Solid State Physics

Lecture 8 The Debye model

Professor Stephen Sweeney
Advanced Technology Institute and Department of Physics
University of Surrey, Guildford, GU2 7XH, UK

s.sweeney@surrey.ac.uk

Solid State Physics - Lecture 8

Recap from Lecture 7

Concepts of temperature and thermal
equilibrium are based on the idea that
individual particles in a system have
some form of motion

Heat capacity can be determined by

considering vibrational motion of
atoms

We considered two models:

Dulong-Petit (classical)
Einstein (quantum mechanical)
Both models assume atoms act
independently this is made up for in
the Debye model (today)
Solid State Physics - Lecture 8

Dulong-Petit

Summary of Dulong-Petit and

Einstein models of heat capacity
Dulong-Petit model (1819)

Einstein model (1907)

Atoms on lattice vibrate

independently of each
other
Completely classical
Heat capacity
independent of
temperature (3NkB)
Poor agreement with
experiment, except at
high temperatures

Atoms on lattice vibrate

independently of each
other
Quantum mechanical
(vibrations are quantised)
Agreement with
experiment good at very
high (~3NkB) and very low
(~0) temperatures, but
not inbetween

Solid State Physics - Lecture 8

A more realistic model

Both the Einstein and Dulong-Petit models treat each

atom independently. This is not generally true.

When an atom vibrates, the force on adjacent atoms

changes causing them to vibrate (and vice-versa)

Oscillations can be broken down into modes

1D case
Nice animations here: http://www.phonon.fc.pl/index.php
Java applet: http://dept.kent.edu/projects/ksuviz/leeviz/phonon/phonon.html
Solid State Physics - Lecture 8

3D case

Debye model

Basic idea similar to Einstein model, with one key difference:

Einstein:
Energy of system = Phonon Energy x Average number of phonons
Debye:
Energy of system = Phonon Energy x Average number of phonons x number of modes

Einstein: number of modes = number of atoms

Debye: each mode has its own k value (and
hence frequency)

Solid State Physics - Lecture 8

The number and type of

modes are the key difference

Modes: lattice vibrations

Modes exist in various areas of physics/nature

Butterfly wing-beat

Water Molecules

Guitar modes

Solid State Physics - Lecture 8

Modes: Quantum mechanics

Modes are quantised in units of
mode is

where the fundamental frequency of each

The Einstein model assumed that each oscillator has the same frequency
Debye theory accounts for different possible modes (and therefore different

Modes with low will be excited at low temperatures and will contribute
to the heat capacity. Therefore heat capacity varies less abruptly at low T
compared with Einstein model

Low frequency modes

correspond to multiple
atoms vibrating
together (sound or
acoustic waves)

Solid State Physics - Lecture 8

Standing waves: revision

Consider a vibrating string

n=4

Lowest (fundamental) frequency

n=3
n=2

More generally
n=1

L
Other results follow:

2L
n L
2
n

vn
vn
f
2f
2L
L
v

n
L

Solid State Physics - Lecture 8

Standing waves in a 1D crystal

Consider solid as a continuous elastic medium:
N atoms, 3 degrees of freedom 3N standing modes
a

2 n n
k

L
Na

1D array of atoms:
L=Na

max 2 L 2 Na kmin
Fundamental mode
(n=1)

Na

min 2a kmax

Highest order mode

(n=N)
Therefore we get N modes for N atoms
Solid State Physics - Lecture 8

nmax N

Standing waves in 2D crystals

Fundamental mode (2D)

Each component of the wave is quantised

separately and added in quadrature

k x ky

x
L

y
L

Magnitude of k-vector for mode

kx

ky 2
L
2

Corresponding angular frequency

2f 2

vk

v 2

Solid State Physics - Lecture 8

Standing waves in 2D crystals:

Degeneracy
ky

kx
L

2
L

ky

2
kx
L

x
y
L

2
k
5
L
L L
2

2
k
5
L
L L
2

In both cases

v 5

so these two modes are degenerate

As frequency increases, more and more states share the same frequency & energy
(called DEGENERACY)
Solid State Physics - Lecture 8

Back to reciprocal space (2D)

We can represent each mode as a

point in reciprocal (k) space

Q. How many modes are available at a

particular k value?
A. Need three pieces of information:
1. How big is an individual k-state
2. How much of k-space is covered at a
particular k
3. Account for degeneracy

kl 2
g k dk
dk
2
Solid State Physics - Lecture 8

Number of States in 3D
In 3D we consider the number of states
within a sphere of radius k
Sphere volume =

kz

4 3
k
3

ky

volume of k-state =

3
l3

kx

Vk
g k dk
dk
2
2

k-state

Solid State Physics - Lecture 8

Number of States in 3D
Vk 2
g k dk
dk
2
2
We know that

Hence

kz

vk d vdk

V 2
g d
d
2 3
2 v

ky
kx

i.e. the number of standing waves (modes)

increases as 2

Sound can propagate with 2 transverse and 1 longitudinal

wave in a solid total no. of states = 3g()d

Solid State Physics - Lecture 8

k-state

Debye frequency
For any one wavelength of oscillation there are shorter wavelength oscillations that
will also have the atoms in the same position on the lattice (c.f. aliasing in electronics)
There is a minimum wavelength which can
oscillate which corresponds to a maximum
frequency, max (Debye frequency)
We can calculate max since we know (from
earlier) that the maximum number of states
= 3N

