Wave Mechanics: Advanced General Theory


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Table of contents :
Front Cover
Title PAge
PREFACE
CONTENTS
1. CLASSICAL MECHANICS AS THE LIMITING FORM OF WAVE MECHANICS
1. Motion in One Dimension; Par tial Reflection and Uncer tainty in the Sign of the Velocity
2. Compar ison between the Schr ddinger and the Classical Equation of Motion in One Dimension; Aver age Velocity and Current Density
3. Gener alization for Non-stationar y Motion in Thr ee Dimensions; The Hamilton-J acobi Equation
4. Compar ison of the Appr oximate Solutions of Schrödinger ’s Equation; Comparison of Classical and Wave-mechanical Aver age Values
5. Motion in a Limited Region; Quantum Conditions and Average Values
2. OPERATORS
6 . Operational Form of Schrödinger’s Equation, and Operational Representation of Physical Quantities
7. Characteristic Functions and Values of Operators; Oper ational Equations; Constants of the Motion
10. Orthogon a lity and Norm a lization of Characteristic Functions for Discrete and Continuous Spectra
3. MATRICES
11. Matrix Representation of Physical Quanties and Matrix Form of the Equation s of Motion
12. The Correspondene between Matrix and Classical Mechanics
13. Application of the Matrix Method to Oscillatory and Rotational Motion
14. Matrix Representation in the Case of a Continuous Spectrum
4. TRANSFORMATION THEORY
15. Restricted Transformation Theory; Matrices defined from different ‘Points of View’
16. Transformation of Matrices
17. Transformation Theory of Matrices as a Generalization of Wave Mechanics; Transformation of Basic Quantities
18. Geometrical Representation of the Transformation Theor y
5. PERTURBATION THEORY
19. Perturbation Theory not involving the Time (Method of Stationary States)
20. Extension of the Preceding Theory to the Case of ‘Relative Degener acy* and Continuous Spectr a; Effect of Perturbationon Various Physical Quantities
21. Perturbation Theory involving the Time; General Processes;Theory of Transitions
22. First Approximation; Theory of Simple Transitions
23. Second Approximation; Theory of Combined Transitions
24. Theory of Transitions for an Undefined Initial State
6. RELATIVISTIC REMODELLING AND MAGNETIC GENERALIZATION OF THE WAVE MECHANICS OF A SINGLE ELECTRON
25. Simplest Form of Relativistic Wave Mechanics
26. Magnetic Forces in the Approximate Non-Relativistic Wave Mechanics
27. Relativistic Wave Mechanics as a Formal Generalization of Maxwell’s Electromagetic Theory of Light
28. Alternative Form of the Wave Equations; Duplicity and Quadr uplicity Phenomenon
30. More Exact Form of the Two-dimensional Matrix Theory; Electron’s Electric Moment
31. The Exact Four-dimensional Matrix Theory of Dirac
33. The Motion of an Electron in a Central Field of Force; Fine Structure and Zeeman Effect
34. Negative Energy States; Positive Electrons and Neutr ons
35. The Invariance of the Dirac Equation with regard to Coordinate Transformations
36. Transformaion of the Dirac Equation to Curvilinear Coordinates
7. THE PROBLEM OF MANY PARTICLES
37. General Results, Virial Theorem, Linear and Angular Momentum
38. Magnetic For ces and Spin Effects
39. Complex Particles treated as Material Points with Inner Coordinates; Theory of Incomplete Systems
40. Identical Particles (Electrons) and the Exclusion Pr inciple
8. REDUCTION OF THE PROBLEM OF A SYSTEM OF IDENTICAL PARTICLES TO THAT OF A SINGLE PARTICLE
41. Perturbation Theory of a System of Spinless Electrons and the Exchange Degeneracy
42. Introduction of the Spin Coordinates and Solution of the Per tur bation Problem with Antisymmetrical Wave Functions
43. The Method of the Self-consistent Field with Factorized Wave Functions
44. The Method of the Self-consistent Field with Antisymmetrical Functions and Dirac’s Density Matrix
45. Approximate Solutions (Thomas-Fermi-Dirac Equation)
9. SECOND (INTENSITY) QUANTIZATION AND QUANTUM ELECTRODYNAMICS
46. Second Quantization with respect to Electrons
47. Intensity Quantization of Par ticles descr ibed in the Configuration Space by a Symmetrical Wave Function (Einstein -Bose Statistics)
48. Inter action between a ‘Doubly Quantized’ System and an Ordinary System: Application to Photons
49. Electr omagnetic Waves with Quantized Amplitudes; Theory of Spontaneous Transitions and of Radiation Damping
50. Application of Quantized Electron Waves to the Emission and Scattering of Radiation
51. Connexion between Quantized Mechanical (Electron) Waves and Electr omagnetic Waves
52. The Quantum Electrodynamics of Heisenberg, Pauli, and Dirac.
53. Breit’s Formula. Concluding Remarks
REFERENCES
INDEX TO PART I
INDEX TO PART II*
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W A YE MECHANI CS ADVANCED GENERAL THEORY

