Natural bond orbital analysis of nearHartree–Fock water dimer

Alan E. Reed and Frank Weinhold

Citation: J. Chem. Phys. 78, 4066 (1983); doi: 10.1063/1.445134

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 Natural bond orbital analysis of near-Hartree-Fock water
dimer
Alan E. Reed and Frank Weinhold
Theoretical Chemistry Institute and Department of Chemistry, University of Wisconsin, Madison,
Wisconsin 53706
(Received 4 August 1982; accepted 17 September 1982)

We have carried out a natural bond orbital analysis of hydrogen bonding in the water dimer for the near-
Hartree-Fock wave function of Popkie, Kistenmacher, and Clementi, extending previous studies based on
smaller basis sets and less realistic geometry. We find that interactions which may properly be described as
"charge transfer" (particularly the n -a"llH interaction along the H-bond axis) playa critical role in the
formation of the hydrogen bond, and without these interactions the water dimer would be 3-5 kcallmol
repulsive at the observed equilibrium distance. We discuss this result in relationship to Klemperer's general
picture of the bonding in van der Waals molecules. and to previous theoretical analyses of hydrogen bonding
by the method of Kitaura and Morokuma.

I. INTRODUCTION ture and stability.17 This concluSion, closely related

Recent advances in molecular beam electric reso-
nance,l Fourier transform microwave spectroscopy, 2
and other experimental techniques 3 have led to an ex-
plosive growth in our knowledge of the accurate struc-
tures of van der Waals (vdW) molecules. 3-10 The struc-
tures of these weakly bound complexes reveal the opera-
tion of characteristic bonding principles, no less archi-
tecturally intriguing than those governing covalent mole-
cule formation. The wealth of new experimental data
thus presents theoreticians the stimulus and challenge
to extend valence principles in the directions needed to
understand the structure and chemistry of these novel
species.
Hydrogen-bonded species form a particularly interest-
ing and important subclass of vdW molecules, because
of their unusual strength and their obvious relevance to
solvation phenomena. These species are also particular-
ly amenable to theoretical treatment, since the disper-
sion interactions make only a minor contribution to their
binding, 11,12 and a good account of the structure and
energetics is given by the uncorrelated SCF-MO approxi-
mation. The water dimer (H 20)2 is the prototype com-
plex of this type, and has been extensively investigated
at the SCF and CI level with a wide variety of basis
sets, 12-14 culminating in good agreement with the avail-
able experimental structure, 15
We recently described a method of analyzing SCF
wave functions of weakly bound complexes in terms of
localized bond orbitals (BOs), giving a convenient link
to the chemist's language of bonds, lone pairs, etc.,
and helping to throw light on the forces responsible for
binding. The natural hybrid orbital (NHO) procedure 1e - 18
determines these BOs in an optimal fashion by the oc-
cupancy criterion, allowing such an analySis to be car-
ried out without preconceptions for wave functions of
quite general form. The NHO-BO analysis of the SCF
water dimer in various basis sets pointed to the impor-
tance of the intermolecular n-:a~H charge transfer in-
teraction as a dominant contribution to H-bond struc-·
to Klemperer's general picture of vdW molecule forma-
tion, 5 was found to be generally insensitive to details
of geometry, AO basis set, and method of forming the
BOs. However, no attempt was made to refine the
quantitative details of the analysis with wave functions
of the highest available accuracy.
In the present work we have sought to carry out such
a refinement, using the carefully optimized [4,3,1/2,1]
contracted Gaussian SCF wave function of Popkie,
Kistenmacher, and Clementi (PKC), who used it to con-
struct an analytical Hartree-Fock pair potential for the
water dimer. 14,19 Included in the 58 baSis AOs are po-
larization functions on both oxygen and hydrogen. This
basis gives monomer energies that are only about 0.013
a. u. above the Hartree-Fock limit19 (see Table I for
energies).
Since classical bond orbital pictures are closely tied
to minimal basis concepts, the extended PKC basis
presents a Significant challenge to a general NBO an-
alysis. We sought to determine whether the NBO re-
sults were stable with respect to basis set enlargement
far beyond the minimal baSis level (particularly, in-
clUSion of polarization functions), and whether the ac-
curate PKC results were in the line with previous re-
sults17 for small basis sets (with significant superposi-
tion error) and less realistic geometries. A second
objecti ve was to obtain an accurate numerical estimate
of the charge-transfer contribUtion to a realistic H bond.
In the course of this study we also studied the effect of
certain refinements in the NBO procedure, which might
be of importance at the more refined level. 18
Section II outlines the theoretical method of analysis
adopted in the present work. Section TIl presents the
results for the near-Hartree-Fock PKC water dlmer,
and compares them with previous results for smaller
basis sets and less realistic geometries. Section IV
summarizes our general concluslons concerning the
role of charge transfer interactions in the water dimer

