Journal

of

The Pranklin Insiilute

Devoted to Science and t h e M e c h a n i c Arts
Vol. 207

APRIL, 1929

No. 4

EDITORS' NOTE: The following fourteen papers were read

at a Symposium on Q u a n t u m Mechanics, held under the auspices of the American Physical Society in New York City,
December 3~, I928. It is much regretted t h a t the editors
have not been able to procure two other papers which were
read on that occasion.
PHYSICAL M E A N I N G

OF WAVE MECHANICS.
BY

J. C. SLATER, PH.D.,
Harvard University.

AN understanding of the physical meaning of wave

mechanics is essential if one is going to do useful work in
the subject; even purely mathematical research in q u a n t u m
theory is of small value unless it is carried out with the
proper understanding of the physics behind it. For that
reason, it seemed well to start this discussion with a brief
t r e a t m e n t of physical interpretation rather than mathematical
details. Of course, only a small portion of so large a subject
can be taken up; and I have chosen to speak about the
statistical side of wave mechanics, both because this is one
of its most fundamental sides, and because it is a topic t h a t
will fit in well with the other papers.
Wave mechanics is an extension, not of ordinary Newtonian mechanics, but of statistical mechanics; and this simple
observation is enough to explain m a n y of its otherwise pUZ(Note.--The Franklin Institute is not responsible for the statements and opinions advanced
by contributors to the JOURNAL.)
VOL. 207, NO. I 2 4 o - - 3 I

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zling features. Since o r d i n a r y statistical mechanics is a subject a b o u t which there is m u c h misunderstanding, it will be
well to s t a r t with a little description of it. Being statistical, it
m u s t deal with a great m a n y similar objects or events ; b u t it is
necessary at the o u t s e t to u n d e r s t a n d t h a t this b y no m e a n s
limits us to problems where, as in the t h e o r y of gases, there are
a great m a n y identical physical systems. One can perfectly
well t r e a t statistically a problem with even one single degree of
freedom, as for example an oscillator. T h e statistics comes
in in the fact t h a t one works, n o t with single observations,
b u t with ensembles of observations. B y an ensemble, one
m e a n s a set of repetitions of the same e x p e r i m e n t - - j u s t such
a set of repetitions as one actually m a k e s in working a real
physical experiment. One can set u p a simple m a t h e m a t i c a l
picture of an ensemble of observations. Suppose we have a
space with a n u m b e r of dimensions to coincide with the
n u m b e r of m e a s u r e m e n t s we m a k e ; for example, if our
s y s t e m is a mechanical one with n degrees of freedom, there
will be 2n dimensions, n for the co6rdinates of the system,
the o t h e r n for its velocities or m o m e n t a . E a c h time we
m a k e our m e a s u r e m e n t s , we can represent the result b y a
single point in this space, T h e n if we r e p e a t the experiment
m a n y times, we get as m a n y different points as there are
repetitions, and this s w a r m of points is the m a t h e m a t i c a l
picture of the ensemble. In most cases, we wish to suppose
the n u m b e r of trials to increase w i t h o u t limit, so t h a t the
s w a r m a p p r o a c h e s a c o n t i n u o u s distribution, and we can
define a function representing the d e n s i t y of points in our
space. This distribution function then will also serve as a
m a t h e m a t i c a l representation of the ensemble.
T h e particular sort of ensemble to be used in a n y case
d e p e n d s on the physical conditions. W e m u s t judge, as
closely as possible, w h a t sort of distribution of the quantities
we are measuring will really occur in our experiment, and set
up an ensemble accordingly. Here, as in e v e r y case, the
purpose of our m a t h e m a t i c s is to run, so to speak, parallel to
the physics; one can imagine t h e m w r i t t e n in parallel columns,
with a definite correspondence between, such t h a t w h e r e v e r
we can m a k e a physical observation, it can be m a t c h e d with
some feature of the m a t h e m a t i c s . T h e n it is plain w h y we

Apr., I929.1 PHYSICAL MEANING OF" WAVE ~{ECHANICS.

45I

need ensembles: to m a t c h the physical process of repetition.

