Solid State Theory

Physics 545

The lattice specific heat

Statistical thermodynamics of Solids:

Kinetic energy
Introduction of structured solids
Law of Dulong and Petit (Heat capacity) 1819
Einstein Model of Crystals 1907
Born and von Karman approach 1912
Debye Model of Crystals 1912

Electronic energy
Fermi level 1926
Fermi-Dirac distribution
 Law of Dulong and Petit
The crystal stores energy as:

- Kinetic energy of the atoms under the form of vibrations.

According to the equipartition of energy, the kinetic
internal energy is f . ½ . k. T where f is the degree
of freedom. Each atom or ion has 3 degrees of freedom
EK = 3/2 N k T
- Elastic potential energy. Since the kinetic energy convert
to potential energy and vice versa, the average values are
equal Epot = 3 N (½ K x2) = 3 N x (½ k T)

The stored molar energy is then:

E = EK + Epot= 3 NA k T =3 R T€C = dE/dT = 3 R

 Law of Dulong and Petit
Within this law, the specific heat is independent of:
- temperature
- chemical element
- crystal structure

At low temperatures, all materials

exhibit a decrease of their specific
heat Classical harmonic oscillator
€ Quantum + Statistical mechanics
 Normal modes and phonons
• Description of lattice vibrations has so far been purely classical
because we solved classical equations of motion to find the vibrational
modes and dispersion relation of the lattice.
a harmonic potential, the classical approach gives the same modes and dispersion relation as the quantu

• Each mode is the mode of vibration of a quantum harmonic oscillator

with wave vector k and polarisation s and quantised energy:

 ⎜⎛ n k  1 ⎟⎞ h  1
E k,s ,s s   n k,s
⎝ 2 ⎠ e
h  k s / k T
k ,
B
 1


where n is the number of phonons in the mode k,s.

A phonon is a bosonic particle with wave vector k and polarization s
• The more phonons in the mode, the greater the amplitude of vibration.
 Phonon Energy

•The linear atom chain can only have

N discrete K €  is also discrete
Distance
• The energy of a lattice vibration mode
at frequency  was found to be
⎛ 1
u n
⎜ h
 ⎞
h
⎝ ⎟⎠
2
• where ħ can be thought as the energy of a
particle called phonon, as an analogue to
photon

• n can be thought as the total number of

phonons with a frequency  and follows
the Bose-Einstein statistics:
1
n
⎛ h⎞ Equilibrium distribution
 ⎝ kBT ⎠

Total Energy of Lattice Vibration

El  
⎡  n  K , p  1 ⎤hK , p

⎢
⎣
p K 2 ⎥⎦

p: polarization(LA,TA, LO, TO)

K: wave vector

Experimental observations of lattice specific heat

preceded inelastic neutron scattering.
Model crystal: p atoms per unit cell )
N unit cells ) 3pN harmonic oscillators
Thermal energy (quanta) excites crystal and any number of
excitations into quantized energy levels for oscillators.
 Bose-Einstein Statistics

⎛⎞
nk 1 Number of excitations
s ⎜⎟⎝⎠  s⎛ k⎝⎠⎜⎟ ⎞
h in particular mode, k, s
exp 1
kT
B

In harmonic approximation, total energy density

h ⎛ k ⎞
U  1  12hs ⎝⎛⎜ k⎠⎞ ⎟ 1 k,s
 h ss ⎜k ⎟
⎝⎜ ⎟⎠

V k,s V exp ⎛ ⎞

k ⎝ ⎠ 1
TB
s: polarization(LA,TA, LO, TO)
k: wave vector
 Specific Heat (at Constant Volume)

⎛ U ⎞ hs k
CV  ⎜ ⎟
T
1
V  
 h
T k
⎝ ⎠V 
k,s exp s 1
k BT

s: polarization(LA,TA, LO, TO)

k: wave vector
  83
Volume of k-space per allowed k value is Δk V

Fk   V3Fk   Δk
k 8 k
For Δk  0 (i.e., V  )

1 dk
Lim
V V
k

Fk   83
Fk 


 dk h s k
V   T 8 3
s k 
C
h
s
exp 1
kBT
 Density of Phonon States in 1D

A linear chain of N=10 atoms

with two ends jointed
a

Only wavevectors () are allowed (one per mobile atom):

K= -8/L -6/L-4/L-2/L 02/L 4/L 6/L8/L/a=N/L

Only 1 K state lies within a ΔK interval of 2/L # of states per unit range of K is:/2
DOS  # of K-vibrational modes between  and +d :

D() L 1
2 d / dK
 Density of States in 3D

Kx , K N
 0; ; ;...;
y,
2 4 L
Kz
L L

N3: # of atoms

Kz
Ky
Kx 2/L
 VK 2 1 3

D()  d / dK VL
2 ;
2
 Density of States
Define D() such that D() d is total no. of modes with
frequencies in range  to  + d per unit volume of crystal.

