Lattice Vibrations and Related Phenomena

Nabyendu Das

(for Pre-Doctoral Course on Solid State Physics - 2008)

I. INTRODUCTION

When an object is exposed to some kind of excitations or thermal bath, it reacts according to the collective
dynamics of its various degrees of freedom excited at that energy scale. In the solid state physics, we are familiar
with, has a typical energy scale of few electron volts and the behavior of a piece of solid depends mainly on the
dynamics of ions sitting at lattice points and electrons of their outer most shells.
• Adiabatic Approximation: In this approximation one assumes that the electronic degrees of freedom are much
faster that the ionic motions. Hence both dynamics are decoupled enough to treat them separately. This is a good
approximation when melectron
Mion  1 or ωFD  1which fails when electron lattice coupling is strong (melectron is large)
or in case of low electron density materials like high temperature super conducting materials ( F is low). Now we
will discuss the dynamics of ions sitting in a linear chain with the same approximation.

II. LITTLE ABOUT LATTICE

Lattice is simply a periodic structure. If you put atoms in lattice points it becomes a Crystal. Different Lattice
and Crystals are characterized by the symmetry operations. Different Crystals can be formed on same Lattice. e. g.
take an one dimensional lattice of periodicity “a” (say). Then a monoatomic chain will have same periodicity while
diatomic one will have a periodicity “2a”.
Wheather it is Lattice or Crystal, when a particle moves or a waves propagates through a periodic structure, its
position and momentum is describable up to modulo(lattice spacing) and modulo(2π/lattice spacing) respectively.
→
−
In mathematical notation position → −r and →−r + n R (integer times Lattice Translation Vector ) are indistinguishable.
→
− →
− →
−
Samething happens for momenta → −p and →−p + n G , where G is Reciprocal Vector of R and is defined by the relation
→
− → − →
−
R · G = 2π. It clear that in a lattice environment only meaningful interval in momentum space is (0, G ) or
→
− →
−
(− G /2, G /2) and it defines the first Brillouin zone. Middle points of these intervals are called zone center while the
end points are called zone boundary.

III. PHENOMENOLOGY : LINEAR CHAIN

• Monoatomic Linear Chain

a
(Unit Cell)

Monoatomic Linear Chain and Its Longitudinal Vibration

Consider a Monoatomic Linear Chain with atoms of mass “m” and force constant “K”. Now their classical
equation of motion is given by

d 2 un
m = F orce = −K(2un − un−1 − un+1 ) (3.1)
d2 t
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Where un is the displacement of nth atom. Now assuming a wave solution of the form

un = ũ(k)exp[i(kxn − ωk t)] (3.2)

we get
K
mωk2 = K(2 − exp(−ika) − exp(ika)) = 2K(1 − cos(ka)) =⇒ ωk2 = sin2 (ka/2) (3.3)
m
Thus we have a dispersion relation
r
K
ωk = sin(ka/2) (3.4)
m
Each k defines a mode and ωk is the frequency of that mode. Different modes describes different collective vibrational
states of the solid. In k → 0 limit it gives
r
K
ωk = ka/2 (3.5)
m
this describes a sound propagation with velocity
r
dωk K
vsound = = a/2 (3.6)
dk m
• Diatomic Linear Chain : Zone folding

In diatomic case there are two types of atoms in a unit cell. If one assigns Un and un as the displacements
of two different atoms in a unit cell and “M” and “m” as their masses, one will end up with a relation of the form
M +m K p
ωk2 = K ± (M + m)2 − 4mM sin2 (ka/2) (3.7)
Mm Mm
This relation gives an additional branch i.e. Optic Branch which has non zero frequency at zero momentum. These
modes describes the relative motion between atoms in a given unit cell.
a

Optical Branch
2a
(Doubling of Unit Cell)
(Energy)

Acoustic Branch

zone center zone bounadry

(Momenta)
Di−atomic Linear Chain and Its Longitudinal Vibration Mode Structures in Diatomic Linear Chain

The same dispersion relation can be obtained qualitatively be obtained through zone folding as follows.

