Particle in a Box

0 < x < Lx , 0 < y < Ly , 0 < z < Lz

r) ∝ sin kxx sin ky y sin kz z

ψkx,ky ,kz (r

π
� �
sin kxLx = 0 ⇒ kx = nx nx = 1, 2, 3, · · ·
Lx
ky π/Lx
r Lx Ly Lz V
D(k)wavevectors = = 3
π/Ly π π π π

r V
kx D(k)states = (2S+1) 3
π

8.044 L19B1

Plane Wave r) ∝ exp[irk · r]

ψrk (r
Periodic Boundary Conditions

ψrk (r
r + mxLxx̂ + my Ly ŷ + mz Lz ẑ) = ψrk (r
r)

2π
� �
e ikx (x+mx Lx ) =e ikx x ⇒ kx = nx nx = ±1, ±2, ±3, · · ·
Lx

ky Lx Ly Lz V
2π/Lx r
D(k)wavevectors = =
2π 2π 2π (2π)3
2π/Ly

r V

kx D(k)states = (2S+1)

(2π)3

8.044 L19B2

The # of wavevectors with |-k'| < k is the same in

both cases.
1 4 3 V 4 3 V
#wavevectors(k) = πk 3
= πk
8 3 π 3 (2π)3

n2k2 2m √
For free particles; E = → k(E) = 2
E

2m n

4 V V 2m 3/2
#wv(E) = πk(E)3 = E3/2

3 (2π)3 6π 2 n2

d V 2m 3/2 1/2
Dwv(E) = #wv(E) = 2 2
E
dE 4π n
8.044 L19B3
For free particles
�3/2
V 2m
�
Dstates(E) = (2S + 1) 2 E1/2
4π n2

D(ε)

ε
8.044 L19B4

Fermions: Non-interacting, free, spin 1/2, T = 0

kz
D( ε)
kF

ky

εF ε kx

Fermi sea Fermi wave vector kF

Fermi surface Fermi energy EF = n2kF
2 /2m

8.044 L19B5

 4 3 8 V 3

N = 2 × Dwavevectors(k) × πkF = π k
3 3 (2π)3 F

�1/3
2 ∝ (N/V )1/3
�
kF = 3π (N/V )

⎞2/3
n2 k F
2 n2 2
⎛
3π N
EF = = ⎝ ⎠ ∝ (N/V )2/3
2m 2m V

8.044 L19B6

D(�) = a �1/2

� �
N =
F
D(�) d� = 2 a �3/2
0 3 F

� �
U =
F
�D(�) d� = 2 a �5/2 3N �
=5 ∝ N (N/V )2/3
0 5 F F

8.044 L19B7
Consequences: Motion at T = 0

P = h̄Pk
p PF = h̄PkF
p h̄ k
vF = m F

Copper, one valence electron beyond a filled d shell

N/V = 8.45 × 1022 atoms-cm−3

kF = 1.36 × 108 cm−1 vF = 1.57 × 108 cm-s−1
pF = 1.43 × 10−19 g-cm-s−1 EF /kB = 81, 000K

8.044 L19B8
Consequences: P (T = 0)

U =3
5 N EF EF ∝ (N/V )2/3

∂U ∂EF
� � � �
P =− 3
= −5N 2 (N/V )E
= 5
F

∂V N,S ' ∂V NN
EF
−2
3 V

∝ (N/V )5/3

∂P
� �
5 (P/V ) at T = 0

= − 3

∂V N,T

8.044 L19B9



1 ∂V 31 3 1
KT = − = =
V ∂P N,T 5P 2 (N/V )EF

For potassium
EF = 2.46 × 104K = 3.39 × 10−12 ergs
(N/V )conduction = 1.40 × 1022 cm−3

KT = 1.40×10221.5 = 31.6 × 10−12 cm3-ergs−1

×3.39×10−12

The measued value is 31 × 10−12 !

