Elementary Excitations in Solids, Molecules, and Atoms: Part B

Elementary Excitations
in Solids, Molecules,
and Atoms
Part B
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Elementary Excitations
in Solids, Molecules,
and Atoms
Part B
Edited by
J. T. Devreese
Department of Physics and
Institute for Applied Mathematics
University of Antwerp
Antwerp, Belgium
A. B. Kunz
Department of Physics
University of Illinois
Urbana, Illinois
and
T. C. Collins
Solid State Physics
Research Laboratories
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Dayton, Ohio
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Published in cooperation with NATO Scientific Affairs Division
Lectures presented at the NATO Advanced Study Institute on Elementary Excitations
in Solids, Molecules, and Atoms, Antwerp, Belgium, June 18-30, 1973
Library of Congress Catalog Card Number 74-1247
ISBN-13: 978-1-4684-2825-4 e-ISBN-13: 978-1-4684-2823-0

DOl: 10.1 007/978-1-4684-2823-0
© 1974 Plenum Press, London,

Softcover reprint of the hardcover 1st edition 1974
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PART B
LIST OF LECTURERS
M. Ba1kanski
Facu1te des Sciences, Laboratoire de Physique des
Solides, Universite de Paris VI, 9 Quai Saint-Bernard
Tour 13, Paris VI, France
M. Cardona"
Max-P1anck-Institut FestkBrperforschung, 7000 Stuttgart,
Germany
J.T. Devreese
Departement Natuurkunde and Leerstoe1 van Toegepaste
Wiskunde voor de Wetenschappen, Universiteit Antwerpen,
Antwerpen, Belgium
R. Evrard
Institut de Physique, Universit~ de Li~ge, Sart Tilman
par Li~ge I, Belgium
J. Hermanson
Physics Department, Montana State University, Bozeman,
Montana 59715, U.S.A.
B. Horovitz
Nuclear Research Center-Negev, P.O. Box 9001, Beer-Sheva,
Israel
W. Huybrechts
Rijksuniversitair Centrum Antwerpen, Groenenporger1aan 171,
B-2020 Antwerp, Belgium
E. Kartheuser
Institut de Physique, Universit~ de Li~ge, Sart Tilman
par Li~ge I, Belgium
A.B. Kunz
University of Illinois, Department of Physics, Urbana,
Illinois 61801, U.S.A.
L. F. Lemmens
Universitaire Instel1ing Antwerpen, Departement Natuur-
kunde, Universiteitsp1ein 1, B-2610 Wi1rijk, Belgium
v
vi LIST OF LECTURERS
G.D. Mahan
Physics Department, Indiana University, Bloomington,
Indiana 47401, U.S.A.
K.H. Michel
Universitaire Inste11ing Antwerpen, Departement Natuur-
kunde, Universiteitsp1ein 1, B-2610 Wi1rijk, Belgium
K.L. Ngai
Naval Research Laboratories, Washington D.C. 20375, U.S.A.
P.-O. Nilsson
Chalmers University of Technology, Institute of Theor-
etical Physics, S-402 20 Gtlteborg 5, Sweden
R.M. Pick
Universite de Paris VI, Departement de Recherches
Physiques, Esca1ier 22, 4 Place Jussieu, 75230 Paris
Cedex 05, France
J. Ruva1ds
Department of Physics, University of Virginia, McCormick
Road, Charlottesville, Virginia 22901, U.S.A.
L.J. Sham
University of California San Diego, Department of Physics,
La Jolla, California 92037, U.S.A.
V. Van Doren
Rijksuniversitair Centrum Antwerpen, Groenenborger1aan 171,
B-2610 Wi1rijk, Belgium
PREFACE
The Advanced Study Institute on 'Elementary Excitations in

Solids, Molecules, and Atoms' was held at the University of
Antwerp (U.I.A.) from June 18th till June 30th 1973. The In-
stitute was sponsored by NATO. Co-sponsors were: Agfa-Gevaert
N.V. (Mortsel-Belgium), Bell Telephone Mfg. Co. (Antwerp-Belgium),
I.B.M. BelgiumN.V. (Brussels-Belgium), the National Science Founda-
tion (Washington D. C. - U. S .A.) and the Uni versi ty of Antwerp (U. I .A.) .
A total of 120 lecturers and participants attended the Institute.
Over the last few years, substantial progress has been made
in the description of the elementary excitations of the elec-
tronic and vibrational systems and their interactions. Parallel
with this, the experimentalists have obtained outstanding re-
sults, partly as a result of availability of coherent light sour-
ces from the far infrared through the visible region, and partly
because of the availability of synchrotron radiation sources in
the soft X-ray region. The results of today will lead to fur-
ther progress over the next years. It was the purpose of this
NATO Advanced Study Institute to present a state of the art,
namely a survey of experiment and theory.
Although the title of the Institute incorporated Solids,
Molecules, and Atoms, the emphasis was on Solids. However, the
study of elementary excitations in Solids, Molecules, and Atoms
involves many common techniques and insights. E.g., bandstruc-
ture calculation starts from atomic wave functions. The methods
of studying correlations are often similar in Solids, Molecules
and Atoms. Therefore it is hoped that molecular and atomic
physicists as well as solid state physicists will benefit from
these lectures.
The material in these lectures is presented in two parts.
Part A deals with the excitation energies of the electronic sys-
tem. Band theory, study of exchange, correlation and relaxation
phenomena are included here as well as the collective excita-
tions. Part B is devoted to the vibrational excitations and
their interactions wi th radiation fields and electrons.
I would like to thank the lecturers for their collaboration
and for preparing a number of manuscripts. Thanks are also due
to the members of the International Advisory Committee: Profes-
sors, M. Balkanski, F. Bassini, F.C. Brown, M.H. Cohen, W. Hayes,
S. Lundqvist, G.D. Mahan, N.H. March, and D. Schoemaker. Further
vii
viii PREFACE
I am much obliged to Professor A.B. Kunz and Dr. T.C. Collins,
who acted as co-directors.
The secretarial tasks of the Institute were extremely heavy,
partly because the Institute was organized on a new campus. Dr.
V. Van Doren, Drs. W. Huybrechts and Miss R.M. Cuyvers receive
special thanks for their outstanding contributions to the prac-
tical organization, and to the editing of the lectures. Dr.
V. Van Doren, Drs. W. Huybrechts, Dr. F. Brosens and Dr. P. Car-
don de Lichtbuer also contributed to the preparation of the
lectures and the subject index. The author index was prepared
by Miss R.M. Cuyvers. To these co-workers I express here my
sincere gratitude.
All those who further contributed to the success of the
school by way of practical organizational help, copying lecture
notes, organization of social programs etc., all the members of
the physics department of the U.I.A. and my co-workers of R.U.
C.A. are sincerely thanked.
,I gratefully acknowledge the financial support of the NATO
Scientific Affairs Division and the co-sponsors. This support
made it possible to invite a panel of distinguished lecturers
and to provide a substantial number of grants to students.
My sincere thanks also to the Board - especially Prof. F.
Ned~e, president, and Prof. L. Vandendriessche, rector, - and
the administrative directors of the University of Antwerp
(U.I.A.) who provided accomodation and very valuable organiza-
tional support.
Jozef T. Devreese
Professor of Theoretical Physics,
University of Antwerp, (U.I.A. and R.U.C.A.)
Director of the Advanced Study Institute
February 1974
CONTENTS OF PART B
List of Lecturers ......................................... v
Preface vii
Contents of Part A ........................................ xi
PART B
PHONONS
Electronic Influence on Lattice Dynamics. ...... ..... ...... 1

L.J. Sham
Phonon Calculations in Metals and Insulators .............. 25
R.M. Pick
Excitations in Superfluid Helium .......................... 43
J. RuvaLds
Hydrodynamic Excitations in Anharmonic Crystals and in
Ferromagnets .............................................. 79
K.H. Michel
ELECTRON-PHONON INTERACTIONS
Electron Interaction with Surface Modes ................... 93

G.D. Mahan
Electronic Transitions and Relaxation Phenomena in Polarons 131
J. Devreese~ R. Evrard~ E. Kartheuser
The Self-Energy Problem in Quantum Dielectrics ............ 199
J. Hermanson
Electrons and Phonons in Narrow Gap Semiconductors ........ 213
M. Balkanski
Light Scattering in Solids ................................ 245
M. Balkanski
Resonant Raman Scattering in Semiconductors ............... 269
M. Cardona
ix
x CONTENTS OF PART B
SEMINARS
Formalism of an Ab Initio Calculation of Phonon Dispersion

Curves in the Hartree-Fock Approximation (Abstract) ....... 293
V.E. Van Doren~ P. Van Camp
Two-Phonon Deformation Potentials, Second Order Raman
Scattering, and Superconductivity in Degenerate
Semiconductors ............................................ 295
K.L. Ngai~ A.K. Ganguly
Temperature Dependence of Free Polaron Optical Absorption 317
W. Huybrechts~ J. Devreese
Peierls-Fr~hlich Instability and Superconductivity in
Linear Chain Crystals ..................................... 325
H. Gutfreund~ B. Horovitz~ M. Weger
The Absorption and the Ground State Energy of Free Polarons 333
L.F. Lemmens~ J. Devreese
EXPERIMENTAL STUDIES ON INSULATORS AND METALS
A Review of the Experimental Properties of Insulating

Solids .................................................... 343
A.B. Kunz
Optical Absorption and Photoemission Experiments on Metals
and Alloys ................................................ 351
P. -0. Nilsson
Author Index to Part B .................................... 367
Subject Index to Part B ................................... 375

CONTENTS OF PART A
PART A
PLASMONS
Many-Body Effects at Surfaces .. .......... ..... ............ 1

P. W. Anderson
Inelastic X-Ray Scatterings from Electrons in Matter 31
P.M. Platzman
Introduction to Collective Excitations in Solids .......... 65
A. Lucas
Plasmons in Inhomogeneous Electron Gases .... ";" ............ . 97
N.H. March
ELECTRONIC STRUCTURE IN CRYSTALS
Hartree-Fock Model Calculation for Atoms and Crystals plus

Corrections to the Hartree-Fock Excitation Energies ....... 117
T.C. Collins, R.N. Euwema, G.G. Werfer, G.T. Surratt,
N.E. Brener, J.L. Ivey and D.L. Wilhite
Ab Initio Energy Band Methods ............................. 159
A. Barry Kunz
Effects of Exchange and Correlation in the Electron
Bandstructure Problem ..................................... 189
L. Hedin
Many-Body Perturbation Theory for Non-Uniform Electron
Systems ................................................... 231
D.F. Scofield
ATOMS MOLECULES AND LIQUIDS
Many-Electron Effects in Spectra of Electrons Bound in

Atoms and Solids .......................................... 281
S. Lundqvist
Soft X-Ray Spectra of Molecules ........................... 313
A. Barry Kunz
xi
xii CONTENTS OF PART A
Collective Excitations of Dipolar Liquids .......... , ...... 329
Roberto Lobo~ John E. Robinson and Sergio Rodriguez
SEMINARS
Dynamical Image Charge Interactions ....................... 345

J. Heinrichs
Fine Structure Correction of the Edge Singularity in the
X-Ray Spectra of Metals ................................... 355
Pierre Longe
Author Index to Part A .................................... 361
Sub j ect Index to Part A .................................... 367

ELECTRONIC INFLUENCE ON LATTICE DYNAMICSt
L.J. SHAM
Department of Physics, university of California,

San Diego, La Jolla, California 92037 USA
1. INTRODUCTION
In a vibrating lattice, the effective force between two ions
consists of Ci) the direct ion-ion interaction and Cii) the in-
teraction via mediating electrons. The electronic contribution
to the lattice dynamics is very important in many classes of cry-
stals spanning from metals to insulators. The electronic contri-
bution in simple metals has been fairly satisfactorily treated
by the method of pseudopotentials, essentially treating the elec-
trons as nearly free. However, there remains an enormous class
of transition metals, their compounds, covalent and ionic crys-
tals, in which there are important electrons which are not near-
ly free nor yet so tightly bound so as to be moving rigidly·with
the ion. In section 2 we shall describe a method which takes in-
to account the effects of these electrons on the lattice dynamics.
Rather than studying in detail the application of this method
to the calculation of phonon spectra in a wide variety of crys-
tals, we choose here to use this method to study two examples
where the electronic contribution to lattice dynamics is so dra-
matic that it is the deciding force of the very stability of the
crystal structure. In section 3, the structural phase transi-
tions of Nb3Sn and V3Si are explained in these terms. The impor-
tance of these compounds is, of course, their membership in the
class of superconductors with high transition temperatures. In
section 4, we discuss the metal to insulator transition of a one-
dimensional model of a solid. Hopefully, our results may be rel-
t Research supported by the National Science Foundation, Grant

No. GP-28997.
1
2 L.J. SHAM
evant to the organic solids which are currently under intensive
investigations around the world.
2. MICROSCOPIC FORMULATION OF LATTICE DYNAMICS
A EFFECTIVE INTERACTION BETWEEN IONS

We confine our treatment to the harmonic approximation, that
is, in the lattice energy, we include terms only up to the sec-
ond order in the ionic displacement from equilibrium. The ion
is meant here an entity which includes the nucleus and those core
electrons which are so tightly bound that they move rigidly with
the nucleus in a lattice vibration. The rest of the electrons
will be treated as capable of responding to the motion of the
ions in a more relaxed fashion, under the influence of the electron-
ion 'pseudo-potential', which includes the effect of repulsion
due to the fact that the outer electron wave functions must be
orthogonalized to the core electron wave function.
For notational simplicity, let us consider a linear chain.
Let the equilibrium positions of the ions be Xt and the displace-
ment from equilibrium be Ut. All the formal results in this sec-
tion are easily extended to a complex crystal in three dimensions,
for example by extending in places the index t to mean tKA, which
respectively label the particular unit cell, the particular atom
in the cell and the Cartesian direction. We refer elsewhere for
the full flourish of these indices [1]. In subsequent sections,
we shall, however, be very careful to point out which results are
valid only in one dimensional chains and which only in three di-
mensional solids.
The total effective force on the ion t due to the displacement
Ut' of another ion t' is given by
(2.1)
where ~(t,t') is called the force constant. It consists of two

parts: (1) the direct ion-ion Coulomb interaction, (2) the elec-
tronic contribution, given by
- ~ (t,t')u (2.2)
where Vi(r - Xt) is the electron-ion pseudo-potential and ont'(r)

is the first order change in the electronic density due to the
ionic displacement UtI, which causes a change [aVi(r - Xt,)/aXt']
Ut' in the electron-ion potential, thus giving
(2.3)
ELECTRONIC INFLUENCE ON LATTICE DYNAMICS 3
x(r.r') is known as the electron density response. In gener-
al, it is a function of the frequency of the lattice vibration
under consideration. In the adiabatic approximation, the zero
frequency or static limit is used.
Once the force constants are known, the normal modes of the
lattice vibrations are easily determined [2].
B THE ELECTRON DENSITY RESPONSE

From equations (2.2,3) we see that the electronic contribution
to the force constant depends on the knowledge of (1) the elec-
tron density response (also known as the electron screening) and
(2) the change of the electron-ion potential (also known as the
unscreened electron-phonon interaction). Dr Pick will consider
the latter in more details in his lectures. Let us concentrate
on the former here.
From the definition (2.3), when a crystal is perturbed by a
weak electric field oV, it induces a change on in the electron
density given by
on(r) = jdr'x(r.r' )oV(r'). (2.4)
Thus, a test charge will see an effective potential
(2.5)
where VCr - rl) denotes the Coulomb repulsion between electrons.

By analogy with electrostatics, we can define a polarizability
function X(r.r') by
on(r) = jdr'x(r.r')o~(r')' (2.6)
i.e. the induced charge per unit total effective potential rather
than the applied potential.
It is also convenient to introduce the dielectric function
e(r.r'), defined by
(2.7)
The usual procedure to determine the density response X(r.r')

is to first calculate the polarizability x(r,r') in some approx-
imation, thus obtaining the dielectric function
e = 0 - Vx.' (2.8)
4 L.J. SHAM
using a short-hand notation having the coordinates and the inte-
gration understood. Then invert the dielectric function by the
integral equation
-1 -1
e = 8 + VXe , (2.9)
and finally, arrive at the density response
X= xe -1 (2.10)
For a more careful discussion of these concepts and the rel-

ations, we refer to the book by Pines and Nozieres [3].
In principle, we possess a systematic scheme (such as the per-
turbation theory) to calculate the polarizability. However, what
constitutes a satisfactory approximation is still under active
investigation. Let us adopt here the simplest approximation
(also known as the random phase approximation [3]). Each elect-
ron is regarded as moving independently in the effective field
o¢. The change in density of the independent Fermion system due
to the potential 8¢ gives the polarizability [4]
fi - f'
X(1" ,1'" ) L
i j Ei - Ej +
J
W
1jJ'(1")1jJ."'(1")1jJ"~(1"')1jJ'(1"')
J l J l
(2.11)
where 1jJj(l") and Ej denote the single-particle wave function and

energy. fj is the occupation number and w is the frequency of
the perturbing potential.
If we make use of the translational symmetry of the crystal,
then
(2.12)
where x~ is a lattice vector. Then, the polarizability of rel-

evance in a phonon wave vector q (reduced to the first Brillouin
zone) is
x(l",l'" ;q) (2.13)
where N is the number of unit cells in the crystal. It is still

given in RPA by equation (2.11) with, however, the states i, j
restricted to the Bloch states vk and v' k + q respectively. We can
define similar quantities for X and e by equation (2.13) and
they are still related by equations (2.8-10). In terms of Four-
ier transforms, the non-vanishing elements are of the form X(q +
G, q + G') where G and G' are reciprocal lattice vectors.
For simple metals, the free electron approximation makes X(l",
1"') a function of relative distance only. Then the inversion of
the dielectric function is trivial. However, in a crystal, the
only property we have is equation (2.12). Approximation of X(r,
r') by X(r - r') will miss important crystal properties.
In the long wavelength limit (q + 0), the density response
contains some singular terms due to the long-range nature of the
Coulomb interaction. These terms can be separated and treated
exactly. For the case of insulators [5,6], the dynamical matrix
for the phonon consists of two parts, a long-range interaction
between sublattices with effective charges defined microscopic-
ally screened incompletely by the dielectric constant and a short-
range part. The neutrality condition of the effective charges
of the sublattices gives a restriction (or sum rule) on the be-
havior of X(q + G,q + G') for small q. This also ensures that
the frequency of the acoustic modes is proportional to q in the
long wave limit. The Lyddane-Sachs-Teller relation is also given
a microscopic proof.
For the conducting crystals [?], in the long wave limit, again
the long-range part can be separated from the short-range inter-
action in the dynamical matrix. It can be further shown that the
long-range part is actually screened out in conductors, giving
another set of sum rules on the density response function. Be-
cause of this, in contrast with the insulator case, a relatively
simple expression for the elastic constants can be derived from
the short-range part of the dynamical matrix.
C THE WANNIER REPRESENTATION

For finite q and electrons far from being free, the inversion
problem of equation (2.9) is not trivial. It was first pointed
out by Sinha [8] and by Hayashi and Shimizu [9] that if the elec-
tron bands involved in the polarizability are well approximated
by the tight-binding approximation, the kernel x(r,r' ;q) of the
integral equation (2.9) is of the separable form. Hanke
[10], Pick [11] and I [12] independently show that if we express
the electron wave functions in the Wannier representation, then
x(r,r' ;q) is always of the separable form.
Consider a number of Bloch bands with some points of degene-
racy but separated from other bands. Des Cloizeaux [13] shows
the exsistence of the Wannier functions related to these Bloch
waves with exponential decay at infinity. The Wannier functions
~A(r - x~) are related to the Bloch waves by
(2.14)
In terms of these Wannier functions, equation (2.11) for the

polarizability assumes the separable form
x(r,r' ;q,w) (2.15)

6 L.J. SHAM
h is short for the indices Al,A2,£' Fh(q,r) is the form factor
Fh (q,r)
and the pOlarizability matrix is
fv'k+q - fvk
x eVA' 1 (k)C v' A' /' (k + q) (2.17)
£v' k+q - £vk - w
The solution of the integral equation (2.9) reduces to the

inversion of the matrix
OM' - XM' (2.18)
where
L JdrJdr'Fh,·,(q,r)v(r-r')Fh,,(q,r')8 h "h,(q,w). (2.19)

h"
Then, the density response becomes
x(r,r' ;q) L Fh(q,r)Shh'(q,w)Fh'*(q,r'), (2.20)

M'
where the matrix S is given by
S = 8·E. (2.21)
This scheme is practical only if the matrix E is not too

large. This means that the Wannier functions have to be well
localized. For d-electrons in transition metals and bound elec-
trons in insulators, one can use the atomic orbitals and the size
of E is manageable. A separable ansatz of a form similar to
(2.15) was first used by Sinha and coworkers [14] to calculate
the phonon spectrum of silicon. However, they did not construct
the form factor Fh(q,r) from the knowledge of the electron band
structure. Applications of the scheme outlined above have been
given by Hanke [10] for Pd and Ni and by myself [12] for Nb3Sn.
All three calculations demonstrate the importance of the so-cal-
led local field effects which are taken into account in the in-
version of the dielectric function just described. It is hoped
that more applications will be made in the not-too-distant future.
3. STRUCTURAL PHASE TRANSITIONS IN A-IS COMPOUNDS
A THE MA.RTENSITIC TAANSFORMATION

There is a class of intermetallic compounds A3B with 8-tung-
sten (A-IS) structure, where A is always a transition metal ele-
ment. They have been subjected to intensive experimental and
theoretical studies. The main reason is that among these com-
pounds are superconductors with very high transition tempera-
tures. They also have a number of other interesting properties,
such as unusual temperature-dependence of electronic and phonon
properties. For a comprehensive review of the work on this class
of materials up to 1971, we refer to the review articles by Weger
and Goldberg [15] and by Testardi [16].
V3Si and Nb3Sn were found to be cubic (A-IS) at room tempera-
tures and on cooling to low temperatures (about 22°K and 4SoK
respectively) transformed to a tetragonal structure [17,18]. The
Cll - C1 2 shear constant is strongly temperature dependent, de-
creasing rapidly on cooling from room temperature to very small
values just above the structural phase transition temperature
[19,20]. Neutron scattering measurements [21,22] verify that the
frequencies of phonons of wave vectors in the (110) direction
polarized in the (110) direction have similar temperature depen-
dence. Nb3GexA£1-x with x = 0.3 and 0.2S were recently observed
also to undergo structural transformation at about 24°K [23].
The fact that all four compounds have very high superconducting
transition temperature with Nb3GexA£1-x being the record holder
[24], to date, at 21 oK, heightens the interest in their structur-
al transformation. However, note that Nb 3A£ [25] and Nb 3Ga [26]
have comparable Tc but do not undergo structural transformation,
though their shear constants do decrease on cooling.
B LA.BBE-FRIEDEL MODEL
The structural transformation can be understood as a result
of the softening of the long wavelength Cll - C12 elastic mode,
i.e. with small wave vector in (110) direction with polarization
in (110) direction, driven by the electrons.
The cubic structure of the A3B compound is shown in figure 1.
The A-atoms form a network of chains running in the directions
of the cubic crystal axes. Weger [27] and Labbe and Friedel[28]
observed that, since an A-atom has its nearest neighbors on the
same chain, a reasonable approximation for the d-electron band
is a tight-binding band taking into account only the overlaps of
nearest neighbors on the same chain. Thus the d-electrons from
the A-atoms run only along a chain. This one-dimensional charac-
ter gives rise to very flat pieces of the Fermi surface, a feat-
ure found by the positron annihilation experiment [29]. Weger
and Goldberg [30] have considered improvements of this tight-
8 L.J. SHAM
,.
I 8
I
I z
I 70
I
I
4
-- )-
I ____-3_
-
/
/
/ x
/
/
.A
OB
Figure'l - Crystal Structure of A-IS Compounds A3B.
binding approximation.
The Fermi level is taken to be near the band edge of one of
these tight-binding d-bands where the density of states is high.
This was first proposed by Clogston and Jaccarino [31] to ex-
plain the unusually strong temperature dependence of the elec-
tronic magnetic properties. That the Fermi energy measured from
the band edge is of the order of IOOoK rather than electron volts
means that the d-electrons are not highly degenerate at room tem-
perature, thus explaining the strong temperature dependence of
many electronic properties.
With this model of the electronic band structure, Labbe and
Friedel [28] gave an explanation of the structural transforma-
tion. Since there are chains running in three directions, in
the cubic phase there are three degenerate bands with their edges
near the Fermi level. Uniform distortion of a chain changes the
overlap integral and, therefore, shifts the band edge. At zero
temperature, it is energetically favorable for the three bands
to split, thus giving rise to a uniform distortion in the lat-
tice, which just changes the cia ratio, rather like a Jahn-Tel-
ler effect.
At finite temperatures, from the consideration of the free
energy, the CII - Cl2 shear constant is shown to decrease on
cooling from room temperature [32].
Labbe-Friedel's theory of the structural transformation leads
to a first order phase transition. Until recently, experiments
have found no evidence of discontinuities of a first order tran-
sition, such as a jump in the tetragonal distortion [17] or lat-
ent heat [33]. This led to a belief that the structural trans-
ition is of second order. Then, the tetragonal distortion can-
not be the fundamental order parameter. Anderson and Blount [34],
therefore, suggested that an optical mode, which softens on cool-
ing, drives the tetragonal distortion. By using the Landau the-
ory of second order phase transition, they considered the pos-
sible anharmonic coupling terms in the free energy between the
soft optic mode and the tetragonal distortion and, for symmetry
reasons, deduced that the optic mode must be of symmetry [34,35]
r 1S ' r 2S or r 1S '. A search by X-ray measurement [36] did not
turn up a relative sublattice displacement of one of these types.
C LATTICE DYNAMICS IN THE CUBIC PHASE

From the discussion in the preceding subsection, we see that
it would be of interest to investigate the nature of the struc-
tural transformation by theoretical and experimental studies of
the lattice dynamics of the cubic phase as a function of temper-
ature.
A calculation of the phonon frequencies can be made by apply-
ing the method of section 2 [12]. The Weger-Labbe-Friedel model
for d-electrons is adopted. For the three degenerate tight-bind-
ing bands closest to the Fermi level, the associated wave func-
tions are given by
_l .k" -+-
(2N) 2 L el aX~A¢A(~ - ~~A)' (3.1)
~
where A denotes one of the three groups of A-atom chains in A3B,

¢A denotes the appropriate d-electron atomic wave function and
the sum is over atoms of chains running in the A direction. All
other electrons are treated as nearly free.
The electron screening is separated into two parts: the near-
ly free s-p electrons screen the Coulomb interaction to short-
range as usual and the tight-binding d-electrons screening is
treated by the method described in section 2C. For the d-elec-
tron screening, if we keep only the leading non-overlap term,
the form factor (2.16) becomes, on using (3.1)
-+- -+-
FA(q.r) = (2N) -1 'i'
L e iqaX£A 1¢A(r
-+-
- -+-
X~A)
12 , (3.2)
~
which is just a density wave of localized d-electrons.

For the question of lattice instability, we need only consider
phonons with long wavelength. For q -+- 0, if we separate out the screen-
ing due to the long-range interaction, we need only consider the short-
range' local field' effects [12]. From equation (2.17), the polariz-
ability matrix is simplified to
(hk"+q - hk")
~ (£Ak"+q - £Ak - w)
(3.3)
For finite w, as q -+- 0, 6A vanishes. Thus, strictly speaking,

there is no d-electron contribution to the zero wave-vector opti-
cal phonon mode. However, in the adiabatic limit (putting W = 0
10 L.J. SHAM
first), 8A(q ~ 0, W = 0) is finite. The zero wave-vector phonon
frequencies are of interest in this limit for two reasons: (1)
they may apply to optical modes with small q which makes the
electron-hole excitation energy larger than the phonon frequency,
(2) they apply to the optical modes which are coupled to the long
wavelength elastic waves.
The inversion of the screening matrix is simplified by the
approximation of equation (3.2), to that of a 3x3 matrix. The
short-range part of XAA'(q ~ 0) only has two independent elements
because of the cubic symmetry of the crystal: the diagonal ele-
ment Xll and the off-diagonal X12. The same is true of EAA ',
thus,
1
(3.4)
1
(3.5)
The results of the zero wave-vector phonons are as follows.

Since there are 8 atoms per unit cell, there are 24 phonon bran-
ches. Three of them are acoustic modes and have zero frequencies.
The motions of the A-atoms for various modes are illustrated in
figure 2.
!
3x [15' 2X[25
0--- 0--- 0--- 0---
(a)
r r
[',5,[25
(b)
(e)
Figure 2 - Zero wave-vector lattice modes.
The d-bands contribute to none of the modes except r12. All the
modes in figure 2(a) involve rigid displacements of whole A-atom
chains and, therefore, cannot excite the d-electrons near the
Fermi level in the Weger-Labbe-Friedel model. The optical modes
in figure 2(b) involve rotation of pairs of A atoms about an axis
perpendicular to the chain and, therefore, to the first order,
do not alter the distance between d-atoms and thus the overlap
integrals. Only f2 and f12 modes in figure 2(c) involve oscil-
lations of A-atoms against each other in the same chain, thus
exciting the d-electrons. For f2, a mode with cubic symmetry,
the contributions from the three d-bands cancel. Thus, if it is
true that the nearest neighbor intrachain d-electron overlap is
larger than the inter-chain overlaps, f12 is the only optical
mode which could be strongly temperature dependent. This rules
out the possibility of the structural transformation being a sec-
ond order phase transition driven by a soft optic mode of sym-
metry f15, f25 or f15'. Estimates of the high frequency f12
mode show that it does not decrease much on cooling.
The elastic constants are deduced from the frequencies of the
long wavelength acoustic modes using the procedure of reference
[7]. The cubic crystal has three independent elastic constants.
The bulk modulus is Cll + 2C12' The d-electron screening of the
bulk compressional wave is given by Ell + 2E12 of equation (3.5)
and is strong. The temperature dependence in the harmonic ap-
proximation comes entirely from the d-electrons through the pol-
arizability in equation (3.3). This quantity appears in XAA ,
for the electron screening and also in the numerator for the bulk
modulus due to the d-electron-phonon coupling. Their approximate
cancellation leaves the bulk modulus weakly temperature depend-
ent, which is in accord with experiments [19,20].
The shear constant C44 comes from change of the angle between
two families of chains. Thus, in our model, there is no d-elec-
tron contribution and only weak temperature dependence. This is
true for V3Si [19] but not for Nb 3Sn [20], where the next-near-
est-neighbor interchain overlap is apparently quite important.
The shear constant Cll - C12 is associated with the tetrag-
onal distortion which conserves volume. Our calculation gives
the form
ew (3.6)
y + (1 - eU)
The first term is the usual contribution due to ion-ion inter-

action screened by all the electrons except the d-electrons under
consideration. The second term is the d-electron contribution.
(1 - eU)-l is just the d-electron screening, equation (3.4).
Since XII and X12 are nearly equal, screening in a shear wave is
very small. W is the d-electron-phonon coupling. e is the W7 0,
q 7 0 limit of equation (3.3). Since the Fermi energy is small,
at room temperature the chemical potential is below the band edge
and the d-electron distribution is spread out giving a small pol-
arizability e. As the temperature is lowered to below the Fermi
temperature, the large density of states begins to give e a large
negative value, thus lowering the shear constant creating an in-
stability towards a tetragonal shear deformation.
The third term is the coupling of the shear wave to the sub-
lattice displacement of f12 mode. Representation of f12 mode in
12 L.J. SHAM
figure I shows that such a coupling is physically reasonable.
Mathematically, it comes from the second order k·p perturbation
term expressing the small q acoustic phonon frequency in terms
of the wave-vector optical modes. Selection rule eliminates all
but the f12 mode. Although the coupling M2 is small, it means,
that when the Cll - C12 mode goes soft, the tetragonal distortion
will produce a sublattice displacement of f12 type.
D NATURE OF THE STRUCTURAL TRANSFORMATION

Experiments [19,20] and the preceding theoretical considera-
tion show that the phase transition is driven by the lowering of
the (110) shear mode with (110) wave·,vector. The smallest q wave
goes soft first. Theory ascribes the softening to the non-de-
generate d-electrons near the Fermi level. The tetragonal dis-
tortion then is discontinuous at the transition, the result of a
first order phase transition, This is recently found in Nb3Sn
by careful X-ray measurements [37].
Associafed with the uniform tetragonal distortion is a sub-
lattice motion of f12 type, i.e. nearest-neighbor A-atoms of
chains in the y-direction, say, move toward each other, those of
chains in the z-direction move away the same amount and those in
the x-direction remain uniformly spaced. (See the arrows in fig-
ure 1). Elastic neutron measurements of the Nb3Sn in the tetra-
gonal phase [38] first discovered the f12 sublattice displace-
ment.
By considering the long wavelength limit, it is possible [40]
to construct an effective Hamiltonian which couples the d-elec-
trons to the tetragonal distortion and the f12 sub lattice dis-
placement. Then, free energy calculation gives a quantitative
'description of the weak first order structural phase transition
with both the shear distortion and the sublattice movement. To
reproduce the measured sublattice displacement, we deduce the
energy of the f12 mode to be about 21 meV.
A further confirmation of the Labbe-Friedel mechanism for the
structural phase transition is the effect of magnetic field on
the transition temperature Tm. Dieterich and FUlde [39] calcu-
lated the depression of Tm due to a high field which splits the
spin bands and thus reduces the effective density, of states and
hence Tm. This very small change is recently measured [41].
In the theory which explains shear instability in terms of d-
electron contribution, the phonons are treated in the harmonic
approximation. It is clear that in the neighborhood of the phase
transition, the (lio) phonons of wave vectors in (110) direction
must be very soft and quite anharmonic. Anharmonicity was used
by Shirane and Axe [22] to explain the central peak which they
observed in the neutron scattering function.
4. PEIERLS' INSTABILITY IN ONE-DIMENSIONAL SOLIDS

A HIGHLY CONDUCTING ORGANIC SOLIDS
Recently, two groups at Johns Hopkins [42] and at the Univer-
sity of Pennsylvania [43] respectively synthesized a highly con-
ducting organic solid: tetrathiofulvalene (TIF) tetracyano-p-
quino-dimethane (TCNQ). The temperature dependence of the con-
ductivity is metal-like above about 60 0 K and insulator-like be-
low. The Johns Hopkins group found the maximum conductivity (at
66°K) to be 1.47 x 10 4 (n cm)-l. It is only one or two orders
of magnitude lower than copper at room temperature (6 x 10 5
(n cm)-l, better than any other known organic solids. The Penn
group has observed some seventy crystals which have similar be-
havior. However, most astonishingly, they found that three of
the crystals have much larger conductivity peaks near 60 0 K (> 10 6
(n cm)-l).
The two groups pointed out that a possible explanation of the
low temperature insulating phase is the Peierls' instability [44].
At room temperature, the crystal structure of TTF-TCNQ is mono-
clinic [45], with chains of TCNQ and chains of TTF. TTF is an
electron donor and TCNQ an acceptor. Because of the very small
interchain overlaps, electrons are confined to the one-dimension-
al TCNQ chains and holes to the TTF chains. Thus, we have the
possibility of Peierls' instability which we shall study in more
details.
Two explanations have been given for the extraordinary conduc-
tivity peaks observed by the Penn group. The discoverers them-
selves [43] believe that it is superconductivity fluctuation due
to electron-electron pairing via the softened phonons. The Pei-
erls' instability interferes with this superconducting phase and
should be stabilized away by some means. Bardeen [46] suggested
that the peaks are fluctuations of a superconducting state of a
different kind, with a mechanism proposed by Fr5hlich [47]. In
this theory, although the chains distort as Peierls has sugges-
ted, a superconducting current-carrying state can be constructed
with the electrons moving with the lattice distortions. This is
completely different from the BCS mechanism for superconductiv-
ity [48]. If either explanation is true, then it might be pos-
sible to make a superconductor with Tc at 60 o K, an event of gi-
gantic import [49].
We are still at the beginning stages of this exciting discov-
ery. There are controversies in experiments as well as in in-
terpretations. For example, as an attempt to stabalize the Pei-
erls' instability, the Penn group [43] substituted an assymmet-
ric cation (ATTF) for TTF so as to introduce a small amount of
disorder through the orientation of ATTF ions, and found a repro-
ducible large conductivity peak. However, measurements of micro-
wave conductivity of both TTF and ATTF salts by the Johns Hopkins
group [50] do not show large fluctuation peaks. These authors
are at pains to point out that, while in the case of TTF-TCNQ,
it is possible that their crystals may not be of sufficiently
good quality, in case of ATTF-TCNQ there is a definite contra-
diction.
It is also of tremendous interest to study the possible the-
oretical explanations of this phenomenon using a simple model.
Patton and I [51] have taken a simple one-dimensional model and
14 L.J. SHAM
studied (1) the possibility of BCS-pairing above Peierls' insta-
bility, (2) the conductivity property of the Peierls state (is
it an insulator or a superconductor?), and (3) the fluctuation
conductivity just above the transition temperature. Our find-
ings will be described in the rest of these lectures in the hope
of eliciting helpful comments. Hopefully, they will also serve
as a useful introduction to this fascinating subject.
B THE LATTICE INSTABILITY

We adopt a one-dimensional tight-binding model for the elec-
trons in the TCNQ chain when the molecules are equally spaced at
distance a apart, with the Hamiltonian
I KoC£tC£ + I JO(C£+l tc £+ C£tC£+l), (4.1)

£ £
where JO measures the nearest-neighbor overlap and Ko the site

energy and crystal field terms. The longitudinal vibration of
the TCNQ chains is also treated in the same fashion, with the
Hamil tonian
(4.2)
Although there is evidence that the electrons are well confined

to chains, the phonons are quite three-dimensional from low temp-
erature specific heat [43] (~T3) and from the lattice stability
consideration. We take this into account by confining the trans-
verse wave-vector of the electrons to the first Brillouin zone
but by confining the transverse wave-vector of the phonons to a
much smaller fraction (which is a measure of its interchain coup-
ling) .
The electron-phonon interaction is given by
Hep KI I c£tC£(U£+1 - U£)

£
+ JI I (C£+ltc£ + C£tC£+I)(U£+1 - U£). (4.3)

£
The first term is due to a change of the crystal field terms in

a lattice vibration and the second due to a change in the over-
lap.
The electron-electron interaction is neglected. When two
electrons land on the same TCNQ molecule, they can be quite far
apart, thus reducing their Coulomb interaction [52,53]. It is
further reduced by the large polarizability of the TTF molecules
[42,43].
Apply the elementary transformation to the wave-vector repres-
entation:
_1
Ct = N 2
iU
L Cke ,
k
Pt [MJ~
N Le iqtP q , (4.4)
q
Ut = (NM)
_1
2 L e i q t Uq ,
q
k and q are wave-vectors defined independently of the lattice

constant a, restricted to the first Brillouin zone (-TI,rr). N
denotes the number of molecules in a chain. Then, the Hamilton-
ian becomes the sum of
He L EkCktCk (4.5)
k
where
Ek = KO + 2JOcosk (4.6)
and the spin indices are understood,
2
L (PqP-q + rlq UqU_ q ),
1
Hp 2: (4.7)
q
with
rlq (4C)
M ~ ISln2:q,
. I 1 (4.8)
and
_1
Hep = N 2 L Mk' - k - q)g(q,k)Ck,tCkUq (4.9)
k'kq
where I::. denotes the wave-vector conservation (modulo 2rr) and

_1
g(q,k) =M 24isin~q {Klcos~q + Jlcos(k + ~q)}. (4.10)
16 L.J. SHAM
In the following, we shall drop explicit consideration of the
crystal field term K1, for simplicity.
Equation (4.5) gives one electronic band which is exactly
half-filled at T =0 (i.e. kr = ~/2) if there is one electron per
site. We have ignored the holes along TTF chains which may
change the Fermi level [50]. Peierls [44] pointed out that a
lattice distortion with every other molecule moving through the
same distance u will produce a band gap at ±kr, thus reducing
the electronic energy. This is balanced against a smaller in-
crease in the lattice energy. The displacement and energy gap
can be determined by minimizing the total energy at T = 0 [47].
The mathematics for the Peierls' state is so analogous to the
BCS state that we can obtain the low temperature thermodynamic
properties by two other methods, the Green's function method of
Gorkov [54] and the Bogoliubov-Valatin transformation [55].
However, let us be forewarned about the drastic distinction be-
tween the two systems in electromagnetic properties, which will
be studied later.
Thus, without details, we shall quote the results for the
thermodynamic properties for the weak coupling case. There is a
gap equation
(4.11)
with
E2 (4.12)
k
At T 0, this gives
i ie -1 e -1/1. ,
8 JO (4.13)
where
(4.14)
The sublattice displacement u is given by
t.kr
u = --- (4.15)
i 2J1i
At finite temperatures, the gap decreases to zero like the BCS
superconductor [56] at the transition temperature Tp ,
(4.16)
where y = 1.7811 is an Euler constant. The specific heat behav-

ior is also similar.
The Peierls' instability may be regarded as due to the soft-
ening of the phonon with the wave-vector 2k r . The lowering of
the phonon frequency is due to the Kohn effect [57]. Calculate
the phonon self-ener~y in RPA (cf. equation (2.11)). At T = 0,
there is a term ~ lnl2kr - ql due to the electrons excited across
the Fermi sea with momentum transfer 2k r . This causes unstable
phonons near 2kr [58]. In three-dimensional solids the curvature
of the Fermi surface lessens the number of such electron-hole
pairs and weakens the Kohn effect to Iq - 2krllnlq - 2krl. In a
one-dimensional chain, the Kohn effect is enhanced by the flat
Fermi surfaces [59]. At finite temperatures, the blurring of the
Fermi surface weakens the Kohn effect. As the temperature is
lowered, the frequencies of the phonons near the zone edge (2kr =
n) decrease until at Tp, the 2kr phonon first reaches zero fre-
quency.
At temperatures (1 + £)Tp just above the transition temperat-
ure, the phonon Green's function with q close to 2kr is given by
(4.17)
Thu r,
the frequency of the n-phonon (p = 0) goes to zero as (T -
Tp)2 as T tends to Tp. The dispersion of the phonons near n is
glven by the function
L(x) = ~(l + x)lnlx + 11 + ~(l - x)lnl1 - xl, (4.18)
with the coherence length
IJol (4.19)
2kBTp'
The last term on the right of equation (4.17) represents the dam-
ping of the soft phonons. This is again similar to the Cooper
pair t-matrix [60].
These results are obtained using only the simple electron-hole
bubble for the phonon self-energy and can be regarded as the mean
field theory results. Unlike the superconductivity case, impuri-
ties tend to destroy Peierls' state and lower the gap and the
transition temperature.
As a digression, we note that the possibility of Peierls' in-
stability in the A-IS compounds has been considered by Labbe and
18 L.J. SHAM
Friedel [61] and rejected. However, recently, this has been sug-
gested again [62,43]. There appears to be three reasons against
the structural transformation in A-IS compounds being a Peierls'
instability: (1) the reason, given by Labbe and Friedel [61], is
that kF is very small in V3Si or Nb3Sn which lowers Tp consider-
ably, compared with the temperature at which the long wavelength
shear mode goes unstable; (2) electron-electron interaction which
has the effect of weakening the Kohn effect softening of the pho-
non [1] has been neglected; and (3) the measured temperature de-
pendence of the conductivity and the smoothness of the phonon
frequency from the neutron range to the ultrasonic range [21,22]
contradict the exsistence of a 2kF soft mode.
C BCS SUPERCONDUCTIVITY
We examine the possibility of BCS-type superconductivity in
our one-dimensional electron-phonon model. The one-dimensional
superconducting fluctuation due to the BCS-pairing mechanism [60]
has been suggysted by the Penn group [43] to explain the extra-
ordinary conductivity peak near 60 o K.
The BCS-type superconducting transition temperature Tc is de-
termined by the temperature at which the binding of the Cooper
pair (e.g. electrons kt and k+) due to phonon-mediated attrac-
tion occurs [54]. In the one-dimensional model, the attraction
between electrons comes mainly from the soft phonons near the
zone edge (q ~ 2kF = TI). The condition for a singular solution
of the Cooper pair t-matrix is approximately
S-IN-l L Ig(TI,~TI)12D(p + TI,iw)G(TI + p,iE + iw)

p,w
x G( - TI- p, - iE- iw) = 1, (4.20)
where D is the phonon Green's function given by equation (4.17)

and G is the electron Green's function. E is put to zero after
the energy summation.
Examination of equation (4.20) yields three possible reasons
why the soft phonons destroy rather than enhance BCS"-type super-
conductivity.
(1) Lowering the phonon frequency w would raise Tc only if
w > Tc' If w ~ T c ' then these phonons do not provide
attraction for electrons to form a Cooper pair. This is a
very general result valid for all kinds of materials. To
show this, we evaluate equation (4.20) by using bare elec-
tron Green's functions and the phonon Green's function of
equation (4.17) neglecting the damping term. We obtain an
electronic term,
_ 2JTI ~ tanh(Ep/2kBT c ) 1
1 - g 2TI . 2 . w 2 - E 2 + ••. , (4.21)
-TI Ep P P
where wp is the renormalized frequency of n + p phonon and
~ = 1. The function tanh(£/2k BTc )/2£ is approximately con-
stant for 1£1 ~ 2kBTc and 1/21£1 outside. If wp > 2kBTc'
the phonons provide attraction for the Cooper instability
as usual [54]. If wp < 2kBTc, elementary integration shows
that equation (4.21) cannot be satisfied. That is, phonons
of frequencies comparable or less than kBTc do not help to
bind Cooper pairs. In fact, they tend to destroy the pairs.
(2) If the electrons are dressed by the soft phonons, their
energies acquire a fluctuating gap which further tends
to suppress the BCS-pairing.
(3) Thermal occupation of phonons also tend to destroy BCS-
pairing [63]. Although this effect is small in ordin-
ary solids, it does also provide a de-pairing mechanism for
soft phonons [64]. If this term is evaluated for the soft
phonons neglecting the damping, it goes iike (T - Tp )-3/2.
Rice and Str~ssler [65] has suggested that this large term
suppresses superconductivity. However, if the phonon damp-
ing term is included as in equation (4.17), the thermal pho-
non term is much reduced, being dominated by the damping
term rather than the soft frequency contribution (T-T p )-3/2,
So we feel that while this term helps to suppress BCS super-
conductivity, it is not as decisive as the two preceding
reasons.
D ELECTRIC RESPONSE OF THE PEIERLS' STATE

We have calculated the response to an electric field for the
Peierls' state below Tp by Gorkov's method [54]. Contrary to
Fr~hlich "[47], we have found it to be like a semiconductor rather
than a superconductor. There is another reason against a super-
conducting state. If in Fr~hlich's treatment we include the lat-
tice effect of making -2kr and 2kr phonons to be the same for the
commensurate case of one electron per site (kr = n/2), then the
current-carrying state is eliminated. In other words, the order
parameter is real and, therefore, carries no current. Even in
the non-commensurate case, it appears that a 'diagonal long range
order' [66] like the Peierls' state does not carry supercurrent.
Although we have considered alternative coupling schemes besides
the obvious one, it is still possible that we may have missed a
non-decaying current-carrying state as envisagedbyFr~hlich [47]
and Bardeen [46].
We have examined the possibility of conductivity fluctuation
above the Peierls' transition Tp. Unlike the superconductivity
case, the sum of diagrams in figure 3(a) is negative and goes lik€
(£c/£)~ where £c «< 1) is the ratio of the effective phonon
phase space to electron phase (cf. section 4 B) and £ = (T-T p )/
T. Thus, the fluctuation is insulator-like and tends to lower
t~e conductivity. The analogue of the Aslamazov-Larkin [67] dia-
gram, figure 3(b), vanishes for an electron band with electron-
hole symmetry [68]. It is small even if there is no electron-
20 L.J. SHAM
(a) (b)
- - - - electric perturbation
- - - electrons
'V\fV\.f' phon ons
Figure 3 - Processes contributing to fluctuation conduc-

tivity.
hole symmetry. It is possible to explain the conductivity and

dielectric behavior observed by the Johns Hopkins group [42,50]
and of the 'ordinary' crystals of the Penn group [43], but not
the extraordinary conductivity peak in terms of the Peierls'
state in a simple one-dimensional model.
We have not explicitly taken into account the large polariz-
ability of the TTF molecules in our simple model. It is conceiv-
able that some of our conclusions will be changed by a better
model. This is under further investigation.
ACKNOWLEDGEMENTS
I wish to thank Professor B.T. Matthias, Professor J. Bardeen
and Professor W. Kohn for helpful conversations. With pleasure,
I acknowledge again the invaluable contribution of my colleague,
Dr. B.R. Patton, to section 4 of these notes.
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Lett .• 26. 1324.
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lished).
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13. 390; (1966). Phys. Rev .• 149, 296.
lB. Mailfert. R•• Batterman. B.W. and Hanak. J.J. (1967). Phys.
Lett •• A24. 315; Vieland. L.J. (1972). J. Phys. Chern. Solids.
33. 58l.
19. For V3Si: Testardi. L.R. and Bateman. T.B. (1967). Phys. Rev .•
154. 402.
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154.628; Rehwald. W. (1968). Phys. Lett •• A27. 287.
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State Commun .• 9. 347.
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23. Kodess. B.N •• Kurithzin. V.B. and Tretjakov. B.N. (1971).
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(1971). Sov. Phys. JETP Lett •• 14. 225.
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E .• Hull. G.W. and Maita. J.P. (1967). Science. 156. 645;
Arrhenius. G•• Corenzwit. E •• Fitzgerald. R.• Hull Jr.,
G.W., Luo, H.L •• Matthias, B.T. and Zachariasen, W.H. (1968).
Proc. Nat. Acad. Sci., 61, 621.
25. Willens. R.H., Geballe, T.H., Gossard, A.C., Maita,J.P.,
Menth, A., Hull Jr., G.H. and Soden, R.R. (1970). Solid State
Commun., 7, 837.
22 L.J. SHAM
26. Webb, G.W., Vieland, L.J., Miller, R.E. and Wicklund, A.
(1971). Solid State Commun., 9, 1769.
27. Weger, M. (1964). ReV. Mod. Phys., 36, 176.
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303.
29. Berko, S. and Weger, M. (1970). Phys. Rev. Lett., 24, 55;
(1972). Computational Physics, (eds. Herman, F., Dalton, N.W.
and Koehler, T.R.), (Plenum Press), p. 59.
30. Weger, M. (1970). J. Phys. Chem. Solids, 31, 1621; Goldberg,
I.B. and Weger, M. (1971). J.Phys., C4, 188L.
31. Clogston, A.M. and Jaccarino, V. (1961). Phys. Rev., 121,
1357.
32. Barisic, S. and Labbe, J. (1967). J. Phys. Chem. Solids, 28,
2477; Cohen, R.W., Cody, G.D. and Halloran, J.J. (1967).
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(1966). Phys. Rev., 143, 390; Vieland, L.J. and Wicklund, A.W.
(1968). Phys. Rev., 166, 424.
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33, 58l.
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41. Maita, J.P. and Bucher, E. (1972). Phys. Rev. Lett., 29, 931.
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(1973). J. Amer. Chem. Soc., 95, 948.
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Garito, A.F. and Heeger, A.J. Solid State Commun •.
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Rev. 108, 1175.
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May Issue, p.17.
50. Bloch, A.N., Ferraris, J.P., Cowan, D.O. and Poehler, T.O.
Solid State Commun., (submitted for publication).
51. Patton, B.R. and Sham. L.J. (to be published).
52. Epstein. A.J., Etemad, S., Garito, A.F. and Heeger, A.J.
(1972). Phys. Rev., C5, 952.
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Rev., B1, 2929.
54. Abrikosov, A.A., Gorkov, L.P. and Dzyaloshinski, I.E. (1963).
Methods of Quantum Field Theory in Statistical Mechanics,
(Prentice Hall, New Jersey), chapter 7.
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PHONON CALCULATIONS IN METALS AND INSULATORS
R.M. PICK
Universite de Paris VI,

Departement de Recherches Physiques,
Escalier 22, 4 Place Jussieu,
75230 paris Cedex OS, France
A. GENERAL INTRODUCTION
The application of the microscopic theory of phonons to ac-
tual calculations is the subject of these lectures. In prin-
ciple I should thus cover the whole field of inorganic, and
organic crystals. In practice the situation is exactly the re-
verse because calculations have, in fact, been restricted only
to simple metals, i.e. metals without partly filled d shells,
except for few cases which shall be discussed either briefly
here or in L.J. Sham's lectures.
On the other hand, the basic reason for the present situa-
tion has to be understood if we want to have a prospective view
of it.
The basis of the microscopic theory was founded in the
early sixties at a time when computers were neither fast,
nor very large, and their use limited to some happy few.
The theory could thus be applied only to cases where dras-
tic simplifications were possible, which was the case for
simple metals, and very rewarding results were obtained
during that period.
When the theory got fully developed, by 1969, it was then
logically shaped in a form which was a mere continuation of
that used in the case of simple metals. But, it turned out
that this form was by no means suitable for the case of
other substances, particularly, semiconductors and insula-
tors. The amount of computation needed to obtain any sig-
nificant result appeared then to be, all of a sudden, ex-
tremely large. This explains why the first attempts to
25
26 R.M. PICK
use the microscopic theory in such cases has only started
very recently,
But the microscopic theory is, in fact, much more versa-
tile than its original formulation suggested, and it can
indeed be cast into forms which are, presumably, more ap-
propriate to numerical computations than the earlier ver-
sions. This is why I shall only briefly discuss the metal-
lic aspect of the problem, which is, in some respects, an
old subject. The rest of the lectures will be devoted to
the developments of schemes which will, hopefully, render
in the near future phonon calculations feasible in insula-
tors.
B. CALCULATIONS IN METALS
1 INTRODUCTION
Let us call Us La the displacement in the a-direction of the
atoms in the cell'L, and Css ' ,LL,aS the force constant coeffici-
ent which couples two displacements. The microscopic theory of
phonons, in its adiabatic version, shows that, (apart from a
constant which is of no interest here) the Fourier transform of
this coefficient is given by
x
( q + G') SZs'e - i ( q+G' ) Rs ' (Bl.l)
where
q is a first Brillouin zone vector,

G is a reciprocal lattice vector,
Zs is the charge of the nucleus 5, which is at Rs in
its cell,
-1
S (q + G,q + G')
-1
xlq+G'1 , (Bl.2)
e- 1 (q + G,q + G')isthe Fourier transform of the

inverse dielectric function of the crystal.
The exact calculation of (Bl.l) being impossible, the prac-

tical problem is to find which approximations can be made.
The first one consists in noticing that the core electrons
rigidly follow the nuclei when the latter move, so that they
should not play any role in the computation of force constants.
PHONON CALCULATIONS 27
This is usually taken into account by defining local pseudo-
potentials.
A local pseudopotential may be defined as the one seen by
the outer valence electrons and may be written as
VCr - Rs,L) -
-
f Ir -1 r' I zS(r'
~----~ - Rs,L)d
3
p' ,
where zS(r - Rs,L) is some charge distribution centered around

Rs,L' The effective charge [ZS(q)]q=O of this local pseudo-
potential is, by definition, Zs, the nuclear one, minus that of
the core electrons, and ZS(q + G) is such that it rapidly de-
creases for increasing Iq + GI. The Hartree, (or self-consist-
ent) Hamiltonian of the electrons is then simply
I
s,L
(Bl.3)
where (psc(r») is the valence electron charge distribution in

the crystal.
It is very easy to realize that the force constants will now
be obtained by:
(a) expressing the dielectric function, then S-l(q + C,
q + G'), with the help of the sole eigenfunctions and
eigenvalues of (Bl.3);
(b) replacing in (Bl.l) Zs by ZS(q + G).
One must nevertheless point out that several approximations
are made all at once in the preceding procedure:
(a) It is by no means evident that an object like a local
pseudo-potential does exist;
(b) The actual wave functions are not the solutions of
(Bl.3), because they must be orthogonal to those of
the core electrons. If one proceeds to this orthogonal-
ization, one expels, from the vicinity of the nucleus,
some electronic charge which has to be redistributed in
the rest of the crystal;
(c) Not any exchange term, which would compensate for the
use of a Hartree Hamiltonian in (Bl.3), has been in-
troduced there. This is, in principle, a large error.
Fortunately, the microscopic theory is only used in the
case of metals where neither the wave functions, nor the
eigenvalues of (Bl.3) are actually used.
The second approximation is specific to the case of simple
28 R.M. PICK
metals and will now be discussed.
2 APPLICATION TO SIMPLE METALS

The basic simplification with simple metals comes from the
fact that one can show that their pseudo-potentials are weak
enough to perturb only very slightly the electronic function of
a free electron gas. It is then legitimate to admit that, in
SCq + G,q + G')
= OG,G' + Iq +1 GI 41TX(q + G,q + G') Iq +1 G' I ' (B2.l)
the susceptibility function xCq + G,q + G') could be taken to

be that of a free electron gas, i.e.
with
x =
Iq + GI
2kr .,
is the Fermi momentum of the free electron gas.
The inversion of (B2.l) is then straightforward and one can

concentrate on the various questions raised in the introduction
of this section, namely:
(a) which pseudo-potential can be used;
(b) what is the importance of exchange and correlation
effects;
(c) what is the influence of the use of pseudo-wave func-
tions instead of the real ones.
The answers are as follows:
(a) There is no real answer to the first question.
On the one hand, the use of the approximate notion
of a pseudo-potential which is local is not limited to the
phonon problem. The same notion appears:
- in the computation of the exact eigenvalues of (Bl.3)
(or of its exchange modified version) thus on the exact
shape of the Fermi surface;
- in the binding energy of the crystal, thus in the
crystal structure of the solid;
- in the electron-phonon coupling, thus in the value
of the electrical resistivity ...
A long review article by V. Heine and M.L. Cohen [1] des-
scribes the best pseudo-potentials which simultaneously
fit all those data and any plausible one should not differ
very much from those.
On the other hand one could expect to improve our know-
ledge of the pseudo-potential of a given element by trying
to find, inside the above category, one which fits best the
phonon data. This turns out to be impossible because for
small values of Iql all pseudo-potentials are identical,
and for large Iq + GI values, the inverse dielectric func-
tion is weak enough to forbid any accurate determination
of ZS(q + G). For instance, for Aluminium, W. Hartmann
[2] obtained an equally good fit (with less than 3% error)
by using two different pseudo-potentials:
(B2.3a)
and
(B2.3b)
which differed by more than 20% for Iq + GI equal to the

second non-zero reciprocal lattice vector. Phonons are
thus not very sensitive tests for the choice of pseudo-
potentials.
(b) The role of exchange and correlation.
Various authors have tried to test this point by as-
suming that the dielectric function was much more affected
by the exchange and correlation properties than by the non-
zero value of the pseudo-potential. They have thus used
various electron gas expressions for Seq + G,q + G') which
took those effects into account in different manners and
checked their influence in using those various seq + G,
q + G') with the same pseudo-potential.
We can quote as a good example of this attitude the
work of D.L. Price et al. [3] on various alkali metals.
They took the pseudo-potential (B2.3a) with four forms of
x(q + G,q + G'):
- one was the self-consistent (or RPA) expression
(B2.2);
- the three others could be expressed as
x(q+G,q+G') = oG,G'XSC(q+G,q+G')
S -1
x{l - f<lq+GI)x C(q+G,q+G')oG,Gd , (B2.3)
30 R.M. PICK
as suggested by J. Hubbard [4], and f( Iq + GI) was
- the original Hubbard form [4]
2
u
feu)
2(u 2 + kr 2 + krT 2) ,
where krT is the Fermi-Thomas length;

- the Geldart-Vosko [5] modified form
where a 2 is such that x(q,q) satisfies the compressi-

bility sum rule in the long wave length limit;
- the self-consistent Singwi [6] expression which
leads to a correct pair correlation function of the
electron gas at every possible distance r.
Price et al. [3] found a systematic decrease of all
the phonon frequencies when going from the first to the
last approximation for Li, Na and K.
On the other hand, in Magnesium, E.R. Floyd and L.
Kleinman [7] found an increase in frequency when going
from the RPA to the Hubbard susceptibility, but obtained
also a decrease with respect tothe RPA when they used the
Kleinman-Langreth [8] form of the susceptibility, which
is a more sophisticated one.
The net effect of exchange and correlation seems thus
to be a lowering of the phonon frequencies as soon as one
takes seriously the,effect into account. It affects the
different wave lengths in different manners and can be as
large as 20% for some of them in the Price example. One
must nevertheless remember that those are only free elec-
tron gas results and that they may be different in real
solids.
(c) The effect of the orthogonalization to the core elec-
trons can only be tested when the pseudo-potential is
not a fitted one but is derived from first principles as
it is the case in the W. Harrison [9] or R. Shaw [10] cal-
culations. (In fact those authors use non-local pseudo-
potentials, but for the sake of clarity I shall not discuss
this point here). One can then show that the orthogonaliza-
tion effect is equivalent to a change of the charge of the pseudo-
potential; this change is usually a 10% one with individual fluc-
tuations of ±3%, and its effect is the same on every frequency.
3 CALCULATIONS ON OTHER METALS OR SEMICONDUCTORS

Very few calculations exists for non-simple metals because
the problem of inverting the S(q + G,q + G') matrix is, in the
general case, a formidable one and its possible solutions will
be discussed in the following part. I shall just point out here
that, on top of the calculations discussed by L.J. Sham for the
A-IS compounds, there exists to my knowledge:
(a) two calculations based on the factorization scheme
(see section C.2), one for Silicon by S. Sinha et al.
[11] which we shall briefly discuss in that section and
one by H. Hanke [12] in Nickel, where the d-electrons are
supposed to form a completely flat band, decoupled from
the conduction electrons;
(b) one calculation on Silicon by R.M. Martin [13] where
the role of the off-diagonal terms of S(q + G,q + G')
are inconsistently treated as rigid charges placed at the
center of mass of two neighboring atoms, and interacting
by an unscreened Coulomb potential with the charged Si
atoms.
The available informations are thus too poor for any conclu-
sion.
C. MICROSCOPIC THEORY OF PHONONS AND INSULATORS
1 INTRODUCTION
From a phenomenological point of view, when Kohn [14] anomaly
effects may be neglected, the phonon spectrum of metals can be
obtained from a direct Born-von Karman description of the total
energy of the crystal
£ =~ I Vs ,LaCss ' ,LL,aSVs ' ,L'S (CI.l)

a,S
s,s'
L,L'
where the force constant Css ' LL,aS is a very fast decreasing
function of the relative dist~nce IRs L - Rs' L' I. Due to the
symmetry of the force constant coeffi~ients with respect to the
interchange of indices, (Cl.l) is equivalent to the equation of
motion
s·· a
M Vs,L (Cl.2)
where MS is the mass of the atoms.

In insulators, the existence of long range electric forces
between the ions forces one to extend the preceding description
in the following way:
- First, (Cl.2) has to be modified as
32 R.M. PICK
L css 'LL,a8U,
, s , L,8
8,a' ,L'
(CI.3)
where Xss' ,LL,a8 is a mechanical polarization coeffi-

cient (not symmetrical in the interchange a,s,L <=>
8,a' ,L') and Es ',L,8 is the 8-component of the elec-
tric field on the atom a' ,L' ;
- Second, the polarization in the a-direction of the
atom a,L is given by
Ps, La
(Cl.4)
where xTss' ,LL,a 8 is the transposed matrix of

Xss' , LL,a8 and Ass' , LL,a8 is a non-local, symmetric
electric polarization coefficient;
- Finally, the local electric field and the local pol-
arization are related by
(Cl.S)
The set of the three equations (CI.3,4,S), where the C, X,

and A are rapidly decreasing functions of the relative distance
IRs L - Rs' ,L' I, is sufficient to describe all the properties
of an insulator phonon spectrum both in the short and long wave
length limit, provided the charge neutrality condition is ful-
filled, i.e.,
L Xss' ,LL,a8 0, ¥ a,8. (Cl. 6)

a,a'
L,L'
Nevertheless, the usefulness of these equations has usually
turned out to be small because the range of the C and X coeffi-
cients is not very short. The number of parameters to be fit-
ted becomes too large to obtain any meaningful fit, and the
whole procedure becomes questionable.
An alternative to the preceding method is provided by the
shell model (originally proposed by B.G. Dick and A.W. Overhaus-
er [15]) and its extended versions (due to U. Schroder and H.
Bilz [16]).
The basic idea is that one can take more or less into account
the role of the electrons by a classical description:
- The crystal is first divided into atoms (or cores)
and electrons (or shells) and a charge ZS (resp. yS)
is given to each atom (resp. shell) existing at a
point s,L;
- The shells (which are supposed to simulate the elec-
tronic distribution) are allowed not only to displace
but also to deform. In consequence, while variables
Us,L are attached to the core movements, variables
Ws,L , attached to the shells, are of a more general
nature, and the index a describes, among other informa-
tion, the point s-symmetry group representation accord-
ing to which Ws,L a transforms. For instance Ws,L a
could describe a movement of a shell, as well as its
symmetric or antisymmetric deformation etc .... ;
- The total energy of the system is then written as
e: =~ L
as
ss'
LL'
+ I U
s,L aJj ss',LL' ab ws',L' b
ab
ss'
LL'
+ ~ I (Cl. 8)
ab
ss'
LL'
where, for instance
Jjss' ,L1'ab
(Cl. 9)
which means that each force constant contains a short

range part (Dss' LL,aS in the present case) plus a dir-
ect Coulomb inte:action between the corresponding
charges if both variables U and W describe a displace-
ment;
34 R.M. PICK
- The equation of motion of each variable is finally
obtained by writing that the generalized force on each
variable is equal to minus the derivative of £ with
respect to this variable and that the mass of each
electron is zero, while that of a core is Ms;
- At last, the charge neutrality of the primitive cell
is expressed by the condition L ZS + L yS = o.
s s
The success of this model relies on three facts:
(a) the short range forces one needs to use are always
very short range indeed: to my knowledge, one or two
second nearest neighbors have always been sufficient to
describe any phonon spectrum;
(b) Fits can be obtained with physically reasonable values
for the effective ionic charges;
(c) The method is not restricted to insulators and gives
good results in e.g. semiconductors or metallic car-
bides. .
Its success has thus been a challenge to theoreticians, and
since 1968 there have been various attempts to justify this mod-
el from the microscopic point of view. The next sections will
be devoted to the description of the most successful ones, and
to what can be learned from them.
2 THE SINHA FACTORIZATION ANSATZ

A basic difficulty of the microscopic theory is the inversion
of the Seq + G,q + G') matrix (equation (B2.l)). S. Sinha andR.P.
Gupta [17] proposed to solve this problem by the following An-
satz:
Seq + G,q + G') oG,G' + L
I;' Cq
- *
+ G)ars (q + G)Nss,a SCq)
as
ss' (C2.l)
where Rs would be some chosen site (analogous to those intro-

duced in the shell model), and Nss,aSCq) would be some periodic
function of q.
The argument supporting (C2.1) is the following: in an insul-
ator,
xCq+G,q+G')
I;' \
I
( cp i k e -iCq+G)orl' )(. I
cpJ k + q cpJ k + q e
iCq+G')orl i )
cp k
2 L L •• (C2.2)
k ij Elk - EJk+q
where k is a first Brillouin zone vector, i labels any occupied
band and j any empty band.
Now, the matrix element of the numerator of (C2.2) may be
written as
( ¢i k Ie -i(q+G)orl'
¢Jk+q
)
(C2.3)
where Pa is the electron momentum operator.

If each band is sufficiently narrow, the matrix element of
the rhs of (C2.3) does not depend very much on k. Also, the
denominator of the rhs does not depend on k or on G if Ei k -
Ejk+q is large enough and if the numerator is anyhow very
small for large IGI.
Then if one uses (C2.3) into (C2.2) it is not unlikely that
the summation on k will lead to (C2.l). Its main interest is
that Seq + G,q + G') can be formally inverted. In fact, as can
be verified, one obtains
-1 \
S (q + G,q + G') = cG,G' - L
as
ss' (C2. 4)
where
(C2.5)
Xe i ( q+G) (Rs - Rs ' ) .

0
(C2.6)
One may then use directly (C2.4) into (Bl.l), modified by the
use of some local pseudo-potentials to obtain the expression of
Css,aS(q). But it is a purely algebraic matter to prove that
the same force constant could have been obtained from a shell
model in which
Css ' , LL,aS
, 3 3
xzs (r' - Rs' ,L,)d 1'd 1", (C2.7a)
36 R.M. PICK
-
Dss' ,LL'
as
xr , Cr - 3
Rs' ,L')d rd r',
3
(C2.7b)
1'ss' , LL,aS
, 3 3 -1 S
xfs Cr' - Rs' ,L')d rd r' + N sst ,LL,a, (C2.7c)
expressions in which zSCr - Rs) is the charge density creating

the local pseudo-potential (see section B), [SCr) is the Four-
ier transform of rCq + G) while N-1 ss ' ,LL,aS is that of
N-1ss ' aSCq).
(C2.7) shows that the factorization Ansatz of Sinha et al.
is strictly equal to a shell model in which:
(a) all the electronic variables describe shell displace-
ments;
(b) each charge is simply replaced by a charge distribu-
tion (zSCr - Rs,L) for the cores and [SCr - Rs,L) for
shells);
(c) the only short range forces appear in the shell-shell
interaction through the term N-1 ss ' ,LL,aS, all the
other forces being strictly of Coulomb origin;
(d) clearly the charge neutrality of the crystal is rela-
ted to the zSCr - Rs) and [SCr - Rs ), and the exact
relation is discussed in Sinha's paper.
Sinha et al. also generalized their Ansatz in order to be
able to describe not only insulators but also semiconductors,
and from a computation of eCq + G,q + G) by J.P. Walter and
M.L. Cohen for Silicon, they derived, by assuming that
p., Ir - Rsl < r c,

o·, Ir - Rsl > r c'
(Rs being a silicon site), a phonon spectrum in rather good

agreement with experiment.
Though Sinha's result for Si is somewhat encouraging, two
kinds of criticism can be given to his procedure:
(a) The factorization Ansatz has to be justified;
(b) The shell model obtained suffers from three deficien-
cies with respect to the phenomenological one:
- There are neither core-core, nor core-shell short
range forces;
- All the shell variables describe displacements, while
'experimentally', the necessity of e.g. symmetric de-
formation variables is well established;
- The ac~ual core charges are the pseudo-potential
ones, which have nothing to do with the ionic one for
an anion (for instance, for a chlorine atom, the
former is +5e while the latter is -e), while the 'ex-
perimental' core charge is smaller than the ionic one.
We shall see in the last two sections how one can remedy
those criticisms.
3 THE EXACT FACTORIZATION PROCEDURE

We shall see in this section how the Sinha et al. factoriza-
tion procedure can be exactly justified with the help of Wannier
functions.
Let us recall that the Wannier functions related to a given
band i are
(C3.1)
where the summation runs over all the vectors k inside the first
Brillouin zone and RSi L represents the point of the L-th cell
with respect to which the corresponding Wannier function has the
maximum symmetry.
(In fact the preceding definition has to extended to the case
of band complexes, formed by n bands completely disconnected
from all the other bands. But, as the subsidiary difficulties
associated with the use of band complexes do not affect the gen-
eral scheme, we shall neglect them here).
(C3.1) can also be expressed under the equivalent form
(C3.2)
(C3.2) may then be used in order to express the matrix element

already discussed in the preceding section. One finds
= t fWiCr - RSi,O)e-iCq+G)Cr-Rsi,O)wjCr - RSj,t)d 3r
i[Ck+q)Rs ]' t-Cq+G)oRSi,O]

xe ' , (C3.3)
38 R.M. PICK
where
o is the index of the origin cell,
t is the index of another cell,
and where we have used the fact that Wannier functions can al-
ways be chosen real.
(C3.3) may then be used to compute the susceptibility func-
tion (C2.2)- when the summation on k is performed one obtains,
in very good analogy with the preceding Ansatz:
x(q + G,q + G') L JA*(q + G)NAB(q)JB(q + G')

A,B
(C3.4)
where
JB(q + G) _ fpB(r - RSi,o)ei(q+G)(r-Rsi,O)d3r
fw i (r - RSi,O )ei( q+G) (r-Rsi,O )w j (r - RSj, t> d3r, (C3. 5)
B _ i,j,t,
-i(k+q)(Rt-Rt' )
o·l , l., o·],]., 8'11 L .::::..e---:_ _: - - - _ (C3.6)
k Ei k - Ejk+q
(C3.4) can then be used to obtain Seq + G,q + G') with the help
of equation (B2.l). It is then apparent that:
- (C3.6) is the exact definition of Sinha's periodic
tensor N(q), (but with different indices);
- the composite index B = i,j,t has replaced Sinha's
indices a,s;
- JB(q + G) plays the same role as (q + G)afS(q + G)
did in the preceding section. Indeed, for G = 0, in
the q 7 0 limit JB(q) is proportional to Iql because
the Wannier functions form an orthonormal set, and in
B, the two indices i and j are always different.
One can now repeat the same procedure as in section 2 to ob-
tain the force constants, and to identify them with those of a
shell model. One now obtains for its coefficients:
same expression as (C2.7a),

Ts 1. s ,.1, LL' ab
-1 b
+ N sis'i,LL,a (C3.7c)
The comparison between (C2.7) and (C3.7) shows that the in-
troduction of the Wannier functions has three advantages:
- It justifies, with only a slight modification,
Sinha's Ansatz;
- It shows that it is not possible to use only dis-
placement variables, as was implicitly supposed in
section 2. The actual variables have to be interpreted
not as displacements but as the amount of charge trans-
ferred from an occupied Wannier function wi.(r - RSi,L)
to the primitively empty Wannier function w] (r - Rsj,L+t)
under the influence of a core motion;
- It indicates that the short range interaction term
N-1 sis 'r ,LL,ab is the only one which has no classical
analog, as it involves only energy differences between
various states.
Nevertheless, the absence of core-core and core-shell short
range interactions, as well as the appearance of the pseudo-pot-
ential charge has still to be remedied.
4 THE INTRODUCTION OF THE IONIC CHARGES

The replacement, inside the equations (C3.7) of the pseudo-
potential charges by the ionic ones has recently been shown to
be possible [22], at least for ionic crystals, and to lead to a
complete formal agreement with the shell model. We shall not
enter here into any detail, but shall rather give here the bas-
ic idea, and discuss some of its consequences.
For the valence band it is quite reasonable to assume that
the Wannier functions are well localized around some core. One
can thus take, as a first approximation to the ionic charge
distribution
zS(r - Rs,L) + I jwi(r - Rsi ,L)j2,(C4.1)

i(s)
where I means that this summation is restricted to the bands

i(s)
40 R.M. PICK
i for which Rsi,L coincides with Rs,L. Then
As the Wannier functions form a complete set of functions one

can write
owi(r - Rs~,
. L) \' ab
------==----
ora = ~ bl.. Hss·
~,
LL wU(r - Rsu,L+t), (b - u,t) (C4.3)
where the coefficient HSisi,LLab is
Hs ~•s ~,
· LLab (C4.4)
VTOT(r) being the one-electron potential of the crystal. (C4.3)

implies that
o[pSion(r - Rs,L) - zS(r - Rs,L)]

oRs,L a
can be expressed as a linear combination of products of Wannier

functions, one of them being always a valence one centered at
Rs,L. It is then possible to make, in the total energy E of the
shell model, the interaction coefficients of which are (C3.7),
the following change of variable:
Vs. Lb
~,
\' Hsis,LLbaUs,L·
l..
a (C4.5)
a,s
When the total energy is expressed in terms of U and V, the in-

teraction coefficients become
-ess ' ,LL as

\' ab - 1 bb ' b' S (C4.6)

(Contd) + L Hssi,LL N siSi' ,LL' HSi's' ,L'L' ,
b,b'
SiSi'
Dss " LL aS [fpSion(r - Rs,L) Ir 1 pB(r' - RS'i,L')

1 ,
= d
3R s,L a - r' I
(C4.7)
3 3,]
x d rd r +
\'
L HsSi,LL ab N-1sisi' ,LL bb' ,
b,si
while TSisi' ,LL ab remains unchanged.

