Theories of the Photoelectric Effect

Karl K. Darrow

Citation: Review of Scientific Instruments 4, 467 (1933); doi: 10.1063/1.1749179

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 SEPTEMBER, 1933
PHYSICS FORUM
Theories of the Photoelectric Effect
T oelectric
begin with: I here use the term "photo-
effect" in its earliest sense, de-
noting the extraction of electrons from solids
(chiefly metals) by light of the visible or the
ultraviolet range of the spectrum, with photon
energies of, say, ten electron-volts or less. It has
lately become the custom to extend the term to
cover the ionization of gases by light and the
extraction of tightly-bound electrons from atoms
by x-rays and the Becquerel effect and the
alterati<1n of the conductivity of selenium by
light and many other phenomena. This is re-
grettable because in its original scope the name
referred to a neatly-definable field of physics,
set apart from all others not so much by theory
as by the methods of experimentation.
All of the theories of this photoelectric effect,
from the "classical" theory onwards, are based
on the conception of a metal as a region of space
populated by electrons and surrounded by a
potential-wall which no electron can climb unless
it has absorbed the energy of a photon. In all
but the latest theories it is assumed that the
region is equipotential and that the electrons are
"free"-two statements which, when analyzed,
turn out to mean practically the same thing.
Formerly one thought of the equipotential region
as made up of the interspaces between the atoms
and of the free electrons as a special category
roaming constantly through these interspaces,
distinct from the "bound" electrons permanently
attached to the atoms. After the introduction of
the Fermi-Dirac statistics it became the custom
to think of the free electrons as a special category
able to traverse the atoms without deflection or
loss of energy, so that for them the whole volume
of the metal would be, in effect, an equipotential
region. Attempts are now being made to take
proper account of the influence of the atoms,
467
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R. S. I. VOLUME 4
considered as spaces of high and variable po-
tential; but I will leave these for another time
and for the early part of this article retain the
idea of the equipotential region.
Let K 0 stand for the initial kinetic energy of a
free electron; v for the frequency of incident
light able to produce the photoelectric effect;
hv for the energy of a photon of that light; V for
the potential-difference between the inside and
the outside of the wall, the "height of the
potential-step," also known as the "work-func-
tion" of the metal. Let energy values be expressed
in electron-volts and potential differences in
volts. Then the fundamental idea of all the
theories appears in the inequalities:
Ko<V; Ko+hv> V. (1)
The classical theory is simply this picture,
with the special feature that Ko is supposed to
be negligibly small. Usually, though not always,
this is an acceptable approximation to the idea
that the free electrons within the metal have a
Maxwellian distribution. 1 Thence follows im-
mediately the famous Einstein equation for the
kinetic energy K (here expressed in electron-
volts) which the electrons have when they
emerge from the metal:
K=hv- V. (2)
K plotted against v should appear as a straight
1 At room temperature the mean value of Ko would then
be about 0.02 electron-volt and most of the electrons would
have values of Ko less than three times this figure. The
resulting modification of the phenomena should be appreci-
able with metals having a threshold in the long-wave part
of the visible spectrum; but the data, as I will later stress,
indicate that the distribution of the electrons within the
metal is not Maxwellian so that it is not worth while to
consider the question further from this standpoint. See
DuBridge, Phys. Rev. 43, 727ff. (1933).
 468
line, of which the slope is to be identified with
the quantum-constant h and the intercept on the
v-axis with the work-function of the metal.
As all physicists know, this equation is found
to be true with close approximation for the
fastest electrons emerging from illuminated
metals. Not only is the kinetic energy Kmax of
these found to be approximately a linear function
of v for any metal but the slopes of the lines of
various metals all agree with each other and
with the values determined for the quantum-
constant by other methods. Moreover, there is an
agreement involving the additive constant of the
equation which has an important bearing on
the theory. According to classical ideas, when
two metals are welded together they are to be
regarded as two regions of space populated by
free electrons and differing in potential by the
relatively small amount P deduced from the
Peltier effect (generally a small fraction of one
electron-volt). Between a point just outside one
of the metals and a point just outside the other,
there should then be a potential difference equal,
except for this smal1 quantity P, to the difference
(V 1 - V 2) between the work-functions of the
metals. This is interpreted as the Volta or
"contact" potential difference; and in a number
of cases, it has actual1y been found that the
contact p.d. between two metals is sensibly
equal to the difference between their values of
the additive constant in Eq. (2).
Thus the classical theory justifies itself in two
such important ways that one can scarcely
dream of supplanting it by anything totally
different. The present quantum-mechanical the-
ories of metals, however, are so much like the
classical picture that they are able to share in
these successes. What more can be expected of
them?
