The Sommerfel d free-electro n theor y o f metals

1. Quantum theory of the free-electrongas 7

7
2. Fermi-Dirac distributio
n function and chemica
l potentia
l8
2
3. Electronic specific heat i n metals and thermodynami
c functions 8
6
4. Thermioni
c emissio
n from metals 8
8
Appendi
x A . Outline of statistica
l physics and thermodynami
c relations 8
9
Al. Microcanonica
l ensembl
e and thermodynami
c quantities 8
9
A2. Canonica
l ensembl
e and thermodynami
c quantities 9
1
A3. Grand canonica
l ensembl
e and thermodynami
c quantities 9
3
Appendi
x B. Fermi-Dirac and Bose-Einstei
n statistic
s for independen
t particles . 95
Appendi
x C . Modified Fermi-Dirac statistic
s i n a model of correlatio
n effects . . . 9 8
Further reading 10
0

In this chapter w e discus

s the free-electrontheory of metals, originally develope
d by
Sommerfel
d and others
. The free-electronmodel, with its paraboli
c energy-wavevecto
r
dispersio
n curve, provides a reasonabl
e descriptio
n for conductio
n electron
s i n simple
metals
; i t also may give useful guidelines fo r other metals wit h more compUcate
d
conductio
n bands. Becaus
e of the simplicity of the model and its density-of-states
, we
can work out exphcitly thermodynami
c properties
, and i n particula
r the specific heat
and the thermioni
c emission
. I n the Appendice
s we simomariz
e for a genera
l quantum
syste
m the thermodynami
c functions o f more frequentuse i n statistica
l physics
. The
Fermi-Dirac and Bose-Einstei
n distributio
n functions fo r independen
t fermions and
boson
s are discussed
; finally we obtain the modified Fermi-Dirac distributio
n function,
in a model case of correlatio
n among electron
s i n localized states.

1 Quantu

m theor y o f th e free-electro n ga s

An electron i n a crystal feels the potential energy due t o al l the nuclei and al l the
other electrons
. The determinatio
n of the crystallin
e potentia
l i n specific materials i s
a rather demandin
g problem (see Chapters I V and V) . However i n several metals, i t
turns out reasonabl
e t o assume that the conductio
n electrons feel a potentia
l which
is constan
t throughou
t the sample; this model, suggeste
d b y Sommerfel
d i n 1928, i s
77

II I TH E SOMMBRFEL D FREE-ELECTRO N THEOR Y O F METAL S

78

Ef
^vac"

Ep+

E ( k ) = E c +^
2m

vacuum

vacuum

metal
' ' '''..'.'.'.''.'.' .

^F^c
^c-^

S^^^m^^t

kp k

-k.

(b)

(a)

Fig. 1 (a ) The Sommerfel

d model for a metal. The energy Ec denote
s the bottom of the
conductio
n band; ^vac denote
s the energy of an electron at rest i n the vacuum
; the electron
affinity i s x = ^vac Ec Th e Fermi energy i s denote
d by EF, and the work function W
equals x ~ ^F- (b ) Free-electro
n energy dispersio
n curve along a direction
, say /c^, in the
reciproca
l space
. At T = 0 all the states with k < kp are occupie
d by two electron
s of either
spin.
still o f value fo r a n orientative understandin
g o f a number o f propertie
s o f simple
metals
.
In the Sommerfel
d model, the Schrodinge
r equation for conductio
n electron
s inside
the metal takes the simple form
p + F
2^^^'^

^{T) =

E^{V),

(1)

where Ec denotes an appropriat

e constan
t specific o f the metal imder investigatio
n
(see Fig. 1) . The number o f "free electrons
" o f the metal i s assmne
d t o correspon
d
to the number o f electron
s i n the most external shell of the composin
g atoms. For
instanc
e i n alkali metals, w e expect one free electron per atom, since an alkali atom
has just one electron i n the most external shell. I n aluminum (atomic configuratio
n
l5^,25^2p^,3s^3p^
) w e expect three free electron
s per atom.
At first sight i t could appear surprising that th e conductio
n electrons i n actual
metals (o r i n any type of solid) feel a n approximatel
y constan
t potential, a s strong
spatia
l variations of the crystallin
e potentia
l occur near the nuclei. However, the conduction electrons are hardly sensitiv
e to the region close to the nuclei, becaus
e of the
orthogonalizatio
n effects due to the core electron states
; thus the "effective potential"
or "pseudopotential
" (see Section V-4 ) for conductio
n electrons may indeed become
a smoothl
y varying quantity, eventuall
y approximate
d with a constant
; these are the
underlyin
g reasons for the succes
s of the free-electro
n model (o r of the nearly-freeelectro
n implementations
) i n a number of actual metals.
The eigenfunction
s of the Schrodinge
r equatio
n (1), normalize
d to one in the volume

SOLID STAT E PHYSIC S 7

V o f the metal, are the plane waves

V;{k,r) = - ^ e * ' ; (2

the plane waves are just a particula

r case of Bloch functions
, when the periodic modulating part i s constant
. The eigenvalue
s of Eq. (1 ) are

For simplicity, throughou

t this chapter
, we set the zero of energy at the bottom Ec of
the conductio
n band, and thus take Ec = 0 ; wheneve
r necessary
, we can reinstat
e the
actual value of Ec by an appropriat
e shift i n the energy scale. [I n some situations
, for
instanc
e i n the discussio
n of photoelectro
n emission
, i t can be more convenien
t t o set
the zero of energy at the vacuum level, i.e. Evac = 0 ; in other problems
, for instanc
e in
the discussio
n of many-bod
y effects, the zero of energy is generall
y taken at the Fermi
level, i.e. Ep = 0 ; of course any choice i s lawful, provided one keeps i n mind which
choice has been done].
Conside
r now an electron gas with N fre e electrons i n a volume V , and electron
densit
y n = N/V. T o specif
y the electro
n density of a metal it is customar
y to conside
r
the dimensionles
s paramete
r r ^ connecte
d to n by the relation

where as = 0.529 A i s the Bohr radius; Vsasrepresent

s the radius of the sphere that
contain
s i n average one electron
.
We evaluate r ^ fo r alkali metals (fo r instance)
; Li , Na, K , R b have bcc structure
with cube edge a equal t o 3.49 A , 4.23 A , 5.23 A an d 5.5 9 A , respectively
. I n the
volume a^ we have two atoms and two conductio
n electrons
. From Eq. (4 ) we obtain
(4/3)7rrf a| = a^/2 an d thus