1 1 1 d  dS
D()  d  8 3  dk ( - s) 8 3  dkn dS  3 
8 k k
1 dS
D    3 
 k k 
8
and for any function Q(s(k))
dk 3
 s  Q  k 
8  d   D     Q  

s

 h k
Hence CV    h
 D    d
T exp 1
kkBT
 Lattice Specific Heat
 ⎡ n K , p
El   1⎤
 h K ,
 p
p: polarization(LA,TA, LO, TO)

p K
⎢ 2 ⎥⎦ K: wave vector
⎣

4 KdK
   
2
El   ⎢⎣
⎡ n K , p 2⎥⎦1 ⎤h K , p dK
⎡ 1
2L3 p  ⎣⎢n K , p  2 ⎦hK , p 2 L3
p

Dispersion Relation:K  g 

1
n  D d
Energy
Density:
l   ⎤
h
VK
2
 p ⎡⎢⎣  2 ⎥⎦
D()  1
2 2 d / dK
Density of States (Number of K-vibrational modes between  and +d
 d n
Lattice Specific Heat: C l  d l   D
 dhdT
dT p
 High-Temperature “Classical” Limit:
h x« 1
k BT

C 
k T  D    d  k D    d  3 pNk
V
T
 B B  B

which is the same as the classical result (Dulong and Petit law: 3R
J/mole/K for a monatomic solid). The reason for this is because at
this level of approximation the energy associated with a quantum of
lattice vibration, h, exactly cancels out and therefore it doesn't
matter how big that quantum is (including zero).
 Low Temperature Limit:
Only low-frequency acoustic modes excited.
 ssc k for each branch, where c s is initial
s
slope of the particular phonon dispersion
k
curve. (Note that cs is related to the elastic
constant for the mode, e.g., for [100]L elastic
waves

c11
c s  v100 L 


where c11 is an elastic constant and 

the density
 Low Temperature Limit:
1  k 2 sin 1 k2 1 k2 1 2
D  2 c  c

d  cos0 
2 2  2 2 s c s 2 2
3

2
s 0 cs ss s s

2 ⎡ ⎤ 2
 1 1 1 3
 ⎥
2 ⎢
2

⎢ c 3 c3  3 ⎥  2 c
2 3
c
⎣⎢ L T1 T2 ⎥⎦

max 32 x  h h
h dx   d
CV  T  h
 d k BT k BT
0 exp k B T  1 2 2 c 3
hmax
 k T
4
3 kBT 2
2
⎛k T⎞
3
3 x
CV  B  dx kB⎜ B ⎟
T hc3 2
2  x
e 1

5 ⎝ hc ⎠
0
at low temperatures the specific heat is proportional to T3.
 Einstein Model
Each molecule in the crystal lattice is supposed to vibrate
isotropically about the equilibrium point in a cell delimited by
the first neighbors, which are considered frozen.

System of N molecules

the system can be treated as 3N

independent one- dimensional
harmonic oscillator
Motions in the x, y and z axis are
Independent and equivalent
 Einstein Model
System of 1-Dim Harmonic Oscillator

Quantized expression of the energy:

v = h (v+1/2) v = 0, 1, 2, ...
Partition function (without attributing 0 to the ground state)
q =  e-(h(v+1/2)/kT) = e-(h/2kT)  e-(h/kT) v
Considering the vibrational temperature  =   h/k
q = e-/2T
1- e-/T
The molecular internal energy
Umolecular = - d[Ln(q)] / d ]N, = k T2 d[Ln(q)] / dT ]N, V
V

U = k  (1/2 +  1 )
molecular
e /T - 1
 Einstein Model energy of the system
System of N 3-Dim Harmonic Oscillators

