# Chapter Ten

Systems of interaction of particles

Aman Wassie,
Department of Applied Physics
University of Gondar
Contents

• Thermodynamics of crystal lattice(Solid)
• Lattice vibration and norm, modes
• Phonons
• The Debye model., The Debye temperature.
• Specific heat of the solid in the Debye model.
• Non ideal classical gas
• Calculation of parti. Function for low densities
• Equation of state and virial coefficient
• Vander wals equation
Introduction
• The regular lattice of atoms in
a uniform solid material have
energy associated with the
vibrations of these atoms.
• The vibrations take the form of
collective modes which
propagate through the
material.
• Such propagating lattice
vibrations can be considered to
be sound waves. And their
propagation speed is the speed
of sound in the material.
• The vibrational energies of molecules are quantized and
treated as quantum harmonic oscillators.
• Quantum harmonic oscillators have equally spaced energy
levels with separation ΔE = h.
• So the oscillators can accept or lose energy only in discrete
units of energy h.
• The collective vibrational modes can accept energy only in
discrete amounts, and these quanta of energy have been
labelled "phonons".
• Phonon corresponds to coherent motion of all the atoms in a
solid
– quantized lattice vibrations with typical energy scale of
ℏ? = 0.1??
• Like the photons of electromagnetic energy, they obey Bose-
Einstein statistics.
• The energy of the elastic waves, • The energy of Quanta of
or sound waves, inside a solid electromagnetic radiation
medium can be considered to be
quantized in the form of phonons. photon
• PHONONS
• PHOTONS
• Quanta of lattice vibrations
• Energies of phonons are quantized • Energies of photons are
quantized as well
h s hc
E phonon  E photon 
 
~a0 =10-10m
~10-6m

h
p phonon  p photon 
h
 
Phonon
• Phonons are quantized lattice vibrations
– store and transport thermal energy
– primary energy carriers in insulators and semi-conductors
• Phonons are characterized by their
– Energy, wavelength (wave vector)
– polarization (direction)
– branch (optical/acoustic), acoustic phonons are the primary
thermal energy carriers
• Since the phonons have integral angular momentum, the assembly
of phonons in the solid may again treated as a boson gas.
• Its statistical occupation (Bose-Einstein), quantized (discrete)
energy, and only limited numbers at each energy level
– we can derive the specific heat!
• At finite temperatures, the
atoms in a crystal vibrate. If
the atoms only make small
displacements from their
equilibrium positions,
– the minima of the bond
potentials can be
approximated as parabolas
and
– the forces between the atoms
can be described by linear
springs.
• Any possible motion of a
mass-spring system can
be described in terms of
its normal modes.
• In a normal mode, all of
the atoms move with the
same frequency.
• There are as many normal
modes as there are
degrees of freedom in the
problem.
• To illustrate this point, we
may consider the
Hamiltonian of a classical
solid composed of N atoms
whose positions in space
specified by the coordinates
(x1, x2,.…., x3N).
• In the state of the lowest
energy, the values of these
coordinates may be denoted
by
( xi  xi )
• Denoting the displacements
of ?1ҧ , ?ҧ2 , … , ?ҧ? the atoms
from their equilibrium
positions by the variables

i (i=1,2,…3N),
• The kinetic energy of the
system in the configuration
(xi) is given by
3N 3N
K  21 m xi2  21 mi2
i 1 i 1
• Atoms interact with a potential Φ(r=x) which Φ=
Φ(?1 , ?2 , … , ?? )

• Let’s perform a Taylor series expansion around the equilibrium
positions:

?Φ 1 ?2Φ
Φ = Φ xത i ෍ xi − xത i + ෍ xi − xത i xj − xത j
?xi xi =തxi
2 ?xi ?xj xi =തx
i i i

• The main term in this expansion represents the (minimum) energy of
the solid when all the N atoms are at rest at their mean positions ;

• This energy may be denoted by the symbol 0.
• The next set of terms in the expansion is identically equal to
zero,
– because the function (xi) has its minimum value at (xi)=( x)i and hence
all its derivatives must vanish there.

– The second-order terms of the expansion represent the harmonic
component of the atomic vibrations.
• If we assume that the overall amplitudes of the atomic
vibrations are not very large
 j
 1
xj
• The second term
1 ?2Φ
??,? = ෍ ?? − ?ҧ? ?? − ??ҧ
2 ??? ??? ?? =?ҧ
?,? ?