as 2 yirj
the values for r ^ are 3.25, 3.94, 4.87 and 5.20 for Li , Na, K and Rb, respectively
.A
similar reasonin
g can be done for other crystals
. For instance
, the crystal structur
e of
Al i s fee, with lattice constan
t a = 4.05 A. I n the volume a^ we have four atoms and
twelve conductio
n electrons
; from Eq. (4) we have {4:/3)Trr^a%= a^/12 and Vg = 2.07.
Metallic densitie
s of conductio
n electron
s occin: mostly i n the range 2 < Vg < 6 .
The ground state of the electron system at T = 0 is obtaine
d accommodatin
g the N
available electron
s into the N lowest available energy levels up to the energy ' F, called
the Fermi energy; each state of wavevecto
r k and energy E{k) < Ep accommodate
s
two electron
s of either spin. I n the k-space
, the Fermi surfaceE{k) ~ Ep separates
the occupied band states of energy E{k) < Ep fro m the unoccupie
d band states of
energy E(k) > Ep. Fo r the free-electro
n system at T = 0 , the occupied states fil l a
Fermi sphere of radius kp^ as schematicall
y indicated i n Fig. 2.
To determin
e kp, w e require that the total number o f electron
s within the Fermi

80

II I TH

E SOMMERFEL D FREE-ELECTRO N THEOR Y O F METAL S

^z Ferm

i surface

Fermi sphere

Fig. 2 Schemati
c representatio
n in the k-spac
e of the Fermi spher
e of occupie
d states and of
the Fermi surfac
e of the free-electro
n gas. At T = 0 each state of wavevecto
r k, with k < kp,
is occupie
d by two electron
s of either spin.
spher
e of wavevecto
r kp equals the number N of electron
s available i n the crystal; we
must have
4

^^^^ V

where we have used the standar

d prescriptio
n of Eq. (11-44) for convertin
g the sumover
k into the correspondin
g integral times V/{2TT)^. Pro m Eq. (5) , the Fermi wavevecto
r
kp becomes
fc^ = Sn^n; (6a

using Eq. (4) , we have

1/3 1

^g

V 4 / r^UB

rsi

(6b)

sO^B

The Fermi velocityi s given by

(7a)
m
It i s convenien
t to conside
r the dimensionles
s ratio vp/c^where c is the velocity of the
light. W e divide both members of Eq. (7a) by c, and remembe
r that the Bohr radius
is as = h^/me^an d that the fine structur
e constan
t i s 1/ a = hc/e^ = 137.036; we
obtain
vp kp .

Kp

= aas Kp

^ H H . (7b

137.036 rs ^
^
c mc
We thus see that i n the ordinary range o f metallic densities
, the Fermi velocity i s
about one hundredt
h of the velocity of light.
The Fermi energy a t T = 0 is given by
2m

ft2 1.92 2
2m ai

SOLID STAT E PHYSIC S 8

We notice that h?/2ma% = IRydberg = 13.606 eV; we can express the Fermi energy
as
EF =

^(i

n Rydberg) . (8

Typical values of Ep fo r metals are i n the range 1 - 10 eV . Since 1 eV/A:B=11605 K ,

the Fermi temperatureTp, defined as ksTp = Epis of the order of 10^ 10^ K.
The ground-stat
e energy JBQ at T =0 of the free-electro
n gas is given by

Convertin
g as usual the sum over k into an integral times V/{2n)^,on e has
2m ^^''(27r)

32m5

Using Eq. (5 ) and Eq. (8 ) we obtain

^=

g Sf = ^ (i

n Rydberg)
. (9

The average energy of each electron at zero temperatur

e i s (3/5) EpWe can here anticipate that the ground-stat
e energy, given by Eq. (9) , i s only the
leading term i n the high density hmit (r g<C 1) of the exact expressio
n of the groundstate energy of the homogeneou
s electron gas (see for further aspects and discussio
n
Section
s IV- 7 and IV-8) . In spite of this and other limitations
, the Sommerfel
d picture
is nevertheles
s of help to describ
e orientativel
y and prehminarl
y a numbe
r of propertie
s
of simple metals.
Prom the paraboU
c dispersio
n relation '(k) = h?k'^/2m of the free-electro
n gas, we
can calculate the density-of-state
s D{E) fro m the relationshi
p

where dk i s the volume element i n the reciproca

l space. Performin
g the integral with
the same procedure
s adopted i n Section II-7 , we obtain
D{E)=^V^^^E^/^
E>0,

(10a

Since the integrate

d density-of-state
s / D{E) dE ior 0 < E < Epequals N, we can
write the density-of-state
s (10a) i n the form

In particula
r for E = Ep w e have
DiEF)^~.(11
The plot of D{E) i s shown i n Fig. 3.

82

II I TH

E SOMMERFEL D FREE-ELECTRO N THEOR Y O F METAL S

Fig. 3 Density-of-states
, i n units of N/EF, fo r a free-electro
n gas (the conductio
n band
region occupie
d by electron
s has been shadowed)
; the average electron energy (3/5) Ep i s
also indicated
.

2 Fermi-Dira

c distributio n functio n an d chemica l potentia l

Fermi-Diracdistribution function
Conside
r a n assembl
y of identical particles a t thermal equilibrium moving independently i n a given volume. I f the particles obey the Pauli exclusion principle, the occupatio
n probability o f a one-particl
e quantiun state o f energy E i s given b y th e
Fermi-Dirac function

