A profound formal distinction exists between the theoretical concepts which physicists have formed regarding gases and other ponderable bodies and the Maxwellian theory of electromagnetic processes in so-called empty space. While we consider the state of a body to be completely determined by the positions and velocities of a very large, yet finite, number of atoms and electrons, we make use of continuous spatial functions to describe the electromagnetic state of a given volume, and a finite number of parameters cannot be regarded as sufficient for the complete determination of such a state. According to the Maxwellian theory, energy is to be considered a continuous spatial function in the case of all purely electromagnetic phenomena including light, while the energy of a ponderable object should, according to the present conceptions of physicists, be represented as a sum carried over the atoms and electrons. The energy of a ponderable body cannot be subdivided into arbitrarily many or arbitrarily small parts, while the energy of a beam of light from a point source (according to the Maxwellian theory of light or, more generally, according to any wave theory) is continuously spread an ever increasing volume.
The wave theory of light, which operates with continuous spatial functions, has worked well in the representation of purely optical phenomena and will probably never be replaced by another theory. It should be kept in mind, however, that the optical observations refer to time averages rather than instantaneous values. In spite of the complete experimental confirmation of the theory as applied to diffraction, reflection, refraction, dispersion, etc., it is still conceivable that the theory of light which operates with continuous spatial functions may lead to contradictions with experience when it is applied to the phenomena of emission and transformation of light.
It seems to me that the observations associated with blackbody radiation, fluorescence, the production of cathode rays by ultraviolet light, and other related phenomena connected with the emission or transformation of light are more readily understood if one assumes that the energy of light is discontinuously distributed in space. In accordance with the assumption to be considered here, the energy of a light ray spreading out from a point source is not continuously distributed over an increasing space but consists of a finite number of energy quanta which are localized at points in space, which move without dividing, and which can only be produced and absorbed as complete units.
In the following I wish to present the line of thought and the facts which have led me to this point of view, hoping that this approach may be useful to some investigators in their research.
We start first with the point of view taken in the Maxwellian and the electron theories and consider the following case. In a space enclosed by completely reflecting walls, let there be a number of gas molecules and electrons which are free to move and which exert conservative forces on each other on close approach: i.e. they can collide with each other like molecules in the kinetic theory of gases.1 Furthermore, let there be a number of electrons which are bound to widely separated points by forces proportional to their distances from these points. The bound electrons are also to participate in conservative interactions with the free molecules and electrons when the latter come very close. We call the bound electrons ``oscillators'': they emit and absorb electromagnetic waves of definite periods.
According to the present view regarding the origin of light, the radiation in the space we are considering (radiation which is found for the case of dynamic equilibrium in accordance with the Maxwellian theory) must be identical with the blackbody radiation -- at least if oscillators of all the relevant frequencies are considered to be present.
For the time being, we disregard the radiation emitted and absorbed by
the oscillators and inquire into the condition of dynamical
equilibrium associated with the interaction (or collision) of
molecules and electrons. The kinetic theory of gases asserts that the
average kinetic energy of an oscillator electron must be equal to the
average kinetic energy of a translating gas molecule. If we separate
the motion of an oscillator electron into three components at angles
to each other, we find for the average energy of one
of these linear components the expression
We shall now proceed to present a similar argument regarding the interaction
between the oscillators and the radiation present in the cavity. Herr Planck has
derived2 the condition for the
dynamics equilibrium in this case under the supposition that the radiation can
be considered a completely random process.3 He found
If the radiation energy of frequency is
not continually increasing or
decreasing, the following relations must obtain:
We wish to show in the following that Herr Planck's determination of the fundamental constants is, to a certain extent, independent of his theory of blackbody radiation.
Planck's formula,4 which has
proved adequate up to this point, gives for
We therefore arrive at the conclusion: the greater the energy density and the wavelength of a radiation, the more useful do the theoretical principles we have employed turn out to be: for small wavelengths and small radiation densities, however, these principles fail us completely.
In the following we shall consider the experimental facts concerning blackbody radiation without invoking a model for the emission and propagation of the radiation itself.
The following treatment is to be found in a famous work by Herr W. Wien and is introduced here only for the sake of completeness.