J. F R E NK E L PROFESSOR AT THE PH Y8IOO-TECHNICAL INSTITUTE, LENINGRAD

DOVER PUBLICATIONS, INC. 19 5 0

FIRST AMERICAN PRINTING BY SPECIAL ARRANGEMENT WITH OXFORD UNIVERSITY PRESS First Edition 1934

PRINTED AND BOUND IN THE UNITED STATES OF AMERICA

P R E F AC E HE present volume forming the second P art of my Wave Mechanics is devoted (as foreshadowed in the Preface to P art I) to the mathe­ matical development of the general ideas underlying the new mechanics, connecting it with classical mechanics and constituting it a complete self-supporting theory. In building up the mathematical framework of this theory I have limited myself to what I consider its most essen­ tial elements, leaving aside a number of questions which have a metho­ dological value only (such as the group theory) or which are met with in the solution of special problems. I t is my intention to consider some of these questions later on in connexion with the special problems which will be discussed in P art III (Advanced Special Theory’) ; I have carefully avoided complicating the general scheme of the theory by such special questions—with a few exceptions inserted for illustration (the relativistic theory of the hydro­ gen-like atom, for example). To make the general scheme more comprehensible I have not spared space, dealing with especially important general questions (such as the transformation and the perturbation theory, or the relativistic theory of the electron) at much greater length than would be necessary from the point of view of an adequate presentation to a sophisticated reader. I must cordially thank the editors for their readiness to meet my de­ mands on space, which have resulted in a book larger than was originally contemplated. I must also thank M. L. Urquhart and Miss B. Swirles for help in correcting the English and the proofs. The present book, like P art I, is complete in itself, and can be read without acquaintance with P art I, provided the reader is familiar with some elementary account of wave mechanics, and is ready to explore its mathematical depths to obtain a profounder insight into the theory and to prepare himself for applying it to various special problems. The earlier portions of this book were written in 1931 while I was in America; it was completed in Leningrad nearly two years later. Some of the shortcomings of the book are due to this interruption and the impossibility of revising it in 1933 from the very beginning. A list of the more important references for each section is given a t the end of the book; it is followed by a short index which should enable the reader to locate easily all the more im portant subjects treated.

T

LENING R AD

Nov. 1933

J . P.

C O NT E NT S I.

II.

CLASSICAL MECHANICS AS THE LIMITING FORM OF WAVE MECHANICS 1. Motion in One Dim ension; Par tial Reflection and Uncer tainty in the Sign of the Velocity . . . 1 2. Comparison between the Schrodinger and the Classical Equation of Motion in One Dim ension; Aver age Velocity and Current Density . . . . . . . 7 3. Gener alization for Non-stationar y Motion in Three Dimensions; The Hamilton-J acobi Equation . . . .1 5 4. Comparison of the Appr oximate Solutions of Schrodinger ’s E quation; Comparison of Classical and Wave-mechanical Aver age Values . . . .2 4 5. Motion in a Limited R egion ; Quantum Conditions and Aver age Values . . . . .3 4 OPERATORS 6. Oper ational For m of Schr odinger ’s Equation, and Operational Repr esentation of Physical Quantities . . .4 7. Char acteristic Functions and Values of Operators ; Operational E q u ation s: Constants of the Motion . . . .5 8. Pr obable Values of Physical Quantities and their Change with the Time . . . . . . .6 9. Tho Var iational For m of the Schrodinger Equation and its Application to the Per tur bation Theor y . . .6 10. Or thogonality and Nor malization of Char acteristic Functions for Discr ete and Continuous Spectr a . . . .7

III. MATRICES 11. Matr ix Repr esentation of Physical Quantities and Matrix For m of the Equations of Motion . . . . .8 12. The Correspondence between Matrix and Classical Mechanics . 13. Application of the Matr ix Method to Oscillator y and Rotational Motion . . . . . . . 14. Matr ix Repr esentation in the Case of a Continuous Spectr um .