In addition to the maximum energy of the
photoelectrons of which the theories give so
good an account, there are two other features of
theirs with which the classical picture (or at
least, so much of it as I have quoted) is quite
incompetent to deal. These are the distribution·
in-velocity of the emerging electrons and the
number of them ejected by light of given in-
tensity. To account for these, it is necessary to
have the right idea about the number and the
distribution-in-velocity of the corpuscles inside
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PHYSICS FORUM
the metal; and it is necessary also to attack
three other fundamental problems. One of these
is the question of the probability that a photon
of given energy, entering a metal of given nature
and given thickness, shall impart its energy to
an electron. This would be the only problem, if
we could be sure that every electron which
receives the energy of a photon infallibly goes
straight to the surface of the metal, that is,
to the inner side of the potential-wall, without
suffering any deflection or loss of energy on the
way, and then infallibly goes through the wall
to the outer world if its kinetic energy is suf-
ficient. But we have no right to be sure of any-
thing of the sort: it is far more likely that some
of the electrons in question lose energy and
suffer deflections on their way toward the surface
and that some of those which arrive at the po-
tential wall are reflected back into the metal
even though their kinetic energy be sufficient to
take them clear out. Also, it is possible (according
to quantum mechanics) for electrons to traverse
potential walls of certain types, even though
their kinetic energy be not sufficient for such a
feat by classical ideas. It appears, therefore,
that there are three fundamental problems: the
one already stated and the problem of the be-
havior of electrons passing through a metal and
that of the behavior of electrons impinging on a
potential wall. Seemingly it is necessary to solve
all three, in order to predict that which is ob-
servable: to wit, the number and distribution-in-
velocity of the photoelectrons expelled, by light
of given intensity and given wave-length and
given angle of incidence and given state of
polarization, from metal of given nature and
given thickness.
Evidently this is a very large order. It is not
surprising to find that theorists as a rule have
attacked not more than one of the problems at
a time, meanwhile assuming excessively simple
solutions for the others.
RESULTS OF SUBSTITUTING THE DISTRIBUTION-
FUNCTION OF FERMI AND DIRAC FOR
THAT OF MAXWELL
It will be recalled2 that when corpuscles con-
form to the Fermi-Dirac distribution with tem-
2 See, for instance, my article in Rev. Mod. Phys. I,
90-154 (1929).
 PHYSICS FORUM 469

perature OaK, they are distributed over a se- I therefore confine this discussion to the latter,
quence of permissible kinetic-energy-values ex- which is as follows: the number of electrons which
tending upward to a particular value Wi. At incident light of frequency v can expel is pro-
absolute zero there are no corpuscles with kinetic portional to the number-per-unit-volume-of-
energy greater than Wi, which, therefore, is a metal of those electrons for which !mx 2 is
sharp upper limit to the quantity denoted by greater than (Wo-hv). This number, call it N B ,
Ko in Eqs. (1). Then the kinetic energy K,nax is evaluated by Fowler from the Fermi-Dirac
which the fastest electrons retain after their distribution function.
escape from the metal is not (hv - V) but Any electron which is expelled belongs initially
(hv+ W i - V): In experimenting near the abso- to this group. The number of electrons which
lute zero, one would still expect to get a straight- actually are expelled, by a given number of
line relation between Kmax and v similar to photons, is proportional to N B and to the three
Eq. (2); one would plot the line as before and probabilities aforesaid. If all of these probabilities
determine from its intercept the additive con- are sensibly independent of v over an appreciable
stant which figures in that equation but that range of frequencies or wave-lengths, then over
constant would now be interpreted not as V but this range the photoelectric current I produced
as (V - W i )_. Henceforth I will follow Sommer- by a given number of photons per second will
feld's practice of denoting the work-function by vary with frequency in the same manner as N B·
W u , so as always to keep it in mihd that the This set of assumptions is commonly known
Fermi-Dirac distribution is being assumed. As as "Fowler's theory," as it was developed by
the temperature T is raised from absolute zero, R. H. Fowler in a paper which he published
more and more of the corpuscles transfer them- during his stay a couple of years ago at the Uni-
selves to permissible energy-values greater than versity of Wisconsin. In evaluating N B, he made
Wi, leaving a corresponding number of per- certain approximations which restrict the va-
missible values vacant in the range below Wi. lidity of the results to a range of frequencies
We will now assume that an electron can cross extending upwards and downwards by a few
the potential wall if it receives enough energy percent from Vo, the "threshold frequency at
through absorbing a photon. This assumption, absolute zero" defined as (Wa - Wi) Ih. This is
however, is not fully defined by the foregoing probably no disadvantage as the probabilities
words. Suppose, for definiteness, that the surface aforesaid may themselves vary appreciably with
of the metal lies in the yz plane. Imagine an v and the broader the range of v, the more
electron beneath the surface, moving with ve- serious these variations would become. The
locity components x, if, z; its total kinetic energy actual range is apparently not too narrow for
K 0 is the sum of the three terms !mx2, !m??, convenience, as Fowler uses arcs of current-vs.-
!mz2; but of these three, the two last are not wave-length curves extending over two or three
available for helping the electron over the wall hundred Angstroms in testing his solutions.
