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442

The Theory o f the Surface Photoelectric Effect in Metals— I

B y K . M it c h e l l , B .A ., P e te rh o u s e , C am b rid g e

(C om m unicated b y R . H . Fow ler, F .R .S .— R eceived M arch 28, 1934)

Introduction

1. I n th e e lectro n th e o r y o f m e ta ls i t is u su a lly a ssu m e d t h a t th e electrons

can be re g a rd e d as m o v in g in d e p e n d e n tly in a p erio d ic p o te n tia l field, and for
c e rta in p ro p e rtie s i t is sufficient to use th e sim p ler Som m erfeld model, in
w hich th e p o te n tia l in sid e th e m e ta l is c o n s ta n t. T he p h o to ele ctric effect is
n o t, how ever, one o f th ese , as th e e le c tro n s a re effectiv ely free, a n d , as is well
know n, th e p h o to e le c tric effect c a n n o t ta k e place w ith free e le c tro n s on account
o f th e im p o ssib ility of sa tisfy in g s im u lta n e o u sly th e law s o f conservation of
en erg y a n d m o m e n tu m .
B ecause o f th is , T a m m a n d S c h u b in f h a v e p ro p o se d t h a t th e photoelectric
em ission fro m a m e ta l sh o u ld b e re g a rd e d a s a risin g fro m th e su perposition of
tw o effects, th e surface effect, d u e to th e r a p id ch an g es of p o te n tia l energy at
th e surface of th e m e ta l, a n d th e v o lu m e effect, d u e to th e in te rn a l variations
o f p o te n tia l ; a n d h a v e f u rth e r g iv en a th e o r y o f th e surface effect for an
id ealized case. T heories a p p a re n tly o f th e su rfa c e effect, in t h a t th e y neglect
p o te n tia l v a ria tio n s in sid e th e m e ta l, h a v e also b een g iv en b y F ro h lic h J and
W entzel,§ a n d th e re s u lts o f a ll th re e th e o rie s a re a t v a ria n ce . T he question
is e x a m in ed a n ew in th e p re s e n t p a p e r, a n d th e conclusion is rea c h e d t h a t none
of th e e a rlie r th e o rie s c a n b e a c c e p te d as re p re s e n tin g th e surface effect even
for th e v e ry id ea liz e d case co n sid ered . T he th e o r y w h ich is believed to be
c o rre c t is given, a n d c e rta in re s u lts b rie fly discussed, leav in g to a la te r paper
a m ore d e ta ile d c o m p a riso n w ith th e e m p iric a l facts.

The Model
2. To give a co m p lete th e o ry of th e p h o to e le c tric effect, it w ould be necessary
to calcu late th e p ro b a b ility o f a n e le c tro n in a n y s ta te in sid e th e m e ta l absorb-
t ‘ Z. P h y sik ,’ v o l. 68, p. 97 (1931).
{ 6 A nn. P h y sik ,5 v o l. 7, p. 103 (1930). A corrected version is g iv en b y Som m erfeld and
JBethe, in 6 G eiger-Scheel H an d b u ch der P h y s ik ,’ 2n d ed ., v o l. 2 4 /2 , p. 468.
§ Som m erfeld F estsc h r ift, “ P rob lem e der M odernen P h y sik ,” ed ited b y P. Reb^e,
p. 79, H irzel( 1928).
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Surface Photoelectric Effect in Metals 443

in g a q u a n tu m of energy, a n d m ak in g a tra n s itio n to som e s ta te of g rea ter

energy. A ctually, of course, we h av e no definite know ledge of th e electron-
sta te s inside th e m etal, a n d it is necessary, b o th for th is reason, a n d for con­
siderations of sim p licity , to find som e sufficient a p p ro x im a te m odel. The
general conception of a m eta l is of a tr ip ly periodic c ry s ta l la ttic e of m etallic
ions, w ith th e electrons m oving in th e self-consistent field due to them selves
a n d th e ions. The ions will be v ib ra tin g a b o u t th e ir m ean positions, b u t it is
usual to assum e th e am p litu d e s of th ese v ib ra tio n s to be sm all, so t h a t to a
first a p p ro x im atio n th e electrons can be ta k e n as m oving in a periodic field o f
potential. I t is th e n found t h a t th e electronic energies fall in to c e rta in b an d s,
which are s e p a ra te d b y “ fo rb id d en zo n es.”
The perfect p e rio d icity w hich is assum ed above w ill o b ta in only w hen th e
crystal la ttic e is supposed to e x te n d to in fin ity in all directions. The in tro ­
duction of a surface, as is n ecessary for th e p h o to electric effect, w ould th e n
lead to difficulties, a n d for th is reason we m u st fu rth e r idealize th e m odel b y
assum ing th a t th e p o te n tia l energy in th e in te rio r is c o n sta n t. N um erous
characteristic pro p erties, am ong th e m th e b a n d s tru c tu re , th e n d isap p ear,
and th is fac t m u st be k e p t in m in d w hen discussing th e resu lts o f th e th e o ry
of th e photoelectric effect founded u p o n th is m odel. T he surface is now an
essential feature. W ith o u t it, th e electrons w ould be e n tire ly free, a n d th e
photoelectric effect w ould be im possible, as energy a n d m o m en tu m could
not be sim ultaneously conserved. W entzel (loc. cit.) trie d to av o id th is
difficulty b y considering a d am p ed lig h t w ave, a n d o b tain e d non-zero resu lts
thereby. The dam p in g of th e lig h t w ave im p licitly assum es t h a t th e electrons
are bound, an d we m u st th e n ob ject to W en tzel’s th e o ry t h a t it is n o t in te rn ally
consistent.
Two courses are now open to us. W e m a y e ith e r in tro d u ce th e surface
explicitly, using a c o n sta n t p o te n tia l energy inside th e m etal, or neglect th e
surface, an d re tu rn to th e m odel in w hich th e p o te n tia l is a periodic function
of th e space co-ordinates. T am m a n d Schubin (loc. cit.) h av e adduced con­
siderations suggesting t h a t th e photoelectric em ission can be sp lit in to tw o
parts, w hich th e y propose to call th e surface a n d volum e effects, determ ined
by th e tw o m ethods above, a n d th e y fu rth e r argue t h a t th e volum e effect
will be relativ ely sm all n ear th e threshold. W hile we can n o t be convinced
of th e v a lid ity of th e ir conclusion, as th e y consider only a v ery special case,
we m ust regard th e calculation of th e surface effect as being, in some respects
a t least, a first ap p roxim ation to a com plete th eory. The present paper will
be restricted to th is point.
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444 K. M itchell