A n d the task of setting up the proper one m u s t definitely be
one of finding a parallel to the physics.
For example, suppose t h a t our s y s t e m were a linear
oscillator; t h a t we first took it, w i t h o u t energy; at an
a r b i t r a r y time gave it a definite energy, the same in each
repetition of the experiment; and t h e n at a later time measured its co6rdinate and m o m e n t u m , plotting t h e m in a
two-dimensional space. T h e n the ensemble of repetitions of
this m e a s u r e m e n t will be easy to describe; the points will all
correspond to the same energy, and will all lie on a curve
in the two-dimensional space whose equation is e n e r g y
= c o n s t a n t (an ellipse, since our s y s t e m is an oscillator).
But, on account of the a r b i t r a r y time w h e n the e n e r g y was
c o m m u n i c a t e d , the phase will be different each time the
m e a s u r e m e n t is made, and the points of the swarm will be
distributed in a uniform fashion a b o u t the ellipse, according
to a law which could be readily found. This ensemble is
well k n o w n in statistical mechanics; it is the microcanonical
ensemble. It is useful in t h e r m o d y n a m i c s , when we wish to
work with systems of c o n s t a n t energy.
As a n o t h e r example, we m i g h t t a k e our same oscillator,
b u t expose it to different external circumstances. We now
couple it, with small forces of interaction, to a s y s t e m with
a great m a n y degrees of freedom, and a definite energy. At
a definite time, we m e a s u r e its co6rdinate and m o m e n t u m .
In this case, the oscillator can acquire a n y e n e r g y b y interaction, and sometimes it will have one value, sometimes
another, b u t the relative chances of the different values will
be distributed according to a law which can be calculated.
As before, the phases will be arbitrary. T h e swarm of
particles in the ensemble will t h e n cover the whole of this
two-dimensional space, with a d e n s i t y t h a t can be definitely
found. This is the canonical ensemble. It is particularly
useful in t h e r m o d y n a m i c s , because it represents w h a t one
m e a n s by a s y s t e m at c o n s t a n t t e m p e r a t u r e ; t h a t is, a
s y s t e m capable of interchanging e n e r g y with a m u c h larger
s y s t e m - - t e m p e r a t u r e b a t h - - o f fixed properties.
T h e two ensembles we have m e n t i o n e d are the most
useful in the application of statistical mechanics to thermo-

452

J . C . SLATER.

lJ. I:. I.

dynamic problems; but statistical mechanics is a nmch wider

subject in its possibilities, and an indefinite number of other
ensembles m a y be useful. Suppose we still take our oscillator;
but let us now give it approximately a definite energy, with
approximately a definite phase, the precise values varying
from one repetition of the experiment to another. Then, if
we measure the co6rdinate and m o m e n t u m at a definite time,
all the points in our swarm will be clustered together in a
small region of the two-dimensional space. This is the sort
of ensemble that could be used to describe a measurement,
almost definite, t h a t was subject to small errors. The amount
of spreading of the swarm would be directly connected with
ideas of probable error.
Wave mechanics, being a form of statistical theory,
operates with ensembles. T h e y are represented mathematically by giving the distribution function representing the
swarm of points. Thus, the familiar 6~* gives the density
of points in a space in which the various co6rdinates of the
system are plotted. This is, it is true, different from the
space usually used in ordinary statistical mechanics, where
co6rdinates and m o m e n t a both are plotted. But the difference is not essential, from the present point of view, and it
is easy to show the relation of the two methods. There are
some other differences; we can not, for example, restrict all
the points of the ensemble to too small a region, or we meet
the difficulty of the principle of indeterminateness. But the
essential principles are the same. Just as in ordinary statistical mechanics, we must here choose the ensemble, determined by $, by considering the sort of statistical distributions
actually present in the repetitions of the experiment being
performed.
An ensemble, in statistical mechanics, takes the place of
a single set of measurements in ordinary mechanics; and as
such it is but the beginning of the problem. Our real task is,
for example, to trace what happens to the system as time
goes on. Given an initial ensemble, we wish the final ensemble. This is where mechanics enters the problem; and
here a characteristic and important difference in method
between classical mechanics and wave mechanics appears.
In classical statistical mechanics, we consider each separate