Q = q3N € U = 3N Umolecular

U = 3 N k  (1/2+ 1

)
e /T - 1
Internal energy

3/2 Nh + 3 NkT

3/2 Nh

0.0 0.5 1.0 1.5 2.0 2.5

kT/h
Einstein Model the heat capacity of the system

System of N 3-Dim Harmonic Oscillators

The heat capacity of the crystal is then

C = dU / dT

3Nk
Heat capacity

U = 3 N k  (1/2+ 1
)
e /T - 1
C = 3 Nk (/T)2
/T
e
––/T–––
0.0 0.5 1.0 1.5 2.0 2.5 ( – 1)2
T/
 Einstein Model
Assumed model for crystal to be 3n harmonic oscillators, each of
frequency, 
E k  hE 
BE

D     E  h  k 
3n  CV    D    d

Substituting this into Equation  Texp h k  1 kBT


⎛ hE ⎞2 ⎛ hE ⎞ ⎛ ⎞
⎜ ⎟ exp⎜ ⎟ exp⎜ E⎟
⎝ k BT ⎠ ⎝ k BT ⎠  3R⎛ E ⎞ 2
⎝ T⎠  3R  F⎛  E ⎞
C
V 3nk B ⎜⎟ E⎜ ⎟
⎛ ⎛ h E ⎞ ⎞
2 ⎝ T ⎠ ⎛ ⎛ ⎞ ⎞2 ⎝ T ⎠
⎜ exp⎜ ⎟  1⎟ ⎜ exp⎜E ⎟  1⎟
⎜ ⎝k T ⎟ ⎝T⎠ ⎠
⎝ B⎠ ⎠ ⎝

⎛ E ⎞
T
E», FE ⎜ ⎟ ⎝ T⎠
 1, so CV  3R (the classical high-temperature limit).
⎛ E ⎞
⎛2  E ⎞ ⎛ E ⎞ CV dominated by the exponential term, which is not found
T
E«, FE ⎜ experimentally at low temperatures.
T ⎟  ⎜ T ⎟ exp⎜ T ⎟
⎝ ⎠ ⎝ ⎠ ⎝ ⎠
 Einstein Model
Comparison of the observed
molar heat capacity of diamond
(+) with Einstein’s model. (After
Einstein’s
original paper-1907)
comparison with experiment
The value of  = 1325 K was
given to produce an agreement
with the experiment at 331,1 K.
 or   k is the parameter
that distinguishes different
substances:
   a m
where
E is Young’s modulus
m is atomic mass
and a is the lattice parameter
Einstein model gives also a
qualitatively quite good agreement
on term of  calculated from the
elastic properties
 Einstein Model results and limitation

The Einstein Model of crystals takes into account the alteration

of the heat capacity by:
- temperature
- chemical element
- crystal structure
This model explained the decrease of the heat capacity at low
temperature.

However:
This decrease is too fast! The experimental results evolve as T3

Reason is that the Einstein model does not consider the

collective motion and only consider one vibrational frequency.
 Born and von Kármán approach

System of N atoms possess 3N degrees of freedom, all expressing

vibrational motion.
Thus, the whole crystal has 3N normal modes of
vibration characterized by their frequencies i =i/2

THE LATTICE VIBRATIONS OF THE CRYSTAL ARE

EQUIVELENT TO 3N INDEPENDENT OSCILLATORS
3N

E =  hi (1/2 + (e(h /kt)-1)-1)

i
 Propagation of sound wave in solids
notion

This propagation could be solved using the classical concepts since

the atomic structure (dimensions) can be ignored in comparison to the
wavelength of a sound wave.

The 3-D wave equation 2 (r) + k2 (r) = 0

where: k is the magnitude of the wave vector k =
2/

Wave phase velocity v =   = /2  k

 Propagation of sound wave in solids
standing waves in a box

The 3-D wave equation of motion solved in a cubic box with the side L
n1 n2 n3 (r) = A sin(n1 x / L) sin(n2 y / L) sin(n3 z / L)

The wave vector in the Cartesian coordinates is k(n1/L, n2/L, n3/L)

In the k space, formed by the allowed values of k(n i = 1, 2, ...), is

composed of cubic point lattice with the separation of /L and
the volume of Vu= (/L)3.
 Propagation of sound wave in solids
Density of states