T he sim p lest possible a ssu m p tio n we c a n m ak e as to th e fo rm of th e potential

b a rrie r a t th e surface o f th e m e ta l, is t h a t th e p o te n tia l energy m akes a sudden
ju m p b etw een tw o c o n s ta n t v alues, as i t w ould w ith a double lay e r of electricity
on th e surface. T his fo rm is o b v io u sly a n id ea liz a tio n , w hich is justified
m ain ly b y th e fa c t t h a t th e c a lc u la tio n s w ith it c a n be c a rrie d o u t simply,
w hile we a re u n a b le to p u t fo rw ard w ith c e rta in ty a n y a lte rn a tiv e form . The
im age field is a v e ry p lau sib le suggestion, one m oreover w hich is to a certain
e x te n t e x p e rim e n ta lly confirm ed b y th e a c c u ra te re su lts given b y th e Schottky
re la tio n for electro n em ission in ac ce lera tin g fields. I t re sts u p o n th e assump­
tio n t h a t effects d u e to space ch arg e a re negligible, a n d th e re seem s to be no
reaso n to d o u b t th is .
F ro h lic h a n d T a m m a n d S c h u b in (loc. cit.) h a v e g iv en th eo ries o f th e photo­
electric effect in m etals, tre a tin g th e m e ta l as a reg io n of c o n s ta n t potential
en erg y s e p a ra te d fro m th e o u tsid e re g io n s b y a n a b r u p t ju m p in potential,
a n d d isre g a rd in g th e reflection a n d re fra c tio n o f lig h t a t th e surface. Quite
a p a r t fro m th is la s t p o in t, n e ith e r of th e se th e o rie s can be a c cep ted as giving
a correct ac co u n t of th e surface effect. F ro h lic h considers a th in m etal, and
hence h as twTo surfaces, a t b o th o f w h ich e x c ita tio n w ill ta k e place. As a
resu lt, n o t o n ly does th e in w a rd em issio n fro m th e b a c k surface contribute
to th e c u rre n t o u tsid e th e m e ta l, b u t also th e in w a rd em ission fro m th e front
surface, p a rtly reflected fro m th e b a c k (p erh ap s w ith m u ltip le reflections),
m ak es a fu rth e r c o n trib u tio n . E v id e n tly , th e n , we are g e ttin g som ething
m ore co m p licated th a n th e surface effect, a n d because th e sim ple m odel used
pro v id es no m ech an ism for th e d e -e x c ita tio n of electrons, a n d fu rth e r, because
of th e large p a r t w hich wdll u n d o u b te d ly be p la y e d b y th e reflection coefficient,
for w hich th e sim ple p o te n tia l ste p yields a p oor a p p ro x im a tio n , F rohlich’s
th e o ry does n o t give a s a tis fa c to ry p ic tu re even of th e p a r t of th e em ission in
th in films due to th e tw o surfaces. T he sam e ob jectio n s a p p ly w ith equal
force to th e th e o ry p re se n te d b y S om m erfeld a n d B eth e, w hich is essenti­
ally a co rrection of F ro h lic h ’s th e o ry . H ere, to o , we m u st ob ject to the
m eth o d of ta k in g in to a c co u n t th e effect of th e angle of incidence of th e light,
w ith o u t ta k in g in to a c co u n t also re fra c tio n a n d reflection. T h eir result
(loc. cit., p. 471, e q u a tio n (24.23) ) gives in finite em ission for grazing incid­
ence.
T am m a n d S chubin, on th e o th e r h a n d , m ak e use of a n infinite block of
m etal, a n d hence calcu late th e effect o f a single surface d ire c tly . As, however,
th e y m ak e use of a n in com plete sy ste m of eigenfunctions in a p p ly in g th e per­
tu rb a tio n th e o ry , th e ir resu lts are in error.
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Surface Photoelectric Effect in Metals 445

The q u an tu m m echanical p e rtu rb a tio n th eo ry can be applied in tw o d istin ct

m ys, which we m ay call th e sta tio n a ry a n d n o n -sta tio n a ry m ethods, to th e
jroblem considered. In th e form er th e whole system , m etal a n d lig h t w ave
md photoelectric current, is assum ed to be in a sta tio n a ry sta te , while in th e
a tte r th e m etal alone is supposed to be in a s ta tio n a ry sta te , a n d th e light
wave is suddenly tu rn e d on a t a definite tim e. A fter a long tim e we should
expect a stead y sta te to be reached, a n d w ould n a tu ra lly expect th e properties
of th is sta te to be th e sam e as those of th e sta te considered b y th e sta tio n a ry
method. M athem atically th e tw o differ only in th e m ethods ad o p ted to
solve th e sam e differential equation, th e first order equation of th e p ertu rb atio n
theory. In th e sta tio n a ry m ethod, th e to ta l w ave function is w ritte n dowm
directly, appealing to physical considerations to ju stify th e exclusion of those
parts of it representing electrons m oving tow ards th e surface of th e m etal.
In the n o n-stationary m ethod, th e to ta l wave function is determ ined as an
expansion in a series of solutions of th e u n p ertu rb ed problem . These p a rtia l
wave functions th e n have no direct physical significance, and we cannot exclude
any of them on a priori grounds. I t is here th a t Tam m a n d Schubin fall into
error. R em arking t h a t th e to ta l w ave function m ust represent a stream of
electrons m oving outw ards from th e surface of th e m etal, th e y conclude
wrongly th a t th e sam e m ust be tru e of each p a rtia l wave function entering
into the expansion. This evidently am ounts to arguing t h a t “ th e group
velocity m ust be outw ards from th e surface, hence so m ust th e wave velocity
of every wave ” — a well-known non sequitur.f
In the present paper th e correct result for th e surface effect, using th e pro­
posed model, is derived b y th e tw o m ethods outlined above, and th e results
of more general calculations, in which account is ta k e n of th e refraction an d
reflection of light a t th e m etal surface, are quoted and shortly discussed. A
later paper will present a m ore detailed com parison w ith experim ental results.

Calculation by the Stationary Method

3.1. The Method—W e consider th e behaviour of a single electron in th e
metal, using the model proposed in th e preceding section, and calculate th e
t In a metal bounded by an infinite plane, where the wave equation separates in rect­
angular Cartesian co-ordinates, a certain arbitrariness remains in the wave functions
representing free states, in th at we can have outward and inward m oving waves o f the
same energy, both of which m ust be included in our expansion. In an atom, w ith the wave
equation separating in spherical polar co-ordinates, the behaviour of the wave function at
the origin determines a definite com bination of the inward and outward waves, and the
same difficulty does not arise.
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446 K . M itchell

p e rtu rb a tio n p ro d u c e d b y a n in c id e n t lig h t w ave. T he m e ta l is taken to

