and G. M.

POUND:
T. HALICIOGLU Calculation of Potential Energy Parameters 619

phys. stat. sol. (a) 30, 619 (1975)

Subject classification: 4; 8; 12; 21

Department of Theoretical Chemistry, Middle East Technical University, Ankara ( a ) and

Department of Materials Science and Engineering, Stanford University, California (b)

Calculation of Potential Energy Parameters from

Crystalline State Properties
BY
T. HALICIO~LU
(a) and G. M. POUND
(b)

A simple method is developed to calculate Mie (Lennard-Jones) potential parameters

for metals, using crystalline state physical properties a t any given temperature. Calculated
values are in good agreement with some values reported in the literature.
Es wird eine einfache Methode zur Berechnung der Mieschen (Lennard-Jones) Potential-
parameter fur Metalle aus den physikalischen Eigenschaften des kristallinen Zustands bei
jeder vorgegebenen Temperatur entwickelt. Die berechneten Werte befinden sich in guter
Ubereinstimmung mit einigen in der Literatur veroffentlichten Werten.

1. Introduction
Pairwise additive central potential functions are widely used in various
problems related t o the solid state. For example, in the description of surface
adsorption [1 t o 41, nucleation [5 t o 71, and intermetallic phase [8, 91, some-
what satisfactory results have been obtained by considering only two-body
potential functions (despite the recognition that many-body interactions make
considerable contributions [lo]). I n most cases, pair potential functions contain
two or more adjustable parameters that should be determined by experiment.
For interactions between metal atoms, potential energy parameters are generally
calculated from crystalline state physical properties (such as cohesive energy,
compressibility, lattice constants, etc.) extrapolated t o 0 "K [11, 121. Ex-
perimental values of physical properties near T = 0 "K, however, are some-
times difficult t o find, and in many instances their accuracy is questionable.
Here, a simple method is developed to estimate the parameters of a pair
potential function using crystalline state properties a t any given temperature.
As an example we will consider the well-known Blie (Lennard-Jones)potential
function, and make use of heat capacity data in addition t o other physical
properties of the crystalline state. No many-body interactions will be taken into
account.
2. Theory and Calculations
The interaction potential energy u(rij),of two atoms, i and j , separated by
a distance, r l j , is given in terms of the Mie (Lennard-Jones)potential by

where the parameter E represents the depth of the potential a t the minimum
and u is the closest distance a t which u(rij)is equal t o zero. The total potential
620 and G. M. POUND
T. HALICIOELU

energyof interaction, @, of a large crystal of N atoms may be expressed con-

sidering pairwise additivity of the Mie (Lennard-Jones)potential as [ 111

where a and b are lattice sunis that depend on the geometry of the crystalline
structure.l) The nearest-neighbor distance, r , is related to the volume, P, of
the crystal by
V = gXr3, 13)
where g is another geometrical constant that depends on the lattice structure.2)
If AH is the amount of enthalpy required t o transfer N atoms (isothermally)
from its crystalline state t o the vapor phase we have
AH =H, - H, . (4)
Here, H , and H , denote the total enthalpies (heat contents) of the vapor and
the crystalline states, respectively. For lower vapor pressures ( P = 1 atm,
where the ideal gas law is applicable) we may write

For the crystalline state we have

H,= @ +El +PV,
where El represents the vibrational energy of the crystal (including the zero
point energy). Combining (4), ( 5 ) and (6) one obtains
@ =$RT - AH - E l - P V . (7)
Now, if we combine (2) with (3), and differentiate with respect t o V , we
obtains)
(b(g). 0").
(g),=T - 2a

The heat capacity a t constant pressure, C,, of the crystal is given by

or using (6) one obtains

c -- -
(g)p+(g)p
+- (g)
. P

Since for a given crystal the vibrational energy El is a function of V and T ,

we niav write

For example, for a f.c.c. structure a = 12.131 and b = 14.454 (see [13]).
2) For a f.c.c. structure g =Vm (see pi]).
3, The total potential energy of interaction, @, defined by (2) is independent of P.
However, to be consistent we prefer t o keep the variation of @ with respect to V in form
of (aqav),.
 Calculation of Potential Energy Parameters from Crystalline State Properties 621

or for P = const

(g)p+(g)
(2)p=(2)T V *

The last term, (aEJaT),, is simply equal to C,, the heat capacity a t constant
volume. (Because a t constant V the only contribution is due to vibrational ener-
gy, i.e. (a@/aT), = 0.)
Next, we consider the thermodynamic relation [14j
a2
Cp-CC,=TV-,
x
where LY and x are the cubical thermal expansion coefficient and the isothermal
compressibility, respectively. Combining (lo), (12), and (13), we find

Finally, using ( 2 ) , (3), and (7)) we obtain

and using (3), (8), and (14)

Now, (15) and (16) can be used t o estimate numerical values of E and a from
physical properties of a crystal. The term (aE,/aV), that appears in (16) may
be simply calculated using the Griineisen relation [ l l ] , which is given as

where 8, is the characteristic temperature of the crystal. I n our calculations

the values of El and (aE,/aO,), are estimated using tables given in [15].4)
Calculated values of E and a for various metals are given in Table 1. Physical
constants that are used in the computation are also tabulated in Table 2.

