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Lattice dynamics

So far we have assumed the atoms to be stationary. In reality this is never he case as even
at zero temperature the atoms undergo zero point motion in accordance with Heisenberg’s
Uncertainty Principle. As the atoms are coupled through the interatomic potential, their
oscillations around the equilibrium positions are highly correlated and can be described in
terms of lattice waves. These lattice dynamics play an important role in the thermal
properties of solids (e.g. specific heat, thermal conductivity).

Elastic waves in a solid


Before addressing the coupled vibrations of atoms, we review the propagation of elastic
waves in the continuum approximation—the long wavelength limit where the solid is
considered to have a uniform density. The elastic distortions propagate at the speed of
sound ‫ݒ‬௦ . Displacements of the material ‫ ܝ‬can be parallel or perpendicular to the
propagation vector ‫ = |ܓ|( ܓ‬2ߨ/ߣ).

displacements u

Longitudinal wave, L. ‫ܓ ∥ ܝ‬ Transverse wave, T. ‫ܓ ⊥ ܝ‬


(compression wave) (shear wave)

The displacements ‫ ܝ‬are given by

‫ܝ = ܝ‬૙ ݁ ௜(‫ିܚ⋅ܓ‬ఠ௧) in 3D

or

‫ݑ = ݑ‬௢ ݁ ௜(௞௫ିఠ௧) in 1D

The speed of sound ‫ݒ‬௦ = ߱/݇ is equal to the slope of the


dispersion relation (the plot of ߱ vs ݇), and is constant
(independent of ݇ or ‘dispersionless’).
డఠ
The group velocity ‫ݒ‬௚ = is equal to ‫ݒ‬௦ . In general, the
డ௞
speed of sound for transverse and longitudinal waves is
not the same (‫ݒ‬௦௅ ≠ ‫ݒ‬௦் ).

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The Harmonic approximation
To describe lattice vibrations we will model the lattice as atoms attached by ideal springs of
spring constant ‫ܥ‬. This is equivalent to approximating the interatomic potential ܷ(‫ )ݎ‬by a
harmonic potential and is known as the Harmonic
approximation.

Expanding ܷ(‫ )ݎ‬about the equilibrium separation ܽ

డ௎ (௥ି௔)మ డమ ௎
ܷ(‫ )ܽ(ܷ = )ݎ‬+ (‫ ݎ‬− ܽ) ቀ ቁ + ቀ మቁ +⋯
డ௥ ௥ୀ௔ ଶ డ௥ ௥ୀ௔

డ௎
Since we are expanding about the minimum, ቀ ቁ =0
డ௥ ௥ୀ௔
and for small (‫ ݎ‬− ܽ) we can truncate the expression at the
quadratic term, leaving us with

(‫ ݎ‬− ܽ)ଶ ߲ ଶ ܷ
ܷ(‫ )ܽ(ܷ = )ݎ‬+ ቆ ଶቇ
2 ߲‫ ݎ‬௥ୀ௔

This is the Harmonic approximation. The force ‫ ܨ‬is

߲ܷ ߲ଶܷ
‫=ܨ‬− = −(‫ ݎ‬− ܽ) ቆ ଶ ቇ
߲‫ݎ‬ ߲‫ ݎ‬௥ୀ௔

Comparing this to Hooke’s law ‫ = ܨ‬−‫ ݎ(ܥ‬− ܽ), shows that the spring constant ‫ ܥ‬is the
curvature of the interatomic potential around the equilibrium separation

߲ଶܷ
‫=ܥ‬ቆ ቇ
߲‫ ݎ‬ଶ ௥ୀ௔

Excitations of 1D monoatomic chain


Consider a 1D chain of identical atoms of mass ݉ connected by ideal springs of spring
1
constant ‫ ܥ‬with equilibrium separation ܽ.

th
If the n atom is displaced by ‫ݑ‬௡ from its equilibrium position, it will experience a net force

‫ܨ‬௡ = ‫ݑ(ܥ‬௡ାଵ − ‫ݑ‬௡ ) − ‫ݑ(ܥ‬௡ − ‫ݑ‬௡ିଵ )

= ‫ݑ(ܥ‬௡ାଵ − 2‫ݑ‬௡ା + ‫ݑ‬௡ିଵ )

1
The displacements of the masses in our 1D model could represent the displacements of atomic planes in a
crystal.

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nd th
From Newton’s 2 law, the equation of motion for the n atom is

