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- Fundamental University Physics, Volume 3 (Quantum and Statistical Physics) - Alonso, Finn
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Figure 1 Schematic model of a crystal of sodium metal. The atomic cores are Na' ions: they are

immersed in a sea of conduction electrons. The conduction electrons are derived from the 3s

valence electrons of the free atoms. The atomic cores contain 10 electrons in the configuration

l s 2 2 s 2 2 pI~n an alkali metal the atomic cores occupy a relatively small part (-15 percent) of

the total volume of the crystal, hut in a nohle metal (Cu, Ag, Au) the atomic cores are relatively

larger and may he in contact with each other. The common crystal structure at room temperature

is hcc for the alkali metals and fcc for the nohle metals.

In a theory which has given results like these, there must

certainly be a great deal of truth,

H.A. Lorentz

We can understand many physical properties of metals, and not only of the simple metals,

in terms of the free electron model. According to this model, the valence electrons of the

constituent atoms become conduction electrons and move about freely through the volume of the

metal. Even in metals for which the free electron model works best, the charge distribution of the

conduction electrons reflects the strong electrostatic potential of the ion cores. The utility of the

free electron model is greatest for properties that depend essentially on the kinectic properties of

the conduction electrons. The interaction of the conduction electrons with ions of the lattice is

treated in the next chapter.

The simplest metals are the alkali metals-lithium, sodium, potassium, cesium, and

rubidium. In a free atom of sodium the valence electron is in a

electron becomes a conduction electron in the 3 s

3s

conduction band.

A monovalent crystal which contains N atoms will have N conduction electrons and N

positive ion cores. The

1 s , 2 s ,2 p

+

Na

10

shells of the free ion, with a spatial distribution that is essentially the same when

in the metal as in the free ion. The ion cores fill only about

+

Na

15

ion is

0.98 A , whereas one-half of

The interpretation of metallic properties in terms of the motion of free electrons was

developed long before the invention of quantum mechanics. The classical theory had several

conspicuous successes, notably the derivation of the form of Ohms law and the relation between

the electrical and thermal conductivity. The classical theory fails to explain the heat capacity and

the magnetic susceptibility of the conduction electrons. (these are not failures of the free electron

model, but failures of the classical Maxwell distribution function).

There is a further difficulty with the classical model. From many types of experiments it

is clcar that a condition electron in a metal can move freely in a straight path over many atomic

distances, undeflected by collisions with other conduction electrons or by collisions with the

atom cores. In a very pure specimen at low temperatures, the mean free path may be as long as

108 interatomic spacings (more than 1 cm).

Why is condensed matter so transparent to conduction electrons? The answer to the

question contains two parts: (a) A conduction electron is not deflected by ion cores arranged on a

periodic lattice because matter waves can propagate freely in a periodic structure, as a

consequence of the mathematics treated in the following chapter. (b) A conduction electron is

scattered only infrequently by other conduction electrons. This property is a consequence of the

pauli exclusion principle. By a free electron Fermi gas, we shall mean a gas of free electrons

subject to the pauli principle.

Consider a free electron gas in one dimension, taking account of quantum theory and of

the principle. An electron of mass m is confined to a length

wavefunction

n (x)

quantum theory

H= /2 m , where

is the momentum. In

2

2 d n

H n=

=n n

2 m dx 2

H = ;

Where

We use the term orbital to denote a solution of the wave equation for a system of only one

electron. The term allows us to distinguish between an exact quantum state of the wave equation

of a system of

N

by assigning the

electrons to

wave equation for one electron. The orbital model is exact only if there are no inter-actions

between electrons.

n ( 0 )0 ;

n ( L ) =0

potential energy barriers. They are satisfied if the wavefunction is sinelike with an integral

number n of half-wavelengths between 0L :

n= A sin

2

x

n

( )

1

n =L

,

2 n

d n

n

n

=A

cos

x

dx

L

L

( ) ( )

n=

2 n

2m L

d n

dx

=A

n

n

sin

x

L

L

( ) ( )

is given by

( )

We want to accommodate

Figure 2 first three energy levels and wave functions of a free electron of mass m confined to a

line of length L. The energy levels arc labeled according to the quantum number n which gives

the number of half-wavelengths in the wavefunction. The wavelengths are indicated on the wave

function. The wavelengths are indicated on the wavefunctions. The energy

of the level of

2

n 2

(

)

2m 2 L .