o ccupy all space to th e n e g a tiv e side o f th e p lan e of y z , a n d th e light wave
of fre q u e n c y v, is su p p o sed to be in c id e n t u p o n th e surface in a directio n making
a n angle 0 w ith th e #-axis. F o r co nvenience, th e p lan e o f in cidence is supposed
to be th e p lan e of x y , a n d re fra c tio n a n d reflectio n o f th e lig h t w ill be neglected
T he in itia l w ave fu n c tio n s a re d e te rm in e d , a n d th e lig h t w ave is considered
to a c t as a sm all p e rtu rb a tio n . Tw o e q u a tio n s a re fo u n d to determ ine this,
to th e first o rd er, in sid e a n d o u tsid e th e m e ta l, a n d th e s e a re to be solved in
such a w a y t h a t th e p e rtu rb e d w av e fu n c tio n a n d its first d e riv a tiv e s shall be
co n tin u o u s a t th e surface. T h e gen eral so lu tio n o b ta in e d in th is w ay still
co n ta in s tw o a r b itr a r y c o n s ta n ts. T hese a re d e te rm in e d fro m th e condition
t h a t th e to ta l w ave fu n c tio n m u s t re p re s e n t electro n s m o v in g a w a y from the
surface, b o th in sid e a n d o u tsid e th e m e ta l. T he c u rre n t o u tsid e th e m etal due
to th e g iven in itia l s ta te c a n th e n b e c a lc u la te d , a n d th e re s u lt sum m ed over
th e co n d u c tin g electro n s to o b ta in th e to ta l em ission.
3.2. The In itia l W ave Functions — T h e w ave e q u a tio n fo r a n electron in th
m e ta l, u n d e r th e influence o f a lig h t w av e w hose v e c to r p o te n tia l is A and
sc ala r p o te n tia l zero, is

h2 h da ihe
\ 2u + — \u = — (A, g ra d u )y (1 )
8n2m 2 izi dt 2rcmc

w here V is th e p o te n tia l e n e rg y o f th e e le c tro n in th e m eta l,

V = — Ava, x < 0 |
( 2)
Y = 0, x> 0 J’
a n d e is th e ch arg e on th e electro n .
W e rep lace A b y zero to o b ta in th e e q u a tio n for th e in itia l w ave functions.
S e ttin g
u = uk — e x p (2niFiktJh), (3)

we o b ta in th e o rd in a ry S c h ro d in g er e q u a tio n for a n electro n in a field V,

8n2m
V 2^ + (E * -V ) o. W
~hT
A s Y is a fu n c tio n o f x alone, th is e q u a tio n is separable.
E q u a tio n (4) is to be solved for b o u n d s ta te s , for w hich

Fa < 0 E*. + hva,

su b je c t t o th e co n d itio n s t h a t tpk m u st be everyw here finite, a n d and
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Surface Photoelectric Effect in Metals 447

<\ik/dx m ust be continuous on th e plane x = 0. W e introduce three quantities

x, Jcy, kz, such th a t
8tt2w
(E fc + hva)— kx2 -f' k f + kz2, ( 6)

nd denote by p the positive value of the expression

= (pva — kx2)K (7)

diere
' 8n2m
( 8)
h ’

The appropriate solution of (4) is th en seen to be

= cnk (e~ ikx* + a keikxx ) eikvy + ikzz , z < 0

(9)
e-* W +iV , x>0 J‘
vhere a fc is an undeterm ined constant, and ak and bk are constants determ ined
oy the continuity relations a t x = 0,

6fc = 1 +

p6fc = i£x (1 —

Evidently kx, k y, and kz m ust all be real, and kx m ay be restricted to positive

values only.
3.31. The Perturbation produced by the Light Wave—W e will suppose now
that the am plitude of th e light wave is small. Then in equation (1) we set

u — u k + v, ‘ (11)

where uk is given by (3) and (9). Terms in uk on the left-hand side of (1)
will go out, and hence, neglecting products of v and term s involving A, we
obtain the first order equation of the pertu rb atio n theory,

\/2V _|_ Jl — — \ v = — ihe (A, grad uk). ( 12)

8ru2m 27zi dt 2imvc

Suppose now th a t the vector potential of the light wave is given by

A = 2a cos 2ttv { t + ^ P s 6 + sin 6| , (13)

where a is a constant vector. Replacing the cosine by its exponential expres­

sion, we see th a t the right-hand side of (12) will fall into two parts, having the
time factors exp {27ri (Efc di Av) t/h}, and so v will also fall into two parts

VOL. OXLVI.— A. 2 I
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448 K. Mitchell

h av in g th ese sam e tim e facto rs. T hese p a r ts e v id e n tly correspond to photo

electric e x c ita tio n a n d to s tim u la te d em ission ; th e la tte r m a y be neglected
im m ediately, b y o m ittin g th e co rresp o n d in g te r m fro m (12). Setting

v = 4>(x, y, z) ex p {2 (E* +
we o b ta in th e e q u a tio n for cf>,

(E* + hv- V)

= - ^ ( a , g ra d +*) e x p (2 m v — - ° + ^ sin 6). (l5)

A gain, th e rig h t-h a n d side o f (15) is th e su m o f th re e term s, involving respec­

tiv ely , ax,a„, az, w hich ca n b e re g a rd e d a s in d ep e n d e n t, since b o th th e an
incidence a n d th e p lan e o f p o la riz a tio n o f th e lig h t w ave can be varied inde­
p en d en tly . T he corresp o n d in g c o n trib u tio n s to <f> w ill th e n be additive, and
th e y m a y be determ ined, s e p a ra te ly b y s e ttin g

<f>— ^x<l>x+ + (16)

w here th e 7H a re c o n sta n ts, a n d dpi co rresponds to a*, fo r z.

3.32. W e proceed to th e d e te rm in a tio n of S e ttin g
. _ 4m e
‘''x (17)

q= { k 2+ p.v)i,
r = { k f + p- (v - vj}*, (19)
w here in (18) a n d (19) th e p o sitiv e values o f th e ro o ts a re to be tak en , and r
is supposed to be real, th e e q u a tio n s o b ta in e d a re

v 2^ + (?2 + V + * .* )& , .
= — ik x (e~%kxx — akeikxx) eikvy+ikzze x
\ C l
x < 0 , (20)
V 2<^ + (r2 + k y2 + k 2) <f>x
= — pbk e~px elkvy+lkzz e x p ^2 m v X CQS ^ ^ S3‘n ^ J, x 0. (21)

T he solutions <f>x are re q u ire d to be everyw here finite, to rep re sen t w aves moving
o u tw ard s from th e surface, b o th inside a n d ou tsid e th e m etal, a n d further to
be such t h a t cf>x a n d d<j>x/dx are co ntinuous on th e p lan e x — 0.
W e will now neglect 27c v/c in com parison w ith k x a n d ky. This is per­
m issible for th e m a jo rity of electrons in th e m etal, th e o rder of m agnitude of
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Surface Photoelectric Effect in Metals 449

:;v/c being 105 a n d th a t of kx for th e im p o rta n t electrons being 10s cm -1

nLe particular integrals of (20) a n d (21) th e n depend upon y an d z th ro u g h th e
fstor exp ('ikvy + ikzz), a n d it is found t h a t th e y do n o t by them selves
*&isfy th e co n tinuity relations. W e m u st th e n ad d to th e m those p a rts of
te com plem entary functions having th e sam e y- a n d z-factors, an d representing
(itgoing waves. The solutions th u s o b tained a re f

