c
= +
c
x x+dx
A
C = Young modulus
Mass x Acceleration Net Force resulting from stresses
Elastic Waves
Equation of motion
2 2
2 2
u u
C
t x
c c
=
c c
 
2
2
( ) ( ) ( )
u
Adx S x dx S x A
t
c
= +
c
 
( ) ( )
S
S x dx S x dx
x
c
+ =
c
. S Ce =
du
e
dx
=
2
2
.
.
u
S C
x
S u
C
x x
c
=
c
c c
=
c c
2 2
2 2
( )
u u
Adx C Adx
t x
c c
=
c c
Cancelling common terms of Adx;
Which is the wave eqn. with an offered
soln and velocity of sound waves ;
( ) i kx t
u Ae
e
=
k = wave number (2/)
= frequency of the wave
A = wave amplitude
/
s
s
v k
v C
e
=
=
Elastic Waves
s
v k e =
The relation connecting the frequency and wave number is
known as the dispersion relation.
k
Continuum
Discrete
0
* Slope of the curve gives
the velocity of the wave.
At small k (scattering occurs)
At long k 0 (no scattering)
When k increases velocity
decreases. As k increases further,
the scattering becomes greater since
the strength of scattering increases
as the wavelength decreases, and
the velocity decreases even further.
Dispersion Relation
Speed of Sound Wave
The speed with which a longitudinal wave moves through a
liquid of density is
L
C
V v
= =
C = Elastic bulk modulus
= Mass density
The velocity of sound is in general a function of the direction
of propagation in crystalline materials.
Solids will sustain the propagation of transverse waves, which
travel more slowly than longitudinal waves.
The larger the elastic modules and smaller the density, the
more rapidly can sound waves travel.
Speed of sound for some typical solids
Solid
Structure
Type
Nearest
Neighbour
Distance
(A)
Density
(kg/m
3
)
Elastic bulk
modules
Y
(10
10
N/m
2
)
Calculate
d Wave
Speed
(m/s)
Observed
speed of
sound
(m/s)
Sodium B.C.C 3.71 970 0.52 2320 2250
Copper F.C.C 2.55 8966 13.4 3880 3830
Aluminum F.C.C 2.86 2700 7.35 5200 5110
Lead F.C.C 3.49 11340 4.34 1960 1320
Silicon
Diamond
2.35 2330 10.1 6600 9150
Germanium
Diamond
2.44 5360 7.9 3830 5400
NaCl
Rocksalt
2.82 2170 2.5 3400 4730
V
L
values are comparable with direct observations of speed of sound.
Sound speeds are of the order of 5000 m/s in typical metallic, covalent
and ionic solids.
Sound Wave Speed
They can be characterized by
A propagation velocity, v
Wavelength or wavevector
A frequency v or angular frequency =2v
An equation of motion for any displacement can be
produced by means of considering the restoring forces
on displaced atoms.
A lattice vibrational wave in a crystal is a repetitive and
systematic sequence of atomic displacements of
longitudinal,
transverse, or
some combination of the two
As a result we can generate a dispersion relationship
between frequency and wavelength or between angular
frequency and wavevector.
Sound Wave Speed
Lattice vibrations of 1D crystal
Chain of identical atoms
Atoms interact with a potential V(r) which can be written in
Taylors series.
( )
2
2
2
( ) ( ) ...........
2
r a
r a
d V
V r V a
dr
=
 
= + +

\ .
r
R
V(R)
0
r
0
=4
Repulsive
Attractive
min
This equation looks like as the potential energy
associated of a spring with a spring constant :
a r
dr
V d
K
=


.

\

=
2
2
We should relate K with elastic modulus C:
Ka C =
( )
a
a r
C Force
=
) ( a r K Force =
Monoatomic Chain
The simplest crystal is the one dimensional chain of identical atoms.
Chain consists of a very large number of identical atoms with identical
masses.
Atoms are separated by a distance of a.
Atoms move only in a direction parallel to the chain.
Only nearest neighbours interact (shortrange forces).
a a a a a a
U
n2
U
n1
U
n
U
n+1
U
n+2
Start with the simplest case
of monoatomic linear chain
with only nearest neighbour
interaction
) 2 (
1 1
..
+
+ =
n n n
n
u u u K u m
If one expands the energy near the equilibrium point for the n
th
atom and use elastic approximation, Newtons equation becomes
a a
U
n1
U
n
U
n+1
Monoatomic Chain
0 ) 2 (
1 1
..
= +
+ n n n
n
u u u K u m
The force on the n
th
atom;
) (
1 n n
u u K
+
The force to the right;
The force to the left;
) (
1
n n
u u K
The total force = Force to the right Force to the left
Monoatomic Chain
a a
U
n1
U
n
U
n+1
Eqns of motion of all atoms are of this form, only the
value of n varies
All atoms oscillate with a same amplitude A and frequency .
Then we can offer a solution;
( )
.
0
exp
n
n
n
du
u i A i kx t
dt
e e
(
= =
Monoatomic Chain
( )
0
exp
n n
u A i kx t e
(
=
( )
( )
2
..
2
2 0
2
exp
n
n
n
d u
u i A i kx t
dt
e e
(
= =
..
2
n
n
u u e =
na x
n
=
0
n n
u na x + =
Undisplaced
position
Displaced
position
Monoatomic Chain
Equation of motion for n
th
atom
..
1 1
( 2 )
n
n n n
mu K u u u
+
= +
( ) ( ) ( ) ( )
( )
0 0 0 0
1 1
2
e e 2 e e
n n n n
i kx t i kx t i kx t i kx t
m K A A A A
e e e e
e =
+
+
kna
( 1) k n a
( 1) k n a +
kna
( ) ( ) ( ) ( )
( )
2
e e e 2 e e e
ika ika
i kna t i kna t i kna t i kna t
m K A A A A
e e e e
e
= +
Cancel Common terms
( )
2
e 2 e
ika ika
m K e
= +
( ) ( ) ( ) ( )
( )
2
e e 2 e e
i kna t i kna ka t i kna t i kna ka t
m K A A A A
e e e e
e
+
= +
Monoatomic Chain
( )
2
e 2 e
ika ika
m K e
= +
2cos
ix ix
e e x
+ =
e e 2cos
ika ika
ka
+ =
( )
2
2cos 2
2 (1 cos )
m K ka
K ka
e =
=
( )
2
1 cos 2sin
2
x
x
 
