Cent. Eur. J. Phys.

• 7(1) • 2009 • 193-197

DOI: 10.2478/s11534-008-0122-1

Central European Journal of Physics

Relations between Varshni and Morse potential

energy parameters
Research Article

Teik-Cheng Lim1∗ , Rajendra Acharya Udyavara2

1 School of Science & Technology, SIM University, Singapore

2 ECE Department, Ngee Ann Polytechnic, Singapore

Received 31 May 2008; accepted 30 July 2008

Abstract: A set of relationships between the Morse and Varshni potential functions for describing covalent bond-
stretching energy has been developed by imposing equal force constant and equal energy integral. In
view of the extensive adoption of Morse function in molecular force fields, this paper suggests two sets of
parameter conversions from Varshni to Morse. The parameter conversion based on equal force constant is
applicable for small change in bond length, while the parameter conversion based on equal energy integral
is more applicable for significant bond-stretching. Plotted results reveal that the Varshni potential function
is more suitable for describing hard bonds rather than soft bonds.
PACS (2008): 33.15.Dj, 33.15.Fm, 34.20.Cf
Keywords: Morse • Varshni • potential energy • parameter conversion
© Versita Warsaw and Springer-Verlag Berlin Heidelberg.

1. Introduction parameter, has been adopted for describing 2-body inter-

Numerous interatomic potential energy functions have
been introduced over the years, and have been reviewed
by Varshni [1], Maitland et al. [2], Murrell et al. [3], Erkoc
[4] and Sathyamurthy [5], to name a few. The Morse po-
tential [6]
action energy in molecular mechanics force fields, such
as CVFF [7], DREIDING [8], UFF [9] and ESFF [10]. A
generalized version of Morse potential was adopted by
Biswas and Hamann [11] for describing the 2-body en-
ergy portion of many-body condensed matter system. In
Varshni’s [1] review, one of the seven potential functions
introduced was of the form

   2
UMorse = D {1 − exp [−α(r − R)]}2 , (1) UV arshni = D 1 − exp −β(r 2 − R 2 ) , (2)

which partly resembles the Morse potential. Although

where D= bond dissociation energy, r= internuclear dis-
the Varshni potential is not as pervasive as the Morse
tance, R= equilibrium bond length, and α = Morse shape
potential in molecular and condensed matter modeling,
the fact that the Varshni potential was introduced almost
∗
E-mail: alan_tc_lim@yahoo.com three decades after the Morse potential gives credence

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 Relations between Varshni and Morse potential energy parameters

to the former’s comparative advantages for some diatomic

molecules. An example of the Varshni potential function
application can be seen in the bond-stretching energy por-
tion of the Kaxiras-Pandey [12] for describing the many-
body interaction energy of silicon, whereby the 2-body
interaction part is a general form of the Varshni potential.

Figure 3. The Morse potential energy for Molybdenum (circles)

and Rubidium (triangles) based on Girifalco and Wiezer
[19], and the converted Varshni potential energy curves
for Molybdenum (bold curve) and Rubidium (fine curve)
based on both “local” and “global” relation.

In this paper, we examine the relationship between the

Figure 1. The Morse potential energy for Molybdenum (circles)
and Rubidium (triangles) based on Girifalco and Wiezer
[19], and the converted Varshni potential energy curves
for Molybdenum (bold curve) and Rubidium (fine curve)
based on “local” relation.
Morse and Varshni potential functions such that parame-
ters from each function can be converted to the other. A
suggestion is then made on the applicability of the Varshni
potential based on the observed discrepancies of the plot-
ted potential energy curves.

2. Analysis
Although each potential energy function consists of three
parameters, they both can be reduced into one-parameter
potentials when recast in non-dimensional forms

UM h  r i h  r i
= exp 2αR 1 − − 2 exp αR 1 − (3)
D R R

and

     
UV r2 r2
= exp 2βR 2 1 − 2 − 2 exp βR 2 1 − 2 ,
D R R
(4)
where (UM /D) and (UV /D) represent the dimensionless
Morse and Varshni potential energy respectively, (r/R) is
the dimensionless bond length, while (αR) and (βR 2 )are
Figure 2. The Morse potential energy for Molybdenum (circles)
and Rubidium (triangles) based on Girifalco and Wiezer
the dimensionless shape parameters. In order to more
[19], and the converted Varshni potential energy curves clearly distinguish the repulsive terms from the attractive
for Molybdenum (bold curve) and Rubidium (fine curve) terms, the forms of Morse and Varshni potential functions
based on “global” relation.
as shown in Eqs. (3) and (4) differ from Eqs. (1) and (2)
as UM = UMorse − D and UV = UV arshni − D respectively.