݉‫ݑ‬ሷ ௡ = ‫ݑ(ܥ‬௡ାଵ − 2‫ݑ‬௡ା + ‫ݑ‬௡ିଵ )



We look for wave-like solutions ‫ݑ‬௡ = ‫ݑ‬଴ ݁ ௜൫௞௫೙ ିఠ௧൯ where ‫ݔ‬௡଴ = ݊ܽ is the equilibrium position
th
Recheck of the n atom, ݇ = 2ߨ/ߣ and ߣ is the wavelength of the lattice wave. u_n = u_0 exp [i(kna - w)]
how these
results
were Using ‫ݑ‬௡ାଵ = ݁ ௜௞௔ ‫ݑ‬௡ and ‫ݑ‬௡ିଵ = ݁ ି௜௞௔ ‫ݑ‬௡ , the equations of motion become
found ->
−݉߱ଶ ‫ݑ‬௡ = ‫ܥ‬൫݁ ௜௞௔ − 2 + ݁ ௜௞௔ ൯‫ݑ‬௡


which, using cos ݇ܽ = (݁ ௜௞௔ + ݁ ି௜௞௔ ) gives

−݉߱ଶ = 2‫(ܥ‬cos ݇ܽ − 1)
Using: 1 - cos(x) = sin^2 (x/2)
݇ܽ
= −4‫ ܥ‬sinଶ
2

i.e.

4‫ ܥ‬ଶ ݇ܽ
߱ଶ = sin
݉ 2

This is the dispersion relation for a 1D monoatomic chain. It describes how the frequency of
the wave changes with wavevector (wavelength). Every ݇ represents a solution.

Note that the dispersion relation is independent of ݊, i.e., we get the same relation starting
from any atom. Note also that although the motions of individual atoms are coupled (if one
atom starts vibrating it will transfer energy to adjacent atoms and set them into motion), our
wavelike solutions are uncoupled. Each ݇ has a definite frequency ߱ and oscillates
independently of other modes, i.e., the solutions are normal modes. This independence is a
result of the harmonic approximation (i.e., the fact that we assumed ideal springs with spring
constants that are independent of how much the spring is extended or compressed by a
passing lattice wave).

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Finite chain of ܰ atoms
For an infinite chain of atoms, any value of ݇ is a solution, i.e. ߱(݇) is a continuous function.
For a finite chain of ܰ atoms, we should expect to find ܰ modes corresponding to ܰ
equations of motion. To do so, we need to take into account the boundary conditions of the
ends of the chain. There are two possibilities:
i) Consider the ends to be either fixed or free
ii) Periodic boundary conditions (a.k.a. Born-von Karman boundary conditions)
Both give the same physics as long as they are applied consistently. We will choose periodic
boundary conditions, which can be visualised as a chain with its ends joined to form a ring
(for fixed-end boundary conditions see Kittel, chapter 5).
Periodic boundary conditions mean ‫ݑ‬௡ = ‫ݑ‬௡ାே , i.e. ‫ݑ‬଴ ݁ ௜௞௡௔ =
‫ݑ‬଴ ݁ ௜௞(௡ାே)௔ , so that ݇ܰܽ = 2ߨ‫݌‬, where ‫ = ݌‬0, ±1, … is an integer

݇= ‫݌‬
ܰܽ
ଶగ
Therefore there are ܰ possible values of ݇ within a range of

గ గ
(e.g. for − <݇≤ ) spaced by
.௔ ௔

Δ݇ =
ܰܽ
In practice, ܰ is a very large number and therefore ߱(݇) is essentially a continuous function
of ݇ for many intents and purposes.
Uniqueness of the 1 st Brillouin Zone
గ గ
As in our discussion of X-ray diffraction, the first BZ, i.e., − ≤ ݇ ≤ has a very special role
௔ ௔
as it contains all the physically unique solutions ݇.
From the periodicity of the dispersion relation we can see that waves with ݇ differing by a
ଶగ
reciprocal lattice vector ‫= ܩ‬ have the same frequency ߱. In fact, they actually also

represent the same pattern of atomic displacements, i.e. the same lattice wave:
2ߨ ௜௞௡௔ ଶగ
௜ቀ௞ା ቁ௡௔
݇→݇+ ,݁ →݁ ௔ = ݁ ௜௞௡௔ ݁ ௜ଶగ௡ = ݁ ௜௞௡௔
ܽ
ଶగ
The displacements of discrete atoms represented by a high-frequency wave ݇ + and a

low frequency wave ݇ are indistinguishable.