=

\ .
2 2
4 sin
2
ka
m K e
 
=

\ .
2
4
2
sin
2
K ka
m
e
 
=

\ .
4
sin
2
K ka
m
e
 
=

\ .
Maximum value of it is 1
max
4K
m
e =
versus k relation;
max
2
/
s
K
m
V k
e
e
=
=
0 / a 2 / a / a
k
Monoatomic Chain
Normal mode frequencies of a 1D chain
The points A, B and C correspond to the same frequency, therefore
they all have the same instantaneous atomic displacements.
The dispersion relation is periodic with a period of 2/a.
k
e
C A B
0
Note that:
In above equation n is cancelled out, this means that the eqn. of motion
of all atoms leads to the same algebraic eqn. This shows that our trial
function U
n
is indeed a solution of the eqn. of motion of nth atom.
We started from the eqn. of motion of N coupled harmonic oscillators. If
one atom starts vibrating it does not continue with constant amplitude, but
transfer energy to the others in a complicated way; the vibrations of
individual atoms are not simple harmonic because of this exchange
energy among them.
Our wavelike solutions on the other hand are uncoupled oscillations
called normal modes; each k has a definite w given by above eqn. and
oscillates independently of the other modes.
So the number of modes is expected to be the same as the number of
equations N. Lets see whether this is the case;
4
sin
2
K ka
m
e =
Monoatomic Chain
p
a
Nk
k p
Na
p Na
t t
2 2
= = = =
Establish which wavenumbers are possible for our one dimensional chain.
Not all values are allowed because nth atom is the same as the (N+n)th as
the chain is joined on itself. This means that the wave eqn. of
must satisfy the periodic boundary condition
which requires that there should be an integral number of wavelengths in
the length of our ring of atoms
Thus, in a range of 2/a of k, there are N allowed values of k.
( )
0
exp
n n
u A i kx t e
(
=
p Na =
n N n
u u
+
=
What is the physical significance of wave numbers
outside the range of ?
2/a
x
Monoatomic Chain
u
n
u
n
x
a
This value of k corresponds to the
maximum frequency; alternate atoms
oscillate in antiphase and the waves at this
value of k are standing waves.
7 2 8
4 7 1.14
7 4 7
4
a
a k
a a a
t t t
= = = = =
7 2 6
3 7 0.85
7 3 7
3
a
a k
a a a
t t t
= = = = =
2
2 ; a k k
a
t t
= = =
White line :
Green line :
k relation
Monoatomic Chain
u
n
x
u
n
a
The points A and C both have same
frequency and same atomic displacements
They are waves moving to the left.
The green line corresponds to the point B
in dispersion diagram.
The point B has the same frequency and
displacement with that of the points A and C
with a difference.
The point B represents a wave moving to
the right since its group velocity (d/dk)>0.
The points A and C are exactly
equivalent; adding any multiple of
2/a to k does not change the
frequency and its group velocity, so
point A has no physical significance.
k=/a has special significance
=90
o
x
2 2 n
n n
n
k
a
t t
t
= =
2 2 sin90
1
a d d a = =
Bragg reflection can be obtained at
k= n/a
2 2
4 sin
2
ka
m K e =
For the whole range of k ()
Monoatomic Chain
u
n
x
u
n
a
/a
k
K V
m
K
s
/
2
e
e
=
=
k
e
C A B
0
k relation (dispertion diagram)
/a 2/a
At the beginning of the chapter,
in the long wavelength limit, the
velocity of sound waves has
been derived as
Using elastic properties, lets see
whether the dispersion relation
leads to the same equation in the
long limit.
1 ka
If is very long; so
sinka ka ~
c Ka
=
2
K
a
m
m
a
=
K
V a
s
k
m
e
= =
2 2
2
4
4
k a
m K e =
c
V
s
=
Since there is only one possible propagation direction
and one polarization direction, the 1D crystal has only
one sound velocity.
In this calculation we only take nearest neighbor
interaction although this is a good approximation for the
inertgas solids, its not a good assumption for many
solids.
If we use a model in which each atom is attached by
springs of different spring constant to neighbors at
different distances many of the features in above
calculation are preserved.
Wave equation solution still satisfies.
The detailed form of the dispersion relation is changed but
is still periodic function of k with period 2/a
Group velocity vanishes at k=()/a
There are still N distinct normal modes
Furthermore the motion at long wavelengths corresponds to
sound waves with a velocity given by (velocity formul)
Monoatomic Chain
Chain of two types of atom
Two different types of atoms of masses M and m are
connected by identical springs of spring constant K;
U
n2
U
n1
U
n
U
n+1
U
n+2
K
K K
K
M M
m
M
m
a)
b)
(n2) (n1) (n) (n+1) (n+2)
a
This is the simplest possible model of an ionic crystal.
Since a is the repeat distance, the nearest neighbors
separations is a/2
We will consider only the first neighbour interaction although it
is a poor approximation in ionic crystals because there is a
long range interaction between the ions.
The model is complicated due to the presence of two different
types of atoms which move in opposite directions.
Our aim is to obtain k relation for diatomic lattice
Chain of two types of atom
Two equations of motion must be written;
One for mass M, and
One for mass m.
Chain of two types of atom
M m M
m M
U
n2
U
n1
U
n
U
n+1
U
n+2
Equation of motion for mass M (n
th
):
mass x acceleration = restoring force
Equation of motion for mass m (n1)
th
:
..
1 1
( ) ( )
n
n n n n
M u K u u K u u
+
=
1 1
( 2 )
n n n
K u u u
+
= +
..
1 1 2
( ) ( )
n
n n n n
mu K u u K u u
=
..
1 2
( 2 )
n
n n n
mu K u u u
= +
1
1
Chain of two types of atom
M m M
m M
U
n2
U
n1
U
n
U
n+1
U
n+2
0
/ 2
n
x na =
( )
0
exp
n n
u A i kx t e
(
=
Offer a solution for the mass M
For the mass m;
: complex number which determines the relative amplitude
and phase of the vibrational wave.
( )
0
exp
n n
u A i kx t o e
(
=
( )
..
2 0
exp
n
n
u A i kx t e e
(
=
1
..
1 1
( 2 )
n
n n n
M u K u u u
+
= +
( ) ( ) 1 1
2 2
2 2 2
2
k n a k n a
kna kna
i t i t
i t i t
MAe K Ae Ae Ae
e e
e e
e o o
+    
   
