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GRUNEISEN PARAMETER OF METALS BASED ON FREE ELECTRON THEORY

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International Journal of Mechanical and Production
Engineering Research and Development (IJMPERD)
ISSN (P): 2249–6890; ISSN (E): 2249–8001
Vol. 10, Issue 3, Jun 2020, 5107-5114
© TJPR Pvt. Ltd.

GRUNEISEN PARAMETER OF METALS BASED ON FREE ELECTRON THEORY

G.E. ADESAKIN 1, O. OLUBOSEDE2, A.T. FATIGUN3, E.O. ALIYU4, E.A. OYEDELE5, M.A.
ADEKOYA6, O. G. EDEMA7, A.O. AKINBOLUSERE8, S.I. OTOBO9, T.O. EWUMI10
1,3,5,10
Department of Physics, Ekiti State University, Ado-Ekiti, Nigeria
2
Department of Physics, Federal University Oye- Ekiti, Nigeria
4
Department of Computer Science, Adekunle Ajasin University, Akungba Akoko
6
Department of Physics, Edo University, Iyamho, Nigeria
7,8
Department of Physical Sciences, Federal Polytechnic, Auchi, Edo State, Nigeria
9
Department of Basic Sciences, Federal Polytechnic, Auchi, Edo State, Nigeria
ABSTRACT

We present an efficient theoretical approach for computing the Gruneisen parameter of metals based on free electron
theory. The experimental value of Fermi energy and the poisson ratio of metals is used for computation. The result
obtained agree quite well with experimental value this prove that free electron theory is useful in theoretical predictions
of some properties of metals. The study revealed that Gruneisen parameter of metals depend on electronic concentration,

Original Article
conduction electron, electron compressibility and number of valence electron per unit cell. The Gruneisen parameter of
metals decreases as strain and temperature between the interacting electron increases for most metals except potassium
whose gruneisen parameter does not increase nor decrease as deformation increases. These could be due to its high
electron mobility and strong electron cohesion. The trend exhibited by Molybdenum in this work is due to variable
valence electron exchange between the interacting ions which make it to be mostly affected by strain. Deformation
affects Gruneisen parameter of metal.

KEYWORDS: Gruneisen parameter, Deformation, Strain, Poisson ratio, Free electron theory & Electronic
concentration

Received: Jun 10, 2020; Accepted: Jun 30, 2020; Published: Jul 27, 2020; Paper Id.: IJMPERDJUN2020485

INTRODUCTION

The free electron theory of metals refers to the case in which the atomic valence electrons are treated as if they are
free rather than being bound to the lattice points. The basic assumption of the free electron theory is that metals is
equivalent to a gas of free electrons in an empty box that can be described by a time independent Schrodinger’s
equation (Kakani and Kakani, 2004). The simplest model for describing electrons in solids is to assume that the
valence electrons are free to move anywhere throughout the volume of the material and behave as a delocalized gas
of free electrons (Kachhava, 1992). Many thermal properties of solid are determined by electron vibrational
behavior, e.g. heat capacity, thermal conductivity and thermal expansion (Animalu,1977). The specific heat at
constant volume is the change in internal energy and temperature (Elliott, 1997). The internal energy per unit
volume is a collection of classical particles at inverse temperature contained in a volume (Ashcroft and Mermin,
1976). Internal energy in metals are: the vibrational energy of the metallic atoms about their mean lattice position
and the free energy of the free electrons (Pillai, 2010). The excitation of phonons contributes to change in internal
energy of solid (Efthimious, 2003). The band gap energy is the minimum energy required to excite electrons from

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5108 G.E. Adesakin +, O. Olubosede, A.T. Fatigun, E.O. Aliyu, E.A. Oyedele,
M.A. Adekoya, O. G. Edema, A.O. Akinbolusere , S.I. Otobo, T.O. Ewumi

