The basis set convergence of the HartreeFock energy for H 2

Frank Jensen
Citation: The Journal of Chemical Physics 110, 6601 (1999); doi: 10.1063/1.478567
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JOURNAL OF CHEMICAL PHYSICS

VOLUME 110, NUMBER 14

8 APRIL 1999

The basis set convergence of the HartreeFock energy for H2

Frank Jensena)
Department of Chemistry, Odense University, DK-5230 Odense M., Denmark

~Received 9 November 1998; accepted 7 January 1999!

By using completely optimized basis functions, it is shown that the HartreeFock energy for the H2
molecule converges exponentially, both with respect to the number of basis functions of a given
type and with respect to the highest angular momentum functions included. With a basis set
including up to h-functions, a subnanohartree accuracy can be obtained. These results clearly
suggest that estimation of the complete basis-set limit should employ different extrapolation
schemes for the HartreeFock and correlation energies. 1999 American Institute of Physics.
@S0021-9606~99!30114-8#

used a fitted inverse power function ~with functional behavior ;L 23.4! for extrapolation to the basis-set limit.10
The HF energy for atomic systems depends only on basis functions of the types actually being occupied, e.g., the
energy of a hydrogen atom depends only on the number of
s-functions, the energy of a carbon atom depends only on the
number of s- and p-functions, etc. For molecular systems,
however, the charge polarization is described by higher-order
angular moment functions, and the energy consequently depends not only on the number of functions of a given type,
but also on the types of higher angular momentum functions
included. In order to extrapolate the energy to the HF limit, it
is of interest to know the functional behavior of both these
convergences.
The simplest molecular system is H2, which has a prototypical two-electron covalent bond. The HF limit at an internuclear distance of 1.40 a.u. is known from numerical
HartreeFock calculations,11 and H2 thus provides a case
where the detailed convergence behavior can be established,
both in terms of number of functions ~M! of a given type and
in terms of the highest angular momentum functions ~L! included in the atomic basis.

I. INTRODUCTION

Traditional ab initio electronic structure calculations employ an independent particle solution, the HartreeFock
~HF! approximation, at the initial stage, and subsequently
add many-body corrections, the electron correlation energy.1
The one-electron solutions, the ~molecular! orbitals, are expanded in a suitable set of basis functions, traditionally chosen as a nuclear centered set of Gaussian functions, as these
are computationally efficient.2 The exact solution for a given
Hamiltonian is the value obtained in the limit of recovering
all the electron correlation using a complete basis set. Since
a complete basis set is not possible in actual calculations, the
infinite basis-set limit must be estimated by extrapolation
from results obtained with increasingly larger ~finite! basis
sets.
The computationally difficult part is the correlation energy, although it only accounts for ;1% of the total energy.
Theoretical analysis3 indicate that for a basis set saturated up
to angular momentum L ~L50 is an s-function, L51 a
p-function, L52 a d-function, etc.!, the dominating term
~from second-order perturbation theory! should converge as
(L11) 23 . Also including higher-order effects shows that
the correlation energy should converge as an inverse power
series,3 i.e., A(L11) 23 1B(L11) 24 1C(L11) 25 1... For
the popular correlation-consistent basis sets,4 an L 23 behavior has been observed computationally,5 although other
schemes have also been used.6 An L 23 convergence is quite
slow and is the major problem in calculating accurate correlation energies.
The HF energy, on the other hand, is known to converge
much faster. Surprisingly, very little is known about the actual convergence behavior. Computationally, the energy of
the hydrogen atom has been shown to converge exponentially with the number of s-functions,7 and for molecular systems the HF energy calculated by the correlation-consistent
basis sets can normally be fitted very well by an exponential
function of the type A1B exp(2CL).8 Petersson et al., however, have argued that the convergence should be ;L 25 and
used this in their complete basis set models,9 and Truhlar has

II. BASIS SET OPTIMIZATION

For atomic systems it is possible to smoothly converge

towards the basis-set limit by selecting the basis set exponents z from a parameterized formula, such as that for eventempered basis sets.12

z i 5 ab i ,

ln~ ln b ! 5b ln M 1b 8 ,

~1!

ln a 5a ln~ b 21 ! 1a 8 .
The constants a, a 8 , b, and b 8 depend only on the atom type
and the type of function. This formula guarantees that the
basis set approaches completeness as M `.
For atomic systems, even-tempered basis sets monotonically approach the HF limit, and this is also the case for
molecules if microhartree accuracy is sufficient.13 At higher
accuracy ~e.g., nanohartree!, however, the energy calculated
by increasingly larger even-tempered basis sets becomes os-

a!