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Teik-Cheng Lim, Rajendra Acharya Udyavara

A local relation between parameters of both functions can Girifalco and Wiezer [19]. Of the 16 cubic metals, we se-
be obtained by imposing equal curvatures at the minimum lect Molybdenum and Rubidium due to their highest and
well-depth lowest values of αR respectively. The other dimensionless
shape parameter, βR 2 , was easily obtained from Eq. (6)
   
∂2 UM ∂2 UV for the local approach. The same parameter by global ap-
= , (5)
∂r 2 r=R ∂r 2 r=R
proach was obtained from Eqs. (8) and (10) numerically.
These dimensionless shape parameters are listed in Table
1.
to give
α = 2βR. (6) Fig. 1 shows the Morse potential energy of Molybde-
num and Rubidium, and their corresponding Varshni en-
A global relation between both sets of parameters is ob-
ergy curves based on the local approach. It is observed
tained by imposing equal energy integral from equilibrium
that by using the local approach, the Varshni curve gives
bond length to bond dissociation
very good agreement with the Morse energy for very small
∞ ∞
Z Z change in bond length. However, the Varshni energy ob-
UM dr = UV dr, (7) tained by the local approach tends to underestimate and
R R overestimate the Morse energy for r < R and r > R
respectively. The overestimation is especially significant
to give at the point of maximum negative curvature in the range
1.4R < r < 1.8R. This observation suggests Varshni’s
r
3 π h p i

− erf(∞) − erf
suitability for quantifying very hard bonds that exhibit a
= 2βR exp 2βR 2
2α 8β rapid rise followed by a rapid drop in interatomic force
r h
π p i
during bond-stretching.
− erf(∞) − erf βR exp βR 2 . (8)
β
The global approach ensures equal area bounded between
the potential energy curves of the same bond between r =
R and r → ∞. Due to the more rapid rise in the Varshni
The error function

∞
energy with bond length, the global approach decreases
2 X (−1)n x 2n+1
erf(x) = √ , (9) the curvatures at the minimum well-depth. As a result
π n=0 n! (2n + 1) the Varshni energy by global approach underestimates the
Morse energy for r < R to a greater extent, but gives
is then approximated as better overall correlation with the Morse energy for r >
R, as shown in Fig. 2. Specifically, the Varshni curve
s   underestimates the Morse energy from r = R but with
ax 2 + (4/π)
erf(x) ≈ 1 − exp −x 2 , (10) the former’s inherent rapid rise in energy, it surpasses the
ax + 1 Morse energy in the range 1.4R < r < 1.8R such that

where  
8 π−3
a=− . (11)
3π π−4
Z C Z C Z ∞ Z ∞
Although the local approach by equal curvatures or by UM dr − UV dr = UV dr − UM dr, (12)
equating series expansion at r = R has been developed R R C C

recently [13–18], a major concern regarding this approach

is its significant discrepancies for large bond stretching.
As such, a global approach is investigated here in order to
where C demarcates the bond length at which the Varshni
evaluate its validity. The local approach is nevertheless
included in this paper for comparison.
3. Results and discussion
energy crosses over the Morse energy.

Having shown the comparative advantages of both con-

To observe the comparative advantages of both ap- version methods, we split the Varshni function into two
proaches, we adopt the Morse parameters obtained by parts

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 Relations between Varshni and Morse potential energy parameters

Table 1. Varshni parameters by local and global approaches from

Morse parameters for molybdenum and rubidium.

Metal αR βR 2 (local) βR 2 (global)

Molybdenum (Mo) 4.487510 2.243755 1.81915121
Rubidium (Rb) 3.097641 1.5488205 1.16515739

      (
UV r2 r2 βR 2 (local) ; r ≤ R
= exp 2βR 1 − 2
2
− 2 exp βR 1 − 2
2
. (13)
D R R βR 2 (global) ; r ≥ R

Considering the fact that the Morse function is much more widely employed for describing bond-stretching energy in
computational chemistry and condensed matter softwares, it is more likely that the Varshni parameters should be used
for Morse function in two parts with


 2βR 2 ; r≤R
αR = nq 
π
√

qπ  √

o−1 . (14)
 −2R
3
8β
erf(∞) − erf 2βR exp 2βR − β erf(∞) − erf
2
βR exp βR 2
;r ≥ R

Apart from the local and global approaches described in potential function, as well as to use Morse parameters
the preceding pages, there is yet another approach for for plotting Varshni potential energy curves. The effort
obtaining parameter relationships between both functions. of finding a conversion formula is much more economical
By imposing equal bond stretching energy as the bond and time-saving as compared to (a) separate experimenta-
dissociates tions to obtain parameters of different potentials, and (b)
lim UM = lim UV , (15) curve-fitting from experimental data for obtaining param-
r→∞ r→∞
eters of different potential functions. With the parameter
we have conversion in place, parameters of one potential can be
α = βr. (16) generated from those of another potential very quickly.

Although this relation is valid as r → ∞, it appears to be

of little practical value since (UM ) = (UV ) = 0. As such
the use of local and global approaches, as described in
Eq. (14), would be sufficient (see Fig. 3).
4. Conclusions
Two methods for converting Morse parameters into Varshni
parameters and vice versa have been developed herein.
The local approach equates the equivalence of force con-
stants from both functions, thereby enabling good corre-
lation for r < R and r ≈ R. The global approach imposes
equal integral of bond energy from the point of equilib-
rium to bond dissociation, thereby providing good corre-
lation for r > R. The developed relations allow Varshni
parameters to be used in any software that uses Morse
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Teik-Cheng Lim, Rajendra Acharya Udyavara

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