 
 
\ . \ . \ . \ .
 

= +

\ .
For n
th
atom (M):
2 2 2 2 2
2 2
2
kna kna kna kna
ka ka
i t i t i t i t
i i
MAe K Ae e Ae Ae e
e e e e
e o o
       
   
\ . \ . \ . \ .
 
= +


\ .
Cancel common terms
2
2 1 cos
2
ka
M K e o
 
=

\ .
2cos
ix ix
e e x
+ =
2
2 2
2
ka ka
i i
M K e e e o o
 
= +

\ .
Chain of two types of atom
2
2 2 2 2 2
2 2 2
2
kna kna kna kna
ka ka ka
i t i t i t i t
i i i
mAe e K Ae Ae e Ae e
e e e e
oe o
       
   
\ . \ . \ . \ .
 
= +


\ .
..
1
1 2
( 2 )
n
n n n
mu K u u u
= +
( ) ( ) ( ) 1 1 2
2 2 2
2 2
2
k n a k n a k n a
kna
i t i t i t
i t
A me K Ae Ae Ae
e e e
e
o e o
     
 
  

\ . \ . \ . \ .
 

= +

\ .
Cancel common terms
For the (n1)
th
atom (m)
Chain of two types of atom
2
2 cos
2
ka
m K oe o
 
=

\ .
2cos
ix ix
e e x
+ =
2
2 2
1 2
ka ka
i i
ika
me K e e oe o
 
= +

\ .
2
2 2
2
ka ka
i i
m K e e oe o
 
= +

\ .
Now we have a pair of algebraic equations for and as a
function of k. can be found as
A quadratic equation for
2
can be obtained by cross
multiplication
2
2
2 cos( / 2) 2
2 2 cos( / 2)
K ka K M
K m K ka
e
o
e
= =
=
PHONONS
Quanta of lattice vibrations
Energies of phonons are
quantized
~a
0
=10
10
m
phonon
h
p
=
PHOTONS
Quanta of electromagnetic
radiation
Energies of photons are
quantized as well
photon
hc
E
=
~10
6
m
photon
h
p
=
Energy of harmonic oscillator
Obtained by in a classical way of considering the normal modes
that we have found are independent and harmonic.
e c

.

