi)aL 2ukvkWOa_k 2WIUkVkaL tanh2Xk}aL Wl(u~+vi)a_k = cosh2Xk{ Wo  WI cosh2Xk{W l + wo tanh2Xk}a_ k · .
t _ t Following the same procedure. (aLak)O ~ 00. (atak)o = (<I>olaLakl<I>o) = (<I>olvi + Ukvkata~ kl<I>o)· Because (<I>oltXL = (akl<I>o»t. t ] _ { [ ak. (aLak)o ~ O. 2 k (atak)O= "2 1 +NV 2m .SOLUTIONS: CHAPTER 2 (NVk )2 (Ek + NVk ) + Ek + NV k 2 Ek+ 2EkNVk E + NV • k k A7 But. Wo W 1 tanh2Xk = WI + Wo tanh2Xk NV _ (Ek + NVk )NVk k Ek+ NVk =0.Aak. k As k ~ 0.k _UktXktXk 2 t + UkVk ( tt aka __+ k a_ktXk ) +vi(l + a~ka_k) 2t + Vk 2+2t ukakak vka_ka_k + UkVk( at a~k + akak)' (c) ak<I>O=O..2 2m 2m 1.H  cosh2Xk E~ + 2EkNVk} Ek+NV k a k . one can get [a.. k ~ 00.1). .H]=cosh2Xk{ E~ + 2EkNVk} Ek+NV k ak=Aak" (b) aLa k = (ukaL + vkak)( Ukak + vkat_k) 2t + ukvkakak t t + ukvkakak + vkak 2 _ ukakak a t..2k k2) NV '( "2kZ)2 +2 (. so (atak)o vi=sinh 2Xk Hcosh2Xk.
[a.A8 QUANTUM THEORY OF SOLIDS S( (aka k ) ~ FIG. Take A_ 2 2 t{w Iw 2 + 4e 2 }. 7. H] = (uw + w)a + usb Aa = A(ua + vb). v .2.w + Iw + 410 2 2s b } = UA( a + : b) = Aa. . Let a=ua+ vb. H nwata+ c(abt + bat) = wata + s(abt + bat). A u c 1. where A is an eigenvalue. Hw ± 1 W+ 4e 2 }.H] =u[w+e~]a+usb U [ w w+ Iw2 + 4s2] a+ usb 2 =U' w Iw2 + 410 2 2 { a+ 2e w lw 2 + 410 2 2 b } w=u' ~2 2 +4102 { a.{A_W} _ ~ w+ Iw +4s e 2 [a.1. In matrix form. Then. The sketch of < atak)O as a function of k. (W~A _\)(~)=O. Solve for A. uW AU + sv = 0 and uS AV = O.
3 4'1TnaXa w =0.2£ (w + v'w 2 + 4£2). w2 = 4'1Tne m 2 4'1Tne • = (1 + 4'1TnaXa)' 2 wp 1 1 +4'1TnaXa 1 + 4'1TnaXa From Phys. a .4£2 )b. (15).5(g/cm )6 x 10 108 g 1.. ) = 1 2 = 1+ ( mw + 4'1TnaXa 4'1Tne 2 + 4'1Tn aXa' mw 2 e= 0.8.24 cm3 • 3 23 !"::: 6 X 10 /cm na 22 . 92. x 10.SOLUTIONS: CHAPTER 3 A9 Let u= 1 a v 1 . p. Pe1ec = Xana E • ne 2E 2' mw From the atomic system Patomic PP £ e1ec + Patomie = ( 4'1Tne2 2 ::2 + naXa )E.v'w 2 .4 1O.2£ P (w . 1 a . CHAPI'ER 3 1. From Eq. is the transformation.( w + v'w2 + 4£2 ) b 2£ 1 For A+ = Hw+ v'w 2 + 4£2 }. Xa!"::: 2.6wp ' . 890. Rev. H = A+ptp + A_ata.
L. L AL L+l pr1e. . w2 L  I. r a. L+1 AL = B L a 2L + 1 • L+ 1 =1+ 2 .B using [s.' L 2L + 1 CHAPTER 4 1.. we treat as w2 p e= 1 2' W r a dielectric sphere with Di = eEi' Ei = . H] = [s".B JL (Sjx Sj+6x +Sjy Sj+6Y )] .B j Sz = LSjz· j [S". QUANTUM THEORY OF SOLIDS <Pe = 1 .\7<p. the nonnal component of D is continuous. H JL Sj' Sj+6 2/LBHoLSjz' j. (i) Also. [ LS. Outside the sphere \7 2<Pe = 0. <Pi = L BLrLPr'eim</>.:Sjz] = o. so From (i) and (ii). .. L+1 DeL=ALr+2 a DiL= LBLaLle.rn At r a. JL Sj' Sj+S] J.m</>.AlO 2. Ee = L rn De' Inside the sphere. • J.. L wL 2 wp ~AL = B L a 2L + 1e. the tangential component of E is continuous A L /a L + 1 BL a L .z.
fiS 1 2 2S J J J J ( 11) (11 2 .aja j a j j+ = 2S11 fijl' .Sjx Sj+IIX1 + [Si".ajaj t )1/2 a al' j t fiS 1. HS/ + Sj)' 1 1 Sy = :( 2l S/ .atata J J 4S J J J ] 4S J ] j .j+"Sj+ 8y Sjx ill fii. a.ill fit.SjySI+8y]} {ill fi.. ~ata.aJaj /2S)..Sl' Sj = fiS aJ (1. t ( 2S 2S .atata ·./J j.~aatata. II = .)a. 2 2S J J 2 2S J J J 4SJJJJ = 2s{aJ ·at J ~ata.. ata.aJa j ta}{ II fijl' + aJaJal' tt ltt +l 2al'al'aj'a 2 aj. j.a ·at .Sj).al'al' t )1/2( 2S .l. 2S J J ) a t fiS(lJ ~.11 fijl" [ Sx. S/ I2S (1.11 L SjySj+8x + L SjxSj +8y j. Sy] = illS". ~ata.a} J = 2Sh8j'j lIaJaj fijj'  taJ( II fijl' + aj. 4SJJJJ ata.a·+ !. j.. j +8SjySj+8x } J i.Sj. ata.a·. 2.l1 11 = J = L L {[Si".1I L SjxSj+6y L SjySj +8x } = O.ajaj 2i [S/' S..SOLUTIONS: CHAPTER 4 i. t ) 1/2 al'aj' t ( 2S ..aja/2S )1/2 aj' Sx [Rx' Sy1 + [ Sj ] .1I Other commutators can be evaluated by following the foregoing approach.+ !...illJ{ 1. .)] = t ) 1/2 aja}..jSjxSj+8y .2ajaj fij}' = 2Sj ..)I2S(1 ~..].jSjySj+8x + ill fi i . 1 4i [(S/ ( + Sj)' (S) ..
. 1 o . Since 1 a j <1>o = 0.b k .i . Sj' S . S ..]ljat<1> IN" ~ J o· 0 1 J Sj.A12 QUANTUM THEORY OF SOLIDS S 3. .l . S2= LSi' LSj= L {SixSjx+SiySjy+SizSj.+ Si. ).. .. 5.2NSLbtb k + NS(l + b6bo + b6 bo) = (NS)2 + NS ... . ) J 1 = IN 1 ik Xj L )• i e. ) k = (NS)2 .)( S/ .. although the zcomponent of the spin does change. t/lk = V2SN ~ eikOXjI2§IS .r. Sj . IS .2NS L bt b k • k*O A magnon at k = 0 corresponds to all spins moving in phase so that the total spin is unchanged. } i i.= /2S aJ(1.1. • ..S J.i 6 = L {~(st + Si)(~/ + Sj) . S. 't'k = btk <1>0 = elk.i i..Sm = '¥ t/I k L e ik·x] INo 12§ J o· 0 J s <1>0 = IS.Si.aJa jl2§)l/2.S/) + SizSjZ} = ~(2NS)( bob6 + b6 bo) +(NS ptbk)(NS.Sj) + SizSjZ} = L {~(stSj. S.pt.i (st i. Sj<1>o = 12§ aJ<1>o.. The one magnon state is . The ground state is <1>0 with all the spins aligned along one direction.
[Sjy. inSj = [Sj' H].2IloHo[Sjz.lSlySl+8z .in [Sj8zSjy 8 a = .l+8SlzSl+8y} = in [Sjz Sj+8y + in [~'8ySjz a a . [Sj. I. I. [Sjx.in 8j.J [ Sl' Sl+8 . H = . a I [ SjX.SOLUTIONS: CHAPTER 4 A13 j.in[Sj_ 8y Sjx' a a So. in8jx = [SjX.in [Sjy Sj+8z . ~S'Z 1 ~ . a + 8j . a = in[ { 8j ./Sjx Sl+8z + 8j . a = [ {in 1.jSlz Sl+8y + in 8j.lSjz Sl+8x 8j.a j 6.8X Sj) x' a [Sl' Sl+8] [ Sjy.l+8SlySl+8z in 8j.21l 0 H O[SlZ]' l.l+8SlxSl+8z I. [Sl' Sl+8] I. a + 21loSjX H. [Sl' S/. a = in [SjySj+8x a + in [Sj8xSjy a . [Sl' S/+8] I. a 8] = in(Sj_8 x Sj  Sj x Sj+8).SjX Sj+8) H=Hoz.8 8l . . . H] = [SjX.l+8 Slz Sl+8x } = .in [ a ( Sj x Sj + 8) x t in [ ( Sj .in [Sjz Sj+8x in[Sj_8xSjz a 8 + in [SjxSj+8z + in [Sj8zSjx' a 8 [ SjZ.in [SjxSj+8y .J [ Sj' Sj+8 .ihSjy ' ~S'Z 1 ~ ihSjx ' Sj= J[(Sj _8X Sj.
A14 QUANTUM THEORY OF SOLIDS so Taking the x and y components. yr ) 2Sj .2 =2a 2 yr2.S/8 Sjz Sj$8 Sjz + S/Sj+8z} =+= i2J. 2 2 a2 a a ) L(8. Sj + 8 Sj _ 8 = Sj + (8 . yr ) Sj + i (8 . 2'1T '1T 0 L Na ==a. !laS/) + 21'oHoS/ ]. classically S X S= o.cos(k· 8)) + 2J.Jil [1. Let Ll8Sj = Sj+8 + Sj8' S/ = (+ i){ J~ (S/ !laSjz For spin wave mode.dk = .t oS 2 X H. N N . Zf3= N 1 1 2 S X yr 2 S + 2J. For IS ±/SI« 1.2 + + .toHo. yr ) Sj + i (8 . ( ax 8 ay2 az s = 2Ja 8.'1T/a N L a {'1T/a [llsin kal]. S/ = (+ i) [ JS~ (2S/ Let S·± = LlSe±i(k.8 = zSj + (8· yr )2Sj' For simple cubic case. L [ l(ly:) 1/ ] k =  1 j'1T/a .sin ka] dk. yr ) 2Sj .rr wt ) then J ' w = 2JS'L(1. Sz =:: Sjz !laS/) + 2I'oHoS/}.toHoSj±. (8 .yr)2=2a 2 . 10 (Sz) =:: S. 8j± = =+= iJ'L 8 {S/Sj8z . where z is the coordination number· S" = Sj  Sj+8 + Sj. 8 For long wavelength case.
wr: = wi. at. ~ sin20 k h(wr: . So.W k H = L {( hwr: cos 2 Ok + hwi sin2 Ok k 2c k sin Ok cos 0k)At Ak + (hwr: sin2 Ok + hwi cos 2 Ok + 2c k sin Ok cos 0k)Bt B k }. b k.Ak sin Ok· Bt = at sin Ok + b"k cos Ok· b"k = Bt cos Ok .AtBk sin2 Ok + Bt AkCOs 2 Ok) + c k( At Bk cos 2 Ok .k'· Similarly.[b"k.wi) + ckcos20k = 0 and 2c k tan20 k = (P m) .sin ka) dk  7T/2a 2a = 'TT Z = 2. Substitut ing at. ak = Akcos Ok + Bk sin Ok· b k = Bk cos Ok .Bt Ak sin Ok cos Ok) + C k( . h Wk .726. 1 20 k = 'TT/2. . Ii.Bt Ak sin2 Ok) = o. the cross tenns must vanish: hwr:( At Bk cos Ok sin Ok + Bt Ak sin Ok cos Ok) + hwi( .] + sin2 Ok [ b k . B k.SOLUTIONS: CHAPTER =  4 a + A15 'TT a 17T/2a(1 . H = 1 0 7T / 2a (1 .] = sin Ok cos Ok{ [at.b k sin Ok' Bk = ak sin Ok + b k cos Ok· [At. f3 = 0.sin ka) dk =  2a [ . Sk.'TT 'TT 2a a 1] = 0. ak'] .b"k sin Ok' Ak = a k cos Ok . bt] = o.] } = [ A k . 10. ak' bt. L {hwr:ata k + hwib"kbk + ck(akb"k + at b k )}· k Define at = At cos 0k + Bt sin 0k .At sin Ok' At = at cos Ok . b k into H.AtBk cos Ok sin Ok . Ok = 'TT/4. tan20 k ~ sin Ok = cos Ok = 00. At] = cos 2 Ok [a k .sin ka) dk 0 1 7T / a 'TT (1 . At crossover.363. So. the other commutators can be worked out.
cX} = 8jk . Tk 1 0° 1) kT (° Td 1·· T jl 1 (0 ° 0)j_(0 0) T T 1 ° j j . {Cj.( ~ 1 ~ t (0 0) . . ° [a j . Let aj = l~ g) j' then [a j' a J = 0. H= L{Ii(wCk)AtAk+li(w+Ck)BtBk}..A16 QUANTUM THEORY OF SOLIDS S( Let w~=w{:=w. 7] . {Cj. at= /2 (At+Bt). a k = /2 (Ak+B k ). {Cj. j =1= i. {cj . k.l(~ ~)k + T.( ~ } .ck}=Tl··1j_l(~ gLTl··Tk .l (~ ~)k + 7] ...< k. = 0. for j> k. (0 0) 1 ° j1j Tk . . a.10k ~)J~ ~L g)k g g) k (~ +1j .. Tk  ~ L . cl} = 0. Tk'(~ ~)k(~ ~t. 1 bk = /2 (BkA k )· 1 CHAPTER 5 1. 1j2 = 1. wB=w+C k . then {cj Similarly. .Tkl(~ 1( + 1j . Tkl(~ = 1j(~ gL· ..Tk1(g ~)k+Tl· . T. k wA=wCk. {Cj'CJ}~(~ ~L(~ ~L+(~ ~L(~ ~L =(~ ~)=1. for j < k. {aj' 1j} = and . _  ~ l.. j=k. .CX}=Tl···1j_l(~ gtTl· . Tk . bt= 1 1 /2 (BtAt). cX} = 0.
i <j. J ..nJ. C k } = 0. Ck } 0)(0 0) + (0 0)(0 0) =O. {Cj .k') = N 2 (27T)3 f d 3k a 47T k }.X")l/I(X") and consider p(x)l/It(x')lvac) = f d xll/lt(X") ~(x . 4. it is easy to show the equivalent between Eqs.=k. )(1 .SOLUTIONS: CHAPrER 5 AI7 = ~. 1 fd 3rF 2 (k r) = fd 3r 2 fd3kfd3k'ei(kk'). TJl · 0 (0 1) j ( 0 )1" ( )J. (g ~)i ~ (g . 'Tk.xl)l/I(x")l/It(x')lvac) 3 . (23) and (27). = 0·1' .l(~ ~L(~ ~)k + ~ . T k . j> k. = 1 = N 1 N 2 = N. )1( h"'( )j Similarly. j Similarly.r F N (27T)6 1 = N 2 (27T )3 1 fd 3kfd 3 k' ~(k . Similarly. =(0 1 0 1 0 1 0 1 0 {Cl. = (~t = 11). ~(~)i = (~)/ Ti(~)i (~L· T 1 . it is easy to show b. Let p(x) = f d 3xll/lt(X") ~(x . 1J·· .1 1 0 k 1 (0 0) (0 0) 0 =0. cll' ·n j ··) =(In)Ojl" ·I j ···) =Tl'''~I(g ~t( If jth state is occupied..) • J 2.nd t ~)i ~ t = = O. {Cj .. jth state is unoccupied. cl} = o.
