PROBLEMS IN QUANTUM MECHANICS BY F. CONSTANTINESCU A.v. Humboldt Fellow, University of Munich, and University of Cluj, Rumania AND E. MAGYARI University of Craiova, Rumania TRANSLATED BY Vv. V. GRECU EDITED BY J. A. SPIERS © ee PERGAMON PRESS Oxford » New York + Toronto Sydney + BraunschweigPergamon Press Ltd., Headington Hill Hall, Oxford Pergamon Press Inc., Maxwell House, Fairview Park, Elmsford, New York 10523 Pergamon of Canada Ltd., 207 Queen’s Quay West, Toronto 1 Pergamon Press (Aust.) Pty. Ltd., 19a Boundary Street, Rushcutters Bay, N.S.W. 2011, Australia ‘Vieweg & Sohn GmbH, Burgplatz 1, Braunschweig Copyright © 1971 Pergamon Press Ltd. Al Rights Reserved. No part of this publication may be repro- duced, stored in a retrieval system, or transmitted, in any form oor by any means, electronic, mechanical, photocopying, record- 1g or otherwise, without the prior permission of Pergamon Press Ltd. First edition 1971 Library of Congress Catalog Card No. 73-116573 PRINTED IN HUNGARY (08 006826 x.Contents FoREWORD A Note on THE Layour oF THIS BOOK (Craper I. THE MATHEMATICAL FORMALISM OF QUANTUM MECHANICS 1, Hilbert Spaces 2, Operators in Hilbert Space 3, The Matrix Representation of Vectors and of Operators Problems Solutions Cuaprer II, SiupLe QUANTUM SysTEMS 1, The Eigenfunctions and the Energy Spectrum 2. The Transmission of Particles through Potential Barriers 3. Motion in a Central Field Problems Solutions Cuaprer IIL. MEAN VALUES AND UNCERTAINTY RELATIONS 1. The Mean Values of Dynamical Variables 2. The Uncertainty Relations Problems Solutions (CiapTer IV. THE SEMI-CLASSICAL APPROXIMATION, 1, ‘The Wavefunction in the WKB Approximation 2. Formulae for connecting WKB Wavefunctions on Opposite Sides of Turning Points Problems Solutions ‘Cuaprer V. PICTURES AND REPRESENTATIONS 1. The Schrédinger, the Heisenberg and the Interaction Pictures 2. Representations 3. The Density Operator Problems Solutions (Chaprer VI. ORBITAL ANGULAR MOMENTUM AND SPIN 1, Properties of Angular Momentum Operators 2. Spin 3. Angular Momentum and Rotations of Coordinate Axes. The Addition of Angular Momenta Problems Solutions vii vii eke 21 21 23 32 15 75 16 1 93 93 95 98 112 112 113 115 115 119 143 143 143 144 146 152Contents Cuaprer VIL. Systems oF IDENTICAL PARTICLES. SECOND QUANTIZATION 1, Symmetry and Anti-symmetry of State Vectors 2, Isotopic Spin 3. Second Quantization Problems Solutions (CitapTer VIII, PERTURBATION THEORY. THE VARIATIONAL METHOD 1, Stationary State Perturbation Theory 2, The Variational Method Problems Solutions (CrtapTer IX, TIME-DEPENDENT PERTURBATIONS. RADIATION THEORY 1, Time-dependent Perturbations 2, Radiation 3. The Interaction of Radiation with Atomic Systems Problems Solutions Crater X, COLLision THEORY 1. Potential Scattering 2. The Lippmann-Schwinger Equations Problems Solutions CiapTer XI. ATOMS AND MOLecutes Problems: Solutions Ciapter XII, ReLativistic Quantum MECHANICS 1, Definitions, Notation, Conventions 2, Elements of Relativistic Mechanics 3, The Klein-Gordon Equation and the Dirac Equation Problems Solutions ‘APPENDIX, CERTAIN FUNCTIONS USED IN QUANTUM MECHANICS 1, Hermite Polynomials 2, Legendre Polynomials and the Associated Legendre Functions 3, Spherical Harmonics 4, Laguerte Polynomials 5. The Gamma Function 6. Bessel Functions of the First Kind 7. Spherical Bessel Functions 8. The Hypergeometric Function 9. The Confluent Hypergeometric Function GeNeRAL REFERENCES Iypex ‘Onuee Tires IN THE SERIES 180 180 181 183 187 203 203 204 205 207 225 225 226 227 229 232 263 263 268 270 215 321 322 323 337 337 338 339 341 396 396 396 398 399 399 401 402 404 405 4Foreword ‘Wuen Dr. Constantinescu and Dr. Magyari approached me about the possibility of the pub- lication of an English edition of their collection of problems on quantum mechanics I was very pleased to arrange this. Although there exist a few good collections of this kind, none of those has the same extensive coverage which the present volume gives, and I felt that it would be a valuable addition to the existing literature. Quantum mechanics courses are getting more and more advanced, and topics which only a few years ago were deemed to be fit only for graduate courses now appear in undergraduate courses. It is thus very much to be welcomed to have a problems book which covers such topics as the Dirac equation, second quantization, many-body problems, and the density matrix. I hope and expect that quantum mechanics teachers as well as students will find the present book a great help, and I wish it every success. Magdalen