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Padé approximation methods applied to the

intermolecular force series
a a
Y.H. Pan & William J. Meath
a
Department of Chemistry , University of Western Ontario , London 72 ,
Canada
Published online: 22 Aug 2006.

To cite this article: Y.H. Pan & William J. Meath (1971) Padé approximation methods applied to the
intermolecular force series, Molecular Physics: An International Journal at the Interface Between
Chemistry and Physics, 20:5, 873-880, DOI: 10.1080/00268977100100841

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 MOLECULARPHYSICS, 1971, VOL. 20, No. 5, 873-880

Pad6 approximation m e t h o d s applied to the

i n t e r m o l e c u l a r force series

by Y. H. PAN and WILLIAM J. MEATH

Department of Chemistry, University of Western Ontario,
London 72, Canada
(Received 20 October 1970)

The H(ls)-H +, He--He, H(ls)-H(ls) and H(ls)-H(2s) interactions are

considered as model systems for investigating the use of the Pad6 approximation
method in summing the R -1 intermolecular force series. Various Pad6
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approximants and partial sums of the R -1 expansions of the second-order

Coulomb interaction energies are compared with the corresponding non-
expanded results for each interaction. The computations are based on Uns61d's
average energy approximation and on exact results for the H( ls)-H + interaction.
The results indicate that the Pad6 approximation method is a simple, useful
way to remove some of the difficulties associated with the slow rate of
convergence of the R -1 force series but that it does not alleviate the problems
associated with the asymptotic divergent nature of the series. The results
for the H(ls)-H + interaction illustrate a possible difficulty in using Uns~ld's
method in the calculation of interaction energies.

l. INTRODUCTION
T h e neglect of charge overlap (and exchange) effects between interacting
molecules or atoms yields the usual R -1 expansion of the interaction energy.
T h e R -1 expansions are series representations [1-4] of the interaction energy
including charge overlap effects but excluding electron exchange effects and are
therefore representations of the Coulomb or direct interaction energy. While
these expansions are useful in many applications of intermolecular forces there
are problems [1, 3, 5-8] associated with their use. As a representation of the
Coulomb interaction energy the asymptotic nature of the R -1 expansions limits
their usefulness for ' s m a l l ' values of R while the slow rate [7] of convergence
of the series limits their usefulness for ' l a r g e r ' values of R. T h e meaning of
' s m a l l ' and ' l a r g e ' has been discussed [7] previously.
T h e purpose of this paper is to investigate the possibility of using Pad6
approximation methods (see for example [9-11]) to remove some of the difficulties
associated with the direct use of the R -1 expansions of the interaction energy.
T h e H ( l s ) - H +, H e - H e , H ( l s ) - H ( l s ) and H(ls)-H(2s) interactions are considered
as model systems for this purpose. Various Pad6 approximants and partial sums
of the R -1 expansions of the second-order Coulomb interaction energies are
compared with the corresponding non-expanded results [3, 7] for each interaction.
T h e computations are based on Uns61d's average energy calculations and on
exact results for the H ( l s ) - H + interaction. T h e results for the H ( l s ) - H +
interaction illustrate a possible difficulty in using Uns61d's method for calculating
interaction energies. T h e discussion in this paper supplements the recent
discussion of the dependence of charge overlap effects on the nature of the
interaction given in [7].
 874 Y . H . Pan and W. J. Meath

2. THE R - I EXPANSIONS FOR THE SECOND-ORDER INTERACTION

ENERGIES AND THE PADE APPROXIMANTS
Consider the interaction of two molecules or atoms a and b where electron
exchange is neglected. The interaction energy through second order is given
by [1-4, 12]
Eab = E - E(O)= E(1) + E(2) + . . . . (I)
where
E<I) -~<~F(o)l ge]q;'(o)); E(2)= <~<0) I VeI~F(1)). (2)
Here E(o) is the energy of the isolated species, ~F(~ is the zeroth-order wave
function representing the isolated species and Fe is the Coulomb interaction
between all the particles in atom a and all the particles in atom b; for details see
[I-4, 7, 12]. The E(n), n > 0, are the non-expanded nth-order interaction energies.
Each perturbed interaction energy can be written in the form
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E(n) = E~ ,(n) + E(n)exp (-R), n = 1, 2 . . . . , (3)

where E(n)exp (-m is zero when exponentially decreasing [13] terms of the argument
R are ignored (see w also). For the interactions considered in this paper

lira E(1)=0; lim E(2)= lira ER-I(2)=- ~ C2mR-2m, (4)