~fd3 x'".t{x') 1j. Bosons: 1j.(X) .X') 1j.s L.{x) + f d x'1j.t{x')1j. Fennion: 1j. (x) N = 3 1 = 3 = 3 = 3 = 1j.{x).{x')] 3 =1j. f d x' f d y1j.t(x')lvac) is an eigenvector of p(x) with eigenvalue 8(x ./x').t(x')1j. (x) 1j. [ "'.! (x')1j.!{x'): s m 1j.A18 = QUANTUM THEORY OF SOLIDS SC f d x"1j.t{x') 1j. so p{x)1j.a{x) at = [1j. 1j.t{x') 1j.{x) 7. 1j.{x)N = = f d x '1j. (x) 1j.! .{x') f d x'[ 1j.s.y)1j. H].t{x')1j. 0.{x")] Ivac).{x) 3 = (N + 1)1j. = (N + 1)1j.x')1j./x') +i s.a. (x) 1j. 3 H= Lfd S 2 3 x'1j.a{x) .{x) + N1j.{x)1j.(x') :~ "'s(X')] P x') 8as 1j.{x) + N1j.{x') 1j.{y)1j.{x')] 1j. So.t{x')1j.(x').X") [8{x" .s{x') m 2 2 = L f d 3x'[ 8{x s .!{x')1j.t{x')lvac) = 8{x .{x') 8{x . 6.x') + 1j.Hx') :m 1j.L f d 3X'1j.x') 1j.{x).{y)g 3 c X 8{x' .t{x')lvac). f d x'1j.x').lvac) = x8{x. in a1j.a{x)] 2 1j.{x)N f d x'1j.s{x')1j. (x') f d x'[ 1j.t(x')lvac) is a state for an electron at x'.t{X") 3 1j..{x') 8{x .
~(x')l/.a(X) + gl/. I = [ 1/> .(x).a(X) p2 = 2m l/. CHAPTER 6 4.s(x')l/.(y)l/.s. For ih~~(x) = [l/. the steps are the same to prove the result. Use { l/.s(x') = l/.a(x) .~.s(x) +~ g L s.y)1/> "(Y)1/>.s(x'). Otherwise.SOLUTIONS: CHAPTER 6 A19 p2 = 2l/. 2 I = gl/.~(x)l/.(y) 3 X l/.y)l/. ih~a(x) = ~l/. ~ Ef 3 d3 x' f d3y1/>~(x')ft.w2XO  Let x = xoe. s ' f d x' f d y{ l/. ~2 ne 2/m w + iT'/w (1.s(x') l/.t(x')l/.1(x)l/.a(x) + m L f d3x'l/.~(x)l/. eE/m iwT'/xo = eE/m.y)l/. (w+iT'/)w (w + wp)(w .(x)l/.(y)g8(x' .a(x)l/.s(X')l/.~(x')2l/.(x')] g = 2" ~l/.a(x). because l/.w. l/.s .4~ne~/m W +~T'/w e(w) = 11 2 W _Po . i x ).p(x)l/.a(x).~. p(x)l/./x') l/. (x)l/.~.(y) 8(x' .~(x')l/.a(x) s m 2 p2 P .L f d3X'l/. 1(x)l/. a =1= f3.a(x) }. H]. s(x).Hx')l/. Xo = 2 . w2 + ~T'/w e(w) w2+iT'/w 2 w + iT'/w .~(X') 2 s m l/.~(x)l/.iwt .~(x). there is an extra " " sign.wp ) + iT'/w· . s'(x')} = 0.s'(y) l/.a(x)g 8(x' . • W +~T'/w ne 2E/m P=nex = =aE o w2 + iT'/w ' D = E + 47TP= a= JE.2" ~l/. 2m x + T'/X = eE/m .
. ' . Fro] from Eq.. _ 2'1Tne 2 q2 1° o 6.4'1Tne mw 2 for large w. (121).q) = 1._l.>+ "':0 + is + '" + :"0 .A20 QUANTUM THEORY OF SOLIDS SOLUTI< 1 W(W+ill) E(W) ~ 2w(wwp)+illw 7..J 2 In dw.. is the principal value. { .{ 1 t ( 1 ) 2'1Tne i. 11+0 lim.{ ~ { 4'1Te 1 + 2 2 L wnol (nIPqlQ) wq n 2 = 1 2+ wnol (nlp_qIO) 2} 1 4'1Te 2 n 4'1Tne 2 =1+·q2=1+q2 m w2 mw 2 ' 2 9.'1TW q 2'17' p 2 + 2'1Tne q2 } = L {wp q 2 }. 8. E(W.q) = 1 7 L 1(nIPqlO) 12 n 4'1Te 2 Ush wit1 .is } ~ 1 4'1Te 2 2 q L n 2 1 (nIPqlQ) 1 wh~ I ( 1:wno ) ~ 1 ( 1+: wno )) .F + } q '17' 0 E q2 = _ 1 L { ~ . 1° o =) = ~(w + i ll 2 ){g. where g. E( w.wwp i2'1T8( W .W p )}..F(~) = E  '1Tw8(wwp )' 2 E int_ XJ .
_q2= n T 4'1Tne '1T = ____ _'1_ _ _ = w2 2 q2 m 0 2 W m 2 p. we have fOO i20 w~ e. q) 00 Using result in Prob. From Eq.wno) dw n . 00Y( w.i20 ) 00 dw· w .8( W2 W nD ) I} = ( '1T 4'1Te 2 2) "2LW no I(nIPqIO)I +1(nlpqIO)1 q n 2 2 '1T 4'1Te 2 . 8. q) = L 1(nlplIO) 12 8( w n 2 1 (nlplIO) 1 wno ).q) = gWP Y( w.. 6 and taking a contour along the real axis with a great circle closed in the upper half plane.q) = 100 dw· E 2(W.1 2 R W~)'1T = R+oo i'1Tw! 1a 9.q) 1 o 4'1T =  i foo 8'1T dw w E( W. E( W. q) dw = 100 L 1 o 0 8( w . q) + iR21'" doe (1 .R 0 = ° where R is the radius of the circle.q)) 2 1 o dw· W { 4'1Te q 2 [ L I (nIPqIO) I '1T8(w + W no ) n 2 I (niPqiO) I' . (64). t = dWWf( 00 e(:.q) 00 = iR 2(. 00 dw O'l( w.SOLUTIONS: CHAPTER 6 A21 7. f oo dw· W· E(W. 00 dO'l(W.
k'+q.A22 QUANTUM THEORY OF SOLIDS SOLt = = 00 L (OIPqln)( nlp~IO) = (OlpqP~IO) n NY(q).k'+q' .k'+q'( Ok. from Eq.ak+q.f3~k.Ok+q.f3k) .k  . f3 t } = 0.kak + q at' +q. (121). from Eq. Ok.(q')] = f3kak+qat'+q. q).f3 .f3kf3~k.k ' +q' Ok. f3 t } = 0 are used.k'  f3~k.f3kak+q Ok.0. + ak'+q. 10.f3 .f3~k.f3~k {at. At.ak+q)f3~k' . +q. at} = 0.(q')] = at+qf3~kal+q._q2.q)= yew.a k + q .k.ak+q = Ok+q.at'+q. [At(q).k' . (64) 1 = 2 {l 0 OO dw w L (nlp~lO) 1 1 2 n O( w . 1 dw w Y( w.k' .f3 .at' +q. _ ~ t 12 W no + ~ 2" ~ 1(nIPqlO) 2" '' 1(nlpt_qIO) 12 wno n n 1 n = .f3 . + q.k'+q. + 1 dwwLI(nlp~qI0)12 o(ww o 00 n Y(w.at' +q.at+qf3~k.k ( Ok+q.at'+q.Ok+q.at+qf3~k t t IJt IJt .k)ak+q . At.q) o = 1 dw w L (nlp~lO) o 00 1 n 1.at.k' . k' +q.f3~k.kak+q = f3 .k .f3~ k. {at.wno ) no )}.f3~k.f3 . = Ok+q.f3~k.f3~k' . 2m 11.at' +q' ( Ok.at.ak+qfJk'fJ . and {f3 t .f3~k.f3~k' . [Ak(q).f3kak+q  = Ok+q.k = .at'+q.f3~k. CH} 12 O( w W no ). 2.
2 h I'l'Ka q . .q . 2 c h2 .qc) c 1 C[m* hpc s (2'TT)2 l qm In q2 12k . (21).SOLUTIONS: CHAPTER 7 A23 For unperturbed vacuum state f3~kf3kIO) = 0. Now. qc .500» 1. L / k'q' 1.(q')] == 8 k .2pwq . nq) 12 Ek Ek_q  hWq where H' = ie.1i erg. 1 M*2C[ From Eq. 2 8'TT hpc! . hC 2 d£ = __ 1 L 2p~ q q n 2m' C[m* 2'TT = hpc s (2'TT )3 = (2k' q .k' 8q.csq l qm jl q2dqd/L 2 2 * m Q 0 1 (2kq/L . a!. at'+q.+ q.10 8 emI.ak'+q.5. 2. 4M*2Cs2 C[q. (N) .)4. So. 5 X 10 5 em/sec. (N) = 'TT2 pch=3 s l qm 0 q (q + q cf ' dq M* is the 1 10· mass of the proton.q Idq 0 2k 2k+q+qc .c k •• ).2M*c s/h. qc = 2m*cs /h. 1 M*2C[ lqm~ dq (N) == 'TT2 h 3 pc s 0 q~ 10 8 qm/qc . Cs  qm .h. 2q2 = 'TT2 h3 pcs . d£ = L q 1(k . C 1 .IO) = O. [Ak(q).10 9  1 M*2C[ 'TT2 h 3 pcs 1 q. nq + 11 H 'lk. 1 M*2C[ q. CHAPTER 7 1.q'. At.q.5 X 10. p .q.q . ..
qm .0.11 erg = 0. 10 X 10. + bq eiqox2 . For qm» k > qo' then C~m* qm 2 f1£ == . i. we have 2k 1.iq .qc = in 2k 1 InI 2k + q + q J 1+ q+q.J " bq q q (bq eiqoxI  t e.qc + lqOq2dq in 12k  0 I} 2k+q+qc where qo is chosen such that qo> qc' For qm» k» qc' 2kqqc in 2 k I =0.. ) ~ 2x = 2k _ q :k ..27 g. lnI2k+q+q.I =in l+x' 1 1 X 2k where x = . 2k 2k»qq" I 1 The first integrand can be approximated as 2q.bZ e.. near qm' For large q.1 eV.10 8 emI.12 erg == 0.25 X 10. q qm _2q2dq qo q+qc .q .p(x 2 ) 1 i41TFe" i.e. .iq °X I bq °X2 ) .A24 QUANTUM THEORY OF SOLIDS S Because the factor q 2..lipc s (21T)2 2( {f = x + :' + . X 10.J q q H = IiWlL b!bq q tb = liw li..5 X 10 5 em/sec..1 .11 erg..q . the contribution of the integrand comes mainly from large q..lipc s 41T 2 • With C1 . 6 f1£ 4. Cs .p(x 1 ) + e. + e. m* .5.5 X 10. q+qc C~m* f1£ .9 p ..q+qc 2k .
SH + HS+ (iS2H ... S].SHS+ iHS2) + ..i q Xl q i4'1TFe q + bq e iq Xl + bq e iq X2 ) + k (4'1TFe )2 IiWlq2 (2 + e iq (Xl  X2) + e.S] + .J Ii 2 q q wlq +   4. u=1.xl i4'1TFe liwlq + e iq X2 ) ] .i4'1TFe( . at [a q . S] + ![[Ho. . S] + . 6. v.Xat. S].( .iq X2 ).2(4'1TFe)2 lq _ l e (x x2) q IiWlq2 The last tenn is obtained by q q in the sum..e iq x l + e.i q .( e iq .b t e .. from [a q .. So. = Ho + XH' + [Ho. b.iq . H] = . H] = Xa q .X 2) = X{ubq + v). at. =H+ [H.S] + i[[Ho + XH'..S + iS 2  ••• )H(l + S + iS 2 + . v .] = 8q .. H = esHe s = (1... . ) =H ..liwlq Consider t liw 1at a = liw 1 bq q q [ . S] + ~[[XH'.Xl q i4'1TFe liwlq + e. H=Ho+XH' H=Ho+ XH' + [Ho+ XH'. a. X. S] + ..S] + i[[H. q " we get u*u = 1. H] = i4'1TFe _ liuwlbq + (elq:~l + q .. = u*b! + v*..J . we want to find u. S] + X[H'. Furthennore. .SOLUTIONS: CHAPI'ER 7 A25 Let a q = ubq + v. [at. S]. X = liw l . b + [ .( e .iq X2 ) ] bteiq x2 q = liwlbtb q q ..iq (X l  X2») H = IiwlLa t a _" 2(4'1TFe )2 q q 4.S]. and with [a q .
t _ m n H = Ho + t [[Ho.Em (ml(a t + a)ln) =~m. S] + 0(A3) = Ho .HoS = AH'. we have (nISHolm) . A (nIHln) = = (nIHoln) + A 2 2" (niH'S  SH'ln) (nISlm)(mIH'ln)} nnw +  L {(nIH'lm)(mISln) m L { 1(nIH'lm) 12 m = nnw + A2 2 _ 1 (nIH'lm) 12}. S] = 0.n+lVn+ 1 + ~m. then AH' + HoS . _ Ho= nwata. c. where n> 1. From SHo .SHo = 0 implies ISI. S] + A[H'. H = nwata + A(a t + a) =Ho+ AH'. S] + 0(A3).A26 If S is chosen. En .m+l vm + 1 nw = ~n. S].En result in b is used. S] + A[H'. ~n.A.nlrn. S] + 0(A3) = Ho + t[AH'.t[AH'. (nla t + aim) EnEm 7. Em . such that QUANTUM THEORY OF SOLIDS SOL AH' + [Ho. nw nw .(nIHoSlm) = (nIAH'lm) Holm) = Emlm) A(nIH'lm) (nISlm) = E Em =1= En· T.mlVm nw (nIHln) nnw +"2  A2{ (n+l) n nw + nw _(n+l) nw +~}=nnw~. H' = (at + a). O All the terms in fI are either of the order of A or An.