• Take a mono atomic linear chain of lattice spacing “a” and obtain the dispersion curve. Plot it over the
Brillouin zone ±1/2a

• In Diatomic case lattice spacing becomes “2a”. Mark ±1/4a as new zone boundary.

• Now add ±1/2a to the wave vector in the region (-1/4a, -1/2a) and (1/4a, 1/2a) respectively and plot
them.
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0 1/4a 0 1/4a
0 1/2a

Schematic Description of Zone Folding

•The result is qualitatively similar to what we have found earlier!

• Generalization to 3D
For N atoms in an unit cell, Total number of branches are 3N. Three of them are acoustic and rest 3N-3 are optic.
Among 3 acoustic branches there is one longitudinal and rest 2 are of transverse type.
Quantization: Phonon
In classical picture each collective mode (momentum k) can be mapped into a single oscillator with frequency ω k .
Quantization of such oscillators will yield an energy spectrum

En,k,s = (n + 1/2)h̄ωk,s (3.8)

Where En,k,s denotes nth eigenstate of a vibrating lattice with k th momenta and s is the band index. Quantum of
these oscillator system can be described as a quasi-particle of well defined momentum (up to reciprocal lattice vector)
and energy and are called Phonon. In harmonic approximation phonons are independent and have infinite life time.
But in practical case they interact because of anharmonicity and their life time becomes finite.
• Continuous Symmetry Breaking and Acoustic mode: In a broken symmetry point of view, formation of a
lattice structure can be seen as a breaking of continuous translation symmetry. Natural consequence of it is occurrence
of a low lying mode and it is nothing but the acoustic mode! In liquid or gas sound propagates. This corresponds to
longitudinal acoustic modes. Transverse sound propagation occurs only in solid.

IV. THERMAL PROPERTIES

• Specific Heat
Einstein Phonons
ch
ran
lB
tica
Op
Doulong − Petit
w 3R
D
(Frequency)
A
co

Debye
us

Einstein
Cv
tic
Br
an
ch

Debye Phonons

(Momenta) q
D T
Einstein and Debye Approximations Typical Sp.Heat vs Temperature Curve

•Dulong and Petit 1819: Atoms in a solid vibrates as independent classical oscillators. Average energy
per atom <  >= 3kB T and cv = 3KB . Molar Specific heat is Cv = 3N KB = 3R.
• Problems:
1) Cv in metallic elements decreases rapidly at low temperature and vanishes at 0K.
2) Diamond has exceptionally low Cv at room temperature
Einstein 1907: Now vibrating atoms (N atoms in one mole) form 3N independent quantum oscillators.
1 1 1 ω0 2 exp(βω0 )
< E >= 3N ω0 (< n > + ) = 3N ω0 ( + ), Cv = 3R( ) (4.1)
2 exp(βω0 ) − 1 2 kB T (exp(βω0 ) − 1)2
In this picture
ω0 2
Cv = 3R f or ω0  T, Cv = 3R( ) exp − (βω0 ) f or ω0  T (4.2)
kB T
Problem again! Predicts rapid decrease than found experimentally.
Debye 1907: Atoms do not vibrate independently. They form a system of coupled oscillators. The frequency
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spectrum contains altogether 3N normal modes. The number of modes are distributed over a large frequency range,
the total number being fixed.

ωD ωD
1
Z Z
< E >= ωdωg(ω)f (ω) ∼ dωω 3 (4.3)
0 0 exp(βω) − 1

In Low temperature (i.e. T  ωD )

∞
1
Z
4
< E >∼ T x2 dx ⇒ Cv ∼ T 3 (4.4)
0 exp(x) − 1

Still !! Einstein model refers to dispersionless optic phonons, the Debye model refers to sound wave like acoustic
mode and its extrapolation up to zone boundary. In real solid both types of modes exists with complicated dispersions.