College, Oxford D. TER HAAR, A Note on the Layout of this Book EAcH chapter is essentially self-contained, and is in three parts. In the first part, basic propositions relating to a particular topic are given and some consequential theorems are stated without proof. In the second part, a set of graded problems leads the reader to prove the theorems already stated, and to derive further theorems and applications. Detailed solutions of the problems are given in the third part. Equations in the first part are labelled with the number of the chapter (in roman numerals) followed by a serial number; those in the second and third parts with the number of the problem followed, respectively, by a serial letter or a serial number. The letter A followed by a number is a reference to an epuation in the Appendix.CHAPTERI The Mathematical Formalism of Quantum Mechanics 1. Hilbert Spaces A set of entities E is said to constitute a linear (complex) space if, on the elements of the set, operations of commutative addition, and of multiplication by a complex number, are defined and are such that the results of these operations are also element of E. The term “vector” is often used to denote the elements of such a space; these vectors should not be confused with the vectors of ordinary geometric space. Let H'be a linear (complex) space such that, to every pair of elements x, y of H,, there can be made to correspond a complex number, called the scalar product (x,y) of the elements x and y, and having the following properties: @ &%=0,%), (b) (arte, ») = Gr y+ Ors ¥), ©) Ax, y)= 4%, ys 06 Ay) = ACY), (4) (x, x) = 0, the equality holding only for the “null element” x = 0. The “norm” of an element is defined to be ||x|| =+4/G. His then said to be a Hilbert space provided it is complete.* In any Hilbert space a set of elements can be found, such that any element of the space can be written as a linear combination of these. Such a set is called a basi: In quantum mechanics, every state of a physical system is associated with a vector, some- times called a “ket”, and denoted by the general symbol | ), into which may be inserted symbols denoting eigenvalues, quantum numbers, etc., which specify the state in question. From the principle of superposition of states, it follows that the ket vectors of a system together form a linear space. + An ordered set {x4} of elements of # is said to converge to the limit xo, if || x,—xoll + 0 as 1 + oo, Ifa y ordered set {x4} of H, which is such that || x,—~%m || + 0 as 1, m - oo, converges to a limit which is an -lement of H, then H is said to be “complete”.Problems in Quantum Mechanics The scalar product of any two ket vectors |) and |v) of a system is a complex number, written as (v|u). The symbol (v| is sometimes called the “bra” vector corresponding to the ket |v), since a “bra” and a “ket” together form a “bra(c)ket”. This somewhat whimsical terminology is due to Dirac. The set of all ket vectors of a system form a Hilbert space. 2. Operators in Hilbert Space Any procedure A whereby each vector |1) of a Hilbert space H is related to one and only one vector |v) = A|u) of that space is called an operator of that space. An operator A is said to be “linear” if, for any vectors |w) and |v), and any complex numbers A and 4, A(A\u)+ 4 \0)) = AA|u)+ wAlo). (1) Two operators A and A+ are said to be Hermitian adjoints if, for any vectors |v) and u) of H, (wl At |u) = Cul Aloy*. 2) An operator A is said to be “Hermitian” (or “self-adjoint”) if A = 4*. An operator U is said to be “unitary” if UU* = UtU = If A is an operator and |u) is such that Alu) = alu), (13) where a is a real or complex number, then |1) is said to be an “eigenvector” of A with the “eigenvalue” a. The eigenvalues of Hermitian operators are always real numbers. There may exist more than one linearly independent eigenvector of 4 with the same eigenvalue a. Any linear combination of these is then also an eigenvector of 4 with the same eigenvalue a. The number of such linearly independent eigenvectors (if greater than one) is called the “degener- acy” of the eigenvalue a. The set of all eigenvalues of A is called the “spectrum” of 4. The spectrum of an operator may be discrete, or may be continuous, or may have a dis- crete part and acontinuous part. Let us denote by | mr) an eigenvector of 4 with the eigenvalue a, belonging to the discrete part, and by |v9) an eigenvector of A with the eigenvalue a, belonging to the continuous part of the spectrum. (Here r and g are indices which distinguish between degenerate states having the same eigenvalue.) For the eigenvectors of Hermitian operators, the following orthonormalization relations are satisfied for all values of the indices (provided that for degenerate eigenvalues a suitable choice of eigenvectors is made): (nr \n'’) = San See» {nr| vo") = 0, a4) (v0 ¥'o") = 5(v—v') (0-0), where 6,,,., is the Kronecker delta and 6(v—»') is the Dirac delta function. 