Carbon Nanomaterials

Lecture 6

Crystal vibrations
and Density of States

1D lattice model - Vibrations

Atoms in a periodic array with a lattice vector a

Atomic displacement
κ
(δxi+1 − δxi)2
∑2
Total potential energy Vtot =
i

Force field

Newton eq. of motion

Determination of normal modes

Solution ansatz

Solution: Plug the ansatz into the Newton eq. and write as a function of

2
𝜔
𝜅
 1D lattice model - Vibrations
• Two types of normal modes in a one-dimensional crystal.
The upper one is a high-frequency mode, λ = 2a, and
the bottom a low-frequency mode, λ ≫ a (λ = 2π /k)

( ) is periodic in → + 2 /a

Real lattice

Reciprocal lattice
3
𝜔
𝜅
𝜅
𝜅
𝜋
Properties of the dispersion relation

• Since sin x ≈ x for small x

κ
=a k = vsound k
m
2π ω ω
v = λν = =
k 2π k
• At small k (long wave length), is a
linear function of k

• At larger k (short wave length), is not

longer a linear function ω 1 κ ka
λν = = v(k) = 2 | sin( ) |
k k m 2

• Typical lattice spacing are O(10−8cm), and typical frequency are O(10−13sec-1):
the velocity of the wave is O(105 cm/sec).

• Recall: A sound wave is a vibration that has a long wavelength as compared to the
interatomic spacing (humans can hear sound wave-lengths roughly between 1cm
and 10m).
4
𝝎
𝝎
Properties of the dispersion relation
ω 1 κ ka • Waves with different k (different wave
λν = = v(k) = 2 | sin( ) |
k k m 2 length) will travel with different velocities

• At larger k (short wave length), two wave velocities are defined

vgroup = dω/dk the group velocity is the speed at which a wavepacket moves
vphase = ω/k the phase velocity is the speed at which individual maxima and
minima move
• At small k (long wave length), the two wave velocities match, but otherwise they are
different

• At the Brillouin zone boundaries the

group velocity becomes zero

• At the Brillouin zone boundaries the

dispersion relation is flat: this is a
general principle

• Recall: Red squares: phase velocity; Green circle: group velocity. Animation from Wikipedia: Group velocity

• Recall: Sound velocity in air: ∼ 350 m/s; Sound velocity in water: ∼ 1480 m/s;
Sound velocity in iron: ∼ 6000 m/s;
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Properties of the dispersion relation
ω 1 κ ka • Waves with different k (different wave
λν = = v(k) = 2 | sin( ) |
k k m 2 length) will travel with different velocities

• At larger k (short wave length), two wave velocities are defined

vgroup = dω/dk the group velocity is the speed at which a wavepacket moves
vphase = ω/k the phase velocity is the speed at which individual maxima and
minima move
• At small k (long wave length), the two wave velocities match, but otherwise they are
different

• At the Brillouin zone boundaries the

group velocity becomes zero

• At the Brillouin zone boundaries the

dispersion relation is flat: this is a
general principle

• Recall: Red squares: phase velocity; Green circle: group velocity. Animation from Wikipedia: Group velocity

• Recall: Sound velocity in air: ∼ 350 m/s; Sound velocity in water: ∼ 1480 m/s;
Sound velocity in iron: ∼ 6000 m/s;
5
The first six modes of a 1D chain

• Animation showing the first 6 normal modes of a one-dimensional lattice: a linear

chain of particles. The shortest wavelength is at top, with progressively longer
wavelengths below. In the lowest lines the motion of the waves to the right can be
seen. Animation from Wikipedia: Phonons
6
The first six modes of a 1D chain

• Animation showing the first 6 normal modes of a one-dimensional lattice: a linear

chain of particles. The shortest wavelength is at top, with progressively longer
wavelengths below. In the lowest lines the motion of the waves to the right can be
seen. Animation from Wikipedia: Phonons
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Elementary excitation in solids and density of states, DOS
• Electron waves in crystals
• Vibration waves (norma modes) in crystals

Counting states
• Number of electron states
• Number of vibrational states (normal modes)

DOS
• The DOS(E ) is defined as the number of energy state in a dE interval around a E value
• The knowledge of the DOS is a key quantity to evaluate the thermal properties of solids
7

Counting the states: Number of normal modes

• Naively, it would appear that to obtain a normal mode we can chose any value of k
within the Brillouin region, −π /a < k < π /a, kmax = 2π /a. This is not the case.