(Em .... a. ) 10) 10) + SIO) + ..  = 1 0 ) + i.En) t t for A =1= 0...! 82+ .Lin) 2 n A2 . 7. )(10) + ~ln)O(A2) + . 1 _ + S2 + . <Po does not have boson in first order of A. S] + 0(A3 ).SOLUTIONS: CHAPTER 7 A27 d. The electric field produced by the polarization is given by ~ ...2 = az 4'1T~ a2 Rz ·P= 4'1TC . ) <I> 2! 0 _ = (1 +S <I> = eS<I> o 0 = = = (1 +8+ . <1>0 HoIO) = EoIO).. n =10) .J n ~ In)(nlt[AH'. S]IO) EOEn + ... (E + 4'1T P) = o. fI = Ho + HAH'.II) <1>0 has boson A /iw + . Consider. + Lln)(nISIO) + ... . P az2 .{L [(nla + alm)(mla + alO) t t m (EoEn){EoEm) _ (nla + alm)(mla + aIO)]} + .. =10) + ..z paz ~ 2 a cJ> ·E= .. to 1st order of A.. aR acJ> z "Pz "Cpe zz =zCP=z .. E= ~cJ>(z)= z az..En){Eo .
_ ak elkx 1 IV' H' = 4'I1eCp L. 2pwq (atak_qbq+ ataHqbZ)· Wq H'.iqZ ) (bq e iqz + bq .. nq + 1IH'lk. H'(z) = 4'11Cp eL. we have H' = f ~*(x)( e<t>(z ))~(x) d x. t e. The electronphonon interaction is e<t>(z).q. . In second quantized fonn.iqZ ) = e<t>(z).A28 QUANTUM THEORY OF SOLIDS S( So. nq) 1 8( € k 2 liwq  € k q) C Tk 4. The mobility ILk = m phonon interaction is 1 The scattering rate due to electron = Ii L q 2'1T { 1 (k . nq) 12 8( € k + IiWq = 2'1T (4'1TeCp Ii )2[ (_li_) {( nq + 1) 8( € k q 2pwq liwq  € k q) + nq 8( € k + liwq  € k +q) }. R z =" i. q k J where V is the volume of the sample. nq . ~ _ql/2. q (bq e iqz + bqt e. = csq. PWq P is the density of the medium. <t>(z) = 4'1TCp R i z ). V. 3 ~(x) = t 1. eTk.1IH'lk..q J 2 1. = qz. € k +q)} + I(k + q. b.. L. q J q 2pw 1..
.T1!2 CHAPTER 8 4.=ihct +ihc .1 = k 2'1T (4'1TeC) L (m) e h P q h 2pw 1 Ekq) q x {( nq + 1) 8( Ek  hWq  + nq 8( Ek + hWq 1 nq = Ek + q ) } • 1 1' ehwqfJ _ fJ = kBT' then n +1===n q _ kBT q hWq .Tl/2 . taCk zhc k . ~kl = (: x T w:) \ (41TeeS (2~ )3 f d 3q ( 2P:.T 1!2.... aNk aC k act ih.q)) + 8( :: q( 2k cosO.S SOLUTIONS: CHAPTER 8 2 ( A29 J.L"k 1 . {8( :: q(2kcosO. 2m T h2k2 ) k . J. .k' In semiconductor.L. at k at at k .at = Ek CkCk . kBT> hwq . . Ek» hwq .J CkICk/ ~ t t t "". 1 J. Also.q))} .q )( :::l ~.CkC_kV I.k BT.Lk . Nk = ctc k .
k k' bk=ckJ. t t c ~ ih.Ck.k.ct'i C!. b k . .kCk = O. Cki c k' J.Ck' Ck . Ck ' i = s 2b k b k . c ki =Ck' J._ z" a Ck QUANTUM THEORY OF SOLIDS SOLUT: act k t _  _ EkCkC k t _ C. ck' ickJ.k' J. Ck i ct' i c k i c .A30 'I:.}· 6. C _ kCk' The ground k k k' state wavefunction is I~o) and ' the excited state is I~e) = + lrtal' l~o). v <~el {b k . b k . b k .VL' Ct' C~k. Ck'i c kJ.LCkVL'C!.k J.k' J. Ck i Ck ' i C .k.Ct'C k at k k k ' k k' = =  a <~elc1 LCtC!.Cki· k' k <<l>el : 5.LCtC!. Cki C~k' J. because ckiCkilO) fork =1= k'.} = 2b k b k . c k i ' C .C!. C ki =2C .k ' J.kVL'c. t t bt k .k' J. c k i k k <~ollr = (1.Cki Ck'J. Ck J. {b k .k ' J. c  kJ. = <~el where Ck = Uklrk ct = + Vklr!.Vklrt· C!.k.k J.Ck.) 8 kk .k.kJ. c k ' i ] = ckJ. ] = [Ck J. H red LEk(CtC k C~kC_k) ..J C .ct' i 8 kk .8 kk..ct'i C~k' J. t t _ t Ck' i C . Ck i nki = (1. = (8 kk. . fork=k'.CkVLC. CkJ.nkJ.VLC .k ' J.ck'ickJ.k = Uklr~k  Vklrk' . + L'CkC!.kVL'c. .kCk k K' k' k F k C LCtC!. .p C . <<I>elc ~ C~k' J. [b k .Ck' ickJ.kVL'c_k.Cki =0.{1. CkJ.LNk = . C . } =2c _ k ' J.) 8 kk .k ' J.c ki c [ b k' bt] k '  k. ckiC . + Cki C~k' J. (1.k J.k V~' i.n ki ) 8 kk .k.k' Uklrt + Vklr _ k' C_ k = Uklrk .L'C!.c _ k ' J.. .nkJ.C k . ckJ.k . Ck i t = CkJ.  c ct'i Ck i )C!. =0 =0. ck'i .
2VU 1V1U2V2 =E.V L' Uk.£.ukvk(a _ k.vk.k' k ld +2VU 2V2L'U kVk .V L' k.k =F= 1. k'.V~)E2 k + 2V( U1V 1 + U2V2 ) L' UkVk .ckckl<I>e) = (<I>0Ia 2 a 1( uk.at.Vk. . k arbitrary or vice versa. (<I>el.'S SOLUTIONS: CHAPTER 8 A31 Consider (i) (<I>elctckl<I>e) = (<I>0Ia 2a 1( ukat + Vka .k'~1.k' ct.2.VkEk .2 + U~El + U~E2 2 2 2 V2 E2 + U1 El 2 + U2 E2. u~atak is nonvanishing.a_ka~k) contributes.V1E 1  _"2 Consider (ii) (<I> elct.Vk. we have (<I>0Ia 2 a 1[( u 1 v 1 u 2v 2)al ala_2a~2 + (UIVlu2v2)a_la~la_2a~2 + ( U1V1U2V2)ar a 1ata 2 + (UIVlu2v2)a_la~lata2] at atl<I>o) = O.UkVk = .2VU 1V1U2U2· k (<I>eIHredl<I>e) . Combining the term of C~kC_k' (<I>eILEk( ct Ck k + C~kC . k = 1 or 2.vkat)( Ukak + vka~k)at atl<I>o). there is no contribution for k' = 1. only via_ka~k contributes.a k' )( uk. c~k.UkV k + 2VU 1 VI L' UkV k k.VL' k.a~k. Uk'Vk.k )( uka k + Vka~k)at atl<I>o) For k =F= 1. 95.k)l<I>e) = L k ViEk k~1.a~k' .VOEI + (U~ .2. k = 2 or vice versa. . + vk.(<I>OIHredl<I>O) = (U: .) X (uka .c~k.a k .k . Similarly.ckckl<I>e) = .2 Uk. k' = 1. from Eq.
E For k' = . E = 2A k " Ak' + Ak".1 V/l2+E~ ' L'Uk sin Ok = k= 2 L' k k V 1 Ek /l V tan Ok = V' /l2 /l2 E= E2 1 (/l2 + En 1/ 2 (/l2 + E~)1/2 2V + E2 2 + + _ _ __ 2 (/l2 + En 1/ (/l2 + E~)1/2 /l /l 4 (/l2+E~)1/2' (/l2+Enl/2 2 /l2)1/2 (2 /l2)1/2 = ( El + + E2 +  V /l2 (/l2 + En 1/2( /l2 + E~ "2' r/ 2 =A 1 +A 2  ~ V/l2 21\11\2 ::::::A 1 +A 2 . Ok u~  vi = cos 2 1/2  ° 2 sin 01/2 = COS ° 1 = V /l2 + E~ /l El . ICPe) = at.ICPo). 8. 2U 1V 1 = 2 sin °1/2 cos °1/2 = sin 01 = . Let the nonnal electron density of state be DN(E) and the superconducting electron density of state be DiE). + /l ) 1/2.at. Ek = (E~ + /l2)1/2. k dEk =DN(E ) dE Ds(Ek) =DN(Ek ) dE dEk ) k k 2 2 )1/ DN ( Ek )( /l2 + Ek Ek .. In general. = where Ai = (E.A32 QUANTUM THEORY OF SOLIDS Let Uk = COS 2' Ok Vk = sm 2' . there is oneone correspondence between them. D/E k ) dE k = DN(Ek) dE k ..k".=DN(E k ) ' Ek Ek I( = Ek 2 /l2)_. DN (V Ek lEi _ /l2 .
From Eq. We let it be 1. (33).1 0tK.I I4>) = 1 I  ( 4>101 K. Ds(E) = DN(EF)E VE2. E>~. (49): 1 (klvlk) = (klp/mlk) Ii =  m I:(k + G)I fG(k) 12 G = '. (4)IOIIK4>). we drop the subscript. 7.~2 )Ek _ DN( EF )Ek JE~ _ ~2 JE~ _ ~2 • Since k is a region near the near k F.0tl4>) = (4)IOIKII4>).1. D/E) =0 .1= From Eq. 1. where g is the volume of the sample. from K01K.K.1K I4>) = (4)IK. Ik) = eikoxI:fG(k) eiGoxy'{f. K. 2. (32). Eq.I I4» = KI4».VkE(k).s SOLUTIONS: CHAPTER 9 Ds(E) A33 ~ I 6 IDN~eF) 6 1~_ E FIG.0tK. Ds(E) as a function of E. (4)IOIIK4>) = «4>IK.I4» = (4)1°114>). so. (klvlk) = (klP/mlk). Ds(Ek) = 0.0tK. CHAPTER 9 1 1 1. Ds(Ek) = Ek>~' DN( JE~ .8.)IK4» = 1 1 (4)IK.( 4>10 1 K 14» = O.~2 • )e ). E<~. from prob. (K4>IOIIK4» = «4>IK10tK1)K214» = (4)IK. G . (4)I OII K 4>) = . v = p/m. ot. For Ek <~.
we get h2 h2 .G' h h f ei(k+G')' rei(k+G) ' r d 3r + G) fc!.L (k + G)I fG(k) 12 + L 2 (k + G)2'V kl fG(k) 12 m G G m 8 + L'Vkfc!(k)LV(Gg)fg(k) G g + L fc!(k) L V(G .g) fi k )} G m G g ~ <.(k) ~ I fG(k) 12}.G' mG. G G Because (<Pkl<pk) = 1 = L fc!(k)fG.G' f ei(k+G)'r ei(k+G')·r d 3r = L G 1 2 fG(k) 1.g)'Vk fik ) G g = ('V ke(k)) L 1fG(k) 12 + e(k) L 'V kl fG(k) 12.G) 2 . (47). =  L(k+ G)I fG(k) 1 mG From Eq. 'V k{ L 2h2 (k + G)21 fG(k) 12 + L fc!(k) L V( G .7k{.A34 QUANTUM THEORY OF SOLIDS S4 plk) (klpjmlk) = ~'V(LfG(k) ei(k+G) .(k) G.(k) fG(k) 8( G' .r) = l hL(k + G)fG(k) ei(k+G) ' r.(k) fG(k) = L (k mG. G G h =  L (k + G) fc! . . Carrying out the gradient operation.
