3a.

Lattice Dynamics

Introduction

Lattice Vibrations of 1D crystals

Monoatomic chain

Diatomic chain

Periodic boundary conditions

Lattice Vibrations of 3D crystals

G. Bracco-Material Science SERP CHEM 1

Lattice Dynamics
In previous lectures we have assumed that the atoms were at rest at their
equilibrium position. This can not be entirely correct

→ Atoms vibrate about their equilibrium position even at absolute zero!

The energy they possess at T=0 is known as zero point energy.

The amplitude of the motion increases as the atoms gain more thermal energy
at higher temperatures.

In this chapter we discuss the nature of atomic motions, referred to as lattice

vibrations.

In crystal dynamics we will use the harmonic approximation → amplitude of

the lattice vibration is small.

At higher temperature some anharmonic effects occur.

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 Lattice Dynamics
• The atomic position is a lattice position only in average

• We exclude diffusion events: the atom vibrates always around the same
lattice point

• Classical mechanics will be initially employed to describe the atomic

motion

• Motion of a system of atoms connected by springs

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Lattice vibrations of 1D crystal

Chain of identical atoms
Atoms interact with a potential V(r), for small vibrational amplitude it can
be expanded in Taylor’s series around the equilibrium position r=a.
Harmonic approximation: retain terms up to the quadratic one.

(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= 
 

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 Monoatomic Chain

• The simplest crystal is the one dimensional chain of identical atoms.

• Chain consists of a very large number of identical atoms with identical
masses.
• Atoms are separated by a distance “a”, the lattice periodicity.
• Atoms move only in a direction parallel to the chain.
• As a further approximation: only nearest neighbours interact (short-range
forces).

a a a a a a

Un-2 Un-1 Un Un+1 Un+2

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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

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 Monoatomic Chain
• All atoms oscillate with a same amplitude A and frequency ω. Then we can try
a solution

un = A exp i ( kxn0 − ωt ) 

= −iω A exp i ( kxn0 − ωt ) 

. dun
un =
dt
d 2 un
u n = 2 = ( i ) ω 2 A exp i ( kxn0 − ωt ) 
.. ..
2
u n = −ω 2un
dt
Undisplaced
xn = na+un
Displaced
x 0
n = na position
position

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Monoatomic Chain
m௡ = α(௡ାଵ -2௡ +௡ିଵ )

mω2‫ ݁ܣ‬௜(௞௫ ೙ ିன௧) = α(‫ ݁ܣ‬௜(௞௫ ೙శభ ିன௧) -2‫ ݁ܣ‬௜(௞௫ ೙ ିன௧) +‫ ݁ܣ‬௜(௞௫ ೙షభ ିன௧)
଴ ଴ ଴ ଴

0௡ = na , 0௡ାଵ = (n + 1)a, 0௡ିଵ = (n − 1)a

Cancel Common terms  ௜(௞୬ୟିன௧)

-mω2 =α( ௜௞ୟ -2+ ି௜௞௔ )

With some algebra

ସα ௞௔
eika + e − ika = 2 cos ka
ω(k)= sin ( ) → dispersion relation ω(k)
(1 − cos x ) = 2 sin 2 
௠ ଶ x

2
ସα
Maximum value ωM=
௠

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 Monoatomic Chain
• Dispersion relation: ω versus k relation
ω
గ గ 
ߨ -
௔
൏λ൑
௔ ߨ

  2
λ൏െ λ൐ (redundant) 
ܽ ܽ
v  ⁄ Phase velocity

k • Function with periodicity 2π/a

-π/a π/a
• The waves with wave numbers k and k+2π/a describe the
same atomic displacement

• Therefore, we can restrict k to within the first BZ [-π/a, π/a]

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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)

• Our wavelike solutions are uncoupled oscillations called normal modes:

each k has a definite ω given by above eqn. and oscillates independently of the
other modes.

• the number of modes is expected to be the same as the number of

equations N.

