Beruflich Dokumente
Kultur Dokumente
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
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 )
r
The general form for U harm is:
harm 1
u(R)D (R R0)u (R0)
P
U = 2 RR0 ,
The Adiabatic Approximation
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
( 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
/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
0
W L X W K
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
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
T2
T1
k
0
The Low-Temperature Lattice Specific Heat
(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
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