\

+ =
2
1
n
n
Make a transition to Q.M.
Represents equally spaced
energy levels
e
e
e
e
Energy, E
Energy levels of atoms
vibrating at a single
frequency
It is possible to consider as constructed by adding n excitation
quanta each of energy to the ground state.
n
c
e
e c
2
1
0
=
A transition from a lower energy level to a higher energy level.
e e c

.

\

+

.

\

+ = A
2
1
2
1
1 2
n n
( )
2 1
unity
n n c e c e A = A =
absorption of phonon
The converse transition results an emission of phonon
with an energy .
Phonons are quanta of lattice vibrations with an
angular frequency of .
Phonons are not localized particles.
Its momentum is exact, but position can not be
determined because of the uncertainity princible.
However, a slightly localized wavepacket can be
considered by combining modes of slightly different
and .
e
e
e
Assume waves with a spread of k of ; so this wavepacket will
be localized within 10 unit cells.
a 10
t
This wavepacket will represent a fairly localized phonon moving with
group velocity .
dk
de
Phonons can be treated as localized particles within some limits.
1D crystals
e
k
Multiply by
e
k
Energy of
phonons
Crystal momentum
Phonons are not conserved
They can be created and destroyed during collisions .
Thermal energy and lattice vibrations
Atoms vibrate about their equilibrium position.
They produce vibrational waves.
This motion is increased as the temperature is
raised.
In a solid, the energy associated with this vibration and perhaps also with
the rotation of atoms and molecules is called as thermal energy.
Note: In a gas, the translational motion of atoms and molecules
contribute to this energy.
Therefore, the concept of thermal energy is fundamental to an
understanding many of the basic properties of solids. We would like to
know:
What is the value of this thermal energy?
How much is available to scatter a conduction electron in a metal;
since this scattering gives rise to electrical resistance.
The energy can be used to activate a crystallographic or a
magnetic transition.
How the vibrational energy changes with temperature since this
gives a measure of the heat energy which is necessary to raise the
temperature of the material.
Recall that the specific heat or heat capacity is the thermal energy
which is required to raise the temperature of unit mass or 1gmole
by one Kelvin.
The energy given to lattice vibrations is the dominant
contribution to the heat capacity in most solids. In nonmagnetic
insulators, it is the only contribution.
Other contributions;
In metals from the conduction electrons.
n magnetic materials from magneting ordering.
Atomic vibrations leads to band of normal mode frequencies from zero
up to some maximum value. Calculation of the lattice energy and heat
capacity of a solid therefore falls into two parts:
i) the evaluation of the contribution of a single mode, and
ii) the summation over the frequency distribution of the modes.
Heat capacity from Lattice vibrations
n
n
n
Pc c
=
_
Avarage energy of a harmonic
oscillator and hence of a lattice
mode of angular frequency at
temperature T
Energy of oscillator
1
2
n
n c e
 
= +

\ .
The probability of the oscillator being in this
level as given by the Boltzman factor
exp( / )
n B
k T c
Energy and heat capacity of a harmonic
oscillator, Einstein Model
0
/ 2 3 / 2 5 / 2
/ 2 / 2 /
/ 2 / 1
1
exp[ ( ) ]
2
.....
(1 .....
(1 )
B B B
B B B
B B
n
B
k T k T k T
k T k T k T
k T k T
z n
k T
z e e e
z e e e
z e e
e e e
e e e
e e
e
=
= +
= + + +
= + + +
=
_
0
0
1 1
exp /
2 2
1
exp /
2
B
n
B
n
n n k T
n k T
e e
c
e
=
(
   
+ +
 
(
\ . \ .
=
(
 
+

(
\ .
(*)
According to the Binomial expansion for x1 where
/
B
x k T e =
n
n
n
Pc c
=
_
Eqn (*) can be written
_
/
1
2 1
B
k T
e
e
e
c e = +
'
(ln )
x
x
x x
c
=
c
( )
( )
( )
_
2 2
/ 2
_
2
/
_
/ 2 / 2
_
/ 2
/
2 2
_
2
2 2
/
1
(ln )
ln
1
ln ln 1
ln 1
2
2
4
1
B
B
B B
B
B
B
B B
k T
B
k T
k T k T
B
k T
B
B
k T
B
B B
B
k T
B
z
k T k T z
z T T
e
k T
T e
k T e e
T
k T e
T k T T
k
e
k k T
k T
k T
e
e
e
e e
e
e
e
c
c
c
e
c
e
e
c
c c
= =
c c
  c
=

