Eur. Phys. J.

Plus (2022) 137:545

https://doi.org/10.1140/epjp/s13360-022-02733-4

Regular Article

Analysis of melting of some metals using pressure dependence of the Grüneisen

parameter in the Lindemann law

D. Ashwini1,a , Vijay S. Sharma2,b , K. Sunil3,c

1 Department of Physics, I. B. S. Khandari Campus, Dr. Bhimrao Ambedkar University, Agra 282002, India
2 Department of Mechanical Engineering, Delhi Technological University, Delhi 110042, India
3 Department of Physics, I. E. T. Khandari Campus, Dr. Bhimrao Ambedkar University, Agra 282002, India

Received: 21 January 2022 / Accepted: 17 April 2022

© The Author(s), under exclusive licence to Società Italiana di Fisica and Springer-Verlag GmbH Germany, part of Springer Nature 2022

Abstract In order to obtain the melting curves representing the relationship between melting temperature and pressure for a material
with the help of Lindemann’s law, we need an accurate evaluation of the bulk modulus and the Grüneisen parameter at different
pressures. We have used the results determined from the reciprocal K-primed equation of state and the reciprocal gamma relationship
in the Lindemann formulation to calculate melting temperatures and slopes of the melting curves for ten metals, viz. Cu, Mg, Pb,
Al, In, Cd, Zn, Au, Ag, Mn at different pressures. The results are found to present reasonably good agreement with the experimental
data up to 16 GPa, except in few cases such as Al. The melting curves of five metals, viz. Cu, Mg, Zn, Au, Ag, are extended into
a megabar pressure range using the present method and compared with the data reported in the recent literature. The agreement
with the experimental data is improved to a great extent when we use the Stacey law of melting in place of the Lindemann law. The
method developed in the present study has the advantage that the melting curve can be determined analytically without using power
computers.

1 Introduction

Arafin et al. [1, 2] have presented a formulation for the pressure dependence of melting temperature T m for a material which yields
the following expression
  
K 0 P 2(γ0 −1/3)/K 0
Tm (P)  Tm0 1 + (1)
K0

where T m0 is the melting temperature, γ0 is the Grüneisen parameter, K 0 is the bulk modulus, K 0 is the pressure derivative of
bulk modulus, all at zero pressure (P  0). Equation (1) has been derived [1, 2] from the Lindemann law [3, 4] incorporating two
assumptions. First, bulk modulus of solids depends linearly on pressure

K  K 0 + K 0 P (2)

and the second assumption is that the Grüneisen parameter does not depend on pressure, i.e., γ (P)  γ0 . Both of these assumptions
are not valid. Variation of K with P does not follow Eq. (2) because the bulk modulus depends nonlinearly on pressure such that the
slope dK/dP decreases with the increase in pressure [5] and attains a constant values equal to K ∞  in the limit of infinite pressure

[6]. The Grüneisen parameter γ is not a constant quantity. The pressure derivatives of gamma have very significant magnitudes in
terms of second-order and third-order Grüneisen parameters, q and λ, respectively. They are useful for investigating higher-order
thermoelastic properties of solids [7, 8]. In spite of the invalidity of the two assumptions, Eq. (1) has been found to yield reasonable
agreement with the experimental melting data [9, 10]. It appears therefore that there is a lucky cancellation of errors arising from
the two inaccurate assumptions employed in the derivation of Eq. (1) by Arafin et al. [1, 2].
Subsequently Arafin and Singh [11, 12] considered the following quadratic expressions for bulk modulus K and the Grüneisen
parameter γ in powers of pressure

K  K 0 + a1 P + a2 P 2 (3)

a e-mail: adashwinidixit@gmail.com
b e-mail: vss7694@gmail.com
c e-mail: k.sunil.ibs@gmail.com (corresponding author)

0123456789().: V,-vol 123

 545 Page 2 of 11 Eur. Phys. J. Plus (2022) 137:545

Table 1 Values of input parameters of metals K 0 , K 0 and γ0 from the compilation by Kholiya and Chandra [9]. The other parameters K ∞
 , γ , A and B
∞
are calculated as described in the text

Metal K0 K 0 
K∞ γ0 γ∞ A B
(GPa) Equation (11) Equation (12)

