A S Kompaneyets - Basic Concepts in Quantum Mechanics-Mir Publishers (1966)

Basic concepts
in quantum mechanics
ALEXANDER KOMPANEYETS
REINHOLD PUBLISHING CORPORATION

I tl
Basic concepts
Translation editor's preface
Q u a n tu m M echanical concepts underlie m any of the most

startling and exciting discoveries in the world of science and
technology. T h e basic ideas of q u a n tu m mechanics are readily
accessible to the student who can u n d erstan d physical optics.
T h is requires th a t he ab an d o n many concepts th a t apply to
macroscopic objects when he considers ph en o m en a on the
atomic and subatomic scale. Professor Kompaneyets has given
here a splendidly clear presentation of these fu n d am en tal n o
tions with a m in im u m of mathematics. H e has even been able
to outline some of the more arcane areas of the subject such as
q u a n tu m field theory and to give some feeling for the concepts
involved.
Students in elementary physics and chemistry should be able
to read a n d absorb the m aterial with little difficulty. T h is is
not limited only to the person m ajoring in physics or chemistry,
for there is no calculus and the subject is developed with the
use of analogies to familiar ideas in light and sound.
Changes from the Russian original have been kept m inim al;
where changes have been made, they have been in the interests
of clarity and precision. T hese have been incorporated into the
text and no a tte m p t has been m ade to distinguish between
the original and the revisions since it would have been d e tri
m ental to the basic pedagogical purpose of the book.
L eon F. L andovitz
January, 1966
Basic concepts
ALEXANDER S. KOMPANEYETS
Professor of Physics
Institute of Chemical Physics of the Academy of Sciences
U.S.S.R.
Translation editor: LEON F. LANDOVITZ

Yeshiva University
New York, N. Y.
T ra n s la te d by Scripta Tcchnica, Inc.

T ranslation read and approved by the author
New York
REINHOLD PUBLISHING CORPORATION
Chapman & Hall Ltd., London
Copyright © 1966 by
Reinhold Publishing Corporation
All Rights reserved
Library of Congress Catalog Card Number: 66-18964
Printed in the United States of America
Preface
Spectacular advances have been made by the science of physics

in o u r own time. These include no t only the enormous techno
logical progress, somewhat anticipated by m a n ’s desires (tele
vision, to m ention one such instance) but, above all, the
emergence of towering generalized concepts b ro u g h t forth by
h u m a n thought. Such ideas are a p a rt of existing reality,
inasm uch as they reflect the true laws of nature. These ideas
alone have enabled m odern science to explore a n d penetrate
the innerm ost nature of matter.
It has been suggested that m odern theories of physics are
difficult to e x p o u n d in easy-to-understand terms, because their
basic concepts, unlike those of the old classical theories, cannot
be readily visualized. In classical physics too, however, there
arc qu ite a few concepts that seem to be easily visualized only
because we have somehow become accustomed to them (heat
capacity or magnetic field intensity are good examples). T h e re
is little d o u b t that the concepts of q u a n tu m physics could
eventually be rendered no less accessible to visualization. T h e
challenge, however, m ust be m et here by the educator rath er
than by the scientist. T o be sure, some of the more intricate
m athem atical derivations will have to be taken for granted,
bu t there is no harm in th at as long as their meaning, in terms
of physics, has been m ade clear.
T h e prospect is a tem p tin g one, when we consider that to
i i 1 o s i -- \
vi Preface
this day the students in some schools are still being presented
with the same, hopelessly o utdated Bohr's model of the atom
with its orbitals, for which there really is no physical justifica
tion.
T h is supplem entary book is intended for introductory
physics courses. It is assumed that the stu d en t has already
studied the elem entary concepts of wave motion, since the
a u th o r feels that such concepts are basic to the u n d erstan d in g
of q u a n tu m theory. T h e a u th o r’s aim is to show that the basic
concepts of q u a n tu m mechanics can be defined w ith o u t re
course to higher mathematics. T h e m ain difficulty for the
reader will lie here in assimilating some of the entirely novel
concepts associated w ith q u a n tu m mechanics. Should he prove
equal to the challenge, an unparalleled achievement of the
h u m a n m ind will be his to contem plate— a u n iq u e feat that
has altered all of our ideas on the n a tu re of motion.
T h e exposition of m aterial in this book follows a systematic
conceptual, rath er th an historic, sequence. Ideas presented in
their logical continuity will be grasped more fully. As we go
along, however, an occasional excursion into history proves to
be useful. T h e inevitable evolution of ideas can be better
understood when viewed in retrospect.
A lexander S. K ompaneyets
Contents
Preface v
1 Geometric and wave optics 1
2 The uncertainty principle 23
3 Quantum laws of motion 41
4 Motion of electrons in an atom
5 Electron spin 87
6 Structure of the atom 98
7 Electrons in crystals 113
8 Quantized fields 128
9 Dirac's theory 140
Selected Readings 148
Index 149
Geometric and wave optics
W h en speaking of motion, we generally visualize a body or a

“p o in t” m oving in space along some trajectory. However, in
n a tu re we e n co u n ter just as often an o th er form of m otion—
wave motion, which can either be perceived by the eye (light),
or the ear (sound).
In the final analysis, seeing is connected with the process
of wave propagation. Everyone probably knows that light con
sists of electromagnetic oscillations, i.e., periodic variations
in the electrom agnetic field in space and in time. However,
people have no t always associated the propagation of light
with wave motion. Isaac Newton, the founder of mechanics,
as well as of physical optics, supposed th at light is carried
by a stream of particles or corpuscles. T h e two words have the
same m eaning, b u t “corpuscle” emphasizes the special nature
of light particles. In fact, a wide range of optical phenom ena
can be explained with the aid of the particle concept. T h is
branch of optics is called geometric optics; the trajectories of
the corpuscles correspond to rays of light. For example, a ray
of light in a homogeneous m edium travels in a straight line,
and a particle also travels in a straight line when there are no
forces acting on it.
T h e action of mirrors is based on the law of light reflection:
i.e., the angle of incidence a is equal to the angle of reflection
/? (Fig. 1). T h e same law holds for the elastic reflection of par-
2 Basic concepts in quantum mechanics
A"
Figure 1
tides from a barrier; this law can be illustrated by a ball
bouncing off a wall, or by a billiard ball off the cushion.
If one considers how the law of reflection of particles fol
lows from the general principles of mechanics, one must first
assume that the reflection is elastic, which means that the
kinetic energy of the body is conserved on impact. T h e kinetic
energy, on the o th er hand, is equal to half the product of the
mass by the square of the velocity. However, since mass is
also conserved, the m agnitude of the velocity will rem ain u n
changed. T h e velocity of the particle at impact on a barrier is
represented in Figure 1 by A C , the square of which (the
square of the velocity) equals the sum of the squares of its
components: (AC )2 = (A B )2 -f (B C )2.
It will now be shown th at the tangential com ponent of the
velocity (in this case BC) remains unaltered on impact. For
this it is necessary to assume that the reflecting surface is per
fectly smooth, i.e., th at there are no frictional forces that
w ould change the motion of the particle in the direction p aral
lel to the surface. If there are no such forces, then, by New
to n ’s second law of motion, the com ponent of m o m entum *
in this direction will also be conserved. Consequently, the
com ponent of velocity in the direction parallel to the re
flecting surface will be conserved (CB' = CB).
* Momentum : mass x velocity.

Geometric and wave optics 3
In the right triangles A B C a n d A 'C B ' we have AC = CA'
by the law of conservation of energy (the square of the velocity
remains the same), a n d BC = CB' by the law of conservation
of m om entum .
Hence the rem aining sides A B a n d A 'B ' are also equal in
length b u t not in direction (like A B and B 'A "), since a co
incidence in direction would mean th at the body was not re
flected from the surface b u t has penetrated the reflecting m e
dium (point A "). B 'A ' must therefore point upw ard. Since
the triangles are congruent, it follows th at the angles also are
equal and hence a — j3. Later the same law will be deduced
from the wave theory of light.
T h e action of lenses, which depends upon the refraction of
light, can also be described in terms of ray optics. T h e fu n d a
m ental law of refraction (Snell’s law) may be deduced from the
corpuscular hypothesis as follows.
Let us suppose that in a denser m edium the particle has a
higher velocity. In effect, this is the way an optically dense
m edium is defined in the corpuscular theory of light. T h e com
p o n en t of velocity along the b o u n d ary between two media
must be conserved (BC — CB') for the same reason as in the
case of reflection (no retarding force parallel to the boundary).
In Figure 2, C A ' represents the velocity after refraction. For
A'
Figure 2
this lo be greater than the velocity before refraction, B 'A '
must be longer than B A , so that the angle /? is less than the
angle a, which is required by Snell’s law for the denser me
dium. Since BC = CB', it follow's that v sin a = v' sin /3, so
th a t the ratio of the sines of the angles of incidence and re
fraction is equal to the ratio of the velocities in the two
media. T h is will be a constant for the two given media, from
which follows Snell’s law.
In order for the angle of refraction to be less th an the angle
of incidence, the corpuscular theory requires the velocity of
light in a relatively dense medium , such as water or glass,
to be greater th an in a vacuum. However, an experim ent per
formed by Foucault in the m iddle of the last century showed
that the velocity of light in water is less th an in air. It would
have been impossible to perform a direct experim ent of this
kind not only in Newton's day, b u t for a century and a half
after him. Hence the corpuscular theory of light attracted
m any adherents. N ot only was it consistent with experience,
b u t all the applied optics of that era belonged to the field of
ray, or geometric optics, which was concerned with optical
instruments, such as telescopes and microscopes.
Even in N e w to n ’s time, however, certain know n light phe
nom ena could not be explained by the corpuscular theory.
Newton discovered and described one of these phenom ena
himself. If a convex lens is placed on a plane glass surface
(Fig. 3a), a system of b rig h t and dark rings can be observed
in reflected light around the point of contact (Fig. 3b). It
is impossible to explain how these rings are formed purely
in terms of the laws of refraction and reflection of light.
b
Figure 3
Geo metric and wave optics 5
Newton supposed that light is propagated in w hat he called
“fits,” b u t it is difficult to say w hat he m eant by this. Evi
dently, even for N e w to n ’s successors, w ho accepted his cor
puscular theory of light, the m eaning of these “fits” was o b
scure.
Huygens, a contem porary of Newton, introduced a wave
theory of light, by which he explained not only the refraction
and reflection of light, b u t also N e w to n ’s rings a n d related phe
nomena.
It m ight appear impossible to form ulate the laws of ray
optics, such as Snell’s law, in terms of waves. T h e two seem to
have little in common: a moving wave front is a surface and
a ray is a line. In fact, however, a correspondence between
them can be easily established. T h e ray at a given p o in t in
space is perpendicular to the wave front at th a t point. W h en
a stone is dropped into water, circular ripples travel ou t from
the p o in t where the stone entered. Each circle is a wave front,
and the radius drawn from the center to the circle is a ray
(Latin, radius). Of course, the circles or waves are a visible
reality, while the radius is an imaginary line.
W h en a ship is moving th rough water, its prow sets u p a
system of circular ripples at every instant, so th at waves cre
ated at different instants may arrive simultaneously at a given
point. T h e only exceptions are the points lying on a common
tangent to all the circles and passing th rough the prow of the
ship (Fig. 4). (T he ship is assumed to be moving faster th an
the waves it sets up, or else the waves w ould all lie one inside
the other.) Every point of this tangent is reached by only one
Figure 4
wave front— the most forward one (the others are unable to
reach it). For example, the wave arriving at point A was cre
ated when the prow of the ship was at point A ', while the wave
arriving at D was set u p when the prow was at B ', a n d so on.
T h e waves arriving at p o in t C between them were set u p at
different times, a n d the crests of some waves are superimposed
upon the troughs of others, so that the resultant wave at C
may be weakened in comparison with the wave front. O n the
other hand, there is a wave crest everywhere along the line
A B , b u t now it is no t circular bu t rectilinear. T h e crest moves
forward through the water in the direction shown by the
arrow, parallel to the radii A A ' a n d BB'.
T h u s w hen circular waves are superimposed, they may form
a rectilinear wave front. T h e waves propagated from a point
source in space are spherical, bu t if sources are distributed
on a plane a n d em it waves together (a more detailed definition
will be given), then the fro n t will also be plane and parallel
to the plane of the sources.
Huygens did not know the exact law of emission and p ro p a
gation of waves, which was only discovered about 20 years
later. For purely intuitive reasons he assumed th a t each point
on a wave front is itself a source of waves. Figure 5 illustrates
this idea for a circular front. H ere A is the wave front at a
p articu lar time (the waves em itted in accordance with H u y
gens’ hypothesis are indicated by the broken lines), and B
Figure 6
is the envelope form ing the wave front of these new waves
at a subsequent time. Waves in three dimensions are p ro p a
gated in a sim ilar way.
T h e diagram th at has been considered provides a q u a lita
tive description of the p ro p ag atio n of waves. H uygens’ hy
pothesis gives the simplest exp lan atio n of optical phenom ena
w ith o u t recourse to complicated calculations. Rigorous eq u a
tions usually give only small corrections to the results o b
tained by the simple application of H uygens’ principle.
Reflection will be considered first (Fig. 6). According to
H uygens’ principle, each point on the incident wave front A B
may be considered as a source of new waves. As the point A is
displaced to the right, taking successively the positions A x,
An, A :i, etc., it emits new waves all the time. T h e common
tan g en t of these waves is the reflected wave front A 'B '. It can
readily be verified th at the incident and the reflected wave
fronts are inclined at ecpial angles to the reflecting surface
A A '. It cotdd not be otherwise, since both waves are p ro p a
gated in the same m edium and therefore have the same ve-
locity; b u t if the lines A B and A 'B ' form equal angles with the
reflecting surface, the perpendiculars to these lines, indicated
by the arrows, will also form equal angles to it. T h u s the law
of reflection has been deduced from the wave representation,
which in the given case is equivalent to the ray representation.
T h e law of refraction may be deduced just as simply (Fig.
7). Waves from p o in t A en ter the second m ed iu m lying below
the dividing boundary A A '. If one supposes that the second

m edium is optically denser, in accordance with Snell’s law,
angle (3 must be less th an angle a. T h e refracted wave front
must therefore make a smaller angle with the b o u n d ary A A '
than with the incident wave front. It is immediately clear
from the diagram that for this to be true, the velocity of the
waves in the second m ed iu m must be less than in the first. T h e
refracted ray, indicated by the lower arrow, will then lie
closer to the perpendicular to the dividing boundary. C o n
sequently the wave representation of light requires a lower
velocity- in an optically denser medium . As previously seen,
the corpuscular representation leads to the opposite conclusion.
T h u s the wave theory is also capable of ex p lain in g the re
fraction of light. T h e law of refraction has the same form as
in the corpuscular theory, b u t the ratio of the sines is not
now equal to the reciprocal of the ratio of the wave velocities,
bu t to the ratio of the velocities itself. Hence, according to the
wave theory, the velocity of light in water is less th an in air.
This is in agreement with F o u c a u lt’s experim ent.
It is then seen that the ray (or corpuscular) representation
certainly reflects some part of the tru th although it is clearly
incom patible w ith the wave representation. It m ust not be for
gotten, however, that design calculation for m any optical de
vices— telescopes, cameras, etc., are based on the ray theory.
T h is agreem ent is explained prim arily by the one-to-one corre
spondence between the plane wave front a n d the ray p erp en
dicular to it. It follows that whenever a plane wave front can
be draw n th ro u g h a p o in t of a light wave, a ray of light may
also be d raw n th ro u g h th a t point. One does not have to con
sider w hether there is some kind of particle or m aterial point
moving along the ray. A lthough in the case of light this cer
tainly does not happen, the laws of ray optics are widely a p
plicable. G reat success has been achieved in recent decades in
electron optics, where images are formed n o t by rays of light
bu t by beams of moving electrons (e.g., in a television set),
a n d the o rdinary laws of geometric optics have been verified
in quite a n o th er physical region. Later it will be shown that
they are even more valid for electrons than for light. T h is
means that far greater magnifications can be obtained in elec
tron microscopes than those possible w ith ordinary light m icro
scopes, so th at even the line structure of cells of organisms can
be revealed.
We have thus found that the laws of optics and mechanics
are in many ways equivalent. T h e same phenom enon may be
explained equally well from the two points of view— the cor
puscular a n d the wave— w ith o u t considering which is the true
explanation. N o th in g is changed if we replace the construc
tions of electron optics w ith a wave representation in terms of
H uygens’ principle, or if we speak of the paths of light cor
puscles in a camera. (W hen we discuss the p a th of the rays in
a camera we are n o t at all interested in the velocity of light in
the lens.) T h is one-to-one correspondence was found as early
as 1825 by W . R. H am ilto n , b u t the true significance of the
analogy he form ulated d id no t become clear u n til a century
later.
As previously stated, no t by any means can all light p h e
n o m en a be described on the basis of geometric optics. One
Figure 8
case has already been given— N ew to n ’s rings, which can only
be explained by the w’ave theory. Before explaining them,
however, we m ust first consider the fu n d am en tal properties
of waves and oscillations.
Let us begin with the basic definitions regarding the os
cillatory m otion of a point. In the discussion we shall en
counter the sim ple harm onic oscillation (so nam ed because
these oscillations correspond to pure tones in acoustics) far
more than any o th er kind.
Consider a point A m oving in a circle (Fig. 8) of u n it radius
and m aking v revolutions per second. Since the circumfer
ence of a circle of u n it radius is equal to 2tr, the point travels
a distance of 2,-rrv every second. Let us look at the point in the
plane of the figure. T h e displacement of its projection (point
A') will lie between the extreme points B j and B 2, which de
fine the a m p litu d e or range of the oscillations of the point.
In the extrem e positions (A , and A 2). the velocity of A ' moving
along the line is zero— the p o in t changes direction and goes
back the way it came. At these instants, A is m oving along
the line of sight (we arc looking at it in the direction indi-
cated by the arrow), so that the c o m p o n en t of its velocity along
the line B lB 2 is zero. At the p o in t O', the com p o n en t of the
velocity along the line of sight is a m axim um .
T h e oscillations of the p o in t A ' are said to be harmonic.
T h e angle O 'O A = </> is called the phase of the oscillation, and
v is its frequency.
T h u s v is the n u m b e r of oscillations per second, a n d w =
2~v is the change in phase per second. T h e phase angle may,
of course, be reckoned from any position, n o t necessarily
from 0 0 ' . T h e p o in t D differs from A by a phase of n (in
radian measure, or 180° in an g u lar measure). Consequently,
we also say th at the p o in t D ' differs in phase from A ' by v, or
th at they are in opposite phase. Points A ' and D ' are the same
distance from O', b u t on opposite sides of it; their velocities
are opposite in sign b u t equal in m agnitude. T h e projection
of the p o in t E, however, moves in the same direction as the
projection of A , even though the projections themselves are
equal and opposite. T h erefo re the phases of the projections of
E and A are n o t opposite; in fact, the phase difference is
2t t — 2</>.
T h e properties of simple harm onic oscillations are as fol
lows:
1. T h e y are characterized by their am plitude and frequency.
2. T h e position of the oscillating point is prescribed by its
phase.
3. T o each phase there corresponds an opposite phase.
4. T h e phase may be reckoned from any position of the
point.
We shall require these definitions in q u a n tu m mechanics,
although there they will not refer to an oscillating point.
Considering wave m otion w ithin the same kinem atic frame
work, we shall discuss the rotation, not of a single point, b u t
of a transparent cylinder on the lateral surface of which there
is a helical line A-lA 2A 2A i Ar, . . . (Fig. 9). If the cylinder is
tu rn ed through some angle, the point A 1 will move to B 1, A 2
A3 B4 A7
Figure 9
to Z?2, etc. W e shall use primes to indicate the projections of
the points on a plane. T h e initial position of the helical line
will then have the form of the wave A \ . . . A 'a, and the
position after rotation will be B \ . . . B'q. N ow the wave B \
. . . B'q appears to be displaced to the right w ith respect to
the initial position.
T h e projection of each point of the helical line onto the
plane of the sketch performs simple h arm o n ic oscillations like
those just considered. In an infinitely long wave, there are an
infinite n u m b er of points that are in phase. T h e distance be
tween any two such neighboring points is called the w ave
length, which is denoted by the letter A.
T h e wavelength is the distance through which the wave ad
vances du rin g one tu rn of the helix. T h e helix makes v revolu
tions per second, so that the wave advances a distance vA, and
the distance per u n it time is the velocity c. T h u s the velocity
of the wave is c = rA. For a given velocity, the frequency and
wavelength are connected by the inverse relationship A = c/v
(it is well known from radio that “sh o rt” waves are the same
as "high-frequency” waves; wavelengths and frequencies are
often shown together on the dial of a radio set). We shall use
this connection between wavelength and frequency a great
deal.
In com paring the definitions of harm onic oscillations and
progressive harm onic waves, we see that in the latter case there
is an additional fu n d am en tal characteristic— the wavelength
or the velocity of propagation. T h e wave in Figure 9 repre
sents the displacement of a point from the median line. Instead
of displacement, we could obtain curves for other quantities,
e.g., the velocity of the point. T h e broken curve in Figure 9
represents the velocity distribution of the points for the same
time as the solid curve gives the displacements. (If the broken
line is also taken to represent displacements, then it will corre
spond to a wave displaced by a q u a rte r period from the solid
line.) Since the broken curve is displaced by a q u a rte r of a
wavelength, it follows that when the displacement is m axi
mum, the velocity of the oscillating point is zero, and vice
versa. It is a characteristic of simple harm onic oscillations
that the curves of displacement and velocity are identical in
form bu t displaced in phase by - / 2 . N o other type of oscilla
tion has this property.
A traveling simple harm onic wave may represent not only
a kinem atic q u an tity such as position or velocity, b u t any
q u an tity at all that varies according to this law. For example,
in a sound wave corresponding to a pure musical tone p ro
duced in a pipe, the compression of the air will be represented
by a progressive simple harm onic wave. W hen overtones of
double, triple, etc., frequency are superimposed on the pure
tone, a progressive b u t n o n harm onic wave is obtained that will
have the same frequency as the harm onic wave. T o make
Figure 9 refer to a sound wave, we must assume th at the crests
of the waves refer to the compression of the air and the troughs
to rarefactions.
Light sensations in the eye are produced by electromag
netic waves with wavelengths between 0.0004 and 0.0007 mm.
Here the oscillating quantities are the intensities of the elec-
trie and magnetic fields in space— which has been known since
the work of J. C. Maxwell (ca. 1870). U p to that time the p rin
cipal difficulty of the wave theory of light was the question:
w hat was it that oscillated in a light wave? W h a t physical
q u a n tity was varying periodically? N ot know ing the answer
to this question, Newton, who was acquainted w ith H uygens’
work, could no t accept it.
For a long time after Newton many people did no t believe
in the wave theory for the same reasons as N ewton. However,
at the b eginning of the nin eteen th century, Fresnel a n d Young
gave decisive su p p o rt to the wave theory with their convincing
experiments.
These experiments were based on a very im p o rta n t property
of waves— their ability to combine. If two waves arrive at some
point of space, the resultant displacement (or whatever analo
gous quantity) is equal to the algebraic sum of the displace
ments in each wave considered separately. In sound waves the
variations in air density are added, and in light waves the
variations in the electromagneticO field strength.
O If the two
waves have the same am plitude, and the crest of one wave
coincides with the trough of the o th er at a p articu lar point,
then when superimposed they will completely cancel each
other out at this point.
U n d er what conditions can this p h en o m en o n occur? Clearly
the waves arriving at the given point must be always in o p
posite phase to each other. R a n d o m canceling at a single in
stant of time cannot be observed.
H ow can it be arranged so that the two waves have a con
stant phase difference? T w o sources of light (e.g., two candles
or two incandescent lamps) emit their light independently
of each other. It is impossible to get them to em it light strictly
in phase, i.e., coherently. Only very recently has a way been
found to cause separate atoms to radiate coherently (in what
are know n as lasers).
T h is difficulty may be overcome if a single wave is divided
into two waves moving along different paths, and then if the
Figure 10
two are com bined again. If different num bers of waves can
be fitted in to these two paths, then after they meet, they will
have a tim e-in d ep en d en t phase difference, i.e., they will be co
herent. If the phase difference is equal to an odd integral m u l
tiple of 77 and the am plitudes are equal, then the waves will
cancel each o th er out. In the example of N e w to n ’s rings (Fig.
10), the light is partially reflected from each surface dividing
different optical media, i.e., from the in n e r surface of the lens
and the o u te r surface of the glass plate. In the case of ray 1,
for example, the wave reflected from the plate always has to
travel a length of A./2 more than the wave reflected from the
spherical surface of the lens (A/4 in each direction, dow n and
up). Such waves should cancel each other out; b u t at the dis
tance 01 from the center we observe a bright ring, no t a dark
one, while a dark spot is seen at the center.
T h is does no t disprove the wave theory of light but merely
shows th at in one of the reflections an extra half wave is lost,
since the fu rth er a ltern atio n of rings takes place in the proper
order. T h e changes from bright to dark rings correspond each
time to a change in the phase difference between the rays by
half a wave, i.e., a change of 77 . Details on the reasons for losing
the half wave on reflection (in this case from the internal
surface of the glass) may be found in optics textbooks. T h e
essential fact is that coherent waves are obtained by reflection
from two surfaces. W ith o u t the concept of coherence and
the principle of superposition, it is impossible to understand
the origin of N e w to n ’s rings.
W e m ust p o in t out a fact that is fundam ental to all that
follows: the wave n atu re of light becomes a p p aren t in this ex
p erim e n t because, and only because, the rays are traveling
th ro u g h a region of space comparable in size to the wave
length of light— in this case the thin region between the con
vex and plane glass surfaces. In this region the phase differ
ence, which varies from rin g to ring, is set up.
In the exam ple of N e w to n ’s rings, the wave nature of light
was revealed only in the alternating rings of brightness and
darkness (i.e., a change in the intensity distribution). H ere the
notion of light rays is not violated, b u t there are many cases
where the very concept of light rays is rendered untenable.
P h en o m en a of this kind, which were studied in detail by
Fresnel and Young, dealt a shattering blow to the corpuscular
theory of light.
As a typical example, suppose a beam of parallel rays of
light strikes a plane opaque screen A with a slit ab (Fig. 11).
W o rk in g strictly by the principles of ray optics, one would
expect to see a ban d on screen B, equal and parallel to the slit,
ss
s'
s' s' s'
<ss'
. b s' s'
* ^'
* \
------- A - \\ . ^ s'
------- ►—yrn c
a
A 6
figure 11
and that the rest o£ the surface would not be illum inated. In
fact the image on screen B is m uch more complicated. T h e
bright ban d opposite the slit does in fact appear, b u t in ad
dition there is a system of other bright bands parallel to it.
It is easy to perform this experim ent: stick a piece of foil on
glass and ride a narrow slit on it w'ith a razor; the parallel
beam of rays can be produced with a lens having a source of
light at its focus, or else by another wider slit illum inated
from behind.
H o w can the bands be explained? Consider the triangle
abc in which ab coincides with the slit and the length of ac
equals half a wavelength. By H uygens’ principle, any point
of the wave may be considered as a new source. By construc
tion, waves incident at points b and c have opposite phases,
since the phases at a and b are the same, and point c differs
from p o in t a by half a wavelength. It follows that on a line
jo in in g b and c there is no other pair of points with opposite
phases. Secondary waves em itted by all points on be in ac
cordance w ith H uygens’ principle cannot cancel each other
out. As a result the bright ban d on screen B proves to be wider
than the slit itself, even when the beam striking A is strictly
parallel, and the rays th at give the bright band beyond the di
rect projection of ba on B are no longer parallel b u t inclined
at some angle. It is immediately evident from Figure 11 that
this angle is twice the angle abc in the triangle, since the waves
diverge on either side of the norm al to B.
T h e angle abc is approxim ately equal to the ratio of the
sides ac and ab, provided the wavelength is much less than the
■width of the slit, as is usually the case. T h e rays are thus in
clined to the slit’s norm al at an angle determ ined by the ratio
of the wavelength and the width of the slit. T h e breakdow n of
geometric ray optics again occurs when the wavelength cannot
be considered sufficiently small in comparison with the region
in which the light is propagated.
Let us now apply H uygens’ principle to a triangle in which
the side ac is equal to a whole wavelength, so that the points b
and c differ in phase by 2 tt. T h e n for each p o in t on the seg
m ent be, a n o th er p o in t with opposite phase may be found.
Points lying in the first half of the segment will correspond to
points of opposite phase in the second half. Consequently,
waves proceeding from these points will cancel each o th er out
and no illu m in atio n will be obtained on the screen in that d i
rection. T h is gives the first dark ban d next to the central
bright one. W h en ac = 3A/2, two thirds of the segment be
will correspond to waves that cancel each other out, while one
third of the waves will have n o waves of opposite phase. A n
other bright band will be obtained on the screen, although
this will be weaker th an the central ban d given by all the
points of be. F u rth e r bright bands of decreasing illu m in atio n
are obtained for ac — 5A/2, 7A/2, etc.
T h e nonrectilinear propagation of waves is called diffrac
tion. T h e greater the ratio of the wavelength to the size of
the slit, the greater the degree of diffraction. For example,
sound waves having wavelengths in the 10-100 cm range tu rn
ro u n d corners easily and can pass through the crack of a d o o r
(or th rough a keyhole) th a t has not been completely closed.
For effective sound insulation the smallest cracks must be
avoided.
If the light source undergoing diffraction is white, the bands
will be colored. T h is is due to waves of different wavelengths
diverging at different angles. T h e long-wave red rays are bent
the most and the short-wave violet rays the least.
Diffraction may be used to resolve light into a spectrum.
For this purpose one needs a system of slits, called a diffraction
grating (Fig. 12). Rays coming from each slit will reinforce
each other if the path difference between them is one, two,
three, etc., wavelengths. A phase difference of one wavelength
means, of course, that the waves are completely in phase. If
a.2c2 — tqc, — a2c2 — a2c2 = . . . = A, a first-order b a n d will be
obtained, if this difference equals 2A, there will be a second-
order band, and so on. W h en the light striking the grating
contains many different colors (different wavelengths), each of
Cl „
oiN
'.V'"
\
' C2
02^
03
\ C4
CU
\ c5
05
\
Figure 12
these bands will be resolved in to a spectrum. T h e more slits
or “lines” the diffraction grating has per millim eter, the
greater the distance between the bands, a n d the better the
resolution of different wavelengths of the spectrum.
T h e same light wave m ust pass th ro u g h all the slits of the
grating, so th at its coherence is completely preserved. T h e
diffraction spectrum is o b tain ed only by the action of the
g ra tin g as a whole. T h is can n o t be explained in terms of ray
optics: one ray would pass th ro u g h one slit a n d would not, it
w ould seem, have a n y th in g in com m on w ith a ray passing
th ro u g h a n o th er slit. However, if we talk about a wave that
possesses a definite phase a n d com pare th at phase in different
slits, diffraction becomes completely intelligible. Phase is a
characteristic of a wave a n d no t of a ray— a wave front posses
ses a definite phase at a given instant of time. Once again, the
breakdow n of ray optics arises because the wavelength is com
parable w ith the spacing in the grating. M odern gratings have
several thousand lines per millimeter.
Electrom agnetic waves w ith m uch smaller wavelengths than
light are called X rays. X-ray diffraction would be very diffi
cult to produce w ith gratings of the type just discussed. H ow
ever, crystals can be used as diffraction gratings because their
atoms are arranged in a strict order. T h is was the explanation
a b
Figure 13
given for the regular form of crystals long before X-ray diffrac
tion was used to verify the fact th a t the atoms in crystals do
actually form regular lattices in space. In certain substances,
e.g., graphite, the lattice consists of sheets placed in a stack.
In each sheet the atoms lie at the corners of hexagons, forming
a honeycomb pattern. T h e corners in one sheet lie opposite
the centers of the hexagons in the n e x t sheet.
In other lattices the atoms may lie at the corners of cubes
and at the centers of their faces (face-centered lattice: Fig.
13a), or at the corners and centers of the cubes (body-centered
lattice: Fig. 13b). In both of these arrangem ents the atoms are
more densely packed than in graphite.
Let us now consider a simplified scheme of the X-ray diffrac
tion in a crystal lattice. In any crystal one may select a n u m b e r
of parallel planes in which the atoms arc arranged regularly,
such as the planes containing the bases of the cubes, or planes
passing through the diagonals of the faces. Let us represent this
system of planes schematically (Fig. 14a) in the form of a
series of horizontal lines. T h e plane incident wave front is re
placed by a single ray A B perpendicular to it. T h is ray is par
tially reflected from each plane at points B 1, B 2, B 3, etc., so
th a t reflected rays B yA y, B 2A 2, B 3A 2, etc., come from these
points. Each of these rays represents its own wave front.
It is clear th a t the reflected waves will reinforce each other
if, and only if, the phase difference between them is equal to
27r,477-,67r, and so on. In all other cases, they cancel each other
out, since for every wave front A n there is some other wave
fro n t A m w ith opposite phase. Suppose, for exam ple, th a t the

phase difference is 9/10 of 2v and then consider the first and
the sixth wave fronts. T h e phase difference betw een them is
7r, w hich m eans th a t wave front A x is cancelled by A G, A 2 by
A 7, etc.
O f course, phase differences divisible by 2-rr are no t o b tain ed
at every angle of incidence. T o o b tain the correct phase differ
ence betw een waves reflected from adjacent planes, let us con
sider F igure 14b. T h is is a sym m etric representation of two
rays reflected from adjacent planes. T h e wave fronts betw een
them are given by the perpendiculars B 1C1 an d B XC2 (the wave
fro n t is always p e rp e n d icid a r to the ray). T h e ray reflected
from the low er p lan e travels along a p ath th a t is longer than
th a t of the ray reflected from the u p p e r surface by C}B 2 +
B 2C2 = 2jBoC2. If the distance betw een the planes is d, the p ath
difference is clearly e q u al to 2d sin 6, which in tu rn m ust eq u al
nX w here n is an integer. H ere 0 is the angle th a t the in cid en t
and reflected rays m ake w ith the plane. T h e eq u atio n 2d sin 6
— nX also defines 6. R eflection from such a system of planes
will not take place at any o th er angle.
By com paring the reflecting pow er of differently oriented
planes, we may d eterm in e exactly from which plane a given
reflection takes place. For exam ple, in the plane co n tain in g
the cube faces, the atom s occur m ore densely th a n in other
planes thro u g h the cube. H ence reflection from the cube faces
w ill be the strongest. X-ray diffraction d ata for a crystal can
be used to determ ine n and 6 in the fu n d am en tal eq u atio n
2d sin 6 — n \ . T h e distrib u tio n s of atom s in Figures 13a and
13b give different systems of diffraction spots, so th a t they may
be distinguished by their X-ray diffraction photographs. T hus,
if the distance betw een the planes is know n, it is easy to find
the w avelength of the incident X rays. Conversely, if the wave
length is know n, the d istrib u tio n of the spots defines the stru c
tu re of the crystal, w hich is often far m ore com plicated th an
the cases shown in Figures 13a and 13b.
In order to fam iliarize the reader w ith the calculation of
atom ic constants, we shall show how to d eterm in e the distance
betw een the reflecting planes in a cubic lattice of the type
shown in Figure 13b. In each cube there are only tiro atoms,
one at the center and one at one of the coiners. T h e atoms at
the o th er corners m ust be taken as belonging to oth er cubes.
T h e mass of each atom equals the atom ic w eight divided by
A vogadro's n u m b e r (6.024 x 10-3), and the mass of the cube
is therefore tw7ice as great. T h e mass p er cubic centim eter
equals the density of the crystal, and hence the n u m b er of
cubes per u n it volum e of the crystal can be easily worked out.
T h is also gives the size of a single cube. G enerally, it is of the
ord er of 10_s cm— a characteristic len g th in atom ic physics
th a t will be frequently encountered. T h is length is com parable
w ith the w avelength of X rays and confirms the general rule:
diffraction phenom ena arise when the dim ensions of the region
d eterm in in g the p ro p ag atio n of the war es are com parable with
the w avelength.
2 T h e uncertainty principle
I t was shown in the preceding sections that there are two