2Ch. |. The Mathematical Formalism of Quantum Mechanics If the set of all eigenvectors |7r) and | vo) of the Hermitian operator A spans (by linear combination) the entire space H, this set is said to be complete, and the operator A is said to be an “observable” (the operator 4 is then capable of having a physical interpretation). The operator [4, B] = 4B—BAiscalled the “commutator” of the operators 4 and B. If [4, B] = 0, Aand B are said to commute. If two observables 4 and B commute, they have a complete set of eigenvectors in common, and conversely. 3. The Matrix Representation of Vectors and of Operators For any given vector |), the number (n|u), where |) is an eigenvector of some observ- able A, can be regarded as an element having “row number” ” of a one-column matrix (u); the whole matrix is then said to be a “representation” of the ket |z). The bra vector (u| is represented by the Hermitian adjoint matrix whose elements are (u| 1). For a given operator Q, the eigenvectors |m) and |) of A enable one to define the num- ber 2,,, = (n|Q|n), which can be regarded as the element with “row number” m and “col- umn number” 7 of'a square matrix (2). The whole matrix is then said to be a representation of the operator Q. Note that, in this representation, A itself is represented by a diagonal matrix. Properties of representations: (a) The Hermitian adjoints of operators are represented by the Hermitian adjoints of the matrix representations of the original operators. (b) Algebraic relations between vectors and operators lead to equivalent algebraic rela- tions between their representative matrices (thus, in particular, the equations which define the eigenvalues and eigenvectors of operators become matrix eigenvalue equations). (c) The trace Tr(2) of any Hermitian operator Q, defined as )° 2,,,, is independent of the representation used to define it. Let us denote by |), and by |), eigenvectors of the observables A and B, respectively. The two sets of eigenvectors define two possible representations, {4} and {B} say. The transformation from the first representation (of vectors and operators) to the second can be made with the help of the unitary matrix S = ((w/n)), thus @)s = SWa as) (Q)z = SOQ)aS*. as) If there is a one-to-one correspondence between the vectors |) and |), the matrix S is square and corresponds to a unitary operator U such that |n) = U|w). U is then said to define a unitary transformation of vectors and operators. Under a unitary transformation of vectors and operators, all scalar products remain unchanged and all Hermitian adjoints transform into Hermitian adjoints. If |g) is the state vector of some physical system at a given time ¢, then the “matrix” (t|¢) = (0), say, with “row number” r = the position vector(s) of the particle(s) constitut- 3Problems in Quantum Mechanics ing the system, is called the “wavefunction of the system in coordinate representation”. Note that the scalar product of two state vectors can be written, in terms of wavefunctions, as follows: Wd) = Jvleyield)ae = fp") bdr Problems 1. Derive the Schwartz inequality [dujoy| = Vl) VQl0), in which |) and |v) are any two vectors of a Hilbert space H. 2. Derive the triangle inequality* Vr olutoy = Vuln) + VO). 3. Show that the validity of the relation (1B) = Lem) (ui B) Ga) for any arbitrary vectors |«) and |), is a necessary and sufficient condition for the system of orthonormal vectors |11), |u2), ...,|%,), . .., to be complete. 4. Let S1 be a subspace of a Hilbert space H and S its complementary orthogonal sub- space. Any vector |) can be written as a sum of its projections in the two subspaces, | 1) = lus,)+|us,). Show that the projection operator Ps,, which is such that |s,) = Ps,|u), is Hermitian, and satisfies the equation P2, = Ps. 5. Show that if the subspace S; of the preceding problem is taken to be the subspace spanned by a single normalized vector |a), then the corresponding projection operator is given by Pa = |a)(al. 6. Show that if |r) denotes the eigenvectors of an observable, the following “closure relation” is valid Y |r) (ar| = 1. 