m=

e(^-.)/lT + i ' (12

where /i i s the chemica

l potential
, fc^ i s the Boltzmann constan
t and T the absolute
temperatur
e (see Appendix B) . The chemica
l potentia
l / i for the Fermi-Dirac distribution i s also commonl
y addresse
d a s the Fermi energy or Fermi level Ep] following
a common use, the terms "chemical potential" an d "Fermi energy", a s well as th e
symbol
s fi and Ep^ are used by us as synonymous
.
The behaviou
r of the Fermi-Dirac function i s shown i n Fig. 4. I f /x E > ksT th e
distributio
n function approache
s unity; i f f j - / i > fc^T, f{E) fall s exponentiall
yto
zero with a Boltzman
n tail. A t T = 0 the Fermi-Dirac distributio
n function becomes
the step function Q{IJLQ E), where /i o denotes the Fermi energy a t T = 0 ; at zero
temperature
, all the states with energy lower than/X Q are occupie
d and all the states
with energy higher than /i o are empty. A t finite temperatur
e T , f{E) deviates fro m
the step function only i n the thermal energy range of order fcjgT aroun
d /x(T).
We conside
r now the properties o f the function {df/dE). A t T = 0 w e have
{df/dE)
=
S{E /io). A t finit e temperatur
e T < ^ Tp , i t holds approximatel
y
that {df/dE) 6{E /i) (see Fig. 4) . I n fact, a t finite temperatur
e the function
{df/dE)i s very steep with its maximum at E = / i and differs significantl
y from zero
in the energy range of the order of fc^T around /i . It i s easy to verify that {df/dE)
is an even function o f E around / i and vanishe
s exponentiall
y for IE * /i| ^ fc^T; w e

83

SOLID STATE PHYSIC S

J.

ii

.ill H

(iU=*'=* '

9E/T;^ i i

Fig. 4 Th e Fermi-Dirac distributio

n function f{E) an d energy derivative {-df/dE) a t
T = 0 and at a finite temperatur
e T , with T < TF ; /x o denote
s the chemica
l potentia
l fi{T)
at T = 0.
also have
+00

( - | ^ ) d E = - [ / ( o o ) - / ( - o o])=

(13)

-oo

Sommerfeldexpansion
Let us conside
r an integral of the type
r+oo

L<^'<-i)<'^-

(14)

where G(JE ) i s a function regular and (infinitely) differentiable around /x . W e can

demonstrat
e the following relation
+00

a/.
G{E){-^)dE
=

G(/x) + l^{kBTfG"{^)+

77r4,

l^(fcBr)^G""(M) +

(15)

-oo

where energy differentiatio

n order i s indicate
d by the correspondin
g number of apices
.
To prove Eq. (15), conside
r the series expansio
n of G{E) i n powers of E around the
chemica
l potential

G() = GW.(E-rt(g)^^^+l(E-rt=(0)^^_^ + ...;

84 II

I TH E SOMMERFEL D FREE-ELECTRO N THEOR Y O F METAL S

insertin
g this expressio
n into Eq. (14), and using Eq. (13), we obtain

Odd powers of {E - /x ) in the expansio

n have been omitted becaus
e they give zero
contribution
. The coefficien
t of G"{^)can be written as
1 C^"^

8f

/*"^

JE-fj,)/kBT

-2L (^-"^-al'^- L <^-'"'[e.^-.v>..,ii-ST^

r+00

(e^ + 1)2 '

^0

(in the last passag

e we have denote
d by x the dimensionles
s variable x= {E^i)/kBT).
To perform the integra
l in the x variable
, we notice that
-2x

^0 J

\dx

o
_(

_ 7r 2

This explains the numerica

l coefficien
t i n front of G"{^)i n expressio
n (15). Successiv
e
terms in expansio
n (15) can be calculate
d in a similar way.
Equatio
n (15) is known as the Sommerfeld
expansion.
T o appreciat
e the fact that
it is a rapidly convergen
t expansio
n for T <^TF, conside
r the case in which G{E) has
a power dependenc
e on E of the type G{E) E^; then it is easy to verify that the
terms of the expansio
n (15) are of the type of {kBT/yif,{ksT/^Y ^^ equivalentl
y
{T/Tp)\{T/TFY etc. .
The Sommerfel
d expansio
n (15) can be rewritten also in a slightly different form.
Most often the function G{E) vanishe
s for energies E below some threshol
d energy
and, furthermore
, G{E) behave
s reasonabl
y well at infinity so that G{E) f{E) -^ 0 for
E -^ 00. When these condition
s are verified, it is convenien
t to perform an integratio
n
by parts in the firstmembe
r of Eq. (15); we have
/-

+ dG{E) ^^^^^^^ ^^^^^ ^(fc^T)2G"(/x) + ... . (16

dE '^ ' ~
"^ ' 6

Let us indicate with T{E) the derivativ

e G'{E) , or equivalentl
y
G{E)= / V{E')dE'

Eq. (16) become

s

j^'^T{E)f{E)dE
=

j '^ T{E)dE+'^{kBTf{^^^_

which is a usefu
l expressio
n for the given function T{E).

+0{T')

(17)

SOLID STAT E PHYSIC S 8

Temperature dependence of the chemical potential

The chemica
l potentia
l /i depend
s (slightly) on the temperature
; in the study of severa
l
transpor
t properties
, the temperatur
e dependenc
e of the chemica
l potentia
l (whatever
small i t might appear a t first sight) has quite important consequences
, and now we
work out explicitly the behaviou
r of IJL{T).
Let D{E) b e the (single-particle
) density-of-state
s fo r both spin directions for the
metallic sample of volume V; no particula
r assumptio
n on D{E) o r on the conductio
n
band energy jB(k ) i s done a t this stage. Let N b e the total number o f conductio
n
electron
s o f the sample. A t any temperatur
e T , w e have that /i(T ) i s determined
(imphcitly
) enforcing the equality
+ 00

D{E) f{E) dE .

-oo

Such an integral has in genera

l a rather complex structure
. However i f T < C Tp and
if D{E) i s reasonabl
y smooth at E ^ /JL (both condition
s are i n practice quite well
satisfied)
, w e can perform the integral using the Sommerfeld expansion (17) , where
the function T{E) stands now for D{E). W e have
AT = r D{E)

dE + ^ f c | T 2 D ' ( / i) + 0{T^) , (18

where the prime indicates differentiatio

n wit h respect t o the energy, and terms o f
the order of [T/TpY ca n be safely omitted since T < C Tp a t the ordinary temperatures of interest
. W e now differentiat
e both members of Eq. (18 ) with respec
t t o the
temperature
, taking into accoun
t that ^i = ^{T). W e obtain
0 = D ( M ) ^ + y 4 T D ' ( M) (19

[we have neglecte

d the term {K'^l%)k%T'^D"{n)(dfi/dT)because of order {T/Tpf wit h
respec
t to D{n) {dfi/cIT) ]. Prom Eq. (19) i t follows
^=
^!LklT^^
.
dT ~ T"^^ Difi)