forms of m otion in classical physics: displacem ent of bodies
along trajectories and prop ag atio n of waves. T h e latter cannot
alw a)s be reduced to the m otion of particles in space. Even
th ough waves in w ater or air can be described by the m otion
of the particles of the m edium , the variation in electrom ag
netic fields cannot be represented by the displacem ent of p a r
ticles. In spite of the difference in these types of m otion, the
laws governing them are sometimes very sim ilar. T h is holds
w hen the w avelength is sufficiently small in com parison w ith
the geom etric dim ensions of the region in which the wave
process is propagated. For exam ple, w hen rays are focused by
a lens, the dim ensions of the lens are very large in com parison
w ith the w avelength. O n the other hand, the region n ear the
focal p o in t may be considered small, and appreciable diffrac
tion phenom ena arise there. Again, the images of stars in a
telescope are su rro u n d ed by diffraction rings, which are im
possible to elim inate. T hese rings are no t due to defects of the
telescope’s optical system th a t could be elim inated by com
bin ing different lenses; diffraction is connected w ith the wave
n ature of light.
In the preceding ch ap ter we said th at the laws of electron
optics, which are, essentially, deduced from the corpuscular
theory, can also be established from H uygens’ principle if we
suppose -that the electron m otion obeys some wave laws. As
long as we are considering large regions, the corpuscular and
the wave approaches lead to the same results. W hat, however,
will happen in small regions? In the case of electrons we do not
know in advance w hat dim ensions should be considered small:
are they the same as in ordinary optics, or are they even
smaller?
It turns out th a t if a beam of electrons is passed th ro u g h
a crystal, the resulting diffraction p a tte rn is the same as th at
of X rays. In fact, the diffraction of electrons was first observed
by Davisson an d G erm er after H eisenberg an d Schrodinger had
fo rm ulated the laws of q u a n tu m mechanics, b u t we shall give
a systematic ra th e r than a historical description. Science does
no t develop according to a preordained plan; the result, corre
sponding to an objective state of affairs in n atu re, is p re
determ ined, although it may be reached in circuitous ways.
W e m ust therefore consider the diffraction of electrons!
Electrons are beyond d o u b t not waves b u t particles— u n d er
no circum stances is th eir charge o r mass divided. 'We can
never observe a p art of the charge or a p art of the mass of an
electron, whereas we always regard a wave as a divisible con
tinuous entity. Each electron leaves a single spot on a p h o to
graphic plate. If we use a beam of very low intensity and pass
the electrons one by one through a crystal, the individual spots
will be grouped in a single picture th a t is the same as for the
diffraction of X rays. In the same way, a p rin te r’s block is m ade
u p of in d iv id u al dots, which when seen as a w hole give a clear
p icture of th e ir subject.
A d irect diffraction experim ent shows th a t each electron
moves through the lattice like a wave c o n trib u tin g to the
diffraction pattern , w ith o u t ceasing to be an indivisible p a r
ticle. A lthough this may seem paradoxical, it is an ex p eri
m ental fact. H ow ever, in a n u m b er of cases the electron moves
purely as a particle, ex h ib itin g no wave properties. F or ex
am ple, in the picture tu b e of a television set the electrons
move along trajectories that, at least in p rinciple, may be
predicted as strictly as the orbits of planets. W hy then does the
The uncertainty principle 25
electron behave sometimes as a wave and som etim es a p a r
ticle?
Let us rem em ber th a t light too shows this same tw ofold be
havior. W hen refracted by a lens, it travels in a straight line,
b u t w hen it strikes a diffraction grating it exhibits its wave
n ature. A ll depends upon the ratio betw een the w avelength
and the size of the region in w hich the m otion takes place.
W h at w avelength, then, corresponds to the m otion of an
electron? If the same equation as the one for X rays is used,
the w avelength may be m easured directly from the diffraction
p attern . O th er atom ic particles may also e x h ib it diffraction,
e.g., protons. However, it is m ore convenient n o t to transm it
protons th ro u g h a crystal, b u t to scatter them from the regu
larly arranged atoms on the crystal surface. T h is m ethod re
calls the diffraction of light ra th e r th an of X rays; b u t here
too the diffraction p a tte rn enables us to determ ine the wave
length. In every case we o b ta in the follow ing result: the
w avelength is inversely p ro p o rtio n al to the m om entum of the
particle, i.e., to the product of its mass and velocity.
T h e coefficient of p ro p o rtio n ality between the w avelength
and the m om entum of the particle is a universal constant, as
im p o rtan t as the elem entary charge or the velocity of light.
D enoted by the letter h, it is called P lan ck ’s constant. In w hat
units is h m easured? Since the w avelength equals h divided by
the m om entum , A = h /m v , P lan ck ’s constant h m ust have the
dim ensions of w avelength m u ltip lied by m om entum . Let us
find the dim ensions of h in the CGS (or MKS) system. M o
m entum has the dim ensions of mass times velocity, i.e., g
cm /sec. H ence P lanck’s constant has the dim ensions of g
cm 2/sec. W e observe th a t these are the dim ensions of energy X
time (energy has the dim ensions of g cm2/scc2).
T h u s in order to find the characteristics of the wave m otion
of an electron, we m ust introduce an o th er universal constant
into physics. It is universal because it is the same for all p a r
ticles and for all m otions. T h e w avelength associated w ith
the m otion of a p ro to n is expressed in terms of its m om entum
by the same form ula as for an electron (of course, the mass
and velocity of the p ro to n are substituted, b u t P lan ck ’s con
stant rem ains the same).
P lanck’s constant describes a law of n a tu re th a t was no t
included in N ew to n ’s laws. T hese laws did n o t contain any
universal constants: in saying th a t force equals mass times
acceleration, we do not have in m ind any n a tu ra l u n its of
force, mass, and acceleration (or length, mass, and tim e in
w hich they may be expressed). O u r m etric system of m easure
m ent is the result of conventions agreed u p o n by m en and
docs not belong am ong the laws of physics.
W e say, for exam ple, th a t the m eter is 1/(4 • 107) the length
of a m eridian of the earth. T h is is entirely conventional— both
the choice of a m eridian of the earth as a u n it of length and
the choice of a forty m illio n th (and not, let us say, a h u n d re d
m illionth). B ut P lanck’s constant is the same for the whole
universe. C onsider, for exam ple, N ew to n ’s second law, which
connects force, mass, and acceleration w ith the p a rtic u la r m o
tion th a t we are studying. O n the oth er hand, in the eq u a
tion A. = h /m v , P lanck’s constant h is always the same for any
X, m, and v. P lanck’s constant occurs in a law connecting
physical quan tities: w avelength, mass, and velocity. T h is is
truly a law and not a definition of a q u a n tity (like, for ex
am ple, “m om entum equals mass times velocity”). T h e wave
length is d eterm ined from diffraction experim ents; the velocity
is the distance traveled by the particle in u n it tim e. T hese
q u an tities are connected by the expression X — h / m v , b u t
unlike N ew to n ’s laws, they contain the dim ensional constant h.
If we take the mass of an electron as the u n it of mass and
its charge as the u n it of charge, then by adding P lan ck ’s con
stan t to o u r list, we may free ourselves com pletely from the
a rb itrary units of the m etric system. T h is leads to the atom ic
system of units. T h e u n it of length in this system is .52917 X
10~8 cm, w hich is of the same o rd er as the lin ear dim ensions
of the atom (cf. end of C h ap ter One).
O f course, even this system of units still retains an elem ent
of convention: why, for exam ple, is the u n it of mass taken
as the mass of the electron and n o t the mass of the proton,
which is 1836 times greater? W e may also pose the question:
why is it exactly this n u m b er of times greater? However, it is
m eaningless to ask why the mass of the electron equals 9.107 X
10-28 g; for the gram is an a rb itrary u n it, th o u g h t u p by men.
Electrons and protons, on the o th e r hand, exist in n a tu re and
do n o t depend on us. W hy the p roton is 1836 times heavier
th an the electron is not know n, for still far too little ab o u t the
stru ctu re and interdependence of particles is know n.
In the GGS system of units, h = 6.625 X 10~27. T h e sm all
ness of this q u a n tity in o u r system of m easurem ent shows
how m uch sm aller m echanical quantities are on the atom ic
scale than on the scale of the quantities encountered in every
day life. Since the value of h is now know n, we can answer
o u r fu n d a m e n tal question: why does an electron have w'ave
properties in a crystal b u t not in a television picture tube?
Probably everyone know7s th a t a high voltage— ab o u t 20,000
volts— is necessary for a television set. T h is m eans th a t the
electrons m ust reach a high velocity in the p icture tube. If
we know the voltage applied, can we calculate this velocity?
T h e voltage is the p o ten tial difference in the gap in which
the electrons are accelerated. If the charge of the electron is e
and the p o ten tial difference is <£, then it may be shown th a t
as the electron passes through the p o ten tial difference </> it ac
quires an energy equal to e<f). Energy is m easured in ergs, b u t
since the charge c is a universal constant, the energy of the
electron can be m easured in units of po ten tial difference, as is
usually done in atom ic physics. T h e energy of an electron
m oving th ro u g h a p o te n tia l difference of one volt increases
by one electron-volt, abbreviated 1 eV.
Electron-volts can be converted in to ergs w ith o u t difficulty.
T h e charge of an electron equals 4.8026 x 10-10 electrostatic
units and a volt equals 1/3 0 0 of an electrostatic u n it. H ence
one electron-volt equals 1.6 x 10-12 ergs.
An electron in a television picture tube at first has relatively
little energy, b u t it eventually acquires 20,000 eV, which is
eq u iv alen t to 1.6 X 10-12 X 2 x 104 = 3.2 x 10~8 ergs. H ow
ever, the energy of a m oving electron equals half the pro d u ct
of its mass by the square of its velocity (m v2/ 2). Since the mass
of the electron is approxim ately 9 X 10-28 g, we find th a t the
square of the velocity is 3.2 X 10_8/4 .5 X 10-28 = 7.1 X
1019 cm 2/sec2 and the velocity itself is 8.4 x 109 cm /sec. T h e
m om entum (mass x velocity) is therefore eq u al to 9 X 10-28
X 8.4 x 10° = 7.5 x 10_ 18 g cm /sec. Finally, the w avelength is
A = h / m v = 6.625 x 1 0 - 27/7.5 X 10~18 = 0.89 x 1 0 - 9 cm.
Now, the d iam eter of the electron beam in a television set
is ab o u t 0.1 m m or 10~2 cm. T h is is some 10 m illion times
greater th an the corresponding w avelength. H ence it is clear
th a t the wave properties of electrons will no t ap p ear in the
picture tube, b u t w ould certainly give rise to diffraction p h e
nom ena if the same electron beam were passed th ro u g h a crys
tal. In the television picture tube, the wave properties of elec
tro n m otion are an unnecessary com plication (just as ray optics
are q u ite sufficient for a cam era lens*).
T h e wave properties associated w ith the m otion of electrons
in crystals in no way contradict the existence of particle tra
jectories in other kinds of electronic apparatus.
L et us now consider a very im p o rtan t question: how far may
we use the classical concepts of trajectory? U p to now we have
only discussed extrem e cases: the electron beam in a picture
tube, where the classical concept of a trajectory can be used,
and diffraction of electrons in a crystal, w hich can n o t be con
sidered, even qualitatively, w ith o u t the concept of wave m o
tion. In the first case the m otion is lim ited to a region of 0.01
cm, and in the second to the in ter p la n ar distance in the
crystal (10-8 cm). W h at then is the order of m agnitude of a
region of m otion for which the concept of a trajectory is in
applicable and for w hich the m otion m ust be considered in
term s of a wave?
* But not for a microscope where the objects to be studied are comparable
in size with the wavelength of light waves.
C onsider the beam of a searchlight. W hy do we consider
this a geom etric ray? Light, of course, is a wave m otion in
every case, and according to the definition of a searchlight,
the waves cannot diverge too far from the direction of the
ray. In o th er words, the concept of a particle trajectory is
m eaningful w hen the am p litu d e of the wave associated w ith
the m otion rap id ly becomes zero on eith er side of the trajec
tory. It is then im probable th a t we shall find a particle in a
place forbidden by the classical (nonwave) laws. In the exam ple
illu strated in Figure 11 we considered the effect of a lateral
restriction on the prop ag atio n of waves. O nly an infinitely
wide beam of rays can be strictly parallel, b u t then it has n o
lateral boundary. O nly such a beam corresponds to a perfectly
p lane wave front, w hich gives a single, precisely defined direc
tion of wave propagation. (T h e beam of a projector, or a
ra d a r beam , is b o unded at the sides, an d is therefore only ap
proxim ately parallel.) T h e m om entum of the particle coincides
w ith this direction, and hence a particle for which the m o
m en tu m is defined precisely w ith respect to m ag n itu d e and
d irection has no defined position, i.e., the beam in this case is
infinitely wide, w ith its “ trajectory” ex ten d in g th ro u g h all
space.
If we wish to define the position of the p article in at least
one plane, we have to m ake it pass th ro u g h a slit in th at
plane. W h at happens then? In the exam ple considered in
C h ap ter O ne (Fig. 11) we saw th a t if the slit is of b re a d th d,
the wave com ing out of it is n o t strictly parallel, b u t lies
w ithin an angle approxim ately equal to A/2d (in the same
n o ta tio n as in Fig. 11). F u rth er, ac — \ / 2 , ab = d = b re a d th
of the slit. If we assume th a t the ra tio ac/ab is small, the angle
of span of the beam th a t has passed th ro u g h the slit is clearly
sm all too.
In w hat d irection does the velocity of a particle lie after it
has passed th ro u g h the slit? As we have ju st seen, the only
particle possessing a strictly defined velocity d irectio n is one
whose m otion suffers no lateral restriction. If the wave emerg-
ing from the slit is not strictly parallel, b u t lies w ith in some
angle, th en the d irectio n of the velocity of the particle also
lies w ith in th a t angle. H ow ever, if the velocity, being a vector,
is inclined at some sm all angle, th en it has a p erp en d icu lar
com ponent, ap p ro x im ately equal to the p ro d u ct of the velocity
an d th a t angle. H ence after passing th ro u g h a slit of b re a d th d,
the velocity of the particle undergoes a certain deviation in
the plane of the slit, although we do no t know, of course, at
precisely w hat angle the particle is m oving. It will be m oving
somewhere w ith in the angle defined by the diffraction rela
tionships.
W e may therefore say th a t the velocity possesses an u n
certainty. T h e position of the particle also possesses an u n
certainty: the particle has passed th ro u g h the slit of b read th d
and not th ro u g h a single p o in t of it. Instead of using d, we
d enote the u n certain ty in the position of the particle by the
m ore m eaningful symbol A x, and likewise the u n certain ty in
the velocity by Aw. T h e un certain ty in the m om entum is then
Ap — m&v. Let us now m u ltip ly the u n certain ties in position
an d m om entum together. T h e first of these is d and the second
is:
T h e variables cancel on m u ltip licatio n and we ob tain a rela

tio nship th a t is fu n d am en tal to q u a n tu m mechanics:
ApAx ~ h ***
T h is m eans th a t the pro d u ct of uncertain ties in m om entum
an d position is equal to P lan ck ’s constant. T h e m ore p re
cisely the coordinate is defined, i.e., the sm aller is Ax, the less
precisely can the m om entum be given, since Ap is inversely
p ro p o rtio n al to Ax. Conversely, the m ore precisely the mo-
* Factor 2 allows for the fact that the deviation may be up or down.
** Using advanced mathematics we can show that the exact statement of
the uncertainty principle is:
ApAx > {h/2-rr
m enium is defined, the worse the definition of the p a rtic le ’s
p o sitio n is.
W e shall constantly encounter this facp in all experim ents
on diffraction, since it is im possible to force a wave to be
propagated w ith the same precision as th at w ith w hich a p a r
ticle moves. B ohr and H eisenberg analyzed a n u m b er of
thought-experim ents (gedanAetz-experiments) in which the co
o rd in ate of a particle and its m om entum could be defined w ith
the greatest possible precision (aside from in stru m en tal errors).
It was found th a t in all cases these two q u an tities could n o t be
physically determ ined (i.e., exactly m easured) a t_ th e _ sa m e
time. M easurem ent, if it could be free from exp erim en tal
errors, is a physical determ in atio n of a q u an tity , since k reveals
the properties of the objects of m easurem ent and n o t of the
m easuring systems. O bjects are also d eterm in ed solely th ro u g h
m easurem ent in classical physics.
Let us recall a well-known fact from the history of physics.
For a very long tim e inventors tried to construct, or at least
to design, a p erp etu al m otion m achine, i.e., an im aginary m a
chine th a t w ould do useful work w ith o u t an ex tern al supply
of energy. Peter the G reat of R ussia was so interested in this
idea th a t he founded an academy especially for this research.*
However, if we even w ith o u t know ing the general p rin cip le
of the conservation of energy analyze any actual design of a
p e rp e tu a l m otion m achine, we can always find a m istake in it.
All these unsuccessful designs or im aginary experim ents have
led physicists to the conclusion that a p erp etu al m otion m a
chine sim ply can n o t be constructed. T h is assertion is one way
of expressing the conservation of energy principle.
Sim ilarly, the im aginary experim ents on the m easurem ent
of position and m om entum led B ohr and H eisenberg to a n
o th er conclusion, no less fu n d am en tal to physics: the posi
tion and the m om entum of a particle do no t exist sim u ltan e
ously as precisely definable q u antities. T h is is know n as the
* See V. L. Kirpichev; B e s e d y o m ekhanike (Discussions on mechanics),
Gostekhizdal, 1951, p. 289.
uncertainty principle. It is im possible even in p rin cip le to
devise a procedure th a t w ould b rin g ab o u t the precise de
term ination, i.c., m easurem ent of both position an d m om en
tum . T h is is not a subjective defect in the experim enters,
b u t an objective law of n atu re.
For those w ho wish to refute the u n certain ty p rin cip le by
means of im aginary experim ents, the sad fate of the inventors
of p erp etu al m otion m achines is w aiting. E instein tried to
devise such an experim ent, b u t even he, of course, could not
prove stronger than n atu re. T h is exam ple m ust now serve as a
cautionary tale for critics of the u n certain ty p rin cip le who are
still to be found am ong people interested in physics an d even
am ong a sm all n u m b e r of physicists.
T h e uncertainty principle in no way denies the existence
of m om entum an d position as precise physical q u an tities; it
m erely asserts th at they cannot exist sim ultaneously as precise
q u antities. Each of them separately may be m easured or given
w ith as m uch precision as desired.
T h is assertion contains a denial of deep-rooted physical con
cepts. In speaking of the trajectory of a particle, we u n d e r
stand th a t at every in stan t of tim e it has a definite position
and velocity (or m om entum ). T h e u n certain ty p rin cip le ren
ders this assertion m eaningless, of course, only as far as m icro
scopic particles are concerned. For m acroscopic particles,
P lanck’s constant on the right-hand side of the u n certain ty
relationship is a very sm all q u an tity , and consequently the
velocity and position may be defined sim ultaneously for
m acroscopic particles w ith practically any necessary degree of
precision; i.e., the trajectory concept is always valid in practice
for m acroscopic particles.
T h u s q u a n tu m m echanics provides its own special concept
of m echanical m otion w ithout trajectories. T h e analysis of
m otion along trajectories makes it possible to p redict fu tu re
data uniquely in term s of the past. In q u a n tu m m echanics, this
p red ictio n has a probabilistic character. O f course, this does
n o t totally deny the laws of m otion; it sim ply m eans th a t the
laws of q u a n tu m m echanics give us the p ro b ab ility of ob
tain in g different values of various q u an tities and do no t
refer to the q u an tities themselves. W e may describe the
p ro bability th at an electron will strike this or th at p o in t of
a p h o tographic plate, b u t cannot in principle predict which
p o int it will actually strike.
H ence, unlike the classical laws of m otion, the qu an tu m -
m echanical laws of m otion incorporate the concept of p ro b
ability, an d this is not connected w ith im perfections in the ap
paratus, b u t rests in the n atu re of things.
E xperim ent show's th a t the p ro bab ility d istrib u tio n for
electrons striking a p h o tographic plate obeys the same laws
as those for the diffraction of electrom agnetic waves. W e have
already m entioned th a t the diffraction of electrons is com
pletely in d ep en d en t of the intensity of the electron beam
and occurs even w hen the electrons pass th ro u g h the crystal
practically one by one. H ow ever, electrom agnetic waves arc
diffracted because a wave has different phases on different
planes of an atom ic lattice. C onsequently, the electron also
m ust have different phases on different planes. W e recall
th a t to o b ta in the diffraction of electrom agnetic waves, light
from a single source m ust be used— only then docs the phase
of the wave have a definite value on each plane. W e called
this a coherent wave. In this sense every electron is coherent
w ith itself alone, ju st as every source of light is.
C oherent waves can cancel each o th er o u t w hen th eir
phases arc opposite; b u t the probabilities of an electron strik
ing this or th a t p o in t of the plate cannot cancel each other,
for they are positive by definition. In the same way, in the
case of diffraction of light, the intensities do no t cancel each
o th er out, since they are also essentially positive. O nly the
electrom agnetic field strengths, i.c., the am plitudes of the
waves, may be added or subtracted. Sim ilarly, in the case of
electrons, the am plitudes of the probabilities of finding an
electron at a given p o in t of space may cancel each other out.
O nly the am plitudes an d n o t the pro b ab ilities can possess
wave properties. H ence the m otion of an electron in a crystal
is described by a reave function sim ilar to the electrom agnetic
wave in the p ro p ag atio n of light. T h e intensity is equal to
the square of the am p litu d e of the electrom agnetic oscillations;
sim ilarly, the p ro bability of finding an electron at this or th a t
p o in t of space is equal the square of the am p litu d e of the
wave fu n ctio n describing its m otion.
T h erefore, we may answer the direct question: w hat oscil
lates d u rin g the m otion of an electron? T h e answ er is th at
the am p litu d e of the pro b ab ility of finding it at a given p o in t
of space oscillates. T h is am p litu d e has the properties of a wave.
T h e probability concept is n o t com pletely foreign even to
classical or N ew tonian mechanics. Let us begin w ith an ex
am ple taken from everyday life and then show th a t in q u a n tu m
m echanics probability, being connected w ith the very n atu re
of things, goes far m ore deeply.
I t is well know n th a t w hen one is shooting at a target, b u l
lets do not strike the same p o in t twice. T h e b etter th e m arks
m an the closer the shots, b u t there is always some scatter.
Even w ith perfect aim there w ould still be scatter, for ex
am ple, caused by slight differences in the pow der charges.
Even a poor m arksm an can sometimes h it the b u ll’s-eye
by chance— b u t it is extrem ely unlikely th at he will h it the
b u ll’s-eye five times in succession. T h e scatter of the shots on
the target reveals the skill of the m arksm an or, in other
words, the probability th a t he w ill h it the m ark. For a
sufficiently great n u m b er of shots we could o b tain a sm ooth
curve of the d istrib u tio n of the im pact probabilities on the
target.
In classical m echanics the pro b ab ility concept is in tro d u ced
because it is im possible to reproduce in itial conditions of
m otion perfectly. T h is is the basis of the game of “ heads or
tails,’’ which is frequently used to exp lain the most im p o r
ta n t propositions of probability theory.
T h e concept of probability a m p litu d e cannot arise in clas
sical m echanics: if we do not know the trajectory of a
particle precisely, we can calculate only the p robability of
its passing through this or th at p o in t of space, e.g., the p ro b
ability of h ittin g the b u ll’s-eye. In q u a n tu m physics, the m atter
is q u ite different— m otion does not take place along trajec
tories, ju st as the propagation of light in diffraction does not
correspond to any light rays. W e cannot describe the trajec
tory of an electron in a crystal simply because it does not
exist. H ere we m ust use the concept of p robability am plitude.
A n o th er concept n o t ap p earin g in classical m echanics is
th a t of the phase of a wave function. Of course, only the phase
differences are revealed by the diffraction phenom ena in the
case of scattering by different lattice planes. Since the final
diffraction p a tte rn is com pletely in d ep en d en t of w hether the
electrons pass through the crystal all at once or one at a time,
we have to recognize th a t the wave function of an individual
electron possesses a phase. Each electron in this experim ent is
coherent w ith itself, like the light wave in the diffraction
experim ent, and hence the p a tte rn obtained on the p h o to
graphic plate does not in the least recall the d istrib u tio n
curve for bullets on a target. T h e b etter the definition of the
in itia l conditions of m otion of the electrons and the more
ideal the crystal, the sharper and clearer is the diffraction
p attern.
It is not the electron itself th at has a wave-like character
b u t only the am p litu d e of the probability of finding it at
some p o in t in space. In this sense it is m ore correct to speak
of the wave-like character of m o tio n , for diffraction phenom ena
are also observed in the m otion of other atom ic particles.
W hy is there no diffraction in the case of the m otion of
ordinary bodies, such as bullets, stones and missiles? W e have
seen th a t the w avelength is inversely p ro p o rtio n al to the mass
of the particle. If the mass of the particle is 1 g and its velocity
is only 1 cm /sec, then by the fu n d am en tal form ula A = h /m v ,
the w avelength is A = 6.6 X I0 -27 cm. It is inconceivable, how
ever, th a t any position could be specified w ith such enorm ous
precision. Even the radius of an atom is of the order of
10- s cm. It follows th at the laws of wave m echanics simply
have no effect on the m otion of such m acroscopic bodies, b u t
it goes w ith o u t saying th a t classical m echanics may be applied
to them . A tom ic particles, especially electrons, may be called
microscopic bodies. Classical mechanics may often be a p
plied to them too. For exam ple, the m otion of an electron
in a television picture tube is classical.
In an ordinary optical microscope, the lim it of resolution
is determ ined by the w avelength of light, for objects m uch
sm aller th an this cannot be observed. Electrons w ith energy
of 20,000 eV have a w avelength of 10-9 cm. T h is is 100,000
times sm aller than th a t of visible light, and hence an electron
microscope may be used to observe and p h o to g rap h objects
100,000 times sm aller th an an optical microscope can.
As we have already seen, the concept of a classical trajectory
is n o t alw'ays applicable to the m otion of electrons. In the
atomic, m icroscopic region everything is determ in ed by the
law's of w'ave mechanics.
T h e laws of q u a n tu m M echanics contain the concept of
probability, or m ore precisely, the probab ility a m p litu d e; and
this is not at all connected w ith our subjective lack of know l
edge of the in itia l conditions of m otion. As a precise physical
concept, a trajectory has no physical existence in relatio n to
m icroparticles. Cfr/zv /
T h e q u a n tu m laws of m otion do no t negate the classical
laws; they only im pose a q u a n tita tiv e lim it on th eir ap p lica
bility. T h is lim it is given by the uncertain ty relationship,
which still employs classical concepts of position and m om en
tum . So long as Ap and Ax are sm all in com parison with
p an d x, which characterize a given actual m otion along a
trajectory, the classical laws of m otion may be applied; btit
if the uncertainties in these q u an titie s eq u al or exceed the
q u an tities themselves, the q u a n tu m laws are necessary. U n
like the classical laws, these predict the results of experim ents
not uniquely b u t in pro b ab ility form.
W e also note th a t q u a n tu m m echanics can n o t answ er at all
the question of w hat an electron is or w hat is its structure.
T h is is the concern of the theory of elem entary particles— a
science th a t is far from com plete. -The nam e m echanics u n d e r
lines the fact th a t we are studying specific laws of m otion and
not the n a tu re of m oving objects. Sim ilarly, classical m echan
ics is concerned w ith the m otion of planets a ro u n d the sun
b u t n o t w ith the p lan ets’ com position or in te rn a l structure.
Q u a n tu m m echanics explains the m otions of electrons about
the nucleus of an atom on the basis, an d solely on the basis,
of the properties of nuclei and electrons th at are im p o rtan t
in a given actual case. Q u a n tu m m echanics solves this problem
as com pletely as classical m echanics solves the fu n d am en tal
problem of astronom y.
In this sense q u a n tu m and classical mechanics are com
plete to the same degree. T h e equations of classical mechanics
can be obtained “in the lim it” from the q u a n tu m equations
simply by allow ing P lan ck ’s constant h to tend to zero. (More
precisely, the w avelength associated w ith the m otion becomes
infinitely sm all in com parison w ith the region in which the
m otion takes place. However, the w avelength is directly
p ro p o rtio n al to P lanck’s constant so that, form ally, this is
eq uivalent to h tending to zero.) T h e u ncertainties Ap and
Ax become, so to speak, disconnected, an d may be m ade as
sm all as desired independently of each other. T h erefo re the
trajectory concept becomes valid.
W hen a theory of elem entary particles is finally developed,
it will no d o u b t change and extend the present-day concept
of m otion in q u a n tu m mechanics, b u t it will have to be
retained as a lim itin g case. W e may be sure of this in advance,
since q u a n tu m m echanics gives a correct and consistent de
scription of a definite range of n a tu ra l phenom ena. Since the
laws governing these phenom ena cannot change, n or in te rn a l
consistency become inconsistent, q u a n tu m mechanics w ill al
ways rem ain correct in its own range of application, just as
classical m echanics has rem ained applicable in its own dom ain
even after the advent of q u a n tu m m echanics; b u t w hen the
theory of elem entary particles is established, we shall also have
to take in to account the theory of relativity (see C hapter
Eight).
T h e un certain ty principle contains an assertion th a t is con
siderably m ore general th an is evident from the uncertainty
relationship, ApAx = h for the specific q u an tities p. and x.
T o show this, let us o b ta in sim ilar relationships for an o th er
p air of variables. W e observe first of all th a t the com ponents
of m om entum and position to w hich the uncertainty relatio n
ship refers m ust be taken in the same direction. T h ey do not
refer to variables taken in m utually p erp en d icu lar directions.
T hese com ponents may be defined sim ultaneously w ith any
desired degree of precision.
L et us now r ecall the definition of an g u lar m om entum from
mechanics. L et the m otion take place in a given p lan e (Fig.
15) and consider an axis p erp en d icu lar to the plane. T h e
lin ear m om entum of the particle is represented by a vector
lying in the plane. A ngular m om entum is defined as the
p ro d u ct of the lin ear m om entum by the length of the p erp en
d icu lar draw n from the p o in t w here the axis cuts the plane to
the vector p. In m echanics we often use ro ta tio n a l m otion
or, in general, m otion ab o u t a center of force. In fact it turns
o u t th a t if the force acts along a line draw n from the center
to the particle (this holds good for the force of gravity and for
electrostatic forces), then an g u lar m om entum is constant. In
Figure 15
this case we m ust draw the axis p erp en d icu lar to the plane
th rough the center of force. T h u s in Figure 15 the axis can
pass through the nucleus of an atom.
T h e proof of the law of conservation of an g td ar m om entum
may be found in textbooks on mechanics. W e ought n o t to
form ulate it in the same way, since we are considering m otion
according to quantum -m echanical laws, i.e., m otion w ithout
trajectories. H ow ever, there is rem arkable agreem ent betw een
the two systems; if a certain q u a n tity is conserved in classical
m otion, th en it is also conserved in q u a n tu m m otion. Of
course, this assertion is lim ited som ew hat by the u ncertainty
principle; for only q u an tities th a t can coexist sim ultaneously
can be conserved sim ultaneously. T h e fact th at the same con
servation laws hold in b oth classical and q u a n tu m m echanics
is of fu n d am en tal im portance. T h is is called the correspond
ence prin cip le, for it allows us to w rite dow n q u a n tu m eq u a
tions of m otion if we know the form of the classical equations
for a given m echanical system.
Let us now re tu rn to the an g u lar m om entum . D enoting
m om entum as usual b y p and the p erp en d icu lar distance from
the axis by r, we have, by definition, th a t the an g u lar m o
m entum M = pr. Since p and r are perp en d icu lar, they may
be defined sim ultaneously; b u t if we speak of the displacem ent
of the particle along a trajectory, then in accordance w ith the
u n certainty principle, it can be defined only w ith an u n
certainty Ax. It is clear from the diagram th a t Ax = rA<£
w here the azim uth <j> is the angle that, together w ith the dis-
tance from the axis, gives the position of the particle on the
plane (we are not obliged to use C artesian coordinates x and
y)-
From the un certain ty relatio n sh ip we have ApAx = h, b u t
since Ax = rA<£, we have Ap ■ rAcj> = h. T h is may be rew ritten
A (rp) • A $ = h since r is p erp en d icu lar to p. R em em bering
the definition of an g u lar m om entum , we o b tain the uncer
tainty relationship for the an g u lar m om entum an d the azim uth
angle: AMA<£ = h. W e see th a t the an g u lar m om entum can-
no t exist as a precise q u a n tity sim ultaneously w ith the azim uth
angle. If, for exam ple, the an g u lar m o m en tu m is know n
precisely (and is conserved since the force is central), th en the
position jof the particle in its orbip is com pletely u n defined.
W e shall often re tu rn to this point.
L et us now consider how we are to u n d e rsta n d the law of
conservation of energy in the light of the u n c e rta in ty principle.
As we know, the energy consists of two parts, kinetic and
p o tential. T h e kinetic energy of a particle d e p e nds o n its
velocity, and the p o te n tia l energy on its position. For ex
am ple, the p o te n tia l energy of a particle in a g rav itatio n al
field is p ro p o rtio n al to the height to w hich it is raised.
Sim ilar expressions may also be obtain ed for an electrostatic
field.
H ow ever, a position coordinate and the co rresponding ve
locity do not exist sim ultaneously. Does this m ean th a t the
u n certa in ty p rin cip le revokes the law of conservatio n of en
ergy? N ot at all, for we have already said th a t the conserva
tion laws of classical and q u a n tu m m echanics are the same.
Thje difference is th at in q u a n tu m m echanics the energy of a
p article cannot be divided exactly in to kinetic and p o te n tia l
energies. O nly the total energy has a precise m eaning and
only the total energy is conserved. T h e conservation co n d i
tions are exactly the same as in classical m echanics: n o work
may be done on the system by ex tern al forces. Since the
energy is conserved, such systems are said to be conservative.
In p a rticu lar, energy is conserved in a closed system, i.e., one
th a t does n o t in teract w ith su rro u n d in g systems.
^ Quantum laws of motion
W ave m otions u n d e r extrem ely diverse conditions have m uch