(C4.6) implies that at the same time, we have introduced the
movements of the assumed ionic charges and the short range forces
of a quantum origin, and the same is clearly true for (C4.7).
Equations (C4.6,7) and (C3.7c) are thus the exact analog of
the phenomenological coefficients. This analogy is still more
complete if we notice that, for a given site si, one can always
make linear combinations of the variable b so that pB(r - RSi,L)
has a given symmetry property with respect to si. All the pro-
perties of the shell model are then completely reproduced.
(C4.6,7) also show the large arbitrariness of shell models:
the expressions we have derived have been obtained under the
a~sumption that pSion(r - Rs,L) was the ionic charge distribu-
t~on. Other formulae could as well have been taken as start-
ing points; they would have led to numerically different re-
sults.
In summary, the recent theoretical efforts have given a def-
inite foundation to the shell model. But the expressions of
the various coefficients are still too complicated, as such, to
allow for simple computations. An effort to discover the pos-
sible and practical simplifications or approximations is now
needed. Nevertheless, the possibility of computing phonon spec-
tra of insulators by following those or similar lines does not
seem to be beyond the capacity of present time computers.
REFERENCES
1. Cohen, M.L. and Heine, V. (1971). Solid State Phys., 24, 37.
2. Hartmann, W.M. and Milbrodt, T.O. (1971). Phys. Rev., B3,
4133.
3. Price, D.L., Singwi, K.S. and Tosi, M.P. (1970). Phys. Rev.,
B2, 2983.
4. Hubbard, J. (1957). Proc. Roy. Soc., A243, 336.
5. Geldart, D.J.W. and Vosko, S.H. (1966). Can. J. Phys., 44,
2137.
6. Singwi, K.S., Sjolander, A., Tosi, M.P. and Land, R.H.
(1970). Phys. Rev., Bl, 1044.
? Floyd, E.R. and Kleinman, L. (1970). Phys. Rev., B2, 3947.
42 R.M. PICK
8. Langreth, D.C. (1969). Phys. Rev., 181, 753.
9. Harrison, W. (1964). Phys. Rev., 136, AII07.
10. Shaw, R.W., Jr. and Pynn, R. (1969). J. Phys., C2, 2071.
11. Sinha, S.K., Gupta, R.P. and Price, D.L. (1971). Phys. Rev.
Lett., 26, 1324.
12. Hanke, W. Phys. Rev., (to be published).
13. Martin, R.M. (1969). Phys. Rev., 186, 871.
14. Kohn, W. (1959). Phys. Rev. Lett., 2, 393.
15. Dick, B.G. and Overhauser, A.W. (1958). Phys. Rev., 112, 90.
16. Schroder, U. (1966). Solid State Commun., 4, 347; Nusslein,
V. and Schroder, U. (1967). Phys. Stat. Sol., 21, 309; Bilz,
H. (1972). Computational Solid State Physics, (Plenum Press,
New York), p. 309.
17. Sinha, S.K., Gupta, R.P. and Price, D.L. Phys. Rev., (to be
published).
18. Walter, J.P. and Cohen, M.L. (1970). Phys. Rev., B2, 1821.
19. Pick, R.M. (1971). In Phonons, (Flammarion Press, Paris),
p. 20.
20. Hanke, W. (1971). In Phonons, (Flammarion Press, Paris),
p. 294.
21. Sham, L.J. (1972). Phys. Rev., B6, 3584.
22. Gupta, R.P. and Pick, R.M. (To be published).
EXCITATIONS IN SUPERFLUID HELIUMt
J. RUVALDS
Physics Department, University of virginia,

Charlottesville, Virginia 22901
1. INTRODUCTION
The elementary excitation spectrum of liquid helium has been
the subject of intensive theoretical interest following the
pioneering work of Landau in 1947 [1]. In order to explain the
observed superfluid and thermodynamic properties of helium at
very low temperatures, Landau proposed that the excitation spec-
trum of the liquid consists of phonon excitations at small mom-
enta, free particle excitations at very large momenta, and rot on
excitations with an energy minimum ~O at intermediate momenta.
The roton dispersion may be expressed in the form
(k - ko)2
E(k) = ~o + ----
2lJ
(1.1)
and the effective mass lJ, as well as the energy gap ~O and mom-
entum kO may be obtained accurately from recent neutron scatter-
ing data. The existence of a roton energy gap is essential to
understand the thermodynamic properties in the superfluid state.
Furthermore, the possible frictionless flow of liquid helium at
low velocities may be understood in terms of the excitation
spectrum as suggested by Landau [1]. For example, the critical
velocity Vc = minE(k)/k, which is the upper limit for superfluid
flow, corresponds to the kinematically allowed creation of an
excitation in the superfluid. The Landau spectrum of equation
t Work supported by the National Science Foundation; Grant No.

NSF-GH-32747.
43
44 J. RUVALDS
(1.1) yields Vc = ~o/ko. Hence the roton excitations which ex-

hibit a finite energy gap are of particular interest in the
superfluid.
A microscopic theory of the excitations in a weakly interact-
ing Bose gas was first considered by Bogoliubov [2]. His theory
is based on the assumption that a finite fraction NO of helium
atoms is in the zero-momentum condensate. By means of a canon-
ical transformation, Bogoliubov then obtained an excitation dis-
persion of the form
(1. 2)
where £k = k2/2m4 is the free helium particle dispersion and

V(k) denotes the Fourier transform of the interatomic helium
potential. For reasonable models of the interaction potential
V(k), the form of the Bogoliubov spectrum EB(k) is in qualita-
tive agreement with the form of the excitations proposed by
Landau on phenomenological grounds. It is interesting to note
that, within the framework of the Bogoliubov theory, the exist-
ence of an energy-gap in the spectrum is a consequence of the
finite occupation of the zero-momentum condensate.
An alternate approach to the theory of the excitation spec-
trum of liquid helium has been presented by Feynman and Cohen
[3]. Using a variational technique, they were able to derive a
spectrum which exhibits rot on like structure, but gives a value
for the gap ~ considerably larger than the experimental value.
A number of attempts has been made to derive the excitation
spectrum for a system of Bosons from first principles. Lee,
Huang, and Yang [4] have obtained a phonon-like spectrum for a
model system of a low density gas of hard spheres. Other micro-
scopic theories of the interacting Boson system have been pre-
sented by Brueckner and Sawada [5], Beliaev [6], Hugenholtz and
Pines [7], and Gavoret and Nozi~res [8]. Generally speaking,
these theories are remarkably successful in the phonon region
of small momenta; however, they do not yield a satisfactory de-
scription of the roton region of the excitation spectrum.
An alternative microscopic approach to the excitation spec-
trum of a Bose gas has been developed by Feenberg and coworkers
[9]. These theories develop a method of correlated basis func-
tions (CBF) which may be used to calculate various properties
of the excitation spectrum from first principles.
From the experimental point of view, inelastic neutron scat-
tering [10] has provided a direct and accurate probe of the ex-
citation spectrum and verified some of the proposed features of
the spectrum to the extent shown in figure 1. Thus the exist-
ence of a low energy spectrum (phonons and rotons) has been de-
monstrated. However, the neutron data reveal considerable struc-
ture at energies E ~ 2~O which cannot be understood in terms of
previous theories considering non-interacting elementary excita-
tions.
EXCITATIONS IN SUPERFLUID HELIUM 45
56.--------,,--------,---------,--------or--------,
48
40
32
~
Ll.I
;>,
2?
"
'"
Ll.I
24
16
o 1.6 4.0
- Momentum k(A - I)
Figure 1 - The excitation spectrum as derived by Feynman

and Cohen (dotted curve), and the excitation spectrum ob-
tained from neutron scattering experiments of reference
[10] (solid lines). Note that the experimental results
show the existence of two branches in the spectrum with a
peculiar dispersion in the vicinity of 2~0. The neutron
data taken at T = 1.loK yield the following parameters:
~O = 8.6S oK, ~l = 13.9°K, kO = 1.91 X-I,
kl = 1.1 X-I,
\l0 = 1.06 x 10- 24 g, and \ll = 3.3 \l0.
In recent years there have been vigorous experimental and

46 J. RWAms
theoretical efforts to determine the nature of the interactions
between excitations in superfluid helium. The coupling of excit-
ations provides an explanation for some of the anomalous feat-
ures of the neutron data as we shall see below, and may be suf-
ficiently strong to form bound states of excitation pairs.
The purpose of the present paper is to review our current un-
derstanding of the excitations in liquid helium with particular
emphasis on their interactions. This effort is motivated prim-
arily by the recent recognition that an arbitrarily weak attrac-
tive coupling gives rise to bound states of roton pairs [11,12]
The formation of these two-roton bound states results in a sig-
nificant modification of the single excitation spectrum by hybri-
dization of one-phonon states with bound rot on pairs. This hy-
bridization mechanism provides a simple physical explanation for
the existence of two branches in the excitation spectrum as ob-
served in recent neutron scattering data [10]. Furthermore, the
final state interactions responsible for the binding produce a
strong renormalization of the two-roton spectrum as well. The
latter 5pectrum has been studied using Raman scattering experi-
ments by Greytak, et al. [13,14], and exhibits several anomalous
features. In particular the Raman scattering data provides evi-
dence for the existence of a bound roton pair in the i = 2 angu-
lar momentum state [14].
The strong effective coupling of rotons is a consequence of
the very large density of states corresponding to pairs of these
excitations formed near the energy minimum of the spectrum [11].
Alternately, the physical origin of the strong coupling may be
associated with the small group velocity of excitations near the
roton minimum [12]. As a result, the Born and Hartree-Fock ap-
proximations break down for roton scattering and the final state
interactions must be taken explicitly into account. We discuss
the two-roton bound state problem in section 2, using a simple
phenomenological model for the roton coupling.
In section 3 we present a discussion of the level repulsion
or hybridization of one phonon excitations with coupled pairs of
excitations. The hybridized excitations are then discussed in
view of the two-branch structure recently observed by neutron
scattering experiments [10] and shown in figure 1.
Several theories of the roton lifetime have been developed
which take into account the multiple scattering of rotons [15].
These calculations demonstrate the inadequacy of the Born approx-
imation results for this problem and establish upper bounds on
the roton broadening in the s-wave scattering channel. The lat-
ter result suggests that scattering in several angular momentum
channels is required to obtain agreement with experiment, and
therefore a point contact model for roton coupling is inadequate.
Analogous conclusions have been drawn from theoretical calcula-
tions of the temperature dependence of the roton energy [15]
which is also dominated by roton-roton collisions. These results
are discussed in section 4. As shown in section 4, there has
been considerable progress in the understanding of the roton
scattering processes on the basis of simple phenomenological
models of the roton coupling. It should be noted, however, that
these models are inadequate in several respects and, in partic-
ular, do not yield quantitative agreement with the experiment-
ally measured values of the roton lifetime.
Recently there have been attempts to develop a microscopic
theory of roton interactions and thereby bridge the gap between
recent work based on phenomenological coupling models and the
microscopic formulation of excitations in Bose systems. In the
past the density operator has been used successfully as a collec-
tive variable in the theory of quantum liquids. The formulation
of the excitation spectrum of a Bose liquid using density collec-
tive variables was first analyzed by Bogoliubov and Zubarev [17],
who developed microscopic expressions for three-phonon coupling,
which is responsible for hybridization effects discussed in sec-
tion 3. These processes have also been considered by Feenberg
and coworkers [9], and more recently by Sunakawa, et al. [18,19].
A microscopic approach to the theory of direct roton-roton scat-
tering processes has been developed by Rajagopal, Bagchi and Ruv-
aIds [20]. We have derived the Hamiltonian for the direct coup-
ling of a pair of excitations by an extension of the Sunakawa
formalism based on collective density variables. The contribu-
tion of the new direct processes (derived in reference [20]) to
the scattering amplitude of the roton-roton collision is found
to be of the same order of magnitude as the indirect processes
(second-order in the three-phonon vertex) considered by Sunakawa,
et al. [19]. The roton-roton interaction is seen to be attract-
ive, in qualitative accord with previous phenomenological theor-
ies [11]. However, the strength of the 'bare' coupling is an
order of magnitude larger than estimates based on experimental
data. To resolve this discrepancy a renormalization procedure
has been outlined which reduces the strength of the roton-roton
interaction, bringing the coupling in closer agreement with prev-
ious estimates. Thus the renormalization of vertex functions and
quasiparticle propagators is shown to be of great importance in
relating microscopic theories to phenomenological parameters ob-
tained from experiments [20]. The current status of microscopic
theories of the excitation interactions is discussed in section
5 of this paper.
It is well known that the addition .of small concentrations of
He 3 to liquid He 4 produces several interesting changes in the
thermodynamics of the superfluid [21]. In this case the Fermion
He 3 quasiparticles are strongly 'dressed' or renormalized by the
interaction with the Boson excitations (phonons and rotons) char-
acteristic of He 4 . This situation is formally analogous to the
Polaron problem in solids which is a consequence of strong elec-
tron-phonon coupling. In section 6 we briefly discuss the scat-
tering of quasiparticles in He 3 -He 4 mixtures, with an emphasis
on the general features of the scattering amplitudes which may be
related to the scattering of excitations in other systems. The
general results bear formal similarities [22] to two-roton scat-
48 J. RWAWS
tering problem discussed in section 2 and may have relevance to
the theory of excitations in solids as well.
The last section of the present paper contains some conclud-
ing remarks emphasizing the similarities between excitations in
superfluid helium and various excitations in solids. It is in-
teresting to note that the strong effective coupling of excita-
tions appears to be a general feature in solids as well as in
the superfluid state; for instance, bound pairs of phonon and
magnon excitations may occur in solids, and the hybridization of
one- and two-excitation states can have a significant effect on
their physical properties, as demonstrated previously by several
authors.
2. TWO-ROTON BOUND STATES

The existence of bound roton pairs in superfluid helium was
first suggested by Ruvalds and Zawadowski [11] and independently
by Iwamoto [12]. By considering the final state interactions
for the scattering of two quasiparticles they found that the
binding of two excitations near the energy minimum (or maximum)
region of the spectrum, i.e., rotons with k ~ ko (or 'maxons'
with k ~ kl), occurs for arbitrarily weak values of the coupl-
ing between excitations [11,12]. An attractive coupling lowers
the energy of the excitation pairs and gives rise to a bound
state of two rotons, whereas a repulsive interaction produces
binding of two maxons. These theoretical efforts were stimul-
ated by anomalous structure in the two-roton Raman spectrum meas-
ured by Greytak and Yan [13], which exhibits a strong peak cor-
responding to the creation of two rotons by the light scattering
process and a peculiar minimum in the energy range corresponding
to the creation of two maxons. This anomalous structure has been
attributed [11,12] to the binding of roton pairs by an attractive
coupling between excitations; an attractive coupling also dep-
letes the density of states in the two-maxon region in agreement
with the Raman data.
Later Greytak and co-workers obtained more accurate data on
the Raman spectrum of liquid helium which demonstrated that the
observed peak was at an energy below the two-roton continuum
[14], and that the scattered roton pair was in a d-state of rel-
ative angular momentum. Thus their Raman data [14] provided con-
vincing evidence for the exsistence of a bound state of two rot-
ons in the i = 2 channel.
According to the Stephen theory [22] of light scattering from
liquid helium, the Raman spectrum samples only the d-wave two-
roton states, so that the existence of bound pairs in other angu-
lar momentum channels cannot be ruled out by the Raman data.
To simplify the discussion of the bound state formalism in the
present section we shall consider the model Hamiltonian
H
(2.1)
where the unrenormalized spectrum E(k) is considered to be the

continuous phonon-roton branch proposed by Landau [1], and de-
rived by Feynman and Cohen [3], Bkt (Bk) denotes the creation
(destruction) operator for an excitation of the liquid helium;
g3 and g4 are momentum-independent coupling parameters which
give rise to hybridization and direct scattering of excitations
respectively. The validity of this model will be discussed below.
To examine the structure of two-roton bound states we restrict
attention to the energy region extending from the roton minimum
~O to the local maximum ~l shown in figure 1. Hence we treat the
roton-roton scattering as a two-body problem, since the contri-
butions from,coupling to small q phonons are not taken explicit-
ly into account and the population of roton states is small in
the temperature range of interest. In our treatment, phonon ex-
change processes are considered to be included in the effective
g4 coupling parameter.
The mathematical development can be conveniently expressed
using Green's function techniques [11]. Hence we introduce the
propagator for a single elementary excitation
(0) Z(k) 1
(2.2)
G1 ( k ,w ) = -w--"""::E:-;(';":'k+)-+-'i=r - w - E(k) + ir '
where we consider the strength Z(k) to be unity and the excita-

tion lifetime r- 1 is considered constant.
The scattering process for two excitations can be expressed
in terms of a Bethe-Salpeter equation for the two-excitation
Green's function which includes multiple scattering terms to all
orders. The propagator for two free excitations is given by
xG (0) (k w') (2.3)

1 "
where K =kl k2
+ is the total momentum of the excitations. It
is convenient to rewrite equation (2.3) in the form
F(K,w)
= fP2 (O)(K,W' )dw' (2.4)
w - w' + 2ir
50 J. RWAWS
where P2(0)(K,w') denotes the joint density of states for two
excitations. Using the simple point contact model for the ro-
ton-rotan coupling, it is a straightforward task to solve the
Bethe-Salpeter equation by summing the diagrams representing
the multiple scattering of two rotons [11]. The result for
the Green's function for interacting excitations is
2F(K,w)
(2.5)
The poles of the propagator G2(K,w) determine the energies of

bound excitation pairs. Thus the binding criterion, 1 - g4
ReF(K,w) = 0, is simply related to the coupling g4 and the
joint density of states P2(0)(K,w) appearing in equation (2.4).
Although the present model Hamiltonian can form only bound
states with a-like symmetry, the extension of our analysis to
states with finite angular momentum is straightforward and is
discussed elsewhere [11,12].
The density of states P2(0)(K,w) exhibits different structure
in various momentum regions and, since the binding criterion is
sensitive to the form of P2(0)(K,w), we shall discuss two repre-
sentative cases separately. First we consider the K= 0 case which
is observable by light scattering experiments and then proceed
+
to discuss the K 0 region which is pertinent to the neutron
data.
A BOUND STATES WITH K = 0

In Raman scattering experiments the momentum of the light is
very small relative to the rot on momentum and consequently the
light samples only the two-excitation spectrum with total mo-
mentum zero. We limit our discussion of the spectrum to the
idealized case of infinite roton life-time (r = 0), and refer
the reader to reference [11] for the finite lifetime analysis.
Since the primary energy of interest is quite close to the
external points of the dispersion curve shown in figure 1, it
is a good approximation to use a parabolic form for the excita-
tion dispersion:
(k - ko )2
Eroton ~O + (2.6a)
2~O
(k - kl)2
Emaxon ~l - (2.6b)
2~1
where the 'maxon' label simply refers to excitation near the ~l

local maximum. The unperturbed joint density of states follows
from equation (2.6) and is given by
EXCITATIONS IN SUPERFLUIn HELIUM 51
(2.7)
The above formula is, of course, valid only near the threshold
regions w ~ 2~0 and w ~ 2~1. It is apparent that the unrenorm-
alized spectrum of equation (2.7) exhibits two singularities as
shown by the dotted lines in figure 2.
10
:1
~
'c'"::J
y= 0
t' I - 0.05
,
g~ =
1: 6
\
~
"
.!: \
W \
4
<3
,
I I
II
\ I
::.:
.....
~ ..... /
'~""'"
--------' .,,/
0
- 0.4 - 0.2 0 0.2 0.4 0.6 O. 1.0 L2
Ener gy (E)
Figure 2 - Calculated joint density of states P2 for two

rotons with zero total momentum plotted as a function of
dimensionless energy £ = (w - 2~0)/2D. Dotted lines in-
dicate the spectrum in the absence of interactions., In-
clusion of an attractive roton-roton coupling removes the
singularities at £ = 0 and £ = 1, shifts the spectrum to
lower energies, and splits a two-roton bound state off
below the two-rot on continuum as shown by the solid lines.
In this figure the single-roton lifetime was taken to be
infinite, i.e., y = 0, and g'4 = ~k02rr-2(~0/2D)~g4.
The influence of interactions on the two-roton spectrum is

manifested by a renormalization of the density of states P2(w)
and also by broadening associated with a finite roton lifetime.
In the interest of clarity, we neglect lifetime effects and
present a calculation of the spectrum only in the vicinity of
the two-roton energy and not display explicitly the contribu-
tion from the maxon region (w ~ 2~1)' Combining equations (2,
4,7) we obtain
52 J. RUVALDS
F(K = O,E) = 2 ( 2k0lT ) 2 ~021 J2D _1

°E- X 2dx
x + i8
(2.8)
in terms of the variables x = w' - 260, E w - 260, and a cut-

off energy D = 61 - 60.
Below the two-roton continuum, i.e., E < 0, a trivial inte-
gration in equation (2.8) yields
- i8. (2.9)
In the limiting case 8 + 0, we use equation (2.5,9) to obtain

the renormalized density of states
1
P2(K,w) - 4lT ImG 2 (K,w), (2.10)
which takes the form
P2(K = O,E < 0) = __1__ 8[1 - g4ReF(K O,E < 0)]. (2.11)
2g4
A bound state of two rotons with energy below the continuum

exists if the argument of the 8-function in equation (2.11)
vanishes. It follows, then, from the analytic structure of
F(K = O,E < 0) given in equation (2.9), that a bound solution
exists for arbitrarily weak attractive coupling. In the weak
coupling limit the binding energy from equations (2.9-11) is
found to be
(2.12)
The fact that a bound state of two rotons is created by arbi-

trarily weak coupling is a consequence of the singularity in
the unperturbed two-roton density at the E = 0 threshold. It
is easy to show, and reasonable on physical grounds, that an
attractive coupling cannot give rise to a bound state of the
two maxons, but rather depletes the two-maxon density of states.
A similar calculation in the energy region w ~ 261, shows
that a repulsive coupling (g4 > 0) would create a bound pair of
maxons above the two-excitation continuum under consideration,
i.e., at w > 261' The latter situation is realized in solids
where the repulsive anharmonic coupling can produce a bound
state of two phonons, providing that the strength of the anhar-
monic interactions exceeds a critical value [23].
Turning now to the continuum energy region E > 0 equation
(2.4) gives
EXCITATIONS· IN SUPERFLUID HELIUM 53
Substituting this expression into equation (2.10) we obtain the

renormalized spectrum
_l
A E 2
O,E = '4 14 )
1]2 + (nAg4) 2E-1
> 0) -;=[1------;---.--....::---,-~----- (2.
g~ln I E~l+ (2D)~1
E2 - (2D)2
where A = 2(ko/2n)2~0~. The complete spectral function

P2(K = O,E) from equations (2.11,14) is plotted in figure 2,
and exhibits the strong renormalization of the two-excitation
spectrum by relativity weak coupling (the coupling parameter
g4 used in figure 2 was chosen to give qualitative agreement
with the Raman data of reference [13]). The two-maxon contri-
bution to the spectrum, although not calculated here, is also
shown in figure 2. It is interesting to note that an arbitrar-
ily weak interaction g4 +
0, regardless of sign, removes both
singularities in the unperturbed spectrum P2(O)(K = O,E) at en-
ergies w = 260 and w = 261 respectively. This feature follows
from the singular nature of the unperturbed density of states
at the continuum thresholds. Thus a weak coupling gives rise
to a bound roton pair with considerable intensity and depletes
the spectrum within the continuum to the extent shown in figure
2. It is interesting to note that the value of the coupling
strength used in figure 2 is considerably smaller than values
of the coupling estimated from viscosity measurements [11].
To make an accurate comparision between the above theory and
experiment, it is necessary to include a finite roton lifetime
in the calculation of the spectrum [11] and take into account
the instrumental broadening. Such an analysis was carried out
by Greytak and co-workers [14] and yields good agreement for
the line shape as well as the position of the two-roton peak in
the Raman spectrum.
It is in principle possible to form bound states of two ro-
tons (or two maxons) in various angular momentum channels. In-
deed, as we shall see below, there is substantial evidence for
stronger coupling in other ~-channels which are not involved in
the Raman process. It may be possible to observe bound pairs
in other ~-channels by light absorption or polariton-like mea-
surements on liquid helium in the presence of an external elec-
tric field [24]. Unlike the usual polariton modes in solids
which involve the coupling of light to an optical phonon, pola-
rization modes in superfluid helium are formed by light coupl-
ing to pairs of elementary excitations. The latter mode coupl-
ing has been calculated by considering the atomic polarization
associated with density fluctuations of two quasiparticles with
small total momentum, which involves the field-induced dipole
54 J. RUVALDS
moment of helium atoms [24].
B STATES WITH K l 0
At finite values of the excitation pair total momentum K,
the unperturbed density of states P2(0)(K l 0) is nonsingular,
but does contain discontinuities at the energy continuum thres-
holds w = 2~0 and w = 2~1. In the vicinity of these thresholds,
it is possible to express the density of states in simple ana-
lytic form [11], and calculate the renormalized spectrum using
equations (2.4,5,10). Again, for simplicity, we consider only
the two-roton region and follow closely the discussion in ref-
erence [11].
A straightforward derivation yields the unperturbed density
of states, accurate near the 2~0 energy, as
(2.15)
which is valid in the range 2(~oE)~ < K < 2kO [11]. Using equa-
tion (2.4) we then obtain
2D dx
F(K,E) = 2PO(K) J0 E - x + ir ' (2.16)
and, to a good approximation,
(2.17)
It follows from equations (2.5,17) that a bound state of two ro-

tons with finite total momentum is split off from the continuum
by arbitrarily weak attractive coupling, and exhibits a sharp
peak in the two-roton spectrum with a binding energy given by
(2.18)
The dependence of the binding energy on the coupling strength

in equation (2.18) is analogous to the case of bound electron
pairs which appears in the Bardeen, Cooper and Schrieffer (BCS)
theory of superconductivity [25].
The experimental consequences of the bound state formation
at finite K are complicated by the level repulsion between the
bound states and single excitation states with momentum k = K
[11]. The hybridized spectrum and its relevance to previous
theories and experimental data, is discussed in section 3.
EXCITATIONS IN SUPERF"LUID HELIUM 55
3. HYBRIDIZATION OF SINGLE EXCITATIONS WITH ROTON PAIR STATES

The level mixing or hybridization of a single excitation
with an excited pair quantum state was first suggested by Fermi
[26] to explain the Raman spectrum of C02 in terms of hybrid-
ized molecular vibration levels. In molecules the vibrational
energy levels have negligible dispersion so that a 'Fermi Re-
sonance' of one mode coupled to the overtone of another level
is manifested in the C02 Raman spectrum by the appearance of
two sharp peaks in contrast to the single vibrational mode peak
expected for noninteracting states [26].
In liquids and solids, the analogous level repulsion of ex-
citations may occur, but, in general, the hybridized pair spec-
trum is substantially broadened by the dispersion of the excita-
tions. Some examples of hybridized excitations in solids are
coupled magnon states [27] and interacting phonon modes [28,29].
In the case of superfluid helium various techniques have
been employed to calculate three-phonon interactions which give
hybridizatibn of one and two-phonon excitations. Pitayevski
[30] noted that the single excitation branch exhibits an instab-
ility toward decay into a pair of rotons at energies near 2~O.
As is apparent from figure 1, the lower energy part of the spec-
trum (the phonon-roton branch) is stable because decay proces-
ses are not kinematically allowed; however, as the excitation
energy approaches 2~O the lower energy phonon branch is reduced
in intensity by interactions with two-roton states and termin-
ates as predicted by Pitayevski and verified by neutron scatter-
ing experiments [10].
Phonon hybridization in liquid helium has also been consider-
ed by Miller, Pines, and Nozieres [31], by Feenberg and co-work-
ers [9], and very recently by Sunakawa, et al. [18,19]. Micro-
scopic expressions for the three-phonon vertex have been derived
using density fluctuation variables [17-19], and it has been
shown [19] by numerical computations that the associated shift
of the single excitation energies is significant and reproduces
the experimentally observed dispersion with good accuracy. The
latter calculations employ models for the interatomic helium po-
tential to obtain the renormalized sound velocity and roton en-
ergy in essential agreement with experiment [19].
In the present discussion we emphasize the distortion of the
phonon spectrum induced by phonon coupling to roton pairs.
This hybridization splits the one-phonon spectrum into two
branches [11] and thus provides a simple physical explanation
for the anomalous structure in the neutron data shown in figure
1. For simplicity we employ the model Hamiltonian of equation
(2.1) and treat the hybridization coupling g3 as a phenomeno-
logical parameter. Then the hybridization effects are descri-
bed by the excitation self energy ~l(k,w) which enters in the
phonon propagator
-1
Gl (k,w) w - E(k) - ~l(k,w) + ~ir. (3.1)
56 J. RUVALDS
and is given by
(3.2)
where G2 is the propagator for an excitation pair. The self

energy shifts the one-phonon energy and may give rise to inter-
esting structure in the one-phonon spectrum,
(3.3)
From equations (3.1,2), it is clear that poles in G2(k,w) would

give rise to secondary peaks in the one-phonon density of states
Pl(k,w) which is observable by neutron scattering. It is of in-
terest to include the final state interactions in the calcula-
tion of G2 (as discussed in section 2), since arbitrarily weak
interactions give rise to poles in G2(k,w) corresponding to
bound states of excitation pairs. Following the formalism for
binding of two excitations with finite total momentum (section
2), it can be shown [11] that the one-phonon density of states
for these hybridized excitations takes the form
Pl(k,w) =- _7[1 Im[w - E(k) + ~2'r - g3 2

1 -
2F(k,w) J-l (3.4)
g4F(k,w) ,
where
(3.5)
The influence of bound roton pairs on the single quasipar-

ticle spectrum Pl(k,w) is shown in figure 3. In this figure
the value of K = 0.3 ~-1 was chosen so that the two-roton
structure is well separated in energy from the one-phonon peak
at w = 5.S o K. If the rotons are non-interacting (g4' = 0) the
effect of hybridization is to shift the one-phonon peak slight-
ly and induce relatively smooth structure near the two-roton
threshold indicated by the arrow. As the roton-roton coupling
increases to g4' = -0.2, a secondary asymmetric peak in Pl ap-
pears very near to, but above the threshold energy 2~O: the lat-
ter peak corresponds to a two-roton resonance. There are two
possible regions in which a true bound state with energy
WB < 2~O can occur, namely: (a) in the weak hybridization reg-
ime such as the K = 0 region, where the bound state is only
slightly shifted in energy by the level repulsion, or (b) a mo-
mentum region such that the direct roton coupling is strong.
Case (b) is exemplified by the curves for g4' = -0.4 in figure
3 and represents a situation which may be attainable experi-
mentally.
1.0
0.8
0.6
0.4
0.5
+6 0.2
JJ--=--~~~--:C::=::=-J g~ = - 0.4
s
-
~
I 0.5
-(
r'l +6
0 0.4
II
0.3
~ I)L----~----'----_J' g~ = -0.2
"-
0.2
8
.5u 0.1
8-
ell g~ = 0
\0 20 '30
Energy (OK)
Figure 3 - Calculated one-phonon spectrum PI as a func-

tion of energy showing the evolution of a two-roton re-
sonance. The dfmensionless hybridization coupling is
g3' = g3[pO/~OJ2 = 0.3 for all three curves. As the
dimensionless roton-roton coupling parameter g4' = g4PO
is increased, an asymmetric peak appears near 2~0 cor-
responding to a two-roton resonance. The arrow indic-
ates the bottom of the two-roton continuum 2~0' For
sufficiently strong coupling, e.g. g4' = - 0.4, a bound
roton pair state is split off below the continuum.
The physical origin of the resonance structure is apparent

from figure 3: as the attractive roton coupling g4' increases
in magnitude the two-roton density of states P2(K,w) is pushed
to lower energies and exhibits a strong peak structure near 2~0'
This resonance structure appears in the one-phonon density of
states PI(K,w) due to the hybridization.
There has been speculation based on more recent neutron re-
sults [32J questioning the existence of two-roton bound states
with finite total momentum. The new data of reference [32] is
in the low momentum range, K = 0.3 ~-l, corresponding to the
weak hybridization regime. The new results for K = 0.3 A-I
provide a good check on the theory, since the upper branch ap-
pears as a well-defined peak as shown by the dots in figure 4.
Our theoretical spectrum PI(K = 0.3 ~-l,w) theory gives a good
fit to the data at K = 0.3 ~-l, especially when we consider the
large uncertainties in the data due to instrumental broadening.
As a further check on the theory we have calculated the so-
called multiphonon contribution from non-interacting phonon
58 J. RUVALDS
0:5 r---------,---------r---------,
- - - RZ theory
0.4 •
9.9,
Multiphonon
=
=
-0.15
0.3
0.3
S
-
I
•
I
<
....
.;:;
II
r
91 +6
0.2
or
• • •
0.1 •
_---e
• II
I
0
• ••
to
/
20 30
EnergyrK)
Figure 4 - The recent neutron data of Woods, et al. [32J

is shown by dots. The theoretical single-quasiparticle
spectrum is shown by solid lines using the following para-
meters: the single phonon energy wI + ir l = 5.5 + i(I.I)OK
estimated from the neutron peak at the one-phonon energy
and a roton width r = O.32°K taken from the Raman data of
reference [14]. The roton coupling parameters g3' and g4'
were adjusted to fit the observed line shape. The two-
roton resonance structure near the continuum edge 2~O (see
arrow) shows very good agreement with the data, in con-
trast to the mUltiphonon contribution (dashed curve) ex-
perimental points. The one-phonon peak near S.SoK has
been reduced by a factor of 6.
excitations. The mu1tiphonon cross section follows from equa-

tions (2.10,17) in the limit g4 = 0, and is proportional to
P2(K,w) = - n-1ImG2(K,w). The calculated multiphonon spectrum
is shown by dashed lines in figure 4 and clearly is in contrast
to the observed peak structure. Thus we conclude that the neu-
tron data in the low momentum region provide further evidence
for the existence of two-roton resonances, and demonstrates the
importance of final state interactions for the scattered quasi-
particles. More recently, microscopic computations [33] of the
hybridized spectrum over a wider momentum range have yielded
good agreement with the neutron data when the two-roton reson-
ance structure is incorporated in the calculations.
Future neutron scattering experiments at higher pressures
would be of considerable interest and may yield new insight in-
to the physics of interacting excitations in liquid helium.
For example, the pressure dependence of the coupling parameters
may be extracted from a lineshape analysis of the neutron data.
Of particular interest, in this connection, is the softening
and instability of the roton mode at high pressures, which is
associated with the liquid-solid phase transition [34,35].
4. THEORIES OF THE ROTON LIFETIME

Kinematic considerations rule out possible decay of a roton
into other excitations, and therefore collision broadening is
the primary limiting mechanism for the roton lifetime. At tem-
peratures T > 1 0 K, the broadening is dominated by roton-roton
scattering so that the temperature dependence of the width is
proportional to the number of rotons thermally excited, as veri-
fied by experiment [13,14].
The theory of roton broadening was first discussed by Landau
and Khalatnikov (LK) [36] using a phenomenological point con-
tact model for the roton interaction Hamiltonian. They calcu-
lated the lifetime using the Born Approximation which gives the
'Golden Rule' result that the roton width is proportional to
the square of the scattering matrix element times the density
of final states. A comparision of the LK theory with experi-
mental measurements of the line width gives a very large value
for the roton coupling [36], which is not consistent with other
estimates [11].
As discussed in section 2, the strong effective coupling of
rotons casts doubts on the validity of the Born Approximation,
and suggests that final state interactions must be taken into
account. Several authors [37] have gone beyond the Born Approx-
imation to calculate the roton lifetime taking into account mul-
tiple scattering events. At low temperatures the theoretical
analysis is greatly simplified by the smallness of the roton
number NR(T). Keeping only terms to lowest order in NR(T) , and
using the simple model Hamiltonian of equation (2.1), the roton
self energy may be expressed as [37]
ImE(k,w) (4.1)
60 J. RUVALDS
where the Bose factor nB(w) = (ew/T - 1)-1 determines the tem-
perature dependence of the lifetime. To lowest order in scat-
tering, the density of final states is given by [11]
(4.2)
and P2(O) = 0 for w < nO. Thus the LK result is obtained by sub-
stituting equation (4.2) into equation (4.1) and performing a
straightforward integration which yields
where the roton number is given by
1 k 2( k T)1/2 -~O/T (4.4)

(2n)3/2 0 ~O B e ;
kB is Boltzmann's constant and the roton parameters kO, ~o' and

~O are defined in figure 1.
The multiple scattering terms may be included, as in section
2, to obtain the renormalized two-roton density of states
P2
(K )
,w
=- ~ 1m
2n
F(K,w)
1 - g4F (K,w) , (4.5)
which can be inserted into equation (4.1) to give the roton

self energy
2 I k + k O-g4 kF (k,W)I}
x 1m{ 2F(k,w) + g4F (k,w) In k- kO _ g4 kF (k,w) ,(4.6)
including final state interactions. As shown in figure 5, the

result of equation (4.6) exhibits a strong energy dependence in
contrast to the LK result. Yau and Stephen [37] first noted
that .equation (4.6) exhibits an upper bound on the rot on broaden-
ing as a function of the coupling g4, and, that the upper limit
is smaller than the measured roton width [37]. Hence it has
been concluded [37] that scattering in various angular momentum
channels must be important since the above model includes only
s-wave scattering. The physical origin of the upper broadening
limit is related to the depletion of the density of states near
2~O by the formation of two-roton resonances: this depletion is
reflected in the decrease of the self energy at w ~ ~O (see fig-
ure 5), and reduces the self energy contribution according to
1.0
..... --,
\ LK
\
\
\
\ \
.l~_._. __
------
o.~ __________________ ~ __________________ ~
0.9 1.0 1.1
'"8
0.5
x
S-
o
~
....E
I
0
0.9
Energy in units of .1.0
Figure 5 - Imaginary part of the roton self-energy versus

energy both in units of ~O at temperature T = 1 0 K. The
solid lines correspond to the results given by equation
(4.6) the dotted lines to numerical integration. In (a)
and (b) the coupling is g4 = -1. 8 x 10-38erg cm 3 and g4 =
-0.9 x 10-38erg cm 3 , respectively. For details of the com-
putation see Solana, et al. in reference [15].
equation (4.1).
Roton collisions also dominate the change on the roton en-
ergy as a function of temperature. The renormalized energy is
related to the real part of the roton self energy and has been
62 J. RUVALDS
calculated by various techniques [38]. Here again the final

state interactions are important and give rise to an upper lim-
it on the real part of the roton self energy which falls below
the experimental values [38]. TUttI:! has shown that scattering
in several angular momentum channels must be included to bring
the theoretical results in accord with experiment.
Until recently, existing theories of the roton lifetime and
energy have been based on phenomenological models of the roton
coupling which are inadequate in several respects as discussed
above. In section 5, we discuss some recent attempts at micro-
scopic derivations of the excitation interactions which may be
used to calculate the roton lifetime from first principles.
5. MICROSCOPIC APPROACHES TO THEORY OF EXCITATION INTERACTIONS

As mentioned in the Introduction, various theories [5-9] of
the liquid helium excitation spectrum have been developed from
first principles. These theories generally agree in the low-
momentum phonon region, but do not yield an accurate descrip-
tion of the roton part of the spectrum.
The extension of microscopic formulations to quasiparticle
interactions describing three-phonon matrix elements has been
made by Feenberg [9], Bogoliubov and Zubarev [17], and Suna-
kawa, et al. [18,19]. These terms have been calculated numer-
ically [18,19] over a wide momentum span and are responsible
for renormalization of the sound velocity and the excitation
energies, in strikingly good agreement with experiment.
The problem of direct scattering of two excitations has been
discussed from a microscopic point of view by Rajagopal, Bagchi
and Ruvalds [20]. The latter theory is relevant to the forma-
tion of bound excitation pairs (section 2) and, in principle,
may be extended to calculate the roton lifetime and other pro-
perties of the superfluid. The derivation of an interaction
Hamiltonian using density fluctuation operators [17-20] is only
briefly outlined here since the general formalism is beyond the
scope of the present work. The amplitude for the scattering of
two excitations is derived in the general form to leading order
in perturbation theory. It is then used to estimate the effec-
tive roton-roton coupling in terms of the analysis based on the
collective variable approach. The microscopic theory yields an
attractive coupling of two rotons, but the coupling strength is
an order of magnitude larger than the phenomenological estimates
based on experiments [20]. A renormalization procedure is then
outlined which reduces the strength of the roton-roton interac-
tion, bringing the coupling in closer agreement with previous
estimates.
We consider N interacting helium atoms each of mass m4 en-
closed in a cubic box of volume V. The system is descibed by
the Hamiltonian (written in the usual second quantized notation)
where the creation (destruction) operators akt (ak) obey the
commutation relations:
(5.2)
and V44 (q) is the Fourier transform of the interatomic helium

potential. We introduce density operators
N
p(x) -+p'(x) (5.3)
V
where
_l
PklO N 2
L ap+~ktap-~k (5.4a)
p
1
Pk=O N2 (5.4b)
which have previously been used by several authors [17-20] to

derive an effective excitation Hamiltonian. The analysis is
based on the assumption that the fluctuations in p'(x) do not
become as large as N/V, and involves the expansion of [N/V +
p'(x)]-l in powers of (V/N)p'(x) to the desired order. The
density operators are related to the Boson excitation operators
Bk and Bkt, by the transformation [18-20]
1
Pk = P'k)2(B_ k +Bk t ), k +0 (5.5)
where
k
(5.6)
and c 2 (k) = 4Nm4V44(k)/n2V. Using these density operators, the

spectrum for non-interacting excitations is the Bogoliubov-
Zubarev result [17]
(5.7)
which does not involve the condensate density, in contrast to

the earlier Bogoliubov spectrum [2], derived on the quasipar-
ticle representation. For reasonable models of the helium po-
tential V44 (Q) the spectrum EBZ(k) displays the qualitative be-
havior suggested by Landau, but is higher in energy than the ob-
served dispersion. Sunakawa and co-workers [18,19] have attri-
buted the latter discrepancy to three-phonon coupling, which
64 J. RUVALDS
results in a strong hybridization of the excitations. These
interactions are represented by the interaction Hamiltonian
[17-20]
where
Details of the numerical computations for the shifts in excita-

tion energies we refer the reader to references [18,19]. In
addition, it is interesting to note that this approach has re-
cently been successfully applied [33] to calculate the two-
branch hybridized spectrum observed in the neutron data [10].
Turning now to the direct excitation scattering terms we
write down the fourth-order coupling contribution (from refer-
ence [20]):
(5.9a)
(5.9b)
where the prime in the summation excludes operators having zero

momentum index. In principle the Hamiltonian equation (5.9)
yields the residual roton interactions in terms of the inter-
atomic helium potential, and may be used to calculate the scat-
tering amplitude of two quasiparticles.
Consider the scattering of two excitations of initial mo-
menta p and pI going into a final state with momenta p + q and
pI - q in perturbation theory. We treat ~ in first order and
~3 in second order and thus keep track of the equivalent pro-
cesses explicitly [20]. The initial state is
(5.l0a)
and the final state is
(5.l0b)
where q + 0, (p' - p), and p + p'. The lowest order scattering

amplitude is then,
(5.11)
where E = EBZ(P) + EBZ(P'). The direct contribution to the

scattering amplitude for two quasiparticles follows from equa-
tions (5.10) and (5.11) and is given by
(5.12)
The other contribution to the scattering amplitude comes from

processes which involve a virtual excitation in the intermediate
state. These processes are represented diagrammatically in fig-
ure 6. The calculation of (p + q,p' - qIT3Ip,p'> is straight-
forward [20] and the final result can be expressed as
(5.l3a)
where
Ml(P,P' )Ml(P + q,p' - q)

EB(P) + EB(P') - EB(P + p') (p + P' + 0)
(5.l3b)
o (p + P' = 0)
(5.l3c)
The remalnlng scattering amplitudes can be represented as the

product of two bare vertex functions multiplied by the propagat-
or of the intermediate excitation when energy and momentum are
66 J. RUVALDS
p' p'-q
p'
A,=
p'-q
> <
p
.
p+p'
p+q
p+q
p+q
p'-q
p' p+q p p'-q
p p'-q p' p+q
Figure 6 - Diagrammatic representation of scattering am-

plitudes for two excitations with initial momenta P and
P' respectively. going into final state designated by mom-
enta P + q and p' - q. Here only the three-excitation
vertex contained in the Hamiltonian H3 of equation (5.8)
is considered. and therefore the interaction is mediated
by quasiparticle exchange.
conserved at each vertex. Define the unrenormalized propagator

for the quasiparticle,
1
(5.14)
The amplitude A2 , ... ,A 5 of figure 2 can then be written as [20]
(i = 2, ... ,5), (5.l5a)
where
Q2 - q, rl2 EB(p) - EB(p + q),
Q3 q, rl3 EB(p') - EB(p' - q),

(5.l5b)
(Contd)
Q4 P + q - p' , rl4 EB(P) - EB(P' - q),
Qs = p' - q - p, ~s = EB(p') - EB(P + q), (5.l5b)

(Contd)
P2 p, P'2 P' - q,
P3 p' , p' 3 P + q,
P4 p, P'4 P + q,
Ps :: p', p'S = p' - q,
and the bare vertex functions can be written as the symmetrized

combination
(5.16)
It is straightforward, on the basis of these formulas, to write

down diagrammatic rules for evaluating these amplitudes. The
advantage of the diagrammatic formulation lies in the ease with
which renormalizations of vertex functions and propagators can
be introduced - a subject which we take up below. We now con-
sider the scattering amplitudes for two excitations in the ro-
ton region and show that the total amplitude is negative under
two typical physical situations. From this we conclude that
the microscopically calculated coupling of two rotons contains
an attractive component.
In the limiting case of small q and p + p' = 0, the scatter-
ing of two excitations at the roton minimum EB ~ ~O requires
that Ipl, Ip' I, Ip + "ill, and Ip' - "ill are all of order PO, the
momentum of the roton minimum. Hence the quantities appearing
in equation (5.12) can be estimated by noting that Ap ~ 1. The
result is [20]
(5.17)
Similarly, using the relations EBZ(q) = sq for small q (where

s = ~2c(O)/2m4 is the sound velocity), Aq = q/c(O), and
EBZ(2PO) = 2~O' it follows that [20]
(p + q,p' - qIT3Ip,p') - (5.18)
Adding the amplitude of equations (5.17) and (5.18) gives

3'P? P0 2
< O. (5.19)
m4N
68 J. RUVALDS
which implies an attractive effective coupling between rotons.
Another estimate of the coupling for two rotons scattering
through an angle of 60° in the center of mass frame also gives
an attractive coupling of roughly the same magnitude as in equa-
tion (5.19). However the coupling strength turns out to be of
order 6~O, which is an order of magnitude larger than estimates
based on phenomenological theories [11], and would suggest gross
distortions of the excitation spectrum, contrary to experimental
observation. Therefore it is important to treat the renormaliza-
tion of vertices and roton propagators, which may reduce the ef-
fective coupling.
The scattering amplitude (p + q,p' - qIT3Ip,p'), estimated
above to leading order in the perturbation theory, is consider-
ably modified when the bare vertex functions and propagators are
replaced by the corresponding renormalized quantities. We shall
discuss the renormalization in two steps, first considering the
propagators and then the vertex functions. The simplest way of
introducing renormalization effects is through the diagrammatic
analysis bf figure 6 and equation (5.13) and (5.16). In the
center of mass frame (p + p' = 0), Al remains zero while Ai for
i = 2, ... ,5 are given by (5.15) with the renormalized propagator
D(Qi,ni) replacing the bare propagator DO(Qi,ni) of the inter-
mediate excitation. Figure 7 (a) shows the Dyson's equation for
Q,n
I
Q,n
+ Q',n'
Q,n
Q-Q',n-n'
(a)
(b)
Figure 7 - Dyson's equation for: (a) quasiparticle propa-

gator, and (b) the three-excitation vertex function.
These equations represent the major contributions to the
renormalizations considered in the next text.
the propagator DCQ,fJ); we have neglected diagrams with a back-
ward-going excitation line in the intermediate state because
the corresponding self energy is proportional to the number of
excitations which is vanishingly small at very low temperatures.
A comparision of figure 7(.a) with figure 6 indicates that the
vertex functions associated with the self energy insertion are
of the type MI' In fact we may use equation (5.15) to write
down the Dyson's equation for the renormalized propagator
x DOCQ - Q',fJ - fJ' )MICQ',Q - Q' )DCQ,fJ). (5.20)
After a trivial integration over fJ', the above equation may be

rewritten (at T = OOK)
(5.21)
However, a central problem with this result is that the Q'-

integration appearing in the denominator diverges if the bare
vertex function MICQ,Q - Q') is used in the integrand. The
problem is obviated by cha~ging the bare vertex function MI to
the renormalized function MI. The way to renormalize the ver-
tex function is shown diagrammatically in figure 7(b). For
the sake of consistency, the remaining vertex function M2 must
be renormalized also. The effect of all this is to change the
scattering amplitude (5.13) to
L A·1 L (5.22)
i=2 i=2
where Pi, P'i, Qi, and fJi have the same meaning as before, and
70 J. RW~S
It is possible to estimate qualitatively the effect of renor-

malization on the scattering amplitude in certain limits. For
the case of forward scattering (q ~ 0) the renormalization of
the amplitudes A2 and A3 may be estimated from the shift of the
sound velocity due to hybridization. Such an estimate [20] in-
dicates that the T3 scattering amplitude is reduced significant-
ly by the renormalization, thereby bringing the microscopic re-
sult for the roton coupling into closer agreement with experi-
ment. Similarly, the T4 scattering amplitude is reduced in
strength by renormalizations [20].
It is of interest to note that even though the direct coupl-
ing strength calculated microscopically is repulsive, the net
effective coupling between two rotons is found to be attractive
because of competing scattering processes. Thus the present
microscopic analysis supports the theoretical predictions [11,
12] of the existence of two-roton bound states.
On the basis of the results of this section, it seems worth-
while to perform quantitative calculations of the effective
scattering amplitude of two excitations, starting from models
of the interatomic helium potential and proceeding in a self-
consistent way to include renormalization effects from first
principles.
6. EXCITATIONS IN HE3-HE4 MIXTURES

Our current understanding of excitations in superfluid mix-
tures of He 4 with dilute concentrations of He 3 is based on the
work of Landau [1] and Landau and Pomeranchuk [39]. They pro-
posed that the noninteracting excitation spectrum consists of
the He 4 phonon-roton branch and, in addition, exhibits a Fer-
mion He 3 quasiparticle branch with dispersion Ek = EO+ k 2 /2m*,
where the effective mass m* takes into account the backflow of
He 4 atoms surrounding the He 3 impurity. These basic features
of the low energy excitation spectrum have been extensively
verified by experiment [21] and are shown in figure 8; note
that the Fermion quasiparticle-hole continuum [40] intersects
the phonon-roton branch of the liquid.
The coupling of the Fermion He 3 excitations to the phonons
in the superfluid bears a formal resemblance [41] to the Po-
laron problem in solids and has a significant influence on the
physical properties of the mixtures. For example, the concen-
tration dependence of the sound velocity can in part be ex-
plained by the coupling of long wavelengths to the He 3 quasi-
particle-hole continuum [42]. Furthermore, transport proper-
ties such as spin diffusion, viscosity and thermal conductivity
depend on the scattering of the quasiparticles. In the low tem-
perature limit the He 3-He 3 scattering is dominant, whereas at
temperatures near 1 0 K the He 3-phonon, He 3 -roton, and other
quasiparticle cross sections must be taken into account. The
He 3-He3 coupling has been calculated by Emery [43], Bardeen,
Baym and Pines [44] and by McMillan [45].
In the present discussion we shall focus attention on the
~r--------.--------'---------~--~---'~~~---'
32
24
4.0
Momentum k(A - 1)
Figure 8 - Excitation spectrum of superfluid He 3-He 4 mix-

tures. The solid line shows the phonon-roton spectrum of
the He 4 excitations and the shaded region represents the
Fermion He 3 quasiparticle-hole continuum at a 2% He 3 con-
centration.
coupling of He 3 quasiparticles to excitations near the roton en-

ergy continuum and emphasize the strong analogy of this case to
the multiple scattering of excitations in pure He 4 discussed in
the previous sections. The cross section for He 3-roton scatter-
ing was first derived by Khalatnikov and Zharkov [46] using the
Born Approximation and a point contact model for the quasipar-
ticle interactions. Another physical mechanisin coupling these
excitations is the hybridization of phonons and the He 3 contin-
uum [47].
For simplicity let us describe the quasiparticle interactions
by the model Hamiltonian
L (ck+qtckBq + h.c.) + (Contd)

k,q
72 J. RUVALDS
(Contd) (6.1)
where okt (ok) denote He 3 quasiparticle operators and Bkt (Bk)

represent phonon-roton operators as in the previous section.
The Y3 coupling describes decay of a phonon into a He 3 quasi-
particle-hole pair, and Y4 represents the effective strength of
the direct scattering of He 3 quasipartic1es and phonons. We
discuss these processes in turn below.
Consider first the influence of hybridization on the roton
excitations; the roton self energy associated with these pro-
cesses is of the form [48]
r6.2a)
2
Po
+ 2m'"
P02
In [: : :::: + - -
2m'"
• - PoVr ~ ~]}, (6.2b)

t::. + PoVr
and Pr = mvr is the Fermi momentum, m* = 2.4m3 is the He 3

quasiparticle effective mass, and n3 is the He 3 particle den-
sity. For concentrations such that Po2/2m* - povr > t::., the He 3
continuum lies above the roton energy, and the self energy
~3(PO,t::.) is purely real. The critical concentration (0 = 2.5%)
[48] determines the onset of kinematically allowed decay of a
roton into the He 3 continuum, which yields an imaginary part of
the se1 f energy corresponding to this roton damping. This feat-
ure makes it possible to estimate the coupling strength Y3 from
recent Raman data on He 3-He 4 mixtures [49], which is dominated
by two-roton processes, by considering the concentration depend-
ence of the 1inewidth. The theory [48] predicts a non-linear
dependence of the roton lifetime in the He 3 concentration owing
to the onset of decay processes at high concentrations; this pe-
culiar behavior of the rot on 1inewidth in mixtures is supported
by the available Raman data at low concentrations [49]. A com-
parision of equation (6.2) with the Raman data yields an esti-
mate of the upper bound on Inl < 3.5x 10- 27 erg cm 3/ 2 . This
value of the Y3 coupling gives a small shift of the roton energy
with He 3 concentration. Furthermore, the Raman [49] and neutron
[50] data on the mixtures show a negligible change in the roton
energy, which suggests that the hybridization processes in He 3 -
He 4 mixtures are indeed very small.
Collision scattering mechanisms for rotons (or phonons) and
He 3 quasiparticles are described by the Y4 interaction in our
model Hamiltonian equation (6.1). These processes have been in-
voked to explain the spin diffusion in He 3 -He 4 mixtures by
Khalatnikov and Zharkov [46], who calculated the quasiparticle
cross section in the Born Approximation. However, the estimated
value of the coupling, IY41 ;: 8 x 10- 38 erg cm 3 , seems very large
(by comparision the roton-roton coupling is g4 = Ix 10-38 erg
cm 3 ), and inconsistent with Raman [49] and neutron [50] data,
because this coupling gives a large shift of the roton energy
which is not observed. It should be noted that these estimates
are based on the lowest order in perturbation theory.
Multiple scattering of rotons and He 3 quasiparticles must be
included in theories of the cross section, in part because of
the strong coupling estimated previously [46] and because of
the small group velocities of the scattering excitations. It
has been shown [48] that the Born and Hartree-Fock approxima-
tions break down for roton-He 3 scattering, and that the final
state interactions playa vital role in renormalizing the exci-
tation spectrum. At low He 3 concentrations it is possible to
calculate the scattering cross-section to all orders in Y4 keep-
ing only terms linear in He 3 concentration n3. The roton self
energy due to collision processes is given by
(6.3a)
where
2
Po
m~t: 2).1r
- 2 PDln (6.3b)
21T 2P0 2
2m1'
(6.3c)
here (PIT = (8m*kBT/1T)~ is the thermal average momentum of a

He 3 quasiparticle, PD is a momentum cut-off parameter, and
).Ir- 1 = ).10- 1 + (m*)-l.
The real part of the self energy equation (6.3) leads to an
energy shift of the roton minimum as a function of the He 3 con-
centration. The leading term Y4n3 is simply the Hartree-Fock
result and the multiple scattering series has been summed to
all orders in Y4. The result of equation (6.3) exhibits an up-
per -bound on the roton energy shift which is independent of the
coupling and the cut-off parameter PD. Thus the maximum slope
74 J. RUVALDS
of the roton energy is
060\ 1 -38 3
on3 =- 2B(pO'~) -
1. 2 x 10 erg cm , (6.4)
max
which is an order of magnitude smaller than the Hartree-Fock

result using previous estimates of Y4 [46], and is in good
agreement with neutron [49] and Raman [48] experimental data.
Thus it is important to include the final state interactions in
calculations of the roton energy shift.
The linewidth of a roton due to collisions with He3 quasipar-
ticles is given by the imaginary part of L4 in equation (6.3),
in contrast to the Born Approximation result Y42n3B(Po.6). When
multiple scattering terms are included, as in equation (6.3),
the collision broadening has an upper bound
(6.5)
which is again independent of Y4. Thus the slope of the line-

width versus n3 cannot exceed B-1(PO.6) == 2.4 x 10- 38 erg cm 3 .
This value is in accord with Raman data [49], whereas the Born
Approximation results [46] give a much larger linewidth.
It should be emphasized that these results are based on a
simple model of the quasiparticle interactions neglecting the
momentum dependence of the coupling. Recently Tan and Woo [51]
have presented microscopic calculations of the He 3-roton coupl-
ing, and obtained a reasonable fit to the spin diffusion data
using the Born Approximation. It would be of considerable in-
terest to extend these calculations to include final state in-
teractions in the scattering amplitude, and thereby test the
importance of the momentum dependence of the quasiparticle
coupling.
7. CONCLUDING REMARKS
The scattering of excitations in superfluid helium has many
similarities to cases of interacting excitations in solids.
Thus the general features discussed here, in particular the im-
portance of final state interactions, may have relevance to
coupling of magnons, phonons and other excitations in solids.
The problem of interacting magnon states has been studied in
some detail [27,52], and more recently the existenee of bound
phonon pair states has been recognized [23]. As discussed in
the text, binding of two excitations is determined by the
strength of the coupling of various excitations and may indi-
cate other bound combinations; for example, possible bound mag-
non-phonon states in metamagnetic materials [53].
It should be noted that the effective strong coupling of
certain excitations, e.g. rotons, in liquid helium is a conse-
quence of their small group velocities or, equivalently, a large
density of final scattering states. Although these criteria for
strong coupling are not necessarily satisfied by excitations in
solids, the 'bare' excitation interactions in solids may be
strong enough to warrant re-examination of theories based on the
Born and Hartree-Fock approximations. For example, anharmonic
coupling of phonons may give rise to bound states [23] and
strong hybridization of phonons [2B,29], so that it seems worth-
while to examine the effect of final state interactions on the
lifetime and energy renormalizations of the phonon excitations
in solids.
Finally, we remark on the similarity of the Hamiltonian for
a He 3 impurity in superfluid He 4 to the Frohlich Hamiltonian
which describes a polaron in a crystal. In the context of the
present paper we have examined the renormalization of rotons
in He 3-He 4 mixtures due to quasiparticle scattering processes.
However, anomalies in the ion mobility and other experiments
[54] on He 3-He 4 mixtures may indicate a strong renormalization
of the He 3 quasiparticles as well. The renormalization of the
He 3 excitation spectrum in these mixtures requires a self-con-
sistent analysis, which may provide an interesting challenge
for theoretical techniques previously applied to polarons in
solids.
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HYDRODYNAMIC EXCITATIONS IN ANHARMONIC CRYSTALS
AND IN FERROMAGNETS
K.H. MICHEL
Departement Natuurkunde, Universiteit Antwerpen, Belgium
1. INTRODUCTION
The purpose of this seminar is to give a survey of some ther-

mal hydrodynamic excitations in dielectrics and in magnets. The
advances in experimental methods as light scattering, neutron
scattering and heat pulse techniques have stimulated the inter-
est in this subject.
Hydrodynamic motion describes the long time - large wavelength
behavior of many-(quasi) particle systems. Consequently the fre-
quency z of a hydrodynamic excitation is very low and the corre-
sponding wave-number q small:
z « -1 . q«
1
i
T '
where T and t stand respectively for the average relaxation time

and for the mean free path of the (quasi)-particles. This fact
has several consequences. Firstly only the slow (secular) vari-
ables enter the hydrodynamic description, therefore the number
of hydrodynamic equations is small. The underlying physical
idea of separating the slow from the fast motion was already pre-
sent in the old method used by Maxwell for the formal solution
of the Boltzmann equation [1]. The same picture has been at the
origin of the projection operator technique which was put for-
ward in the last ten years by Mori, Zwanzig [2] and others [3].
There the time behavior of the hydrodynamic variables {Aa} is
written as
79
80 K.H. MICHEL
(1.1)
Here l' stands for the time evolution (Liouville) operator. The
first term on the rhs denotes the projection of the 'current'
on the slow quantities themselves while the second term accounts
for the projections in the space of non hydrodynamic variables.
P and Q are the corresponding projection operators, P + Q = 1.
The secular part leads to cooperative oscillatory motion (re-
storing forces) while the non secular part yields damping like
a random force in the theory of Brownian motion [2]. One main
advantage of this technique for the derivation of hydrodynamics
is the fact that one needs not to derive a kinetic (Boltzmann)
equation, the introduction of a quasi-particle representation
is not directly required. The relevant response functions can
be written in terms of susceptibilities and current correlation
functions in a very general way. Only when it finally comes to
the explicit evaluation of these quantities, a quasi-particle
representation and (other) approximations have to be introduced.
2. CONNECTION WITH RESPONSE THEORY

Let us recall some formulas of linear response theory [4-6]
and relate them to the concepts of Mori's theory by the use of
Kubo's relaxation function. The representation we used here is
taken from reference [7]. The dynamic suseptibility for two
operators A, B is given by the retarded commutator
(2.1)
for Imz > O. This quantity can be represented as [7] (X stands

for the corresponding matrix)
x(z) = [z - n + M(z)f 1 [M(Z) - nno. (2.2)
Here XO stands for the static susceptibility (Aa,A8) _ Xa8 (O),

n denotes the restoring force matrix
n = iilXO-1 , (2.3)
where the operators Aa belong to the Hilbert space of hydrody-

namic quantities: Aa,8 € hp , Ph = hp • The frequency dependent
damping is given by
(2.4)
where~ stands for the resolvent operator [z _ ~-1].