7 4 2 8 5

5 97 106 120

IV. TRANSFORMATION THEORY 15. Restr icted Tr ansfor mation T h eor y; Matrices defined from differ­ e n t ‘Points of View’ . . . . . 127 16. Transfor mation of Matr ices . . . . . 138 17. Tr ansfor mation Theor y of Matr ices as a Gener alization of Wave Mechanics; Tr ansfor mation of Basic Quantities .148 18. Geometrical Repr esentation of the Tr ansfor mation Theor y 162 V. PERTURBATIO N THEORY 19. Per tur bation Theor y not involving the Time (Method of Station­ ar y States) . . . . . . . 177 20. Extension of the Pr eceding Theor y to the Case of ‘Relative Degener acy* and Continuous Spectr a; Effect of Per tur bation on Var ious Physical Quantities . .189

C O NT E NT S 21. Per tur bation Theor y involving the Tim e; General Pr ocesses; Theor y of Tr ansitions . , . . .197 22. Fir st Appr oxim ation; Theor y of Simple Tr ansitions .214 23. Second Appr oxim ation; Theor y of Combined Tr ansitions . 226 24. Theor y of Tr ansitions for an Undefined Initial "State . 230 VI.

RELATIVISTIC REMODELLING AND MAGNETIC G E NE R AL I­ ZATION OF T HE WAVE MECHANICS OF A SINGLE ELECTRON 25. Sim plest For m of R elativistic W ave Mechanics. . . 239 26. Magnetic For ces in the Appr oximate Non-R elativistic Wave Mechanics . . . . . . . 247 27. R elativistic Wave Mechanics as a For mal Gener alization of Maxwell's Electr omagnetic Theor y of Light . 259 28. Alter native For m of the W ave E quations; Duplicity and Quadr uplicity Phenomenon . . . . . 268 29. Pauli's Appr oximate Theor y in the Two-dimensional Matr ix F or m ; the E lectr on’s Magnetic Moment and Angular Mo­ mentum . . . . . . . 279 30. Moro E xa ct For m of the Two-dimensional Matr ix T h eor y; the Electr on’s Electr ic Moment . . . . . 297 31. The E xa ct Four -dimensional Matr ix Theor y of Dir ac . .311 32. General Tr eatment of the Spin E ffect; Angular Momentum and Magnetic Moment . . . . . . 323 33. The Motion of an Electr on in a Centr al Field of For ce; Fine Str uctur e and Zeeman Effect . . . . 330 34. Negative Ener gy St a t es; P ositive Electr ons and Neutr ons 344 35. The Invar iance of th e Dir ac Equation with regard to Coor dinate Tr ansfor mations . . . . . . 349 36. Tr ansfor mation of the Dir ac Equation to Curvilinear Coor di­ nates . . . . . . . 363

VII.

T H E PROBLEM OF MANY PARTICLES 37. General R esults. Virial Theor em, Linear and Angular Momentum 369 38. Magnetic For ces and Spin Effects . . . . 378 39. Complex Par ticles tr eated as Mater ial P oin ts with Inner Coordi­ nates ; Theor y of Incom plete System s . . 386 40. Identical Par ticles (Electr ons) and the E xclusion Pr inciple 392

VI I I . R EDUC TION OF T H E PROBLEM OF A SYSTEM OF I DE NT I ­ CAL PARTICLES TO THAT OF A SINGLE PARTICLE 41. Per tur bation Theor y of a System of Spinless Electr ons and the E xchange Degener acy . . . . . 400 42. Intr oduction of th e Spin Coor dinates and Solution of the Per ­ tur bation Pr oblem with Antisymmetr ical W ave Functions . 410 43. The Method of the Self-consistent Field with Factor ized W ave F unctions . . . . . . . 423 44. The Method of the Self-consistent Field with Antisymmetr ical Functions and Dir ac’s Den sity Matr ix 428 45. Appr oxim ate Solutions (Thomas-Fer mi-Dir ac Equation) 439

CONTENTS IX. SECOND (INTENSITY) QUANTIZATION AND QUANTUM ELECTRODYNAMICS 40. Second Quantization with respect to Electrons . 47. Intensity Quantization of Particles described in the Configura­ tion Space by a Symmetrical Wave Function (Einstein-Bose Statistics) . . . . . . . 48. Interaction between a ‘Doubly Quantized* System and an Ordin­ ary System: Application to Photons . . . . 49. Electromagnetic Waves with Quantized Amplitudes; Thoory of Spontaneous Transitions and of Radiation Damping . 60. Application of Quantized Electron Waves to the Emission and Scattering of Radiation . . . . . 51. Connexion between Quantized Mechanical (Electron) Waves and Electromagnetic Waves . . . . . 62. The Quantum Electrodynamics of Heisenberg, Pauli, and Dirac 53. Breit's Formula. Concluding Remarks REFERENCES

.