3N

max

3g d
0

max

3V
V
3
d

max
2 3
2 3
2 v
2 v
2

Solid State Physics - Lecture 8

So,

max

2 N
v 6

1
3

Some crystal modes of vibration

Phonon animations here: http://www.phonon.fc.pl/index.php

Solid State Physics - Lecture 8

Debye model: Total average energy of System

From earlier: Energy of =
system

max

Phonon
Average no.
x
energy
of phonons

1

3g d

1
exp
k BT

Integrate over
all modes

(NB: Ignoring zero-point energy)

Solid State Physics - Lecture 8

max

No. of
modes

3g
d

1
exp
k BT

Debye model: Total average energy of System

E

max

3g
d

1
exp
k BT

3V
E
2 2 v 3

V 2
From before: g d
d
2 3
2 v

x
k BT

Make substitution:

4
B

3Vk T
E
2 2 v 3 3

max

3
d

1
exp
k BT

and define Debye temperature:

x3
dx
exp x 1

max
D
kB

From which (finally) we can

extract the heat capacity, C

Solid State Physics - Lecture 8

The Debye Temperature D

This is perhaps the most useful parameter in the Debye theory
It allows us to predict the heat capacity at any temperature
It provides an indication of the temperature at which we approach the
classical limit of the Dulong-Petit theory

D max
kB

From earlier, we know that

Therefore,

max
2 N
6

DkB

and

2 N
6

max v 6 2
V

1
3

13

So if we know N/V then we can predict the

speed of sound in a solid

Solid State Physics - Lecture 8

The Debye Temperature D: examples

High D corresponds to a large max
Large max implies large forces, low max implies weak bonds
Diamond D = 2230K

Dulong-Petit poor fit at room temperature. Strongly bonded

Iron

D = 457K

Dulong-Petit reasonable fit at room temperature.

Lead

D = 100K

Dulong-Petit good fit at room temperature. Weakly bonded

Solid State Physics - Lecture 8

Debye model: Heat Capacity

4
B

3Vk T
E
2 2v 3 3

x3
dx
exp x 1

where

x
k BT

At high T:

exp( x) 1 x ...

x is small
D

x
dx
exp x 1

Vk T
E
2 v

4
3
B
D
2 3 3

E 3Nk BT

and since

so
3

x
dx
1 x ... 1

DkB

2 N
6

Heat capacity, C

dE
3Nk B
dT

Solid State Physics - Lecture 8

x 2 dx

D3
3T 3

13

Dulong-Petit !

dE
Cmolar
3N A k B
dT

Debye model: Heat Capacity

4
B

3Vk T
E
2 2v 3 3

x3
dx
exp x 1

where

At low T:

Take limit that D/T and use identity

so

x3
4
0 exp x 1dx 15

3Vk B4T 4 4 3 4 Nk BT 4
E

2 3 3
2 v 15
5 D3
Heat capacity, C

x
k BT

DkB

N
6

13

Debye T3 law

T
dE 12

Nk B
dT
5
D

Solid State Physics - Lecture 8

Debye T3 law

Heat Capacity (mJ mol-1 K-1)

Heat capacity for solid Argon (from Kittel)

T3 (K3)

Solid State Physics - Lecture 8

Comparison of Dulong-Petit, Einstein

and Debye models of heat capacity
Dulong-Petit

Solid State Physics - Lecture 8

Thermal Conductivity

Thermal conduction is a measure of how much heat energy is

transported through a material per unit time

In metals conduction is due to free electrons (a later lecture)

In non-metals conduction is largely due to phonons

most hard insulators have a low thermal conductivity

Phonons have energy and can therefore conduct heat

Scattering mechanisms limit the thermal conductivity of non-metals,
due to
Imperfections (grain boundaries, point defects, dislocations)
Phonons themselves can scatter other phonons (Umklapp
processes we wont cover that here)
Solid State Physics - Lecture 8

Thermal Conductivity

Thermal conductivity

Thigh

Tlow

1 dE
dT
Q

A dt
dx

Area, A

Energy flow along x

1 dE dx
1 dE dx

A dt dT
A dT dt

i.e. thermal conductivity scales with heat capacity

Solid State Physics - Lecture 8