unless something happens to it which deflects its These solutions are as follows, the symbol J.I.
course into the x direction without robbing it standing for h(v- vo)lkT:
of its energy. Should we assume that such an 1= CP(Wa-hv)-Y(J.I.)
electron can escape, if, when it absorbs a photon,
the sum (KQ+hv) is greater than Wa? Or should lI.) = e~ _ e2~ + e3~ - . .. J.I.~O
we make the more drastic assumption that it {f( ,.. 22 32 '

cannot escape unless (!mx 2+hv) is greater than 7T 2 [ e-2~ e-3~ ]

Wa? The latter seems the more plausible but f(J.I.) =6+!J.l.2 - e-~-22+32-'" ,
the former cannot be dismissed a priori; some-
J.I.~O (3)
thing might happen to the electron to deflect it
into the x direction after it had absorbed in which C stands for the factor, unknown but
the photon; but the two assumptions lead to assumed to be independent of v and T, which
markedly different results and the former (ac- embodies the probabilities aforesaid and also
cording to Fowler) is disqualified by the data. depends on the units chosen for current, energy,

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 470 PHYSICS FORUM
etc. Taking logarithms of both sides, we get:
(4)
in which cf> stands for the logarithm of f, and B
for that of the quantity C(Wa-hv)-l. The func-
tions cf> and f are universal functions. DuBridge
has published3 a table of the values of cf>(p,) and
the values of log \p,I, over the range from p, = - 8.0
to p,= +50.0.
There would be no insuperable difficulty in
testing formula (4) as it stands; but over the
narrow range of frequencies close to Vo for which
(4) is tentatively assumed to be valid, the
quantity (Wa-hv)-I; varies but little;4 and it is
customary to make yet one more approximation
by assumin'g this quantity, and consequently B
of Eq. (4), to be constant.
Suppose now that measurements of current be
made at various frequencies and temperatures
and that log (I/P) be plotted against p.; then,
if the theory is acceptable, all the points must
lie along a single smooth curve, identical in shape
with the curve of cf>; and it must be possible to
bring the two into perfect coincidence by shifting
either parallel to the axis of ordinates, the
amount of the required shift being the value of B.
This sounds easy but there is the difficulty that
p" being by definition h(v- vo) /kT, involves the
constant Vo which must be deduced from the
data themselves. The test is therefore more
troublesome than it seems at first but if success-
fully carried through it rewards us with the
proper value for the threshold frequency vo.
Fowler's procedure consists in gathering to-
gether the various measurements made with
various frequencies of light at a single tempera-
ture and plotting log (liP) against hv /kT. If the
theory is acceptable, all the points must lie upon
a single smooth curve which can be brought into
coincidence with the theoretical curve by giving
it both a shift parallel to the axis of ordinates
and a shift parallel to the axis of abscissae. The
latter shift is then equal to hvo/kT. Let the
process be repeated with data obtained at
3 Phys. Rev. 39, 109 (1932). DuBridge takes logarithms
to base 10, a precedent which may as well be followed.
4 The value of Wa is believed to be greater by several
electron·volts than that of hvo, while over the range in
which the tests of the theory are applied hv differs by only
a small fraction of one electron-volt from hvo.
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another temperature T' with various frequencies
of light; the necessary horizontal shift should
then be hvolkT' and should stand to the other as
T to T'. DuBridge recommends the procedure of
gathering together the measurements made with
a given frequency of light at various tempera-
tures and plotting log (liP) against log (liT);
the horizontal shift required to make the curve
coincide with the theoretical curve (which in
this case is obtained by plotting cf>(p.) against
log (p,)) should be equal to log h(v-vo)/k and
thus provides a value for Vo which should be the
same whatever the frequency chosen.
