Anharmonic Effects

Kushantha Withanage1 and Suresh Thapa1

1 Department

of Physics, Central Michigan University, Mount Pleasant, Michigan 48859, USA

Abstract
This report is about the anharmonic effects on the heat capacity and thermal conductivity of materials. In studying anharmonic effects on heat capacity, the experimental data have been helpful for order-of-magnitude calculations only. But, the theoretical
calculations which are based on simulations have been a successful way of studying anharmonic effects on heat capacity across a wide range of material. We also discussed the
lattice thermal conductivity, its importance and how it is related to the anharmonicity.

Introduction
If the particles in materials are subjected to a harmonic potential, one can expect
the heat capacity to reach Dulong-Petit value (3R) at high temperature, a crystal to have
constant volume with increasing temperature and thermal conductivity to be infinite. But,
we do not experimentally observe these characteristics in a real solid. This can be explained
with the anharmonic interaction between particles. The anharmonicity has effects on heat
capacity, thermal expansion, thermal conductivity, elasticity, phase transition, defect mobility and melting and so on in materials. In fact, the anharmonicity is everywhere in the
nature. Even the interatomic interaction in the most simplest molecule H2 is governed by a
anharmonic potential. Figure 1 shows how the potential of a homogeneous diatomic molecule
deviates from the harmonic potential approximation.

Figure 1: Morse Potential, "Morse Potential." Wikipedia.,

<https://en.wikipedia.org/wiki/Morse_potential>
1

Meanwhile, thermoelectric material has been playing an important role in areas such as
converting waste heat into power.1 The conversion efficiency is expressed as ZT = S 2 T /k,
where S is the Seebeck coefficient, is the electrical conductivity, T is the and k is the thermal
conductivity which can be defined as k = ke +kL where ke and kL are the electronic and lattice
contributions to the thermal conductivity. Enhancing ZT can be achieved by increasing S
or , or by decreasing k. But, S, and ke are interconnected. So, there are limitations in
enhancing by playing with these three parameters only. Since, the lattice contribution to
thermal conductivity, kL , is associated with anharmonicity in the lattice vibration, studying
anharmonicity in thermoelectric material has been important to improve ZT . Again, the
lattice thermal conductivity, kL is connected with heat capacity, Cv via kL = 1/3Cv Vs l (=
1/3Cv Vs2 ), where Vs is phonon velocity, l is phonon mean free path and is the phonon
relaxation time.2 This relation gives enough evidence for the lattice thermal conductivity to
be associated with anharmonicity.

Theory/Methods
Heat Capacity
The simple models for heat capacity (Dulong-Petit, Einstein and Debye) are based on
harmonic Potential. As long as the effects from anharmonic terms are small, they can be
considered as perturbations to the harmonic potential. But, the quantitative evaluation of
anharmonicity effects has remained a challenge due to unknown accuracy of the leadingorder anharmonic perturbation theory.3, 4 Therefore, in order to have a satisfactory model
for internal energy, a good understanding about interatomic interaction is essential.3, 4
U=

1X
1X
1X
0
0
0
0
x (r0l l ) +
x (ll0 )(ulx ulx ) +
xy (ll0 )(ulx ulx )(uly uly )
2 ll0
2 ll0 x
4 ll0 xy
1 X
0
0
0
+
xyz (ll0 )(ulx ulx )(uly uly )(ulz ulz )
12 ll0 xyz
1 X
0
0
0
0
xyz (ll0 )(ulx ulx )(uly uly )(ulz ulz )(ul ul )
+
48 ll0 xyz

(1)

Andritsos et al.3 mention that the most common approach to understand and include
anharmonic effects into heat capacity is to expand the potential energy U in a Taylor series
in the atomic displacements (1). As Cowley4 claims that the anharmonic coefficients in the
expansion are complicated to evaluate. Therefore, some approximations are necessary to
evaluate them. But those approximations are found to be quite inadequate for real systems,
this method is useful for order-of-magnitude calculations only.3 Assuming the interactions
to include only pair and short-range interactions ,from low order perturbation theory, for
example Cv for a face centered cubic lattice is given as,5
172.3 (000 (r0 ))2 1 h
2 1 00
1 I V (r0 )
+
T