(20

This equation
, togethe
r with the obvious condition /x(T ) = /X Q for T = 0 allows us to
obtain fi{T) a t any temperatur
e T , provided T <^TF. W e notice that:
(a) If the density-of-state
s D{E) fo r E ^ ^o increase
s with energy
, then the chemica
l
potentia
l / x decrease
s with temperatur
e (and vice versa). I n the case D{E) i s constan
t
for JEJ /xo, the chemica
l potentia
l / i is temperatur
e independent
.
(b) For a free-electro
n gas D{E) a E ^ ^ rpj^^n D'{fi)/D{fi)=
1/2AA . The integratio
n
of Eq. (20) i s straightforwar
d and gives/x^ - /x g = -{7r'^/e)k%T^.The n
/x(T) = /x o

7r2 /kr.T\^^

-T5(^) \=A'-T2{B

(21)

This relation gives/ x as a function o f T and shows that /x(T ) decrease

s slowly with
increasin
g temperatur
e for the free-electro
n gas.

86 II

3 Electroni

I TH

E SOMMERFEL D FREE-ELECTRO N THEOR Y O F METAL S

c specifi c hea t i n metal s an d thermodynami c function s

The heat capacityat constantvolumeof a sample i s defined b y

where 8Q i s the amount o f heat transferre

d fro m the external world t o the system,
and dT i s the correspondin
g change i n temperatur
e of the system, kept at constant
volume V. Th e heat capacity i s an extensiv
e quantity, i.e. a quantity proportiona
l to
the volume of the sample
; for this reason
, dependin
g on the natinre of the system under
investigation
, i t may become preferabl
e t o introduc
e the specificheat per mole, or the
specific heat per unit volume, or per unit cell, or per composin
g atoms or electrons
.
We can express the heat capacity (22 ) i n convenien
t alternative forms. From the
firstla w of thermodynamics
, we know that the change dU of the internal energy of a
system
, i n a transformatio
n i n which an infinitesima
l quantity of heat 6Q i s received
by the system and 8L i s the work done on the system by externa
l forces, i s given by
dU = 6Q^6L.
In the case the externa
l forces are only mechanica
l forces, exerting a pressur
e p on the
system
, we have 8L = pdV\ i f the volume V o f the system i s kept constan
t during
the transformatio
n then 6L = 0; it follows dU = 6Q and
C . = ( f ) ^ . (23a

In the case of reversible transformations

, th e second la w of thermodynamic
s states
that 6Q = T dS, where S i s the entropy of the system
. W e have thus
C.=T{)^.(23b

We now calculat
e the heat capacity of an electron gas, using Eq. (23a). The internal
energy of the Fermi gas i s
+ 00

ED{E)f{E)dE

-oo

= ED{E)

dE + ^klT^[Difx)

+ tiD'{^)] + 0{T^) , (24

where the standar

d Sommerfel
d expansio
n (17) has been used. By differentiatin
g wit h
respec
t t o the temperatur
e both members o f Eq. (24) , and keeping only the most
relevan
t among the terms containin
g (d///dT), we have

SOLID STAT E PHYSIC S

87

Fig. 5 Electronic contributio

n Cv{T) t o the heat capacit
y of a metal at constan
t volume, as
a function o f temperature
; the same expressio
n holds for the electroni
c contributio
n to the
entropy
.
Using Eq. (19), and replacing D{IJL) with JD(/xo)j we obtain

CviT) =

-klTD{^o)

(25)

Prom Eq. (23b), i t can be noticed that expressio

n (25 ) represent
s also the entropy of
the electron system.
The specific heat per unit volume cy = Cy/V become s

cv{T)= ^klT DJtM)) iT,

V

(26a)

where

1 KQ

(26b)

The contributio
n t o the specific heat from conductio
n electrons i s proportiona
l toT
for all temperature
s of interest
, since T i s always much less than Tp- Th e electronic
contributio
n become
s the leading one at sufficientl
y low temperatures
, where it prevails
over the T^ Debye contributio
n originated b y the lattice vibrations (see Section IX 5). W e also notice that th e knowledge o f the density-of-state
s D{fio) a t th e Fermi
energy /i o completel
y determine
s Cy ; this gives a first insight o n the importanc
e of
the electronic states a t o r near the Fermi surface i n metals. I n discussin
g transport
phenomena
, impurity screenin
g etc. we will further see the basic role played by the
electroni
c states lyin g i n the thermal interval o f the order ksT aroun d th e Fermi
energy
.
I t i s interestin
g t o specify Eq . (25 ) fo r th e case o f the free-electrongas, where
D{fjLo) = (3/2 ) N/fio according to Eq. (11). We have
7r2 T

Cv{T) = -jkBN.

(27)

For comparison
, w e recall that the classica
l statistica
l mechanic
s would give the expressio
n Cv = iS/2)kBNfo r the heat capacity of a gas of TV non-interactin
g particles
.

88 II

I - TH E SOMMERFEL D FREE-ELECTRO N THEOR Y O F METAL S

The correct result (27) can be interprete

d noticing that only the electron
s in the thermal interval ksT around the Fermi energy /X Q = ksTp ca n vary their energy, and thus
the effective number of electron
s with "classica
l behaviour
" i s not N bu t rather th e
fraction T/Tp o f N.

4 Thermioni

c emissio n fro m metal s

We can apply the Fermi-Dirac statistics t o study under very simplified conditions
the thermionic emission from metals, i.e. the emission o f electron
s from a metal i n
the vacuum because of the effect o f a finite temperature
. For our semi-quantitativ
e
considerations
, we do not conside
r i n detail possibl
e reflection o f electron
s impinging
at the surface
; we simply assum
e that all the electron
s that arrive at the surface wit h
an energy sufficient t o overcome the surface barrier ar e transferre
d t o the vacuum
(and swept away by some small apphed electric field without accimiulatio
n o f space
charge)
. The model electroni
c structur
e of the metal, with electron affinity x s^nd work
function W, i s illustrate
d i n Fig. 1 ; we wish to obtain the number of electron
s which
escap
e from the metal, kept at temperatur
eT.
I n the metal, the electron
s are distribute
d i n energy accordin
g to the Fermi-Dirac
statistics
. Let us indicat
e with z the directio
n normal to the surface
; the curren
t density
of escapin
g electron
s i s given by

where Vz = hkz/m. Notic e that expressio

n (28) , i n the case Vz is just replaced b y a
drift velocity v independen
t o n k (and the integratio
n over kz extends from oo t o
-hoc) , would give the standar
d density Js = {e)nv. Th e Umitation i n Eq. (28 ) fo r
the integration o n kz i s just t o make sure that th e escaping electrons have enough
kinetic energy fi?kl/2m> x i n ^^^z direction to leave the metal.
In order t o perform the integral (28), let us notice that