Cu 133.5 3.88 2.33 2.01 1.00 0.4975 1.1708

Mg 36.8 4.30 2.58 1.51 1.12 0.6623 0.5949
Pb 42.7 5.70 3.42 2.63 1.54 0.3802 0.9204
Al 73 4.50 2.70 2.17 1.18 0.4608 1.0439
In 42.68 480 2.88 2.04 1.27 0.4902 0.8560
Cd 42 6.50 3.90 2.40 1.78 0.4167 0.5660
Zn 65 4.60 2.76 2.25 1.21 0.4444 1.0543
Au 167 5.70 3.42 3.03 1.54 0.3300 1.0921
Ag 103.6 4.70 2.82 2.40 1.24 0.4167 1.0992
Mn 158 4.60 2.76 1.95 1.21 0.5128 0.8656

and
γ  γ0 + b 1 P + b 2 P 2 (4)
where K 0 and γ0 are the values of K and γ , respectively, both at zero pressure, a1 , a2 , b1 and b2 are constants for a given solid.
Using Eqs. (3) and (4) in the Lindemann law of melting
 
d ln Tm 2 γ − 13
 (5)
dP K
and then integrating Eq. (5), Arafin and Singh [11, 12] calculated values of T m at different pressures for metals as well as non-metals.
However, it has been found [13, 14] that Eqs. (3) and (4) are not valid at high pressures. Hence the model used by Arafin and Singh
[11, 12] is not physically acceptable. Equations (3) and (4) yield the Grüneisen parameter, bulk modulus and its pressure derivative
which are not consistent with the thermodynamic constraints [5, 6]. Values of γ and K  cannot be negative for normal materials at
any pressure [15, 16]. From the point of view of melting, normal materials are those which do not exhibit any maxima or minima
in their melting curves.
Recently Sunil et al. [17] have developed a method for determining melting curves of MgO and LiF using the Lindemann law
by taking into account the pressure dependence of Grüneisen parameter with the help of the reciprocal gamma relationship in terms
of P/K [15]. This relationship has been found to be consistent with the Stacey reciprocal K-primed equation of state [18] and also
with the thermodynamic constraints for the higher-order thermoelastic properties in the limit of infinite pressure [15]. In view of
the successful application of the model in case of MgO and LiF [17], we apply it to calculate melting curves of ten metals viz. Cu,
Mg, Pb, Al, In, Cd, Zn, Au, Ag, Mn. The results are compared with the available experimental data [19–28] and also with those
obtained from a theoretical model [9] based on the instability of the thermal equation of state originally due to Shanker et al. [29,
30]. We make use of the reliable values of P, K and K  for the metals under study determined with the help of the Stacey reciprocal
K-primed equation of state [5, 8, 18]. The relevance of the present study becomes clear from the recent important investigations
based on the experimental techniques using the Laser-heated diamond anvil cells and synchrotron X-ray diffraction measurements,
and based on the ab initio simulation method to determine melting curve and phase diagram of Mg [31], Zn [32], Pt [33], Nb [34],
Au [35], Ir [36], and Cu [37]. The theoretical methods include the accurate DFT calculations and molecular dynamics which are
very time-consuming and have high cost of computing. On the other hand, the present method based on the Lindemann law can be
used conveniently for determining melting curves without the help of power computers.
Hieu and Ha [38] obtained high-pressure melting curves of silver, gold and copper using the volume dependence of gamma,
γ  γ0 (V /V0 )q with a constant value of q equal to one. Further, they used the Vinet equation of state [39] to transform the volume
data to corresponding values of pressure in order to determine melting temperatures at different pressures. It has been discussed at
length by Stacey and Davis [5, 6] that the volume dependence of γ with q  1 and also the Vinet EOS are not consistent with the
thermodynamic constraints for solids. In the present study, we have used valid expressions to change gamma in terms of K and P.
This is an innovation in the calculation method. An additional innovation for calculating the melting temperatures under different
pressures is the procedure based on Euler’s finite difference calculus.
It is worth mentioning here that Ma et al. [40] have recently developed a model for the pressure dependence of melting temperature
for metals based on the Force-Heat Equivalence Energy Density principle [41]. An equivalent relationship between the heat energy
variations during cooling and the mechanical work during pressurization for the solidification of molten metal has been applied to
derive an expression for melting temperature at different pressures in terms of bulk modulus K and its first pressure derivative K  ,
both at zero pressure [40]. The model thus developed by Ma et al. predicts melting curves for metals in good agreement with the