<f>x = {c* ciqx — ^ (e-*** — efV ) | eikvy+ikz*, x<

J > = { b x e~irx — ^ e~px \ <,*,»+«.* x > 0, (23)

l [JLV J

"iere bx and cx are co n stan ts determ ined b y th e co n tin u ity relations,

( l - a k) = b x)
[XV [XV
(24)
iqcx— — (1 + ak) = — irbx + j
[XV [XV J

limination of cx, using (10), leads to th e result

b- 2k*(p — (25)
x iv ( q+ r) [xv + '
3.33. (f>y and <f)z can be determ ined sim ilarly. In these cases, however, it
easily seen th a t th e equations corresponding to (20) a n d (21) have as in-
^mogeneous term s th e expressions for dtyk/dy or d ^ J d z in th e tw o regions, when
*v/c is again neglected. The p articu lar integrals, th en , are th e expressions
or (l/fjiv) d<\>k/dy or (l/[xv) dtyjdz, and these, as well as th e ir first derivatives
ith respect to x , are already continuous a t x = 0 . No term from th e particu lar
itegral is then needed, and th e contribution to th e cu rren t vanishes.
This result will be modified by tak in g in to account th e neglected term
tuv/ c, but the resulting current will still be very sm all in com parison w ith th a t
iven by the term (f>x.
3.34. In the region x > 0 th e whole wave function is now

= [a kbk e~p
ex2”iEktlh

+ Xx | bxe~irx— ^ e~vx J- e2ui (Ex + hv) (26)

t There is nothing to prevent us from adding on further parts o f the complementary

motions, w ith different y - and 2 -factors. These, however, m ust satisfy the conditions at
= 0 separately, whence it is seen th at the current due to them must be continuous in
rossing the boundary, and hence everywhere zero, since it is outwards in both regions,
his argument plainly involves no confusion between group and wave velocities.

2 I 2
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450 K. Mitchell

om itting term s coming from <j>y and <f>wh

The current density can now be calculated from th e general expression

. eh[ du* * du \
'■ = i s ( * ¥ ~ u d i) (27)

where th e asterisk denotes th e conjugate complex. E vidently, then, the only

term in (26) giving a non-zero contribution to th e current will be the term in
exp (— irx ), provided r is real. W e th u s obtain th e results

j* = I K K I2, if + [XV > [XV0, (28)

j* = 0 , if + [xv ^ [xva. (29)

The current density th u s obtained is due to th e in itial sta te given by (9),

for which th e electron density inside th e m etal has th e m ean value

2 I a fc (30)

3.41. Summation over the Conducting Electrons—According to the electron

theory of m etals, th e m ean num ber of electrons in u n it volum e having momenta
in the ranges h k j2 iz to h (kx + dkx)/2 tz, etc., is given by th e Fermi-Dirac
d istribution function

_2_________________ dkx dky dkz_______________ /gp

87t3 1 + exp {h2 (k 2 + k 2 + k 2 — fxv)/87r2m&T} ’

where k is B oltzm ann’s constant, T is th e absolute tem p eratu re, and

fjiv = (3tt2w)^, (32)

n being th e num ber of conducting electrons in u n it volume. We now equate

the tw o expressions (30) and (31) for th e electron density of the state con­
sidered, and su b stitu te th e resulting value of | <xk \2 in (28) or (29) to obtain
th e current due to the electrons in th e m etal w ith m om enta in the above
ranges. The result is th en in teg rated over all possible m om enta to obtain the
to ta l photoelectric current density,

t = e3 a x2 'Ja f f f ______________ dkxdkvdkz _________ _ _ (33)

“ J
27t4to2c2v2 j J 1 + exp {h2(kx 2+ k 2+

This is to be integrated over all states for which r is real, th a t is

K 2+ (XV > [XVa.

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Surface Photoelectric Ejfect in Metals 451

3.42. F o r all o rd in a ry tem p e ra tu re s, th e em ission will be given w ith sufficient

: curacy, except in th e im m ediate neighbourhood of th e threshold, b y tak in g
rto be zero in (33). The exponential is th e n to be replaced b y zero or infinity
rcording as k 2 + k 2 + k 2 — fxv is negative or positive. The sym bols
and kz th e n d isap p ear from th e in teg ran d , a n d th e in teg ratio n s w ith respect
1- these variables can be carried o u t b y in tro d u cin g plane polar co-ordinates.

dky dkz = p dp dcf), (34)

id in teg ratin g betw een th e lim its 0 to 2n, for </>, a n d 0 to ( ptv — k 2)*, for p.
7e th u s obtain, using (18) a n d (19),

P'1"'2 ,7/, ([XV — k 2) { k 2 + [i. (v — vj}*1

(35)
M P8_ , , l * l ( h 2 + [xv)i + f e 2 + [ x ( v - v j } * ] 2 ’

ie lower lim it being 0, if v > va, an d {pi (va — v)}*, if v < va.

Calculation by Variation of Constants

4.1. In th e calculation to be given now it is assum ed th a t th e lig h t is tu rn e d

n a t an a rb itra ry tim e, conveniently t = 0, an d th e change in th e w ave functio n
t a later tim e t is determ ined. S ta rtin g from eq u ation (12), we seek to o b tain
complete space-tim e description of events b y expanding v i n a series of solu-
Lons of the u n p e rtu rb ed problem , w hereas previously u k -f- v was regarded as
epresenting a sta tio n a ry sta te of th e whole system . I t is shown here t h a t in
he lim it as t ten d s to infinity, th e value of v calculated b y th e m ethod of
ariation of constants ten d s in to agreem ent w ith th e value obtained b y th e
tationary m ethod.
We commence by determ ining th e free states for th e unp ertu rb ed problem .
Ls regards their x-factors, these are n o t now com pletely determ ined, b u t we
an conveniently separate th em in to tw o sets, representing outgoing and in-
ling waves outside th e m etal. The expansion can th e n be m ade in term s of
aese. A lternatively, we m ay determ ine suitable linear com binations of
utgoing and ingoing waves of th e sam e energy, so th a t th e usual norm alization
ad orthogonality conditions are satisfied. The tw o m ethods are precisely
quivalent, b u t the form er seems clearer, and will be adopted here.
4.2. The Free States —W e proceed to solve equation (4) for

E/ > 0 . (36)
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452 K. Mitchell

To avoid confusion we w rite a suffix / in place of th e previous Jc. Introducing

qu an tities g, gy, gz, such t h a t

8iz2m
( E /+ h va) = g2 +gv 2 + g f (37)

a n d denoting b y / t h e positive value of th e expression

/ = — (^v0)4, (38)

th e outgoing w aves are given b y

= (e~i9x+
(39)
= bf e~ifxei+ igzz, x > 0

a n d th e in w ard m oving w aves b y

= {afe~iBX+ eigx) e V + x
(40)
= bfeifxeigvy + ig*z, > 0J
w here
1+ — 6/1
(41)
( i — «/) = f bJ

uf + a n d u f will be used to d enote ^ / + exp (2ro’E and exp (2iziEftjh)

respectively.
4.31. Determination o f the Expansion — W e seek to solve (12) b y assuming
for v a n expansion of th e fo rm f