• The periodic boundary condition method

xn+N = xn : N is the number of atoms

0 2π/L Nπ/L

• The vector k is a quantised, discrete, variable. The distance between two allowed
values of k is

• There is precisely one normal mode per mass in the system, that is, one normal
mode per degree of freedom in the whole system.
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Counting the states: Number of electron states
• The periodic boundary condition method for electron states

xn+N = xn

0 2π/L Nπ/L

• The vector k is a quantised, discrete, variable. The distance between two allowed
values of k is

9
Density-of-states: k-space vs. energy-space
Free electron dispersion relation

D(E) = N(k)/(dE/dk)
• The sketch, the considerations and the formula are valid for both the
electron waves and the vibration waves in crystals 10
Density-of-states in k-space
DOS

0 2π/L Nπ/L

Example from 1D:

Nπ/L Nπ/L
L
∫0 ∫0
DOS dk = dk = N
π

• The DOS in k-space is uniform

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DOS, g(ω), for a 1D monoatomic chain
Na 1
g(ω) =
π dω/dk
dω κ ka Na 1
=a cos( ) g(ω) = g(ω = π /a) = ∞
dk m 2 π a κ ka
cos( 2 )
m

Exercise:
Show that
g(ω) ∝ ω 2

Same,
but tilted

g(ω)

The density of states will diverge when dω/dk is equal to zero

12

Normal modes for a 1D diatomic chain

• For each k we find two normal modes, usually referred to as the two branches of the
dispersion
• Thus since there are N different k values, we obtain 2N modes total (if there are N
unit cells in the entire system)

Long-wavelength low-
energy branch of
excitations with linear
dispersion
(corresponding to ω−)

Here the dispersion is shown for the case of κ2 =

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Normal modes for a 1D diatomic chain

• An example in which the extended zone is useful
• If the two atoms in a unit cell are not too different from each other,
we can think about the dispersion as being a small perturbation to
a situation where all atoms are identical.
• When the atoms are made slightly different, a small gap opens up
at the zone boundary, but the rest of the dispersion continues to
look mostly as if it is the dispersion of the monatomic chain.

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DOS, g(ω), for a 1D diatomic chain

Na 1
ω± g(ω) =
π dω/dk

• The extended zone representation of the

• The density of states
dispersion relations

g(ω)

Same,
but tilted

15
Dispersion relation of monoatomic solids in 3D
• The exact lattice dynamic calculations of two- and three-dimensional lattices
proceeds in such the same way that we did until now, but the actual calculations
are much more difficult

• Typical dispersion curves for

the normal-mode frequencies
in a monoatomic Bravais
lattice.
• The curves are for lead (FCC),
and are plotted in the
extended-zone scheme along
the edges of the triangle
shown below

• Path followed for the extend-

zone scheme:
Γ→X→W→X→K→Γ

Brillouin zone

16

Dispersion relation and DOS of monoatomic solids in 3D

• The exact lattice dynamic calculations of two- and three-dimensional lattices
proceeds in such the same way that we did until now, but the actual calculations
are much more difficult
1D 3D

Na 1 V 1
• FBZ of iron (BCC g(ω) = g(ω) =
π dω/dk 4π 3 dω/dk
in real space)
g(ω) ∝ ω 2