Suppose we have radiation occupying a volume . We assume that the observable
properties of the radiation are completely determined when the radiation density
is given for all frequencies.5 Since radiation of different frequencies are
to be considered independent of each other when there is no transfer of heat or
work, the entropy of the radiation can be represented by
can be reduced to a function of a single variable through formulation of the condition that the entropy of the radiation is unaltered during adiabatic compression between reflecting walls. We shall not enter into this problem, however, but shall directly investigate the derivation of the function from the blackbody radiation law.
In the case of blackbody radiation, is such
a function of that the
entropy is maximum for a fixed value of energy; i.e.,
>From this it follows that for every choice of as a function of
The following equation applies when the temperature of a unit volume of
blackbody radiation increases by
This is the law of blackbody radiation. Therefore one can derive the law of blackbody radiation from the function , and, inversely, one can derive the function by integration, keeping in mind the fact that vanishes when .
>From existing observations of the blackbody radiation, it is clear that the law
originally postulated by Herr W. Wien,
This formula gives immediately
If we confine ourselves to investigating the dependence of the entropy on the
volume occupied by the radiation, and if we denote by the entropy of the
radiation at volume , we obtain
This equation shows that the entropy of a monochromatic radiation of sufficiently low density varies with the volume in the same manner as the entropy of an ideal gas or a dilute solution. In the following, this equation will be interpreted in accordance with the principle introduced into physics by Herr Boltzmann, namely that the entropy of a system is a function of the probability its state.
In the calculation of entropy by molecular-theoretic methods we frequently use the word ``probability'' in a sense differing from that employed in the calculus of probabilities. In particular ``gases of equal probability'' have frequently been hypothetically established when one theoretical models being utilized are definite enough to permit a deduction rather than a conjecture. I will show in a separate paper that the so-called ``statistical probability'' is fully adequate for the treatment of thermal phenomena, and I hope that by doing so I will eliminate a logical difficulty that obstructs the application of Boltzmann' s Principle. here, however, only a general formulation and application to very special cases will be given.
If it is reasonable to speak of the probability of the state of a system, and
futhermore if every entropy increase can be understood as a transition to a
state of higher probability, then the entropy of a system is a function of
, the probability of its instantaneous state. If we have two
noninteracting systems and , we can write
The last equation says that the states of the two systems are independent of each other.
>From these equation it follows that
This system, which, for example, can be an ideal gas or a dilute solution, possesses an entropy . Let us imagine transferring all movable points into a volume (part of the volume ) without anything else being changed in the system. This state obviously possesses a different entropy , and now wish to evaluate the entropy difference with the help of the Boltzmann Principle.
We inquire: How large is the probability of the latter state relative to the original one? Or: How large is the probability that at a randomly chosen instant of time all movable points in the given volume will be found by chance in the volume ?
For this probability, which is a ``statistical probability'', one obviously
It is noteworthy that in the derivation of this equation, from which one can easily obtain the law of Boyle and Gay-Lussac as well as the analogous law of osmotic pressure thermodynamically,6 no assumption had to be made as to a law of motion of the molecules.
In Sec. 4, we found the following expression for the dependence of the entropy
of monochromatic radiation on the volume
If monochromatic radiation of frequency and energy is enclosed by
reflecting walls in a volume , the probability that the total radiation
energy will be found in a volume (part of the volume ) at any randomly
chosen instant is
>From this we further conclude that: Monochromatic radiation of low density ( within the range of validity of Wien's radiation formula) behaves thermodynamically as though it consisted of a number of independent energy quanta of magnitude .
We still wish to compare the average magnitude of the energy quanta of the
blackbody radiation with the average translational kinetic energy of a molecule
at the same temperature. The latter is
according to the Wien formula, one obtains for the average magnitude of an
If the entropy of monochromatic radiation depends on volume as though the radiation were a discontinuous medium consisting of energy quanta of magnitude , the next obvious step is to investigate whether the laws of emission and transformation of light are also of such a nature that they can be interpreted or explained by considering light to consist of such energy quanta. We shall examine this question in the following.
According to the result just obtained, let us assume that, when monochromatic
light is transformed through photoluminescence into light of a different
frequency, both the incident and emitted light consist of energy quanta of
magnitude , where denotes the relevant frequency. The
transformation process is to be interpreted in the following manner. Each
incident energy quantum of frequency is absorbed and generates by
itself-at least at sufficiently low densities of incident energy quanta - a
light quantum of frequency ; it is possible that the absorption of the
incident light quanta can give rise to the simultaneous emission of light quanta
of frequencies etc., as well as to energy of other kinds, e.g.,
heat. It does not matter what intermediate processes give rise to this final
result. If the fluorescent substance is not a perpetual source of energy, the
principle of conservation of energy requires that the energy of an emitted
energy quantum cannot be greater than that of the incident light quantum; it
It should be strongly emphasized that according to our conception the quantity of light emitted under conditions of low illumination (other conditions remaining constant) must be proportional to the strength of the incident light, since each incident energy quantum will cause an elementary process of the postulated kind, independently of the action of other incident energy quanta. In particular, there will be no lower limit for the intensity of incident light necessary to excite the fluorescent effect.