G lr L 2 (k + G)2V kl fG(k) 12 G m = 1i 2 L G 1i 2 2m (k + G)2 {( V k fG(k)) fG(k) + fG(k)V k fG(k)}. mG 8. .+G. .L (k + G)I fG(k) 1 = Ii vke(k). (49).g)V k f.(k) G g G g to give Le(k) {V k fG(k)) fG(k) + fG(k)V k fG(k)} G 2 = Le(k)vkl fG(k) . Ii 2 1 hVke(k) 1 = m L(k + G)I fG(k) 12.IS SOLUTIONS: CHAPTER 9 A35 so.g) fg(k) + LfG(k) L V(G .) Ii { a~yG(k)12} a p = m ~ 8~pl fG(k) I + ~(k~ + G~) ak 2 1 fG(k) I 2} . This result combines with L V k fG(k) L V(G . 1 G so. or VkL 1fG(k) 12 = O. From Eq. G Ii h ak h ak 1 2 1 a ~ e(k) = mL(k~+G~)lfG(k)12. G Ii aak p e(k) = m L ~ Ii {a ak P G (k~ + G~)I fG(k) 12 +(k.
rj ) d j) 3 r = 8jj . = " i [ r H] . p f =.!:. Eq. G "" m (!!!:. a2 m 8"" + m ~G" ak" a 1 fG(k) 12.). where j vs(r .2 2 m* (~. jvs(r . (CPk(x)lcpk(X) = 1 = = So.} In the atomic limit. P. ~ ~ {8•.r m d 3r = f vs(r)p"v)'(r) d r.) = (8Ip"ly).) m* "" = = 8 + 2h2 .Eso . (50).rj')p"v)'(r .rj)p"vi r .. (y Olk"i0 8 )(08I k "l<)y) ~ 6 E)'o . (08Ip"iOy) = (vslp"lv). <Po)' IN IN 1 1 1 ~ v)'(r } r).A36 QUANTUM THEORY OF SOLIDS From Eq.<Po)' = ~p"v)'( r . 1akaak E(k). h II' .= 1...( vslp"lv).rj')p"v/r .G' f<!.r j ) d 3 r... (56): " "" + ~:a. 3 (vslp"lv)') = j vs(r . (46). } (08Ip). ( 1) .iOY) = N ~.r j ).. h h h ak" ak" E(k) = From Eq. L G.". a ak" 1 ~ 1fG(k) 12 = O. L. }. 9. a:" IfG(k) I'}.(k)fG(k)jei(k+G') r ei(k+G) r d 3 r L G 1 fG(k) 12...
18)(8Ir"IY) I) y c5 = 8!J.I08)(08Ip"IOy) m I) EyO  Ec50 m }.:r 1 vN L eik · (tn+xj')v ( y x j' x ·..2 L' (Ec5 I) 2m Ey)1 (Ylr!J.10 8 ). ) "!J. (CJJkylp!J.2~'(Ec5Ey)I('YIXI8)12=o. 2 J.. let xi' = tn .t n IN 1 . (56). 8!J. 2· {( * m m "!J.( ::.) J = e ik.j08)(081 EyO ." 2 from Eq." =8!J. Ec50 m = (CJJoyIP!J.Ec50 y If the crystal has inversion symmetry.ICJJky) = Izk." .xJ.301. (CJJkylp!J.) ( 81 m Iy =  i i i(81[r"."+ m 1z2 L'~(EyEc5)2(Ylr!J. TCJJk/ X) = CJJk/ X + t n ) =ru vN 1 L . = 1'1 3 Izk m ) .xjv/x + tn . 2· L' (OyIP!J.' . J eik. CJJkY(X) = CJJoy(x) + (CJJkylp!J.fromp. ~e'k ' Xjvy(x .Ec50 L' I) (081Izk· plOy) (OyIP!J..xi)' J 11.L =1= v.m L " .!.ICJJky) L' I) CJJOc5(X) EyO  1 (081Izk· pjOy) . m ) 2m ( m* xx =1.ICJJky) = L 1'1 3 Izk " . H]ly) = . E 0.xi' =r.!. (CJJoyIP!J. V y ).18) 12.i(E y 2 E c5 )(8I r"ly)· m ) 21m ( m* !J.:'IDS SOLUTIONS: CHAPI'ER 9  A37 ~r P.ICJJo y) = o..ICJJo y) + 1 +m ~ L' m I) Izk · plOy) (OYlp!J.
1 I 1 !l. JC2z 2JC2 0 0 2 0 + !l.2 + !l. Table (1) 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 2 e 2 my 0 0 Character table for !l.A38 CHAPTER 10 1. !l.GI4 !l. Character table for f: QUANTUM THEORY OF SOLIDS SOU.3 !l.5 !l. JC2z 2 2JC2 D.2 !l.y md.2 f51 2 5 Similarly. F.1 + !l.5 .4 !l.5 4 D + E + F + G =!l. Table (2) !l. e 1 1 1 1 2 2C4x 1 1 1 1 0 JC2y ' JC2z 1 1 1 1 0 0 e 2C4x Clx JC2y . G as basic functions.E. D ~ G/2 7T = (0 1 0) M5 = ~1 + ~2 E ~ G/2 7T = (0 1 0) F ~ G/2 7T = (0 0 1) G ~ G/27T = (0 0 1) Construct the character table with D.d' 1. I e 2C4x Clx JC2y . !l.1 !l. !l.211 1 1 From Table (1): 0 f =!l.F. E.1 + !l. f5 = ~1 + ~2' M5 = ZI + Z2 (M5 is equivalent to f5) 2.1 o Clx 1 1 1 1 2 o o 2JC2 1 1 1 1 The character table for !l. CH) e C2z fl f2 f3 f4 f5 2C4z 1 1 1 1 0 mx.2 + !l.
1 w Let p = x + iy.SOLUTIONS: CHAPTER 11 A39 CHAPTER 11 1. m inpx = [Px' H] =  pz in { e H2 eH} . H] = 2m 2px + e. where m 2 eH wc = . pz is a constant of motion. then p = i + iy = (Px + ipy) + ~(y .· me p= m(px+iPy) + 2 (yii)= iwcp· 1 w C . 2m x e Similarly. _1_(2 2m P y e i= . H 2m { p2 z eHy ) 2+ ( P _ _ eHx ) 2} .( pA 2m e =  1 A 2e = (_ Hy Hx 2 ' 2 ' 0).2X + Py. e)2 . H =1... z = z(o) + Pz(O) t m . y= _eHX). +(P +x y ini = 2e in { eHY} [x..( 2p + . eHY) i =1 . 2m 2e e = 2 p x = _1_ 2m {p 2 eH _ e H2 x} y e 2e 2 2 eH y 2e' p = y _1_ { _ p eH _ e H2 Y} = _ eH i 2e ' 2m y e 2e 2 pz=o.ix).
_= dl dt J eHo · 2= eHo p'2+ p '2= _V V2 +V V. e c Let l be the distance between A and B (Fig. e vyHo. .y plane). p= w~p.y plane 5. x y C Y x c.l { dt= T= ¢eHo V~~. 11.l C d1 dt=.1 to H in k space on a constant energy surface. i> = c H = (0. Vol is the velocity . e Px =   v X H. B. (hannonic oscillator function in x .l to the constant energy surface. eHo v. 2 2 h k E = _ _ Z n 2m .eis oscillatory.' ~pspace V~L dl FIG.. The motion in the x .1). c d1 CHA 1. 11. The solid curve is a constant energy surface. + ( n+ 1 ) hw 2 c 3.1. dl is along the path between two points A.A40 QUANTUM THEORY OF SOLIDS SOLU' This implies p . <p  iwct .0. c Py= vxHo· . dl=hdk u' V~Ii( ak ~ then 2 ch as eHo T= 2 2 ch a ch ( ak ) eHo aE(k) . Ho). 1 e ikzz .¢dS= a. Electron moves in an orbit .1 dk= eHo ¢ a.: a'{k)) .
dt l' e For steady state. CHAPTER 12 1.~HX 1 = [px. dt l' e dV 2 v2 e m2+ m 2 . k x ] = kzk x .kzk y . These can be written as h 2 k X k = ihe H2.kykx' [kz. e [kx. e hky=py . and 3.px] e = ihe H.= eEl + v2 H. Use component fonn with the Landau gauge.vIH. Let the principal axes be 1. hkx =p~. k z ] = 0.1 + tlt2 t m l 1 m ~2ml e1' e1' [l 2 m2 (!J .Hx. the equations of motion in the transverse directions are dV I VI e ml + m l . dt = 0. k" ky] = [p"py.~HX 1 = e H[x. e ze kxk= heH.kxkz' [ky. A = (0.SOLUTIONS: CHAPTER 12 A41 5. . the corresponding effective masses are m l = m 2 . 2. k x ] = 0. kz] = kykz . and ma' Let H be applied in the direction 3. e1' dv VI) I e1'i (v 2 . e hk z = Pz · [kz. /i 2 [ [ky.= eE2 . x. ky] = kxky .O)H.
2.1 + ~1~2 ~l eT ml eT m2 eT ~2 m l eT m2 (!:J.= eE2 ... 0'0 ' ~= eTH . For infinite circular cylinder. we should apply transfonnation to have the direc tion of H not along axis 3. m l = m 2 = m.El • ml The effective conductivity in direction 1 is independent of magnetic field. 0'12 = 0'21 O'oTw l /(l + ~2).1 + ~1~2 m El + ~2 m E2 l l _ .A42 QUANTUM THEORY OF SOLIDS S( where ~l = eTH mlc' ~2 = eTH m 2c' ( i2 il) ne = .= eEl + v2 H. and E not along axes 1 and 2.W l eH =. C V3 m3 T v2 e = eE3' V3 = O. T VI T e C m. For J~ = J~ = 0. Let H be m. E2 = ~lEl' il ne (eT eT) = . m3 + along axis 3. VI) ( v2 = 1 + ~2 eTlm ( ~ 1 n(!:).. then the equations of motion are 00. me mc 0'11 = 0'22 = 1 + ~2 = 0'0 = ne 2T 1m.vlH. 1 + ~1~2 2 ne (eT ) m (1 + ~1~2)El l ne T = .=TWl. . In general. so the transverse magnetic resistance is zero.
c c m 3V3 e e = eExcos8 + vIHcos8siny C e 7" + . The conductor does not carry any current along the axis of the cylinder. HI = . z of ec 1 2 ( 3 8 1= (COS Ysin .v IHsin8. 7" v = eEx sin 8 cos y + eEy sin y . E I = Ex sin 8 cos y + E y sin y .' .. c c e e m~ = eEx sin 8 sin y + eEycos y + eEzcos 8 sin y 7" v . If H is perpendicular to axis 3. E3 = Ex cos 8 + E z sin 8. y. z).. 2 and 3.v3 H cos 8 sin y. '1.sin y sin 8 cos 8 sin y cosy ~OS8COSYl (Xl sm ycos8 y sin 8 o z be H3 = H sin 8.2.H cos 8 cos y. ..12..[DS SOLUTIONS: CHAPTER 12 A43 z . E2 = .eEz cos 8 cos Y + v2 H sin 8 .'. m 2.( I r . y. then the conduction property is independent of the field.v 2 H cos 8 cos y..v3Hcos8cosy . 2 y x FIG. X. H2 = H cos 8 sin y. . ...E z cos 8 cos y.Ex sin y sin 8 + E y cos y + E z cos 8 sin y. and do not coincide with 1.3) with respect to (x. . . In general...1.. The relative orientation of (1. C e V3= O.
sin 0 ( ~ cos y + sin y) cos y .O'yx < WIT. eT eT Ex sin 0 cos y + .1. z.EzcosOcosy. ( vx) Vy = Vz (Sin~COSY sm y cosOcosy sin y sinO cosy sin ycosO COSO) o (VI) V2 • sinO V3 eT/m Vx = ~(sin20Ex + ~sinOEy. 3. O'xy:::: . l+s eT/m Vy = 1 + ~2 ( ~ sinOEx + Ey + ~ cosOEz )' eT/m Vz = ~( cosO sinOEx .cos 0(cos y . As H increases.sinOcosOEz ).~ sin y cos O( ~ cos y + sin y) VI) = eT/m ( v2 1 + ~2 [~:J.WIT. sin O( cos y . O'yy:::: O'u' O'yz = . O'yz . sin 0 :::: 1.~ sin y) sin y + ~ cos y .~cosOEy + cos 20Ez)' 1 +s 0'0 0' = sin2 0 ~sinO ~sinO sinOcosO) ~cosO 1 + ~2 1 ~cosO .E y cos y m m eT eT . .HsinOv l + EzcosOsiny. me m V2 = . C} 2. me m eH Let WI = me' ~ = TW 1 sinO.O'zx .Ex sin 0 cos y + .~ sin y ) .A44 QUANTUM THEORY OF SOLIDS SO eT eT VI = . 0« 1. sinOcosO cos 0 2 o«1.l "'IT axis 3.E y sin y m m eT eT + HsinOv2 .
SOLUTIONS: CHAPTER 13 A45 CHAPTER 13 2. Consider p2 [UO(X)'Yk(X)] = p. a..2 + V )ub ) = 'oub).k r .2 + V} uo(xl'I'.kx . . 1. uo(X)'".2m \7 2UO p2 + uo(x) 'Yk(x) = EkUO(x)'Yk(X).f cp:(x')e 0 3.. < _ ik x . {[pUo(X)] 'Yk(X) + UO(X)P'Yk(X)} = [p 2UO (X)] 'Yk(X) + 2pu o(X) ·P'Yk(X) + UO (X)p2'Yk(X).kxd3 __ A CPk(X) = UO(X)'Yk(X)..Lcp/ elk).2 + V}'Pk(X) = 'k'Pk(X). c 1 _ LI(elk)1 c 2 = L(kle)(elk) c = ~Lfeik~c(X)d3x c .(x) = '. (.k = /IT e. 2m But.' d 3x' 11e .:~ . :~ . t/. { I· { :~ . /i2 ] 1 (X) 'Yk(X) + VUO(X)'Yk(X) + 2pu o(x) . P'Yk(x) 2m [ .eX .(x).DA· .