c
\ .
c
(
=
c
(
 
c c
=
( 
c c
\ .
(
= +
( )
/
/
1
2
1
B
B
k T
k T
e
e
e
e
e
e
(
( = +
(
(
_
/
1
2 1
B
k T
e
e
e
c e = +
=
T
B
k
e
n
e
e
(number of phonons) x (energy of phonon)=(second term in )
_
c
The second term in the mean energy is the contribution of
phonons to the energy.
c
Mean energy of a
harmonic oscillator
as a function of T
low temperature limit
T
e
2
1
T k
B
T k
B
e
1
2
1
_
+ =
T
B
k
e
e
e
e c
e c
2
1
_
=
Zero point energy
Since exponential term
gets bigger
is independent of frequency of
oscillation.
This is the classical limit because the
energy steps are now small compared with
the energy of the harmonic oscillator.
So that is the thermal energy of the
classical 1D harmonic oscillator.
c
..........
! 2
1
2
+ + + =
x
x e
x
T k
e
B
T
B
k
e
e
+ =1
1 1
2
1
_
+
+ =
T k
B
e
e
e c
_
1
2
B
k T c e = +
_
B
k T c ~
c
high temperature limit
T
e
2
1
T k
B
Mean energy of a
harmonic oscillator as
a function of T
B
k T
B
k T e
Heat Capacity C
Heat capacity C can be found by differentiating the average energy of
phonons of
1
2
1
_
+ =
T
B
k
e
e
e
e c
( )
( )
2
2
1
k T
B
k T
B
B
B
v
k
e
k T
d
C
dT
e
e
e
e
e
c
= =
( )
( )
( )
2
2 2
1
k T
B
k T
B
v B
B
e
C k
k T
e
e
e
e
=
k
e
u =
( )
2
2
1
T
T
v B
e
C k
T
e
u
u
u
 
=

\ .
Let
( )
2
2
1
T
T
v B
e
C k
T
e
u
u
u
 
=

\ .
Area=
2
e
T
B
k
B
k
e
Specific heat vanishes
exponentially at low Ts and tends to
classical value at high temperatures.
The features are common to all
quantum systems; the energy tends
to the zeropointenergy at low Ts
and to the classical value of
Boltzmann constant at high Ts.
v
C
v
C
k
e
u = where
Plot of as a function of T
, T K
3R
This range usually includes RT.
From the figure it is seen that C
v
is
equal to 3R at high temperatures
regardless of the substance. This fact
is known as DulongPetit law. This law
states that specific heat of a given
number of atoms of any solid is
independent of temperature and is the
same for all materials!
v
C
Specific heat at constant volume depends on temperature as shown in
figure below. At high temperatures the value of C
v
is close to 3R,
where R is the universal gas constant. Since R is approximately 2
cal/Kmole, at high temperatures C
v
is app. 6 cal/Kmole.
Plot of as a function of T
v
C
Classical theory of
heat capacity of solids
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
=
where N is Avagadros number, k
B
is Boltzmann constant and
R is the gas constant. The differentiation wrt temperature
gives;
3 3
B
Nk T RT =
23 23
3 3 6.02 10 ( / ) 1.38 10 ( / )
v
C R atoms mole J K
= =
24.9 ;1 0.2388 6
( ) ( )
J Cal
Cv J Cal Cv
K mole K mole
= =
v
d
C
dT
c
=
c
Einstein heat capacity of solids
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 that the whole solid
had a heat capacity 3N times
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 isolated.They are continually exchanging their energy with
their surrounding atoms.
Even this crude model gave the correct limit at high temperatures, a
heat capacity of
DulongPetit law where R is universal gas constant.
( )
2
2
1
T
T
v B
e
C k
T
e
u
u
u
 
