DEBYE MODEL

In thermodynamics and solid state physics, the Debye model is a method developed by Peter
Debye in 1912 for estimating the phonon contribution to the specific heat (heat capacity) in a
solid.[1] It treats the vibrations of the atomic lattice (heat) as phonons in a box, in contrast to
the Einstein model, which treats the solid as many individual, non-interacting quantum
harmonic oscillators. The Debye model correctly predicts the low temperature dependence of
the heat capacity, which is proportional to
the Debye T3 law. Just like the Einstein
model, it also recovers the DulongPetit law at high temperatures. But due to simplifying
assumptions, its accuracy suffers at intermediate temperatures.

Derivation
The Debye model is a solid-state equivalent of Planck's law of black body radiation, where
one treats electromagnetic radiation as a gas of photons in a box. The Debye model treats
atomic vibrations as phonons in a box (the box being the solid). Most of the calculation steps
are identical.
Consider a cube of side . From the particle in a box article, the resonating modes of the
sonic disturbances inside the box (considering for now only those aligned with one axis) have
wavelengths given by

where is an integer. The energy of a phonon is

where is Planck's constant and is the frequency of the phonon. Making the approximation
that the frequency is inversely proportional to the wavelength, we have:

in which

is the speed of sound inside the solid. In three dimensions we will use:

in which

is the magnitude of the three-dimensional momentum of the phonon.

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 article on phonons.) This is one of the limitations of the Debye model, and
corresponds to incorrectness of the results at intermediate temperatures, whereas both at low
temperatures and also at high temperatures they are exact.

Let's now compute the total energy in the box,

where
is the number of phonons in the box with energy
. In other words, the total
energy is equal to the sum of energy multiplied by the number of phonons with that energy
(in one dimension). In 3 dimensions we have:

Now, this is where Debye model and Planck's law of black body radiation differ. Unlike
electromagnetic radiation in a box, there is a finite number of phonon energy states because a
phonon cannot have infinite frequency. Its frequency is bound by the medium of its
propagationthe atomic lattice of the solid. Consider an illustration of a transverse phonon
below.

It is reasonable to assume that the minimum wavelength of a phonon is twice the atom
separation, as shown in the lower figure. There are atoms in a solid. Our solid is a cube,
which means there are
atoms per edge. Atom separation is then given by
the minimum wavelength is

, and

making the maximum mode number

(infinite for photons)

This is the upper limit of the triple energy sum

For slowly varying, well-behaved functions, a sum can be replaced with an integral (also
known as Thomas-Fermi approximation)

So far, there has been no mention of

, the number of phonons with energy
Phonons
obey BoseEinstein statistics. Their distribution is given by the famous BoseEinstein
formula

Because a phonon has three possible polarization states (one longitudinal, and two transverse
which approximately do not affect its energy) the formula above must be multiplied by 3,

(Actually one uses an effective sonic velocity

, i.e. the Debye temperature

(see

below) is proportional to
, more precisely
, where one distinguishes longitudinal and transversal sound-wave velocities (contributions
1/3 and 2/3, respectively). The Debye temperature or the effective sonic velocity is a measure
of the hardness of the crystal.)
Substituting this into the energy integral yields

The ease with which these integrals are evaluated for photons is due to the fact that light's
frequency, at least semi-classically, is unbound. As the figure above illustrates, this is not true
for phonons. In order to approximate this triple integral, Debye used spherical coordinates

and boldly approximated the cube by an eighth of a sphere

where is the radius of this sphere, which is found by conserving the number of particles in
the cube and in the eighth of a sphere. The volume of the cube is unit-cell volumes,

so we get:

The substitution of integration over a sphere for the correct integral introduces another source
of inaccuracy into the model.
The energy integral becomes

Changing the integration variable to

To simplify the appearance of this expression, define the Debye temperature

Many references[3][4] describe the Debye temperature as merely shorthand for some constants
and material-dependent variables. However, as shown below,
is roughly equal to the
phonon energy of the minimum wavelength mode, and so we can interpret the Debye
temperature as the temperature at which the highest-frequency mode (and hence every mode)
is excited.
Continuing, we then have the specific internal energy:

where

is the (third) Debye function.

