A short review on phonon and Thermodynamic properties

of materials

1.Introduction
The study of materials behaviour at high pressure provides a very good
understanding of the structural, electronic, and dynamical properties of the
system and the basic mechanisms that are responsible for these properties.
Wide band gap oxides at high pressures are of considerable current interest
particularly because of their diverse technological applications in ceramics and
materials industries.
Potential applications of ceramic materials at high temperatures and pressures
require understanding of their vibrational and thereby thermodynamic
properties. Such a study is also helpful in understanding the bonding
mechanism and effects of temperature and pressure on various physical
properties. Thermodynamical properties, such as heat transport and specific
heat, play an important role in the understanding of the limits of materials for
nuclear reactors and also for optoelectronic applications. These properties are
mediated by the quantum vibrations of the atomic lattice, as described by the
phonon-dispersion relations. Mechanical properties, such as the elastic
stiffness constants, can also be extracted from the lattice dynamics. Study of
Behaviour of materials under a wide range of temperature and pressure were
done using different methods and approaches. The investigation of phase
transitions of Oxides(BeO) has always attracted scientific attention due to its
fundamental and technological importance. Up to now, the controversy exists
among theory and experiments regarding the sequence of phase
transformations and the related transition pressure in Oxides.
It is obviously crucial to take into account the thermodynamic properties which
are combined with the effect of temperature in the investigation of the
properties of metals and intermetallics as well as their applications. Thermal
properties of solids such as thermal expansion depend on their lattice
dynamical behaviour.
2. Background Theory

Neutron cross section

neutron cross section is used to express the interaction between an incident
neutron and a target nucleus. The neutron cross section σ can be defined as
the area in cm2 for which the number of neutron-nuclei reactions taking place
is equal to the product of the number of incident neutrons that would pass
through the area and the number of target nuclei. The standard unit for
measuring a nuclear cross section is the barn, which is equal to 10−28 m² or
10−24 cm². 
Neutron scattering

scattering of neutrons from a N particles system with a random distribution of

spins or isotope types can be expressed as the sum of a coherent part and an
incoherent part. The coherent part includes the effect from the interfering
wave and incoherent part depend on the sum of the non-interfering wave.
The coherent and incoherent scattering include both elastic and inelastic parts.
The elastic scattering takes place with no energy change. thermal elastic
scattering considered to be scattering from the entire lattice, thus the effective
mass of the target is very large, and the neutron does not lose energy in the
scattering process. Thermal inelastic scattering results in an energy loss (gain)
for the neutron with a corresponding excitation (deexcitation) of the target.
Thermal scattering law
Differential scattering cross section for thermal neutrons for gases, liquids or
solids consisting of randomly ordered microcrystals can be written as
σb
√
'
E
σ ( E → E' , µ) = 2 kT E
s (α , β )

--------- (1)
where E and E' are the incident and secondary neutron energies in the
laboratory system, µ is the cosine of the scattering angle in the laboratory, σ bis
the characteristic bound scattering cross section for the material, kT is the
thermal energy in eV, and S is the asymmetric form of the scattering law. The
scattering law depends on only two variables: the momentum transfer
 E + E−2 μ √ E E
' '
α=
AkT

------------( 2)
where A is the ratio of the scatterer mass to the neutron mass, and the energy
transfer
E' −E
β=
AkT

β is positive for energy gain and negative for energy loss.

The scattering law can be written as

∞
1
s (α , β ) = ∫
2 π −∞
iβ ^t −γ ^t
e e dt

where t^ is time measured in units of ℏ/(kT) seconds. The function γ(t^ ) is given
by
∞
γ ( t^ ) =∫ P ( β ) ¿ ¿] e− β ¿d𝛽
−∞

Where
P( β )
P ( β )=
2 β sinh ⁡(β /2)

and where ρ(β) is the frequency spectrum of excitations in the system

expressed as a function of β.
∞

∫ p ( β ) dβ=1
0

Phonon
phonon concept was introduced by Igor Tamm in 1932. Phonon are basically
quanta of lattice vibration like photon representing quanta of electro magnetic
radiation.
Thermal inelastic scattering results in an energy loss (gain) for the neutron with
a corresponding excitation (deexcitation) of the target. The excitation may
correspond to the production of one or more phonons in a crystalline material,
to the production of rotations or vibrations in molecules. The energy of a
elastic mode of vibration occupied by n phonons is given by

ε = n+( 12 )ℏω

Since phonon coordinate contain relative coordinate of atom, so phonon do

not carry any momentum. The inelastic scattering of phonon involve creation
or absorption of phonon is described by the selection rule.

k + G = k'±K

Where K is the phonon wave vector and G is the reciprocal lattice vector.