=

\ .
3 3
B
Nk R =
e
At high temperatures, all crystalline solids have a specific heat of
6 cal/K per mole; they require 6 calories per mole to raise their
temperature 1 K.
This arrangement between observation and classical theory break
down if the temperature is not high.
Observations show that at room temperatures and below the
specific heat of crystalline solids is not a universal constant.
6
cal
Kmol
B
k
e
v
C
T
3
v
C R =
In all of these materials
(Pb,Al, Si,and Diamond)
specific heat approaches
constant value asymptotically
at high Ts. But at low Ts, the
specific heat decreases
towards zero which is in a
complete contradiction with
the above classical result.
The Discrepancy of Einstein model
Einstein model also gave correctly a specific heat tending to
zero at absolute zero, but the temperature dependence near T=0
did not agree with experiment.
Taking into account the actual distribution of vibration
frequencies in a solid this discrepancy can be accounted using
one dimensional model of monoatomic lattice
Density of States
According to Quantum Mechanics if a particle is constrained;
the energy of particle can only have special discrete energy
values.
it cannot increase infinitely from one value to another.
it has to go up in steps.
These steps can be so small depending on the system that the
energy can be considered as continuous.
This is the case of classical mechanics.
But on atomic scale the energy can only jump by a discrete
amount from one value to another.
Definite energy levels
Steps get small
Energy is continuous
In some cases, each particular energy level can be
associated with more than one different state (or
wavefunction )
This energy level is said to be degenerate.
The density of states is the number of discrete states
per unit energy interval, and so that the number of states
between and will be .
( ) c
( )d c c d c c + c
There are two sets of waves for solution;
Running waves
Standing waves
0 2
L
t 2
L
t
4
L
t 4
L
t
6
L
t
k
These allowed k wavenumbers corresponds to the running
waves; all positive and negative values of k are allowed. By
means of periodic boundary condition
2 2 2 Na
L Na p k p k p
p k Na L
t t t
= = = = = =
an integer
Length of
the 1D
chain
Running waves:
These allowed wavenumbers are uniformly distibuted in k at a
density of between k and k+dk. ( )
R
k
running waves ( )
2
R
L
k dk dk
t
=
In some cases it is more suitable to use standing waves,i.e. chain
with fixed ends. Therefore we will have an integral number of half
wavelengths in the chain;
Standing waves:
0
L
t
2
L
t
6
L
t
4
L
t 5
L
t
2 2
;
2 2
n n n
L k k k
L L
t t t
= = = =
3
L
t
7
L
t
k
0
L
t 2
L
t 3
L
t
These are the allowed wavenumbers for standing waves; only
positive values are allowed.
2
k p
L
t
=
for
running waves
k p
L
t
=
for
standing waves
These allowed ks are uniformly distributed between k and k+dk
at a density of
( )
S
L
k dk dk
t
=
( )
2
R
L
k dk dk
t
=
DOS of standing wave
DOS of running wave
( )
S
k
The density of standing wave states is twice that of the running waves.
However in the case of standing waves only positive values are
allowed
Then the total number of states for both running and standing waves
will be the same in a range dk of the magnitude k
The standing waves have the same dispersion relation as running
waves, and for a chain containing N atoms there are exactly N distinct
states with k values in the range 0 to . / a t
modes with frequency from e to e+de corresponds
modes with wavenumber from k to k+dk
The density of states per unit frequency range g(e):
The number of modes with frequencies e and e+de will be
g(e)de.
g(e) can be written in terms of
S
(k) and
R
(k).
dn
dR
Choose standing waves to obtain
( ) g e
Lets remember dispertion relation for 1D monoatomic lattice
2 2
4
sin
2
K ka
m
e =
2 sin
2
K ka
m
e =
dk
de
dk
de
d
dk
e 2
cos
2 2
a K ka
m
= cos
2
K ka
a
m
=
1
cos
2
K ka
a
m
1 1
cos
2
m
ka
a K  

\ .
;
( ) ( )
R
dn k dk g d e e = =
( ) ( )
S
dn k dk g d e e = =
( ) ( )
S
g k e =
( ) ( )
S
g k e =
( ) g
Na
e
t
=
( ) ( )
S
g k e =
( )
1 1
cos / 2
m
a K ka
2
cos 1 sin
2 2
ka ka
   
=
 
\ . \ .
2 2 2
sin cos 1 cos 1 sin x x x x + = =
( ) ( )
S
g k e =
2
1 1 4
4
1 sin
2
m
a K
ka
 

\ .
Multibly and divide
( ) ( )
S
g k e =
2
1 2
4 4
sin
2
a
K K ka
m m
 

\ .
( )
S
L
k dk dk
t
=
Lets remember:
( ) g
L
e
t
=
2 2
max
2 1
a
e e
L Na =
2
max
4K
m
e =
2 2
4
sin
2
K ka
m
e
 
=

\ .
( )
2
g
N
e
t
=
( )
1/ 2
2 2
max
e e
 
= +

\ .
}
( )
1/ 2
2 2
max
2N
e e
t
 
= +

\ .
}
3
3
3
/
0 0
1 1
B
B
kT x
k T
x
k T
d dx
e e
e
e
e
 

\ .
=
} }
Zero point energy=
z
c
2
/ 2 3 3
0
1 1 2
2 1 2
kT
L T
V
d
e v v
e
e e
c e e
t
 
 
= + +
 
\ .
\ .
}
( )
3
2 3 3
/
0
1 2
2
1
z
kT
L T
V
d
v v
e
e
e
c c e
t
 
(
 

= + +
( 

\ .
\ .
}
B
x
k T
e
=
B
k T
x e =
B
k T
d dx e =
( )
4
4
3 3
/ 3
0 0
15
1 1
B
kT x
k T
x
d dx
e e
e
t
e
e
=
} }
( )
4
4
2 3 3 3
1 2
2 15
B
z
L T
k T
V
v v
t
c c
t
 
= + +

\ .
2
4 3
3 3 3
1 2
4
30
v B
L T
d V
C k T
dT v v
c t
 
= = +

\ .
3
2
3 3
2 1 2
15
B
v B
L T
k T d
C V k
dT v v
c
t
 
 
= = +
 
\ .
\ .
at low temperatures
How good is the Debye approximation
at low T?
3
T
3
2
3 3
2 1 2
15
B
v B
L T
k T d
C V k
dT v v
c
t
 