HYDRODYNAMIC EXCITATIONS 81
For two operators A, B, the symbol (A,R(z)B) denotes Kubo's re-
laxation function [4]
_() [XC - X(z)]

<!> z = -,;;.....---
z (2.5)
In the next sections we will apply these concepts to derive the

hydrodynamics of an anharmonic crystal and of a ferromagnet.
3. HYDRODYNAMICS OF AN ANHARMONIC CRYSTAL

3.A DIFFUSIVE HEAT MOTION [7]
We start from a Hamiltonian for a Bravais lattice of N-part-
icles in the form
H L ~ni(~)ni(~)
n
00
+ L ~ V(n1i1···nviv)~i (n1)···~i (n v )' (3.1)

v=O v. 1 v
where ~i(~) and ni(~) denote respectively the lattice displace-

ment - and conjugate momentum operators for the atom ~ in direc-
tion i. They satisfy the usual quantum mechanical commutation
rules. V denotes the lattice potential. The relevant hydrody-
namic variables are ~, nand E(n) where the latter denotes the
energy density (L E(n) = H). We subtract from E(n) the part
n
which is proportional to ~ and get E(n) = E(n) - (E,~)(~,~)-l~.
~(n), n(n) and E(n) constitute the set {Aa}.
In Fourier space we use ~(q), n(q), and E(q) where
A(q) =L e-iq-R(n)A(n).
n
For these variables, the matrices which enter the dynamic suscep-
tibility expression (2.2) are found to be
o i o
-iD 0 -Sq/C (3.2)
o -TSq 0
Here Dij(q) stands for the inverse of the static displacement

susceptlbility (~i(q),~j(q)), S is the tension tensor given by
(ni(q),HE(q)) = - TSij(q)qj, C denotes the specific heat at fix-
ed strains: (E(q),E(qJ) = C(q)T. We remark that only in the
82 K.H. MICHEL
q -+- 0 limit these quantities have this thermodynamic meaning [7].
The damping matrix is given by
o o o
M(z) o p1f 1f pH.; CT (3.3)
o pe:1f Pe:e:;CT
Here p1f1f stands for the frequency dependent viscosity
(3.4a)
pe:e: is related to the thermal conductivity by
(3.4b)
and a similar expression stands for pe:1f. These quantities are

given by formulas of type (2.4). Finally
Xo o 0"
~J
o
o o CT
From the matrix equation (2.2) we can deduce all 9 dynamic cor-
relation functions. We are interested in the displacement-dis-
placement- and energy-energy response functions which are acces-
sible respectively to neutron and light scattering and to heat
pulse experiments. Eliminating the momentum correlation func-
tions we get in the hydrodynamic limit
[ Z"ik - (Cij ,kR. - iznij ,kR)qjqR, iSijqj;C
-izqjSjkT z + iAjNjqR, 1
( h (-q) ; cJ>n (q) ) z {Ok(-q);O(q))z 1
x [
(e:( -q) ;cJ>n(q)z ( e: ( -q) ; e:( q) ) z
[, 0
~J
-iTS
-iTCAjR,qjql 1
(3.6)
Here Cij,k£ stands for the isothermal elastic constants which
are related to the inverse of the displacements susceptibility
by
(3.7)
Writing down the coupled equations for (¢;¢}z and

tains after elimination of (£;¢)z the equation
[z2 0ik - Cij,k£qjq£ + P(z,q)](¢k(-q);¢n(q»)z 0in (3.8)
with
P(z,q) (3.9)
The latter quantity is a complicated function of z and q, the

relative magnitude of z and A~2 determines the nature of the
sound resonances. For z < Aq (short wavelength regime), the
heat diffusion is sufficiently efficient to establish isothermal
conditions between regions of dilatation and compression in the
lattice; the resonances of the displacement correlation function
are given by isothermal sound waves. The isothermal elastic con-
stants enter the elastic sum rule [8~. In the opposite limit
(long wavelength regime) when z > Aq , the restoring forces are
given by the adiabatic elastic constants [10]:
(3. 10)
These resonances do not exhaust the elastic sum rule, consequent-

ly there is another resonance which has to be taken into account
near z = O. This is the so called Landau-Placzek peak (see e;g.
reference [5]) which is due to the heat conduction pole in P(q,z).
It is of particular importance for light scattering experiments
at phase transitions (critical opalescence).
The appearance of the heat conduction pole in P(q,z) is the
reason that simple perturbation theory breaks down for the des-
cription of the coupling between elastic and thermal motion.
One has to take into account an infinite number of singular terms
[9,10b]. One obtains then a Boltzmann-type integro-differential
equation [9-11]. This Boltzmann equation had to be solved by
an eigenfunction technique [lOa] which selects the low lying
modes to obtain the hydrodynamic equations. The present method
avoids this detour. Furthermore, only when it comes to the ex-
plicit evaluation of the coefficients which enter equations
(3.6), approximations have to be made.
84 K.H. MICHEL
3.B SECOND SOUND

So far we have taken n, ¢ and £ as hydrodynamic variables.
In that case the heat motion is diffusive. If now we consider
the quasiparticle momentum density Pq as an additional (almost)
conserved quantity, the heat motion can exhibit an oscillatory
character. As for this effect, the coupling to the elastic de-
formations is not essential, we limit ourselves to a discussion
of the energy density E(q) and quasi-momentum density
(3.12)
Here we have introduced phonon operators [12]

1
bk a = ~eja(k)[(2w(k,a)~¢j(k) + i(w(k~a»)2nj(k)] , (3.13)
wherew(k,a) is given by
3
Dij(k) = L ei(k,a)w 2 (k,a)ej*(k,a), (3.14)
a=l
and where ei(k,a) are polarization vectors of branch a. It is
essential to note that due to the presence of Umklapp processes,
quasi-momentum is not strictly a conserved quantity. Indeed the
momentum flux can be written as
(3.15)
where u is proportional to a reciprocal lattice vector. It is

different from zero only for Umklapp processes. Therefore, its
scalar product with any other vector vanishes exponentially like
e- d / T where d is a constant of the order of the Debye tempera-
ture. The following 2 x 2 matrices are relevant for the hydrody-
namic equations:
5<0 (3.16)
where C = (E(q),E(q»/T and Pij (Pi(q),Pj(q». The restoring

force matrix is given by
[
0 qkdikPij -1 1 (3.17)
qkdik/TC 0
(E~i). The damping is governed by the matrix

o 1
1' (3.18)
lIijPij
with lIij = ITPP ij + WUUij. Here AEE, ITPP, and wUu are given by
generallzed Kubo formulas of type (2.4) for the operators E, P
and u respectively. Substituting first these matrices into eq-
uation (2.2) we obtain the system of coupled equations
(z + AEE) EE d -1 Pi E ( ) = AEE, (3.19a)

TC X (q.z) - qk jkPij X q.z
qkdik) EE -1 P·E
(- ~ X (q.z) + (z + lIikPkR, )x 1 (q.z) =- qkdik. (3.19b)
In the hydrodynamic limit we can write for the transport coef-

ficients
(3.20a)
(3.20b)
In order to keep the notation simple, we assume cubic symmetry

(then the tensors become diagonal: Pij = POij etc.).
The resonances of the system (3.19) are found to be
z = - ~i(q2Ds + WUU )
± ~(- (q
2 2
Ds + ijjUU) +
2
40 s q + 4 k2 A'p
-1 2
(q IT' + ijjUU»2
l
(3.21)
where we have used the notation
Ds IT' + A', (3.22a)
(3.22b)
The nature of the resonances depends on the relative magni-

tude of 0sq, WUU and Ds where we remark that Ds ~ os2/WN where
wN is a typical relaxation frequency for momentum conserving
phonon collisions (normal processes). Several cases have to be
discussed:
-UU , q2Ds or equivalently
W
(3.23)
Then expression (3.17) reduces to

86 K.H. MICHEL
(3.24)
These are the resonances of second sound [13]. Whenever the

frequency window condition (3.23) is realized, the energy den-
sity of the phonon system exhibits an oscillatory motion, second
sound [14]. Such thermal waves which are known since a long
time in superfluid Helium have been discovered more recently in
solid Helium [15] and finally in other insulator crystals [16].
The realization of the window condition is inhibited by phonon-
impurity scattering which disSipates quasimomentum as do Umklapp-
processes. The purity of the sample constitutes therefore the
major difficulty for the observation of second sound.
(2) wUu ~ csq « wN; the leading term of the 'propagating'
solution is given by
for wUu = 2c s q the modes get critically damped. For still

higher temperature, we get into the region
(3) csq « wUu ~ wN. Here the distinction between normal

and Umklapp-processes becomes irrelevant, quasimomentum
is no longer a slow quantity, the heat motion becomes pure-
ly diffusive as was discussed in part (a) of this section.
Then
(3.26)
4. HYDRODYNAMICS IN A FERROMAGNET
Generally speaking the variety of hydrodynamic phenomena is
broader in magnetic systems than in a gas of phonons. This is
due to the variety of symmetries of the magnetic Hamiltonian in
spin space [17,18J. From the point of view of experiment, a
great advantage is the fact that the magnetic correlation func-
tions are directly accessible by neutron scattering [19].
We will restrict ourselves here to a discussion of hydrody-
namics in ferromagnets in the ordered phase. As a Hamiltonian
we take the so-called Heisenberg model [20]:
H - ~ L J( I~ - ~'I )(S~XS~,x + S~YS~,Y + S~ZS~,Z)

~,~
(4.1)
where J is the exchange coupling and where h is an external

field in the z-direction.
From symmetry considerations it follows that the motion of
longitudinal variables like energy density E and magnetization
MqZ = Y L Stzeiqort is decoupled from the motion of the trans-
t
verse quantities Mq± = y(SqX ± iSqy). We will restrict us there-
fore, to a discusslon of longitudlnal hydrodynamic motion.
4.A HYDRODYNAMICS WITHOUT MOMENTUM CONSERVATION

The relevant hydrodynamic quantities are the magnetization
MqZ and the orthogonalized energy density
(4.2)
The relevant matrices are
[ :""0
0
(4.3)
1
5<0
xE:E: o
n 0, (4.4)
[ pMM(z)/XO pME:( z )./xE:E: 0

N(z)
pE:M(z)lxo pE:E:(z)jxE:E: o 1. (4.5)
In the hydrodynamic limit we can write for these matrix elements

(we restrict ourselves to cubic symmetry)
pAB . 2 AB
AB = l.q D •
X
Then the hydrodynamic equations are found to be
1. (4.6)
The resonances of this system are given by two diffusive modes:
(Contd)
88 K.H. MICHEL
(Contd) (4.7)
The spectral function which enters the neutron scattering law

can be deduced directly from the system (4.6). One finds [21]
x"(q,w) :: ImX(q,z)
wD+q2 D+ - DEE wD_q2 - D_ + DEE}

{ (4.8)
= Xo w2 + (D+q2)2 D+ - D_ + w2 + (D_q2) D+ - D_
where z = w + ia, a + +0. For DEM + 0, D+ + DMM, D_ + DEE and

consequently one realizes that the first term on the rhs of eq-
uation (4.8) describes essentially magnetization diffusion while
the second term with weight proportional to (DEE - D_) accounts
for the energy (or temperature) diffusion which appears as a
second central resonance in the magnetization scattering func-
tion.
4. B THE SECOND MAGNON

In addition to the longitudinal magnetization MZ(q) and the
orthogonalized energy density dq), we now consider the quasi-
particle momentum as a hydrodynamic variable. We write
Pq = ~ kak-~qtak+~q' (4.9)
where ak t and ak are mag non creation and annihilation operators

[20J. As a consequence of the periodic structure of the lat-
tice, P g is not strictly conserved and an equation of type
(3.15) fiolds:
(4.10)
The system of hydrodynamic equations [21 ] now reads (we restrict

ourselves to cubic crystals)
z + iq2DMM . 2DME
1-q -qcM
iq2DEM z + iq2DEE -qc E x (Contd)
-qcM -qc E z + i(q2 DPP + WUU )

(Contd) XMMCq,z) xMe:Cq,z) XMPCq,z)
x xEMCq,Z) xEE(q,z) Xe:PCq,z)
xPMCq,z) XPe: Cq ,z) Xe:e:Cq,z)
. 2DMM
-1-q -q 2DMe: +qaM
. 2DEM
-1-q -ilDE E +qae:
+qaM +qaE -iCq2DPP + WUU )
XMMo 0 0
x 0 Xe:e: O 0 (4.11)
0 0 p
Here the meaning of the different variables is obvious from the

considerations made in section 3 and subsection 4.a. If one
disregards the term wUu which accounts for momentum dissipation
by Umk1app-processes, the present system is formally very anal-
ogous to a material liquid. Indeed the magnetization, quasi-
momentum and energy density here are the analogues of the mate-
rial particle density, momentum and energy respectively in a
liquid. However, in the magnetic case we have additional dif-
fusion coefficients DMM and DMe:, De:M which vanish in a liquid
with quadratic dispersion. The resonances of the .system (4.11)
depend again on the relative magnitUde of the quantities aq,
wUu and of the diffusion coefficients D ~ a 2/wN. The quantities
WN and wUu are respectively the relaxation frequencies for mom-
entum conserving normal magnon collision processes and for mom-
entum dissipating magnon Umk1app-processes. In particular for
asq within the window wU < asq < w, one finds from equation
(4.11) a diffusive mode
.D 2
1-rq (4.12)
where
(4.13)
with
90 K.H. MICHEL
(4.14 )
and two damped propagating modes
Zs =± csq - 1 • [ q 2D s
2~ + WUU] (4.15)
with
(4.16)
The interesting fact is the propagating mode called second mag-

non [22,21]. It enters the dynamic magnetic correlation func-
tion [21a,b]
x"(q,w) Imx(q,z)
(4.17)
+ wq 2c 2 (q 2D s + WUU ) - wq2[ _DMM + DT(l - CM 2Cs - 2 )](w 2 - C S 2q2 )}

(w 2 - cs 2q2)2 + [w(Dsq2 + wuu )]2
From the susceptibility sum rule
21njdwX"(W) = Xo (4.18)
one finds that the integrated strength of the diffusion process

is (1 - CM 2Cs - 2 ) while each of the two propa~ating modes contri-
bute a factor ~CM2cs-2. The quantity CM2cs- is the analogue of
the weight factor Cv/C p in the hydrodynamics of liquids. In the
present case it is noteworthy to realize that the weight factor
depends on the magnetic field: CM 2/C s 2 varies from 0 to 3/5 with
h going from 0 ~ 00.
So far the second magnon has not been discovered by experi-
ment. This is not surprising if one realizes that-it is not
sufficient to realize the window condition for Umklapp and nor-
mal scattering processes (by choosing the adequate temperature)
but that also impurities are disastrous for momentum conserva-
tion. The main difficulty consists to our opinion in the prep-
aration of extremely pure magnetic samples.
This is a crucial necessity. Even if this can be realized
one is faced in the ferromagnet with the difficulty of separa-
ting the magnon resonances from the diffusive central peak.
This could be a difficult resolution problem. It has therefore
been proposed to consider anisotropic antiferromagnets like MnF2
or K2NiF4. There the staggered magnetization plays the role of
the magnetization in ferromagnets. However, this is not a con-
served quantity although it couples to the energy. This coup-
ling is responsible for a diffusive central peak at temperatures
outside of the window condition [23]. By lowering the tempera-
ture, one should come into the window condition regime; then the
central mode should gradually disappear and its entire strength
should go into two propagating resonances at w = ± csq, the sec-
ond mag non [24]. So far this still awaits experimental verifi-
cation.
REFERENCES
1. See e.g. Waldmann, L. (1958). In Handbuch der Physik, Vol.
XII, (ed. Flligge, S.), (Springer-Verlag, Berlin), p. 364.
2. Mori, H. (1965). Frog. Theor. Phys., 33, 423; Zwanzig, R.W.
(1960). J. Chern. Phys., 33, 1338.
3. Kawasaki, K. (1968). Frog. Theor. Phys. (Kyoto), 39, 1133;
Wegner, F. (1968). Z. Phys., 216, 433; Schofield, P. (1968).
Phys. Lett., 26A, 489.
4. Kubo, R. (1957). J. Phys. Soc. Japan, 12, 570.
5. Kadanoff, L.P. and Martin, P.C. (1963). Ann. Phys. (NY), 24,
419.
6. Zubarev, D.N. (1960). Sov. Phys. Uspekhi, 3, 320.
7. G6tze, W. and Michel, K.H. (1973). In Lattice Dynam~cs,
(eds. Maradudin, A.A. and Horton, G.K.), (North Holland).
8. G6tze, W. (1967). Phys. Rev., 156, 95l.
9. Sham, L. (1967). Phys. Rev., 156, 494; 163, 40l.
10. GCitze, W. and Michel, K.H. (1967). Phys. Rev., 156, 963.
lOb. Same authors, (1967). Phys. Rev., 157, 763, (1969). Z. Phys.,
223, 199.
11. Klein, R. and Wehner, R.K. (1968). Phys. kondens. Mat., 8,
141; (1969). Phys. kondens. Mat., 10, l.
12. See e.g. Leibfried, G. and Ludwig, W. (1961). In Solid State
Physics, vol. 12, (eds. Seitz, F. and Turnbull, D.),
(Academic Press, New York), p. 275.
13. Ward, J.C. and Wilks, J. (1951). Phil. Mag., 42,314; (1952).
Phil. Mag. 43, 48; Dingle, R.B. (1952). Froc. Phys. Soc.,
A65, 374; SUssmann, J.A. and Thellung, A. (1963). Froc. Phys.
Soc., 81, 1122; Chester, M. (1963). Phys. Rev., 131, 2013;
Kwok, P.C. and Martin, P.C. (1966). Phys. Rev., 142, 495;
Ranninger, J. (1969). J. Phys., C2, 929.
14. Prohofsky, E.W. and Krumhansl, J.A. (1964). Phys. Rev., 133,
A1403; Guyer, R.A. and Krumhansl, J.A. (1964). Phys. Rev.,
133, A14ll; (1966). Phys. Rev., 148, 766; (1966). Phys. Rev.,
148, 778.
15. Ackerman, C.C., Bertman, B., Fairbank, H.A. and Guyer, R.A.
(1966). Phys. ReV. Lett., 16, 789.
16. McNelly, T.F., Rogers, S.J., Channin, D.J., Rollefson, R.J.,
Gobeau, W.M., Schmidt, G.E., Krumhansl, J.A. and Pohl, R.O.
(1970). Phys. ReV. Lett., 24, 100; Jackson, H.E., Walker,
C.T. and McNelly, T.F. (1970). Phys. ReV. Lett., 25, 26.
92 K.H. MICHEL
17. Tani, K. (1964). Frog. Theor. Phys. (Kyoto), 31, 335.
18. Hohenberg, P.C. and Halperin, B.I. (1970). Phys. Rev., 188,
898; Kawasaki, K. (1970). Ann. Phys. (NY), 61, 1.
19. Van Hove, L. (1954). Phys. Rev., 95, 1374.
20. See e.g. Keffer, F. In Handbuch der Physik (Encyclopedia of
Physics~ Vol. XVIII~ 2), (Springer-Verlag, Berlin), p. 1.
21. Schwabl, F. and Michel, K.H. (1970). Phys. Rev. B2, 189;
Michel.K.H. and Scwabl, F. (1970). Phys. kondens. Mat., 11.
144. '
22. Ghurzi. R.N. (1965). Fiz. Tverd. Tela, 7. 3515; (1966). Sov.
Phys. Solid State, 7, 2838; Gulayev, Yu.V. (1965). Zh. Eksp.
Teor. Fiz. P.V. Reakt, 2, 3; (1965). Sov. Phys. JETP Lett.,
2, 1; Reiter, G.F. (1968). Phys. Rev., 175, 631; Oleinik,
I.N. (1970). Zh. Eksp. Teor. Fiz., 58, 119; (1970). Sov.
Phys. JETP, 31, 600.
23. Schulfhof, M.P., Heller, P., Nathans, R. and Linz, A. (1970).
Phys. Rev. Lett., 24, 1184; Tucciarino, A. et al. (1971).
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24. Michel, K.H. and Schwabl, F. (1971). Phys. Rev. Lett., 26,
1568.
ELECTRON INTERACTION WITH SURFACE MODESt
G.D. MAHAN
Department of Physics, Indiana University,

BloomingtolJ, Indiana, USA
1. INTRODUCTION
The important excitations of solids are plasmons, phonons,
excitons, magnons, etc .. Almost invariably, each of these ex-
citations of the bulk solid has a surface mode counterpart.
Thus there are suface plasmons, surface phonons, and maybe
surface excitons and surface magnons. Certain of these modes
are electrostatic in origin, and their properties may be deriv-
ed by a classical analysis using Maxwell's equations. It is
these modes which are the subject of this review. This by no
means includes all of the important suface excitations, e.g.,
Rayleigh waves are omitted. The modes which we do include may
be described by a common mathematical formalism. These are sur-
face plasmons on a metal, surface optical (SO) phonon? and sur-
face excitons. These are also the excitations which have been
the subject of most of the recent theoretical and experimental
investigations.
The first lecture discusses the properties of these surface
modes. The second lecture describes how surface modes couple
into electrons. This interaction is used to calculate a variety
of phenomena. Lastly we discuss how spatial dispersion affects
these modes, which is the subject of much current research ef-
fort.
Surface plasmons on a metal were historically the first sur-
face modes to be discovered. First came Ritchie's theoretical
prediction [1,2], and later a detailed experimental verification
[3,4]. Ritchie has recently published an excellent review of
t Research supported by the National Science Foundation.
93
94 G.D. MAHAN
surface plasmon properties [4].
The extension to other surface modes began with the classic
series of papers by Fuchs and Kliewer [5], beginning in 1965.
They derived the optical modes of vibration for a slab. They
described the surface modes and their wave functions. These SO
phonons are now called 'Fuchs-Kliewer' modes. The modes were
first detected experimentally in the electron energy loss exper-
iments of Ibach [6]. The coupling of these modes to electrons
was first derived by Lucas, Kartheuser and Badro [7,8]. This
permitted the calculation of energy loss spectra, not only for
electrons, but for other excitations as well [9,10].
After this the history becomes much more confused, since ev-
ery new result was obtained independently by several investiga-
tors. Thus the importance of surface modes in the formation of
image charges was published independently by Lucas [9], Mahan
[11], Ritchie [12] and Feibelman [13]. This followed the earl-
ier discovery that the van der Waals forces are also caused by
surface modes [14,15]. The dynamical image potential, which in-
cludes the motion of the particle, was done independently by Ray
and Mahan [16], and by Sunjic, Toulouse and Lucas [17]. The sur-
face polaron problem was published by the latter group, by Sak
[18], and also Evans and Mills [19], although apparently Kart-
heuser did it first [20].
2. CLASSICAL DERIVATION OF SURFACE MODES

The surface modes are entirely classical in nature. Some of
the finer details, such as the surface plasmon dispersion rela-
tion, or the damping constant, may require a quantum mechanical
treatment. But the basic properties of these modes may be de-
rived entirely classically. This is certainly the best way to
begin the discussion of surface modes. This approach was ap-
plied to surface plasmons by Ritchie [1,4] and to other modes
by Fuchs and Kliewer [5], and Economu [21].
Maxwell's equations are the starting point in the derivation
of these modes
'V·D 47TP, (2.1)
'V·B 0, (2.2)
'VxE 1 aB (2.3)
c at '
'V x H = 1: aD + 47TJ (2.4)

c at c
The surface modes generate electric and magnetic fields at the

surface. The electric and magnetic fields are determined inside
and outside of the surface, and the eigenvalue condition which
determines the surface modes are obtained by matching, at the
surface, the fields inside and out.
ELECTRON INTERACTION WITH SURFACE MODES 95
There are several basic assumptions which are made in this
derivation. The first is that there are no charge density or
currents in the problem, p = 0 = J. The second is more signif-
icant, and less justifiable from a physical point of view. This
is that the dielectric response function £(w) depends only upon
frequency. A more general description would have the dielectric
function depend upon both q and w, £(q,w). The approximation
of neglecting the q-dependence is probably justified in some
cases, but not others. The main reason for making the approxim-
ation is theoretical expediency. The equations are much easier
to solve, and has permitted significant theoretical development.
This approximation was followed in the earliest work, and so we
are following the historical pathway. Much of the current re-
search effort is not devoted to putting in the q-dependence.
This makes the theory much more complicated. This aspect is
discussed extensively in section B.
All modes are assumed to have the time dependence e- iwt : w
is the eigenvalue frequency, which needs to be determined. As-
suming a linear medium, with B = ~H and D = £E, permits H to be
eliminated,
o. (2.5)
First review the properties of bulk ~odes. In an infinite

medium, they have a spatial variation elq-r where q is the wave
vector of the mode
2
w
q x (q x E) + c 2 dW)j.l(w)E o.
Longitudinal modes, in the bulk, have qilE (or q x E 0) which

gives the eigenvalue condition that
o. (2.6)
Our concern is with electrostatic type modes, which have £(w) =

o in the bulk. Magnetic modes, such as magnons, have ~ = o.
We shall set j.l = 1, although surface magnon modes may also be
described by the present formalism. Transverse modes, in the
bulk, have qlE which gives the eigenvalue condition
dw) (2.7)
It will be shown below that surface modes obey the eigenvalue

equation, at large wave vectors, of
dw) = - 1. (2. B)
96 G.D. MAHAN
Now in many solids the dielectric response function is well

represented by a set of classical oscillators.
dw)
Each oscillator is represented by a transverse frequency WTj and

a coupling strength Bj. In the absence of damping, a graph of
E(W) versus W 1S snown in figure 1. The response function E(W)
o~-----------+--~~------4-.-~~------r--1
-1
Figure 1 - A plot of the dielectric response function E(W)

as a function of W for a two oscillator system. Each os-
cillator has a transverse frequency WTj where E = ~, a
longitudinal frequency where E = 0, and a surface mode
frequency where E -1.
diverges at each WTj After each divergence, it must cross the

or1g1n again, and at this point E = 0 gives the longitudinal
bulk modes WLj. The point at which it crossed E = -1 gives the
surface mode eigenfrequency Wsj. This value must lie between
that of the longitudinal and transverse modes.
Of course the situation is confused if damping is included, such

that the real part of ReE may never equal -1. This complication
is ignored for the moment. The essential point is that there
is a surface mode counterpart for each type of bulk mode excit-
ation. So there are surface optical phonons to go with bulk LO
and TO modes. There are surface Wannier excitons and surface
plasmons. No matter which excitation is your favorite, it prob-
ably has a surface counterpart.
The surface mode eigenvalue equation is obtained by solving
equation (2.5). Assume there is a flat, infinite, surface be-
tween a solid and the vacuum, as shown in figure 2. Cubic mat-
L
z
Figure 2 - The interface between the vacuum (z < 0) and

the solid (z > 0). A surface wave vector k is travelling
in the x direction.
erials are isotropic at long wave lengths, so choose the surface

mode to be travelling in the x direction with a wave vector k.
In general, this is a two dimensional wave vector. All field
amplitudes behave as ei(kx-wt). If z is the direction normal to
the surface, all derivatives a/ay vanish. From equation (2.5)
we get that
(2.9)
which has the solution
E = Eoexp(-yizi). (2.10)
One can show that the H field obeys the same equation (2.9)
with the same exponential solution (2.10). The electric fields
98 G.D. MAHAN
inside the surface must be matched to those outside. In order

to get the relationship between the various (x,y,z) components
of the fields, one has to return to equations (2.1-4) and write
out the components
(2.1) o
iw ikEy -- iw
c £Ex, (2.4a) c Hz (2.3c)
- ciw £E z · (2.4c) (2.4b)
These equations divide into two groups. One set relates Ex, Ez ,
and Hy . These are transverse magnetic (TM) modes, and are the
equations of interest. The other set relates Hx , Hz, and Ey .
These are the transverse electric (TE) modes. They do not give
a surface mode. The proof of this is left as an exercise to the
reader.
Inside the solid there is a dielectric function £(w), and the
exponential factor is Yi = (k 2 - £(w)w2/c2)~. Outside the solid,
in the vacuum, £0 = 1 and YO = (k2 - w2/c2)~. The z-component
of the electric field has the form
(z > 0),
Ez -- Ez 0 e YOz e ikx (z < 0),
where Ezi and EzO are constants. The Ex component is obtained

from equation (2.1):
- -
i y·E le
. -y·z
1 e
ikx
k 1 Z (z > 0)
=ki ~Ti'
Yl)Z
0 YOz ikx
e e (z < 0)
and matching Ex at the surface gives
(2.11)
The Hy component is obtained from (2.4c)

By =- (:c) F:E z =- (:c) t:Ezie-Yizeikx (z > 0)
- (~)E
kc
OeYOzeikz
z (z < 0)
and matching at the surface gives
cE
~ zi = E z·
0 (2.12)
This result is also obtained by making the normal component of

D continuous at the surface. The eigenvalue equation for sur-
face modes is obtained by dividing equation (2.11) by (2.12).
Yi
- = - YO (2.13)
t:
or
[k2 _ w c2
2
t:(W») 2 __1__
1
= _ [k2 _ W2) l2
dw) c2
After squaring (2.13), it may be rearranged into
dw)
(1 + dw» ,
(2.13')
which is a standard way to express the result. The surface mode

dispersion relation w(k) may be obtained from the implied plot
of k(w). One aspect of this equation may be discerned immedi-
ately. Since YO and Yi are, by definition, both positive quan-
tities, (2.13) shows that surface modes only exist at frequen-
cies where t: < O. At very large wave vectors, k » w/c both YO
and Yi approach the value k. In this limit the eigenvalue con-
dition simplifies to (2.8).
A SURFACE PLASMONS ON A METAL

In a metal, the plasmons of the bulk material have a corres-
ponding surface plasmon. The dielectric function is
w 2
dw) 1- ~ (2.14)
w2
The bulk modes are determined by t: = 0, which gives the bulk

plasmon w = wp' At large wave vectors, surface plasmons have
t: = -1, which gives wsp = wp/12. However, it is also possible
100 G.D. MAHAN
to solve equation (2.13) exactly with the dielectric function
(2.14). Squaring (2.13) yields the quadratic equation (wk = ~k)
with solutions
(2.15)
These roots are sketched in figure 3. Only the lower dispersion
/
/ ck
/
/
/
a /
/
//
//
/
/
/
-----r----------------
/
/
/
/
L.
k_
Figure 3 - The curve labeled W- gives the dispersion rel-

ation for surface plasmons on a metal. The curve w+ is
a bogus root, which does not represent an actual surface
mode.
curve represents true surface plasmons, as only here do we sat-

isfy the condition that £ < O. It is natural to ask where the
other dispersion relation came from: what modes do they repre-
sent? Notice that these modes lie above the line W =wk , so
they represent solutions where W > wk and thus YO is complex,
and Yi is also. So this mode W+ does not satisfy (2.13). This
solution is obtained because we actually solved the square of
equation (2.13), and it does satisfy the squared equation.
Since it does not satisfy (2.13), it is a bogus root which must
be discarded.
At large wave vectors, wk » wP ' the surface plasmon mode
does approach the asymptotic value
The surface plasmon has a mixed character, with both longitudi-

nal and transverse electric field components. The dispersion
curve for surface plasmons w_ bends over at low wave vector be-
cause these modes mix with the photon modes wk' Photons have a
transverse electric field, and they mix with any mode which also
has transverse components. This mixing also occurs with bulk
modes, and the combined modes are called 'polaritons' [22].
Similarly, the mixing of surface modes with photons could be
called 'surface polaritons'. An excellent review of surface
plasmons has been given by Ritchie [4].
B SURFACE OPTICAL PHONONS

Ionic solids have optical phonons which produce long range
electric fields. These ionic motions contribute to the dielec-
tric response function. It is common to represent the low fre-
quency dielectric function by [23]
E:(w) (2.16)
where £00 is the electronic contribution to £(w), and WTO is the

transverse optical (TO) phonon frequency. The bulk longitudinal
optical (LO) phonon modes are obtained by setting £ = 0, which
gives the Lyddane-Sachs-Teller relation
Often the dielectric function (2.16) is expressed by the equiv-

alent formula:
At large wave vector, the surface optical (SO) phonon modes are
obtained from £ = -1, which gives
102 G.D. MAHAN
The exact surface polariton dispersion relation, valid for all

wave vectors, is obtained by inserting the dielectric function
(2.16) into the eigenvalue equation (2.13'). After some rear-
ranging, this becomes the quadratic equation
4
o W
with the solution
(2.17)
These two modes are plotted in figure 4, with parameters suita.ble
, ,,
, ,,
,
, ,,
,
20
, ,,
,
, ,,
,
, ,,
- hw.o
,,
10
"
,.",'".."
.. j
,.{"
,,
.i~
10 20
hw. (i n meV)
Figure 4 - Dispersion relations for the surface modes of

RbI. The straight line is W = wk, while the two curved
lines are the roots of (2.17). Surface modes only exist
for wLO > W > wTO,which is the solid portion of the curve.
After Wang, S.Q. and Mahan, G.D. (1972). Phys. Rev., B6,
4517.
for RbI. Of the two solutions, W+ is another bogus root which
must be discarded. It does not satisfy the condition that £ < O.
The root w_ starts at the origin for zero wave vector, and
approaches wso at large wave vector. However, in the wave VeC-
tor region k < wTolC it is also a bogus root which must be
discarded. Actual surface modes are just the solid part of the
line. The dispersion curve begins at the point k = wToIC, and
W = wTO, and then extends to high wave vector. The root w_ is
bogus at small wave vectors because w_ > ck, so YO is complex,
£ > 0, etc. The crucial physical point, as illustrated in fig-
ure 1, is that £ is only negative in the region wTO < W < WLO,
and only in this region cart surface modes exist. This disper-
sion curve was first obtained by Fuchs and Kliewer, who were
doing numerical solutions for finite ionic slabs [5]. They are
called 'Fuchs-Kliewer Modes'. The analytical derivation was
first done by Wang and Mahan [24]. As discussed below, these
theoretical predictions are verified in detail by experiments.
C SURFACE EXCITONS
Wannier excitons in semiconductors, and Frenkel excitons in
organic solids, also contribute dispersion to the dielectric
function. Near an isolated exciton absorption line in a cubic
semiconductor, one may write
This predicts for the longitudinal and surface excitons the eig-
envalues
2 47f Sj]
WLj WT/(l + £. (£ 0)
]
2 + 47fS'] ) -1)
WSj WTj (1 (£
(1 + £j)
This case is so mathematically similar to the previous discus-

sion of Fuchs-Kliewer modes, that no additional details need to
be included. Obviously one gets a dispersion relation w_(k)
which starts at the point k = wTj/c, W = WTj' These modes have
not yet been observed experimentally, because actual values of
47fS' are small.
Some experimental and theoretical results have been reported
on surface Frenkel excitons in solid anthracene. But the experi-
mental results [25] are inconclusive, and the theoretical res-
ults are not based upon the type of electrostatic modes discus-
104 G.D. MAHAN
sed here [27]. Another mechanism for surface modes has been sug-
gested, which is not convincing to this writer. No one has yet
worked out, for anthracene, the type of modes we are discussing.
D ANISOTROPIC SOLIDS
Some recent experimental and theoretical results have been
done on anisotropic solids [27]. Otto just completed an ex-
haustive study of the surface optical phonons of quartz [28].
Quartz has many optical phonon modes, many with surface count-
erparts. It is quite anisotropic, with many phonon modes which
can vibrate in only a few directions. The dielectric function
is a tensor. A straightforward extension of the classical the-
ory predicts some strange dispersion curves, all which are veri-
fied by Otto's experiments.
3. EXPERIMENTS ON SURFACE MODES

An experimentalist wanting to detect modes would probably
first try an optical absorption experiment, since bulk excitons
and phonons show up strongly in optical experiments. Unfortu-
nately this does not work on surface modes. They have too much
wave vector. Consider figure Sa. A photon of frequency w has
(a)n = 1 (b)n = 2
k--- k-
Figure 5 - (a) For a given frequency w, the photons have

a smaller wave vector than the surface modes. (b) This
is not helped if the surface of the metal is coated with
a dielectric constant EO. Although thr photon wave vec-
tor is increased by an amount n = (EO)2, the surface plas-
mon dispersion curve is also altered, so that it still
has more wave vector than the photon.
a wave vector w/c. But a surface mode of the same frequency has
a much larger wave vector. So wave vector conservation prevents
the direct absorption of a photon by creation of a surface mode.
This argument is only valid if the surface is ideally smooth, on
an atomic scale. In practice, actual surfaces have some rough-
ness. This roughness is a source of momentum, which enables the
photon to create surface modes. Such processes have actually
been studied for surface plasmons on a metal [4]. However, this
is not a good way to study surface modes.
Experimentalists have clearly devised ways of overcoming this
wave vector problem. These experiments will now be described.
A GRATINGS
Surface plasmons have been studied using metal gratings [3,
29]. The grating is ruled directly on the surface of the metal,
with a repeat distance d. The grating provides a source of wave
vector g = 2rr /d. In an optical reflectivity experiment, from the
surface of the metal grating, Fourier components of the electric
file not only have the wave vector of the phonon, but also with
added multiples of g. There is direct conversion of photons to
surface plasmons whenever, for a given frequency, the wave vec-
tor of the surface plasmon equals ng plus the component of pho-
ton wave vector parallel to the surface
~sp = ~ll + r1lJ.
These conversions show up in the reflectivity as sharp dips in

the reflectance spectra. These dips were first observed by R.F
Woods [30] in 1902, and correctly interpreted by Fano [31], but
they were not used to study the dispersion of surface plasmons
until the recent work of Teng and Stern [3]. Some results of
Ritchie et al., are shown in figure 6. Gratings have not yet
been used to study other types of surface modes.
B ELECTRON ENERGY LOSS

Ibach [6] obtained the first experimental verification of
surface optical phonons by measuring the energy loss of elec-
trons specularly reflected from the surface of ZnO. AS shown
in figure 7, electrons enter at an angle e to the normal. Ibach's
resul ts for ZnO are shown in figure 8. Many electrons are
elastically reflected, and have the incident electron energy Ei.
Other electrons have lost an amount of energy nEo, where Eo is
the separation between peaks, and n'is the number of peaks away.
Electrons lose energy because they create surface excitations,
where EO is the energy of the surface excitation, while n is the
number of excitations created. For the (1100) surface of ZnO,
Ibach predicts from the infrared data.
1iWTO 50. 3 meV,
tzwso 69.0 meV,
1iwLO 73.1 meV.

106 G.D. MAHAN
).2 ..............---r---,----,---.....,---r---r-"""7":r---,
2.8
2.4
>...
l. 2.0
~
..,3
1.6
1.2
0.8
0.4 0.6
Figure 6 - Grating experiments measure the dispersion rel-

ation of the surface plasmon on gold and aluminium. From
Ritchie. R.H •• Arakawa. E.T .• Cowan. J.J. and Hamm. R.N.
(1968). Phys. Rev.Lett •• 21. 1530.
Figure 7 - The experimental geometry used to measure sur-

face modes by electron energy loss. The electrons are
shot at the surface with an angle 8 to the normal. are
specularly reflected. and their energy is measured.
The experimental value of EO = 68.8 ± 0.5 is in excellent agree-

ment with the theoretical value of nwSO.
A very striking feature of Ibach's results is that he does
not observe any energy loss peaks corresponding to the creation
of bulk LO phonons. It is not surprising that he observes SO
1.0
I I
T= 286°K_ - 0.8 T = 127 oK -
s
o
0.6
.€c
]"
20me~
-
,
0.4
x4
\ x4 x4" x4
k
0.2
~ oV l/~ ~ - o ~
V V~ -
-100 100 200 300meV -100 o 100 200 300 meV
Energy loss
Figure 8 - Energy-loss spectrum of 7.5 eV electrons after

specular reflection from the (1100) surface of a ZnO crys-
tal. 8 = 45. From Ibach, H. (1970). Phys. Rev. Lett.,
24, 1416.
phonons, but it is surprIsIng that he does not detect the LO.

The explanation is that an electron, which is outside of the sur-
face of a solid, cannot excite bulk excitations. Electrons in
Ibach's experiment have very low energy, 10-100 eV, and do not
penetrate even an atomic layer into the solid surface. These
experiments provide proof that electrons outside of a surface do
not excite bulk excitations. The theoretical explanation will
be provided below.
Electron energy loss experiments on liquid and solid metals
have been reported by Powell [32]. His electrons are in the
kilovolt range, and generally penetrate into the solid before
reflecting. So he observes loss peaks corresponding to the ex-
citation of both surface and bulk plasmons. An exception is
when electrons are shot at the surface near grazing angles (1°).
Here only surface plasmons loss peaks are observed. The elec-
tron does not penetrate significantly into the solid, and can-
not excite surface plasmons.
The energy loss spectra may be described by a Poisson distri-
bution
-Q
e Qn
nr-
where Pn is the probability of exciting n excitations. The di-
mensionless parameter Q is the average number of excitations
which are excited. Stern has suggested a simple formula for Q
[33]
2
7Te
Q
2fzvcos8
108 G.D. MAHAN
where V is the velocity of the electron. This formula describes

Ibach's and Powell's data quite well [10].
C OTTO'S EXPERIMENT
The most important experiment for studying surface modes was
introduced by Otto for the study of surface plasmons [34]. He
calls it 'attenuated total reflection'. It has been widely
used to study surface optical phonons [35-37]. It is capable
of measuring the complete dispersion relation of the surface
modes in the region of strong coupling to photons.
The difficulty with the optical detection of surface modes
is that they have too much wave vector. For a given frequency,
the wave vector of light is increased in a dielectric medium by
the refractive index. This suggests putting a coating of diel-
ectric layer on the surface of the metal. The optical photons
will have a larger wave vector, and be capable of direct conver-
sion to surface modes. Actually, this does not work. If a
coating of dielectric EO = n 2 is put on the surface, the sur-
face modes also change their dispersion relation as indicated
in figure Sb. They also have larger wave vector, and are still
unable to be made directly by photons.
Otto found an ingeneous resolution to this difficulty. The
dielectric layer is not put directly upon the surface, but is
separated from the surface by an air gap of about 1000 A. His
scheme is shown in figure 9. Light is internally reflected from
-
Figure 9 - The experimental geometry used in Otto's ex-
periment. The photons are internally reflected from the
inside of a prism, which is separated from the surface
by an air gap.
a prism. Inside of the prism, the light has a wave vector par-
allel to the surface of kll = wnsine/c where n is the refractive
index of the prism. Direct creation of surface modes occurs
whenever (kll,w) is a point on the surface mode dispersion rel-
ation. Because of the air gap, the surface modes are little
affected by the prism, and have a dispersion relation shown in
figure Sa. The trick is to get the prism far enough from the
surface so as not to disturb the usual surface modes, but near
enough to get some coupling to the evanescent wave which leaks
out of the prism into the air gap. The experiments measure the
reflectance, at a fixed angle e, as a function of varying fre-
quency w. Sharp dips are found in the reflectance, as shown in
figure 10. Figure 11 shows the dispersion curve obtained by
[%] WT Ws WL
100 -------------
.~
c
~
.5 k = l.023k o
."
~
<.)
~ 80
e l.056k o
m
.?;>
OJ
c
....
~ 1.125k o
.5
/'
2.00k o
60
360 400 [em-I]

Wavenumber
Figure 10 - Attenuated total reflection experiments on

GaP by Marshall, M. and Fisher. B. (1972). Phys. ReV.
Lett., 28, 811. The reflectivity is measured as a func-
tion of frequency for fixed angle e. The horizontal axis
is frequency, in wave vector units. The reflectivity
dips occur at different frequencies for different angles e.
Marshall and Fisher for GaP [36]. The results are in complete
agreement with the simple classical theory outlined in the pre-
vious section.
D SURFACE MODE PROPAGATION

Schoenwald, Burstein, and Elson [38] reported experiments on
the propagation of surface modes over macroscopic distances.
110 G.D. MAHAN
'j'l
I =
;-ko w/C
Itm )
400
J.
~---~-----------------------,=
I ____0 - 0 0 0
1 / 0
I 0
f-
:,' I
/.
-
18
,
- - Theory
I~
o 0 0 Experiment
I
w,- I
I
360 l-
I -
I
1
1.0 I.S 2.0 2.S
Wave vector k
Figure 11 - Dispersion of surface polaritons in GaP, us-

ing the experimental data of figure 10. Experimental ac-
curacy is given by the size of the rectangles, and the
solid line is the theoretical curve. Marshall, N. and
Fi sher , B. (1972). Phys. Rev. Lett., 28, Bll.
The experimental arrangement is shown in figure 12. Two prisms
Figure 12 - The experimental geometry used to make sur-

face modes propagate along a surface. They are created
at the apex of one prism, and propagate over to the other.
After Schoenwald, J., Burstein, E. and Elson, J.M. (to be
published) .
are put on a metal surface, separated by a distance L A 10.6 l.I

laser was aimed at the apex of one prism to create surface
modes. They propagate to the second prism, where they are det-
ected. A graph of signal versus ~ yields an exponential, whose
slope determines the mean free path of the surface modes.
ELECTRON INTERACTION WITH SURFACE MODES III
4. ELECTRON COUPLING TO SURFACE MODES
The properties of surface modes have been developed in the
previous sections. Now we discuss the coupling of these modes
to electrons. The electrons could occur naturally in the solid
near the surface, or else be imposed as part of an experiment.
The surface modes are accompanied by an electric field. The
electric field acts on the electron. This is the mechanism for
the coupling between the surface modes and the electron. The
mathematical form of this coupling is very simple if one approx-
imation is made: neglect, the mixing with photons at small wave
vector which causes the dispersion curve to bend over-neglect
the polariton effects. Then the surface mode's frequencies are
a constant, independent of wave vector. The corresponding elec-
tric fields are those obtained by replacing Yi and YO by the
wave vector k
. -klzl e ikx sgn(z),

Ez~e
'E i -klzl ikx (4.1)

Ex = - ~ z e e .
There is good justification for these approximations. The reg-

ion of phase space affected by polariton effects is of size
k ~ w/c. In computing the influence of the surface modes upon
the electron, a summation (or integration) is performed over the
surface modes. The volume of two-dimensional phase space affec-
ted is of the size (w/c)2. So the polariton effects are essen-
tially a relativistic or radiative correction which is generally
small. This argument has one shortcoming: no one has yet ver-
ified it in detail, since no one has yet derived the correct
electron-surface mode coupling in the polariton region [39].
The electric fields in (4.1) may be expressed as the gradient
of a potential
t = Ez~ e
. -klzl e ik'n
- ~
where ~ and p are two-dimensional wave vectors in the surface

plane. So the surface mode creates an electrostatic potential
t(z,p). This permits one to immediately write down the Hamil-
tonian for the interacting system of electrons and surface modes
H = HOe + HOs + Hr, (4.3)
(4.4)
112 G.D. MAHAN
(4.5)
where HOe' and HOs are the Hamiltonians of the unperturbed elec-
tron and surface modes, respectively, and HI is their interac-
tion. Since surface modes are classical oscillators, their cre-
ation and destruction operators ak and ak t obey boson statistics
[ak,ak t ] = 1. The electron part HOe' may be as complicated as
one likes, but it is usually simple. It will be specified below
for several examples.
The interaction term has three factors: the coupling const-
ant rk will be specified below, the spatial dependence is due
to the potential (4.2), and the linear combination of operators
ak + a_kt. The operators can also be written in terms of har-
monic oscillator coordinates
Pk = i[~S) (ak t - ak),
HOs + HI ~ L (Pk 2 + ws 2Qk 2 + 2(2Ws)~rkeik'Se-klzIQk).

k
So (4.5) states that the interaction is proportional to the dis-

placement Qk of the modes from equilibrium. There is not a term
proportional to Qk2, since this implies that the mode energyw s
gets changed by the presence of the electron. This does not
happen, and the mode only gets displaced from equilibrium.
The coupling constant rk has been derived by several methods
[7,8,24]. It has the form
where A is the area of the surface, and the parameter C is dif-

ferent for the different excitations.
(surface plasmons) (4.6a)
£00 - 11) (SO phonons) (4.6b)

£00 +
(surface excitons) (4.6c)

This completes the specification of the interaction between el-
ectrons and surface modes.
s. ELECTRON COUPLING TO BULK MODES

It was stated earlier that an electron, outside of a solid
surface, does not couple to bulk modes. But an electron does
couple to these modes if it is ins~de of the surface. In fact,
the coupling of the electron to plasmons, phonons, and excitons
constitutes the plasmeron [40], polaron [41], and electronic
[42] polaron problems. We will now derive the form of the
coupling for an electron near the surface.
The first step is to demonstrate that bulk modes do not in-
fluence electrons which are outside of the surface of the solid.
Start with the fact that the normal component of D is conserved
at the surface. This provides a relation between the z-compon-
ent of the electric fields inside and out:
But bulk modes have £ 0, which determines that
(2.1) shows that EOx = 0 also, as is EOy. So all components of

the external electric field vanish. There is no coupling to el-
ectrons outside of the surface. By reciprocity, neither can the
external electron excite bulk modes.
The actual form of the coupling to bulk modes was first de-
rived by Lucas, Kartheuser and Badro [8] for a finite slab. The
extension to the semi-infinite slab, of present concern, is
straightforward. These bulk modes also produce electric fields
which are derivable from a potential of the ~ form
e ik- I I 'P-sin(kzz)e(z),
where (k l I,k z ) are the components of the three dimensional wave

vector parallel and perpendicular to the surface. In the half-
space of the slab one has k z > O. The form of the interaction
is
where b k , bk t are the operators for the bulk modes. The const-
ant D depends upon the mode
114 G.D. MAHAN
D2 2 (plasmons)
47Te Ptwp
D2 47Te 21iwLO (1
- - £10) (LO phonons)
£00
D2 2 47TSj
47Te 1iwLe (excitons)
£j(£j + 47TSj)
6. IMAGE POTENTIAL
About the easiest problem to solve using (4.3) is the image
potential self energy of an electron fixed a distance 2 from
the surface. To keep the problem simple, put the electron out-
side, so bulk modes may be omitted from consideration. Since a
fixed particle has no kinetic energy, the effective Hamiltonian
for the problem is just (2 < 0).
This may be solved by just completing the square
The last term gives the self energy

2
e
- 42'
which is just the classical image charge result. The fixed el-
ectron has an electric field which acts upon the surface modes,
and polarizes them. These modes, when polarized, create elec-
tric fields which act back upon the electron. This is the sour-
ce of the image potential. The bulk modes are not involved, as
long as the electron is outside.
The above result is just valid for the image charge outside
of a metal, where only surface plasmons are involved. For an
insulator, the static image potential is
e 2 (£0
- 4z £0
- 1)
+ 1 .
This is the contribution from SO phonons
e 2(£0 - 1 £00 - 1)
42 £0 + 1 £00 + 1 '
plus the contribution from surface excitons
The above calculation, for a charge fixed in space, is rather

easy. The case which is more useful experimentally, and more
difficult theoretically, is when the charged particle is moving.
This is called the dynamical image charge problem, which was
discussed by Ray and Mahan [6]. Their solution followed an earl-
ier treatment of Lucas et al. [10], of a related problem. Of
course the problem cannot be solved exactly. An approximation
which, once made, permits an exact solution, is to solve the
case where the particle is travelling at the surface with a con-
stant velocity. To keep the problem simple, assume the motion
is in the 2 direction with a constant velocity v. The wave fun-
ction of the surface modes, in the interaction representation,
has a time development given by
i'h ,}t 1ji(t) Hr(t)1ji(t)
where
2(t) = vt
If the particle started at t = -00 and 2 = -00 , the solution. is
1ji(t) exp[ - i I (h(t)ak + Ik*(t)ak t )]1ji(-oo)
r
k
rket(vk+iws )
Ik(t) r k _oodt'e k
vt 'e~wst
· ,
vk +- iws
The exponential operators may be untangled by using Feynman's

theorem [43]
e A+B e Ae Be _l[A
2 ,
B]
with the result

116 G.D. MAHAN
1ji(t) = rre-~IIk(t)12e-iIk"'at e- iIkak1ji(_oo)

k
It is convenient to assume zero temperature, so that 1ji(-oo) is
the state of no modes 10), and aklo) = O. This gives the wave
function in its desired form
1ji(t) = rre-~IIk(t)12e-iIk*(t)aktlo).
k
Using this wave function, we evaluate the expectation of the
Hamiltonian (6.1), and identify this result with the induced
self-energy of the electron
V(Z,v) = (1ji(t)IHI1ji(t»)
Ltlw slh(t)1 2 ,
k
(6.1)
The results may be collected into the final form [16] (t z/v)
V(z,v) = - 1Te Ws
2 2f-d-2k2 k1 2
e 2kz
2 2 .
(21T) (w s +Vk )
This integral cannot be done exactly, but it may be expressed

in the standard form
2
V(z ,v) - -zv-
e ws
f(-2zw s /V),
(6.2)
f(x) =fOOdo.e-o. X •
01 + 0. 2
Since f(O) = 1T/2, the potential is finite everywhere. It does

not diverge at z = 0, as in the static case. At large values of
x,f(x) + 1/x, so the image potential approaches its static val-
ue e 2 /4z at large values of z. Figure 13 compares the constant
velocity potential with the static potential, for an electron
with 1.0 eV kinetic energy, approaching a surface with a surface
plasmon of hws = 0.71.eV.
The result (6.2) is applicable for the dynamical image poten-
tial outside the surface of a simple metal. For an ionic crys-
tal, one gets a sum of terms like (6.2), for each of the differ-
Z(A)
-~8.0~--------,6.-0----------4~.O----------2T·0--------_,0
r-___
.::"':':::::::::-......-.,-'- .......
...... ,.:.:..... .
........ ......
-0.5
.... ... '"

... ,".".".
,, ".
,, ".
".
".
\
\
"....
'....
\ t ••
\
\
\
E = l.OeV \
\ -1.5
\
\
\
\
\
\
'----........- - - - -.......- - - - - - - ' - - - - - - - " ' - - - - - - - ' -2.5
Figure 13 - The image potentials of an electron with kin-

etic energy 1.0 eV solid with surface energy 0.717 eV.
Solid line is the classical theory e 2 /4z, dashed line is
the constant velocity result (6.2~, while the dotted line
is the self-consistent solution. After Ray, R. and Mahan,
G.D. (1972). Phys.Lett., 42A, 301.
ent SO phonons and surface excitons. Each of these terms has

the type of coupling indicated in (4.6).
The average number of surface modes excited may be obtained
from (6.1).
V(z,v)
N(z)
tzws
118 G.D. MAHAN
So N(O) is the number of modes excited when the electron comes

from infinity to the surface. The quantity in (3.2) is just
twice N(O)
2V(O,V)
Q 2N(O) (6.3)
fzws
This is because Q is computed for a round trip, where the elec-

tron goes from infinity to the surface and back to infinity.
Using (6.2) gives Stern's result (3,2) for Q (for cosS = 1).
Since (3.2) predicts quite well the experimental Q's the experi-
ments indirectly verify the dynamical image charge theory.
So the image potential is related to the average number of
excitations. Our system has been idealized to a closed system
of electron plus surface modes. Any energy. gained by the elec-
tron must be given up by the surface modes. The negative image
potential of the electron is produced at the expense of exciting
an eqUivalent energy's-worth of surface modes. In a classical
system, the number of surface modes excited would be exactly
(6.3). In a quantum mechanical system the number of excita-
tions obeys a Poisson distribution (3.1), and Q is the average
number excited.
One advantage of (6.3) is that any improvement in estimating
the dynamical image potential provides an identical improvement
in the estimate of Q. For example, it is possible to estimate
the maximum value of Q. According to (3.2), Q increases with-
out limit as v is reduced. This is physically unreasonable.
If a ~ery slow particle approaches the surface, the strong image
potential causes it to accelerate. Because V(z,V) is smaller
for larger v, the acceleration reduces the image potential.
This problem may be solved self-consistently, and provides an
estimate of Qmax. The self-consistent, semi-classical, solution
is given by Ray and Mahan [16]. A particle with initial veloc-
ity Vo has initial kinetic energy ~mvo2:
(6.4)
For constant value of vo, the equation may be solved to obtain

v(z) and hence the self-consistent potential. The dotted line
in figure 13 shows this potential for our previous example.
The maximum potential depth is obtained at 2 = 0 for a part-
icle with Vo = O. Solution of (6.4) in this case yields
This gives for the maximum well depth

Ryd,
and for the maximum value of Qmax
2Vmax 7I 2/ 3rs1/2
-~ 31 / 6 21 / 2
It should be possible to measure Qmax' A very low energy elec-

tron will get trapped at the surface if it excites any excita-
tions, since its energy will then be less than that of the vac-
uum. But the probability of the electron not making any excit-
ations is exp(-Qmax), and this should be measurable. If an el-
ectron approaches the surface with a kinetic energy less than
hwsp the probability of it getting trapped is 1 - exp(-Q).
Another method has been used to derive the dynamical image
potential [17,44,45]. This appears to be a mathematically dif-
ferent method of arriving at the same physical answer. This
other method proceeds by Fourier analyzing the time response
into frequency space. The electric field outside the surface
is obtained by matching boundary conditions in the usual way.
The answer contains a factor
£(w) - 1
£(w) + 1 '
which is expected for image potentials. For a particle coming

directly at the surface, the appropriate frequency is w = ikv.
This theory eventually leads to the image potential
_ e 2 fd 2 k e2kz £(ikv) - 1
V(z ,v)
471 k £(ikv) + 1
However, by using £ = 1 - wp 2/w 2 , this result is identical to

(6.2). But the two methods do not appear to give the same ans-
wer in the case of a particle entering at an oblique angle to
the surface normal [44].
7. SURFACE POLARONS
In our previous discussion of electron interaction with sur-
face modes, the electron motion was restricted to be perpendic-
ular to the surface. Let us now solve the complementary problem
of electron motion parallel to the surface. Imagine that the
electron is trapped at the surface plane z = 0, and is unable to
move in the z-direction. But it has plane wave behaviour in the
other two dimensions, parallel to the surface. This is a two
dimensional polaron problem with the Hamiltonian
120 G.D. MAHAN
(7.1)
where P, q, and p are all two dimensional vectors. This model

could describe electrons trapped in the surface states of semi-
conductors, or in artificial inversion layers. Surface polar-
ons have been discussed by Sak [18], and Evans and Mills [19].
They treated the three dimensional motion altogether, which is
more complicated.
The Hamiltonian (7.1) is analogous to the FrBhlich polaron in
three dimensions. For 'weak' coupling, to be defined later,
good results should be obtained from second order perturbation
theory
C2 N + 1
M(2)(k) = -A L-1q
q [£k - £k+q - fiws + £k - £k+: + ~wsJ, (7.2)
1
N
e Sws - 1
At k 0 and T =0 (N = 0), the self energy is
In analogy with the FrBhlich polaron, this set is equal to

- ashw s , which provides a definition of the surface polaron con-
stant
(7.2)
Weak coupling is evidently the case where a < 1. In terms of

this constant, the perturbation theory (7.2) predictions may be
obtained for the effective mass and electron life time
The correction to the effective mass is a s /4, whereas it is a/6

for the three dimensional polaron. The surface mobility is
~ = eT/m, which has exactly the same form in two and three dim-
ensions, except for the difference between as and a.
Sak, and Evans and Mills have also worked out the Lee, Low
Pines theory, and strong coupling theory. These also resemble
their three dimensional counterpart, except for details. So the
two dimensional polaron of the surface behaves very much like
its three dimensional counterpart.
8. SPATIAL DISPERSION: SURFACE WANNIER EXCITONS

So far our theory has neglected the q-dependence of E(q,W).
With this neglect, the theory has advanced to a sophisticated
stage, and is able to explain many of the experiments. Herring
has remarked that this is because the experiments have been done
only on systems where q dependence is not important [46]. For
example, LO phonons are not very dispersive in ionic solids, so
the SO phonons are probably not either. Here a local theory
seems to work well. So why not pick a system in which the bulk
modes are known to be very q-dependent, and examine the corres-
ponding surface modes?
Wannier excitons in semiconductors are capable of center-of-
mass motion. A classical description of these modes is that
they are a polarization wave which is able to move around. This
spatial motion makes the dielectric response r-dependent which,
after Fourier transforming, is q-dependent. This q-dependence
is called spatial dispersion, in contrast to the frequency dep-
endence which is ordinary dispersion [47-49].
Let us quickly review what is known about the ordinary opti-
cal properties of these excitons. The resonant energy has quad-
ratic q-dependence
wo +
ttl
2m '
: : wo 2 + bq
2
,
hwo
b =-
m
which enters the resonant energy denominator
47TS
E(q,W) = EO + (8.1)
W0 2 + bq2 - w2
The equation (2.5) which defines the refractive indices (~ 1),
nw{?c) 2
[=- __
dq,w)
is now a quadratic equation for q2, with the two roots

122 G.D. MAHAN
q
2
HQ 2 i-
2
E:oko ] ± ~ (Q
[2
- E:OkO)
2 2
i-
4TIBk02]~
b ' (8.2)
!(w2
b - wo 2) ,
=e .
w
kO
This behaviour is explained in figure 14. The dotted line shows
w'
,I ck
I
I
I
Ws. ___ ___/ _____ - - - - - -...-
----~------- --
I
I
I
I
,I
I
I
I
I
I
I
I
k"
Figure 14 - The solid curves are the dispersion relations

for bulk polaritons in this Wannier exciton system. These
roots are given in (8.2). At frequency w' there are two
propagating modes in the solid. A surface mode at wse
coexists with a bulk mode at the same frequency with wave
vector kit.
the photon curves kO/E:O and the exciton dispersion curve. The
solid line shows the two solutions (8.2) which are obtained by
the mixing of these two modes. At the frequency w' there are
two modes, ql and q2, in the system, and two refractive indices
nj = qj/ko. Consider the optical experiment where light of fre-
quency w' is reflected from the surface at normal incidence.
As shown in figure 15, outside the surface there is an incident
I and a reflected R beam, while inside there are two independent
waves Tl and T2 which leave the surface. The electric field in-
side is
------0._ T I
R
------0.- T 2
Figure 15 - During an ordinary optical reflection experi-

ment at frequency w' (see figure 14), there are two modes
Tl and T2 in the solid.
The incident intensity I is assumed known, while R, Tl and T2

are unknowns which must be determined by the boundary conditions.
The two standard boundary conditions are that the tangential
components of E and H are conserved at the surface, which gives
For normal optical systems, where there is only one wave inside,
this is sufficient to solve the problem. Now we need an addit-
ional boundary condition, or ABC. This problem was first dis-
cussed by Pekar [47], who also suggested that the ABC should be
that the total polarization from both waves should be zero at
the surface
This has gained wide acceptance, although other suggestions are

that ap/az = 0 at the surface, or even some linear combination
of these two possibilities [50]
p + '
1\
ap
az = 0.
124 G.D. MAHAN
The ABC is not yet known with certainty. The bulk reflectivity
experiments, which clearly show spatial dispersion effects, can
be interpreted with more than one choice of ABC [50]. Our lack
of knowledge of the ABC also hinders the discussion of surface
excitons. But this is interesting, as perhaps surface excitons
provide another experiment which helps measure the ABC.
For bulk modes in a solid, the longitudinal and transverse
waves are given by the equations
(longi tudinal)
(transverse)
How are these relationships altered for surface modes? The ans-
wer was given by Maradudin and Mills [51]. Surface modes have a
two-dimensional wave vector k in the plane of the surface, and
an evanescent component exp(-yz) perpendicular to the surface.
y can be considered a complex z component of wave vector. So if
we write our dielectric function as dq lI,qz,w), the equations
which determine the yare
o (8.3a)
(k 2- 2 2
y )c
(8.3b)
w2
A proper derivation of these equations has been given by Haxton

and Mahan [52]. Notice that if £(w) has no q-dependence, then
(8.3b) is identical to (2.9) of the local theory, while (8.3a)
gives no surface mode in the local theory.
The dielectric function (8.1) is suitable for both longitud-
inal and transverse components. Using it in (8.3a) gives one
solution for y, which we label Y3
Using it in (8.3b) gives a quadratic equation for y2 with two

roots which are labeled Yl and Y2
2 ~
Yl,2 = {k2 + ~[k02£O + Q2 ± (k02C£O _ Q2)2 + 4n~ko ) ]}
So there are three surface mode components on the inside which

must be matched to the single field component outside the sur-
face. For example, in the geometry of figure 2 and section 2,
the Ex, Ez , and By components inside the surface have the form
H i - ( Y2 2 - k2) e -Y2Z) e ikx '

[E1 ( Y 2 - k2) e -Y1Z +E2
y-
- kO- -
n 1 Y2
while outside they are exactly as before
Ez = Ezoe YOz e ikx ,
iyo E 0 YOz ikx

Ex = k z e e ,
E 0 ikx
Hy = kEkO z e
YOz
e ,
Four equations are needed to eliminate the four field amplitudes

EzO, T1, T2, T3, and hence obtain the eigenvalue equation. Eq-
uating Ex and Hy provide two equations, so now two ABC's are
needed. A believer in P = 0 at the surface would obtain the two
ABC's by setting Px = 0 and P z = 0: our TM mode has two direc-
tions of electric field, so two directions of polarization. Any
other choice of boundary conditions also leads to two ABC's,
which are sufficient to solve the problem. So the eigenvalue
equation for surface modes depends upon the ABC, and recall that
these are not yet known [53]. So the sutface modes themselves
are not yet understood.
Including spatial dispersion makes the surface modes problem
very complicated. Not even the eigenstates are understood.
Further developments of the theory, such as the interactions
with electrons, are yet in the future. This is a subject of ac-
tive research and future promise.
In spite of the fact that the surface eigenvalue relation is
not yet known, there is one statement which can be made with
fair certainty: surface modes do not exist. The argument for
this goes as follows: if surface modes exist, they are likely
to be between the longitudinal and transverse frequencies
For example, at the position Wse in figure 14. But there is al-
so a bulk mode at this frequency. If one tries to localize a
wave packet at the surface, it can mix with bulk modes at the
126 G.D. MAHAN
same frequency, and simply wander away from the surface. This
view is reinforced by noticing that one of our three roots, Y2,
is actually imaginary and is in fact the bulk modes itself. So
the solution to (8.3) actually yields the bulk transverse state,
plus two evanescent components at the surface. In the local di-
electric theory of section 2, there is a gap in the bulk freq-
uency spectrum between WT and WL in which it is possible to have
real bound surface states. Apparently this cannot happen once
spatial dispersion is introduced into the physics, because there
is no longer a gap.
One immediately thinks of two ways in which this difficulty
may be avoided. The first is to discard Y2 and try to build a
surface state with just the two evanescent components. But this
corresponds to a particular choice of ABC's, and there is no
compelling reason to think that this choice is right. The sec-
ond method is to try to look for surface states outside of the
frequency region between WTe and WLe. But there is no reason
to think that this is right either. The modes must be well be-
haved in the limit that b ~ o.
The most likely interpretation is that the surface mode be-
comes a surface resonance. A bulk mode, wandering near the sur-
face, prefers to spend its time there because it looks like a
bound state. So it is likely that, in Otto's experiment, ref-
lectivity dips may still be observed which correspond to the
surface resonance. Perhaps the width of the reflectivity dips
is related to the admixture of T2 in the wave function, which
is the width of the surface resonance. Otto's experiment, which
has not yet been done for surface Wannier excitons, may tell us
about the ABC's.
There is extensive theoretical work on the spatial dispersion
effects of surface plasmons [54-56]. Much of this work has cen-
tered about an interesting formula which relates the surface im-
pedance Z = (ExIHy)z=o to an integral over the dielectric func-
tions
The surface impedance provides almost any theoretical quantity

of interest. For example, the reflectivity is obtained from the
equations
which has the solution
R - I[~)
1 Z
+
Or surface modes are obtained by matching Z inside and outside
of the surface. Z = - iyOc/w, or
For a local theory Et = q, = dw), the dqz integral is easy, and

this equation gives the earlier result (2.13). This formula now
provides the surface mode eigenvalue equation for systems with a
q-dependent dielectric function.
These results were first obtained by Fuchs and Kliewer [54].
They are derived by assuming that electrons reflect specularly
from the inside metal surface. In macroscopic terms, this cor-
responds to the choice ap/az = 0, as is explicitly mentioned in
Fuchs and Kliewer's derivation. Other derivations claim this
result is true for all boundary conditions, which of course is
not true [55].
We find it amusing that the surface plasmon theorists believe
in ap/az = 0, while the exciton people believeP = 0. Of course,
both may be true since metals are different than semiconductors.
Our view is that both subjects are in a mess.
There is a simple physical interpretation of these various
boundary conditions. It is best illustrated by an example, so
consider the Wannier excitons. The exciton contribution to the
po1arizability
dq,w) EO + 47Tct(q,W) ,
ct(q,w) B ,
wo 2 + bq2 - w2
has a Fourier transform into real space
B
ct(r,w) =- - e -Qr
47Tbr '
Q (w 2 _ w2)~b-~
0
This spatial dependence is a simple consequence of the motion

of the excitons. Consider, using figure 16, the polarization
response of a solid at the point (p,z) caused by an electric
field at (p' ,z'). The first path is the direct route labeled A.
The second is the route B, where the excitation reflects from
the surface. It appears to come from the image point (p' ,z').
So the response may be written as the sum of these two contri-
butions (superposition principle)
P(e,z) = fde f:dZ'[ctC e - e',z - z') + Act(e - e',z + z')]E(e',z'l.

128 G.D. MAHAN
.- -- B_--- /-.
(p', -z')
- (p', z')
-/
/
IA
--_
-. I
(e, z)
/
Figure 16 - A spatial dispersive media is obtained when

the excitations can move. An excitation created at (p',
z ') can get to another point (p ,z) by two paths: by the di-
rect route A, or by reflecting from the surface B. The
latter route appears to corne from the image point (p' ,z').
The reflected components are multiplied by the parameter A which

is yet unspecified. The choice A = -1 means that at the surface
z = 0
P(p,O) = fde'f:dZ'[a(e - e' ,z') - aCe - e',z')]E(e' ,z') o.
While the choice A 1 gives
ap
az (p,O) = o.
So the difference between the various boundary conditions merely

reflects how the excitation changes phase upon reflection. An-
other suggestion has been that A = 0, which was used by Maradudin
and Mills [51] and also Birman's group [53].
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ELECTRONIC TRANSITIONS AND RELAXATION PHENOMENA
IN POLARONS
J. DEVREESEt
Departement Natuurkunde,
Universitaire Instelling Antwerpen, Wilrijk
and
Faculty of Science, Rijksuniversitair Centrum Antwerpen,
Belgium
R. EVRARD
Institut de Physique Theorique,
universite de Liege, Belgium
E. KARTHEUSER11
Physics Department, Purdue University, Indiana, USA
GENERAL INTRODUCTION
This is a series of four lectures concerning the excitation
spectrum of polarons. The polaron model serves here to illus-
trate the effects of the interaction between elementary excita-
tions. In the first lecture the Hamiltonian describing the
polaron is derived.
In the second and third lectures the excited states of the
system are analyzed wi th different approximations. In the fourth
lecture we present a new self-consistent treatment of the
equations of motion describing the system.
t Also at the Solid State Physics Department of the SCK-CEN,

Mol, Belgium.
11 On leave of absence from the Institut de Physique, Univer-
site de Liege, Belgium
131
LECTURE I: THE FROHLICH HAMILTONIAN
1. INTRODUCTION
Elementary excitations of atoms, molecules and solids, like
hole-electron pairs, plasmons, excitons, vibrations or phonons,
etc ... are somewhat abstract concepts. In general, the excita-
tions of actual systems are not so simple, but consist of cou-
pled excitations. The situation is more or less similar to
that prevailing in quantum field theory. In this case, the
elementary excitations are quanta of free fields, whereas the
real particles appear as coupled excitations of these fields.
The effects of the coupling between elementary excitations
are generally far from being negligible. They can lead to a
more or less large discrepancy between the observed properties
and the predictions based on uncoupled excitations.
The main purpose of the present lectures is to throw some
light on these effects of the interaction between 'elementary
excitations' by studying a simple model in detail. This model
consists of a charged particle, a conduction electron for ex-
ample, in interaction with the excitations of a continuous pol-
arizable medium. The normal modes of the medium are polariz-
ation waves and it is assumed that the frequency of these waves
does not depend on their wave-length. In solid state physics
this is known as the FrBhlich polaron-model [1,2]. The quanta
of the polarizable medium are then long-wave optical phonons
in ionic crystals.
In the first lecture, we show how the electron-phonon in-
teraction Hamiltonian can be derived using the concept of diel-
ectric constant and we give a brief description of the main
features of the model. The other lectures are devoted to the
study of the effects of this interaction mainly on the optical
properties of the system.
2. DIELECTRIC CONSTANT OF THE POLARIZABLE MEDIUM

It is well known that a polarizable medium has two types of normal
modes of vibration, namely the transverse and the longi tudinal waves.
Let us suppose that for a given k-vector, these are two degenerate
transverse modes and a single longi tudinal mode. This is the case
for large wave-length optical phonons in cubic crystals with
two ions per unit cell. Let Wt and we be the frequencies of
133
134 DEVREESE, EVRARD AND KARTHEUSER
transverse and longitudinal modes respectively. It is assumed
here that these frequencies do not depend on the phonon wave-
length. This is known to be the case for optical phonons at
the limit of large wave-length. Obviously, the dielectric con-
stant has then the same property: it depends on the frequency
only, so that
E = dw).
To describe the absorption of electromagnetic radiation at

the frequency of transverse modes, the dielectric constant must
have a pole at w = Wt, (at least, if the damping is neglected).
A more complete study [3] leads to
dw)
Let us call Eoo and EO the values of the dielectric constant

for w tending to infinity and zero respectively. This leads to
dw) Eoo + (1.1)
3. NORMAL MODES AND COUPLING WITH A CHARGED PARTICLE

The total electric field is given by
where D
is the electric displacement. Since liE tends to zero
when w goes to Wt, this relation shows that the transverse mode
of oscillation of our model does not produce any electric field.
Thus the electron of the polaron model is coupled to the longi-
tudinal phonons only. To obtain the coupling strength, let us
first consider a classical charge distribution p(t,t) oscillat-
ing at the frequency w:
In the situation studied here, the resonance frequencies are

in the far infrared, and the oscillations are therefore rela-
tively slow. The situation is then quasi-static and the laws
of electrostatics can be applied. This leads to
ELECTRONIC TRANSITIONS AND RELAXATION PHENOMENA. I. 135
where the potential ¢t(p,t) is defined by
() ¢t (+t)-I
E W r, -
p(P',t)d3,
V 1+ + 1 r .
r - r'
This is not the most general solution. Indeed, the expression

(equation (1» of the dielectric constant has a zero for
Noting that
it becomes obvious that
+
¢t(r,t)
1
= E(W) JV I~p(p~t)
_ ~'I 3 -±
d r' + ¢o(r)e
iWot
8(w - WO) (1. 2)
is the general solution of the problem under consideration. In

this expression (equation (2», ¢t(p) is an arbitrary function.
If the potential is expanded in plane waves
one obtains, for the electric field
This shows that the electric field has longitudinal components only.
Therefore the normal modes which give rise to the electric field are
the longitudinal optical phonons. The two contributions to the
expression (equation (2» of the potential have the following
meaning: The first one represents the Coulomb potential of the
charge distribution p(p,t). This Coulomb potential is modified
by the ionic polarization as well as by the electronic polariza-
tion. The second contribution is the electric potential and the
free longitudinal phonons produced in different ways: optically,
thermally, etc ..
It is clear that, when the frequency w increases beyond the
infrared resonances of the medium, the amplitude of the forced
oscillations of the phonons decreases rapidly. Then, the field
has no longer anything to do with the ionic polarization. It
is either produced directly by the charge distribution or due
to the electronic polarization. In this situation of high fre-
quency, one obviously has
~oo
(+ )
r,t = -
1 J 1+p(p~ +,t) I_ d3~,
L
£00 V r - r
where ~oo(p,t) is the electric potential at high frequency, i.e.

at a frequency far beyond the phonon frequencies, but still be-
low the ultraviolet resonances of the electronic polarization.
In the whole range of frequencies in which we are interested
i.e. from very low frequencies to frequencies close to the vis-
ible, the contribution of the electronic polarization as well
as the Coulomb field (in vacuum) of the particle are practical-
ly frequency independent. This is due to the fact that, for
the frequencies considered here, the electronic polarization
follows nearly perfectly the motion of the charge. As we are
not interested in these contributions, let us subtract them from
the potential to obtain the true ionic contribution:
Hfi, t)
+ iwot
+ ~o(r)e c(w - wo)' (1. 3)
4. EQUATIONS OF MOTION, LAGRANGIAN AND HAMILTONIAN

The next step is to obtain the equation of motion for the
electric field which can be derived from the electrostatic po-
tential (equation (3)) by means of
E(fi,t) =- ~~(fi,t)
(Contd)
(Contd) - e iwot o(w - wO)v<l>O(r).

~ ~
(1.4 )
For this purpose, let us take the second derivative of equation

(4) with respect to time. This gives
~c;;, t) = w2 (_1_ - ...!..) V J p(1i~ t) d 3r'

d w) £00 V It - t, I
+ wo2e iwot o(w - wo)V<I>(;)
2-± ~
- Wo f','(r,t)
( 2
+wO-w 2) (-
1 - -1
-]v±
£00 dw)
JV Itp(1i~- t'l
t) d 3r ,
.
Using the expression (equation (1)) of the dielectric constant,
we verify that
so that the equation of motion for the field can be written as
A possible expression for the Lagrangian which leads to this

equation is obviously
L = 2cJ V ~2 ~
{E (r,t) - Wo
2-±2 ~
b (r,t)
where c is a constant to be determined. To obtain the value of

this constant, let us notice that equation (5) is the Lagrangian
of a distribution of harmonic oscillators in interaction with
the charge distribution p(r,t). The corresponding Hamiltonian
is therefore
(Contd)
(1. 6)
Let us momentarily consider the case of a static charge with no

free phonons present, i.e.
+-+
E(r, t) = o.
The energy has a minimum value when
which, as expected, is the difference between the total electric

field of the charge distribution and the Coulomb field (includ-
ing the contribution of the electronic polarization in the lat-
ter). This difference obviously represents the electric field
of the ionic polarization. Introducing this result into the
Hamiltonian (equation (6)) gives the electrostatic energy Ei due
to the ionic polarization
Integrating by parts and using
leads to
(1. 7)
Let us now compute this electrostatic energy in a different way.