in com m on. T h is allows us to explain m any cases of atom ic
particle m otion if n o t quan titativ ely , at least qu alitativ ely
w ith the aid of obvious optical an d acoustic analogies.
W e m ust here consider in detail, first of all, the behavior
of a wave on the b o u n d ary betw een two m edia. Figure 2
shows the p ath of rays refracted from such a boundary. T h e
angle betw een the ray and the norm al to the b o u n d ary is
sm aller in the denser m edium . If we now allow the angle of
incidence (i.e., the angle to the norm al) to increase u n til it
reaches 90°, the refracted ray w ill also m ake a larger angle
w ith the norm al, alth o u g h it will always be less th an 90°.
T h e angle corresponding to 90° incidence is called the angle
of total in te rn a l reflection. In fact, a ray m oving in the re
verse direction, i.e., from the denser m edium , at an angle
greater than the angle of total in te rn a l reflection, w ill n o t
be able to p en etrate the optically ra re r m edium at all, and
will be totally reflected back into the denser m edium . It is
for this reason th a t air bubbles in w ater appear silvery from
a certain angle. T o ta l in te rn a l reflection is also used in pris
m atic binoculars. Because of reflection from the in tern al
surfaces of special prisms, the image appears “rig h t side u p ”
instead of inverted.
T h e phenom enon of to tal in te rn a l reflection may be equally
well explained by eith er the wave o r the corpuscular theory.
Both lead to the same law of refraction.
H ow ever, as an exam ple, here is one com plication th a t can
no t be explained from the corpuscular p o in t of view. Let us
assume th a t the ra re r m edium is totally enclosed inside the
denser m edium an d is in the form of a very th in layer with
ap p roxim ately the thickness of a single w avelength. In this
case the reflection from the layer will cease to be total even
w hen it should be according to the laws of geom etric optics.
T h e ex p lan atio n is th a t the waves still p en etrate a little into
the ra re r m edium , even w hen they strike it at an angle greater
th an the angle of total in te rn a l reflection. In this case the
waves are very rapidly a tte n u ate d in the ra re r m edium and,
m ost im p o rtan t, do n o t carry any energy very far into it. If
th e optically ra re r m edium is sufficiently thick, all the energy
will be reflected back in to the denser m edium (total reflec
tion); b u t w hen the ra re r m edium takes the form of a thin
layer, the wave, not being com pletely atten u ated in it, is
partially transm itted in to the denser m edium . T h e denser
m edium “picks u p ’’ the wave and carries it further. T h e
wave is propagated in it w ith o u t a tten u atio n . T h u s w hen a
wave strikes a th in layer of the optically ra re r m edium , the
reflection ceases to be total. O f course, ray optics cannot ex
p la in this: a ray is reflected from the geom etric surface of the
m edium , and “know s” n o th in g about w hat happens beyond
the surface. Once again we discover th a t the wave n a tu re of
light is dem onstrated d u rin g prop ag atio n in a region com
parable w ith a w avelength, in this case— in a th in layer.
T h is case, however, is essentially different from diffraction
since, in a d d itio n to ord in ary traveling waves, there is also
an a tte n u ate d wave in the layer (waves th a t pass th ro u g h a
slit in a screen arc n o t atten u ated ). Figure 9 shows a wave th a t
is not a tte n u ate d in space; all its crests are of the same height.
Figures 16 and 17 show two types of a tte n u ate d wave. In the
first the oscillations arc still preserved, b u t in the second they
arc elim inated com pletely. T h is depends on the a tte n u a tin g
f»9«re 16
torce. Yigure IS shows the typical course o£ a wave that is

partYy attenuated in a layer, and then transmitted into the
denser medium where it is not attenuated. In this case there
is a considerahle decrease in the height o£ the crests.
We must note one detail in the diagram. All three sections
of the wave are smoothly joined without any discontinuity.
The slopes on both sides ol the point where they join are
the same.
T h i s is b e st in te rp re te d w ith th e ex am p le of a so u n d wave.
Since th e fu n d a m e n ta l laws of wave m o tio n are the same we
may choose as a n analogy th e case th a t is the easiest to study.
A n acoustic analogy w ill be suitable for our purpose because.
am ong o th e r reasons, phenom ena such as total in te rn a l re
flection also occur in sound waves. W e m ust first explain the
physical m eaning of the slope of the wave in this case. We
assume th a t the wave represents a v ariatio n of pressure, w hich
is a m axim um on the crests and a m in im u m in the troughs.
T h e greatest d rop in pressure occurs halfw ay betw een crest
and trough. If a curve were constructed for the d istrib u tio n of
the velocity of the air, at the points of m axim um and m in i
m um pressure it w ould be zero, an d where the pressure drop
was greatest it w ould be a m axim um . In o th e r words, the
velocity curve has the same shape as the pressure curve, b u t
is displaced th ro u g h a q u a rte r of a w avelength (Fig. 9). A t
every p o in t the velocity is defined sim ply as the slope of the
pressure curve; b u t the velocity of m a tte r can n o t suffer a
d iscontinuity on the b oundary betw een two m edia, for if it
did, m a tte r from the first m edium w ould p e n etrate in to the
second, w hich is im possible. T h e velocity curves m ust th ere
fore jo in sm oothly. By N ew to n ’s th ird law there can be no
pressure ju m p on the boundary: action m ust equal reaction.
T h e velocity cannot approach the boun d ary w ith a different
slope on e ith e r side, since th a t w ould en tail a discontinuity
in the velocity.
T h e same p rinciple can be justified for waves of p ro b a
bility am p litu d e. W e chose a sound wave for clarity: the
m athem atical q u a n titie s for w hich co n tin u ity has been estab
lished have a sim ple physical in te rp re ta tio n in the case of
sound, b u t the result will be the same.
W e have already spoken of the princip le of correspondence
betw een classical and q u a n tu m m echanics. Any concept of
classical m echanics may be transferred in to q u a n tu m m echan
ics if it does not conflict w ith the un certain ty p rin cip le. In
p articu lar, the concept of position has a m eaning, although
not, of course, at the same tim e as m om entum . It follows th a t
the concept of p o te n tia l energy is valid, provided th a t kinetic
energy is left undefined— the two canno t exist sim ultaneously
for a given state of a particle.
Quantum laws of motion 45
For sim plicity we shall consider m otion in one dim ension,
since the p o ten tial energy then depends on a single coordinate.
W h at obvious m eaning can be given to p o ten tial energy in the
wave picture, i.e., if we use the prob ab ility am p litu d e, or
the wave function? We are no longer b o u n d to consider a
given position coordinate as the coordinate of the particle
itself— it is only the arg u m en t of the wave function, the
square of which determ ines the possibility of finding the
particle at a given point.
P oten tial energy th a t varies in space will correspond to a
varying index of refraction. T h is assertion may be readily
verified. T h e sum of p o ten tial and kinetic energies is the
total energy, which is constant. C onsequently, the greater the
p o tential energy for a given total energy, the sm aller will be
the kinetic energy. A nd the sm aller the kinetic energy, the
sm aller the velocity of the particle. As we have seen, since
the w avelength is inversely p ro p o rtio n al to velocity, the m otion
of the particle in a region w ith varying p o ten tial energy
corresponds to wave propagation in an inhom ogeneous m e
d iu m where the w avelength varies. T h is in tu rn means th a t
the index of refraction varies from p o in t to point. If we call
the to tal energy E and the potential energy U, then the
kinetic energy equals E — U. O n the o th er hand, the kinetic
energy is m v 2/ 2, from which v = \ / 2 ( E — U )/m and the wave
length is A = h / m v = h/^J2m(E — U). A variable d ep ending
on a single coordinate can be conveniently p lotted on a graph,
as can also be done in the case of p o ten tial energy. Let us
consider some typical exam ples.
1. U niform field of force. T h e g rav itatio n al field on the
surface of the earth an d the electric field in a plane capacitor
are exam ples of uniform fields of force. W e know th a t po
ten tial energy is defined as the work th a t m ust be done to
b ring a body to a given point. In the case of a constant force
the work is sim ply the pro d u ct of the force and the distance
traveled along the direction of the force, so th a t the p o ten tial
energy in a constant uniform field is p ro p o rtio n al to the p ath
length, i.e., to the position coordinate. T h e g rap h of this rela
tionship is, as is well know n, a straig h t line whose slope
is clearly equal to the force, because it is num erically equal
to the work done per u n it p ath length.
2. Elastic force. T h is is the nam e given to a force th at is
p ro p o rtio n al to the distance of the body on which the force
acts from the position of eq u ilib riu m . T h e force in a stretched
spring may serve as an exam ple: the greater the extension,
the greater the force. In q u a n tu m theory we do no t encounter
bodies such as springs, b u t we see at once from the p o ten tial
energy curve th a t elastic forces are not restricted to springs.
Let us first draw the g rap h of the force as a function of the
distance. Since these are p ro p o rtio n al qu an tities, the graph
will be a straight line (Fig. 19), b u t this is still not w hat we
need. W e m ust calculate the work req u ired to displace a p ar
ticle from the origin O to some o th er position, for exam ple,
the p o in t A. It is now im possible to assert, as in the previous
case, th a t the work is simply eq u al to the pro d u ct of force
times distance, since the force is different at different points
of the path. If the force were the same everywhere, the work
w ould be equal to the area of the rectangle O B xBA . In the
present case, as may be seen directly from the sketch, it is only
half as great, i.e., it is eq u al to the area of the triangle OB A.
T h e length A B is p ro p o rtio n al to the O A, and since the area
Figure 20
equals ^ OA ■A B , it is p ro p o rtio n al to the square of OA. T h e
graph of the latter relationship is shown in Figure 20, where
the curve is draw n for displacem ents from O on either side of
the origin.
A t O (or the position of equilibrium ) there is no force on
the particle. W hen the particle is displaced, a force acts upon
it, which tends to restore it to O, so th a t the e q u ilib riu m at
this p o in t is stable. W e may now clarify the m eaning of an
elastic force: it is the force acting on a particle n ear the posi
tion of stable equ ilib riu m . If, for exam ple, an atom in e q u i
lib riu m in a m olecule is displaced, an elastic force acts u p o n it.
For sufficiently great displacem ents, the force is no longer p ro
p o rtio n al to the displacem ent, and the p o ten tial energy curve
is no longer as shown in Figure 20. However, it is often
sufficient to consider only sm all displacem ents.
3. Electrostatic force, inversely proportional to the square of
the distance. H ere again the work can n o t be taken as equal
to the pro d u ct of force and distance, since the force is vari
able. A sim ple construction such as th a t of Figure 19 is of no
help; b u t we can find the expression for the p o ten tial energy
w ith o u t higher m athem atics. A t a distance r the force equals
a/r 2 (where a is a constant of proportio n ality ) an d at a dis
tance r + Ar it is a/(r + A r)2. If A r is small, we can replace
both values of the force by their geom etric m ean a/r(x + Ar),
i.e., we take the force to be approxim ately constant in the in-
terval Ar, and so the work done in Ar equals aA r/r(r + Ar),
which is equal to (a /r ) — a/(r + Ar). W e now consider the next
interval betw een r + Ar and r + 2Ar. H ere the w ork equals
a/(r + Ar) — a/(r -f- 2Ar). A dding up the w ork done in the in
tervals (r, r + Ar) an d (r + Ar, r + 2Ar), we see th a t in te r
m ediate term a/(r + Ar) disappears. T h e same will h ap p en
if we take an o th er interval, an d so on. Finally, the w ork equals
the difference in the values of a/r at the ends of the path . If
the p o ten tial energy is defined as the w ork done in tran s
ferring the particle from infinity to a given point, then at
infinity the term a / ( r — oo) w ill vanish, and we w ill be left
w ith only a/r. T h e graph of this relatio n sh ip is given in Figure
21 .
Since the force in the given case is attractive (a is negative),
it acts in the direction of decreasing distance, i.e., against
the direction of r, and hence the p o ten tial energy curve lies
entirely below the r axis. For repulsive forces, w hich obey the
inverse square law (e.g., like charges), the curve will lie en
tirely above the r axis.
T h e form of the dependence of p o ten tial energy on distance
could be guessed in an extrem ely sim ple way. Since the force
is inversely p ro p o rtio n al to the square of the distance, and
the dim ensions of w ork are equal to the dim ensions of force
Figure 21
m u ltip lied by length, we may conclude th a t the p o ten tial en
ergy is inversely p ro p o rtio n al to the first pow er of the distance.
However, it is im possible to prove by this m eans th a t the con
stan t coefficient-—in this case a— is the same for the force and
for the work. Indeed, for an elastic force, the constant co
efficient in the p o te n tia l energy was sm aller by a factor of 2,
although the dim ensions were the same. H ence for a force
inversely p ro p o rtio n al to the square of the distance we needed
a stricter derivation.
T h e p o ten tial energy curve will allow us to m ake fu rth er
deductions m ore easily, and the reader m ust u n d erstan d th eir
significance very clearly. Figure 20 gives a p lo t of the w ork th at
m ust be done to displace a particle from the origin to a given
point, and Figure 21 plots the w ork of transferring the p a r
ticle from infinity to the given point. W e should add th a t tests
(educational, n o t physical) show th a t 90 percent of the diffi
culty in u n d erstan d in g the concepts of q u a n tu m m echanics
arise from an insufficient grasp of elem entary laws of mechan-
ics, a n d only 10 percent is connected w ith the new ideas.
Q u a n tu m m echanics is a c o n tin u atio n of classical m echan
ics. T h is does n o t m ean of course th a t it could be logically
deduced from N ew ton’s laws of m otion. A n elem ent of con
jecture m ust always exist in the creation of new theories.
T h u s, 3 years before the diffraction of electrons was d em on
strated experim entally, Louis de Broglie proposed th a t the m o
tion of electrons should ex h ib it wave properties. D eveloping
de B roglie’s idea, Schrddinger obtained an eq u atio n for the
wave function and thus created the m athem atical ap p aratu s
of q u a n tu m m echanics. W o rking com pletely independently,
H eisenberg found another, equally valuable form of q u a n tu m
m echanics. O nly later was d irect experim en tal confirm ation ob
tained. T h is does n o t m ean th a t de Broglie, Schrodinger and
H eisenberg had no experim ental basis for th eir work. O n the
contrary, an enorm ous q u a n tity of experim ental m aterial had
already been accum ulated th a t could n o t be explained by classi
cal theory.
H ow ever, q u a n tu m theory in its old p rim itiv e form did no t
ex p lain the diffraction of light. Seeking a solution for this
difficulty, de Broglie proposed a synthesis of the corpuscular
an d wave representations.
W e m ust always rem em ber th a t in tu itio n is fru itfu l only
w hen actual laws of n a tu re are discovered w ith its aid. For
one correct guess there are in n u m erab le w rong ones, gen
erally m ade by people w ishing to teach w ith o u t b o th e rin g to
learn.
L et us now re tu rn to the p o te n tia l energy curves. T h e ex
am ples ju st considered (the second and especially the th ird )
are extrem ely im p o rta n t in q u a n tu m m echanics, b u t it is
im possible to o b ta in deductions from them by sim ple m eans
w ith o u t higher m athem atics. W e shall, therefore, consider one
m ore curve, w hich is not enco u n tered in reality, b u t which
helps us to u n d erstan d all the fu n d a m e n tal laws of m otion
in q u a n tu m m echanics.
4. B o x w ith im penetrable lualls. T h e “b o x ” th a t we shall
consider is one-dim ensional in form, i.e., a straig h t line along
w hich a particle can move freely w ith o u t p erform ing work
or having work done on it by extern al forces. T h is corre
sponds to the flat bottom of a box. W h en m oving along the
bottom of the box the particle does no t change its p o ten tial
energy. H ow may we define the in p e n etrab ility of the walls
physically? W e m ust assume th a t the w ork needed to pene
trate the wall, how ever slightly, is infinite: b u t we know th at
the work done on the p article an d the p o ten tial energy can
be represented by the same curve, which m ust rise vertically
up at the walls of the box. T h e p o te n tia l energy curve for
an elastic force also tends to infinity, b u t gradually. In the
la tte r case, infinite w ork m ust be done to rem ove the particle
an infinite distance from the origin. In the case of the box, in
finite w ork is req u ired to rem ove the particle even the sm allest
distance beyond the lim its of the box (Fig. 22a). W e can now
establish w hat the curve m ust look like if by doing a finite
am o u n t of work we can p e n etrate beyond the wall. T h e g rap h
Figure 22
rep resenting this a m o u n t of w ork will rise vertically at the
b o u n d ary of the box, an d then become h o rizontal again, since
no m ore work is necessary for fu rth er displacem ent (Fig. 22b).
O u r know ledge is now sufficient to consider all the m ore
im p o rta n t cases of m otion of a q u a n tu m particle. W e shall
have to seek the wave function according to the form of the
p o te n tia l energy curve. T h is is one of the fu n d am en tal p ro b
lems of q u a n tu m mechanics, ju st as finding the trajectory from
the form of the p o te n tia l energy is a fu n d am en tal problem
of classical mechanics. T h e wave function does not, of course,
replace the trajectory in any way; we are no t dealing w ith
physical waves b u t w ith pro b ab ility am plitudes.
In Figures 19-22, the total energy could be p lo tted together
w ith the p o te n tia l energy. T h e total energy has a d irect m ean
ing as a m echanical q u a n tity ; p o ten tial energy is only needed
for finding the wave function. T h e total energy is conserved;
i.e., being the same at all points it has a g rap h w ith the sim plest
possible form : a straig h t horizontal line.
Flow far can this line be continued? L et us take, for exam ple.
Figure 22b. W e assume th a t the total energy is less th an the
d e p th of the “p o te n tia l w ell,” i.e., less th an the work needed
to get the particle o u t of the well. In classical m echanics the
particle cannot get o u t of the well at all: the entire region of
classical m otion lies betw een the points A and B (Fig. 23). T o
A B
«>*
Figure 23
the left of A an d to the rig h t of B the total energy is less th an
the dep th of the p o te n tia l well. H ence outside the well the
kinetic energy is a negative q u an tity . H ow ever, this is im
possible— kinetic energy is of course h alf the p ro d u c t of the
mass (a positive q u a n tity ) by the square of the velocity (also
positive). N egative kinetic energy w ould correspond to an
im aginary velocity th at, of course, the p article can n o t have.
Classical m otion w ith total energy less th an the d ep th of the
p o te n tia l well is thus lim ited by the size of the well, an d the
p a rticle m ust rem ain in the well.
In q u a n tu m m echanics the to tal energy is well defined, b u t
because of the un certain ty principle, the p o te n tia l and kinetic
energies are not separately well defined; these q u an tities can n o t
exist sim ultaneously.*
T h is is connected w ith the fact th a t position an d velocity can
not be sim ultaneously defined, so th a t it is im possible to assert
th a t to the left of A or to the rig h t of B or anyw here else at all,
the particle has any given velocity. T h e lim itatio n im posed by
classical m echanics is thus rem oved: a p article may perfectly
well a p p ea r in a classically forbidden region.
In o th e r words, the wave fu n ctio n for the particle does not
become zero im m ediately beyond the lim its of the well— there
is a finite p ro b ab ility of finding the particle th ere too. If we
use the wave analogy as we have done before, then here we
m ust draw a parallel w ith total in te rn a l reflection. W e have
already said th a t a particle w ith total energy E corresponds
* Wc note that in quantum mechanics it would be possible to define the
mean values of the potential and kinetic energies for the whole region
of motion where the wave function is not zero. These mean values do exist
simultaneously and satisfy the same relationships as in classical mechanics.
to the de Broglie w avelength A = h /m v — h / \ / 2 m E in the well

w here U = 0, an d A = h /y/2 m (E — U) outside the well. H ow
ever, since U > E the la tte r q u a n tity is im aginary, w hich turns
ou t to correspond to the a tte n u atio n of the wave as in Figure
17. A light wave is sim ilarly a tte n u ate d in the optically rarer
m edium in the case of total in te rn a l reflection. W ith in the
fram ew ork of ray optics, which corresponds to classical m e
chanics, the ray of light does not p en etrate the optically ra re r
m edium if the angle of incidence is greater th an the angle of
total in te rn a l reflection. T h e laws of wave optics tem per this
categorical p ro h ib itio n . Instead, we find th a t an atte n u ate d
wave may still be propagated in the forbidden region of
classical mechanics. It m ust be em phasized th a t this analogy
w ith optics is based only on the sim ilarity between the laws
of wave m otion; there is no real physical sim ilarity. In the
case of total in te rn a l reflection of light we have dam ped os
cillations. O n the other hand, the wave function in the clas
sically forbidden region falls off sm oothly (cf. Figs. 17 and 23).
T h e analogy w ith the general laws of wave m otion may
nevertheless be taken fu rth er. A t the beginning of the ch ap ter
it was shown th a t waves m eet sm oothly at any bou n d ary
separating m edia— one passes in to the oth er w ith o u t ju m p or
break. T h e wave function is shown in Figure 23 by a d o tted
line. For a given total energy, the deeper the well, the faster
the function is a tte n u ate d outside it. In the lim itin g case of an
infinitely deep well^or “ box,” such as in Figure 22a, the func
tion "simply vanisheT on' the"boundary. In o th er words, even a
q u a n tu m p a rticle cannot get o u t in this case.
L et us consider this very sim ple case first. It shows th a t in
the well, the energy of the particle is far from arb itrary . W e
know th a t an oscillating q u an tity is zero w hen the phase of
the wave equals 0, 7-, 2ir, etc. H ence if the wave function be
comes zero at the boundary, the length of the well m ust be
eith er half the de Broglie w avelength, o r a whole w avelength,
or one-and-a-half w avelengths, or two w avelengths, i.e., any
integral n u m b er of half wavelengths. Let us denote this integer
by n. T h e length of the box m ust therefore be a — \nX , bu t
since X = h /\/2 m E , the energy of the particle in the box m ust
be equal to one of the values E n = n 2h 2/8 m a 2 and can take no
o th er values.
T h is result is of fu n d am en tal im portance. It shows th a t the
energy may not always be a continuous en tity as in classical
m echanics. T h is is called the quantization of energy* and the
values assum ed are called energy levels, since all the possible
values may be arranged one above the o th er as levels.
If the well is of finite depth, as in Figure 22b, the position
in p rinciple does not change. As long as the total energy is
less than the depth of the well, the wave function m ust join
u p sm oothly on both boundaries w ith an a tte n u ate d curve
of the form shown in Figure 17. A lthough the length of the
well no longer has to be a whole n u m b er of half waves (the
am p litu d e is not zero at the boundaries of the well), it is
clear th a t a sm ooth connection cannot be obtained for every
w avelength. T h e heights and slopes of the curve m ust be the
same on e ith er side of the boundary. T h ese so-called boundary
conditions w ill also restrict the energy E to certain values
b u t these are not expressed so sim ply in term s of n as in the
case of an infinitely deep well. W h at is still m ore im p o rtan t is
th at for a well of finite depth the n u m b er of energy levels is
also finite. T h e last of these levels lies a little way below the
u p p e r boundary of the well.
W hen the energy of the particle is greater than the d ep th of
the well, the position changes considerably. H ere the wave
fu n ction outside the well is also not a tten u ated , since there too
E > U, b u t a sm ooth connection of this function w ith the
fu n ction inside the well is possible for any value of the energy.
An u n a tte n u a te d wave line, of course, may start w ith any
slope, so th a t the wave function inside the well may be con-
* The Latin word q u a n t u m means ‘‘amount.” A system with quantized
energy may receive or give up only definite amounts, q u a n t a , of energy
corresponding to the difference between the possible levels. Hence the term
“quantum mechanics” is used.
ncctcd w ith the function outside for any value of the energy.
It follows th a t the energy in this case does n o t assume a n u m
ber of discrete values, b u t varies continuously as in classical
mechanics.
It is easy to observe the basic difference betw een these two
cases. W h en the energy is less th an the d ep th of the well, the
p ro b ab ility th a t the particle w ill be very far from the well is
extrem ely small, and tends to zero in the lim it of very great
distances. H ere the wave function is atten u ated . T h is means
th a t the particle can n o t leave the well com pletely. Classically,
it can move only w ith in the lim its of the well, while in q u a n
tum theory it can get o u t of the well, b u t only “ tem porarily.”
H ence we say th a t a q u a n tu m particle is bound to the well,
or th a t it is in the bou n d state. It turns ou t th a t only b o u n d
states are quantized. W hen the energy lies above the u p p er
b o undary of the well, the wave function outside the well is no t
a tte n u ate d , and the p ro b ab ility of a particle m oving away to
an infinite distance is now certainly not zero. T h is means, how
ever, th at it m ust go o u t of the well and n o t re tu rn to it.
Classically, this m otion corresponds to an u n b o u n d state, the
energy of w hich varies continuously.
T h e assertion expressed here does not refer only to “sq u are”
wells of the form show n in Figure 22a, b. T h e b o u n d state
allows only a n u m b e r of discrete values of the total energy,
b u t the free state allows a continuous range of values. T h e set
of all possible values of the energy of a given system is called
its energy spectrum . T h e b o u n d state has, as we say, a discrete
spectrum , and the free state has a continuous spectrum . T h is
term inology bears some relatio n to the o ptical spectrum , which
we shall discuss later.
Interestingly, the term “spectrum ” was applied to m ath e
m atical problem s of wave m otion by m athem aticians long be
fore the creation of q u a n tu m mechanics. T h e well-known ex
tern al resem blance betw een the line spectrum observed in
optics and the set of points or dashes rep resen tin g a discrete
sequence of num bers clearly helped to p ro m p t this usage.
T h e re are also wells in w hich the particle has only b o u n d
states. W e have already considered a very sim ple exam ple— an
infinitely deep rectan g u lar well. A n o th er exam ple is the po
ten tia l well corresponding to an elastic force. T h e p o ten tial
energy curve may in p rinciple go as high as we please, w hile
the total energy c an n o t be greater th an the p o te n tia l energy
everywhere. A horizontal line m ust intersect the p o te n tia l en
ergy curve som ew here. H ence here too we m ust o b tain only
discrete energy levels. U nlike the case of an infinitely deep
re ctan g u lar well, the wave fun ctio n w ill n o t becom e zero at
the p o ints w here the line rep resen tin g the total energy cuts
the p o te n tia l energy curve, b u t a particle w ith finite energy
w ill n o t be able to get m ore th a n a lim ited distance away from
the well.
T h e energy spectrum in this case has an exceptionally simple
form , w hich consists of an infinite n u m b e r of e q u id istan t levels
(Fig. 24). T h e distance betw een the levels may be o b tain ed as
follows. L et us forget q u a n tu m theory for the m om ent. An
elastic force gives rise to sim ple harm on ic oscillation of a p a r
ticle w ith frequency v. W e shall borrow this ch aracteristic of
oscillatory m otion from classical m echanics, alth o u g h no h a r
m onic oscillations occur in the q u a n tu m case. T h e distance
betw een the q u a n tu m levels then equals hr, and the energy of
the lowest level is h r/2 . H ence the energy levels are given by
E„ = (n + \)h v w here n is an integer.
W hy does the lowest or ground state} as it is called, n o t lie
at the b ottom of the well; i.e., why is the g ro u n d state energy'
n o t eq u al to zero? T h is is easy to u n d e rstan d from the u n cer
tain ty principle. W ith strictly zero energy it w ould have strictly
zero m om entum . T h e u n c ertain ty of position w ould then be
infinitely great; i.e., the particle could be at any distance from
the well; b u t it is bou n d to the well. H ence b o th the position
and the m o m en tu m of the particle in the g ro u n d state as in
all the others are som ew hat sm eared, alth o u g h least of all in
the ground state (cf. the lowest level in Fig. 24). In the g ro u n d
state of a q u a n tu m oscillatory m otion, the u n certain ties of po
sitio n and m o m en tu m are the least possible an d are h alf as
Figure 24
great as in the case of free m otion. T o m ake this m ore precise,
the energy of a particle is, classically,
E = \m vl + \k x 2
\2 P
-m + 2W
Now, in the g ro u n d state, the energy an d m o m en tu m are re
lated by the un certainty re la tio n
1 h_
px =
2 2t t
T hus’ £ - i ( s ) , ^
T h is is illu strated in Figure 25.
? + 5
b ’
Figure 25
It is clear th a t the m in im u m energy occurs w hen
1 h 1
2 2tt yjkm
1 ( h \ * \ 1_ V T m 1 H 1 = 1 h_ fk_
4 \2 7 t/ 2 m \ h 2 2 2ir y/km 2 2tt \ m
2 2t t
T h e classical frequency of oscillation is given by
Eg = \hv
Eg is the m in im u m energy consistent w ith the u n certain ty
p rinciple.
W e have already in d icated th a t atom s in a m olecule are
b o u n d by forces resem bling elastic forces. T h e result o b tain ed
here, therefore, has an im m ediate ap p lic atio n to the energy
of m olecular oscillations even though m olecules can n o t be
represented by infinitely deep wells. T h e re is always a finite
energy of dissociation of m olecules in to atoms.
U n d e r these conditions the p o te n tia l energy curve resem bles
th a t of Figure 22b, b u t w ith the sh arp corners ro u n d e d off.
A bove the u p p e r b oundary, as usual, the energy sp ectru m be
comes con tin u o u s— this is the state of m olecules th a t have dis
sociated in to atoms. In the well there are u p to a h u n d re d
levels, the low er ones being e q u id istan t from each o th e r so
th a t F igure 24 is a good a p p ro x im a tio n to the tru e situ atio n
for a large n u m b e r of the low er levels.
T h e discrete n a tu re of the energy levels and, in general, the
discrete n a tu re of the states, have a direct analogy in o th er
cases of wave m otion. T h u s an infinitely deep square-w ell p o
te n tia l corresponds exactly to a string w ith rigidly fixed ends.
An in teg ral n u m b e r of h alf w avelengths m ust fit in to the
length of the string. T h e fu n d am en tal tone corresponds to one
half wave, the first overtone corresponds to two, and so on.
A well of finite d ep th may be com pared to a string fixed not
rigidly b u t elastically, for exam ple, a string fixed to two long
flexible rods. T h e energy spectra of particles in the well cor
respond to the frequency spectrum of the oscillations of the
string.
De B roglie’s idea was fo rm u lated in relation to the free
m otion of particles. Schrodinger proposed th a t in the case of
bound m otion, phenom ena arise th a t are analogous to the
oscillations of strings, i.e., a discrete set of possible states.
Waves of any w avelength are possible in an infinite string,
which corresponds to a continuous spectrum . Even before
Schrodinger, it was know n th a t energy may be quantized and
th a t a p p ro x im ate m ethods existed, proposed in 1913 by Bohr,
for finding the energy levels, b u t only Schrodinger was able to
deduce q u a n tizatio n n a tu ra lly from the general principles of
wave m otion. A t the same time, Schrodinger’s wave eq u atio n
in the lim itin g case of very sm all wavelengths leads to the
classical laws of m otion, ju st as ray optics can be obtained
from wave optics in the lim iting case. T h u s H a m ilto n ’s optical-
m echanical analogy (see C h ap ter One) is considerably ex
tended; it operates n o t only w hen optics is reduced to rays
and m echanics to trajectories, b u t in the wave region too.
W hile in H a m ilto n ’s tim e (1825) this analogy may have been
regarded as a m athem atical curiosity, after Schrodinger’s dis
covery in 1925 it acquired a deep physical significance.
T h e general properties of wave m otion allow even m ore
im p o rta n t deductions. For exam ple, it is well know n th at the
greater the n u m b er of “nodes” (nonoscillating points) on a
string, the h igher the frequency of the string. W hen the length
of the string is exactly one-half w avelength, there are no such
points. T h is is the fun d am en tal frequency of the string. T h e
first overtone corresponds to one node, an d so on. In a sim ilar
m anner, the m ore “nodes” or “zeros” the wave function has,
the hig h er the energy level of the particle. T h is is easy to
u n d erstan d : the m ore nodes (or zeros) there are, the shorter
the de Broglie waves; b u t the w avelength is inversely p ro
p o rtio n a l to the velocity. T h e velocity, w hich is in inverse
ratio to the w avelength, is in direct ratio to the n u m b er of
zeros (or nodes) of the wave function. T h u s, the energy in
creases w ith the n u m b e r of nodes.
Let us now apply the wave analogy to a question th a t was
treated at the beginning of this chapter. We said th a t in a
th in layer of an optically rare substance lig h t may be p ro p a
gated at an angle greater than the angle of total in te rn a l re
flection. W e likened the incidence of a wave at such an angle
to the incidence of a particle on the wall of a p o te n tia l well
of finite d ep th . I t is now easy to see w hat w ill correspond to
the th in layer— a fairly sm all “p o te n tia l b a rrie r” beyond which
there is once again a region of low er p o ten tial energy. For a
particle m oving according to the classical laws, it does n o t m a t
ter in the least w hat lies beyond the b arrier: the particle can
no t p en etrate the b arrier. H ow ever, in the case of q u a n tu m
m otion, the picture is q u ite different.
For o u r discussion we shall not choose the idealized case
of a rectan g u lar b arrier, b u t shall tu rn im m ediately to a real
physical problem . W e shall begin by re m in d in g the reader
w h at is m eant by the alp h a decay of a radioactive nucleus. In
such decay, a helium nucleus is spontaneously ejected from a
heavy nucleus. T h e helium nucleus consists of two protons and
two n eu tro n s and is called an alp h a particle. T h e read er may
ask: why a helium nucleus and not, say, a single p ro to n or
n eu tron? T h e reason is th a t nuclear forces, alth o u g h very large,
become satu rated , like chem ical valency forces. In an alp h a
particle, the nuclear forces are highly satu rated , and the p a r
ticle is com paratively weakly b o u n d to the rest of the nucleus.
In the case of an in d iv id u a l p ro to n or n e u tro n , the n u clear
forces are n o t satu rated and hence these particles are strongly
b o u n d to the rem ain in g protons and neu tro n s in the nucleus.
T h ey can n o t escape from it spontaneously, unless ex tern al
energy is supplied to the nucleus.
Let us now try to describe the ap p ro x im ate form of the p o
ten tia l curve for an a lp h a particle in the nucleus. B oth the
nucleus and the alp h a particle carry positive charges. H ence
there is an electrostatic repulsive force betw een them , at least
w hen they become separated by a distance at which the n u clear
forces (which b in d strongly b u t act only over short distances)
no longer operate. T h e p o ten tial energy curve for a repulsive
force has the same form as the curve in Figure 21 b u t, as we
said at the time, lies above the r axis.
U n til it escapes, the alp h a particle is b o u n d to the n u
cleus; i.e., it is in a p o ten tial well, the form of w hich we do
n o t know precisely. However, since nuclear forces act over
short distances, the walls of the well m ust be com paratively
steep (in com parison w ith the long-range, repulsive C oulom b
force). T h is form of the p o te n tia l energy curve for the nuclear
forces shows th a t the particle w ill cease to experience nuclear
forces once it leaves the lim its of the nucleus. M ore precisely,
this is the definition of the “boundary of the nucleus.”
T h e form of the p o ten tial curve as a whole is shown in
Figure 26. T h e broken line indicates the ap p ro x im ate place
w here the electrical forces begin to prevail over the nuclear
ones. T h e diagram also shows the m agnitude of the to tal en
ergy. A t an infinite distance from the nucleus this m ust lie
above the p o te n tia l energy curve so th a t the alp h a particle
Figure 26
can have a positive kinetic energy. O therw ise it w ould always
rem ain b o u n d in the nucleus, like the p article in the po
ten tial well in Figures 22b and 23. T h e energy of an in d iv id u al
p ro to n or n e u tro n lies on a curve sim ilar to Figure 26 b u t be-
low the r axis. T h is indicates th a t it is impossiblcTfor it to
escape from the nucleus. T h e fact th a t an alp h a p article has
an excess of energy sufficient for it to escape is explained, as
we have said, by the satu ratio n of the n uclear forces w ithin
it. T h a t is why the well is shallow er for alp h a particles th an
for in d iv id u al nucleons (protons or neutrons).
Between A and B (Fig. 26) the total energy is less th an the
p o tential. If the m otion of the alpha particle obeyed the laws
of classical m echanics, then for the given energy it could no t
cross the region A B nor escape from the nucleus at all. In
q u a n tu m m echanics, however, the alp h a particle can pen etrate
the b arrier; i.e., it can enter the classically fo rb id d en region
and move out beyond the barrier.
T h e passage of the alp h a particle th ro u g h the b a rrie r is
analogous to incom plete reflection of light from a th in layer
of optically rare m aterial; b u t it m ust n o t be assumed th a t it
can easily get past the b arrier. If th a t were so, an alp h a particle
w ould never be found in the p a re n t nucleus at all. In fact the
wave fu n ctio n suffers such strongo a tte n u a tio n across the b a rrie r
__
th a t the pro b ab ility of crossing it and escaping from the n u
cleus is extrem ely small. If we assume th a t a particle in the
nucleus “ru n s ” from one side to the other, then each tim e
it “h its” the side it has one chance in 1039 of og ettingO out. O n
the terrestrial tim e scale, this w otdd correspond to a prison
sentence of 1010 years, i.e., 10,000 m illion years for the alp h a
particle.
U nlike a prisoner serving a fixed term , each tim e the p a r
ticle “ h its ” the side, the probability of escape, alth o u g h very
small, is always the same. A particle may rem ain in the n u
cleus a very short tim e or a very long tim e. It is com pletely
im possible to predict in advance ju st w hen a given alp h a p a r
ticle will escape, ju st as it is im possible to p red eterm in e at
w hat p o in t a given electron will strike the p h o tographic plate
in the diffraction experim ent. T h e probabilistic n atu re of the
law of alp h a decay is a d irect consequence of the uncertainty
principle.
In a d d itio n to long-lived radioactive nuclei, there are some
th a t decay on the average in 10-5 seconds. O n the nuclear
scale, this is also a very long tim e: there is one chance in 1017
of the particle escaping every tim e it hits the side. T h is differs
from the previous case by a factor of 1022. T h e energy of the
short-lived nucleus, which it transm its to the alp h a particle,
is only twice as great as th a t of a long-lived one (two and
1022) ! N o classical laws could explain such a strong dependence
of the tim e of decay on the energy. In q u a n tu m mechanics
the p e n etrab ility of the b a rrie r is calculated in a com pletely
n a tu ra l m anner. T h e fu n d am en tal n a tu re of the law is deduced
even w ith o u t taking the radius of the nucleus in to account;
the only terms req u ired are the charge of the nucleus, the
velocity of the escaping alp h a particle and, of course, P lanck’s
constant. If we carry out the form al process of going to the
lim it of classical m echanics by lettin g P lanck’s constant tend
to zero, the probability of alpha decay becomes zero. H ence
it w ould be hopeless to try to deduce the law of alpha decay
somehow on the basis of classical ideas.
T h e q u a n tu m law of alpha decay was discovered in 1927 by
Gamow, C ondon and G urney, independently of each other.
T h is was one of the first trium phs of the young science of
q u a n tu m mechanics, w hich was still at th a t time n o t univer
sally recognized.
Motion of electrons in an atom
In p o p u la r accounts the atom is represented by a “cocoon”—