 
= = +
 
\ .
\ .
The lattice heat capacity of solids thus
varies as at low temperatures; this is
referred to as the Debye law.
Figure illustrates the excellent aggrement
of this prediction with experiment for a
nonmagnetic insulator. The heat
capacity vanishes more slowly than the
exponential behaviour of a single
harmonic oscillator because the vibration
spectrum extends down to zero
frequency.
3
T
The Debye interpolation scheme
The calculation of is a very heavy calculation for 3D, so it
must be calculated numerically.
Debye obtained a good approximation to the resulting heat
capacity by neglecting the dispersion of the acoustic waves, i.e.
assuming
for arbitrary wavenumber. In a one dimensional crystal this is
equivalent to taking as given by the broken line of density of
states figure rather than full curve. Debyes approximation gives the
correct answer in either the high and low temperature limits, and the
language associated with it is still widely used today.
( ) g e
s
k e u =
( ) g e
1. Approximate the dispersion relation of any branch by a linear
extrapolation of the small k behaviour:
Einstein
approximation
to the
dispersion
Debye
approximation
to the
dispersion
vk e=
The Debye approximation has two main steps:
2
3
9
( )
D
N
g e e
e
=
2 3 3 3 3
1 2 3 9
( ) 3
2
L T D D
V N N
v v t e e
+ = =
Debye cutoff frequency
2. Ensure the correct number of modes by imposing a cutoff
frequency , above which there are no modes. The cutoff
freqency is chosen to make the total number of lattice modes
correct. Since there are 3N lattice vibration modes in a crystal
having N atoms, we choose so that
0
( ) 3
D
g d N
e
e e =
}
2
2 3 3
1 2
( ) ( )
2
L T
V
g
v v
e
e
t
= +
2
2 3 3
0
1 2
( ) 3
2
D
L T
V
d N
v v
e
e e
t
+ =
}
3
2 3 3
1 2
( ) 3
6
D
L T
V
N
v v
e
t
+ =
D
e
D
e
D
e
2
( ) / g e e
The lattice vibration energy of
becomes
and,
First term is the estimate of the zero point energy, and all T dependence is
in the second term. The heat capacity is obtained by differentiating above eqn
wrt temperature.
/
0
1
( ) ( )
2 1
B
k T
E g d
e
e
e
e e e
= +
}
3 3
2
/ / 3 3
0 0 0
9 1 9
( )
2 1 2 1
D D D
B B
k T k T
D D
N N
E d d d
e e
e e e
e e
e e e
e e e e e
e e
(
= + = +
(
(
} } }
3
/ 3
0
9 9
8 1
D
B
D
k T
D
N d
E N
e
e
e
e e
e
e
= +
}
dE
C
dT
=
( )
/ 2 4
2 3 2
/
0
9
1
D
B
B
k T
D
k T
D B
dE N e
C d
dT k T
e
e
e
e
e
e
e
= =
}
3
/ 3
0
9 9
8 1
D
B
D
k T
D
N d
E N
e
e
e
e e
e
e
= +
}
Lets convert this complicated integral into an expression for
the specific heat changing variables to
and define the Debye temperature
x
D
O
B
x
k T
e
=
D
D
B
k
e
O =
The heat capacity is
d kT
dx
e
=
kT
x e =
( )
4 /
2 4
2 3 2
0
9
1
D
T
x
B B
D
x
D B
k T k T dE N x e
C dx
dT k T
e
e
O
 
 
= =


\ .
\ .
}
( )
3
/
4
2
0
9
1
D
T
x
D B
x
D
T x e
C Nk dx
e
O
 
=

O
\ .
}
The Debye prediction for lattice specific heat
D
D
B
k
e
O = where
3
/
2
0
9 3
D
T
D D B B
D
T
T C Nk x dx Nk
O
 
O ~ =

O
\ .
}
How does limit at high and low temperatures?
High temperature
D
C
D
T O
2 3
1
2! 3!
x
x x
e x = + + + +
( )
( )
4 4 4
2
2 2 2
(1 ) (1 )
1 1
1
x
x
x e x x x x
x
x
x
e
+ +
= = =
+
X is always small
D
T O
( )
3
/
4
2
0
9
1
D
T
x
D D B
x
D
T x e
T C Nk dx
e
O
 
O ~

O
\ .
}
3
4
12
5
B
D
D
Nk T
C
t
 
~

O
\ .
How does limit at high and low temperatures?
Low temperature
4
4 /15 t
D
C
For low temperature the upper limit of the integral is infinite; the
integral is then a known integral of .
We obtain the Debye law in the form
3
T
Lattice heat capacity due to Debye interpolation
scheme
Figure shows the heat capacity
between the two limits of high and low
T as predicted by the Debye
interpolation formula.
3
B
C
Nk T
Because it is exact in both high and low T
limits the Debye formula gives quite a good
representation of the heat capacity of most solids,
even though the actual phonondensity of states
curve may differ appreciably from the Debye
assumption.
Debye frequency and Debye temperature scale with the velocity of sound in
the solid. So solids with low densities and large elastic moduli have high . Values of
for various solids is given in table. Debye energy can be used to estimate
the maximum phonon energy in a solid.
Lattice heat capacity of a solid as
predicted by the Debye interpolation
scheme
( )
3
/
4
2
0
9
1
D
T
x
D B
x
D
T x e
C Nk dx
e
O
 