The comparison with equation (7) will then determine c.
The work to bring a charge cp(r) from infinity to the neigh-
bourhood of the distribution pet') is, in a medium of dielec-
tric constant EO
~w = ~f
u
d3 f
d 3 , pet' )op(t)
£0 V r V r r - r'1'* '* 1
- _1_
- 2 £0
~f
u
d3 f
V r V r
d 3 , p(t)p(t')
1-+r - -+r' 1 '
so that the electrostatic energy Es of the charge distribution

p (t;)
is
Es -- ~f d 3 fd 3 , p(t)p(t')
1-+r - -+,
r 1 .
2 £0 V r r (1. 8)
The energy for the electron in interaction with the electronic

polarization only is
(1. 9)
After subtraction of this electronic contribution (equation (9))

from the total energy (equation (8)),. one is left with the ionic
contribution
E·1
which is to be compared with equation (7). This comparison

gives
or
-1
c = (4n) -1 wo -2 [--
1
£00
1J
- --
£0
. (1.10)
5. CANONICAL VARIABLES AND QUANTIZATION

There is a difficulty in the determination of the momentum
canonically conjugated to the electric field. Indeed since
E(t;,t) =- ~~(t,t),
the three components of the vector electric. field are not in-
dependent. It is easier to expand the potential in plane waves
writing
4>ct;.t) = _1_, I qt(t) eitor , (1.11)

(VC)2 k k
where V is the volume of the system. The reason for the factors
(Vc)~ and k in the denominator will become clear further on.
This expansion gives for the electric field
( 1.12)
As the field and potential are real quantities, one must have
Introducing the result (equation (12» into the expression (equa-

tion (5» of the Lagrangian leads to
L ~ r
~
(
0 °
~q-t - Wo qtq-t
2 )- . 1-
wo
(4TIV)~
(1
-
£",
-
_1)~
£0
k
x Ik ~k qk-+fVe itor[±fv V r
_ -+, I d3r ']d 3r,
1-+p(p.t)
r
where use has been made of the expression (equation (10» of c.

The momentum canonically conjugated to qk is obviously
The definition of the Hamiltonian is
H I TINt - L.
k
Since
one obtains
H ~ I (~t~-t + W0 2qtq_t)
k
Quantization requires that
while all the other commutators are zero.

If the charge is a point charge e (an electron for instance)
whose position is P, the charge distribution is
and the Hamiltonian becomes
Usually the phonon annihilation and creation operators at and

atk are used instead of the canonical variables qt and rrR.
These creation and annihilation operators are defined by
qk = -
and obey the following commutation rules:
all the other commutators being zero. With this definition the
condition q-t = q}?< is satisfied.
In terms of these operators, the Hamiltonian becomes
with
k V
- ~ UIWO)21(-
ie (271)
Vk = - 1-
Eoo
-1 )
EO
~•
Most generally, this interaction coefficient Vt is expressed in

terms of the coupling constant a defined as
where m is the mass of the particle and E is given by
1 1 1
= --
£ Eoo EO
This coupling constant compares the energy, in a medium of di-

electric constant £, of an extended particle of size Oi/2mwo)~
with the energy ~WO of a phonon. It can be shown that the
length <~/2mwo)~ is the polaron radius at weak or intermediate
coupling strength.
For a negative charge (an electron for instance), the inter-
action coefficient can be expressed in terms of the coupling
constant as
- '/... - ( fi-) 4 -
fiw - (471) ~ a 12
k 2mwo V •
One must still add the kinetic energy of the particle to ob-
tain the complete polaron Hamiltonian
p2
H = 2m + fiwo i a"kta"k
<Vka"ke
i"kor + ~'atte
-i"kor ),
where the zero of energy has been chosen at the zero point
energy of the phonon field. Another notation which will be
used in the next lecture consists in replacing the sum over
ELECTRONIC TRANSITIONS AND RELAXATION PHENOMENA. l . 143
the k-space by an integration
~ + ~fdk
3
+ 871
k
and in defining
a(t.) [ V
871 3
)~ ak,
+
at(t.) (8:3 r1
at t ,
v(t.) ( V )
871 3
~ Vk = - .
1-
~Wl
T 2mwO
tz ) & la
71/2·
The new operators obey the following commutation rules
[a(t.),at(t.')] = oCt. - t..),

while all the other commutators are zero. These notations are
preferable when one deals with scattering processes.
Finally, let us point out that it is possible to use the pol-
aron Hamiltonian (equation (6)) written in the configuration
space, which is
with
-1
-1
c = (471) wo -2 (--
1
Eoo
1 )
- --
EO
.
However, the commutation rules for the components of EC$) and

++
E(x) are somewhat complicated. Indeed
(Contd)
(Contd)
in a a \ e
it· c~-;t, )
- Vc -ax-· -aX-R,-' L -'---k-2--
] k
so that finally
. 2(1 1)
1.-'hwO
a
£00 - £0 aXj axR, ,
a
I~
1
- ~, I
But, one has
this shows that the potential ¢(x) obeys the following non-
local commutation rule
which is somewhat unexpected.
REFERENCES
1. Devreese, J.T. (ed.) (1972). Polarons in Ionic Crystals and
Polar Semiconductors, (North Holland).
2. Kuper, C.G. and Whitfield, G.D. (eds.) (1963). Polarons and
Excitons, (Oliver and Boyd).
3. Born, M. and Huang, K. (1954). Dynamical Theory of Crystal
Lattices, (Clarendon Press).
LECTURE II: OPTICAL ABSORPTION OF POLARONS IN THE WEAK AND
STRONG COUPLING LIMIT
1. INTRODUCTION
The object of this lecture is twofold. First, we outline
the general formalism of the equation of motion approach to pol-
aron theory, with particular emphasis on a solution of these
equations by successive iterations in the weak coupling limit.
Second, we discuss the problem of optical absorption by free
charge carriers in the limit of weak and strong electron-LO-
phonon interaction. Special attention will be given to the in-
ternal structure of the polaron system. We shall show that a
new kind of internal excitation, the so-called 'Relaxed Excited
(resonant) States', RES, appear in the phonon-continuum when the
electron-LO-phonon coupling strength becomes large enough. As
a consequence of this, the theoretically predicted optical ab-
sorption spectrum for alkali-halides (intermediate and strong
coupling) reveals a drastically different behaviour from that
expected for polar semiconductors (weak electron-phonon coupl-
ing).
The first part of the program is carried out in section 2
and the second in section 3. Finally, the last section will be
devoted to a brief review of existing theoretical and experi-
mental results, as well as a discussion of recent optical meas-
urements in the light of the present work.
2. OPTICAL ABSORPTION IN THE WEAK COUPLING LIMIT
2.1 EQUATIONS OF MOTION METHOD

This approach (which has also been the basis of our recent
self-consistent treatment exposed in lecture IV) is particularly
interesting for two main reasons:
(a) There exists a classical analogue of these equations
[1];
(b) The method is well adapted to treat dynamical proper-
ties [2J such as the optical transitions.
Bearing in mind that the time derivative of an operator A is
given by
i U
~ [B,A] + at ' (11.1)
145
one can easily derive the equations of the motion for the pol-
aron problem from Frohlich's Hamil tonian establi shed in lecture I:
we obtain
..;. -+(t)
ret) = E.lEJ... (I 1. 3)
m
aCk,t) + iwaCk,t) . V*Ck)

- 1 . - -li- e
-iko~Ct) ,
(11.5)
. VCk) ikot;Ct)
1.- -1'1- e (II. 6)
Equations (3,4) are related to the time evolution of the elec-

tron position ~Ct) and momentum operator pCt) respectively,
whereas the last two equations (equations (5,6)) describe the
time evolution of the phonon creation atCk,t) and annihilation
operator aCk, t).
We shall solve the problem in two steps:
First, we perform ~n exact eli~ination of the polarization
field variables aCk,t) and atCk,t) [1];
Second, we solve the remaining force-equation for the elec-
tron by an iteration procedure.
Equations (5,6) can be solved using the method of variation
of parameters. This leads to following formal expressions for
the field amplitudes:
a(k,t) = aCk,to)e-iwCt-to)
_ ~ V*Ck)e-iwtf t dTe-i[korCT)-wT], (11.7)

to
ELECTRONIC TRANSITIONS AND RELAXATION PHENOMENA. II. 147
and
at(k, t)
+ ~ V(k)eiWtJ t dTei[kor(T)-wT]. (ILS)

to
A suitable choice of the time to (inital condition) gives a

very clear and simple physical meaning to the field operators
defined at to. In fact, our choice is based on the 'in-and-
out-formalism' used in quantum scattering theory. Following
this formalism, we consider an adiabatic switching of the elec-
tron-phonon interaction at a time to far in the past or far in
the future. The cut-off term e- E1T1 resulting from this proced-
ure leads then to a non-interacting electron-phonon system at
to = _00 and at to = +00 respectively, and relations (11.7,S) may
be used to construct new time independent quantities
lim {a(k,to)e iwto }

ta+- oo
where E ~ +0, as well as their complex conjugate
The connection between the new operators defined in expressions

(II. 9,10) and the causal scattering solutions now becomes evident:
Let us call !p*) an eigenstate of the polaron Hamiltonian Hwhere
the polaron is characterized by its momentum P*. It follows from
equation (11.10) that if the creation operator a(+)t(k) acts on
the state !P*), this leads to a new eigenstate
(II.ll)
of the Hamiltonian H, which contains one additional free phonon

of wave-vector k scattered by the polaron. Notice that the sol-

ution (equation (11.11)) derivedjhere for the polaron problem
is closely related to the scattering solution obtained for the
first time by Wick [3,2] and is nothing other than the well-
known 'Incoming Wave'. In other words, the operator a(+)t(k)
not only creates an 'incoming' plane wave but also all spheri-
cal 'outgoing' polarization waves of the scattering process.
In a similar way one can construct another set of formal solu-
tions, the 'anticausal scattering solulions'.
The incoming wave amplitudes a(+)t(k) and a(+)(k) are of con-
siderable importance here for two reasons: On the one hand,
their matrix elements between eigenstates of the total Hamilton-
ian are known and, on the other hand, their existence allows us
to obtain an exact ~xpression of the time dependent phonon opera-
tors at(k,t) and a(k,t) provided we know the electron position
operator ret) as a function of time.
Ma]fing, use of the' incoming scattering' operators a( +) t(k) and
a(+)(K) defined in expressions (11.10,9) one reduces the equa-
tions of motion to the following relations
• +
p=P.., (11.12)
m
~ = ijdkkV*(k){a(+)t(k)
+ *V(k)j:oodte-i[k~(t)-wt]e-Eltl}ei[k~(t)-Wt] + h.c.(II.13)
where h.c. stands for the Hermitian conjugate of the first term
in the right hand side of equation (11.13).
Notice that the last equation expr~sses simply ~he c2n:erva-
tion of the total polaron momentum (dP/dt) = 0. SInce P IS a
constant of the motion we have
(11.14)
or
tCI1.lS)
while there difference (equation (11.14) minus equation (11.15))

yields:
pet) =p + ijdkka(+)t(k)V*(k)jt dte-Eltle-i[k~(t)-Wt]

to
- jdkk IV(~12Ir dte-e:ltli[kr(t)-wt]12 + h.c. (11.16)

______ to
t An operator OCto) defined at time to will be written 0 in
all subsequent equations.
Unfortunately, the relations (11.12), (11.13) or (11.16) can-
not be solved exactly. A self-consistent solution valid at all
values of the coupling parameter 0, will be presented in the
next lecture (lecture III).
Here we are interested in the weak coupling limit where an
iteration procedure seems to be very well adopted. For such a
procedure it is important to begin with a solution for the elec-
tron motion which is as simple and as accurate as possible.
One then has to introduce this solution in the right hand side
of equations (11.13) or (11.16) and finally to determine the
correction to the initial trial solution by integration.
It is clear from equations (11.13) or (11.16) and (11.9,10)
that at t = to we are dealin~ with a free electron in transla-
tion movement with momentum p which might be accompanied by free
phonons not interacting with it. In the framework of an itera-
tion method, the zero order solution to introduce in the right
hand side of equations (11.13) or (11.16) is
p(t) = p. (II.17)
An integration over time in equation (11.16) is then performed,

making use of the exact relation [2]
while keeping in mind that at the end of the calculations the

limit £ ~ +0 has to be taken. This yields
(II.19)
The second term in equation (11.19) is a correction to the

translation movement due to the static part of the polarization
field.
At zero temperature T = 0, no free phonons are present in
the systemt. Thus at t = to, the polaron momentum ~~, the tot-
al momentum of the system P
and the electron momentum pare
equivalent quantities.
In other words, in the bases defined at t = to, we have
plto) = ~~Ito) = plto), (II.20)
t The basis state at t = to is thus the vacuum state and

a(+)(k)lo) = o.
and the polaron mass m'" is given by
(11.21)
This leads to the well known perturbation result [4]
m'~ 1
-= (11.22)
m 1 - ~
6
Similarly, we obtain for the polaron ground-state energy
(11.23)
the weak coupling result [2,4]
p.,2
EO = 2m;' - a~w. (11.24)
2.2 APPLICATION TO OPTICAL ABSORPTION

Let us first briefly define the Optical Absorption Constant:
In optical measurements the most important observable quantities
are the transmission coefficient T and the reflection coeffici-
ent R. Both are connected through following relations
(1 - R2 )e- Kd
T (11.25)
1 - R2e- 2Kd
and
(n - 1)2 + k 2
R (11.26)
(n + 1)2 + k 2 '
with the optical index of refraction n, the absorption coeffic-

ient k, the crystal thickness d and the 'absorption constant'
20.k
K (11.27)
c
where 0. is the frequency of the incident light beam.

A theoretical calculation of this last quantity can be set
up in the framework of ordinary time-dependent perturbation
theory: Let us suppose that an incident light beam of frequency
0. and intensity I(0.) interacts with the polaron system and un-
dergoes absorption. The 'absorption constant' is then defined
as the ratio of the energy absorbed per unit time and per unit
volume to the incident flux:
(II. 28)
where N is the number of charge carriers per unit volume and W

the probability per unit time that the system undergoes a trans-
ition from a given initial state Ii) to some final state If)
with the absorption of energy ~n from the external perturbation.
The transition probability is given by Fermi's golden rule,
(11.29)
Using a dipole approximation f2r the electromagnetic field de-

scribed by a vector potential A, one has
A = Aocosnt
and
V=--
eAoP
(11.30)
m '
where p is the electron momentum operator.
Let us consider a light beam polarized along the z-axis and
use a representation of the a-function
t(ll. 31)
then we end up with the following expression for the 'absorption

constant'
(II. 32)
where
(II. 33)
Substituting the results for Pz(O) and Pz(t) (11.19) into the
expression (equation (I I. 33)) we obtain at T = 0 (zero tempera-
ture),
e 2 2'ITO ((
-Xd k
n - w - t.:J + 2m'"2))
+ ~k
. (II. 34)
+ Here Re stanos for the real part of the bracket factor {}.
Assuming that optical transitions accompanied by emission of

'one-LO-phonon' are predominant in the limit of weak electron-
phonon coupling, yields (equations (11.19,34))
(II.36)
with
a 'h
X2 J:....Jlkkz2
=m 2 - -
12 2mw
(II.37)
For simplicity, a small drift velocity along the z-axis has

been considered in expression (11.36).
In the case of polarons at rest (v = Pz*lm* 0), we obtain
r(~) =0 if ~ < w (11.38)
and
In the case of finite charge carrier velocity
(II. 40)
we find
(a) For ~ < w
(II.41)
with
2 2 l 2
n±(y) = [yy ± (y y - 1)2] , (11.43)
y (11.44)
(b) For rl = w
(II .45)
(c) For rl > w
(11.46)
with
F2[;,A] • f l dy
-1
2
y.. n(y")
(1+ B2y2)~
exp [ - t[; - l]n(Y)] (11.47)
2 2 1)~]2,
n(y) [By + (B y + (11.48)
B =A[;-lr~· (11.49)
In figures 1 and 2 the results [5] for r(rl) have been drawn
for A = 0, 0.4, 0.5 and for a = 0.2 and 1 respectively. These
results confirm the calculations in reference [18] (formula
(26)) where it was demonstrated that at T = 0 the threshold of
the absorption spectrum shifts to lower values of the incident
light frequency and that the intensity of the peak increases as
a result of the application of a weak static electric field on
the system.
3. OPTICAL ABSORPTION IN THE STRONG COUPLING LIMIT
3.1 LANDAU-PEKAR VARIATIONAL METHOD

In the limit of strong coupling, the electron moves in a pot-
ential well due to the important polarization it induces in the
lattice. If the coupling is strong enough, the frequency of
vibration of the electron in the potential well becomes very
large in comparison with the LO-phonon frequency and the polar-
ization can only adapt itself to the mean charge distribution
of the electron wave packet. In this case, the usual strong
coupling method adopted is that of Landau and Pekar [6]. The
Landau-Pekar adiabatic approximation is set up by a product of
the electron </>(1") and field wave function q,. This implies that
there is no correlation [7] between the instantaneous position
0:16
A = 0.5
Cl = 0.2
0.12
t
~
t...
0.08
0.04
0. 0.5 LO 1.5 2.5 3.0
0./0)-
Figure 1 - Velocity dependence of the optical absorption

constant r(n) for a = 0.2 as a function of the incident
light frequency n for the values of the reduced velocity
A = v/(nw/2m)~, A = 0,0.4,0.5. (Reference [5]).
of the electron and that of the ions. Thus for a polaron in

the j-th excited state, we have
where ~j represents the field as deformed by the quasi-state

electron charge distribution el~j(r)12. One then obtains
~j = Sj -110) (11.51)
where no free phonons are excited, and
(11.52)
if free phonons are present.

0.8
). = 0.5
IX = 1.
0.6
t
g
~
0.4
0.2
o. 0.5 3.0
njw-
Figure 2 - Velocity dependence of the optical absorption

constant r(~) for a = 1. r(n) as a function of the incid-
ent frequency ~ for three values of the reduced velocity
A = 0, 0.4, 0.5. (Reference [5]).
Here the unitary operator
(I I. 53)
depends on the Fourier transform
7
Pj(K) = e fl ¢j(r) 12 e ittdr~ (II. 54)
of the electron charge distribution in the j-th excited state.

For large a, the electron is accompanied by an important dis-
tortion of the lattice and its wave function is nearly local-
ized. As a first approximation ¢(r) can be described by an
isotropic harmonic oscillator. Within this approximation and
using the electron oscillation frequency n as a variational

parameter, the energy levels E, the oscillation frequencies n
and the polaron mass m* have been calculated by several authors
[6-10]. Typical results for j = 0,1 are listed in Table I.
TABLE I
Properties of the Strong CoupLed
PoLaron InternaL Excitations
Groundstate First RES First FCS
2
EO=-0.106anw EFC = EO + hno = O. 046 a 2nw
2 2 2
nO = 0.14 a w nl=0.068 a w nO = 0.14 a w
For the sake of clearness, let us briefly comment on the re-

sults listed in Table I: Strong electron-LO phonon coupling al-
lows the possibility of internal polaron structure. Besides the
groundstate Eo-level (see figure 3) there might exist two differ-
ent types of first excited polaron states depending on whether
Figure 3 - Internal excitations at strong coupling: EO=

ground state, El = First relaxed excited State; EFC:
Franck-Condon State.
the electron excitation takes place with or without 'lattice re-
laxation'. More precisely, these two different excitations are:
(1) The 'Franck-Condon' type excited state (FCS) Erc: This
is a state in the same potential well as that of the
groundstate (solid line in figure 3) and lies ~~O above EO
in the harmonic approximation. In other words, during a
FC-excitation the lattice distortion remains the same as
the distorlion due to the initial electron charge distri-
bution po(k).
(2) The 'Relaxed Excited State' (RES) El: This is a state
for which the potential well o{ the lattice polarization
adaRts itself to the new electronic charge distribution
Pl(k) (see dashed lines in figure 3). As a result of a
larger extension of ~1(~) (~1 < ~O see Table I) a shallow-
er potential is expected. Therefore El is lower than Erc.
Of course strictly speaking, those excited states are 'reson-
ances' lying in the phonon cop.tinuum (oblique lines in figure 3).
However, it has been demonstrated by the authors [10-12] that
the RES is much more stable than the FCS whose lifetime is ex-
pected to be of the order of
tz 1
(11.55)
lrc 'V Erc - EO « w
for a > 5. Indeed, a lifetime calculation [16] gives
1
lRES 'V 0.05 w (11.56)
for the same value of the electron-phonon coupling strength.

Thus, in the calculation of the optical absorption constant by
means of Fermi's Golden Rule, we shall use the RES type as a
set of eigenstates of the unperturbed Hamiltonian.
3.2 APPLICATION TO OPTICAL ABSORPTION

Starting from the expression for r(~) outlined in section 2.2
(equations (11.28,29)),
= I I(flvl i ) I
2
r(~) o(Ef - Ei - tz~) (II. 57)
f
the present authors [11] have calculated the contributions to
r(~) arising from the RES and its one- and two-phonon scattering
states in the summation over the final states If).
The first contribution to r(~) corresponds to a transition
between Eo and El (vertical line in figure 4) and is called the
'Zero-Phonon Peak' in colour center theory.
When the possibility of a decay of the RES towards Eo is in-
cluded, this gives rise to a Lorentzian.
~
!- 0.4
L.. uc
o
-'!!-
0.3
IX = 5
0.2
0.1
--
o
n
w
Figure 4 - Optical absorption by polarons for a 5: Zero-

Phonon Peak and one-phonon side band. (Reference [11]).
The one-phonon contribution 'One-Phonon Side Band' leads to
(II. 58)
and starts at a photon frequency
-wn = (11.59)
The one-phonon peak intensity decreases when the electron-

phonon coupling strength is enhanced (see figure 5), however,
for large a mUltiple phonon contributions have to be considered.
The two-phonon contbibution is given by a sixfold integral:
The result obtained in reference [12] is shown in figures 6 and

7 for a = 6 and a = 9 respectively. We see clearly from figures
6 and 7 that the two-phonon contribution can no longer be neg-
(t =5
o
--
Q
w
20
Figure 5 - Absorption with emission of a single phonon as

a function of the photon frequency ~ and at different coupl-
ing strengths. (Reference [11]).
lected compared to the one phonon peak intensity for large val-
ues of a. (Upper part of figures 6 and 7). However, because
(11.61)
for a = 6 it is expected that the zero-phonon and the combined

one and two-phonon peak intensities (bottom of figure 6) account
for most of the absorption peak for this value of a. Finally
[14], it should be noted that one can always imagine the optic-
al excitation as due to a transition from EO towards EFe (figure
3, transition 1), inserting a set of FC-type intermediate states
in expression (11.57). Because of the instability of the Franck-
Condon state, this transition is then immediately followed by a
decay of the FCS towards the RES or one of its scattering com-
ponents (see figure 3, transition 2). This means that the com-
plex structure of the absorption spectrum obtained at strong
20
1:1=9
10
10
F.e.
15 o
Frequency Frequency
Figure 6 Figure 7
Optical absorption at strong coupling: (1) Upper part: One-
and two-phonon side bands rl(n), r2(n); (2) Bottom: Combined
one- and two-phonon peak intensity; the vertical line indic-
ates the position of EFC. (See Table I). (From Reference
[12]).
coupling describes in fact the actual 'Franck-Condon' state.
4. DISCUSSION
Optical absorption by polarons has recently received increas-
ing attention from experimentalists [13,14], as well as from
theoreticians [15-20]. From the theoretical point of view, the
first calculation of the optical absorption by free polarons
has been performed by Gurevich, Lang and Firsov [15] and is
based on the Green's function theory in the weak coupling limit.
More recently, Devreese et al. [17] have carried out a treat-
ment in the framework of Feynman's Path Integral theory and for
all coupling strengths. A detailed discussion of these calcula-
tions will be given in lecture III. Finally, the Lee-Low-Pines
polaron formalism has been applied by Devreese et al. [18] in
their study of the weak coupling optical absorption constant.
Let us now discuss the present weak and strong-coupling re-
sults in the light of the existing theoretical and experimental
work:
For weak electron-phonon coupling (a , 1), the optical absorp-
tion constant depicted in figures 1 and 2 (dashed curve A = 0),
shows one single unsymmetric peak starting EO above the polaron
ground-state level ~w. The position and shape of this one-phon-
on absorption peak is in agreement with the experimental results
in CdO [13] and Te [14] as well as with the previous mentioned
theories.
In the case of finite carrier velocity A 1 0 (solid lines in
figures I and 2), two interesting features may be noticed: First,
the absorption threshold undergoes a 20% shift towards lower
photon frequencies Q when the carrier velocity reaches a value
A = 0.5. This effect is clearly expected from the polaron en-
ergy-momentum relation [2]. A shift of the one-phonon peak has
also been obtained by J.T. Devreese, et al. [18]. A similar
displacement of the threshold has been predicted as a result of
a finite temperature treatment of the optical absorption con-
stant [15,29].
Second, the present calculation reveals a sensible enhance-
ment of the peak intensity (see figures I and 2) for finite car-
rier velocity. This behaviour is mainly due to an increase of
the k-space available for the emitted phonon when the charge
carrier is accelerated by an external electric field. Unfortun-
ately, there exist no experimental results concerning the effect
of a DC-electric field on optical absorption by free polarons.
For strong electron-phonon coupling (a > 5) we find an ab-
sorption spectrum drastically different from the weak coupling
result. (See figures 4 to 7). Strictly speaking, our strong
coupling treatment (Landau-Pekar approximation) is only valid
at a > 10 where the continuum approximation breaks down. Never-
ertheless, it seems logical to admit that some of the interest-
ing features encountered at strong coupling, such as the possi-
bility of 'lattice relaxation' may survive in an intermediate
coupling formalism. This point will be confirmed in the follow-
ing lecture.
Although the strong coupling formalism has no direct applica-
tion to optical absorption by free polarons, it is worthwhile
to mention a few applications related to bound polarons, such
as colour centres and excitons. As a matter of fact, optical
absorption measurements by these more complex polaron systems,
show a strong coupling type absorption (emission) spectrum [21-
28]. The present theory has been successfully applied [29] to
optical absorption by F-centres in AgBr [21] (figure 8). The
experimental curve in figure 8 shows phonon side bands spaced
by 0.9 nw. The authors can account for a 5% shift of these side
bands with respect to Pzw, when the distribution of phonon frequ-
encies and phonon dispersion is included. Alternatively, it is
possible that surface effects are rather important in these re-
flectivity data. Indeed, the experimental peak distance (w exp )
is quite close to the surface phonon frequency (see Table I)
defined by [31]
(II. 62)
t
o
a = 0.075
ex = 1.7
d 80
P= l
experiment : Brandt & Brown . x = 0.9
K = 1.6
i. = 69.
W"
Toyozawa 'S theory
40
Figure 8 - Comparison between Brandt's and Brown's experi-

mental results for the induced absorption in AgBr and the
present theory [29]and Toyozawa's theory [30].
for a semi-infinite slab. Here £0, £00 and WT are respectively

the static dielectric constant, the high frequency dielectric
constant and the long wavelength transverse phonon frequency.
The recent high-resolution optical reflectivity data of alkali
halides by Baldini et al. [26] and Petroff et al. [27] give fur-
ther evidence for surface effects. Indeed, the structure of
the exciton lines in these measurements seem to be related to
the contamination of the surface. Moreover, because of the
large value of the measured absorption constants (~106 ~m-l) a
penetration of the light beam of the order of 50 to 100 A is ex-
pected. Therefore absorption by 'surface excitons' should be
favoured as compared to 'bulk excitons' and the phonons involved
in the exciton side bands are 'surface phonons'. A calculation
of the optical absorption by surface excitons can in principle
be accomplished starting from the surface polaron Hamiltonian
[32] written for the exciton case. This problem will be treated
in a subsequent paper. More details about electron-surface-
phonon interaction can be found in Professor Mahan's lectures.
In conclusion, we have seen that optical absorption by free
polarons gives rise to a 'single unsymmetric peak' in the weak
coupling limit and a sharp zero-phonon line followed by a series
of phonon-side-bands in the limit of strong electron-phonon
coupling. In the next lecture, the question "What happens in
the intermediate coupling range?" will be answered.
TABLE II
Dielectric Properties
Low and high frequency dielectric constants £0,
£00; long wavelength transverse wT and optical
wLO frequencies; distance between side-bands
wexp and surface phonon frequency wI.
WT
cm- l
AgBr 10.60 4.68 91.50 137.7 124 ± 6 131.6
KI 4.68 2.68 109.5 144.5 132 ± 4 135
LiI 11.03 3.8 213.06 362.97 312 ± 24 334
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C. (1972). Nuovo Cim., B12, 118, 137.
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Polar Semiconductors, (ed. Devreese, J.T.), (North Holland
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5. Kartheuser, E.P. (1973). Solid State Commun., 12, 385.
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Stat. Sol. (b), 44, 795.
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Devreese, J. Phys. Rev ..
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Rev., BS, 2367.
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Stat. Sol., 48, 77; (1969). Annual Scientific Report of
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Amer. Phys. Soc. II, 18, 474.
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Rev. Lett., 23, 846.
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Kamimura, H. (1971). Phys. Rev. Lett., 27, 1377.
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LECTURE III: RELAXATION OF THE ELECTRON-PHONON SYSTEM IN THE
POLARON PROBLEM
O. INTRODUCTION
0.1 RELAXED EXCITED STATES

Relaxed excited states, which were introduced for polarons in
lecture II, are of a quite general nature and of fundamental in-
terest.
Let us give a few examples of relaxed excited states (RES):
If an atom is ionized by exciting an electron from a deep core
level, the electronic configuration of the remaining elec-
trons will be different after the transition;
When an exciton is created in a solid the electronic distrib-
ution changes. As is well known this relaxation phenomenon
may be responsible for 30 to 40% of the width of the band-
gap in alkali halides;
The concept of a relaxed excited state is quite common in col-
or center studies. The idea that after an electronic tran-
sition to a Franck-Condon state the ionic lattice readapts
is quite familiar in this field.
In lecture II the concept of the polaron RES has been intro-
duced and analyzed for strong electron phonon coupling. In
this lecture we will show how the relaxation phenomenon can
be described quite accurately for this problem. Because of
the general nature of the relaxation phenomenon we thought
it was worthwhile to bring this up at this school.
0.2 DESCRIPTION OF THE RELAXED EXCITED STATE

AT ALL COUPLING FOR POLARONS
It is of great theoretical importance to be able to describe
relaxed excited states of polarons at all coupling. Indeed the
coupling between a meson field and a nucleon e.g. might lead to
resonances which are formally equivalent to the RES which we
encounter in polaron theory. The fact that for polarons the only
all-coupling description available until recent was formulated
in terms of path integrals might be an important obstacle to make
165
progress because path integrals do not allow for the treatment of

spin, isospin, relativity etc.
Recently, however, the present authors introduced a self con-
sistent method which works at all coupling and which does not re-
lyon path integrals. Hopefully this method, which is presented
in part IV of these lectures, will be useful in other fields.
The treatment of relaxed excited states for polarons has also
practiaal value. The mobility, the optical absorption and the
behaviour in magnetic field of polarons are certainly influenced
by relaxation of the system in the final states. From a ~ 3 on
these effects might be quite important.
0.3 PRESENT SITUATION

As stated in lecture II the influence of relaxed excited sta-
tes on the optical absorption of polarons has been studied in
1969 by the present authors. It was shown that for strong coup-
ling the main optical transition takes place towards a final
state which is a RES. For weak coupling it is possible to show
that relaxed excited states play no role to order a. Until rec-
ently it was unclear whether or not the path integral treatment
[1] by FHIP [2] which is supposed to be quite accurate for all
coupling takes into account relaxation. In [3] it has been shown
how lattice relaxation can be treated in the FHIP approximation.
Recently the present authors have proposed a theory based on
a self consistent solution of the equations of motion which can
treat the relaxation process at all a and which does not invoke
path integrals.
In this lecture we present elements of the path integral form-
alism and its application by FHIP to the impedance function cal-
culation. Subsequently it is shown how the FHIP approximation can
be applied to study the optical absorption of polarons (Devreese
et al. in [3,4,5]).
The self consistent equation of motion method will then be
presented in part IV.
1. RELAXED EXCITED STATES AND THE FEYNMAN MODEL OF THE POLARON

One of the most succesful approaches to the polaron problem
has been developed by Feynrnan and coworkers [1,2,6]. In [1] Feyn-
man introduces for a variational principle which enables him to
obtain an upper bound for the polaron self energy. As well known
the path integral formulation of quantum mechanics takes the clas-
sical action as starting point and does not involve operator
calculus. It allows one to calculate the propagator or the den-
sity matrix of a system as an 'integral over all paths'. Feyn-
man's variational principle makes it possible to obtain an upper
bound for the energy by choosing any 'trial action', in analogy
to the variationa1 principle of quantum mechanics where a trial
wave function has to be considered. In [1] an harmonic approxi-
mation for the potential is taken and both the grounds tate ener-
gy and the effective mass of the polaron are evaluated. Typical
ELECTRONIC TRANSITIONS AND RELAXATION PHENOMENA. III. 167
for the path integral treatment is the elimination [2] of the
phonon variables from the problem. This is in contrast with the
well-known L.L.P. approximation in which the electron variable
is eliminated. In [1] Feynman, Hellwarth, Iddings and Platzman
(FHIP) developed a linear response theory, within the path inte-
gral formalism. Roughly speaking their formalism is equivalent
to the Kubo formalism. Again the phonon variables are elimina-
ted from the description. The calculation of a statistical aver-
age for the velocity of the electron then leads to the evalua-
tion of 'double' path integrals.
In these path integrals the polaron action is replaced by the
same trial action as that used in [1] to describe the ground-
state. The purpose of FHIP is to calculate the mobility of the
polaron. In an attempt to give some insight about the spectrum
of excited polaron states FHIP calculate the real part of the
frequency dependent impedance function z(~) of the polaron.
However, the structure of this frequency dependent function Re
z(~) is characterized by peaks at the threshold for emission of
one phonon, and at the frequencies corresponding to the creation
of Franck-Condon states along with the emission of one real pho-
non. However, the relaxed excited states do not show up in the
spectrum of Rez(~) and this seemed quite puzzling after the in-
vestigation on relaxed excited states by the present authors [7].
We have shown, however, [3] that, if one calculates the optical
absorption (~ Rel/z(~») in the FHIP approximation, internal re-
laxed excited states appear and are even dominant if a ~ 5. Our
calculation of the optical absorption in the FHIP formalism con-
firms the optical spectrum as it was expected from our strong
and weak coupling work. The function Rez(~) as plotted by FHIP
has been misleading as it was considered to represent the opti-
cal absorption instead of Rez(~) [8,9]. From the function Rez(~)
FHIP calculatel!! the mobility J.lFHIP by considering the limit as
~ tends to zero. The weak coupling limit of the mobility obtain-
ed by FHIP differs by 3kT/2 from the Langreth-Kadanoff result J.lKL
(J.lFHIP = 3J.lKL/2z with z = nw/kT). It is generally accepted that
the Langreth-Kadanoff formula is correct if a ~ 0 and T ~ O. In
our opinion the fact that no realistic distribution function for
the velocities of polarons is introduced by FHIP is responsible
for the factor 3kT/2 difference between the Langreth-Kadanoff
and the FHIP results.
On the other hand the FHIP theory takes into account lattice
pelaxation as follows from our investigation [3] of the optical
absorption spectrum.
From the formal point of view the FHIP approximation has one
drawback: what one might call the upside-down apppoximation:
The series expansion for the impedance is guessed from two terms
of the series in order to obtain a resonant behaviour. In our
recent self consistent treatment [11] we have been able to av-
oid this difficulty.
Finally in a work of Thornber and Feynman [6] the mobility of
polarons at all electrical field strengths has been evaluated.
Although some formal difficulties remain in this work it consti-
tutes a generalization of the Kubo linear response theory.
It is not possible to give a full detailed treatment here of
the path integral approach to polarons. Nevertheless, as most
people are not familiar with the path integral formalism, an at-
tempt will be made to explain the essential ideas of this ap-
proach. OUr main purpose then is to show how such an approach
contains, to some approximation, information about reLaxation of
the phonon system as follows from [1] and our calculations in
reference [3].
The division of the subsequent paragraphs is as follows. In
section 2 and section 3 the path integral formalism as developed
and applied to the polaron problem by Feynman [12,13] is exposed.
In section 4 the FHIP calculation of the impedance function of
polarons is summarized. In sections 5-7 our calculations on the
relaxed excited states and their properties, using the Feynman
model of the polaron, are reviewed. The material presented in
sections 2,7 will enable one to evaluate the present understand-
ing of reLaxed excited states by means of path integrals. The
significance of the new method, presented in part IV will then
be understood.
2. ELEMENTS OF THE PATH INTEGRAL FORMALISM [12,13,14]

For detailed treatment of path integrals we refer to the ori-
ginal Feynman paper [12] where the technique was discovered, to
the excellent review by Schultz [13] and to Feynman's and Hibbs'
book [14]t. Path integral theory starts from the remark by Pauli
that the propagator for infinitesimal time differences can be ex-
pressed in terms of the classical Lagrangian of the system if the
system has a classical analog. For a one-dimensional one part-
icle system e.g. with Lagrangian L(x,x,t) the propagator for the
evolution from x' ,t' to x",t' + £ is:
(x",t' + £I~' ,t') = [21T~1i£)~exp[ih£ L[x' ; x" ,X" : x' ,t')] ,

(IILl)
m is the mass of the particle. Path integrals extend the expres-
sion (1) to finite time differences. This is done by a summa-
tion of (1) over all possible paths of trajectories possible in
going from x",t' to x",t" which one can express as follows:
I "t" x,
\x, 't') = n~
I' If
A ... fdx
A J=O
n L(xj' ,Xj ,tj) ]
dx exp [''1-,,-£ .1..
A l ... -E.
(III. 2)
t In this section 2 and in section 3 we will follow closely

Schultz's expose [13] of the Scottish Summer School. For more
details we refer the reader to this paper.
From figure lone sees how possible paths are constructed.
1"1------------------ X" - - - - - - - - -
t" ~---------------- xn -----0----
t,r--------X 2 - - - - - - - - - - - - - - -
t'~-----------------------------------------
x ------------ X" ---------------...,.x

Figure 1 - Space-time trajectories.
An integration over xl,x2, ... x n provides us with all the paths.

Although some prescriptions on the character of the paths have
to be made it is important to realize that path integrals have
a meaning also without those prescriptions. The 'path integral'
(equation (2)) satisfies Schrtldinger' s equation in x", ttl and is de-
noted by the following shorthand notation:
(x",t"lx' ,t') (IIl.3)
If one can calculate the path integral equation (3) one has
all information about the wave functions and energies of the
system. Indeed one can write (x",t"lx' ,t') also in terms of the
wave functions and eigenvalues for the energy of the system un-
der study:
(x",t"lx' ,t') L q,n'" (x" )q,n (x' )e -iEn( t"-t' )/11. (III. 4)
n
Taking a kindt of Fourier transform of (4) on (t" - t') one has
F.T. (x",t"lx' ,t') (IlLS)
t Integratinq namely from 0 to ~ and not from -~ to +~.

170 DEVREESE, EVRARD AND KARTHEU SER
The energies and wave functions of the system are obtained as

poles and residues of the Fourier transform of the path integral
in the complex E-plane. In principle one can calculate equation
(3) by performing actual time-sZicing i.e., by performing the
integrations following the prescription (equation (2)). This is
only possible however, for quadratic actions (quadratic in x and
x) so that, at first sight, the applications are very restricted.
Nevertheless, there has been some progress recently in calculat-
ing path integrals for more complicated systems. Although in
these calculations no actual time slicing is performed they use
the path integral as starting point for WKB or perturbation cal-
culations [15,16]. Also a number of numerical studies on path
integrals have permitted solutions in some problems of scatter-
ing theory [17] and in the theory of liquid helium [18].
In practice the path integral formalism has produced the
first theory of polarons which is presumably valid with good
preCIsIon at all coupling~.
Before turning to the polaron problem, where path integrals
have been applied most succesfully, let us briefly state some
advantages and disadvantages of the path integral description:
Advantages:
From the formal point of view the theory allows one to
easily establish the classical limit by letting n ~ O.
The formalism does not involve operators so that the
full mathematical tools of analysis can be used.
In describing problems of interacting fields and par-
ticles the path integral theory allows one to eliminate
field variables without difficulties with boundary con-
ditions.
Disadvantages:
Path integrals do not provide an adequate treatment of
physical quantities which have no classical analog (spin,
isospin, etc .... ).
Finally we write the path integral for some simple systems:
FREE PARTICLE [12]
(x" , t"lx' 't')

FP [ 27ri1i(t"m - t' )J-~
exp
[ime2tz(t"
x " - X,)2]
_ t') . (III. 6)
~ From an alternative formulation of polaron theory valid at

all a see part IV and reference [11].
ONE DIMENSIONAL HARMONIC OSCILLATOR [12J
( X"t"x't')
, ,
-[ mw
H.O.- 27fiiisinwT
J~ (II!.?)
x
r.imw [(x' 2 + x" 2 )cotwT - 2X'X"cscwT] ] ,
eXPL2h
where T = til - t' and w is the frequency of the oscillator.
FORCED HARMONIC OSCILLATOR IN ONE DIMENSION [12]
(y(t)x is the external force term)
(IlL8)
where Sy is the classical action of the forced harmonic oscil-

lator.
HYDROGEN ATOM
In f12] the following expression for the transform Jd 3r

(pll,t" r',t') of the density matrix (= propagator for imaginary
times) for the hydrogen atom is given, after summation of a ser-
ies expansion of this transform in terms of quadratic path in-
tegrals:
w 3 fts,s
fdrS (fS~2
0 0 exp - ~ or dt + e
dt ) ~
2fsolt(t)1 Dr(t)
,
where S l/kT and e is the charge of the electron. W contains

information on the s-states only.
ONE-DIMENSIONAL o-FUNCTION POTENTIAL
The expression for a particle in a o-function potential was

evaluated in [19]:
W(xO) = f::dxsP(XS'XO)
Erf(~~~ IJ + e -y IxO leh2 SErfc [(>~~ I) - y48] , (111.10)
where P is the density matrix with
veX) = - yo (x) ,
and S = 1'!kT.
3. PATH INTEGRALS AND POLARONS
THE GROUNDS TATE
In this paragraph the work of Feynman [1] on the groundstate

properties of polarons is reviewed using Schultz's review paper
[13]. The first step is to write the Lagrangian of the polaron:
(111.11)
where
(III.11b)
-+-+
Decomposing P(r,t) using the amplitudes Qk of the normal modes
one gets:
kx > 0,
-+-+
P(r,t) (%) ~ L "tkQk(t) rostt}
-+ (III.11c)
k sink.t kx < 0,
with
"tk = k!lkl·
In these equations PCp) is the polarization vector, p is the
electron coordinate.
One has to deal then with the following path integral:
(IILI2)
Let
(IIL13)
then the k-th 'component' of L due to the field is:
(IIL14)
It follows:
(IILIS)
The expression for (Qk"t"IQk't') is known (equation (S)). Now

'imaginary times' are formally introduced: T' = it', T" = it".
One still has:
p = (:t>"Q"T"I:t>'Q'T') = L CPn(:t>",Q")CPn>,,(:t>',Q')e-En(T"-T'). (IIL16)

n
Because we are essentially interested in the decay rate of

e-EoCT"-T') which is the dominant term of equation (16) for
T" - T' -+ one simplifies the calculation by mUltiplying both
00
the left and the right hand side of equation (16) with Ink'=o,T')
and Ink",T") respectively
If one sums equation (17) over all intermediate states it still

has the same asymptotic behaviour, as equation (16) and this
asymptotic behaviour then fixes EO. It is easy to show that:
r,
(IlL IS)
(nk" = o,T"lnk' = O,T') ==Go "
= exp{ 4;wf Yk( T)Yk(a)e -w It-a IdTda} .
T
Therefore one can write:
(IlLIg)
+ 4;fWfJdTdlJe-wIT-1J1 ~ Yk(T)Yk(IJ)}.
The summation over k is easily performed and one obtains
(III. 20)
Until here everything is rigorous within the framework of the

Frtlhlich model.
It seems impossible to calculate equation (20) exactly. In
order to perform an approximate calculation Feynman introduces
at this point his variational principle for path integrals. The
starting point is that
(III. 21)
where x is a random variable with a normalized probability dens-

ity:
Jdxp(X)f(X). (III.22)
For any So one now has:
where now:
(III.24)
It is then easy to show that:
Eg ~ Eo - s, (III.2S)
where Eg is the true polaron groundstate energy, EO the ground-

state energy corresponding to the model action So and a is def-
ined by (S - SO) ~ aT for large 'time' differences T.
It is now possible to calculate an upper bound for the self-
energy by choosing any trial action So for the system.
Feynman makes the following bold assumption for the trial
action:
So
This choice of So makes it possible to perform all necessary

path integrals because the path integrals representing EO and
a can now be reduced to those for quadratic actions. C and W
are variational parameters and one has to minimize EO - a with
respect to those parameters to find the best energy for a given
SO·
It is important to discuss the physical meaning of equation
(26). This action corresponds to two particles bound together
by a harmonic force. Therefore to zero-th order the approxima-
tion replaces the influence of the field on the electron by
that of a fictitious particle bound harmonically to the elec-
tron. However , it should be reali zed that the term a ~ (S - So) IT
contributes significantly to the energy so that So does not con-
tain all the physics of the approximation. The reason for choos-
ing the form of equation (26) for So is mathematical. The quad-
ratic action in equation (26) leads to path integrals which can
be evaluated analytically. From the physical point of view it
may be argued that a parabolic approximation is meaningful as
an average for the potential.
When the ground state energy resulting from So as defined in
equation (26) is calculated it is found to be lower than any
other published result.
For an exactly solvable model [20] we showed that the Feyn-
man So gives results for the self-energy of the polaron which
are accurate to within 1.5% at all coupling.
It is certainly remarkable that we have at our disposal a
theory which provides such accurate binding energies at all
coupling between the electron and the field.
4. EXCITATIONS OF THE POLARON IN THE FEYNMAN MODEL

The preceeding paragraphs have given enough introductory mat-
erial to proceed to the path integral treatment of the impedance
function of polarons.
In 1962 Feynman, Hellwarth, Iddings and Platzman (FHIP) pro-
posed a theory for the polaron mobilityt. As explained before,
this theory gives a Kubo-like linear response result at all
t We follow the original paper [2] and also refer the reader,
for more details, to Platzman's review article [21].
coupling and so is not limited to the Boltzmann approximation.

As stated before, this theory leads to misleading results for
the excited states of the polaron when Rez(n), the real part of
the impedance function is plotted as was done in FHIP [2]. In
a further calculation we have shown [3] how the optical absorp-
tion spectrum has to be calculated in the FHIP approximation
and how the resulting spectrum is far more realistic. In what
follows we will explain the essential ideas of the FHIP method.
It will become apparent that quite sophisticated techniques are
necessary to study resonances of polarons at all coupling.
FHIP consider the alternating external field E = Eoe lnt charac-
terized by the frequency n.
Then
J.(~) 1 int (III. 27)

" = z(n) Eoe ,
- J::iG(T - a)E(a)da, (II!.28)
one has:
(II!. 29)
which now relates the response function G(n) to the impedance

Z(n) .
(X(T») is now evaluated using path integrals:
(II!. 30)
U is the unitary time development operator and the prime on U-l

in equation (30) indicates that time increases to the right,
whereas it increases to the left in U(T,a). The expression for
U is
(III. 31)
Xis the vector position of the electron, E

is the external ap-
plied field. H is the unperturbed polaron Hamiltonian. The
indices s are written to remember that a time ordered operator
formalism is used. After some operator algebra one obtains:
Defining
-1
9 Tr{U(b,a)Pa U' (b,a)}, (III. 33)
and
E(s) ~o(s - a) + noes - T), (III. 34)
one has:
G(T - a)
0"
2
a
= 21 ~a I
fl ~,n=O
. (III. 35)
At this stage FHIP eliminate the phonon variables from the

expression for g. (This can be done both by a technique similar
to that used for the groundstate problem [1] or by disentangling
techniques). After the elimination of the phonons a double path
integral for 9 is obtained
(III. 36)
where ~ is a fairly complicated expression:
+ i0.2- 3 / 2 f +OO dt f+oo ds [-i1t-s

e
l+ + 2P(S)cos(t - s) (III. 37)
-00 -00 IX( t) - X( s ) I
+ eilt-sl +2P(S)cos(t-s) _ 2{e-ilt-sl +2P(S)COS(t-S)}]
IX'(t) - X'(s)1 IX'(t) - X(s)1 '
pes) is defined as follows:
1
P( S) (III.38)
furthermore
~ = m= e w = 1,
and
X(t) - X'(t) =0 as t ~ ±oo.
Until this point everything is exact. Two crucial approxima-

tions are now made by FHIP.
(1) The Coulomb-type terms in equation (37) are replacedby
a quadratic approximation (~ + ~o) e.g. for the third
term in equation (37) there comes:
-iw(t-s)
x[e + 2P(Sw)cos(t - s)]. (III. 39)
Although this is the same type of approximation as that

used for the groundstate properties of the polaron, it is
more difficult to justify this approximation for excited
states which are important now. It is clear that the trial
action, e.g. (39), itself contains Franck-Condon type ex-
cited states only.
Furthermore, it would not lead to finite life-times,
although the final states are in the continuum;
(2) An 'upside down' approximation is made: g is first de-
veloped as follows:
It takes a considerable effort to calculate the two path

integrals in the rhs of equation (40) and it seems unreal-
istic to try higher order terms.
From equation (40) one obtains, to the same degree of
approximation,
(III.4l)
However, this expression for G(~) does not provide any

resonances and FHIP conjecture that the expression
1
~Z(~) - ---- (III.42)
GO(~)
is far more accurate and is the one to be used. We call

this approximation an 'upside down' approximation. There
is no real justification for it in the FHIP approximation
except that for simplified cases (particle bound to a fix-
ed point) equation (42) works. In part IV it is seen that
our self-consistent method avoids this difficulty and leads
to equation (42) directly.
We omit any further details and write the results for the
impedance in the FHIP approximation:
(III. 43)
with
f
OO
0[1 - e
irlu
] ImS(u)du (III.44)
and
20 -3/2 iu
S(u) = 3/11 {[D(u)] (e + 2P(S)cosu)} , (III.45)
2 [2
D(u) = ~ v - w
2 Cl - . + 4P( sv)sin2(.~vu» _ iu + uQ2]
el'IJU • (III.46)
v 2 vw 2 IJ
Although the main purpose of FHIP is to calculate the mobil-

ity of polarons (~-1 = Im(irlZ(rl)/rl)ln+o) the authors also plot
a number of curves which represent Re(rlZ(rl». In figure 2 one
of these plots is shown for a = 5.
16
14
1/I'---' ~
~ / ~ ./
II
12
IT ~
,. 10 1\
1=<
.§
~
\
\ J
4
fU
10 12 14 16 18 20 22
" = 5
Figure 2 - ReZ(rl) for a = 5 (from reference [2]).
The peaks occur at the thresholds for one phonon emission

and at the thresholds for the creation of a Franck-Condon excit-
ed state along with the emission of one phonon. As stated be-
fore these curves have been considered to represent the optical
absorption by different authors [8,9] FHIP remark that they do
not expect an accurate description of the excited states of pol-

arons from their calculation. As we will see in the next para-
graph this is due to the calculation of nReZ(n) instead of the
absorption.
5. RELAXED EXCITED STATES AND THE FEYNMAN MODEL [3]

In the present paragraph we will discuss the calculation of
Devreese et al. [3] on the internal structure of polarons in
the FHIP approximation. The calculation by FHIP indicates that
the Feynman model for the polaron does not contain reZaxation
of the Zattice in the finaZ state. This is in contradiction
with the mechanism for the optical absorption as we expect it
from our studies at strong coupling [7] where reZaxation plays
an important role.
In order to solve this difficulty we wrote down the opticaZ
absorption for the Feynman polaron [3]. If equation (41) is
used (expansion of the conductivity) we obtain for the optical
absorption rcr(n):
(III. 48)
This expression is proportional to Imx(n) but it is singular

for n = v. It became apparent that also in the calculation of
the optical absorption the upside-down approximation is of cru-
cial importance and that to obtain the optical absorption, one
should expand z(n) rather than cr(n). In doing this, however,
it was found [3] that the optical absorption is modified dras-
tically from the simple form Imx(n) studied by FHIP to:
r (n) = _1_ lim n1mx(n) (III.49)

Z c£on S->-<x> n4- - 2n 2Rex(n) + 1x(n) 12 .
The function Rex(n) is rather difficult to study numerically

and for the details we refer the reader to reference [3] where
an analytic evaluation of equation (49) is given. Let us mere-
ly point out here that the following transformation was useful
in performing the computer calculations:
Rex
2
~ 1mfCXl du (1 - cos nu ) e i(l+uv)u
3/TI 0 (R - iu)(n+3)/2
2 l
X 1n [ (1 + nv + x) ]2
. (III. SO)
n2 - (1 + nV + x)2
The optical absorption as given by equation (49) was worked
out numerically in [3]. In figure 3 we present the results for
a = 1 and in figure 4 for a = 6.
0.2
1 phonon
,~
I'
II
I,
0.15
II
II
I ,
I I
I
IX = 1
0.05
o 10
Figure 3 - Optical absorption of polarons for a = 1. Full

curve: present calculations; dotted curve: perturbation
result of Gurevich et al ..
Contrary to ImX(Q) as plotted by FHIP this function rz(Q) ex-

hibits structure consistent with the mechanism for the optical
absorption proposed in [7] and discussed in lecture II. Indeed
for a = 6 a strong peak appears at substantially lower frequen-
I
I
I
I
R.E.S. :
I
I
I
I
I
I
I
1.5 I
I
I
I
I
I
a=6
0.5
Figure 4 - Optical absorption r z of po1arons at a = 6.

The RES peak is very intense compared with the Franck-
Condon peak. The frequency n = V is indicated. (From
reference [2]).
cies than the FC frequencies. This peak we attribute to the

relaxed excited state. One also sees one-phonon emission and
sidebands of the RES-transition which form a Franck-Condon en-
velope.
We conclude that from [3] it follows that the path integral
treatment of polarons provides a method which describes relaxed
excited states of polarons. The optical absorption obtained in
[3) at all a is consistent with the weak and strong coupling
results as discussed in lecture II.
6. TEMPERATURE DEPENDENCE OF THE OPTICAL ABSORPTION [5)

Recently [5) the behaviour of the optical absorption of pol-
arons in the FHIP approximation as a function of temperature
has been examined by Huybrechts and Devreese. The resulting
curves show how the lattice relaxation in the final state re-
mains important at relatively high temperatures. These results
are discussed in more detail in a separate paper in this volume.
For our present purpose we had plotted the optical absorption
for different temperatures for a = 5 in figure 5.
0.5
---·_·1
g - - - - 0.25
~
0.4 -0.001
I
,
I
0.3
\
\
...... ....... IX = 5
0.2
\ .....
'.'.
OJ
_....----
.......
' ........
............
.......... -.. .....
0 4 6 9 n-
Figure 5 - RES-structure in the absorption spectrum for
different temperatures (a = 5). (From reference [22).
The absorption spectra for weak electron-LO phonon coupling

a = 1 (Te: a = 0.23 [16) and CdO a = 0.75 [17,18)) are shown
in figure 6.
The main conclusion in reference [5) is that for weak coupl-
ing a $ 2 the structure in the absorption spectrum (due to emis-
sion of one real phonon) disappears as T z ~e (e is the Debye
temperature). The structure due to the RES, however, (a ~ 5)
persists at higher temperatures and is only slightly destabil-
ized when T z ~e.
7. A GROUNDSTATE THEOREM FOR POLARONS [4,22]

Lemmens, De Sitter and Devreese [22) studied the accuracy of
rz(~) as calculated in reference [3] from equation (49).
A grounds tate theorem for the Frtlhlich-polaron was derived
with this purpose. They have shown that the first moment of
the absorption spectrum is proportional to the kinetic energy
g
.... 0.9
, ---0.001
kT
hw
\
- - - - - - 0.01
\ -._._.- 0.5
0.8 \ -"-"-'1
••••••••••••••• " 2
0.7
0.6
0.5
at = 1
0.4
0.3
0.2
0.1
o
... -
Figure 6 - Temperature dependence of the polaron absorp-
tion spectrum in the weak electron-phonon coupling region
(a = 1).
of the polaron. While the electron-phonon interaction does not

depend on the electron mass, the coupling constant a does; this
allows one to relate the kinetic energy with the groundstate en-
ergy using the Feynman-Hellmann theorem.
The following groundstate theorem relating r(~), the optical
absorption coefficient, to Eo(a) the groundstate energy, was de-
rived [4]:
Eo(a) = - 3~nfad~'foodW wr(w). (IlLSl)

e2 0 a 0 II
This theorem was used to test the accuracy of the calculation

of the optical absorption of reference [3]. Using rz(w) from
equation (49) as calculated in reference [3] the double integral
in (51) was performed numerically for a ~ 5. The results for
Eo(a) obtained this way are very close to the variational re-
sults of Feynman [1] for the energy of the groundstate as can
be seen from Table I. The derivation of equation (51) is given
in the paper by Lemmens and Devreese in the present proceedings.
TABLE I
a EO EF
Theorem
0.5 -0.503
1.0 -1.014 -1.012
1.5 -1.533
2.0 -2.059
2.5 -2.593
3.0 -3.135 -3.133
3.5 -3.687
4.0 -4.251
4.5 -4.831
5.0 -5.430 -5.440
8. SELF CONSISTENT EQUATION OF MOTION METHOD

The present authors have developed a new approach to the pol-
aron problem which is essentially valid at all coupling and which
adequately describes relaxed excited states. This approach does
not invoke the path integral formalism and is more suitable to
generalization to spin - and isospin problems.
In a separate contribution [11] we give some more details
about this work. It has thus been possible to treat the Heisen-
berg equations of motion which were already used in earlier work
to study the 'classical' aspects of the polaron [23] and the
weak coupling limit [24] self-consistently keeping one real
phonon in the field. The only further approximations in the
self-consistent treatment involve the replacement of certain
frequency distribution by one single frequency. Our results
are analytically rather similar to those of FHIP. However, they
are obtained without any recourse to the 'upside-down approxima-
tion' of FHIP discussed earlier. Also at each step the physical
meaning of the approximation is quite clear. We refer the in-
terested reader to [11] for more details about this self-con-
sistent method which we hope will be useful in the further
study of the relaxation process.
As a final remark we want to point out that there is a close
analogy between the polaron RES-peak in the optical absorption
and the main response peak for the electron gas as obtained by
Hedin and Lundqvist [25]. Both peaks correspond to a coherent
state. Furthermore, the plasmon sidebands calculated in [25]
are similar to the phonon sidebands for the polaron. This point
deserves further investigation.
CONCLUSION
In lecture III the general nature of relaxed excited states
has been stressed. It has been shown how such states are im-
plicitly present in the Feynman model for the polaron and how
it is possible in this case to treat the relaxation process in
quantitative detail. The existence of such states is confirmed
by the application of a sum rule [4].
We briefly mentioned our self-consistent equation of .Jotion
approach to the polaron problem [11]. This approach is valid
at all coupling and describes the excitations of the system in
a natural way.
REFERENCES
2. Feynman, R.P., He11warth, R., Iddings, C. and P1atzman, P.
(1962). Phys. Rev., 128, 1599.
3. Devreese, J., De Sitter, J. and Goovaerts, M. (1972). Phys.
Rev., B5, 2367.
4. Lemmens, L. and Devreese, J. (1973). Solid State Commun.,
12, 1067.
5. Huybrechts, W., DeSitter, J. and Devreese, J. (1973). Bull.
Amer. Phys. Soc., Section II, 18, 474.
6. Thornber, K.K. and Feynman, R.P. (1970). Phys. Rev., B1,
4099.
7. Kartheuser, E., Evrard, R. and Devreese, J. (1969). Phys.
Rev. Lett., 22, 94.
8. Thornber, K.K. (1971). Phys. Rev., B3, 1929.
9. Mott, N.F. (1971). Comments Solid State Phys., 3, 123.
10. Langreth, D.C. and Kadanoff, L.P. (1969). Phys. Rev., 133,
A1070.
11. Evrard, R., Devreese, J. and Kartheuser, E. (To be pub-
lished). See also lecture IV of the present paper.
12. Feynman, R.P. (1949). Rev. Mod. Phys., 20, 367.
13. Schultz, T.D. (1962). In Polarons and Excitons, Scottish
Universities' Summer School 1962, (eds. Kuper and Whit-
field) .
14. Feynman, R.P. and Hibbs, A.R. (1965). Quantum Mechanics and
Path Integrals, (McGraw Hill Book Company, New York).
15. Gutzwiller, M. (1967). J. Math. Phys., 8, 1779.
16. Goovaerts, M.J. and Devreese, J. (1972). J. Math. Phys.,
13, 1070.
17. Gelman, D. and Spruch, L. (1969). J. Math. Phys., 10, 2240.
18. Fosdick, L. and Jordan, H. (1966). Phys. Rev., 143, 58.
19. Goovaerts, M., Babcenco, A. and Devreese, J. (1973). J.
Math. Phys., 14, 559.
20. Devreese, J. and Evrard, R. (1966). Phys. Lett., 23, 196.
21. Platzman, P.M. (1962). In Polarons and Excitons, Scottish
Universities' Summer School 1962, (eds. Kuper and Whitfield).
22. Lemmens, L., De Sitter, J. and Devreese, J. (1973). Phys.
Rev., B8, 2717.
23. Evrard, R., Devreese, J., Kartheuser, E. and Grosjean, C.C.
(1972). Nuovo Cim., B12, 118, 137.
24. Kartheuser, E. (1968). (Ph.D. thesis), (Universite de
Li~ge).
25. Hedin, L. and 1undqvist, S. In Solid State Physics, Vol.
23, (eds. Seitz and Turnbull).
LECTURE IV: A SELF-CONSISTENT EQUATION OF MOTION APPROACH TO
THE POLARON PROBLEM
1. INTRODUCTION
In this communication we will report a new method of treat-
ing the Fr~hlich polarons which is based on a self-consistent
solution of the Heisenberg equations of motion. This method
provides a self-consistent s')lution for p(t) (the momentum
of the electron) in which terms linear in the creation and an-
nihilation operators for one real phonon are presented. Fur-
thermore, as a second approximation a distribution of frequen-
cies related to the recoil energy of the electron is replaced
by a mean frequency. The method is applied here to the calcul-
ation of the optical absorption by free polarons and to the mo-
bility in the Boltzmann approximation where the results are
closely related to those obtained by Feynman-Hellwarth-Iddings-
Platzman (FHIP) [1] so that our self-consistent equation of mo-
tion technique seems reliable at all coupling. From the formal
point of view the self-consistent equation of motion method has
the characteristic that it is written in the conventional lan-
guage of quantum mechanics. Until now the only 'all coupling'
treatment for polarons was due to Feynman [2] and FHIP [1] and
was expressed in the path integral formalism. As path integrals
do not allow for the treatment of spin, isospin or relativity,
it is useful to have a method valid at all coupling written in
the conventional formalism of quantum mechanics. The hope is
then not only to provide for an independent way of treating the
polaron problem but also to give a starting point for general-
izations to particle physics.
2. THE SELF-CONSISTENT EQUATION OF MOTION FORMALISM

As stated, our starting point consists of the Heisenberg
equations of motion for polarons. These equations have been
studied before by Gross [.3] who tried to introduce a small-oscil-
lation approximation by Evrard [4] who used them as a guide
to obtain weak and strong coupling results. More recently
Evrard, Devreese, Kartheuser and Grosjean [5] studied the clas-
sical equations of motion and formally eliminated the phonon
variables from the equations. Kartheuser [6] studied a number
of physical properties at weak coupling of the polaron with an
189
iteration method. For the formulation of the polaron problem
with the equations of motion we refer to these references and
especially to [6]. For the polaron Hamiltonian and the well-
known notations we refer to [7-9].
Let us start from the integrated equation of motion:
p( t) - p( to)
+ h.c. (IV.la)
and
- 1ii . -iwtft
Vk"e dt'e
-i[k·t;(t')-wt'] -Elt'l
e. (IV.lb)
to
It suffices to remember that ak(t) is a phonon annihilation op-

erator in the Heisenberg representation, pet) and the can- ret)
onical conjugate position and momentum operators of the elec-
tron, to a time far in the past (t» to), k the phonon wave vec-
tor and Vk the strength of the electron-phonon interaction.
The operator a+(k) is an annihilation operator for incoming
waves. A basic observation is that:
(IV.2)
s is an index indicating that the ordered operator formalism is

used. Equation (2) allows us to write an integral equation for
pet) in terms of its expression at earlier times:
ELECTRONIC TRANSITIONS AND RELAXATION PHENOMENA. IV. 191
(Contd) - I klV;12 {f dt'exp[if'dt" k·P~t")]

k to to
xe -idk)(t'-tO)/he -E It' I}X{h. c.}, (IV.3)
(ak - a+(k) and t is the position operator, t to)

where
Equation ~3) is an exact equation in the Frohlich model of

the polaron. Using the zeroth order iteration PO(t) = pone
sees that the general form for the first order iterated solution
is:
(IV.4 )
In the present work p is taken to be a c-number. At t = _00

p is the total polaron momentum operator which commutes with
the Hamiltonian. Although this does not entitle us to replace
pin equation (4) by a c-number in any operator expression we
will make this approximation to start with.
The solution (equation (4)) is now introduced into the basic
equation (equation (3)). Subsequently equation (3) is develop-
ed up to an order linear in ak and akt. To obtain the solution
in the form (equation (4)) involves a tedious calculation requir-
ing ordering of the operators in equation (3) and the actual
calculation at tile double integrals over time in equation (3).
The details of this calculation will be published in forthcom-
ing papers [10,11].
We are finally led to:
p(t) - p(tO)
- g*(k' ,Yk') - g(k' ,Yk' - Yk)]x (Contd)

(Contd) (IV. Sa)
This expression is now compared with equation (4) and then

self-consistency is required by comparing equation (5) with
equation (4). In equation (5)
(IV.sb)
with
gctt' - til) exp[FCk.t' - til) - FCk)) (IV.sc)
and
FCtt' - til) = L Ilk' 12 _0_'

k'
f- k)2
m
e
-iYk' Ct'-t")
Yk' 2 + £2
. (IV.Sd)
After some algebra the self-consistency requirement leads to:
_ _ ~ 1ik 2
Yk - W m" + 2m" ' (IV.6)
where p is the total momentum of the polaron and m* the effect-

ive mass.
Furthermore:
x[gCk' .Yk') + g*Ck' .+Yk)
- g*Ck' .Yk') - gCk' .Yk' - Yk)]}-1, (IV.7)
which is an integral equation for fk.

This expression for fk is the starting point for calculation
of the physical properties of polarons.
In going to equation (7) we have supposed p = 0 to simplify
matters.
Equation (sd) can still be simplified, to
(IV.8)
The next step now is to reduce the denominator in equation
(7). First g(1<.,8) is calculated. Therefore a series expansion
of exp[F(k,t) - F(k,O)] is made. From equation (Sd) it is clear
that g(k,r) = exp[F(k,r) - F(k)] contains a spectrum of frequen-
cies Yk. Our approximation is then to replace this spectrum of
frequencies by a single frequency w(l + BfAf-1), where:
(IV.9a)
1 12 3/2
Bf =JCO
dxx f(x) ~ . (IV.9b)
o (1 + x)2
Mathematically the approximation of replacing the frequency dis-

tribution by one single frequency arises when we express an in-
tegral of the type
Jo '1'(z Od~
CO
+ ~
as a continued fraction involving the zeroth and first moment

of 'I'(~) ~ O. Af and Bf are determined numerically by an itera-
tive procedure leading to self-consistency. At this point it
is relatively easy to calculate the expression:
M(z) (IV.lO)
with z = 0 or z = Yk'
It follows readily that:
M(z) = exw 3 Jcodre-e: Ir Ie -i(l + z/w)wr

3/11 0
(IV.11)
In an analogous way we calculate
3fcodre -e: Ir Iexp [-z}z. -k 2)r x

w ex
-- (Contd)
3/11 0 2m
(Contd) (IV.12)
One still has
F(k) (IV.13)
with
-5 -2
VrO w
2 2 Af. (IV.14)
121T m
When Af and Bf are determined numerically (or analytically

in the limits a ~ 0 or a ~ 00) we can calculate a number of phys-
ical properties of polarons using equations (11-13) in equation
(7) to obtain fk and then equation (4) to obtain p(t).
We have applied these formulas to obtain the self-energy and
the effective mass. We find the correct asymptotic expansions
for a ~ 0 and for a ~ 00. Also the domain a < 4 has been inves-
tigated numerically. In this region our results differ at most
by 5% from the corresponding Feynman results. To demonstrate
the significance of the method, however, we will apply it to
the problem of the opticaZ absorption and the mobiZity because
these quantities involve the excitation spectrum of the polar-
ons.
3. APPLICATION OF THE FORMALISM TO THE OPTICAL ABSORPTION

The optical absorption is proportional to ~:
(IV. 15)
where Ip*) is a polaron eigenstate with total momentum PO'.

Using equation (4) in equation (15) one easily finds:
(IV.16)
Putting
(IV.17)
one has
x {I +:2 {:/71 ilmj""dre-e:lrle-iWr[DCr)]-3/2C1-COSnr)

o (IV.18)
+ :/71 Imf:dre-e:lrle-iWr'[DCr)]-3/2sinnr}}-1
Because of the formal resemblance of this expression to some

formulas obtained by FHIP [1] in the path integral formalism, we
define:
(IV.19)
After simple manipulations we then obtain:
This formula is almost exactly the same as the one obtained

by Devreese et al. [10] for the optical absorption of polarons
in the Feynman model. The only difference is in the numerator
where we obtain only the first term of a series obtained in
[10] .
If the results are worked out numerically we find the absorp-
tion spectra obtained in [10] to within 5% for a < 4. Also the
strong coupling limit is in agreement with the results of [10].
However, our self-consistent formalism does not lead to a
Franck-Condon sideband structure.
A very important aspect of the present treatment is that the
denominator in equation (20) which is the result of FHIP's 'up-
side down' approximation is obtained directly here without any
such approximation. This denominator describes the sharp reson-
ances due to the RES.
4. APPLICATION OF THE FORMALISM TO THE MOBILITY OF POLARONS

(BOLTZMANN APPROXIMATION)
It seems relatively easy to calculate a number of physical
properties of polarons within the present formalism. We will
still present some results on the mobility in the Boltzmann
approximation. We have to calculate:
-1
T (IV.2l)
where Ip,k) characlerizes the initial polaron state, P is the

polaron momentum, k is the phonon wave vector, and R is the re-
actance matrix.
Using the Chew and Low equations and disentangling some 2Per-
at or expressions we get after introducing our solution for P(t):
The details of the derivation of equation (22) will be published

elsewhere.
Aga~n we replace the frequency spectrum in F(k,t) by one
single frequency. We are then led to:
This leads to an expression for the mobility which is similar

to that obtained by FHIP for a < 4 with two important differ-
ences:
(a) The factor 3kT/2 which occurs in the FHIP expression
but not in the Kadanoff result is absent here;
(b) The asymptotic limit for the mobility derived from
equation (23) if a + 0 is ~ = ~O(l - a/6) the well-
known result obtained by Kadanoff. The FHIP theory does
not provide this limit correctly. The Bessel function
IO(Cf) in equation (23) assures the correct asymptotic
limit;
(c) The mobility, as obtained here, tends to zero for a+ oo
contrary to all previous theories and this is due to
the factor IO(Cf).
This lecture IV will be published in detail elsewhere [11,
12].
REFERENCES
1. Feynman, R., Hel1warth, R., Iddings, C. and Platzman, P.
(1962). Phys. Rev., 127, 1004.
2. Feynman, R. (1955). Phys. Rev., 97, 660.
J. Gross, E. (1951). Phys. ReV., 84, 818.
4. Evrard, R. (1965). Phys. Lett., 14, 295.
5. Evrard, R., Devreese, J., Kartheuser, E. and Grosjean, C.C.
(1972). Nuovo Cim., B12, 1~8, 137.
6. Kartheuser, E. In reference [9].
7. Fr~hlich, H., Pelzer, H. and Zienau, S. (1950). Phil. Mag.,
41, 221.
8. Kuper, C.G. and Whitfield, G.D. (1963). Polarons and
Excitons, (Oliver and Boyd).
9. Devreese, J. (ed.) (1972). Polarons in Ionic Crystals and
Polar Semiconductors, (North Holland).
10. Devreese. a.• Huybrechts. W. and Lemmens. L. (1971). Phys.
Stat. Sol. (b). 48, 77; Devreese, J .• DeSitter, J. and
Goovaerts, M. (1972). Phys. Rev., BS, 2367.
11. Evrard, R., Devreese. J. and Kartheuser, E. A Self-Consist-
ent Equation of Motion Approach to Polaron Theory. I. The
Formalism, (to be published).
12. Devreese, J., Evrard, R. and Kartheuser, E. A Self-Consist-
ent Equation of Motion Approach to Polaron Theory. II.
Mobility Problem, (to be published).
THE SELF-ENERGY PROBLEM IN QUANTUM DIELECTRICS
J. HERMANSON
Physics Department, Montana State University,

Bozeman, Montana 59715
In these lectures we will study two important aspects of

electron-electron interactions in insulators: (1) quasiparticles
(electronic polarons) and (2) sidebands in excitation spectra,
associated with the final-state emission of quanta of the di-
electric polarization field. Thus we will be concerned with (the
real and imaginary parts of) the self-energy of an electron in
a quantum dielectric. Our study will be based on simple models
which illustrate the essential physical aspects of the problem.
1. THE SCALE OF THE SELF-ENERGY

A THE CORRELATION HOLE
An electron placed in condensed matter repels electrons in
its vicinity. The resulting decrease of Coulomb interaction en-
ergy, called the self-energy, or correlation energy, can be eas-
ily estimated for the case of 'maximal correlation' in which the
electron is at the center of a sphere of volume (4n/3)r s 3 = N-l
(N = electron density), and all other electrons are outside the
sphere [1]. If the electron is slow this 'correlation hole' will
follow its motion adiabatically and the self-energy will be
(1)
In the 'fast' limit we may assume the electron has uniform prob-
ability density throughout the sphere, and self-energy
199
200 J. HERMANSON
3 e 2
- - -
5 !'s
(2)
Since !'s is about 2 Bohr radii in typical insulators (alkali

halides and rare-gas crystals), E ~ -1 Ry.
B CLASSICAL POINT CHARGE IN A DIELECTRIC

The self-energy of a classical particle (M + 00) is found from
the energy density of the polarization field
L~-L~
81TE: q 81T
(3)
q q
for a crystal of unit volume. The second term in (3) is the
field energy in vacuum, which must be subtracted from the (smal-
ler) field energy in the dielectric, leaving a negative self-en-
ergy. From Maxwell's equation iqoDq = - 41Te and
< o. (4)
Note that the induced charge density
Pq ind e (1 - E:~) > 0 (5)
so that (1 - l/E: q ) is a kind of 'susceptibility'. If Q is the

scale of dielectric dispersion in q-space, EeL ~ - e 2 Q/1T.
C SEMICLASSICAL CHARGE
To include the effect of electronic recoil, add the kinetic
energy ~2/2MR2 to (4) if the electron is confined to a region
of size R:
(6)
A 'large' electronic polaron QR» 1 has
Varying the polaron radius R we find

SELF-ENERGY PROBLEM IN QUANTUM DIELECTRICS 201
(7)
for the stable configuration, where the dimensionless coupling

constant [2]
(8)
in terms of ~~p' the quantum energy of the polarization field.