i.e., a nucleus su rro u n d ed by the trajectories of electrons. A t
one tim e the structure of the atom was actually supposed to
have this form . T h e nucleus was discovered in 1911 by R u th e r
ford, and in o rd er to explain why the electrons did n o t fall into
it, it was n a tu ra lly assumed th a t they m oved in orbits like
the planets aro u n d the sun. A fter all, N ew to n ’s law of gravi
tatio n and C o u lo m b ’s law of attractio n seem very sim ilar. In
both cases the force is p ro p o rtio n al to the square of the dis
tance.
H ow ever, im m ediately the follow ing difficulty arose: an
electron m oving in an o rb it experiences a centrifugal accelera
tion. From the theory of electrom agnetism it is know n th a t
an accelerating charge m ust em it electrom agnetic waves th a t
g radually d ra in away its energy. I t follows th a t an electron
m oving in an o rb it w ould finally have to fall in to the n u
cleus.
T h is deduction is in striking conflict w ith experience:
atom s are stable and electrons do not fall in to the nucleus;
hence the p lan etary m odel of the atom is inadequate.
Nevertheless, in 1913 B ohr found an extrem ely satisfactory
solution for the problem : he supposed th a t in spite of the
laws of electrodynam ics there are orbits in w hich an electron
em its no rad iatio n , and he gave a sim ple rule for finding where
these m ust be. B ohr was unable to justify this rule theoreti-
Motion of electrons in an atom 65
cally, b u t he guessed th a t these separate discrete orbits were
somehow connected w ith the then still unknow n q u a n tu m
laws of m otion. T h e peculiarity of q u a n tu m m otion was re
vealed here by the fact th a t o u t of all the orbits th a t could be
im agined, only certain ones were possible. In contrast, the
orbits of the planets could be q u ite different and the laws of
classical m echanics w ould not be contradicted. T h e peculiarity
of q u a n tu m m otion lies in the fact th a t only certain states of
m otion are possible in the atom .
L ater, w hen q u a n tu m m echanics was created, it tu rn e d out
th a t B o h r’s hypothesis of stable orbits followed as an ap p ro x i
m ate rule. O riginally B ohr him self used the classical laws of
m otion in conju n ctio n w ith the alien postulate of the stability
of certain select orbits.
Even in this im perfect form, the theory had a rem arkable
success. T h e spectrum of the hydrogen atom (i.e., the set of
all the optical frequencies it radiates), followed q u ite n atu rally
from it. Long before B ohr, B alm er had fo u n d an em pirical
form ula for the frequencies in the hydrogen spectrum , and
B ohr deduced this form ula from his own postulates of m otion.
T h e first postulate stated th a t the an g u lar m om entum (see
C h ap ter Tw o) of an electron in an o rb it is an integral m u ltip le
of P lanck’s constant divided by 2 tt. T h e second postulate was
th at in a tran sitio n from one o rb it to an o th er lig h t is ra d i
ated w ith a frequency eq u al to the energy difference betw een
the orbits, divided by h.
W hy are there such orbits? O nly m odern q u a n tu m m echan
ics can answer this question. B ohr him self could no t do it,
and hence he called his supposition a postidate. H ow did he
guess th a t P lanck’s constant m ust be divided by 2-n- in order
to o b ta in the angular m om entum in the orbit? A ccording to
his own words, no o th er coefficients w ould fit B alm er’s for
m ula. W hat, then, of the second postulate? By 1913 it was
know n th a t light is em itted an d absorbed as q u a n ta of energy
hv. H ence the second postulate sim ply expresses the law of
conservation of energy on emission and ab sorption of electro-
m agnetic waves. W e shall have m ore to say on the origin of
these light q u a n ta an d th eir relatio n sh ip to the wave theory
of light.
W hen attem pts were m ade to apply B o h r’s theory to atom s
m ore com plicated than hydrogen atom s agreem ent w ith ex
p erim en t was by no m eans always satisfactory. M oreover,
B o hr’s theory was com pletely unable to explain why a hydro
gen m olecule consisting of two protons and two electrons (or
even the positive ion of the hydrogen m olecule, in which
there are two protons an d one electron) could be stable.
In the previous ch ap ter it was shown th a t a b o u n d particle
cannot have ju st any energy; its energy is quantized. A n elec
tron b o u n d in an atom obeys this ru le perfectly. T h is follows
w ith o u t special postulates from the general laws of q u a n tu m
mechanics.
H ow ever, in q u a n tu m m echanics m otion does no t take place
in trajectories, and even the concept of a definite p a th be
comes m eaningless. T h is is clear from the u n certain ty rela
tionships, from which it follows th a t an electron in an atom
has no trajectory. In fact the lin e a r dim ensions of the atom
are of the o rd er of 10~8 cm. T h is value m ust be taken for x
in the u n certain ty relationship. T h e n Ap = h /A x or 6.6 x
10~10, an d since the mass of an electron is 9 x 10-28 g, the
u n certain ty in the velocity is 0.75 X 109 cm /sec. T h e u n cer
tainty in the kinetic energy can now be fo u n d from the for
m ula
AE = \m (A v)2 = 2.2 X 1 0 -10ergs
Since one electron-volt equals 1.6 X 10~12 ergs, the u n certain ty

in the energy is ab o u t 140 eV.
B ut the p o te n tia l energy of the electron in the field of the
nucleus is far less. T h is too is q u ite easy to estim ate. T h e force
on the electron due to the nucleus is e2/ r 2 by C o u lo m b ’s law,
and the corresponding p o te n tia l energy is —e2/ r . If we substi
tute Ax for r an d 4.8 x 10-10 absolute electrostatic u n its for
the charge c, we find th a t the p o ten tial energy is of the order
of 2.5 X 10-11 ergs or ab o u t 14.5 eV. W e have, however, al
ready seen th at the u n certain ty in the kinetic energy is 140 eV.
How are we to u n d erstan d this? Clearly, we cannot divide the
energy of m otion of the electron in an atom in to kinetic and
p o tential energy. For if the kinetic energy were fo u n d to ex
ceed the p o te n tia l energy, the total energy in Figure 21 w ould
lie above the r axis, w hich means th a t the kinetic energy of
the electron is positive even at infinity. T h e electron will thus
escape from the atom , which is in conflict w ith the supposed
stable existence of the hydrogen atom . It follows th a t we are
no t allow ed to divide total energy into kinetic and p o ten tial
energies w hen we seek an estim ate of the u n certain ty in the
position of the trajectory of the electron.
H ence the supposition th at there is a definite electron
trajectory in the atom leads to variables with uncertainties
th a t are several times greater than the variables themselves. It
follows th a t there can be no such trajectories.
In view of the great im portance of this result we shall try
to deduce it again som ew hat differently. In order th a t the
electron be b o u n d to the nucleus, the kinetic energy m ust be
less than the po ten tial, i.e., less th an 2.5 x 10-11 ergs. H ence
it is easy to see th a t the velocity cannot exceed 2.3 x 108 c m /
sec. T h e de Broglie w avelength is h /m v , so th a t it is b o u n d
to be greater than 10-7 cm; b u t this is ten times greater than
the size of the atom itself, an d so it is clear th a t if the m otion
takes place in a region th a t is ten times sm aller th an the cor
responding w avelength it is im possible to speak of any trajec
tory. T h e atom is thus a typical quantum -m echanical object.
T h e rep resen tatio n of the atom as a tangle of trajectories is
sim ply a symbol, som ething q u ite conventional an d arb itrary .
T h e actual properties of the m otion of an atom ic electron
are described by q u a n tu m mechanics, and its energy corre
sponds to one of the possible levels in a p o ten tial well of the
form shown in Figure 21. H ow ever, now there is n o th in g left
th a t resembles a trajectory. If we attem p t even to represent the
atom on paper, we m ust su rro u n d the nucleus by a “sm eared”
cloud. T h e density of the cloud at a given p o in t m ust corre
spond to the probability of finding the electron at th a t point,
i.e., to the square of the am plitude of the wave function. It is
not the electron itself that is smeared, b u t its wave function.
It follows from the uncertainty principle th a t an atomic
electron of given energy has an undefinable position. W hat
will happen if we still try to measure it? T h e linear dimensions
of the atom are of the order of 10~8 cm, and in order for “ posi
tio n ” to have some m eaning, we m ust m easure it to b etter than,
say, 10~9 cm.
T o obtain an accuracy of 10~9 in the m easurem ent of posi
tion, we have to direct at our atomic electron another electron
w ith a de Broglie wavelength of 10-9 cm. If they collide, then
the atomic electron has actually been recorded in a sufficiently
small region of space.
T h e “m easuring” electron has a velocity of 0.7 X 1010 c m /
sec— this is easily calculated from its de Broglie wavelength.
T h e energy is also simple to calculate— 14,000 eV. W hen an
electron w ith so much energy strikes an atomic electron, it
will transfer a large fraction of its energy to the latter. How
much, precisely? It is impossible to answer this question, since
the im pact takes place somewhere in a region of 10~9 cm. It
is equally impossible to say anything more precise about it
since that was the de Broglie w avelength of the incident elec
tron. Consequently we do not know exactly how the process
of im pact took place; did the electrons collide “head-on” or
only “touch” each other lightly? As a result of the m easure
m ent, the electron th at we have been exam ining has obtained
an indeterm inate m om entum (indeterm inate energy). T h is
shows how the determ ination of position in q u an tu m m echan
ics differs from the process of applying a ru ler to a motionless
body, which is w hat we understand by m easurem ent in classi
cal physics. Q uantum m easurem ent has a considerable effect on
the m easured object, and this effect increases w ith the increas
ing accuracy of the m easurem ent. In classical mechanics it is
always assumed that m easurem ent has no influence at all on
the system to w hich it is applied. O bserving a p lan et does not,
of course, produce any difference in its m otion; b u t the same
does n o t apply to the m easurem ent of electrons.
T h e unknow n m om entum transm itted d u rin g the m easure
m ent of position is ju st th a t req u ired by the u n certain ty p rin
ciple for the given accuracy of m easuring the position. W e
have already show n th a t the u ncertain ty Ax in the position
is of the order of A. T h e oncom ing particle may transm it any
m om entum from zero to its total m om entum p, so th a t the
un certainty Ap in the m om entum equals p. By de B roglie’s re
lationship p = h/X , and hence ApAx = pX — h.
It is som etim es asked: if particles were discovered th a t were
m uch lig h ter th an electrons, w ould th a t n o t im prove the ac
curacy of our m easurem ents on electrons? W e have just seen,
however, th a t the mass of the particle did n o t come in to our
discussion at all. Provided th a t P lanck’s constant has a finite
value, the process of m easurem ent will d istu rb any system,
an d it w ill be im possible to control any disturbance. O f course,
for m acroscopic systems the disturbance is negligible, b u t for
hy p othetical particles lighter than electrons everything w ill be
ju st the same as for electrons. T h e same un certain ty re la tio n
ship ApAx = h w ill apply to these particles, so th a t w hen they
collide w ith electrons, the accuracy of m easurem ent will n o t be
im proved. M oreover, it is already know n th a t there are p a r
ticles “lig h te r” th an electrons; for exam ple, photons have zero
mass.
T h e analysis of im aginary experim ents, in clu d in g th a t of the
two colliding electrons, led H eisenberg and B ohr to the for
m u latio n of the uncertainty principle. Clearly it is no t some
defect in the m ethod of m easurem ent th a t is u n d e r discussion,
b u t the very n a tu re of the m easuring process as applied to
the microcosm.
W e have already rem arked th a t E instein tried to find an
im aginary e x p erim en t th a t w ould circum vent the u n certain ty
principle. In one instance he proposed the use of g rav itatio n al
forces. H ow ever, B ohr po in ted o u t th a t the grav itatio n al field
d u e to the light waves also taking p a rt in E in stein ’s im aginary
ex perim ent w ould have to be taken in to account, and this
b ro u g h t back the un certain ty p rin cip le ApAx h.
If we analyze the source o£ o u r conviction th a t classical ob
jects always move along trajectories, we find th at this is con
nected w ith the possibility th a t u nrestricted m easurem ent has
no effect on the objects. For q u a n tu m objects this is im
possible not because of any defects in ex p erim en tal m ethods,
b u t because, an d only because, P lan ck ’s constant has a finite
value. T h e re is therefore every fo u n d atio n for concluding th at
in a given state an electro n ’s position an d m o m en tu m can n o t
b o th be physically real at the same tim e. W e may have one
or the other, or of course both, b u t only w ith some u n cer
tainty. It is pointless to ask if they can n o t be m easured to
gether because they do not exist sim ultaneously or, conversely,
if they do not exist together because they can n o t be m easured
sim ultaneously. It is one an d the same assertion.
T h e purely negative statem ent of the u n certain ty p rin cip le
is not in itself sufficient for fo rm u latin g the system of eq u a
tions of q u a n tu m m echanics. H ere the correspondence p rin
ciple is of considerable im portance. A ccording to this p rin
ciple, the same q u an tities are conserved u n d e r sim ilar co n d i
tions in b oth q u a n tu m and classical m echanics. For exam ple,
we have already noted th a t an g u lar m o m en tu m is conserved
in a central force field.
T h e significance of the correspondence p rin cip le may also
be seen from the follow ing exam ple. Suppose th a t we have
to m easure the energy of a quantum -m ech an ical system. T h e
m easurem ent will be perform ed w ith an a p p aratu s th at obeys
the laws of classical m echanics. If the law of conservation of
energy holds good in the whole system, consisting of th e object
and the ap p aratu s, the energy im p arted to the a p p aratu s m ust
e q u al the energy given up by the object, i.e., the q u an tu m -
m echanical system. Clearly, if the conservation law did not
apply, this d ed u ctio n w ould not be valid. It has no t been ob
tain ed by p u re guesswork b u t on the basis of ex p erim en tal
facts th a t confirm the ap p licab ility of the law of conservation
of energy on the atom ic scale. T h e same applies to the o th er
conservation laws, e.g., those of an g u lar an d lin ear m om entum .
O ne can fo rm u late q u a n tu m equ atio n s of m otion from the
correspondence p rinciple.
W e m ust n o t sim ply take this to m ean th a t in q u a n tu m
m echanics the wave fu n ctio n som ehow replaces the trajectory
of classical m echanics. W here does this wave fu n ctio n come
from? W e have said th a t every m easurem ent modifies the state
of a q uantum -m echanical system so th a t it is in general totally
different from w hat it was before m easurem ent. T h u s, as soon
as we try to determ in e the state of a system, the system is gen
erally no longer in th a t state.
In o rd er to u n d e rstan d w hat is m ean t by m easurem ent, let
us consider a rough b u t useful analogy. Suppose th a t we have
to test a q u a n tity of m atches for "strik ab ility .” If we were
to strike all the m atches in the batch, the test w ould be useless
for practical purposes. W e m ust test 1,000 or 10,000 m atches
chosen at random . If for exam ple, 99 p ercent are satisfactory,
then it is highly p ro b ab le th a t the o th e r m atches, w hich were
n o t tested, will also ignite in ninety-nine cases o u t of a h u n
dred. If the o riginal batch is uniform , the test indicates the
striking pow er of the m atches w ith increasing precision as the
n u m b e r of m atches tested is increased.
In the diffraction ex p erim en t an electron th a t has already
struck the p h o to g rap h ic plate is, of course, in a com pletely
different state from the one it was in w hen passing through
the crystal. Nevertheless, if a clear diffraction p a tte rn is p ro
duced on the plate, we may be sure th a t all oth er electrons
em itted u n d e r the same conditions will be d istrib u ted over
the plate in the same way. From the diffraction p a tte rn , we
can determ in e the velocity of the electrons, i.e., th e ir state
before they passed th ro u g h the crystal. However, one cannot
say in advance w hich p o in t on the plate each in d iv id u al elec
tro n w ill strike. T h e g reater the n u m b er of tests, the b e tte r our
u n d e rstan d in g of the p ro bability of an in dividual event.
W hen we toss a coin, the pro b ab ility of its com ing dow n
“ h eads” is always one half, however m any times we have tossed
it before. T h is ex p erim en t also allows ns to d eterm in e the
p ro b ab ility of an event b u t n o t to pred ict the event itself. In
principle, a coin could be tossed by some ultra-accurate device
th at w ould record its position and control its m otion. H ow
ever, the p o in t of the gam e w ould then be gone because each
in d iv id u al event w ould be p redeterm ined . T h e difference w ith
electrons is th a t a co n tro llin g device of this k in d can n o t
physically exist; this follows from the u n certain ty principle.
Even a single a tte m p t to observe the trajectory destroys any
chance of co n tro llin g the system. Such are the objective physi
cal properties of the m easurem ent process in q u a n tu m m e
chanics: m easurem ent yields the pro b ab ility a m p litu d e for a
system before it is subjected to m easurem ent. For this purpose
we have to “sp o il” a certain n u m b e r of sim ilar systems; b u t
in p rinciple we may always assume th a t there are m any m ore
systems of the same kind left th a t have no t been “sp o iled ” by
m easurem ent. H ence in the whole set of systems, m easured and
unm easured, m easurem ent determ ines the state p rev ailin g be
fore it was perform ed, i.e., som ething d ep en d in g n o t on the
observer b u t on n a tu re itself. T h e wave fu n ctio n for the sys
tem yields the p ro b ab ility th a t a given result will be o b tain ed
as a result of m easurem ent before m easurem ent is perform ed.
T h e electron m otion in an atom has its own set of wave
functions corresponding to the possible q u a n tu m states. In
the present ch ap ter we shall define these states w ith reference
to a single electron. T h e properties of all the electrons in an
atom taken together will be considered later.
T h e q u a n tu m state is characterized by the full set of con
served qu an tities, w hich may be found by using the corre
spondence p rinciple. Firstly, energy m ust be conserved in the
atom , if no ex tern al forces are doing work on it (such forces
may be produced, for exam ple, by the variable electrom ag
netic field of a light wave or a m oving electron). If the atom
is isolated from such disturbances, its energy w ill be conserved,
ju st as the energy of a classical system th a t is isolated from
ex tern al disturbances is conserved. W e shall, assum ing th a t the
nucleus an d all the o th er electrons give rise to a constant
resu ltan t field th a t acts on the given electron, for the tim e
being apply the law of conservation of energy to the m otion
of an in d iv id u a l electron in the atom . T h is is q u ite sufficient
for classifying the states of the electron.
W e may take the field acting on the electron to be a central
one; i.e., we assume th a t the total force acting on the electron
always points strictly tow ards the nucleus. T h e an g u lar m o
m entum , conserved as explained in C h ap ter Tw o, can th en be
used as a basis for the fu rth e r classification of atom ic states.
T h e classification is m ade easier because the com ponent of the
a n g u lar m om entum along any axis draw n th ro u g h the nucleus
can only equal some integral m ultiple of h/2-rr. It is convenient
to en u m erate the states by integers, just as is done w ith any
o th er objects.
W e shall now prove this fu n d am en tal property of an g u lar
m o m entum in q u a n tu m mechanics. First of all we define the
concept of a com ponent of an g u lar m om en tu m along an axis.
Figure 15 shows the plane of m otion of a particle an d the axis
p erp e n d icu la r to this place; the an g u lar m om entum is calcu
lated w ith respect to this axis, and is said in this case to be
p arallel to it. T h e n using the ordinary rules we can find its
co m ponent along any o th e r axis. In this sense the an g u lar
m om entum has the properties of a vector, i.e., a directed q u a n
tity.
By considering the un certain ty relationships for the an g u lar
m om entum , we see th a t a radius of ro ta tio n exists sim u ltan e
ously w ith the com ponent of the m om entum p p erp en d icu lar
to it. T h e total length of the circum ference 2nr m ust be an in
tegral m u ltip le of the de Broglie w avelength A. If this were no t
so, the phase of the wave at a given p o in t w ould n o t be single
valued; every tim e we m ade an im aginary rev o lu tio n ro u n d
the axis, we w ould o b tain a new phase at the given point.
T h is is incom patible w ith the definition of phase.
I t follows th a t the con d itio n for the phase of the wave
fu n ctio n to be single valued is 2-n-r = kX, w here k is an integer.
M u ltip ly in g b o th sides of the first e q u atio n by p and rem em
bering th a t X = h /p , we have 2-n-rp = kh , and since rp = M , we
conclude th a t the com ponent of the an g u lar m o m en tu m along
a given axis can only take one of the values h k / 2tt.
In p a rticu lar, k may equal zero. T h is m eans th a t the a n g u
lar m o m en tu m is zero w ith respect to the given axis. N egative
values of k correspond to ro ta tio n in th e opposite d irectio n .
W e m ust n o t th in k th a t there is no ro ta tio n w hen k = 0; rest
is im possible in q u a n tu m m echanics. By the u n certain ty p rin
ciple, if a particle is a t rest an d has a given azim uth <£, th en it
has no a n g u lar m om entum , n o t even zero an g u lar m o m en tu m .
All values of $ are equally p robable for any value of k, and
w hen k = 0, m otion in eith er d irectio n — clockwise or co u n ter
clockwise— is equally probable.
In classical m echanics, the an g u lar m o m en tu m of a particle
a b o u t an axis is zero w hen it is m oving in the same plan e con
tain in g the axis; b u t in q u a n tu m m echanics it is im possible
to represent m otion so explicitly in the case k = 0. T h e p a r
ticle is revolving a b o u t the axis in bo th directions at once.
T h is w ould, of course, be im possible if particles m oved along
trajectories. W e have already learned, how ever, th a t q u a n tu m
particles obey nonclassical laws of m otion. For exam ple, w hen
a particle strikes a crystal and is scattered, the scattering takes
place on every p lan e sim ultaneously.
Stern and G erlach verified the q u a n tiz atio n of the an g u lar
m o m entum in an e x p erim en t th a t was as im p o rta n t for q u a n
tu m m echanics as was the ex p erim en tal d em o n stratio n of the
diffraction of electrons. Before describing this e x p erim en t we
m ust e x p lain certain m agnetic properties of th e m oving elec
tron.
U nlike electrical charges, m agnetic poles can never be sep
arated, and therefore an elem entary m agnet can be represented
by a sm all compass needle. In fact, however, m agnetic action
is always produced by currents, and in order to set u p the
same m agnetic field as th a t of the needle (but at a distance
considerably greater th an the size of fhe m agnet), it is suffi
cient to take a circular loop w ith an electric cu rren t flowing
in it. In an external m agnetic field such a loop, provided it
can tu rn freely, w ill behave like a compass needle and may be
used instead of a compass in the e a rth ’s field.
T h e relative positions of the needle and the loop are as
follows: the needle is placed at the center of the loop and
p erp en d icu lar to its plane. If w hen looking at the loop we
see th a t the cu rre n t is flowing counterclockw ise, then the n o rth
pole of the m agnet is facing us.
All this refers only to the positions of the loop and the
needle. W e have to com pare th e ir forces, i.e., the m agnetic
field they set up. For this, the needle and the loop m ust have
equal m agnetic m om ents. T h e m agnetic m om ent of the cu r
ren t loop is equal to the product of the cu rren t strength and
the area enclosed by the loop, divided by the velocity of light
c. T h e proof of this is given in books on electrom agnetism .
Let us now tu rn to the electron. A revolving electron is
eq u iv alen t to a current. If it perform s n revolutions per second
and its charge is —e* th en a to tal charge of —ne per second
will pass throitgh any plane p erp en d icu lar to the m otion. By
definition, this is the cu rren t strength i — —ne. T h e area en
closed by the loop is 7rr2, so th a t the m agnetic m om ent set u p
by the electron is /z = — nevr2/c . T h e electron travels a distance
of 2-n-rn per second, so this is its velocity v. A ccordingly, the
m agnetic m om ent may also be w ritten in terms of the velocity
in the form /x = —erv/2c. Let us now divide the n u m erato r
and the d en o m in ato r by the mass of the electron m and replace
the pro d u ct m v by p, the m om entum of the electron. T h e
pro duct rp is the an g u lar m om entum M , so th a t the m agnetic
m om ent of the electron due to its o rb ital m otion is propor-
* The minus sign here and in the following discussion is connected with
the fact that the electron has a negative charge.
tio nal to its an g u lar m om entum . W e often say too th a t the
m agnetic m om ent is p ro p o rtio n a l to the an g u lar m om entum
H - —e M /2 m c.
W e have ju s t seen th a t the co m ponen t of the an g u lar m o
m en tu m along a given axis is quantized, so th a t the com ponent
of the m agnetic m om ent is also qu an tized and takes one of the
values /jl = —(eh/4~m c)k. T h e coefficient of the integer k is the
n a tu ra l u n it of m agnetic m om ent for the electron. T h e u n it
of m agnetic m om ent is called the B ohr m agneton an d is eq u al
to 10_2° in the CGS system of units.
A particle w ith a m agnetic m om ent tends to be a ttracted to
the poles of a m agnet. P robably everyone has seen iron filings
collect a ro u n d the ends of a m agnet. T h e y become m agnetized
by the field an d themselves become m agnetic. In an ex tern al
field they tu rn in to alig n m en t w ith the field ju st like a com
pass needle, b u t th en the n o rth pole of the little m agnet is
som ew hat closer to the south pole of the big m agnet (which
is causing the field), so th a t the re su ltan t field attracts the little
m agnet tow ard the big one. Since in a u n ifo rm m agnetic field
both poles of the little m agnet experience eq u al an d opposite
forces, the little m agnet sim ply turns b u t does n o t change its
position. T h e attractive pow er of a m agnet is caused by the
lines of force being crow ded together at the poles.
L et us re tu rn to the Stern-G erlach e x p erim en t illu strated in
Figure 27. O ne pole of a m agnet, say the n o rth pole, is shaped
like a wedge, so th a t the lines of force are crow ded together
at the p o in t. A beam of atom s is directed p arallel to the edge
of the wedge. T hese atom s come from a sm all crucible in
w hich a suitable substance is heated u n til it vaporizes an d is
directed in to the beam . T h e energy req u ired for vaporization
does n o t usually change the energy state of the atom s, so th a t
they em erge in th e ir g ro u n d state, i.e., w ith the least possible
in te rn a l energy. W e have already said th a t since an atom ic
electron experiences a cen tral force the a n g u lar m o m en tu m
as well as the energy is conserved.
C onsider an axis draw n vertically upw ard, and suppose th a t
the n u m b e r k, w hich gives the com ponent of the an g u lar m o