123
Eur. Phys. J. Plus (2022) 137:545 Page 3 of 11 545

Table 2 Values of V /V 0 , P, K, K  determined from the Stacey reciprocal equation of state

Cu Mg

V /V 0 P K K V /V 0 P K K
(GPa) (GPa) (GPa) (GPa)

1 0 133.5 3.88 1 0 36.8 4.30

0.9946 0.735 136.3 3.85 0.9809 0.74 39.9 4.17
0.9877 1.7 140 3.81 0.9580 1.73 44 4.03
0.9792 2.93 144.7 3.76 0.9482 2.19 45.8 3.97
0.9743 3.66 147.4 3.74 0.9288 3.18 49.7 3.87
0.9720 4.0 148.7 3.72 0.9113 4.15 53.3 3.79
0.9678 4.65 151.1 3.70 0.8957 5.12 57.1 3.72
0.9617 5.63 154.8 3.67 0.8740 6.58 62.4 3.64
0.9539 6.9 159.4 3.64 0.8566 7.81 66.5 3.58
0.9373 9.8 169.8 3.56 0.8470 8.54 69 3.54
0.9214 12.8 180.4 3.50 0.8326 9.75 73.2 3.50
0.9056 16 191.4 3.44 0.8188 10.97 77.3 3.46
Pb Al

V /V 0 P K K V /V 0 P K K
(GPa) (GPa) (GPa) (GPa)

1 0 42.7 5.70 1 0 73 4.50

0.9829 0.77 47 5.49 0.9899 0.757 76.4 4.42
0.9683 1.5 50.9 5.34 0.9781 1.7 80.5 4.33
0.9470 2.7 57.1 5.14 0.9629 3 86 4.23
0.9390 3.2 59.7 5.08 0.9478 4.4 91.9 4.14
0.9238 4.2 64.6 4.97 0.9399 5.2 95.3 4.10
0.9102 5.2 69.5 4.87 0.9256 6.7 101.4 4.02
0.8952 6.4 75.3 4.78 0.9126 8.2 107.5 3.96
0.8735 8.1 81.9 4.65 0.8987 9.9 114.2 3.89
0.8567 9.6 88.1 4.57
0.8406 11.1 93.9 4.49
0.8330 11.9 97.2 4.46
In Cd

V /V 0 P K K V /V 0 P K K
(GPa) (GPa) (GPa) (GPa)

1 0 42.68 4.80 1 0 42 6.50

0.9841 0.71 46 4.66 0.9844 0.69 46.4 6.26
0.9549 2.2 52.8 4.44 0.9740 1.2 49.6 6.11
0.9410 3 56.4 4.36 0.9076 5.5 74.4 5.45
0.9178 4.5 62.9 4.22 0.8939 6.7 80.8 5.34
0.9120 4.9 64.6 4.19 0.8834 7.7 85.9 5.27
0.8973 6.0 69.2 4.12 0.8693 9.2 93.5 5.18
0.8817 7.2 73.8 4.04 0.8573 10.7 100.5 5.11
0.8763 7.7 76.0 4.02 0.8485 11.9 105.9 5.06
0.8590 9.2 81.6 3.95
0.8385 11.2 89.2 3.87
0.8308 12 92.1 3.84

123
 545 Page 4 of 11 Eur. Phys. J. Plus (2022) 137:545

Table 2 continued

Zn Au

V /V 0 P K K V /V 0 P K K
(GPa) (GPa) (GPa) (GPa)

1 0 65 4.60 1 0 167 5.70

0.9904 0.64 67.9 4.52 0.9975 0.42 169.4 5.67
0.9838 1.1 70 4.47 0.9930 1.2 173.8 5.61
0.9576 3.1 78 .7 4.29 0.9874 2.2 179.4 5.54
0.9381 4.8 85.9 4.17 0.9820 3.2 184.9 5.48
0.9297 5.6 89.3 4.12 0.9794 3.7 187.6 5.46
0.9177 6.8 94.3 4.06 0.9742 4.7 193.1 5.40
0.9090 7.7 97.8 4.02 0.9698 5.6 198.0 5.36
0.8942 9.4 104.9 3.95 0.9640 6.8 204.4 5.30
0.8855 10.4 108.6 3.91
0.8758 11.6 113.1 3.87
Ag Mn