( )

Identical. That is, each orbital can be occupied by at most one electron. This applies to electrons

in atoms, molecules, or solids.

In a linear solid the quantum numbers of a conduction electron orbital are n and m, where

ms=

1

2 , according to spin

orientation. A pair of orbitals labeled by the quantum number n can accommodate two electrons,

one with spin up and one with spin down.

If there are six electrons, then in the ground state of the system the filled orbitals are

those given in the table:

More than one orbital may have the same energy. The number of orbitals with the same energy is

called the degeneracy.

Let

nf

denote the topmost filled energy level, where we start filling the levels from the

bottom (n=1) and continue filling higher levels with electrons until all N electrons are

accommodated. It is convenient to suppose that N is an even number. The condition

determines

nf

2 nf =N

2

2 nf

2 N

f =

=

2m L

2m 2 L

( )

( )

n=nf

The ground state is the state of the N electron system at absolute zero. What happens as

the temperatuere is increased? This is a standard problem in elementary statistical mechanics,

and the solution is given by the Fermi-dirac distribution gives the probability that an orbital at

energy

f ( )=

1

exp

+1

kB T

[ ]

`The quantity

problem in such a way that the total number of particles in the system comes out correctly- that

is, equal to N. at absolute zero

T 0

the function

temperatures f ()

2.

is equal to when

F =

f ( )

. At all

Figure 3 Fermi-dirac distribution function (5) at the various labeled temperatures, for

T f=

f

=50000 K . The results apply to a gas in three dimensions. The total number of

kb

at each

temperature may be read off the graph as the energy at which f =0.5 .

The quantity

is the chemical potential (TP, Chapter 5), and we see that at absolute zero the

chemical potensial is equal to the Fermi energy, defined as the energy the topmost filled orbital at

absolute zero.

The high energy tail of the distribution is that part for which

called the Boltzmann or Maxwell distribution.

k b T

; here the

()/k B T

. This limit is

f ( ) exp

The free-particle schrodinger equation equation in three dimensions is

2 2

2

2

+

+

( r )=k k (r )

2 m x2 y2 z2 k

If the electrons are confined to a cube of cube of edge L, the wavefunction is the standing wave

n ( r )= A sin

Where

nx , n y , nz

( nL x )sin ( nL y ) sin ( nL z )

x

we did for phonons in Chapter 5. We now require the wavefunctions to be periodic in x, y, z,

with period L. Thus

And similarly for the y and z coordinates. Wavefunctions satisfying the free particle schrodinger

equation and the periodicity condition are of the form of a traveling plane wave:

Any component of k of theform

of the form

2 n / L

condition over a length L, where n is a positive or negative integer. The components of k are the

quantum numbers of the problem, along with the quantum number m, for the spin direction. We

confirm that these values of kx satisfy (8), for

exp [ ik x ( x + L ) ]=exp

exp

i 2n ( x + L )

L

i2 nx

exp ( i2 n )=exp (

=exp ( i k x )

( i2 nx

)

L

L )

x

k=

2 2 2 2 2 2

k=

( k +k + k )

2m

2m x y z

by k =2

p=i , whence for the orbital (9)

p k ( r ) =i k ( r )=k k (r ) ,

So that the plane wave

k

In the ground state of a system of N free electrons, the occupied orbitals may be

represented as points inside a sphere in k space. The energy at the surface of the sphere is the

Fermi energy; the wavevectors at the Fermi surface have a manigtude

kF

2

F=

k

2m F

From (10) we see that there is one allowed wavevector that is, one distinct triplet of

3

of volume 4 k F /3

2 3

)

L

4 k F /3 V 3

2.

= 2 k F =N

3

2

3

(

)

L

Where the factor 2 on the left comes from the two allowed values of the spin quantum number

for each allowed value of k. then (15) gives

k F=

32N

V

1 /3

Figure 4 in the ground state of a system of N free electrons the occupied orbitals of the system

fill a sphere of radius

wavevector

kF

kF

, where

F = k F /2 m

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