Anharmonic Effects

• There are some well-known, observed properties of

solids which are known to be due to the lattice
vibrations, but which
Can’t be accounted for by the
Harmonic Approximation.
• That is, their explanation requires that the interatomic
potential expansion in powers of the displacements must
go beyond the quadratic term in the displacements.
• In the Harmonic Approximation, the interatomic
potential had the form:
• That is, some properties require that the next few
terms in the expansion of the interatomic potential
beyond the quadratic terms must be kept.
• Effects which require going beyond the quadratic
terms in the potential expansion are called
Anharmonic Effects.
+ higher order
terms

• Unfortunately, there is no general theory of

anharmonic effects. The theory techniques for
dealing with these effects are developed case by case,
depending on what property is being discussed.
 Thermal expansion & thermal conductivity
are two is examples of anharmonic effects.
• In the 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 the anharmonic effects phonons collide with
each other and these collisions limit thermal
conductivity which is due to the flow of phonons.
 Phonon-Phonon Scattering
•The coupling of normal modes by the anharmonic
terms in the interatomic forces can be pictured as
collisions between the phonons associated with the
modes. A typical collision process is shown here.

After the collision a newphonon is produced

Phonon1 3 , k3 Conservation of
 ,k Energy:
1 1
3  1  2
Phonon2 Conservation of
2 , k 2 k3  k1  k2 Momentum:
So: k3  k1  k2
3  1  2
 One-Dimensional Example:  
•Phonons with wavenumbers in the 1 Brillouin Zone:
st 
a
k
a
•If k3 lies outside this range, add a suitable multible of
(2/a) to reflect it back into the first Brillouin Zone.
•Then, k3 becomes: This phonon is indistinguishable
n 2
k3   k1  k2 from a phonon of wavevector : k3  k1  k2
a

Phonon3 has k  Phonon3 has k  
a
a
Longitudinal  3 3'  3
Transverse 1 2 1
2 2
a
k k
 0   0 
 
a a a a
Normal process n  0  n  0  Umklapp process
(due to anharmonic effects)
 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.
Heat Transport is an example of thermal conduction.
• Heat Transport 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 can
be modeled be by using 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 P in the z direction is

1 _ dP
flux  l 
3 dz
Constant average
Angular average
speed for molecules
Mean free path
•In the simplest case where P is the number density
of
particles, the transport coefficient obtained from
above equation is the diffusion
1 coefficient
_ :
D  l
3
 1 _ dP
flux  l 
3 dz
•If P is the number density of particles, the transport
coefficient obtained from this equation is the
Diffusion Coefficient: D 
1 _
l
3
•If E is the energy density, then the flux W is the heat
flow per unit area so that 1 _ dE 1 _ dE dT
W  l  l
3 dz 3 dT dz
•(dE/dT) is the specific heat C per unit volume, so that
the
thermal conductivity K has1the form:
_
K  l C
3

E
 Heat Conduction in Phonon Gases
& Classical Gases: Essential differences
Phonon Gas Classical Gas
•No flow of particles
•Speed is approximately constant.
•Average velocity & kinetic energy
•The number & energy densities per particle are greater at hot end,
are greater at the hot end. but number density is greater
•Heat flow is primarily due to at cold end. Energy density is
phonon flow, with phonons uniform due to the uniform
being created at the hot pressure.
•Heat flow is solely by transfer of
end & destroyed at the cold
kinetic energy from one particle to
end. another in collisions which is a minor
effect in phonon case. cold
hot cold
hot
 Temperature dependence of thermal
conductivity K

1 _
K  l C Approximately equal to
Vanishes exponentially at 3 velocity of sound and so
low T’s and tends to temperature independent.
classical value at high T’s
?
•Temperature dependence of phonon mean free length is
determined
by phonon-phonon 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  D the
heat capacity is given by temperature-independent classical result
of C  3Nk B

• 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 T 1

Then the thermal conductivity of

. 1 _
K  l C  T 1
3
• Experimental results do tend towards this behavior at
high temperatures as shown in figure (a).

10

10 0

0 1
T 10-1 T3
10-1

5 10 20 50 100 2 5 10 20 50 100
T (K ) T (K )
(a)Thermal conductivity of a (b)Thermal conductivity of artificial
quartz crystal sapphire rods of different diameters
 Conduction at intermediate temperatures
Referring figure a
• At T<  D; the conductivity rises more steeply with falling
temperature, although the heat capacity is falling in this region. Why?
k  /a
• This is due to the fact that Umklapp3 processes which will only
occur if there are phonons of sufficient energy to create a phonon
with
• So Energy kof
D
phonon must be the Debye energy ( )
The energy of relevant phonons is thus not sharply defined but

their number is expected to vary roughly as
when , e  / bT
D

where b is a number of order unity

 D / bT
2 or 3. Then
le
• This exponential factor dominates any low power of T in thermal
T3
conductivity,
 Conduction at low temperatures
for phonon-phonon collisions becomes very long at low T’s and
eventually exceeds the size of the solid, because
l
number of high energy phonons necessary for Umklapp processes
decay exponentially as

eD / bT
is lthen limited by collisions with the specimen surface, i.e.
l  Specimen diameter 3
T dependence of K comes from Cv T
which obeys law in this
region
3
12 Nk B  T 
4
Cv
CD   
5 
 D Temperature dependence of
dominates.