V /V 0 P K K V /V 0 P K K
(GPa) (GPa) (GPa) (GPa)

1 0 103.6 4.70 1 0 158 4.60

0.9930 0.74 107.1 4.64 0.9951 0.76 161.5 4.56
0.9800 2.2 113.7 4.54 0.9907 1.5 164.8 4.52
0.9716 3.2 118.3 4.47 0.9878 2.0 167.1 4.50
0.9674 3.7 120.5 4.44 0.9836 2.7 170.3 4.47
0.9596 4.7 124.9 4.39 0.9808 3.2 172.5 4.45
0.9544 5.4 128.0 4.36
0.9499 6.0 130.6 4.33
0.9432 6.9 134.5 4.29
0.9387 7.6 137.5 4.26

available experimental data [27] and also provides insights into the fundamental understanding of quantitative effect of pressure on
melting temperature.

2 Method of analysis

In the limit of extreme compression, volume V tends to zero, pressure P tends to infinity, K also tends to infinity, but the ratio P/K
remains finite [42]
 
P 1
  (6)
K ∞ K∞

Equation (6) has the status of an identity. The subscript ∞ represents the limit of infinite pressure. K ∞  is the value of K  

dK/dP in the limit of infinite pressure. K decreases with the increase in pressure and attains a minimum value equal to K ∞  in the

limit of infinite pressure. The theory of infinite pressure extrapolation has been developed [5, 6] by considering a material to remain
in the same structure or phase, i.e., the material is supposed to be compressed down to extreme limit, volume tends to zero without
exhibiting any phase transitions. Using Eq. (6), Stacey [18] proposed the following relationship for reciprocal K 
  P
1 1 K∞
  + 1−  (7)
K K0 K0 K

On integrating Eq. (7), we get

   
K K  P −K 0 /K ∞
 1− ∞ (8)
K0 K

123
Eur. Phys. J. Plus (2022) 137:545 Page 5 of 11 545

0.12
0.026
0.10 Cd
0.022
Cu
0.08
(GPa)-1

(GPa)-1
0.018 0.06
dln Tm

dln Tm
0.04
dP

dP
0.014
0.02

0.010 0.00
0 4 8 12 16 0 2 4 6 8 10 12
P (GPa) P (GPa)

0.070
0.070

0.060 Mg 0.060 Zn

(GPa)-1
0.050
(GPa)-1

0.050

dln Tm
0.040 0.040

dP
dln Tm
dP

0.030 0.030

0.020 0.020
0 2 4 6 8 10 12 0 2 4 6 8 10 12

P (GPa) P (GPa)
0.034
0.12
0.032 Au
0.10 Pb

(GPa)-1
0.030
0.08
(GPa)-1

0.028
0.06
dln Tm
dP
0.026
dln Tm

0.04
dP

0.024
0.02
0.022
0.00
0 1 2 3 4 5 6 7
0 2 4 6 8 10 12

P (GPa) P (GPa)

0.060 0.045

Al 0.040 Ag
0.050
(GPa)-1

(GPa)-1

0.035
0.040
dln Tm

0.030
dP

dln Tm
dP

0.030
0.025

0.020 0.020
0 1 2 3 4 5 6 7 8 9 10 0 1 2 3 4 5 6 7 8

P (GPa) P (GPa)
0.0210
0.09

0.08
In Mn
0.0200
0.07
(GPa)-1
(GPa)-1

0.06 0.0190
0.05
dln Tm
dln Tm

dP
dP

0.04 0.0180

0.03
0.0170
0.02
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
0 2 4 6 8 10 12
P (GPa) P (GPa)

Fig. 1 Melting slopes for ten metals calculated from Eqs. (13) and (15)

Further integration of Eq. (8) gives

     
V K 0 P K 0  P
ln  
− 1 + 2 ln 1 − K ∞ (9)
V0 K∞ K K∞ K

123
 545 Page 6 of 11 Eur. Phys. J. Plus (2022) 137:545

1400
2000 Cd
Cu
1200
1800

1000
1600
Tm (K)

Tm (K)
Present Study Eqs. (15)-(19) 800
1400 Present Study Eqs. (15)-(19)
Theoretical [9] using Eq. (20)
Theoretical [9] using Eq. (20)
1200 Experimental [27] 600
Experimental [27]