4066 J. Chern. Phys. 78(6), Part 11,15 March 1983 0021-9606/83/064066·08$2.10 © 1983 American Institute of Physics

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 A. E. Reed and F. Weinhold: Orbital analysis of near-Hartree-Fock water dimer 4067

TABLE I. Variation of the OH bond (in terms of its constituent 0 and H hybrids) with basis set, using the WSW NBO procedure.

Oxygen hybrid Hydrogen hybrid

Energy Polariz. Coeff.
Calculation Functs, (a, u.) %s %p %d %s %p on oxygen
Contracted Guassian sets, SCF:
DHP minimala 7 -75.506 23.00 77.00 100.00 0.8163
Dunning double zetab 14 -76.009 23.94 76.06 100.00 0.8583
Dunning double zeta + polarizationc 26 -76.047 24.53 75.27 0.20 99.41 0.59 0.8612
PKC [4s3pld/2s1pJd 29 -76.055 24.71 75.09 0.20 99.60 0.40 0.8627
PKC [4s3p2d/2s2pjd 41 -76.060 24.79 74.90 0.31 99.67 0.33 0.8629
Slater type orbital set:
(5s4p2d/3s1p), SCl'" 39 -76.064 24.06 75.37 0.57 99.56 0.44 0.8589
(5s4p2d/3s1p), SD-CI" 39 -76.340 23.35 76.20 0.45 99.61 0.39 0.8586
Estimated Hartree-Fock limit;<! - 76. 0675 ± 0.0010
Estimated nonrelativistic limit" -76.4376 ± 0.0024

aReference 24.
"s. Huzinaga, J. Chem. Phys. 42, 1293 (1965); T. H. Dunning, ibid. 55, 717 (1971).
cBasis set of footnote b, augmented by polarization functions of Y. Yamaguchi and H. F. Schaefer, J. Chem. Phys. 73, 2310
(1980).
dReferences 14 and 19.
"References 22 and 23.

and the relationship to the general theory of hydrogen procedure then consists of (i) symmetric orthogonaliza-
bonding and Klemperer's picture of vdW molecule for- tion of the "occupied" AOs on each center among them-
mation. selves; (ii) Schmidt orthogonalization of residual Ryd-
berg AOs on each center to each member of the occupied
set; (iii) symmetric orthogonalization of the Rydberg
II. METHOD
AOs among themselves. In the LSL procedure the sym-
The procedure for transforming the SCF-MO wave metriC orthogonalization of steps (i) and (iii) is the con-
function from LCAO to LCBO form was generally simi- ventional Lowdin type which minimizes
lar to that described previously. 18.17 The first step is
DCC
to transform from the arbitrary input AO basis to the
orthonormal set of natural atomic orbitals (NAOs), L: II CPt - cp,112 .
I
(2.1)
having optimal occupancy for the molecule of interest.
The NAOs di vide naturally into a set of core plus valence In the modified procedure, a corresponding occupancy
orbitals having high occupancy (the "natural minimal weighted symmetric orthogonalization is employed,
which minimizes 18 •20 '
basis" NMB functions) and a residual set of small or
zero occupancy (the "natural Rydberg basis" functions), DCC
spanning the remainder of the input AO Hilbert space.
The second step is to form an optimal orthonormal set
L Will cpr - cp,112 ,
I
(2.2)