447 462 474 484 494 502 500 512 519

INDEX TO PART I

523

INDEX TO PART II

525

ADVANCED GENERAL THEORY I CLASSICAL MECHANICS AS THE LIMITING FORM OF WAVE MECHANICS

1. Motion in One Dimension; Par tial Reflection and Uncer tainty in the Sign of the Velocity In the first part of this book we have given a general outline of the development and present state of wave mechanics, emphasizing the physical meaning of the new conceptions and avoiding, as far as pos­ sible, formal questions connected with the mathematical expression of these new conceptions. We have thus been led astray from the old conceptions based on classical corpuscular mechanics, deepening, as it were, the abyss separating the old from the new mechanics. A systematic study of the formal questions referred to above reveals the wonderful fact that in spite of the fundamental physical difference between the new and the old mechanics, they are extremely similar from the mathematical point of view, i.e. from the point of view of the mathematical expression of the various physical quantities and the mathematical equations connecting them. This formal similarity forms a bridge over the abyss between the old and the new mechanics, enabling one to consider the latter as an extension or rather a refine­ ment of the former and to establish a one-to-one correspondence between the old ‘classical* and the new ‘quantum* conceptions, quan­ tities, and equations—a correspondence which often looks like an identity. The existence of such a correspondence is a very instructive example of the fact—many times already illustrated by the development of physics—that a drastic revision of our physical conceptions can be associated with a simple improvement in the underlying mathematical scheme. We shall start by considering the simplest case of the wave-mechanical equation, i.e. the equation describing the stationary motion of a particle in one dimension: g + — ( W - U ) t = 0, ( 1) the potential energy U being supposed to depend on x only (and not upon t, otherwise the total energy W would not be constant). 3505.6

B

2

CLASSICAL MECHANICS AS LIMITING FORM

§1

If U were constant, then this equation would have a solution of the formt

0 = Aeiax

(la)

representing a sine wave travelling in the direction of the positive x-axis, a being the positive square root of the expression %n2m(W—U)/hl (sup­ posed to be positive). I t must be borne in mind, however, th at (1 a) is only a particular solution of ( 1), the general solution being t/f = A'eiax+ A'e -ia*, (1b) which represents the superposition of two sine waves of the same length travelling in opposite directions. The fact th at ( 1) has two independent particular solutions, representing, under the condition U = const., waves travelling in opposite directions, and th at its general solution is equal to the sum of these two, is a consequence of the fact th at ( 1) is a linear equation of the second order. In the general case, either for a constant or a variable U(x), the function $, which is a complex quantity, can be written in the form . (2 )

where A = \\f/\ is its modulus and is its argument (both of them of course being real). This representation of 0 and negative if cty/dx < 0 ). Such an interpretation is, however, in general wrong, as is clearly shown by taking for ip the expression (lb ) corresponding to U — const. Assuming A' and A ” to be real, we get in this case Acos

defining x and v = dx/dt as functions of the time. This equivalence is readily recognized as soon as we realize what is meant by defining the velocity (or momentum) of a particle as a function of its coordinate. Let us suppose that equation (9) has been integrated, and that x and v have been determined as functions of the time t. Then, eliminating the time t between them, we can express one of them, e.g. vt as a func­ tion v(x) of the other. The acceleration d2x/dt2 can then be calculated by means of the formula d2x __dv __ dv dx _ d v __ d /v2\ dt2 ~~ dt~~ dx dt ~~ dxV d x\2 j c

10

CLASSICAL MECHANICS AS LIMITING FORM

52

so that equation (9) can be written in the form d mvz __ dx (2) or

dU dx

- - + U = const. £

If mv — g is replaced by dsjdx and the constant is denoted by IT, we get equation (7). We thus see that this equation expresses not only the law of con­ servation of energy, but at the same time the classical law of motion. It should be mentioned that both laws are equivalent to one another only in the special case which we arc considering here of motion in one dimension (see below). Another way of interpreting equation (7), or rather the fact implied 1 ds in it that the velocity v — — — of the particle is determined not as 17 m dx r a function of the time but as a function of the coordinate x, is to replace the single particle under consideration by an infinite number of copies of this particle, filling space (or the line x) in a continuous way, so that at any instant t a copy is to be found situated at, or rather passing through, any point x. This method is similar to one used in hydrodynamics except that, in the hydrodynamical case, the copies of a particle are replaced by actual particles (supposed to be identical), moving under the combined influence of external forces and forces of mutual action (represented by the hydrostatic pressure). Provided we are not interested in the individuality of the particles, i.e. in the question which particle is to be found at a given point, the motion of the particles can be specified by defining the velocity of the particle passing through each fixed point as a function of the coordinates of this point and, in general, of the time. If the velocity does not depend upon the time (it should be remembered th at the velocity we are speaking of refers not to a definite particle but to a definite point) the motion is called stationary or steady. Thus the picture which can be associated with equation (7) is that of an assembly of copies of the particle under consideration, streaming steadily and filling space in a continuous way. If we select from this assembly a definite copy which at the time t was passing through the point x, then, knowing the dependence of the velocity v upon x, we can follow its motion and determine both the velocity and position of this particular copy as functions of the time. For instance, at the