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 Monoatomic Chain
For a finite chain of N atoms we have to
choose the boundary conditions: 0 1 8
Since the solution is a travelling wave, a
suitable condition is the
periodic boundary condition (PBC)
8
u0(t) = uN(t) 0
N=8

This conditions (generally in 3D) is called

Born–von Karman boundary condition

un = A exp[i(kX n − ωt )], The value of k is discrete

u N = u0 ⇒ exp(ikNa) = 1 with spacing ∆k=2π/Na
m 2π
∴k = , m = 1, 2L N Each k describes a normal
N a mode of the vibration
N N
or m=− + 1,L
2 2

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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.

Velocities of wave (phase velocity, group velocity):

• k ～ 0, Linear dispersion ω = (ωMa/2)k→ phase velocity = group velocity
This is the long wavelength condition for elastic sound wave ω
vp =
k
dω
• k ～ π/a, group velocity ～ 0 → no transmission of energy vg =
dk
Bragg condition: in 1D, waves are reflected back (2θ=180°→θ=90°)
→ 2d sin(θ)=nλ → 2d=n(2π/k) at k= π/a→d=a, therefore at these points
Bragg condition is verified.
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 Monoatomic Chain
If k ∼0 →λ is very long and waves are not sensitive to Continuum
ω
the lattice structure of the crystal → continuum
approximation of the material.
Discrete

ka<<1 → sin(ka)≈ka →ω = (ωMax a/2)k

 k
Sound velocity Vs= (ωMax a/2)= a 0


α ௄௕
Or using macroscopic parameters Vs= ೘⁄ = ,   density Kb=bulk modulus
ೌ ఘ
Remember that in 1D

Longitudinal Waves

Wave polarization

Transverse Waves
in 2D and 3D
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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,…,∞)


 
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 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. ௠

• The detailed form of the dispersion

relation is changed but ω is still
periodic function of k with period 2π/a
• Group velocity vanishes at k=(±)π/a
• There are still N distinct normal modes
• Furthermore the motion at long
wavelengths corresponds to sound waves

number of modulations = number of further

neighbor interactions to be considered
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Lattice with basis: diatomic chain

• Two different types of atoms of masses M1 and M2 are connected by
identical springs of spring constant α;

(n-1) (n) (n) (n+1) (n+1) cells

α α α α
M2 M1 M2 M1 M2 a)

b)

Vn-1 Un Vn Un+1 Vn+1

• This is the simplest possible model of an ionic crystal.

• Since a is the periodicity, the nearest neighbors separations is a/2

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 Diatomic chain
M2 M1 M2 M1 M2

Vn-1 Un Vn Un+1 Vn+1

We will consider only the first neighbour interaction although it is a poor
approximation in ionic crystals because electrostatic interaction is a long range
interaction.

Equation of motion for mass M1 (nth):

mass x acceleration = restoring force

M1
 =   −  +   −  =  +  − 2 

Equation of motion for mass M2 (nth):

M2
 =   −  +   −  =  +  − 2

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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

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 Diatomic chain
Two branches of dispersion
curves: optical & acoustic
a
assume M2 > M1 d

Patterns of vibration:
a

c
similar

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Diatomic chain

In long wavelength region (ka«1); sin(ka/2)≈ ka/2 in ω(k), using a Taylor expansion:

(1 + 2) 12)  22

2 = 1± 1− 22
12 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) 12
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)

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 Diatomic chain

• The other limiting solutions of equation ω2 are for ka= π (k at BZ),

→ sin(ka/2)=1. In this case
(1 + 2) ± (2 − 1)

 2 =
12

2 Optical modes: light atoms in the cell oscillate out

 2 =
1 of phase with other light atoms, heavy atoms are at
rest
Acoustic modes: heavy atoms in the cell
2

 2 = oscillate out of phase with other heavy atoms,
2 light atoms are at rest

• The bandwidth
݉ܽ‫ ݔ‬−
݉݅݊of both modes depends on α: in particular,

decreasing the coupling α the curve for optical mode tends to become flat
(dispersionless modes)

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Monotomic chain →Diatomic chain

2a
a
If M1=M2

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
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 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 total number of k points is N, number of cells, the total Degrees

Of Freedom (DOF) is 2N equal to number of the atoms (this remains
true for complex crystals in higher dimensions)

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Modes for the diatomic chain

• The acoustic branch has this name because it gives rise to long
wavelength vibrations which travel with the speed of sound and ω→0 for
k→0. The 2 atoms generally vibrate with a small phase difference

• 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

Amplitude of vibration is strongly exaggerated!