Electronic mail: frj@dou.dk

0021-9606/99/110(14)/6601/5/$15.00

i51,2,...,M

6601

1999 American Institute of Physics

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6602

J. Chem. Phys., Vol. 110, No. 14, 8 April 1999

Frank Jensen

cillating, i.e., extending a basis set with one additional function may cause the energy to increase. The reason is that the
description of the bonding orbital~s! is sensitive to the exact
exponents in the valence space. The even-tempered formula
shifts all exponents when M increases, and in some cases this
leads to an increase in the energy as the important valence
exponents are shifted away from their optimal values. More
sophisticated parameterizations, such as the well-tempered
formula,14 show the same problem.

S S DD

z i 5 ab i21 11 g

i
M

i51,2,...,M .

~2!

In the present investigation, we have consequently relied

on a complete optimization of all basis set exponents and
expansion coefficients for each basis set size.
The optimizations have been performed by a pseudoNewtonRaphson approach with ln(z) as the variables and
using gradients generated by central finite differences.15,16
Energies were calculated using the GAUSSIAN 94 program
package.17 The target accuracy for terminating an optimization was ;0.01 nanohartree (10211 hartree); however, the
final results indicate that the combined numerical errors ~incomplete optimization, the use of numerical gradients, and
round-off errors associated with integral evaluations and solution of the SCF equations! are ;0.5 nanohartree.
Two types of basis set convergence are of interest; the
behavior as a function of number of s-functions only ~reaching the s-limit!, and the behavior as a function of maximum
angular momentum functions ~reaching the HF limit!. The
latter requires determination of the energy limit for using
s-functions only, using s- and p-functions only ~sp-limit!,
using s-, p-, and d-functions only ~spd-limit!, etc. For a given
maximum L-value, a completely optimized basis set of a
given composition ~number of s-, p-, d-, etc. functions! was
determined by a pseudo-NewtonRaphson method. Four criteria were used for deciding whether such a solution corresponded to the given L-limit:
~1! The energy lowering by addition of one extra basis function with either larger or smaller exponent should be
0.01 nanohartree or less.
~2! The energy lowering by addition of one extra basis function between existing exponents should be 0.01 nanohartree or less.
~3! Removal of any basis function should increase the energy by at least 0.01 nanohartree.
~4! The molecular orbital coefficients for each angular momentum type basis function should be of the same sign
and show a curve as a function of basis set exponents
with a single maximum. For a given type of function,
this means that u c i u , u c i11 u for z i , z i11 until a maximum u c k u is encountered, after which u c i u . u c i11 u for
z i , z i11 .
If either criteria ~1!, ~2! @subject to criterion ~4!# ~3!, or ~4!
was failed, one basis function was added or removed, followed by reoptimization.
The necessity of criterion ~4! became evident during this
work. Without these restrictions, it is possible to generate,
for example, s-type basis sets which have two neighboring

TABLE I. HartreeFock energy convergence for H2 as a function of number of s-functions.

Ns

Energy

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21

0.976 189 542 0

1.098 820 632 3
1.123 021 277 8
1.127 152 963 8
1.128 144 140 1
1.128 441 779 5
1.128 511 869 1
1.128 532 151 9
1.128 538 849 3
1.128 540 754 7
1.128 541 875 2
1.128 542 219 3
1.128 542 310 4
1.128 542 335 0
1.128 542 341 8
1.128 542 346 0
1.128 542 347 9
1.128 542 348 5
1.128 542 348 6
1.128 542 348 6
1.128 542 348 7

functions entering the molecular orbital with coefficients of

different sign. Upon optimization of such a basis set, the two
exponents converge toward each other, and thus effectively
create a p-type function centered at the bond midpoint. In
practice, the optimization fails once the two exponents become sufficiently close, as the overlap matrix becomes
nearly singular. That such solutions are artificial is evident
from the fact that they disappear once the next higher angular momentum functions ~i.e., p-functions! are added. In general, it was observed that addition of functions with intermediate exponents @criterion ~2!# for the highest angular
momentum type of functions could lead to lower energies,
but these extra functions entered the molecular orbital with
opposing signs, and therefore indicate a lack of functions
with one higher L value.
III. RESULTS AND DISCUSSION