Differentiating with respect to

we get the dimensionless heat capacity:

These formulae treat the Debye model at all temperatures. The more elementary formulae
given further down give the asymptotic behavior in the limit of low and high temperatures.
As already mentioned, this behaviour is exact, in contrast to the intermediate behaviour. The
essential reason for the exactness at low and high energies, respectively, is that the Debye
model gives (i) the exact dispersion relation

at low frequencies, and (ii) corresponds to

the exact density of states

frequency interval.

concerning the number of vibrations per

Debye's derivation
Actually, Debye derived his equation somewhat differently and more simply. Using the solid
mechanics of a continuous medium, he found that the number of vibrational states with a
frequency less than a particular value was asymptotic to

in which is the volume and is a factor which he calculated from elasticity coefficients
and density. Combining this with the expected energy of a harmonic oscillator at temperature
T (already used by Einstein in his model) would give an energy of

if the vibrational frequencies continued to infinity. This form gives the

behavior which is
correct at low temperatures. But Debye realized that there could not be more than
vibrational states for N atoms. He made the assumption that in an atomic solid, the spectrum
of frequencies of the vibrational states would continue to follow the above rule, up to a
maximum frequency
chosen so that the total number of states is
:

Debye knew that this assumption was not really correct (the higher frequencies are more
closely spaced than assumed), but it guarantees the proper behavior at high temperature (the
DulongPetit law). The energy is then given by:

where

where

is

is the function later given the name of third-order Debye function.

Another Derivation
First we derive the vibrational frequency distribution; the following derivation is based on
Appendix VI from.[5] Consider a three-dimensional isotropic elastic solid with N atoms in the
shape of a rectangular parallelepiped with side-lengths
. The elastic wave will
obey the wave equation and will be plane waves; consider the wave vector
and define

. Note that we have

(1)

Solutions to the wave equation are

and with the boundary conditions

have

at

, we

(2)
where
relation

are positive integers. Substituting (2) into (1) and also using the dispersion
, we have

The above equation, for fixed frequency , describes an eighth of an ellipse in "mode space"
(an eighth because
are positive). The number of modes with frequency less than
is thus the number of integral points inside the ellipse, which, in the limit of

(i.e. for a very large parrallelepiped) can be approximated to the volume

of the ellipse. Hence, the number of modes

with frequency in the range

is
(3)

where
is the volume of the parrallelepiped. Note that the wave speed in the
longitudinal direction is different from the transverse direction and that the waves can be
polarised one way in the longitudinal direction and two ways in the transverse direction; thus
we define

Following the derivation from,[6] we define an upper limit to the frequency of vibration
;
since there are N atoms in the solid, there are 3N quantum harmonic oscillators (3 for each x-,
y-, z- direction) oscillating over the range of frequencies
. Hence we can determine
like so:
(4)
.

By defining
, where k is Boltzmann's constant and h is Planck's constant, and
substituting (4) into (3), we get
(5)
;
this definition is more standard. We can find the energy contribution for all oscillators
oscillating at frequency . Quantum harmonic oscillators can have energies
and using Maxwell-Boltzmann statistics, the number
of particles with energy

is

.
The energy contribution for oscillators with frequency is then
(6)

By noting that
frequency ), we have

(because there are

modes oscillating with

From above, we can get an expression for 1/A; substituting this into (6), we have

Integrating with respect to yields

Low temperature limit

The temperature of a Debye solid is said to be low if

, leading to

This definite integral can be evaluated exactly:

In the low temperature limit, the limitations of the Debye model mentioned above do not
apply, and it gives a correct relationship between (phononic) heat capacity, temperature, the
elastic coefficients, and the volume per atom (the latter quantities being contained in the
Debye temperature).

High-temperature limit

The temperature of a Debye solid is said to be high if

leads to

. Using

if

This is the DulongPetit law, and is fairly accurate although it does not take into account
anharmonicity, which causes the heat capacity to rise further. The total heat capacity of the
solid, if it is a conductor or semiconductor, may also contain a non-negligible contribution
from the electrons.

Debye versus Einstein

Debye vs. Einstein. Predicted heat capacity as a function of temperature.

So how closely do the Debye and Einstein models correspond to experiment? Surprisingly
close, but Debye is correct at low temperatures whereas Einstein is not.
How different are the models? To answer that question one would naturally plot the two on
the same set of axes... except one can't. Both the Einstein model and the Debye model
provide a functional form for the heat capacity. They are models, and no model is without a
scale. A scale relates the model to its real-world counterpart. One can see that the scale of the
Einstein model, which is given by

is
. And the scale of the Debye model is
, the Debye temperature. Both are usually
found by fitting the models to the experimental data. (The Debye temperature can
theoretically be calculated from the speed of sound and crystal dimensions.) Because the two

methods approach the problem from different directions and different geometries, Einstein
and Debye scales are not the same, that is to say

which means that plotting them on the same set of axes makes no sense. They are two models
of the same thing, but of different scales. If one defines Einstein temperature as

then one can say

and, to relate the two, we must seek the ratio

The Einstein solid is composed of single-frequency quantum harmonic oscillators,

. That frequency, if it indeed existed, would be related to the speed of sound
in the solid. If one imagines the propagation of sound as a sequence of atoms hitting one
another, then it becomes obvious that the frequency of oscillation must correspond to the
minimum wavelength sustainable by the atomic lattice,
.

