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Physical Chemistry III: Statistical-thermodynamic
Statistical thermodynamic 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
25-11-2002
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Structured Solids (The 14 Bravais lattices)
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Law of Dulong and Petit 1
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
E
K
= 3/2 N k T
- Elastic potential energy. Since the kinetic energy convert
to potential energy and vice versa, the average values are
equal E
pot
= 3 N (½ K x
2
) = 3 N x (½ k T)
The stored molar energy is then:
E = E
K
+ E
pot
= 3 N
A
k T = 3 R T  C = dE/dT = 3 R

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Law of Dulong and Petit 2
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
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Einstein Model approximation
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


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Einstein Model molecular processing
System of 1-Dim Harmonic Oscillator

Quantized expression of the energy:
c
v
= hu (v+1/2) v = 0, 1, 2, ...
Partition function (without attributing 0 to the ground state)
q = E e
-(hu(v+1/2)/kT)
= e
-(hu/2kT)
E e
-(hu/kT)

v

Considering the vibrational temperature u = u
E
= hu/k


The molecular internal energy
U
molecular
= - d[Ln(q)] / d| ]
N, V
= k T
2
d[Ln(q)] / dT ]
N, V

q =
e
-u/2T
1- e
-u/T
U
molecular
= k u
(1/2 + )
1
e
u
/T
-
1
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System of N 3-Dim Harmonic Oscillators

Q = q
3N
 U = 3N U
molecular

Einstein Model energy of the system
0.0 0.5 1.0 1.5 2.0 2.5
2000
4000
6000
8000
10000
12000
14000
16000
18000
20000
3/2 Nhu + 3 NkT
3/2 Nhu
I
n
t
e
r
n
a
l

e
n
e
r
g
y
kT/hu
U
= 3 N k u(1/2 + )
1
e
u
/T
-
1
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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
U
= 3 N k u(1/2 + )
1
e
u
/T
-
1
C = 3 Nk (u/T)
2
––––––
e
u/T
(
e
– 1)
2
u/T
0.0 0.5 1.0 1.5 2.0 2.5
0.0
0.2
0.4
0.6
0.8
1.0
3Nk
H
e
a
t

c
a
p
a
c
i
t
y
T/u
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Einstein Model comparison with experiment
Comparison of the observed molar
heat capacity of diamond (+) with
Einstein’s model. (After Einstein’s
original paper-1907)
The value of u
E
= 1325 K was
given to produce an agreement with
the experiment at 331,1 K.
u
E
or e
E
= ku
E
/÷ is the parameter
that distinguishes different
substances:
e
E
~ A (a E/m)
1/2

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 u
E
calculated from the
elastic properties
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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 T
3

Reason is that the Einstein model does not consider the
collective motion and only consider one vibrational frequency.
Einstein Model results and limitation
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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 u
i
=e
i
/2t

THE LATTICE VIBRATIONS OF THE CRYSTAL ARE
EQUIVELENT TO 3N INDEPENDENT OSCILLATORS

E = E hu
i
(1/2 + (e
(hu
i
/kt)
-1)
-1
)
3N
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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 V
2
|(r) + k
2
|(r) = 0
where: k is the magnitude of the wave vector k = 2t/ì


Wave phase velocity v = ì u =ì e/2t = e/k

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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
u
n1 n2 n3
(r) = A sin(n
1
t x / L) sin(n
2
t y / L) sin(n
3
t z / L)

The wave vector in the Cartesian coordinates is k(tn
1
/L, tn
2
/L, tn
3
/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 t/L and the
volume of V
u
= (t/L)
3
.

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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) (4tk
2
) dk /(t/L)
3
= Vk
2
dk/(2t
2
)

In term of circular frequency:
f(k) dk = f(e) de
= (Vk
2
/2t
2
) (dk/de) de
= V e
2
de /(2 v
2
v
g
t
2
)

Where v
g
= de/dk
is the group velocity
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Propagation of sound wave in solids
Density of states
In a non dispersing medium v
g
= v

f(k) dk = f(e) de = V e
2
de /(2 v
3
t
2
)

The wave vector has three independent modes:
1 longitudinal and 2 transversal modes

f(e) de = V e
2
de /(2 t
2
) (1/v
L
3
+ 2/v
T
3
)
In an isotropic Medium v
L
= v
T
=v
m

f(e) de = 3V e
2
de /(2 v
m
3
t
2
)