« = Jf — oo
dgv [
J — oo
dgz f
Jo
d /C f + (t) uf + + f
J —oo
dgy
J — oo
fdgz
Jo
f Gf (t) uf .
(42)

In sertin g th is expansion in (12), a n d assum ing th e v a lid ity of inverting the

order of in te g ra tin g a n d o p eratin g b y

— - V 2 4- h . __ y (43)
87z2m 2m dt
it is found t h a t th e rig h t-h a n d side is a n expansion like (42), b u t w ith Cf (t)
replaced b y dCf jdt. W e th e n m u ltip ly b o th sides b y ur a*, where a denotes

t W e om it the part o f the expansion due to the bound states, which m ust also be inserted.
I t can easily be verified, however, th a t th is gives the term in exp ( — px) obtained in (26),
and this makes no contribution to the current.
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Surface Photoelectric Effect in Metals 453

- o r —, and integrate over all space, inverting th e order of th e space and

lom entum integrations to o b tain th e result

° dgv j dgz | £ df — f d ru f +U+ £ d f dCf^ ® j d

e
(A, grad uf a*. (44)
me
The orthogonality relations subsisting betw een th e free states (39) and (40)
an be w ritten in th e form

diUf+Uf** = j Uf * - 8 ( / - / ' ) 8 (gy - g \ ) 8 (gz - g'z)

M 45)
dzuf +u'f~* = \ +* = N / 2) 8 ( / - / ' ) 8 (gy - 8 (gz - g'z)

diere N/ (1) and N / 2) are to be determ ined, and S ( / — / ' ) denotes th e D irac
)-function. In sertin g these values in (44), an d replacing a b y + and — in
urn, we obtain th e sim ultaneous equations

N dCf+ + N / 2) dCf~ = — [ dxA,

( grad u k)
dt dt meJ
_ y (46)
N / 2) d~ ? r ^ + N / 1' dCf ^ — — \ dx (A, grad uk) uf ~*
dt dt me J J

Eliminating dCf ~ (t)jdt , and perform ing th e tim e-integration, assum ing th a t
at tim e t = 0, when th e light is tu rn e d on, th e electron is in the state k , we
obtain the result
exp {2tzi (E fc -f- hv — E.^) t/h} — 1
C / (t) = (* | a | (47)
2m (E fc + hv — E f )/h
where

(k1a 1/)+ = I dT(a>grad +*>W 1’^ * - N'<2)+/"*>

X exp 2niv (x cos 0 + y sin 0)/c. (48)
Here, as in the stationary m ethod, we have o m itte d a further term which has
the time-factor exp 2m (E fc — E r — hv)tjh, and which corresponds to stim u­
lated emission.
Neglecting the exponential term exp 2 m v (x cos 0 + y sin 0)/c, we see th a t
j a | / ) + will involve th e factors 8 (ky — gy) 8 (kz — gz). We shall th en
write
(* I a l / ) + = (* I a | f ) 0+ S (K - 9y) S (K - gz). (49)
4.32. We now insert (47) in (42), and carry out the resulting integrations
to obtain the value of v. In virtue of (49), the integrations w ith respect to
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454 K. Mitchell

gy and gz can be carried o u t a t once, leading to th e resu lt for v, outside the

m etal,
exp {2m (E fc -f - hv — E /) t/h} — 1 | a | / )0+ 6/
v = (k e - i f x + i k y y + i k z e 2niKft!h
2Tci (E fc -f- hv — E f)jh
exp {2m (E fr + hv — E ;) t/h} — 1
+ (A; | a | / )0~bf e ^ +iV +iV e2ldV ' \
2m (E fc -f" hv — E f)/h
(50)

where (1c | a | / ) 0~ is th e corresponding m a trix elem ent to (Jc | a | / ) 0+, in

the expression for C /- (t ).
In both th e integrals occurring in (50), we m ay suppose x a n d t to be great.
The factors occurring can th e n be sp lit up in to those v ary in g quickly or slowly
w ith /. The en tire c o n trib u tio n to b o th in tegrals will come from th e immediate
neighbourhood of th e resonance value given b y

E / — E fc -f- hv. (51)

W e can th e n give th e slow ly v a ry in g facto rs th e ir values a t th e resonance point,

an d p u t th em outside th e sign o f in teg ratio n . D enoting b y r th e value of /
a t th is po in t, we have

•v br eikvy+ikzz+2ni(Ek+h'')tlh {e~ir* (& |aj r )0+ Y + eirx (% |a| r )0~ Y'}, (52)

where ^ _ f® « 1 — exp 2t nE( , — E

Jo 2 tw (E/ — E r)/A

\j/*' __ f°° 1 exP 2rcl(Ey E r) tjh ei(f~r)x

Jo J 2b * ( E , — E r)Jh
M aking th e su b stitu tio n
( / — »*) 1= 'Q’ (54)

a n d tak in g 73 betw een th e lim its i 00 ? on account of th e greatness of t, we can

reduce Y and Y ' to th e form s

vp h 47i2m f 00 dri f . x , hr x\
1 cos ------------ 7}
27t h2r J -oo r) l t j \2nm t)
■x , • / hr x\ \
+ sin
t 1 \2 tcm t) 1 J
>■ j (5 5 )
_h 47t2m f 00 ^73 f . ___ x j ___ [ h r , x
I^ COS — 7} — 1 cos \ + —) "^3
27t h2r J —00 1 \27rm t)

• *„ 11*-
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Surface Photoelectric Effect in Metals 455

whence we deduce th a t for positive x a n d t

x ^ hr
XF =
t " 2jum

x ^ hr >• . (56)
Y = 0,
t 27rm

T ' = 0, for all values of xjt

Hence, m aking t infinite, we find th a t outside th e m etal v has th e form

47r2m br {lc | a | r) 0+ e-irx+ikyy+ikzz

v — (57)
hr

4.4. W e m ust now evaluate (Jc | a | r) 0+ to show t h a t th e results o b tain e d

by bo th m ethods are th e sam e. In th e first place we re m a rk t h a t N / (1) a n d
N / 2), defined in (45), will contain factors due to th e x-, y -, a n d ^-integrations
separately. If, th en , in (48) we neglect exp 2niv (x cos 0 -f- y sin 0)/c it will
be seen th a t th e factors in N / (1) a n d N / 2) due to th e y- a n d ^-integrations will
disappear from th e result, a n d we need calculate only th e facto r due to th e
^-integration. F ro m (4) we sep arate ou t a n e q u atio n for th e ^-factor of th e
wave function. W riting dow n th e resulting equations for th e ^-factors X r
and X r * of tw o w ave functions a n d tp/*, m ultiplying b y X r * and X f respec­
tively, and su btracting, we deduce