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 Diatomic chain
to understand the energy difference between acoustic & optical modes
Let’s examine the oscillation pattern for acoustic modes

k→0 (long wave length) shorter wavelength

The phase difference between neighbors is generally small

Instead for optical modes

The difference is always very close to the out of phase

The spring are less compress in acoustic mode → lower energy for acoustic
branches

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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
 = ∑      ′

assuming a sinusoidal solution , ,    #∙% ,  polarization vector

the solutions are similar to 1D case but with 3 different polarizations

1x Longitudinal Waves

Wave polarization
2x Transverse Waves

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Three dimensional vibration
Along a given direction of propagation, there are 1 longitudinal wave and 2
transverse waves, each may have different velocities,

• monoatomic systems have only acoustic branches

Sodium (BCC)
Monoatomic

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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)


1 THz→/  
/ 0.0041356 eV= 4.1356 meV

1 THZ→ (1 1012 Hz)/c =33.3564095 cm-1
Energy difference:
Longitudinal modes usually corresponds to a greater compression of the
springs with respect to transvers ones → higher energy
Longitudinal Waves

Transverse Waves
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Neon (FCC) monoatomic

All modes are acoustic (Monoatomic system)

Transverse mode are degenerate along [001]
and [111]. The maximum frequency is lower
than that of sodium since van der Waals
interaction in neon is weaker than metal
bond in sodium.

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

This is related to the FCC structure: atom A of plane I

interacts with nearest neighbor C atoms in plane II and with
next nearest neighbor B in plane III.

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3D crystal with atom basis

For a 3-dim crystal, if each unit cell has p atoms, the degrees of
freedom (DOF) are 3p for each cell (polarization L, T1 e T2)

3 acoustic branches, 3(p-1) optical branches

• If a crystal has N unit cells, then each branch has

N normal modes (number of k-points for each dispersion curve).

• As a result, the total number of normal modes of the whole

crystal is 3pN (= total DOF of this crystal).

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 3D crystal with atom basis FCC lattice with 2-atom basis (diamond)

∼9Thz cm-1
P=2 atoms (Ga, As),

then there are

3 acoustic branches L, T1 e T2

3 optical branches L, T1 e T2

The covalent bond is stronger than previous bonds

therefore maximum frequency is higher.

Γ Is the center of the first BZ and X, K, W, and L

special points on BZ boundary.

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Diamond FCC lattice with 2-atom basis (diamond)

P=2 atoms (C, C), ∼39Thz

then there are

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!)

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NaCl (Sodium Chloride structure)

The structure corresponds to two

interpenetrating FCC lattices
two atoms in the unit cell
→ p=2 (6 vibrational branches)

The lattice vibration spectrum shows

acoustic (A) and optical (O) modes with
longitudinal (L) and transverse (T)
polarization.

The stronger interaction determines a

maximum frequency higher than the
case of neon and sodium

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α-Al2O3

Conventional Hex.cell Primitive Trigonal cell

Even for the more complex
structure of α-alumina with 10
atoms in the primitive cell
(p=10, 30 vibrational branches),
there are 3 acoustic branches
and 27 optical branches

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 PBC or Born–von Karman boundary condition
The concept of periodic boundary condition can extended to 2D and 3D
A finite 2D area is mapped on a torus
X: u0,n(t) = uM,n (t) M,N integers
N cells

Y: um,0(t) = um,N (t)

In 3D it is not possible to make a

M cells graphical representation
1 8 1 8

Moreover any finite system can be considered as

part of an infinite system
1D: un(t) = un+N(t)
3D: ul,m,n(t) = ul+N1,m,n(t)
ul,m,n(t) = ul,m+N2,n(t)
ul,m,n(t) = ul,m,n+N3(t)

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