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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
e
D

f(e) de = 3N
 f(e) de = 9Ne
2
de/e
D
3

Now the sum can be replaced with an integral

E
3N
..... = ƒ
e
D

.....f(e) de
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Debye Model The energy of the crystal
E = E c
i
3N
1
= E [(1/2)ħe
i
+ ÷÷÷ ]
3N
1
ħe
i
ħe
i
kT
e -1
= ƒ [(1/2)ħe + ÷÷÷ ] f(e) de
ħe

e -1
ħe

kT
0
e
D
= ÷ Nku
D
+ ÷ NkT ƒ ÷÷ dx

Where u
D
=ħe
D
/k x
D
= ħe
D
/kT x = ħe/kT
9
8
9
x
D
3
e -1
x
3
x
0
x
D
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Debye Model The heat capacity of the crystal
T0
X·
t
4
/15
E = 9Nħe
D
/8
Vibrational zero-point energy

 C
v
= dE/dT]
v
= 0
x
D
3
/3
E = 9Nke
D
/8 + 3NkT

 C
v
= 3Nk
T·
X 0
dx
e
x
NkT
x
Nk E
D
x
x
D
D
}
÷
+ =
0
3
3
1
9
8
9
u
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Debye Model The heat capacity at low temperature
C
v
=dE/dT)
v
T enters this expression only in
the exponential term (|)
Cv= 3Nk {÷ ƒ ÷÷÷ dx }
3
x
D
3
x
4
e
x
(e
x
-1)
2
0
x
D
When T<<u
D
ƒ ÷÷÷ dx = 4t
4
/15
x
4
e
x
(e
x
-1)
2
0
x
D
 C
V
= ÷t
4
N k ÷
12
5
T
u
D
3
ref5
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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)
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Einstein-Deby Models
Lattice structure of Al
Cubic Closest Packing
The lattice parameter a = 0,25 nm
The density µ=2,7 g/cm
3
The wave velocity v =3,4 km/s
O
elst

O
E
/ O
elst
= 0,79

O
D
/ O
elst
= 0,95
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Periodic Table
23
Cubic close packed, (a) Hexagonal close
packed (a, c)
Body centered cubic
(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)
Lattice parameter
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Deby Temperature
C
V
= ÷ t
4
N k ÷

12
5
T
u
D
3
E = ÷ Nku
D
+ ÷ NkT ƒ ÷÷ dx

Where u
D
=ħe
D
/k x
D
= ħe
D
/kT x = ħe/kT
9
8
9
x
D
3
e -1
x
3
x
0
x
D
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The limit of the Debye Model
 The electronic contribution to the heat capacity was not considered
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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“

Electrons build up a Fermi sea, and the surface of this sea is the
Fermi Level. Surface fluctuations (ripples) of this sea are induced
by the electric and the thermal effects.

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

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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.








0 200 400 600 800 1000
0.0
0.5
1.0
E-E
F
< 0
E-E
F
> 0
f
(
E
)
Temperature
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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 K
F
The total number of electron in this outer orbital is:

Because electrons can
Adopt 2 spin orientations
} }
= =
F
K
T
dk k
L
dk k f N
0
2
3
2
3
2 ) ( 2
t
k
F
T
V
N
3
2
3t
=
3 2
3
3t
V
N
k
T
F
=
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Electronic contribution to the
internal energy
The wavefunction of free electron is:



Its substitution in the Schrödinger equation:

) . (
) , (
t kx i
Ae t x
e +
= +
2
2 2
2
) , (
2
) , ( ) , (
x
t x
m
t x t x E
c
+ c
÷ = + V = +

2
2
2
k
m
E

=

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Electronic contribution to the
internal energy
| |
3
2
2
2
3
2
2
2
3
2 2
t
(
¸
(

¸

= =
V
N
m m
T
F F
k E
 
Fermi Energy
Fermi Temperature
k
E
F
F
T
=
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Temperature effect on 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.
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Electronic contribution in the heat capacity of a metal
| |
T k E
m V
C
dN E f E
T
C
E f E
T
C
E
T
C
F
e
v
V N
i i
e
v
V N
i
i i
e
v
V N
e e
v
2 2 / 1
2 / 3
2 2
,
0
,
1
,
2
2
) ( 2
) ( 2
|
.
|

\
|
=
(
¸
(

¸

c
c
=
(
¸
(

¸

c
c
=
c
c
=
}
¿
·
·
=

t
Ref 3
33
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).
T T C
v
. .
3
¸ o + =
34
Summary
Terms that replaced the partition function are:
Density of state (collective motion)
Fermi function (electronic contribution)
35
References
1 http://hyperphysics.phy-astr.gsu.edu/hbase/thermo/
2 http://www.plmsc.psu.edu/~www/matsc597c-1997/systems/
3 http://web.mit.edu/5.62/www/notes/25.pdf
4 http://www.cartage.org.lb/en/themes/Sciences/Physics/
SolidStatePhysics/Electrons/ElectronicHeat/ElectronicHeat.htm

5 Statistical Physics, F. Mandl
6 Thermodynamique statistique à partir de problèmes et de résumé de
cours C. Chahine, P. Devaux
7 An introduction to statistical thermodynamics, T. L. Hill
8 Statistical mechanics, J. E. Mayer, M. G. Mayer