• Thermal conductivity

P
l v
θ
x x

lcosθ

•Ideal Gas Treatment: Thermal current

π
∂U 2π 1 ∂U 1 ∂T
Z
j =< vx U (x − lcosθ) >θ = − vcosθ lcosθ sinθdθ = lv = lvcv (4.5)
0 ∂x 4π 3 ∂x 3 ∂x

Where l is the mean free path, v is the velocity of a phonon and U is the energy density of the system. Now thermal
conductivity
1 1
κ= lvcv = τ v 2 cv (4.6)
3 3
τ is the lifetime of the phonon. For harmonic phonon it is infinite and hence thermal conductivity. Real solid does not
have infinite thermal conductivity. So one needs to go beyond harmonic approximation and include anharmonicity.
The effects of anharmonicity can be described as the interaction between harmonic phonon.

• Scattering among Harmonic Phonons:

q1 q2 q1
q − q1 q q
q
q2 − q1 − q2
− q2

q1 − q1 q2 q1
q q q q
− q1 − q2
q2 − q2

Three Phonon Interaction

In first row a phonon with momentum q is destroyed, and in second row a phonon with momentum q is created

Normal vs Umclapp : Normal Process : Momentum is conserved i.e. kf inal = kinitial . This processes involve small
momentum exchange between phonons and have dominant contribution at low temperature.
Umclapp Process : Momentum is conserved up to modulo(Reciprocal Vector) i.e. kf inal = kinitial ±integer ×G. This
processes involve large momentum exchange between phonons and have dominant contribution at high temperature
−θ
with a typical factor exp( Debye
T ).
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k k+k’
k
k+k’−G k+k’
G k’
k’

Umclapp Process Normal Process

• Finiteness of Thermal Conductivity

To explain finiteness of thermal conductivity in a real solid, one has to consider anharmonicity, scattering of phonons
with boundary, impurity etc.
• For T  θD , cv is independent of temperature and τ ∼ 1/T , so K ∼ 1/T .
• For T  θD , τ is independent of temperature (mean free path is very large and limited only by the boundary.)
and K ∼ cv ∼ T 3 .
• In the intermediate temperature regime phonon phonon scattering is very important. In normal process momentum
is redistributed and leads to the resoration of equilibrium while in U process momentum is absorbed by the crystal
as a whole and there is a net resistance to the heat flow. Now the resistance ∼ 1/τ U ∼ exp(−θD /T ). In this regime
K ∼ T n exp(θD /T )

1/T
T3

T
Typical Thermal Conductivity Curve

• Melting

In a phenomenological assumption, solid melts when the amplitude of the ionic vibration reaches some criti-
cal fraction of inter-atomic spacing. This is known as Lindemann Criteria. Now mean square displacement of an
atom at lth site is given by
1 X 1 1 T X 1
h|u(l)|2 i = (hnk,s i + ) ∼ 2 (4.7)
MN ωk,s 2 MN ωk,s
k,s k,s

Where M is the mass of the atom. In Debye model,

T 3V 4πq 2 3T V qD 9T V 4π 3 6π 2
Z
2
h|u(l)| i = dq = = with = r s = 3 (4.8)
M N (2π)3 c2 q 2 2π 2 M N c2 M θD N 3 qD

Define
h|u(l)|2 i 9T
ξ= = =⇒ Tm = ξm M (rs θD )2 /9 (4.9)
rs2 (rs θD )2 M
The fact that ξm for most solids lie in the range 0.05 to 0.07, is very interesting. A subtle question is “why such a
small amount of fluctuation is enable to melt a solid?” Answer to this question is that when solid melts into liquid,
near the transition temperature the liquid has sufficient amount of short range correlations such that the potential
energy difference between liquid and solid is very low.
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• Thermal Expansion

From the equations of thermodynamic states the coefficient of thermal expansion α is given by