R - - + ov R - - ~ ao R-+ ce m = K

where the C2m a r e independent of R and depend on the properties of the isolated
molecules only [4, 8]. These results can be obtained directly [1] from (2) if
charge overlap [3] is neglected (schematically R-+cc) and the R -1 multipole
expansion used for the interaction potential energy Ve. Here K = 2 for the
H(ls)-H + second-order induction energy and K = 3 for the second-order dispersion
energies corresponding to the other three interactions considered in this work.
The exact results for E(2), ER-,(2), E(2)exp (-n) and the C2m, for all m, are given
for the H(ls)-H + interaction by [6, 13, 14]. Corresponding results for the
non-expanded energies are not available for the other interactions.
Often UnsSld's approximation [15] is useful in discussing intermolecular
forces. Here the interaction energy is given approximately by [1, 7, 16-18]
/~aO= E (1) +/~(2) _}_ . . . . (5)
E(2) = __ ~1 [(t~f(0) [ Ve2 1tif(0)) __ (E(1))2], (6)

where A is an 'average energy' and the tilde indicates that these results are
approximations to the exact interaction energies. The actual choice of A will
not be of concern in this paper since only relative effects where A cancels [7]
will be considered. The decomposition and R -1 expansion of/~(2) are completely
analogous to those for the exact second-order energy, see (3) and (4); the Unsbld
results will be denoted by a tilde. The results for the non-expanded second-order
energies and the C2m, all m, for the H(ls)-H +, He-He, H(ls)-H(ls) and
H(ls)-H(2s) interactions are given in [7, 16-18]; see [7] for a discussion of the
last three interactions.
In order to discuss Pad6 approximant methods [9-11] for summing the R -1
power series for the interaction energy it is convenient to write (4) in the form

l i m E ( 2 ) = - X K ~ C2(n+K)Xn, (7)
 Intermolecular force series 875

where X = R -2. The [N, M ] Pad6 approximant corresponding to (7) is then

given by
[N, M] = - XKpM(x)/QN(X), (8)
where
M N
PM(X) = ~ piXi, O~v(X)= 1 + 2 qixl" (9)
i=0 i~l

The ( M + 1) coefficients p, and the N coefficients qt are obtained by requiring

that the power series expansion of (8), in the variable X = R -2, equal (7) term
by term through order ( N + M + K ) . This requirement yields a system of
( M + N + 1) linear equations which can be solved for the pi's and q,'s;
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Pi= ~ C2(K+t-t)qt; i-----0,1, 2, . .. , M,

j=0
N
(10)
- C2(~+M+O = ~ C2(K+M+~-j)q~; i= 1, 2. . . . . N,
j=l

where q0---1 and Ct= 0 for l< 2K. An entirely analogous analysis can be made
for UnsSld's results; replace E(2), C2tn+r) and IN, M ] by j~t2), C2Cn+K) and
[N,-M] respectively. It is clear that in order to obtain a [N, M ] Pad6 approximant
for Et 2) we need to know the first ( N + M + I ) term in (7) and for notational
convenience we define the truncated series

S ( ~ ) = - X K ~ C2(n+K)X% (11)
n=0

where co= N + M, as the partial sum corresponding to the IN, M ] Pad6 approximant
of E(2). The corresponding UnsSld's partial sum will be denoted by ~q(r
In general one partial sum can define more than one Pad~ approximant. According
to practical experience [10], for a constant value of w, the most accurate Pad6
approximants for a function are the IN, N] and the [N, N - 1 ] approximants;
our calculations support this statement. Also since the coefficients {p} and {q}
may be positive or negative, see (10), the Pad6 approximant (8) may differ in sign
with respect to E(~); in this case the Pad6 is not available for the given values
of X for our purposes.

3. A P P L I C A T I O N S AND DISCUSSION

Various Pad6 approximants were obtained for the H(ls)-H +, He-He

H(ls)-H(ls) and H(ls)-H(2s) interactions in UnsSld's approximation and for
the H(ls)-H + interaction using exact results. Only some of the calculations for
the 1Xg+H(ls)-H(2s) and H(ls)-H + interactions are given explicitly and discussed
in detail here in order to avoid repetition. Many of the trends are analogous to
those discussed in [7] for the direct use of the R -1 expansions; see [19] for more
details.
Strictly speaking the R -1 expansions are asymptotic to ER-,(2) and not to
the total non-expanded second-order energy E~g). This is easy to see for the
UnsSld calculations and for the exact H(ls)-H + result where explicit expressions
are available for the relevant energies. Thus ER-,(~) is comprised of functions
 876 Y . H . Pan and W. J. Meath