1000 400
0 2 4 6 8 10 12 14 16 0 2 4 6 8 10 12

P (GPa) P (GPa)
2000 1200
Mg Zn
1800
1100
1600
1000
1400

Tm (K)
Tm (K)

900
1200
Present Study Eqs. (15)-(19)
Present Study Eqs. (15)-(19) 800
1000 Theoretical [9] using Eq. (20)
Theoretical [9] using Eq. (20)
Experimental [27]
800 Experimental [27] 700

600 600
0 2 4 6 8 10 12 0 2 4 6 8 10 12

P (GPa) P (GPa)

1400 1700
Pb Au
1200 1600

1000 1500
Tm (K)

Tm (K)

800 1400 Present Study Eqs. (15)-(19)

Present Study Eqs. (15)-(19)
Theoretical [9] using Eq. (20)
Theoretical [9] using Eq. (20)
600 1300 Experimental [27]
Experimental [27]

400 1200
0 2 4 6 8 10 12 0 1 2 3 4 5 6 7 8

P (GPa) P (GPa)

1600
1700
Al Ag
1400 1600

1500
Tm (K)

Tm (K)

1200

Present Study Eqs. (15)-(19)

1400
Present Study Eqs. (15)-(19)
Theoretical [9] using Eq. (20)
1000 Theoretical [9] using Eq. (20)
Stacey law of melting Eq. (23), 1300
present study Experimental [27]
Experimental [27]

800 1200
0 2 4 6 8 10 0 1 2 3 4 5 6 7 8

P (GPa) P (GPa)
800
1700
In Mn
700
1650

600
Tm (K)

Tm (K)

1600
500 Present Study Eqs. (15)-(19)
Theoretical [9] using Eq. (20) Present Study Eqs. (15)-(19)
1550
400 Experimental [27] Theoretical [9] using Eq. (20)
Experimental [27]

300 1500
0 2 4 6 8 10 12 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5

P (GPa) P (GPa)

Fig. 2 Melting curves for ten metals

123
Eur. Phys. J. Plus (2022) 137:545 Page 7 of 11 545

Fig. 3 Melting slopes for five 0.030

metals at high pressures calculated
0.025
from Eqs. (13) and (15)
0.020
Cu

(GPa)-1
0.015

dln Tm
0.010

dP
0.005

0.000
0 50 100 150 200 250
P (GPa)
0.07

0.06

0.05

(GPa)-1
0.04
Mg
0.03

dln Tm
dP
0.02

0.01

0
0 20 40 60 80 100 120 140 160 180
P (GPa)

0.07

0.06

0.05
(GPa)-1

Zn
0.04

0.03
dln Tm
dP

0.02

0.01

0
0 20 40 60 80 100 120
P (GPa)

0.035

0.030

0.025
(GPa)-1

0.020
Au
0.015
dln Tm
dP

0.010

0.005

0.000
0 50 100 150 200 250 300
P (GPa)
0.050

0.040

Ag
(GPa)-1

0.030

0.020
dln Tm
dP

0.010

0.000
0 50 100 150 200 250
P (GPa)

123
 545 Page 8 of 11 Eur. Phys. J. Plus (2022) 137:545

Fig. 4 Melting curves for some 8000

metals at high pressures
Cu
6000

Tm (K)
4000 Present Study, Eqs. (15-(19)
ab initio [45]
Hieu and Ha [38]
2000
Simulation Method [45-47]
Stacey law of melting Eq. (23), present study

0
0 50 100 150 200 250 300 350 400 450
P (GPa)

5000
Mg
4000

3000

Tm (K)
Present Study, Eqs. (15)-(19)
2000
ab initio molecular dynamics [48]

Experimental [44]
1000
Stacey law of melting Eq. (23), present study

0
0 25 50 75 100 125 150

P (GPa)
6000
Zn
5000

4000
Tm (K)

3000

Present Study, Eqs. (15)-(19)

2000 Simon Equation [27]
Experimental [27]
1000 Experimental [32]
Stacey law of melting Eq. (23), present study

0
0 20 40 60 80 100 120 140 160

P (GPa)
16000
Au
14000

12000

10000
Tm (K)

8000

6000 Present Study, Eqs. (15)-(19)

Hieu and Ha [38]
4000 Thermal Vacancy Model [43]
Ideal Model [43]
2000
Stacey law of melting Eq. (23), present study