3. Discussion
For those metals that are included in our calculation, the values of E and a
are found t o be dependent mainly on AH and V , respectively. The other physical
properties (such as heat capacity, thermal expansion coefficient, compressibility,
etc.) used in the computation have relatively small effects on the values of E
and a when varied within limits of possible experimental error^.^)
Calculated values of E and a are in good agreement with some values reported
in the literature. For example, Goodman's [2] calculated values of E and a for

4) In the calculation of El and (&?&/a@,), the zero point energy and its derivative
have been taken into account.
5 ) For each case, numerical values of AH*/&and crjr remain quite constant as pointed out
by Goodman [2]. However, this constancy holds only if A H is large enough t o dominate
the left side of (15). For substances with smaller A H this condition will no longer be valid.
622 and G. M. POUND
T. HALICIO~LU

Table 1
Calculated values of potential parameters
for various metals

metals

A1 4551 2.620
Ca 2 497 3.600
Au 5123 5284*) 2.637 2.637*)
Pb 2 743 3.197
Ni 6030 2.282
Pd 4951 2.520
Pt 7910 2.542
Ag 4001 2.644
cu 4750 2.338
Cr 5825 2.336
Fe 6 108 2.321
Li 2 383 2.839
Mo 9 723 2.551
W 12391 12429*) 2.562 2.566*)
Na 1600 3.475
K 1328 1328*) 4.285 4.321*)

*) Values reported in [2].

Table 2
Physical constants of various metals used in calculations of potential energy parameters
(at T = 298 OK)

AH V CP
metals (kcal/g-atom) ( cm3/g-atom) (cal/g-atomdeg)
[I61 ~ 7 1

A1 77.40 9.99 5.82 69.9 1.356 401.5

Ca 42.37 25.90 6.26 67.5 6.26 225.0
Au 87.30 10.20 6.06 41.7 0.57 172.5
Pb 46.60 18.27 6.32 87.0 2.31 86.5
Ni 102.67 6.59 6.23 37.5 0.528 425.5
Pd 84.33 8.89 6.21 34.8 0.522 271.5
Pt 134.97 9.102 6.18 26.7 0.36 236.5
Ag 68.1 10.28 6.07 56.7 1.023 216.0
cu 80.86 7.09 5.86 51.0 0.733 323.0
Cr 94.85 7.23 5.58 22.5 0.536 $45.0
Fe 99.5 7.1 6.0 36.9 0.59 $11.0
Li 38.58 13.0 5.78 135.0 9.20 353.5
Mo 158.7 9.41 5.68 15.6 0.35 374.0
W 202.4 9.53 5.92 13.5 0.305 327.0
Na 25.85 24.0 6.72 213.0 15.6 163.0
K 21.42 45.0 1.07 249.0 40.3 131.5

*)Average values have been considered.

 Calculation of Potential Energy Parameters from Crystalline State Properties 623

Au, K, and W agree quite well with our results (see Table 1). The parameters
of the Morse potential for various metals are calculated by Girifalco and Weizer
[12]. Their results for the depth of the potential and the closest distance a t
which the potential equals zeroa) show some agreement with our calculations.
However, their results for K and Na deviate considerably.
Because they simplify various formulations, central pairwise additive potential
functions are still used in many problems related to metals. Therefore, a simple
method of calculating the potential parameters should be helpful. The approach
described here calculates the Mie (Lennard-Jones) potential parameters from
physical properties of the crystalline state a t any given temperature. This
should provide a considerable siinplication in finding the required data for
a variety of systems. Furthermore, it is believed that similar formulations car
easily be derived to calculate parameters of other types of potential functionn
using crystalline state properties for temperatures other than 0 OK.

Acknowledgements
The authors would like t o express their thanks t o Prof. J. A. Barker for
helpful discussions, and t o the Materials Science Division of Ames NASA
Research Center for providing computer facilities. Furthermore, the support
provided by the NATO Scientific Affairs Division (No. 858) is gratefully
acknowledged.
References
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[ 5 ] J. V. DAVEand F. F. ABRAHAM, Surface Sci. 26,557 (1971).
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171 D. ROBERTSON and G. M. POUND, CRC Critical Rev. Solid State Sci. 4, 163 (1974).
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[I31 J. E. JONES and A. E. INGHAM, Proc. Roy. SOC.A 107, 636 (1925).
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[I61 R. HULTGREN, R. L. ORR, P. D. ANDERSON, and K. K. KELLEY,Selected Values of
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graphy, Kynock Press, Birmingham 1962.

(Received June 16, 1975)

s, The closest distance a t which the Morse potential equals zero is r, - (In 2/c(), where
r, and G are Morse potential parameters. For details see [12].
41 physica (a) 30/2