their ground state (Kittel, 1976). The excitation of electrons in metals is as important as that of phonons when it is included
in the picture gives different behavior of specific heat and thermal expansion coefficient at low temperature. This effect is
explicitly treated by modeling electrons as Fermi liquid which requires a many body picture (Efthimious, 2003). The
concept of phonons determines the thermal properties of crystals and their specific heat (Kittel, 1976). Expansion
coefficient, bulk modulus, density and specific heat are properties of Grüneisen parameter. Grüneisen parameter can be
presented in terms of elastic moduli and their pressure derivatives (Elliott,1997). Grüneisen parameter provide relationship
between thermal and mechanical parameters such as adiabatic variation of temperature with density. Gruneisen parameter
is a quantity that can be measured directly by experiment (Efthimious, 2003). Gruneisen parameter is an important
parameter that figures in the thermodynamical properties of solids which provides a measure of the anharmonicity of
crystal (Rogalski and Palmer, 2000). Debye model describe the behavior of the specific heat as a function of temperature
(Pillai, 2010). Metallic deformation simply means conversion of metals into different shapes or sizes (Backofen, 1972).
Metals are deformed by appllying compressive, torsion or tensile force or by high-powered technology. Before now,
different theoretical model has been developed and used to study different properties of metals, Xun Zhang et. al, (2019)
develop a thermodynamic model of temperature-dependent potential energy based on Molecular dynamics simulations,
investigate the temperature dependent Grüneisen parameter of bulk material. He obtained thermodynamics quantities
which links the material properties of bulk modulus, heat capacity at constant volume, thermal expansion coefficient and
volume together. These thermo-mechanical properties and Grüneisen equation of state yield temperature dependent
analytical solutions of Grüneisen parameter. Manish (2014), studied the Gruneisen parameter, thermal expansion and some
thermodynamic properties of nickel-disilicide (NiSi2) using the density-functional theory. The Gruneisen parameter
dispersions, thermal expansion coefficients, heat capacities and bulk modulus were ccomputed from volume dependence
phonon frequencies. The result obtained are in good agreement with experimental value and other theoretical computation
result. Rakibul, et, al (2013) developed a nonlinear optimization algorithm to extract the parameters of metals using
modified Debye model approach based on optimization method. The results obtained were in excellent agreement with
experimental value when compared. The extracted parameters were used to determine the complex relative permittivity of
metals in optical and electromagnetic spectrum. Adesakin et. al (2019) developed a model for computing current density,
drift velocity and electron mobility of metals based on free electron theory. The results obtained agreed with experimental
value. This proved the usefulness of free electron theory in the theoretical prediction of some properties of metals. The
current density of metals reduces as deformation rises while the drift velocity and electron mobility rise as the strain
increases. Adesakin et. al (2019) studied the Debye temperature and Debye frequency of some metals using quantum
Einstein theory. The result obtained agreed with experimental value. Debye temperature and Debye frequency of metals
falls as strain rises. This shows that Debye properties of metals are influenced by deformation. Adesakin (2017) computed
the effect of strain on the bulk modulus and electron compressibility in metals using pseudopotential formalism. The
computed result agree quite well with experimental value. Bulk modulus and electron compressibility are affected by
deformation. Adesakin (2018), examined the electronic heat capacity of strained metals using Einstein model formalism.
The result obtained revealed that electronic heat capacity of metals relied on average distance between interacting electron.
The computed result agree with experimental value. The electronic heat capacity increases as strain increases. Here,
Gruneisen parameter of metals were computed and studied using free electron theory formalism. The results obtained were
compared with theoretically experimental value.

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Gruneisen Parameter of Metals Based on Free Electron Theory 5109

THEORETICAL CONSIDERATION

In solids, the potential energy for the ionic motion varies with interatomic separation and can be written for a given atom as
Taylor expansion about its equilibrium position ⃗⃗⃗⃗
𝑅0 in the form
2 3 4
⃗⃗⃗⃗0 ) + 1 𝐾(𝑅⃗ − ⃗⃗⃗⃗
𝐸(𝑅⃗) = 𝐸(𝑅
1
𝑅0 ) − 3 𝜇(𝑅⃗ − ⃗⃗⃗⃗
1
𝑅0 ) − 4 𝜉(𝑅⃗ − ⃗⃗⃗⃗
𝑅0 ) − ⋯ ⋯ ⋯ (1)
2

where 𝑅⃗ is the average interatomic distance, ⃗⃗⃗⃗

𝑅0 is the zero-temperature separation and the presence of the third,
fourth and higher order term called an-harmonic terms is associated with thermal expansion of solids. The physical effect
which is related to phonon modes and the specific heat is the thermal expansion of a solid. The thermal expansion
coefficient 𝛼 is defined as the rate of change of the linear dimension L of the solid with temperature T, normalized by
linear dimension at constant pressure P is