The first of the tests were made by Fowler on
data for Ag, Au and Ta obtained at the Uni-
versity of Wisconsin by three of Mendenhall's
students, Winch, Morris and Cardwell. The
ranges of wave-length (to judge from the graphs)
were 2200-2630, 2250-2550, 2800-3130, respec-
tively, the upper ends thereof being near the
greatest wave-lengths at which current could be
detected. The absolute temperatures were 293°,
673°,873°; 296°, 733°, 1013°; 293°, 973° for the
three metals, respectively. Fowler made similar
tests of data from Goetz for tin in two solid
phases and in the liquid state. Shortly afterwards
appeared a very thorough study of palladium by
DuBridge and Roehr, who measured at no fewer
than eight temperatures between 305 and 1078°,
and at six wave-lengths between 2225 and 2482.
The results of these tests have been notably
favorable to Fowler's theory. DuBridge applied
both of the above-described procedures to the
data for palladium and one of his figures" shows
how beautifully, with the second procedure, the
points of observation are brought by suitable
shifts to the theoretical curve. The horizontal
shifts, for the six wave-lengths 2225, 2302, 2345,
2378, 2399, 2482, were 3.75, 3.65, 3.56, 3.47,
3.36 and 2.19; and from these last were deduced
the following very concordant values of hvo in
electron-volts: 4.98, 4.98, 4.94, 4.94, 4.95, 4.96.
The other procedure applied to the same data
produced the value 4.97 ±0.01. The second pro-
cedure applied to data of Morris for gold (five
wave-lengths ranging from 2302 to 2536) gave
values of hvo all comprised between 4.78 and
4.83. Fowler's own analysis of the data of Winch,
D Fig. 3, Phys. Rev. 39, 115 (1932).
 PHYSICS FORUM
Morris and Cardwell by the first procedure led to
values ranging from 4.71 to 4.76 for Ag; from
4.86 to 4.92 for Au; from 4.10 to 4.14 for Ta;
and his analysis of Goetz' data for Sn led to
the values 4.39, 4.28, 4.17 at the temperatures
358°,483°,673°, values of which the differences
may well be real, as the tin was in three different
states at the three different temperatures. It is
evident that if hvo varies with temperature, it is
the first procedure which is appropriate.
Much emphasis is laid by the foregoing authors
upon the extremely long-continued and vigorous
preliminary heating of the metals. in vacuo,
though it is not obvious why the assumptions of
the theory might not be expected to apply to
metals not so harshly treated; unless indeed it
be supposed that a metal not thus treated has a
potential wall constructed in such a way that its
ability to reflect electrons coming up to it from
within the metal varies very rapidly with the
energy of these.
However, Welch made observations on several
metals (Ca, Fe, Co, Ni, Cu, Zn, Ge) which had
not been heated and found "a very good fit to
Fowler's theoretical curve." The metals were
examined in a tube containing gas at a pressure of
the order of 10- 6 mm Hg; the surfaces were
filed clean and groups of observations were made
at time-intervals ranging from 10 minutes to 2
hours after the filing (always at room tempera-
ture); the values of hvo changed slowly with the
lapse of time, downward with germanium, up-
wards with the rest.
The assumptions of Fowler's theory lead also
to predictions about the distribution-in-velocity
of photoelectrons, which I will next take up.
The problem of distribution-in-velocity is a
tough one, both experimentally and theoretically.
The ideal experiment would supply us with the
total number and the distribution-in-speed of the
electrons emitted in any direction, i.e., in any
cone with its axis pointing in any direction
(relative to the normal to the metal surface and
to the plane of incidence of the light). Very few
experiments, however, come near to this stand-
ard. Most belong to one or the other of two types:
the "parallel-plane" type in which emitter and
collector are parallel-plane surfaces, and the
"sphere" type in which the emitter is as small
as practicable and is placed centrally in a
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471
spherical collector as large as practicable. The
experimenter takes current-voltage curves, the
collector being more negative than the emitter
and the p.d. between these two being varied
from zero to the highest amount with which a
current is still perceptible. The derivatives of
these curves are closely related to distribution-
in-energy functions. In apparatus of the parallel-
plane variety, this derivative is the distribution
in respect to the quantity !me, the symbol ~
standing for velocity-component normal to the
planes. 6 In apparatus of the other type, the de-
rivative approaches the true distribution in
kinetic energy when the ratio of the diameters
of emitter and collector approaches zero; if this
ratio differs appreciably from zero, a correction
must be applied. Data of these kinds are the only
ones against which the theory in question has so
far been checked.