=

O
\ .
}
/
D
T O
1
1
Solid Ar Na Cs Fe Cu Pb C KCl
93 158 38 457 343 105 2230 235
( )
D
K O
D
O
D
O
D
e
Anharmonic Effects
Any real crystal resists compression to a smaller volume than its equilibrium value
more strongly than expansion due to a larger volume.
This is due to the shape of the interatomic potential curve.
This is a departure from Hookes law, since harmonic application does not produce
this property.
This is an anharmonic effect due to the higher order terms in potential which are
ignored in harmonic approximation.
Thermal expansion is an example to the anharmonic effect.
In harmonic approximation phonons do not interact with each other, in the absence
of boundaries, lattice defects and impurities (which also scatter the phonons), the
thermal conductivity is infinite.
In anharmonic effect phonons collide with each other and these collisions limit
thermal conductivity which is due to the flow of phonons.
( )
2
2
2
( ) ( ) ....................
2
r a
r a
d V
V r V a
dr
=
 
= + +

\ .
Phononphonon collisions
The coupling of normal modes by the unharmonic terms in the
interatomic forces can be pictured as collisions between the phonons
associated with the modes. A typical collision process of
phonon1
phonon2
1 1
, k e
2 2
, k e
3 3
, k e
After collision another phonon is
produced
3 1 2
k k k = +
3 1 2
k k k = +
3 1 2
e e e = +
3 1 2
e e e = +
and
conservation of energy
conservation of momentum
Phonon3 has
k
a
t
; Phonon3 has and Phonon3=Phonon3
k
a
t
1
2
k
c
a
t
0
a
t
3'
Umklapp process
(due to anharmonic effects)
3
1
2
k
c
a
t
0
a
t
Normal process
3
Longitudinal
Transverse
0 n =
0 n =
Phonons are represented by wavenumbers with
k
a a
t t
s s
If lies outside this range add a suitable multible of to bring
it back within the range of . Then, becomes
3
k
3 1 2
2 n
k k k
a
t
= +
where , , and are all in the above range.
2
a
t
3 1 2
k k k = +
k
a a
t t
s s
2
k
3
k
1
k
This phonon is indistinguishable
from a phonon with wavevector
3
k
Thermal conduction by phonons
A flow of heat takes place from a hotter region to a cooler region
when there is a temperature gradient in a solid.
The most important contribution to thermal conduction comes from
the flow of phonons in an electrically insulating solid.
Transport property is an example of thermal conduction.
Transport property is the process in which the flow of some quantity
occurs.
Thermal conductivity is a transport coefficient and it describes the
flow.
The thermal conductivity of a phonon gas in a solid will be
calculated by means of the elementary kinetic theory of the transport
coefficients of gases.
Kinetic theory
In the elementary kinetic theory of gases, the steady state flux of a property
in the z direction is
P
_
1
3
dP
flux l
dz
u =
Mean free path
Angular average
Constant average speed for molecules
In the simplest case where is the number density of particles the transport
coefficient obtained from above eqn. is the diffusion coefficient .
If is the energy density then the flux W is the heat flow per unit area so that
_ _
1 1
3 3
dE dE dT
W l l
dz dT dz
u u = =
Now is the specific heat per unit volume, so that the thermal
conductivity;
_
1
3
K l C u =
P
_
1
3
D lu =
P E
/ dE dT C
Works well for a phonon gas
Heat conduction in a phonon and real gas
The essential differences between the processes of heat
conduction in a phonon and real gas;
Phonon gas Real gas
Speed is approximately constant.
Both the number density and energy
density is greater at the hot end.
Heat flow is primarily due to phonon
flow with phonons being created at the
hot end and destroyed at the cold end
No flow of particles
Average velocity and kinetic energy per
particle are greater at the hot end, but the
number density is greater at the cold end,
and the energy density is uniform due to the
uniform pressure.
Heat flow is solely by transfer of kinetic
energy from one particle to another in
collisions which is a minor effect in phonon
case.
hot
cold
hot
cold
Temperature dependence of thermal conductivity K
_
1
3
K l C u =
Approximately equal to
velocity of sound and so
temperature independent.
Vanishes exponentially at
low Ts and tends to classical
value at high Ts
B
k
?
Temperature dependence of phonon mean free length is determined by
phononphonon collisions at low temperatures
Since the heat flow is associated with a flow of phonons, the most effective
collisions for limiting the flow are those in which the phonon group velocity
is reversed. It is the Umklapp processes that have this property, and these are
important in limiting the thermal conductivity
Conduction at high temperatures
At temperatures much greater then the Debye temperature the heat capacity is
given by temperatureindependent classical result of
The rate of collisions of two phonons phonon density.
If collisions involving larger number of phonons are important, however, then the
scattering rate will increase more rapidly than this with phonon density.
At high temperatures the average phonon density is constant and
the total lattice energy T ; phonon number T , so
Scattering rate T and mean free length
Then the thermal conductivity of .
1
T
D
O
3
B
C Nk =
_
1
3
K l C u =
1
T
3
T
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