0
0 100 200 300 400 500 600 700 800

P (GPa)
14000
Ag
12000

10000
Tm (K)

8000

6000
Present Study, Eq. (15)-(19)

4000 Hieu and Ha [38]

Thermal Vacancy Model [43]
Ideal Model [43]
2000
Stacey law of melting Eq. (23), present study

0
0 50 100 150 200 250 300 350 400 450 500

P (GPa)

123
Eur. Phys. J. Plus (2022) 137:545 Page 9 of 11 545

where V 0 is the value of volume V at P  0. Realizing that γ and K  change with pressure in a similar manner, both decrease with
the increase in pressure, and attain constant minimum values γ∞ and K ∞  , respectively, Shanker et al. [15] proposed the reciprocal

gamma relationship analogous to Eq. (7) as follows:

1 P
 A+B (10)
γ K
where
1
A (11)
γ0
and
 
 1 1
B  K∞ − (12)
γ∞ γ0
Using Eq. (10) in the Lindemann law, Eq. (5), we get
d ln Tm 2 2
 − (13)
dP AK + B P 3K
The input parameters used in calculations are given in Table 1. Values of K 0 , K 0 and γ0 are based on the experimental data
compiled by Kholiya and Chandra [9]. Values of K ∞  are determined using the relationship K   (3/5)K  given by Stacey [6].
∞ 0
The validity of this relationship has been discussed at length in an earlier paper [17]. Values of γ∞ are then calculated from the
following equation [5, 6]
1  1
γ∞  K∞ − (14)
2 6
Equation (14) has the status of an identity. The results for V/V 0 , P, K, K  are given in
Table 2 obtained using the input parameters in Table 1 and the Stacey equations (7)–(9).

3 Results and discussion

Using the method based on Euler’s finite difference calculus, Eq. (13) can be rewritten as follows:
1 Tm
 (15)
Tm P
where
2 2
 − (16)
AK + B P 3K
and, then we get

Tm  Tm − Tm0

 P Tm (17)

so that
Tm0
Tm  (18)
1 −  P
A stepwise calculation can be performed, for example, by taking P  1GPa . T m at 1 GPa is determined by taking  at 1 GPa
and the experimental value of T m0 at zero pressure. T m at 1 GPa is then designated by T m1 and T m at 2 GPa by Tm2 such that
Tm1
Tm2  (19)
1 − P
Values of T m1 at 1 GPa have been used to determine T m2 at 2 GPa taking  at 2 GPa, and P  1G Pa. We proceed further
in a similar manner to determine T m at higher pressures. The accuracy of Euler’s method is increased when the size of interval P
is reduced. Calculations can be performed for any finite value of interval P. To determine T m2 at any pressure P, we have to use
T m1 at pressure P – ΔP, and  at the same pressure P. In fact,  represents the melting slope dlnT m /dP (Eqs. 13 and 16). The
results for  determined from Eq. (16) are shown in Fig. 1 for the ten metals under study. Results for the melting curves are given

123
 545 Page 10 of 11 Eur. Phys. J. Plus (2022) 137:545

in Fig. 2 and compared with the available experimental data [19–28]. Kholiya and Chandra [9] have used an alternative method for
determining melting curves based on the instability of thermal equation of state [29, 30] which yields
 
Tm − T0 K K 0 + 1
 (20)
Tm0 − T0 K 0 (K  + 1)
where T0 is the reference temperature or room temperature. Values of K 0 and K 0 are taken from Table 1. K and K  at different
pressures are given in Table 2. The melting curves were determined by Kholiya and Chandra [9] using Eq. (20). These are also
included in Fig. 2 for the sake of comparison. The two theoretical models Eq. (13) and Eq. (20), yield results for melting curves in
reasonably good agreement with each other, and also with the experimental data [19–28]. There are few exceptions such as Al for
which the calculated values of T m differ substantially from the experimental data (Fig. 2). This is possibly due to the inadequacy
of the Lindemann law in case of some metals [14]. Using some basic principles of thermodynamics of solids, Stacey obtained the
following formulation (Eq. (80) of Reference [6])
d ln Tm
 −2γ (21)
d ln V
which gives
 
1 dTm 2γ
 (22)
Tm dP K
where K  −V (d P/d V ). With the help of Eq. (10) in Eq. (22), we get
 