Note that RO and E(RO) are independent of n~p for a classical
dielectric!
2. THE TOYOZAWA MODEL OF A QUANTUM DIELECTRIC

The interaction of an electron with a quantized polarization
field can be represented approximately in terms of the Hamilton-
ian
KEpartic1e + KEfield + HI' (9)
where EO is the energy of the field quantum (a dispersionless

'exciton') and aqt, as are boson creation, destruction opera-
tors for the field [3J. The linear particle-field interaction,
the third term in (9), may be derived by considering the polar-
ization potential, ~(r), due to the presence of an electron in
the medium:
E - v¢ = - 4nP
_ 4niPq
(10)
Iql
Thus
HI =- e~(r) = ~'i' [4nie)

~ Pqe
iq or
• (ll)
In the usual way, P q is regarded as a generalized coordinate of

the ~ield, and is written as a linear operator
(12)
202 J. HERMANSON
where y is real. Then the interaction Hamiltonian
H _ \' (41Tie y } ( iq·!, _ t -iq'!')

I - ~ Iq I J aqe aq e , (13)
which is Hermitian in consequence of (12). Although this has

the form of (9) we must determine the coefficient y explicitly
in terms of the parameters EO and £q specifying the dielectric.
We do this on the basis of a simple macroscopic consideration
[4] .
As is well-known, the interaction between two charges is
screened by the static dielectric constant £0 at large separa-
tion r ~ 00 [5~61. (This is because the frequency of relative
motion w ~ h/mr2 ~ 0). Suppose an electron interacts with an
infinitely massive impurity of charge +e, located at r = O. The
total electron-impurity interaction
2
V(r) = - ~ + L (r) (14)
r
contains the 'direct' Coulomb interaction and the 'indirect' in-

teraction L(r) due to the virtual exchange of 'excitons', as de-
scribed by the Hamiltonian
HI = L vq[aq(e iq .!' - 1) - aqt(e- iq '!' - 1)]. (15)

q
In the limit as r ~ 00 (w ~ 0), the interaction energy is compu-

ted for fixed r (adiabatic limit) as
L =- LI(lqIHI(r)lo)12
q
- ~ L IVq l 2 + E2 L IVql2eiq.!,
Eo q 0 q
(16)
The 'indirect' interaction
(17)
must be such that
2 2
V(l" -+ 00) - ~ + E(l") e
1" EcY'
Thus
/ = EO[l _ ~J
81f EOJ
(19)
Note that in this macroscopic approach the electron-exciton in-

teraction Vq depends only upon Eq-+O. This means that while long-
range correlation is properly treated, the Toyozawa model cannot
be expected to describe effects depending on dielectric response
at small distances ~ Q-l. In the past a somewhat arbitrary cut-
off has been introduced in q-space to derive non-divergent self-
energies [7,8]. A proper microscopic theory ought to contain
an interaction which depends on the detailed dielectric response
Eq, not just EO. Such a theory would lead to non-divergent self-
energies automatically, and could make full use of present know-
ledge of the dielectric function. Indeed, since measurable quan-
tities such as band gap are critically sensitive to short-range
correlation, a microscopic theory based on Eq should challenge
many-body theorists to go beyond RPA!
3. A MICROSCOPIC THEORY [9]

We now discuss a simple model which incorporates q-dependent
dielectric response. In this approach we derive a linear elec-
tron-boson interaction from the electrostatic potential and a
microscopic consideration, namely the requirement that the lon-
gi tudinal t sum rule I be satisfied. Our resultant interaction
Hamiltonian depends on Eq' not just EO, and the associated field
quanta resemble plasmons rather than excitons.
We begin with a model dielectric function
w2
£(q,w) 1 - P (20)
w2 - b. q 2 + iwrq
where wp = (41fNe2/m)~ is the plasma frequency for a free-elec-

tron gas of density N. This is a natural generalization of the
Lorentz model to finite q, and satisfies the sum rules [10]
204 J. HERMANSON
(21)
To interpret this model in physical terms consider (a) the ab-

sorption spectrum
(22)
a Lorentzian band centered at 80 with width rO (<<80); (b) the

energy-loss spectrum
another Lorentzian but centered at the frequency
(24)
with width rq«Qq); and (c) the static screening limit
(25)
From (a) and (b) we infer that (20) describes a medium with op-
tical (transverse) excitations across an energy gap ~~80 and
longitudinal excitations ('plasmons') with complex dispersion
(26)
From (c) we can determine 8q so that (20) has the right static
limit E q :
wp 2
8 2 (27)
q
Consequently the 'plasmon' dispersion is

(28)
In other words, to the extent that £2 and Im£-l can be repres-

ented as Lorentzians, and to the extent that £q is known from
theory or experiment, (20) is a valid representation of dielec-
tric response. For some purposes (e.g., computation of self-en-
ergies) our model will be extremely useful, whereas for others
(e.g., detailed interpretation of loss structure) a more specif-
ic treatment would be necessary.
Before deriving the interaction Haml1tonian we introduce a
model £q which is simple and which possesses correct limiting
behavior:
W 2
1 + - _.....p'---::o-..". (29)
[~o + ~~r
Thus
~q = [wp 2 'Ii 2) 2]
+ [ ~O + ~ ~. (30)
1
The scale of dielectric dispersion in q is Q (2m~O/'Ii)2. Equa-
tion (29) is essentially the same as an interpolation formula
derived by Penn [11] for an isotropic model of a semiconductor,
with the important feature that it corresponds to single-part-
icle excitations at large q »Q:~q -+- 'li q 2/2m, as q -+- "'. For
small q « Q the 'plasmon' energy
(31)
consistent with the finding of Horie [12].

We now derive a microscopic electron-'plasmon' interaction,
begining with Poisson's equation
(32)
Thus
(33)
where ¢ and p are the potential and number density of the elec-
206 J. HERMANSON
tronic medium. To quantize the field we write
(34)
where Yq is real, but depends on q, as we shall see below. Equa-

tion (33) may now be written as
(35)
We determine Yq from a microscopic relation, the longitudinal

sum rule on oscillator strengths [10]
(36)
where 10) and In) are the ground and excited states of the many-
electron system and EnO is the transition energy. In positing
our model dielectric function (20) we have implicitly assumed
that there is only one excitation branch for longitudinal probes,
namely a 'plasmon' of frequency Qq given by (28). For this mod-
el the sum over n in (36) has only one term corresponding to a
plasmon of wave-vector q. Then we have simply
(37)
2
[ 41Te )
q2
21
Yq
12 = 21Te 2 h
q2 wp
[1 _-1:....) ~
Eq'
which should be compared with the form (19) in the macroscopic

Toyozawa model. The present result vanishes more rapidly at
large q, since (1 - l/Eg) ~ 0, q »Q. A natural question arises
-- how can we be sure tne microscopic model yields the correct
screening behavior at large r? One answer is to assert that the sum
q ~ °
rule is not restricted to large q (small r) so that the limit
must be given correctly. To see that this is the case, we
compute L(r), in the adiabatic limit, for the electron-impurity
problem, as we did in (17). We find
2
L(r) 2 I 1~51 e iq •r
q q
(Contd)
(Contd) = [1 _ ..l...Je 2 (38)

EO I'
V(r -+ (0)
e2
- -I' + [1 - ..l...J~ = - LEoI'
EO I'
Thus correct macroscopic behavior is automatic in this microscop-

ic description.
To summarize, we have developed an effective electron-plasmon
interaction (35) and (37) which simulates the less tractable
electron-electron interaction in insulating solids. The q-dep-
endent coupling strength Vq depends on the electron density N
and the dielectric function Eq which are regarded as input par-
ameters (in the 'Penn model' Eq is specified by an average en-
ergy gap h~O and N). Since the loss function is approximated
by a Lorentzian, physical quantities which depend on the detail-
ed spectral distribution ImE-1(qw) will be inadequately descri-
bed by our model.
On the other hand this microscopic model is expected to have
great power in attacking problems where only overall properties
of the loss function are important. Thus the theory may be ex-
pected to yield accurate integrated intensities in excitation
processes, though spectral fine strueture is not contained in
the model.
4. APPLICATIONS
A QUASIPARTICLES
An electron (or hole) placed in an insulator polarizes the
valence shells, creating a correlation hole. The resulting en-
tity composed of an electron and its accompanying cloud of pol-
arization ('virtual plasmons') is termed a quasiparticle. The
renorma1ized energy is
(39)
for an electron with effective mass m* near the band edge where,
from (35),
L(k) (40)
and IVq l2 is given by (37). Two effects arising from (40) are:
(1) the band gap is redueed
208 J. HERMANSON
( 41)
Leo)
(2) the effective mass is enhanced (consider the term in

(40) proportional to k2):
1 -+ -
1- [1'1) 2
-
m'" m'~ 2 m
-
L ( 42)
q
The latter effect is insignificant compared with electron-phon-

on mass enhancement [13] since the phonon frequency is several
orders of magnitude smaller than the plasmon frequency.
However, the band gap reduction is truly significant, as one
can see by neglecting the recoil term in (41):
L(O) (43)
Interestingly, this is precisely the classical self-energy (4).

Within RPA [11], Q ~ kF' and
e 2 kF
Leo) " - -1T- = - 0.17 [:~) liwp
(44)
" - !3 liw p " - 5 eV.
The effect of recoil is to reduce the self-energy by about 30%

in alkali halides; exchange leads to a further reduction of ab-
out 10-20%. When we consider that both the electron and hole
have self-energies that reduce the gap, the total RPA reduction
must be about !Ry, on the scale of the energy gap itself! We
can only conclude that the RPA severely overestimates dielectric
response for large q [14], and await the arrival of a better di-
electric function.
B Two QUANTUM EXCITATIONS

A linear electron-boson interaction of the type (35) contains
the possibility of sideband structure in excitation spectra.
For example, in an optical transition the excited electron (or
hole) may interact with the polarization field, leaving it in an
excited state; the total energy for this process is equal to the
sum of the energy of the electron-hole pair and the energy of
the field. In a naive interpretation of the model Hamiltonian
(35) one might expect replica structure at high energy separated
by a 'plasmon' energy nnO from the primary one-electron struc-
ture. On the other hand the Toyozawa model seems to imply repli-
cas in 'exciton' energy EO above interband absorption structure.
These interpretations are 'naive' inasmuch as neither model in-
corporates the spectral complexities of the energy loss function.
In the first model a 'plasmon-pole' approximation to £(qw) is
made, consistent with the sum rule, and in the second model only
£0 enters, and the 'exciton' energy EO' since it is based on a
macroscopic consideration. The microscopic model should give
reliable estimates for the integrated intensity of the sideband
structure; however, this structure, centered near nnO (not EO),
would in reality be spread over a spectral region encompassing
about 10 eV! To gain an appreciation for the complexity of the
sideband structure, imagine a convolution of the interband ab-
sorption structure and the loss function. The resulting spec-
trum would contain exciton replicas of exciton peaks, plasmon
replicas of exciton peaks, replicas of interband peaks, and so
on. This dilution of many-body intensity over a wide spectral
range may render the two-quantum excitations virtually undetec-
table against the interband background, even when the integrated
intensity is substantial. In most cases the most intense excit-
ation would be the pair: exciton + plasmon.
To compute an upper bound for two-quantum intensities, con-
sider the interaction between an optical exciton and the 'plas-
mon' branch introduced in section 3. The amplitude for plasmon
emission by the exciton is VqPq, where the form factor
(45)
in terms of the electron and hole masses m1 and m2; Vq is given

by (37) and ~(r) is the envelope function of the excIton. From
the Golden Rule we compute the relative two-quantum transition
rate as
2
f2Q _ I IVqPql
f1Q - q (nnq)2
~ 'i' 2TTe 2[1 111 12 , (46)

~ nnO ~ q2 - £qJ Pq
210 J. HERMANSON
omitting exciton recoil. Note that Pq + 0 for small q since the
exciton is electrically neutral. To estimate the dependence of
(46) on exciton radius a, assume m2 = 00. Then
qa« 1
(47)
qa » 1.
For small exci tons (Qa « 1)
( 48)
due to charge cancellation, whereas for large excitons (Qa» 1),
r2Q
r 1Q
+ _1_o qL
fir/
27Te 2
q2
[1 _:q)
c.
" ~ 1iwp " ! (49)

flr/O 3 4'
for alkali halides. It is clear that the upper bound for two-
quantum intensities in typical insulators is 25% of the inter-
band intensity. However, this limit is reached only for 'large'
excitons where r1Q ~ 1~(o)12 ~ a- 3 is very small; thus f2Q is
almost certainly undetectably small for these states. For the
'small' exciton (e.g. Is), the ratio f2Q/f1Q is about 10- 2 at
best, in agreement with earlier work [15] based on the Toyozawa
model.
We conclude that sideband structure associated with intense
(small) excitons has an integrated intensity at least two orders
of magnitude weaker than the main peak due to charge cancella-
tion, and this structure, which should resemble the loss func-
tion, is about 10 eV wide. Our conclusion does not support pre-
vious interpretations of high energy spectra in terms of plasmon
[16] or exciton [17,18] 'replicas', but suggests that band the-
ory (including gap renormalization) may be fully adequate to ex-
plain the optical properties of insulators at high energies. A
similar conclusion has been reached in metals, where charge can-
cellation also reduces sideband intensities [19], and where high-
energy spectral structure [20] previously attributed to plasmon
emission has been given a more satisfying interpretation in
terms of standard energy band theory [21].
REFERENCES
1. Wigner, E. and Seitz, F. (1933). Phys. Rev., 43, 804.
2. Frohlich, H. (1937)". Proc. Roy. Soc., A160, 230.
3. Toyozawa, Y. (1954). Prog. Theor. Phys. (Kyoto), 12, 421;
Kunz, A.B. (1972). Phys. Rev., B2, 606.
4. Frohlich, H., Pelzer, H. and Zienau, S. (1950). Phil. Mag.,
41, 221.
5. Kohn, W. (1958). Phys. Rev., 110, 857.
6. Roth, L.M. and Pratt, G.W., Jr. (1959). Phys. Chern. Solids,
8, 47.
7. Fowler, W. Beall. (1966). Phys. Rev., 151, 657.
B. Wang, S., Arora, H.L. and Matsuura, M. (1971). Phys. Rev.,
B4, 3685.
9. Hermanson, J. (1972). Phys. Rev., B6, 2427.
10. Pines, D. (1963). Elementary Excitations in Solids, (W.A.
Benjamin, Inc.).
11. Penn, D. (1962). Phys. Rev., 128, 2093.
12. Horie, C. (1959). Prog. Theor. Phys. (Kyoto), 21, 113.
13. Brown, F.C. (1963). In Polarons and Excitons, (eds. Kuper,
C.G. and Whitfield, G.D.), (Plenum Press, New York), and
other references therein.
14. Pines, D. (1961). The Many-Body Problem, (W.A. Benjamin,
Inc.) .
15. Hermanson, J. (1969). Phys. Rev., 177, 1234.
16. Brown, F.C., et al. (1970). Phys. Rev. Lett., 25, 927.
17. Miyakawa, T. (1962). J. Phys. Soc. Japan, 17, 1898; Sagawa,
T., et al. (1966). J. Phys. Soc. Japan, 21, 2587.
lB. Devreese, J.T., Kunz, A.B. and Collins, T.C. (1972). Solid
State Commun., 11, 673; Kunz, A.B., Devreese, J.T. and
Collins, T.C. (1972). J. Phys., C5, 3259.
19. Hermanson, J. (1972). Phys. Rev., B6, 400.
20. Whang, U.S., Arakawa, E.T. and Callcott, T.A. (1970). Phys.
Rev. Lett., 25, 646; (1972). Phys. Rev., B6, 2109.
21. Ching, W.Y. and Callaway, J. (1973). Phys. Rev. Lett., 30,
441.
ELECTRONS AND PHONONS IN NARROW GAP SEMICONDUCTORS
M. BALKAN SKI
Laboratoire de Physique des Solides,

Universite de Paris VI, France
I. BAND STRUCTURE AND OPTICAL PROPERTIES IN SMALL GAP

SEMICONDUCTORS AND ALLOYS
1. INTRODUCTION
There are two categories of zero gap materials: one in which
the lowest lying conduction band edge is degenerate with the
highest lying valence band edge by reasons of symmetry and the
other in which a cross over point between the conduction and
valence bands exists for a given composition due to shifts of
energy levels corresponding to spin-orbit and relativistic cor-
rections.
To the first category belongs the grey tin (a-Sn) [1], HgTe
[2], HgSe [3], HgS [4], and Cd3As2 [5] having diamond or zinc
blende structures for which the direct energy gap is either id-
entically zero or negative. These materials are called the per-
fect semimetals or the symmetry-induced zero gap semiconductors.
Since the gap is zero one would expect at low temperature
the system to be unstable toward exciton formation [6] and thus
to collapse into a new ground state of coherent bound electron-
hole pairs. The new phase [7] would belong to one of three
space groups of lower symmetry and should occur at about 5 OK.
Such a phase transition has not been observed and the explana-
tion of this fact lies in the electronic dielectric function.
The screening associated with this specific band structure is
of a new kind susceptible to reduce the electron-hole interac-
tion and produce other anomalous effects which we shall discuss
in the second part of this paper.
To the second category belong materials in which a zero gap
is achieved by alloying or by applying external pressure. The
variation of concentration or of pressure shifts the energy lev-
213
214 M. BALKANSKI
els in such a way that the top of the valence band may coincide
with the bottom of the conduction band. The effective masses
tend toward zero with the energy gap and the material is a band
crossing-induced zero gap semiconductor.
In approaching the zero gap some strong coupling between plas-
mons and phonons occur which perturbs the normal behavior of
these semiconductors. We shall examine here the consequences of
this breakdown of the Born-Oppenheimer approximation. It is not
immediately clear how either of these two structures can remain
stable at low temperatures. It is often argued that at suffic-
iently low temperatures free electron screening will be inade-
quate to prevent formation of bound electron-hole pairs. As
such sharp phase transitions are not observed it is clear that
a complete examination of the electronic dielectric function is
necessary to understand the anomalies observed in the behavior
of the electron and phonon contributions.
The general form of the complex dielectric function can be
written
E(W) = Eoo + ~Einter + ~Eintra + 6E ph'
The first term corresponds to the high frequency dielectric con-
stant Eoo. Since Eoo is due to vertical interband transitions
from the valence band to all high conduction bands except those
corresponding to the energy gap, it involves relatively high en-
ergies and it is therefore independent of frequency and momentum
transfer, the imaginary part consequently vanishes. ~Einter is
precisely the contribution in the energy range close to EG. In
the case of lead salts for example this contribution is due to
the transition L6+(L1+) ~ L6-(L2-) before the band crossing and
to L6-(L2-) ~ L6+(L1+) after the cross point. In the case of
HgTe this is the contribution due to ra ~ ra interband transi-
tions. 6Eintra gives the contribution due to intraband free
carrier transitions. 6E ph is the contribution due to phonons.
In the low energy spectrum the most striking effect is the
mixing of the plasmon mode which is purely electronic contribu-
tion and the normal vibrational mode which is purely lattice
contribution leading to a breakdown of the Born-Oppenheimer ap-
proximation.
A detailed analysis of the dielectric function [8] in narrow
gap semiconductors has been recently carried out and all these
contributions calculated. We shall outline briefly the results
in the second part of this paper.
2. ELECTRONIC BAND STRUCTURE
2.1 THE IV-VI SEMICONDUCTOR COMPOUNDS
2.1.1 General Properties

Both types of materials under consideration have some spec-
ific characteristic features which distinguish them from each
ELECTRONS AND PHONONS IN NARROW GAP SEMICONDUCTORS. I. 215
other and also establish the difference with the other semicon-
ductors or semimetals.
The IV-VI compounds form ternary alloys which are semiconduc-
tors on both sides of the zero gap point whereas the IV-VI com-
pounds give rise to ternary systems which are semimetals on the
meaning rich side and semiconductors on the Cadmium rich side
in HgxCdl-xTe for example.
The general properties of these IV-VI semiconductor compounds
are schematically the following: (a) The energy gap of the lead
salts: PbS, PbSe, PbTe increases [9] with temperature which is
the opposite of what is generally known for other semiconductors
whereas SnTe and GeTe have a band gap which decreases [10] with
temperature in agreement with the general theory; (b) The free
carrier (electrons and holes) moblities are very large; (c) The
TO mode frequencies at k = 0 are very low. For some compounds
such as GeTe and SnTe for example the TO mode undergoes a sig-
nificant frequency shift with temperature [11]; (d) The low fre-
quency (static) dielectric constants of the lead compounds are
relatively large [12]; (e) Some of the compounds GeTe, GeTe-SnTe
alloys are supraconductors [13].
Lead chalcogenides have the cubic NaCl-type structure of the
m3m symmetry class possessing a center of inversion. The unit
cell is a face-centered cube and the coordination number for all
the atoms is six.
The nature of chemical binding in lead chalcogenides is mixed
ionic-covalent, i.e. they are usually classified as polar semi-
conductors. In this type of binding the properties are governed
by the dominant (ionic or covalent) component, i.e. by the degree
of ionicity.
A rather strong ionicity in this type of semiconductors is
supported by the LO-plasmon coupling giving rise to a mixed
oscillation which is a limitation for the laser action [14] in
these small gap materials.
2.1.2 Electronic Band Structure of the IV-VI Compounds
2.1.2.1 High Energy Bands: Eoo
The mInImum energy gap for these compounds occurs at the

point L(111) of the Brillouin zone. A schematic representation
of the ordering of the electronic energy bands for PbTe is given
in figure 1.
The remarkable feature here is the importance of the relativ-
istic correction on the Ll+ level which is a level having an S
type symmetry around the Pb atom. That is the existence of this
heavy atom which renders the relativistic correction so import-
ant; to such an extent as to invert the normal order of the lev-
els L2' and Ll+'
Band structure calculations have been carried out by the
first principal OPW method [15-17] and the empirical pseudo-
potential method [13,18-20].
216 M. BALKAN SKI
L~
,,
(1,1, t) \ ,,
.6 L ----
,, \
\
,, L;' ,L,
, ,
.,,; I \
'"
...q
~
-a
, I
I
, \
A,
-
L', \ L;'
2 ,\
""\'
,,
0. I \
::l
I \ d.,
"~ .5 \
,,
\ \ L~
~ \ \
6
Eg
'"e? I L~
I
"
.0
I L3
"'" I
d. 2
"""
~
-- --
I
Ul
.4 I
I
"" L~, L~
,
I
I L~
0 Kinetic Simple Anti- Relativ- Spin-

energy cubic symmetric istic orbit
(empty- potential potential corrections energy
!attice) (schematic)
Figure 1 - Band structure at (Ill) zone edge for PbTe

calculated by OPW method. Al = 0.044, A2 = 0.046,
61 = 0.078, 63 = 0.081, EG = 0.014. (From Pratt Jr., G.
W., and Ferreira, L.G. (1964). Proceedings of the Con-
ference on The Physics of Semiconductors~ PaPis~ 1964,
(Dunod») .
Further calculations are currently being carried out along

these two directions called for by the continous improvement
of the experimental results.
Relativistic OPW band calculations [21J at key points in the
reduced zone are carried out for GeTe, SnTe, PbTe, PbSe and PbS
which account for most of the characteristic features of the ex-
perimental reflectivity spectra.
In order to compare the different energy band structures cal-
culated in recent years by different authors, we have plotted
at the same scale a certain number of the most representative
ones. This comparision is shown in figure 2.
It is commonly believed at the present time that photoemis-
sion studies may improve our knowledge of the electronic energy
band structure of solids. Recent measurements [23J of the photo-
emission of PbSe shows a very rich structure in the energy dis-
tribution. Such a set of results is difficult to interpret with-
out a detailed knowledge of the electronic energy band structure
and a good theory on the photoemission.
Recent pseudopotential calculations [22J give a good basis
- 10 PbSe
-12
__ .--_._. --_. --. --. - - .-__'

" -'-"~·I~:. -~.""i ~ . _ .. _ . _ ._.
-14
.--_.--_.---------_.---.------------
-_ .--_ . .
r K S X r L
Figure 2 - Energy band structures of PbSe given by:

------- Overhof , H. and Rossler, U. (19 70). Phys. Stat.
Sol., 37. 691; - - Herman, F., Kortum, R.L., Ortenburger,
I . B. and van Dyke, J .P . (19 68). J . de Phys., 29, C4-29;
---- Rabii, s. (196 8). Phys. Rev., 167, 801.
for discussion of experimental results. We have used two elec-

tronic band structure calculations [21,22J to exploit recent
photoemission measurements [23J on PbSe.
In figure 3 is given a temptative attribut i on of the most
eminent photoemission transitions proceeding from points in the
Brillouin zone of maximum density of states to higher energies.
218 M. BALKAN SKI
WI
1!
.
.", .
" ()
In
- 24 E::t = =:::::::::::==:11 0
r I< It X
Figure 3 - Vertical transitions deduced from photoemis-

sion experiments superimposed on the energy band struc-
tures of PbSe. (a) From Herman, F., Kortum, R.L., Orten-
burger, I.B. and van Dyke, J.P. (1968). J. de Phys., 29,
C4-62. (b) From Kohn, S.E., Yu, L.Y., Petroff, Y. Shen,
Y.R., Tsang, Y. and Chen, M.L. Phys. Rev ..
Only direct transitions are considered for the purpose of il-
lustrating the method.
A first peak appears for incident energies in the range of
6.6 to 8.6 eV and is displaced by the quantity ~ = ~nw. This
peak is attributed to transitions from a flat region of the
valence band situated at Ev = -1.1 eV and conduction bands whose
energies are situated between 5.5 eV and 7.5 eV. Looking into
the band structures considered in figure 3 only the Q region
near the W point has a sufficiently flat valence band. The iden-
tification of the other observed transitions proceeds by analog-
ous considerations.
Table I gives a synthesis of the experimental results and pos-
sible attributions for the transition at different points of the
Brillouin zone.
TABLE I
Energy in the Energy in the Location in the

Valence Band Conduction Band Brillouin Zone
Ev -1.1 eV ± 0.1 8.6 eV ~ Ec ~ 6.6 eV Q near W
Ev -1.2 eV ± 0.1 9.2 eV ~ Ec ~ 7.8 eV Q near W
Ev ="-2 eV ± 0.1 8.4 eV ~ Ec ~ 6.8 eV A,'i. around rS-

Ev = -2.7 eV ± 0.1 7.7 eV ~ Ec ~ 6.3 eV A,'i. around r6-
2.1.2.2 Band Extrema Near the Zero Gap.

Contribution to the Complex Dielectric Function
The contribution to the dielectric function due to the inter-
band transitions between the uppermost valence band and the low-
est conduction band of a narrow gap semiconductor can be written
~£inter
x [f(EF) - f( £F - WI)] 117:~ I I dw I ,
where f(E) is the Fermi-Dirac function, dS represents the ele-

ment of a constant energy surface WI and M is the matrix element
depending on the band structure parameters.
In the case of PbSe, for example, Martinez [14] has calculat-
ed ~£inter(w) using the parameters deduced for the band struc-
ture at the L-point of the Brillouin zone.
220 M. BALKANSKI
t·* Model Around the L-Point of the Brillouin Zone
To calculate the energy band parameters at the L-point Mar-
tinez uses a six-bands model. Such a model depends on ten para-
meters: five matrix elements, three energies and two values of
the spin-orbit interaction, it is therefore necessary to confront
the obtained results with all available experimental informations
in order to test their plausibility. Haying to deal with a small
gap semiconductor one has to apply the k·i theory appropriate
for the case of quasi-degeneracy. Martinez has pursued the cal-
culations to third order in perturbation theory and obtained for
£( k.) :
2 2
± [~£G + (~(C - A)£G + F)kt
2 2 2
+ (~(D - B)£G + H)k z + (WI + ~(C - A)(D - B»kt kz
All previous calculations agree that the direct gap is situ-

ated at the L-point, that there are three bands of odd parity
with regard to the Pb nucleus above the gap and three bands of
even parity below, and that relativistic and spin-orbit inter-
action corrections are important.
The spin-orbit interaction not only leaves the degeneracy of
the L3+ and L3- levels but also mixes the wavefunctions of the
levels L6-(L3-) and L6-(L2-) with L6+(L3+) and L6+(Ll+). It is
also responsible to some extent for the nonparabolicity of the
bands.
The order of the bands at the L-point and the energy variation
as a function of pressure as calculated by Martinez are given in
figure 4.
In this calculation one admits that the elastic constants and
the linear compressibility are constant with pressure, the de-
formation potentials are also taken to be constant with pressure
and the values used are these calculated by Rabii [1?] except
for that corresponding to point L+ which has been adjusted to
fit the experimental variation of EG with pressure.
2.1.3 Energy Band Structure in the Pbl-xSnxSe Mixed Crystals

The calculations performed by Martinez [14] concerning the
conduction and valence band extrema at the L-point are car-
ried under the assumption that the band parameters around the
energy gap depend only on the magnitude of the gap and not on
the factor under which the gap variation is achieved. This vari-
ation can be obtained indifferently for example by the addition
of tin or by the application of pressure at OaK.
In the case of the crossing of the bands and the band inver-
Lo{L,)
Ii- ..;
.... Lo {L2)
o
L~{Li)
>
"
-1 -
L~L~
-2 -.
-
L~{L~}
10 20 30
PIKbarl
Figure 4 - Relative energy band variation in PbSe at

point L as a function of pressure. (From Martinez.
(1972) (Thesis, Paris».
sion in Pbl-xSnxSe the effective masses at the band extrema de-

duced in this calculation are:
2F 1 2F
- - + 2A, - + 2C,
EG mtc EG
1 2H 1 H
mR,v
- -E + 2B, --
mR,c
= EG + 2D.
G
In these algebraic expressions the energy gap EG = E(L 6-) -

E(L6+) is positive before crossing and negative after the cross
over point. F, H, B, D, are always positive and A, C always
negative.
All masses tend toward zero with EG. After the band crossing
the contributions to the conduction and valence band extrema
change sign inducing a change of sign for the effective masses.
222 M. BALKAN SKI
But the contribution of the other bands do not change sign
therefore for values of EG symmetrical with regard to the zero
point the effective masses are larger on the SnSe side than on
the PbSe one.
Let us consider for example the transverse effective mass of
the valence band at the L-point, one gets:
1 2F
- - = - EG + 2A.
Clearly mtv goes to zero with EG' After the band crossing, EG
becomes negative and this equation gives the transverse effec-
tive mass of the conduction band mtc' When EG is increasing and
for EG < 0, a critical value EGO = FIA is reached for which
l/mtc = O. Beyond this value the minimum gap is no longer di-
rect and the conduction band develops three lower minima lying
off the L"point in the plane of the hexagonal face of the Bril-
louin zone. The transverse effective mass of the conduction
band gives a second critical gap EGl - FIC which is 0.52 eV
at ODK.
The results of these calculations are schematically drawn in
figure 5.
£:
I
u
i:l;
II
I
I
I
I
I
I
I
I
I
I
I
I
I
I
EL• -EL6 >O:EL< -Eu <0
• I ..
Figure 5 - Band crossing model for the alloys Pbl-xSnxSe.

(From Martinez. (1972). (Thesis, Paris)).
In PbSe we have m£/mt > I for the two bands in the model
shown in figure S. It is easy to see that this anisotropy
decreases continuously approaching the point of band crossing.
The band becomes isotropic for an energy gap of approximately
-0.08 eV.
2.2 Band Structure of II-VI Compounds and Alloys
2.2.1 Energy Bands of CdTe and HgTe

The second type of band crossing we are considering is that
occuring in the Hgl-xCdxTe alloy. Before discussing the elec-
tronic band structure of the alloys, let us briefly consider
that of the two components.
Recent measurements of the optical reflectivity in the vis-
ible and ultraviolet region have stimulated electronic band
structure calculations [24] using the empirical pseudopotential
method. Spin-orbit coupling is included using the method of
Weisz [25] as modified by Bloom and Bergstrasser [26]. The lnl-
tial form factors for CdTe [27] and HgTe [28] are slightly mod-
ified to improve the agreement between the experimental and the
theoretical reflectivities. Only one adjustable parameter is
varied to give the correct splitting of the valence bands at r
for CdTe and L for HgTe.
The electronic band structures of CdTe and HgTe in the prin-
cipal symmetry directions are shown in figures 6 and 7.
-2
L6 x7
-4~L------------~r~------------~x~--~U~.~K--------------~r
Figure 6 - Electronic band structure of CdTe in the prin-

cipal symmetry directions. (From Chadi, D.J., Walter,
J.P., Cohen, M.L. Petroff, Y. and Ba1kanski, M. (1972).
Phys. Rev., B5, 3058).
224 M. BALKANSKI
HgTe
-\~----~----~r~----~-------X&---~U~.~K------~------~r
k
Figure 7 - Electronic band structure of HgTe in the prin-

cipal symmetry directions. (From Chadi, D.J., Walter,
J.P., Cohen, M.L., Petroff, Y. and Balkanski, M. (1972).
Phys. Rev .• B5, 3056).
The fundamental gap in CdTe of 1.59 eV of f between bands 4
and 5 produces the usual MO singularity in £2(W) at the thres-
hold energy of 1.59 eV. The spin-orbit splitting of the valence
bands at f is ~O = 0.91 eV. The measured and calculated reflec-
tivities are compared and prominent features of the reflectivity
spectra are identified with critical-point transitions in spec-
ific regions of the Brillouin zone. The symmetry and contribu-
tion to the reflectivity of important critical points are listed
and discussed in detail in the original paper [24].
HgTe is at the f point a zero gap semiconductor with the con-
duction and valence bands degenerate at fa. Away from f the en-
ergy of the top valence band is expected to increase slightly
i.e. HgTe is in principle a semimetal. Unlike CdTe and most
other zincblende structures, HgTe has an inverted order of bands
f6 and fa. The calculated fa - f6 energy difference is 0.30 eV.
The calculated spin-orbit splittings ~O = fav - f7v and ~l =
L4-5v - L6v are 0.94 and 0.62 eV, respectively.
In the reflectivity curves the enhancement of some experimen-
tal peaks relative to the theoretical peaks, particularly near
the first A and L transitions, are probably caused by excitons
[29].
Relativistic KKR calculations of the energy bands of HgTe
and HgSe are also available [30]. The general features are ana-
logous to that shown previously.
2.2.2 Energy Band in the Hgl-xCdxTe Mixed Crystal System

Hgl-xCdxTe mixed crystal is a good example of the semimetal-
semiconductor transition. It has therefore been the object of
extensive experimental and theoretical investigations. The
theoretical work has always suffered the difficulty of the lack
of a first principal theory, in which the band edges of a mixed
crystal can be described with sufficient accuracy.
Considering that all experimental results are calling for a
model where the electronic states do not deviate from those of
a perfect crystal and may be described with the concept of en-
ergy bands, calculations by the KKR method based on the band
structure results [30] on HgTe have been performed [31].
Calculations based on the empirical pseudopotential method
[32] are also available [33]. In these calculations the same
pseudopotential form factors for HgTe have been used as those
obtained [24] for HgTe and CdTe by fitting the theoretical op-
tical reflectivity spectra to experimental data. The form fac-
tors for CdTe have been modified slightly because of the use of
an increased number of plane waves in the expansion of the wave
functions.
Thepseudopotentials for the alloys are taken to be the aver-
age of the HgTe and CdTe pseudopotential including the spin-or-
bit component of the Hamiltonian. The pseudopotential form fac-
-tors are also scaled [34] for the small changes in the lattice
constant which are almost linear with x.
While HgTe has an inverted band order and the fundamental
band gap r6 - ra is negative, CdTe has standard II-VI bands with
EG = 1.60 eV. Therefore the main effect of admixing CdTe to
HgTe is the shift of the r6 band (metals-electron) to higher en-
ergies, as it can be seen in figure 8.
The calculated [33] variation of the energy gap defined as
EG = E(r6) - E(ra) is found to be linear with x at OOK and changes
sign when x increases from 0.16 to 0.17. This variation is shown
in figure 9.
The exact value of x at which the semimetal-conductor transi-
tion occurs is temperature dependent: at higher temperatures the
value of x at which the transition occurs is lowered due to the
fact that EG of HgTe as well as of CdTe decreases with tempera-
ture.
At OOK for CdS concentration x < 0.16 the uppermost valence
bands and the lowest conduction bands stick together in a point
and form a fourfold degenerate r6 term. For x > 0.16 a direct
gap occurs since the r6 term is higher in energy than the ra
term and the mixed crystal becomes semiconductor. Since the up-
per valence bands originate mainly from tellurium p-electrons
one can expect them to remain nearly unchanged when Hg is sub-
stituted in part by Cd.
226 M. BALKANSKI
1.0
HgTe HgO.84Cdo.16Te HgO.83Cdo.17Te CdTe
2.2
V
0.8
2.0
0.6
1.8
0.4
1.6
;> r6 ;>
~ 0.2 0.2 ~
» »
...
00
e!l
"
<:
~
0 0 "<:
~
-0.2 r6 -0.2
/"
J\
-0.4 -0.4
-0.6 -0.6
Figure 8 - Band structure for the top two valence bands

and the fast conduction band for HgTe, CdTe and two al-
loys near the transition point. (From Chadi, D.J. and
Cohen, M.L. (1973). Phys. Rev., B7, 692).
In a first principal calculation by the KKR method Overhof

[31] uses a model in which all the bands left unchanged except
for the s-bands which are shifted in energy to produce the fun-
damental band gap. Calculations are carried out using the KKR
method which allows to investigate the details of the energy
bands in a small region of the Brillouin zone.
In this model it is impossible to derive EG as a function
of the CdTe admixture. One, therefore, has to choose differ-
ent s-shifts and to calculate the energy bands. The resulting
fundamental band gap, however, indicated which composition corres-
ponds to the calculated energy bands, since the dependence of the fun-
damental band gap on the composi tion is known experimentally.
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1.6r--r--r--r--,.--,.--,.---,r---,---,--P
1.4
1.2
1.0 _d_o___ e _
e_---e-
~ ,,~
j I0.6e-e_--- d,
0.4
0.2
o 0.2 0.4 0.6 0.8 1.0

HgTe x CdTe
Figure 9 - Calculated energy gap and spin-orbit split-

tings ~O E(PS) - E(P7) and ~l = E(LS,6) - E(L6) for
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228 M. BALKANSKI
Supplement, p. 589.
11. Pawley, G.S., Cochran, W., Cowley, R.A. and Dolling, G.
(1966). Phys. Rev. Lett., 17, 735; Pawley, G.S. (1968).
J. de Phys., 29, C-4, 145.
12. Burstein, E. and Egli, P. (1955). Advances in Electronics
and Electron Physics, 7, 56.
13. Cohen, M.L., Tung, Y. and Allen, Ph.B. (1968). J. de Phys.,
29, C-4, 163.
14. Martinez, G. (1972). (Thesis), (Paris).
15. Conklin, J.B., Jr., Johnson, L.E. and Pratt Jr., G.W.
(1965). Phys. Rev., 137, A1282.
16. Ferreira, L.G. (1965). Phys. Rev., 137, A1601.
17. Rabii, S. (1968). Phys. Rev., (1968). 167, 801; 173, 918.
18. Lin, P.J. and Kleinman, L. (1966). Phys. Rev., 142, 478.
19. Lin, P.J., Saslow, W. and Cohen, M.L. (1967). Solid State
Commun., 5, 893.
20. Bernick, R.L. and Kleinman, L. (1970). Solid State Commun.,
8, 5G9.
21. Herman, F., Kortum, R.L., Ortenburger, I.B. and van Dyke,
J.P. (1968). J. de Phys., 29, C-4, 62.
22. Kohn, S.E., Yu, P.Y., Petroff, Y., Shen, Y.R., Tsang, Y.
and Cohen, M.L. Phys. Rev., (to be published).
23. Pinchaux, R., Petroff, Y., Dagneaux, D. and Balkanski, M.
(1972). Conference on The Physics of IV-VI Compounds and
Alloys~ Philadelphia~ March 1972.
24. Chadi, D.J., Walter, J.P., Cohen, M.L., Petroff, Y. and
Balkanski, M. (1972). Phys. Rev., B5, 3058.
25. Weisz, G. (1956). Phys. Rev., 149, 504.
26. Bloom, S. and Bergstresser, T.K. (1968). Solid State Commun.,
6, 465.
27. Cohen, M.L. and Bergstresser, T.K. (1966). Phys. Rev., 141,
789.
28. Bloom, S. and Bergstresser, T.K. (1970). Phys. Stat. Sol.,
42, 191.
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31. Overhof, H. (1971). Phys. Stat. Sol. (bJ, 45, 315.
32. Cohen, M.L. and Heine, V. (1970). Solid State Phys., 24, 37.
33. Chadi, D.J. and Cohen, M.L. (1973). Phys. Rev., B7, 692.
34. Wolley, J.C. and Ray, B. (1960). J. Phys. Chern. Solids, 13,
151.
II. PHONONS IN NARROW GAP SEMICONDUCTORS
1. INTRODUCTION
Recent experiments on zero gap materials as well as in the
case of the symmetry induced zero gap semiconductors [1] as in
the case of zero gap achieved by level inversion [2], have shown
that a strong coupling occurs in the optical modes frequency
range between the plasmon oscillations and the longitudinal op-
tical modes. One is then led to think that the adiabatic ap-
proximation is violated in the frequency region where excita-
tions such as plasmons, phonons and band to band transitions
are of the same order of magnitude. It is then inappropriate
to treat them as separate terms in the contribution to the com-
plex dielectric function. This has been clearly shown [1] in
the case of HgTe which we shall discuss here in some extent.
The violation of the adiabatic approximation occurs [3] in
the case of pure a-Sn at T = 0 for acoustic phonons of velocity
c and wavevector q < 2~cmOc/~ since their energies lie in a con-
tinuum of electron-hole excitations. Sherrington finds a den-
sity response function with leading term of order q3/2 in con-
trast to q2 for insulators and constant for metals. An effect-
ive charge neutrality sum-rule analogous to that of insulators
is required to ensure linear dispersion as q + O. In the range
q > 2~cmOc/~ the adiabatic approximation is valid and the linear
term in the response function is of the order q.
Further theoretical work is certainly desirable to take into
account the non-adiabatic effects in the optical modes. Mercury
Telluride is an example where the experimental knowledge suggests
now that this should be a fruitful area of investigation.
2. DIELECTRIC FUNCTION IN HgTe [1]

The earliest work on the phonon spectrum of HgTe was that of
Dickey and Mavroides [4] at 8°K, then of Ivanov-Omskii, Kolomiets,
Molkova, Markov and Mekhtiev at 80 0 K [5]. The observation of
infrared-active phonon modes is complicated by the band structure
of HgTe. In the region of the LO and TO modes, around 100 wave-
numbers, at non-zero temperatures, electronic intraband transi-
tions and interband ra-ra transitions should overlap with the
infrared-active TO mode. We shall see, moreover, that this is
an oversimplified view of the problem and that other oscillators
229
230 M. BALKANSKI
have to be taken into account, to derive the right parameters
for lattice vibrations and distinguish quantitatively between
several contributions to the dielectric function.
The general form of the complex dielectric function can be
written:
(1)
with: £00 = the high-frequency dielectric constant due to all

interband transitions except r8 + r8; ~£inter = contribution
due to r8 + r8 interband transitions; ~£intra = contribution
due to intraband carriers in the r8 band; ~£ph = contribution
due to phonons.
2.1 INTERBAND CONTRIBUTION: ~£inter
A consequence of the zero value for the gap at r point is

that interband r8 + r8 transitions from the heavy-hole valence
band to the electron conduction band, although symmetry-forbid-
den to first order, are nonetheless possible for all photon en-
ergies in intrinsic material. The influence of such transitions
on the static dielectric function of zero gap semiconductors was
studied by several authors [6-9]. Comparatively little was done
on the interband contribution to the dynamic dielectric function
~£interCw). Sherrington and Kohn calculated the frequency-dep-
endent dielectric function for a-Sn [10] at OOK and recently,
Broerman [11] gave expressions for the dielectric function of
a-Sn in the infrared at finite but very low temperatuxes.
In HgTe the optical r8 + r8 transition is direct (k selection
rule). The matrix element is linear in It I . The material con-
tains a negligible concentration of extrinsic charge carriers
at high enough temperatures. The hole effective mass mv being
much larger than me, it can be taken as infinite as regards the
density of states. Non-parabolicity of the band is taken into
account to calculate me*CE) and Er (Fermi level) of electrons
relative to the bottom of the band as a function of temperature.
At a given temperature, the effective mass is taken as constant
and equal to its value at the Fermi level me*CEr).
At finite temperature, taking into account the occupancy of
the initial and final states, in the RPA formalism, the contri-
bution of transitions between valence and conduction bands to
the imaginary part of the dielectric function is given by
lI£"inter , k ,v , eCw,T)
ELECTRONS AND PHONONS IN NARROW GAP SEMICONDUCTORS. II. 231
with:
(3)
[1 E - EFI]-l .
exp ( e kT )
Ie +
Here, rnO is the free electron mass, Ik,v) and Ik,c) denote val-
ence and conduction band states, p is the projection of the mom-
entum operator on the direction of incident light, and E is the
energy of the states with the origin at the ra point. The
transition probability
2
3 2 2 rnO . 2
- 'Ii k-2- Sln e (4)
16 1.1
with 1.1- 1 = rn e - 1 + rnv - 1 has been calculated by Sherrington and

Kohn [10]. Setting
A (5)
we get
L'le:"inter(w.T) = AUIW)-2:1 { [ l+exp [EF ~ ] -1 [ l+exp (EF kT)

-kT)
- 'liw~ ] - 1
- [1 + exp (EF]
kT
] -1 [1 + exp (EF
- - 'liW]] -I}
kT .(6)
The calculated curves of L'le:"(w) for different temperatures

are shown in figure 1. In these calculations we have used effec-
tive masses on the Fermi levels and electron concentrations ob-
tained by Hall effect measurements.
232 M. BALKANSKI
12
8
285"• • • • •
••••
••••
o 200
Figure 1 - Imaginary part llE:"inter of the fa -+ fa inter-

band contribution to dielectric function, versus wavenum-
ber for several temperatures calculated from equation (6).
The real part 6£'inter is obtained by performing the Kramers-

Kronig inversion on the expression of 6£"inter, this amounts to
solving:
6£'inter Cw )
f:
1
1 w'2dw'
= ~ {
1 + exp [ - !~) (w'
2
- w2 ) [1 + exp [EF ~T~W')]
f:
1
1 w'2dw'
(7)
1 + exp[!~) (w' 2 - w2 ) [1 + exp [- EF + kT OW'J] )
The integration is easily performed by the method of residues:
6£' inter = A{(~w)~

1 [( 1 + eXPl-
( EF)]-l[
T 1 + exp
(EF +
B
~W1]-1
J
(Contd)
(Contd)
00
+ L (8)
v=o
with !3 kT, Pv = n!3(2v + 1),
This series has rather slow convergence (like v- 3 / 2 ). However,

in the case of the calculation of ~£'(w) for different temper-
atures shown in figure 2, 1000 terms are sufficient.
o 600 800
Figure 2 - Real part ~£'inter of the interband ra-ra con-

tribution to dielectric function versus wavenumber for
several temperatures, calculated from equation (a).
2.2 INTRABAND CONTRIBUTION: ~£intra
The free carriers contribution according to the classical

Drude-Zener theory is
234 M. BALKAN SKI
(9)
r is the damping parameter for free carriers (in em-I).

2.3 PHONON CONTRIBUTION: ~£ph.
In the frame of the classical theory of independent harmonic

oscillators, the phonon contribution to the dielectric function
is given by
where ~j is the wavenumber of the transverse mode for each oscil-

lator in em-I,. FI the oscillator strengths, and r j the damping
parameters in cm- .
In the case we shall discuss here, two independent lattice
oscillators (j = 2) will contribute to the dielectric function.
Equation (1) can then be wriiten as a set of separate equa-
tions for the real and imaginary parts of the wavenumber depend-
ent dielectric function:
d~) £' (~) + i£"(~),
with
£ '
(11)
£"
(12)
3. DISCUSSION OF THE EXPERIMENTAL RESULTS

Absolute values for reflectivity versus wavenumber recently
measured by Grynberg and Le Toullec are given in figure 3.
ELECTRONS AND PHONONS IN NARROW GAP SEMICONDUCTORS 235
80 80
\~II<---r\
"I "
'-I \\
60 \
60
40
: "
....................
20
40 60 80 100 120 140 160 180 60 80 100 120 140 160 180 200 220
Wave number [em-l] Wave number [em - l]
1'"0 ,.. 87'K

", 285°K
~ II +-!
80
, I
\, "," ~ II +-
\
60
" i
\
60
.:
40 \ ;" "I
", 40
\
",
\~ \ ..................---
20
~ 20
WF
40 60 80 100 120 140 160 180 200 220 190 210 230 250 270 290 310 330 350 370
Wave number [em-l] Wave number [em - l]
Figure 3 - Reflectivity curves versus wavenumber for sev-

eral temperatures between SOK and lSSoK. Dots are experi-
mental points. Solid curves are calculated. The position
of Fermi level is shown as wF'
Other spectra at intermediate temperatures were measured and

analyzed, but need not be shown here. In this figure dots re-
present experimental points at one wavelength. The full line
is a theoretical fit, calculated from equations (11,12) using
the relations:
£"(w) 2 2
2nK, £ 1 (w) n - K , (13)
and
(n - 1)2 + K2
R (14)
(n + 1)2 + K2 '
where n is the refractive index, K the extinction coefficient,

and R the reflectivity.
One should note that £00 cannot be given directly by reflec-
tivity curves for w » wTO as in the case of finite gap semicon-
ductors where E » ~wTO and where direct plotting of the square
of refractive index versus A2 extrapolates to £00' Here, the
complicated variation of ~£inter makes it necessary to treat £00
236 M. BALKANSKI
as a fitting parameter. The best fit for parameters Eoo and r
was calculated by a computer procedure. Variations of Eoo
strongly influence the form and position of the high energy re-
flectivity minimum, especially at low temperatures and the ab-
solute value of reflectivity on the high energy side. Eoo is
therefore determined with a computational uncertainty of ±0.5.
Parameter r is quite sensitive to the plasmon edge. Therefore,
at low temperatures (So, 30° and 5S0K) where this edge is not
observed, no values for r can be given. In the reflectivity
fit, at low temperatures, the computed reflectivity is somewhat
higher than the observed-data near the lattice LO phonon fre-
quency: reflectivity minimum.
The qualitative features of the reflectivity spectra shown
in figure 3 are readily apparent: (i) The phonon mode spectrum
which is isolated at SOK, then mixed in the plasma mode at high-
er temperatures, but always visible in the region 100-130 cm- l ;
(ii) The variation in frequency of the plasmon-phonon minimum
with increasing temperature, which are directly observable at
S7°K and above; (iii) At intermediate temperatures, a more com-
plicated structure around 100 cm- l is due to the interaction of
of plasmon modes with two phonon-like oscillators, as is discus-
sed later on.
On figures 4 and 5 two typical results are presented for the
150...--------r-------r--------,
E"
E"
,r,\
E'" +E"
100 0.10
,,, ,
I \
~ I \
\ ~~
,, ,
\
so \ 0.05
I \
\
, ...
./,.,1,' '- --
80 120 160 200
Wave number [em-I]
Figure 4 - Imaginary part E" of the dielectric function

(solid line) and Im(-E-l) = E"/(E"2 + E'2) (dashed curve)
versus wavenumber at aOK, obtained by Kramers-Kronig ana-
lysis of the experimental reflectivity curve. Maxima of
E" and E"/(E"2 + E'2) correspond to nTO = 117 cm- l and
nLO = 132 cm- l respectively.
HOOK
120 004
EA' en
-::lIz+e,z
90
l\ 1\ 003 ~
'tv~
!\
'tv
1\
60 002
J
" I· ./ \~ 001
~.\ ~/"
.... .
• I N •• " ...... '"'"'- ____ _
'--.--
so 100 150 200
Wave number [em-I]
Figure 5 - Imaginary part E" dielectric function (solid

line) and Im(-E- l ) = E"/(E"2 + E'2) (dashed line) versus
wavenumber at 110oK. Curves are obtained from equations
(11,12). Black points and squares were obtained from
Kramers-Kr6nig analysis of experimental reflectivity at
110oK. Two transverse modes (corresponding to maxima in
E") rll = wTO and rl2 are present, as well as three longi-
tudinal solutions (maxima of E"/(E"2 + E'2».
values of Im(-E- l ) = E"/(E"2 + E'2) and E" derived form reflec-

tivity curves at SOK and 1100K by Kramers-Kr6nig analysis.
Maxima of E" correspond to the frequency of transverse (dis-
sipative) oscillators. The crystal TO frequency is thus visible
as a strong peak in E" at rll = wl/2rrc = 117 cm-l at SOK and l1S
cm- l at 110oK. We may note that the result for rll is in good
agreement at SOK with Raman scattering measurements [12]. A dis-
tinct maximum rl2 appears in E" at slightly smaller wavenumbers.
The variation of rll and rl2 is given in figure 6. Points on the
rll and rl2 frequency curve versus temperature at 30 0K and 5SoK,
where Kramers-Krtsnig inversion could not be performed, only
represent the frequencies that had to be introduced into the re-
flectivity fit to account for the variation of reflectivity in
this region.
Maxima of the E"/(E'2 + E"2) = Im(-E- l ) curve are connected
with oscillators having longitudinal polarization character. At
SOK, only the LO phonon mode is clearly apparent. At higher
temperatures, e.g. 110oK, two principal maxima correspond to rl+
and rl_ plasmon-phonon coupled modes [13,14], whereas the small
maximum at ~l07 cm- l is connected with another mode rl2'
The parameters of those oscillators are evaluated in the fol-
lowing way: The background coming from the interband and intra-
238 M. BALKANSKI
120 __ x___x______ ___ ox__

x
!:""'
I x_-_x--- x--x--
! )10"'-
cf 11
105
.-.--.-............
"'-~
!:""'
I
! 100
a
........
95
SO 100 ISO 200 250 300
T[OK]
Figure 6 - Temperature dependence of nl and n2 modes.

Experimental values obtained from Kramers-Kronig analys-
is of reflectivity data are marked as crosses (n l ) and
black squares (n2)' Curve of n2(T) was extrapolated in
the temperature region below 30 o K.
band contribution to (" is subtracted and the remalnlng peaks

are decomposed into two Lorentzian curves. The temperature de-
pendence of the damping parameters fl and f2: half-width of the
(" peaks associated with the nl, TO phonon, and n2 modes, is ex-
hibited in figure 7. The oscillator strength is derived from
the ("(w) curves, by the usual formula
F = ~f ("(w) dw. (13)

11 w
peak
Fl, the oscillator strength of the fundamental TO phonon, is

practically temperature independent: Fl = 4.7. On the contrary,
F2 is strongly temperature dependent and weaker in intensity. The
dielectric constant jump (~F2) due to this mode is larger than
unity above 87°K which denotes a fairly strong oscillator.
An interesting qualitative feature is the fact that, as the
temperature increases and N (number of electrons per cm 3) grows,
the n- solution for a plasmon-phonon modes (near to the first
reflectivity minimum just below 100 cm- l ) comes closer and clos-
er to the first reflectivity maximum just above 100 cm- l repre-
sentative of mode n2 but does not pass it. This type of inter-
action with the free carrier plasma suggests a transverse char-
acter for mode n2.
20
IS
!g(' 10
"5.
o
'S
o 300
Figure 7 - Temperature dependence of damping parameters

rl and r2. Black points and stars correspond to the half-
width of £"(w) for nl and n2 (Kramers-Kronig analysis of
reflectivity spectra). Open circles are the extrapolated
values used in the theoretical fit.
4. PLASMON-PHONON COUPLING
In a simple model with one LO and one TO frequency, one should
expect two singularities [13,14] as two maxima of the function
Im(-£-l) representing longitudinal modes. Those frequencies gen-
erally labelled n+ and n_ correspond to longitudinal oscilla-
tions with the lattice and electron plasma vibrating respective-
ly in phase and 180 0 out of phase [15].
In HgTe, the situation is more complex: due to its band struc-
ture, the contribution t.£"inter(w) must be included. Moreover,
it is necessary to include another oscillator n2 with strong pol-
ar character. This is demonstrated in figure 8 where are plotted
as dots the square of the wave-number of the maxima in [£"/(£"2 +
£1 2 )] (I~(-£-l) versus carrier concentration in units of Ne 2/
na 2mc . Arrows indicate the temperature corresponding to experi-
mental data. Those points correspond to longitudinal solutions.
Stars indicate experimental maxima of £". Lines are the computed
values of the maxima of £" and ImC-c l ). The existence of three
longitudinal solutions is evident on curves of £1 computed by
Kramers-KrBnig inversion (figureS).
It is clear from all experimental evidence presented here that
in order to account for the behavior of a zero gap semiconductor
in the infrared region of the spectrum, it is necessary to con-
sider the contribution of electrons when one discusses the phonon
240 M. BALKAN SKI
-e-L
::;-'6 --O--T
I
'8
175.
4
150;/
130;"/
3 110;/
87~
2.J:....---
1
*- -- -- -~- -:a::.=a- -a==--e==-=-===-t;
::::a::.=a=t:.a. •..----.._..--==....-""-==...-_••,_
o 20 40 60 80 100
Figure 8 - Plasmon-phonon dispersion curve. Black points

and stars correspond to longitudinal and transverse modes
respectively (maximum of experimental £"/(£"2 + £'2) and
£'(w) curves, see figure 5). Solid and dashed lines
correspond to longitudinal and transverse solutions of
equations (11,12). Absolute temperatures are indicated
(arrows) for each experimental point.
spectrum.
No satisfactory fit of reflectivity curves is possible if one
does not take into account the contribution ~£inter at all tem-
peratures, but, especially at low temperatures where ~£inter has
a strong variation in the reststrahlen region. ~£inter varies
significantly in this wavelength region between SO and SOoK.
The values for WTO and WLO at SOK are: WTO = 117 cm-l,wLO 132
cm- l , and the value for £00 can be taken as 10.4 ± 0.5 at low
temperatures. At higher temperatures plasmon-phonon coupling
occurs and WLO loses its meaning as purely mechanical mode:
this frequency shifts then with carrier concentration.
In the low energy region the contribution of ~£inter is the
dominant contribution in the determination of the frequencies
of the Q_ mode. On the high energy side, especially in the case
of high temperatures or strongly doped crystals, ~£'inter is al-
mos t flat and of the same order of magni tude as £00 (e. g.: M.' inter =
7; £00 = 7 at 400 cm- l and 300 o K) and the total ~£'inter + £00 =
14. It would be a mistake to use this value as a 'phenomen-
ological' £00 for the application of Drude - Zener theory to
free carrier absorption because, at this temperature and wave-
number ll£"inter is still about 2. Direct use of the Drude-
Zener theory under those conditions would, for instance, lead
for this reason to erroneous values of me '-' calculated by this
method.
With the form for ll£inter' on the contrary, this fit can al-
ways be done within the limits of experimental error, with the
notable exception of the ~+ reflectivity minimum where a better
fit would imply modifying the value of ll£inter in this region.
One is aware, at the start, that the way we wrote the value of
£(w), in equation (1), implies that the adiabatic approximation
is valid and that all oscillators are independent. This clearly
must not be the case, especially when the interband transitions
have a value close to the LO phonon in the material. Among
other things, a breakdown of the adiabatic approximation would
be equivalent to modifying the wavefunctions of electrons and
therefore the matrix elements, especially for hWF < ~WLO. At
the present time, no complete theory to our knowledge has yet
been published although work is in progress on this point [16].
For lack of other information, we therefore treated the problem
as an adiabatic one, suggesting that the small discrepancy be-
tween experiment and best-fit at the LO reflectivity minimum is
due to a partial breakdown of this approximation.
5. MODES DUE TO IMPURITIES

An interesting problem is the orlgln of the ~2 oscillator.
This oscillator is fairly strong: F2 > 1, at high temperatures.
It couples with the plasmon mode and gives an ~+ mode between
~2 and ~l (TO). Its oscillator strength increases with tempera-
ture. It becomes so weak at gOK as to be unobservable. Such a
mode is present apparently in CdO.2HgO.aTe [17] although the
authors do not draw attention to it. We do not plan here to
give a definite explanation for its origin, but rather list some
possibilities in order of increasing likeliness. It is diffi-
cult to assign this mode to some electronic process because of
its temperature dependence and polarization character. For the
same reason, and also its intensity, multiple-phonon absorption
is unlikely: either addition or difference processes would have
different temperature dependence, whatever the frequencies used.
Phonon excitation at the edge of the Brillouin zone can be in-
duced by a high density of impurities and have been observed in
non-polar [18] and polar [19] crystals at points of high density
of states. Those peaks are, as a rule, orders of magnitude sma~
ler (a few cm- 1 ) and in the case of HgTe, they would imply an ex-
tremely large number of defects. This explanation cannot never-
theless be ruled out, despite the temperature variation of F2.
A gap mode would be a more satisfactory explanation. A cal-
culation based on a simple model [20] shows that the local mode
of Te substituted to Hg falls outside the phonon frequency gap.
On the contrary, Hg substituted to Te would give a gap mode at
105 cm- 1 (as compared to ~2 = IDS cm- 1 at low temperatures).
242 M. B~Sn
Actu~lly, this may be coincidental since apparently the density

of defects is high enough for the wavefunction of the corre-
sponding phonons to extend to neighboring defects sites. In
this situation the wave can propagate and have transverse and
longitudinal character. Therefore, those frequencies, calcula-
ted for local modes, must be taken only as approximation for a
high density of defects.
It is possible to build up a model for electrically neutral
Mercury substitutionals with Hg in the so-called 'monovalent
state'. A (2Hg)++ complex has long been known to exist and com-
pounds like Hg2S and Hg2Se have been prepared [21J. Here, a
high concentration of Hg in the (2Hg)++ valency state would be
the kind of defect least likely to affect electrical properties,
since it would amount to a solid solution of Hg2Te in HgTe; this
type of defect would arise by substituting Hg to Te into 3(HgTe)
pairs, thus giving 2(Hg2Te). Unfortunately, evidencing this
hypothesis is not straightforward and we can only suggest it as
a possibility. Additional weight is given to this explanation
by the tact that HgTe grown from stoichiometric melts is con-
sistently p-type: indeed creation of Hg2Te defects in HgTe leaves
extra Tellurium as a p-type doping agent. Those defects would
be then responsible for the n2 mode which we also observed by
reflectivity experiments in HgTe crystals grown from the melt by
the method of Bridgman.
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(eds. Maradudin, A.A. and Nardelli, G.F.), p. 367.
16. Sherrington, D. (1972). J. Phys., C4, 2771.
17. Carter, D.L., Kinch, M.A. and Buss, D.D. (1970). ThePhysics
of SemimetaZs and Narrow-Gap Semiconductors 3 Proceedings of
The Conference at DaZZas 3 Texas 3 1970, (eds. Carter, D.L.
a~d Bate, R.T.), p.- 273.
18. Ba1kanski, M. and Nazarewicz, W. (1962). J. Phys. Chem.
SoZids, 23, 573.
19. Slack, G.A. and Roberts, S. (1971). Phys. Rev., B3, 2613.
20. Gaur, S.P., Vete1ino, J.F. and Mitra, S.S. J. Phys. Chem.
SoZids, (to be published).
21. A number of references can be found on this point, for
instance, in: Pascal, P. (1962). Nouveau Traite de Chimie
MineraZe 3 VoZ. 5, (Masson, Paris),
LIGHT SCATTERING IN SOLIDS
M. BALKANSKI
Laboratoire de Physique des Solides,

universite de Paris VI, France
1. INTRODUCTION
A powerful way of investigating the fundamental properties of
condensed matter is to consider the interaction of the radiation
field with the solid. This interaction appears generally in two
types of phenomena: resonance and scattering.
The resonance spectroscopy has many different aspects all ba-
sed on well established experimental techniques such as optical
absorption and emission, electron spin resonance, nuclear mag-
netic resonance.
The scattering spectroscopy is newer in the field of solid
state physics but shows an extraordinary vigor of development
these latest years.
We shall be concerned here essentially with light scattering
and to begin with we shall briefly compare the optical'absorp-
tion and light scattering.
1.1 COMPARISON BETWEEN OPTICAL ABSORPTION AND LIGHT

SCATTERING
In both phenomena momentum and energy conservation principles
are obeyed. The selection rules for optical transitions and
light scattering are established on the basis of symmetry con-
siderations. The probability amplitude is proportional to ma-
trix elements of the form
(fIKli),
where i and f denote the initial and final state wave-functions
245
246 M. BALKANSKI
respectively, and 1C the perturbation operator which for optical
absorption is the electric dipole moment V and for light scat-
tering is the polarizability tensor n.
The crystal being subject to a group G of symmetry elements
the wavefunctions i and f belong to the vector space defining a
representation ri of the group. The condition for (fIXli) i 0
is to have in the decomposition in a direct sum of irreducible rep-
resentations of the direct product rf®r an irreducible repres-
entation contained in rio
V transforms like xyz coordinates of a space point by the sym-
metry operations of the group. It is then easy to establish
which is the allowed processus for an optical transition knowing
the initial and final states. These conditions are simple and res-
trictive. It is impossible to sort out from a large set of eq-
uivalent possibilities.
For the light scattering the selection rules are different
and often complementary. The symmetrical tensor n transforms
like the vectorial space of six functions
222
x, y, z,
xy, xz, yz.

To establish which processes will be active in light scattering,
it is necessary to see how the six dimensional vectorial space
is transformed by the operations of the space group of the crys-
tal under consideration. In light scattering one is then more
specific on the space configuration of the perturbation. The
informations obtained are richer and complementary to that given
by the optical absorption.
1.2 DIFFERENT LIGHT SCATTERING EFFECTS

When a beam of monochromatic light passes through a trans-
parent medium, a small part of the light is scattered in all di-
rections with changed frequencies. The scattering processes are
usually classified into three groups: Raman, Brillouin and Ray-
leigh scatterings.
In Raman scattering the frequency of the scattered light dif-
fers from that of the incident light beam by the frequency of an
optical phonon or an elementary excitation polarizing the lattice
in a similar way. The Raman scattering is independent of the
scattering angle:
~WS(Raman) = ~wi ± ~Woptical phonon'
Light is then scattered with relatively large frequency shifts,

independent of scattering angle, but the possibility of observ-
ing a given transition depends on the orientation.
In Brillouin scattering the frequency of the scattered light
LIGHT SCATTERING IN SOLIDS 247
differs from that of the incident light by the frequency of an
acoustical phonon or analogous elementary excitation and it var-
ies continuously with the scattering angle:
~WS(Br l'11 OUln

. )(8) ~Wi ± ~Wacoustical phonon'
Brillouin scattering occurs with small frequency shifts, varying

continuously with scattering angles.
In Rayleigh scattering the frequency of the scattered light
is independent from nature of the scattering particle or the an-
gle of scattering, it only depends on the efficiency of the scat-
tering. Rayleigh scattering occurs then without frequency shifts.
Let us consider some applications of these different types of
light scattering.
2. RAYLEIGH SCATTERING
When light which is not absorbed by a medium passes through
the sample almost the whole of the light beam is unaffected, but
a very small part of it will be scattered in directions different
from that of the incident beam. The part of scattered light
which has the same frequency as the primary light has suffered
Rayleigh scattering.
It is easy to calculate the total amount of light energy per
second scattering in all directions by a single atom. If the atom
is considered as a single oscillator and neglecting damping, one
gets classically:
This result shows two aspects: the total energy that is scatter-
ed is proportional to the incident energy per square meter (~£O
cE02) and to the cross section for scattering Os = ( I nro2/3)
[w4/(w2 - w02)2].
We see thus that the intensity of Rayleigh scattering is prop-
ortional to the fourth power of w. If white light is used the
blue end of the spectrum is scattered more intensively than the
red one, this is why the sky is blue.
In Rayleigh scattering the polarizability is regarded as hav-
ing no time dependence. The induced electric moment oscillates
with the same frequency w as the incident light and radiates
scattered light also at this frequency.
Let the system, molecule or atom, which scatters the light be
fixed and be irradiated with natural light along the positive y
direction (figure 1). Each one of the components of the elec-
tric field vector will induce oscillating electric moments.
Since an oscillating moment cannot radiate in its own direction
only the Py and Pz will contribute to the scattering in the x
248 M. BALKANSKI
Figure 1 - Polarization of Rayleigh scattering for natur-

al incident light, after Woodward, L.A. (1967). Raman Spec-
troscopy, (ed. Szymanski, H.A.), (Plenum Press, New York).
direction. The contributions will be plane polarized with their

electric fields in the y and z directions. The ratio of the
scattered intensities IylIz is known as the degree of depolariz-
ation of the scattered light. When the scattering molecule is
isotropic the Rayleigh light is completely polarized. In a flu-
id when the constituents are freely rotating the Rayleigh scat-
tering corresponds to the average over all molecular orientat-
ions.
The polarizability variations can be related to density fluc-
tuations.
The Rayleigh scattering as well as the Brillouin scattering can
be seen as scattering on the fluctuations in densi ty and the lines
are therefore completely polarized. The intensi ty of the scattered
light can be related to fluctuations in pressure and entropy which
are expressed in terms of known thermodynamic parameters.
Near the critical point of second order phase transition for
instance, the order parameter describing the system shows very
large amplitude fluctuations which relax back to equilibrium
more slowly as the critical point is approached. The studies of
the intensity and frequency distribution of light scattered near
the critical point provide detailed information on the diverg-
ence of the fluctuations and their relaxation times in fluids.
LLGHT SCATTERING IN SOLIDS 249
Analogous behavior is to be obser~ed near points of phase tran-
sitions in solids [1].
3. BRILLOUIN SCATTERING
Brillouin scatterin~ is characterized by a small frequency
shift varying with scattering angle caused by thermal fluctua-
tions in the medium.
Let us consider a thermal or 'Debye' wave at frequency Ws
propagating with velocity ±V as shown in figure 2.
-v
£Os. As....LI_ _ _ _ _
!'-1_ _ __
~
----- /)
~w.±~ I <I>
Figure 2 - Diagram showing light scattering at angle 8

(and Bragg reflection at ~) by moving thermal waves, after
Stoicheff, B.P. (1968). Proceedings of the International
Conference on Molecular Spectroscopy, Brighton, April
1968, (ed. Hepple, J.). (The Institute of Petroleum, Great
Britain), p. 261.
Light with incident frequency wo interacts strongly with waves

satisfying the Bragg condition: Ws = 2wo(V/c)nxsin(~8). Since
the thermal waves are moving with velocity ±V the scattered
light suffers a Doppler shift in frequency and exhibits a fre-
quency doublet at the angle 8 given by
This is the Brillouin equation.[2].

