4.

Thermal Properties of the Lattice

We discuss some thermal properties of solids
: such as their heat capacity, thermal conduction, thermal expansion, and melting
 caused by the motion of the atoms around their equilibrium position (the contribution of the lattice)

For some thermal effects,

the thermal motion of the free electrons in metals
: will be treated in the next two chapters

one atom per unit cell (in infinite chain)  two atoms per unit cell (in infinite chain)  a finite chain of atoms 
three-dimensional solids

4.1 Lattice Vibrations

The atoms in a crystal can vibrate around their equilibrium position

; the restoring force from the interatomic potential

in chapter 3

: assumed to be a linear restoring force (by considering only the first three terms in the series)
 harmonic approximation [a lattice vibration  a harmonic oscillator]

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4.1.1 A Simple Harmonic Oscillator

the vibrations of a solid with N atoms

; simply 3N independent harmonic oscillators (in three different directions)
[but, the oscillators are all coupled to each other]

(assumption)
the force constant = ′′(a) in Taylor series

x : a displacement from the equilibrium position

(for convenience, x ~ zero in the equilibrium position)
M : the mass of the vibrating atom

The frequency of such a harmonic motion:

2
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𝜙
The total energy for a one-dimensional harmonic oscillator
: the sum of kinetic and potential energies

The mean energy of the oscillator in contact with a heat bath

= kBT

At the highest displacement,

the oscillator has only potential energy

; usually a small percentage of the lattice spacing

3
4.1.2 An Infinite Chain of Atoms

A more realistic model for crystal vibrations

: a chain of atoms
: simple, but, the oscillators are coupled to each other

4.1.2.1 One Atom Per Unit Cell

Consider a one-dimensional atomic lattice

with one atom per unit cell [a lattice constant: a]

The atoms can move out of their equilibrium position along the direction of the chain

The atoms at the lattice sites

: connected to their neighbors with springs of a force constant

4
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 The equation of motion for atom n

un : the displacement of the nth atom in the chain

 solved by a kind of wave that is only defined on the lattice sites

k=2 : the one-dimensional wave vector with the wavelength

: the wavelength of the oscillation
u : the amplitude of the oscillation

5
𝜆
𝜋
∕
𝜆
 =

If (k) is chosen for a given wave vector k

It describes waves propagating along the chain

[What is special] It is only defined on the actual lattice sites

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𝜔
 Dispersion relations
: relations which connect a frequency or energy to a wave vector

A particular solution of (k) : a vibration is not localized to one particular atom in the chain
: called a normal mode
(All the atoms move with the same frequency)

How do the atoms actually move?

[Case 1]
For a very small k ≪ /a,

k = 2 /  the wavelength of the mode ≫ the lattice constant

; atoms that are close to each other must very nearly move in phase

at a certain instant in time,

the atoms in its vicinity perform essentially the same motion

7
𝜋
𝜆
𝜋
𝜔
 The particular atomic structure is thus not important
: the chain as a macroscopic elastic medium

: the dimension of a velocity

Phase velocity : /k
Group velocity : / k

phase velocity = group velocity

8
𝜈
𝜔
𝜕
𝜔
𝜕
 [case 2: short wavelength limitation]

The shortest possible wavelength: two lattice spacings

: k = /a  = 2a

The atom two lattice spacings away must perform the same motion

The atom on the neighboring lattice site, on the other hand, is half a wavelength away
: move in the opposite direction

For k = ± /a,
the group velocity of the wave ~ zero
: standing waves

9
𝜋
𝜋
𝜆
 (k) is periodic in k with a period of 2 /a
: This periodicity corresponds precisely to one reciprocal lattice “vector” in one dimensional crystal

 the actual motion of the atoms is also unaffected if we add a reciprocal lattice vector to k

10
𝜔
𝜋
4.1.2.1 The First Brillouin Zone

The dispersion relation (k) and even the motion of the atoms themselves is unaffected
, if we change the wave vector by multiples of the reciprocal lattice vector 2 /a

First Brillouin zone of the lattice

: the region between k = − /a and k = /a
(often said to be placed in reciprocal space or k-space)

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𝜔
𝜋
𝜋
𝜋
 4.1.2.3 Two Atoms Per Unit Cell

b : the lattice constant

2 /b : the length of the reciprocal lattice vector

One of the two atoms in the unit cell is placed at the origin and the other at b/2