Phonon density of states

Phonon density of states denote the number of modes per unit frequency
range for a given polarization. the phonon density of states in three
dimensions for each polarization is,

( )( )
2
ⅆN vk ⅆk
D ( ω) = =
ⅆω 2 π 2 ⅆω

Where ω is the angular frequency and k is the momentum.

Specific heat
It is a amount of heat required to change the temperature of unit mass of
substance by unit degree temperature. If ∆ Q represents the quantity of heat
energy to a substance m and rise in temperature is∆ θ , then

3.Approaches and methods used to calculate thermodynamic properties

 Study of Behaviour of materials under a wide range of temperature and
pressure were done using different methods and approaches.
A. Density functional theory: -
one of the most popular quantum mechanical methods to matter is density
functional theory. It is useful to compute the band structure of solids. In
quantum mechanics, we know that wave function of the system contains all
information about the system. Density functional theory gives a versatile way
to solve the many body problem. It maps the many body problem into single
body problem very systematically. For this Density functional theory promotes
particle density n(r) from one observable and the calculation of all other
observables depends on that.
The conceptual structure of Density functional theory can be given as,
n(r) ⇒ φ (r 1 ,r 2 , … … … ..r N )⇒ v ( r)
B. Local density approximation
The LDA consists of close by approximating the accurate exchange-correlation
energy of a system by using the exchange-correlation energy of a
homogeneous electron gas of the equal density. The LDA is only dependent on
the local density (Clark, 2003). The LDA states "The contribution to the
exchange-correlation energy from an infinitesimal volume 'dr' is same as a
homogenous electron gas (jellium) with the same density at r". In LDA, the
correlation function of inhomogeneous gas is approximated by that of
interacting homogeneous gas.
C. Generalised Gradient Approximation
Langreth and co-workers made generalised gradient approximation which is
meant for the exchange-correlation hole, through contribution of small wave-
vector to the expansion of the 2nd order density-gradient of Fourier transform.
D. The Pseudopotential
The pseudopotential idea is basically an extension of the orthogonalized plane
wave method. It explains the fitting of free electron calculation in actual band
structures. The pseudopotential approach replaces the effect of core electrons
upon valence electrons with a suitable potential such that after some point this
potential behaves like all electron potential.
 There are many open and paid software for calculation of Phonon
density of states and thermal properties.
o VASP
o QUANTUMESPEWSSO
o ABINIT
o SIESTA

4. CONCLUSION
Authors have instigated Phonon density of states and thermal properties for
several materials such as ZrW 2 O8,Mg, Be, Graphite etc. calculations have done
for different range of temperature and pressure using ab initio approach.
VASP, QUANTUMESPRESSO, ABINIT, SIESTA, PHONOPY softwares has used to
generate phonon density of states. But Analytical approach has not been
reported for phonon and thermodynamic property calculations.

5. REFERENCE
• Shashi Shekar P. Adiga, Vivekananda P. Adiga, Robert W. Carpick and
Donald W. Brenner Kodak Research Laboratories, Eastman Kodak
Company, Rochester, NY 14650, U.S.A. 2 School of Applied and
Engineering Physics, Cornell University, Ithaca, NY 14853, U.S.A. 3
Department of Mechanical Engineering and Applied Mechanics,
University of Pennsylvania, Philadelphia, PA 19104, U.S.A
• A. I. Hawari, I. I. Al-Qasir, V. H. Gillette, B. W. Wehring, T. Zhou
Department of Nuclear Engineering, P.O. Box 7909, North Carolina State
University, Raleigh, NC 27695-7909
• ZHU, YUWEI. Thermal Neutron Scattering Cross Sections for Silicon
Carbide. (Under the direction of Ayman I. Hawari).
• Prof. S. Lakel, Dr. F. Elhamra Laboratory of Physical Materials University
of Laghouat BP 37G Laghouat, Algeria E-mail: said.lakel@yahoo.fr Prof.
S. Lakel, Dr. K. Almi Material Sciences Department Faculty of Science
University Biskra Biskra 07000, Algeri
• Yong Pan a, Weiming Guan b a School of Materials Science and
Engineering, State Key Laboratory of Oil and Gas Reservoir Geology and
Exploitation, Southwest Petroleum University, Chengdu 610500, China b
State Key Laboratory of Advanced Technologies for Comprehensive
Utilization of Platinum Metals, Kunming 650106, China