In terms of quantum mechanics, Brillouin scattering corres-
ponds t~ scattering of incident photons of frequency wo and wave
vector ko with creation of acoustical normal modes, phonons (ws
and q) and scattering of a photon (w' and k') with angle 8 (fig-
ure 3).
The predicted Brillouin spectrum is shown in figure 4, it con-
sists of Stokes (wo + ws ) and anti-Stokes (wO - ws ) components.
The frequency shift ~w for a well defined scattering angle 8
gives directly the phonon frequency and velocity. The width r
of the Brillouin component of the spectrum is a measure of the
damping or attenuation of the wave. Thus Brillouin scattering
250 M. BALKAN SKI
phonon
w,q
/
Incident photon
f\JV\.JV-----T
wo, ko
Scattered
photon
w',k
Figure 3 - Schematic representation of light scattering

by acoustical phonons.
Exciting frequency
Wo Brillouin shift
I---- Ws ---111---- Ws ----l
Figure 4 - Diagram of the predicted Brillouin spectrum,

after Stoicheff, B.P. (1968). 'Brillouin Spectroscopy with
Lasers', Proceedings of the International Conference on
Molecular Spectroscopy, Brighton, April 1968, (ed. Hepple.
J.), (The Institute of Petroleum, Great Britain), p. 261.
opens the whole field of 'acoustical spectroscopy' whose possi-

bilities are very broad now that lasers are available as light
sources.
Brillouin scattering is not only a powerful analytical means
for investigation of dispersion relations of acoustic waves, for
obtaining informations on molecular motions or molecular struc-
tures, for studying the physical properties of media which af-
fect the velocity of acoustic waves, but leads also to the pos-
sibility mentioned by A. Kastler [3] to generate hypersonic
waves.
The Brillouin shift being relatively small the experimental
conditions are quite restrictive. For liquids for example the
velocity of light being ~I05 cm/sec and the refractive index ~l,
for back scattering (8 = 180°) of optical radiation with freq-
uency wo 5 x 1014 cm/sec, Ws = 2 x 5 x 1014 x 10 5/3 x 1010 'V 3 x 10 9
cm/sec'V 3 Gc/s or 0.1 cm- l which demands high resolution spec-
troscopy. The requirements are: intense monochromatic exciting
radiation (laser source) well defined, accurately measured scat-
tering angle.
Laser excitations, Fabry-Perot interferometers and sensitive
detection make out of Brillouin spectroscopy an extremely power-
ful tool into phase transitions. An anomalous change in the fre-
quency shift of both the longitudinal and transverse Brillouin
compounds with temperature has been found in ferroelectric phase
transition. Figure 5 shows the results of Gammon and Cummins [4]
on triglycine sulphate.
A sharp discontinuity of the intensity ratio of the Rayleigh
to Brillouin scattering is formed near the glass transition temp-
erature of polyethyl methacrylate [5] shown in figure 6.
These are only few examples of the use of light scattering in
the study of critical phenomena.
4. RAMAN SCATTERING
The essential difference between Brillouin and Raman scatter-
ings resides in the fact that the incident light is scattered
with relatively larger frequency shifts, independent of scatter-
ing angle which implies that the scattering is due to phonons of
higher frequencies corresponding to rotational and vibrational
transitions of individual molecules and optical normal modes in
solids. The interaction of light with the crystal corresponds
to creation or annihilation of an elementary excitation which can
be a lattice vibration but also localized electronic states, pol-
aritons, spin waves, plasmons, Landau levels, etc ..
The specific time dependent polarization corresponding to
each type of elementary excitation which renders it Raman active
contains important physical informations leading to better un-
derstanding of these phenomena. With the powerful means of Ram-
an spectroscopy available now the accumulation of accurate ex-
perimental data suscites a great interest on the side of theor-
ists and provides one of the most promising methods of investi-
gation into the elementary excitations of matter.
The diversity of fundamental processes for which Raman scat-
tering is a suitable probe bring it to the stage of a most gen-
eral method of investigation.
4.1 LIGHT SCATTERING FROM PHONONS

Each elementary Raman scattering event involves the destruc-
tion of a photon of frequency Wi, incident from a light source,
the creation of a scattered photon of frequency ws , and the cre-
ation or destruction of a phonon of frequency w. We choose to
consider here only the Stokes component of the scattering, so
that Wi = Ws + w. The properties of the anti-Stokes component
can always be obtained by simple substitution.
252 M. BALKANSKI
., • .
.510
•
V ----...
.,•r
.509 Longitudinal
(j = 90° •
.508
::-
•
!
7
I
.507
a
<J
.j .
.506 •
• •
.505
_e_e_e
.504 •
• •
34 38 42
r
.230
Transverse
/J = 90°
.226
•
.222 J
r
::-
I
8
.£.
a
<J .218 •
•
~.
"- I
.. ~"-.)
.214
.210 •
34
TeC)
Figure 5 - Graphs of Brillouin shift versus temperature

for longitudinal and transverse components (at a scatter-
ing angle of 90°) of the ferroelectric crystal triglycine
sulphate, after Gammon, R.W. and Cummins, H.Z. (1966).
20
19
18
17
16
15
N'"
::9
14
13
12
11
10
20 30 40 50 60 70 80 90
Temperature °C
Figure 6 - Graph of the intensity ratio of Rayleigh to

Brillouin scattering, Ic/2Ib versus temperature near the
glass transition temperature of polyethyl methacrylate,
after Peticolas, W.L., Stegeman, G.I.A. and Stoicheff, B.
P. (1967). Phys. ReV. Lett., 18, 1130.
Figure 7 illustrates the Raman scattering process in terms of

the elementary interactions between the radiation, the electrons
and the lattice. This explicitly assumes that in Raman scatter-
ing the light interacts with the lattice vibrations through the
intermediary of the electrons in the crystal.
Most theoretical work on Raman scattering explicitly assumes
that the radiation interacting with the lattice vibrations goes
254 M. BALKANSKI
Figure 7 - Diagram representing the scattering of a phot-

on wi by a phonon w, after Loudon, R. (1964). Adv. Phys.,
13.
through the intermediary of the electrons in the crystal. The

virtual intermediate states involve the excitation of electron-
hole pairs which may be interacting or free. The problem of
calculating the scattering intensity has been considered in many
different ways. We shall only briefly sketch here the method
used by Loudon [6]. The Raman scattering tensor is obtained in
treating the three steps scattering process by third order time-
dependent perturbation theory. This approach uses second quan-
ization of the radiative field to calculate the probability per
unit time liT that one of the incident photons is destroyed in
a Raman scattering process, given by the usual third order ex-
pression
1 271
T = n6
(Ui - l,l;no + l;oIHil a )(aIHil b)(bIHil ni,o;no;o) 2

x L (w a - wi)(wb - wi)
a,b
where ni, 0 and nO are the numbers of incident photons, scatter-

ed photons and optical phonons, a and b run over complete sets
of intermediate states Hi = HER + HEL' The HER part contributes
in two of the matrix elements while i t is the HEL part which con-
tributes in the third matrix elements. The final zeros in the
initial and final states quantum numbers indicate that the elec-
trons are in their ground state before and after the scattering
event.
Evaluation of the summations and the matrix elements lead to
the scattering efficiency. Numerical estimations indicate that
Raman scattering efficiency may typically be of order 10- 6 or
10- 7 .
When the incident radiation frequency wi approaches the fre-
quency of an intermediate electronic state wa b one runs into a
resonant behavior. '
4.1.1 Resonant Raman Effect

The resonant Raman effect has proved to be an useful tool for
investigating electronic states in solids because of the spec-
ific way they intervene in the Raman scattering amplitude. Let
us just consider two cases as an example of intermediate state
interactions in resonance Raman scattering [7].
If we write the amplitude of Raman scattering by phonons in
an abbreviated form '
with PbO the dipole matrix element between ground state 0 and an
intermediate state b, Dab matrix element of an electron-phonon
interaction operator between intermediate states, and Pfa the
dipole matrix element connecting the intermediate state band
the final state f.
In the case of a non-interacting Bloch picture for an insu-
lator with two simple parabolic energy bands, one can easily
calculate the frequency dependence of the scattering amplitude
as the incident frequency approaches the direct gap, wi ~ wg ,
In the Bloch picture then there is an enhancement, but no

singularity in the Raman amplitude as wi ~ Wg.
In the case of intermediate state interaction exciton picture
the electron and hole are taken to interact via their screened
Coulomb interaction. The spectrum of energy states is now a
continuum plus the discrete states of a single exciton series.
The entire discussion of the previous picture is then changed
qualitatively. The Raman amplitude becomes,
where RI is the exciton Rydberg. Damping must round off the di-
vergence and a phenomenological damping constant can be added to
this equation.
The critical role which the intermediate state interaction
has in producing the difference between these two expressions is
evident. Owing to the intermediate state interaction the inter-
mediate density of states changes which converts the non-singu-
lar behavior of the Bloch picture to the divergence (modulo dam-
ping) in the exciton picture.
Thus Raman scattering not only informs about the particle en-
ergy hwO from which light is scattered but also about details of
intermediate state interactions and consequently about the nat-
256 M. BALKANSKI
ure of the intermediate states.
4.1.2 Selection Rules

Not all the phonons scatter light. The Raman active lattice
vibrations are determined by selection rules established by stan-
dard group-theoretical methods. It is shown that a phonon can
participate in a first order Raman transition if and only if its
irreducible representation is the same as one of the irreducible
representations which occur in the reduction of the represent-
ation of the polarizability tensor.
The intensity of Raman scattering depends in general on the
directions of observation and illumination relative to the prin-
cipal axes of the crystal. The angular variation of the scat-
tering gives informations about the symmetry of the lattice vi-
bration responsible for the transition.
Thus if, for example, the only changing components in the
polarizability tensor are xy and yz for a given lattice vibra-
tion, to observe the Raman effect of that phonon we first ar-
range the polarization of the incoming laser radiation parallel
to the x axis and observe the scattered light with its polar-
ization in the y direction and vice-versa. One thus determines
the Raman-active phonons with each of which we can associate a
polarizability tensor and a definite symmetry.
Multiphonon processes are studied in a very analogous way
with the difference that the energy and momentum conservations
concern all the participating phonons.
The presence of impurities in a lattice gives rise to local-
ized vibrational states whose specific Raman effect allows the
identification of the impurity and the precise description of
its environment.
4.1.3 Ferroelectric Phase Transition

Light scattering is widely used as a method of investigations
of phase transitions. We shall consider here as an example the
ferroelectric phase transition.
In approaching the critical temperature in SbSI for example
one observes a frequency shift of the low frequency Raman active
TO mode centered at 45 cm- 1 . The apparent soft mode behavior
has been shown to consist in fact of a frequency shift and mode
coupling between two optical modes exhibiting level repulsion
and exchange of intensities [8,9] as it can be seen in figure 8.
4.2 LIGHT SCATTERING FROM MAGNETIC EXCITATION

In an ordered magnetic material like the ferromagnets such as
Fe, Ni the non-zero atomic spins are all parallel with the same
orientation whereas in the antiferromagnets like MnF2, FeF2 the
spins of the successive magnetic ions are anti parallel and in
ferrimagnets the antiparallel spins are of different magnitude.
Any misorientation of a spin gives rise to a travelling wave as
the spins are all coupled. Such a spin wave or magnon scatters
o C
- D '_ _
._~~
o B o
~ D------~~---a
o A
I 30 o • 000
Ei
~
8
20
10
25 20 15 10 o
Figure 8 - Frequency shift of the three lowest-frequency

optical modes as a function of ~ = Tc - T. The variat-
ion of T is induced by hydrostatic pressure. The closed
circles and the triangles represent data obtained at T =
oOe and T = 1. sOe, respectively; the stars and open circles re-
present data at T = 3°e. For comparison, data obtained with P
200 bar and represented by the squares are also given in
the same curve.
light very much like the phonons. An increase of temperature

generally destroys the magnetic order. In decreasing the temp-
erature magnetic ordering takes place at the Neel temperature
TN' The dispersion relations of magnons are generally not flat.
First order light scattering concerns magnons at the center of
the Brillouin zone and second order light scattering comes from
combinations of zone boundary magnons.
In recent years a consistent effort has been developed [10]
to understand light scattering by spin waves, exciton-magnon
coupling and localized magnons in different temperature ranges
and magnetic fields.
For an antiferromagnet for example there are three ranges of
temperature and three of magnetic fields which are of interest
for mag non behavior:
258 M. BALKAN SKI
and
H = 0, He < H < H'.
He defines the first order AFM-SF transition and H' defines the
second order SF-PM transition.
The particular spin arrangement in a system depends upon both
Hand T as well as on particular values of the exchange and an-
isotropy parameters in the spin Hamiltonian. The magnon disper-
sion relations are quite complicated in general and combined ex-
perimental and theoretical efforts are necessary to come to a
clear picture.
To show how specific Raman scattering be in such an investi-
gation we should take as an example the one magnon spectrum of NiF2
at low temperature and under an external magnetic field. The
mag non branch Ek± is degenerate only at the Brillouin zone boun-
daries and split quite noticeably at small k's. The spin motion
excited in the + and - modes resemble respectively antiferromag-
netic-like (AFM) and ferromagnetic-like (FM) motions in simple
systems. The AFM mode scatters strongly when both incident and
scattered photons are polarized perpendicular to Hand to each
other (axz); the FM mode scatters most strongly in the ayz pol-
arization as it is shown in figure 9.
4.3 SPIN-FLIP IN SEMICONDUCTORS

Light scattering on free electrons in a semiconductor subjec-
ted to an external magnetic field results into the spin-flip Ra-
man scattering effect. Figure 10 shows this processus for a
Landau level ~ = 0 where the conduction band state 0+ is initi-
ally occupied and the 0+ state empty. An incident photon is ab-
sorbed in exciting an electron from the valence bands to the
state 0+. The electron in the state 0+ recombines with the hole
in the valence band with emission of the scattered photon.
These virtual transitions do not need to obey energy conserva-
tion law, for the intermediate states energy is conserved over
the entire processus. The net energy variation in this proces-
sus is gSH:
The scattered frequency is consequently tuned with the inten-

sity of the applied magnetic field.
At low intensity of the incident light beam the power scat-
tered light beam is linearly proportional to that of the inci-
dent beam: this is spontaneous Raman scattering. When the in-
cident intensity rises behind a certain threshold level, popula-
tion inversion can be reached and the scattered intensity jumps
·bya factor of 103 : stimulated Raman scattering is then achieved.
Figure 11 shows these two regions.
In figure 12 is demonstrated the tunnability range in InSb
Magnon scattering polarizations

NiF 2 -10'K
yliH
AFM
ksc
~IN I
- --
Esc
E
IN
X(ZX)Z
H = 95kOe
30x IO~II
FM
X(ZY)Z
H = 95kOe
30x IO~II
AFM
o 15 45
Frequency shift (cm ~ ')
Figure 9 - One-magnon spectra of NiF2 at lOoK in 95 kOe

field. w+ (AMF) and w- (FM) modes exhibit different pol-
arization selection rules, from Fleury, P.A. (1971). In
Light Scattering in Solids, (ed.Balkanski, M.), (Flammar-
ion, Paris), p. 154.
pumped by a C02 laser.

Spin-flip Raman scattering is also performed in the visible
region of the spectrum with CdS [11] as shown in figure 13.
Such light sources are now used in high resolution spectroscopy
as demonstrated in figure 14 giving a very high resolution spec-
trum of iodine vapor taken with a CdS SFR source.
260 M. BALKANSKI
Energy
n=2
n = 1
n=O
__-L__~______~gPH
"wi = "w, + gPH
_-f'r-::::---------- k z
Figure 10 - Energy band scheme for spin-flip Raman scat-

tering in a semiconductor.
4.4 LIGHT SCATTERING FROM ELECTRONIC EXCITATIONS

When light scattering is considered as a probe for electron-
ic systems a critical magnitude is the characteristic length
Achar which gives the length scale of the medium: interparticle
spacing, screening length, etc .. The parameter kAchar divides
the scattering up into two definite regimes.
For kAchar »l scattering takes place from a single particle
and the scattering spectrum reflects the single particle proper-
ties of the medium.
For kAchar «1 the scattering is from many particles and the
scattering spectrum will reflect the collective properties of
the medium.
In a metallic plasma the interatomic distances and the Thom-
as-Fermi screening length ASC are roughly equal:
Wp is the plasma frequency which sets the characteristic energy

••
......
•
•
•
••
10 •
:;
,e.
::s
0
l;
;J
8. •
i
.9-
c::
(0'
1.3 E 16 g .1 !!
Noncollinear
.~
"
~
~co=:
(0 10'
Relative 10.6/l Power input
Figure 11 - SFR scattered power output at A ~ 11.5 ~ as a

function of pump power at 10.6 ~ (in arbitrary units) for
n-InSb with ne '" 1. 3 x 1016 cm- 3 • T '" 18 K and B '" 40 kG.
The maximum pump power is "'1.0 kW inside the sample and
the maximum SFR laser output is "'10 W peak. from Patel. C.
K.N. and Shaw. E.D. (1971). Phys. Rev .• B3. 1279.
262 M. BALKANSKI
14.6
2SO InSb
n,=2xl016 cm- 3
13.8
200
12.2 .,
1
11.4 ..c:
~
..2
~
~-+---+--+---+---1--+---+--1--+---I1O.6 ~
-50
9.8
-100
-ISO
Magnetic field (kG)
Figure 12 - Tuning curves for anti-Stokes, Stokes, and

second Stokes components of the stimulated spin-flip Ram-
an scattered radiation from lnSb (n e = 2 x 1016 cm- 3 ) pum-
ped with 10. 6 ~ radiation from a high-pressure C02 laser,
from Aggarwal, R.L., Lax, B., Chase, C.E., Pidgeon, C.R.
and Limbert, D. (1971). Appl. Phys. Lett., 18, 383.
scale for the longitudinal collective modes of the plasma.

For atoms or equivalently tight binding electrons in a solid
the characteristic length is crudely a Bohr radius,
-8
AChar < 10 em,
while the characteristic energies range from a few volts for

light elements on up as z increases.
In a solid state plasma, i.e. a doped semiconductor, the
scale of length is quite different. For a typical carriers con-
centration 1015 cm- 3 ,
ICdSI
N = 5x 10 15 cm- 3
To:: 2°K
H = 32.400 Gauss
Slit: 0.8 cm- I
X(Z'X)Z
<((i,H) = 4SO
Anti-stokes
-5 -2.5 o 2.5
Frequency shift in cm - I
Figure 13 - Spin-flip Raman scattering in CdS in the

X(ZX)Z configuration. The excitation line is completely
attenuated through an adequate heating of the I2 cell.
For light the typical wavelengths are 10 4 X and the k's are cor-
respondingly in the range of 10 5 cm- l . The solid states plasma
are conveniently investigated for their collective mode scatter-
ing by light. In figure 15 is presented a typical light scat-
tering spectrum where the peaks are related to the longitudinal
264 M. BALKAN SKI
10 15 20 25 (kG)
Vapeur de 12
A
c
I
v
2
A~ 19428, 71 em-I
B~ 19428, 19 "
C~ 19427,74 "
Figure 14 - High resolution spectra of I2 vapor around

5145 Aobtained through spin-flip Raman scattering in
CdS. The frequency shifts from excitation line are de-
duced from the magnetic field by taking a g-factor value
of 1.76. Negative frequency shifts correspond to anti-
Stokes line and positive ones to the Stokes line.
and transverse phonon frequencies and to the plasma frequency of

the electron gas. At low carriers concentration the two peaks
represent the La and TO modes. As the carriers concentration
increases the LO phonon mode begins to couple to the plasmon and
the coupled plasmon-phonon mode w+ and w_ appears on both sides
of TO.
For the investigation of metal plasma and atoms inelastic x-
ray scattering becomes far more appropriate [12]. Indeed a typ-
ical X-ray source of 10 keY has a wavelength of approximately 1 X
and corresponding wavevector k = 109 cm- l and will allow to
probe the electronic excitation spectrum to really large k or
equivalently down to atomic dimensions.
;.;....------
9.5 X 10 17
1.8 X 10 18
~---------------
I
600
I
550
I
500
I
450 400 350 300 250 200 150
Frequency shift (cm - 1)
Figure 15 - The spectrum of 1 ~ laser light scattered

from n-type GaAs.
In the scattering of X-rays by a single free electron moving

with momentum p the frequency shift of the light is given by
The first term in the right hand side of this equation is the so-
called 'Compton recoil' and the second the Doppler shift due to
the motion of the particle. In the optical regime the h 2 k 2 /2m
term is negligibly small and the Doppler term dominates the sin-
gle particle spectrum.
For X-rays the dominant term in the delta function is the re-
coil energy ER = h2 k 2 /2m. Physically this approximation is eq-
uivalent to consider that the wavelength of the photon is so
small (large k) that it interacts with an individual electron
and ejects it from its bound state instantaneously (large recoil
energy). In this short period the potential energy of interac-
tion remains constant so that one may think of an electron as
free, i.e. moving in a constant potential.
An example of Compton spectrum due to the conduction elec-
trons in Li [13] is shown in figure 16. The difference from the
expected spectrum from free electron gas resides in a high mo-
mentum tail resul ting from two effects: presence of ion poten-
tials and Coulomb interactions among electrons.
l
266 M. BALKANSKI
"
- • L, -[100]
\. o L, - [110] Experiment
\ --- AL,-[l11]
\ _ . - L, -Free electron gas
, \
1.5 \.
1.0
Figure 16 - The Compton spectrum of the conduction elec-

tron in Li metal.
Inelastic X-ray scattering in solids is still a rather new

field and it is clear that it will prove to be an important tool
for obtaining informations about the electronic properties of
solids. An improvement in resolution will allow one to study in
some details the nature of electronic wavefunctions in the neigh-
bourhood of reasonably high temperature transitions.
This brief enumeration of different uses of light scatter-
ing techniques in the investigations of the fundamental proper-
ties of solids is obviously incomplete and aims only to give a
restricted number of examples showing the possibilities and the
power of this method which has been put into great use now.
REFERENCES
1. Ginzburg, V.L. (1963). Sov. Phys. Usp., 5, 649.
2. Brillouin, L. (1922). Ann. Phys., 17, 88.
3. Kastler, A. (1964). C.R. Acad. Sci. (Paris), 259, 4233.
4. Gammon, R.W. and Cummins, H.Z. (1966). Phys. Rev. Lett., 17,
193.
5. Petico1as, W.L., Stegeman, G.I.A. and Stoicheff, B.P. (1967).
6. Loudon, R. (1963). Proc. Phys. Soc., 82, 393; (1963). Proc.
Roy. Soc., A275, 218.
7. Birman, J.L. (1971). Light Scattering in Solids, (ed. Balk-
anski, M.), (F1ammarion, Paris).
8. Harbeke, G., Steigmeier, E.F. and Wehner, R.K. (1970). Solid
State Commun., 8, 1765.
9. Ba1kanski, M., Teng, M.K., Shapiro, S.M. andZio1kiewicz, M.K.
(1971). Phys. Stat. Sol. (b), 44, 355.
10. See for example: Macfarlane, R.M. and Morawitz, H.; Moeh, P.,
Gosso, J.P. and Dugautier, C.; Fleury, P.A. (1971). In Light
Scattering in Solids, (ed. Ba1kanski, M.), (F1ammarion,
Paris)., p. 134; p. 138; p. 151.
11. Amza11ag, E., Dugautiar, C., Moch, P. and Ba1kanski, M. Solid
State Commun., (to be published).
12. P1atzman, P.M., Eisenberger, P. and Tzoar, N. (1971). Light
Scattering in Solids, (ed. Ba1kanski, M.), (F1ammarion, Par-
is), p. 80.
13. Migdal, A.B. (1958). Sov. Phys. JETP, 34, 1438.
RESONANT RAMAN SCATTERING IN SEMICONDUCTORS
M. CARDONA
Max-Planck-Institut fUr Festkorperforschung,

Stuttgart, Federal Republic of Germany
1. INTRODUCTION
The phenomenon of Raman scattering is known since 1928 but in-
vestigations of this effect in semiconductors are relatively re-
cent [1]. While this may be surprising in view of the large
amount of basic research in semiconductors since the discovery
of the transistor, it is due to the fact that the usual semicon-
ductors (Ge, Si, GaAs, etc.) are opaque to the standard radiation
sources. Thus, the scattering volume in which the interaction of
the radiation with the solid occurs is small, determined by the
penetration depth of the radiation (inverse of the absorption co-
efficient) which can be as small as a few hundred X. Therefore,
the scattering efficiency is very weak and studies have only be-
come possible with the advent of strong lasers and spectrometers
with excellent scattering light rejection. The measurements are
usually performed in the back-scattering configuration, in the
manner sketched in figure 1.
The probability of a Raman process in which a photon is des-
troyed, one or more elementary excitations (e.g., a phonon, an
electron-hole pair, a plasmon, a magnon) are destroyed or created,
and a new photon is created, can be calculated by perturbation
theory of the appropriate order. The simplest Raman process is
that of first order in which only one elementary excitation is
involved.
A very simple theoretical treatment of Raman scattering is pos-
sible when the frequencies ni of the excitations are small com-
pared with the relevant electronic frequencies responsible for
the polarizability (the ionic polarizability is negligible in the
usual Raman scattering with visible or nearly visible light).
269
270 M. CARDONA
laser
focusing
lense collecting lense stokes antistokes
sample
f-_-- printer, plotter
Figure 1 - Schematic diagram of a set up used for Raman

measurements in the back-scattering configuration.
Let us consider, for instance, the case of scattering by phon-

ons. Pseudo-momentum and energy conservation are expressed by:
WL Ws + L (±ni) , (la)
i
1<.L 1<.s + L (±cli) , (lb)

i
where Land s refer to the incident (laser) and scattered phot-
ons respectively, ni and qi to the excitations, the plus sign
to a creation and the minus sign to an annihilation of an exci-
tation. Usually, IkLI ~ Iksl is negligible compared with the
typical dimensions of a Brillouin zone, thus equation (lb) re-
duces to:
O. (2)
In first order scattering we only can excite phonons at the cen-

ter of the Brillouin zone; phonons of any q can be excited in
higher order.
Let us consider the phonon displacement ui = uOi exp (±init).
This displacement has been assumed to be very slow and thus it
effectively modulates the electric susceptibility X at the fre-
quency ni:
RESONANT RAMAN SCATTERING 271
d d2
X (W) + ~U·
dUi l + dUidUj
X U'U'
l ]
+ ••••
The induced polarization for an applied field E EO exp(-iwLt)

thus becomes:
(3)
Thus, we have radiating dipoles of frequencies:
These dipoles produce the scattered radiation which, according

to classical electrodynamics, has the intensity:
First order:
Il a: 41 ~
W d 12 (ui 2);
Second order:
(4)
Thus, we see that Raman scattering yields information about the

frequency of elementary excitations, in the case discussed above
phonons. Through the derivatives of X which appear in equation
(4), it also yields information about the electronic transitions
which are responsible for the susceptibility X(w). It is well
known [2] that the susceptibility x(w) exhibits usually weak
singularities at the energy of interband gaps or critical points.
These singularities appear more strongly in a modulation spect-
rum in which the derivative of X with respect to some parameter
(such as the phonon amplitude in our case) is measured [3].
Thus, a measurement of the scattering cross section as a func-
tion of scattering frequency WL = Ws can be used to obtain in-
_formation on the electronic structure in the form of energies
of interband critical points (gaps). Such experiments, referred
to as resonant Raman scattering, require a large number of laser
lines evenly spaced throughout the region of measurement or a
tunable laser such as the recently developed dye lasers [4].
272 M. CARDONA
More information is obtained if the absolute strengths and
the line shapes of the function:
(5)
found in a resonant Raman experiment are analyzed. These de-

rivatives represent changes in the electronic susceptibility
produced by the phonon interaction. In the neighbourhood of a
resonance (critical point) they select the electron-phonon in-
teraction at the states which form the critical gap. By study-
ing the resonances associated with the various gaps available
one can obtain a great wealth of information concerning elec-
tron-phonon interaction.
These qualitative statements can be illustrated by writing
down the expression for X near a singularity:
X = Af(w - Wo) + B, (6)
where f(x) is a function singular at w = Wo and B a non-singular

function which can thus be assumed constant for w in the vicin-
ity of woo From (6), we obtain:
dv
:::..A
du
= -dA
du
dwo
f(w - wo) - Af' (w - wo) -
du
(7)
The derivatives of dA/du and dwo/du are electron-phonon inter-

action parameters. In particular, dwO/du represents the effect
of the phonon deformation on the singular gap and is, in gen-
eral, a difference between the effects on the corresponding con-
duction and valence states (e.g., the phonon deformation poten-
tials of these states). The term dA/du contains effects of
phonon deformations on dipole matrix elements and effective mas-
ses. These effects arise from the mixture produced by the
phonon, of states involved in the gap with states of a third
band. In the language of perturbation theory one thus speaks
of three-band terms. The terms in dwo/du involve only two bands,
one of which is modulated by the phonon. We shall discuss in
sections 2 and 3 two typical but rather different cases of cur-
rent work on resonant Raman scattering.
2. SCATTERING IN HEAVILY DOPED Ge AND Si

As mentioned, first order Raman scattering can be used to de-
termine the frequency of phonons with k = O. This determination
can often be made in semiconductors with an accuracy of about
one part in 10 4 , which is superior to that obtained in neutron
scattering wo£k. (We should, however, point out again that only
phonons with k = 0 are first order active, while the whole phon-
on spectrum is obtained with neutron scattering).
Thus, Raman scattering can be used to determine the effect of
perturbations such as stress [5], temperature [6], and doping
[7]. Figure 2 shows the effect of heavy Ga doping on the
wr-------------------------------------------------------~
•
.. \
I·~
15
d~,
I \.
o \
d· 0 \
I \ \--IntrinSic
0. •
o
oo\•\
..
d ~
orP \
\~/
o '.
\
..\
.
~
'0 ••
•• ~
O~--~----~---t----~--~----~--~~--~----+_--~----~
(w-wo)cm- 1 - - - -
Figure 2 - Effect of doping on the optical phonons of p-

type Ge at k = 0, as obtained in first order Raman scat-
tering at room temperature. The frequency of the phonon
of undoped Ge is 3 cm- 1 . (From reference [7]).
optical phonons of Ge at k = 0, a shift to lower frequencies

(mode softening) and a broadening. The first question which a-
rises is whether this is an electronic effect, due to the added
holes, or an atomic effect of the added impurities. It is easy
to conclude that the former is true since the observed effect
depends only on the hole concentration and not on the specific
acceptor used (AI, Ga, In). A similar effect is observed in p-
type Si (see figure 3). In this case, it has been shown that
this effect disappears upon compensating the material [9], thus
confirming its electronic nature. The effects shown in figures
2 and 3, a shift and a broadening of the phonons due to the
presence of holes must thus be due to the interaction of the
holes with the phonons, i.e., to the self-energy of the phonons
in the presence of holes. A theoretical description of the ef-
fect enables us to determine from the measured shift and broaden-
ing the hole-phonon coupling constant [7]. Actually this de-
scription, in its simplest form [7], is similar to that of the
effect of doping on the elastic constant C44' The optical phon-
on has r2S' symmetry like a pure shear strain along [111].
Such strain (or the phonon distortion) splits the valence bands.
274 M. CARDONA
Si P- Type
T _ 300 oK
1
~
I
o
x
§'"
8
'0
.8E
Z"
(w - wo)cm - '
Figure 3 - Effect of doping on the optical phonons of p-

type Si at k = 0, as obtained in first order Raman scat-
tering at room temperature. The phonon frequency of un-
doped Si is 5 cm- l . (From reference [7]).
After this splitting a lowering of the free energy can be

achieved by bringing all the holes to the higher one of the
split bands. This lowering, quadratic in the strain or in the
phonon displacement, produces a decrease in the stiffness con--
stant and the phonon frequency. A requirement for this de-
crease, however, is that the holes have sufficient time to scat-
ter to the upper split valence bands within the period l/w of
the phonon or of the ultrasonic radiation used to measure the
elastic constants, i.e., WT < 1, where T is the appropriate
scattering time. The time T is of the order of the scattering
time which determines the resistivity, 10- 13 sec. Therefore
for ultrasonic measurements of C44 (w ~ 10 8 sec- l ) WT is indeed
«1 while for optical phonons WT ~ 1. This last condition
means that a considerable delay must exist between the phonon
distortion and the hole population distribution induced by scat-
tering to the upper split valence band. This delay represents
an imaginary part in the self-energy , i.e., a broadening of the
phonon frequency of the order of its shift, as shown in figures
2 and 3. It is interesting to note that a decrease in C4 4 is
also observed for heavily doped n-type Ge [8], a result of the
splitting of the [111] electron valleys produced by the strain.
Such doping, however, does not yield any shift in the phonon
frequency: the relevant T is now the intervalley scattering time
which is of the order of 10- 10 sec. Thus, in this case WT» 1

and upon splitting of the valleys due to the phonon distortion
the electrons do not have time to scatter to the lowest energy
valley.
In the light of the discussion above, the effect of heavy
acceptor doping on the phonon frequency should be similar in Ge
and in Si. Figures 2 and 3, however, exhibit a rather substan-
tial difference. While the phonon line of heavily doped p-type
Ge (figure 2) is symmetrically broadened, that of Si shows a
strong asymmetry, the high energy side being less steep than the
low energy one. Even more striking is the fact that this asym-
metry depends strongly on the frequency of the scattering laser
radiation [9,10], the line becoming more symmetric at higher
frequencies (see figure 4).
Si (Boron)
p = 1.6 X 1020 em- 3
T=300K
o 4545A
b. 4880A
a 5145A
1
Exciting
wavelength
• 5682A
• 6471 A
-60 -40 -20 0 20 40 60 80

[w-Q] (em-I)
Figure 4 - Raman line shapes vs. scattering wavelength for

p-Si. The solid lines are theoretical fits, with equa-
tion (2), to the experimental lines (discrete points).
The curves have been shifted vertically with respect to
each other with the antiresonance minimum in each case de-
fining the base line. (From reference [10]).
276 M. CARDONA
The asymmetric line shapes of figure 4, looking like a mix-

ture of the real and the imaginary part of a Lorentzian func-
tion, are not foreign to the spectroscopist. They obtain, as
shown by Fano [11], whenever a discrete excitation frequency
overlaps and interferes with a continuous excitation background.
They appear in atomic spectroscopy as a result of the interfe-
rence of an excitation from a core level to a discrete excited
state and the excitations from a higher (valence) level to the
continuum. Particularly beautiful are the line shapes observed
for the 38 + p transitions of argon and the 28 + p transitions
of neon [12]. These asymmetric lineshapes are determined by
two parameters: r, representing the matrix element of the inter-
action of the discrete state with the continuum, and q, repre-
senting the ratio of the oscillator strength of the discrete
line to that of the continuum. The line shape is given, in
terms of the reduced frequency E = (w - n)/r (n is the frequency
of the discrete state) by the expression [11]:
(8)
It is of pedagogical value to give a qualitative physical

feeling for the meaning of this Fano effect and the line shape
of equation (8). Let us confine ourselves to the mixture of
discrete and continuum excitations produced by the first order
perturbation theory. A state within the continuum at an energy
w, Iw)o, mixes with a certain amount of discrete state In).
The amount of admixture is given by the matrix element of the
interaction (wlvln) divided by the corresponding energy denomin-
ator according to:
(9)
The oscillator strength of a certain transition from the" ground

state 10) to Iw), produced by an operator ~ (for dipole optical
absorption the linear momentum p, for Raman scattering the pol-
arizability) is thus represented by:
Thus, we see that. depending on the relative phase of (wloPlo)

and (wlvln)(nl~lo), the symmetric oscillator strength which
would be found for the decoupled excitation to (wlo is decreased
at one side of the frequency n and increased at the other or
vice versa.
The solid lines of figure 4 are fits with equation (8) to the
experimental points. These fits, for a given sample, can be
made with an 'interaction' parameter r independent of laser frequen-
cy and a laser frequency dependent q. We therefore conjecture that
there is a continuum of excitations overlapping the phonon frequency
n. In order to make our argumen t wa ter- tight, we now have to answer
the following points:
(1) what is the microscopic nature of this so far phenomen-
ological continuum?
(2) is there a laser frequency dependent ratio of discrete
to continuum excitation probabilities?
(3) why does this Fano-type interference effect appear in
Si but not in Ge?
In order to answer question (1), let us refer to figure 5
which illustrates the valence bands of Si.
Si - Valence bands
12.5 12.5
[110] [100]
Figure 5 - Valence bands of Si. The arrows show the in-

tervalence band transitions of the electronic continuum.
Wm is the low energy cutoff of the continuum. (From
reference [10]).
We note that, in constrast to Ge, the top valence band is nearly

fiat. The horizontal line ~ represents the Fermi energy of a
heavily p-doped specimen. The vertical arrows indicate that in
this case inter-valence-band transitions are possible. Because
of parity, these transitions are infrared forbidden and Raman
278 M. CARDONA
allowed at k = O. We thus obtain a possible continuum of elec-
tronic transitions which, for a sufficiently doped specimen
overlaps with the frequency of the k = 0 phonons. In Ge, be-
cause of the fact that the top bands along [110] have a larger
curvature, and because of the larger spin-orbit splitting, the
overlap of the continuum with the phonon frequency does not oc-
cur within the doping range allowed by the solubility of accept-
ors. Hence, this electronic continuum would also answer ques-
tion (3). It should be noted that the inter-valence-band elec-
tronic transitions inspite of being strictly dipole forbidden
atk k
= 0, they become allowed at + 0 where the finite density
of states resides. Such transitions have been exhaustively
studied in Ge and a number of similar semiconductors [13].
Let us now consider question (2). The electronic and the
vibronic scattering being completely different processes it is
in principle possible to have a ratio of their probabilities q
dependent on the frequency of the scattering radiation. We have
seen in section 1 that the vibronic scattering can resonate as
strongly as dx/dw near an electronic gap. The lowest direct gap
of Si (indirect gaps are too weak to exhibit strong resonances)
occurs at 3.3 eV and thus one expects the phonon scattering
probability to increase significantly in going from the red to
the blue. In the electronic scattering from valence band V2 to
VI the incident photon brings the electron in V2 to an excited
conduction state and the scattered photon brings this back to
band VI. Thus, the process is rather similar to the elastic
virtual transitions which determine the electrical susceptibil-
ity X, except that in the latter processes the initial and final
valence states are the same (VI + VI). In the spirit of the ap-
proximation of section 1, in which one neglects the frequency n
compared with that of the electronic excitations which determine
x, one can neglect the difference in energy between VI and V2 in
the expression for the electronic scattering probability. Under
these conditions the resonant structure of this probability and
that of the expression for X become the same: a sum of squares
of a dipole matrix element from the valence to the conduction
bands divided by w - we - wv , where we and Wv are the energies
of the corresponding valence and conduction states. We have
therefore reached a conclusion which can, at least qualitatively,
positively answer question (2): the phonon scattering probabil-
ity resonates like dX/dw, much stronger than the electronic
scattering probability which resonates like x. In reference
[10], it is shown that this answer is also quantitative.
One last point can be made in support of the electronic-vi-
bronic interaction just described. The Fano interference is
particularly striking whenever the transition probability to the
background is much stronger than that to the discrete state. If
we neglect \nl~lo) in the first order perturbation expression of
equation (10) we just obtain the flat background. The next logi-
cal step is therefore to go to second order perturbation theory:
the discrete state, with nearly negligible oscillator strength
repels the strongly allowed continuum. The resulting scattering
spectrum is thus represented by a 'window' (in the case of ab-
sorption a transparent region within the continuous absorption,
see figure 6) in the middle of the strong structureless back-
ground. In p-type heavily doped Si we have two possibilities
10 I
-
8-
~
·c - -
-e.!!..'"
\ Ar 3s
\
6 \ /---- ------\ -
C
v I / \ /---j ,,_-
·v
c: I I I , '( -
~ I , I, II
c
.S! 4t- I I 'I II
I II II
a
<5
1l t- 4p : : 5p II 6p II'
« II ~
21- II ~
\:• -if-
Slit width
,
t-
o
26 27 28 29
(cV)
Figure 6 - Absorption spectrum of gaseous argon in the

region of transitions from the 3s core levels to discrete
empty p states. (From reference [12]).
of increasing the Raman electronic background with respect to