1 ∂V 1 h ∂P
∂T iV 1 ∂P
α= h iP = − ∂P
= h iV (4.10)
3V ∂T 3V h ∂V iT 3B ∂T
∂P
Where B = −V h ∂V iT is the Bulk Modulus. Now from thermodynamic relations
     
∂F ∂S ∂U
P = − , F = U − T S and T = (4.11)
∂V T ∂T V ∂T V

pressure can be written solely in terms of internal energy as

0
!
T
∂ dT ∂
Z
0
P = − U −T U (T , V )
∂V 0 T 0 ∂T 0
T
Z T 0
∂ X 1 ∂ dT ∂
= − [U eq + ( + n(ωk,s ))h̄ωk,s ] + T (n(ωk,s )h̄ωk,s )
∂V 2 ∂V 0 T 0 ∂T 0
k,s
∂ X1 X ∂
= [U eq + h̄ωk,s ] − n(ωk,s ) ωk,s (4.12)
∂V 2 ∂V
k,s k,s

Where n(ωk,s ) = (exp(βωk,s ) − 1)−1 . Thus

 
1 X ∂ ∂
α=− h̄ ωk,s n(ωk,s ) (4.13)
3B ∂V ∂T
k,s

Recall
X h̄ωk,s ∂
cv = ns (k) (4.14)
V ∂T
k,s

Define
h̄ωk,s ∂ V ∂ωk,s ∂lnωk,s
cvs (k) = ns (k) and γk,s = − =− (4.15)
V ∂T ωk,s ∂V ∂lnV
Grüneisen parameter
P
k,s γk,s cvs (k)
γ= P (4.16)
k,s cvs (k)

γcv
α= (4.17)
3B
Assuming all γk,s are same, an estimate for Grüneisen parameter in Debye model can be made as follows
3
V 4πqD ∂lnωD ∂lnqD
3
= N =⇒ γ ∼ − =− = constant (4.18)
2π 3 ∂lnV ∂lnV
This shows main contribution of temperature variation of α comes from cv . Hence α ∝ cv .

• Sound Propagation in “Phonon Gas”, Second Sound :

In ordinary gas sound propagation means oscillatory disturbance of local density of molecules. This takes place
provided,
1) Collision between molecules conserve number, energy and momentum.
2) The collision rate 1/τ is larger than the frequency of the sound (ω).
In “Phonon Gas” :
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1) Phonon number is not conserved.

2) Momentum is conserved up to modulo(Reciprocal Vector)
Then ?? Different conservation laws are required to maintain local equilibrium. The equilibrium distribution
function for phonon is determined only by temperature (n(ωk,s ) = (exp(βωk,s ) − 1)−1 ) while the same requires both
temperature and density for ideal gas. Hence for sound propagation in phonon gas number conservation is not a
problem.
Absence of strict momentum conservation is a serious problem here. But at low temperature(T  θ Debye ), umclapp
processes are suppressed exponentially and one can assume strict momentum conservation to a good accuracy. Thus
a sound like propagation namely Second Sound, is possible in phonon gas when the frequency of the sound obeys an
window condition
1 1
ω (4.19)
τU τN
Where τN and τU are the collision time for the normal and umclapp processes respectively.
What does oscillate?? :. The second sound can be regarded as an oscillation in the local phonon number. Since
their chief attribute is that they carry energy, this can be regarded as an oscillation in local energy density. Again,
local equilibrium number and local energy density in a phonon system is uniquely determined by the temperature,
second sound can be treated as an wave like oscillation in temperature. Such kind of excitations are observed in solid
He4 and NaF.
Caution!! : To observe this phenomena one needs extremely pure sample and sufficiently low temperature.

V. REFERENCES

1) Solid State Physics - Aschroft/Mermin

2) Structure and Dynamics - Martin T. Dove

3) Intruduction to Solid State Theory - O. Madelung