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st
Thus the wavevectors within the 1 BZ represent a complete set of solutions. The total
st గ
number of modes within the 1 BZ is ቀ2 ቁ /Δ݇ = ܰ, as expected.

Note, the modes ±݇ are distinguishable because of their time dependence ‫ݑ‬௡ (‫= )ݐ‬
‫ݑ‬଴ ݁ ௜(௞௡௔ିఠ௧) . It is a travelling wave and can have positive or negative phase velocity ߱/݇.

But at the BZ boundary where ݇ = ± , this sense of direction is lost

‫ݑ‬௡ (‫ݑ = )ݐ‬଴ ݁ ௜(±௡గିఠ௧) = ‫ݑ‬଴ (−1)௡ ݁ ି௜ఠ௧

This is a standing wave with opposite displacements of adjacent atoms. Therefore the

݇ = ± solutions are the same.

Recall that a wave with ݇ on the BZB satisfies the Bragg condition and will therefore be

diffracted. So we can think of the incident wave ݇ = ± being scattered into the opposite


direction to form a wave with ݇ = ∓ . The incident and backscattered waves superpose to

form a standing wave. When the Bragg condition is satisfied, a travelling wave cannot
propagate in a lattice.
When ݇ = ߨ/ܽ, ߣ = 2ߨ/݇ = 2ܽ and satisfies Bragg’s law
݊ߣ = 2ܽ sin ߠ with ݊ = 1 and ߠ = 90° (2ߠ = 180°).

Group velocity, ‫ݒ‬௚


The group velocity represents the velocity of wave packet propagation

߲߱ ߲ ‫ܥ‬ ݇ܽ ‫ܥ‬ ݇ܽ
‫ݒ‬௚ = = ቌ2ඨ sin ቍ = ܽඨ cos
߲݇ ߲݇ ݉ 2 ݉ 2

‫ݒ‬௚ → 0 as ݇ → ߨ/ܽ(at BZB).


In the long-wavelength limit, ݇ → 0

‫ܥ‬ ݇ܽ ‫ܽ݇ ܥ‬
߱(݇) = 2ඨ sin ≈ 2ඨ
݉ 2 ݉ 2

߱ ‫ܥ‬
‫ݒ‬௣ = = ܽඨ = ‫ݒ‬௚ = ‫ݒ‬௦
݇ ݉

The phase velocity ‫ݒ‬௣ equals the group velocity ‫ݒ‬௚ and is equal to the speed of sound ‫ݒ‬௦ .
The linear (“dispersionless”) region near ݇ = 0 corresponds to the long-wavelength elastic
waves in a solid; i.e. when ߣ ≫ interactomic spacing, the detailed atomic structure becomes
irrelevant and we recover the same behaviour as in a continuous medium.

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Excitations of 1D diatomic chain
We now consider a 1D chain with a two-atom basis, the two types of atom having masses ݉
and ‫)ܯ < ݉( ܯ‬.

The equations of motion are


‫ݑܯ‬ሷ ௡ = ‫ݒ(ܥ‬௡ − 2‫ݑ‬௡ + ‫ݒ‬௡ିଵ )
݉‫ݒ‬ሷ௡ = ‫ݑ(ܥ‬௡ାଵ − 2‫ݒ‬௡ + ‫ݑ‬௡ )
Try travelling wave solutions
‫ݑ‬௡ = ‫ݑ‬଴ ݁ ௜(௞௡௔ିఠ௧)
‫ݒ‬௡ = ‫ݒ‬଴ ݁ ௜(௞௡௔ିఠ௧)
Substituting into equations of motion gives
−߱ଶ ‫ݑܯ‬଴ = ‫ܥ‬൫‫ݒ‬଴ + ‫ݒ‬଴ ݁ ି௜௞௔ − 2‫ݑ‬଴ ൯
−߱ଶ ݉‫ݒ‬଴ = ‫ܥ‬൫‫ݑ‬଴ ݁ ௜௞௔ + ‫ݑ‬଴ − 2‫ݒ‬଴ ൯
We can express these coupled equations as a matrix equation
2‫ ܥ‬− ߱ଶ ‫ܯ‬ −‫ܥ‬൫1 + ݁ ି௜௞௔ ൯ ‫ݑ‬଴
ቆ ቇ ቀ‫ ݒ‬ቁ = ૙
−‫ܥ‬൫1 + ݁ ௜௞௔ ൯ 2‫ ܥ‬− ߱ଶ ݉ ଴