m en tu m along this axis, can assume the three values k = + 1 ,
0, —1. If there is a com ponent + 1 , then there m ust also be a
com ponent —1, since the “u p ” and “dow n” directions are
chosen in a purely conventional m anner. T h e re are atom s in
the beam w ith all these values of k. T h e atoms for which
k = + 1 have m agnetic m om ents in the opposite direction to
the m agnetic field. T h e ir south poles p o in t tow ard the n o rth
pole of the external m agnet. T h is m eans th a t they m ust be a t
tracted tow ard the p o in t of the wedge. Atoms for which k =
—1 are repelled from the point, and atoms for which k = 0
experience no force at all. As a result, those atom s for which
k = 1 are deflected upw ard, those for w hich k = —1 are de
flected dow nw ard, an d those w ith k = 0 co n tin u ed undeflected.
T h e original beam is thus split in to three separate beams. If
the an g u lar m om entum were not qu an tized an d could take
any desired value, as in classical mechanics, then instead of
three separate beams we w ould obtain a continuous fan. T h e
Stern-G erlach ex p erim en t thus provides direct evidence of
the q u a n tizatio n of an g u lar m om entum .
L et us now consider fu rth e r properties of the an g u lar m o
m entum . W e have already said th a t it is a vector q u an tity , i.e.,
it may be resolved in three m utually perp en d icu lar directions.
Such a resolution is show n in Figure 28. In the xyz system the
an g u lar m om entum lies along the z axis and its com ponents
in the x and y directions are zero, b u t in the x'y'-z' system,
which has been rotated w ith respect to the first one; the an g u
lar m om entum has com ponents M r , M y., M \.. II we construct
a p arallelepiped w ith sides M x., M y., M z,, then M will be the
diagonal. By P ythagoras’ theorem it is given by M 2 = M 2, +
M 2, + M 2Z.. L et us consider w hat this m eans in q u a n tu m m e
chanics.
For this purpose, we shall re tu rn to the Stern-G erlach ex p eri
m ent. W h at will h a p p en if we tu rn the m agnet w ith respect to
the beam th ro u g h a small angle, say 10°? T h is m akes no differ
ence to the beam of atoms, there is n e ith e r “u p ” n o r “d o w n ”
n or any o th er special direction for them . T h e original beam
will again be split in the m agnetic field in to the three beam s
as before, so that, let us say, both M , an d will take id e n ti
cal integral values, w ith the z an d z' axes inclined at 10° to
each other. At first glance this seems im possible. If we m easure
off a conventional u n it of length in one d irectio n an d then
take its projection on a straig h t line inclined at 10° to the
original direction, then the projection (com ponent) will eq u al
0.986, w hich is clearly not an integer. W ith in the fram ew ork
of classical m echanics this parad o x cann o t be resolved.
T h e fact is th a t the two com ponents of the an g u lar m o
m entum on different axes can n o t exist sim ultaneously. W e
can not have, say, one com ponent M z, = 0.986/i/27t an d an o th er
M x, = 0.16/j/2t7. T h is is in agreem ent w ith Pythagoras’ theo
rem: 0.9862 -f 0.162 = 1, b u t it does n o t agree w ith q u a n tu m
m echanics. T h e re is one an g u lar m om en tu m and only one z
com ponent. In the case we have been discussing this has only
three possible values, + 1 , 0, an d —1. M x>a n d M y>are simply
no t equal to an y thing at all; they do n o t exist. W h en one com
p o n en t of the an g u lar m om entum is know n, it is impossible
to determ ine the two o th e r com ponents exactly, ju st as it is
im possible to determ ine position and m om entum sim ultane
ously in the same state. A definite physical state of the system
can possess one and only one z com ponent of the an g u lar m o
m entum , w hich is thus q u ite different from the o th er vector
q u a n tity — the lin ear m om entum , the three com ponents of
w hich may sim ultaneously have precise values.
Now let one of the beams in to w hich the original beam was
split be passed th ro u g h an o th er such m agnet. If the second
m agnet is parallel in space to the first, the beam will n o t be
split again, since it has already been sorted o u t by the first
m agnet, an d the M z com ponents of all the atoms are the same.
H ence all its atom s are deflected the same am o u n t in the
second m agnet, and if the beam w ith k = 0 is chosen, there is
no deflection at all.
It is sufficient to tu rn the second m agnet th ro u g h some angle
to split any of the three beams once again in to three. For the
an g u lar m om entum has no definite com ponent in the new d i
rection of the m agnetic field. T h e an g u lar m o m en tu m does no t
have com ponents sim ultaneously in the two directions, old and
new. T h e state w ith M = hk/2ir does n o t correspond to any
definite k', i.e., M r . I t is m ade up of three states w ith k' =
1, 0, or —1, if M z>= hk'/2ir. O n the other hand, the state w ith
k ' = 1, i.e., w ith definite M z,, is resolvable in to three others
w ith k = 1, 0, an d —1.
A ny field will sp lit the given in itia l beam in to n o t m ore th a n
three parts, no m a tte r how m any times it is passed th ro u g h
the m agnetic field. W e can never o b tain five, seven, etc., beams.
O nly three values of the com ponent of the an g u lar m om entum
are ob tain ed along a given axis: h/27r, 0, an d —h/2-rr. Let us
m easure the an g u lar m o m entum in units of h/2-n. C learly this
is the most n a tu ra l u n it. W e can th en say th a t the m axim um
com ponent of the beam u n d e r consideration w ill never exceed
1 (in o th e r cases it can be 2, 3, or higher). In classical m echan
ics we w ould be able to m ake a sim ple d ed u ctio n from this: if
the com ponent of the an g u lar m om en tu m vector can never
exceed a certain value, then the an g u lar m o m en tu m itself, i.e.,
its absolute m agnitude, m ust equal th a t value. T h e m axim um
com ponent of a vector is equal to the absolute m ag n itu d e of
the vector itself. Does it n o t follow from this th a t the absolute
m agnitude of the an g u lar m o m en tu m in the beam , which for
any sp littin g gives a m axim um com ponen t eq u al to 1, is itself
1?
W e m ust n o t h u rry o u r argum ent. T h e absolute value of
the an g u lar m om entum is, as always, M 2 = M x -f M 2 + M 2.
B ut w hen M , = 1 we cannot assert th a t M,, = M x = 0. In gen
eral, the three com ponents of the an g u lar m o m en tu m do not
sim ultaneously exist, so th a t w hen M~ = I, M x an d M y do no t
equal an y th in g at all.
T h e value of M 2 may be deduced as follows. Let us suppose
th a t the beam lies along the x axis, and th a t the m agnetic field
is directed first along the y axis and then along the z axis. W h at
w ill be the mean value of M 2? W e shall always o b ta in three
beams, no m a tte r how the m agnetic field is oriented. In two
beam s of the three M 2 = 1 an d in the o th e r Af2 = 0. In any
case, the m ean value of M 2 equals §. Sim ilarly, the m ean
value of M 2 will again equal §, since it makes n o difference
w hich axis we call the z axis and w hich we call the y axis. Now
let us suppose th a t the beam is traveling along th e y axis. T h e
m ean value of A /2 is once m ore §. Since the m ean value of M 2
m ust be equal to the sum of all three m ean squares of the
com ponents, an d each of the la tte r equals §, the m ean value
of M 2 equals 3 X § = 2. T h is result is only determined by the
m axim um com ponent of the an g u lar m om entum ; it is not
eq u al to it. T h e m ean value in all cases is the same, just like
the m axim um com ponent itself. H ow ever, if averaging a q u a n
tity always gives the same value, it is useless to talk ab o u t the
m ean: we can sim ply say th a t this is the value itself. T h u s the
absolute m ag n itu d e of the an g u lar m om en tu m can exist sim ul
taneously w ith one of its com ponents, and the o th e r two com
ponents do n o t exist. T h e a n g u lar m o m en tu m can have a
com ponent, b u t only along one axis at a time. T h is is usually,
b u t n o t necessarily called the z com ponent.
W e should n o t be surprised th a t the absolute m ag n itu d e of
the a n g u lar m om entum is greater th an its m axim um z com
ponent. T h e m ean squares of those com ponents which do
no t have a strict m eaning sim ultaneously w ith M z m ake a
definite c o n trib u tio n to the m ean, and since squares are always
positive, we have M 2 = M% + M 2 + M \ > M 2.
T ru e , there is one im p o rta n t exception: w hen the absolute
m ag n itu d e of the an g u lar m om entum is zero, all three com
ponents are sim ultaneously eq u al to zero. Physically this is
shown in the Stern-G erlach experim en t by the fact th a t the
beam is sim ply not split at all, as if the field h ad n o direction,
which m eans th a t all com ponents of the an g u lar m om entum
are zero.
If the absolute m agnitude of the an g u lar m om entum is no t
equal to zero, then the beam may be divided an infinite n u m
ber of times by its successive passage th ro u g h differently in
clined fields. T h e z com ponent of the an g u lar m om entum is
therefore established anew each time. Each beam w ith a defi
nite z com ponent of the an g u lar m om entum in the direction
of the previous field, acquires new com ponents in the direction
of the new field it is crossing and retains from the old field
only the relative am plitudes for all three new com ponents. If,
for exam ple, the new field is inclined at a sm all angle to the
old, then the strongest beam w ill be the one in w hich the
z com ponent of the an g u lar m om entum is equal to the value
in the old beam . L et the old co m p o n en t be eq u al to 1. A fter
crossing a field th a t is in clined at a sm all angle to the p re
ceding one, the beam for w hich the z co m p o n en t in the new
field equals 1 w ill be the m ost intense. Beams w ith the o th er
two com ponents w ill also be present, alth o u g h weaker.
In p rin cip le the sp littin g affects every in d iv id u a l atom , b u t
the law is revealed only in experim ents involving large n u m
bers of in d iv id u al atom s. T h is shows again the p ro b ab ilistic
n a tu re of the q u an tu m -m ech an ical laws.
N ow th a t we have described the basic p roperties of an g u lar
m om entum , we may consider the m o tio n of an in d iv id u a l
electron in an atom : we know all the constants th a t describe
its m otion in space. L ater we shall find one m ore constant;
however, this refers n o t to the m otion of the electron in space
b u t to its in te rn a l m o tio n (see n ext chapter). W e shall in the
m eantim e classify the m otion of the electron according to the
constants of its m o tio n in space or, as we say, its o rb ital m otion.
T h e re are three such constants: the energy, the absolute m ag
n itu d e of a n g td a r m om entum , an d the an g u lar m o m e n tu m ’s
z com ponent, w hich is always an integral m u ltip le of h /2 - .
In this connection it is very im p o rta n t to re tu rn once m ore
to the follow ing problem . T o w hat e x te n t does an in d iv id u al
electron in an atom really possess all these values in d e p e n d
ently of the o th e r electrons? O f course, only a hydrogen atom
possesses a single electron; all o th e r atom s have as m any elec
trons as are needed to neutralize the charge on the nucleus (the
n u m b e r is e q u al to the atom ic n u m b e r of the elem ent in M en
deleyev’s periodic table). In fact, there is a Aery com plicated
force acting on each electron. T h e m any-body p ro b lem has not
been solved analytically even in classical m echanics. Indeed,
it is even m ore com plicated in q u a n tu m m echanics, and can
no t be solved num erically even on high-speed com puters, al
th o u g h it is possible th a t m odifications of cu rren tly available
com puters w ill m ake such solutions possible in the fu tu re.
H ow ever, in q u a n tu m m echanics we may successfully apply
an a p p ro x im a te sem iq u an titativ e m eth o d th a t w ill take us a
very long way in u n d e rstan d in g all the fu n d am en tal laws of
m otion of electrons in com plicated atoms. T h is m ethod was
proposed by H a rtre e and m uch im proved by Fok. In this
m ethod the actions of all the o th e r electrons on the one u n d er
consideration are replaced by a m ean force. A ccording to Fok,
this is n o t sim ply the field of the sm eared charge of the electron
cloud (as the p ro bability field is called). Since it is impossible
to track the m otion of an in d iv id u al electron and the elec
trons are indistinguishable from each other, the qu an tu m -
m echanical p h enom enon of "exchange” occurs w hen there is
some interaction. T h is depends not only on the p ro b ab ility of
finding the electron at this or th a t point, b u t also on the phase
of the wave function. W hen we calculate the exchange in te r
action betw een electrons, we take each of them to be sim ul
taneously in two states. In p rinciple the electrons can only be
in these states one at a time, b u t the in teractio n “mixes them
u p ,” so th a t it is im possible to say which of the electrons is in
a given state. A ccording to Fok the agreem ent betw een the
theory and experim ent is substantially im proved w hen ex
change is taken in to account.
T h e field due to all the o th e r electrons on the electron
u n d er consideration is called the "self-consistent” field. It
allows us to replace the many-body problem approxim ately
by an equiv alen t one-body problem . W e note th a t "exchange”
occurs in the equations as a result of the ap p licatio n of an
ap proxim ate m ethod; it docs not occur in the exact equations.
It is very im p o rta n t th a t the self-consistent H artree-Fok field
is central, because the electron then possesses the same con
stants of m otion as in the hydrogen atom , where the field is
sim ply a C oulom b field. T h is perm its the states of an electron
in any atom to be classified just as in the hydrogen atom : by
energy, an g u lar m om entum , and z com ponent of angular
m om entum along an arbitrary direction.
Strictly speaking, an individual electron in an atom does not
have a total an g u lar m o m en tu m or total energy; these pa
ram eters refer to the atom as a whole. H ow ever, a qu alitativ e
d escription based on the concept of separate states of each elec
tro n in the field of all the others always gives satisfactory re
sults. It allows the true state of the whole atom (for w hich we
still cannot calculate the wave function ) to be com pared in a
one-to-one correspondence w ith some ap p ro x im ate state th a t
can be characterized by constants of m otion of the in d iv id u al
electrons.
L ittle can be added to w hat was said in the previous ch ap
ter concerning the energies of indiv id u al electrons. A lth o u g h
energy calculations are fairly com plicated, com puters may be
used to solve them approxim ately. B ound states correspond
to a discrete spectrum , an d free states to a co n tin u o u s one.
T h e free state of an electron in an atom corresponds n o t to the
atom b u t to a positive ion n e ar w hich the electron is m ov
ing. Such an electron may eith er move “p a st” or else em it a
q u a n tu m of light (a photon) and become b o u n d to the atom
(this is called free-bound em ission). In the la tte r case the p h o
ton m ust rem ove sufficient energy from the electron, so th at
it no longer has a co n tinuous b u t a discrete spectrum . Some
times the p h o to n takes away less energy th a n is necessary for
this to occur. T h e electron then rem ains free even after em is
sion. T h is is called free-free em ission; it is im p o rta n t w hen
m a tte r is heated so strongly th a t all the atom s are com pletely
ionized— i.e., w hen they lose all th e ir electrons.
C alculating the energy of an electron is difficult because the
energy depends on the actual form of the field acting on the
electrons. O n the o th e r hand, an g u lar m o m en tu m does no t
d epend on the form of the field at all; it is only necessary for
the field to be central. T h e n an d only th en is the a n g u lar m o
m e n tu m conserved (i.e., it characterizes the state).
As we have shown, the m ag n itu d e of the an g u lar m om en
tu m is d eterm in ed by its m axim um z co m ponent. F or a spe
cific electron this integer is denoted by I , the a zim u th a l q u a n
tum n u m b er. T h e term “q u a n tu m n u m b e r” refers to any n u m
b er th a t in some way describes a q u a n tu m state. T h e term
“ a z im u th a l” was ad o p ted from the old theory of B ohr. In quan-
turn m echanics the n u m b er / denotes the state of m otion of a
particle n o t according to the azim uth, b u t ra th e r according
to the angle th at is analogous to the geographical latitu d e of
the point. T h e azim uth corresponds to the longitude 4> (see
Fig. 15), w hich is connected w ith the com ponent of the an g u
lar m om entum k, called the m agnetic q u a n tu m num ber. We
can u n d erstan d this nam e if we recall th at k can be d eterm ined
w ith the aid of the Stern-G erlach experim en t according to the
com ponent of the m agnetic m om ent in the direction of the
external m agnetic field.
T h e states / = 0, 1, 2, and 3 are called the s, p, d, and / states
respectively. T hese term s were originally used in spectroscopy
to denote certain spectral lines as “sharp ,” “ p rin cip al,” “d if
fuse,” and “ fu n d a m e n tal.”
W e found in the previous ch ap ter th a t the greater the
energy of the b o u n d state, the greater the n u m b er of nodes or
zeros of the wave function. T h is is also tru e for wave functions
relating to o th e r physical q u an titie s th a t assume discrete values,
e.g., the an g u lar m om entum . T h e argum en t of these functions
is no longer the distance from the nucleus, b u t an angle an alo
gous to the geographical la titu d e (more precisely, its com ple
m ent to 90°). T h e nodal lines may be sim ply represented on
the surface of a u n it sphere. W e have chosen the case w hen
k = 0 (Fig. 29a). If k 0, some nod al lines degenerate to
Figure 29
single points at the poles. T h e dependence of the wave func
tio n on the azim uth is com plicated and itself has no zeros,
b u t its real an d im aginary parts vanish as m any times as k is a
m u ltip le of unity.
P J Electron s p in
In m echanics we often use the concept of a mass point, whose

position in space is com pletely defined by three coordinates.
A mass p o in t in classical m echanics is by no m eans a p o in t in
the m athem atical sense of the w ord. T h u s the earth moves
a b o u t the sun as if the masses of the earth and of the sun were
en tirely concentrated at these mass points. T h e ir actual sizes
have no significance at all. In fact the earth perform s an o th er
m otion as well— it rotates ab o u t its axis—-but this in te rn a l
m otion does not affect the m otion of its cen ter of gravity. T h e
difference betw een p o in t and extended bodies in m echanics is
d eterm ined by w h eth er o r n o t in te rn a l m otion (if any) affects
the m otion of the center of gravity. In this sense a b u lle t is
no t a p o in t since its ro ta tio n a b o u t its axis has a considerable
effect on its flight th ro u g h the a ir (otherw ise why m ake it
rotate?), b u t the earth does behave like a mass p o in t. '
W hen speaking ab o u t an electron in an atom we have so far
considered the electron as a p oint. H ow ever, ex p erim en t shows
th a t in fact the electron also possesses an in te rn a l m otion,
which is rem iniscent of ro ta tio n ab o u t an axis. It certainly does
n o t follow from this th a t the electron has geom etric dim en
sions, for the laws of its ro ta tio n are sim ply n o t connected w ith
any q u an tities sim ilar to the radius of a ro ta tin g body. T h e
in te rn a l m otion in the case of an electron is a p u re q u an tu m -
m echanical m otion an d cannot be considered the displacem ent
of som ething in space. U nlike the ro ta tio n of the earth , the
in te rn a l m otion of an electron has a considerable effect on its
state in the atom , an d in this sense the earth is m ore like a
p o in t th a n an electron is!
Any physical concept is best defined by describing the p h e
nom enon or e x p erim en t th a t reveals it and it alone. Let us
suppose th at the Stern-G erlach experim en t is carried o u t w ith
hydrogen atom s in the state of least energy, i.e., the g ro u n d
state. In these atom s the azim uthal q u a n tu m n u m b er is zero
(£ = 0), an d hence the m agnetic q u a n tu m n u m b er k = 0. P ro
ceeding from this, one w ould expect th a t the beam of hydro
gen atom s w ould n o t be split: the zero an g u lar m om entum
w ould always have a zero z com ponent. If the hydrogen atoms
for some reason have an an g u lar m om entum , division into
at least three beams w ould take place: for £ — 1, k takes the
values + 1 , 0 , an d —1. H ow ever, the beam does in fact split
in to two. Any in teg ral an g u lar m om entu m should give an odd
n u m b e r of z com ponents (betw een 1 and —1, 2 and —2, etc.);
b u t here the largest z com ponent of the an g u lar m om entum
m ust be equal to + T h e n there is the o th er z com ponent equal
to — i.e., there are ju st two values of this com ponent.
O u r ded u ctio n th a t the angular m om entum m ust have in
tegral z com ponents is based on the req u irem en t th at the phase
of the wave function in space m ust be single valued. In other
words it is caused entirely by the orb ital m otion. From the
m ost general theorem s of q u a n tu m m echanics it can be shown
th a t the z com ponent of an g u lar m om en tu m along any given
axis may be in some cases an integral m u ltip le and in other
cases a half-integral m u ltip le of h/2~; b u t according to the
same theorem for a given an g u lar m om entum , the z com
p o n en t o n to the axis w ill certainly change in steps of one.
T h e reader m ust take this result on faith, since there is no
easy way of proving this. If the largest z com ponent is + then
there is only one o th er z com ponent possible, nam ely —
T h is is clearly ju st the exam ple we considered in the Stern-
G erlach ex p erim en t for hydrogen atoms.
T h e half-integral value of the an g u lar m om entum indicates
Electron spin 89
th a t it is n o t connected w ith orb ital m otion. C onsequently, the
electron by definition m ust have some form of in tern al m otion.
T h e sp littin g of the beam in the m agnetic field showed th at
u n d e r certain conditions this m otion affects the o rbital m o
tion. A n electron is thus not a m aterial p o in t in the m ath e
m atical sense; i.e., it also possesses some free in tern al m otion.
However, geom etric concepts such as length do no t apply at
all to this m atter. A ng u lar m om entum has the dim ensions of
P lanck’s constant, not of length.
If we m ust com pare the in tern al m otion w ith some classical
concept, we m ay th in k of rigid-body rotatio n , e.g., a b u llet in
flight or a sp inning top. T h e intrinsic an g u lar m om entum of
an electron is called, for brevity as well as for historical rea
sons, the “sp in .” W e have already said th a t in a central force
field the an g u lar m om entum is conserved. Strictly speaking,
this refers only to the total an g u lar m om entum , which is m ade
up of the o rbital and the spin angular m om enta.
T h e sp littin g of the beam by the m agnetic field is caused by
the m agnetic m om ent of the electron. E xperim ent shows th a t
the p ro to n in the hydrogen atom has the same spin an g u lar
m om entum , w ith com ponents ± a , as the electron, b u t its m ag
netic m om ent is m uch sm aller. H ence u n d e r ordinary ex p eri
m ental conditions the beam sp littin g is due solely to the elec
tron m agnetic m om ent, although in p rin cip le there should
also be an ad d itio n al “hyperfine” sp littin g due to the p ro to n
m om ent. W e have already shown th at the coefficient of p ro p o r
tionality betw een the m agnetic m om ent and the o rb ital angu
lar m om entum of a charged particle is e/2m c. It is found,
however, th a t in the case of the electron spin, the coefficient
is e /m c , which is twice as great as th a t for o rbital an g u lar
m om entum . Since the spin z com ponent in ordinary units is
h / 4-7T, the m agnetic m om ent is e h / ^ m c , i.e., one B ohr m ag
neton. W e shall see later th a t this result is in fact only a p
proxim ate.
O u r deduction of the relationship betw een the m agnetic
m om ent and an g u lar m om entum referred only to o rb ital mo-
tion. T h e new coefficient e /m c does n o t in v alid ate the deduc
tions concerning the o rb ital m otion. D irac ex p lain ed the co
efficient w ith the aid of his own special wave eq u atio n for the
electron. T h is e q u atio n differs from the o rd in ary Schrodinger
eq u atio n because it takes in to account the requirem ents of the
theory of relativity and the in te rn a l spin m otion of the elec
tron. T h e coefficient e /m c is ob tain ed au to m atically in D irac’s
theory.
In the case of the p ro to n the situ atio n is q u ite different.
T h e ra tio of its m agnetic m om ent to the an g u lar m om entum
is 2.8 times g reater th an predicted by D irac’s theory. A n e u
tron has no overall electric charge. D irac’s theory m ust th ere
fore give it zero m agnetic m om ent, b u t in fact the n e u tro n
does have a m agnetic m om ent equal to —1.9 (in the same units
as the m agnetic m om ent of the proton). T h e m inus sign in
dicates th a t the m agnetic m om ent of the n e u tro n is opposite
to its spin.
W e are still u nable to explain these facts from any first
principles. If we com pare electrons and n uclear particles, we
arrive at the follow ing conclusions. T h e electron interacts w ith
the electrom agnetic field fairly weakly, and solely on account
of its charge. T h e force of this in teractio n is so sm all th a t the
electron m ay be considered an in d ep en d en t particle in an
ex tern al electrom agnetic field. Is there an y th in g to p rev en t o ur
using the same approach for the p ro to n and the neu tro n ? W e
have already seen th a t the specifically n uclear forces are con
siderably stronger than electrom agnetic forces. T h e zero-order
ap p ro x im atio n , in w hich these forces are not taken in to ac
count, is so rough th a t it disagrees considerably w ith ex p eri
m ental data on the m agnetic m om ents of nuclear particles.
A b etter ap p ro x im atio n can n o t be form u lated at present be
cause no reliable m ethod for calculating such strong forces as
yet exists.
T h e difficulties w ith the m agnetic m om ents of the p ro to n
an d n e u tro n do not indicate any disagreem ent of q u a n tu m
m echanics w ith experim ent. T h e y m ust be referred to the
Electron spin 91
theory of elem entary particles, w hich is still incom plete. T h e
q u a n tu m m echanics of H eisenberg an d Schrodinger is n o t
concerned w ith the stru c tu re of elem entary particles. In th eir
theory every particle is characterized by its mass, energy, and
spin. T h e m agnetic m om ent associated w ith the spin is as
sum ed to be an a d d itio n al property th a t m ust simply be taken
in to account as an ex p erim en tal fact. Q u a n tu m m echanics for
particles n o t subjected to n u clear forces is as com plete an d as
consistent as the classical m echanics of N ew ton, and is to the
same degree u n in terested in the n a tu re of m oving particles.
T h is division of atom ic physics in to q u a n tu m m echanics
and the theory of elem entary particles is n o t at all artificial.
W hen studying the stru ctu re of elem entary particles, we are
dealing w ith dim ensions of the order of 10~13 cm and less.
T h e corresponding u n certain ty in the velocity tu rn s o u t to be
eq u al to, or g reater than, the velocity of light (the la tte r is
tru e for electrons); b u t at such high velocities the theory of
relativity m ust be taken in to account. Any physical theory
th a t does so is said to be relativistic. T h u s D irac’s theory is the
relativistic q u a n tu m m echanics for electrons. T h is gives the
correct gyrom agnedc ra tio for electrons. N o relativistic theory
of nuclear particles has yet been form ulated. T h e forces acting
at distances of the o rd er of 10-13 cm are the very strong n u
clear forces, whose n a tu re has n o t yet been elucidated, whereas
the forces acting on the electron are electrom agnetic forces,
ab o u t w hich enough is know n. T h e general situ atio n is th a t
theory cannot yet predict the m agnitud e of the gyrom agnetic
ra tio for the p ro to n and the n e u tro n as well as for m any oth er
nuclear phenom ena.
N onrelativistic q u a n tu m m echanics is concerned only w ith
types of m otion in w hich the velocities of the particles rem ain
small in com parison w ith the velocity of light. T h e erro r in
troduced if relativistic effects are ignored is of the order of the
ratio of the velocity of the particles to the velocity of light.
Let us estim ate this erro r for electrons in different atoms, i.e.,
atom s w ith atom ic n u m b e r Z ru n n in g from 1 in hydrogen to
92 in uran iu m . Schrodinger’s eq u atio n involves only the mass
of the electron, its charge, and P lan ck ’s constant. In a strictly
nonrelativistic theory the velocity of light plays no p art. From
m, e, and h it is possible to construct one and only one p aram
eter w ith the dim ensions of velocity. Let us do this. W e have
already seen th a t the p o ten tial energy of the C oulom b forces
is equal to the squares of the charge divided by the distance.
T h is means th a t (charge)2 = (energy) X (length). F u rth er, a
q u a n tu m of energy is equal to the pro d u ct of P lan ck ’s constant
and the frequency. B ut frequency has the dim ensions of the
reciprocal of time, so th a t h = (energy) x (time). Let us now
divide the first eq u atio n by the second. T h e dim ensions of
energy cancel and we are left w'ith
(charge)2 _ length
= velocity.
h time
N o other q u a n tity w ith the same dim ensions can be fo rm u
lated from m, c, and h. W e thus begin to suspect th a t the
relativistic correction to Schrodinger’s eq u atio n m ust be of the
order of m agnitude of the square of the charge divided by h
and by the velocity of light. T h is is eq u al to the ratio of the
velocity of an electron in an atom to the velocity of light.
C alculations show th a t in fact this correction is larger by a
factor of 2tt (w c have seen several times that h does no t en ter
equations by itself b u t is often divided by 2tt). S u b stitu tin g
num erical values for the constants wc find 2ire2/ h c = 1/137.
T h is result is dim ensionless and is therefore in d e p en d e n t of
o u r choice of system of units.
T h e tran sitio n to nonrelativistic theory form ally consists in
tak ing the velocity of light to be infinite, ju st as in passing
to the classical theory from the q u a n tu m one h is taken to be
zero. O f course, the erro r in troduced by the nonrelativistic
ap p ro x im atio n is th at a q u a n tity th at actually equals 1/137
is taken to be infinitely small. (T he n o n relativ istic theory is
correct for the hydrogen atom to the o rd er (1/137)2.) In an
atom w ith atom ic n u m b er Z, the e rro r is of the o rd er of
Electron spin 93
(Z/137)2, which for u ra n iu m turns out to be ab o u t 0.45. H ow
ever, w hen the estim ated erro r is com parable w ith unity, the
erro r in the variable u n d e r consideration is com parable w ith
the variable itself, and calculations become im precise. Schro-
d in g e r’s nonrelativistic wave eq u atio n is th en hardly applicable
and com plete agreem ent of theory and ex p erim en t is ob tain ed
only w ith D irac’s relativistic eq u atio n . Schrodinger’s eq u atio n
is satisfactory for all electrons in atom s w ith Z, say, u p to ten.
T h e relatio n sh ip betw een the nonrelativistic and relativistic
theories may be illu strated by the follow ing scheme:
Theory of relativity
N ew tonian mechanics
(Einstein’s mechanics)
c = °o
h = 0
h = 0
c = 3 X 1010 cm /sec
i _____________ I ____________
Q uan tu m theory of the

N onrelativistic quantum
electrom agnetic field and
m echanics
the electron (Dirac)
c = oo
c = 3 X 1010 cm /sec
h = 6.62 X 10~27 erg sec
h — 6.62 X 10~27 erg sec
Only the second box on the rig h t is incom plete because we

have as yet no theory in which the ratio 1/137 could be o b
tained autom atically. M oreover, nuclear forces are still not
com pletely understood, and it is not clear w hether the u n i
versal constants used up u n til now will be sufficient. T h e
history of physics shows th a t w henever a new universal con
stant appears, there has to be a p ro fo u n d re th in k in g of the
basic principles of physics.
L et us now re tu rn to the gyrom agnetic ratio e /m c . T h is
contains the velocity of light in its den o m in ato r, and accord
ing to the above classification is a relativistic q u an tity . Before
we discuss w hat effect the m agnetic m om ent has on the m otion
of an atom ic electron, we m ust recall how it was discovered.
T h e ratio e /2 m e was first in tro d u ced in the classical theory of
the electron. E instein then proposed verifying by an ex p eri
m ent the fact th a t this is the ra tio of the m agnetic m om ent
to the an g u lar m om entum . H e suggested th a t if m agnetization
of a steel rod produced a resu ltan t m agnetic m om ent of the
electrons, then a resu ltan t an g u lar m om entum sh o u ld also
appear. T h is ex perim ent was carried o u t by de H aas a n d it
was found th a t the ratio of the m agnetic m om ent and the
an g u lar m om entum was twice as great as the value given by
classical electron theory, in w hich only the o rb ital m otion of
the electron was taken in to account. T h e spin had still n o t
been discovered and de H aas’s result could n o t be understood.
L ater U hlenbeck an d G oudsm it discovered spin by analyzing
spectroscopic data. It then becam e a p p a re n t th a t the m ag
netism of iron is connected w ith the spin of its electrons and
n o t w ith th eir o rb ital m otion.
Let us now consider the effect of spin on the o rb ital m otion
of electrons. W e m ust first note th a t spin is extrem ely im p o r
ta n t for a p ro p e r u n d e rstan d in g of the stru ctu re of many-
electron atoms, i.e., in the many body problem of q u a n tu m
m echanics. W e shall consider this in the follow ing chapter.
For the present we shall confine o u r a tte n tio n to the “spin-
o rb it” in teractio n of a single electron. (In the Stern-G erlach
ex p erim en t this in teractio n was produced as a result of the
ap p licatio n of the ex tern al m agnetic field.) T h e cause of this
in teraction is now easy to u n d erstan d : both the o rb ital m otion
and the spin have associated m agnetic m om ents, and two
m agnets always in teract w ith each other. T h e energy of this
in teractio n is p ro p o rtio n al to the p ro d u ct of the m agnetic m o
m ents. Each of them contains the velocity of light in its de
n o m inator, so th a t an essentially relativistic expression is
o b tain ed th a t is inversely p ro p o rtio n al to the square of the
velocity of light. For an individual electron, the spin-orbit
in teractio n may be q u ite rigorously calculated from D irac’s
Electron spin 95
eq u ation, and not merely as a correction. T h e p ictu re of the
two m agnets is purely a m eans of visualizing the problem and
can n o t be used to give precise results.
H aving estim ated the order of m agnitude of the effect of
spin on o rb ital m otion, we shall now discuss how it becomes
ap p aren t. T h e spin com ponent has only two values in any
given direction, e.g., in the direction of the o rb ital angular
m om entum . H ence if the m axim um com ponent of the o rb ital
m otion is as usual eq u al to I, the to tal an g u lar m om entum
(orbital plus spin) of the electron w ill have the m axim um z
com ponents I + ’ and I — depen d in g on w hether the spin
is p arallel or a n tip a rallel to the o rb ital an g u lar m om entum .
T h e difference betw een the energies of an electron w ith spin
p arallel an d a n tip a rallel to the o rb ital an g u lar m om entum is
of the same order of m ag nitude as the energy of in teractio n of
the two “m agnets.” As a result, the energy level of an atom
w ith given t splits in to two sublevels or, as is said in spectros
copy, has a fine structure. T h e w ell-know n yellow line of so
d iu m is d ouble because the excited level (from w hich the elec
tron re tu rn s to the g ro u n d state w ith the emission of yellow
light) exhibits fine-structure sp littin g into two sublevels.
H ow m uch sm aller is the m ag n itu d e of the sp littin g than
the distance betw een the original levels? W e have already said
th a t it contains c2 in the denom inator. T h is means th a t the
corresponding relativistic correction for an atom w ith atom ic
n u m b e r Z is (2?rZe/h e )2 = (Z/137)2. In very heavy atom s this
may reach 0.45 so th a t the stru ctu re is no longer very “ fine.”
In such cases it is b e tte r to use the exact solution of D irac’s
e q u a tio n ra th e r th a n the ap p ro x im ate correction.
M any-electron atoms also have the spin-spin m agnetic in te r
action. T h is m ust be distinguished from the spin-spin in te r
action of an o th er kind th a t is im p o rta n t in m any-body p ro b
lems (see n ex t chapter). T h e m agnetic in teractio n of the spins
also leads to a form of fine stru ctu re like th a t of the spin-orbit
in teractio n . Since the atom ic n u m b e r of the elem ent does no t
occur in the expression for the spin-spin m agnetic energy, the
la tte r leads to corrections th a t are com p arab le w ith the spin-
o rb it ones only for sm all values of Z. F o r large Z the spin-orbit
in teractio n p redom inates over the spin-spin in teractio n .
T h e re su lta n t a n g u lar m om entum of the electron is d en o ted
by j. C learly
j = t + i or = i —\
T h e nucleus also has a m agnetic m om ent if it has an g u lar

m om entum . For exam ple, the deuteron , w hich consists of a
p ro to n an d a n e u tro n , has a re su ltan t spin equal to 1. H ence
the an g u lar m om enta of the p ro to n an d the n e u tro n are p a ra l
lel. T hese particles are in the s state in the d eu tero n , i.e., they
have zero o rb ital a n g u lar m om entum . C onsequently the m o
tion of the p ro to n does n o t create an o rb ita l m agnetic m om ent.
T h e e n tire m agnetic m om ent of the d e u tero n m ust be of spin
origin. W e have already said th a t the m agnetic m o m en t of the
p ro to n equals 2.8, an d th a t of the n e u tro n —1.9 n uclear
m agnetons (this is 1836 times sm aller th an the value for elec
trons, since the mass appears in the d en o m in ato r). Because the
spins of the p ro to n and the n e u tro n are p arallel, we m ust ex
pect a d eu tero n m agnetic m om ent equal to 2.8 — 1.9 = 0.9.
T h is is verified closely by experim ent.
U sing sim ilar a lth o u g h m ore com plicated argum ents we can
p redict the m agnetic m om ents of m any lig h t nuclei, and o b tain
close agreem ent w ith experim ent.
T h e electron an d n u clear m agnetic m om ents also in teract
w ith each o th e r like m agnets, b u t since the n u clear m om ents
are ap p ro x im ately a th o u san d times sm aller the resu ltan t
sp littin g of the atom ic levels is correspondingly sm aller th an
the fine stru ctu re. T h is sp littin g is called the hyperfine struc
ture.
H ow are we to calculate the n u m b e r of hyperfine-structure
sublevels in to w hich a fine-structure level is divided? L et the
total a n g u la r m o m en tu m of the electron be / an d th a t of the
nucleus J, an d let us take the co m ponen t of ] along /. In this
way, we o b ta in the follow ing values of the resu ltan t an g u lar
Electron spin 97
m om entum F: F = + ], j + ] — 1, . . . , j — J. For exam ple,
if j = 3/2 and J = 1, then F — 5/2, 3/2, 1/2. W hen the n u
clear angular m om entum is the larger, the resu ltan t m om ent
varies in a sim ilar way from J + j to J — j. T h is rule of ad d i
tion of angular m om enta applies in general to any two such
m om enta.
Structure of the atom
In the two preceding chapters we saw th a t the m o tio n of an