of directed hybrids and polarization coefficients from
these NAOs, leading to the final set of natural bond
orbitals (NBOs). These NBOs have maximal occupancy
properties analogous to the usual natural orbitals (NOs),
but are localized on one or two atomic centers ("lone
pairs" and "bonds, " respectively) rather than de localized
over the entire molecule.
where WI =(CP,I i'w ICPI) is the occupancy of CPl' The
latter procedure, which we shall refer to as the "WSW
method, " reduces the dependence on a preconceived
number of occupied AOs to be included in the valence
shell of each atom, and seems to be preferable in the
treatment of ionic compounds.

In the present work we conSidered refinements in both
of these steps, which will be outlined before the sub-
sequent NBO analysis is described.
A. NAO transformation
The three-step Lowdin-Schmidt-Lowdin (LSL) pro-
cedure adopted previously was modified by the inclusion
of an occupancy weighting criterion. In each case the
one- center blocks of the denSity matrix t w are first
diagonalized to obtain a new set of AOs {CPI} ordered by
occupancy. The three-step LSL orthonormalization
The WSW criterion (2.2) tends to more strongly
preserve the shape of valence orbitals of atoms with
nearly filled valence shells, whereas the LSL criterion
(2.1) treats nearly filled and nearly empty valence shells
on an equal footing. As a consequence, the apparent
charge transfer from a more electronegative to a less
electronegative atom will tend to be somewhat reduced
by the WSW criterion. We have tabulated both LSL and
WSW results below to facilitate comparisons with the
earlier results, and to indicate by the differences the
inherent imprecision of some of the quantities calcu-
lated.