• Dispersion relation of iron (results from • DOS of iron Acoustic

the Castep code) phonons

17
Normal modes and DOS of monoatomic solids in 3D
• The exact lattice dynamic calculations of two- and three-dimensional lattices
proceeds in such the same way that we did until now, but the actual calculations
are much more difficult

• FBZ of aluminium
(FCC)

• DOS of aluminium
• Dispersion relation of aluminium

18
Normal modes and DOS of silicon (Si) （FCC）

19
Elementary excitation in solids
• Electron waves in crystals
• Vibration waves (normal modes) in crystals

20

Lattice vibrations and phonons

• Quantum correspondence of a classical harmonic system (any quadratic Hamiltonian)

• The paradigm for a classical harmonic oscillator is a mass m attached to a spring of

force constant k

d2x
Hooke’s law: F = − k x = m
d 2t
Solution: x(t) = sin(ωt) + B cos(ωt)

ω= k /m

1 2 1 2 2
V(x) = k x V(x) = ω mx
2 2
Parabola equation • In the neighbourhood of a local minimum the potential
can be approximated with a parabolic function

• The quantum problem is the solution of

the time independent Schrödinger
equation with the harmonic potential

D. J. Griffiths and D. F. Schroeter. Introduction to quantum mechanics. Cambridge University

Press, third edition, 2018.
21

Lattice vibrations and phonons

• Solution of the Schrödinger equation

where An is a normalisation constant

n = 60

• Quantum features: the probability of finding the particle outside the allowed x range is not
zero; For odd states, the probability at the equilibrium position is zero
• For large values of n, the quantum behaviour starts to be similar to the classical one

D. J. Griffiths and D. F. Schroeter. Introduction to quantum mechanics. Cambridge University Press, third edition, 2018.
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Lattice vibrations and phonons
• Quantum correspondence of a classical harmonic system (any quadratic Hamiltonian)
• Quantum correspondence: If a classical harmonic system has a normal oscillation mode
at frequency ω, the corresponding quantum system will have eigenstates with energy:
1
En = ℏωk(n + )
2
• For the case of a lattice, the only thing different is that our harmonic oscillator can be a
collective normal mode not just the motion of a single particle.

• Phonon energy:

in which cs is the speed of sound inside the

solid
The minimum wavelength of a
phonon is twice the atom separation

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Lattice vibrations and phonons
• Quantum correspondence of a classical harmonic system (any quadratic Hamiltonian)

• Quantum correspondence: If a classical harmonic system has a normal oscillation mode

at frequency ω, the corresponding quantum system will have eigenstates with energy:

1
En = ℏωk(n + )
2
• At a given wavevector k, there are many possible eigenstates, the ground state being the
n = 0 eigenstate which has only the zero-point energy ℏω(k)/2.
• The lowest-energy excitation is of energy ℏω(k) greater than the ground state
corresponding to the excited n = 1 eigenstate. Generally all excitations at this wavevector
occur in energy units of ℏω(k).
• Each excitation of this “normal mode” by a step up the harmonic oscillator excitation ladder
(increasing the quantum number n) is known as a “phonon”

• Definitions:
• A phonon is a discrete quantum of vibration
• A phonon is the quantum mechanical description of an elementary vibrational motion
in which a lattice of atoms or molecules uniformly oscillates at a single frequency
(normal mode in classical mechanics).
• Phonons can be thought of as quantized sound waves, similar to photons as
quantized light waves. As photons, phonos are also referred to as quasi-particles
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Lattice vibrations and phonons

• Phonons, as photons, are bosons, and it is possible
to put many phonons in the same state

• As for photons, the number of phonos

occupying a given mode is given by

in which β = 1/(kBT )

• Energy expectation of phonos with wavevector k

• Total energy of the 1D harmonic model

• The evaluation of the thermodynamic properties will be the subject of next

lecture
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Lattice vibrations and phonons
• Explicit expression of the sum over k