8.044 L19B10
Magnetic Susceptibility

ε
� = Hẑ
H εF
k,↑ = (k) + µeH
k,↓ = (k) − µeH
µe H
D ( ε) D ( ε)

8.044 L19B11

    
N D(EF )   N D(EF ) 
N↓ − N ↑ =  + µe H − − µe H
2 2 2 2

= µeHD(EF ) ⇒ M = µ2
e
HD(EF ) ≡ χH

χ = µ2
e
D(EF )

This expression holds as long as kT « EF , so χ is

temperature independent in this region. This is not

Curie law behavior. It is called Pauli paramagnetism.

8.044 L19B12
Temperature Dependence of < n�k,m >

< n�k,m >= f (E) only, as in the Canonical Ensemble

<n>
~ kT
1
T=0

T << εF/ k B
εF ε
8.044 L19B13

Estimate CV

Classical Quantum

# electrons N N
# electrons influenced N ∼ N × kT
�F

Δ� 3 kT ∼ kT
2
3 N kT (kT )2
ΔU 2 ∼N �F

CV 3N k ∼ 2N k kT
2 � F

Exact result: CV = π 2 N k kT
2 �F

8.044 L19B14
 � ∞
N = < n(�, µ(T ), T ) > D(�) d�

This expression implicitly determines µ = µ(T ).

� ∞
U = < n(�, µ(T ), T ) > � D(�) d�

To determine CV from this expression one must

take into account the temperature dependence of
µ in addition to the explicit dependence of < n >
on T .

8.044 L19B15

<n>
~ kT
1
T=0

T << εF/kB
εF ε

[< n > −1/2]] = − [[< n > −1/2

]]
[
at E = µ + δ at E = µ − δ

8.044 L19B16

 D(ε)

ε
µ εF

Because D(�) is an increasing function of �, µ must

decrease with increasing temperature.

8.044 L19B17

Elementary Excitations Excitations out of the ground

state in interacting many-body systems.

For a 3D Coulomb gas of electrons

ε(k) Plasma oscillations (plasmons)

Collective modes: H.O.s

Quasi-particles
2k2
(‘dressed’ electrons) = 2m∗
k

8.044 L19B18

Other collective modes

Phonons, lattice vibrations in solids
Spin waves, in Ferromagnets
Ripplons, waves on surfaces

Other quasi-particles
Polarons, (electron+lattice distortion)
in ionic materials

8.044 L19B19
Some possible electronic densities of states in solids

D(ε) metal D(ε) insulator

εF ε ε
wide

D(ε) intrinsic semiconductor D(ε) doped semiconductor

εF ε εF ε
narrow

8.044 L19B20

Finding µ(T ) in an intrinsic semiconductor

<n>
1 D(ε)

0 εG ε
µ εF

Assume the energy gap is � kB T .

8.044 L19B21
 1

-5 -4 -3 -2 -1 0 1 2 3 4 5

Comparison of 1/(ex + 1) with e−x when x > 0 and

1 − ex when x < 0.

8.044 L19B21a
 < ne > → e−(E−µ)/kB T = e−(EG−µ)/kB T e−(E−EG)/kB T

V 2me 3/2
� �
Dstates,e(E) = (E − E ) 1/2
G
2π 2 n2
� ∞
Ne = < ne > D(E) dE
EG

V 2me 3/2 −(EG−µ)/kB T � ∞ √ −δ/kB T

� �
= 2 2
e δe dδ
2π n 0
�3/2
V 2mekB T
�
= e−(EG−µ)/kB T
4 πn2
8.044 L19B22

 < nh > = 1− < ne > → e−(µ−E)/kB T

V 2mh 3/2 1/2

Dstates,h(E) = (−E)
2π 2 n2
0

Nh = < nh > D(E) dE

−∞

V 2mh 3/2 −µ/kB T ∞ √ −δ/kB T

= 2 2
e δe dδ
2π n 0

V 2mhkB T 3/2 −µ/kB T

= 2
e
4 πn
8.044 L19B23

 N h = Ne

3/2 −µ/kB T 3/2 −(�G−µ)/kB T

mh e = me e

(mh/me)3/2 = e−�G/kB T e2µ/kB T

(3/2)kB T ln(mh/me) = −�G + 2µ

µ = �G/2 − (3/4)kB T ln(me/mh)

8.044 L19B24
MIT OpenCourseWare
http://ocw.mit.edu

8.044 Statistical Physics I

Spring 2013

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