the optical phonon: (a) to go to lower scattering frequencies
and (b) to increase the doping. Figure 7 shows the Raman spec-
tra taken with two different laser lines (4880 and 6471 ~) for
four different dopings. The spectrum taken with the red line
of the Kr+ laser for p = 4.0 x 10 20 cm- 3 shows clearly the win-
dow-type Fano line just described which evolves into the more
conventional peak as the laser line moves to shorter wave-
lengths.
In the light of the present discussion the .Raman spectrum of
heavily doped p-type Si represents a rather interesting and
unique type of discrete-continuum Fano process. The parameter
q, the ratio of discrete to continuum scattering strengths, can
be varied within a rather broad range by varying the parameters
just mentioned. Application of a high uniaxial stress [10]
eventually raises the lower threshold of the continuum above the
phonon frequency and eliminates the effect. In the intermediate
stress limit the Fano parameter depends on the magnitude of the
280 M. CARDONA
(c)
• <4880A.}
~citiDa p = 4.0 X 1019 cm ->
·6471 A wavelenith
··e-
~
.~
~r-~,..........~'"
~~~~~~~~~~~~~~
.!.
.~..
(b)
P = 1.6 x 1()lOcm- l I. \
f A} Exciting
~
• p = 1.7xlO '9 cm - l
(d)
i [, • 4880
·
6471 A wavelength
j
i
- 60 - 40 - 20 o 20 40 60 - 40 - 20 o 20 40 60
[w- O] (cm -I )
Figure 7 - Raman line-sha~es for two scattering wave-

lenghts (4880 Xand 6471 A). The solid lines are
theoretical fits, with equation (8), to the experimen-
tal curves (discrete points) for different values of
the carrier concentration. (From reference [10]).
applied stress.
3. SECOND ORDER SCATTERING

Equation (2) restricts first order scattering to phonons
near the center of the Brillouin zone. For a germanium or
zincblende-type semiconductor such optical phonons have r l5 sym-
metry. Of the three irreducible components of the symmetric
Raman tensor (rl5,rl2,rl) only the ~l5 contributes to first or-
der scattering. In second order two-phonon scattering all sym-
metry components and all values of ql are possible provided
ql + q2 '"
O. Two r l5 phonons with ql + 0, for instance, q" '"
y~eld rl5 = rl + rl2 + rl5, all poss~ble ~rreducible components
of asymmetric tensor. By appropriate choice of the sample
orientation, and that of the incident and scattered polariza-
tions, it is possible to separate the three components and thus
to obtain three independent scattering spectra [14].
The two phonons which participate in the second order process
may belong to the same (overtone processes) or to different
branches (combinations). In general, overtones and combinations
appear simultaneously in all irreducible components of the sec-
ond order spectra. Through a not totally understood accident
of nature the second order spectra of germanium- and zincblende-
type semiconductors are particularly simple: their r1 (fully
symmetric) component only contains phonon overtones while the
rlS component ·contains combinations (see reference [15] and
other references therein). It is possible to give a simple,
heuristic argument to justify this. Its non-rigorous nature is
evidenced by the fact that the rl-overtone, rlS-combination
separation does not hold for the alkali halides [16]. The heur-
istic argument goes as follows: the overtone of two phonons has
the symmetry of the square of some irreducible representation
and thus always contains the identity rl (this conclusion is
rigorous; however, it may also contain other components, i.e.
[r 1S ]2 = r 1S + r 12 + r 1 . In this case the r 1S and r 12 compo-
nents seem, for unknown reasons, to be very weak). A two-phon-
on combination will often, especially at high symmetry points,
consist of two phonons of different symmetries. Therefore,
their products do not contain the identity rl. The flaw in this
second part of the argument is that most of the phonons at a
general q point have very low symmetry of the group of the q
vector and usually all belong to the identity representation in-
spite of coming from different branches. One may, however, hope
that selection rules derived for a large number of high-symmetry
points will remain nearly valid by continuity in the low-sym-
metry region between them.
We show in figure 8 the rl component of the second order
spectrum of Ge (the strong peak at 300 cm- 1 is the first-order
line) in comparison with the density of two phonon states [17J.
This density of states is simply the density of one phonon states
obtained from neutron data, with the horizontal scale multiplied
by a factor of two. We see the strong similarity between the
curves, in particular the beautiful agreement between Raman and
neutron critical points found for the transverse acoustic branch
between 100 and 250 cm- 1 . The Raman peak at 600 cm- 1 (twice the
energy of the q ~ 0 phonon!) does not correspond to a peak in
the density of states and its origin is not clear.
Figure 9 shows the three irreducible components of the second
order spectrum of GaP for creation of two optical phonons. The
rl component has two features, related to the creation of two LO
phonons (740-810 cm- 1) and two TO phonons (650-730 cm- 1) , respec-
tively. The r15 spectrum reproduces the combination density of
states for creation of a LO and a TO phonon. The f12 component,
as usual in the germanium-zincblende materials, is nearly negli-
gible.
The rich structure of the second order spectra of figures 8
and 9 is particularly appropriate for resonance Raman studies.
When approaching an electronic gap (Eo = 0.8 eV in Ge, 2.8 eV
in GaP; El = 2.1 eV in Ge, 3.7 eV in GaP) each one of the fea-
tures of the first and the second order spectra will resonate,
possible in different ways as corresponds to different resonance
mechanisms. These thoughts are illustrated in figure 10, where
282 M. CARDONA
,
2L(I,2) 2X(I,2) 2W( I,2) 2L(3) 2X(3,4) 2X(5,6) 2r(4,5,6)
t , t 21:(4)
t t 2L(5,6)t t
t
2~(1) 21:(2) 2W(3,4) t 2L(4) 2W(5,6)
c: 100 t t t
.2
t>
~ _ _ _ Reduced R aman
e"'"'
()
cro seclion
; ----- DensilY of slales

E
a:'"
"0
"
.g
ilSO
,
0.:
I
I
I
I
I
I
I
\ .... _,___ I
,-,,-' -~
O~~=I~OO~---~-~~-~------~
~-------~
~-------J
~~--~
F requency (cm- I )
Figure 8 - rl component of the second order Raman spec-

trum of germanium (---) compared with the density of two
phonon overtone states obtained from neutron scattering
(---- ) . (From reference [17]).
we have plotted a mixture of the r15 and rl components of the

Raman spectra for four different values of the scattering fre-
quency WL both sides of the EO gap. The intensities have been
normalized so as to have the height of the first order allowed
TO peak equal to one. In the configuration of the measurement
the first order LO peak is forbidden and it is, indeed, very
weak for wL away from the gap. For wL close to wo, this for-
bidden line becomes almost as strong as the allowed TO peak.
We thus conclude that the forbidden LO peak resonates more
strongly than the allowed TO, a rather general property of for-
bidden effects. Whatever mechanism induces this forbidden ef-
fect can, in general, be described as an additional derivative
of X (equation (3)) with respect to some symmetry breaking param-
eter and thus it has sharper structure near resonance than the
allowed process.
According to figure 10, the overall two TA spectrum resonates
in a manner not qualitatively different from the one TO peak.
A similar conclusion applies to the 2TO(L) and 2LO(~) critical
point features. In the optical phonon region, however, two
r,
------rl~
'"'
·S
::t
100 --·_·_·r 12
t:'
~
~
.~
~
.5
c 50
e'"
''""
0
,
.2TO(I:)
650 700
Figure 9 - Optical branches of the second order Raman

spectrum of GaP. (From reference [17]).
strong peaks appear very near resonance. The stronger of these

two peaks occurs at a frequency equal to that of two LO phonons
at r and therefore cannot be described as a feature in the
joint density of states. The weaker one occurs at the sum of
the frequencies of one TO and one LO phonons at r. These struc-
tures are totally absent away from wo and resonate very sharply
in a manner analogous to the forbidden LO peak.
These three sharply resonant peaks (forbidden LO, TO + LO at
r, two LO at r) have all in common the participation of a LO
phonon at r. They are therefore believed to be due to the elec-
trostatic field which accompanies such phonons in an ionic mate-
rial (FrBhlich interaction). It can be shown that such field
produces a strong intraband scattering of the electronic states
which results for the first order peak, in a strong q-dependent
term in the Raman tensor (spatial dispersion). Thus, q cannot
be assumed to be rigorously zero and, in a series expansion of
the Raman tensor, terms linear in q appear multiplied by the
gradient of the Raman tensor with respect to q. The simple
selection rules derived for the q-independent Raman scattering
are broken down.
Figure 11 shows the height of the two-LO(r) resonant peak as
a function of WL - WOo The theoretical curve represents the
Frb~lich-interaction-induced forbidden LO resonance [18]. The
shape of this resonance can be qualitatively obtained with the
following argument. The function f(w - WO) of equation (6) is,
for the direct gap wo, neglecting exciton correlations:
-2 l l l
f(w - wO) =W [2W02 - (w - WO)2 - (w + WO)2]. (11)
284 M. CARDONA
100 200 300 400 500 600 700 800
2TA(X-K) I.~O L~0301

0.Q2 ,
2LO(I: 0.Q2
2TO(L), •
0.Q2 0.02
....
~
0.0\ WL -wo = 0.0\
0-
f-< -0.057eV
~
,-,
0:
oj
e
oj 0 0
I¥ 2LO(r)
';:;:' 1.0 .458 .688
."
t~ H TO+LO(r)
c: 0.08 0.08
(.;
WL -roo =
0.059 eV
0.04 0.04
0.04 0.04
Figure 10 - First and second order Raman spectra of GaP

(rl and r15 components) at four values of wL - Wo (two
positive and two negative) corresponding to laser fre-
quencies near the EO gap. The intensities have been nor-
malized to make the height of the first order TO peak
equal to one. (From reference [15]).
10'
!I
0+ + Experimental
Points
Theory from
Ref. 18
10'
......, 10'
t
J
Jj...'"
u'"
~
~
I-
0
...l
~ 10'
10
o
I~ 1'::-.o----::0:'::.8----:0.L...6----::o.L...4----::o'::-.2-~0~--::0.'::-2---='0.4
WL -wo(eV)
Figure 11 - Height of the two LO (r) resonant peak as a

function of scattering frequency. (From reference [15]).
Taking the second derivative (forbidden process) and squaring it

we obtain for the leading term of the Fr5hlich interaction in-
duced resonance the shape Iw - wol- 3 . Except for the rounded-
off top, this is precisely the shape of the solid lines in fig-
ure II.
A similar argument yields for the allowed first order TO
peak a weaker resonance with the leading term Iw - wei-i. Be-
cause of the spin-orbit splitting of the EO edge (EO - EO + ~O),
we shall discuss this shape in somewhat more detail. The EO gap
takes place between a fourfold degenerate p-like valence band of
ra symmetry (equivalent to total angular momentum J = 3/2) and
the conduction band. The r15 TO phonon cannot modulate the en-
ergy of the completely symmetric s-like conduction band. It
does, however, split the ra states into two and therefore con-
tributes a dwO/du term to equation (7). This is precisely the
286 M. CARDONA
term of Iw - wol- l leading shape. The EO t AO gap does not
split under the action of the phonon (it is only twofold Krarners
degenerate): the TO resonance near it does not have an fl term
(equation (7)) and is only due to a coupling via the phonon of
the r7 state with ra, i.e. the dA/du term of equation (7).
These results are illustrated in figure 12. The dashed curve
I~r---------------~---------------------------------'
mo = wO+T
no
+++++ Present measurements
'(
I
1
c c c c C Scott et al.
, I
1\
- - - - - - - 19'1> 12 , I
I \
-------lg(w/molI 2 I \
10' I \
'++ \\
,,
\
\
,,
.....
.....
.....
1(J"
103.L:-_ _~':""'"----f:;----+':----~---7;------;;':;---~,
-u -~ -u -M -~ 0 ~ M
'ilL -wo(eV)
Figure 12 - Resonant Raman scattering of the TO allowed

line near the EO and EO t AO gaps of GaP. (From refer-
ence [15]).
corresponds to the Xl function (splitting of the fa edge) while

the solid line includes also the coupling of fa with f7' This
last curve, suitably broadened, agrees better with the experi-
mental points which, however, do not resolve the EO + 60 edge.
This edge has been recently resolved in measurements using a
pulsed dye laser [19]. The resolved EO + 60 resonance is in-
deed weaker than that at EO.
The resonance of a peak in the f15 component of the second
order spectrum (e.g. TO + LO of figure 9) is very similar to
that of figure 12. The peaks in the rl component, however, ex-
hibit considerable differences because of the fact that a rl
perturbation modulates the rl conduction band and both r8 and
r7 valence bands. As a result, both the EO and the EO + AO re-
sonance are of the X'. variety and similarly sharp. This is il-
lustrated in figure 13 where both the EO and the EO + AO reson-
ances are seen for the 2TA peak in the rl component of the spec-
trum.
--+-+-+ --2TA(X-.K)
'-'-e-.-e-.-.-.- 2TA(X-. K)(fO(r)
;!<
,
_.-o--._._._._._.-e-._,,;.;/.........
......
~
"~
I. ;
-. '..
~
~1~.O~-----·O~.8~-----O~.6~-----~O.74------~O~.2----~O~----~O.~2----~O.4
Figure 13 - Resonance Raman scattering of the 2TA peak

observed in the rl component of the second order Raman
spectrum of GaP. The solid line is calculated. The
dashed-dotted line represents the ratio of the strength
of the second order peak to that of the first order TO
line. The dashed line joins the experimental points for
the strength of the 2TA line. (From reference [15]).
According to equation (7) the leading term in the resonance

of an allowed first order spectrum is determined by the elec-
tron-phonon coupling constant dwO/du. The resonance of a sec-
ond order peak which does not involve Frohlich interaction is
288 M. CARDONA
determined by:
222
d2 X dWO) d X (dWO) dX d Wo
- 2 X(w) = -d -
(d- -- = (12)
du du dwO du dWQ2 du J + dwO du 2
Term B in equation (12) has the same shape as the leading reson-
ance in the first order spectrum while term A resonates faster.
The experimental results of figure 13 and others [15] show that
term B is dominant. Thus, by measuring the ratio of the second
order resonance to that of the allowed TO peak one can find the
ratio
2
d WO(dWo ,-l (13)
du 2 du J
dwO/du is known to have, in the proper units, a value around
300 eV in germanium and zincblende-type materials. We thus can
obtain from the experimental Raman resonance data and equa-
tion (13) the electron-two-phonon coupling constant d2wo/du2.
This coupling constant DO has, for most two phonon processes in
GaP, rather large values around 103eV. We present in Table I
the electron-two phonon interaction constants obtained to date
for germanium and zincblende-type semiconductors by a number of
experimental methods.
The values of DO listed in Table I show a rather consistent
trend around 10 3 eV and thus are much larger than the electron-
one phonon interaction constants (dO'" 30 eV). We must there-
fore expect appreciable effects of the electron-two phonon in-
teraction and, probably, a poor convergence of the power series
expansion of wo as a function of u. The reason for the large
values of DO compared with those of dO is to be sought. in the
theoretical expressions of these parameters:
(13)
Because of the strong divergence of V2V near the atomic origins,

a very large DO can result when ~ is an s-like function (e.g.,
f1 conduction band) and thus has a finite value at those ori-
gins. The divergence of VV, which enters into the expression
for the electron-one phonon constant is sufficiently weaker to
make the core contribution not so important and thus do smaller
(the matrix element of VV is strictly zero for an s-like state).
Calculations of Do based on equation (13) have been performed
for the f2' conduction band of germanium [15,20J. They yield
values of Do between 10 5 and 106 eV, three orders of magnitude
larger than those obtained experimentally! The reason for this
TABLE I
Values of the electron-two-phonon interac-
tion constant found experimentally for sev-
eral semiconductors.
Material
D
and Method
eV
phonon
GaP
2TA Ramant 390
2TO " 965 } f,

210 " 1260
TO+ 10 " 450 r15
2TA, 2TO free carrier '\, 1 000

absorption1l rl
InSb
magneto-
2TA '\, 1 000 rl
phonon§
magneto-
2TO '\, 10 000 rl
absorptiontt
Si mob i l ity1l 11 '\, 1 000 III
t Reference [15].
11 Ganguli. K. and Ngai, K.L. (To be pub-
lished).
§ Ngai, K.L. (To be published).
tt Ngai, K.L. and Johnson. E.J. (1972) .
Phys. Rev. Lett .• 29, 1607.
1111 Ngai, K.L., Norton and Henvis. (To be
published) .
is seen if we consider equation (13) for an isolated atom: DO

can be between 105 and 10 6 eV and yet a given energy level does
not change its energy at all when the atom is displaced an
amount u. Actually, the chan~e in energy to second order in u
is not only produced by DO ~ \~1~2VI~), the second order Hamil-
tonian in first order perturbation theory, but also by the first
order Hamiltonian ~v taken to second order through all possible
290 M. CARDONA
intermediate states. We can therefore define a renormalized DO:
(14 )
Obviously, for a free atom both terms in equation (14) must ex-
actly cancel each other. In a solid, because of the bonding,
this cancellation is not exact and a remainder (of the order of
1% ~r less) is left [15]. We thus obtained experimental_values
of DO (usually the experiments measure the renormalized DO and
not DO) in qualitative agreement with the theoretical estimates
[15] .
By referring to equation (12), we note that the sum of equa-
tion (14) just performed is formally similar to the two terms
which enter into the second order Raman scattering: first de-
rivative of Wo taken twice and second derivative taken once.
It can be shown that it is possible to use in the B terms of equation
(12) a renormalized d2wo/du2, provided the intermediate states
which mainly contribute to equation (14) are all far from reson-
ance.
ACKNOWLEDGMENTS
I would like to gratefully acknowledge the help of Drs. R.
Besserman, F. Cerdeira, T. Fjeldly, K. Ngai and B. Weinstein,
on whose work the present lectures are mainly based.
REFERENCES
1. See, for instance, various articles in: (1971). Light
Scattering in SoZids, (ed. Balkanski, M.), (Flamarion,
Paris); (1966). Light Scattering in SoZids, (ed. Wright,
G.B.), (Springer-Verlag, New York).
2. Cardona, M. (1969). ModuZation Spectroscopy, (Academic
Press, Inc., New York).
3. Cardona, M. (1973). Surf. Sci., 37, 100.
4. Sch~fer, F.P. (1973). Dye Lasers, Topics in AppZied
Physics, VoZ. I, (Springer-Verlag, Berlin, Heidelberg,
New York).
5. Buchenauer, C.J., Cerdeira, F. and Cardona, M. (1971). In
Light Scattering in SoZids, (ed. Balkanski, M.), (Fla-
marion, Paris), p. 280; Cerdeira, F., Buchenauer, C.J.,
Pollak, F.H. and Cardona, M. (1972). Phys. Rev., BS, 580.
6. Hart, T.R., Aggarwal, R.L. and Lax, B. (1970). Phys. Rev.,
Bl, 638.
7. Cerdeira, F. and Cardona, M. (1972). Phys. Rev., BS, 1440.
B. Keyes, R.W. (1967). SoZid State Physics, VoZ. 20, (Academic
Press, New York), p. 37.
9. Besserman, R., Jouanne, M. and Balkanski, M. (1972).
Proceedings of The InternationaZ Conference on The Physics
of Semiconductors, Warsaw 1972, (PWN, Polish Scientific
Publishers, Warsaw), p. 1181.
10. Cerdeira, F., Fjeldly, T.A. and Cardona, M. Phys. Rev. (in
press) .
11. Fano, U. (1961). Phys. Rev., 124, 1866.
12. Madden, R.P., EdeEer, D.L. and Codling, K. (1969). Phys.
Rev., 177, 136.
13. Braunstein, R. and Kane, E.O. (1963). J. Phys. Chern. SoZids,
23, 1423.
14. Loudon, R. (1964). Adv. Phys., 13, 423.
15. Weinstein, B.A. and Cardona, M. (1973). Phys. Rev., (Sept-
ember, 15th).
16. Krauzrnan, M. (1969). In Light Scattering Spectra of SoZids,
(ed. Wright, G.B.), (Springer-Verlag, New York), p. 109.
17. Weinstein, B.A. and Cardona, M. (1973). Phys. Rev., B7, 2545.
18. Zeyher, R., Ting, C.S. and Birman, J.L. Phys. Rev., (to be
published) .
19. Bell, M.I., Tyte, R. and Cardona, M. (To be published).
20. Lin-Chung, P.J. and Ngai, K.L. (1972). Phys. Rev. Lett., 29,
1610.
FORMALISM OE AN AB INITIO CALCULATION
OF PHONON DISPERSION CURVES
IN THE HARTREE-FOCK APPROXIMATION
v . E. VAN DOREN and P. VAN CAMP
Institute for Applied Mathematics,

Rijksuniversitair Centrum Antwerpen, Antwerpen, Belgium
The theory for an ab initio calculation of phonon disper-

sion curves of semiconductors or insulators, has been given be-
fore in several papers [1].
The main difficulty, prohibiting such calculations has been
the many-electron wave functions and energies, which are very
difficult to compute. The usual way around this, then, is to
introduce the Hartree-Fock approximation which assumes that
the electron wave function can be written as a properly anti-
symmetrized product of single electron wave functions. However,
no such calculations have ever been done. Realistic Hartree-
Fock electron wave functions and energies have been substituted
for by different parameters. Reviews of all the effort, con-
cerning the calculation of phonon dispersion curves, can be
found elsewhere [2], but the types which have been used quite
successfully, are the shell model and pseudopotential model.
Both represent the complicated electron screening and electron-
nuclear interaction by an effective potential. However, in the
last five years, Hartree-Fock calculations yielding realistic
charge densities, have become available [3] and therefore the
time has come to start a phonon dispersion calculation from
first principles.
In this seminar, the formalism is laid out in detail to make
an ab initio calculation in the Hartree-Fock approximation and
a detailed analysis of the different matrices, leading to the
dynamical matrix is given.
293
294 V.E. VAN DOREN and P. VAN CAMP
REFERENCES
1. Johnson, F.A. (1969). Proc. Roy. Soc., A310, 79, 89, 101,
111; Sham, L.J. (1969). Phys. Rev., 188, 1431; Pick, R.M.,
Cohen, M.H. and Martin, R.M. (1970). Phys. Rev., Bl, 910;
Sham, L.J. (1974). In this volume, p. 1.
2. For example, see Pick, R.M. (1974). In this volume, p. 25;
Cochran, w. (1971). Critical Reviews in Solid State Sciences,
pp. 1-44.
3. For a list of ab intio Hartree-Fock calculations, see Kunz,
A.B. (1974). In this volume, p. 343.
TWO-PHONON DEFORMATION POTENTIALS,
SECOND ORDER RAMAN SCATTERING,
AND SUPERCONDUCTIVITY IN DEGENERATE SEMICONDUCTORS
K.L. NGAI and A.K. GANGULY
Naval Research Laboratory,

Washington, D.C. 20375 USA
1. ELECTRON-TWO-PHONON EFFECTIVE HAMILTONIAN

In the initial magneto-optical studies [1] of carrier-two-
phonon interactions, heneeforth referred to as I, strong coupl-
ing between electrons and two non-polar optical (NPO) or TO
phonons was observed in InSb. Magneto-optical resonant carrier-
phonon(s) coupling effects in the two optical phonon energy reg-
ion bear clear evidence that 2NPO phonon interaction occurs with
significant strength in InSb. In this work, several other exam-
ples are given that corroborate the physical importance of two-
phonon deformation interaction in semiconductors. Our main pur-
pose is to show that two phonon-induced intravalley,· and/or in-
tervalley electron-electron interaction is an important mechan-
ism for superconductivity in low-carrier-density systems such
as degenerate semiconductors.
The electron-phonon interaction Hep is usually given as an
expansion in its atomic displacements Una of the a-th atom in
the n-th cell:
(1)
n,a n,a
n' ,ct'
(2)
As was indicated in I, an electron interacts with two phonons

either by H2 or by a repeated application of HI through inter-
mediate states. The latter process is formally written as
295
296 NGAI AND GANGULY
Hl(E - H)-lHl, where H is the total Hamiltonian for the elec-
trons and the lattice. Interference of matrix elements between
H2 and Hl(E - H)-lHl may result in some cancellation and weaken
the resultant electron-two-phonon interaction. For the case of
long wavelength acoustic phonon modes, the results of interfer-
ence and cancellation are dramatic as shown by Holstein [2] and
Herring [3]. However, for two NPO phonons, in spite of inter-
ference, it may be argued that cancellation is incomplete. In-
deed, as pointed out in I, for near zone-edge optical phonons
with large momentum transfer, translational invariance of the
crystal no longer enforces detailed cancellation of H2 and
Hl(E - H)-lHl as happens for the case of long wavelength acous-
tic phonons. However, the assumption made in I that only H
gives rise to the observed resonant electron-2NPO phonon coupl-
ing is not necessary. In general, finite contributions to
Hl(E - H)-lHl exist with all possible intermediate states from
all bands. The results and conclusions of I remain unchanged
if the deformation potential determined therein is taken per-
taining to the effective Hamiltonian H2 eff as defined immediate-
ly below. This persistent interference of matrix elements is
most conveniently handled by defining an effective carrier-two-
phonon interaction Hamiltonian H2 eff. The procedure is illus-
trated diagrammatically in figure I and corresponds to the
+ +
Figure 1 - Schematic definition of the effective Hamilton-

ian H2 eff (see text).
following expression:
(4)
2
pna (wqnjwq'n'j,)2
l '
MA'A(Q) = (FA' leiQ·~IFA)' (5)
where IFA) is the envelope function of electron states,

SUPERCONDUCTIVITY IN DEGENERATE SEMICONDUCTORS 297
is the field operator for phonons of branch n and polarization
j, and Q= q + q'. p is the mass density and a is the lattice
constant of the crystal. ~,the two-phonon effective deforma-
tion potential, is a function of qnj, q'n'j'. It is expected
to be smaller than the value determined from Hep (2) term alone
because of interference with the second order Hl term.
It is found convenient to rewrite H2 eff in a form that re-
sembles ordinary electron-deformation potential interaction
with one phonon. This is accomplished by first replacing the
sums over q and q' by sums over Q and q. For a fixed Q, let
the set of critical points in the joint energy density of states
for all combinations of two ph~nons nJq and n'j'q' with the sum
of their wave-vectors q + q = Q be indexed by =.
Further, 4e-
note the energy of these two-phonon critical points by hw=(Q).
Second, the summation over q is transformed to integration over
the variable ws, which depends on the parameters njn'j', and is
the sum Wnjq + Wn'j'q'. Let
f(q;nj ,n' j' ,Q) (6)
Then
L 1. f(q;nj,n'j' ,Q) = (21TQ)3 L jdqf(q;nj,n'j' ,Q)

nj,n'j' q nj,n'j'
= ( 21T
Q)3 L jN(ws)f(q(ws);nj,n'j' ,Q)dws. (7)
nj,n'j'
N(ws) in equation (7) is the joint 4ensity of states of phonon

pairs nJq and n'j'q' with q + q' = Q. We replace L N(ws)
nj,n'j'
by
Here Qc = volume of the primitive cell. For a crystal with zinc-

blende structure and lattice constant a such as InSb, Qc = ~a3.
Note that the indices nj and n'j' are subsumed in =. Hence =
can be defined as an index for the critical points of the com-
binations of two phonons Inj~) In'j' ,Q - q). From equation (8)
we see that the quantity p=(Q) has the meaning of the fraction
of the Brillouin zon~ (BZ) volume that constitute the critical
point = for a fixed Q. This meaning can be brought out more
clearly by considering a hypothetical case of a lattice with
two totally dispersionless phonons nhjh and nh'jh' with constant
frequencies Wh and wh' respectively. Let =h be the critical
point energy hw~ = hWh + hWh'. Then from equation (8), we must
have P~h(Q) = 1 for any Q.
Continuing from equation (8), we substitute into equltion (7)
The quantity f(w~(Q);nj,n'j' ,Q) is an average of f(q;nj,n'j' ,Q)

over all sets of phonon pairs {inJq),ln'j' ,q')} that constitute
~. If we define ro~ by ro~2 = Av{wqnjwqn'j'} as the average over
~ of the product WqnjWqn'j" We assume that D(qnj,q'n'j') de-
pends on ~ and Q only, then
+ +
Y. -:t -:t = _fl \' p_,,(QW"(Q)
L -qf('{;nj,n'j',,,) flc~ w~- (10)
nj,n'j'
Substitution back into equation (3) gives,
We have rewritten the product of p~(Q~~(Q) as (~p~)Q,~. The

product ~{q},~~{-q+Q},~ symbolically stands for the totality of
all pairs of phonons that constitute~. Since flc = ~a3 for
InSb, we have an alternative expression for H2 eff as
1
H2eff -- A?A (2Pfl:2w~)2d~(Q)MA'A(Q)CA'tCA~{q},~~{Q-q},~, (12)
Q,~
with
(13)
This last form of H2 eff resembles a one-phonon deformation pot-

ential interaction with deformation potential d~(Q). In the
present formulation of carrier-two-phonon interaction, proper-
ties of the lattice normal vibrational modes that are nec~ssary
to describe the interaction are th~ ensemble {~,w~(Q),p~(Q)}.
The first two quantities ~ and w~(Q) can often be estimated by
ins~ection of the phonon dispersion curves. On the other hand,
p~(Q) can only in principle be obtained if we know the phonon
spectrum over the entire BZ. This information is generally not
readily available from present day lattice dynamics experiments
SuPERCONDUCTIVITY IN DEGENERATE SEMICONDUCTORS 299
or calculations. One advantage of the effective Hamiltonian
formulation is that this information is absorbed into the observ-
able quantity (~~)Q,= or d=(Q) which are directly related to
experimental observations.
In the experiment reported in I, electron excitations were ob-
served to couple resonantly with several 2NPO phonons =. The
electronic spectrum was fitted [1,4] with the only adjustable
parameters (~p~)Q=O,= assumed,to be polarization independent.
We found [5] for example, (:)P2)= = 1.5 x 10 4 eV for = being the
2TO(L,-L) critical point at 44 meV. We have subsequently de-
termined values of (Vp~)= from several different kinds of ex-
periments [6-10] and for various semiconductors. These involve
the analysis of two-phonon magnetophonon resonance [6], the
wavelength dependence and magnitude of free carrier absorption
[7], temperature dependence of mobility in Si [8], two-phonon
resonance [9] and non-resonance [10] Raman scattering in semi-
conduc.tors. These examples conclusively demonstrated that 2NPO
scatterings exert observable effects in a variety of physical
phenomena. Further, these [6-10] establish the order of magni-
tude of (~p~)= for two-phonons to be between 10 3 and 10 4 eV for
both III-V compound and group IV semiconductors [11]. These
values are appropriate for slightly doped materials in which
dielectric screening is unimportant.
A first principles calculation of the matrix elements of the
deformation potential (equations (12,13)) is extremely difficult,
because contributions from intermediate states of all bands have
to be included. However, the matrix element of Hep (2) alone is
amenable to quantitative computation. Lin-Chung and Ngai [12]
have used the OPW method and obtained the deformation potential
~(2) that corresponds to H ep (2) alone for the conduction band
of Ge at r to be 3.5 x 10 5 eV. The plane wave part of the elec-
tron wave function ~ gives only a contribution of 10 3 eV to~(2).
This OPW equation of~OPW(2) from H2 alone indicates that the
two-phonon deformation potentials can be large. Since~, the
value deduced from experiment, is smaller than the calculated
value neglecting the second order one-phonon contribution, the
interference and cancellation is demonstrated. The purpose of
the OPW calculation should be taken in this spirit. Weinstein
and Cardona [9] have examined the magnitude of~(2) from several
approaches and arrived at essentially the same conclusions. At
certain symmetry points of the Brillouin zone, ~(2) has the form
The Slater's approximation to the core functions contained in

the orthogonalized plane wave function ~ are of the form r n - 1
exp(-Zeftr/n). The effective Z for any core state is given by
the expression Z - s, where S is a shielding constant, and Z
the true nuclear charge. Hence we expect that for a group of
semiconductors of the same type, the larger the atomic number
of the elements involved, the larger is ~(2). This dependence
of~(2) on atomic number is noteworthy.
Another interesting point is a possible band-structure de-
pendence of the effective deformation potential~, that corres-
ponds to Hep (2) + Hep(l)(E - H)-lHep(lJ. Consider an electron
at some band minimum, say r. If we make a working hypothesis
(albeit not completely justified) that a single band intermedi-
ate state, say L or X, closest in energy to r dominates the
contribution to Hep(l)(E - H)-lHep(l), then for materials such
as InP, GaP, AISb, etc., where either L or X is nearly degener-
ate with r, the intermediate state denominator is nearly reson-
ant and has a larger value. Concomitant interference with
Hep (2), could possibly imply a smaller resultant effective de-
formation potential~. For materials such as InSb, InAs, ZnS
or ZnSe, where r is far from other band minima, the Hep(l)x
(E - H)-lHep(l) contribution could be smaller than that of
Hep (2), resulting in a larger value of~. This trend seems to
be obeyed by the meager amount of experimental information on
~. We observe ~ for InSb [1,5] is larger than that for GaP [9].
Also ~(ZnS) [10] is larger than ~(GaP).
2. SECOND ORDER RAMAN SCATTERING AND EXCITON-TWO-PHONON

DEFORMATION POTENTIAL INTERACTION
Whenever available, experimental data of second order (two-
phonon) Raman scattering give a direct measure of the physical
importance of two-phonon deformation potential interactions.
Recently, due to advances in laser technology, both resonant
and non-resonant Raman scattering spectra have been obtained
for a variety of semiconductors. In this section we give a
theory of second order resonance Raman scattering in insulating
crystals applicable to zone-edge phonons. The scattering pro-
cess will be viewed as the absorption of the incident photon
(frequency w+X , t wave vector Xand polarization t) and the crea-
+
tion of the scattered photon (frequency WX' ,t' wave vector x'
and polarization t') with the emission of two phonons of frequen-
cies wqtj, wq,t'j', wave vectors ~,~', polarizations t,t, and
branch indices j,j'. Energy and momentum conservation require
that
and q - q' = X - X' :; O.
Thus the individual phonon wave vectors q or q' can have all
possible values throughout the Brillouin zone in contrast to
the one phonon scattering where only q = 0 is allowed. Thus
the second order spectra will have a continuous background with
peaks at wave vector regions corresponding to the critical points
where the joint density of two-phonon states is large. These
critical points usually fall at large q values near the zone
edge. Hence, in this paper we will not consider 2LO phonon
scattering at the zone center but concentrate on two phonon pro-
cesses (various combinations of TO, LO, TA,LA) at the zone e~ges.
The electron-phonon interaction for large q may be treated in
the deformation potential approximation for all types of phonons.
We consider only Stokes scattering. Three types of proces-
ses can occur in second order Raman scattering as shown in fig-
ure 1. In processes of type (a) the two phonons are emitted
simultaneously due to the second order interaction between elec-
trons and phonons. The three real transitions consisting of
the annihilation of the incident photon, the creation of the
scattered photon and the creation of two phonons are accompan-
ied by three virtual electronic transitions in which first an
exciton is created, then the exciton is scattered and finally
the exciton is destroyed by the recombination of the electron
and the hole. There are six possible orderings of the three in-
teractions involved. In processes (b) the two phonons are emit-
ted separately due to the first order electron-phonon interac-
tion acting twice. The four real transitions are accompanied
by four virtual electronic transitions in which an exciton is
created, suffers two scatterings and finally is destroyed.
There are 24 possible orderings of the four interaction ver-
tices. The type (c) processes are just iterations of the first
order Raman scattering [13] with an intermediate photon state.
Type (c) processes will be neglected since they involve electron-
photon interactions of higher order. In the following we will
consider the diagrams (a,b) only for the calculation of scatter-
ing cro6s-section near resonance. The contribution of other
diagrams of their respective classes are often negligible near
resonance. The various interactions can, of course, take place
through scattering of both electrons and holes.
We will consider a single excited electron in the intermedi-
ate state. These states will be taken as Wannier excitons [14]
represented by
(14)
where ~cv(k - K,k) is the antisymmetrized product function with

one valence Bloch state ei(k-K)~uv(k - K,P) replaced by a con-
duction state eik·~uc(k,p). UcvAK(k) is the wave function for
the relative motion of electron and holes. We will make iso-
tropic effective mass approximation and neglect the wave vector
dependence of the periodic part of the Bloch states. The excit-
ation energies are given by [14]
Ecv + £A + 2(me* + mh*) , (15)
where K'" K - (k c - kv), kc and kv being the minimum and maximum

of conduction and valence bands, respectively. The exciton eig-
envalues EA and eigenfunctions
vc-~e-i(ahkv.~+aekc·~) L
k
are determined by
(16)
where ~ is the reduced electron-hole mass and V(r) is the elec-

tron-hole interaction potential. Vc is the volume of the unit
cell and
me;'~
and ae
The matrix elements of exciton-photon and exciton-phonon in-

teractions in Wannier representations are given in reference
[ge]. The matrix elements of exciton-two-phonon interactions
(Hex-p) bilinear in exciton operators are given by
L
*+.
'14- 1;;, J
£t,I;;' ,j'
, (17)
where
and
~(l)(e'v'A' ,elvlAl,q) (e' I"t·~(l) Ie)f>.. , A(aeq)oV1V
- (v'I!·.1j(l)lv)f>..'A<-ahq)oclc' (19)
Here
For Q = 0, we have fA'A(Q) = 0A'A if e' = e and v' = v.

In equation (17) Xl'" = q - (kCl - kv - X) or q - (k c -kvl - X)
and Q = q + q' Q= 0 for Raman scattering. Changing the vari-
ables q,q' to ~ = q + q' and q in a manner analogous to equations
(3-11), we obtain
(e'v'A'x'IHex-pleVAK)
=
I'
L
NP;/nOK'-K"Q[
- , 3)l;l;'
(2)
(e'v'A' -t,
,CVA,l,I)
-+ 2MNa 2 w-;o
Q,:;: -
l;,l;'
pt, (1) (e'v' A' ,CVA ,Q - q::: >pt(l) (elvl Al ,CVA ,q:;:)]
I 2 2 ' (20)
elvlAl 1'1 Kl'"
EC1Vl + £Al + Fiw:;: - Fiw x£ + 2 (me'" + mh"')
where q:;: is the wave vector at critical point _.
Similarly, in case of interactions linear in the exciton
operator, we get
(eVAKIHex-plo)
(21)
where
(22)
and
(23)
The intraband matrix elements of the deformation potential are

non-zero for even parity or mixed parity phonons. The inter-
band matrix elements are usually smaller than for intraband
ones.
At each critical point we can then define an effective two-
phonon deformation potential interaction. The bilinear exciton-
two-phonon interaction has the form
1
Hex-p eff ( 'Ii )2 dl;l;'(C'V'A"CVA)B A'K,t(C'V')

2MNa 2w-;;
J~
1;,1;'
XBAK(CV)bq~tbQ-q~to(K' - K - Q), (24)
and the linear exciton-two-phonon interaction term is
Here Bt (B) is the exciton creation (annihilation) operator for

an exciton and
dl;l;'(c'V'A,CV).) (26)
(27)
with
8)1;1;,(c'V'A' ,CVA) = 3)1;1;,(2)(C'V'A' ,CVA,Q)

8)1;,(l)(C'V'A' ,CIVIAl,-q~)8)I;(l)(ClVlAl'CVA,q~)
, (28)
~2Kl,·,2
E C1v1 + £A1 + ~w~ - ~wX£ + 2(me* + mh*)
8)1;,(1)(CVA,C1V1A1,q~)8)1;(1)(C1V1A1'0)
(29)
1i2Kl",2
In using the effective exciton-phonon interaction we take

into account only part of the 24 terms of figure 2b, i.e., those
diagrams where an electron-photon vertex does not fall between
the two electron-phonon ~ertices. If the electron-hole correla-
tion is neglected and IAK) are considered to be free electron
(hole) states, then the matrix elements of the effective deforma-
tion potential in equation (28) are similar to those obtained
from infrared absorption experiments [1,7,8]. In the infrared
absorption the contribution to the deformation potential comes
only from one-carrier scattering. In the present case both el-
ectron and hole scatterings take place. The resultant deforma-
r--~
+ 5 other terms
(a)
+ 5 other terms
~ + 23 other terms
(b) ---~~ + 23 other terms

---~-= ~.
~--- L. _ _ _ _ _ ~
+ 23 other terms
+ 35 terms
+ 35 terms
(e)
+ 35 terms
+ 35 terms
Figure 2 - Diagrams of the three types of processes con-

tributing to the two-phonon scattering: ~photon line,
---- electron (hole) line, and ---- phonon line.
tion potential is made up from the difference between the elec-

tron and the hole contributions. So the effective deformation
potential as measured from resonant Raman scattering is, in gen-
eral, expected to be smaller than that obtained from magneto-
optical absorption experiments Il,?]. In cases where scatter-
ing by one of the carriers is forbidden due to crystal symmetry,
the two types of measurements would yield identical deformation
potentials. Thematrix elements of the deformation potential
given in equation (29) do not arise in infrared absorption.
The initial state of the system will be specified by Inl'O,
n~,n~I,O) with nl incident photons, no scattered photon, n~ and
n~1 phonons at critical points ~ and ~I, and ground electronic
state. The final state is Inl - l,l,n~ + l,n~' + 1,0). Consid-
ering Hex-R and Hex_peff as the perturbing terms in the Hamil-
tonian, third order perturbation theory gives for the differen-
tial scattering cross-section from the initial to the final
states
2
d02TO e 4V n1(n=: + 1) Ws
~ = 4c 4h 2m4a 4M2N I- W=: 2W i
where Wi and Ws are respectively the incident and scattered fre-

quencies and.~ the velocity of light, Q-= q + q'. The Raman
tensor Rtt,(lJ) is given by (keeping only the most resonant
term)
R ,(ij) h2 I <1>c'v' A' (O)<1>cvA (O)"'(v' It' 'plc')

££
cVA
c'V'A'
For simplicity, consider a two band model, i.e. c = c', v = v'.

Neglecting the nondiagonal terms (A +
A') in equation (31) we
have
R
££
,(ij) 'h I Ih(O) 12(vlt'·plc)(clt·plv)tJij(CV,CV)P=:~
A
-1 -1
x(Ecv + £1. - 'liws) (Ecv + £A - 'liwi), (32)
where ~ij(CV,cv) is obtained from rquation (28) with c' = c,

v' = v. The quantity tJij(cv,CV)P=:2 is a parameter of the theory,
and it is adjusted so as to give the experimental intensity.
£1. and <1>1.(0) for the discrete and the continuum states are given
by
n = 1,2, ... ,00,

(33)
for continuum states,

and
1
for discrete states,
(34)
1Taexp(1Ta)
for continuum,
Vsinh(1Ta)
where EB = ~2/2~ao2 is the exciton binding energy, aO the excit-

on radius, ~-l = me",-l + mh,~-l, and a = l/kaO. From equations
(32-34) we get
1 + coth[k: )
+ --
1 foo dkk o . (35)
21TaO 0
tzws - Eg _ 'h k J [tzw. _E
[ 2 2 _ 'h 2 k 2 )
2~ 1 g 2~ J
Eg is the band gap Ecv. Performing the integration in the com-
plex k-plane, we obtain
[2~)3/2 [
x
1
21Tw:;;:1/2 T nL
00
'hw:;;:J n
[EB )3/2 -3
e(x) in equation (35) is the step function. When ~ws < Eg ,
coth(x) ~ icot( Ixl). For one phonon scattering [12], the Raman
tensor has the same form as equation (36) except ~ij(CV,cv) is
replaced by the one phonon deformation potential and Ws = Wi - W:::
and the rhs of equation (36) is multiplied by 2. The result
for uncorrelated electron-hole pair can be obtained from equa-
tion (36) by taking the limit ao ~ 00, i.e. EB ~ O. Then
1 (2
x 8'1Tw::: ;
)3/2[(E':f- - Ws )1/2 -
(E~ - Wi
)1/2] . (37)
The poles in equation (32) at ~wi = Eg - EB/n 2 or ~ws = Eg -

EB/n 2 will be rounded off if the damping of the exciton is tak-
en into account. The ratio of two phonon (at critical point :::)
to one phonon intensities for fixed incident and scattered pol-
arization directions is then given by
where R££,(i), the Raman tensor [12] for one phonon scattering
can be obtained from equation (36) by replacing ~ij(CV,cv) by
the one phonon deformation potential Di(l)(cV,cv), Ws by Wi - W:::
and multiplying the rhs by 2.
In figure 3.~e plot the real and imaginary parts of the Ram-
an tensor R££(~J) as a function of incident photon frequencies
for CdS and GaP. For CdS we have used the experimental value
of EB/~w~ = 0.75. For GaP the excitonic effects are small and
R££'{~~)-is calculated with uncorrelated electron-hole pair.
R££,(~J) is real for nWi < Eg showing that only virtual elec-
tronic transitions can take place in this freque~~y range.
In figure 4 we plot the squared moduli IR££'(~J)12 !9r GaP
and CdS as a function of incident frequencies. IR££'(~J) 12 is
symmetric for free electron-hole scattering and strongly asym-
metric for correlated electron-hole motion. In the latter case
the discrete and the continuum contributions to R££, have the
same signs below the gap but opposite signs above the gap. The
magnitudes of the discrete and the continuum parts are roughly
the same above the gap and thus a strong cancellation occurs
above the gap.
For GaP theory and experiment agree quite well below the
band gap. Above the band gap the agreement is much improved if
the spin-orbit splitting of the valence bands are considered
[9a]. From the experimental value [9a] I2TO(L)/ITO(r) = 0.05,
103~---------------------------------------------------,
~
, ,Is exciton
10' ,,
I
Eg
IO~ ;~2-----7;,1O,.----...,8!----~6-----4~----:-2-----.,0!----:!---~4c---+6--~,.--___.,Il::_O----J
Figure 3 - Plot of the two phonon Raman tensor as a func-

tion of (wi - Wg)/w~ for Wi < Wg. (a) CdS: the solid (E)
and the dashed (E) lines represent, respectively, the real
part of REE' due to discrete and continuum states. (b)
REE' for GaP is represented by the solid (F) line.
we get from equation (38) cVp:::~ ~ 1.3 x 10 3 eV for GaP assuming

that D(l) = 40 eV. In InSb SIP::::?: 'V 1. 5 x 10 4 eV. As explained
at the end of section 2, ~p:::~ for GaP is expected to be much
less than that of InSb.
The effective two-phonon deformation potential given by equa-
tion (28) is a frequency-dependent quantity. The denominator
of the second term is small near resonance and a large cancel-
lation occurs between the two terms of equation (28) lowering
the value of the deformation potential. Far below resonance
the second term decreases and there is less cancellation. Thus
the deformation potential should be smaller in the case of re-
sonant Raman scattering and approaches the value obtained from
DC mobility. It is therefore expected that the ratio I2TO/ITO
for non-resonant Raman scattering would be larger than that for
the resonant case. Indeed, experimental results for non-reson-
ant scattering in materials with wide band gap such as Si, Ge,
C, ZnS, ZnO and for resonant scattering in GaP, CdS, ZnSe show
that I2TO/ITO is larger in the former case [10].
10'....---------------------------,
I~
lis exciton
I
I
I
,
I
I
=
a::s'" 103 f- I
I
C I
g I
:e I
$
I
I
~!~ }(THEO)
10' f- I
~
I +++ GaP (EXPT)
I
I I
I
k
I
/
/
;-
;-
//'
101--
" ...
Figure 4 - I2TO(L) for GaP and I2TO(L) for CdS as func-

tion of incident frequencies. The solid curve is for
GaP and the dashed curve for CdS. The experimental [9a]
points are represented by + sign.
3. SUPERCONDUCTIVITY IN LOW-CARRIER DENSITY SEMICONDUCTORS

The search for superconductivity in a semiconductor has been
a subject of great interest [15]. These investigations were
stimulated by Cohen's theory [15] of superconductivity in many-
valley semiconductors. Experimentally, superconductivity has
been observed in degenerate semiconductors GeTe, SnTe and SrTi03.
For a review see reference [15]. Cohen's many-valley theory
has been successfully applied to these materials [16,1?]. As
stated by Cohen [15], large attractive electron-electron inter-
action arising from the exchange of intervalley phonons is due
to (1): the large momentum transfers in intervalley processes
involving little screening, and (2): the existence of a number
of valleys enhancing the density of states. These ideas can
best be described if we write the attractive electron-phonon-
electron interaction in the form [15]
Vkk,ph (39)
(nwk_k,)2 - (Ek - Ek,)2 '
where Wk-k' is the phonon frequency of wave number q = Ik' - kl

and Mk-k' is the matrix element. If the semiconductor were not
many-valley, only intravalley processes contribute to equation
(39). Because intravalley phonon processes involve small momen-
tum transfer q, the reduction of Vk k,ph from screening would
inhibit superconductivity. Cohen's'model of a manx-valley semi-
conductor allows intervalley processes with k and K' in valleys
whose origins are separated by qo. This implies the momentum
transfer, Iql ~ Iqol, is a large quantity and screening is re-
duced. We see that within the framework of attractive one-phon-
on exchange interaction between electrons, a degenerate semicon-
ductor would not be a superconductor unless it is many-valley.
All three superconducting semiconductors GeTe, SnTe and SrTi03
have been b,elieved to be many-valley [15]. However, Mattheiss
[18] recently recalculated the energy bands of SrTi03 finding
that the conduction band in SrTi03 consists of warped bands at
zone center rather than many-valley at X [15]. This, if true,
would rule out the Cohen-Koonce [15,16] many-valley mechanism.
An alternate one-phonon theory was proposed by Appel [19] for
SrTi03 as due to intravalley exchange of soft Al g optical phon-
ons. The Al g mode deformation potential has recently been cal-
culated by Allen [20] to be much too small compared with the value
assumed by Appel. Thus, Appel's soft mode mechanism does not
appear to influence superconductivity in SrTi03'
The remainder of the lecture is to show that electron-elec-
tron interaction due to two-phonon exchange (defined through
the effective Hamiltonian equation (11] is a likely cause for
superconductivity in some semiconductors. This new mechanism
[21] makes no prerequisite assumption that the band structure
of the material has to be many-valley, and possibly resolves
now that SrTi03, even ifnot many-valley, can still be a superconduc-
tor. We allow the band structure to be either single or many
valley. ~eff in equation (11) can be separated into intraval-
ley ~eff(ra) and intervalley R2eff(er) components
( 40)
( 41)
The superscripts 'ra' and 'er' on the Qsummation in e~ations
140,41) mean the momentum transfer Qhas its origin at Q = 0 and
Q = qO (the separation of the valleys in k-space), respectively;
(42)
with a si~ilar definition for g~ ereff(Q). The quantities

d=,raeff(Q) and d=,ereff(Q) are-~aturally called the two-phonon
intra- and inter-valley deformation potentials, respectively.
In ~eff(ra) and ~eff(er) each of the critical points = are
combinations of large wave numbers near zone edge phonons. In
this lecture, we shall consider the case when the band structure
is not many-valley. Then only U2eff (ra) with IQI = 0 is present.
We shall drop the label Ira' from now on. According to the def-
inition of the effective Hamiltonian via figure 1, the Bardeen-
Pines attractive interaction due to the exchange of two phonons
consists of four distinct processes as depicted in figure 5.
Figure 5 - Two-phonon induced attractive electron-electron

interaction. ~tl) is the one-phonon vertex and ~(2) the
two-phonon vertex.
Since the semiconductor is degenerate, screening of the free

carriers must be taken into account. This dielectric screening
aspect that occurs in the superconductivity considerations is
absent in all cases considered earlier where nearly pure semi-
conductors are involved. Since large momentum transfer ~q~ oc-
curs in every single phonon vertex~(l), the vertex is nearly
unscreened. Whereas every genuine two-phonon vertex ~(2) in-
volves a small momentum transfer ~Q, the vertex is drastically
screened. Hence the presence of the free carriers and its diel-
ectric screening has very different effects on the components
H2 and Hl(E - H)-lHl' This is physically similar to the situa-
tion of non-resonant second order Raman scattering where the
explicit frequency dependence of the term Hl(E - H)-lHl would
tend to perturb the detailed cancellation inherent in two-phonon
interactions, as discussed in section 2.
The results of band structure [12,9a] calculation of~(2) has
shown that H2 is quite large. The concomitant cancellation be-
tween H2 and Hl(E - H)-lHl implies that the latter is of approx-
imately equal strength. The drastic difference in the screening
effects on these two terms implies that predominantly Hl(E - H)-Ix
HI enters into the consideration of the pairing interaction in
the BCS type of theory. Let us denote the total dielectric func-
tion by £(q,w) and write out explicitly the contributions to
d~eff from H2 and Hl(E - H)-lHl as
~-;:: = 3)-;:: ( 2) + 3)-;:: (ll) . (43)

- - -
The screened electron-two-phonon interaction would then be de-
scribed by equation (42) but with the expression for ~-;:: in equa-
tion (43) replaced by
~~ (ll)
+ (44)
£(Q,w~) £2(q~,w~)
From the discussion presented earlier, it is meaningful, as

a first approximation, to put £(q~,w~) = 1 and neglect the first
term in (44) as compared with the second. In the BCS theory,
the interaction lJ~(ll) contributes the attractive kernel
( 45)
where
(46)
In equation (45) o~ = nw~/EF, 8~ = ~w~/EF' 0 = ~w/EF and EF is

the Fermi energy. The kernel in the energy gap equation [15]
is
(47)
Kl and Kc arise from one-phonon and Coulomb intravalley inter-

actions. We should remind ourselves that the intravalley one-
phonon kernel Klra is smaller than the Coulomb kernel in most
degenerate semiconductors ever considered, and would not, by
itself, produce a superconducting transition. It is useful to
make a comparison with Cohen's [15] one-phonon intervalley in-
teraction even though we are primarily concerned here with not
a many-valley semiconductor. The two-phonon kernel K(ll) en-
joys the same privileges as Cohen's intervalley one-phonon ker-
nel Kler in being unscreened. If the Fermi surface is not in a
many-valley configuration (e.g. SrTi03), Cohen's Kler should be
dropped. However, K(ll) which enjoys the same privilege as
Cohen's Kler is still present and contributes a large attractive
part to the total kernel. Thus superconductivity in SrTi03, if
indeed not many-valley, can be caused by two-phonon intraband
processes. If the Fermi surface is many-valley (SnTe and GeTe) ,
each of the kernels Kler, and K(ll) make contributions to the
total kernel. The relative importance of two-phonon (intra- or
inter-valley) processes as compared with Cohen's intervalley
processes can be assessed by a comparison of d~(ll) with the
product aqO~. ~ is the one-phonon intervalley-deformation pot-
ential [15]. The k- and w-dependences of K(ll) are identical
to Kler.
We have solved the gap equation [15] with the total kernel
K = Klra + K(ll) for SrTi03. Klra is taken as equation (3) of
Koonce et al. [16]. K(ll) is given by equation (45) appropri-
ately screened [16] by the dielectric function. The normal-
state parameters used in evaluation of the kernels are the same
as in reference [16]. For a two-phonon deformation potenti~l
d::(ll) that corresponds by equation (46) to a value of (.v(ll)p:1)::=
8.6 x 10 3 eV, the calculated T c versus the concentration n curve
fits the data of reference [16] well. Technical details of the
calculation and the extension of the considerations to the gen-
uine many-valley semiconductors will be presented elsewhere [21].
REFERENCES
1. Ngai, K.L. and Johnson, E.J. (1972). Phys. Rev. Lett., 29,
1607.
2. Holstein, T. (1959). Phys. Rev., 113, 479.
3. Herring, C. (1961). In Proceedings of The InternationaZ
Conference on Semiconductor Physics~ Prague~ 1960, (Acad-
emic Press, New York), p. 60.
4. In reference [1] it was argued that for near zone-edge NPO
phonons, detailed cancellation is not probable. However,
the assumption made there that only H2 contributes to two-
phonon scattering is unnecessary. Finite contributions to
Hl(E - H)-lHl with intermediate states from all bands exist.
Interference is still expected but cancellation is unimport-
ant for InSb type band structure. The results and conclu-
sions of reference [1] remain unchanged.
5. The value of ("P~)L,-L given here differs from 5.6 x 10 4 eV
obtained in reference [1]. This difference is due to:
(1) the form of lt2 eff in equations (3-S) which does not have
the factor 2/3 and, ~2) the sums over j and j' absorbed in
the definition of tp2 in reference [1] are now explicit.
6. Magneto-phonon effects: Stradling, R.A. (1972). Proceedings
of the Eleventh International Conference on The Physics of
Semiconductors, Warsaw, Poland, 1972, p. 261; Ngai, K.L.
(To be published).
7. Free carriers absorption: Ganguly, A.K. and Ngai, K.L. Phys.
Rev., (to be published).
8. Mobility of Si: Ngai, K.L., Norton, P. and Henvis, B.W. (To
be published).
9. Resonant Raman scattering: (a) Weinstein, B.A. and Cardona,
M. Phys. Rev., (to be published); (b) Cardona, M. NATO Sum-
mer School Lecture Notes, Antwerpen, 1973; (c) Ganguly, A.K.
and Ngai, K.L. Phys. Stat. Sol., (to be published).
10. Non-resonant Raman scattering: Ngai, K.L. and Ganguly, A.K.
(To be published).
11. It is interesting to note a similar situation: the hole-
nonpolar-optical-phonon deformation potential for all 111-
V's and IV's are of the same magnitude ~40 eV.
12. Lin-Chung, P.J. and Ngai, K.L. (1972). Phys. Rev. Lett.,
29, 1610.
13. Ganguly, A.K. and Birman, J.L. (1967). Phys. Rev., 162, 806.
14. Knox, R.S. (19S3). Theory of Excitons, Supplement No.5 of
Solid State Physics, (Academic Press, New York).
15. Cohen, M.L. (1964). Phys. Rev., 134, ASll; Cohen, M.L.
(1969). In Superconductivity, (ed. Parks, R.), (Dekker, New
York), p. 61S.
16. Koonce, C.S., Cohen, M.L., Schooley, J.F., Hosler, W.R. and
Pfeiffer, E.R. (1967). Phys. Rev., 163, 380.
17. Allen, P.B. and Cohen, M.L. (1969). Phys. Rev., 177, 704.
18. Mattheiss, L.F. (1972). Phys. Rev., B6, 4718.
19. Appel, J. (1969). Phys. Rev., 180, S08.
20. Allen, P.B. (1973). Bull. Amer. Phys. Soc. II, 18, 327.
21. A preliminary report of this mechanism has appeared in an
article by Kaplan, R. and Ngai, K.L. Comment. Solid State
Phys.. For details see Ngai, K.L. (To be published).
TEMPERATURE DEPENDENCE OF FREE POLARON OPTICAL ABSORPTION
w. HUYBRECHTS and J. DEVREESEt
Rijksuniversitair Centrum Antwerpen, Belgium
I. INTRODUCTION
A free electron (or hole) in a polar semiconductor can absorb
infrared energy as a consequence of its interaction with the wave-
length LO phonons.
In calculating the free carrier absorption due to this inter-
action, the charge carrier accompagnied by a self-induced polar-
ization well can be treated as a quasi-particle called polaron.
This concept is discussed in the lectures by Devreese-Evrard-
Kartheuser.
Research into the infrared free polaron absorption has been
made for the first time by Visvanathan [1] and by Gurevich-Lang-
Firsov (GLF) [2]. Of late the absorption coefficient has been
studied in two different ways.
In the first approach the calculation of the optical-absorp-
tion of free polarons is worked out using the fact that the ab-
sorption of infrared energy by the polaron in its groundstate
goes with emission of a LO-phonon [3,4]. This method enables to
use in a very instructive way the canonical transformation form-
alism of Lee-Low-Pines [5]. This investigation confirms the GLF-
approximation linear in a (electron-phonon coupling constant) to
the absorption coefficient in the zero-temperature case. Enlarge-
ment of this formalism leads to a correction of order a 2 on the
GLF result [4,6]. This way to tackle the problem has the gain to
be very simple and informing, however, the applicability of the
results is restricted to weakly polar semiconductors (a < 1).
t Also: Departement Natuurkunde, Universitaire Instelling

Antwerpen, and SCK/CEN, Mol, Belgium.
317
318 w. HUYBRECHTS AND J. DEVREESE
A second approach to the calculation of th~ optical-absorption

coefficient [7,8] starts from the dynamical impedance function
for free continuum polarons as calculated by Feynman-Hellwarth-
Iddings-Platzllian (FHIP) [9]. The intricacy of this method is a
loss. Nevertheless it is possible to ascertain the absorption
coefficient for all values of the electron-phonon coupling with-
in the framework of the FHIP-approximation.
In the following the behaviour of the optical absorption co-
efficient as function of the frequency n is examined for various
temperatures.
2. DISCUSSION OF THE FREE POLARON ABSORPTION

As in references [3,7], we start from the expression:
4nN nImX(n)
(1)
2
no [n - ReX(n)]2 + [ Imx(n)]2 '
defining the polaron absorption coefficient as function of the

frequency n in units ~ = m = w = e = 1, where m is the bandmass
of the electron and w is the frequency of the LO phonon. In equ-
ation (1) N is the density of free polarons and
Imx(n) = Imf:dUSin(I"lU)S(U), (2)
Rex(n) Imf:du[1 - cos(I"lU)]S(u), (3)
with
where P(x) = (eX - 1)-1, 6 = l/kT, R = (v 2 - w2 )/w 2v and v, ware

parameters depending on a and determined by calculating the en-
ergy of the groundstate of the polaron. The notation used in
equations (2-4) is consistent with the work of FHIP.
The function ImX(n) (2) can be calculated analytically and
results in:
ImX(n) = ~(£.)3 6
31n w
3/2 sh(~6n)
sh(~6)
'"
L
bn
22n+2n!an+1
n=O
n 4
n!
x
L
k=o
k! (n - k) ! L IYil n+1Kn+l(aIYil), (5)
i=1
with
Yi n ± [(n - 2k)v ± 1],
FREE POLARON OPTICAL ABSORPTION 319
where i = 1, ... ,4 corresponds with the four possible combinat-
ions of sign in Yi.
In equation (5):
(6) .
and
. RS (7)
b = sh( ~sv)
The expression for Rex(~) (3) is computed in collaboration

with Dr. J. De Sitter on the IBM 1130 of the Rijksuniversitair
Centrum Antwerp. For further details of calculation we refer to
[10] •
Previous to discussing the general behaviour of the polaron
absorption coefficient for different temperatures we extract from
equations (1-4) the asymptotic limit ~ + 00, and an approximation
to r(~) valid in the limit of weak electron-phonon coupling.
In the asymptotic limit ~ + 00, Imx(~) (2) and Rex(~) (3) can
be simplified into:
Imx(~) Rex(~)
2a
=~ [1 +
~
2P(S)]Y~, (8)
such that r(~) reduces to:
(9)
This result is identical with the asymptotic behaviour of the

perturbation results proposed by Visvanathan [1] and Gurevich-
Lang-Firsov [2].
In the limit of weak electron-phonon coupling (a + 0) we have
v = wand R = 0 in equation (4), so that S(u) (4) and consequent-
ly Imx(~) (2) and Rex(~) (3) are linear in a. For frequencies
~ ~ 1 and in the limit a + 0, r(~) (1) can be approximated by
r(~) = 4nN Imx(~) (10)

no ~3
where Imx(~) is given by equation (5) with a S/2 (6) and b 0

(7). The final result is:
1
r (~) =
4nN2a[~)2 sh(~S~)
no 3 n sh(~S)
(~ + 1)K1[~S(~ +
x
[~ ~ 1, a + 0] .
320 W. HUYBRECHTS AND J. DEVREESE
This approximation confirms the perturbation result of Gurevich-

Lang-Firsov.
The absorption coefficient r(~) (1) is shown for weak elec-
tron - LO phonon coupling in figure 1. At T = 0 the peak in
the structure of the absorption coefficient r(~) in ~ = 6w/5 is
t \
kT
lim
~ 0.9 ----0.001
~
\ - - - - - 0.01
\ -._._.- 0.5
- •• _ •• _- 1
0.8
\ ••...•....•.•.. 2
". \.
"
. \
0.7
\\
'-t
",.\'.,.
0.6
\
0.5 ....... .
........ \ \ " "'
..... .
IX = 1
.\........'.
~ '
0.4
:~
"
.\ "t •••
'\ ".
0.3
"
'.
'" '"..........
".
"
" ' ...... .
.", "" ..... ..................
0.2 "
....... ..... "- ..

0.1
........ -.-.-
o
Figure 1 - Free polaron absorption in weakly polar semi-

conductors (a 1).
entirely due to the emission of one real LO phonon by the polar-

on as a consequence of the absorption of infrared energy. As
temperature increases (0 < T < ~w/2k), the absorption coeffi-
cient is composed of a Drude-like background, resulting from
the scattering of the polaron on the thermally excited optical
phonons, together with the peak situated around ~ = 6w/5, which
is a consequence of the emission of a LO phonon by the polaron.
By further increase of temperature (T > ~w/2k) the thermally
excited phonons destroy the polarization induced by the charge
FREE POLARON 321
carrier in the polar lattice. This is seen in figure 1 where
the absorption coefficient has a Drude-like behaviour compara-
ble with free carrier absorption. In the limit n + 0 the value
of the absorption coefficient decreases with increasing tempera-
ture. This is consistent with the lowering of the mobility due
to the scattering of the charge carrier on the optical phonons.
In the asympotic limit n + 00, r(n) behaves as predicted by equa-
tion (9).
In the intermediate coupling region (0 > 2) the temperature
dependence of the absorption spectrum is of the same type as
discussed in case of weak coupling. Nevertheless the peak in the
structure of the absorption coefficient is maintained even at
higher temperatures (figure 2). The more the electron-phonon
\ kT
\ /iw
\. 1
'.
\
0.5
0.1
\ 0.001
-,........ - ..,",
0.4
\,
..
,,
,
\ \
\. ..
0.3 \, '.
\ ~
"'. \.\
'., ~'. (%=2
0.2
\
\
\.\
\ \.
\ \ \ ",
0.1
., '.,
.'., ..... "'.............
......, ._-
o 4 6 --n-
Figure 2 - Free polaron absorption (0 2).
322 w. HUYBRECHTS AND J. DEVREESE
coupling is important, the more dominant is the role of this
typical polaron structure in the absorption coefficient.
As coupling increases (a > 4) the transition to the relaxed
excited state (RES) [7] remains the dominant peak in the struc-
ture of the free polaron absorption coefficient for low temper-
atures (T < nw/5k) (figure 3). As temperature is increased
kT
hw
-----0.25
ac o.s ---0.001
0< = 5
0.1
o 2 4 6 9 --n-
Figure 3 - Free polaron absorption in polar semiconductors
with intermediate electron - LO phonon coupling (a = 5) -
low temperatures.
(T > nw/5k) the thermal excitation of optical phonons diminshes

the stability of the RES. This is illustrated in figure 4
kT
t hw
g 0.5
- •• - •• -
-._._. l
2
- - - - - 0.5
---0.25
0.4
0<=5
""
0.3
0.2
..................
-.~:.:.-....,,~.:.:-
...............
.. -- .....
............. .,.........-....... .., ...
0.1
........... ...................
6 9
•
0 4
Figure 4 - Free polaron absorption in po~ar semiconductors

with intermediate electron - LO phonon coupling (a = 5) -
high temperatures.
FREE POLARON 323
(a = 5) where for temperature T = hw/k, the structure of the
polaron absorption coefficient shows a broad peak with maximum
around n = 3.8 w. Increasing the temperature broadens the peak
together with a decrease of the maximum and a shift of the po-
sition to higher values of frequency.
3. CONCLUSION
The calculation of the temperature dependent behaviour of
the free polaron absorption as shown, bears out the asympotic
behaviour of the perturbation result of Visvanathan [1] and
Gurevich-Lang-Firsov [2]. In the limit of weak coupling (a-+ 0)
it could be shown that the Gurevich-Lang-Firsov result is a
valid approximation to our predicted result for frequencies
n > 1. As coupling increases (a > 0.5) the role of the correl-
ation between the optical phonons can not be neglected [4] and
our 'approximation to the absorption coefficient (1) has to be
worked out completely.
The temperature dependent behaviour of the polaron absorp-
tion shows a free carrier background on which a typical polar-
on structure is superposed. In the low coupling region (a < 1)
the peak on the spectrum disappears for high temperatures.
This implies that the interaction of the free carrier absorp-
tion in CdO (a = 0.75) as done in reference [11] does not agree
with our prediction. On the other hand, the experimental re-
sults in polar materials such as: Te (a = 0.23) [12] and n-GaAs
[13] are consistent with our theory. In the intermediate and
strong coupling region (a > 2) the polaron-peak in the struc-
ture of the absorption spectrum is maintained even at higher
temperatures. The general behaviour of free polaron absorption
as function of temperature suggests a further comparison of
the predicted results with experiments in materials such as
SrTi03 [14] and BaTio3 [15].
REFERENCES
1. Visvanathan, S. (1960). Phys. Rev., 120, 376.
2. Gurevich, V., Lang, I. and Firsov, Yu. (1962). Sov. Phys.
Solid State, 4, 918.
Stat. Sol. (B), 48, 77.
4. Huybrechts, W. and Devreese, J. (1973). Phys. Rev., B8, 5754.
5. Lee, T., Low, F. and Pines, D. (1953). Phys. Rev., 90, 297.
6. Huybrechts, W. and Devreese, J. (1971). (Technical Report),
(BLG 458, S.C.K., Mol, Belgium), (unpublished).
Rev., BS, 2367.
8. Huybrechts, W., De Sitter, J. and Devreese, J. (1973).
9. Feynman, R., Hellwarth, R., Iddings, C. and Platzman, P.
(1962). Phys. Rev., 127, 1004.
10. Huybrechts, W. and Devreese, J. (To be published).
324 W. HUYBRECHTS AND J. DEVREESE
11. Finkenrath, H., Uhle, N. and Waidelich, W. (1969). Solid

12. Selders, M., Gspan, P. and Grosse, P. (1971). Phys. Stat.
Sol., B47, 519.
13. Osamura, K. and Murakami, Y. (1972). Jap. J. Appl. Phys.,
11, 365.
14. Baer, W. (1966). Phys. Rev., 144, 734.
15. Berglund, C. and Braun, H. (1967). Phys. Rev., 164, 790.
PEIERLS-FROHLICH INSTABILITY AND SUPERCONDUCTIVITY
IN LINEAR CHAIN CRYSTALS
H. GUTFREUND
The Racah Institute of Physics, The Hebrew University,

Jerusalem, Israel
B. HOROVITZ and M. WEGER
Nuclear Research Center-Negev,
P.O. Box 9001, Beer-Sheva, Israel
The Racah Institute of Physics, The Hebrew University,
Jerusalem, Israel
Recently, there has been an increased interest in linear

chain crystals. These are generally of two kinds: S-tungstens
like V3Si or Nb3Sn which are built of 3 orthogonal linear
chains [1]. These crystals possess the highest known Tc: ~20oK.
The other kind are organic salts like the TTF-TCNQ which has
recently shown a high conductivity peak at 60 0 K [2]. Also the
compound K2Pt(CN)4BrO.3.3H20 is built from linear chains [3].
To study these materials we use a simplified model of elec-
tron-phonon interaction in one dimension:
Cp, aq are electron and phonon destruction operators. We use

£p = p2/2m and concentrate on the phonon dispersion and weight
function. Phonons are responsible for the lattice instability
and also can be used to form Cooper pairs.
The poles of the phonon Green's function are given by
2w q 0 2
w O.
D(q,w)
325
326 GUTFREUND, HOROVITZ AND WEGER
We approximate IT by
which has the physical meaning of an electron-hole excitation.

The validity of this assumption has been studied [4]. In fig-
ure 1 we see the region ImITO ~ 0, where electron-hole excita-
tions are possible. We see two regions of possible signific-
ant interaction: q ~ 0 and q ~ 2PF.
Figure 1 - The region of possible electron-hole excitation

energies and momenta in a one-dimensional system (shaded
area) .
q ~ 0 is actually dealt with by the Tomonaga model [5], and

we shall concentrate on the peculiar effects· near q = 2PF. In
this region we assume gq2 and Wqo to be constants and define
the problem by two parameters: 8 ~ g2PF 2 , aO = W2PFO/ 2£F' Per-
forming analytic continuation to ITO(q,w) we get the solutions
for T = 0 [6] in figure 2.
We see two major effects: the appearance of a double branch,
and the appearance of solutions with Rew = Imw = 0 in the lower
branch. This reflects the strong Kohn anomaly in one dimension,
due to the large phase of q = 2PF electron transitions. The up-
per branch is a phonon resonance in the region of electron-hole
excitations, and therefore Imw ~ O.
A solution Rew = Imw = 0 means a static distortion which is
the Peierls-Fr~hlich instability [7,8].
It turns out that a single distortion at q = 2PF is enough
to stabilize the system. Such a distortion introduces a gap
in the electron spectrum at Ipi = ~q = PF· Using an electron
PEIERLS-FROHLICH INSTABILITY 327
1.0~---r------"---~----.----...-----'
0.8
0.6
0.4
0.2
-0.03 0.03
x
Figure 2 - A typical phonon dispersion curve at T O. near
.q = 2PF. for s = 0.25 and a = WO/2EF = 0.01. The broken
lines correspond to w = ±2vFq'. The broken curves are the
negative-imaginary parts of the damped solutions with w 0 +
(the higher one) and with w = 0 (the small bump around w = O.
q = 2PF). Momentum is measured in units of x = (q - 2PF)/
2PF = q'/pp.
dispersion with a gap ~, we find a single distortion appears

. [4] at q = 2PF if ~ = 8E~e-2/s.
The same result was obtained by Fr~hlich [8] by minimizing
the energy of the system with the distortion as a variable. In
+
figure 3 we have the phonon .dispersion for T = 0, ~ o. If
~ ~ wo the upper branch does not appear.
It is instructive to consider the weight function (or the
spectral density function) B(q.w) in figure 4. The lower branch
is a a-function. It moves up from w = 0 and the upper branch
diminishes in strength.
Let us now extend the calculation to T + o. We are interest-
ed in T« TF, so that we use an inclined step function for np
and solve analytically for ITo(q.w,T). We find a temperature
such that the solution Rew = Imw = 0 first appears. This is
the transition temperature to the distorted lattice. We obtain
[9]
1- 2/s
Tp = 2EFe (Tp« EF).
A similar result was obtained by Kuper [11].

The phonon dispersion at T = Tp is shown in figure s. Again,
the upper branch exists only if wo ~ Tp. In figure 6 we see how
the weight function B(q,w) develops with temperature at q = 2PF.
At T = Tp we note a divergence B(q,w) ~ l/w.
1.0'r---r---r--rr---~-r-"'-r- --r--'"T"'T---r--,
\ \ I
\ S = 0.325 ---\ I
\ \ I
0.8
\
\
\
"
\
\
\
\
,
\
0.6 \
,,
'~---
0.4 \
\
\
0.2
- 0.008 - 0.006 - 0.004 - 0.002 0.002 0.004 0.006

x
Figure 3 - A typical phonon dispersion of the deformed
lattice at T = 0, for s = 0.25 and a = 0.01. The broken
curve is the imaginary part of the damped branch, which
exists only between the singularity lines (broken lines).
When s = 0.325, these lines are too high for the damped
branch to occur.
To summarize the features of the instability, let us define

the critical parameter Sc(q,T) such that for Sq = Sc(q,T) an
instability appears at that q and T. This is shown in figure 7.
At T = 0 we see that for any s 0 the lattice is unstable at +
q = 2PF. However, for T ~ TF the curve is flat, and a modest
variation of Sq with q may produce instability at some other q
values. This IS the feature of the Labbe-Friedel-Barisic model
for the S-tungstens [10]. They deal with T ~ TF and show that
an instability near q = 0 dominates the Kohn instability at q =
2PF, thus producing the martensitic transformation observed in
these materials.
Now the question arises about the electric conductivity of
the distorted lattice. Due to the gap at ipi = PF it cannot be
a usual conductor. However, Fr~hlich [8] and recently J. Bar-
deen claim that the system can show fluctuation towards super-
conductiv~ty. The idea is that the lattice distortion can have
a phase el~, and if ~ = ~(t) the distortion can move, carrying
with it the whole sea of electrons. We consider, on the other
hand, the possibility of usual superconductivity with Cooper
pairs [9].
We use the McMillan simplified formula [12]
IOr------------.-----------.------------r-----------,
a ...... x = 0
b ...... x = 0.001
c ...... x = 0.002
c d ...... x = 0.003
e ..... :x = 0.004
b f... ... x = 0.005
0.1
0.01 0J:---L---'-...L..L-..1.:0:L:.5L.1.------'L----'--:-I:1.0::----L---------,I:L:.5,....------'--....;~
w/wo
Figure 4 - The spectral density B(q,w) in the distorted

lattice at T = 0 for a = 0.01, S = 0.25 and for various
values of q around 2PF, measured in units of x= (q- 2PF)/
2PF. The vertical arrows correspond to the undamped
branch and their height is the contribution of this
branch to the sum rule foo~ B(q,w)dw = 1.

OWO
Tc -- ee -(1+1.)/1. ,
where A is an effective coupling given in our case by
SWOfOO 1
--4- 0 ; B(q,w)dw
1
e should measure the average energy of the phonons
e ~ f:WB(q,W)dW = wo,
which is an exact sum rule.

The equation for Tc is solved, and we obtain:
1.0r--""T""---.----.----.----.-----r----r----..----,
0.8
Figure 5 - A typical phonon dispersion near q = 2PF, at

T = TITF = 0.0018 (T = Tp), for a = 0.1 and s = 0.25.
The broken curves are the negative-imaginary parts of the
two branches. The higher broken curve corresponds to the
higher'excitation branch.
1.01 .--=::J:----,----,---.,.--,,----,
0.8
0.6
Critical coupling
S,(q,T)
0.4
T/TF = 0.Q1
T/TF = 0.001
0.2
T=O
o 0.5 1.0 1.5 2.0 2.5

qjPF
Figure 6 - Critical coupling curves Sc(q,T) for several

values of T = TITF.
tOr--.,---,---r--,TT'"--r--,--,.---,I'TT-.....,---,r---,--.,
TfTF = 0.005
0.1
to
F---------+---------+-------~
TfTF = 0.05
0.5 0.75
Figure 7 - The function wOB(q,w) for a = 0.1, s 0.25,

q = 2PF and various values of T/TF.
In figure 8 we see curves for Tc and Tp and we note the pos-

sibility that Tc > Tp ' if e is high enough. For TTF-TCNQ Tp =
60 o K, TF ~ 0.2 eV, so that s = 0.375. Now we claim that Tp is
a transition to an insulator, and Tc ~ Tp in this case, i.e. we
are near the intersection of the Tc and Tp curves. However, we
should be careful about the formula we use for Tc. As noted by
Patton and Sham [13] phonons with w ~ T tend to suppress Tc.
So our curve for Tc should be corrected near the intersection
with Tp , and bend downwards.
If the intersection is at 60 o K, then we need e of several
hundred degrees which must correspond to an optical branch of
the system.
REFERENCES
1. For a recent review, see: Weger, M. and Goldberg, I. (1973).
Solid State Physics, (eds. Seitz, Turnbull and Ehrenreich),
(Academic Press).
2. Coleman, L.B. et al. (1973). Solid State Commun., 12, 1125.
3. Comes, R., Lambert, M., Lanois, H. and Zeller, H.R. (1973).
Phys. Rev., B8, 571.
4. Horovitz, B., Weger, M. and Gutfreund,H. (Preprint).
5. Engelsberg, S. and Varga, B.B. (1964). Phys. Rev., 136,
A1582.
6. Horovitz, B., Gutfreund,H.,and Weger, M. (1972). Solid
a Tp
0.04
b Tc,6/2TF=0.035
c Tc, 6/2TF =0.01
0.03
0.02
0.01
0.15 0.2 0.25 0.3 0.35 0.4 s
Figure 8 - Tp (curve (a» and Tc (curves (b,c» for two

values of 8/2TF as a function of the coupling parameter
s. The dotted vertical line indicates the s value for
TTF-TCNQ.
7. Peierls, R.E. (1953). Quantum Theory of Solids, (Oxford,

London), p. 108.
8. fr6hlich, H. (1954). Proc. Roy. Soc., A223, 296.
9. Gutfreund, H., Horovitz, B. and Weger, M., J. Phys., C,
(to be published).
10. Labbe, J. and Friedel, F. (1965). J. Phys., 27, 153, 303;
Barisic, S. (1972). Ann. Phys., 7, 23.
11. Kuper, C.G. (1955). Proc. Roy. Soc., A227, 214.
12. McMillan, W.L. (1968). Phys. Rev., 167, 331.
13. Patton, B.R. and Sham, L.J. (Preprint).
THE ABSORPTION AND THE GROUND STATE ENERGY
OF FREE POLARONS
L.F. LEMMENSt and J.T. DEVREESE~
Department of Physics and Institute for Applied Mathematics,

University of Antwerp, Wilrijk, Belgium
1. INTRODUCTION
A ground state theorem [1] valid for the self-field of a part-
icle is discussed; the theorem relies on the long wave-length be-
havior of the current-current correlation function. Using the
scale properties of the polaron system, the ground state energy
is related to the kinetic energy by a differential equation with
an appropriate initial condition and it was possible to show ex-
act relations between the ground state energy and the number of
virtual phonons in the polaron-cloud and the interaction energy
[2] which are an extension of the Pekar relations.
The ground state energy derived from the optical absorption
for free polarons [3], using the expression of the function x(w)
obtained by Feynman-Hellwarth-Iddings-Platzman (hence forth de-
noted by FHIP) [4], was compared with the ground state energy
calculated by Feynman [5]. It turns out that there is no signi-
ficant deviation between both values for the ground state energy.
2. DERIVATION OF A SUM RULE

Let us consider the current-current correlation function for
a free charge carrier in interaction with a phonon-field. This