Since i n genera
l the work function V F > fc^T , we can safely neglect the imity i n the
Fermi distributio
n function i n Eq. (28). We thus obtain
_ (-e ) h
T^ /

kzdkz

/ dkx
oo ^ o

hHkl + kl + kp

/ dkyexD

ksT2mkBT

We now use the standar

d result for Gaussia
n functions
+00

dkxexp

y/2'KmkBT
2mkBT

SOLID STATE PHYSICS 8

Table 1 Experimenta
l values of the work function W for some metals
.
metal

W(eV)

metal

W(eV)

Li
Na
K
Cs
Ag
Au

2.49
2.28
2.24
1.81
4.3
5.2

Al
Ga
Sn
Pb
Pt
W

4.2
4.1
4.4
4.0
5.6
4.5

and obtain
ft2fc2

*^5 = ^ " 2 T~ / k^dk^exp

/^
ksT2mkBT

The integral can be easily performe

d with the change of variable (ft^fc^/2m) /x = a:,
and we arrive at the Richardso
n expressio
n

The absolut
e value of the numerica
l factor i n the Richardso
n law (29) i s
^ ^
=

120.4 amp c m ^
' . K '^ , (30

in many metals, measure

d values are indeed i n the range 50 120 amp cm~^ K~^.
A quantitativ
e treatmen
t of the electron emissio
n from metals requires a number of
refinement
s of the simplified model here considered
. I n the model of Fig. 1, the metalvacuum boundar
y i s represente
d by an abrupt discontinuit
y i n the potential
. I n reality
an electron outside the metal feels an attractive image potential (t o be determined
in principle quantiun mechanically
) wit h consequence
s o n the reflection coefficient
of escapin
g electrons
. The image potentia
l also leads to a reductio
n of the apparent
work function i n the presenc
e of applied electric fields (Schottky effect). Th e work
function i s also sensitiv
e to various effects,for instance
, surface impurities and charge
modification
s a t the surface. Observed values of the work function fo r some metals
are reported i n Table 1 ; for a more complete Ust see for instance H . B . Michaelson
"Handboo
k of Chemistr
y and Physics
" edited by R. C. Weast (CR C Press, Cleveland
1962); D. E. Eastman
, Phys. Rev. B2, 1 (1970) and reference
s quoted therein.

APPENDIX A . Outlin e o f statistica l physic s and thermodynami c

relations
A l. Microcanonical ensemble and thermodynami
c quantities
The basic principles o f classica
l and quantimri statistics can b e foimd i n standard
textbook
s on statistica
l physics
; the purpos
e of this appendi
x i s simply to summariz
e
the "recipes" for the connectio
n between statistic
s and thermodynamics
.

90 II

I TH E SOMMERFELD FREE-ELECTRON THEORY OF METALS

Let US conside
r a physica
l system compose
d by N identical particles confined within
a volume V. Quantum mechanic
s provides for this confined system discretize
d energy
levels; we label with an integer number m al l the distinct eigenstate
s of the system i n
increasin
g energy order Em {--- < Em < Em-\-i < Em-\-2 < ) The eigenstate
s of
the system are also called microstates
o r accessiblestatesof the system.
For system
s with a large numbe
r of particle
s and volume, the spacing
s of the different
levels become
s extremel
y small (i f not zero), and the total energy E of the system can
be regarde
d as an almost continuou
s variable. Instead of focusingon each individual
microstate
, i t i s convenien
t to conside
r the quantity W{E^ V, N) which givesthe total
numbe
r of distinct microstate
s lying in the interval ( A, + A) , where A < ^ JB.
Let us indicate with {E, V , N) th e parameter
s that define a particula
r macrostat
e
of the given system. I n general, fo r a given macrostat
e (JE , F, iV), there i s a large
numbe
r W{E, V , N) o f correspondin
g microstates
; accordin
g to the standar
d concept
s
of the microcanonical
ensemble^it i s assume
d that the macrostat
e (", V, N) i s equally
likely to be i n any of the distinct microstate
s W{E, V , N) lyin g in the energy interval
(; - A , J5 + A ) around E.
The thermodynamic
s o f the physical system i s completel
y determine
d b y the expressio
n of the entropy, which i s given by
S = kBlnW{E,V,N)\;{Al)
from the basic expressio
n (^41) of the entropy, the rest of the thermodymic
s follows.
Let u s consider quasistati
c transformation
s wit h (infinitesimally) slo w varations
of the macroscopi
c parameter
s E^ V,AT so as t o guarante
e that th e transformation
s
involve only thermodynami
c equilibrium states. The change of entropy (^41) fo r a n
infinitesima
l transformatio
n can be written as

-(iX,/-(iL/-(iL- - <- )
From the first and second principle o f thermodynamics
, w e can also write fo r an y
infinitesima
l reversible transformatio
n
dE = TdS -pdV - f /idN . {A3)
From equation
s (^2) and (^43) we obtain

We have thus the three basic relations

1 /a5

dEJvM

(A4)

(A5)

SOLID STAT E PHYSIC S 9

Relation (A4) provides the absolutetemperatureT; relation (A5) provides the equation
of state(i.e. a relation among p, V and T); relation (^46) provide
s the chemicalpotential
/x.
Formula
e (i44), (^45) and (^6) are just the ones that follow from the basic expressio
n
(^1) o f entropy and from the basic laws of thermodynamics
; from them any other
desire
d thermodynami
c function ca n b e obtained. Fo r instance
, the Helmholtzfree
energyi s given by F = E - T 5 ; the Gibbs free energy is G = E - TS -\- pV] th e
enthalpyi s given by H = E-^pV=
G-\-TS.
A2. Canonica l ensembl e an d thermodynami c quantitie s
Conside
r a physica
l syste
m containin
g N identical particle
s confine
d within the volume
V] a s before w e label with a n integer number m al l the distinct eigenstate
s o f the
syste
m i n increasin
g order of energy EmWe are now intereste
d i n the statistica
l descriptio
n o f the system i n equiUbrium
with a surroundin
g thermal bath at temperatur
e T , and thus free to exchang
e energy
with it. The equilibrimn propertie
s of the system are calculate
d by averagin
g over all
its accessibl
e states of energy E ^, assignin
g to each state a weight Pm proportiona
l to
the Boltzmann factor exp{l3Em)wit h / 3 = l/ksT. B y requiring the normalizatio
n
of the weights to imity, we obtain t he Gibbsor canonicaldistributionprobability