which makes the Einstein temperature

and the sought ratio is therefore

Now both models can be plotted on the same graph. Note that this ratio is the cube root of the
ratio of the volume of one octant of a 3-dimensional sphere to the volume of the cube that
contains it, which is just the correction factor used by Debye when approximating the energy
integral above.

Debye temperature table

Even though the Debye model is not completely correct, it gives a good approximation for
the low temperature heat capacity of insulating, crystalline solids where other contributions
(such as highly mobile conduction electrons) are negligible. For metals, the electron
contribution to the heat is proportional to , which at low temperatures dominates the Debye
result for lattice vibrations. In this case, the Debye model can only be said to approximate
for the lattice contribution to the specific heat. The following table lists Debye temperatures
for several pure elements:[3]
Aluminium
Beryllium
Cadmium
Caesium
Carbon
Chromium
Copper
Gold
Iron
Lead

428 K
1440 K
209 K
38 K
2230 K
630 K
343.5 K
170 K
470 K
105 K

Manganese
Nickel
Platinum
Sapphire
Silicon
Silver
Tantalum
Tin (white)
Titanium
Tungsten

410 K
450 K
240 K
1047 K
645 K
Zinc 327 K
215 K
240 K
200 K
420 K
400 K

The Debye model's fit to experimental data is often phenomenologically improved by

allowing the Debye temperature to become temperature dependent;[7] for example, the value
for water ice increases from about 222 K[8] to 300 K[9] as the temperature goes from Absolute
zero to about 100 K.

Extension to other quasi-particles

For other bosonic quasi-particles, e.g., for magnons (quantized spin waves) in ferromagnets
instead of the phonons (quantized sound waves) one easily derives analogous results. In this
case at low frequencies one has different dispersion relations, e.g.,
magnons, instead of

for phonons (with

density of states (e.g.,

magnon contribution to the heat capacity,

in the case of

). One also has different

). As a consequence, in ferromagnets one gets a

, which dominates at

sufficiently low temperatures the phonon contribution,

. In metals, in
contrast, the main low-temperature contribution to the heat capacity,
, comes from the
electrons. It is fermionic, and is calculated by different methods going back to Arnold
Sommerfeld.

References
1. Debye, Peter (1912). "Zur Theorie der spezifischen Waerme". Annalen der Physik
(Leipzig) 39 (4): 789.
2. Shubin, Mikhail; Sunada, Toshikazu (2006). "Mathematical theory of lattice
vibrations". Pure and Appl. Math. Quaterly 2: 745-777.

3. Kittel, Charles (2004). Introduction to Solid State Physics (8 ed.). John Wiley & Sons.
ISBN 978-0471415268.
4. Schroeder, Daniel V. "An Introduction to Thermal Physics" Addison-Wesley, San
Francisco (2000). Section 7.5
5. Hill, Terrell L. (1960). An Introduction to Statistical Mechanics. Reading,
Massachusetts, U.S.A.: Addison-Wesley Publishing Company, Inc.
ISBN 9780486652429.
6. Oberai, M. M.; Srikantiah, G (1974). A First Course in Thermodynamics. New Delhi,
India: Prentice-Hall of India Private Limited. ISBN 9780876920183.
7. Patterson, James D; Bailey, Bernard C. (2007). Solid-State Physics: Introduction to
the Theory. Springer. pp. 9697. ISBN 978-3-540-34933-4.
8. Shulman, L. M. (2004). "The heat capacity of water ice in interstellar or interplanetary
conditions". Astronomy and Astrophysics 416: 187131.
Bibcode:2004A&A...416..187S. doi:10.1051/0004-6361:20031746. edit
9. Flubacher, P.; Leadbetter, A. J.; Morrison, J. A. (1960). "Heat Capacity of Ice at Low
Temperatures". The Journal of Chemical Physics 33 (6): 1751.
Bibcode:1960JChPh..33.1751F. doi:10.1063/1.1731497. edit