(<?2 - g'2) X , X r * = (f2 - f ' 2) X fX r * = ^

Integrating w ith respect to x betw een th e lim its ^ It, where I t is very large
and positive, a n d rem em bering th a t X an d d X jd x are continuous a t x = 0,

d xX fX r *
r‘ ~ f ‘ \d x ■' dx '/ * - *
dXf Y *
X ,\ . (59)
Tx X '' dx /a s — = R

In (59) we insert exphcit expressions for X f and X r *, and th en integrate

the resulting equation w ith respect t o / ' over a range in c lu d in g /' = f . Since
j '2 __ g’2 — we k ave j ' ^ / ' = y dg\ Then we set I t ( / ' —/ ) = y) and
It (g' — </) = £ in th e first and second term s of (59) respectively, and tak e yj
and £ between th e lim its ^ oo , on account of th e greatness of R. As we see
from (45), the integral w ith respect to / ' of th e left-hand side of (59) will be
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456 K. Mitchell

eq u al to e ith e r N / x) or N / 2>, d ep en d in g u p o n th e p a rtic u la r X f a n d chosen

a n d hence we find a fte r som e re d u c tio n , u sin g (41), th e re su lts

<i) —
- f
t.
N / 2> = ~ f L - a

S u b stitu tio n o f (60) in to (48) th e n gives

(* |a l/) o + = ^ a • f (J j°° J * { a * + ( a A + » A ) X ,} (X ,+ * - afX f ~*),

f " ( 61)

w ith a n obvious n o ta tio n . T h a t th e te rm s in a n d a z go o u t is ev id en t from

th e fa c t t h a t th e b o u n d s ta te s a re o rth o g o n a l t o all th e free sta te s. Replacing
X fc, XyA b y th e x-facto rs of (9), (39), a n d (40), th e in te g ra tio n s in (61) can be
easily c a rrie d ou t, u sin g a convergence fa c to r ex p z2x for th e ran g e x < 0,
a n d finally, rep lacin g f b y r, we o b ta in th e re s u lt

(* I a | r ) 0+ = — — . - ^ - . ^ . ( x . k bk ax. (62)
me 2rcq v
E v id e n tly th e n

h Ik \ a \ r\ + — — a a 2 ^ (p — ik x) _
hr r( 1 1 )o _ he ' [xv (2 +
a n d th e tw o m e th o d s of c a lc u la tio n a re in a g re e m e n t, as we see b y comparing
(57) a n d (26).
4.5. Comparison with the Result o f T a m m and Schubin — T a m m a n d Schubin,
using th e m e th o d o f v a ria tio n o f c o n s ta n ts, o b ta in a re s u lt differing from our
fo rm u la (35) b y h a v in g a n e x tra fa c to r

___________ 4 ( k 2 + [XV)___________ (64)

[(*.* + (XV)* + f e 2 + [x (v - vj}*]2
in th e in te g ra n d . T h e ir c a lc u la tio n differs fro m ours in th e follow ing re sp e e tt •'
in place o f th e full e x p a n sio n (42), th e y o m it th e second in te g ra l over the
inw ard -m o v in g w aves, a n d th e n d e te rm in e C/ + b y th e u su a l argum ent-, as given
in Section 4.31, lead in g to th e re s u lt

(ka| | / ) + = 1 d-z (a, g ra d 4*x) +* e x P ( cos 6 + sin 0)/c, (65)

t F or d etails o f th e calcu la tio n see B loch in zev , ‘ P h y s. Z. S ow jet U n io n ,’ vol. 1, p. *81

(1931).
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Surface Photoelectric Effect in Metals 457

vhere
C/+ a n d (& |a |/)+ are c o n n ected b y (47).

Since th e incom ing waves actu ally m ake no c o n trib u tio n to th e current, th is
would be correct if th e ingoing a n d outgoing w ave functions of th e sam e energy
were o rth o g o n a l; th a t is, if N / (2) were zero. Since, however, th is is no t so,
0/ + is given by (48) ra th e r th a n by (65), an d since th e final results are different
t is evident th a t th e result deduced from (65) m ust be wrong.

Discussion

5.1. Interpretation of the Results — I t is interesting to investigate in some

detail th e expression (33) for th e current. I f we suppose th e incident light
wave, whose vector p o ten tia l A is given b y (13), is polarized w ith th e electric
vector in th e plane of incidence, so th a t

a = | a | (— sin 6, cos 6, 0), (66)

then th e ra te a t which light energy is incident upon th e surface will be

2 tcv2 cos 0 2 tcv2 cos 0 . a x2

(67)
c sin2 0

Dividing th e expression (33) b y (67) we obtain th e em ission per u n it incident

energy, P a, which can be w ritten

p __ e3 vtt sin2 0 dkxdky dkz

* 47r2m2c cos 0 8 tt3 1 + exp A2 (kx2 + k y2 + Az2 — {xv)/8iz2rnkT

x iv1.' (&*2+ k ? 4 {k* + f e 2 + n(v ~ v J P

(i.v)4 ' { ( k 2 + p.v)s + { k 2 + p. (v — v j }*]2 ’
/68x

where the integrations are to extend over all electrons in th e m etal whose
normal velocities are sufficient to enable th em to escape, a fter absorbing a
quantum .
The integrand of (68) can be split into three factors, th e Ferm i-D irac dis­
tribution function
dkxdkydkz
(69)
&tz3 1 + exp h2 (k x2 + k y2 + hz2 — [xv )/87c2m&T 5

the boundary transm ission coefficient for the simple potential step

4 (Ax2 4- p.v)4 { k 2 + p (v — v„)|4

(70)
[(Ax2 + (av)4 + { k 2 + [X(v — v j} 4]2 ’
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458 K . M itchell

a n d a resid u a l fa c to r
1
v4 ’ f e 2 + (xv)* ’ , (71>

w hich, in th e fa c to r v~ 4, is re m in is c e n t of th e e x c ita tio n p ro b a b ility for the