J. Chem. Phys., Vol. 78, Part II, No.6, 15 March 1983

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 4068 A. E. Reed and F. Weinhold: Orbital analysis of near·Hartree-Fock water dimer
B. NBO transformation
The NBO transformation for the water dimer can also
be carried out in two distinct ways. The earlier method
was to apply the method to the dimer without restriction,
optimizing the form of each BO with respect to the elec-
tron distribution of the dimer. The alternative is to
form dimer BOs using the fixed NBO transformation
for the isolated water monomer. In the latter approach
only the orthonormalized NAOs are recalculated at each
distance and orientation, whereas the BO polarization
and hybridization coefficients are held fixed at the
monomer values. Bond orbitals formed in this manner
will be called "fixed monomer NBOs" to distinguish them
from the ordinary "dimer NBOs" employed in previous
work. The difference between these two treatments will
give a measure of the internal rearrangements or po-
larization changes within each monomer as the dimer
forms. Both fixed monomer and dimer results will be
tabulated below to indicate the numerical magnitude of
these differences.
C. Energy analysis
When the overall transformation from input AOs to
final NBOs has been obtained, the SCF-MO wave func-
tion can be tranSformed from LCAO to LCBO form.
The energy can be decomposed into its contributions
from the occupied BOs (core pairs, lone pairs, and
bond pairs, collectively labeled (7) and unoccupied BOs
(antibonds and Rydberg orbitals, collectively labeled
(7*) by deleting various basis functions from the SCF
variational space. For example, the effect of the ac-
ceptor antibond (7~lH4 along the H-bond axis (see Fig. 1)
can be determined by deleting the corresponding row
and column from the BO Fock matrix, and recalculating
the SCF energy in the absence of this function. 21 By
deleting various antibonds or Rydberg orbitals of donor
or acceptor monomers, a rather detailed picture can
be built up of the contribution E",,* of unoccupied BOs
to the SCF energy. Correspondingly, the term E"" re-
maining when all such unoccupied BOs are deleted may
be associated with the energy of perfect Lewis structures,
with all electrons paired up in doubly occupied bond
orbitals. The latter term includes all the dominant
effects of the Pauli exclusion principle (steric repulsion
between doubly occupied orbitals), the electrostatic in-
teractions between the permanent dipole moments of the
H6
/ H
~~ 5
OI--H4"----- 0 2 ~~e '
/ .. R •
H3
FIG. 1. Geometry and atom labels for water dimer calculations. als. Thus, in the [4, ::I, 1/2, 1] baSiS, 0.0019 electrons
The dimer is chosen to have a linear hydrogen bond ( 0t-H4-
O2=0'') and a plane of symmetry through the electron acceptor
(H30 t H4) monomer. e is the tilt angle between the plane of the occupancy.
electron donor (H502~) monomer and the H-bond axis. Through-
out the calculation the monomer geometry is held fixed with
ROH = 0.957 A and HOH = 105
0
•
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bonds, etc. The term E aa *, on the other hand, repre-
sents the much smaller effects of donor-acceptor (or
charge transfer) de localization away from a perfectly
localized LewiS structure. When the total SCF energy
is expressed as a sum of these two types of contribu-
tions
(2.3)
the donor-acceptor term E",,* is apparently only a negli-
gibly small perturbation (- 0.013%) on the dominant
E"" term for both the monomer and dimer. However,
when the contributions to the interaction energy tl.E are
taken into account
tl.E =Edlmer - 2Emonomer =tl.Eaa + tl.Eaa * ,
the donor-acceptor interactions tl.E"rs* are by no means
negligible. Our present objective is to obtain estimates
of these terms for an SCF wave function comparable to
the best available for the water dimer.
III. RESULTS
A. H2 0 monomer
The data in Table I summarize the features of the OH
bond in various basis sets, using the WSW-NBO proce-
dure on the H20 molecule. Throughout this paper the
geometry of the H20 monomer has been fixed with a
bond length of 0.957 A and a bond angle of 105 close 0
,
to the experimental geometry. The OH bond orbital is
the sum of an oxygen hybrid orbital and a hydrogen hy-
brid orbital, each multiplied by a polarization coeffi-
cient. The NBO OH bond depends somewhat on the basis
set, but its features seem to approach a well-defined
limit as the Hartree-Fock limit is approached. Although
most of the entries refer to SCF wave functions in con-
tracted GaUSSian basis sets, we also carried out the
NBO analYSis for the Rosenberg-Shavitt22 SCF and CI
wave functions constructed from a large basis (39 func-
tions) of Slater type orbitals (STO). Table I shows that
the STO baSis functions lead to NBOs that are rather
similar to contracted Gaussian results of comparable
accuracy. The only significant effect of Cion the form
of the OH bond orbital is to reduce the s character of
the oxygen hybrid by about O. 7%. As can be seen, po-
larization functions enter as small, but rather well de-
fined corrections to the natural hybrids. Both oxygen
and hydrogen hybrids derive contributions of a few
tenths of a percent from their polarization functions.
Table II lists the other NBOs of nonzero occupancy
in the PKC [4, 3, 1/2, 1] basis. The "in-plane" orbitals
are directed in the plane of the nuclei while the "out-of-
plane" orbitals have a node in this plane. As the basis
set on hydrogen is enlarged, some of the charge in the
nearly doubly occupied orbitals (especially, the out-of-
plane oxygen lone pair) delocalizes into hydrogen orbit-
are in the Rydberg NBOs on each hydrogen. However,
in tbe monomer the oxygen Rydberg NBOs have zero
When the LSL orthogonalization procedure is used
instead of the WSW (see Sec. II A), the following changes
J. Chem. Phys., Vol. 78, Part II, No.6, 15 March 1983
 A. E. Reed and F. Weinhold: Orbital analysis of near-Hartree-Fock water dimer 4069

TABLE n. One-center hybrid orbitals of H20, [431/21) basis, using the WSW NBO procedure.
All additional Rydberg orbitals had occupancy less than 0.0001.