which only has solutions if the determinant of the matrix is zero, giving
߱ସ ‫ ݉ܯ‬− ߱ଶ 2‫ ܯ(ܥ‬+ ݉) + 4‫ ܥ‬ଶ − ‫ ܥ‬ଶ ᇣᇧ
൫1 + ௜௞௔
ᇧᇧ݁ᇧᇧᇧᇤᇧ൯൫1ᇧ− ௜௞௔
ᇧᇧ݁ᇧᇧᇥ൯ = 0
ଶାଶ ୡ୭ୱ ௞௔

߱ସ ‫ ݉ܯ‬− ߱ଶ 2‫ ܯ(ܥ‬+ ݉) + 2‫ ܥ‬ଶ (1 − cos ݇ܽ) = 0


Solving for ߱ଶ we get the dispersion relation

2‫ ܯ(ܥ‬+ ݉) ± ඥ4‫ ܥ‬ଶ (‫ ܯ‬+ ݉)ଶ − 8‫ ܥ‬ଶ ‫(݉ܯ‬1 − cos ݇ܽ)


߱ଶ =
2‫݉ܯ‬
Note, two atoms per primitive cell gives us 2 branches in the dispersion relation.
Let’s examine the limiting cases:
గ ଵ
1) Small ݇, ݇ ≪ → 1 − cos ݇ܽ ≈ ݇ ଶ ܽଶ
௔ ଶ


2‫ ܯ(ܥ‬+ ݉) 2‫ ܯ(ܥ‬+ ݉) 2‫݉ܯ‬ 1 ଶ
߱ = ± ൬1 − ଶ
⋅ ݇ ଶ ܽଶ ൰
2‫݉ܯ‬ 2‫݉ܯ‬ (‫ ܯ‬+ ݉) 2
ᇣᇧᇧᇧᇧᇧᇧᇧᇤᇧᇧᇧᇧᇧᇧᇧᇥ
ଵ ெ௠
≈൬ଵି ௞ మ ௔ మ ൰
ଶ(ெା௠)మ
so
2‫ ܯ(ܥ‬+ ݉) 1 1 2‫ܥ‬
߱ଶ ≈ = 2‫ ܥ‬൬ + ൰ =
‫݉ܯ‬ ‫݉ ܯ‬ ߤ
where ߤ is the “reduced mass”; or

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‫ܥ‬
߱ଶ ≈ ݇ ଶ ܽଶ
2(‫ ܯ‬+ ݉)
ଶ஼(ெା௠)
i.e. ߱ = ට – independent of ݇
ெ௠
஼ ஼
or ߱ = ܽට ݇ – linear in ݇ with ‫ݒ‬௦ = ‫ݒ‬௚ = ‫ݒ‬௣ = ܽට ;
ଶ(ெା௠) ଶ(ெା௠)


(compare this with ߱ = ‫ݒ‬௦ ݇, ‫ݒ‬௦ = ܽට for monoatomic chain).


2) At zone boundary, ݇ = , 1 − cos ݇ܽ = 1 − (−1) = 2, therefore

‫ ܯ(ܥ‬+ ݉) 2‫ܥ‬ ଵ
߱ଶ = ± ((‫ ܯ‬+ ݉)ଶ − 4‫)݉ܯ‬ଶ
‫݉ܯ‬ 2‫݉ܯ‬

The last term in brackets is equal to ((‫ ܯ‬− ݉)ଶ )మ = (‫ ܯ‬− ݉) and therefore
‫ ܯ(ܥ‬+ ݉) ± ‫ ܯ(ܥ‬− ݉) 2‫ܥ‬ 2‫ܥ‬
߱ଶ = = or
‫݉ܯ‬ ݉ ‫ܯ‬

optical branch

gap (=0 if M=m)

acoustic branch

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Repeated zone scheme

Reduced zone scheme

Extended zone scheme

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Knowing the dispersion relation, we can use the matrix equation to find the relationship
between ‫ݑ‬଴ and ‫ݒ‬଴ :
2
- For optical modes, ‫ݑ‬଴ and ‫ݒ‬଴ have opposite sign
- For acoustic modes, ‫ݑ‬଴ and ‫ݒ‬଴ have the same sign
The atomic displacements are easier to visualise for the transverse (rather than longitudinal)
modes

(zone centre modes)

Acoustic
(low freq.)
Rigid displacement of the chain

Optical
(high freq.)

