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Thermal Properties
Thermal Properties
Thermal Properties
– Thermal Properties
What is a Phonon?
• We’ve seen that the physics of lattice vibrations in a
crystalline solid
Reduces to a CLASSICAL normal mode problem.
The goal of the ENTIRE DISCUSSION so far has been to
find the normal mode vibrational frequencies of
the crystalline solid.
• In the harmonic approximation, this is achieved by first writing
the solid’s vibrational energy as a system of coupled simple
harmonic oscillators & then finding the classical normal mode
frequencies & ion displacements for that system.
• Given the results of the classical normal mode calculation for the
lattice vibrations, in order to treat some properties of the solid,
It is necessary to QUANTIZE
these normal modes.
• These quantized normal modes of vibration are called
PHONONS
• PHONONS are massless quantum mechanical
“particles” which have NO CLASSICAL ANALOGUE.
– They behave like particles in momentum space or k space.
• These quantized normal modes of vibration are called
PHONONS
• PHONONS are massless quantum mechanical
“particles” which have NO CLASSICAL ANALOGUE.
– They behave like particles in momentum space or k space.
• Phonons are one example of many like this in many areas of
physics. Such quantum mechanical particles are often called
“Quasiparticles”
• These quantized normal modes of vibration are called
PHONONS
• PHONONS are massless quantum mechanical
“particles” which have NO CLASSICAL ANALOGUE.
– They behave like particles in momentum space or k space.
• Phonons are one example of many like this in many areas of
physics. Such quantum mechanical particles are often called
“Quasiparticles”
Examples of other Quasiparticles:
Photons: Quantized Normal Modes of electromagnetic waves.
• These quantized normal modes of vibration are called
PHONONS
• PHONONS are massless quantum mechanical
“particles” which have NO CLASSICAL ANALOGUE.
– They behave like particles in momentum space or k space.
• Phonons are one example of many like this in many areas of
physics. Such quantum mechanical particles are often called
“Quasiparticles”
Examples of other Quasiparticles:
Photons: Quantized Normal Modes of electromagnetic waves.
Rotons: Quantized Normal Modes of molecular rotational excitations.
Magnons: Quantized Normal Modes of magnetic excitations in magnetic solids
• These quantized normal modes of vibration are called
PHONONS
• PHONONS are massless quantum mechanical
“particles” which have NO CLASSICAL ANALOGUE.
– They behave like particles in momentum space or k space.
• Phonons are one example of many like this in many areas of
physics. Such quantum mechanical particles are often called
“Quasiparticles”
Examples of other Quasiparticles:
Photons: Quantized Normal Modes of electromagnetic waves.
Rotons: Quantized Normal Modes of molecular rotational excitations.
Magnons: Quantized Normal Modes of magnetic excitations in magnetic solids
Excitons: Quantized Normal Modes of electron-hole pairs
Polaritons: Quantized Normal Modes of electric polarization excitations in solids
+ Many Others!!!
• These quantized normal modes of vibration are called
PHONONS
• PHONONS are massless quantum mechanical
“particles” which have NO CLASSICAL ANALOGUE.
– They behave like particles in momentum space or k space.
• Phonons are one example of many like this in many areas of
physics. Such quantum mechanical particles are often called
“Quasiparticles”
Examples of other Quasiparticles:
Photons: Quantized Normal Modes of electromagnetic waves.
Rotons: Quantized Normal Modes of molecular rotational excitations.
Magnons: Quantized Normal Modes of magnetic excitations in magnetic solids
Excitons: Quantized Normal Modes of electron-hole pairs
Polaritons: Quantized Normal Modes of electric polarization excitations in solids
+ Many Others!!!
Comparison of Phonons & Photons
PHONONS PHOTONS
• Quantized normal modes • Quantized normal modes
of lattice vibrations. The of electromagnetic waves.
energies & momenta of The energies & momenta
phonons are quantized of photons are quantized
h s hc
E phonon E photon
h h
p phonon p photon
Phonon Wavelength: Photon Wavelength:
(visible)
λphonon ≈ a ≈ 10-10 m λphoton ≈ 10-6 m >> a
Quantum Mechanical Simple Harmonic Oscillator
• Quantum mechanical results for a simple
harmonic oscillator with classical frequency ω:
The energy is quantized.
1 n = 0,1,2,3,..
Enn n
2
E
The energy
levels are
equally spaced!
Often, we consider En as being constructed by adding n
excitation quanta of energy to the ground state.
1 Oscillator Ground State
E00 =
2 (or “zero point”) Energy.
If the system makes a transition from a lower energy level
to a higher energy level, it is always true that the change in
energy is an integer multiple of
Phonon Absorption ΔE = (n – n΄)
or Emission n & n ΄ = integers
In complicated processes, such as phonons interacting with
electrons or photons, it is known that
The number of phonons is NOT conserved.