§2

SCHRODINGER’S a n d c l a s s i c a l e q u a t i o n OF MOTION

11

moment t+ dt the copy in question will be situated at the point x+ v dt, and will have the velocity v(x-\-dx) = v(x-{-v dt) = v(x) + ~ v dt, which dx means that its acceleration is equal to vdv/dx, as was obtained above. We have thus shown that the wave-mechanical equation of motion actually reduces to the classical equation in the limiting case when the wave-length associated with the motion of a particle tends to zero, either owing to increase in velocity (which is a thing that can actually happen) or to decrease in the constant h (which is an artifice). The fundamental reason for this lies in the elimination of partial reflection, i.e. of a reversal in the direction of the velocity or, in other words, the elimination of the uncertainty in its sign. Strictly speaking, however, this uncertainty cannot be eliminated. I t is impossible to describe the motion of a particle in the classical way, i.e. as a determinate change of position and velocity with the time. The only way of describing it is to ascertain the 'probability of finding the particle at a given place and the probability that, being at this place, it is moving in the one or the other direction (the magnitude of the velocity being fixed). This intrusion of the probability conception into the description of the motion is necessary because of the ambiguity arising from the alternative: partial reflection or partial transmission. One could say th at this ambiguity—wholly alien to classical mechanics —forms the gate through which the concept of probability penetrates into the realm of physics. The probability of position is measured, as we know, by the product if/if/*t so th at tfj(x)ijj*(x) dx measures the probability that the particle is situated in the region between x and x+ dx. Using the picture of an assembly of copies of the particle in question filling space (or the z-axis) in a continuous way, we can interpret if/if/* dx as the relative number of copies situated within the interval dx (this number is independent of the time so long as ip = i/fle-i2nvt, corresponding to a motion with a definite total energy W = hv).

If the integral J ip*p* dx converges, —oo

if/ can be normalized in such a way that this integral is equal to 1, in agreement with the usual normalization of probability. Otherwise we need not worry about this normalization, since after all only relative values of if/if/* for different points come into account. I t should be noticed th at in the classical description of the motion we can also use a continuous assembly of copies instead of an individual particle, as is actually done when the equation of motion is written in

12

CLASSICAL MECHANICS AS LIMITING FORM

§2

the form (7) corresponding to the determination of the velocity as a function of the coordinate and not of the time. From the point of view of this description the difference between the old and the new theory can be summed up as follows. In the old theory it is always possible to ‘individualize’ a certain copy by following its motion, i.e. by determining its coordinate and velocity as definite functions of time, whereas in the new theory such ‘individualization’ is impossible, the direction of motion being uncertain. It thus becomes necessary to con­ sider the assembly as a whole without attempting to disentangle it, i.e. to trace the motion of a particular copy in time. This being so, the density of the assembly, i.e. the relative number of copies per unit range, or, in other words, tho probability of finding the particle repre­ sented by these copies in a given range, becomes the primary thing th at can and must be determined—whereas in classical mechanics it remains irrelevant and therefore arbitrary. Of course the determination of 00* in wave mechanics is also connected with some arbitrariness, which can only be removed by specifying the boundary conditions or the conditions at infinity for the function 0. Knowing the function 0, one can determine many other things besides the probability of position. Thus by means of it we can determine the probability of the two opposite directions of motion, th at is, of the two opposite signs of the velocity, if the magnitude of the velocity is assumed to be fixed for a given position by the classical relation v = yj{2(W—U)jm} or by de Broglie’s relation v — If p ' is the probability of the positive direction and p" th at of the negative direction, then the average or probable value of the velocity at a given point is given by the formula v= , (p'—p')\v\

(10)

with the condition p ’+ p" = 1. This probable velocity, or the probabilities p, can be determined quite generally with the help of the relation (4), as soon as the physical meaning of this relation is recognized. We shall first see what the expression A 2djdx means in the simple case of a wave travelling in one direction in a force-free space, th at is, a wave representing the free motion of a particle in one direction. We have, in this case, according to (1 a), = oix and consequently A 2 ^ = A2 denote the time of starting from the point xx and arriving at the point x2 respectively. Replacing dt by dxjv, where v is a function of x determined by the equation v2 =

we

get /_

j .