of the form R -n, n> O, exp ( - c R ) E i ( c R ) and exp (cR)Ei(-cR), c > 0 , which
possess asymptotic expansions for large R while E (2)exv (-R) is made up of
functions which have no asymptotic expansions; for examples and discussions
of this point see [1, 3, 5, 13, 16-18]. Hence the R-* expansions and the Pad~
approximants derived from them, are rigorous approximations to E(2) only when
ER -~(2) is considerably greater in magnitude than E (2)exp (-R).
In figures 1 and 2 ratios of the form [S (w)/J~(2)], [S (oJ)/J~R '(2)], ([N.M]/~(2))
and ([N.M]/F.R-,(2)) are plotted as a function of R for the H ( l s ) - H + and
H(ls)-H(2s) interactions in Unsold's approximation. The graphs involving
IN, M ] are truncated as a function of decreasing R at the value of R where [IV, M ]
differs in sign with respect to J~R-,(e) or j~(9); see w In all cases, for values
of R where the R -] expansions have meaning (see below), the partial R -1 sums
and the Padd approximants represent ~ ,(2) much more accurately than
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/~(2) itself until R is sufficiently large that/~(2)exp (-R) is negligible with respect
to/~R-,(~); compare figure 1 (a) with figure 1 (b) and figure 2 (a) with figure 2 (b).
This is much more apparent for the H(ls)-H(2s) interaction where /~(Z)exp (-n)
becomes comparable in size to /~n-,(z) at R ~ 15a0 and is still approximately

1.2 34

\\\ \
1,1
1.0

0.9
1.2"

!
12 34

\',k \
1,1
\"k ', ',
~\,~ ~-[2,2]
1.o \. ".

~ t, a I J I , i I i ! i I l I , i d
3 4 5 6 7 8 9 10
R
Figure 1. Comparison of various partial sums and Pad~ approximants of the expanded
dispersion energy with the non-expanded second-order energy as a function of R
for the H(ls)-H + interaction in Unsfld's approximation. (a) [S(~o)/ER ,(z)]
is represented by - - and the value of co; ([N, M]/ER -*(~)) is represented by
.... and [N, M]. (b) [~(w)/~'(2)] is represented by ~ and the value of
co; ([N,-M]//~(z)) is represented by . . . . and [N, g ] .
 lntermoIecular force series 877

1 2 34
i | \t \~. ', ~ (a)
\ \ ~[1,1] , ttt~2.2]
\ \\~ ', ,,
1.2

1.C[
\ -..--._ . . . . . . . . . . .

O.8

1 2 ? (b)
4 , l ,
1.~ I[I,0~I
~1,I]
t I
[2.1~t ~[2)2]
t t
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1s
J
0.8 ,,, ',,, f

0.4

0.2
i ! | , | I | I I i I i I i I ' 9
8 10 12 14 16 18 20 22 24 26 28 30
Figure 2. Comparison of various partial sums and Pad6 approximants of the expanded
dispersion energy with the non-expanded second-order energy as a function of R
for the H(ls)-H(2s) interaction in UnsSld's approximation. (a) [~(o~)/ER -,(~)] and
(IN, M]/ER-~C2)). (b) [~(oj)//~c~)] and ([N, M]//~'(~)). Graphical representation
as discussed in figure 1.

8 per cent of J~R-,(2) at R=20a0. For the H(ls)-H + interaction ~(2)exp (-R) is
essentially negligible with respect to ~R-,(2) for R > 4a0.
Each Pad6 approximant gives a better representation of 8R -,C2) than the
corresponding partial sum, see figures 1 (a) and 2 (a), for values of R where the
partial sum is a meaningful representation of the second-order energy. Previous
work suggests that the ratio of successive terms in the R -1 expansions of
E(2) should be considerably less than unity for all R; see the discussions of
[1, 3, 5-8] and Singh et al. [20]. For the examples shown in figures 1 (a) and
2(a) the Pad6 approximants are a better approximation to ~R-,(2) than the
corresponding partial sums when
[(C2 (o+K)R -2 (~ 2 (o+K-1)R -2 (o+K-1))] < [3ab ' (12)
where f l ~ 0 . 4 and f l ~ 0 . 6 for the H(ls)-H + and H(ls)-H(2s) interactions
respectively. The numerical results for fl represent average values for the Pad6
approximants indicated in figures 1 (a) and 2 (a). For large values of R better
approximations can be generated by using Pad6 approximates (or partial sums
[7]) corresponding to larger values of ( N + M ) or o~. However, the larger
( N + M ) or co the more rapid is the divergence from the non-expanded results
as R decreases in value; this is easily seen in figure 2 (a). It should be emphasized
that for larger values of ( N + M ) or oJ the Pad6 approximant often yields only a
 878 Y . H . Pan and W. J. Meath