1 𝜕𝐿
𝛼 = 𝐿 (𝜕𝑇) (2)
𝑃

1⁄
The linear dimension of the solid L is related to its volume Ω through 𝐿 = Ω 3, which gives the thermal
expansion coefficient in terms of volume as

1 𝜕Ω
𝛼 = 3Ω ( 𝜕𝑇 ) (3)
𝑃

Expressing this in terms of bulk modulus B, the negative inverse of which the rate of change of volume with
pressure normalized by volume at constant temperature is

1 𝜕Ω
𝐵 −1 = − Ω ( 𝜕𝑃 ) (4)
𝑇

The thermal expansion coefficient in terms of bulk modulus and pressure is obtained with the help of standard
thermodynamic relations as

1 𝜕𝑃
𝛼 = 3𝐵 (𝜕𝑇 ) (5)
Ω

The pressure is given by the negative rate of change of the internal energy E with volume at constant temperature

𝜕𝐸
𝑃 = − (𝜕Ω) (6)
𝑇

When changes in the internal energy E are exclusively due to phonon excitations, the thermal expansion
coefficient is obtained as
(𝑙) (𝑙)
1 −𝜕ℏ𝜔𝑘 𝜕𝑛𝑘
𝛼= ∑𝑘,𝑙 ( ) ( ) (7)
3𝐵 𝜕Ω 𝑇 𝜕𝑇 Ω

(𝑙) (𝑙)
where 𝜔𝑘 is the phonon frequencies, 𝑛𝑘 is the corresponding average occupation numbers at temperature T. the
thermal expansion coefficient in terms of the specific heat is obtained as
𝛾𝑐𝑣
𝛼= 3𝐵
(8)

where 𝛾 is the Gruneisen parameter, 𝑐𝑣 electronic heat capacity at constant volume and B is the bulk
modulus. The Gruneisen parameter is given by

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5110 G.E. Adesakin +, O. Olubosede, A.T. Fatigun, E.O. Aliyu, E.A. Oyedele,
M.A. Adekoya, O. G. Edema, A.O. Akinbolusere , S.I. Otobo, T.O. Ewumi
(𝑙) (𝑙) (𝑙) (𝑙) (𝑙) −1
1 −𝜕ℏ𝜔𝑘 𝜕𝑛𝑘 −𝜕ℏ𝜔𝑘 𝜕𝑛𝑘 (𝑙) 𝜕𝑛𝑘
𝛾 = 𝑐 ∑𝑘,𝑙 𝜕Ω 𝜕𝑇
= −Ω [∑𝑘,𝑙 𝜕Ω 𝜕𝑇
] [∑𝑘,𝑙 ℏ𝜔𝑘
𝜕𝑇
] (9)

Simplifying the notation in this equation by defining the contributions to the specific heat from each phonon mode
as
(𝑙)
(𝑙) (𝑙) 𝜕𝑛𝑘
𝑐𝑘 = ℏ𝜔𝑘 (10)
𝜕𝑇

and the mode-specific Gruneisen parameters as

(𝑙) (𝑙)
(𝑙) Ω 𝜕𝑛𝑘 𝜕(𝑙𝑛𝜔𝑘 )
𝛾𝑘 = − (𝑙) =− (11)
𝜔𝑘 𝜕𝑇 𝜕(𝑙𝑛Ω)

in terms of which the Grunisen parameter takes the form

−1
𝛾 = [∑𝑘,𝑙 𝛾𝑘𝑙 𝑐𝑘𝑙 ][∑𝑘,𝑙 𝑐𝑘𝑙 ] (12)

In this article, Gruneisen parameter of metals were computed using equation (12), its variation with linearly
applied strain is investigated.