(r0 ) + O(T 3 )
Cv = 3N 1 T
8 (00 (r0 ))2
4608 (00 (r0 ))3
3 M T2

(2)

where T is the temperature, N is the number of atoms and kB = 1 and with the assumption
that the are known.
Even though, experimental data like phonon lifetimes and frequency shifts and etc are
helpful to estimate these anharmonic expansion coefficients, there are limitations for the
predictive power of the theory. This is mainly due to the lack of reliable models for interatomic forces. So, to understand anharmonic effect and obtain the quantitative significance
of anharmonic calculations, realistic models are needed.3 The problem of anharmonic effect
in interatomic interaction is particularly significant with modern materials which have complicated interactions such as hydrogen-bonds, magnetic correlations, large number of distinct
atoms and so on.3 It has been shown that the effect of anharmonicity on glass transition on
the heat capacity Cv has been in the form of equation (3).6
Cv = 3N (1 + T )

(3)

where is the thermal expansion coefficient.

The constant heat capacity Cv and thermal expansion appear in relation (3). But, this
can be explained as below. There is a softening of the bulk modulus with temperature at
constant volume due to anharmonicity. More importantly, this relation (3) has only one
parameter and it can be evaluated easily.
Andritsos et al.3 have performed molecular dynamics (MD) simulations and have shown
that relation (3) is in good agreement with simulation results across wide range of crystals.
MD simulations have been more advantageous over experiments to study the equation (3).
Because, when Cv is experimentally evaluated, the relation Cv = Cp - V T 2 B has to be
used, where B is the bulk modulus. Therefore, there is always uncertainty in Cv due to
the uncertainties in and B which are experimentally evaluated. But, MD simulations
allows to perform calculations with constant volume. At high temperature, the deviation
of Cv from 3R could be due to two effects. They are anharmonicity and quantum effect of
phonon excitation. But, MD simulation is classical approach. So, the quantum effect is not
accounted.

Lattice Thermal Conductivity

Lattice thermal conductivity, kL can be expressed as the sum over one longitudinal (kLA )
and two transverse (kT A and kT 0A ).7
kL = kLA + kT A + kT A0

(4)

These partial thermal conductivities are functions of phonon scattering rates 1/c , where
c is the relaxation time. In solid, the total phonon scatering rate8 (1/c ) involves the contributions from normal phonon scattering (1/N ), Umklapp phonon-phonon scattering (1/U ),
mass- difference impurity scattering (1/m ), boundary scattering (1/b ), and phonon-electron
scattering (1/phe ). The amount of the contribution of these five scattering depends on the
nature of the material and the temperature. For instance, Zhang and et al7 claims that
in polycrystalline materials with low impurity concentration, such as the Cu3 SbSe4 and
Cu3 SbSe3 , the latter three phonon scattering contributions can be ignored at temperatures

above approximately 100 K, since the normal and Umklapp phonon-phonon processes dominate the phonon scattering. In that case, According to Debye-Callaway model,9 the partial
conductivities ki (i represents LA, TA or TA modes) are given by
/T
Z i /T i
4 x
[0i
(x)x
e
1

c
ki = C i T 3
dx + R i /T
3
(ex 1)2
0
0

ci (x)x4 ex
2!
i (ex 1)2 dx]
N
ci (x)x4 ex
i
i (ex 1)2
N U

dx

(5)

where i is the longitudinal (transverse) Debye-temperature.

x=

,
KB T

(6)

and
Ci =

4
kB
.
2 2 h
3 vi

(7)

where h
is the plank constant, kB is the Boltzmann constant, is the phonon frequency and
vi is the longitudinal or transverse acoustic phonon velocity.
According to the Slack and et al10 the scattering rate (1/ ) for normal and Umklapp
phonon-phonon scattering isdirectly
proportional to the square of the Gr
uneisen parameter

11
i
which is defined as i = V
.
Here
V
is
the
volume
per
atom.
This
parameter is a
V
measure of bonding anharmonicity which governs phonon-phonon scattering.12 Therefore,
the anharmonicity is used as a tool to tune lattice thermal conductivity in thermoelectric
material.

Summary
The specific heat capacity cannot be explained excluding anharmonic effects. While
dealing with anharmonicity , the Taylor series expansion of the internal energy in atomic
displacements has not been practical way of studying anharmonic effects on heat capacity.
But, theoretical simulations and some experimental data along with some better approximation have been used as a way of studying and explaning the anharmonicity. The relation
between the anharmonicity and the lattice thermal conductivity was also discussed. This
relation has been an useful way to enhance the efficiency of energy conversion in modern
thermoelectric materials. Because, even though there are practical limitatioms, increasing
anharminicity helps to decrease the lattice thermal conductivity.

References
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10

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11

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12

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