13...A46 QUANTUM THEORY OF SOLIDS So.Ek) 'I'N(X) = . c. 13. p2 UO{X) 'I'k{X) 2m + (EO  Ek)U O {X)'I'k{X) 1 = .puo(x)· p'l'N(X). m p2 ] 1 b. x ~ 0. 0 at 'l'N(X) =:. For sstate. ..... "'" o 0 x = FIG. Uo(X) Cel11 Cel12 I • U\ . 2m m uo(x) is the same in each unit cell. In the interior of the cell.. uo(x) [ + (EO . 13. Schematic illustration showing P'l'N(x) = 0 near the center of the cell. The continuity of the wavefunction at the cell boundary required puo(x) = 0 (Fig. p'l'N (x) ~ 0 (Fig..1 .puo{x)· p'l'k{X). X P'l'N(X)=O FIG.1. and pUo(x) the cell boundary..2. Schematic illustration showing uo(x) as a function of x... uo(x) is large at the center of the cell.2) [2 ~P 2 + ( '0  'N ) 1 i' N( x) = o.1). 13. 'I'N(x) is at an extremum.
a. (32). Dxy= ~ L' (yIPxI8)(8Ipyly) m 8 Ey .E8 D yx = ~ ".. 2m CHAPTER 14 3. where tz2k~ EN=EO+ ..J 8 E ... R(~) = (_~)..(YILzIY). b. 'YN{X} = eikN o r/lfi.. 2m . Dxy = R1Dxy . (ylpy I8)(8Ip Iy) m 2 i. 1 iDx. = .Dyx) = DXY =1= O.y = t(Dxy + Dyx) = O.. then R1Dxy = Dxy{Rr}.J x 8 Ey E8 '1T Let R be the rotation operator which rotates by 2 about iaxis. Without so interaction and from Eq.SOLUTIONS: CHAPTER 14 A47 'YN(x) can be described as free particle wavefunction. R1D = _1 ".E y 8  Dyx' From E(k) = LDapkak p and the energy is invariant under af3 the symmetry operation. n is the volume of the sample. (ylpyI8)(8Ip_ xly) xy m 2 i. = ~(Dxy . so Dxy= Dyx' D. D/.
and z/(r) for the band edge at k=O. for k y = 0.y ax (a a) ay/(r) gives an odd function of y. a a (rILzlr) = 0 because we integrate the product of odd func tions in space. On1 £k=[A(k. However. 4. + Ckx=A ( k x + 2A = )2 + Bk. the symmetry axis is in the idirection.. C 4A' 2 £k C2 + 4A Ak~2 + Bk.+k~)+Bk.A48 QUANTUM THEORY OF SOLIDS SOLUTIO Ir) can be one of x/(r). y/(r). 1/12 ) So. we transfonn ( ~) by the rotation matrix ther 5. ax f(r) gives an odd function of x. k~ = kx + 2A . D/y=O. C . For a state with spin parallel to the .axis is £k C Ak! + Bk. we can write the wavefunction as (~). the energy of the state with spin parallel to the .axis.](~ ~)+C(kx(Jykf'x) with iaxis as symmetry axis. II Lz i x ay . H lencj vale] 2' 2' 'T1' 'T1') D1/2(~ 2' H= The wavefunction with the iaxis as the symmetry axis is '" (Jy ( i/12 1/12 ) ( i/I2' ( 1/12 ) = i/12 .
2 A 2" [VIII(x  1 Xn) .VV(X . 4A x 4B Z 4A Ek d func On the energy surface.~ 2 [Vm (x . Xn is the lattice vector.xn 1') + Vv(x .xn)] I to the + 2" [Vm(x . H = .x n ) h = .x n 2 V v (x .h 2 2m V' 2 + L [ VIII (x n X 1 VIII (x n) +  2 X n l' ) .x n . while the valence V atom sites are at 1'.k x h ak x h x h x C ) + 2A 1 aEk 1 v = .V'2+ I)vIII(xX n)+ VV(xX n 1')]. then vx ' vx .x n . let the va 2m n h2 lence III atom sites be at the origin of the unit cell.= 2Bk Z h ak z h Z E k h2 h2 C2 = .axis as we can 4B Z .v2 + .xn 1')] + 1 .2 V v (x . msfonn 5.x n .Xn)] .v 2 +v2 =1 4A x . for example.V V (x . H= .4A' C2 h2 h2 .v2 .V'2 + 2m 2 1 L{ [Vm(x n 2 Xn) + VV(X . vZ ' vz are symmetric and (v) = o.1') 1 I I I + ) . = 1..SOLIDS SOLUTIONS: CHAPTER 14 A49 edge at J = ne(v) = h ne LV'kEk k 1 aE k 1 2A ( v ==(2Ak +C)=.V (x 2111  x n .1') .1')] } • .1') + V v (x .
1 1 VH = 2 [Vm(x Ji2 xn) Vv(x xn)]. L{V_(x n Xn) . z.CPpa(x .xn .T)}._'\72+ L{V+(X 2m n +V_(X Define VS VA = xn) V_(x xn T)}. L { V + (x n X n) + V + (x  Xn T) } .A50 QUANTUM THEORY OF SOLID. The corre sponding wave functions are 'lrpx = V2N 'lrpy = V2N + + + 1 L {cppx(x n xn) + cppx(x . and 1 'lrpa V2N L {CPpa(x n xn) . 2m Ji2 The representation f15 are the antibonding states. H= . where a x. y.T)}.xn .T)}. xn) + cpp/x .xn) + Vv(x . 1 L {cpp/x n 'lrpz = V2N 1 L {cppz(x n f 25' are the bonding states. Xn) + V+(XXnT) . xn) + cppz(x .xn .xn .x n)]. .T) }._'\72 + V S + VA.V_(x Xn T)}. Define V + = 2 [VJJI(x .
Ax . A+ (A_) = splitting between = 2~. A±= and f15 ±~. y. The transition rate is lV/i = h z.Ax .xn  d 3x is proportional to the strength of V _ . ~ n 'T" ) V _ (x 'T" ) }  X n 'T" ) cppAx . 27T 8( Eck Evk  nw )I Pcv1 2 where the dipole matrix IPcv l 2 is assumed to be constant. y z x ~ y z 0 0 0 e I~ 0 0 0 0 ~ 0 0 0 0 0 0 0 ~ 0 ~ 0 0 0 0 0 0 0 0 ~ 0 0 0 0 0 0 0 This can be reduced to three identical eigenvalue problems for x.xn) X + cp. (i'p~IVAIi'p+x) ::::: 2N N f[ cp.xn) + cppAx .xn)CPpx(x .xn) . ( A ~ ~) A = 0.Xn  'T")] x[v_(xx n ). The matrix of VA is: x a a'. z.IVAI'I'p+u) = 0.cp. =1= (i'pu.Xn .ID. CHAPTER 15 1. SOLUTIONS: CHAPTER 15 A51 ('I'p+uIVAI'I'p+u> ::::: 0 ::::: ('I'puIVAI'I'pu>.x( x = ~. f 25 .V_(xXn'T")] X [ cppAx 'T" )] d 3x : : : "2 f {cp.Ax 1 X xn)V_(x . .
Define the joint density of states v JcvdEcv= f dB 1 dEcv' IVkEcvl Using the foregoing expression of Ecv' for finite Ecv the righthand . The band structure near k I = O. S is the constant energy surface of Ecv' Near k!::: 0. Ecv is a minimum.  L 8( Eck c. + A3 k .1. + A2k..v L 8(Eck 1 dEcv Evk hu» = o 3 (2'lT) f dB f Iv kEcvl 8(Ecv  hu».v k Evk  hw) o = ( )3 2'lT f d 3 k c. The constant matrix element absorption coefficient is ex. A l .. FIG.Evk . A 2. 15. Ecv Ecv(O) + Alk. where Ecv = Eck .A52 f QUANTUM THEORY OF SOLIDS SOLU~ s fck 1 10 fYk k 2. and A3 are positive and can be expressed in terms of the effective mass at k = O.
h + P. V2 for Ecv > Ecv(O).V(lr _ 2m ell 2mel2mhU 2mh.l. mell+m hll 2 2 2 2 is R(X.r OF SOLIDS SOLUTIONS: CHAPTER 15 A53 side gives the volume of an ellipsoid.e + P.h V( r) ace of Ecv.l. Xe + mh.L Xh me. /lll 1 mh. J cv = d /2} d {4'1T 1 3 3 JA A A (Ecv . me. .l.Ru(x. +mhll' =+ mel1 m ell 1 1 =+. y.L e _ _ ( me.l. meliZ e + mhIlZh). + P.e 2me.l.Zh)· H = P. ' 1 righthand '" eik.Yh . • D 2 (2'1T) 1 ifAIA2 (hw A3 Ecv(O)) 2. . +mh.Ecv(O)) Ecv 1 2 3 1 1/2 2'1T J (Ecv .L 2mhll 2 2 2 2 __h_2_(_a_ + a ) _ h _a_ 2M.+mh. k.e + P.+mh.l.l.l. = mel.Z) r= Xe Xh = (Xe Xh' Ye .Yh' Ze ..l.l. +A3k. ~nns of the tes where M. ax 2 2 Mil az 2 2 2 h ( a2 a 2) h a2 .l.Ye + mh.Y.l.l. In uniaxial symmetry.l.Ecv(O)) AIA2 A 3 a . ax2 + ay2 2/l11 a32 V(r).2/l. mel.+ ~ + Ph. For dE cv ' we have J cv dEcv = d { 3 4'1T 1 J AIA2 A (Ecv 3 Ecv(O)) 3 /2} . 2meu 2mh.h + P.' mu= 1 /l. H ~ + Pel.
+ mhJ.xh meJ.Z) _ (meJ. In uniaxial symmetry. + mhJ. 1 1 h ( a2 2p.Xe + mhJ. 2. 1. . mel. =+ mel. 2mhJ.LIDS SOLUTIONS: CHAPrER 15 A53 side gives the volume of an ellipsoid. y. For df cv ' we have J cv df cv J cv 4'77' 1 d { . mell =+ 1 m hll land 1/1 = eik. = mel.2MII a 2)  cv ' "3 k . mellz e + mhIlZh).Y. A1A2 A 3 (fcv .V() r ( a2 2MJ. a n 2 (2'77') J 1 (hw A1A2 A 3 fcv(O)) . .fcv(O)) 1/2 .Ye + mhJ. .Ze Zh)' 2 H = Pxe 2 mel.YeYh. m ell + m hll r=xexh=(XeXh. 1 1 p.Ru(x. (fcv . ax 2 + 2 a 2) h a2 ay2 . .J.. h 2 + Pze ++ 2mell 2 Pxh 2m hJ. + 2 Phil 2mhll + 2 P hJ. H = 2mell + 2 Pel.fcv(O)) 3 A1A2A3 d {4'77' 1 df cv 3 JA 1A 2A 3 2'77' 1 i 3/2} .1I a V(r).  V(l r e _ R (X. +m hll . [the f where MJ.. V2 for fcv > fcJO). + mhJ. 2 mel. 2 + 2 ay 2 h a2 2p.mil = 1 m hJ. 3).Yh mel. 2 + Pzh 2mhll 2 .
V2+ 2 2 ( 2 .2Mol (k. l h2 2 h 2 h ( a2 a2 2Pol ax 2 + 112 a 2 2PII ) a .V{r) etk>Ru{r) } . } 2PII az2 = { E . ~v22po 2 h 2 3 2Y(~~ + ~ 2 2 ax 2 ay2 1 _a .2pol ax 2 + ay2 h2 h 2 a2 2 h } V{ r) \f.) + 2M k . e: 2 ). + ky) 2Mllk. Veol T f5. h2 ( a 2 a 2) { .2PII a3 2 2 2 a 2) h h ( a2 2pol ax 2 + .2PII (e ) a 2 =  e: Define v2 a2 +a 2+2' y az 1 PI! a2 a2 1 and + 3 Pol 2 1 1 1 3 PII . = Eeik>Ru{r). then consider 2 2 a 2) h ( a2 h a2 2Pol ax 2 + ay2 . z. eol ell' Po y= 1 eol ell Pol then T h h .2pol ax 2 + ay2 2PII 3. { 2Mol (k.+ k. 1 +  lIe) ol V 2 (e ) 2po 2 3 Pol 3 PII ell 2 2 h ( a2 a 2) h a2 . Let 3 = .A54 QUANTUM THEORY OF SOLIDS SO] H\f.
.) [ ~ 0) o [Ex Ey Ell I.2 x Y 3 e 4'1Ty:=. 3' Let x' =x/{e. V(r) 3.2 + .. E. o Ez then the potential energy V( r) = e</>. 3/~.l Ell 1/ x 2 y2 + + ( E.l ) Ell 32 e 2 Je.l .'\7</>. Assuming the hole is at the origin.l y/{e.l Ell/x + y2 + Z2 e EO/.l yEn e x2 E.az 2 ' o 2 Y = Y'/lo· .[DS SOLUTIONS: CHAPTER 15 A55 For the potential term. a 2</> a 2</> a 2</> a.l e E.l + 3 Ell Je.2 + y2 + Z2 Z ' = = _f!i V. 3· e2 eolx 2 + y2 + Z2 .a .l D=eE = o f. E . e..2 + a. Ho ='\72_.3 ~) 2 2 2 az =  2 2 ytz2(1 a 1 a a ) 3/l 2 ax 2 + 2 a y 2'.l a 2</> ax 2 ( + a 2</> ) ay2 y' +f a 2</> lla32 4'1Te8(x)8(y)8(3).l~ + e y2 f. '\7 • D </> E.. then the potential at the electron satisfies '\7 ·D=e.8(x') 8(y') 8(3'). 2/l0 tz2 e2 Eor H' = y tz2 ' 3 (~'\72.
/ . ao . . With H'. En = E l /n 2 . o Q The cj> part of 1/1 is invariant under H'. we have fourfold degeneracies. so U:2) (:. r o where a o is the effective Bohr radius.E l ..fiii (a o) 3/2 r 2aQ ( 2 ) a e. a slnOe ±~</>.A56 QUANTUM THEORY OF SOLIDS SO From Ho1/1 = E1/1.r e / 2a ( r ) . so there is no offdiagonal matrix element between 1/1200' 1/1210' to 1/121 + 1 and between 1/1211 and 1/1 21. o 3/2 . 4.fiii o /i 2E o o 1/121±1 1 (a ) sf.2) U:2)' = E'=O.E 1/4. we calculate the perturbed energy E' (lsIH'lls). 1/1200 = __ 1 4. E 1s Eg E . where Eg is the gap energy. The zero order energy for n = 1 and 2 states are E ls = Eg ./.I' Furthermore. (this is just the hydro genic Schrodinger equa tion). E2 = Eg. For n 2. '1"210 7 1'0 ' 1 ( a ) 3/2 e _ r/2aQ ( a r ) cos 0. E1 = l'oe4/2E~/i2. State Is is spherically symmetric. the spherical synlinetry of 1/1 200 is in .
r/ 2ao { z 2a~ r 2 2a or2   1 r z2 } + r3 ~2 e.r/ 2ao _r sinOe'4> = .r / 2ao _r sinOe'4> ao az . ao az ..r/ 2ao • z . 2 /1 2 2 a az 2 JLoa o =2E 1 • ( 211 1vr 3 2JLo = _ Y /1 2 2 (211I H '1211) 2 a 21211) JLo z ) 1 3/1 2 a2 !(_ 3 El 4 + ~E 20 Y4 E1 ( 2 ) 15 . E211 =Eg 4 El + 4 yE l ( 2 ) 15 = Eg El ( 4 1 15 Y . (21111211) = . sin3 0 e'4>. 2a o r (x + iy) e. The virial theorem gives T V/2.a22 { e. 2) .} = . (2sIH'12s) = o. 2JLo Consider (2111 a az 2 2 1 211). therefore t¥ 200 does not couple to Similar to lIs).SOLUTIONS: CHAPTER 15 A57 variant under H'.(x + 2 . so (2111 /1 2 vr 2 1211) = E 1/4. = Eg =  E 1 /4. E 2s t¥ 210 by H'./ 2ao { rcos 2 0 sin 0 2a o 2a o 1 20a~ } .} iy) e.a { e.