RESULTS AND DISCUSSIONS

In figure 1 Gruneisen parameter versus electron density parameter is plotted for different groups and periods of metals. The
result obtained indicate that there is agreement between the computed and experimental value. These shows the theory
used in this computation is useful for theoretical prediction of some properties of metals as it takes into consideration all
the factors that Gruneisen parameter of metal relied on. Such as electronic heat capacity, mean free path, electrical
conductivity and some Fermi properties of metals. Figure 1 revealed that the electron in metals whose Gruneisen parameter
were computed and studied concentrated more in the high-density region than low-density region. These revealed that
Gruneisen parameter of metals depend on electronic concentration and valence electron density. The experimental value
for the Gruneisen parameter is obtained theoretically by substituting directly the experimental value of Fermi energy
obtained in Solid State Physics by Charles Kittel, 1976 into the model used. Figure 1 also revealed that the number of
valence electron per unit cell, conduction electron and electron compressibility of metals in high density region is higher
than those in the low-density region and thus responsible for high Gruneisen parameter of metals in this region. Figure 2
shows a plot of gruneisen parameter versus strain for different groups and period of metals. The Gruneisen parameter of
metals decreases as strain increases for most of the metals except potassium whose Gruneisen parameter does not increase
nor decrease as deformation increases. These could be due to its high electron mobility and strong electron cohesion. The
trend exhibited by metals in figure 2 revealed that as deformation increases the interatomic distance between electron
increases and thus reduces the compressibility of the interacting electron which forces the Gruneisen parameter of metals to
decrease as deformation increases. Among all the metals subjected to different deformation in figure 2, Molybdnum is
highly affected by deformation while Potassium is least affected. These could be due to the uncertainties in the variable
valence electron, atomic size and the chemical bonding in the metal. Behavior of metals in figure 2 also revealed that as
deformation increases the vibrational energy and collision between the interacting electron rises which forces the
temperature to increase and then reduces the Gruneisen parameter of metals as deformation increases. With this we came to
the conclusion that deformation affect Gruneisen parameter of metals.

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Gruneisen Parameter of Metals Based on Free Electron Theory 5111

CONCLUSIONS

Gruneisen parameter of metals is computed and studied, the results obtained shows that Gruneisen parameter of metals
depend on electronic concentration and valence electron density. There is agreement between the computed and theoretical
experimental value. The results obtained revealed that Gruneisen parameter of metals in the high-density region is higher
than low-density region due to the number of valence electron per unit cell, high conduction electron and high electron
compressibility that is found in the metals in this region. The Gruneisen parameter of metals decreases as strain increases
for most of the metals examined except potassium whose Gruneisen parameter neither increase nor decrease as
deformation increases. Which may be due to its high electron mobility and strong electron cohesion. The trend exhibited
by Molybdenum is due to variable valence electron exchange between the interacting ions. With this, we conclude that
Gruneisen parameter of metal is affected by deformation.

0.075
0.070 Experimental Value
0.065 Computed Value
0.060
GRUNEISEN PARAMETER

0.055
0.050
0.045
0.040
0.035
0.030
0.025
0.020
0.015
0.010
0.005
0.000
-0.005

1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0

ELECTRON DENSITY PARAMETER (a.u)

Figure 1: Gruneisen Parameter Versus Lectron Density Parameter of Metals

0.035 POTASSIUM
COPPER 0.10 BERYLLIUM
SILVER MAGNESSIUM
0.030
CHROMIUM NICKEL
GRUNEISEN PARAMETER

ZINC
GRUNEISEN PARAMETER

IRON 0.08
0.025 CADMIUM

0.020 0.06

0.015
0.04

0.010

0.02
0.005

0.000 0.00
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
STRAIN STRAIN

0.028
0.08 LEAD
0.026 ALUMINIUM
BISMUTH MOLYBDNUM
0.024 0.07
TITANIUM TUNGSTEN
0.022 GOLD
YTTRIUM
GRUNEISEN PARAMETER
GRUNEISEN PARAMETER

0.020 0.06 PLATINIUM

TIN
0.018 TANTALUM
0.05
0.016
0.014 0.04
0.012
0.03
0.010
0.008 0.02
0.006
0.004 0.01

0.002
0.00
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
STRAIN STRAIN

Figure 2: Gruneisen Parameter Versus Strain for Some Metals

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5112 G.E. Adesakin +, O. Olubosede, A.T. Fatigun, E.O. Aliyu, E.A. Oyedele,
M.A. Adekoya, O. G. Edema, A.O. Akinbolusere , S.I. Otobo, T.O. Ewumi

