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Lattice Vibrations

Chris J. Pickard
500

400

300
(cm )
-1

200

L
100
K W
X

0
W L X W K
The Breakdown of the Static Lattice Model

The free electron model was refined The classical static lattice can only be
by introducing a crystalline external valid for T=0K
potential
It is even wrong for T=0K:
xp h Zero point motion
This allows much progress, but is not
the full story
This is a particular problem for
insulators: unless kB T > Eg there
Ions are not infinitely massive, nor are no degrees of freedom to account
held in place by infinitely strong forces for their many properties
Equilibrium Properties

cv
saturated
the electronic degrees of freedom
alone cannot explain experiment

Density and cohesive energy


zero point motion is important for
cubic (lattice) solid neon and argon, and dominant
for solid helium (a quantum solid )

linear (electronic) Thermal expansion of insulators


T

electronic contribution negligible


Specific heat of a metal: for kbT < Eg
Transport Properties

Conductivity no vibrations, no superconductors


in a perfect metallic crystal there
are no collisions and perfect Thermal conductivity of insulators
conduction
the electronic degrees of freedom
lattice vibrations provide the
are not sufficient
scattering mechanisms

Superconductivity Transmission of sound


interaction between two electrons sound waves are carried by
via lattice vibrations vibrations of the lattice
Interaction with Radiation

Reflectivity of ionic crystals X-ray scattering

Sharp maximum in infrared, far thermal vibrations and zero point


below h = Eg motion diminish the intensity of the
E-field applies opposite forces on peaks
ions there is a background in directions
not satisfying the Bragg condition

Inelastic scattering of light Neutron scattering


small frequency shifts (Brillouin or momentum transfer with the lattice
Raman scattering) is discrete, and provides a probe of
understood via lattice vibrations the lattice vibrations
A Classical Theory of the Harmonic Crystal

A general treatment of the deviation Bravais lattice remains as an average


of ions from their equilibrium positions of the instantaneous configurations
is intractable, so proceed in stages:
1. Treat small deviations classically Denote the position of an atom whose
2. Proceed to a quantum theory mean position is R by r(R):
3. Examine implications of larger r(R) = R + u(R)
movements

To treat the small deviations, we The dynamics of the lattice is


assume each ion stays in the vicinity Pgoverned by the classical Hamiltonian:
P(R)2
of its equilibrium position R, and the R 2M + U
The Harmonic Approximation

U
3D Taylor expand the potential energy
around the equilibrium configuration:
f (r + a) = f (r) + a f (r)+
1 2 3
2 (a ) f (r) + O(a )

At equilibrium the net force is zero,


and the potential energy is given by:
U = U eq + U harm

r
The general form for U harm is:

harm 1
u(R)D (R R0)u (R0)
P
U = 2 RR0 ,
The Adiabatic Approximation

The quantities D in the harmonic configuration the wavefunctions


expansion are in general very difficult change as the ions move
to calculate
Make the adiabatic approximation by
In ionic crystals the difficulties are the separating the typical timescales of
long ranged coulomb interactions the motion of the electrons and ions

In covalent/metallic crystals the the electrons are in their


difficulty comes from the fact that the groundstate for any configuration
contribution to the total energy of the
valence electrons depends on the ionic D is still difficult to calculate
Normal Modes of a 1D Bravais Lattice

K K K K K K K K
Consider ions of mass M separated by
M M M M M M M M M
distance a
Masses M and springs K

For simplicity, assume nearest


neighbour interactions only

u([N+1]a) = u(a) ; u(0) = u(Na)


In the Harmonic approximation, this
is equivalent to masses connected by
springs of strength K:
harm
M u(na) = Uu(na) , U harm =
1 2
P
Born-von Karman BCs 2 K n [u(na) u((n + 1)a)]
Normal Modes of a 1D Bravais Lattice

( k)
Seek solutions of the form:
u(na, t) ei(knat)
2

2 n
The PBCs eikN a = 1 k = a N
with n integer, N solutions and
a k < a

Substitution into
qthe dynamical eqn.
K
gives: (k) = 2 M |sin(ka/2)|

/a 0 /a
k The group and phase velocities differ
substantially at the zone boundaries
Normal Modes of a 1D Bravais Lattice with a Basis

( k)

O
2(K+G)
2K

The analysis can be repeated
2G

The are 2 solutions for each k 2N


A solutions in total:

2 K+G 1
= M M K 2 + G2 + 2KGcos ka

/a 0 /a
k
There are acoustic and optical modes

O
A
Normal Modes of a 3D Bravais Lattice

( k)
The
P dynamical matrix is D(k) =
ikR
R D(R)e , where D(R R0)
is the second derivative of U with
respect to the displacement of ions at
R and R0 at eqbm..
L

T2
The solution of the dynamical
T1 equation is given by the eigen-
equation M 2e = D(k)e, where e
is the polarization vector
k
0
3N solutions for each ion in the basis
Normal Modes of a Real Crystal

500
The dynamical matrix can be built up
from first principles calculations
400

Can use a supercell approach to study


300
certain high symmetry k-vectors
(cm )
-1

200 For arbitary k use linear response


theory a perturbation theory
L
100
K W
X

0
W L X W K

Dispersion curves for Silicon


Connections with the theory of Elasticity

The classical theory of elasticity slowly over the atomic length scale
ignores the microscopic atomic
structure Using the symmetries of D:
Uharm = 14 RR0
P
The continuum theory of elasticity can [u(R0) u(R)]D(R R0)[u(R0) u(R
be derived from the theory of lattice
vibrations Slowly varying displacements
u(R0) =
Consider displacements that vary u(R) + (R0 R) u(r)|r=R

harm 1
P u ( R) u ( R) 1
P
U = 2 R, x x E E = 2 R R D (R)R
A Quantum Theory of the Harmonic Crystal