• Taking a normal coordinates (qi = (xi − xത i ))

?Φ 1
Φ = Φ ?ҧ? +෍ ?? − ?ҧ? + ෍ ??,? ?? ??
??? ?? =?ҧ?
2
? ?,?

• we may retain only the harmonic terms of the expansion and neglect
all the successive ones; we are then working in the so-called
harmonic approximation.
• Note that the inharmonic components are important at phase
transition (from one crystal symmetry to another and solid-
liquid phases)
1  

H

0 
 m
2 i ij
2
 

ij 
i i
,j 

• This equation looks like as the potential energy associated of a
spring with a spring constant, Force constant matrix,

  2 
K   
 x x 
 i j  x x
The harmonic approximation

Consider the interaction potential   (q1 , ..., q3 N )
Let’s perform a Taylor series expansion around the equilibrium positions:

1  2
   st  
1
q j qk   st   Ajk q j qk
2 j ,k q j qk 2 j ,k
when introducing q j  q j m j
Ajk
A jk  force constant matrix Ajk 
m j mk
Since

 2  2 Ajk Akj
 A jk  Akj and Ajk    Akj
q j qk qk q j m j mk mk m j
real and symmetric
We can find an orthogonal matrix T which diagonalizes A
1
T
T

 12 0 ... 0 
 
 0 2 
2
1
such that AT T AT   where
T
T  
 
 0 2
3 N 

 T
T AT  jk
  T jj Ajk Tk k   j  j ,k
j , k 
2

With normal coordinates q j  q T
k
k kj

1
we diagonalize the quadratic form    st  
2 j ,k
Ajk q j qk

From q j  q T
j
j  j j qk    Tk k q k
k

1 1
   st  
2 j , k 
A q q
j k  j  k    st  
2 j , k 
Ajk   T jj q j  Tk k q k
j k

1 1
  st   Ajk T jj q jTk k q k   st    j  jk q j q k
2

2 j , k , j , k 2 j ,k
1
  st   j j
 2 2
q
2 j
• We now introduce a linear transformation, from the
coordinates i to the so-called normal coordinates (qi = (xi −
xത i )) and
3N
 i =   i . j q r .
r 1

• Choose the proper transformation matrix in such a way that the
new expression for the Hamiltonian does not contain the cross
terms, i.e.

H

 1
m
2 
(
q2
i 
22
iq
i)
i
• where ?i (i=1,2,..3N) are the characteristic frequencies of the
so-called normal modes of the system and are determined
essentially by the quantities ?ij or, in turn by the nature of the
potential energy function (xi).
• The expression () suggests that the energy of the solid, over
and above the (minimum) value 0,
– may be considered as arising from a set of 3N one-
dimensional, non interacting, harmonic oscillators,
– whose characteristic frequencies i are determined by the
nature of the interatomic interactions in the system.
• Classically, each of the 3N normal modes of vibration
corresponds to a wave of distortion of the lattice points, i.e a
sound wave.
• Quantum-mechanically, these modes give rise to quanta called
phonons, in very much the same way as the vibrational modes
of the electromagnetic field give rise to photons.
• However, there is one important difference, i.e.
– while the number of normal modes in the case of
electromagnetic field is indefinite,
– the number of normal modes (or the number of phonon
energy levels) in the case of a solid is fixed by the number
of lattice sites in it.
 Taking in to account the quantum approach which a single
harmonic oscillator of quantum number nr is given by
 1
 r =  nr  r .
 2
 where ωr the energy of a particle called phonons and nr is the
total number of phonons with frequency ωr
 we note that the quantum-mechanical eigenvalues of the Hamiltonian ()
Then the total energy is just the sum of all these,

3N
 1
E n1 ...E n 3 N =  0    n r   r .
r 1  2
3N
=  N   n r  r .
r 1 20
1 3N
N   0    r
2 r 1
 This ?? expression gives the energy of the solid at absolute
zero.
 The term Φ is necessarily negative and larger in magnitude
than the total zero-point energy of the oscillators together they
determine the binding energy of the lattice
 Then finally the partition function of the whole solid is simply

Z=  e  E R

n1, n 2
  e    N  n11  n2  2 ... 

n1, n 2
.