electron is characterized by its energy, an g u lar m o m en tu m , z
com ponents of o rb ital a n g u lar m om en tu m , and th e spin z
co m ponent along some axis. In a com plicated atom these four
q u a n titie s are n o t exact constants of m o tio n for an in d iv id u al
electron. N evertheless, the self-consistent field m eth o d allows
(even if n o t rigorously) th e sep aratio n of the m o tio n of in
d iv id u al electrons because in q u a n tu m m echanics the state of
a system is u n iq u e ly connected w ith th e n u m b e r of zeros in
th e wave function. T h is n u m b e r is clearly always an integer.
If it is fo u n d correctly for the a p p ro x im a te wave function,
th en this fu n ctio n will be a good rep resen tatio n of the exact
function, even w hen the zeros o r nodes of the a p p ro x im ate
fu n ctio n do n o t occur at th e same places as in the exact func
tion. Sim ilarly, a caricatu re may catch a likeness even if the
correspondence betw een the in d iv id u al parts is d istorted.
A t the end of C h ap ter F o u r we discussed the d istrib u tio n of
zeros in the a n g u lar m om entum wave function and th e ir de
pendence on the azim uth and la titu d e angles. T h e electron
wave fu n ctio n also depends on the distance from the nucleus.
H ere the wave function may also have several zeros. If we
re tu rn to the three-dim ensional pictu re, these ra d ia l zeros
lie on concentric spheres. T h e an g u lar zeros lie on planes,
which pass th ro u g h the axis and cut the spheres along m e rid
ians, and on cones, w hich have a com m on vertex a t the nu-
Structure of the atom 99
cleus, an d for which the parallels on the sphere represent the
lines of intersection w ith the spheres. In Figure 29b there are
two radial, two la titu d in a l, and two azim uthal surfaces on
which the wave function becomes zero. T h e n u m b e r of rad ial
zeros is called the radial q u a n tu m n u m b er and is denoted by
n r. T h e m axim um com ponent of the an g u lar m om entum I
is called the azim uthal q u a n tu m num ber. In Figure 29b there
are two azim uthal zeros (in the real an d im aginary parts they
are displaced w ith respect to each o th er and hence are not
shown in the diagram ), so th a t the m agnetic q u a n tu m nu m b er
is k = 2. F urtherm ore, there are two m ore zeros on the
parallels, and hence the total n u m b er of an g u lar zeros is 2 +
2 = 4, so th a t I — 4. It is generally agreed th a t wave functions
should be classified not by n r b u t by the sum n = n r + I + 1,
which is called the p rincipal q u a n tu m n u m b e r of th e electron.
T h e convenience of using the p rincipal q u a n tu m n u m b er may
be seen from the fact th a t it is always greater than the
azim uthal num ber. In our exam ple, the p rin cip al q u a n tu m
n u m ber is n — 2 + 4 + 1 = 7. For this value of n, the azi
m u th al q u a n tu m n u m b e r can take the values 6, 5, 4, 3, 2, 1,
or 0.
In ad d itio n to the three q u a n tu m num bers n, I, and k, con
nected w ith o rbital m otion, there is also the spin q u an tu m
n u m b er u. T h e four num bers together specify the state of an
in d iv id u al electron in the atom , i.e., they represent its exact
state. Instead of a we sometimes req u ire the total angular
m om entum of the electron / = I ± T h e p o in t is th a t there
are two ways in which the an g u lar m om entum of in d iv id u al
electrons are com bined to form the resu ltan t an g u lar m o
m entum . In light atoms, and often in heavy ones, the o rbital
angular m om enta are added to form the resu ltan t angular
m om entum of the atom , and the spins are also added sepa
rately. T h is occurs w hen the individual o rb ital an g u lar m o
m enta in teract w ith each o th er m ore strongly th an w ith the
electron spins. T h e com m on effect of all the electrons on the
given electron is stronger than the action of the m agnetic field
associated w ith its spin. T h is couples the o rb ital m otions of
the electrons to each o th er (while the o rb ital m o tio n of each
electron is n o t coupled to its spin). Since in this case the
q u a n tu m n u m b e r j is unsatisfactory we have to use the spin
q u a n tu m n u m b e r <r. If, on the o th e r h an d , the spin-orbit
in teractio n of each electron is large (as often occurs in heavy
atoms), we have to add the values of j of the in d iv id u al
electrons to get the total a n g u lar m om en tu m J of the atom .
T h e basic pro b lem in the theory of m any-electron atom s
is to ex p lain M endeleyev’s periodic table by co m p arin g it w ith
the general principles of q u a n tu m m echanics. For this it is
sufficient to specify the state of the atom by m eans of the
q u a n tu m num bers of the in d iv id u al electrons. T h e fu n d a
m en tal ru le is: there can n o t be m ore th an one electron in an
atom w ith the same four q u a n tu m num bers. T h is is called
the Pauli exclusion p rinciple. It is im p o rta n t to note th at the
set of four num bers includes the spin q u a n tu m n u m ber. In
this sense, the spin itself is a stronger in d icatio n of the gen
eral state of a m any-electron system th an the action of its m ag
netic field. T h e w ord “exclusion” is used to indicate th a t a
state w ith given four q u a n tu m num bers in an atom can be
occupied by only one electron.
Indeed the exclusion prin cip le holds for all particles w ith
half-integral spin. T h is follows from relativistic q u a n tu m
m echanics (C hapter Eight). In the m eantim e we shall ad o p t
P a u li’s p rinciple as a postulate. It is as rigorous, how ever, as
the law of conservation of energy. T h e P au li exclusion p rin
ciple an d the classification of the states of in d iv id u al electrons
by th e ir q u a n tu m num bers are q u ite sufficient for a com
plete in te rp re ta tio n of the periodic system.
T h e first an d lightest elem ent, hydrogen, has only one elec
tro n, w hich moves in the field of a pro to n . T h e p ro to n and
electron a ttra c t each other according to the inverse square
low. In this, and only in this sim ple case does the energy
d ep end solely on the prin cip al q u a n tu m num ber. A p ro fo u n d
connection exists betw een this result of q u a n tu m m echanics
an d the fact th a t in classical m echanics th e trajectories of
particles in an inverse-square field are closed curves (in fact,
ellipses). T h is is one of the m anifestatio n s of the corre
spondence p rin cip le th a t we c an n o t prove here, since u n fo r
tu n ately h ig h e r m athem atics w ould be req u ired . In d eed , the
analogous problem in N ew tonian m echanics also requires the
use of calculus, in v en ted by N ew ton to solve this problem .*
In q u a n tu m m echanics the energy of an electron m oving in
the C oulom b field of the nucleus is inversely p ro p o rtio n a l to
the square of the p rin c ip a l q u a n tu m n u m b e r n , b u t does n o t
d e p en d on I and n r separately.
T h e p o te n tia l energy curve for C oulom b forces is show n in
F igure 21. Zero p o te n tia l energy is reached at an infinite dis
tance from the nucleus; i.c., the curve lies en tirely in th e
negative region. It is now easy to u n d e rstan d th a t an electron
b o u n d in an atom m ust possess negative to tal energy. In fact
any h o rizo n tal line rep resen tin g an energy level w ill cut the
p o te n tia l energy curve. Beyond the p o in t of intersection, the
p o te n tia l energy w ill be greater th a n the to tal energy, since
the k in etic energy, form ally speaking, w ill be negative. In
q u a n tu m m echanics this m eans th a t the wave fu n ctio n in the
co rresponding region is a tte n u ate d (C h ap ter T h ree). Conse
quently, the electron c an n o t escape from the atom as it is
b o u n d to it in discrete states. T h e to tal energy is inversely
p ro p o rtio n a l to the square of the p rin c ip a l q u a n tu m n u m b er,
w hich can n o t be less th an u n ity (rem em ber n = n r -f I + 1 an d
the least values of I and n r are zero). F u rth erm o re, it is clear
th a t —1 /1 2 < —1/ 2 2 < —1/ 3 2 .. . an d the lowest value of e n
ergy, or ground-state energy, of the hydrogen atom corresponds
to n — 1.
H ow m any electrons in any atom can have n = 1? F o r if
n = 1, I m ust be zero. T h e n k = 0 since I is the greatest value
of k. O nly the spin q u a n tu m n u m b e r takes two values <r =
± ^ . T h u s for n — 1, there are only two sets of q u a n tu m num -
* Recently Feyhman was able to prove without using calculus that planets
move in elliptical orbits. His reasoning, however, is by no means simple.
bers: 1, 0, 0, ^ an d 1, 0, 0, — By P a u li’s p rin cip le, no t m ore
th an one electron can be in each of these states. It follows
th a t an atom can contain at most tw o electrons w ith n = 1.
In the atom of helium , the next elem ent after hydrogen,
th ere are ju st two electrons. T hese assume the two possible
states w ith n — 1. T h e energy of these states is very different
from th a t of states w ith n = 2. A fairly large am o u n t of e n
ergy, appro x im ately 20 eV, is req u ired to transfer an electron
in the h elium atom from the g ro u n d state w ith n = 1 into
the n ex t state w ith n — 2. T h e energy req u ired to move a
system o u t of a given state is a m easure of the stability of th a t
state. A system of two electrons w ith n ~ 1 therefore has a
very stable configuration. W e say th a t these two electrons
occupy the K shell. Every atom from helium on has a full K
shell. In the old theory of B ohr, this p ro p erty of the helium
configuration could n o t be explained.
T h e stability of the K shell of the helium atom is the reason
for its very weak reactivity w ith o th er atom s, w hether they be
atom s of h elium or of any o th er elem ent. H eliu m does n o t
form chem ical com pounds an d liquefies only at very low tem
p eratures. T h e la tte r p ro p erty is due to the very slight a ttra c
tion th a t helium atom s have for each other. T h e weakness of
this attra ctio n is connected w ith the stability of the electron
configuration. N e u tra l atom s act on oth er atom s only w hen
they are som ew hat polarized, i.e., w hen the electron shells are
displaced w ith respect to the nucleus. T h is displacem ent and
deform ation causes the resu ltan t negative charge of the elec
trons in the shells not to coincide w ith the positive charge of
the nucleus. T h e atom ic system is then no longer centrally
sym m etric and is capable of e n terin g in to electrical in te r
actions resem bling the actions of m agnets. O w ing to q u a n tu m
effects these electrical forces decrease m ore rap id ly w ith dis
tance th a n do the m agnetic effects. T h ey are exceptionally
sm all in helium because of the stability of the K shell, which
is difficult to deform . T h e rm a l m otion im pedes th e transi-
tion of the weakly in te ra ctin g atom s in to the liq u id state u n til
very low tem peratures are reached.
O n account of this chem ical inertness, h elium is called an
inert gas, or else a noble gas, by analogy w ith noble m etals,
w hich form chem ical com pounds far less readily th a n “base”
elem ents.
A fter helium comes lith iu m . T h e K shell w ith n = 1 is now
com pletely filled, and the L shell w ith n = 2 starts to fill up.
F o r n = 2, I can take two values: I — 0 an d I = 1. If I — 0,
th en k = 0, so that, as in the K shell, there are two states
corresponding to a = If I = 1, k can take three values:
1, 0, —1; b u t for each value of k there are two values of < j,
giving six states. T h u s in the L shell there are in all 2 + 6 = 8
states. T h ese eight states correspond exactly to the first period
of M endeleyev’s periodic table.
In lith iu m only one of the eight possible states is occupied
w ith n = 2, / = 0. T h e b in d in g energy of such an electron is
very m uch less th an th a t of the K electrons. T h e re are two
reasons for this. Firstly, the p rin cip al q u a n tu m n u m b e r is
twice as great. If the same law as in the hydrogen atom ap
plied, the bond energy w ould be four times less th a n for n = 1;
b u t in ad d itio n to this, the m ore strongly b o u n d K electrons
move closer to the nucleus— this may be easily verified by fol
low ing the horizontal line in Figure 21. T h e low er this energy
line is draw n, the m ore quickly the wave fu n ctio n is a tte n u
ated in going away from the nucleus, so th a t close to the
nucleus the to tal energy is less th an the p o te n tia l energy.
H ence the K electrons screen the charge of the nucleus from
the L electron, an d it is b o u n d m ore weakly th an one w ould
expect for a hydrogen-type atom . T h e L electron of the
lith iu m atom is also weakly b o u n d and is considerably fu rth er
from the nucleus, on the average, than the K electrons.
T h is is responsible for the great chem ical activity of lith iu m ,
w hich loses its o u te r electron to o th er atom s very easily. T h is
p ro perty is characteristic of the alkali m etals, of w hich lith iu m
is the first. W e shall now show how to describe the states of
all its electrons. W e have already said th a t the states corre
sponding to / = 0, 1,2, an d 3 are called the s, p, d, and / states.
T h e prin cip al q u a n tu m n u m b er is p u t in fro n t of the letter
so th a t in hydrogen there is a l j electron and in helium there
are two such electrons. T h e n u m b er of electrons is denoted
symbolically by an ex ponent in the spectroscopic n o tatio n :
hydrogen Is, helium (lj)2, lith iu m (ls)22.s.
In beryllium , which comes after lith iu m , the configuration
is (H )2(2.s)2. By P a u li’s principle, no m ore th an two electrons
may be found in the Is and 2s states; b u t we m ust n o t th in k
th a t beryllium has a stable shell of the helium type. T h e rea
son is th at the energy of a 2s electron is no t very different
from th a t of a 2p electron. A lthough the field acting on an
electron in a beryllium atom is n o t strictly a C oulom b one,
the difference from a C oulom b field is still n o t very large since
the field of all the o th er electrons is added to the field of the
nucleus. H ence the energy depends far m ore on the p rin cip al
q u a n tu m n u m b er n than on the azim uthal n u m b e r I. It is
very easy to pass from the 2s state in to the 2p state, so th a t
beryllium is n o t in the least like an in ert gas. It is, of course,
a m etal.
T h e first period begins w ith lith iu m and ends w ith neon,
in which the shell with p rin cip al q u a n tu m n u m b e r n — 2 is
filled. N eon, whose electronic configuration is (ls)2(2s)2(2p)6,
is an in e rt gas. H ence the next electron m ust go in to the shell
w ith n = 3, and will also be weakly bo u n d , like the electron
in lithium . T h e elem ent after neon is in fact the alkali m etal
sodium , w hich begins the second period of M endeleyev’s sys
tem. For each elem ent in the first period there is a co rrespond
ing elem ent in the second period in which the electrons in the
last shell (which is still incom plete) have n = 3 instead of
n = 2. T h u s carbon has the electronic configuration
(\s)2(2s)2(2p)2, and silicon, which has sim ilar chem ical p ro p e r
ties, has the stru ctu re (ls)2(2s)2(2p)G(3s)2(3p)2.
W hen n = 3 the azim uthal q u a n tu m n u m b er may take the
three values 0, 1, an d 2. For I — 0 and 1 there are eight states;
for I — 2 there are ten states, since for I — 2, k may take the
five values 2, 1, 0, —1, and —2, and there are two values of
a for each k. H ow ever, the second period is com pleted w ith
I — \ only; i.e., in this period only 3s and 3p electrons occur.
T h e in e rt gas argon has the configuration (ls)2(2s)2(2/?)6
(3s)2(3p)G- W hy is this configuration so stable? W hy does the
3d subshell n o t start to fill up im m ediately after the 3p state?
It turns o u t th at the 3d state differs considerably in energy
from the 3p state. T h e dependence of the energy on the azi
m u th a l q u a n tu m n u m b er is now beginn in g to m ake its effect
felt.
Let us now consider the physical reasons for this. Firstly,
the in n e r shells of elem ents in the second period contain
enough electrons so th a t the field acting on the electrons in
the o u ter shells is very different from a C oulom b field. T h e
effect of the azim uthal q u a n tu m n u m b e r on the energy now
becomes com parable w ith the effect of the p rin cip al q u a n tu m
num ber.
L et us clarify the reason for this. T h e centrifugal force
m v 2/ r may be rew ritten as (mvr)2/rnr 3 if the n u m e ra to r and
the d e n o m in ato r are m u ltip lied by m r2. B ut m m is the an g u lar
m om entum , M, so th a t the centrifugal force is eq u al to
M 2/ m r 3. T h e centrifugal force is thus inversely p ro p o rtio n al
to the cube of the distance from the nucleus. W e may form ally
in troduce a p o ten tial energy, ju st as for o th er forces, a n d rep
resent it by a curve. W e have already seen th a t the p o te n tia l
energy curve can help us to deduce im p o rta n t in fo rm atio n
ab o u t the special features of m otion. In C h ap ter T h re e we
obtained an expression for the p o te n tia l energy of forces in
versely p ro p o rtio n al to the square of the distance. T h e energy
was inversely p ro p o rtio n al to the first power of the distance.
H ere the p o ten tial energy corresponding to the centrifugal
force is inversely p ro p o rtio n al to the square of the distance,
an d in ad d itio n contains the factor If the read er wishes he
may easily w ork this o u t for him self, m ak in g the necessary
sim ple changes in the proof given in C h ap ter Four.
T h e sign of the p o te n tia l energy of a cen trifu g al force is
also easy to find; since it is a repulsive force, the energy is
positive. In order to move an electron w ith a given an g u lar
m om entum tow ard the nucleus, one m ust do work on it, i.e.,
increase its p o ten tial energy.
L et us now com pare the p o te n tia l energy associated w ith
the centrifugal force an d the p o te n tia l energy of in teractio n
betw een the electron and the rem ain d er of the atom . In im m e
diate proxim ity to the nucleus the energy of the C oulom b field
is inversely p ro p o rtio n al to the distance, because in this region
the nucleus is n o t shielded by the opposite charges of the
electrons. T h is p a rt of the p o te n tia l energy is negative. If an
electron is in the s state, its an g u lar m om entum M is zero, so
th a t the centrifugal p o te n tia l energy is also zero (in classical
theory this w ould m ean th a t the electron moves along a
straig h t line th ro u g h the nucleus).
U nlike a classical particle, an electron w ith zero an g u lar
m om entum does n o t fall into the nucleus; it has zero m om ent
of m om entum (i.e., an g u lar m om entum ) and no trajectory.
W h en the angular m om entum is zero, an electron close to the
nucleus experiences a pure C oulom b force. W hen the an g u lar
m om entum is n o t zero, the centrifugal p o te n tia l energy is
always greater th an the C oulom b p o te n tia l energy, provided
the electron is near enough to the nucleus. T h is is so because
1 /r2 increases m ore rapidly th an —\ / r can decrease. It follows
th a t the p o ten tial energy curve for I > 0 always rises as r de
creases.
If we consider the case of very large r, we find th a t screening
of the nuclear charge by electrons is very im p o rtan t. T h e
attractive p a rt of the p o te n tia l energy curve falls, roughly
speaking, like 1/ r 3, i.e., m ore rapidly th an the centrifugal
energy. C onsetpiently, for large values of r the centrifugal e n
ergy w ill once m ore pred o m in ate over the C oulom b energy,
and the resu ltan t energy will be positive. Somewhere am ong
the in term ed iate values of r the energy will of course be
negative since otherw ise the p o tential well th a t is necessary
for retain in g the electrons w ould not exist. T h e resu ltan t curve
is shown in Figure 30.
T h e energy level in the well is shown as usual by a h o ri
zontal line. T h is is not taken as far as r = 0 in o rd er to show
an im p o rtan t property of states w ith I > 0. T h e centrifugal
energy acts as a b a rrie r preventing a p article from reaching
the origin. N ear the origin this force is infinitely great. T h is
is the same b a rrie r th a t prevents the e a rth from falling into
the sun. H ere again, we en co u n ter the centrifugal force acting.
H ow ever, in the case of classical m otion the straig h t line rep
resenting the total energy is draw n up to the p o ten tial energy
curve, w hile in q u a n tu m m echanics it is draw n to extend in to
the region of negative kinetic energy. A particle w ith i > 0
can n o t reach the origin. Its wave function becomes zero at the
origin, and this happens all the m ore the g reater th e value of
I (i.e., it behaves like r {). W hen I — 0 the electron still does
not, of course, fall in to the nucleus, b u t its wave function is
not zero at the origin. It can n o t get “com pletely” in to the
nucleus because this w ould violate the u n certain ty principle.
If it had a strictly defined position the u n certain ty in its
Figure 30
m o m entum w ould be so great th at the C oulom b field w ould
be unable to re ta in it.
W e can now explain why the 3d subshell does no t start
b u ild in g u p in the elem ents im m ediately follow ing argon.
T h e 4s electrons, as we have ju st seen, ap p ro ach the nucleus
m uch m ore closely; the centrifugal b a rrie r does n o t act on
them . H ence, although the prin cip al q u a n tu m n u m b e r does
increase, the electron moves closer to the nucleus and its b in d
in g energy is greater ow ing to the decrease in the azim u th al
num ber. W hen th en is the p state filled next? T h e p o in t is
th a t in the p state the square of the an g u lar m o m en tu m is
equal, as we have seen, to two, b u t w ith I — 2; i.e., in the d
state, it is equal to six. In this case, k can take the values 2,
1, 0, —1, and —2. T h e m ean square thus equals y b(22 + l 2 +
02 T 12 T 22) = 2, and the square of the an g u lar m o m en tu m
itself, as always, is three times the m ean square of the com
ponents, or six. H ence, the centrifugal energy of the d state
is three times as great as in the p state, and affects the m otion
of the electron to a m uch g reater extent. In the / state the
square of the an g u lar m om entum is twelve and its centrifugal
energy has an even g reater effect on the total energy.
T h e 4s electrons also have far less energy' th an the 3d elec
trons, and hence argon has the configuration of an in e rt gas
even though its shell w ith n = 3 is no t filled up ; i.e., 3d
electrons are missing. W h en the charge on the nucleus in
creases by one, the new 4s electron proves to be weakly bound
as in the two previous alkali metals. T h e new elem ent is the
alkali m etal potassium . It is interesting to note th at although
its atom ic w eight is less th a n th at of argon, its nuclear charge
is greater, so th a t potassium occurs after argon in the periodic
table.
T h e 3d subshell starts to fill w hen the 4s subshell is filled.
However, the 3d subshell does n o t fill in a reg u lar m anner,
for suddenly, w ith the tran sitio n to the next elem ent, there
appears not one new electron in the 3d subshell b u t two— the
second is transferred from the already fdled 4s subshell. T h e n ,
in the next elem ent, the 4s subshell is once m ore filled and
n o th in g happens in the 3d subshell. W e see from Figure 30
th at the p o te n tia l energy curve exhibits a " h u m p ” on the right.
T h is h u m p restricts the m otion of a particle in the direction
of large values of r. As a result, the 3d subshell is situated
somewhere in the m iddle of the atom , essentially where the
total energy is greater th an the p o te n tia l energy. T h e chem ical
p roperties of an atom are determ ined p rim arily by the o u te r
m ost electrons, so th a t w hile the 3d subshell is being filled
the chem ical properties vary irregularly.
T h e 4/ subshell is also fdled out of tu rn , and is responsible
for the sequence of fourteen rare-earth elem ents. It lies com
pletely inside the atom (i.e., there are electrons th a t are ex
ternal to it; th e ir m otion is unaffected by the h u m p of Fig.
30). T h e chem ical properties of the rare-earth elem ents are
very sim ilar. P ure elem ents of this grou p or th eir com pounds
are q u ite difficult to separate from m ixtures.
W e shall n o t weary the reader by reconstructing the en tire
periodic table; we shall merely state th at the system based on
the q u a n tu m num bers of the indiv id u al electrons and on
P a u li’s p rinciple is q u ite sufficient to construct and explain the
w hole of the periodic table.
L et us now say a few words about the n a tu re of chem ical
valence. T h e special property of valence forces is th eir ability
to saturate. T w o atoms of hydrogen com bine to form a m ole
cule of hydrogen, b u t a th ird atom of hydrogen cannot n o r
m ally com bine w ith them . An atom of carbon can com bine
w ith no m ore th a n four hydrogen atom s. Chem ists denote
these com ponents of the valence forces by dashes connecting
the atom ic symbols, for exam ple: H = H. W h en very little
was know n ab o u t atom s, it was th o u g h t th at these lines corre
sponded to some k in d of “hooks” connecting the atoms, com
pletely in the sp irit of L u cretiu s’ poem De rerum nalura (“ On
the N a tu re of T h in g s ”). Nowadays, there is hard ly a chem ist
who believes the physical reality of these hooks, even am ong
those who do n o t wish to accept the ideas of q u a n tu m m e
chanics (of whom, happily, only very few rem ain).
B ohr's old q u a n tu m theory was u n ab le to ex p lain n o t only
the satu ratio n of the valence forces b u t even the stability of
the hydrogen m olecule. Electrons m oving in classical orbits
ab o u t two protons can n o t connect them by a strong bond.
Soon after the creation of q u a n tu m m echanics, H e itle r and
L o n d o n form ulated a very sim ple and clear a p p ro x im ate the
ory of the hydrogen m olecule. T h is n o t only e x p lain ed the
stability and satu ratio n of the chem ical b o n d in the hydrogen
m olecule, b u t also m ade it possible to u n d e rstan d the general
n a tu re of the valence forces.
In p articu lar, it was im p o rta n t th a t an ex p lan a tio n was
fo u nd for covalent bonds, in which there is no transfer of
charge from one atom to another. T h e n a tu re of h etero p o lar
bonds is a different one. For exam ple, in N aC l th e 3s electron
of sodium , which lies outside the filled shells, is transferred
to the unfilled 3p subshell of the chlorine atom , giving it the
stable configuration of argon. In the case of hydrogen, there is
no transfer of electrons from one atom of the Ho m olecule to
the other. Each electron belongs sim ultaneously to b o th p ro
tons. H ow then does the chem ical bond arise?
L et us suppose th at the two protons are forcibly placed at
the same point, so th a t a helium nucleus w ith atom ic w eight 2
(which does n o t occur in n atu re) is form ed. Electrons will go
in to the l j shell around such a nucleus w ith o u t a suspicion of
instability, ju st as they will for an actual H e atom . If the
protons then move a p a rt gradually, they do n o t ru p tu re this
shell b u t only stretch it. T h u s a stable hydrogen m olecule is
ob tained. T h e satu ratio n of the valence forces is therefore also
u n derstandable; in the first 1$ shell of the helium atom of
atom ic w eight 2 there can be only two electrons, w hich have
opposite spins. T h u s the valence lines in the H = H m olecule
correspond to the two opposite spins— a fairly good symbolic
p icture replacing the hooks.
T h is w ord picture m ust, of course, be reinforced by calcu
lations. H e itle r and L o n d o n perform ed such calculations be
g in n in g n o t w ith com bined atom s, b u t w ith atom s an infinite
distance ap art. T h e y were able to show th a t forces arise be
tween these atom s as they approach each other, especially w hen
the electron spins are an tip arallel.
T h e idea of the m u tu a l satu ratio n of electron spins corre
sponding to the satu ratio n of the valence forces proved to be
exceptionally fru itfu l for u n d e rstan d in g covalency in general.
C onsider, for exam ple, how the tetrav alen t n a tu re of carbon
is explained. T h e electronic configuration of the carbon atom
in the g ro u n d state is ( ls)2(2s)2(2p)2. W e have seen th a t in light
elem ents the 2$ and 2p states differ only slightly in energy.
W h en carbon forms a chem ical com pound one of the 2s elec
trons goes in to the 2p subshell so th a t the configuration
(ls)22s(2p):! is obtained. T h e sm all am o u n t of energy necessary
for this tran sitio n is derived from chem ical affinity.
It may fu rth er be shown th a t the spins of all three 2p elec
trons are parallel. If three electrons have identical p rin cip al,
azim uthal, an d spin q u a n tu m num bers, th eir m agnetic q u a n
tum num bers m ust differ. For if / = 1, k can take precisely
three values: 1, 0, or —1. T h e different m agnetic q u a n tu m
num bers correspond to different distrib u tio n s in space of the
“electron clouds.” If these clouds are separated in space, the
electrons will be fu rth e r a p a rt on the average th an if the
“clouds” were superim posed on each other. T h e p o te n tia l
energy of repulsion will then be less on the average, since it
is inversely p ro p o rtio n al to the distance betw een the electrons.
T h is m eans th a t w hen the spins of all three 2p electrons are
parallel, th eir energy is less th an w hen two o u t of the three
electrons have an tip arallel spins. H ow ever, the low er the
energy of the state, the m ore stable it is: the m easure of sta
bility is always the work th a t m ust be done to move the system
ou t of the given state.
It is instructive to note th a t the energy of a system of elec
trons depends on their spin alignm ent, which is n o t at all
connected w ith th eir m agnetic interactio n . By P a u li’s p rin
ciple, the alignm ent of the spins affects the electrons’ electro
static interaction. T h is is at least a th o u san d times greater
th an the m agnetic interaction. W ith o u t the exclusion p rin
ciple, we could not u n d e rstan d why the p o te n tia l energy of
the 2p electrons is least w hen th e ir spins are parallel.
In the (ls)22s(2p)3 configuration there are fo u r u n co m p en
sated spins, one from the 2s electron a n d three from the 2p
electrons. H ence a carbon atom can com bine w ith four atoms
of hydrogen.
It w ould be alm ost im possible to form u late a general q u a n
titative theory of valence, since difficulties even g reater th an
those fo u n d in the theory of m any-electron atoms wro u ld be
encountered. N evertheless, even a q u alitativ e u n d erstan d in g
of the n a tu re of valency forces, based on the H eitler-L ondon
ap p ro x im atio n an d the general picture of satu rate d spins, is
m ost useful.
^ Electrons in crystals
A very extensive branch of physics is devoted to studies of the