2π −π /a ≤ k < π /a
k= p • The total number of k values is N
Na

• For large systems, the allowed k are so close that the sum can be replaced by an integral

• The total energy of the 1D harmonic model

becomes

26
Lattice vibrations and phonons
• By discarding the zero-point energy, and by using the distribution

Exact equation (harmonic crystal)

the energy becomes
Na π/a ℏω(k) ℏω
dk[
π ∫0 2 ]
= +
exp(βℏω(k)) − 1

• Let’s replace the integral over k with integrals of a density of states over frequency
Na 1
g(ω) =
π dω/dk
∞
ℏω ℏω
dk[
∫0 2 ]
E(T)) =
U(T + g(ω)
exp(βℏω) − 1 Exact equations
(harmonic crystal)
∂E(T ))
∂U(T
CV = (( )) =
∂T
∂T

• The DOS(ω), g(ω) is defined as the number of modes in a frequency between ω and
ω + dωaround the value ω
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Normal modes of the diatomic solid
• If the two masses of our lattice are ions of opposite sign, such as NaCl, the vibrational
motion in the optical modes produces oscillating dipole moments.
• An oscillating dipole moments leads to an absorption of infrared radiation

• Infrared spectrum of Na Cl

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Normal modes of the diatomic solid

• The larger the reduced mass, the lower the frequency of the optical modes, and hence
the longer the wavelengths at which the infrared absorption occurs

• The onset of the absorption of infrared radiation by alkali halide

crystals, showing that those alkali halide ion pairs with the heavier
reduced masses begin to absorb at longer wavelength

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Approximate expressions for the density of states
• The Einstein approximation

1D 3D

Na 1 V 1
g(ω) = g(ω) =
π dω/dk 4π 3 dω/dk

g(ω) = 3Nδ(ω − ωE )

• Einstein approximation: Each

atom is independent from the
others, and each one vibrates
with a frequency ωE
• ωE is different for different
materials

ωE
• The experimental density of states of (a)
aluminium and (b) iron
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The Einstein theory of the heat capacity

• In the Einstein model for the specific heat, it is assumed that all normal
frequencies appearing in the partition function are the same

• Before the appearance of the Einstein model, the only available theory was that
known as the Dulong and Petit law:

CV = 3Nk = 3R = 6 cal/deg mole

• Within the partition function formalism,

the Einstein theory correspond to the
assumption:

• The heat capacity becomes: Heat capacity of diamond at constant V, from A.

Einstein, Ann. Physik, 22, 180 1907.

∂E(T )
CV = ( )V
∂T

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The Einstein theory of the heat capacity
• In the Einstein model for the specific heat, it is assumed that all normal
frequencies appearing in the partition function are the same
• The Einstein temperature:
ℏω
ΘE = Dulong and Petit
k
• The heat capacity at
constant V:

• This equation contains only one

adjustable parameters to fit the
experimental CV (T ) for the entire
temperature range: the Einstein
temperature. Every material is
characterised by its value of ΘE
• If the CV (T ) of different
Rescaled temperature T * = T/ΘE
materials are drawn as function
of a rescaled T * , all data fall on
a master curve
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The Einstein theory of the heat capacity

• In the Einstein model for the specific heat, it is assumed that all normal
frequencies appearing in the partition function are the same

• Experimental
• Einstein theory behaviour of
behaviour of CV (T )
CV (T ) at low T:
at low T: ΘE 2 −Θ/T
CV (T ) ∝ T 3 CV (T ) → 3Nk( ) e
T

Exp.

• The low temperature behaviour predicted Einstein theory falls to its zero value
more rapidly than T 3
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The Debye theory of the heat capacity

• The model and the derivation of the model equations
Consider a cube of side L. From the particle in a box, the vibrating modes of particles inside the box
(considering for now only those aligned with one axis) have wavelengths given by:
λn = 2L /n, where n is an integer

The phonon energy is: En = hνn

Making the approximation that the frequency is inversely proportional to the wavelength, we have:
hcs hc n
En = hνn = = s , in which cs is the speed sound inside the box.
λn 2L
The approximation that the frequency is inversely proportional to the wavelength (giving a
constant speed of sound) is good for low-energy phonons but not for high-energy phonons (see
the dispersion relation).