The denominato
r i n Eq. {A7) i s known as canonicalpartitionfunction
Z{T,V,N)=

'e-'''

{AS)

We now show how the thermodynami

c functions of the system can be evaluate
d from
the canonica
l partition function.
To establis
h the connectio
n between statistic
s and thermodynamic
s i t i s convenien
t
to define the canonicalpotentialQ = ^ ( T, V, N) s o that
e-^ " = ^ g-/ 3 Em= z{T, V, N) . (A9)
m

The probabilit
y distributio
n (^47) then takes the form
Pm = e - ^ ( ^ - - ") . (^10

We now show that the Helmholtz free energy F i s just given by the canonica
l thermodynamic potentia
l Ct defined i n Eq. (^49).
Conside
r i n fact a n infinitesima
l reversible transformatio
n i n which the paramete
r

92 II

I TH

E SOMMERFEL D FREE-ELECTRO N THEOR Y O F METAL S

T i s change
d (while V and N ar e kept constant)
. Taking the differentia
l o f Eq. (.49 )
we have
e-^ " d{p n)=^Y^e-^ ^ - Em df3.
m

Multiplying by exp(/3fi) both members of the above equation

, we obtain
cf(/3fi) = ^ e - ^ ( ^ - - ^ ) ; ^ d?/ = ^PmEmdP
=

Udp, {All)

mm

where U denotes the mean internal energy of the system

; Eq. (^11) can be re-written
as
d{pn)=

d{/3U)-0dU .

{A12)

Prom the first and second la w of thermodynamics

, fo r reversible transformation
s
with constan
t volume and constan
t number o f particles
, w e have dU = 6Q = TdS,
Eq. (^12) thus becomes
d(/3f2) = d ( / 3 C / ) - / 3 T d 5,
and we have
T
Integratin
g the above expressio
n from zero temperatur
e to an arbitrar
y temperatur
e T,
and using the third principle of thermodynamic
s to set to zero the arbitrar
y integratio
n
constant
, w e have (f i U)/T = S and il = U TS\ hence the canonicalpotential
fi equalsthe Helmholtzfree energyF = U TS. Usin g Eq. {A9), w e obtain that th e
Helmholtz free energy i s related to the partition function b y the expressio
n
F = -kBT\nZ{T,V,N)
=

- f c ^ T l n ^ e " ^^

(A13)

This i s the basic result of the canonica

l ensembl
e apparatus
.
Other thermodynami
c relationship
s can now be easily established
. For instance
, by
differentiatin
g the free energy F = U TS^w e have
dF = dU-TdS-SdT,
On the other hand, from the standar
d laws of thermodynamics
, w e also have
dU = TdS-pdV+

fidN .

Hence
dF = -SdT-pdV-\-fjLdN,
and we obtain the relations
:

SOLID STAT E PHYSIC S 9

dV

(^15)
T,N

dF_
dN T,V

(A16)

Let u s consider
, fo r instance
, expressio
n (^414) fo r the entropy. Wit h the help of
expressio
n (^413) we have

^ )= ..,5:e-".+.Ti:e-"-j^/E

It i s now easy to verify that the above expressio

n becomes
5 - - f cs 5 3 Pm I n P m, {An)
m

where P^ ar e defined i n Eq. (^47). This shows that the entropy i s determine
d by the
probabiUt
y values P^.
Similarly for the pressur
e we have
(dF
We notice that dEmldV ca n be identified a s the pressur
e acting on the physical
syste
m in the pure quantu
m mechanica
l state of energ
y Em- Then the weighte
d average
of pressure
s in the sum in Eq. (^18) can be identified with the pressur
e p acting on the
physica
l system i n thermodynami
c equilibrium wit h a thermal bath o f temperatur
e
T. I n particular
, at zero temperatur
e we have
P = - ^ ; (^19

at T = 0 , the pressur
e i s just the derivative of the ground-stat
e energy of the system
with respec
t t o the volume.
A3. Gran d canonica l ensembl e an d thermodynami c quantitie s
Conside
r a physica
l system containin
g Ng identical particles confined within the volume V. Th e number Ns of identica
l particles of the system can now fluctuate.For any
chose
n value of iVg, we label with an integer nmnber m al l the distinct eigenstate
s of
the system and we indicate with Em,sthe eigenvalue
s of the system with Ns particles.
We are now intereste
d i n the descriptio
n of the system i n thermodynami
c equilibrium with a therma
l bath at temperatur
e T and with a particle reservoi
r with chemica
l
potentia
l /x. The equilibriu
m propertie
s of the system are calculate
d by averagin
g over
all its accessibl
e states of energy Em^sassignin
g to each state a probabilit
y Pm.s proportiona
l to

94 II

I TH

E SOMMERFEL D FREE-ELECTRO N THEOR Y O F METAL S

With normalizatio
n of the weights to unity, we obtain the grandcanonicaldistribution
probabiUt
y

^-',-...,-.~.,- '^^

'

Tn,s

The denominato
r i n (^20) i s known as the grand canonicalpartitionfunction
^ g r a n d ( r , y , /)i=

5 ^ e-p{Em,s-tiNs)

{A2l)