N    
=e   e  n11
...  e  n3 N 3 N 
 n1   n3 N 
• We note that each harmonic oscillator term is a geometric series, so
the partition function becomes
 N  1   1 
Z e     ...    
1 e  1 e
1
 3N

• The logarithm form of the partition function is

 1  e 

  1
ln Z   N  ln
n 0
• Clearly the sum depends on the dispersion of the crystal, then by
introducing the phonic density of states ? ? ??. Then convert the
sum into integral and z of the system becomes

ln Z   N  ln  1  e  1  ( ) d 
0

• The relation connecting the frequency and wave number is known as
the dispersion relation.
 The mean energy of the solid can now be studied from that
partition function, i.e


 ln Z
E    N     ( )d
 0
e 1

 Its heat capacity at constant volume the system is then given
by
 E    E  2  E 
Cv        k  
 T  v T      v
or

e 
Cv  k     ( )d
2

0 e 
1 2

Let us take the high temp. limit where 23

  
kT

    0
For ω > ωm

e   1    ...

Cv  k   ( )d  3Nk
0
Dulong and
Petit law
Cv  3Nk
• To proceed further, we must have knowledge of the frequency
spectrum of the solid.
• To acquire this knowledge from first principles is not an easy task.
• Einstein, who was the first to apply quantum concept to the theory
of solids (1907), assumed, for simplicity, that the frequencies ?i are
all equal in value!
• The crystal lattice structure of a solid comprising N atoms can be
treated as an assembly of 3N distinguishable one-dimensional
oscillators which oscillate with the same frequency,
• Denoting this (common) value by ?, the specific heat of the solid is
given by
Einstein Model for Lattice Vibrations in a Solid

• The Einstein Model was the
first quantum theory of lattice
vibrations in solids.
• He made the assumption that
all 3N vibrational modes of a
3D solid of N atoms had the
same frequency, so that the
whole solid had a heat capacity
3N times
• In this model, the atoms are
treated as independent
oscillators, but the energes of
the oscillators are the quantum
mechanical energies.
• The mean energy from partition function equation
1 1 
E  3N   
 2 exp      1 
• Hence the molar specific heat of the solid on the basis of this
simple Einstein model is given by
 E    E     1  E 
C v    
 
 
     
  
 T  v    v  T  kT 2  v

 
2 k BT
e
Cv  k B
 B  e
 
2  2
k T 
kBT
1  
2
eT
Let Einstein  Cv  k B   


 T  e T 1

2
temperature
k
• If the temperature is so high that kT >> ℏω or T >> θ, then θ/T < < 1
?
and Expanding of the exponentials ? ൗ? in the above eq(), taking
1
when x  1， 1  x  x     
2

1 x
• Cv yields again the classical result. Simply for T >> θ
Cv = 3Nk=3R
• However, if the temperature is so low that kT << ℏω or T<< θ or
θ/T >>1, and the exponential factor becomes very large compared to
unity. The specific heat then becomes
2
? −?ൗ?
?? ~3? ?
?
• The Einstein model predicts much too low a heat capacity at
low temperatures!
• Thus the specific heat should approach zero exponentially as T
→0. Experimentally the specific heat approaches zero slowly
than this, indeed
c v ∝ T2
as T → 0
• The reason for this discrepancy is the crude assumption that all
atoms vibrate with the same characteristic frequency.
1.0
•good news: Einstein model
explains decrease of Cv for T->0
CV /3NkB

show
C v  T 3 for T->0
0.0
0 1 2 3

T/TE

• Assumption that all modes have the same frequency

refinement
• However, Einstein’s model ignores the fact that the atomic
vibrations are coupled together: the potential energy of an
atom in the crystal depends on the distance from its neighbors:
• This energy is not a sum of single-particle energies. Thus, the
calculation of the partition function may look rather difficult.
• But a system of N coupled three-dimensional oscillators is
equivalent to a system of 3N independent one-dimensional
oscillators. the price to be paid is that the independent
oscillators are not of the same frequency; the normal modes of
vibration of a solid have a wide range of frequencies.
• These modes are not related to the motion of single atoms, but
to the collective motion of all atoms in the crystal –
vibrational modes or sound waves.
• Debye’s model (1912) starts from the opposite point of
view, treating the solid as a continuum, i.e., the atomic
structure is ignored.
• A continuum has vibrational modes of arbitrary low
frequencies, and at sufficiently low T only these low
frequency modes are excited.
• These low frequency normal modes are simply standing
sound waves.