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Lattice Dynamics
Introduction
Lattice Vibrations of 1D crystals
Monoatomic chain
Diatomic chain
Periodic boundary conditions
Lattice Vibrations of 3D crystals
Lattice Dynamics
In previous lectures we have assumed that the atoms were at rest at their
equilibrium position. This can not be entirely correct
The amplitude of the motion increases as the atoms gain more thermal energy
at higher temperatures.
• We exclude diffusion events: the atom vibrates always around the same
lattice point
(r − a )
2
d 2V
V(R) V (r ) = V (a ) + 2 + ...........
2 dr r = a
In equilibrium position first derivative is zero.
Repulsive
This equation looks like as the potential energy
associated of a spring with a spring constant :
0 r0
ଶ
min
Attractive ଶ ୀ
R
r Force=
a a a a a a
Monoatomic Chain
If one expands the energy near the
equilibrium point for the nth atom a a
and use elastic approximation,
Newton’s equation becomes
The force on the nth atom:
• Force to the right Fr = (ାଵ − )
Un-1 Un Un+1
• Force to the left Fl = ( − ିଵ )
• Total force = Fr - Fl
= (ାଵ − 2 + ିଵ )
Eqn’s of motion of all atoms are of this form, only the value of
‘n’ varies
Monoatomic Chain
m = α(ାଵ -2 +ିଵ )
mω2 ݁ܣ(௫ ିன௧) = α( ݁ܣ(௫ శభ ିன௧) -2 ݁ܣ(௫ ିன௧) + ݁ܣ(௫ షభ ିன௧)
-π/a π/a
• The waves with wave numbers k and k+2π/a describe the
same atomic displacement
Monoatomic Chain
Note that:
=
4
sin
2
• In above equation n is cancelled out, this means that the eqn. of motion of all
atoms leads to the same algebraic eqn. This shows that our trial function Un is
indeed a solution of the eqn. of motion of n-th atom.
• We started from the eqn. of motion of N coupled harmonic oscillators (if one
atom starts vibrating it does not continue with constant amplitude, but transfer
energy to the others)
Monoatomic Chain
Displacement of the n-th atom u (t ) = Aei ( kX n −ωt ) , X = na
n n
Pattern of vibration:
• k ~ 0, exp(ikXn) ~ 1.
Every atom move in unison→ Little restoring force.
• k ~ π/a,exp(ikXn) ~ (-1)n.
Adjacent atoms move in opposite directions→ Maximum restoring force.
Longitudinal Waves
Wave polarization
Transverse Waves
in 2D and 3D
G. Bracco-Material Science SERP CHEM 13
Monoatomic Chain
Physical significance of wave numbers outside [-π/a, π/a]?
ଶగ ଼గ
4λ=7a →λ= → =
un ସ /ସ
x
a
ω
ଶగ గ
un 3λ=7a →λ= → =
ଷ /ଷ
x k
-π/a π/a
But and + are not equivalent →
-2 =- is equivalent →same pattern, ω, and velocity
Equivalent vectors + Gn = +n n integer (-∞, …-2,-1,0,1,2,…,∞)
G. Bracco-Material Science SERP CHEM 14
Monoatomic Chain
there is only one possible propagation direction and one polarization
direction → 1D crystal has only one sound velocity.
In this calculation only nearest neighbor interaction although this is a
good approximation for the inert-gas solids, its not a good assumption for
many solids (depends on the range of interactions)
Extending to a model beyond nearest neighbor interaction many of the
features in above calculation are preserved.
ఈ
2
• Wave equation solution still satisfies.
b)
M1
= − + − = + − 2
M2
= − + − = + − 2
Diatomic chain
d 2 un vn-1 un vn un+1
M1 = α (vn + vn −1 − 2un ),
dt 2
d 2v
M 2 2n = α (un +1 + un − 2vn ). a
dt
We need two non trivial independent
u A eikna
Assume n = ik1 ( n +1/2) a e−iωt solutions that are travelling waves
vn A2 e
2α − M 2ω 2 −2α cos(ka / 2) A1
⇒ = 0,
−2α cos(ka / 2) 2α − M 1ω 2 A2
The 2nd grade equation gives
2α − M 2ω 2 −2α cos(ka / 2) two solutions with different
⇒ det = 0. dispersion relations ω(k)
−2α cos(ka / 2) 2α − M 1ω 2
2
1 1 1 1 4sin 2 (ka / 2)
⇒ ω± 2 = α + ±α + − .
M1 M 2 M1 M 2 M 1M 2
Patterns of vibration:
a
c
similar
Diatomic chain
In long wavelength region (ka«1); sin(ka/2)≈ ka/2 in ω(k), using a Taylor expansion:
(1 + 2) 12)
22
2 = 1± 1−
22
12 2 1 + 2 2 2(1 + 2)
Optical modes: Atoms in the cell oscillate out of 2(1 + 2)
phase (for k=0 the center of mass is at rest 2 =
M1un+M2vn=0) 12
Acoustic modes: atoms in the cell oscillate with
22
a small phase difference. 2 =
The sound speed is 2(1 + 2)
ߙ
ܸ௦ = ܽ
2(ܯ1 + ܯ2)
in k
• If M1<M2
Change of Periodicity a →2a
Repeat the dispersion curve
with the new periodicity
• If M1<M2
Opening of gaps
At the BZ boundary
k
G. Bracco-Material Science SERP CHEM 22
Diatomic chain
How many normal modes (k points) in each branch?
un A1eikna −iωt
Imposing PBC on = ik ( n +1/ 2) a e
vn A2 e
u N u0
= ⇒ exp(ikNa) = 1
vN v0
m 2π
∴k = , m = 1, 2L N
N a
N N
or m = − + 1,L Same as before for the lattice with no basis
2 2
• The optical branch is a higher energy vibration and they vibrate generally
in out of phase. If the two vibrating atoms are ions, a dipole is crated during
the vibration that can interact with electromagnetic radiation giving optical
properties to the crystal.
Acoustic mode
Optical mode
The spring are less compress in acoustic mode → lower energy for acoustic
branches
Vibration of a 3D lattice
In 3D the atomic displacement of the atom in a cell (l,m,n→R=la+mb+nc) has
3 components =( , , ) → R+u
The energy of interaction in harmonic approximation between atoms is given
by
మ
V= ∑ ′ where |
ೕ !"
Equation of motion: M
= ∑ ′
1x Longitudinal Waves
Wave polarization
2x Transverse Waves
Sodium (BCC)
Monoatomic
Energy scales:
Wavenumber (cm-1): A wavelength of energy that is also called a reciprocal
centimeter. Wavenumbers are obtained when frequency is expressed in Hertz
and the speed of light is expressed in cm/s (c= 29979245800 cm/s).
Electron Volt (eV): The electron volt is the energy that we would give an
electron (e=1.60217657 10-19 C) if it were accelerated by one volt potential
difference. 1 eV = 1.602 x 10-19 J.
Frequency f and angular frequency ω: the vibrational energy is con h
&
the Planck constant (h= 6.62606957 10-34 Js, = 1.054571726 10-34 Js)
Transverse Waves
G. Bracco-Material Science SERP CHEM 28
Neon (FCC) monoatomic
along [110] the longitudinal mode presents a non monotonic behavior different from a
sinusiodal one: this suggests that at least a next near neighbor interaction is necessary
∼9Thz cm-1
P=2 atoms (Ga, As),
3 acoustic branches L, T1 e T2
3 optical branches L, T1 e T2
3 acoustic branches L, T1 e T2
3 optical branches L, T1 e T2
The covalent bond is even stronger than previous one (the strongest bond!)
α-Al2O3