The energy convergence as a function of s-functions

only is shown in Table I. With a basis set consisting of 19
functions on each center, an energy of 1.128 542 348 6 hartree is obtained. Addition of two more tight functions lowers
the energy by 0.02 nanohartree, and by rounding we estimate
the s-limit for the energy to be 1.128 542 348 7 hartree. The
corresponding optimized exponents are shown as a ln(z) plot
in Fig. 1. Until M 510, the optimal exponents follow a pattern similar to that produced by the well-tempered
parameterization.14 Addition of one extra function causes the
exponents to move in- and outward, and diminish the ratio
between successive values, i.e., a better coverage of the exponent space. For M <10, we have not been able to find
other sets of optimized exponents, i.e., it appears that the
energy hypersurface only contains a single minimum as a
function of basis-set exponents.
As the basis set is increased beyond 10 functions per
atom, the valence region is close to saturated, and the corre-

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J. Chem. Phys., Vol. 110, No. 14, 8 April 1999

Frank Jensen

6603

FIG. 1. Logarithmic value of optimized exponents for H2 as a function

of number of s-functions per atom.

sponding exponents are insensitive toward further extension

of the basis set. The additional ~tight! functions primarily
serve to improve the wave function near the nuclei ~i.e., improving the description of the wave function cusp!. At M
513 a second type of solution appears, which corresponds to
addition of a function with a smaller exponent to the M
512 solution, but it is higher in energy than the solution
corresponding to addition of a tight function. At M 516, the
energies of the two types of solution shift, and the energetically favored extension of the M 515 basis set is by addition
of a more diffuse function. Finally, with M 519 the energy
change by further extension of the basis set is only ;0.02
nanohartree and the s-limit is considered reached. The M
519 basis set has exponents in the range 33106 3
31022 , with ratios between exponents ranging from 7.7 between z 18 and z 19 to 1.9 between z 1 and z 2 .
Introduction of a set of higher angular momentum functions ~e.g., p-functions! was done by initially keeping the
exponents of the lower angular momentum functions ~i.e.,
s-function! constant. Once the energy was sufficiently stable
~;0.1 nanohartree! towards further addition of basis functions, all exponents were optimized simultaneously. This solution was then subjected to further addition or removal of
functions, according to the above criteria. Addition of a set
of functions with angular momentum L tends to reduce the
ratios between exponents in the L-1, L-2, etc. sets of functions, thereby necessitating more of these functions to saturate the exponent space. This coupling between exponents of
different L-values decreases as L increases.
The sp-, spd-, spdf-, spdfg-, and spdfgh-limits for the HF
energy and corresponding basis-set compositions are given
in Table II. The final 22s13p8d4 f 2g2h-basis ~spdfgh-limit!
optimized energy is 1.133 629 571 0 hartree, where the first
h-function causes an energy lowering of 0.48 nanohartree
relative to the spdfg-limit, and the second h-function gives an
additional 0.08 nanohartree. Addition of more h-functions or
an i-function causes changes less than 0.01 nanohartree;

thus, the above energy is effectively converged to the basisset limit. The 22s13p8d4 f 2g2h basis contains 338 individual components, although only the 102 components with
s-symmetry contribute to the energy.18
The numerical HF calculations in Ref. 11 compared results obtained from finite difference and finite element methods, with discrepancies for H2 being 0.35 nanohartree. Subsequent finite difference calculations with larger grids
indicate an HF limit of 1.133 629 571 5 hartree,19 which is
0.5 nanohartree below the present basis-set limit. The discrepancy is most likely due to various numerical errors associated with incomplete optimization, the use of numerical
gradients, and round-off errors associated with integral
evaluations and solution of the SCF equations.
The convergence behavior can be investigated by plotting ln(Ex-E`) as a function of either x or ln(x), where x
denotes either the number of basis functions or the highest
angular momentum functions in the basis set ~x5M or L!.
An exponential ~or geometric! convergence should give a
straight line as a function of x, while an inverse power dependence should give a straight line as a function of ln(x).