(24 a) ^1

or, if a ‘round trip’ is taken instead of a ‘one-way’ trip, i - i m J T J v

dXy

the velocity v being taken with the same sign as dx (i.e. + when x is increasing from xx to x2, and — when it is decreasing from x2 to xx). Now the expression (24 a) for / is identical with that obtained by means of the wave-mechanical definition of the average value of f(x) according to the formula / =

J /(* )# * dx,

(24 b)

ar,

if the function 0 is assumed to vanish outside the region (xv x2) and is replaced by its approximate expression (23 a) for this region. The normalization constant C must be determined by the condition a J dx = 1, th at is, X,

ft

C‘ j ^ = C * j d t = 0 % - l J = 1. *1 tx This agreement of the classical theory with the wave-mechanical theory must hot be overestimated. As a m atter of fact the function tfr does

§4

AVE R AG E VAL UE S

29

not in general vanish outside the classically allowed region, but, as we have just seen, decreases there approximately as c- 2lris*[lh. According to the relation v = ~ ^ the time)

, we can put (dropping the term containing

proximation, to the points inside and outside the region (xv x2). In the latter case, for a point x > x2, we can put |«S°(*)| = f J {2 m (U - IF)} dx, J-i X , , ~\ dx^

w

(W-U )ip

0.

If we multiply this equation by x dip*/dx and the conjugate equation dx*

(W —U)*f** -- 0 by x^—and add, we obtain h2 v /r J dx d /dip dip*\ Xdx\dx dx /

Sir2m h2

By partial integration with respect to x, taking into account the boundary conditions (ip —- 0 and dipj'dx = 0 for x = ± 00), we get +00 Hao +ao d(Ux) dx — 0 , ( f df*dx w dx dx J dx dx h*• J h -J

_

r # * + 8-2r f

-- 00

-Icc

or, since J ipijj* dx = 1 and J fipip* dx —

/ dx dx

dx +

H2

|V -

d(Ux) = 0. dx

Further, by multiplying the SchrOdinger equation by 0*, we obtain

j

dx

+ 8~~ J

( W - U ) t o * dx =

or, transforming the first term by partial integration, S^hn j* dip dip* (W - U ) dx + J dx dx ~~hT

0.

0,

CLASSICAL MECHANICS AS LIMITING FORM

32

We have therefore

W -U + W -^& $ = 0 dx 2(JT—U) ~ x

or

§4

dU dx ’

This is exactly formula (2G) for the special case that we have con­ sidered, f Another illustration of the connexion between the wave-mechanical and the classical theory is given by the similarity of the classical equa­ tions of motion, ^ ^ m —— — ------ , etc., diu dx and the wave-mechanical relations d2x

dU

t

(27)

between the corresponding average (or probable) values of the quantities involved. The relations (27) were found by P. Ehrenfest. They are usually referred to, in connexion with the propagation of a wave packet, as the equations of motion of the ‘centre’ or ‘centroid’ of the latter, th at is, of the point with the coordinates x=

J xifnfi* aV,

y — J yipip* dV,

z=

J zipip* dV.

(27 a)

If the wave function \jt represents a wave packet formed by superposing waves with slightly different frequencies (i.e. motions with slightly different energies), the coordinates x, y, z are certain functions of the time (in the case of a stationary state where the dependence of $ upon the time is specified by the factor e~i27rvl they reduce to constants), so th at we can differentiate them with regard to the time. The corre­ sponding quantities can be defined as the average values of the com­ ponents of the velocity of the particle or its acceleration, etc. We shall prove the relations (27) for the simplest case of a motion parallel to the x-axis (the proof can easily be extended to the case of three-dimensional motion). We have, by the definition of x,

since x and t are independent variables. t The proof given is due to B. Finkelstein.

§4

33

AVE R AG E VAL UE S

Now iff and tft* satisfy the equations dt

4n m\dxz

)

di/t* dt ~ i

where fi =

Srrhn

fl*

TT

Hence dx = ih. ( x U ^ - ^ ^ d x . Tt 4nm J V * te 2 )

By partial integration, in conjunction with the fact that +« dx = f(+co)—f ( —co)

J

vanishes if the function / contains x or dip/dx as a factor (since J tpip* dx must be finite and equal to 1), we obtain f = A . T d x . dt 4rnmi J v dx r d x)

— CO

(27b)

—oo

This expression could be obtained directly from the relation — dt

+ %■ = 0 (which is a special case of (19)) and the formula dx

j = -A — for the current density. Putting j = ^*tJ(x), 4irim\ dx dx J where tJ(x) is the average velocity at the point x, we can rewrite the preceding equation in the form + 00

f dx: = I v(x)ilnp* dx, dt which agrees with the definition of dx/dt as the average value of the velocity of the particle irrespective of its position. By differentiating (27 b) with respect to the time, we obtain