C yy ' cxy ' and eyX . 4) CHAPTER 16 1.e iwt .iwe m then y 2 W e lWe 2Ey+ .E + E m x mw y e e iwee e x. E21 1 Eg El ( 4 1 15 Y . Vy .1. The orbit in kspace and real space.mWeW W« We' x=E + . ze ie y= . In a magnetic field. mw W = . 16.x . e w2x = + iwwey. . m . then use Eq..w2y 2 W X e wx' E y . 2) E 210 = E g El ( 4 1 + 15 Y . the equations of motion for the electron are: e X= m e . eH We= me' y . The first step is to find cxx .A58 QUANTUM THEORY OF SOLIDE SO Similarly. (79) to find w.Ey+ WeVx' m Vx.WeVy.E mw~ x mWWe y' y r  ~kx FIG.
2 C k2:::::i~ W~W*2 • Consider the magnitude W*2 W 2  c2k2W~4' Wp W  Ck WeW */Wp' 2 ..2 W ) • f.Wp e xy WWe ie Y mWWe P y ine 2 Ex.E .2 W w ( x' C 2k 2 w2W2) P 2We 2 (C k2 . W 4 2 2 2 W W P « « W*2. 2 e = yy i4?T 0= W i' W W*2T W*2 = 4?Tn ope 2/m. C2k W 2 2 wp 2 We 2 2 • Wp f. mwwe eyx = WWe Ito the The current due to the electron motion along the open orbit is .WWe f. lop  nope 2 TE = oEy' m y e yx  WWe .WT  ~ WP W 42 0 WeW W 2 e' c 2k 2 WT::::: 1. mw~ x mWWe Y W exx = 2 We ' 2 P • 2 f. WWe c k 2 2 • w*2T =0 • WP f..IDE SOLUTIONS: CHAPTER 16 A59 Px ne 2 ine 2 nex= E .
III q k 2 2 e 1i . i~} .. p] = ili8p = [Ho + H'. Po] + [H'.. 8p].lwt Tr e.wt1lItll Ik) .)1. mvx = Px . tk Ek e .appx) : ' 2 to first order of Ax . = ili(k + qI8p(t)lk) a at (liw + ill)(k + qI8pe.( . e .iq· rep ( t )vx ) Tr( eiqre(po +6 p(t))( Px  ~Ax)) ~ = Tr( e2 iqr ( iq r e c )poAx ) ~ + Tr( e. ( P A e.FlW . me k E + Ek . 2 • lW k x E + k q liw . . (k+qlaplk)= Ek+q Ek (tk.k'k" L 2 e 1i2A "'k 2 tktk+q q~ x 1.Ax.II III _ (k+ql=Aqei. h = ( tk . Po + 8p] [Ho. Po] + [Ho. 2 2 where Eq is electric field.iqZ lk')(k'le8plk")(k"lpxl k ) k..tk+q)(k + ql x ( . me Tr( e iqz e8ppx) (kle. e Ax = A q eiqziwt • (}q) xeiwt = Tr( e.q·re8petwtp me 0 q x m ilip = [H.1i  me (~)Eq~ '" k{ g.Ek liw III .. ) + Tr ( .A60 QUANTUM THEORY OF SOLIDS SOl e 3.'(IIkxllk).Ek)(k + qI8plk).me lW e) '" k Eq~kX 2{ tk Ek+q .e)( AqeiqZiwt)pxlk) W  + (Ek+q .
2 mc w q (2'1T)3 h kq h k .LIDS SOLUTIONS: CHAPTER 16 2 A61 h + i'1T81 kqJL + h m 2m 9 Ek 2  hw ) tk Ek_q hw 2 h2 h q2 )} . [ ( kqJL+ h h '1T8 mc w k m 2m hw ) )] h2 h2q2 '1T8 ( m kqJL . Re{ Tr( e.( C) E'1T. and 9 is the principal value.JL2) [ 8 (h2 kqu + _q2 .( c ) E'1T2 .mc w ( is ld.fk 2 dkdJL d<p k 2(1 mc w (2'1T) 3 hw JL2) cos 2 <p )} 2 )Ik).2.iqZe8ppx)} 2 2 2 2 e h ( C ) EqLk. 2 2 . 2 h2 h ) { 8 ( m kqJL + 2 m q 2 .hw ) m 2m h2 8 ( m kqJL 2 h q2 )] 2m . Ax· where JL = cos 0.hw .hw 2 2 e h ( c ) Eq'1T3 2'1T fk 4 dk mc w (2'1T) 2 h kqJL m 2 h q2 2m hw h (1 .hw dJL q + m w )2] 2k h kq 2 2 e h 2'1T m 1 .{[1 k 4 dk q (2'1T)3 f h 2 kq .i'1T8 ( m kqJL + 2m .2m 2 e h2(c) 2'1T = E q.[1 q m w ( 2k + h kq e h 2'1T f k 4 d k m 1 { m w } =.
For kq» hw.q/2k I} = I. + ~/2k )] e 2'17' =A k 2 dk 2+ . .2  q )2 dJ. (2'17')3 1 4k q J (q X (".zn 1 + q/2k . _ 2 ~/2k 1 I p.  .2 C q (2'17')3 4k q J { (q k) .I{ Tr( e iqZ e8ppx)} = me Aq (2'17' )3 J k4 dk (1.Lcos «j>d«j> h (~)2l kq J.iqZe8ppx)} e h { = AqLk! ~ tk Ek+qEkhw me k _~ Ek  tk Ek .q  } hw . h q 2 e 2m'1T 3 n 3'17'ne 2m =E = E q4 kF 4mvFq q' qh 2 2 hkF= mvF· .L [ 1 + .. L 2k m [2_ 1 2 ~ = e A)3 C q ~Jk2dk (2" p.A62 =. QUANTUM THEORY OF SOLIDS s eh 2 2 ( C ) me w ) w 4'17' E'17'q (2'17')3 h3 q (m 2 lk kdk F 0 2 2 = e h (~)E '1T~( m2) ~ k~ 3 me w q (2'17')3 .I{ Tr( e....L2) e 2 h 2 2 2q/2k 2 2 XdJ..L 2(_ 2k r 2 e A C q 2'17' k ) k 2dkf 1 dJ.J. m h2 ..
e 2'11' k 2q } .eH.l1l) k2 ::::: 2m 2m R 1 .q) = w = :.4'11'.( k'2 k 2)::::: (k.IDS SOLUTIONS: CHAPTER 18 A 63 M For q/2k < 1.cG A e v eHv 5 X 10.f d k k 2 .1 X 10 19 g em/sec for the dimension of the zone in the [0001] direction... (34).. cG e Ge .L. / e2 2'11' 2 k 3 e 2n A . A. /:::::A . 3'1Tne 2 .4= A . me me 4mvFq 3'lTne 2 4'lTi 4'lTZ. for q/2k =1= 1.f k 2 dk { 2+2··2·c q (2'11')3 4k q 2 2 For q/2k > 1. k)] Eq. /:::::A .2k 111. and t ..6 X 10 /sec.2 [ 2 .10 X 10 3 X 4 X 10 5 3X .f k 2 dk { 2+2··c q (2'11')3 q 2k e 2'11' q 2k} .. 4vFQm 4vFqm (}q) x Oq CHAPTER 17 1. 7 CHAPTER 18 1. Eq. So. (30). F = C q(2'11')3 C q(2'11')3 3 c ne 2 ne 2 3'lTne 2 Aq + Aq + = oqEq. I ae k 2 h . Z= 2 '11' I:(2l+ 1)1Jl(k F ). mR . e( w.
EO = el/ iVlgo + 1 3. (88). 2 (Rm) Z 2. . dk dn/dk = L2(21 + l}R/7T. = PF dn dE I dn dk dk dE dn dk dE ). (86). From Eq.Ek)G"1 1:.'\:i Ek 1 + VkdGdk .(21 + I) /i 2k . G kd VkdGdd · = I:.A64 QUANTUM THEORY OF SOLIDS DOS of l/unit wave number Z 7T 2(21 + l)R/7T.Vdk(Gdd )*· '\:i  Gdk = (G kd )* 1 Ek . (~. E EO 1 lEI  E E V>o.. a. E1  EO ~  Vg ' 1_ 1 o ~ EO ( E = : E1 1 o el/vgo +1.. Ek mR) 2 = 7T 2 ~ (21 + I) = ( mR) /i k <kl~lk>. V<o. ( 2 ~ (21 + 1) . PF<kl~lk>./i 2k 6. dE/dk PF = /i 2k/m. 1E1 iVlgolnlE1_~0E_O 1 = o. Fy(e) = f dE ~y(~ go lo d E E E1 = goln . el/ Vgo = 1 + Vgoln ~ l EI = 0. ~ . From Eq.
_1_ _ ~(L)"1d3k. P'ir. {e ikr(l + 2ika) 2zkr i7lo e 1 e ikr } = . .Eo)2 + d 2 CHAPTER 19 1.i'lT8( ~ . eikrp.Ek 1 dk + . Pfree= d ( '17' 2'17' 1( 1 )3 fd k {'17'8(~ 3 a Ek)+'lTa~[8(~Ek)] X IVdkI2(~ (~= Eo)} + d2 pg(~) + dpg IVdk12( ~  Eo) ' aEk (~.)1 1 1 1 sin kr kr' CPs  kr sin kr + _e a. . 1 1 = 2" ikr (eikrp.tkr r = .Ek)' ) (~ = . h. 1 Ek ~_ 1 Ek  ~ + i8 1 1 9i' ~ _ Ek . + _e ikr e ikz = eikrcos() a r' . ~ fdn eikrcos(} ~2'lTfl 4'17' 4'17' 1 dp.IDS SOLUTIONS: CHAPTER 19 A65 Gdd = ~ Eo ..a~ ~ .Ek)2 ~  Eo + id .F(G~). sin (kr + '110) et'llo kr kr 2i ~(eikr+i7l(l _ eikri7lo). 1 IV l2 (~ .id G kk o 1 ~ .. cP = e tkz .
= k X [SIX k] = Sl. (20) and (21). k k' K. (1).(k· Sl )ka] [St (k .p = I: (SrBapSf) a. for swave 4.p I: (Bap .rn(r) d3rr Ei+EjllfeiK. (k" IH'lik) d 2(J f eik"r ~ bn(r)e ik ·r dar dEdf/. Sl)k. e i2TJO = 1 + 2ika. a = Ikbl« 1.p I: (itaSr)(kPSf) (l. Sl )ka] } a a = I: {StSt .tTJo )/2i _ c etTJosin'n k '0  1 From Eqs. n(r) = const.St(k· Sl)ka.A66 QUANTUM THEORY OF SOLIDS S4 Identify the coefficient of e ikr.Ei + Ej l b 2 8(hw if ei(k'k)..r d 3r B(K).(k.kakP)SrSf. eiTJob. For elastic scattering k' = k. = b2 8( hw . This means that particle with .(k· Sl)itast + (it· Sl)~(lka} a = a. 710 = kb. Pl. f e iK . From Eq.rn(r)d3rJ". d (J dEdO 2 k k' ( 2'1T M)2 \(k'f IH'lik) \2 B( hw Ei + Ef)· H'=n(r)b~. a = 2ik (e' 1 _ 1 2 TJo 1) = keJTJo( e tTJo 1  _ e. I: P1P1 = I: { [St . 5.
T.SOLUTIONS: CHAPTER 20 A67 incident momentum k is scattered only to momentum k. No scattering.  . u( t) 1 u(O) + vt. 10 eX . For free atom.. (u(t) [u(O).J Cs q q  1 .1 k~T2 V 271'2 h2 c.. t ~ ) iht M' . for T» e.4 71' V Cs (271')3 i 0 qm 1 1 q dq .U(0»2) T + [u(O). vt] ~ [ u(O). V i 8/ T 0 xdx 1 + xI k~T2(e) T' (271')2 hc. where Qcelt t V/N. J(E) 1 Qceu27T2 3 M = (k~e) h2 c. u(t)]}. CHAPTER 20 1 K2 h ( 1/2 + n s ) L . *K2(U 2) .:E 3 3 MN q csq dent contribution comes from n s . r 4 foo 00 dtei(EE o )" r ltl Q "2 (t). The temperature depen 1 " ns i. .::hwq 2 efJ 1 q ~ _V __ k~_T_2 (8/T_X_dx_ Cs 271'2 h 2c. u( t)] U(0»2)T=(V 2)Tt 2. r = o.. Q(t)= 2"K2{ (u(t) . u(O) + vt] ~ [u(O). ~ [u(O).K 2( U 2) = . the proportionality constant is K2 h 2.
. 2i 2 2 ..VK2(V 2)T' Let energy of the 'Yray be 10. t) = .Ie imx /2h 2i tl k 0 F h2t( mx)2 .__ _ L h2t X {f V (ii2t 2..2 t k  e.. (hit ( mx) k..k.A68 QUANTUM THEORY OF SOLIDS Q(t) = 1 { 2K2 (V 2)Tt 2 + M iht} .i sin k 2 ) dk . h 7' 10.ik2 dk} (hit mx 2i .Ieimx2/2h2tv h2i X {1o V2.1 eV.15 sec. then VK2(V 2)T 10.I 2i 10kFeikxe. t> O.27 X 1015 _10. 2/2h 2 t ~nn ___ L h 2t X {foV 2.. (hit ( mx) k r h't (cos k 2 .i(h2) 2mk2 t dk.i 2m k2 dk h..7 erg. [2rn . lz2te. G(x.T(v2)rt2. ""e.1• Width = CHAPTER 21 1..ik2 dk + foV 2.ik ' dk} 2 l' e.mx .2 t kF  mx h 2t 2 i e..mx ..12 erg .2 ei 2m h t d'k = .h't e.Ieimx2/2h2tf_ mx Ih e .ik ' h. 2/2"2t~nn . t I(E)  r foo 4 00 dtei(EEo)" ihK2 K2 2M t..2 t dk + 10 V0. hK2 Energy shift = 2M' The line width is in Gaussian fonn .. (hit ( F mx ) h.