TABLE II. HartreeFock energy convergence for H2 as a function of highest angular momentum basis function.
Basis
s-limit
sp-limit
spd-limit
spdf-limit
spdfg-limit
spdfgh-limit
HF limita
a

Composition
(21s)
(21s,9p)
(22s,11p,6d)
(22s,13p,8d,4f )
(22s,13p,8d,4f ,2g)
(22s,13p,8d,4f ,2g,2h)

Energy
1.128 542 348 7
1.133 572 319 6
1.133 628 674 6
1.133 629 552 2
1.133 629 570 5
1.133 629 571 0
1.133 629 571 5

Refs. 11, 19.

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6604

J. Chem. Phys., Vol. 110, No. 14, 8 April 1999

Frank Jensen

FIG. 2. Convergence of the HartreeFock energy for H2 as a function of

number of s-functions per atom.

FIG. 3. Convergence of the HartreeFock energy for H2 as a function of the

highest angular momentum functions.

ACKNOWLEDGMENTS

E x 5E ` 1Ae

2Bx

E x 5E ` 1Ax

2B

ln~ E x 2E ` ! 5ln~ A ! 2Bx

ln~ E x 2E ` ! 5ln~ A ! 2B ln~ x ! .

~3!

Both types of plots are shown for the energy dependence on

the number of s-functions in Fig. 2 ~discarding the M 519
point, as it is sensitive to the exact value of the s-limit energy!, and it is clear that the energy converges exponentially
@ln(A)521.8 and B51.2 in Eq. ~3!, correlation coefficient
50.998!, in agreement with the atomic hydrogen system.7
The corresponding plots as a function of highest angular
momentum L are shown in Fig. 3. For the L54 and L55
points ~spdfg- and spdfgh-limits!, E L -E HF is comparable to
the residual error of ;0.5 nanohartree, and these points will
deviate systematically from the expected behavior. This is
partly artificial, as the ;0.5 nanohartree error presumably is
evenly distributed, but appears localized in the energies for
the highest L-limits.
The plot of ln(EL-EHF) against L for the first four points
~s-, sp-, spd-, and spdf-limits! is fitted very well by a straight
line @ln(A)525.4 and B54.2 in Eq. ~3!, correlation
coefficient50.9994#, with the last two points being off the
line due to the residual error. The plot of ln(EL-EHF) against
ln(L), on the other hand, is not nearly as linear, the first four
points suggest a parabolic dependence. Figure 3 clearly indicates that the energy convergence as a function of angular
momentum is also exponential.

This work was supported by grants from the Danish

Natural Science Research Council. The author thanks J. Kobus for performing additional finite difference calculations
for estimating the HF limit.

W. J. Hehre, L. Radom, P. v. R. Schleyer, and J. A. Pople, Ab Initio

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15
Although the theory for analytical gradients of the HF energy with respect
to basis-set exponents has been developed, ~Refs. 16, 20! there is apparIV. CONCLUSION
ently no current functional code for carrying out such calculations. The
numerical differentiation used a step size corresponding to energy changes
of ;0.1 nanohartree.
Fully optimized basis sets for the H2 molecule show that
16
K. Hashimoto and Y. Osamura, J. Chem. Phys. 95, 1121 ~1991!.
17
the HF energy convergence is exponential, both in the numGAUSSIAN 94, M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill,
ber of basis functions of a given type and in the highest
B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. Keith, G. A. Petersson,
J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski,
angular momentum function included. Given the inverse
J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. B. Stephanov, A. Nanaypower behavior of the correlation energy, this clearly suggest
akkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, W. Chen, M. W.
that HartreeFock and correlation energies should be exWong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox,
trapolated separately for estimating the basis-set limit.
J. S. Binkley, D. J. Defrees, J. Baker, J. J. P. Stewart, M. Head-Gordon, C.
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J. Chem. Phys., Vol. 110, No. 14, 8 April 1999

Gonzales and J. A. Pople, Gaussian, Inc., Pittsburgh, PA, 1995. All integral and convergence criteria were tightened, and it was checked that
calculated energies could be reproduced by other electronic structure programs to within 0.1 nanohartree.
18
The largest of the correlation-consistent basis sets for hydrogen, aug-cc-

Frank Jensen

6605

pV6Z, is 11s6 p5d4 f 3g2h in composition and yields a total energy of

1.133 626 851 9 hartree when completely uncontracted.
19
J. Kobus, private communication. The largest grid was 3193595 and used
a cutoff distance of 65 a.u., giving an energy of 1.133 629 571 5 hartree.
20
G. Tonachini and H. B. Schlegel, J. Chem. Phys. 87, 514 ~1987!.

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