Lattice vibration and norm, modes

• 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.
1
• 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 
 
~a0=10 m
-10

~10-6m

h h
p phonon  p photon 
 
2
 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!
3
• 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.

4
 • 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 5
• 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.

6
• The next set of terms in the expansion is identically equal to zero,
– because the function (xi) has its minimum value at (xi)=(xi ) 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
x j

• The second term

• Taking a normal coordinates (

7
• 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 2 
H  0   2 m i    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

8
 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
when introducing q j q j m j

Ajk  force constant matrix A  Ajk

jk
m j mk
Since

2  2   Ajk Akj
 Ajk  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
1
T
T
A
which diagonalizes
 12 0 ... 0 
 2

 0 2 
AT T A T  where
1 T
such that T   
   
 0 9
 3 N 
2
 
T AT
T
 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   A jk qj qk
2 j ,k

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

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

1   T  q T  q   1  2 q q
 st 
2
 j k j j j k k k st 2 
j , k , j , k
A
j ,k
j jk j k

1
 j j
2 2
 st   q
2 j 10
• We now introduce a linear transformation, from the
coordinates i to the so-called normal coordinates (and
3N
 i =   i . j qr .
• Choose the proper transformation
r 1
matrix in such a way that
the new expression for the Hamiltonian does not contain the
cross terms, i.e.
H    21 m(q i2  i2 qi2 )
i

• where 𝜔i (i=1,2,..3N) are the characteristic frequencies of the so-called

quantities 𝛼ij or, in turn by the nature of the potential energy function
normal modes of the system and are determined essentially by the

(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 of11the
• 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 12
 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

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
13
 Then finally the partition function of the whole solid is simply

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

  n11   
=e  N
  e ...  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      3 N 
 1 e   1 e 
14
 The logarithm form of the partition function is

ln Z  N  ln  1  e  1  
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 
0

e   1  ( ) d

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 
 T 
  
  
  k 
  

 v T    v
or
e  

Cv k    2 ( ) d
0 e  
 1 2

Let us take the high temp. limit where 15

 
  
kT

   0
For ω > ωm

e  1     ...


Cv k  ( ) d 3 Nk Dulong
0 and Petit
Cv 3 Nk law
• 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 𝜔i 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 𝜔, the specific heat of the solid is
given by
17
 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.
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 • The mean energy from partition function equation
1 1 
E 3 N  
 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
e kBT

Cv k B
B  e
 
2 2
k T 

1 2 

 
k BT

Let Einstein e T

 Cv k B  

 
2
temperature T  e

T
1
k
19
• 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
2
1
when x  1， 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.

20
 •good news: Einstein model
1.0
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

21
• 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.

22
 Einstein Heat capacity of solids
• Classical theory, the solid is one in which each atom is bound to its side by a
harmonic force. When the solid is heated, the atoms vibrate around their sites like a
set of harmonic oscillators. The average energy for a 1D oscillator is kT. Therefore,
the averaga energy per atom, regarded as a 3D oscillator, is 3kT, and consequently
the energy per mole is

= 3 Nk B T 3RT
• where N is Avagadro’s number, kB is Boltzmann constant and R is the gas constant.
The differentiation wrt temperature gives; C  d 
v
23
dT
 23
Cv 3R 3 6.02 10 (atoms / mole) 1.38 10 ( J / K )
The theory explained by Einstein is the first quantum theory of solids. He made the simplifying
assumption that all 3N vibrational modes of a 3D solid of N atoms had the same frequency, so
2
that the whole solid had a heat capacity 3N times C k    e T
B  
 
v 2
 T  e T  1
In this model, the atoms are treated as independent oscillators, but the energy of the oscillators
are taken quantum mechanically as
This refers to an isolated oscillator, but the atomic oscillators in a solid are not [Link] are
continually exchanging their energy with their surrounding atoms.
Even this crude model gave the correct limit at high temperatures, a heat capacity of

23
Dulong-Petit law where R is universal gas constant.