. G(X.( V :2~1 (k + h~I)) p +i8 2Itl ( ~ (~ 212m mx k+ )) F h21tl h21tl .:. ~ t:fj21tl (k + mx 2m ) __ {( 2m F Jj21tl h21tl )0 ik2dk e .2Itl L 2 1.LIDS SOLUTIONS: CHAPTER 21 A69 . jn2t mx 2 + fa V2.1.{'iT (. 2i fak Feikxe i("2) It I) = ..2Itlv Wi (i1ItImx e ik2 dk} x{ ~ C. (2m X{~C. 2 2 k i . h 2 t .(ftI(kp.y {'iT 1 ( .f2Tn = ..fa V?. fn2IiI Y "2 C V~ mx) .:)) i Ghen ~ 8 1 (. F mx)) h t 2 .i sin k 2) dk} = .Leimx2/2.L 2mk2 It I dk 2· . Jj t( cos k 2 .{'iT (_fn2t mx)} + Y"2 C1 V2.fn2t mx) ..2ty """i(ii rm 2i .2Itl( mx)2 1... fiT fn2IiI mx )} "2 8 ( V ~ h21tl 1 . h2Iti 2i .Leimx2/2.k+ = ... h 2 t .V fn2t(k _ Y"2 2. C1 and 8 1 are Fresnel integrals._e.i y "2 8 1 V2.lmx /2" It I ( Fe 2m ....21tl dk L )0 = __ eimx2/2.
xt) = .. [V! VVp .. xt).Vx)G(x't'.. mz jap(x't'..x mz t' . x'.xt). t» = Tr(jap(xt») en = . [v!(x't')VxVp(xt) .xt)..V!(x't') )Vp(xt) IVo> . (j(x.xt) = Gaa(x't'. jap = .xt) = Gpp(x't'.2 lim Tr{ (V x' m x'+x t' + t V x)GaP(x't'...(Vx. (+i) lim (V x ' 2mz x'+x t' + t en Vx)Gap(x't'. xt) } = .(VV!)Vp]. t en en en x (Volv!(x't') V xVp(xt) .v!(x't'»)Vp(xt)] 2mz Oap(xt») = lim 2 . .( V x.2 .lim (V x ' .A70 QUANTUM THEORY OF SOLIDS 2. m x'+x t' +t en G(x't'.
189 energy.. G. 148.IDS Index » Abelian group. 183. 179 Abragam.. J. 58. 294 Alloys.. 117 hole. P. heat capacity. 173... F. W. 344.. N.J.414 equationofthemotion method. V. G. C. 296 Bloch.. H. H.. 116 Anderson. 163....200 theorem. 62 temperature dependence of sublattice magnetization. 293 Atomic polyhedra. 207. 57 Basis vectors. 368 Born.. P.. 23 Bouckaert. 160. E. 53 Acoustic phonons. 351. I. 194 Bodycentered cubic lattice. 37 Boson gas. 254 Aluminum. fermi gas. J. 151 Bohm. 23. 262 fermi surface. 339. 282 Anomalous skin effect. 21 Adams.. 26. 346 Blatt.. magnetic field effects. 116 Abrikosov... 397 Bethe. 57 Allowed transitions. 249 Bardeen. graphical.. 256 Bands.353 Annihilation.. 12. electron. A. 315 Bar'yakhtar.151. 211 Bogoliubov. 308.296. 233. V.360. B. 126 Bloch.130. 59. N. 193. 315 Band edge.. 286 Acoustic attenuation. 388 Abrahams.. 179 Blount. 328 Born approximation. 251 Attenuation. Brillouin zone. 179. 164 spinanalog method. M.. P. 62. 397 Absorption. 252 Blandin. 313 Antiferromagnet. 157 BCS operators. 193 Aigrain. I. 324 functions. 326 Boltzmann equation. 333 Austin. A. 268 Band structure. 61 Antiferromagnetic magnons. 1 Baym. 206 Bound electron pairs.. degenerate.. linear lattice. E. optical. 260 Analysis. M. 326 Acoustic magnon. 172. A. J.365 Blatt. 397 BCS equation. 234 Argyres. 153 11 . 150.. 57 Bloch equation. A. 58 Aperiodic open orbits. 190 Acceptor states. A. N.. 262 Azbel. 294 Acceleration theorems. 157. E. M. 338 Almostfree electron approximation. F. 29. 178 Beliaev. A. L. 49 Bloch.. 117 Anomalous magnetic moment. 313. 321 Akhiezer.
L. H. 130. 238 Closed orbits.. 99 momentum. 100 groundstate. 170 Cyclotron frequency. 262 Brown. 299 Copper. 306 Curie point. 99 function. 15 Cuprous oxide. 115 Collision drag. 208 Clogston. 151 Casella. H. 236 resonance. 93 Coulomb interaction.. C. C. 111 . R. 366 Current density operator. 379.. 284 Cadmium sulfide. 189 Degenerate k • p perturbation theory 188 de Gennes. 211 facecentered cubic lattice. A. fermi surfaces. 115. K..380 Crystal. 126 Construction. 115 Creation. 4 Density correlation function. R.. P. 299 Cerenkov threshold. 204 Completeness relation. 217. Landau. 284 Conductivity. G.. 129 twoelectron. g values. H. 117 screened. 177 Coordinates. 232. B.. 396 Brueckner. F.. 370 fluctuations. 229 Brillouin zone. 136 Chambers. 305 Cadmium mercury telluride.. J. 253 Bowers. 238 Correlation energy. R. 240 Conjugation. 220 223. 173 Coherent scattering. 305 Callaway. 124. 300. N. 249. A. C. 150 Cooper pairs. M. 226.371 Brooks. 388 de Faget. 100.. M. effective. 100 technique. R. K. 370 pair. 126 Constant. 30 Delta function representation. 94 Coulomb energy. 199 bodycentered cubic lattice. 272 Conduction electrons. dielectric.. 184 INDEX Connected graph. C. 141. 24.. M" 26 Cohen. 94. 346 Deformation potential. electron. 366 de Haasvan Alphen effect. 333 Coherence effects. 148.. 217. 142 Brownian motion. 255.418. 202 simple cubic lattice. 261 de Launay. 174 length. 374 Breakthrough. 32 DebyeWaller factor. 53. 351. 337 Degenerate bands. B. 215. 73 Damping. 117 hole. N. 320. 359 Closed fermi surfaces. scattering.. 262. 305 Centerofmass coordinates. centerofmass. E. 162 Cross sections. 229. 279 Damon. 25 Deaton. 335 Debye temperature. 141 Button. magnetic. 331 Compatibility relations. 276 Canonical transformation. 128 tensor. 235. 259 Cooper. 218.12 Boundary condition. 92... 229 Cohen.. 117 Critical magnetic field. 249 Brown. 417 Budd. J. 302. 257 Harrison. 315 semiconductors. 257 Brockhouse. 368 density. 153.. 234 effective mass. 293. 54. 246 Classical skin depth. 308 Classification of plane wave states. 213 hexagonal closepacked structure. 267..423 Brueckner method. 254. 371 Bragg condition. D. J. 214 linear lattice. WignerSeitz. 227 metals. 246 Burnham. electron. 104 Dangerous diagrams. 205 simple square lattice. 312 sum rule. 134. 203. 373 Cohesive energy.
DEX INDEX 13 Electrical resistivity. electron gas. B. ll7 Diamagnetic susceptibility. L. 306 Diagrams. 93 ion hamiltonian. 324. 298 transverse..277. 329 Dingle. metals. 319 constant. neutron. 360. ll5 correlation. cyclotron resonance. 249. F. virtual phonons. 301. 144 operators. 92. 13. 345 Electric field. 18 Electric dipole transitions. G. 79 momentum. 286 Doppler shift. 336 Effective conductivity. 216. 105 transverse. 164 Equations of motion. 234 External lines. 117 creation.99 electron interaction.278. 61 Equationofthemotion methodBCS equation. 283 Elastic line. metals. lagrangian. 186.. 306 longitudinal.. 208 Energyband data. 115 gas. 19 operator. semiconductor crystals. 149. 232. 225 Diamond. 84 orbits. 107 screening. 25 Goldstone. 8. ll8. 326 Eddy current equation. 110 Divalent metals. 239 Dynamic structure factor. 169 Electron annihilation. 319 ThomasFermi.241 Electrodynamics. 268. 312 Effective mass. J. 294 Dirty superconductors. 124. 30 Direct optical transitions.399 Dysonian line shape. cohesive. 324 response.100 exchange. 273 structure. 99 coulomb. 103. 54. W. 124 7 Density correlation function. 116 response analysis.. J. superconductors. J. 142 Elliott. 101 matrix operator. current. 294 Frenkel. V. 365 Donor states. 308 superconductors. 364 Excited states. 234 zeropoint. 170 Dexter. III Diffraction. 94. 303 Empty lattice.318 Drift velocity. 269. pair. R. 73 Exchange energy. 126. 298 ionic crystals. spheroidal. 302 y . 126 surfaces. dangerous. 126 exchange integral. 417 selfenergy.. E. 161 shift. J. 117 crystal. ham iltonian. Landau. 167 Excitons. 319 Double group. D. 258 phonon interaction. 33. 230.. R.. E.215. 19 matrix. 323 Dzyaloshinsky. oneparticle. 215.. 18 Eshbach. 86. 308 Effective carrier charge. 91 Exchange interaction.. 67 HartreeFock. 91 perturbation theory. 274. 238. 303 Extended orbits. 183 Dispersion relations. 268 Energy.273. 130 metals. 303 Mott. 67 gap parameter a. 271 Energy bands. 107. 212 Dielectric anomaly. 227 mass tensor. 405 Distribution function. 292 mass. 225 Diamagnetism. 151 electron lifetime. 242 Donath. indirect. 339 Dyson chronological operator. 397 Easterling. 190 hall. 24 Diffusion vector. 185. 129 Dyson. 216 Dresselhaus.89 Exchange intE?gral. 110.
213 Factor group splitting. 235. 249 Hamiltonian. H.. F. R. Brillouin zone.. A. 298 Frequency. V. M.250. 124.1 Feynman. 273. 293 Harrison. 89 Heat capacity. 306 Ground state. boson. sum rule.. 262 Herzfeld. U. 142 Henshaw. R. R. W.. 238 construction. density. 343 fsum rule. D. 36. 224 Fermion fields. 319 Hall. 346.. 113. 241 Ham. K. P. fermion. 262. E. 334 Germanium.55 Heine.. V. 333 Harrison.64 Fletcher. M. M. R. 232 stationary sections... 129. 128. 218.397.. connected. 153 surface. 127. F. 111 Form factor. 187. 128 Ferromagnetic resonance. 249 aluminum. 360. 74 Harman. 73 Fluctuations. 222. 234. 424 Graphical analysis. 365 Friedel. 126 linked. r 38 ] ] ] ] 1 1 1 1 . 267 Helicon modes. V. 258.. 201 Gurevich. E. 218.. 164. 23 Gauge invariance.. 172 Gavenda. T.. 19 variables. 155 Group. 116. 415 Grey tin. 84 Ferrell. 105.. 421. 423 Generalized OPW method. R. J. 264. L. 397 perturbation expansion. W.. 33 Herman. 305 Ginzburg. 149. 321 Hellwarth. 401 Frauenfelder.. S. 410 HartreeFock exchange energy. 200. C. 27. P. 259 Hartree approximation. 421 Fourier lattice series..142 Feynman relation. 33 Feynman's theorem. 62 magnon. 333 {I values. magnetic field.296 Hall electric field. III. 303 Falicov. H. 277 Gross. antiferromagnet. 410 HartreeFock approximation. L. R.. superconducting. 30 plasma. 213 Glover. 80. 2:~6 distribution. conduction electrons. 274 Herring. phonons. A. 257 open. 220 Free electron. magnetic. A. 215 Fano. 215. P. 339. 411 Graph. 341. C... 75. L. 388 Frederikse.265... 284 Haering. 75 quasiparticles. 392 Glide plane. G·! magnon. 117 Gorkov. 173 Glauber. 126... L. 216 theory. double. 172 transformation. 128 Gold. 38. 199 wavevector. 260 closed. 301 Galitskii. E. 86. cyclotron. bound electron pairs. 186. F. 57. 109 Field. 105 Friedel. F. 2 transforms. 335 GellMann. 254 Goldstone diagrams. R. 290 magnonphonon.. 3 series.335 Harrison construction. P. 86.141. 255. 82.333.14 Facecentered cubic lattice. 323 scattering. 262.. J. 284 Harmonic oscillator.. 125 ring. 381 Forward scattering. 254 INDEX Geometrical resonances. 88. V. HolsteinPrimakoff. 44 Fermi. 217 Frenkel exciton. J. 397 Gas. 75 quantization. 276. 112 Fermi gas. 198. J. 253. 260.. V. G. magnetic field. 116 Green's functions. R. 26.
12H Keffer. 1 Indirect optical transitions. 406 Kramers operator. 18 Landau. 113. 124. 339 Lax.. 364 Lattice. 27:3.. 141 Longitudinal excitons. 23 Indium antimonide. 84 orbits. E.. 200 Linear lattice. coulomb. empty. excitons. 1. 273.. 305. 16 240 Length.. A. 215 Kubo. 320 Ionic crystals. L. 40 Hutson. 1. 277. 37... 225 gauge. 58 Kuhn. 329 Hopfield. 142 transitions. 27. . 295 Lattice displacement operator. 117 operators. 54. dysonian.. 130 Lee.. 297 Impedance. 305 Interaction. S. 318 Impurity states. D. 68 Kahn.. 172 Longitudinal attenuation phonon. 221. 183. T. 353 Kip.64 Holstein. 104 diamagnetism. R. 49. G. 237 JeIIium. A. S. 112 Lifetime. 320. 113 Low. 336 Huang. C. 200. 117 Lax.. 278 KramersKronig relation. 309. electronelectron. H. thermodynamics. L. 216. W. 289. 283 Lattice series. 277 helium. F. 255.. 150 screening.. 134 Lead.. 192. 304. 323 Jones. ] 24 Linked graphs.. Lehmann representation.. 375 Laue theorem. D. 290 Iddings. fourier... A. 214 field limit.54 Legendy. 3 Ineffectiveness concept. 286 Langer. 273. J. R. 0. 379 Lifshitz. 30 Kaner. 216 deformation potential. 44. W. 232. 306 Irreversible processes. D. F. 241 Hole annihilation. M.237. 389 Kane.. 83 Koster. L. 258 HolsteinPrimakoff transformation.256 Brillouin zone. B. 202 Kadanoff. 351 Kothari. 208 reciprocal.. 255 electronphonon. S. 315.. 97. 2]7 levels.. 186. L. M. :~26 Kleinman. 3:36 Koopman's theorem. band structure. 230. 293. 173 Landau damping. 141. 303 I{ohn.. K. 33... magneto resistance.. 57. 141 magnon. T. scattering. G. P. 250 15 Lagrangian equations of motion. 114 Incoherent neutron scattering. 371 Isotope effect. 298. 53. 318 London equation. A. E. 141 . 54 Localized magnetic states. 296. E. 142 Line shape. 360. 130. 117 creation. 404 Leibfried. F. H. 286. R. second sound. surface. Brillouin zone. M.INDEX Hexagonal closepacked structure. p perturbation theory. 373 Indirect exchange interaction. Longitudinal optical phonons.. 169. 216 33G. 27G Knox. R. 115 James. F. 371 k . 228. 137 Loudon. 397 Linked cluster theorem. R. 220 H. 348 Kohn effect. 125 Kaganov. J. C. T.. 306.. 282 Kramers theorem... 278. 311 Inelastic neutron scattering.. J. 315 Langenberg.):15 structure factor. 284. 58.