In analogy with the Appendix A2, we now show that all the thermodynami
c functions
of the system can be calculate
d from the knowledg
e of the grand canonica
l partition
function
.
To establis
h the connectio
n between statistic
s and thermodynamics
, w e define the
grandcanonicalpotentialllgrand = f^grandCT"
, V, /i) so that

or equivalentl
y
" g r a nd =

- f c ^ T l n Z g r a n d ( T, F , / i) =

- f c ^ T l u J ] e ' ^ ^ ^ - - "^ ^^ > . {A23)

rrifS

Following "mutatis mutandis

" the reasonin
g done in the Appendix A2, we can easily
establis
h that the grand canonica
l potentia
l equals
"grand = C / - T 5 - iV/ i = - f c ^ T h i Z g , a n d ( T, F, /i) {A24)

where U i s the mean internal energy and N i s the mean particle number i n th e
grand canonica
l distribution
. Relation (^424) i s the basic result of the grand canonica
l
apparatus
; all the other thermodynami
c relationship
s follow from it.
From the first and second principles of thermodynamic
s we have
dU = TdS-pdV-]'fidN.
By differentiatin
g "grand and using the above expression
, we obtain
dfigran
d = dC/ ~ TdS - SdT - Wdfi - ^idN = -SdT - pdV - Ndfi .
It follows:

'T,/x

J^_ _ / ^ ^ " g r a n d\

N = -( ^IH^I^ .

'T,V

(A27

SOLID STAT E PHYSIC S 9

Relation (^425) provide

s the entrop
y of the system
; relation (^426) provide
s the equatio
n
of State; relation (^427) provides the mean number o f particles
; all other thermodynamic functions can be easily obtained from the equation
s so far established
.

APPENDIX B . Fermi-Dira c an d Bose-Einstei n statistic s fo r

independent particle s
Fermi-Diracstatistics
We conside
r a physical system compose
d b y N identical particles confined within a
volmne V. Th e particles of the system are regarde
d as non-interacting
(except for an
arbitrar
y small interaction
, t o ensure thermodynami
c equilibrium). W e thus discuss
the energy levels of the many-bod
y system in terms of independen
t one-particlestates.
Quantum mechanics provides fo r a single particle confined within the volume V
discretize
d energy levels; we label with an integer number i all the distinct eigenstates
,
of energies e^, of the single-particl
e quantum problem. Since the particles are noninteracting
, the total energy of the many-bod
y system i s the sum of the energies of
the individual particles
i

where n^ denote
s the number of particles with energy e^; the total number of particles
is
Ar = ^ n i. {B2)
i

We now conside
r specificall
y a system of identica
l Fermi particles
; as a consequenc
e
of the Pauli principle, the possible values of the occupatio
n numbers Ui are either 0
or 1 . The most general accessibl
e state for the system of indistinguishabl
e particles
is defined b y a set of numbers {n^} (i.e. any sequenc
e of integer numbers equal to 0
or 1) . The grand partition function {A21) fo r a quantum system of non-interactin
g
fermions becomes

This sum can be carried out exactly and gives

i

The passag
e from Eq. (S3) t o Eq. (B4) can be done, for instance
, with the following
reasoning
. Conside
r first the particula
r situation of a syste
m with a singleone-electro
n
level, say 1; in this case the sum i n Eq. {B3) provides Z i = 1 -h exp[^(e
i /x)].
Conside
r then the particula
r situation of a system with only two levels, say 1 and 2;
the sum defined i n Eq. (S3) provides Z = Z1Z2 . Similarly, for a system with n levels

96

II I TH

E SOMMERFEL D FREE-ELECTRO N THEOR Y O F METAL S

i, 2, . , ^n, the sum dej&ned in Eq. (53) provides Z = Z1Z 2 . .. ^n and for a system
with any nmnber of levels we obtain Eq. {B4),
Now that the grand canonica
l partition function i s known,we can calculat
e whateve
r
desire
d thermodynami
c quantity
. For instanc
e we can calculat
e the average occupatio
n
numbe
r f{ei) o f a given state {. We have

fisi) = {rii) = J2

grand {nj}

^i -PE^ji^j-t^)

The sum over the configuration

s {rij} ca n b e easily carried out following, mutatis
mutandis
, the procedur
e done for the calculatio
n of Zgrand- We have
-/3(i-M)
^-'gran
e r a nd
d.

.^ L

Ji^i)

^g-^(ei-/i)

We thus recover immediatel

y the Fermi-Dirac statistics
f{ei) =

(B5)

el3(ei-n)+ 1

We can obtain the expressio

n of the free energy and of the entropy of a system of
non-interactin
g fermions
. We start from the expressio
n of the grand canonica
l potentia
l

aigrand = ^keTIn Zgran

d = " ^ B T J] I n [ 1 + e-^(^^-^) ] .

(S6)

From Eq. {A24) w e have for the free energy

-P{ei-ti)

From Eq. (^25), we have for the entropy

ii

We use the identity

/3(i ~ /x) = I n
where fi denotes by brevity f{ei). W e obtain

S = kBY^ - l n ( l - / i ) +

/il n l-fi
fi

(S7)

97

SOLID STAT E PHYSIC S

amd finally
S = -kBYl [fi

I n /i + ( 1 - fi) ln( l - fi)]

(58)

which i s the desired expressio

n for the entropy of non-interactin
g fermions.
Another importan
t expressio
n can be proved for the total number of particles
. From
Eq. (i427), we have
N ^_

f d n ^\

^ ln[

^ ^ B T T -

l + e-^^^-'^)
]

g-/3(ei-/x)

2^ 1 -f- e-/5(et-M)
i

E/^-

Finally for the equation of state (^26) w e have

p=
The energy eigenvalue
s of a particle confined i n a cubic box of volume V L^ ar e
given by
^ = ^ ( l ) ('^ x + 'iy + ^z) n^,njn
We have thus de/dL=

^ = 1,2,3,.. .

2e/L and also

ae _ a e a L _ _ 2

dV~ dLdV~ ZV

(BIO)

Expressio
n (B9) thus becomes

and then
PV =

-U.