Table 1: Gruneisen parameter of undeformed Metals. The experimental values are obtained theoretically from
Introduction to Solid State Physics by Kittel (1976) and Ashcroft and Mermin (1976).
Electron Density Parameter Computed Gruneisen Experimental Gruneisen
Metals
rs(a.u) parameter parameter
K 4.96 2.51814E-4 2.77588E-4
Cu 2.67 0.00557 0.0055
Ag 3.02 0.00301 0.00298
Be 1.87 0.03306 0.03189
Mg 2.65 0.00578 0.00576
Cr 1.86 0.03395 -
Fe 2.12 0.01765 0.01741
Ni 2.07 0.01989 -
Zn 2.31 0.01149 0.01702
Cd 2.59 0.00649 0.00645
Al 2.07 0.01989 0.01957
Bi 2.25 0.01311 0.01308
Ti 1.92 0.02897 -
Y 2.61 0.00624 -
Sn 2.22 0.01402 0.01352
Pb 2.30 0.01174 0.0114
Mo 1.61 0.06987 -
W 1.62 0.06774 -
Au 2.39 0.00969 0.00302
Pt 2.00 0.02362 -
Ta 2.84 0.00409 2.77588E-4

Table 2: Gruneisen parameter of Deformed Metals

Strain
Metals rs (a.u) 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8
K 4.96 2.09E-04 1.77E-04 1.52E-04 1.32E-04 1.16E-04 1.03E-04 9.21E-05 8.30E-05 7.52E-05
Cu 2.67 0.0046 0.0039 0.0034 0.0029 0.0026 0.0023 0.0020 0.0018 0.0017
Ag 3.02 0.0025 0.0021 0.0018 0.0016 0.0014 0.0012 0.0011 0.0099 0.0090
Be 1.87 0.0274 0.0232 0.0199 0.0173 0.0152 0.0135 0.0121 0.0109 0.0987
Mg 2.65 0.0048 0.0041 0.0035 0.0030 0.0027 0.0024 0.0021 0.0019 0.0017
Cr 1.86 0.0282 0.0238 0.0204 0.0178 0.0156 0.0139 0.0124 0.0112 0.0101
Fe 2.12 0.0146 0.0124 0.0106 0.0092 0.0081 0.0072 0.0065 0.0058 0.0053
Ni 2.07 0.0165 0.0139 0.0120 0.0104 0.0092 0.0081 0.0073 0.0066 0.0059
Zn 2.31 0.0095 0.0081 0.0069 0.0060 0.0053 0.0047 0.0042 0.0038 0.0034
Cd 2.59 0.0054 0.0045 0.0039 0.0034 0.0030 0.0027 0.0024 0.0021 0.0019
Al 2.07 0.0165 0.0139 0.0119 0.0104 0.0092 0.0081 0.0073 0.0066 0.0059
Bi 2.25 0.0109 0.0092 0.0079 0.0069 0.0060 0.0054 0.0048 0.0043 0.0039
Ti 1.92 0.0240 0.0203 0.0174 0.0152 0.0133 0.0118 0.0106 0.0095 0.0087
Y 2.61 0.0052 0.0044 0.0038 0.0033 0.0029 0.0026 0.0023 0.0021 0.0019
Sn 2.22 0.0116 0.0098 0.0084 0.0073 0.0065 0.0057 0.0051 0.0046 0.0042
Pb 2.30 0.0097 0.0082 0.0070 0.0062 0.0054 0.0048 0.0043 0.0039 0.0035
Mo 1.61 0.0789 0.0490 0.0421 0.0366 0.0322 0.0286 0.0255 0.0230 0.0209
W 1.62 0.0562 0.0475 0.0408 0.0355 0.0312 0.0277 0.0248 0.0223 0.0202
Au 2.39 0.0080 0.0068 0.0058 0.0051 0.0045 0.0040 0.0035 0.0032 0.0029
Pt 2.00 0.0196 0.0166 0.0142 0.0124 0.0109 0.0097 0.0086 0.0078 0.0071
Ta 2.84 0.0034 0.0029 0.0025 0.0021 0.0019 0.0017 0.0015 0.0013 0.0012

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