101 timeordering. D. 51 statistical. 232 Openorbit resonance. 143 Migdal. 347 Optical transitions. 169 Metallic sodium. 97 Neutron diffraction. critical. 293. 163 Morse. 56 zeropoint sublattice. A. 162 electron dynamics. crystal. 320 Magnetoresistance..397 Oneparticle density matrix. H. 261 MontroU. 307 Magnetostatic modes. 115 Metals. 213J Mitchell. density matrix. J. 38. P. E. 47. 315. A. 62 Nettel. 72 Magnons. 74 Magnon theory. 58 Nakamura. 237 high field limit. L.. macroscopic.. 298 Nagamiya. 53 antiferromagnetic. W.. 223 electromagnetic field. 84 hole. 197. 15 density. 128. C. 379 Magnetization. 37 theorem. 308 electronion hamiltonian. 371 Mass. PI Pl Pl Pl Pi Pi . 262 N eel temperature. 296 Magnetoplasma propagation. 132 Normal product form. Pi P: Pi Pi Pi P. 116 Meissner effect. 174 Matthias.. 34. 184 Monster... 59 Magnonmagnon scattering. 282 Magnetic permeability. 386 Mott exciton. 256 model. 54 optical. 381 Magnetic moment. 48. 64 heat capacity. P. 366 Mattis. 397 Miller. 339 Mean free path. 53 Normal process. 19 representation. R. 30 Moore.49 acoustical. inelastic.. 217 hamiltonian. 48. 318. attenuation. 140 Matrix element. B. direct. 50. 229 Magnetic field. 351. 78 Nozieres. 8 electron. 71 Magnonphonon hamiltonian.. 41 Macroscopic magnon theory. 72 Momentum.. 144 INDEX n C C 0 Metals. 24. 58 Nearly free electrons. anomalous. 61 Magnetoabsorption. P. R. 217 free electron. magnetostatic. electronphonon interaction. 58 field variables. 289 Modes. J. 294 indirect. 225. 24. 55 interactions..53 variables. electrodynamics. 114. 371 Marshall. T. B. R. oscillatory. 294 magnons. P. 333 Magnetic form factor. P. 318 Morel. 323 Magnetic scattering of neutrons. 284. M. D..53 phonons.I6 Luttinger. 237. 63 Magnetic breakthrough. 365 Mattuck.. 84 lattice displacement. 95 spin. 31 Mossbauer effect. 336 Lyddane. 107.. 241 Magnetostark effect. 228 Open fermi surface. 335 Operators. 46 reversal. 368 scattering. 255.. 63 March. H. S. M. polaron effective. 79 dyson chronological. 229 Magnetic field effects.. 142 velocity of sound. T. 8 Optical absorption. 295 0 0 0 0 10 p.. 23 particle density fluctuation.. 101 Onsager. 319 Mirror planes. T. 24 Miller. 290 orbits.
278 Quinn. 12. 6 timeindependent. P. 382 umklapp. 276 Rare earth metals.. 19 orbits. 132 Paramagnetic scattering. 322. 346 optical. Cooper.NDEx' INDEX 17 >n. 141. 293 Oscillatory magnetoabsorption. 345 Photon absorption. atomic. 233. 258 extended. 105 Plasmons. 335 Parallel pumping. 258 magnetic field. A. 229 open. 1 Recoilless emission. 149 tensor. 34. specular. J. 201 longitudinal optical.. 311. 310 distribution function. 84 electron gas. classification of. R. A.. 107. 208 Plasma frequency. 110 Primitive basic vectors.. M. 187 Quantum equations. 228 tions. 69 Process.. L. free. 137 Residual resistivity. 34. 133 cloud. 147 Particle density fluctuation operator. 296 Overhauser. parallel. 229 electron. 234 quantization. small. 135 frequency distribution. G. electrical. 97 ~7 Pincus. 249 electronelectron interaction. I. 234 Perturbation expansion. 140 Polyhedra. 139 effective mass.. 397 Pippard. 273. 229. 250 . 230. 244.. 188 Quasiparticles. 216 Reciprocal lattice. J. 30 ~presentation. J. 153 Privorotskii. 228 Orthogonalized plane wave. 263 Oscillations. 230. normal. 372 Pekar. 361. 133 Parameter ~. phonon. 113 Peschanskii. 102. degenerate. 244. 112. A. 93 Potential. 175 varying. aperiodic open. 164 Orbits. 333 Plane wave states. 386 acoustic. 232. 255.142 OPW method. fermion. 232. 232. 234 hole. 37 Resistivity.238. 294 residual. 245. W. 233. 130. 134 Reitz. P. harmonic. energygap. 311 Piezoelectric semiconductor. summary. 161 Proton. J. 225. 128.. 105 dispersion relation. 24. 5 Quasimomentum. 209 amplification. 1 Pairs. 36 Platzman. 15 k· p. 335 Phillips. V. B. 129 Poynting vector. 23 Reflection. Green's func Quantization. p. 417 k . 254 Orbach. 251 WignerSeitz. 151 Relaxation time. 36. 104. 114.. 233. field.. 21 Reduced zone scheme. 116 Pair correlation function. 234 closed. 232. 142 Polarization. 34 Polaron. 247 periodic open. 313 cloud. 186. 141 Pumping. 173. 230. S. screened. 169.. C. 220. 196 theory. 312. 116 timedependent. 102. 69 Periodic open orbits. 37 Oscillator. 47 Pines... 346 surface. 9 Raman processes. D. 95 Pseudopotential. 263 generalized. 28 Random phase approximation. 365 Phonons. 336 boson gas. R. 415 Quantized flux. 16 waves. 241 Pincherle.
314 Reversal. W. 234 Spinanalog methodBCS equation. dynamic. 167 Superfiuidity. R. F. coherent. V. D. 41 Sanders.. cyclotron. 258 Roth.. 366 Sum rule conductivity. 284 splitting. C. 228 Strong coupling limit. 150. 113 approximation. ground state. 118 charge density. 283 Ruderman. 115. 262 Shinozaki. Brillouin zones. M.. H. 334 openorbit.. 301 Friedel. 279 Square lattice. F. 110. 115 Sondheimer.. R. 149 INDEX IN! Semiconductors. J. T. 305 Roth relation. R. T. C. H. 360 8 spheres. 371 magnonmagnon. 115 Screened potential. 114 dielectric.. magnetization. 33. Y.18 Resonance. 27 length. 314 Sound. S. 205 Simple square lattice. 129 Suhl. 366 Rodriguez.. 411 Superconductors. Th Ti~ f Tir Tir Tir (J s Tit Tol Tn g Trf Tn . 257 Singwi. 215. 206 Sodium. 375 inelastic neutron. 101 Semiconductors. A. 220 Shull. 351 Small representation. fermi surface.. 320 Rosenstock. 424 Rocher. Brillouin zone. 143 Space inversion. 224 Statistical operator. 308 Skin effect. 130. S. 351. 186.. 226. crystals. 271 cyclotron resonance. dielectric.. 379 paramagnetic. D. 104 Scattering. 111 length.. K. 373 inelastic lattice. 383 forward. 371 Silicon. electrodynamics of. L. 56 Rigid band theorem. 192 Shoenberg.. 203 Stationary sections. spin resonance in. 421. 271 Spin resonance. 28 liquid helium. Trl Tn "\ TSl Tu U U Un Va V . D... 279 piezoelectric. 382 Schrieffer. 268 crystals. 155 Superconductivity. 71 of neutrons. 335 Response. 198. 373 cross section. 275 Simple cubic lattice. 128 1.33. 234. H. 279. 380 ferromagnetic. 116 Reuter.. M. G. 177 Structure factor. 148.. Th. 112. 250. 26 Sm r Sm Tel Tel 1 t Tel Tel Th. 157 Spin operator. 341. 234 geometrical. E. H. magnetic. 298. 217.. P. 169 excited states. 371 Skin depth.. classical. A.. 56 Shirkov. 181.. 129. Th Th. K. 251 Sachs. 31 Rosettes.. 343 Superconducting. 172 Schultz. 279 Sham.. 103 method. 313 Spheroidal energy surfaces. 30 Seitz. G. 183 Specular reflection. metals. 344 Ring graphs. 151. 323 in semiconductors. anomalous. 51 Spinorbit coupling. 317 Rose. 201 Smoluchowski. velocity of. J. 112 Second sound. 151 Shockley. 266 Selfconsistent field. 129 liquid. E. Brillouin zone. 421 incoherent. 196. 313 Slater.. L. 308. 250.. 336 Sawada. 141 Screened coulomb potential. S. 116 Screening. J. 101 Stokes theorem. energyband data. metallic.
J.DEX INDEX I9 Van Kranendonk.. 286 Ward. 371 Wurtzite. B... S.371 . 268 Thermal averages.. antiferromagnet.ordering operators. 351 theorem.. 294 Virtual phonons. E.305 Surface impedance. 30 Wilson.. H. 163 vertical. 30 Watanabe.. J. E. G. 30fJ. 362 Vector representation. rt. R. H. Jr.. 214 operator. J. 32 Neel.. S.. 240 Thomas. 282 symmetry. 136 Tight binding approximation. G. relaxation.362 Yttrium iron garnet. 112. 58.. 56 Zeropoint energy. 149 Von der Lage. A. 143 Vertical transition.. K. 197 functions.y.. 225 Teller. 407 Thermodynamics. 302 indirect. 178 Umklapp process. D.. 53 Wavevector. 57 Van Vleck. 99 WignerSeitz boundary condition. 294 electric dipole. 206. M" 128.. 271 oxide. 194 Wannier effective wave <'quntion. 237 Zinc blende. 303 wave attenuation. C. 271. allowed. 8 Time reversal invariance.. 252 Vosko. diamagnetic. 292 functions. H. 336 Wick chronological operator. 284 Yosida. 270 Time. 267 method. 57. J. 62 Tetrahedral bonding orbitals. 360. 133 Unlinked part. E. Cerenkov. 110. 246 Transverse dielectric constant. D. 294 direct. ] 05 Threshold. 304 Zwerdling. 113 WolIan. 305 Yafet. 114. 27fJ equation. 324 excitons. 356 Transitions. 250 polyhedra. electronelectron interaction. 124 U operator. group of. 58. A.369. T. dielectric constant. 61 sublattice magnetization. ~84 !24 f. metals.. G. 306 ThomasFermi. 298. 266 Wigner limit. 61 Ziman. 148.. canonical. 207. Debye. 31. M. 250. L. 297 temperature. 0. 336 Weinstock. 163 Temperature dependence of sublattice magnetization. 135 Time. 315 resistivity. 305.. E. 270. 182 Tinkham. H. 151 gauge. 41 Temperature. J.. 195. 162. 237 Wolff. 379 White. 162. 253. R. 201 Weinreich.. 48. A" 351 Woll. 0. G... F. 8. 399 Wigner. 93 Wilks. 360.371 Woodruff.. V. Valenceband edge. 68 Tunneling. Y. J. 294 Transport equation. P. 172 Transition element impurities.. 311 Susceptibilit. 186 Velocity of sound.. H. 62 transition. 348 Walker. 332 Tsukernik. C. 296 Landau. 73 Wannier. 119 es.. 151 Transformation. 289. 304. 151 Tolmachev. irreversible proc esses. 250. L. 284 Van Hove.. 296. 249 Woods.
The second part considers Fermi surfaces and electron wave functions. The third part applies correla tion functions to timedependent effects in solids. and magnon fields. Earlier he had been a member of the solid state physics group at Bell Laboratories. with an introduction to Green's functions.. and develops the group theoretical description of Brillouin zones.T. His undergraduate work in physics was at M. JOHN WILEY & SONS New York Chichester Brisbane Toronto Singapore . electron.tion of theoretical solid state physics. He is a member of the National Academy of Science and of the American Academy of Arts and Sciences. About the author ••• Charles Kittel taught solid state physics at the University of California. His Ph. and at the Cavendish Laboratory of Cambridge University.I. CUl minating in the BCS theory of superconductivity. Berkeley from 1951 to 1978. He is the author of a widely used introductory book on solid state physics.QUANTUM THEORY OF SOLIDS is a modern presenta. It builds directly on the same author's Introduction to Solid State Physics and is planned as a one year graduate course for experimental and theoretical physicists. was from the University of Wisconsin.D. The first part of the book treats phonon. It is well suited for self study because the text contains 110 problems . He has been awarded the Oliver Buckley Prize for Solid State Physics and the Oersted Medal of the American I Association of Physics Teachers.
It is well suited for self sludy because Ihe lext contains 110 problems . and develops the group theoretical description of Brillouin zones.JOHN WILEY & SONS New York Chichester Brisbane Toronto Singapore . cul minating In the BCS theory of superconducllvity..l and at Ihe Cavendish Laboratory of Cambridge University. Earlier he had been a member of the solid state physics group at Bell Laboratories. His undergraduale work in phYSICS was at M. . He is the author of a widely used introductory book on solid state physics . electron. and magnon field s. The second part considers Fermi surfaces and electron wave functions. Charles Killel taught solid state physics at the Universlly of California. with an introduction to Green's fu nctions. He is a Oersted Medal of the American ' Association of Physics T member of the National Academy of Science and otthe American Academy 01 Arts and Sciences. About the aut hor . The first part of the book treats phonon.l. Berkeley from 1951 to 1978.QUANTUM THEORY OF SOLIDS is a modern presentqtion of theoretical sotid state physics. He has been awarded the Oliver Buc kley Prize for Solid State Physics and the eachers. was Irom the University of Wisconsin . His PhD . The third part applies correla tion functions to timedependent effects in solids. It b~itd s directly on the same author's Introduction to Solid State Physics and is ptanned as a one year graduate course lor experimental and theoretical physicists.. .