3508.6

F

34

CLASSICAL MECHANICS AS LIMITING FORM

8t r2m2 J LI —CO

- - s w —nQO K

^ ^

\&r2

s D - ^ s H

§4

M 7 cte J

*

= - . * £ Yw + p d x i Stt W J dx r r iewhere

d2x a /2

at/ &r

— = f «/n/f* dx dx J dx r r — CO

is the average (or probable) value of the force acting on the particle. I t must be emphasized that this value refers not to the average (or probable) position of the particle, determined by the centre of the packet (otherwise this centre would move exactly according to the classical mechanics), but to all possible positions. If the dimensions of the packet are very small (which means that the uncertainty in the estimation of the particle’s velocity is very large) the motion of its centre closely follows classical motion. This, however, persists only for a very short time, for the packet will spread, the rate of this spreading being the larger the smaller its original dimensions (i.c. the larger the original uncertainty in the velocity). 5. M otion in a L im ited Region; Q uantum Conditions and A ver­ age Values We shall now investigate the case of a (three-dimensional) motion restricted classically to a finite region of space (where W—U > 0 ), and derive the 'quantization rules’ characteristic of such a motion with the help of the approximate wave-mechanical theory based on the classical determination of the phase or action function d(= SQ) by means of the Hamilton-Jacobi equation. A motion of this kind must obviously have a periodic or quasi-periodic character, so that the path described by the particle may fill up the whole region or pass many times in various directions through the same or nearly the same point (as, for instance, in the simple case of the oscillatory motion of a particle along a straight line). If the particle is replaced by a continuous assembly of its copies, a rather complicated picture results, different copies passing simul-

o M OTIO N I N A L IM IT E D R E G IO N taneously through the same point with velocities which are in general different both in regard to direction and (if the field of force varies with the time) in regard to magnitude. The latter must, of course, remain a single-valued function of the coordinates in the case of motion with a given (constant) value of the total energy W. The function = sjm, which can be defined as the velocity potential, must, however, in this case (as well as in the general case of non-conservative motion) be a multiple-valued function of the coordinates. Considering the copy assembly as a kind of fluid, we can illustrate the case in question by the familiar type of fluid motion with closed stream-lines, each stream­ line representing the path of all the particles situated on it. In the associated wave picture these closed paths of the separate particles or copies must be interpreted as closed rays. Now a fluid motion of this type can be irrotational if, for instance, the fluid is flowing in a closed tube or around some closed tube. The velocity v of the particles, as a function of their coordinates, can then be represented as the gradient of a potential , provided the latter is defined as a multiple-valued function of the coordinates. In fact, taking the integral of the velocity along a line a connecting two points Px and P2i then, since the projection vG of v on the line element da is, by definition, equal to rf^/r/cr, we get §

If the line is closed, i.e. if the points P1 and P2 coincide, this integral should be equal to zero, irrespective of the shape of the line, unless we assume th at for closed lines of certain type the potential $ may change after a ‘round trip ’ by an amount Aequal to the value of the integral § va da taken along the corresponding closed line. If the latter coincides with a stream-line, the integral will certainly be different from zero, since along this line we must have va = MNow it can easily be proved that in the case of irrotational motion the integral § va da, which is called the ‘circulation’, will have the same value for all closed lines of the same fa mily, i.e. of the same general type. In the case of a fluid flowing around a closed tube along closed stream­ lines (Fig. 1), we must distinguish closed lines of two families: those which do not surround the tube, and those which do. For the former the circulation will be equal to zero, while for the latter it will have a certain value different from zero. This result follows from the trans­ formation of the line integral § va da, by means of Stokes’s formula,

36

CLASSICAL MECHANICS AS LIMITING FORM

§6

into the integral § (curlv)„ dS over any surface S limited by the line a. In the case of the lines of the first family the surface S will be situated entirely within the fluid, so th at the integral will vanish, since the motion is supposed to be irrotational (curlv = 0 ). In the case of the lines of the second family the surface S will cut the tube around which the fluid is flowing. Since for points inside the tube the idea of velocity has no meaning, we can replace the surface S by another surface S' bounded by two closed lines of the second family. Stokes’s formula applied to this surface which lies wholly within the fluid, and for which therefore the integral § (c u t \ y )n dS vanishes, leads to the result that

the integral § va da taken over the double boundary of S' must vanish if the ‘round trip ’ is made in opposite directions along the two con­ stituent lines, whence it follows th at the circulation will have the same value for both lines if the round trip is made in the same direction. I t may be mentioned th at exactly similar results are met with in the theory of the magnetic field generated by a linear electric current. This field—outside the wire along which the current is flowing—is also irrotational, so th at the magnetic field strength can be defined as the gradient of a certain magnetic potential. With every trip around the wire along any closed line (encircling this wire only once) this potential must change by a definite value, namely 47ri, where i is the strength of the current. The preceding results can be applied without substantial modification to the flow of the fictitious fluid represented by the copy assembly of a particle moving in a limited region. In the copy assembly, however, we must remember that different copies may be imagined to pass simultaneously through the same point in different directions. This is,

§6

MOTION IN A L IM IT E D R E G IO N

37

of course, impossible in the case of real particles. In particular, closed stream-lines may degenerate into ‘double lines’, i.e. unclosed lines along which the copies move first in one and then in the opposite direction (oscillatory motion).f The ‘circulation’

f Instead of one particle one can consider a continuous assembly of its copies, distributed not in the ordinary space as before, but in the phase-space with a density depending in general upon the time.