That is, phonons can be created & destroyed during such
Thermal Energy & Lattice Vibrations
As was already discussed in detail, the atoms in a
crystal vibrate about their equilibrium positions.
This motion produces vibrational waves.
The amplitude of this vibrational motion
increases as the temperature increases.
21
Einstein Model of a Vibrating Solid
In 1907, Einstein extended Planck’s ideas to matter:
he proposed that the energy values of atoms are
quantized and proposed the following simple model
of a vibrating solid:Each atom is independent
Each vibrates in 3-dimensions
Each vibrational normal mode
has energy:
En n , n 0,1, 2,...
hf
22
In effect, Einstein modeled one mole of a solid
as an assembly of 3NA distinguishable
oscillators. He used the Canonical Ensemble
to calculate the average energy of an oscillator
in this model.
E En f B ( En )
n 0
A En e En / kT
n 0
23
To compute the average, note that it can be
written as 1 dZ
E
Z d
Z has the form:
Z f B (n ) e n
n 0 n 0
Here, [1/(kT)]
Z is called
The Partition Function
24
With [1/(kT)] and En = n, , the partition
function Z for the Einstein Model is
1
Z e n
n 0 1 e
This follows from the
geometric series result
1
S x n
, | x | 1
n 0 1 x
25
1 dZ
E Z e n (1 e ) 1
Z d n 0
27
The Einstein Model of a Vibrating Solid
Einstein, Annalen der Physik 22 (4), 180 (1907)
CV for Diamond
28
Thermal Energy & Heat Capacity:
The Einstein Model: Another Derivation
•The following assumes that you know enough
statistical physics to have seen the Cannonical
Ensemble & the Boltzmann Distribution!
•The Quantized Energy of a Single Oscillator has
the form:
Finally, the _
1
/ k BT
result is: 2 e 1
_
1 (1)
/ k B T
2 e 1
•This is the Mean Phonon Energy. The first term in
(1) is called the Zero-Point Energy. As mentioned
before, even at 0ºK the atoms vibrate in the crystal &
have a zero-point energy. This is the minimum energy
of the system.
•The thermal average number of phonons n(ω) at
Temperature T is given by The Bose-Einstein
Distribution, & the denominator of the second
term in (1) is often written:
1
n( )
e k BT
1
_
1 n( )
1
/ k B T (1) (2)
2 e 1 e k BT
1
•By using (2) in (1), (1) can be rewritten:
<> = ћω[n() + ½]
•In this form, the mean energy <> looks analogous to a
quantum mechanical energy level for a simple harmonic
oscillator. That is, it looks similar to:
2
e k BT
e k BT
kBT Cv k B
2
d
Cv k BT
2 2
1
2
dT
e
k BT
1 e k BT
2
e T
Cv k B
Let
T 2
k e T
1
Einstein Heat Capacity CV
2
eT The specific heat CV in this
Cv k B
approximation vanishes
2
T e T 1
exponentially at low T &
tends to the classical value
where
k at high T. These features
Cv are common to all
kB quantum systems; the
energy tends to the zero-
Area =
2 point-energy at low T & to
T
the classical value at high T.
kB
•The specific heat at constant volume Cv depends
qualitatively on temperature T as shown in the
figure below. For high temperatures, Cv (per mole) is
close to 3R (R = universal gas constant. R 2 cal/K- mole).
So, at high temperatures Cv 6 cal/K-mole
3R The figure shows that
Cv = 3R
Cv
at high temperatures for all
T,K
substances. This is the classical
Dulong-Petit law.
This states that specific heat of a
given number of atoms of any solid
is independent of temperature & is
the same for all materials!
Einstein Model for Lattice Vibrations in a Solid
Cv vs T for Diamond
Einstein, Annalen der Physik 22 (4), 180 (1907)
Points:
Experiment
Curve:
Einstein
Model
Prediction
Einstein Model of Heat Capacity of Solids
• 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
2
eT 3 Nk B 3R
Cv k B
2
T e T 1
L
S (k )dk dk DOS of standing wave
L
R k dk dk DOS of running wave
2
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 .
The density of states per unit frequency range g():
4K 2 ka K ka
2
sin 2 sin
m 2 m 2
d 2a K ka 1
cos g ( ) S (k )
dk 2 m 2 K ka
a cos
m 2
1 m 1
g ( ) S ( k )
a K cos ka / 2
sin 2 x cos 2 x 1 cos x 1 sin 2 x ka 2 ka
cos 1 sin
2 2
1 m 1 4 Multibly and divide
g ( ) S (k )
a K ka 4
1 sin 2
2
Let’s remember:
1 2 L
g ( ) S (k ) S (k )dk dk
a 4K 4K 2 ka
sin
m m 2 L Na
4K 2 ka
g ( )
L2 1
2
sin
a max m 2
2
2 4K
True density of states max
2
m
g ( )
2N 2
g ( )
max
2 1/ 2
K
True DOS(density of states) tends to infinity at max 2 ,
m
since the group velocity d / dk goes to zero at this value of .