(zone boundary modes; only or is moving)

Generalisation to 3D
In 3D we always have 3 acoustic branches: two transverse (TA) and one longitudinal (LA)
For a two-atom basis, there is then a total of 2 × 3 = 6 branches: 3 acoustic and 3 optical.
For a ‫݌‬-atom basis, there is a total of 3‫ ݌‬branches: 3 acoustic and 3(‫ ݌‬− 1) optical.
Again, for each longitudinal optical branch, there are two transverse.

2
Optical modes are so called because if the two different masses are ions of opposite charge then optical
modes lead to creation of dipoles as the positive and negative ions move in opposite direction. Such modes
can be excited by the electric field of an electromagnetic wave of optical frequency, hence optical modes.
Acoustic modes are so-called because long wavelength acoustic modes correspond to sound waves.

3-9
Some examples of phonon dispersion relations
Solid neon (monoatomic, fcc)

Reproduced from Y. Endoh et al., Physical Review B 11, 1681 (1975)


- All modes are acoustic (just one type of atom)
- Sinusoidal dispersion
- Transverse modes are degenerate (i.e. have the same frequency and hence energy)
along high symmetry directions (e.g. [100], [111])
- More complex along [110] (next-nearest neighbour interactions)

NaCl (fcc with 2-atom basis)

Reproduced from G. Raunio et al., Physical Review 178, 1496 (1969)


- 2-atom basis so now have acoustic and optical modes
- Along [111] we have alternating planes of Na and Cl atoms, hence the dispersion
along reciprocal space direction labelled ሺߦǡ ߦǡ ߦሻ is most like our linear chain model

3-10
Quantisation of lattice vibrations
So far we have considered the lattice vibrations from a purely classical point of view but just
as for EM waves, the energy of lattice vibrations is quantised. By analogy with photons, a
quantum of energy of a mechanical excitation is called a phonon. In the quantum theory of
phonons, each elastic mode of frequency ߱ is treated as a quantum harmonic oscillator
(QHO) and has energy
1
ℰ = ൬݊ + ൰ ℏ߱
2

The ℏ߱ is the zero-point energy due to Heisenberg’s Uncertainty Principle. When a mode

is excited to quantum number ݊, we say it is occupied by ݊ phonons. Classically, we can
think of larger ݊ as corresponding to a larger amplitude of the wave.
Each mode ݇ corresponds to a QHO with frequency ߱(݇), so the total energy is
1
‫ = ܧ‬෍ ℰ(݇) = ෍ ൬݊(݇) + ൰ ℏ߱(݇)
2
௞ ௞

Phonons are boson (spin 0) so there is no restriction on the number ݊ of phonons in a mode.
They obey Bose-Einstein statistics and ݊ is given by
1
݊(߱) =
݁ ℏఠ/௞ಳ೅ −1
For many purposes we can think of phonons as a sort of particle (a “quasiparticle”) that
carries energy ℏ߱ and momentum ℏ݇ known as crystal momentum. It is not a true
momentum as phonons involve only relative displacements of atoms rather than the
displacement of the crystal as a whole but crystal momentum can be exchanged during
interactions with external probes (e.g. EM waves, neutrons) and is conserved within a
reciprocal lattice vector ۵.
Inelastic scattering from phonons
Phonon dispersion curves can be measured using neutron scattering. When neutrons are
scattered inelastically by a crystal (i.e., final energy ≠ initial energy), phonons are created or
destroyed. Both energy and momentum are conserved, however, as the crystal momentum
is only defined to within a reciprocal lattice vector, momentum conservation involves a ۵that
st
brings ‫ ܓ‬୮୦୭୬୭୬ to the 1 BZ.
Energy conservation
±ℏ߱௣௛௢௡௢௡ = ‫ܧ‬௜ − ‫ܧ‬௙
Momentum conservation neutron

±‫ ܓ‬୮୦୭୬୭୬ = ‫ ܓ‬୧ − ‫ ܓ‬୤ + ۵


A neutron spectrometer measures ‫ܧ‬௙ and
‫ ܓ‬୤ so that the ‫ ܓ‬and ߱ of the phonons can
be reconstructed to give the dispersion
curve.

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