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
• Like the photons of electromagnetic energy, they obey Bose-
Einstein statistics.
• The energy of the elastic waves, or • The energy of Quanta of
sound waves, inside a solid medium can electromagnetic radiation
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 =
l l
~a0=10-10m
~10-6m

h h
p phonon = p photon =
l l
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 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 (r=x) which )

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

• 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) and
i
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

• Taking a normal coordinates (

• 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
2

ij
i
j
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  1
 =  st  � q j qk =  st  �A%jk q%%
j qk
2 j ,k �
q j� qk 2 j ,k
j = qj mj
when introducing q%
Ajk
Ajk = force constant matrix A%jk =
m j mk
Since

�2  �2  Ajk Akj
= Ajk = Akj and A%jk = = = A%
kj

q j� qk �qk �qj m j mk mk m j
real and symmetric
%
We can find an orthogonal matrix T which diagonalizes A
1 T
=T
�w1
2
0 ... 0 �
� �
�0 w2
2

A%T = T A%T = W
1 T
such that T where W=� �
�M O �
�0 2�
w3 N �

( T A%T
T
) jk
= �T j�j A%j �k �Tk �
j ��
,k
k = w
2
j d j ,k

With normal coordinates q j = �q%T
k
k kj

1
we diagonalize the quadratic form  =  st  � A%jk q%%
j qk
2 j ,k

From q j = �q%T j� j�
j k �= �
q% Tk �
k qk
j� k

1 %��q%% 1
 =  st  � A q
j k j� k �=  st  � A%j�k ��T j�j q j �Tk �
k qk
2 j��
,k 2 j��
,k j k

1 %��T �q T �q =   1 w 2d q q
=  st 
2
� jk jj j kk k
j ��
,k , j ,k
A st � j jk j k
2 j ,k
1
=  st  �j j
2 j
w
2
q
2
•• We now introduce a linear transformation, from the
coordinates i to the so-called normal coordinates (and

3N
 i =  w 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 (
q
2
i w
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 wi 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  wr .
 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  w r .
r =1  2
3N
=  N   ( n r )  w r .
r =1 20
1 3N
N =  0    w 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w1  n2 w 2 ... 

n1, n 2
.

   n1w1   
=e  N
  e ...  e  n3 N w3 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    w1 ...   w3 N 
1 e  1 e 
• The logarithm form of the partition function is

( )

ln Z =  N  ln  1  e  w1
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  w1  (w ) dw )
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 w
E = =  N     w  (w ) dw
 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  w
Cv = k  (   w ) 2
 (w )dw
0 (e  w
1 ) 2

Let us take the high temp. limit where 23
w
 w =
kT

 (w ) = 0
For ω > ωm

e w = 1   w  ...


Cv = k   (w ) dw = 3 Nk
0
Dulong and
Petit law
Cv = 3 Nk
• 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 = 3 N w   
 2 exp (   w )  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
hw

( hw )
2
e kBT

Cv = k B
( kBT ) e
( )
2 hw 2
2 q
kBT
1 �q � e T
Let Einstein hw Cv = k B � � q
q=
( )
2
temperature �T � e T  1
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,<<
2
�1 x x
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
• 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
cv ∝ 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

0.5 •bad news: Experiments
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.

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