Constant density of states can be obtained by ignoring the
dispersion of sound at wavelengths comparable to atomic spacing.
The energy of lattice vibrations will then be found by
integrating the energy of single oscillator over the distribution
of vibration frequencies. Thus
1
/ kT g d
0
2 e 1
2N 2
Mean energy of a harmonic
max for 1D
2 1/ 2
oscillator
y ky
+ - L
L
L
- +
+ -
0 x kx
L
U U 0 sin k x x sin k y y
L
1
L / 4 k 2 dk
8
kz V 1
s k d k 3 4 k 2 dk
3
8
2
Vk
s k d 3k 2 dk
dk
2
k ky Vk 2
S k 2
2
kx
Vk 2
• k 2 is a new density of states defined as the number
2
of states per unit magnitude of in 3D.This eqn can be obtained
expression of g .
High and Low Temperature Limits
Each of the 3N
lattice modes of a d
3Nk BT crystal containing N C C 3 Nk B
dT
atoms
T
=
kB
This result is true only if at low T’s only lattice modes
having low frequencies can be excited from their ground
states;
Low frequency long
sound waves
vs k vs
k
k
0
a
k 1 dk 1 Vk 2 dk
vs and g 2
k vs d vs 2 d
2
V 2
vs 1
g at low T
2 2 vs
vs depends on the direction and there are two transverse, one
longitudinal acoustic branch:
V2 1 V2 1 2
g g 2 3
3
2 vs
2 3
2 vL vT
1 V 2 1 2
/ kT 2 3 3 d x
0
2 e 1 2 vL vT
k BT
V 1 2
3
z 2 3 3 / kT d k BT
2 vL vT 0 e
1 x
3
k BT 3 k BT
x kT d dx
V 1 2 k T
4 3
d x
4
z 2 3 3 B 3
2 vL vT 15 0
e / kT
1 0
e 1
B
dx
k BT
4
3
x3
0 e / kT 1 d 3 0 e x 1dx
4 15
3
d 2 1 2 k BT
Cv V kB 3 3
2
at low temperatures
dT 15 v
L vT
Debye Model of Heat Capacity of Solids
How good is the Debye approximation at low T?
3
d 2 1 2 k BT
Cv V kB 3 3
2
dT 15 v
L vT
s k
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.
Debye’s 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 ( )
The Debye approximation has two main steps:
1. Approximate the dispersion relation of any branch by
a linear extrapolation of the small k behaviour:
Debye
Einstein approximatio
approximation n to the
to the dispersion
dispersion vk
Debye cut-off frequency D
2. E nsure the correct number of modes by imposing a cut-off
frequency , above
which there are no modes. The cut-off
D
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 D
D V2 1 2
g ( ) ( 3 3) V 1 2 D 2
2 2 vL3 vT3 0
g ( )d 3 N 2 vL vT
2 ( ) d 3N
0
V 1 2 V 1 2 3N 9N
( )D3 3 N ( ) 3
6 2 3
vL vT 3
2 2 vL3 vT3 D3 D3
9N 2
g ( ) g ( ) / 2
D
3
1
The lattice vibration energy of E ( / kBT )g ( )d
0
2 e 1
9N
D
1 9 N D
3 D
3
becomes E 3 0 ( 2 e / kBT 1) d D3 0 2 d 0 e / kBT 1d
2
D
D
and, 9 9N 3 d
E N D 3
8 D
0
e / k B T 1
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.
dE
The heat capacity is C
dT
D
9 9N
D
d 3
dE 9 N 2 4 e / kBT
E N D 3 CD 3 d
dT D
2 2
8 D 0
e / k B T 1 0
k BT e / kBT 1
4 D / T
dE 9 N k BT k BT 2
x 4e x
CD 3 2 dx
dT D k BT e 1
x 2
0
3 /T
T D
x 4e x
CD 9 Nk B dx
D e 1
x 2
0
where D
D
kB
How does CD limit at high and low temperatures?
High temperature
T D
x2 x3
x is always small e 1 x
x
2! 3!
x 4e x x 4 (1 x ) x 4 (1 x )
x 2
e 1
2 2 2
x
1 x 1 x
3 /T
T D
D CD 9 Nk B
T
D
0
x 2 dx 3Nk B
How does CD limit at high and low temperatures?
Low temperature T D
For low temperature the upper limit of the integral is infinite; the
integral is then a known integral of .
4 4 /15
3 /T
T D
x 4e x
T <T< D CD 9 Nk B dx
e 1
2
D 0
x