function is in the linear response theory given by the following
expression [6]
t Aspirant of the National Foundation of Scientific Research
(N.F.W.O.) .
~ Also at SCK/CEN Boeretang 200, Mol, Belgium.
333
334 L.F. LEMMENS AND J .T. DEVREESE
Xl 1 (w) (1)
where X))(t) is an average over the ground state for low temp-
erature
(2)
Jx(t) is the current operator in the Heisenberg picture and is

given by the moment of the charge carrier multiplied by the ra-
tio of the charge and mass of the carrier, at least in the Frtlhlich
model [7,8] where a parabolic energy momentum relation is con-
sidered for the charge carrier. The mass is the band mass of
the carrier. e(t) is the Heaviside step-function.
exp(~ Ht)~ Pxexp( - ~ Ht), (3)
where H is the Frtlhlich Hamiltonian
(4)
The component Vk of the electron-phonon interaction matrix is

given by
(5)
where Eoo and EO are respectively the dynamic and static dielec-
tric constant. The electron-phonon interaction is independent
of the electron-mass: this is a consequence of the electrostatic
nature of the interaction.
Writing down the spectral representation of the current-cur-
rent correlation function, one shows that the integral over the
positive frequencies of this function is proportional to the kin-
etic energy. To obtain the spectral representation one intro-
duces the complete set of eigenfunctions of the Frtlhlich Hamil-
tonian in (2) and integrates over the time explicitly in (1).
where
ABSORPTION AND GROUND STATE ENERGY 335
An integration over all the positive frequencies of the imagin-
ary part of the current-current correlation function can be done
easily considering that:
x +
1.
"Z-E:
= p[!J - ilTo(x),
X
(7)
where P stands for principal value and o(X) is the Dirac delta
function
(8)
After summation over the complete set one obtains
(9)
For symmetry reasons the x-component of the kinetic energy is

one third of the total kinetic energy.
3. THE GROUND STATE THEOREM AND SCALE TRANSFORMATION

The ground state energy of the polaron is given by
(10)
if this energy depends on a parameter, then the Feynman-Hellmann

theorem states that
(11)
If one takes the inverse of the mass A = 11m as a parameter,

one obtains
(12)
Although one obtains now a differential equation that relates

the kinetic energy with the ground state energy the integral of
this equation is difficult to solve due to the lack of an appropri-
ate initial condition. Now one changes the Hamiltonian to dimen-
sionless units [9]. The energy of the ground state can then be
written as:
(13)
336 L.F. LEMMENS AND J .T. DEVREESE
where'F(a) is a function of the dimensionless coupling constant
a only
(14)
Using the mass dependence of the coupling constant one can ex-
press the kinetic energy as a function of the derivative of the
ground state energy with respect to a
(15)
because
(16)
In the same way the interaction energy can be derived from the
ground state energy
(17)
Using the frequency of the phonons as a parameter, the Feynman-

Hellman theorem states then:
(18)
where N is the mean number of the phonons in the polaron-cloud.

From equation (13) one obtains
because
da
WL - - -- -
dWL -2' a,· (20)
combining equations (18,19) one obtains for the mean number of

phonons N:
(21)
Equation (15) allows for solving the differential equation form-

ally with the initial condition that the ground state energy is
equal to EO (0) for a z.ero.
EO(a) - EO(O) = - 2 fa ~
d '
a'
Ek·
~n
(a') (22)
°
Using the sum rule for the kinetic energy, we obtain the ground
state theorem for the current-current correlation function:
° °
E (a) - E (0) = - -3mJa -
da', JoodW
.- Imx)) (w, a' ) • (23)
e2 ° a ° 7T
4. THE ABSORPTION AND THE GROUND STATE THEOREM

As an example one obtains the ground state energy in the
weak coupling limit (a small) using the expression of Gurevich,
Lang and Firsov [11] for the current-current correlation func-
tion
-3J a da'
~
Joo n-
dw I
mx))
GLF(
w,a
') - a, (24)
where
° °
2 -2 l
ImX))GLF a7TW (w - 1)2 W > 1,
3
(25)
o W < 1;
the units are: m = wL = ~ = e = 1.

In order to obtain an expression for the ground state energy,
which is valid for a wider range of the coupling constant, we
have used the function X(w) as defined in FHIP. Therefore it is
useful to indicate the relation between the current-current cor-
relation function and the function x. The current-current cor-
relation function is defined as the linear coefficient that re-
lates the change of the current in the system with the vector
potential applied to the system [6]:
(26)
In FHIP the impedance function Z(w) is defined as the coeffic-

ient between the current and the applied electric field:
338 L.F. LEMMENS AND J.T. DEVREESE
(27)
Using the relation between the electric field and the vector-
potential one obtains that
iw (28)
x;; (w) Z(w) •
Combining relation (28) with the equation for X(w) which happens
to be an auxiliary correlation function in the FHIP approach:
iwZ(w) = w2 - X(w), (29)
one obtains that
w2 Imx(w) (30)
Imx;;(w)
Comparing this expression for the current-current correlation

function and the expression for absorption in reference [3], it
turns out that the first moment of the absorption is related by
the theorem (23) with the ground state energy. A numerical inte-
gration of (30), using the expression for the real and imagin-
ary part of X(w) obtained in references [3,4], gives a ground
state energy which is very close to the groundstate energy ob-
tained by Feynman [5]. The two energies are compared in figure
1 and in Table I, the ground state energy is given for a set of
TABLE I
a EO Theorem
0.5 -0.503
1.0 -1.014
1.5 -1.533
2.0 -2.059
2.5 -2.593
3.0 -3.135
3.5 -3.687
4.0 -4.251
4.5 -4.831
5.0 -5.430
ex ----
Figure 1 - The Feynman ground state energy is indicated

by a full line, while the dots are the energies calcu-
lated using the ground state theorem.
coupling constants.
The ground state in the strong coupling limit can be de-
duced from (30) by making the observation that the expression
for the absorption has a Lorentzian shape when the coupling
constant a is greater than 6, and that the line-width of the
relaxed excited state (RES) decreases with increasing coupling.
This allows that the current-current correlation function can
be written as:
2
w
w + wO
ImX)) (w) (31)
where wO indicates the peak position of the RES and the line-
width y is given by
y Imx(w)1 ' (32)

w w=wO
and wo can be calculated from:
lim ReX(w) Iw=wo

2
W() (33)
(l-+OO
One obtains then for the ground state energy
(l
2
- ~ , (34)
and Wo is given by
(35)
The derivation we give here, proves only that the expresson for
x(w) contains also the strong coupling limit, a more interest-
ing consequence of this derivation is that the sum-rule (9) can
be used to predict the peak position at least qualitatively
[12] .
5. DISCUSSION
We have derived this ground state theorem for free polarons.
It can be generalized without any difficulty for a whole class
of particle field interactions, which do not depend on the mass
of the particle; as long as the energy momentum relation of the
particle is parabolic; the last restriction is necessary, other-
wise the expectation value of the square of the velocity is not
directly proportional to the kinetic energy, and there is an
additional term in the current-current correlation function
arising from the non-parabolicity [13]. The analysis we made,
concerning the relations between the ground state energy and
other expectation values over the ground state can also be gen-
eralized for the same class of particle-field interactions.
From the Gurevich-Lang-Firsov expression for the current-cur-
rent correlation function we obtain the same ground state en-
ergy, as the second perturbation ground state energy [7] or the
Lee-Low-Pines ground state energy [7]; there is no way to make
a distinction between both with the use of the ground state
theorem, because the current-current correlation function hap-
pens to be identical for both approximations as far as the weak
coupling limit is concerned [14].
From the function X(w) of FHIP we obtained the Feynman ground
state energy. Although both calculations are evaluated in the
framework of the path-integral formulation of Quantum Mechanics,
there is no a priori reason, why they should be equivalently
accurate. The accuracy of the Feynman variational approach
was tested on a exactly soluble model [15]. Obtaining the same
result for the ground state using the FHIP X(w) function we may
claim that this function treats the excited states of the po-
laron with relatively great accuracy and this gives us a justi-
fication for the so called 'up-side down' approximation made by
FHIP in calculating the impedance function Z(w).
From an asymptotic expansion of expression (30) for strong
coupling, we were able to rederive the Pekar result for the en-
ergy of the ground state [10].
ACKNOWLEDGEMENT
The authors would like to thank Ir. J. De Sitter for perform-
ing the numerical calculations and for helpful conversations.
REFERENCES
1. Lemmens, L.F., De Sitter, J. and Devreese, J.T. (1973).
Phys. Rev., B8, 2717.
2. Lemmens, L.F. and Devreese, J.T. (1973). Solid State
Commun., 12, 1067.
Rev., BS, 2367.
4. Feynman, R., Hellwarth, R., Iddings, C. and Platzman, P.
(1962). Phys. Rev., 127, 1004.
6. Ehrenreich, H. (1966). In Optical Properties of Solids,
(ed. Tauc, J.), (Academic Press); Martin, P.C. (1966). In
Probl~me aN-Corps, (ed. Dewitt, C. and Balian, R.),
(Gordon and Breach, New York).
7. Basic information on the model is given in: Kuper, C.G.
and Whitfield, D.G. (eds.) (1967). Polarons and Excitons,
(Oliver and Boyd, London); (1972) In Polarons in Ionic
Crystals and Polar Semi-conductors, (ed. Devreese, J.T.),
(North Holland, Amsterdam).
8. Devreese, J.T. (ed.) (1972). Polarons in Ionic Crystals
and Polar Semi-conductors, (North Holland, Amsterdam).
9. Frohlich, H. (1972). In Polarons in Ionic Crystals and
Polar Semi-Conductors, (ed. Devreese, J.T.), (North
Holland, Amsterdam).
10. Pekar, S.I. (1954). In Untersuchungen Uber die Elektronen-
theorie der Kristalle, (Academie Verlag, Berlin).
11. Gurevich, V.L., Lang, I.E. and Firsov, Yu.A. (1962). Fiz.
Tverd. Tela, 4, 1252; (1962). Sov. Phys. Solid State, 4,
918.
12. Brauers, M., Evrard, R. and Kartheuser, E. Sum Rules for
the Calculation of Properties of F-Centers, (to be pub-
lished) .
13. Wolff, P.A. (1963). Phys. Rev., 132, 2017.
Stat. Sol., 48B, 77.
15. Devreese, J. and Evrard, R. (1966). Phys. Lett., 23, 196.
A REVIEW OF THE EXPERIMENTAL PROPERTIES
OF INSULATING SOLIDS
A.B. KUNZ
Department of Physics and Materials Research Laboratory,

University of Illinois at Urbana-Champaign,
, Urbana, Illinois 61801
In this review, the author attempts to generate a brief

compilation of some important experimental information relating
to the insulating solids. These properties may be regarded as
falling into four classes. These are: (a) general crystallo-
graphic data, (b) electronic data, (c) optical properties, and
(d) mechanical properties. This compilation is not exhaustive
and in preparing it, the author has tried to lean heavily on
previous available compilations. Especially in the case of the
ionic alkali-halides, much of the data has been available for a
substantial amount of time and it is difficult to trace a given
measurement back to its origin. Therefore, except for such
cases as where the author has resorted to the original litera-
ture only the compilation source will be listed. Interested
readers will certainly find additional references in the compil-
ations cited here. The data is presented here in a series of
seven tables.
In Table I, we present a compilation of general crystal pro-
perties and of some electrical properties. Here are found crys-
tal structures, lattice constants, static dielectric constants
(EO) and optical dielectric constant? (Eoo). The results in this
Table are compiled from four sources. These are Mott and Gurney
[1], Kittel [2], Fowler [3], and Van Vechten [4].
In Table II, we find the effective masses of electrons at
the bottom of the conduction band of several insulators. The
ionic crystal data are obtained using cyclotron resonance and
are quoted by Hodby [5]. The rare gas solids data is obtained
by Rossler [6] and is obtained by reducing the binding energy
of excitons in order to deduce effective masses. In the case
343
344 A.B. KUNZ
TABLE I
The various insulating solids considered in this
article are listed. The conunon crystal structure
is given and the lattice constants are presented.
When available the static dielectric constant,
EO, is given as is the optical or high frequency
dielectric constant, Eoo. Lengths are in Kngstroms.
Lattice
Par8Jleter
Systea Structure a <0 <.
cube
edge
Ne face centered cubic 4.52 1.26

Ar face centered cubic 5.43 1.67
Kr face centered cubic 5.69 1.80
Xe face centered cubic 6.24 2.23
LiF face centered cubic 4.02 9.27 1.92
LiCl face centered cubic 5.13 11.05 2.75
LiBr face centered cubic 5.50 12.1 3.16
Lil face centered cubic 6.00 11.03 3.80
NaF face centered cubic 4.62 6.0 1. 74
NaCI face centered cubic 5.63 5.62 2.25
NaRr face centered cubic 5.98 5.99 2.62
Nal face centered cubic 6.48 6.60 2.91
KF face centered cubic 5.35 6.05 1.85
IC1 face centered cubic 6.29 4.68 2.13
IBr 'face centered cubic 6.59 4.78 2.33
II face centered cubic 7.07 4.94 2.69
RbF face centered cubic 5.64 5.91 1. 93
RbC1 face centered cubic 6.58 5.0 2.19
RbBr face centered cubic 6.86 5.0 2.33
RbI face centered cubic 7.35 5.0 2.63
CsF face centered cubic 6.00 2.2
CsCl simple cubic 4.11 7.20 2.60
CsBr siaple cubic 4.28 6.51 2.78
CsI sillple cubic 4.56 5.65 3.03
AjF face centered cubic 4.92 2.4
AgC1 face centered cubic 5.55 12.3 4.01
AgBr face centered cubic 5.77 13.1 4.62
AgI zinc blende 6.47 4.9
CuCl zinc blende 5.41 10.0 3.57
CuBr zinc blende 5.75 8.0 4.08
TlCI simple cubic 3.84 31.9 5.10
TlBr simple cubic 3.97 29.8 5.41
Til simple cubic 4.20
MgO face centered cubic 4.20 9.8 2.95
CaO face centered cubic 4.80 11.8 3.28
SrO face centered cubic 5.14 13.3 3.31.
NlU,CI simple cubic 3.85 6.96 2.62
BeO wurtzite 1. 65 7.35 2.95
CaF2 fluorite 4.72 8.43 1.99
SrF2 fluorite 5.00 7.69 2.08
BaF2 fluorite 5.38 7.33 2.09
EXPERIMENTAL PROPERTIES OF INSULATING SOLIDS 345
TABLE II
The effective mass of electrons at the bottom
of the conduction band is given for several in-
sulators. For the ionic system the polaron
coupling constant, a, is also given. Units are
the electron mass.
Effective
System
Mass
KCl 0.922 3.60

KBr 0.700 3.15
KI 0.536 2.55
RbCl 1.03 3.99
RbI 0.72 3.29
AgCl 0.431 1.91
AgBr 0.2865 1.60
TlCl 0.551 2.60
TlBr 0.525 2.59
Ne 0.52
Ar 0.48
Kr 0.41
Xe 0.31
of the ionic solids the polaron coupling constant is given.

In Table III, we present the value for the plasma frequency
for several solids as deduced from electron energy loss data by
Miyakawa [7]. The values of electron affinity and ionization
potential where accurately known are also given. The numbers
quoted are from the theses of De Stefano [8] and Bauer [9].
In Table IV, the optical band gaps are given for the ionic
solids and for the solid rare gases. Chiefly this data is from
Brown et al. [10] but is augmented by data from Stephan [11],
and values quoted by Kunz and Mickish [12] and by R~ssler [6].
In Table V, the extremal widths of the uppermost p-like val-
ence band of several ionic solids is given. This data is ob-
tained using photo-emission techniques, the most reliable and
accurate method currently available, and is from the work of De
Stefano [8], Bauer [9], and Pong [13].
In Table VI, the energy of the core states in the ionic and
rare gas solids is given. This data is from Brown et al. [10].
346 A.B. KUNZ
TABLE III
In this Table we present the values for the plas-
ma frequency (many body resonance), the electron
affinity and the ionization potential for select-
ed insulators. Energies are in electron volts.
Plasma Electron Ionization

System
Frequency Affinity Potential
LiF 25.3
LiC1 15.8
LiBr 15.7
LiI 13.7-14.7 1.5 7.4
NaF not seen
NaC1 15.0-15.5
NaBr 13.4-14.3
NaI 12.3-13.3 1.5 7.2
KF not seen
KC1 13.9
KBr 13.2-13.5
KI 1l.8 1.1 7.1
RbF 13.0
RbC1 12.9-13.9
RbBr 12.3
RbI 11.1 0.9 6.9
CsF 11. 2
CsC1 1l.8
CsBr 11.3
CsI 10.3-ll.1 0.3 6.5
TIC1 12.4
TIBr 11.8
AgC1 7.55
AgBr 7.15
Finally, in Table VII we give mechanical properties for sev-

eral solids. The cohesive energy, the bulk modulus and the va1-
TABLE IV
The values of the optical band gap are given
for several insulating solids. Results are
in eV. Low temperature data (T ~ 78°K) is
used whenever possible.
Li Na K Rb Cs Ag T1
F 13.7 11.5 10.8 10.3 9.8

Cl 9.4 8.75 8.7 8.50 8.3 5.1 3.41
Br 7.6 7.1 7.4 7.2 7.3 4.3 3.01
I 6.1 5.9 6.34 6.3 6.1 2.92 2.87
System Ne Ar Kr Xe MgO
Band
22 14.2 12 9.15 7.77
Gap
ues of the elastic constants are given. The data are from the
reviews of Tosi [14], Huntington [15], and Kittel [2].
The author attempts to make no theoretical analysis of the
data presented. It is felt that any such attempt in this com-
pilation would diminish the utility of this compilation as an
unprejudiced collection of experimental results. In citing num-
bers in the Tables, due to the extensive nature of them individ-
ual references to each piece of data are not provided.
REFERENCES
1. Mott, N.F. and Gurney, R.W. (1964). Electronic Processes in
Ionic Crystals, (Dover Publications, New York).
2. Kittel, C. (1968). Introduction to Solid State Physics,
(Third Edition), (John Wiley and Sons, New York).
3. Fowler, W.B. (1966). Phys. Rev., 151, 657.
4. Van Vechten, J.A. (Unpublished data).
5. Hodby, J.W. (1972). PoZarons in Ionic CrystaZs and Polar
Semiconductors, (ed. Devreese, J.T.), (North Holland,
Amsterdam) .
6. RoSSler, U. (1970). Phys. Stat. Sol., 42, 345.
7. Miyakawa, T. (1968). J. Phys. Soc. Jap., 24, 768.
B. De Stefano, T.H. (1970). (Thesis), (Stanford University),
(unpublished) .
9. Bauer, R.S. (1970). (Thesis), (Stanford University), (un-
published) .
348 A.B. KUNZ
TABLE V
The extremal widths of the valence band (p-like,
upper filled band only) of several insulators
are given. Results are in electron volts.
Band
System Width
LiCl S.2±0.S
NaCl 3.l±0.3
NaBr 3.S±0.S
NaI 2.7±0.3
KCl 2.3±0.3
KI 2.6±0.3
RbI 2.4±0.3
CsI 2.S±0.3
AgCl 3.0
AgBr 3.3
10. Brown, F.C., Gahwiller, Ch., Fujita, H., Kunz, A.B.,

Scheifley, W. and Carrera, N. (1970). Phys. Rev., B2, 2126.
11. Stephan, G. (1970). (Thesis), (University of Rennes), (un-
published) .
12. Kunz, A.B. and Mickish, D.J. (1973). Phys. Rev., B8, 779.
13. Pong, W. and Smith, J.A. (1973). Phys. Rev., B7, 5410; Pong,
W. (To be published).
14. Tosi, M.P. (1964). Solid State Physics, Vol. 16, (eds.
Seitz, F. and Turnbull, D.), (Academic Press).
15. Huntington, H.B. (1958). Solid State Physics, Vol. 7, (eds.
Seitz, F. and Turnbull, D.), (Academic Press).
TABLE VI
The threshold energies of the core states in
several insulators are given. Results are in
electron volts.
ElelMllt Is(K) 28(Ll) 2p(L2,a)
a. 24.58678
Li 54.S
LiF 53
LiCl 59.4
Liar 58:7
Lil 58.6
685.4 31 8.0
10 Ne 866.9 45.4 18.3
....
11 Na 1072.1 63.3 30.65
NaF 32.0
N.C! 1079.6 33.5
Na8r 32.2
NaI 32.2
28(£1) 2p(LZ.3) 3a(N,l 3p(M2.3)
17 Cl 210.2 200.0 17.5 0.8

LiCI 201.2
NaC! 276.4 202.3 19.3 8.5
lCl 27. 202 19.2 8.'
RbCI 199.2
esCI 200.3
18 Ar 320 244.1 26.S 12.4
I. 377.1 293.6 33.9 17.8

lei 37. 2.7 37.0 20.5
IC8r 37. 2•• 39.7 20.6
" 37. 2.0 36.7 20.1
38(Ml) 3p(NZ.3) 34.(Nl,5) 4s(Nl) "p(R2.3)
35 Br 256.5 181.5 69.0 27.3 '.0

K8r 25' 18' 71.4 31.2 7.7
36 112' 213.8 90.9 24.0 10.6
37 Rb 322.1 238.5 110.3 29.3 14.0

RbCI 112.2 15.5
RbBr IS.7
Rbi 15.6
'7 Ag 717.5 571.4 366.7 95.2 55.9

AaCl '3
'o8r .3
4s(N1) 4p(Rl.a) 4d(Nl.S) 58(01) Sp(OZ.3)
53 186.4 122.7 49.6 13.6 3.3

Nal 52.4
Kl 18. 120 51. 7 16.0 0.3
esI 52.S
5' X. 141.3 64.8
55 Cs 230.8 161.6 76.S 22.7 11.4

esCl 160.8 80.0 12.9
esllT 160.8 12.8
esl IS. I2.S
350 A.B. KUNZ
TABLE VII
In this table we present values for the cohesive
energy (Kcal/mole), the bulk modulus (lOll dynes
/cm 2 ) and selected elastic constants for some in-
sulating solids (10 12 dynes/cm 2 ).
Cohesive Bulk
System Cll C12 C44
Energy Modulus
Ne 0.45
Ar 1. 85
Kr 2.67
Xe 3.83
LiF 242.3 6.71 1.246 0.424 0.649
LiC1 198.9 2.98
LiBr 189.8 2.38
LiI 177.7 1.71
NaF 214.4 4.65
NaCl 182.6 2.40 0.487 0.124 0.126
NaBr 173.6 1. 99
NaI 163.2 1. 51
KF 189.8 3.05
KC1 165.8 1. 74 0.483 0.054 0.066
KBr 158.5 1.48 0.346 0.058 0.0505
KI 149.9 1.17 0.269 0.0362
RbF 181.4 2.62
RbC1 159.3 1. 56
RbBr 152.6 1. 30 0.317 0.042 0.039
RbI 144.9 1. 06 0.256 0.031 0.029
AgC1 0.601 0.362 0.0625
AgBr 0.563 0.33 0.0720
CaF2 1.644 0.502 0.347
MgO 2.86 0.87 1.48
NH4C1 0.390 0.072 0.068
TlC1 0.378 0.148 0.0756
TlBr 0.401 0.153 0.0760
OPTICAL ABSORPTION AND PHOTOEMISSION EXPERIMENTS
ON METALS AND ALLOYS.
P.-O. NILSSON
Chalmers University of Technology,

Gothenburg, Sweden
1. OPTICAL ABSORPTION
In a typical optical experiment monochromatic electromag-
netic radiation, ranging from the infrared (IR) to the ultra-
violet (UV) , is shone onto a specimen surface. The amount of
reflected, transmitted or absorbed intensity as a function of
frequency can be detected as well as the change of polarization
state. From this kind of information the absorbed energy at
frequency w per volume and time, W(w), can be deduced. Clas-
sical electrodynamics gives for this quantity:
W(w) (1)
(E2) is the average of the square of the electric field, £(w)

the imaginary part of the dielectric function, and cr(w) the real
part of the 'conductivity function.
Around 1900 a microscopic model for the electronic structure
of solids in form of classical oscillators was proposed by Drude
and Lorentz. Although this model accounts for many features of
the observed spectra much more information is obtained from the
quantum mechanical treatment. In the random phase approximation,
RPA, local field effects are neglected and one obtains [1]
(Contd)
351
352 P.-O. NILSSON
e2
(Contd) T~ L f 3
klE'Pifl
2 - -
o(Ef(k) - Ei(k) - hw). (2)
. 1Tm w i.f
Here i and f denote initial and final states respectively.
E(k) is the bandstructure, £ the unit vector of the electric
field and Pif the momentum matrix element given by
(3)
Wp is the electron plasma frequency defined by the electron

density N and the optical mass mopt (see equation (6):
Wp = [~o;t
2
r· 1
(4 )
The first two terms in equation (2) give the absorption from
the conduction or 'free electrons', which make transitions with-
in one band, so called intraband transitions. The expression
is equivalent to that in the classical theory for conductivity,
i.e. it is given by oscillators of zero frequency. Without the
introduced relaxation time T, arising from scattering processes,
this quantity would be zero. This, so called Drude absorption,
produces a smooth spectrum with a large amplitude in the IR and
which decreases rapidly with increasing photon energy. The last
term in equation (2) produces structure due to electrons which
make direct electronic transitions between different bands i and
f, so called interband transitions. The integral in equation
(2) can be transformed to
(5)
The superscript b denotes 'bound " referring to the valence elec-

trons in contrast to the 'free' conduction electrons. We ob-
serve that dE2(W)/dw will be discontinous when the denominator
is zero, which defines so called critical points in k-space.
A simple situation occurs for Al in the IR region. The near-
ly free electron band structure can be fairly well represented
with two pseudopotential coefficients VIII and V200' Ashcroft
and Sturm [2] calculated the optical absorption using this band
model and equation (2). The interband transitions are found to
occur between parallel bands. This will obviously give a large
contribution according to equation (5) as the denominator is
zero. In figure I we reproduce the experimental results by Mat-
hewson and Myers [3]. The observed peak corresponds to transi-
tIons involving the (200) reciprocal lattice vector. At lower
energies an additional peak for the (Ill) vector appears and
OPTICAL ABSORPTION AND PHOTOEMISSION EXPERIMENTS 353
x 10"10-0
x
\x
\x
7·5
i
5·0
2·5
1·0 2-0
(eV)
Figure 1 - The optical conductivity of Al films as de-

termined by Mathewson and Myers [3J. The different
curves correspond to temperatures from 198 oK (0) to
505 oK (x).
also a smooth contribution down to zero frequency. The authors

have optimized the five model parameters used for best fit.
The parameters are mopt, T, Ti, VIII and V200, where Ti is an
interband relaxation time. The analysis gives (V200) = 0.79 eV
while Fermi surface data give 0.76 eV. The discrepancy can easily
be accounted for by the approximate band structure. E.g. the
distortions of the bands due to the (lll)-gap was not included
in the model.
An equally simple situation should occur for the alkalies.
The Fermi level is here lower than in Al and the parallel bands
are not filled. Thus we do not expect the strong peak seen for
354 P.-O. NILSSON
AI. However the presence of the Fermi level in the lowest band
introduces a finite low frequency limit of the interband absorp-
tion. A smooth onset is expected in the IR region. Unfortun-
ately there are still large uncertainties in the experimental
results [4]. Furthermore, the closeness of the core levels and
the large Drude contribution complicate the theory. The former
effect can be compensated for with an 'optical pseudopotential'
which orthogonalizes the wave functions to the core ones. A
good fit to experiments was in this way obtained by Bennet and
Vosko [5] and by Stevenson [6]. The latter author also regarded
the interference between interband and Drude transitions by con-
sidering indirect phonon assisted interband transitions.
The optical absorption in the noble metals seems now experi-
mentally quite well established. The bandstructure of these
metals are on the other hand very complex. Recently the integral
in equation (5) was accurately evaluated for Cu by Williams et
al. [7]. In figure 2 we make a comparision with the experimental
Cu
Theory, interband
(Williams et. al.)
"..'i-..
I __
I! .. _
,,/i -.---.--- .. ------
O~I--~~~2------~------~4------~------~6
Photon energy (eV)
Figure 2 - £2(w) for eu as calculated by Williams et al.

[7] and as measured by Pells and Shiga [8]. The extra-
polated Drude absorption and the separated interband con-
tribution is also shown.
results by Pells and Shiga [8]. As seen a very good agreement

is obtained. The spectrum contains contributions from a very
large number of band pairs including several band gaps and cri tical
points. Because of overlap and broadening these details can
not be found in the observed total spectrum. Certain features
can however be identified. E.G., the rise at 4.2 eV is caused
by transitions across the conduction band gap close to the L-
point. The energy fit at this feature was however only obtained
after empirical adjustment of the t = 2 phase shift of the so
called Chodorow potential. The inclusion of correlation effects
may also have had this effect.
The measured interband contributions has most often been ana-
lyzed in literature by inspection of band diagrams in symmetry
directions. Sometimes the integral in equation (5) with con-
stant matrix elements (joint density of states) has been calcu-
lated. These kinds of analyses, particularly the first one, is
necessarily connected with uncertainties.
The intraband contribution has so far been analyzed by the
simple theory given by the two first terms in equation (2). A
fairly reproducible value of wp, or equivalently mopt (see equa-
tion (4)), is obtained [9]. This parameter is connected with
the curvature of the bands at the Fermi level:
(6)
The scattering time T is empirically found to vary with fre-

quency according to
-1 = -1 + 2
aw . (7)
T TO
Such a dependence can be obtained assuming different dominant

scattering mechanisms. As the absolute value of T is strongly
dependent on the crystallographic perfection of the sample, the
main frequency variation may be connected with the fraction of
noncrystalline material, like grain boundaries.
Finally we will illustrate the use of optical absorption for
the study of the electronic structure of alloys. There exists
yet no general theory for optical absorption in substitutionally
disorderd alloys. In most cases we can however still interprete
the main features observed in the spectra. Consider e.g. the
Li-Mg system. In figure 3 the data by Mathewson and Myers are
shown [10]. Pure Li and Mg exhibits typical interband onsets
of monovalent and polyvalent metals respectively as discussed
above. Also in the discarded alloys the absorption edge is pre-
sent. As no extra broadening T is found one can conclude that
in this particular case a virtual crystal model can be used.
This means that the electronic states can still be regarded as
periodic in space and can be discribed with an ordinary band
structure formalism. From the data Mathewson and Myers deduced
that going from Li towards Mg the Fermi sphere increases and
makes contact with the first Brioullin zone boundary for about
70 atomic percent Li.
Alloys containing metals with d- and f-states can not be de-
scribed in the discussed simple manner. These states are fair-
ly localized and produce pronounced structure in the density of
states. Optical transitions from such states to just above the
Fermi level will produce an absorption curve which roughly re-
flects the initial density of states. In this way the 'virtual
IN
VI
Cl'
• L, _10"
6\ !"~ O _7 M,
4 \ o C>l89 M, !litO'·
""ol'l 6 (}JQS M,
, . .I!: • \ • t).4.44 M, ,., • (H44 114 1
"
o , • • (H ) M , OM,
°
, . \ f 0 0-,76 MI • Cl-9l Mi
e ON Ma
, "
1 1 : t
"
I 0 0
.
~ ~
~ 7 " \. . ::-
J t\
~,
6. it
t' I .....
\ .
.., ~.\ j
If-~ ~ , ... ",
~ : •I
6
6 • ~
"6
". "lit.
. .:
I1
.:
i
r\ ~, \~
~ \
\
\. ~"¥ ',/. 05
iIJO·
. \, \.
,1 ..
~~ . : t ,
+j .. \
.~ ~
'~ 'd
~-
I
...._.... \~.~ o
1Iw« V)
, Z
H
IIw C. V) IIwC.V)
~
(/)
Figure 3 - Optical conductivity for Li-Mg alloys as measured by Mathewson and Myers [10] • @
bound' d-electrons of an impurity transition metal in a noble
metal host have been studied in detail . As an example we show
the data on CuNi alloys by Seib and Spicer [111 in figure 4 .
10"
,
.../' ,,/
. /
/ '
/ I/
t '"'
l \"
•
I \ II
I - - - Co ppe r
- - - - - 87 %Cu- 13 %
_ . - 77%Cu- 23 %
10"0f----!'---~---+--~f----+';--~
12
hv(eV)
Figure 4 - The interband part of the optical joint den-

sity of states, wcr(w), for eu and CuNi alloys as measured
by Seib and Spicer [11].
The resonant d-states were found in the 8-P conduction band 1 eV

below the Fermi level forming a 0.6 eV wide band. Qualitative
similar results are found for other systems, e.g. when Ni, Pd or
Mn is alloyed with the noble metals [12]. A more complex situa-
tion occurs when the d-bands of the two constituents overlap,
but the results have in some cases e.g. for AgAu [13,14], been
interpreted. Finally we mention the situation which occurs in
alloys of the type CuZn and Agln. The d-band of the impurity
atom is far below the Fermi level and contributes only very weak-
ly at high energies. The main observation [15] is a movement of
the absorption edge to higher photon energies which means an in-
crease of the distance between the Fermi level and the top of
the host metal d-band. This effect can at least partially be
attributed to the increased Fermi energy arising from the in-
creased electron concentration.
2. PHOTOEMISSION
About ten years ago Berglund and Spicer [16] noticed that
358 P.-O. NILSSON
important information about the electronic structure of the
noble metals could be extracted from measured photoemission en-
ergy distributions, so called EDCs. Somewhat earlier the same
fact had been found for semiconductors. In a typical photoemis-
sion experiment monocromatic light is shone onto a clean sample
surface and the photoemitted electrons are analyzed with respect
to their kinetic energies. Berglund and Spicer used a three
step model for their interpretation of the data. In the first
step the electron is optically excited, in the second one it
travels through the lattice under various interactions, particu-
larly inelastic electron-electron scattering, and in the third
one it escapes through the surface barrier into vacuum. Much
of the data have been, and can be, sucessfully interpreted in
this manner. The two latter processes then produce a smooth
background with a typical broad peak at low kinetic energies.
The band structure information is contained in the first step.
The energy distribution of excited electrons is directly obtained
from equation (2) as
N(E,w) =
Elimination of the delta function gives
N(E,w) (9)
The integration is performed along the intersection line of the

optical and electron energy surface defined by the delta func-
tions in equation (8). .
Consider now a nearly-free-electron band structure and make
the assumption of a constant matrix element over the optical
surface. Equation (9) gives then for a given w a constant for
N(E,w). In figure 5 we show how this model well describes ex-
periments by Nilsson and Eastman [17], where the elctrons are
excited between two s-p conduction bands in silver. For the
calculation the three step model was used. All necessary para-
meters were taken from other experiments. Of particular impor-
tance is the observation and theoretical reproduction of the 101
energy edge of the box shaped feature which confirms the k-con-
versation of the electron at the photoexcitation. Lindau and
Wallden [18J have recorded corresponding curves for Cu down to
low photon energies and in this way obtained a value of 4.15 eV
for the band gap at the L points. This value was used by Wil-
liams et al. [7] in his analysis of optical absorption data as
discussed above.
< III > Ag

hy=7.7e V bY = 10.2 eV
d-bands
t
Expt.
,,
, 2-0PW
,
, lh eory ""-----/
/
... "
I
/
/ "
/
C o~~~~---L--~--~/--L-~L-~---L--~--~~
.;;;
c hv = 6.9 eV
"
.§
c:
.~
·e
,,,
~
,,
_... I
,...- '"
I
,'"
- 3 - 4 - 3 - 2 - I =0 E.
In ilial energy (eV)
Figure 5 - Photoemission energy distributions for Ag

(Ill) as measured and calculated by Nilsson and East-
man [17].
For a more general case, as e.g. for transitions from the d-

band complex of a noble metal, equation (9) has to be evaluated
numerically. Christensen and Seraphin have calculated the band
structure of Au using the relativistic KKR method. Also the
photoemission spectra were calculated but no matrix elements
were included. The influence of these on the peak positions in
the EDCs is however not very strong and a comparision with ex-
periments is meaningful. In figure 6 the experimental results
by Nilsson et al. [20] is shown together with a structure plot
[19] showing the peak positions in the EDCs as a function of
photon energy. As seen, agreement within a few tenths of an eV
is obtained confirming in detail the band structure of Au.
In figure 7 the photoemission results by Eastman [21] on Cu
at high photon energies are shown. As mentioned in connection
with optical absorption d-states are fairly localized which
makes the effect of the k-selection rule less pronounced in the
resul ts. In fact the observed structure in figure 7 can be di-
rectly associated with the d-band. The position and width of
the d-band complex can be determined by pure inspection.
360 P.-O. NILSSON
elp = 3.6eV
C B
- 7 - 6 - 5 - 4 - 3 - 2 - I o
Energy of initial tate (eV)
H
Au. - x - - -x- x - x - x _ x
-x"O
__ x-G ~
6 G·- -x.___ x--~r~-==- - -- --
>"
~
~4
I
1
~ 3
I
__ x-~'-'- A x"1:)
x_ _ x-Q"
..x~ x.L
~15-- 0
°9~~~--~-L~1~:~--~~~L-~1~
1 ~--~~--~~12
photon energy hw (eV) -
Figure 6 - Photoemission energy distributions for Au

measured by P.O. Nilsson et al. [20]. Structure plot
comparing the calculations by Christensen and Seraphin
[19] (x) and the measurements (0).
However for interpretation of the observed fine structures cal-

culations using equation (7) have to be performed. This was
done by Williams et al. [7] for eu up to 40 eV. The matrix
(b) Copper
- Ex periment
--- Theory
(KKR with
matrix
element sl
Expl.
h v = 26.9
eV
c
o
.~ 0
·e
"o
"0
-=
c..
---
o
O~-~8~--
_+7 ---
_+6 ---_~S--~~-_~J~--
_~2 ---
_+I--~~·
In itial energy (e V)
Figure 7 - Photoemission energy distributions for eu as

measured by Eastman [21J and as calculated by Williams
et al. [7].
elements were included. As seen the structures in the EDC's

are still a function of photon energy at these high energies.
Furthermore it is found that it is necessary to stretch the en-
ergy scale of the band structure at high energies above the
Fermi level to obtain agreement with the experiments. This ef-
fect may result from use of an energy independent potential over
a large energy range. Inclusion of correlation effects, which
has not been done so far, could improve the agreement.
There have been comparatively few photoemission studies of
alloys. The CUNi-type alloys mentioned above have been studied
362 P.-O. NILSSON
[22]. Here one obtains an even more clear picture of the elec-
tron energy levels. In this connection we also mention an ex-
periment by Eastman and Grobman [24J, where Pd was evaporated
onto Ag. The Pd d-band is found at 1.2 eV below the Fermi level,
while the Pd impurity d-band in the alloy AgPd is detected at 2
eV. In the concentrated AgPd alloys the Ag and Pd bands are
found [23] to just touch each other. Experiments on alloys with
more separated bands (e.g. in S-CuZn [25]) and with strongly
overlapping bands (e.g. in AgAu [13J) have also been reported.
In the latter case the Au impurity band in AgAu could be detect-
ed. This is not so easy in the corresponding optical experiment
[13,17], because many initial energies are possible for one giv-
en photon energy.
Finally we point out the importance of new kind of photoemis-
sion measurements where the anisotropy of the photoemission is
detected. This can in principle be done by using a single crys-
tal and varying the angle of incidence and the polarization of
the light as well as the detection angle of the photoelectrons.
Recenbly band structure information about Ag [26] and CU [27J
has been obtained in this way. A drastic and pronounced effect
was recently found by Feuerbacher and Fi ttion [28J who studied
the photoemission normal to single crystal surfaces of tungsten.
The results are reproduced in figure 8.
The strong differences between the different surfaces are ex-
pected if one assumes that the only electrons which contribute
are those ones excited on the k-symmetry line associated with
the surfaces normal. In fact good quantitative agreement is ob-
tained when comparison is made with a band structure calcula-
tion by Christensen [29]. Some additional structure is also ob-
served which was interpreted in terms of surface photoemission.
The latter observation points to the need for a more complete
theory for the photoemission process than described above.
In fact more general theories than the three-step model have
appeared. Two approaches leading to equivalent results have
been used. Mahan [30] applied a scattering theory while Schaich
and Ashcroft [31] used a quadratic response formalism. For ob-
lique incidence of the light the electron excitations are modi-
fied by the potential gradient at the surface. This can immedi-
ately be seen if the matrix element is rewritten as:
where V(r) is the crystal potential. We thus conclude that ex-

cept for the ordinary bulk excitations, arising from the per-
iodic variation of V(r), additional excitations can occur at the
surface where V(r) changes rapidly. The extra structure observed
[28] forW was thus attributed to surface induced optical transi-
tions from bands which are close to the bulk bands, to continuum
states. Strong evidence for surface photoemission has been found
in measurements [33,34] of the total photocurrent, the yield, as
a function of photon energy. A much higher current per absorbed
;;;
on ~
a::> '"e?
"c
OJ
'=- "c0
ZIUJ
."."
0
.c
Q.,
Energy below EF (eV)
W(lOO)
Figure 8 - Photoemission energy distributions normal to

three crystal faces of W as bbtained by Feuerbacher and
Fitton [28].
364 P.-O. NILSSON
photon is obtained for p-than for s-po1arized light. Structure
arising from excitations from surface states has also been ob-
served in photoemission [35].
REFERENCES
1. Ehrenreich, H. and Cohen, M.H. (1959). Phys. Rev., 115, 786.
2. Ashcroft, N.W. and Sturm, K. (1971). Phys. Rev., B3, 1898:
3. Mathewson, A.G. and Myers, H.P. (1972). J. Phys., F2, 403.
4. See, e.g.: Smith, N.V. (1969). Phys. Rev., 183, 634; (1970).
Phys. Rev., B2, 2840; Palmer, R.E. and Schnatterly, S.E.
(1971). Phys. Rev., B4, 2329.
5. Bennett, B.I. and Vosko, S.H. (1972). Phys. Rev., B6, 2119.
6. Stevenson, D.J. (1973). Phys. Rev., B7, 2348.
7. Williams, A.R., Janak, J.F. and Moruzzi, V.L. (1972). Phys.
Rev. Lett., 28, 671. .
8. Pells, G.P. and Shiga, M. (1969). J. Phys., C2, 1835.
9. See e.g.: Theye. M.L. (1970). Phys. Rev., B2, 3060.
10. Mathewson, A.G. and Myers, H.P. (1973). J. Phys., F3, 623.
11. Seib, D.H. and Spicer, W.E. (1970). Phys. Rev., B2, 1676.
12. See e.g.: Abel~s, F.(1966). In Optical Properties and Elec-
tronic Structure of Metals and Alloys, (ed. Abel~s, F.),
(North Holland Publishing Company, Amst~rdam), p. 553;
Myers, H.P., Wal1den, L. and Karlsson, A. (1968). Phil. Mag.,
18, 725.
13. Nilsson, P.-O. (1970). Phys. kond. Mat., II, 1.
14. Beaglehole, D. and Erlbach, E. (1972). Phys. Rev., B6, 1209.
15. See e.g.: Green, E.L. and Muldawer, L. (1971). Phys. Rev.,
B2, 330; Pells, G.P. and Montgomery, H. (1970). J. Phys.,
C3, 330.
16. Berglund, C.N. and Spicer, W.E. (1964). Phys. Rev., 136,
Al030.
17. Nilsson, P.O. and Eastman, D.E. Phys. Scripta, (in press).
18. Lindau, I. and Wallden, L. (1971). Phys. Scripta, 3, 77.
19. Christensen, N.E. and Seraphin, B.O. (1971). Phys. Rev.,
B4, 3321.
20. Nilsson, P.-O., Norris, C. and Wallden, L. (1970). Phys.
kond. Mat., II, 220.
21. Eastman, D.E. and Cashion, J.K. (1970). Phys. Rev. Lett.,
24, 310.
22. See e.g. references [11,23]; Norris, C. and Wallden, L.
(1969). Solid State Commun., 7, 99; Wallden, L. (1969).
23. Norris, C. and Myers, H.P. (1971). J. Phys., Fl, 62.
24. Eastman, D.E. and Grobman, W.D. (1973). Phys. Rev. Lett.,
30, 177.
25. Nilsson, P.-O. and Lindau, I. (1971). J. Phys., Fl, 854.
26. Gustafsson, T., Nilsson, P.-O. and Wallden, L. (1971).
27. Gerhardt, U. and Dietz, E. (1971). Phys. Rev. Lett., 26,
1477.
28. Feuerbacher, B. and Fitton, B. (1973). Phys. Rev. Lett.,
30, 923.
29. Christensen, N.E. (To be published).
30. Mahan, G.D. (1970). Phys. Rev., B1, 4334.
31. Schaich, W.L. and Ashcroft, N.W. (1971). Phys. Rev., B3,
2452.
32. Adawi, I. (1964). Phys. Rev., 134, A788.
33. Juenker, D.W., Waldron, J.P. and Jaccodine, R.J. (1964).
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34. Broudy, R.M. (1971). Phys. Rev., B3, 3641.
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28, 1378; Wagner, L.F. and Spicer, W.E. (1972). Phys. Rev.
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AUTHOR INDEX TO PART B
A 227, 228, 242,

Abel~s, F. 129, 243, 245, 259, Bloom, S. 223, 228
364 266, 267, 290 Blount, E.I. 8, 22
Abrikosov, A.A. 23 Bardeen, J. 13, Bogoliubov, N.N.
Ackerman, C.C. 91 19, 20, 22, 54, 23, 44, 47, 62,
Adawi, I. 365 70, 76, 77, 328 75, 76
Afanasev, A.M. 23 BarisH;, S. 22, Born, M. 144
Aggarwal, R.L. 262, 328, 332 Bosacchi, A. 164
290 Barker, A.S. 129 Bosacchi, B. 164
Allen, Ph.B. 23, Barrett, C.S. 21 Bowley, R.M. 72
228, 311, 315 Bartley, D. L. 77 Brandt, R.C. 162,
Amzallag, E. 267 Bate, R.T. 242, 243 164
Anderson, P.W. 8, Bateman, T.B. 21 Brauers, M. 341
22 Batterman, B. 21, Braun, H. 324
Appel, J. 23, 311, 22 Braunstein. R. 291
315 Bauer, R.S. 345, Brenig, W. 130
Arakawa, E.T. 106, 347 Brillouin, L. 266
129, 211 Baym, G. 70, 77 Brion, J.J. 129
Arora, H.L. 211 Beaglehole, D. 364 Brodin, M.S. 129
Arrhenius, G. 21 Beliaev, S.T. 44, Broerman, J.G. 230,
Ascarelli, G. 164 75 242
Ashcroft, 352, 362, Bell, M.1. 291 Brooks-Harris, A.
364, 365 Benj amin, R. 75 76
Aslamazov, L.G. 23 Bennet, B.I. 354, Broudy, R.M. 365
Axe, J.D. 12, 21, 364 Brown, F.C. 129,
22 Berglund, C. 324, 162, 164, 211,
357, 358, 364 345, 348
Bergstresser, T.K. Brown, R.N. 226
B 223, 228 Brueckner, K.A. 44,
Babcenco, A. 187 Berko, S. 22 75
Badro, R.G. 94, Bernick, R.L. 228 Brust, D. 226, 242
113, 128, 164 Bertman, B. 91 Bryskin, V.V. 129
Baer, W. 324 Besserman, R. 290 Buchenauer, C.J.
Bagchi, A. 47, 62, Bil z, H. 21, 33, 290
76, 77 42 Bucher, E. 22
Baldini, G. 162, Birgeneau, R.J. 21 Burstein, E. 109,
164 Birman, J.L. 22, 110, 129, 228,
Balian, R. 341 128, 130, 230, 243
Balkanski, M. 164, 266, 291, 315 Buss, D.O. 243
213, 223, 224, Bloch, A. N. 22
367
368 AUTHOR INDEX TO PART B
C Cowley, R.A. 75, Eisenberger, P.

Callaway, J. 211 228 267
Ca11cott, T.A. 211 Cummins, H.Z. 251, Elson, J .M. 109,
Cardona, M. 269. 252, 266 110, 129
290,291,299, Cyumin, M.E. 77 Emery, Y.J. 70, 77
315 Enge1sberg, F. 331
Carrera, N. 348 Enns, R.H. 20
Carter, D.L. 242, D Enz, C.P. 76
243 Dagneaux, D. 228 Epstein, A.J. 22
Cashion, J.K. 364 Dalton, N. W. 22 Er1bach, E. 364
Celi, V. 76 Des C1oizeaux, J. Esaki, L. 227
Cerdeira, F. 290, 5, 21 Ese1son, B.N. 77
291 De Sitter, J. 163, Etemad, S. 22
Chadi, D.J. 164, 187, 197, Evans, E. 94, 120,
223, 226, 227, 319, 323, 341 121, 129
228 De Stefano, T.H. Evrard, R. 144,
Channin, D.J. 91 345, 347 163, 164, 186,
Chase, C.E. 262 Devreese, J.T. 187, 197, 317,
Chekroun, C. 164 130, 131, 133 341, 342
Chen, M. L. 218 144, 163, 164,
Chester, M. 91 183, 186, 187,
Ching, W.Y. 211 197, 211, 317, F
Christensen, N.E. 323, 333, 341, Fairbank, H.A. 91
359, 360, 362, 342, 347 Fano, U. 105, 129,
364, 365 Dewitt, C. 341 276, 291
Clogston, A.M. 8, Dick, B.G. 33, 42 Fedders, P.A. 22
22 Dickey, D.H. 229, Feenberg, 44, 47,
Cochran, W. 228, 230, 242 55, 62, 75
294 Dieterich, W. 12, Feibe1man P.J.
Codling, K. 291 22 94, 129
Cody, G.D. 22 Dietz, E. 364 Fermi, E. 55, 76
Cohen, M.H. 21, 76, Dingle, R.B. 91 Ferraris, J.P. 22
294, 364 Dolling, G. 228 Ferreira, L.G.
Cohen, M.J. 22 Drude, I. 351, 352 216, 228
Cohen, M. L. 29, Dudinski, M.A. 129 Ferrell, R.A. 128
36, 41, 42, 218, Dugautier, C. 267 Feuerbacher,B.362,
223,224,226, Dzya1oshinski, I.E. 363, 365··-
227, 228, 310, 23 Feynman, R.P. 44,
311, 314, 315 45, 49, 75, 115,
Cohen, R.W. 22 130, 164, 166,
Coleman, L.B. 22, E 167, 168, 174,
331 Eastman, D.E. 358, 175, 176, 177,
Collins, T.C. 211 359, 361, 362, 178, 179, 180,
Comes, R. 331 364, 365 181, 183, 185,
Conklin, J.B. 228 Ebner, C. 76 186,189,195,
Cooper, L.N. 22, Economou, E.N. 77, 196, 197, 317,
54, 76 94, 129 318, 323, 333,
Corenzwit, E. 21 Ederer, D. L. 291 335, 337, 338,
Coret, A. 164 Edwards, D.O. 76 340, 341
Cowan, D.O. 22 Egli, P. 228 Finkenrath, H.
Cowan, J.J. 106, Ehrenreich, H. 21, 163, 324
129 331, 341, 364 Firsov, Yu.A. 160,
AUTHOR INDEX TO PART B 369
164,317,319, Ghurzi, R.N. 92 Hanke, W. 5, 6,
320, 323, 337, Ginzburg, V.L. 266 21, 31, 42
340, 341 Gobeau, W.M. 91 Hanak, J.J. 21
Fisher, B. 109, Goldberg, I.G. 7, Harbeke, G. 267
110, 129 21, 22, 331 Harman, T.C. 242
Fittion, B. 362, Goovaerts, M.J. Harrison, W. 30,
363, 364, 365 163, 164, 186, 42
Fitzgerald, R. 21 187, 323, 341 Harstein, A. 129
Fje1dy, T. 290, 291 Gorkov, L.P. 16, Hart, T.R. 290
Fleury, P.A. 259, 19, 23 Hartmann, W. 29,
267 Gossard, M.C. 21 41
Flores, F. 130 Gosso, J.P. 267 Hatano, A. 76, 77
Floyd, E.R. 30, 41 Goto, T. 164 Haxton, M. 124,
FlUgge, S. 91 Gtltze, W. 91 130, 190
Fomin, I.A. 76 Green, E. L. 364 Hayashi, E. 5, 21
Fosdick, L. 187 Greytak, T.J. 46, Hedin, L. 130, 186,
Fowler, W.B. 211, 48, 53, 75, 77 187
343, 347 Grobman, W.D. 362, Heeger, A.J. 22
Friedel, J. 7, 8, 364, 365 Heine, V. 29, 41,
9, 18, 22, 23, Grosjean, C.C. 228
328, 332 163, 187, 197 Heller, P. 92
FrBh1ich, H. 13, Gross, E. 190, 197 Hellman 335, 336
19, 22, 146, 163, Grosse, P. 164, He11warth, R. 186,
197, 211, 326, 324 189, 197, 317,
327, 328, 332, Groves, S. 226 318, 323, 333,
341 Grynberg, M. 227, 337, 340, 341
Fuchs, R. 94, 103, 234, 242 Henvis, B.W. 289,
127, 128, 130, Gspan, G. 164, 315
164 324 Hepp1e, J. 249,
Fujita, H. 348 Gu1ayev, Yu.V. 92 250
FU1de, P. 12, 22 Gupta, R.M. 21 Herman, F. 22, 217,
Furry, W.H. 23 Gupta, R.P. 21, 34, 218, 228
42 Hermanson, J. 164,
G Gurevich, V.L. 199, 211
Gahwi11er, Ch. 348 160, 164, 317, Herring, C. 121,
Gammon, R.W. 251, 319, 320, 323, 130, 296, 314
252, 266 337, 340, 341 Hibbs, A.R. 186
Ganguly, K. 289, Gurney, R.W. 343, Hodby, J.W. 343,
295, 315 347 347
Garcia-Mo1iner, F. Gustafsson, T. 364 Hohenberg, P.C. 92
130 Gutfreund, H. 23, Holstein, T. 296,
Garito, A.F. 22 25, 325, 331, 314
Gaur, S.P. 243 332 Hopfie1d, J.J. 129,
Gavoret, J. 44, 75 Gutzwiller, M. 186 130
Geba11e, T.M. 21, Guyer, R.A. 91 Hopkins, J. 12, 13,
22 20
Ge1dart, D.J.W. 41 Horie, C. 205, 211
Gelman, D. 187 H Horovitz, B. 23,
Gerbstein, Yu.M. Haering, R.R. 20 325, 331, 332
129 Halloran, J.J. 22 Horton, G.K. 21,
Gerhardt, U. 364 Halperin, B.l. 92 91
Gerlach, E. 129 Hamm, R.N. 106, 129 Hosler, W.R. 315
Huang, K. 44, 75, K Kortum, R.L. 217,

144 Kadanoff, L.P. 91, 218, 228
Hubbard, J. 30. 41 167, 186, 196 Kovdrya, Yu.Z. 77
Huber, D.L. 130 Kagan, Yu. 23 Kristenmacher, T.
Hugenho1tz, N. 44, Kaganov, M.1. 23 J. 22
75 Kamimura, H. 164 Krouzman, M. 291
Hull, G. W. 21 Kane, E.O. 291 Krumhans1, J.A. 91
Huntington, H.B. Kaplan, R' o 315 Kubo, R. 91
347, 348 Karlsson, A. 364 Kunz, A.B. 211,
Huybrechts, W. 164, Kartheuser, E. 294, 343, 345,
183, 186, 197, 94, 113, 128, 348
317, 323, 342 129, 131, 145, Kunzler, J.E. 22
163, 165, 186, Kuper, C.G. 23,
187, 189, 190, 144, 186, 187,
I 197, 317, 341 197,211, 327,
Ibach, H. 94, 105, Kastler, A. 250, 332, 341
106, 107, 108, 266 Kurithzim, V.B. ~1
128 Kawasaki, K. 91, Kwok, P.C. 91
Iddings, C. 166, 92
167, 175, 177, Kebukawa, T. 76,
178, 179, 181, 77 L
183, 185, 186, Keffer, F. 92 Labbe, J. 7, 8,
189, 195, 196, Keller, K. R. 21 17,18, 22, 23,
197, 317, 318, Keyes, R.W. 290 328, 332
323, 333, 337, Kha1atnikov, I.M. Lambert, M. 331
338, 340, 341 59, 71, 73, 76, Land, R.H. 41
Inoue, M. 130 77 Landau, L.D. 43,
Ipatova, loP. 20 Kinch, M.A. 243 44, 49, 59, 63,
Ivanov-Omskii, Kittel, C. 343, 70,75,76, 77,
W.J. 229, 230, 347 153, 163
242 Klein, R. 91 Lang, I.E. 160,
Iwamoto, F. 48, Kleinman, L. 30, 164, 317, 319,
75 41, 228 320, 323, 337,
Kliewer, K.L. 94, 340, 341
103, 127, 128, Langreth, D.C. 42,
J 130, 164 167, 186
Jaccarino, V. 8, Knox, R.S. 315 Lanois, H. 331
22 Kodess, B.N. 21 Larkin, R.I. 23
Jaccodine, R.J. Koehler, T.R. 22 Lax, B. 242, 262,
365 Kohn, S.E. 218, 290
Jackson, H.E. 91 228, 230, 231, Lee, T.D. 44, 75,
Janak, J.F. 364 242 . 317, 323
Janus, J. 77 Kohn, W. 20, 23, Leibfried, G. 91
Johnson, E.J. 289, 25, 31, 42, 211, Lemmens, L. 164,
314 227, 230. 231, 186, 187, 197,
Johnson, F.A. 294 Ko1omiets, B.T. 323,333,341,
Johnson, L:E. 228 229, 230, 242 342
Jordan, H. 187 Kommandeur, J. 22 Le Tou11ec, R.
Jouanne, M. 290 Koonce, C.S. 314, 227, 234, 242
Juenker, D.W. 365 315 Levinstein, H.J.
22
Limbert, D. 262 Martin, R.M. 21, Muldawer, L. 364
Lin-Chung, P.J. 31, 42, 294 Murakami, Y. 324
228, 291, 299, Martinez, G. 219, Myers, H.P. 352,
315 220, 221, 222, 353, 364
Lindau, I. 358, 228, 242
364 Mathewson, A.G.
Linz, A. 92 352, 353, 355, N
Liu, L. 226, 242 356, 364 Nagai, K. 76, 77
Longinotti, L. D. Matheiss, L.F. 315 Nardelli, G.F. 243
21 Mathias, B.T. 20, Nathans, R. 92
Lorentz 351 21 Nazarewicz, W. 243
Loudon, R. 254, Matsuura, M. 211 Newns, D.M. 130
266, 291 Mavroides, J.G. Ngai, K.L. 289,
Low, F. 317, 323 229, 242 290, 291, 295,
Lucas, A.A. 94, Maxwell, 79, 94, 299, 314, 315
113, 115, 129 200 Nijboer, B.R.A.
164 McMillan, W.L. 70, 129
Ludwig, W. 91 77, 328, 332 Nikitine, S. 164
Lundqvist, B. I. McNelly, T.F. 91 Nilsson, P.-O.
129 Mekhtiev, A.Ch. 351,358,359,
Lundqvist, s. 129, 229, 242 360, 364
186, 187 Menth, A. 21 Nojima, K. 76, 77
Luo, H. L. 21 Meyers, H.P. 352, Noolandi, J. 22
353, 355, 356, Norris, C. 364
364 Norton, P. 289,
M Michel, K.H. 1, 315
Macfarlane, R.M. 91, 92 Nozieres, P. 4, 21,
267 Mickish, D.J. 345, 27, 44, 55, 75,
Madden, R.P. 291 348 76, 77
Mahan, G.D. 93, Migdal, A.B. 267 Nusimovic, M.A. 21
94, 102, 103, Milbrodt, T.O. 41 Nusslein, V. 42
115, 117, 118, Miller, A. 55, 76
124, 129, 130, Miller, R.E. 22
162, 362, 365 Mi 11 s, D. L. 94, o
Mahutte, C.K. 130 120, 121, 124, 01einik, I.N. 92
Mailfert, R. 21 128, 129, 130 Ortenburger, I.B.
Maita, J.P. 21, 22 Mirlin, D.N. 129 217, 218, 228
Makatani, H. 71, Mitra, 5.5. 243 Osamura, K. 324
76 Miyakawa, T. 211, Ostrowski, G.E. 77
Malkova, A.A. 230, 345, 347 Otto, A. 104, 108,
242 Miyata, T. 164 129
Maradudin, A.A. 20, Moch, P. 267 Ovchinnikov, A.A.
21, 91, 124, 128, Molkova, A.A. 229 23
130, 243 Montgomery, H. 364 Overhauser, A.W.
Marisova, S.V. 129 Montroll, E.W. 20 33, 42
Markov, Iu.F. 229, Mooradian, A. 242 Overhof, H. 217,
242 Morawitz, H. 267 228
Marshall, N. 109, Mori, H. 79, 80,
110, 129 91
Martel, P. 76, 91 Moruzzi, V.L. 364 P
Martin, P.C. 21, Mott, N.F. 186, Palik, E.D. 226
91, 341 343, 347 Palmer, R.E. 364
Parks, R. 315 Poehler, T.O. 22 S
Pascal, P. 243 Poh1, R.O. 91 Sagawa, T. 211
Patel, C.K.N. 261 Pollak, F .H. 290 Sak, J. 94, 120,
Patton, B.R. 13, Pomeranchuk, l.Ya. 121, 129
20, 22, 23, 331, 70, 77 Sandman, D.J. 22
332 Pong, W. 345, 348 Saslow, W. 228
Paul, W. 226 Powe ll, C. 108, Sawada 44, 75
Pauli, W. 168 129 Sca1pino, D. 23
Pawley, G.S. 228 Pratt, G.W. Jr. Scanlon, W.W. 227
Peier1s, R.E. 14, 2ll, 216, 228 SchHefer, F.P. 290
16, 22, 332 Price, D.L. 21, Schaich, W.L. 362,365
Pekar, S.l. 123, 29, 30, 41, 42, Scheif1ey, W. 348
130, 153, 163, 77 Schmidt, G.E. 91
341 Prohofsky, E.W. 91 Schnatter1y, S.E.
Pells, G.P. 354, Pynn, R. 42 364
364 Schneider, T. 76
Pelzer, H. 163, Schoenwald, J. 109,
197, 2ll R 110, 129
Penn, D.R. 205, Rabii, S. 217, 220, Schofield, P. 91
211 228 Schooley, J.F. 315
Pere1, J. 22 Rajagopal, A.K. 47, Schram, K. 129
Perlstein, J.H. 22 62, 76 Schrieffer, J.R.
Petico1as, W.L. Ranninger, J. 91 22, 54, 76
253, 266 Ray, B. 228 Schroder, U. 33,
Petroff, Y. 162, Ray, R. 94, ll5, 42
164, 218, 224, ll7, 118, 129 Schu1fhof, M.P. 92
228 Rayleigh, L. 129 Schultz, T.D. 163,
Pfeiffer, E.R. 315 Rehwa1d, W. 21, 22 168, 172, 186
Phillips, T.E. 22 Reiter, G.F. 92 Schwab 1 , F. 92
Pick, R.M. 3, 5, Rice, M.J. 19, 23 Scott, Y.F. 76
21, 23, 25, 42, Ringeissen, J. 164 Seib, D.H. 357,
294 Ritchie, R.H. 93, 364
Pidgeon, C.R. 2~o, 94, 101, 105, Seitz, F. 91, 211,
262 106, 128, 129 331, 348
Pinchaux, R. 164, Roberts, S. 243 Selders, M.. 164,
228 Robinson, J.E. 77 324
Pines, D. 4, 21, Rockwell, D.A. 77 Sem~nkov, A.T. 23
44, 55, 70, 75, Rogers, S.J. 91 Seraphin, B.a.
76, 77, 2ll, Ro11efson, R.J. 91 359, 360, 364
317, 323 RBss1er, U. 217, Sham, L.J. 1, 5,
Pitayevski, L.P. 343, 345, 347 6, 20, 22, 25,
55, 76 Roth, L.M. 211 31, 42, 91, 291,
P1atzman, P.M. Rowe, J.M. 77 331, 332
166, 167, 168, Rubio, J. 130 Shapiro, S.M. 267
175, 176, 177, Rudavskii, E.Ya. Shaw, E.D. 261
178, 179, 181, 77 Shaw, R.W.J. 30,
183, 186, 187, Ruva1ds, J. 43, 42
189,195,196, 47, 48, 62, 75, Shekhtman, Sh. 21
197, 267, 318, 76, 77 Shen, Y.R. 218,
323,333,340, Ryder, E.J. 22 228
341
Sherrington, D. 23, Sugakov, V.I. 129 Uh1e, N. 163, 324
227, 229, 230, Sunakawa, S. 47,
231, 242, 243 55, 62, 63, 76
Shiga, M. 354, Sunji~, M. 94, 129 V
364 Surko, C.M. 77 Va1atin, J.G. 23
Shikim, V.B. 77 SUssmann, J.A. 91 Van Camp, P. 293
Shimizu, M. 5, 21 Svensson, E.C. 76 Van Doren, V.E.
Shirane, G. 12, Swiggard, E.M. 226 293
21, 22 Szymanski, H.A. Van Dyke, J.P.
Sikivic, P. 163 248 217,218,228
Si1berg1itt, R. 76 Van Hove, L. 92
Singwi, K.S. 41 Van Kampen, N.G.
Sinha, S.K. 5, 6, T 129
21, 31, 34, 36, Tan, H.T. 74, 77 Van Vechten, J.A.
37, 38, 39, 42 Tani, K. 92 343, 347
Sjtl1ander, A. 41 Tauc, J. 341 Varga, B.B. 243,
Slack, G.A. 243 Teng, M.K. 267 331
Slade, M.L. 226 Teng, Y.Y. 105, Veg1er, J.G. 22
Slusher, R.E. 77 128 Vete1ino, J.F. 243
Smith, J.A. 348 Ter Haar, D. 76 Vie1and, L.J. 21,
Smith, N.V. 364 Testardi, L.R. 7, 22
Soden, R.R. 21 21 Visvanathan, S.
Solana, J. 61, 75, The11ung, A. 91 317, 319, 323
76 Theye, M.L. 364 Vosko, S.H. 41,
Spicer, W.E. 357, Thomas, D.G. 130 354, 364
358, 364, 365 Thornber, K.K.
Spruch, L. 187 168, 186
Stegeman, G.I.A. Ting, C.S. 291 W
253, 266 Tomiki, T. 164 Wagner, L.F. 365
Steigmeier, E.F. Tosi, M.P. 41, 347, Wagner, R.J. 226
267 348 Waidelich, W. 163,
Stephan, G. 345, Toulouse, G. 94, 324
348 129 Wa1atka, V.J. 22
Stephen, M.J. 48, Toyozawa, Y. 162, Waldmann, L. 91
60, 76 164, 211 Waldron, J.P. 365
Stern, E.A. 105, Tretjakov, B.N. 21 Walker, C.T. 91
107, 118, 128, Tsang, Y. 218, 228 Wa1lden, L. 358,
129 Tsukamoto, H. 164 364
Stevenson, D.J. Tucciarino, A. 92 Walley, J.C. 228
354, 364 Tung, Y. 228 Wallis, R.F. 129,
Stimets, R.W. 242 Turnbull, D. 91, 164
Stoicheff, B.P. 331, 348 Walter, J.P. 36,
249, 250, 253, TUtttl, I. 62, 76, 42, 91, 223,
266 77 224, 228
Stradling, R.A. Tyte, R. 291 Wang, S. Q.102,
315 Tzoar, N. 267 103, 129, 130,
Strttss1er, S. 19, 211
23 Ward, J.C. 91
Sturm, K. 352, U Webb, G.W. 22
364 Ueta, M. 164 Weger, M. 7, 21,
22, 23, 325, 331, 364
332 Woerner, J. 75, 77 Z
Wegner, F. 91 Wolff, P.A. 341 Zachariasen, W.H.
Wehner, R.K. 91, Wol1ey, J.C. 228 21
267 Wong, U. K. 77 Zallen 226
Weinstein, B. 290, Woo, C.W. 74, 77 Zawadowski, A. 48,
291, 299, 315 Wood, R.F. 105, 129 75, 76
Weiss, G.H. 20 Woods, A.D.B. 58, Zeller, H.R. 331
Weisz, G. 223, 228 75, 76 Zerbin, LA. 77
Whang, V.S. 211 Woodward, L.A. 248 Zeyher, R. 130,
Whitfield, G.D. Wortis, M. 77 291
144, 187, 197, Wright, G.B. 242, Zharkov, U.N. 71,
211, 341 290, 291 73, 77
Whitsett, C.R. 226 Zienau, S. 163,
Wick, G.C. 148, Y 197, 211
163 Yamagishi, F.G. 22 Ziolkiewicz, H.K.
WicklWld, A. 22 Yamasaki, S. 76 267
Wigner, E.P. 211 Yan, J. 48, 75 Zubarev, D.N. 47,
Wilks, J. 91 Yang, C.N. 44, 75 62, 76
Willens, R.H. 21 Yau, J. 60, 76 Zurobev, D.N. 91
Williams, A.R. 354, Yoki-o, Y. 76 Zwanzig, R.W. 79,
358, 360, 361, Yu, P.Y. 218, 228 91
SUBJECT INDEX TO PART B
A-IS compound 17, 18, 31 Annihilation

A3B compound 7-8, 9 positron - 7
Absorption Anthracene
- coefficient 150-155, 157, solid - 103, 104
269, 318, 320, 321 Antiferromagnet 256
Drude - 352, 354 Ar 279
- energy 351 As1amazov-Larkin diagram 19
exciton - 103 Au 359, 362
free carrier - 241, 299,
321
free polaron - 145-163, Back scattering configura-
179-185, 318-323, 333- tion 269, 270
334 Band crossing 214, 222, 223
infrared - 304 Band structure
magnetic-optical - 295, 305 - in Hgl-xCdxTe crystal
optical - 104, 245, 246, 225-226
279, 351-357 - in Pbl-xSnxSe crystal
Adiabatic approximation 3, 26, 221-222
147, 153, 157, 229, 241 - in semiconductors and
Ag 359 alloys 213-226
AgAu 357, 362 non-parabolic - 220, 230
AgBr 161, 163 - of II-IV compounds 223-
AgIn 357 226
AgPd 362 - of IV-VI compounds 214-
Al 352-354 223
Alkali , Bardeen-Pines interaction
- halides 145, 165, 200, 312
210, 281, 344 Basis
- metals 29, 353 - functions 44
Alloys BaTi03 323
electronic structure of - BCS superconductivity 313
355-357 Bethe-Sa1peter equation 49
optical conductivity of - Bloch picture 255
356-357 Bogo1iubov-Va1atin trans-
optical properties of - formation 16
213-226 Boltzmann
photoemission in - 361-362 - approximation 195-196
A1Sb 300 - equation 80, 83
Anharmonic Born approximation 46, 59,
- coup 1 ing of phonons 52, 75 71-75
375
376 SUBJECT INDEX TO PART B
Born-Oppenheimer approxima- - energy 199

tion 214 exciton - 283
Bridgman method 242 - hole 199~200, 207
Brillouin Correlation function
- equation 249 current - 80
- scattering 246-253 current-current - 333,
- shift 250 337
Brownian motion 80 displacement - 83
Bulk magnetic - 86, 90
- excitation 107 momentum - 82
- exciton 104 pair - 30
- mode 95, 99, 101 Coupling
- phonon 104, 106 anharmonic phonon - 75
- plasmon 99 electron-bulk mode - 113-
- reflectivity 124 114
Bulk modulus 11 electron-exciton - 113
- of insulators 350 electron-phonon - 11, 29,
47, 113, 134-136, 145-
161, 165, 287-290, 319
C 309 electron-plasmon - 113
Canonical variables electron-surface mode -
- in electron-phonon 111-113
coupling 139-144 exchange - 87
Carbides meson-nucleon - 165
metallic - 34 plasmon-phonon - 239-241
Cd3As2 213 roton-phonon - 49, 55, 70
CdO.2Hgo.sTe 241 roton-roton - 46-47, 56,
CdO 323 62
CdS 225, 259, 263, 308-310 Coupling constant 112, 120
CdTe 223-225, 226 - of polaron 142, 336,
Charge density 200 345
Charge neutrality 32, 36, Crystal structure
229 - of insulators 344
Chodorow potential 355 Cu 354, 357, 358-361
C02 55 CuNi 357
Cohen-Koonce mechanism 311 CuZn 357
Cohen's many-valley theory
310, 314
Cohesive energy Damping 249, 255
- of insulators 350 - matrix 82
Color center 157, 165 d-band
Compressibility 220 tight binding - 7-9
Compton recoil 265 Debye
Compton spectrum 265 - wave 249
Conductivity Deformation potential 220,
optical - 351, 353, 356- 272
357 effective - 300, 304
thermal - 82 exciton-two-phonon - 300
Cooper instability 19 intervalley - 312, 314
Cooper pair 18, 19, 328 intravalley - 312
- t-matrix 17-18 one-phonon - 297, 298,
Correlation 28, 29-30, 203, 308, 312
355, 361
SUBJECT INDEX TO PART B 377
two-phonon - 295-314 Drude transition 354
Degenerate band 8-12 Drude-Zener theory 233, 240
Density Dynamical matrix 5
condensate - 63
electron - 2-3
- fluctuation 248 Edge
- fluctuation operator - 62 plasmon - 236
- operator 47, 63 Effective excitation Hamil-
- response 229 tonian 63
Density of states Effective mass 207-208,
optical joint - 357 221, 222, 230
- for phonons 56 electron - 345
- for roton pairs 50-54, - of polaron 120, 150,
57, 60 156, 192, 194
Dielectric constant 5, 202, Elastic constant 83, 220,
334 273, 347
- of insulators 344 - of insulators 350
- of polarizable medium Electron
133-134, 162 - -one-phonon constant
Dielectric dispersion 205 288-290
Dielectric function 3, 26, - -two phonon constant
95-97, 98-99, 101, 102- 288-290
103, 121, 124, 127, Electron affinity
203, 206-208, 213, 214, - of insulators 346
219, 313, 314 Electronic structure
- in HgTe 229-234, 236, 237 - of alloys 355-357
interband - 230, 232, 233, Emission
239 optical - 355-358
intraband - 230, 233 photo - 245
phonon contribution to Energy-loss
234 - of electrons 105, 106-
Dielectric response 203-205, 108
208 Equation of motion
Diffusion - for electric field 136-
- coefficient 89 139
energy - 88 - for polaron 145-150,
heat - 81-83 166, 185-186, 189-196
magnetisation - 88 self-consistent - 185-186,
Dipole 189-196
electric - 246 Exchange 27, 29-30
- moment 53 - coupling 87
Dispersion phonon - 49
dielectric - 205 Excitation
- roton 43 bulk - 107
Dispersion relation - dispersion 44
- of surface mode 99-100, electronic - 260-266
102-105, 106, 108, 110, - interaction (micro-
122 scopic theory) 62-70
Dissipation magnetic - 256-258
momen tum - 89 - spectrum of He 3-He 4
Doppler shift 249, 265 mixture 70-75
Drude absorption 352 - spectrum of liquid He 43,
46
Exciton 201-203, 209-210, Ga 273

301, 307 GaAs 265, 269, 323
- absorption 103 GaP 109, 283-288, 300, 308-
bulk - 104 310
Frenkel - 103 Gap
surface - 93, 103-104, 113, interband - 271
115, 117, 124 - mode 241
Wannier - 103, 127, 301 Ge 296, 272-281, 299, 309
Extinction coefficient 235 GeTe 215, 310-311, 314
GeTe-SnTe 215
Golden Rule 59, 151, 157,
Factorization 209
- Ansatz 34-37 Gorkov method 19
- procedure 5-6, 37-39 Grating 105, 106
Fano effect 276-279 Green's function 16, 49,
F-center 161 160
Fe 256 phonon - 17-19
FeF2 256 Ground state energy
Fermi resonance 55 - of free po1arons 150,
Ferroelectric phase transi- 335-341
tion 256 Ground state theorem
Ferromagnet 256 - for free po1arons 183-
Feynman 185, 335-341
- model of polaron 166-167,
175-183, 189
- theorem 115 Harmonic approximation 157,
Feynman-He11man theorem 335 166
FHIP 166, 167, 175-180, 189, Hartree-Fock
318, 333, 338 - approximation 73
Fine structure 207 Hartree Hamiltonian 27
Force constant 2-3, 26, 31, He
35, 38 solid - 86
Force matrix superf1uid - 43-75, 86
restoring - 80, 84 He 3-He 4 mixture 70-75
Franck-Condon He 3 -quasipartic1e
- state 157, 159, 165, 167, - - continuum 70
182, 195 - operator 72
Frenkel exciton 113 - -roton interaction 71-
Frtlh1ich interaction 283, 75
285, 287 Heat conduction pole 83
Frtlh1ich polaron 47, 70, 120, Heat diffusion 81-83
133-144, 145-163, 165- Heat pulse technique 79, 82
186, 317-323, 333-341 HgS 213
- excitations 175-180 Hg2S 242
- ground-state 172-175 HgSe 213
- self-consistent equations Hg2Se 242
of motion 189-196 HgTe 213, 214, 223-225,
- self-energy 166, 194 229-242
Form factor 223, 225 Hg2Te 242
Fuchs-Kliewer mode 94, 103 HgxCdl-xTe 213, 214, 225-226
Hybridization effective ion-ion - 1-3
- of excitations 49 electron-boson - 203, 208
- of molecular vibration electron-electron - 13-14,
levels 55 18, 199, 207
- of phonons 55, 71 electron-exciton - 203
- of single excitations electron-hole - 302
with roton pairs 55-59 electron-impurity - 202,
Hydrodynamic 206
- excitation 79-91 electron-phonon - 3, 14,
- variable 79, 81, 84, 88 145-163, 295, 301,
Hydrodynamics 313, 334
- of anharmonic crystal electron-plasmon - 205,
81-86 207
- in a ferromagnet 86-91 exciton-phonon - 302, 304
Hypersonic wave 250 exciton-photon - 302
indirect - 303
intervalley electron-elec-
12 264 tron - 295, 310
Image intravalley electron-elec-
- charge 94, 114, 118 tron - 295, 310, 314
- potential 114-119 ion-ion - 1, 11
Impedance one-phonon-exchange - 311
- function 126, 166, 167, one-phonon-intervalley -
337, 341 314
surface - 126 pairing - 313
Impurity 241-242, 256 phonon-phonon - 55-59, 63
In 357 phonon-roton - 49, 55, 70
InAs 300 relativistic - 213, 215,
InP 300 220
InSb 258, 261, 297, 298, 300, roton-roton - 46-47, 56,
309 62
Instability spin-orbit - 213, 220,
Cooper- 19 223, 225, 285
lattice - 12-18 two-phonon-exchange - 311
Peierls - 12-20 Interband
shear - 12, 18 - dielectric function 230,
Insulators 232, 233, 240, 241
bulk modulus of - 350 - gap 271
cohesive energy of - 350 - transition 214, 219,
crystal structure of - 344 230, 352
dielectric constant of - Inter-chain overlap 11, 13-
344 14
elastic constant of - 350 Interference
electron affinity of - matrix elements - 296,
346 299, 300, 313
ionisation potential for Interferometer
346 Fabry-Perot - 251
lattice constant of - 344 Intermediate state inter-
plasma frequency of - 346 action 255
properties of - 343-350 Intraband
Interaction - dielectric function
Bardeen-Pines - 312 233, 234, 240, 241
- scattering 283 Light scattering 245-266
- transition 230, 352 - from electronic excita-
Inversion layer 120 tions 260-266
Ionic charge 39-41 - from magnetic excita-
Ionization potential tions 256-258
- for insulators 346 - from phonons 251-256
- from spin-flip 258-259
Lil 163
Jahn-Teller effect 8 LiMg 355
Linear response 233
Line-shape 276
K 30 Liquid
Kadanoff-Langreth formula 167 - -solid phase transition
KI 163 59
K2NiF4 90 Lornetz model 203
Kohn effect 17-18, 31, 326- Loss function
328 energy - 207, 209-210
Korringa-Kohn-Rostoker method Lyddane-Sachs-Te11er rela-
225, 226, 359 tion 5, 101
k·p perturbation 12
K2Pt(CN)4BrO.3.3H20 325
Kramers-Kronig relation 232, Magnetic excitation 256-258
236, 237, 239 Magnetisation
Kubo formula 80-81, 85, 167, - diffusion 88
168, 175 - matrix 87
Magnon 93, 256-257
- coupled state 55
Labb~-Friedel model 7-9, 328 - -phonon state 74
Landau second - 88-91
- level 258 surface - 93
- theory 9 Martensitic transformation
Landau-Pekar method 153-157, 7, 328
161 Maxon 48, 50, 51, 52
Landau-Placzek peak 83 - -maxon spectrum 53
Laser McMillan formula 328
C02 - 259 Metallic carbides 34
Kr+ - 279 Method
Lattice Bridgman - 242
- dynamics 1-20 KKR - 225-226, 359
- instability 12-18 local pseudopotentia1
Lattice constant 27-30, 35
- of insulators 344 non-local pseudopotentia1
Lead - 30
- chalcogenide 215 OPW - 215, 216, 299
- salts 214, 215 pseudopotentia1 - 1, 215,
Lee-Low-Pines theory 121, 216, 223, 225, 352
160, 167 tight-binding - 5, 7, 14
Level inversion 213, 214, 229 Mg 30,355
Li 30, 265 MnF2 90, 256
Life-time Mobility 309, 321
- of rotons 46, 50-53, 59- - of polaron 166, 167,
62, 72 194-196
surface - 120 Slater type - 299
Mode Organic solid 12-14, 103
bulk - 95, 101 Oscillator strength 238,
diffusive - 87, 89 241, 276
electrostatic - 95 Otto's experiment 104, 108-
Fuchs-Kliewer - 94, 103 109
gap - 240 Overlap
magnetic - 95 inter-chain - 11, 13-14
soft - 7, 8, 12, 311
surface - 93-128
transverse electric - 98 Path integral 160, 166, 168-
transverse magnetic - 98 175, 189, 195
Monovalent state 242 PbS 215, 216
Mori's theory 79 PbSe 215, 216, 217-221
PbTe 215, 216
Pbl-xSnxSe 220-222
Na 30 Pd 6, 357, 362
Nb3A1 7 Peier1s-Fr~h1ich instability
Nb3Ga 7 325-331
Nb3GexA11-x 7 Peier1s' instability 12-20
Nb3Sn 1, 7, 11-12, 18, 325 Peier1s' state 19-20
Nee1 temperature 257 Pekar relations 333
Neutron Penn model 205-207
- measurement 9-12 Phase transition 1, 8, 9.
- scattering 7, 43, 44, 46, 248, 251
59, 79, 82, 86 ferroelectric - 256
Ni 6, 31, 256, 357 liquid-solid - 59
Noble metals 354, 357, 358 second order - 11
Non-parabolic band 220, 230 structural - 7-12
Phonon
Opalescence anharmonic coupling of -
critical - 83 75,
Operator bulk - 104, 106
Liouville - 80 - contribution to dielec-
phonon - 63, 70 tric function 234
resolvent - 80 - density of states 56
Optical - exchange 49
- absorption 145-163, 166- - excitation 46, 241
183, 189, 194-195, 245, - hybridisation 51, 55
246, 278, 317-323, 333- - in insulators 31, 41
341, 351-357 - in metals 26-31
- conductivity 351, 353, - in semiconductors 31-41,
356-357 229-242
- emission 245 - operator 63, 72
- joint density of states - -phonon interaction 55-
357 59, 64
- mass 352, 355 - -roton branch 49, 55,
- pseudopotentia1 354 70
- reflectivity 223 softened - 13, 19
OPW method 215, 216, 299 surface optical - 93, 97,
relativistic - 216 101-103, 106-107, 112-
Orbital 115, 117, 121
Photo-emission 207, 345 Process
anisotropy of - 362 normal - 86, 89, 90
- energy distribution 358- Umklapp - 84, 86, 89, 90
363 Projection operator tech-
- on metals and alloys 357- nique 80
364 Propagator
surface - 362 phonon - 55
Plasermon lf3 phonon-roton - 66
Plasma frequency 203 quasiparticle - 47, 49
- of insulators 346 Pseudopotential 1, 215, 216,
Plasmon 93, 203-206, 209-210 223, 225, 352
bulk - 99 local - 27-30, 35
- edge 236 non-local - 30
- -phonon coupling 239-241 optical - 354
surface - 93, 94, 96, 99-
101, 104, lOS, 108, 112-
114, 116, 126-127 Quadratic response 362
Point contact model Quantum dielectric 199-210
- for roton coupling 46, Quartz 104
'50, 59, 71 Quasi-particle
Poisson distribution 107 He 3 - 70-75
Polariton 53, 101
- effect 111
surface - 101, 110 Radiation field 245
Polarizability 3-5, II, IS, Raman scattering (see scat-
20, 127, 246, 248, 256, tering) 46, 48, 50, 55,
269 237, 246, 251-266,
- matrix 6, 9, 10 269-290
Polarization 7, 123, 125, - by phonons 270-272
247, 248, 251, 271 - electronic 278
- coefficient 32 - in Ge and Si 272-280
- electronic 136, 138, 139 intraband - 283
- field 149-153, 199-201 neutron - 272
- ionic 136, 138, 139 - probability 278
- potential 201 resonant - 255, 269-290
Polaron second order - 280-290
- absorption in semicon- spontaneous - 258
ductors 317-323 stimulated - 258
bound - 161 vibronic - 273
coupling constant of - 345 Raman tensor 306, 307-308
effective mass of - 120 Rare gas
electronic - 113, 199- - crystal 200
200 - solid 343, 345
Frohlich - 120, 133-144, Rayleigh scattering 247-249,
145-163, 165-188, 189- 251
196, 199, 200, 317-323, Rayleigh wave 93
333-341 Reactance matrix 196
surface - 94, 119-121 Recoil
Polyethyl methacrylate 251- electronic - 200, 208
253 exci ton - 209
Positron Reflection
- annihilation 7 - coefficient 150
specular - 105, 106, 127 - interaction 46-47, 57,
total - 108, 109 62
Reflectivity 162, 234-241 - scattering 47-49, 59,
bulk - 124 67, 70
optical - 105 RPA 4, 17, 30, 203, 208,
Refractive index 150, 235 230, 351-352
Relativistic interaction 215,
220
Relaxation effect 157, 161, SbSi 256
165-186 Scale transformation for
Relaxation time 352 polaron 335-337
interband - 353 Scattering
Relaxed excited state 145, - cross section 301, 306
157, 165-166, 180-183, light - 79, 82, 83, 242-
322, 339 266
Renormalisation 47, 62, 68 neutron - 7, 46, 50, 55,
Resonance 79, 82, 86, 88
cyclotron - 343 non-resonant - 299, 300
electron-phonon - 295 3U9, 313
electron-spin - 245 phonon-impurity - 86
Fermi - 55 quasi-particle 47, 65
magnetophonon - 299 Raman - 46, 48, 50, 55,
nuclear magnetic - 245 237, 246, 251-266,
Raman - 255-256 269-290, 295-314
sound - 83 Rayleigh - 247-248, 251
- spectroscopy 245 resonant - 305, 309
surface - 126 roton-roton - 47-49, 59,
two phonon - 299 68, 70
Response Stokes - 301
dielectric - 203-204, 208 X-ray - 265
electron density - 3-6 Screening
linear - 80-81 electron - 3, 9, 11
quadratic - 362 - length 260, 262
Response function - matrix 9
density - 229 Second magnon 88-91
displacement-displacement Second sound 84-86
82 Selection rules 245, 246,
energy-energy - 82 256, 283
Reststrahlen 240 Self-energy 199-201, 203-
Retarded commutator 80 205, 208
Roton electron - 114-116
- dispersion 43 excitation - 55
- energy gap 43 phonon - 17
- life-time 46, 49-53, 59- polaron - 120
62, 72 roton - 59, 60, 72, 73
- self-energy 59, 60, 72, Semiconductor
73 degenerate - 310-314
- temperature dependence 46 many-valley - 310-311,
Roton-roton 314
- bound states 48-55 narrow-gap - 213-226
- density of states 50-55, polar - 145, 317-323
57, 60 resonant Raman scattering
in - 269-290
- -semimetal transition 225 - resonance 126

spin-flip in - 258-260 - state 120, 126
Semimeta1 213-225 - Wannier exciton 97, 121-
Shear constant 7, 8, 11 128
Shear instability 12, 18 Susceptibility 28, 30, 34,
Shell model 33-34, 38, 40-41, 38, 80, 81, 83
293
Si 6, 31, 36, 269, 272-280,
293, 299, 309 Te 323
Slater orbital 299 Tension tensor 81
Sn 213, 229, 230 Tetrathiofu1valene (TTF)
SnTe 215-216, 310-311, 314 - tetracyano-p-quino-di-
Spectral methane (TCNQ) 13-15
- fWlction 88 Thermal
Spectroscopy - fluctuation 249
resonance - 245 - wave 249
scattering - 245 Three-step model 358, 362
Spectrum Tight binding
absorption - 204 - d-band 7-10
excitation - 199, 208 - method 5, 7, 14
Spin-flip Time slicing 170
- in semiconductors 258-260 Tomonaga model 325
Spin-orbit Toyozawa model 201-203, 209,
- interaction 213, 220, 223, 210
225, 285 TPF-TCNQ 325, 331
- splitting 285 Transformation
Spin wave 256 Bogo1iubov-Va1atin - 16
SrTiO 310-311, 314, 323 Martensitic - 7
Sum Rule 83, 90, 203-207, 209, Transition
329, 333-335 AFM-SF - 258
Superconductivity 54, 310-314 Drude - 352, 354
BCS - 18-19, 313 interband - 214, 219, 223,
- fluctuation 13 230, 352, 354
- in linear chain crystals intraband - 230, 352, 354
325-331 - metal 1, 6-7, 357
Superconductor 1, 7 phonon assisted interband
Supraconductor 215 - 354
Surface - probability 230
- exciton 93, 103, 112-115, semiconductor-semimeta1
117, 124, 162 225
- impedance 126 SF-PM - 258
- magnon 93 virtual - 258, 278
- mobility 120 Transmission coefficient 150
- mode 93-128 Transport coefficient 85
- mode propagation 109-110 Trial action 166, 175
- optical phonon 93, 97, Trig1ycine sulphate 251,
101-103, 106-107, 112- 252
115,117,121, 161 Tungsten 7, 325, 328
- plasmon 93-94, 96, 99-101, TWling 258, 262
104, 105, 108, 112-114, Two-roton
116, 126-127 - bound states 48-54, 74
- polaron 94, 119-121 - continuum 48, 50
- density of states 50-54, hypersonic - 250
57, 60 Rayleigh - 93
spin - 256
thermal - 86, 249
Umk1app process 84, 86, 89, Weger-Labb~-Friede1 model 9,
90 10
Window condition 86, 90
Vertex function 47, 65 X-ray

Vertex interaction 301, 304, - measurement 9-12
312 - scattering 264, 265
Viscosity 82
V3Si 1, 7, 11, 18, 325
Zero gap
crossing induced - 214, 229
W 362, 363 symmetry induced - 213, 229
Wannier exciton Zincb1ende 297
surface - 97, 121-128 Zn 357
Wannier representation 5-7 ZnO 105, 107, 309
Wave ZnS 300, 309
Oebye - 249 ZnSe 300, 309

Elementary Excitations in Solids, Molecules, and Atoms: Part B

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Elementary Excitations in Solids, Molecules, and Atoms: Part B

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Elementary Excitations

A series of edited volumes comprising multifaceted studies of contem-

This series is published by an international board of publishers in con-

A Life Sciences Plenum Publishing Corporation

C Mathematical and D. Reidel Publishing Company

PLENUM PRESS • LONDON AND NEW YORK

Library of Congress Catalog Card Number 74-1247

ISBN-13: 978-1-4684-2825-4 e-ISBN-13: 978-1-4684-2823-0

© 1974 Plenum Press, London,

The Advanced Study Institute on 'Elementary Excitations in

List of Lecturers ......................................... v

Contents of Part A ........................................ xi

Electronic Influence on Lattice Dynamics. ...... ..... ...... 1

Electron Interaction with Surface Modes ................... 93

Formalism of an Ab Initio Calculation of Phonon Dispersion

EXPERIMENTAL STUDIES ON INSULATORS AND METALS

A Review of the Experimental Properties of Insulating

Author Index to Part B .................................... 367

Subject Index to Part B ................................... 375

Many-Body Effects at Surfaces .. .......... ..... ............ 1

ELECTRONIC STRUCTURE IN CRYSTALS

Hartree-Fock Model Calculation for Atoms and Crystals plus

ATOMS MOLECULES AND LIQUIDS

Many-Electron Effects in Spectra of Electrons Bound in

Dynamical Image Charge Interactions ....................... 345

Author Index to Part A .................................... 361

Sub j ect Index to Part A .................................... 367

Department of Physics, university of California,

t Research supported by the National Science Foundation, Grant

2. MICROSCOPIC FORMULATION OF LATTICE DYNAMICS

A EFFECTIVE INTERACTION BETWEEN IONS

where ~(t,t') is called the force constant. It consists of two

where Vi(r - Xt) is the electron-ion pseudo-potential and ont'(r)

B THE ELECTRON DENSITY RESPONSE

on(r) = jdr'x(r.r' )oV(r'). (2.4)

Thus, a test charge will see an effective potential

where VCr - rl) denotes the Coulomb repulsion between electrons.

on(r) = jdr'x(r.r')o~(r')' (2.6)

The usual procedure to determine the density response X(r.r')

and finally, arrive at the density response

For a more careful discussion of these concepts and the rel-

where 1jJj(l") and Ej denote the single-particle wave function and

where x~ is a lattice vector. Then, the polarizability of rel-

x(l",l'" ;q) (2.13)

where N is the number of unit cells in the crystal. It is still

C THE WANNIER REPRESENTATION

In terms of these Wannier functions, equation (2.11) for the

x(r,r' ;q,w) (2.15)

and the pOlarizability matrix is

The solution of the integral equation (2.9) reduces to the

OM' - XM' (2.18)

L JdrJdr'Fh,·,(q,r)v(r-r')Fh,,(q,r')8 h "h,(q,w). (2.19)

Then, the density response becomes

x(r,r' ;q) L Fh(q,r)Shh'(q,w)Fh'*(q,r'), (2.20)

This scheme is practical only if the matrix E is not too

3. STRUCTURAL PHASE TRANSITIONS IN A-IS COMPOUNDS

A THE MA.RTENSITIC TAANSFORMATION

Figure'l - Crystal Structure of A-IS Compounds A3B.

C LATTICE DYNAMICS IN THE CUBIC PHASE

where A denotes one of the three groups of A-atom chains in A3B,

which is just a density wave of localized d-electrons.

For finite w, as q -+- 0, 6A vanishes. Thus, strictly speaking,

The results of the zero wave-vector phonons are as follows.