The forces on each atom in a similar manner as before

 obtain two equations of motion, one for each type of atom

12
𝜋
Again, the solutions have the periodicity of the reciprocal lattice 2 /b

Two branches of solutions

: the acoustic branch (with zero for small k)
: the optical branch (with a finite at k = 0)
 possible to couple this vibration with the oscillating electric field of an electromagnetic wave

13
𝜔
𝜋
[the motion of the atoms in the optical branch for k = 0]
- two atoms in the unit cell vibrate exactly out of phase
- a phase difference between the vibration of a given atom and the corresponding atom in the neighboring
unit cell is zero
 the wavelength of the mode must be infinite, consistent with k ~ 0

The particular situation of an ionic crystal

in which the two different ions in the unit cell carry opposite charges

An electromagnetic field (as indicated by the ε-vector) can couple to this motion
(the ions will move as indicated by the arrows)

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 [assumption]
the electric field has a time dependence ε(t) = ε0 exp(i t)
(like the field of an electromagnetic wave)

If matches the frequency of the optical branch at k = 0,

the electromagnetic wave can excite this vibrational mode very efficiently

A typical vibrational frequencies in the optical branch: the order 1013 s-1
 the exciting radiation: infrared spectral range
 a wavelength (~10 um) is very long compared to the unit cell length b
 This implies that the field moves all ions in phase over a very long distance

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𝜔
4.1.3 A Finite Chain of Atoms

A finite but long chain of atoms

 by limiting the length and introducing boundary conditions

For a chain with N atoms,

in which the end is tied to the beginning

; called cyclic boundary conditions or periodic boundary conditions

The dispersion relations (k) are not affected by the chain being finite
, but the periodic boundary conditions restrict the possible k values

the possible values of k

(m : integer)

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𝜔
 N different vibrational frequencies per dispersion branch

Vibrational spectrum for a finite chain of atoms with a length of 10 unit cells and a unit cell length of a
The light gray line: for an infinite chain of lattice constant a

For a macroscopic solid, the number of atoms in any direction is very large
 the distances between the allowed k points are very small
the discrete vibrational frequencies closely resemble the continuum of states for the infinite chain

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𝜔
4.1.4 Quantized Vibrations, Phonons

The quantized character of the lattice vibrations

For one harmonic oscillator,

the quantized energy levels are given by

with l = 0, 1, 2,….

For a chain with N unit cells and one atom per unit cell,
N modes with frequencies (k) and k = 2 m/aN

k : the one-dimensional wave vector, and with a role of a quantum number

(can be used to “label” different modes)
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𝜔
𝜋
In the quantum mechanical picture of the chain,
normal modes can thus be excited in discrete energy quanta of in front of (k)
 called phonons in analogy to photons

Depending on the type of experiment,

photons can have wave character as well as particle character
; same for phonons

(example)
a thermal conductivity
: phonons as “particles” that are generated at the hot end of some sample and conducted to the cold end

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4.1.5 Three-Dimensional Solids

4.1.5.1 Generalization to Three Dimensions

In three dimensions, the one-dimensional k  a true wave vector with three components

For a simple cubic crystal with a lattice spacing a and N atoms in every direction,

nx, ny, nz : integers

L : the macroscopic side length of the crystal

20 𝐤
Γ : always stands for the center of the Brillouin zone, that is, for = (0, 0, 0)
(the zone center is often referred to as the Γ point)

For Aluminum and Diamond,

the acoustic phonon branch with a linear dispersion near the Γ point

For diamond, there are also optical phonons,

both materials have an fcc Bravais lattice
; Al with only one atom as basis, Diamond with two atoms as basis
21
𝐤
4.1.5.2 Estimate of the Vibrational Frequencies from the Elastic Constants

A harmonic potential between the atoms

 (chapter 3) the elastic deformation of solids and the linear relation in Young’s modulus

A rod with a side length of just one lattice constant

(simple cubic crystal with a lattice constant a)

for one atom per unit cell

Young’s modulus  force constant  vibrational frequency in infinite one-dimensional chain

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Estimation of the atomic force constant for diamond and lead
(assumption) the highest vibrational frequency: 2( M)1/2 in a one-dimensional chain

It is admittedly rather crude

 ignoring the true three-dimensional nature of the problem
the existence of optical phonons
“but, it gives the right order of magnitude

Diamond (with light atoms and strong bonds): much higher vibrational frequencies
Lead (with heavy atoms and weak bonds): low frequencies

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∕