For experiments with plane-parallel emitter
and collector, the development of the theory
requires no further labor. Denote by Va any
particular value of the retarding potential be-
tween collector and emitter: then the electrons
reaching the collector should be the same in
number and distribution, that is to say, distribu-
tion in respect to !m~2, as though Va were simply
added onto the work-function Wa of the metal
and hvo (in electron-volts) were augmented by
Va (in volts) and fJ. of Eq. (3) were diminished by
Va/kT. Evidently the effect on the right-hand
member of (3) is precisely the same as that of
diminishing v by Va/h; and the curve of current-
vs.-voltage, over the range from Va = 0 upwards,
should be like the curve of saturation-current-
vs.-frequency from Vo downwards. The earlier
argument thus leads to the prediction that if one
plots log (l/P) against Va/kT for several values
of v, the curves can be brought into coincidence
with one another and with the theoretical curve
by horizontal shifts equal to h(v-vo)/kT (to-
gether with vertical shifts). Experiments of
DuBridge and Hergenrother on molybdenum at
room temperature with wave-lengths 2378, 2482,
2536 and 2654, gave data agreeing with this
prediction "well within the limits of experi-
mental error." The agreement, however, is con-
fined to the faster of the ejected electrons, i.e.,
6 There is absolutely no felicitous name for this quantity.
 472 PHYSICS
to ranges in which Va has at least half the value
'which would suffice to stop all of the electrons.
The lack of agreement elsewhere may be ascribed
to invalidity of the assumption that the prob-
ability of traversal of the potential wall is in-
dependent of the speed of the electron (by
quantum mechanics one would expect this
assumption to depart progressively further from
the truth, the lower the speed) or to defects of
the other assumptions.
For data obtained with the spherical arrange-
ment, the task of the theorist is harder, as he
must make and apply assumptions about the
transverse velocity-components (those parallel to
the emitting surface) of the electrons. DuBridge
assumes, if I follow him correctly, that the dis-
tribution-in-velocity of the electrons inside the
metal which have just absorbed photons is
isotropic, that it is the original Fermi-Dirac
distribution, with all the energy-values increased
by hI'. This presumably is the assumption which
is tested in the work of DuB ridge and Roehr
on molybdenum at temperatures ranging up to
1000°, of which a brief report was made at the
recent Chicago meeting in the words (to quote
from the abstract): " . . . The observed curves
show an excellent fit to the theoretical curves for
the whole range of temperatures and wave-
lengths examined." Another sentence reads:
"From the shifts required to fit the observed
curves, the maximum energy at OOK can be
determined and the values so obtained for a
series of different wave-lengths at any fixed tem-
perature fit closely the Einstein equation." This
probably refers to a test similar to that men-
tioned in the last paragraph, in which the shifts
necessary to bring the observed into coincidence
with the theoretical curve were found to be
equal to (hv-const.).
It thus appears that Fowler's theory is ad-
mirably verified over rather narrowly limited
ranges of frequency, energy (of ejected electrons)
and kinds of metal. This is to be regarded, above
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FORUM
all, as a verification of the Fermi-Dirac dis-
tribution-function; and as such it is highly im-
portant for fundamental theory. Another im-
portant result is that the method of determining
the constant called Vo is altered by the new
ideas. Formerly one determined it by plotting
either the curve of Kmax (maximum kinetic
energy of ejected electrons) against frequency or
the curve of saturation-current against frequency
and either carrying the curve by observation as
far as the axis of frequencies or extrapolating it
to this axis. This involved uncertainties which are
all too well known to those who have worked in
this field and which are due largely to the shapes
of these curves in the immediate neighborhood of
the axis of frequencies. The new method makes
unambiguous use of these shapes in fixing the
value of 1'0. One must admit that the constant
does not have the same interpretation in the old
theory as in the new; in the former it stood for a
constant of the metal (the work-function), in
the latter it stands only for the difference between
two constants of the metal. In both theories,
however, it is interpreted in the same way as
the thermionic constant b (when independent of
temperature), and this identity makes one of the
reasons for measuring it. Finally, the process of
evaluating the quantum-constant h from obser-
vations of photoelectric current is itself altered
by the new ideas.
KARL K. DARROW
REFERE!'ICES
R. H. Fowler, Phys. Rev. 38, 45-56 (1931) and experi.
mental papers there cited.
L. A. DuBridge and W. W. Roehr, Phys. Rev. 39, 99-107
(1932).
DuBridge, Phys. Rev. 39, 108-118 (1932).
DuBridge, Phys. Rev. 43, 727-741 (1933).
DuBridge and Roehr, Bull. Amer. Phys. Soc. 8, No.4
(1933).
G. B. Welch, Phys. Rev. 40, 470-471 (1932).
L. B. Linford, Rev. Mod. Phys. 5, 34-61 (1933)-good
general account.