Total energy in three dimensions: where Ñ(En) is the phonon number with
energy En (see the Bose distribution)

3
In the cubic solid with N atoms (N degrees of freedom), we have nmax = N

Total energy in three dimensions:

where the Bose distribution has been used, and where the factor 3 comes from the three
polarisation state of the (2 transverse and 1 longitudinal)

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The Debye theory of the heat capacity

• The model and the derivation of the model equations
From cartesian coordinates to spherical coordinates:

Integral transformation:

3
where the radius of the sphere is given by R = 6N/π

Integration over θ and ϕ:

Change of integration variable

Total energy:

Debye temperature: Debye function

Total energy:

Heat capacity: Tabulated integral

35
The Debye theory of the heat capacity

36
The Debye theory of the heat capacity
• The Debye model: a summary
• The approximation that the frequency is inversely proportional to the wavelength (giving a
constant speed of sound) is good for low-energy phonons but not for high-energy phonons
(exact dispersion relation E(ν) at low frequencies).

• In the integration interval, the exact number of states is taken into account ( ∫ g(ν)dν = 3N).
• The Debye temperature can be interpreted as the temperature at which the highest-frequency
mode (and hence every mode) is excited.

36

The Debye theory of the heat capacity

• The Debye model: a summary
• The approximation that the frequency is inversely proportional to the wavelength (giving a
constant speed of sound) is good for low-energy phonons but not for high-energy phonons
(exact dispersion relation E(ν) at low frequencies).

• In the integration interval, the exact number of states is taken into account ( ∫ g(ν)dν = 3N).
• The Debye temperature can be interpreted as the temperature at which the highest-frequency
mode (and hence every mode) is excited.

ω = csk
Debye approximation: All
vibrational modes can be
replaced by their behaviour
at small k (long wavelength)
frequency ω = cs k with a
cutoff at a given ωD

ωD
• The experimental density of states of (a) aluminium and (b) iron
36

The Debye theory of the heat capacity

• The heat capacity from the Debye approximations

• The tabulated Debye temperature,

ΘD = hcD /k, for various
monoatomic solids limiting
behaviour

• The Debye equation for CV (T )

contains only one adjustable
parameter to reproduce the
experimental CV (T ) for the entire
temperature range: the Debye
temperature.
• If the CV (T ) of different
materials are drawn as function
of a rescaled T * , all data fall on
a master curve

37

The Debye theory of the heat capacity

• The heat capacity from the Debyeapproximations

• The Debye theory reproduces the low and

high temperature limiting behaviour

38
Beyond the Debye theory of the heat capacity
• Some shortcomings from the Debye theory
• Experimentally, the Debye theory is very accurate, but it is not exact at intermediate
temperatures.
• Metals also have a term in the heat capacity that is proportional to T, so the overall
heat capacity is C = γT + αT 3and at low enough T the linear term will dominate.
• In magnetic materials there may be still other contributions to the heat capacity
reflecting the energy stored in magnetic degrees of freedom.

Heat capacity divided by temperature of silver at very low temperature

plotted against temperature squared. If the dependence were purely T 3,
the curve would have a zero intercept.

39

Readings
• Text books
• Steven H. Simon, The Oxford Solid State Basics, Oxford University Press, 2013.

• Donald A. McQuarrie, Statistical Mechanics, Harper & Row, 1976 - Chapter 11.

• Charles Kittel, Introduction to Solid State Physics, Eight edition, John Wiley & Sons,
2005.

• Wikipedia
• The Debye model: https://en.wikipedia.org/wiki/Debye_model

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