a to m ic p h o to e le c tric effect. O n p u re ly a p rio ri g ro u n d s, w e should have
e x p e c te d th e fa c to r (69), a n in v e rse p o w e r o f v, as in (71), a n d p erhaps the
b o u n d a ry tra n s m is s io n coefficient ; t h e m o d ific a tio n s o f th e s e fac to rs could
h a rd ly h a v e b e e n foreseen.
5.21. Effect o f Refraction and Reflection o f the L ig h t — T h e re s u lt (68) suffers
fro m th e sam e failin g as t h a t p o in te d o u t in t h e th e o r y o f S om m erfeld a n d Bethe,
t h a t it m ak e s th e em issio n p e r u n it in c id e n t e n e rg y in fin ite fo r g razin g incidence.
T his d isa d v a n ta g e c a n be re m o v e d b y ta k in g in to a c c o u n t th e effect o f refraction
a n d reflectio n o f th e in c id e n t lig h t, w h e n w e m a y h o p e to o b ta in a m ore correct
d ep en d en ce u p o n th e an g le o f in cid en ce. T h is sa m e *m o d ific a tio n will also
in crease th e o rd e r o f m a g n itu d e o f th e re s u lts in a b o u t th e r a tio (E^ + E ^ ')2 : E^2,
w h ere E^, E ^ ' re fe r to th e in c id e n t a n d reflec ted b e a m s, th e effect o f th is being
m u c h th e sam e as t h a t of th e e x tr a fa c to r (64) o c c u rrin g in T a m m a n d Schubin’s
re s u lt. W e m a y th e n e x p e c t th is m o d ific a tio n to give im p ro v e d results in
th e se tw o re sp e c ts.
A n e x a c t th e o r y c a n b e g iven, a ssu m in g t h a t th e su rfa c e o f th e m e ta l behaves
as a sim ple d is c o n tin u ity to w a rd s th e lig h t w av e, a n d th e c a lc u la tio n s being
m a d e in th e sim p le m a n n e r p re s e n te d in S e c tio n 3. W e use sy m b o ls a*, ar,
a* to d e n o te th e v e c to r p o te n tia ls o f th e in c id e n t, reflected , a n d tra n s m itte d
b e a m s re sp e c tiv e ly (w hen m u ltip lie d b y th e a p p ro p r ia te e x p o n e n tia l factors),
a n d o b ta in in place o f (24) th e e q u a tio n s

Cx — %* £ (1 — a k) = b x — 3& Z a<x
V-v V-v a tx
(72)
iqcx - ^(1 + a k) = - + A *<° + '

g iv in g th e re s u lt

b _ f e 2 — ipq) + V (P 4 - iq) + a rx) / a <x & (73)

* (q + r) *

w here we h a v e ta k e n fo r Xx, in p lac e o f (17), th e v alu e

. 4Trie (74)
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Surface Photoelectric Effect in Metals 459

We th en o b tain th e resu lt

r _ e3 1 a <» I2 v« fik kj-2 ^ kx^

27i3m2c2v2 J o, [m(va - «.>]! x (q + r)2
x 1f e 2 ~ ipg) + + (at-x + a r„)/ate j2

which reduces to (35) for aix = a ia. = a x,• a ru. = 0. The contributions to
the cu rren t due to th e y- a n d ^-com ponents of v ector p o te n tia l again vanish,
on account of th e c o n tin u ity relations

&iy ~[“ &ry ^ty ')

(76)
^iz “f~ *^rz ^tz J
which are established below.
a r and at can be calculated in term s of ai a n d th e optical constants n a n d k
of th e m etal, b y th e classical electrom agnetic th eo ry . Only th e case where
th e electric vector v ib ra tes in th e plane of incidence need be considered. Using
the conditions th a t th e ta n g e n tia l com ponents of th e electric a n d m agnetic
intensities are continuous a t th e surface, we find th e vector potentials m u st be
given b y th e real p a rts of th e expressions

A t = (aix, — aix cot 6, 0) exp 2rav (x cos 6 + y sin 6 + ct)/c

A r = (a rx, arx cot 0, 0) exp 2 tov (— x cos 0 + y sin 0 -f- ct)jc ,

(77)

A<= (atu, — atx q* » ° ) exP 2™v {(M— »«) * + sin 0 + ct}/c

where
ar x sin2 0 -f- (n — i k )2 — (n — Ik )!cos 0 \
aix sin2 0 + (^ — i/<)2 + (w — i/c)/cos 0 !
(78)
^tx ___________________ ^ r
aix sin2 0 + (n — iK)2 + (w — i#e)/cos 0
I t can be easily verified th a t th e first of equations (76) holds, and th e second
follows from th e co n tin u ity of E z w hen th e incident light is polarized in th e
plane of incidence.
From equations (78) it is found th a t th e ra te a t which energy is incident upon
the surface is

2~c cos 0 sin2 0 * + k 2 + sin2 0)2 cos2 0 + 2n cos 0 (n 2 + k2 + sin2 0)

+ n2 + k2 cos2 20}, (79)
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460 K. Mitchell

a n d th e ra te a t w hich en ergy is absorbed is

TCV2 1 & tx [2 . 4 n( n2+ k2 + sin2 0) cos 0.

2c cos 0 sin2 0 (80)
W e also find
a<* + arg = s in 2 0 + — c)2. (81)

D ividing (75) b y (79) or (80) we o b ta in expressions for th e em ission referred

to u n it in cident or ab so rb ed energy. I t is e v id e n t t h a t th ese expressions
will rem ain finite for all angles o f incidence, as of course th e y m ust.
The final resu lt is m ost co n v en ien tly expressed in te rm s of c e rtain reduced
variables. W e use th e n o ta tio n

= va — v

K 2 = P-V» X 2
(82)
v = £

V = 7] v a

a n d co n v ert th e em ission p e r u n it in cid e n t energy in to coulom bs per calorie

b y m ultiplying b y 1 - 3 9 5 . 10-2 . G iving all th e absolute constants their
a p p ro p riate num erical values, th e re su lt is

sin2 0 cos 0 [{(a2 -j- k2)2 — 2 ( n2— /c2) cos2

+ {2 (n2 — /c2 — cos2 0) + 1} (v) + n K ^3 (ff) +C< (v})1
{(w2 + k2-j- sin2 0)2 cos2 0 - j - 2co
_ -j- + #c2 cos2 20}
where
C . 1 - 3 9 5 . 10~2 = 7 - 5 3 7 . 1013, (83a )
Arc
an d
l+ e + ^ l f" , X 2 ( s - X 2) (l~f~£ X 2) (X 2+ t] - 1 - s )* ^
(1 + e ) V Jo, + ' {(X2 + v3)* + (X 2 + 75 - l - S)i}2 ’ 1

_ 1 + e (85)
Zift),
1 + s + r]

d X . X2 (s~ X2) (X 2+ y ] - l - £ ) * (X 2+ t])* ( 1 + e - X 2)* (g6)

0, + {(X2 + 72)* + (X 2 + 7) - 1 - s)*}2
X 4 (e — Xucx
2) (X 2--+ XV y I r- -*•1 - -'/e)» {87}
^ Jo, (1 + . _ „>i • {(X2 + yj)* + (X 2 + 7J - 1 - s)4}2 •
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Surface Photoelectric Effect in Metals 461