In a Quantum theory the system can independent oscillators the 3N


be in a set of discrete stationary states classical normal modes

These stationary states are the The energy in each mode is discrete,
eigenstates of the harmonic and the
P (R)2
P total energy is:
harm E = ks(nks + 12 )hs(k)
P
Hamiltonian: H = R 2M +
1 0 0
P
2 RR0 u(R)D(R R )u(R )
The integer nks is the excitation
The result is: an N -ion harmonic number of the normal mode in branch
crystal is equivalent to 3N s at wave vector k
Normal Modes or Phonons

So far we have described the state in Instead of saying that the mode k,s is
terms of the excitation number nks in the nks excited state we say there
are nks phonons of type s with wave
This is clumsy if describing processes vector k
involving the exchange of energy
between normal modes, or other Photons of the correct frequency
systems (electrons, neutrons or X- are visible light
rays) Phonons of the correct frequency
are sound
As for the QM theory of the EM
field we use an equivalent corpuscular Dont forget phonons/normal modes
description are equivalent
Classical Specific Heat: Dulong-Petit

The thermal energy density is given The thermal energy density is:
by averaging over all configurations u = ueq + 3nkB T, (n = N/V )
weighted by eE with = k 1T
B
H
The specific heat is independent of T :
R
de H
u = V1 R deH
1
R cv = 3nkB
= V ln deH
This is not observed experimentally
only approximately at high
By
R making a change of variables: temperature where the harmonic
eq
deH = eU 3N constant approximation is bad anyway
The Quantum Mechanical Lattice Specific Heat

The QM thermal energy density is: The energy density is :


u = V1 i EieEi / i eEi u = V1 ks hs(k)[ns(k) + 12 ]
P P P
1
P E
= V ln i e i

The mean excitation number ns(k) =


The sum is over the stationary states ehs1(k)1 is the Bose-Einstein
with energy: distribution function
i 1
P
Ei = ks(nks + 2 )hs(k),
niks = 0, 1, 2, . . . The specific heat is given by:
hs (k)/2 hs k
e 1
P E P
i e i =
k s 1e h s (k ) c v = V ks T e h s (k) 1
The High-Temperature Lattice Specific Heat

When kB T hs(k) all the normal 1 3N


P
cv = V ks T kB T = V kB
modes are highly excited

Writing hs(k) = x, then x is small The next term is constant in T


and we can expand:
1 1 x x2 3 We might try to correct the Dulong-
x
e 1 = x [1 2 + 12 + O(x )]
Petit law, but anharmonic terms
Keeping just the leading term we are likely to dominate where the
regain the Dulong-Petit law: expansion holds or the crystal melts!
( k)

T2
T1

k
0
The Low-Temperature Lattice Specific Heat

In the limit of a large crystal integrate 1. Ignore the optical modes


over the P1st RBrillouin zone: 2. Use the dispersion relationship:
dk hs (k)
cv = T i 3
(2) e h s (k) 1
s(k) = cs(k)k
3. Integrate over all k
Modes with hs(k) kB T will not
contribute but the acoustic branches
will at long enough wavelengths for Making the substitution hcs(k)k =
any T x we obtain, and c as the average
speed of sound:
Make some approximations:

(kB T )4
cv = T const (hc)3
T3
Intermediate Temperature: The Debye and Einstein
Models

The T 3 relation only remains valid acoustic modes, all with = ck, and
while the thermal energy is small integrate up to kD
compared to the energy of phonons
with a non-linear dispersion (much Einstein: optical modes represented
lower than room temperature) by modes of E

The Debye and Einstein models The Debye temperature divides the
approximate the dispersion relations quantum and classical statistical
regimes:
3
Debye: all branches modelled by 3 kB D = hD = hckD = hc 6 2n
Measuring Phonon Dispersion Relations

Normal mode dispersion relations phonon


s(k) can be extracted from
experiments in which lattice vibrations
The same applies or X-rays or visible
exchange energy with an external
light
probe

Energy lost (or gained) by a neutron Neutrons carry more momentum than
emission (or absorption) of a photons in the energy range of interest
Neutron Scattering by a Crystal

Neutrons only interact strongly with nks = n0ks nks


the atomic nuclei, and so will pass
through a crystal, possibly with a The conservation of crystal
2
changed E = p /2Mn and p momentum:
p0 p = ks hknks + K
P
Conservation laws allow the extraction
of information from the scattering This is the same crystal momentum as
for the Bloch states important for
theories of electron-phonon scattering

The conservation of energy: Different numbers of phonons can be


E 0 = E ks hs(k)nks,
P
involved in a scattering event
Zero Phonon Scattering

The final state is identical to the initial changes by hK: q0 = q + K


state
These are just the von Laue conditions
Energy conservation implies that the
energy of the neutron is unchanged
(elastically scattered): q 0 = q We can extract the same
crystallographic information of the
Crystal momentum conservation static lattice as from X-ray diffraction
implies that the neutrons momentum experiments
One Phonon Scattering

The situation where one phonon is For the absorption case:


absorbed or emitted conveys the most p02 p2 p 0 p
2Mn = 2Mn + hs ( h )
information
In an experiment we control p and E
The conservation laws imply:
E 0 = E hs(k) We can choose a direction in which to
p0 = p hk + hK measure, and record the energy E 0 to
map out the dispersion curves s(k)

The additive K can be ignored Multi-phonon scattering events


because s(k + K) = s(k) produce a background

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