(511)

Bose-Einsteinstatistics
In this case, diflFerently from the previous treatment
, the sequenc
e { n j ca n contain
any integer from zero to infinity. Th e grand partition function fo r a system of noninteractin
g bosons i s still given by expressio
n ( 5 3 ), keeping i n mind that rii can now
take any integer value from zero to infinity. The sum (J53) can be carried out exactly
and gives for bosons
2grand(T, F, /i) = J J ^ _ ^-0{e,-n) '

(B12)

98

II I TH

E SOMMERFEL D FREE-ELECTRO N THEOR Y O F METAL S

The passag
e from Eq. (53) t o Eq. {B12) can be done (as before) considerin
g first the
particula
r case of a single one-particl
e level, say ei. I n this case the sum i n Eq. (53 )
become
s
-/3(ei-M)

1 _e-/3(6:i-M )

n i =0

For a system with arbitrary number of one-particl

e levels we thus obtain Eq. (512).
The grand canonica
l potentia
l for a system of independen
t bosons i s

agrand = "^BTlnZgran d =

fc^T^^ln [ l - e'^^^^^) ]

(513)

We can now obtain all the thermodynami

c quantities of interest for a system of non
interactin
g bosons
. The average occupatio
n number of a given state i s given by

m)

1
e0(^i-fi) - 1

(514)

Similarly, the entropy of a system of non-interactin

g bosons i s given by

S = -kBY^ [fi In fi - ( 1 + fi) hi(l -f fi)]

(515)

APPENDIX C . Modifie d Fermi-Dira c statistic s i n a mode l o f

correlation effect s
In the previous Appendix we have considere
d a physica
l system compose
d by N indistinguishabl
e non-interactin
g fermions,confined within a volume V. Suppose that th e
one-electro
n Hamiltonian does not remove the spin degeneracy
; i n the independen
t
particle approximation
, the occupatio
n probabiUty of the spaceorbital(of energy e^),
regardless
of the spin degeneracy,i s then given by

where the factor 2 account

s for the spin degenerac
y of the orbital level.
In Chapter XIII , i n the study of doped semiconductors
, we need to know not only
the occupatio
n probability o f valence and conductio
n states (describe
d b y standard
delocalize
d Bloch wavefunctions)
, but also the occupatio
n probabiht
y of impurity locahzed states i n the energy gap. I n several situation
s (fo r instance for donor levels)
the Coulomb repulsion between electrons may preventdouble occupationof a given
localizedorbital. W e now discuss how this effect (whic h i s the simplest example of
correlatio
n beyond the one-electro
n approximation
) modifies the Fermi-Dirac distribution function.
For sake of clarity, conside
r a band state i n an allowed energy region of the crystal
and describe
d b y a Bloch wavefunction
; a band level can be empty, or occupied b y

99

SOLID STAT E PHYSIC S

4-

E=0
N=0

N=l

E=0
N=0

E=ei
N=l

4-

case (a)
E=Ei

E = 2 ej

N =l

N=2

44^

E=ei
N=l

case (b)

E=ei
N=l

N=l

case (c)

N=2

Fig. 6 Schematic illustratio

n of possibl
e occupatio
n of a given spatial orbital of energy {.
(a) The given level can accept two electron
s of either spin (this is the common situatio
n for
band states
) (b ) The given level can accept only one electro
n of either spin (this situation
is common for donor impurity levels i n semiconductors
) (c ) The given level can accommodate one or two electrons
, hut not zero (this situation i s common for accepto
r levels in
semiconductors)
.
one electron of either spin, or by two electron
s of opposit
e spin; the four possibilitie
s
are illustrate
d i n Fig. 6a. Conside
r now an impurity state within the energy gap and
describe
d b y a localized wavefunction
; a donor level, for instance
, can be empty, o r
occupie
d b y one electron o f either spin, but not b y two electrons o f opposite spin,
becaus
e of the penalty i n the electrostati
c repulsio
n energy; the situatio
n i s illustrate
d
in Fig. 6b.
We calculate fo r both situations the average number o f electrons i n the state {
(regardles
s of the spin direction)
; the average number i s given by

{rii)

(C2)

(3{Em,N-fiN)

In the case of Fig. 6a, Eq. (C2) gives

(rii)

[1 + e-/5(^ M)] [i4-e-/3(i-M)] ^'^7^^

as expected
, the result (CI ) i s recovere
d

/^)-hl

(C3)

100

II I TH

E SOMMERFEL D FREE-ELECTRO N THEOR Y O F METAL S

4f(e)

Fig. 7 Average occupatio

n number (dashed line) for an orbital of energy e that can accept
up to two electron
s of either spin (standar
d Fermi-Dirac statistics)
. The average occupatio
n
numbe
r (solid line) for an orbital of energy e that can accep
t only one electro
n of either spin
is also reported
. For e fi ^ ksT th e two curves coincide
.
In the case of Fig. 6b, we have instead
{rii)

g-/3(ei-/x) _| _ g-/3(et-/x)
I -| _ g-/3(ei-/x) _| _ ^-f3{ei-tM)

le/3(ei-M) + 1

(C4)

The occurrenc
e of the factor 1/ 2 i n Eq. (C4), can be easily understoo
d qualitatively
in the limiting case of a Boltzmann tail (see Fig. 7).
For sake of completeness
, we conside
r also the statistic
s of the accepto
r levels, whose
electroni
c structur
e i s studied i n Chapter XIII . A n accepto
r level can be occupie
d by
two paired electrons
, or one of either spin, but cannot be empty becaus
e of the penalty
in electrostati
c repulsio
n energy between the two holes; the situation i s schematicall
y
indicate
d i n Fig. 6c. The applicatio
n of Eq. (C2) gives
1 g-^(e,-M) + 1
If we indicate by {pi)

(C5)

2 (rii) the mean nmnber of holes, we obtain

(Pi) =

1
le/3(M-i) - f 1

(C6)

Further readin g
N. W. Ashcroft and N. D. Mermin "Solid State Physics
" (Holt, Rinehar
t and Winston,
New York 1976)

SOLID STAT E PHYSIC S 10

H. B. Callen "Thermodynamic
s and an Introductio
n t o Thermostatics
" (Wiley , New
York 1985, secon
d edition)
K. Huang "Statistica
l Mechanics
" (Wiley, New York 1987, secon
d edition)
C. Kittel "Elementar
y Statistica
l Physics
" (Wiley, New York 1958)
R. Kubo "Statistica
l Mechanics
" (North-Holland
, Amsterda
m 1988, sevent
h edition)
A. Miinster "Statistica
l Thermodynamics
" Vols. I and H (Springer, Berlin 1969)
R. K . Pathria "Statistica
l Mechanics
" (Pergamon Press, Oxford 1972)
L. E. Reichl " A Modern Coin-se in Statistica
l Physics
" (Arnold, London 1980)
A. H. Wilson "The Theory of Metals" (Cambridge University Press 1954)