1 dTm 2
 (23)
Tm d P AK + B P
High-pressure melting curves can be determined with the help of Eq. (23) using the Euler finite difference method. The results
for Al thus obtained and shown in Fig. 2 are in better agreement with the experimental data.
The melting curves of five metals, viz. Cu, Mg, Zn, Au, Ag, are extended into a megabar pressure range using the Lindemann
law. Calculated values of melting slopes are given in Fig. 3 and melting curves in Fig. 4. A comparison is presented in Fig. 4 with
the experimental data [27, 32, 38, 43, 44] and with the ab initio molecular dynamics simulations [45–48]. It is found that the values
determined from the Lindemann law shown by continuous curves in Fig. 4 are significantly lower than the experimental data and
simulation studies. When we use the Stacey law of melting (Eqs. 21–23) in place of the Lindemann law, the agreement between
calculated and experimental values is improved to a great extent.

4 Conclusions

The earlier models developed by Arafin et al. [1, 2, 11, 12] are not adequate for describing high pressure melting of solids because
of invalid assumptions regarding the pressure dependences of bulk modulus and the Grüneisen parameter [13, 14]. It is found here
that for developing an adequate theory of high-pressure melting, we should take an appropriate account of the volume dependence
or pressure dependence of gamma in the Lindemann law. This has been done in the present study by using the relationship [15]
between reciprocal gamma and P/K which is consistent with the Stacey thermodynamic constraints. The melting temperatures for
the metals at high pressures calculated from the Lindemann law are somewhat lower than the available experimental data. The
agreement is much improved at high pressures when we use the Stacey law of melting in place of the Lindemann law.
A remarkable feature of the method based on Eq. (13) is that it directly yields values of melting slopes (dlnT m / dP) in terms of
P and K in the denominator. The melting slope is therefore found to decrease regularly with the increase in pressure and tending to
zero in the limit of infinite pressure. This finding is supported by recent studies in the field of melting at high pressures [9, 14, 49].
The melting curves obtained from the vacancy model [49] are of similar nature as those based on the Lindemann law. This is also
confirmed from the recent work on the thermal vacancy model by Cuong and Phan [43]. The Lindemann law as well as the thermal
vacancy model, both are based on the thermodynamic instability of the solid phase.

Acknowledgements We are thankful to the reviewer for his helpful comments which have been used in revising the manuscript. Authors are also thankful
to Professor Jai Shanker for some useful suggestions.

Data availability “This manuscript has associated data in a data repository. [Authors’ comment: The data that support the finding of this study are available
within the article.]”

References

1. S. Arafin, R.N. Singh, A.K. George, Int. J. Thermophyics 33, 1013 (2012)
2. S. Arafin, R.N. Singh, A.K. George, Physica B 419, 40 (2013)