According to the conception set forth above, deviations from Stokes's Rule are conceivable in the following cases:
1. when the number of simultaneously interacting energy quanta per unit volume is so large that an energy quantum of emitted light can receive its energy from several incident energy quanta;
2. when the incident (or emitted) light is not of such a composition that it corresponds to blackbody radiation within the range of validity of Wien's Law, that is to say, for example, when the incident light is produced by a body of such high temperature that for the wavelengths under consideration Wien's Law is no longer valid.
The last-mentioned possibility commands especial interest. According to the conception we have outlined, the possibility is not excluded that a ``non-Wien radiation'' of very low density can exhibit an energy behavior different from that of a blackbody radiation within the range of validity of Wien's Law.
The usual conception that the energy of light is continuously distributed over the space through which it propagates, encounters very serious difficulties when one attempts to explain the photoelectric phenomena, as has been pointed out in Herr Lenard's pioneering paper.7
According to the concept that the incident light consists of energy quanta of magnitude , however, one can conceive of the ejection of electrons by light in the following way. Energy quanta penetrate into the surface layer of the body, and their energy is transformed, at least in part, into kinetic energy of electrons. The simplest way to imagine this is that a light quantum delivers its entire energy to a single electron: we shall assume that this is what happens. The possibility should not be excluded, however, that electrons might receive their energy only in part from the light quantum.
An electron to which kinetic energy has been imparted in the interior of the
body will have lost some of this energy by the time it reaches the surface.
Furthermore, we shall assume that in leaving the body each electron must perform
an amount of work characteristic of the substance. The ejected electrons
leaving the body with the largest normal velocity will be those that were
directly at the surface. The kinetic energy of such electrons is given by
In the body is charged to a positive potential and is surrounded by
conductors at zero potential, and if is just large
enough to prevent
loss of electricity by the body, if follows that:
If one takes , then is the potential in volts which the body assumes when irradiated in a vacuum.
In order to see whether the derived relation yields an order of magnitude consistent with experience, we take , (corresponding to the limit of the solar spectrum toward the ultraviolet) and . We obtain volts, a result agreeing in order magnitude with those of Herr Lenard.9
If the derived formula is correct, then , when represented in Cartesian coordinates as a function of the frequency of the incident light, must be a straight line whose slope is independent of the nature of the emitting substance.
As far as I can see, there is no contradiction between these conceptions and the properties of the photoelectric observed by Herr Lenard. If each energy quantum of the incident light, independently of everything else, delivers its energy of electrons, then the velocity distribution of the ejected electrons will be independent of the intensity of the incident light; on the other hand the number of electrons leaving the body will, if other conditions are kept constant, be proportional to the intensity of the incident light.10
Remarks similar to those made concerning hypothetical deviations from Stokes's Rule can be made with regard to hypothetical boundaries of validity of the law set forth above.
In the foregoing it has been assumed that the energy of at least some of the
quanta of the incident light is delivered completely to individual electrons. If
one does not make this obvious assumption, one obtains, in place of the last
For fluorescence induced by cathode rays, which is the inverse process to the
one discussed above, one obtains by analogous considerations:
We shall have to assume that, the ionization of a gas by ultraviolet light, an
individual light energy quantum is used for the ionization of an individual gas
molecule. From this is follows immediately that the work of ionization (i.e.,
the work theoretically needed for ionization) of a molecule cannot be greater
than the energy of an absorbed light quantum capable of producing this effect.
If one denotes by the (theoretical) work of ionization per gram equivalent,
then it follows that:
There is another consequence the experimental testing of which seems to me to be
of great importance. If every absorbed light energy quantum ionizes a molecule,
the following relation must obtain between the quantity of absorbed light
and the number of gram molecules of ionized gas :
If our conception is correct, this relationship must be valid for all gases
which (at the relevant frequency) show no appreciable absorption without