very diverse properties of crystals: therm al, electrical, optical,
m agnetic, etc. W e shall be concerned w ith only a few of these
properties.
Ju st as in the theory of the atom , w here we first studied the
m otion of an individual electron and then b u ilt u p the atom
as a whole (C hapters F our and Six), we shall now find it con
venient to begin w ith a single electron in a crystal. C onsider
such an electron m oving in the field of all the atom s in a
crystal (self-consistent field). T h is field is due to the nuclei an d
all o th er electrons. It has the same periodicity as the crystal,
and hence the first question is: how docs an electron move in
a three-dim ensional periodic force field?
It is convenient to approach this question from two o p p o
site points of view; one can assume th a t the electron is mov
ing alm ost as freely as in em pty space, or, on th e o th er hand,
th at it is alm ost as b o u n d as in the atom . B oth m ethods give
results th a t agree qualitatively, and hence it is reasonable to
com pare them w ith experim ent in every case.
W e have, in fact, already used the first approach w hen we
considered the electro n ’s diffraction in a crystal. L et us re tu rn
to Figure 14b, and assume th at de Broglie waves ra th e r th an
electrom agnetic waves are p ropagated in the crystal. R eflection
occurs w henever an integral m u ltip le of the w avelength can be
fitted in to the p a th C1B 2C2. For sim plicity let us take the
case w here the wave is p ro p ag ated at rig h t angles to the planes,
so th a t we have a one-dim ensional pictu re instead of the m ore
com plicated three-dim ensional one. It is im m ediately clear
from Figure 14b th a t in this case the wave will be reflected
w henever the w avelength equals twice the p erio d of the lattice.
F o r all o th e r w avelengths the wave will pass th ro u g h the la t
tice w ithout reflection. T h e de Broglie w avelength is A = h /p ,
w here p is the m om entum of the electron. R eflection occurs
w hen 2a = n k. T h u s waves of any len g th pass th ro u g h the
crystal except those for w hich p = n h /2 a , w here n is an
integer.
T h e energy of the electrons used in the diffraction e x p eri
m ent is considerably g reater than the b o n d energy of the
electrons in the crystal, so th a t we may consider the form er
as alm ost free. W e shall now extend o u r arg u m en t to the
b o u n d electrons in the crystal. L et us assume th a t they move
th ro u g h o u t the whole crystal, alm ost as if they were free, b u t
th a t they cannot escape from it. T h e ir energy is given in term s
of m om entum by E(p) - p 2/2 m , since p = m v an d E = m v 2/2 .
T h e g rap h of the energy of a free particle as a fu n ctio n of its
m o m entum has the form of a parabola (Fig. 31a). Close to
points w here p = n h /2 a , however, p ro p ag atio n of de Broglie
waves th ro u g h the crystal is im possible since waves reflected
from successive planes of the crystal cancel each o th e r out.
H ence the tru e dependence of energy on m o m en tu m m ust be
of the form shown in Figure 31b. T h e curve has a sm all dis
co n tin u ity w henever p = h n /2 a , and consists of a n u m b e r of
separate segments. If the projection of each segm ent is taken
on the energy axis, we find th a t the electron spectrum is alm ost
continuous. Some sm all “fo rb id d en ” regions occur, however,
in the continuous spectrum . In Figure 31b, the “ allow ed”
bands are m uch larger than the “ fo rb id d en .”
Let us now consider the opposite approach. W e assume th a t
the electron is firmly b o und in some p o te n tia l well. Figure 32
represents a whole series of such wells corresponding to a
sim plified one-dim ensional m odel of a crystal. T h e wells are
Electron in crystals 115
Figure 31
assum ed to be infinitely deep n e a r th e nuclei, as in F ig u re 21.
T h e h o riz o n ta l line represents the energy level, w hich is th e
same for all th e wells. T h e section of th e curve A B C m ay be
considered as a p o te n tia l b a rrie r against crossing from th e
first well on the left to the n e ig h b o rin g one. T h e sam e applies
to the o th e r wells, so th a t the electro n c an n o t be considered
b o u n d in th e strict sense of the w ord; i.e., it n eed n o t rem ain
in a given p o te n tia l w ell b u t can pass from one to th e n ex t
ad in fin itu m . In this sense we can consider it to be alm ost
free.
If the wave fu n ctio n in n eig h b o rin g wells differs only in
Figure 32
phase and n o t in am p litu d e, it is n o t a tte n u ate d as the electron
passes th ro u g h the crystal. T h e n , in spite of the series of b a r
riers, the electron passes th ro u g h the w hole crystal q u ite freely.
For this to h ap p en the wave functions e x ten d in g from the well
u n d e r the b a rrie r m ust be join ed in such a way th a t th eir
a m p litu d e rem ains the same in n eig h b o rin g wells. For exam
ple, such a fu n ctio n is shown by the broken line in Figure 32.
It is in opposite phase in n eighboring wells. W hen the wave
len g th is very long, the phase of the wave functions in n eig h
b o rin g wells is alm ost the same. Each wave fu n ctio n has its
own p a rtic id a r energy value. For the whole phase in terv al
(from opposite to equal) there is a corresponding in terv al of
electron energy. W e have once again reached the conclusion
th a t there m ust be an interval of allow ed values of the energy
in w hich the electron can move freely th ro u g h the crystal.
T h e higher the energy b a rrie r separatin g the wells, the n a r
row er the interval of allow ed values of the energy. If the well
contains n o t one b u t several levels, a sequence of allow ed in
tervals of energy will be obtained. Each of the levels in the
well corresponds to a separate electron level in the atom : the
allow ed values are o b tain ed from the levels w hen the atom s
form a crystal. W e have thus reached the problem of the m o
tion of an electron in a crystal from the o th er d irectio n , i.e.,
by considering the electron n o t as alm ost free b u t as alm ost
Electrons In crystals 117
bound to an individual atom . However, a q ualitatively sim ilar
picture is obtained (Fig. 33), except th a t now the allow ed
intervals are narrow an d the forbidden ones are wide.
L et us now consider the levels of the atom ic electrons shell
by shell. From the K shell levels we find allow ed bands th at
arc narrow (in com parison w ith the forbidden bands), while
from shells w ith higher q u a n tu m num bers we find g reater in
tervals of allow ed energies. Above the filled electron levels lie
the unfilled levels where electrons occur only as a result of
excitation. Since the electrons in these levels are b o u n d m ore
weakly, b ro ad allow ed bands separated by narrow forbidden
bands arc obtained from them . Sometimes the allowed bands
ex tend so far th a t they p artially cover each o th e r and form a
com bined band. A com bined band is form ed in beryllium from
the bands caused by the extension of the 2s and 2p levels
(which, as we have said before, are fairly close together).
T h e transform ation of the individual atom ic levels into
allow ed bands may also be illustrated by a m echanical model.
W e have already said th at the p roper energies of an atom are
analogous to the frequencies of a stretched string. If two iden
tical strings are stretched on the same resonator and connected
to each other, each frequency will be divided into two. O ne
will correspond to the vibration of both strings in the same
Figure 33
phase an d the o th e r to th eir vibrations in opposite phase.
W hen three identical strings are stretched, the frequency is
split in to three, etc. (the n u m b e r of frequency com ponents is
always the same as the n u m b e r of strings). In the lim it, w hen
there are an infinite n u m b er of stretched strings, allow ed and
fo rb id d en frequency intervals arise, each interval being o b
tain ed from one frequency. T h e w eaker the co u p lin g betw een
the strings, the n arrow er are the intervals. In the lim it of a
very weak coupling they contract in to in d iv id u al frequencies.
W h en the energy band of a crystal is form ed from a filled
atom ic shell, then, by P a u li’s principle, all the places in it
are occupied, ju st as in the shell. If the shell is no t filled, die
band, too, is only partly filled. For exam ple, in the lattice of
sodium , a band is form ed from the 3j subshell. Sodium has
only one electron in this shell; therefore only h a lf the states
th a t the band contains are occupied. If there are N atom s in
the lattice, there could be 2N electrons in the band, b u t in
fact there are only N . Since the stable state always has the
least possible energy, the low er N states are occupied, and the
u p p e r N are free. In beryllium , the ban d o b tain ed from the
2s subshell is filled, b u t it occurs in co n ju n ctio n w ith the 2p
subshell, which is free.
If an external electric field is applied to a crystal possessing
an incom pletely filled band, the electrons in it will accelerate
and their energies w ill increase so th a t they transfer from the
filled p a rt of the band into the unfilled p art. In a com pletely
filled b an d there is no room for fu rth e r electrons. T h u s, w hen
all the bands in the crystal are filled, an applied electric field
can n o t accelerate its electrons. W e have therefore reached an
electronic quantum -m echanical ex p lan atio n of the difference
betw een a m etal an d an insulator: in a m etal there are one or
m ore incom pletely filled bands, w hile in an in su lato r there are
none.
In hydrogen the K shell is only h alf filled, as it contains only
one electron. N evertheless, solid hydrogen is a dielectric and
n o t a m etal. T h is is because solid hydrogen is com posed of
Electrons in crystals 119
molecules and not of individual atoms (see C h ap ter Six).
H ence the m olecular crystal of hydrogen is a dielectric. H ow
ever, u n d e r very high pressures the crystal is transform ed into
an atom ic crystal of hig h er density. According to the calcula
tions of A. A. Abrikosov the necessary pressure w otdd be 3
m illion atm ospheres. Solid hydrogen should then ex h ib it the
properties of a m etal.
A lthough we have stated the conditions u n d er which a
crystal can conduct a current, we have not yet discussed the
n a tu re of conduction. If an electron in a m etal could be accel
erated w ith o u t lim it in an electric field, the m etal w ould pos
sess infinite conductivity. For any value of the field, an infi
nitely large cu rren t w ould be produced. In fact, however, to
every field there corresponds a definite finite cu rren t th a t is
directly p ro p o rtio n al to the applied field (O h m ’s law). T h e
theory m ust therefore explain the finite conductivity of metals.
O u r discussion of the free m otion of an electron in a crystal
referred only to an ideally regular crystal; b u t the electron can
be reflected from any crystal irregularity, preventing it from
being accelerated w ith o u t lim it by the electric field. Even if
the crystal contained no stru ctu ral irregularities or im purities
its o rder w otdd be d isturbed by the therm al m otion of the com
p o nent atoms. W hen an electron moves in a crystal whose
atom s execute therm al oscillations, it exchanges its energy with
the lattice. W hen there is no external field the electron, on
the average, acquires and gives u p the same energy. W hen a
field is applied, however, the eq u ilib riu m is upset. T h e elec
tron im parts the extra energy acquired from the field to the
lattice, increasing its therm al m otion. T h is is responsible for
the p ro d u ctio n of Jo u le heat. At absolute zero the therm al
m otion of the lattice ceases, and the atom ic oscillations no
longer im pede the m otion of electrons. H ence the electrical
resistance of an ideal crystal m ust become zero. F. Bloch, the
a u th o r of the m odern electron theory of m etals, concluded in
1930 th a t n ear absolute zero the resistance of m etals tends to
zero like the fifth pow er of the tem perature.
T h e classical electron theory of m etals was proposed by
D rude at the beginning of this century, soon after the exist-
ence of the electron ceased to be a m ere hypothesis. D rude
regarded electrons as a k in d of gas present in the crystal. It is
well know n th a t every gas, w hether it is m ade u p of in d iv id u al
atoms or o th e r particles (e.g., electrons), has a specific heat of
3 cal/m o le deg, which is in d ep en d e n t of the mass of the p a r
ticles.* H ow ever, in com parison w ith insulators, m etals have
no ad d itio n al specific heat, and D ru d e ’s theory was u n ab le to
ex p lain this.
In 1926 Som m erfeld poin ted o u t th at the Pauli p rin cip le
had considerably changed the situ atio n (the first im petus had
in fact been provided by F erm i’s work). L et us exam ine how
this came about. Since the therm al energy per mole m ust eq u al
3 cal/m o le deg, the value per electron will be p ro p o rtio n ally
sm aller in accordance w ith the n u m b er of electrons in 1 mole,
i.e., it will be 6.024 X 1023 times sm aller. At a tem p eratu re of
SOO0# this gives:
3 X 4 X 107 X 300
6 X 1 0 14 erg
6 X 1023
For com parison w ith atom ic quantities, we can tu rn this
result in to electron volts by dividing by 1.6 X 10-12. T h is
gives approxim ately 0.04 eV. T h e w idth of the allow ed energy
b a n d is of the o rd er of a few electron volts. Suppose th at a
band is only half-filled w ith electrons. T h e distance from the
b ottom of the band to the upperm ost filled level (the so-called
Fermi-level) is ab o u t 4 eV. H ence, an electron occupying
a level fu rth e r than 0.04 eV from the u p p e r boundary simply
can not undergo therm al excitation; th a t w otdd p u t it into one
of the u p p e r levels th a t has already been filled. In o th e r words,
a m an in the m iddle of a crowd canno t force his way ou t of
it, b u t if he is at the edge, he is, of course, able to do so. In
the same way an electron w ith energy th a t is close to the up-
* Provided these particles arc not rotating in space like rigid tops or per
forming internal oscillations.
perm ost filled level can undergo th erm al ex citatio n of 0.04 eV.
For a total w idth of the filled p a rt of the b a n d eq u al to 4 eV,
this constitutes a b o u t a h u n d re d th of the to tal n u m b e r of elec
trons. T h u s P a td i’s p rin c ip le explains why the electrons of a
m etal play such a sm all p a rt in its specific heat. T h is removes
the p rin cip al difficulty of D ru d e ’s theory.
H ow ever, even the Som m erfeld-B loch theory was for a long
tim e u n ab le to ex p lain one Aery striking fact. As early as 1911,
K am erlingh O nnes in Leyden discovered th a t the resistance
of certain m etals suddenly becam e zero at a tem p eratu re sev
eral degrees above absolute zero. T h is p h en o m en o n is called
superconductivity. T h e c u rre n t produced in a rin g of su p er
co n ducting m etal by electrom agnetic in d u ctio n will go on
flowing un d im in ish ed for an indefinitely long time, since none
of the energy is dissipated as Joule heat. S uperconductivity is
also observed in m etals c o n tain in g im p u rities an d stru ctu ral
im perfections, w hich according to B loch’s theory w ould retain
a “ resid u al” resistance even at absolute zero. H ow ever, im
perfection does n o t affect superconductivity.
S uperconductivity rem ained a mystery for m ore th an 45
years u n til B ardeen, C ooper, an d Schrieffer ex plained it. T h e ir
theory was im proved by N. N. Bogolyubov. S uperconductivity
was ex p lain ed after the discovery of the isotope effect. W hen
superconductivity is stu d ied in samples of the same m etals
m ade u p of different pure isotopes, the tem p eratu re of tran si
tion in to the superconducting state is found to d ep en d some
w hat on the atom ic w eight of the isotopes. Isotopes of heavy
elem ents differ only in th e ir atom ic weights; th e ir electron
stru c tu re is the same. C onsequently, superconductivity m ust be
connected w ith some pro p erty of the crystal th at is directly
related to its atom ic weight. T h is can clearly be only the
therm al oscillation of the crystal. It is well know n th a t for a
given elastic force the frequency of oscillation of a body is
inversely p ro p o rtio n al to the square root of the mass. T h e
elastic force is com pletely accounted for by the electronic p ro p
erties, so th a t the en tire difference betw een the isotopes con-
sists of the frequency difference of th e ir therm al oscillations
due to the difference in mass. H ow ever, even after the discov
ery of the isotope effect the e x p lan a tio n of superconductivity
did not follow at once.
F rohlich observed th a t the therm al oscillations m ust lead to
a special form of in teractio n betw een the electrons themselves.
W hen we speak of the resistance of a m etal we m ean th a t the
electron may e ith er absorb energy from the therm al oscillations
or else im p a rt its energy to them . In this sense the in teractio n
of the field of elastic oscillations in the crystal w ith the electron
is very rem iniscent of the in teractio n of an electrom agnetic
field w ith it. H ere too the electron may absorb or rad iate in
dividual portions of energy (quanta). If one electron em its a
q u a n tu m of energy and a n o th er absorbs it, this corresponds to
an in teractio n betw een the electrons. T h e in term ed iate agent
— the field— is, so to speak, elim inated. In em pty space this
agent can only be the electrom agnetic field, b u t in the crystal
there is also the field of the clastic oscillations. F rohlich con
sidered the interaction betw een the electrons tran sm itted by
the elastic oscillations of the crystal from a theoretical p o in t
of view. He started from the fact th a t in different isotopes of
the same elem ent superconductivity begins at slightly d if
ferent tem peratures. However, he was no t able to explain the
p h enom enon of superconductivity itself.
T heory and experim ent still rem ained separated. It was
know n from experim ent th a t the atom ic w eight affected the
tem p eratu re of tran sitio n in to the superconductivity state, and
from theory th a t the atom ic w eight affected the interaction
betw een electrons through the therm al oscillations of the la t
tice; b u t how the one was connected w ith the o th er was re
vealed only after the theoretical work of B ardeen, C ooper,
Schrieffer, and Bogolyubov. T h e energy of the therm al oscilla
tions of the lattice is absorbed and em itted by the electrons
and couples electrons in pairs in w hich the m om enta and
spins are each an tip arallel. T h is “ b o n d ” does not resemble
the electron-nucleus “ b o n d ,” which is due to electrom agnetic
forces. In the present case the Pauli prin cip le plays an essen
tial role. If this p rin cip le did not operate, such pairs w ould be
unstable; they w ould break down and pass in to the free state.
P a u li’s exclusion prin cip le does not allow them to go in to an
u n b o u n d state if the state is already occupied by o th er elec
trons. Some ad d itio n a l energy m ust be supplied before the
m embers of the p a ir can find free places in an energy band;
b u t if energy is req u ired to break up the pair, this means that
the two electrons form a stable bound state.
T h is form of bond does not resemble the bond of an in d iv id
ual electron in a p o te n tia l well. C ontrolled by the action of the
oth er electrons of the system on the pair u n d er consideration,
it is a special effect th a t cannot be understood w ith o u t P a u li’s
principle.
T h e bou n d state is stable against disturbances. W hen an
ex tern al electric field is applied to the m etal, all electrons, in
cluding those in b o u n d pairs, are accelerated in the direction
of the applied field. T h is means th a t alth o u g h originally the
p air h ad zero resu ltan t m om entum , the application of the field
gives rise to a nonzero m om entum com ponent in the direction
of the field. T h e bond is still intact, however, and the m otion
of the lattice cannot break it because it is precisely this m otion
th a t was responsible for the bond in the first place. T h is
m echanism thus avoids the transfer of energy to the lattice
and thereby removes resistance to the flow of currents. Super
conductivity was, in fact, the last phenom enon in physics o u t
side the dom ain of nuclear forces to rem ain un ex p lain ed . Now
there are no such phenom ena left.
In a d d itio n to m etals and dielectrics, an in term ed iate class
of substances exists: the sem iconductors. T h e ir resistance is
m uch higher than th a t of metals, and at absolute zero becomes
infinite, like th a t of insulators. M oreover, this resistance is
very closely connected w ith the p urity of the crystal. H ence it
is clear th a t the pro p erty of sem iconductivity itself m ust be
connected som ehow w ith the im purities in the crystal.
U sually the energy level of an im pu rity atom in a lattice
124 Basic concepis in quantum mechanics
lies somewhat below the lower edge of an unfilled energy band.
If the distance is of the order of a few h u n d re d th s of an elec
tro n volt, then, as we have already seen, an electron from the
im purity atom may become detached th ro u g h th erm al excita
tion and find itself in an unfilled band. U n d er such conditions
electrons behave as if they were free; they carry charge and
tu rn the crystal into a conductor. T h e ir n u m b er in the b an d
is relatively small in com parison w ith the n u m b er of atoms
in the crystal, because the im p u rity co ncentration is usually
low. For a small num ber of electrons th e exclusion p rin cip le
cannot make its effect felt, since so few of the states in the b an d
are occupied. T h e electrons may move freely from one state to
an other w ithout risking a “collision” w ith an occupied state.
T h is resembles D rude’s classical electron theory, except th a t we
are now dealing w ith sem iconductors and n o t metals.
T h e re is also another type of sem iconductor in which the
im purity has a free level a few h u n d red th s of an electron volt
above the u p p er edge of the filled band. T h e th erm al m otion
then transfers electrons from the filled levels to the free level
of the im purity, so th a t unfilled levels or “holes” are left.
T h is term has received universal recognition an d is used in
scientific literatu re w ithout q u o tatio n m arks. A hole behaves
in an electric field like an electron w ith a positive charge.
Sometimes one p a rt of a sem iconductor possesses electron
conductivity and an o th er p a rt hole conductivity. F o r this to
occur there m ust be different kinds of im purities in the re
spective parts. T h e electron type of conductivity is denoted for
brevity by the letter n (negative) and the hole type by p (posi
tive). T h e boundary betw een the regions w here tran sitio n from
one type to the other takes place is called an n p ju n ctio n .
At the np ju n ctio n there m ust certainly be a ju m p in the
electrostatic potential. T h e electrons an d the holes may be
considered as two “gases” w hich tend to fill the whole crystal.
If the particles were n e u tra l there w ould be no obstacle to
this; b u t the displacem ent of charged particles— electrons an d
holes— creates an electric field acting in the opposite direction
to the ap p lied field. Suppose th a t the electrons lie to the left
and the holes to the right. T h e n the field opposing the m otion
of the holes acts from left to right. H ow ever, since the charge
on the electrons is negative, the same field repels them from
rig ht to left. T h is field creates a p o ten tial ju m p at the np ju n c
tion.
L et us now connect the ?t-type and p-type sem iconductor
areas w ith an external wire, so th a t we have the following
circuit: n-type sem iconductor, n p jun ctio n , p-type sem icon
ductor, wire, and the n-type sem iconductor again. If there is no
ex ternal source of energy it is clear th a t n o cu rren t can flow;
otherw ise we w ould have a p erpetual m otion m achine creating
energy o u t of nothing.
L et lig h t fall on an n-type sem iconductor and be absorbed by
the electrons. If the electrons o b tain sufficient energy to over
come repulsion from the np ju n ctio n , the electric field of the
n p ju n c tio n w ill no longer retain them . A c u rre n t will flow in
the circuit, its energy being provided by the incident light.
T h is transform ation of ra d ia n t energy to electrical energy is
called the photoelectric effect.
In this case the conversion efficiency is fairly high, so th at
there is some possibility of using photoelectric devices for
energy conversion. Small am ounts of solar energy are already
being transform ed in to electric energy in satellites’ photocell
batteries. Photoelectric devices have a wide range of applica
tion in sound films, signaling, etc.
A t absolute zero there is no therm al m otion, and the transfer
of electrons to and from the im purities ceases. T h e sem icon
d u cto r then becomes an insulator.
T h e re are crystals th a t are intrinsically m agnetized; i.e., the
m agnetic m om ents of all the atom s are aligned in the same
d irection. T hese are called ferrom agnetic substances, e.g., iron,
cobalt and nickel. All these elem ents possess unfilled 3d sub
shells, which lie w ithin the atom (see C h ap ter Six). T h e elec-
tron spins in these shells are relatively free because the lattice
has little effect on them . H ow ever, w ith respect to each o th e r
the spins are parallel instead of being a rb itra rily aligned.
Before the advent of q u a n tu m m echanics, it was supposed
th a t the m agnetic m om ents tend to becom e parallel th ro u g h
the action of the m agnetic forces betw een them ; b u t it is easily
shown th a t the m agnetism of iro n an d o th e r ferrom agnetic
substances c an n o t be explained by the m agnetic in teractio n
of the spins. L et us calculate the energy of such an in teractio n .
T h e p o te n tia l energy of the two m agnets is equal to the p ro d
uct of th eir m om ents divided by the cube of the distance be
tween them . T h e m agnetic m om ent of the spin is equal to 1
B ohr m agneton, i.e., lO-20 (CGS). T h e distance betw een the
atom s in the lattice is of the o rd er of 10-8 cm. H ence the
energy of m agnetic in teractio n is ap p ro x im ately 10~16 ergs.
T h is is the energy of therm al m otion at one degree above
absolute zero. Since therm al energy is random , it tends to
destroy all o rd er if it is sufficiently energetic. In fact, how
ever, iron loses its m agnetic properties at a tem p eratu re of
ab o ut 1000°K. C onsequently, the spin alig n m en t is controlled
by forces th a t in the lim iting case are a b o u t 1000 times g reater
th an the m agnetic forces.
In the previous ch ap ter we saw th a t there is a special kind
of spin in teractio n th a t has a com pletely different n atu re. T h e
spins are aligned in such a way th a t the electrical in teractio n s
betw een the electrons themselves (C oulom b repulsion) are
m inim al. In this situ atio n b oth the am p litu d e and the phase
of the wave function are im p o rtan t. T h e C oulom b repulsion
is d eterm ined not only by the squares b u t also by the products
of the wave functions of the in d iv id u al electrons. B ut the p ro d
uct of the wave functions of different electrons may be of
e ith er sign, according to the signs of the m ultiplicands. T h is
factor proves to be decisive for the stability of the hydrogen
m olecule: it gives a negative term in the total energy of the
system, which com pensates the positive term due to the re p u l
sion. Since the phase of the wave function is a pure q u an tu m -
m echanical concept, this result cannot be explained w ith the
aid of electrical analogies such as the electron-cloud model.
In the case of the hydrogen molecule, a negative term is
ob tained only w hen the spins of the electrons arc an tip arallel.
However, it is assumed (although no one has yet proved it by
direct calculation) th a t the repulsion betw een the i d elec
trons of iron two atom s is least w hen the spins are parallel.
T h u s it is assumed th a t the electrostatic in teractio n of two
iron atom s depends considerably on the alignm ent of their
spins, i.e., of the m agnetic m om ents. M agnetization is no t the
cause b u t an effect of the parallel alignm ent of the m om ents.
Since the electrical forces are ab o u t a thousand times greater
th an the m agnetic forces, we can u n d erstan d why the mag
netism of iron persists up to ab o u t 1000°K. It w ould be very
interesting to calculate directly the energy of the electrical
in teractio n th a t aligns the spins, but because of the difficulty
of o b tain in g an exact solution of the m any-clectron problem ,
ap p roxim ate m ethods have to be used. Since different authors
use different m ethods, it is n o t surprising th a t contradictory
results arc som etim es obtained.
A large single crystal of iron is n o t m agnetized entirely in
one direction: if it were, a great deal of energy w ould be nec
essary to establish its external m agnetic field. T h e crystal is
divided in to separate layers m agnetized in opposite directions,
so th a t their ex tern al fields tend to com pensate each other. If
we apply an external field to such a crystal, layers w ith m o
m ents in the opposite direction to the field will realign, and
all parts of the crystal will have a single direction of m agnetiza
tion. T h e theory of the layered structu re of ferrom agnetics,
form ulated by L an d au and Lifshits, was later verified by direct
observations.
Quantized fields
In this ch ap ter alth o u g h we shall refer a n u m b er of times to

E in stein’s theory of relativity, we shall assume th a t the reader
has not yet acquired a know ledge of this theory.
T h e p rin cip al difficulty in u n d erstan d in g E in stein ’s theory
is th a t it reappraises o u r custom ary concepts of space and
time. H ence there arise certain “paradoxes,” w hich are in fact
as n a tu ra l as the consequences of the u n certain ty principle;
b u t we shall leave aside these consequences of the theory of
relativity, w hich are especially difficult to grasp. For o u r p u r
poses certain ideas and form ulas taken from relativistic m e
chanics are far m ore im p o rta n t (“relativistic” was defined in
C h ap ter F o u r as “ in accordance w ith the requirem ents of the
theory of relativ ity ”).
It is first essential to have an expression for energy in term ;
of m o m en tu m. W e know from C h ap ter Seven th a t in N ew
tonian m echanics, this takes the form E = p -/2 m 0. In E in stein ’s
m echanics the form ula is q u ite different: E = v/???);c4 -f c-p'2
w here c is the velocity of light ancT*m0 is the mass at rest
A lthough at first glance it w ould seem th at these two formulas
have noth in g in com m on, this is in fact no t so. Let us invest!
gate how E in stein ’s form ula differs from N ew to n ’s.
W hen p = 0 (i.e., w hen the particle is at rest) we havt
E0 = m 0c~. T h e relatio n sh ip betw een the energy an d mass of t
particle at rest is com pletely foreign to N ew to n ian m echanics
T h e q u a n tity rn0c~ is called the rest energy of the particle, ant
Quantized fields 129
is of vital im portance in the various transform ations of p ar
ticles stu d ied in nuclear physics and the physics of elem entary
particles. W e will now show th at the energy of a particle
m oving sloivly in com parison w ith the velocity of light con
sists of the rest energy E0 and an ad d itio n a l term th a t is the
same as the N ew tonian expression for the kinetic energy. W e
denote this by T, so th a t E — E n -f T = m 0c2 + T . S quaring
both sides of this expression, we have:
E 2 = m Y + 2m0c2T + T 2
Suppose, for exam ple, th a t the velocity of the particle is a
h u n d re d th p art of the velocity of light. T h e kinetic energy
\ m 0v 2 is then a 1/20,000 p art of the rest energy: T / E n =
^ X 10~4. T h e square of the kinetic energy will equal 1/(4 ■
10fi) of the square of the rest energy. H ence we may ignore it
in the expression for £ -, and we are left w ith only E 2 =
+ 2m 0c2T; b u t this expression by the fu n d am en tal for
m ula equals m^c4 -f c2p 2. C anceling on both sides and
dividing through by 2m„c2 we obtain sim ply T = p 2/2 m 0,
which m ust hold for slowly m oving particles. T h u s for small
velocities the form ulas of E in stein ’s m echanics reduce to the
N ew tonian form ulas, provided th at no tran sfo rm atio n of p a r
ticles takes place.
It is even m ore interesting to see how the energy behaves
w hen the m om entum is very large. T h e square of the rest
energy makes a sm aller and sm aller co n trib u tio n (in com
parison w ith c2p 2) to the term u n d er the square root. In the
lim it we are left w ith only c2p 2, and o b tain sim ply E = cp.
Such a particle is said to be ultrarelativistic. It is clear from
the expression for the energy th a t the particle may have no
rest mass at all.JT h u s E in stein ’s m echanics does not exclude
the existence of particles w ith zero rest mass, If the reader is
accustom ed to th in k in g th at mass represents the “q u an tity of
m a tte r,’’ he m ust d ro p this idea com pletely. It is m ore correct
to define the mass of a particle as its rest energy divided by
the square of the velocity of light, or, taking c as the u n it
of velocity, sim ply as the rest energy. Some particles have no
rest energy. W e shall see later w hat these particles are.
H aving discussed the form ulas, we shall now tu rn to the gen
eral concepts of the m a tte r (from which in fact the form ulas
emerge).
As we know, N ew tonian m echanics is based on the idea
of action at a distance. T h e best exam ple of this is the law
of gravity: two bodies attract each o th er w ith a force in
versely p ro p o rtio n al to the square of the distance betw een
them . If one of the bodies is displaced even a sm all distance,
the o th er im m ediately “becomes aw are of it” th ro u g h the
change in the gravitional force, however far away the first
body may be. T h is assertion, if we th in k ab o u t it, is extrem ely
strange, and we use it w ith o u t stopping to th in k only through
force of habit.
W hen we consider the m otion of an electron in an atom , we
repeatedly use C oulom b’s law, which is outw ardly very sim ilar
to the law of N ew ton. In fact all electrom agnetic interactions
are p ropagated w ith the same fun d am en tal (and finite) velocity,
r; b u t if the charges are m oving sufficiently slowly, the electro
m agnetic field will always be able to catch up w ith them so
quickly th at their action will seem to be tran sm itted in sta n
taneously. H ence we have the likeness betw een C o ulom b’s law
and the law of gravity. T h e electron in a hydrogen atom has a
velocity of the order of one h u n d re d th of the velocity of light.
It may therefore be assumed th a t its kinetic energy is related
to the m om entum by the N ew tonian relatio n sh ip E = p 2/2 m a.
Since the electron is m oving slowly we may also assume that all
electrom agnetic actions are propagated instantaneously. T h e
theory of relativity states th a t b oth these sim plifications are
directly connected w ith each other. (Einstein also created an
exact theory of g ravitation in which there is no action at a
distance; it is called the general theory of relativity. W e are not
concerned w ith th a t here.)
T h u s the electrom agnetic forces are always p ropagated from
p o in t to p o in t by short-range action. T hese ideas, first ex-
pressed by Faraday an d developed by M axwell, later led to the
creation of the theory of relativity. It denies action at a dis
tance. In teractio n in relativity is always due to some sort of
p ro p ag atio n process. In o rder for an electrom agnetic in terac
tion to take place betw een two charges, one of them m ust
radiate a wave an d the o th er m ust absorb it. W h at happens
before the rad iated charge “receives the signal” ? T o w hat does
the ra d ia ted wave belong? Evidently, to the electrom agnetic
field itself.
H ence we cannot discuss a system of charges w ith relative
velocity close to the velocity of light by using the concept of
an instantaneously tran sm itted force, since otherw ise all con
servation laws w ould break down. It w ould thus seem th a t we
have to regard the electrom agnetic field as part of the m e
chanical system.
H ow ever, an electrom agnetic field as a m echanical object is
an u n fa m ilia r idea. It resembles a continuous m edium , a gas
or a liquid, m ore than a system of separate points. In ord er to
prescribe the state of the electrom agnetic field at a given time,
we m ust define it at every p o in t of space; b u t th e points of
space form a continuous, not a discrete set, and it is im possible
to en u m erate them like the points of a m echanical system.
T h e re exists, however, one very sim ple approach to the p ro b
lem, based on a direct analogy betw een the equations of elec
trodynam ics and the equations describing the oscillations of a
string. T h e two belong to the same class; they describe oscilla
tory m otion. W e have rem arked several times th a t there is a
m athem atical sim ilarity betw een various kinds of physical
oscillations.
Any a rb itra ry oscillation of a string may be resolved into in
dividual sim ple harm onic oscillations. Each of these is ch ar
acterized by a definite n u m b e r of nodes. In o th er words, any
given oscillation of a string is a sum of oscillations w ith o u t
nodes, w ith one node, w ith two nodes, etc. T h e points of the
string itself form a continuous set and can n o t be enum erated;
b u t the oscillations are enum erated very simply by the nu m b er
of nodes: fundam ental, first harm onic, second harm onic, etc.
Each oscillation is characterized by its own am p litu d e and
phase, and most im p o rtan t, takes place com pletely in d e p en d
ently of the others.
D ue to the sim ilarity betw een the equations, the electro
m agnetic field may also be represented by a set of in dividual
oscillations th a t are in d e p en d e n t of each other. Electrom ag
netic oscillations in a circuit consisting of a capacitance and
an inductance are well know n to everyone, b u t a field in
em pty space can also undergo harm onic oscillations.
T h e oscillations in a circuit are often com pared to m e
chanical oscillations: the self-inductance is analogous to a mass
and the capacity to an elastic force. T h is com parison of electro
m agnetic and m echanical oscillation shows th a t the laws gov
ern ing them are identical. T h e laws governing the behavior of
an individual harm onic oscillation of an electrom agnetic field
in em pty space are also the same.
Q u a n tu m m echanics is com pletely analogous in one respect
to classical mechanics: it studies laws of m otion w ith o u t con
cerning itself w ith w hat it is th a t moves. In p articu lar, we can
use q u a n tu m m echanics for a harm onic oscillation irrespective
of w hat it is th a t is oscillating: an atom in a m olecule or an
electrom agnetic field in em pty space. T h e possible values of
the energy are already know n to us. T h ey are hr(?i + -J) where
r is the frequency of the oscillations and n is an integer. T h e
energy of zero-point oscillations is n o t usually taken into ac
count so th a t n indicates the n u m b er of q u an ta w ith a given
energy. Each q u a n tu m has energy hv. If the energy of the field
varies (e.g., if some of it is given to an atom ) then the change
is most definitely discrete. Q u a n ta are absorbed (or radiated)
only in whole num bers, usually one q u a n tu m of a given fre
quency at a time. T h is follows from the laws of q u a n tu m m e
chanics as applied to electrom agnetic oscillations,
s' H istorically the concept of quantizatio n of the electrom ag
netic field was developed in a different way. T h e first steps
in this direction were taken by Planck in 1900, b u t q u a n tu m
m echanics p ro p er d id n o t develop for a n o th er 25 years. A
sim ple developm ent of the kin d we have ju st given was no t
possible in 1900. It is all the m ore enlightening, therefore, to
follow the historical developm ent of an idea th a t led to a
m ajor revolution in physics.
C onsider a closed cavity inside a furnace whose walls radiate
energy in to the cavity. A fter a tim e therm al eq u ilib riu m w ill
be established betw een the w all an d th e ra d iatio n : every
square centim eter of the surface w ill absorb an d em it equal
am ounts of energy per u n it tim e per u n it frequency range.
T h e question is: w hat is the energy of the ra d ia tio n in the
cavity?
W e have already said th a t an electrom agnetic field can al
ways be divided u p in to a n u m b er of in d iv id u al harm onic
oscillations. I t is sufficient to calculate the energy of an in d i
vidual oscillation and then sum over all such oscillations. T h is
yields the energy of the field. W hat, however, was the position
before Planck?
T h e therm al energy of a free particle is 3 cal/m o le deg. An
oscillating particle, unlike a free one, w ill also have p o ten tial
energy th a t is equal on the average to the kinetic energy.
H ence the therm al energy is 6 cal/m o le deg, b u t th e n u m b er
of oscillations is infinite. T h u s we have o b tain ed a co ntradic
tion and clearly the result th a t the energy of ra d ia tio n in
th erm al e q u ilib riu m w ith a substance is infinitely great m ust
be erroneous.
H ow can we overcome this difficulty? Planck proposed th a t
the ra d ia tio n is em itted in finite portions of energy hv. From
this proposition Planck deduced the form ula for the energy
d istrib u tio n in the ra d ia tio n an d o b tain ed excellent agreem ent
w ith experim ent. T h e energy of ra d ia tio n in his theory is finite.
It is im possible to overestim ate the d a rin g of P lan ck ’s h y p o th e
sis. Before his tim e it was assum ed th a t all changes in physical
q u an tities m ust take place sm oothly (“n a tu re makes no
ju m p s’’); b u t this “a x io m ” proved to be incorrect or, rather,
of lim ited application.
T h e n ex t im p o rta n t step after Planck was m ade by E instein.
It was know n th a t w hen the surface of a m etal was illu m in ate d ,
it em itted electrons. E x p erim en t shows th a t the energy of these
electrons depends only on the frequency of the in cid en t light
an d not on its intensity. From the classical p o in t of view, this is
inexplicable: the intensity characterizes the am p litu d e of the
oscillations in the light wave. O ne w ould expect th a t the
g reater the am p litu d e of the oscillations the m ore strongly
the electron w ould be affected an d the g reater w ould be its
velocity of emission.
T h e tru e state of affairs was ex p lain ed very sim ply by E in
stein on the basis of P lan ck ’s hypothesis. If the energy of a
q u a n tu m is hv, and the w ork needed to force an electron o u t
of the m etal is w, the kinetic energy of the em erging electron
w ill be hv — w. T h is relatio n sh ip betw een the frequency of
light an d the energy of the electron is in fact in d e p en d e n t
of the intensity of the in cident ra d ia tio n . T h is has been con
firmed by experim ent.
E instein also realized th a t q u an tizatio n was n o t m erely a
p ro perty of ra d ia tio n b u t a general p ro p erty of all oscillations,
for exam ple, the oscillations of atom s in crystals. Before E in
stein ’s w ork it was generally believed th a t the energy p er os
cillatory m ode in a crystal was 6 cal/m o le deg, an d this led to
the law of D ulong an d P e tit stating th a t the specific h e at of
all elem ents in the crystalline state should be the same. A ctu
ally, this law is n o t satisfied for a n u m b e r of elem ents. For
exam ple, the specific h eat of diam ond, i.e., crystalline carbon,
is m uch less than predicted by the D ulong-P etit law. E instein
established th a t at a given te m p e ratu re q u a n ta of energy hv
will n o t be excited in the crystal if hv is appreciably g reater
th an the th erm al excitation energy. T h e rm a l m otion is no t
d istrib u te d over all oscillation modes of the crystal b u t is con
fined to the low -frequency range. A t low frequencies each m ode
has the energy prescribed by D ulong and P etit, b u t at higher
frequencies there is less energy, an d the crystal as a whole thus
receives less. T h is explains the d e p artu re from the law of
D ulong and Petit. E in stein ’s theory was extended by Debye and
in this m odified form is in excellent agreem ent w ith experi
m ent.
So far we have spoken only a b o u t the energy of a q u an tu m ;
b u t the electrom agnetic field always possesses m om entum : if
we have to consider it as a m echanical system, then we must
also form ulate the laws of m otion for it. T h e expression for
the m om entum of the electrodynam ic field was ob tain ed by
M axwell, the creator of electrodynam ics. T h e m om entum ol
an electrom agnetic wave is equal to its energy divided by the
velocity of light. W hen a wave strikes a wall; it transm its its
m om entum to it. T h e m om entum tran sm itted to the surface
is perceived as a pressure. T h is was observed by Lebedev in
1900.
However, since the electrom agnetic field possesses m om en
tum , then by E in stein ’s theory the m om entum of a photon
m ust be equal to the energy divided by the velocity of light,
as in the case of an electrom agnetic wave. T h e relationship
E — cp refers to an u ltrarelativistic particle for which m„c is
m uch less than p. In the case of a photon, this relatio n is satis
fied for all frequencies, i.e., for all p. C onsequently, the rest
mass of a p h o to n is identically equal to zero. (It is sometimes
said th a t the mass of a p hoton equals its energy divided by the
square of the velocity of light. T h is q u an tity has the d im e n
sions b u t n o t all the properties of mass.)
In fact the energy of a p hoton is p ro p o rtio n al to its fre
quency. H ow ever, frequency is a relative q u an tity . If one moves
tow ard a ray of light it increases, and if one moves in the
direction of the ray it decreases (D oppler effect). T h is will
also apply to a p h o to n ’s energy o r to th a t of any particle.
T h e energy characterizes n o t only the p h oton itself, b u t also
the m otion of the observer. H ence the definition of mass in
term s of the energy of the p hoton does n o t describe the pho
ton itself. T h e only true definition of rest mass is th a t con
tained in the relationship E = + c2p 2, i.e., in term s of
energy and m om entum sim ultaneously. If the observer is mov-
136 Basic concepis in quantum mechanics
ing relative to the particle, m 0 w ill always be the same, alth o u g h
both E and p may vary. O bviously, in this case m„ describes
the particle itself; b u t in this definition the rest mass of the
p h o to n is strictly equal to zero.
T h e existence of the m om entum of a single p h o to n was
confirm ed experim entally by C om pton in 1913. H e observed
the scattering of X rays by electrons. If this is considered ac
cording to the laws of classical electrodynam ics, the argum ent
w ould ru n as follows: the wave strikes the electron, makes it
oscillate, and compels it in its tu rn to radiate. Since the oscil
lations of the electron are in phase w ith the in cid en t wave,
it m ust radiate w ith the same frequency. C om pton showed
th a t in fact the frequency of the scattered ra d ia tio n is always
less th an the incident frequency, and this difference is greater
as the angle of scattering increases.
F urtherm ore, the relatio n sh ip betw een the frequency and
the angle of scattering may be obtained im m ediately if the
laws governing the collision of two elastic spheres are applied.
O ne “sphere” is the particle an d the o th er is the photon.
T h e only difference is th a t the relatio n sh ip betw een the m o
m entum and the energy is n o t E = p 2/2m „ as in the case of
b illiard balls, b u t E = y ' m \c 4 + c2p 2 for the electron and
E = cp for the photon. T h e greater the angle of scattering of
the photon, the m ore energy it im parts to the electron. T h u s
the energy of the p h o to n is reduced; i.e., its frequency is
lower.
C om pton's form ula for the reduction in the frequency in
cludes the ra tio h v /m uc2. T h is is the ratio of the energy of the
p h oton and the rest energy of the electron. T h e g reater this
ratio, the stronger the effect. T h is is the reason why the effect
is appreciable for X rays b u t negligible for visible light.
T h e expression p — h v /c agrees w ith de B roglie’s general
relationship. In fact, of course, the frequency is equal to the
velocity of light divided by the w avelength. S u b stitu tin g this
in to the expression for the m om entum we o b tain p = h/X, or
conversely X — h/ p. T h is was actually de Broglie's startin g
p o in t w hen he deduced the same relatio n sh ip for particles.
D iffraction of electrons confirm ed his hypothesis.
In C h ap ter T h re e we discussed the possibility of m easuring
the position of an electron in an atom w ith the aid of another,
faster electron having a shorter dc Broglie w avelength. T h e
same arg u m en t may be repeated for X rays. An X-ray photon
of short w avelength will transm it to the target electron an
uncontrollable am ount of m om entum , just like a fast electron.
A p hoton of ordinary light is n o t suitable for the exact meas-
urerpent of the position of an electron in the atom : the wave
length of visible light is about 10,000 times greater th an the
radius of an atom . O n the o th er hand, a p h o to n w ith wave
length sm aller than the radius of the atom proves to lie as
rough a m easuring in strum ent as a high-energy electron.
A lthough visible light also exhibits q u a n tu m properties,
these are usually m anifested in energy and no t in a m om en
tum relationship. B ohr’s relationship
is always satisfied w hen an atom emits visible rad iatio n . In