123
Eur. Phys. J. Plus (2022) 137:545 Page 11 of 11 545

3. F.A. Lindemann, Z. Phys. 11, 609 (1910)

4. J.J. Gilvarry, Phys. Rev. 102, 307 (1956)
5. F.D. Stacey, P.M. Davis, Phys. Earth Planet. Int. 142, 137 (2004)
6. F.D. Stacey, Rep. Prog. Phys. 68, 341 (2005)
7. J. Shanker, P. Dulari, P.K. Singh, Physica B 404, 4083 (2009)
8. J. Shanker, K. Sunil, B.S. Sharma, Physica B 407, 2082 (2012)
9. K. Kholiya, J. Chandra, Modern Phys. Lett. B 29, 1550161 (2015)
10. M. Goyal, Chin. J. of Phys. 66, 453 (2020)
11. S. Arafin, R.N. Singh, Int. J. Mod. Phys. B 30, 1750031 (2016)
12. S. Arafin, R.N. Singh, J. Phys. Chem. Solids 91, 101 (2016)
13. A. Vijay, Int. J. Mod. Phys. B 33, 1975001 (2019)
14. J. Shanker, K. Anand, B.S. Sharma, A. Vijay, Int. J. Thermophysics 41, 1 (2020)
15. J. Shanker, K. Sunil, B.S. Sharma, Phys. Earth Planet. Int. 262, 41 (2017)
16. F.D. Stacey, J.H. Hodgkinson, Phys. Earth Planet. Int. 286, 42 (2019)
17. K. Sunil, S.B. Sharma, B.S. Sharma, Inter. J. Modern Phys. B 30, 1850339 (2018)
18. F.D. Stacey, Geophys. J. Int. 143, 621 (2000)
19. N.R. Mitra, D.L. Decker, H.B. Vanfleet, Phys. Rev. 161, 613 (1967)
20. J. Akella, G.C. Kennedy, J. Geophysical, Research 76, 4969 (1971)
21. J.F. Cannon, J. Phys. Chem. Ref. Data 3, 781 (1974)
22. J.A. Moriarty, J.D. Althoff, Phys. Rev. B 51, 5609 (1995)
23. G. Shen, N. Sata, M.L. Rivers, S.R. Sutton, Appl. Phys. Lett. 78, 3208 (2001)
24. M. Minicucci, A. Trapananti, A.D. Cicco, S.D. Panfilis, G. Aquilanti, Phys. Scr. T. 115, 1056 (2005)
25. H. Brand, D.P. Dobson, L. Vocadlo, I.G. Wood, High Pressure Res. 26, 185 (2006)
26. F. Cricchio, A.B. Belonoshko, L. Burakovsky, D.L. Preston, R. Ahuja, Phys. Rev. B 73, 140103 (2006)
27. D. Errandonea, J. Appl. Phys. 108, 033517 (2010)
28. P.D. Tam, P.D. Tan, N.Q. Hoc, P.D. Phong, Proc. Natl. Conf. Theor. Phys. 35, 148 (2018)
29. J. Shanker, S.S. Kushwah, P. Kumar, Physica B 239, 337 (1997)
30. J. Shanker, M.P. Sharma, S.S. Kushwah, J. Phys. Chem. Solids 60, 603 (1999)
31. G.W. Stinton, S.G. MacLeod, H. Cynn, D. Errandonea, W.J. Evans, J.E. Proctor Meng et al., Phys. Rev. B 90, 134105 (2014)
32. D. Errandonea, S.G. MacLeod, J. Ruiz-Fuertes, L. Burakovsky, M.I. McMahon, C.W. Wilson et al., J. Phys. Condens. Matter 30, 295402 (2018)
33. S. Anzellini, V. Monteseguro, E. Bandiello, A. Dewaele, L. Burakovsky, D. Errandonea, Sci. Rep. 9, 13034 (2019)
34. D. Errandonea, L. Burakovsky, D.L. Preston, S.G. MacLeod, D. Santamaria-Perez, S. Chen et al., Commun. Mater. 1, 60 (2020)
35. G. Weck, V. Recoules, J.-A. Queyroux, F. Datchi, J. Bouchet, S. Ninet et al., Phys. Rev. B 101, 014106 (2020)
36. S. Anzellini, L. Burakovsky, R. Tumbull, E. Bandiello, D. Errandonea, Crystals 11, 452 (2021)
37. S.R. Baty, L. Burakovsky, D. Errandonea, Crystals 11, 537 (2021)
38. H.K. Hieu, N.N. Ha, AIP Adv. 3, 112125 (2013)
39. P. Vinet, J. Ferrante, J. Rose, J. Smithj, J. Geophy. Res. 92, 9319 (1987)
40. J. Ma, W. Li, G. Yang et al., Phys. Earth Planet. Inter. 309, 106602 (2020)
41. W.G. Li, F. Yang, D.N. Fang, Acta Mech. Sinica 26, 235 (2010)
42. L. Knopoff, J. Geophys. Res. 68, 2932 (1963)
43. T.D. Cuong, A.D. Phan, Vacuum 179, 109444 (2020)
44. D. Errandonea, R. Boehler, M. Ross, Phys. Rev. B 65, 012108 (2001)
45. Y.N. Wu, L. Wang, Y. Huang, D. Wang, Chem. Phys. Lett. 515, 217 (2011)
46. S. Wang, G. Zhang, H. Liu, H. Song, J. Chem. Phys. 138, 134101 (2013)
47. Z.L. Liu, X.L. Zhang, L.C. Cai, J. Chem. Phys. 143, 114101 (2015)
48. S. Mehta, G.D. Price, D. Alfe, J. Chem. Phys. 125, 194507 (2006)
49. K. Ksiazek, T. Gorecki, High Temp.-High Press. 32, 185 (2020)

123