Defining the density of states come to the determination of the number

of normal modes of standing waves with the lying magnitude between k
and k+dk.
f(k) dk = (1/8) (4k2) dk /(/L)3 = Vk2 dk/(22)

In term of circular frequency:

f(k) dk = f() d
= (Vk2/22) (dk/d) d
= V 2 d /(2 v2 vg 2)

Where vg= d/dk

is the group velocity
 Propagation of sound wave in solids
Density of states

In a non dispersing medium vg = v

f(k) dk = f() d = V 2 d /(2 v3 2)

The wave vector has three independent modes:

1 longitudinal and 2 transversal modes
f() d = V 2 d /(2 2) (1/v 3 + 2/v 3 )
L T
In an isotropic Medium vL = vT =vm
f() d = 3V 2 d /(2 vm32)
 Debye Model
Lattice vibrations are regarded as standing waves of the atomic
planes´ displacement

It is assumed that all normal mode frequencies satisfy the equation

of the density of states

An upper limit for frequencies is, however, set such as

ƒ f() d = 3N
D

€f() d = 9N2 d/D3

Now the sum can be replaced with an integral

3N D
 ..... = ƒ .....f() d
 Debye Model

Debye Approximation:  vs K

Frequency, 
  vs K

g 2  dg 2
Debye Density of D 
 
States 2 2 d 2 2v3s

4 K 3D
Number of Atoms: N 3

2 L 3

Debye cut-off Wave Vector D 6 2

K   13
0 Wave vector, K /a

Debye Temperature [K]

Debye Cut-off Freq. D  vs K D
  1
C(dimnd)
Si
Ge
1860
625
360
Ga
NaF
NaCl
240
492
321
2
Debye Temperature 6 
3 B 1250 NaBr 224
hD
  Al 394 NaI 164
kB
D
kB hvs
 Debye Model The energy of the crystal

U   i
3N

1
3N
ħi
  [(1/2)ħi + ⎯
1
] ħi

e -1 kT

 ƒ [(1/2)ħ + ⎯ħ⎯⎯] D() d

D

ħ
0
e kT -1
 ⎯9Nk + ⎯9 x 3 D
dx
D NkT ƒ⎯x⎯x
8 xD 3 0 e-1
WhereD =ħD/k xD = ħD/kT x = ħ/kT
 Debye Model x
The heat capacity of the crystal
3
9 9 D x
E Nk D  3
NkT  x
dx
8 x D 0
e 1

T€ X€
T€0 0
X€
xD3/3
 /15
4
€E = 9NkD/8 + 3NkT
€E = 9NħD/8
Vibrational zero-point energy € Cv = 3Nk

€ Cv = dE/dT]v = 0
 Debye Model The heat capacity at low temperature

Cv =(dU/dT) v T enters this expression only in

the exponential term ()
Cv= 3Nk {⎯3 x D

xD3ƒ ⎯x⎯4 e⎯x dx }

0 (ex-1)2
x D

When T<< D € ƒ
⎯x⎯4
0
e⎯x
(ex -1)2
dx = 4/15
3
€C V = 12  4 N kT
5 D
 Debye Model-Experiment

The Debye Model gives good fits to the experiment; however, it is only
an interpolation formula between two correct limits (T = 0 and infinite)
 Lattice Specific Heat
D
⎡ 1 ⎤ h 3
⎡9k DT
x3dx ⎤ h

 ⎥
n d2 ⎦ 2 2v3  ⎢⎢ 3 B  ⎥⎥T 4 x
Energy Density l  e 1
x
kBT

 ⎢
⎣

p 0 s ⎢ D 0 ⎥
⎡ ⎤ ⎣ ⎦
T
⎛T⎞ 3
D x
e x dx 4
Specific
Heat ⎜ l  9kB
C ⎟ ⎢

⎥
2

⎝  D ⎠ ⎢⎣ 0 e 1 ⎥⎦
x
10 7
C  3kB  4.7 106 J 3
m 
K
10 6

When T << 10 5
Diamond

D,
3
4
Cl  T Specific Heat, C (J/m -K)3
10 4

l  T
,
CT3
Q
10 3
10
u
10 a
10 2
n
 D
tum Regime
10 2
10 3

Classical
Regime
  1860
K

10 4
Temperature, T (K)
 Einstein-Debye Models
Lattice structure of Al Cubic Closest Packing