§5

MOTION IN A LIMITED REGION

41

where H ' is the new Hamiltonian function which is obtained by re­ placing in the original function H (Q ,P ) the old coordinates and momenta by the new, according to the formulae (30) and (30 a). The transformation defined by these formulae is called a ‘point transforma­ tion*. As already mentioned, it is a special case of the canonical transformations. A canonical transformation (of the coordinates and momenta) is defined by the formulae dd> p- - & < * -$ • (31a) where (Q, P ') is a completely arbitrary function of the original co­ ordinates and the new momenta. If, in particular, we put ® = i PjifiAQ»Q».Q»)

we obtain, by (31 a),

p =i

Q'p = M Q i ,Q2,Q3Y,

=

which corresponds to the point transformation (30), (30 a). The fact th at the original canonical equations (29) are transformed by (31a) into equations of the same canonical form (31) can be shown as follows: We form the complete differential or rather the variation of the function , corresponding to a virtual variation (completely indepen­ dent of the actual motion) of the variables Qy P ':

and differentiate this expression with regard to the time. We also take the time derivative of O

and form its variation. By subtracting the expressions thus obtained, we get, remembering that 8 and dt are commutative,

Now by (29 b) we have

3 0 H .6

o

42

CLASSICAL MECHANICS AS LIMITING FORM

Hence, in virtue of we obtain

H (P , Q) = H '(P 'yQ')y

Since the variations 8Q0 and 8Pp are arbitrary, we can equate their coefficients. In this way we get equations (31). Those canonical transformations, in which the transformed Hamiltonian // ' depends only on the momenta P ' and not on the coordinates Q'y play a special role. Such coordinates are usually called cyclic. The equations (31) reduce in this case to Po — const. i.e.

dt

— --prr = too = const., dPp

Qp = u)pt-\-(f>p.

If the transformation function O leading to cyclic coordinates is known, the mechanical problem can be regarded as solved, for the original coordinates and momenta are then expressed according to the equations (31a) as functions of the time which, besides t, only contain constants Ppy wpy and p. Now it follow's from (31a) that this special transformation function is just the action function s regarded as a function of Qv Q2, Q3 and of three arbitrary constants PJ, P 2y P 3 which necessarily appear on solving the Hamilton-Jacobi equation (16) or (17) by which this function is defined. These constants of integration can be expressed in terms of the three principal moduli of periodicity of the action function J a = (A«s)a with regard to a system of separable coordinates qv q2, q3 (which we need neither actually know nor consider in detail here). Replacing the original constants P'a by their expressions in terms of J v J 2, J a we can write the transformation function in the form s(xyyyz\ J ly J 2iJ 3) and define the constants J a as the new momenta (P^ = «/J. Considered from this point of view these constants are called the ‘action variables’ of the problem. The corresponding cyclic coordinates are called the ‘angle variables’. We shall denote them by tty ( = QpY We have therefore wp = wpt+p, (32) where according to the transformed canonical equations (31) (32 a) and

(32 b)

§5

MOTION IN A L IM IT E D R E G IO N

43

To ascertain the dependence of the old coordinates Qa on the new coordinates wp, we shall introduce for a moment as an intermediate link between them the separation coordinates qJt q2, g3. Expressed ns a function of the latter, the function s assumes the form a -1 To a cyclic alteration of the coordinate qa there corresponds by (32b) an alteration of the coordinate wp by A =- A^dsJdJp. We have therefore, because A^Sp ™ */a if a — /?, and — 0 if oc ^ /?, = 8J° dJp

1 (oc = p), 0 (“ ¥= P)-

These formulae show that when any angle variable wp is increased by 1 and the remaining w»’s are maintained constant, which corresponds to the cyclic alteration of the separation coordinate qp, i.e. to the return of the particle to the original position along a ‘/ 2-curve’, then the action function s increases exactly by Jp. From this it follows that the coordinates Qp, and consequently the momenta Pp, are periodic functions of the angle coordinates with periods equal to 1. Each of them, as well as any function f(Q v Q2, Qz) (or still more generally f(Q , P ) ), can be expressed in the form of a triple Fourier series f — y f e V27r(A-, TCj + k2Wi -f ki u>j) (33) J , 4* , J ki,k2,ki > k ltk„ k. where kx,k2,k3 are integers which can assume all values from —oo to +oo, and f ki kv kz are certain expansion coefficients characteristic of the function /. If instead of the wp we put their values obtained from (32), we get

f =

Y