E qu atio n (83) gives P^, th e em ission per u n it incident energy, in coulom bs

er calorie, in term s of th e optical co n stan ts a n d angle of incidence, th e th reshold
requency, and th e dim ensionless integrals (yj).
5.22. The above m eth o d of ta k in g in to account th e effect of refraction an d
eflection needs a c e rtain a m o u n t of justification. The objection of T am m a n d
tehubin, t h a t th e ab so rp tio n of lig h t b y th e m etal is in p a rt due to photo-
lectric processes, is seen to be u n im p o rta n t w hen it is rem em bered t h a t th e
photoelectric emission of a m etal is rarely as g reat as one electron per 200
juanta, an d is generally v e ry m uch less. U n d o u b ted ly our ideal m u st be a
single th eo ry yielding results for th e optical co n stan ts a n d for th e p h o to ­
electric em ission a t th e sam e tim e, b u t as th is is u n a tta in a b le a t present, we
must con tent ourselves w ith th e th e o ry p resen ted above. W e can alw ays
conceive of th e optical co n stan ts being calculated w ith o u t reference to th e
emission from th e surface, a n d can suppose th e values th u s obtained to be
nserted above.
A nother objection is, however, certain ly valid. The a b ru p t tra n s itio n a t
the surface is only an ap p roxim ation, an d in re a lity th ere will be a gradual
change in th e co n stan ts of th e lig h t w ave over a region of th e order of th e
wave-length of th e incident light. This is large com pared to th e w ave-length
of the electrons in th e m etal, hence also to th e region from w hich th e m ain p a rts
of the m atrix elem ents come. W e m ight th e n expect to o b tain a closer
approxim ation to th e tru e sta te of affairs b y averaging over th e p o sition of
the surface of disco n tin u ity for th e light. W e will avoid th is fu rth e r com ­
plication for th e present.
5.3. The Spectral Distribution Curve—W e will co n ten t ourselves, in th e
present paper, w ith an ex am ination of th e form of th e spectral d istrib u tio n
curve given by (83). Since th e integrals ^ (75) involve th e q u a n tity s = v /v^,
which depends upon th e m etal chosen, it is essential to m ake th e calculations
for a particular m etal.
Our choice m ust evidently fall upon an alkali m etal, in spite of th e uncertain
knowledge as to th eir thresholds, and th e conflicting experim ental results
for them . The reason for th is is th a t th e thresholds of th e heavier m etals
lie in the ultra-violet, and th eir properties have been investigated only over a
frequency range too small to be of interest. W ith th e alkalis, however, the
thresholds lie in the visible p a rt of th e spectrum , and spectral distribution
curves have been obtained over quite wide frequency ranges.
We use the values of v obtained from form ula (32), assum ing th a t there is
one free electron per atom , and use th e experim ental values of vg, the threshold
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462 K. Mitchell

frequency. As, how ever, th e la tte r are n o t a c c u ra te ly know n, we have evaluated

th e in teg rals (•/]) on th e a ssu m p tio n (w hich is p ro b a b ly n e a rly tru e for the
alkali m etals) t h a t v a n d are equal, a n d th e ir values are show n in fig. i
as fu nctions o f r\ = v/v^.
I t will be observed t h a t th e form s o f th ese curves, a n d in particu lar the
positions of th e ir m ax im a , are ra th e r d ifferent, a n d t h a t accordingly the form
of th e resu ltin g sp e ctral d is trib u tio n curve c a n n o t be deduced w ithout taking
a p a rtic u la r m etal. P o ta ssiu m is su itab le. S u h rm a n n a n d T heissingf have
rep o rte d a v a lu e of 4 * 8 4 . 1014 for th e th re sh o ld freq u en cy for th is metal, and
th is lies sufficiently close to th e c a lc u la te d v alu e of v , n am ely 4 •96 . 1014, for the
a ssu m p tio n t h a t v a n d vg are eq u al to be rea so n a b ly accu rate. T aking the near
value vg = 5 . IQ14, assu m in g for th e angle of incidence 6 th e value 60°, and
using for th e o ptical c o n sta n ts th e m ea su red values J for v = 5 • 1 . 1014,

n = 0-068
V ( 88)
k = 1-5 / ’

th e em ission p er u n it in cid e n t en e rg y h a s b een calcu lated , a n d is given in fig. 2

as a fu n ctio n of frequency. T he cu rv e given b y S u h rm a n n a n d Theissing is
also show n in fig. 2 for purp o ses o f com parison.
I n th e first place, we m a y re m a rk t h a t th e o rd er of m ag n itu d e is reasonably
correct, for n o t to o g re a t frequencies. I n th is connection, how ever, it m ust be
rem a rk e d t h a t S u h rm a n n a n d T heissing fail to s ta te th e angle of incidence
or th e s ta te of p o lariza tio n of th e light. T he dependence upon th e former of
our resu lt (83) is, how ever, ra th e r in sen sitiv e in th e neighbourhood of 6 = 60°,
a n d values in th is neig h b o u rh o o d are u su al in e x p erim en tal w ork since they
give th e g re a te st em ission.
T he form o f th e th e o re tic a l curve, on th e o th er h a n d , is in n o t too good
ag reem en t w ith e x p e rim e n tal resu lts. T he general tre n d is correct, but the
curve is to o flat, a n d its m ax im u m occurs a t h igher frequencies th a n observed
m axim a. These featu res could, how ever, be a lte re d b y v ariatio n s in the
o p tic a l c o n sta n ts, a n d hence th e fo rm o f th e curve ca n n o t be ta k e n as con­
clusive u n til m ore is know n of th ese q u a n titie s. The form of th e curve, in
p a rtic u la r th e position of th e m ax im u m , depends also upo n th e value of v,
w hich in its tu r n depends u p o n th e b in d in g of th e conducting electrons. The
effect of th is can be considered fo rm ally as causing a n increase in th e effective

t 4 Z. P h y sik .,’ vol. 52, p. 453 (1928-29).

t 4 In t. C ritical T ab les,’ vol. 5, p. 249.
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Surface Photoelectric Effect in Metals 463

T 1’
F ig . 1— The fu n ction s (v) for v = vv.

P-S "0002

5 §3 -0001

F ig . 2— Theoretical and experim ental spectral distribution curves for potassium .

----- theoretical (equation (83) ) : ----------- experim ental (Suhrmann and Theissing).

VOL. CXLVI.— A. 2 K
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464 Surface Photoelectric Effect in Metals

m ass of the electrons, causing v to decrease, and shifting th e m axim um towards

th e threshold. This and other points will be discussed in a subsequent paper

The au th o r wishes to th a n k Professor R. H . Fowler, F.R .S ., and Mr. A. H

W ilson for th eir constant in terest an d for m any illum inating discussions-
as well as th e M aster and Fellows of Peterhouse, and the Goldsm iths’ Company
for studentships during the ten u re of which th e work was carried out.

Sum mary

6. The theoretical position of th e surface photoelectric effect in metals is

discussed, and objections are raised against th e theories of Wentzel and
Frohlich.
The photoelectric emission due to a single surface is calculated by two
m ethods, and th e results obtained a re in agreem ent. Tam m and Schubin,
using th e same assum ptions, obtained a different result, which is shown to be
incorrect.
The results of a m ore general calculation of th e effect due to a single surface,
tak in g into account th e effect of reflection a n d refraction of th e light wave,
are quoted, and th e theoretical spectral d istrib u tio n curves given for potassium,
a n d com pared w ith experim ent.