E / elst = 0,79

D / elst = 0,95
The lattice parameter a = 0,25 nm
The density =2,7 g/cm3
The wave velocity v =3,4 km/s
€elst
 Lattice parameter

Cubic close packed, (a) Hexagonal close Body centered cubic

packed (a, c) (a)
Cu (3.6147) Be (2.2856, 3.5832) Fe (2.8664)
Ag (4.0857) Mg (3.2094, 5.2105) Cr (2.8846)
Au (4.0783) Zn (2.6649, 4.9468) Mo (3.1469)
Al (4.0495) Cd (2.9788, 5.6167) W (3.1650)
Ni (3.5240) Ti (2.506, 4.6788) Ta (3.3026)
Pd (3.8907) Zr (3.312, 5.1477) Ba (5.019)
Pt (3.9239) Ru (2.7058, 4.2816)
Pb (4.9502) Os (2.7353, 4.3191)
Re (2.760, 4.458)
 Debye Temperature

 ⎯9Nk + ⎯9 dx NkTx ⎯x⎯3

ƒ D
D x
8 x D
3
Where =ħ /k
D
0
D
e -1
xD = ħD/kT x = ħ/kT
3
C V = 12 4N kT
5 D
 The limit of the Debye Model

€ The electronic contribution to the heat capacity was not considered

 Electronic contribution Fermi level

At absolute zero temperature, electrons pack into the lowest

available energy, respecting the Pauli exclusion principle
“each quantum state can have one but only one particle“

s build up a Fermi sea, and the surface of this sea is the

vel. Surface fluctuations (ripples) of this sea are induced by the electric and the therma

So, the Fermi level, is the highest energetic occupied level at zero
absolute

41
 Electronic contribution Fermi function

The Fermi function f(E), drown from the Fermi-Dirac statistics,

express the probability that a given electronic state will be
occupied at a given temperature.
1.0

E-EF < 0

f(E)
0.5

E-EF > 0
0.0

Temperature
 Electronic contribution to the
internal energy

Orbitals are filled starting from the lowest levels, and the last filled or
orbital will be characterized by the Fermi wave vector KF
The total number of electron in this outer orbital is: 3 K F
L
NT  f (k ) 2

2
k dk
dk 3 0
2 2
Because electrons can
Adopt 2 spin orientations

V 3  N 3
2
k
3
3
T

NT 
2 kV F
F
 Electronic contribution to the
internal energy
The wavefunction offree electron is:

(x, t)  i (kx  .t )
Ae
Its substitution in the Schrödinger equation:

2
2
 (x, t)
E(x, t)  (x,
h 2 t)  
h2 2m x2
€ E k 2

2m
 Electronic contribution to the
internal energy
Fermi Energy 2
h h ⎡ NT⎤
 
2 2
E k
2
F  3 3 3 2 2
F
2m 2m ⎢⎣ V⎥⎦
Fermi Temperature

E
T F 
F
k
 Temperature effecton electrons
Metal K Na Li Au Ag Cu
NT /V (10^22 cm^3) 1.34 2.5 4.6 5.9 5.8 8.5
KF (1/A°) 0.73 0.9 1.1 1.2 1.2 1.35
EF (eV) 2.1 3.1 4.7 5.5 5.5 7
TF (K) 24400 36400 54500 64000 64000 81600

Only electrons near from

Fermi level are affected by the
temperature.
Electronic contribution in the heat capacity of a metal
C 
e
v

 e
N ,V

T E
ve  ⎤
CT ⎡ Ei (Ei )⎥
2 f
⎢ ⎦ N ,V
⎣ i1

ve  ⎡  
i ⎤
C  T ⎢E2 f i )dN ⎥
(E
⎣ 0 ⎦ N ,V
 e
C 
V ⎛ 3/ 2
2m ⎟
⎞
1/ 2 2
E k T
⎜
2 2
v ⎝h ⎠ F

2 
 Summary
The nearest model describing the thermodynamic properties of
crystals at low temperatures is the one where the energy is
calculated considering the contribution of the lattice vibrations in
the Debye approach and the contribution of the electronic motion
(this is of importance when metals are studied).

Cv .T  .T3
 Summary
Terms that replaced the partition function are:
Density of state (collective motion)
Fermi function (electronic contribution)