conclusion, we m ust indicate the place of the light q u a n tu m
(photon) in the general system of q u a n tu m m echanics, and
stress its sim ilarities and dissim ilarities to the electron as a
quantum -m echanical particle.
Firstly, they b oth possess exactly the same degree of physi
cal reality. T h is need not be stated at all, b u t the reader m ight
m istakenly th in k th a t the electron exists “by itself” and that
the p h oton is somehow deduced from the wave laws of electro
dynamics. T h e corpuscular properties of light and the wave
properties of electrons cannot be “deduced.” T h ey ap p ear as
ex perim ental facts from w hich the laws of q u a n tu m m echan
ics follow. T h e re is a difference betw een the p h o to n and the
electron, w hich will be explained later. T h is does n o t present
any doubts as to the reality of the photon, w hich is clearly re
vealed by experim ent.
T h e prin cip al difference betw een the p h o to n and the elec
tron is th a t the p h o to n is not affected by the Pauli exclusion
principle. T h e reason why P a u li’s princip le is so necessary for
the electron will be explained in the follow ing chapter. T h is
will not apply to photons; there may be any n u m b e r of p h o
tons in a given state.
A large n u m b e r of photons all m oving in one direction and
all w ith the same frequency and alm ost the same phase (w ith
o u t the phase there w ould be no w avem otion concepts!) will
be perceived as a classical electrom agnetic wave w ith the same
frequency and direction. T h e concept of the electrom agnetic
wave rem ains even in the lim itin g case of classical m echanics.
T h is m eans th a t general wave properties such as diffraction
will be conserved even in the classical case; q u a n tu m m echan
ics gives a deeper u n d e rstan d in g of these processes b u t does
no t have to dem onstrate th eir very possibility, as it m ust in
the case of electrons.
W e should n o t consider the classical wave am p litu d e as
b eing identical to the wave fu n ction of th e p h oton itself. T h e
form er a m plitude determ ines the energy of the electro m ag
netic field. H o wever, the relatio n sh ip betw een the energy and
the n u m b er of photons in volves the frequency; the en erg y of
a p h o to n is p ro p o rtio n al to its frequency. Frequency, on the
o th e r handTis a relative q u a n tity th a t depends on the observer.
It follows th a t the p ro bability of finding a p hoton at a given
p o int of space will always depend on the state of th e observer,
as d oes th e observed frequency itself. A p h o to n is always som e
w hat “sm eared” in space and cannot be localized exactly in
any experim ent, even at the price of know ing its m om entum
only inexactly.
T h e wave function of an electron corresponds in the classi
cal lim it to n o th in g at all, since only one electron may be
found in each state. H ere, the transition to the classical theory
m eans th a t the wave properties of m otion are excluded. T h e
possibility or im possibility of this tran sitio n follows from the
u n certain ty relationships for m om entum and position, u n d er
the special co n ditions of the m otion u n d e r consideration.
W e may observe a n o th e r difference betw een the electron
and the p h o to n : the p h o to n can be absorbed or radiated, but
the electron cannot. T h is is partly because the electron is a
charged particle, and electric charges m ust satisfy a very strict
conservation law. H ow ever, if we speak ab o u t the electron
itself an d n o t a b o u t its charge, this, difference, is. only notice
able in the n o n re la tivistic lim it. In the th eo ry of re la tivity the
position is q u ite different. W id i p ro p e r com pensation of the
charge by o th e r particles, the n u m b e r of electrons may also
vary. T h is will be considered in the following chapter.
Dirac's theory
T h e q u a n tu m theory of the electrom agnetic field is fu n d a

m entally relativistic: the energy of a p h o to n is connected w ith
its m om entum . H ere there cannot be a nonrelativistic lim itin g
case since the rest mass of a p h o to n is identically eq u al to zero.
T h is property can only be exhibited by particles m oving w ith
the velocity of light, a condition fulfilled by photons.
Because an electron possesses finite rest mass an electro n ’s
m echanics p e rm it a nonrelativistic lim it. Indeed, Schrodin-
g cr’s q u a n tu m m echanics, founded on the relatio n sh ip E =
p 2/2rn0, corresponds to this lim it.
However, the conditions u n d er w hich the nonrelativistic
wave eq u atio n is applicable are by no m eans always satisfied.
W e have seen th a t in heavy atom s the ratio of the electron
velocity to the velocity of light may reach 0.6. T h is fact alone
instigated a search for a relativistic wave eq u atio n soon after
Schrodingcr’s work. T h e first such eq u atio n was based on the
form ula E 2 — m \ c4 + c2p 2. However, this generalization was
in adequate for the electron since it did not take spin in to ac
count. T h e m agnetic in teractio n of the spin w ith the o rb it is
a relativistic effect and hence m ust be included au tom atically
in any wave eq u atio n th a t is in accordance w ith the theory of
relativity. An eq u atio n th a t docs not take the spin of the elec
tro n in to account cannot describe its m otion in the relativistic
region.
In 1928 D irac proposed an e q u atio n th a t corresponds not
Dirac's theory 141
num erically b u t sym bolically to the ex tractio n of the square
root in the form ula E = y jm \ c4 + c2p 2. T h e electron spin
m ust be used in this operation. T h u s the spin is in tim ately
associated w ith the o rb ital m otion of the electron to which the
form ula E — \ J m \ c 4 + c2p 2 refers. T h e beauty of the D irac
theory can n o t be conveyed in words w ith o u t form ulas, any
m ore than a m usical com position can w ith o u t notes or sounds.
D irac’s e q u atio n yielded very m uch m ore th an , probably,
even he expected at first. T h e most interesting and u n ex
pected results, w hen first obtained, appeared to present in su r
m o untable difficulties.
W e have already said th a t D irac used his own special
m ethod to extract the square root of the sum m\c* + c2p 2;
b u t the ro o t always has two signs. In n o n q u a n tu m theory this
presents no problem , because E = ± -y/wt^c4 + c2p 2, it is clear
th a t the energy is always greater than + m 0c2 or less than
—rn0c2, b u t can n o t lie betw een +rnc2 and —me2. Since all
q u an tities change continuously in classical mechanics, positive
energy cannot become negative, for it w ould then have to
cross the "fo rb id d e n ” interval of 2m (1c2 (Fig. 34).
In q u a n tu m m echanics the energy can change by jum ps. An
electron em ittin g a p hoton can ju m p from a state of positive
energy to a state of negative energy, and since the la tte r has
no lower bound, it will “ fall” lower and lower. T h u s all elec
trons w ould soon “d ro p ” in to a state of infinite negative en
ergy. T his, as we know, does n o t occur.
____________
2mc2 2m c2
~ (+) ~
vacuum pair
Figure 34
In order to avoid this difficulty, D irac m ade a fu n d a m e n tal
assum ption. H e proposed th a t all the negative energy states
were already filled w ith electrons. E verything th a t actually
h ap pens takes place against a “b ack g ro u n d ” of filled states. If
the electrons obey the P auli exclusion p rin cip le, n o t a single
electron can pass from the states w ith positive energy in to
these filled states, and none of the electrons w ith negative en
ergy can move any fu rth e r dow n.
At first it seems th at the way o u t proposed by D irac is
purely verbal. H ow can we prove th a t all states w ith negative
energy are already filled by electrons?
T o prove this it is sufficient to rem ove one electron from a
negative energy state an d transfer it to a positive energy state
w here there are as m any free places as we wish. In the positive
energy state it easily moves fu rth e r u p by ab sorbing a p h o to n .
T h e n am ong all the filled states there will rem ain one unfilled
level or hole. W e have already considered the pro p erties of
holes in o u r discussion of the conductivity of certain sem i
conductors. H istorically, it is true, the ideas on hole conduc
tivity were fo rm u lated by analogy to D irac’s holes. In b o th
cases the unfilled electron level am ong all the filled ones b e
haves as if it were an electron w ith a positive charge.
In all o th er respects it behaves like an o rd in ary electron as
long as no ordinary electron happens to m eet it. W h en they
do m eet, the electron may be transferred to the unfilled level,
which corresponds to the positive electron, a n d the excess e n
ergy w ill be tran sm itted to the electrom agnetic field. D irac
used this theory to calculate pro b ab ilities of the forw ard and
reverse processes: the creation of a positive electron an d its
“a n n ih ila tio n ” by a negative electron. H ow ever, at th a t time,
in 1930, positive electrons h ad not been discovered, p rin cip ally
because no one h ad th o u g h t of looking for them . T h e o p in io n
of the m ajority of theoreticians ab o u t D irac’s theory wras, to
p u t it m ildly, d istrustful. T h e position changed radically
w hen, in 1933, A nderson discovered the positive electron, or
positron, in cosmic rays. Soon the positron was observed also
Dirac's theory 143
in the beta decay of radioactive elem ents. T o d ay the positron
is a fam iliar particle in physical and even in chem ical labo
ratories.
D irac h ad n o t only predicted a new particle an d w orked out
all its properties in advance— an o u tstan d in g event in the his
tory of physics— b u t also he in tro d u ced a com pletely new con
cept in to science: the concept of antiparticles. For the electron,
the a n tip article is the positron. W hen they m eet they a n n ih i
late each o th er w ith the total destruction of th eir rest mass. T o
express it m ore accurately, th eir total energy, inclu d in g the
rest energy, is transform ed in to the energy of the electrom ag
netic field. W ith o u t in tro d u cin g any gross errors we may say
briefly th a t th e ir mass is converted in to the energy of the elec
trom agnetic field.
L ater it was found th a t the concept of an tip articles is con
siderably w ider th an D irac h ad at first proposed. P au li and
W eisskopf showed th a t a charged particle th a t does n o t obey
the P auli prin cip le may also possess an an tip article. At present
one such p article-antiparticle p a ir is well know n: the positive
and negative pi mesons; b u t it makes no difference w hich is
considered the particle and which the an tip article, for in this
sense th e ir theory is com pletely sym m etrical. D irac’s theory of
the positron is equally sym m etrical. A lthough to start w ith we
spoke of levels filled by negative electrons w ith negative e n
ergy, an d thus reduced the positron to a hole, n o th in g w ould
be changed in our argum ent ab o u t the D irac theory if we con
sidered the electron as a hole in the negative energy levels
filled by positrons. T h e fact th a t in our w orld electrons clearly
predom inate over the positrons (which are rare visitors) is n o t
reflected in D irac’s theory. T h is is one of the problem s to be
solved by the science of the universe as a whole.
If we exclude the n e u tra l pi-zero meson and the photon,
every particle has its an tip article. T h e y have all now been dis
covered experim entally. As far as the first two are concerned,
they bo th coincide w ith th eir own antiparticles. O n reaching
an antiuniverse com posed of antip articles (perhaps in reality
in some d istan t galaxies) photons and pi-zero mesons w ould
rem ain the same. I t w ould be u tterly disastrous to come in to
contact w ith an antiuniverse, for everything concerned w ould
be transform ed alm ost instantaneously in to a cloud of mesons,
a n d w ith in a few m illionths of a second (owing to m eson de
cay) in to electrons, positrons, an d neu trin o s. W h e th e r these
particles w ould in tu rn a n n ih ila te each other, or w h eth er they
w ould be scattered in space before this could h ap p en , is of no
real im portance for us.
T h e existence of antip articles reveals a fu n d a m e n tal p ro p
erty of relativistic q u a n tu m theory; i.e., the to tal n u m b e r of
particles is n o t a constant of m otion. D irac’s eq u atio n as a p
plied to an in d ivid u a l electron is only an ap p ro x im a tio n an d
som etim es cannot explain the actual ph enom ena. In ad d itio n
to the given electron we m ust consider all the electron-posi
tro n pairs to w hich it m ight give rise if it had sufficient energy,
an d all the photons th a t it m ight rad iate or absorb. Since the
expression “if” allows any value of the energy, this m eans th a t
we have to consider the infinite set of all the electrons an d
positrons in the universe a n d every electrom agnetic field th a t
exists or could exist.
T h e problem of considering such an enorm ous set of e n
tities may seem in su rm o u n tab le. In fact the electron does no t
generate a p a ir im m ediately b u t first em its a p h o to n . T h e
electron and the p h o to n do not in teract very strongly w ith
each other. W e already know th a t the m easure of th e ir in te r
action is the constant 2irc~/hc — 1/ 1 37, w hich is sm all in com
parison w ith unity. T h is m eans th a t the electron usually re
acts w ith one p h oton. Interactions w ith m ore than one p h o to n
at a tim e lead to only a sm all correction. T h e m ethod of cal
cu latin g such corrections has been thoro u g h ly w orked out.
T h e com plicated interactions of electrons w ith the electro
m agnetic field lead only to sm all corrections. T h ese correc
tions, however, are som etim es of great theoretical interest. In
C h ap ter Six we stated th a t the energy of the electron in a
hydrogen atom depends only on the prin cip al q u a n tu m num -
Dirac's theory 145
ber. T h is follows from Schrodinger’s nonrelativistic wave
equation. D irac’s relativistic eq u atio n leads to a different re
sult: the energy levels of the electron possess a fine stru ctu re
and depend n o t only on the principal q u a n tu m n u m b e r n b u t
also on the total an g u lar m om entum of the electron, i.e., on
the sum of the o rbital and spin angular m om enta of the elec
tron. Since / = I ± -J, then conversely I = j ± -J. Let us now
exam ine the 2s and 2p levels. T h e first of these has t — 0, so
th a t its total an g u lar m om entum is sim ply equal to the spin,
in this case T h e value of / is w ritten as a subscript to the
term * symbol; hence in the 2s state there can be only the
2s$ level. In the p state we can have / = 3/2 or 1/2. Of
these, the 2pi level has the same p rincip al q u a n tu m n u m b er
2 and the same an g u lar m om entum / = 4 as does the 2si shell;
i.e., according to D irac’s theory they m ust possess the same
energy. H ow ever, this theory takes into account only the in
d iv idual electron and the C oulom b field of the nucleus in
w hich it moves.
Spectroscopists have suspected for a long time th a t th e 2s\
and 2pi states in the hydrogen atom did no t coincide, b u t
could not prove this experim entally. It has been show n in
microwave spectroscopy th a t the 2s\ level differs from the
2p i level by 4 x 10-6 eV.
Every w ell-established discrepancy betw een theory and ex
p erim ent m ust be explained. In the given case there is a com
pletely q u a n tita tiv e ex p lan atio n . Firstly, we m ust no t assert
th a t the electron exists only in the C oulom b field of the n u
cleus. W e have shown th a t the electrom agnetic field can be
reduced to a system of in d ep en d e n t oscillations (see C h ap ter
Eight), and the energy of an oscillation of frequency v is equal
to h v(n + t). Each u n it of n corresponds to a single q u a n tu m ;
b u t to w hat does ^ correspond? It is the energy of the zero-
p o in t state in w hich there are no q u an ta.
If we exam ine the problem of the oscillations considered in
C h ap ter T h ree , we see th a t even in the case of m in im u m en-
* “Term” is another word for “state.”
ergy (in the g ro u n d state) the oscillations do n o t cease; there
is no rest. T h is is a d irect consequence of the u n certain ty p rin
ciple. In the same way, the electrom agnetic field does n o t
vanish even w hen there are no q u a n ta . It perform s its “zero-
p o in t oscillations.’’ In the rigorous theory one can n o t say th a t
the field is e q u al to zero; it is certainly p resent and acts on
every electron. T h is, how ever, was n o t taken in to account in
the ded u ctio n of the energy levels of the hydrogen atom from
D irac’s eq u atio n .
I t is im possible to take this com pletely in to account; b u t it
is possible to find an a p p ro p ria te form ula based on the fact
th a t 1/137 is a sm all num ber. T h e d eriv atio n of the form ula
runs in to the follow ing characteristic difficulty. T h e n u m b e r
of different zero-point oscillations of the field is infinite and
each makes its own co n trib u tio n . H ence the pow er of the n u m
ber 1/137, w hich corresponds to the expected effect in a given
ap p ro x im a tio n , m ust have an infinite coefficient. B ethe was
the first to show how to elim in ate this difficulty. If we con
sider the correction to the energy of a free electron th a t is no t
in the field of the nucleus, then for the same reason (the zero-
p o in t oscillations of the electrom agnetic field) the coefficient
of the necessary pow er of 1/137 will also be infinite. H ence
the real correction to the energy in the field of the nucleus
w ill be o b tain ed only if we su b tract one infinite resu lt from
the other.
T h e su b tractio n of one infinite n u m b e r from an o th er, gen
erally speaking, is not a single-valued op eratio n ; b u t if the re
q u irem en ts of the theory of relativ ity arc carefully observed
in the given case we may carry o u t a com pletely defined sub
traction and, m ost im p o rtan t, o b tain a finite result. T h is cov
ers the p rin cip al p art of the effect observed experim entally.
T h e sm all residue of ab o u t 3 percent is due to the “back
g ro u n d ’’ of the electrons w ith negative energy th a t su rro u n d
the given electron. In the field of the nucleus this b ackground
is som ew hat deform ed as if polarized, and the force acting on
an electron m oving in the field of the nucleus is no t strictly a
Dirac's theory 147
C oulom b force. T h e background electrons move away from
the nucleus, for they have negative mass. T h e correction for
the “ vacuum p o la riz atio n ” exactly covers the 3 percent residue.
E x perim ent confirms the physical reality of the background.
Sim ilarly, we may calculate the correction to the gyromag-
netic ra tio of the electron and classify all the possible correc
tions. T h u s q u a n tu m electrodynam ics now has all the m ain
features of a com plete physical theory.
Selected readings
Born, M., Atomic Physics, Seventh Edition, Hafner, New York, 1962.
Eisberg, R., Fundamentals of Modern Physics, Wiley, New York,
1961.
Feynman, R., Feynman Lectures on Physics, Vol. Ill, Addison-Wesley,
Reading, Mass., 1964.
Heitler, W., Elementary Wave Mechanics: With Application to
Quantum Chemistry, Second Edition, Oxford University Press, New
York, 1956.
Park, D., Introduction to the Quantum Theory, McGraw-Hill, New
York, 1964.
Richtmyer, F. and others, Introduction to Modern Physics, Fifth
Edition, McGraw-Hill, New York, 1955.
Wehr, M. and J. Richards, Jr., Physics of the Atom , Addison-Wesley,
Reading, Mass., 1960.
Weidner, R. and R. Sells, Elementary Modern Physics, Allyn 8; Bacon,
New York, 1960.
Index
Abrikosov, A. A., 119 Box with impenetrable walls, 50-51

Air, velocity of light in, 4, 8
Alkali metal potassium, 108 Carbon atoms, 104, 109, 111-112
Alpha decay, 60-63 Chemical valence, 109-110
Alpha particles, 60-63 Chlorine atoms, 110
Amplitude, 11 Coherent waves, 33
probability, 34-36, 44 Compton, Karl Taylor, 136
Anderson, Carl David, 142 Condon, Edward Uhler, 63
Angular momentum, 38-40, 73-85 Cooper, L., 121, 122
maximum component of, 99 Corpuscular theory of light, 3-4
zero, 106 Correspondence principle, 70-71
Antiparticles, 143-144 Coulomb law of attraction, 64, 66
Atoms: argon, 110 Coulomb field, 83
hydrogen, 82, 83, 89, 100-101, 109, Coulomb force, 61
112, 130, 146 Covalent bonds, 110
spectrum of, 65 Crystals: intrinsically magnetized,
lithium, 103-104 125-126
motion of electrons in, 64-86 properties of, 113-127
nucleus of, 64
structure of, 98-112 Davisson, Clinton Joseph, 24
Attraction, law of, 64 De Broglie, Louis, 49, 53, 59
Avogardro’s number, 22 De Broglie wavelength, 67, 73, 113-
Azimuthal quantum numbers, 84- 114, 137
85, 99 Debye, Peter Joseph Wilhelm, 135
De Haas, W. J., 94
Balmer, Johann Jakob, 65 Diffraction: defined, 18
Bardeen, J., 121, 122 of electromagnetic waves, 33
Beryllium atoms, 104 of electrons, 24-25
Bethe, Hans Albrecht, 146 of protons, 25
Bloch, F„ 119, 121 wavelength and, 18
Bogolyubov, N. N., 121, 122 X-ray, 19-22
Bohr, Niels, 31, 59, 64-66. 69-70, 84 Diffraction grating, 18-19
Bohr magneton, 76 Dirac, P. A. M„ 90, 91, 93
150 Index
Dirac’s theory, 140-147 Force: Coulomb, 61
Doppler effect, the, 135 elastic, 46-47
Drude, Paul Karl Ludwig, 120 electrostatic, 47-50
Dulong, Pierre Louis, 134 uniform field of, 45-46
Dulong-Petit law, 134-135 Foucault, Jean Bernard Leon, 4
Frequencies, 11
Einstein, A., 32, 69, 94, 128-132, 134 classical, 58
Elastic force, 46-47 wavelength and, 12-13
Electromagnetic field as part of the Fresnel, Augustin Jean, 14, 16
mechanical system, 131 Frohlich, H„ 122
Electromagnetic waves, 13-14, 19-20
by an accelerating charge, 64 Gamow, George, 63
diffraction of, 33 Gases: inert, 103, 104
Electrons: coherent aspect of, 33 noble, 103
in crystals, 113-127 General theory of relativity, 130
differences from photons, 137-139 Geometric optics, 1-22
diffraction of, 24-25 Gerlach, Walther, 74
energy of, 68, 84 Germer, Lester Halbert, 24
free-free emission, 84 Goudsmit, S., 94
of hydrogen, 100-101, 130 Gravitation, law of, 64
of iron, 127 Ground state, the, 56-57
motion of, 25-26, 64-86 Gurney, R. W„ 63
internal, 87-90
nuclear particles and, 90 Hamilton, W. R., 9, 59
optics, 9
Harmonic oscillations, 10-13, 56
revolving, 75-76 Hartrce, Douglas Raynor, 83
scattering of X rays by, 136 Hartree-Fok field, 83
spin, 87-97
Heisenberg, W., 24, 31, 49, 69, 91
volts converted into ergs, 27
Heitler, \V„ 110-112
wave properties, 27-28
Helium atoms, 102-103, 110
with zero angular momentum, 106
Heteropolar bonds, 110
Electrostatic force, 47-50
High-frequency waves, 12
Energy: of electrons, 68, 84
Holes, 124-125
kinetic, 44-45, 52, 66-67
Huygens, Christian, 5-8, 14, 17
law of conservation of, 3, 40 Hydrogen, solid, 118-119
potential, 44-51, 66-67
Hydrogen atoms, 82, 83, 100-101,
quantization of, 54
109, 112, 130, 146
rest, 128-129
proton in, 89
spectrum, 55-56
spectrum of, 65
total, 51-52
Hypcrfine structure, 96-97
zero potential, 101
Ergs, electron-volts converted to, 27
Inert gases, 103, 104
Faraday, Michael, 130 Iron, 127
Fermi, Enrico, 120 Isotope effect, the, 121
Feynman, R. P., 101
Fok, V„ 83 Joule heat, 119, 121
Index 151
Kinetic energy, 44-45, 66-67 of protons, 25-26
negative, 52 quantum laws of, 32-37, 41-63
Landau, L„ 127 Neon atoms, 104
Laws: of attraction, 64 Neutrons, 90-91
of conservation of energy, 3, 40 Newton, Isaac, 1, 4, 14, 101
of conservation of momentum, 3 law of gravitation, 64
Coulomb’s, 66 second law of motion, 2, 26
Dulong-Petit, 134-135 third law of motion, 44
of gravitation, 64 Noble gases, 103
of motion, 2 Nucleus of the atom, 64
Newton’s, 2, 26, 44
quantum, 32-37, 41-63 Ohm’s law, 119
Ohm’s, 119 Onnes, Kamerlingh, 121
of optics, 9 Optics: electron, 9
of reflection, 7 geometric, 1-22
of refraction, 3-4, 7-8 laws of, 9
Snell’s, 3-4, 7-8 wave, 1-22
Lebedev, Petr Nikolaevich, 135 Oscillations: amplitude of, 10
Lifshits, L„ 127 classical frequency, 58
Light: reflection of, 1 fundamental properties of, 10
refraction of, 3-4, 7-8 phase of, 11
theories of simple harmonic, 10-13, 56
corpuscular, 3-4
wave, 5-8, 14-18 Particles
velocity of, 4, 8 alpha, 60-63
Lithium atoms, 103-104 in a bound state, 55
London, F., 110-112 electrons and, 90
in the ground state, 56-57
Magnetic poles, 74-75 lighter than electrons, 69
Magnetic quantum numbers, 99 rest energy of, 128-129
Mass point, 87 velocity of, 2
Maxwell, J. C., 14, 130, 135 Pauli exclusion principle, 100
Mendeleyev’s periodic table, 82, 100 Perpetual motion machines, 31
Mesons, pi-zero, 143-144 Petit, Alexis Th£rese, 134
Momentum, 2 Photoelectric effect, the, 125
angular, 38-40, 73-85, 99, 106 Photons, 69, 136
of electrons, 68 differences from electrons, 137-139
in the ground state, 56-57 Planck, M. K. E. L., 132-134
law of conservation of, 3 Planck’s constant, 25, 30, 65, 70, 92
product of uncertainties, 30 Position: of atomic electrons, 68
the uncertainty principle, 23-40 of equilibrium, 47
Motion: of electrons, 25-26, 64-86 the uncertainty principle, 23-40
internal, 87-90 Potential energy, 44-51, 66-67
Newton’s laws of Principal quantum numbers, 99
second, 2, 26 Propagation
third, 44 velocity of, 13
152 Index
Propagation (c o n t i n u e d ) Sound waves, 43-44
wavelength of, IB Spectroscopy, 145
Protons, 90-91 Spectrum: energy, 55-56
diffraction of, 25 of the hydrogen atom, 65
in the hydrogen atom, 89 Spin quantum numbers, 99
motion of, 25-26 Stern, Otto, 74
Superconductivity, 121-122
Quantization of energy, 54
Quantized fields, 128-139 Theories: Dirac’s, 140-147
Quantum mechanics: Dirac’s the of light
ory, 140-147 corpuscular, 3-4
electron spin, 87-97 wave, 5-8, 14-18
geometric optics, 1-22 of relativity, 93, 128-132
laws of motion, 32-37, 41-63 difficulty in understanding, 128
motion of electrons in an atom, general, 130
64-86 Total energy, 51-52
origin of the term, 54
properties of crystals, 113-127 Uhlenbeck, George Eugene, 94
quantized fields, 128-139 Uncertainty principle, 23-40
structure of the atom, 98-112 Uniform field of force, 45-46
Quantum numbers, 84 Units: atomic system of, 26-27
azimuthal, 99 CGS system of, 25, 27
magnetic, 99
principal, 99 Velocity: of light, 4, 8
radial, 99 of the oscillating point, 13
spin, 99 of particles, 2
of propagation, 13
Radial quantum numbers, 99
Reflection: law of, 7 Water, velocity of light in, 4, 8
light, 1 Wave optics, 1-22
particles, 1-2 Wave theory of light, 5-8, 14-18
total internal, 41-42, 53 Wavelengths, 12-13
Refraction: law of, 3-4, 7-8 de Broglie, 53, 67, 73, 113-114, 137
of light, 3-4, 7-8 diffraction and, 18
Relativity, theory of, 93, 128-132 frequencies and, 12-13
Rest energy, 128-129 of propagation, 13
Rutherford, Ernest, 64 Waves: coherent, 33
combining, 14-15
Schrieffer, J„ 121, 122 electromagnetic, 13-14, 19-20, 33,
Schrodinger, Erwin, 24, 49, 59, 90- 64
93, 140, 145 fundamental properties of, 10
Semiconductors, 123-125 high-frequency, 12
Short waves, 12 short, 12
Silicon atoms, 104 sound, 43-44
Snell’s law, 3-4, 7-8 X rays, diffraction, 19-22
Sodium atoms, 118
Sommerfeld, A., 120, 121 Young, Thomas, 14, 16

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A S Kompaneyets - Basic Concepts in Quantum Mechanics-Mir Publishers (1966)

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Basic concepts

REINHOLD PUBLISHING CORPORATION

Q u a n tu m M echanical concepts underlie m any of the most

Translation editor: LEON F. LANDOVITZ

T ra n s la te d by Scripta Tcchnica, Inc.

Spectacular advances have been made by the science of physics

1 Geometric and wave optics 1

2 The uncertainty principle 23

3 Quantum laws of motion 41

4 Motion of electrons in an atom

6 Structure of the atom 98

7 Electrons in crystals 113

8 Quantized fields 128

9 Dirac's theory 140

Selected Readings 148

W h en speaking of motion, we generally visualize a body or a

* Momentum : mass x velocity.

the dividing boundary A A '. If one supposes that the second

fro n t A m w ith opposite phase. Suppose, for exam ple, th a t the

I t was shown in the preceding sections that there are two

T h e variables cancel on m u ltip licatio n and we ob tain a rela­

W ave m otions u n d e r extrem ely diverse conditions have m uch

torce. Yigure IS shows the typical course o£ a wave that is

to the de Broglie w avelength A = h /m v — h / \ / 2 m E in the well

In p o p u la r accounts the atom is represented by a “cocoon”—

AE = \m (A v)2 = 2.2 X 1 0 -10ergs

Since one electron-volt equals 1.6 X 10~12 ergs, the u n certain ty

the n u m b e r k, w hich gives the com ponent of the an g u lar m o­

In m echanics we often use the concept of a mass point, whose

Q uan tu m theory of the

Only the second box on the rig h t is incom plete because we

T h e nucleus also has a m agnetic m om ent if it has an g u lar

In the two preceding chapters we saw th a t the m o tio n of an

A very extensive branch of physics is devoted to studies of the

In this ch ap ter alth o u g h we shall refer a n u m b er of times to

is always satisfied w hen an atom emits visible rad iatio n . In

T h e q u a n tu m theory of the electrom agnetic field is fu n d a ­

Abrikosov, A. A., 119 Box with impenetrable walls, 50-51

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T h e variables cancel on m u ltip licatio n and we ob tain a rela

the n u m b e r k, w hich gives the com ponent of the an g u lar m o

T h e q u a n tu m theory of the electrom agnetic field is fu n d a