7. A projection operator Py, is said to be greater than or equal to another projection operator Py, i.e. Pyy = Py, if the subspace N is contained in M. Show that (a) The relation Py, > Py satisfies the axioms required of any relation of inequality. (©) [Pm, Pw] = 0, + To simplify the writing, the notation | 4,u-+ Ayu) is used instead of Ay |) + 2,|0), 2 and 2, being com- plex numbers. Then (Au-+ Ayol = Af (ul-+ AS. 4Ch. |. The Mathematical Formalism of Quantum Mechanics (c) The relation P,, > Py is equivalent to the statement that (| Pyy|u) > (u| Py|u) for any vector |) of the Hilbert space. 8. Consider a set of vectors | v), in which » is a continuous index which can take all values in the interval (v1, v2). Show that if the vectors | v) are orthonormal in the sense that ("| ») = 6(v’—»), then the operator P= fipanel is the projection operator of the subspace spanned by the set of vectors |»). 9. Show that if unitary operator U can be written in the form U = 1+-ieF, where ¢ is real infinitesimally small number, then the operator F is Hermitian. 10. A Hermitian operator Ais said to be positive-definite if, for any vector |x), (u| Aju) = 0. Show that the operator 4 = |a)(a| is Hermitian and positive-definite. 11. If A is a Hermitian positive-definite operator (see problem 10), then KXu|4|0)| = V@] Alu) VO) Ale). (ila) Show that Tr (4) > 0, and that the equality holds if and only if A = 0. 12. Show that the operator F defined by the relation F = fflsyk(s, )(¢| dt ds, in which the kernel k(s, f) is real, is a linear Hermitian operator. 13. Show that the differential operator ha dx’ is linear and Hermitian in the space of all differentiable wavefunctions (x|) = (2), say, which vanish at both ends of an interval (a, b). 14. The translation operator (a) is defined to be such that Q2@) g(x) = g+a). Show that: (a) Q(@) may be expressed in terms of the operator p = — (b) 2(@) is unitary. 15. Given three operators A, B and C, express the commutator (4B, C] in terms of the commutators [4, C] and [B, C].Problems in Quantum Mechanics 16. Let H(r) be an operator acting on the wavefunctions y(r), and 0 a coordinate trans- formation operator which acts on the wavefunctions in such a way that Oy(r) = y(t’). Show that if H(r) is invariant under the coordinate transformation 0, ie. H(t’) = H(r), then [H, 0] = 0. 17. Find the expansion of the operator (A—B)~ in a power series in 2, assuming that the inverse A~* of A exists. 18, Show that if A and B are two operators satisfying the relation [[4, B], 4] = 0, then the relation [4”, B] = mA”[A, B] holds for all positive integers m. 19. Show that La. x1=—ih, [px] =—nihx 1, n> 1, (19a) dA [p, A] = —ih 7 (19b) where p = ag and A= A(x) is a differentiable function of x. 20. If the characteristic equation f(4) = 0 for an observable A is given, show that f(A) = 0. 21, Let |u) and |») be two vectors of finite norm. Show that Tr (\u)<01) = (|). 22. If Ais any linear operator, show that A* 4 is a positive-definite Hermitian operator whose trace is equal to the sum of the square moduli of the matrix elements of A in any ar- bitrary representation. Deduce that Tr (4* A) = 0 is true if and only if 4 = 0. 23. Show that if A and B are two positive-definite observables, then Tr (AB) > 0. 24. Diagonalize the Hermitian matrix Q= ( es » T@=1 21 ae. by means of a unitary matrix of the form U = clniberghainvivas, aul a) 21 off > Yo -af° 25. The derivative of an operator A(2) which depends explicitly on a parameter 2 is defined to be where dAQ) _,, AA+e)—AQ) a iCh. I. The Mathematical Formalism of Quantum Mechanics Show that d dA aB GAB = GBt4éAT (25a) d,oa! dA ayaa A at, (25b) 26. Show that the operator B(t) defined by the expression Bt) = e!4'Bye-4", where A and Bo are operators independent of the parameter f, is a solution of the integral equation Be) = Bot 4 i) ar|. 21. Show that, for any two operators A and L, ebAe~* = AFL, Ate r[E IZ, Ae te p[E>[2, [, Al] +. (27a) 28. Show that e4e” = e4+#e~(a) (4. if [[A, B], A][[A4, B], B] = 0. (28a) 29. Verify Kubo’s indentity e [A, e-P#] = e-P# f MLA, Hed, (29a) é where A and H are any two operators. 30. Show that a necessary and sufficient condition for two linear operators 4 and B to be equal (to within a phase factor), i.e. for A = Be, is that |u| A|v)| = |(u| Ble) (30a) should hold for any pair of linearly independent kets |) and |). 31. Show that a necessary and sufficient condition for a linear operator U to be unitary is that the matrix elements (i| U| k) of this operator in a given representation should obey the following equations: DiGiviwe=1, FGI GIVI =0, he ky Gla The convergence of the sums may be assumed,