trivial improvement over the results obtained by using the corresponding partial
sum which often occurs only for large values of R satisfying the condition of (12).
For example, the improvement in using the approximants [2,1] and [2,2] is
not visible using the scale of figures 1 (a) and 2 (a); see however figure 2 (b).
The trends for the representation of the total second-order energy by the Pad6
approximants are analogous to those for /~R-,(2) with the poviso that strictly
speaking the R -1 expansions are asymptotic to /~R-,(2); see above and figures
1 (b) and 2 (b).
These results (see below also) show that the Pad6 approximants can accelerate
the convergence of the R -1 expansions for values of R where the expansions are
meaningful. This is particularly the case for interactions involving excited or
larger species where the slow rate of convergence of the R -1 series is more
noticeable, for example see figure 2 and consider the [1,0] Pad& For the
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H(ls)-H(2s) interaction the [1, 0] Pad6 approximant, based on the two-term

partial sum ~q(1), gives a more accurate representation of .E'R-,(2) than the three-
term partial sum S(2) and represents /~(2) about as well as the four-term partial
sum S(3). Numerically for example at R=18a0, the partial sums S(1), ~(2)
and the Pad6 [1,0], respectively, are in error by approximately 18, 11 and 8 per
cent as a representation of/~R-,(~) and are in error by about 33, 24 and 23 per cent
as a representation of/? (2) itself.
The trends and the discussion given here for the H(ls)-H + and H(ls)-H(2s)
interactions in UnsSld's approximation apply equally well to the H e - H e and
H(ls)-H(ls) interactions aside from a change of scale due to the nature of the
interacting species; for a discussion see [7] and [19]. In figure 3 graphs analogous
to figure 1 are plotted for the exact H ( l s ) - H + results. The trends for the
representation of ER ,(2) are very similar to those for the Uns61d calculation,
compare figures 1 (a) and 3 (a). However, the graphs corresponding to the
representation of the total second-order energy are markedly different, see figures
1 (b) and 3 (b), since /~R-,(2) and /~(2)exp (-R) have the same sign while ER-I(2)
and E(2)exp (-R) have different signs for the H ( l s ) - H + interaction. These
results point out a very real difficulty with Uns61d's approximation if the average
energy A in (6) is chosen in the usual way by requiring the exact long-range
results when charge overlap effects are neglected. This approach would
incorporate charge overlap effects properly within ~R-,(2) but could badly
misrepresent the effects of E(2)exp (-n) for interactions like H ( D ) - H + where
~,(2)exp (-R) has the incorrect sign [21].
It should be emphasized that there are several ways [1, 9, 10, 11 (a), 22] to
attempt to remove the divergence and convergence problems associated with
the R -1 expansions of the interaction energies. One method [1] is to truncate
the R -1 expansions by summing them to one-half their smallest term as a function
of R. This approach yields useful representations t of /~R,-(2) and ~(2) but
has the disadvantage that many of the R -1 energies are required to obtain the
result [1, 7]. For example, at R = 18a0 six terms are required for the H(ls)-H(2s)
interaction and at R = 6 a 0 five terms are required for the H(ls)-H + interaction.
J- The graphical illustration of this representation in [7] is not correct. The dashed
line in figure 3 of [7] represents the correct result only in an average sense. In actual
fact, the dashed line is serrated resulting from the successive dropping of terms in the
R-1 expansion as R decreases.
 Intermolecular force series 879

1.2 2 34
\\ '~
1.1
\ ,
1.0

O.9

1 2 34
Downloaded by [University of Alberta] at 22:49 26 April 2015

l ~ (b)

\ \\x.N \ x

1.0 I * I i I ~ l i I e i ~ I

3 4 5 6 7 8 9 10
R
Figure 3. Comparison of various partial sums and Pad6 approximants of the expanded
dispersion energy with the non-expanded second-order energy as a function of R
for the H ( l s ) - H + interaction using exact results. (a) [S(o~)/En -,~2)] and
(IN, M]/En-~)). (b) [S(oJ)/E {2)] and ([N, M]/Et2)). Graphical representation
as discussed in figure 1.

This is a severe limitation [7] since in most practical applications only the first
few terms in the R -1 expansions are known with any degree of accuracy for most
interactions. In such circumstances the Pad6 approximant method appears to be a
simple useful way to remove some of the difficulties associated with the slow rate of
convergence of the R -1 series representation of the interaction energy. However,
it does not alleviate the problems associated with the asymptotic divergent nature
of the series. This is not unreasonable since R -1 is not a good expansion parameter
for the interaction energy for ' s m a l l ' values of R [23]. Indeed the Pad6
approximants probably give a more realistic indication of the asymptotic nature
of the intermolecular force series than the corresponding R -x partial sums.

The authors are grateful for a grant from the National Research Council
of Canada, and for the award of an Ontario Graduate Fellowship to Y. H . P . We
also acknowledge the assistance of H. Kreek who supplied some of the numerical
data used in this paper.

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 880 Y . H . Pan and W. J. Meath

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[15] UNSOLD, A., 1927, Z. Phys., 43, 563.

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