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453

point of the original ensemble, representing a system with

definite initial conditions; find its behavior according to the
principles of Newtonian mechanics; derive in this way a
final point from each initial one, and so a final ensemble from
the initial one. The result, of course, depends on the sort
of external forces to which the system is subjected. [;or
example, if we have the microcanonical ensemble, and expose
the system only to the internal forces natural to the oscillator,
then it can be easily shown that, although the individual
points of the swarm move, the ensemble as a whole remains
unchanged. This would not: be true if an external force
were present. With a canonical ensemble, we are most
interested in finding what happens when the system interacts
with the temperature bath. Here each point moves so as to
change not only its phase, but also its energy, with time;
yet the ensemble is so chosen that it remains unchanged as
a whole. Both these ensembles, since they remain constant
under the action of forces, are useful in the theory of steady
states. The third ensemble we have mentioned, in which all
the points were concentrated close together, naturally behaves
differently; as these systems are exposed to forces, all the
points of the ensemble travel together, so t h a t after the lapse
of an interval of time, the ensemble will consist of a concentrated set of points in some new parts of the space.
The method by which the wave mechanics investigates
the change of the ensemble with time is essentially different.
The problem, briefly, is this: given one ensemble, find
another; given one function, find another. The wave mechanics achieves this directly, without intermediate steps.
A thing which converts one function into another is an
operator; hence the importance of operator theory in wave
mechanics. Functions are conveniently considered in a space
of an infinite number of dimensions where each point represents a function; in this space, an operator changes one
point into another. All the operators we are interested in
are linear operators in function space, and this explains the
importance of linear transformations and matrix theory,
which is bound up directly with them, in wave mechancs.
As is well known, it is not the distribution functions with
which we work directly, but the wave function 4/. For

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example, in the particular case of the change of the ensemble

with time, we find the time rate of change of ~b as a certain
operator acting on ~b:
h O~
- He.
27ri 0t
T h u s the progress of the s y s t e m is shown b y the p a t h of a
point in function space with time, just as in o r d i n a r y mechanics it is shown by the p a t h of a point in o r d i n a r y space
with time. If our problem is as simple as, given the distribution function at one time, to calculate it at a later time,
we need m e r e l y t a k e the point representing the initial ~b;
follow its m o t i o n b y Schr6dinger's equation until the later
time; and the final point will give the distribution function
of the ensemble at the final time.
B u t m o r e often we have a m o r e complicated problem
where our final distribution function is not to be m e r e l y a
function of the same variable as the initial one, only at a
later time, b u t is to be a function of different variables.
For example, we m a y observe the distribution of positions of
particles to s t a r t with; our final m e a s u r e m e n t m a y be the
distribution in energy. In a case like this, it proves t h a t
the process of finding the distribution with respect to a new
q u a n t i t y m e a n s really finding the representation of the same
function ~b with respect to new co6rdinates in function space.
If, for example, the s y s t e m is a quantized one, and we wish
to find t h e distribution in energy, we refer to new "coo r d i n a t e s " in which the " u n i t v e c t o r s " are the orthogonal
functions found in Schr6dinger's theory. T h e distribution
function, as referred to energy, is a discrete one: it consists
of a value crick* giving the probability t h a t the e n e r g y is
t h a t of t h e n t h s t a t i o n a r y state. T h e set of cnc,*'s as a
function of n is as t r u l y a distribution curve, describing an
ensemble, as is ~b* as a function of x, and one form d e p e n d s
directly on the other, as we can see from the relation
= ~(n)cnu~,

where the u.,,'s are the orthogonal functions m e n t i o n e d above.

T h e general t h e o r y of changing from one set of variables to
another, in this way, is the t r a n s f o r m a t i o n t h e o r y of Dirac

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455

and Jordan, and we see t h a t it is just part of the general

scheme of wave mechanics, in finding a distribution function
for the final ensemble from t h a t of the original one.
It is plain from w h a t has been said t h a t the statistical
side of wave mechanics is a very i m p o r t a n t side. To get full
advantage of the m e t h o d s of the subject, the statistical
feature should be constantly kept in mind. Problems should
be followed through mathematically as they are worked
physically; by looking at t h e m in this broad way, m a n y
errors and uncertainties will be avoided.