center %5 %p %d Occupancy Description

0 99.76 0.24 0.00 1. 9999 core
0 50.80 49.16 0.04 1.9991 in-plane lone pair
0 0.00 99.94 0.06 1. 9981 out-of-plane lone pair
H 0.00 100.00 0.0010 out-of-plane Rydberg
H 2.37 97.63 0.0006 in-plane Rydberg
H 21.10 78.90 0.0003 in-plane Rydberg

are noted in the NBO analysis of the PKC monomer:
The oxygen hybrid s character increases from 24.71%
to 26.63% and the oxygen polarization coefficient de-
creases from 0.8627 to O. 8290. The latter change re-
flects the greater relative weight given to the H atom
orbital in the LSL procedure.
B. Water dimer
Two basis sets were used for the water dimer: a
minimal set by Dltchfield, Hehre, and Pople2~ (DHP),
and the extended PKC [4,3,1/2,1] set already mentioned.
The dimer geometry and numbering are given in Fig, 1.
Calculations were done at R = 2.85 A and R = 3. 00 A with
the tilt angle (J =0°. The optimal value of (J with the
PKC basis is in the range between 30° and 45°, but the
energy decrease with respect to 6 =0 is only 0.24
formation is a charge transfer from the in-plane lone
pair on O2 to the 0lH4 antibond. At the minimal basis
level, the picture of hydrogen bond formation involves
only this one charge transfer. However in the PKC
[4, 3, 1/2, 1] basis there are available, in addition to
the anti bonds, 44 Rydberg orbitals which can participate
in charge transfer. The Rydberg orbitals on 010 H4, and
O2 increase in occupancy by about O. 0004, 0.0007, and
0.0010, respectively. The Rydberg occupancies on the
remaining hydrogen atoms show no increase. At the
extended SCF level, the picture of charge transfer during
H-bond formation is therefore not as Simple, but it is
still dominated by the 02 in-plane lone pair to 0lH. anti-
bond charge transfer.
Table IV shows the water dimer energy and charge
transfer analYSiS, done by the four variants of the NBO
0

procedure mentioned in Sec. II. The total charge trans-

kcal/mol, 14 and previous studies using the DHP basis
fer (i. e., the division of the electrons between the two
have shown that the features of the hydrogen bond are
monomers) is determined by the atomic orbital ortho-
relatively insensitive to 6. 17
gonalization procedure used. The charge transfer that
The occupancies of the water dimer NBOs, calculated occurs is from 02 toward H4 • Since the LSL procedure
by the "fixed WSW" procedure, are shown in Table m.
As can be seen, the most significant change upon dimer
°
treats and H valence shells with equal weighting, even
though the H valence shell has lower fractional occupan-

TABLE m. Occupancies of the H20 dimer NBOs constructed from the fixed monomer NBOs using the WSW
procedure, at different values of R, the 0 1-02 distance, with 8 = O. See Fig. 1 for geometry and numbering.

DHP minimal basis PKC [431/21) basis

NBO orbital R=co R =3.00 A R=2.85 A R=co R=3.00A R =2.85 A
01-H3 bond 1.9995 1.9996 1.9996 1.9995 1. 9994 1.9994
01-H4 bond 1.9995 1.9985 1.9979 1.9995 1.9984 1.9980
02-H5 bond 1.9995 1.9988 1.9986 1.9995 1. 9987 1.9986
02-HS bond 1. 9995 1. 9988 1.9986 1.9995 1.9987 1.9986
01 core 2.0000 2.0000 2.0000 1.9999 1.9999 1.9999
O 2 core 2.0000 2.0000 2.0000 1. 9999 1. 9999 1. 9999
0 1 LP (in-plane) 2.0000 1. 9997 1.9996 1.9991 1. 9987 1.9986
O 2 LP (in-plane) 2.0000 1.9871 1. 9796 1. 9991 1.9921 1.9881
01 LP (out-of-plane) 2.0000 2.0000 2.0000 1.9981 1.9979 1.9978
O2 LP (out-of-plane) 2.0000 2.0000 2.0000 1.9981 1. 9983 1.9982
14 0 1 Rydbergs (total) 0.0000 0.0004 0.0004
14 O 2 Rydbergs (total) 0.0000 0.0009 0.0011
4 H3 Rydbergs (total) 0_0019 0.0019 0.0019
4 H. Rydbergs (total) 0.0019 0.0026 0.0027
4 H5 Rydbergs (total) 0.0019 0.0018 0.0017
4 Hs Rydbergs (total) 0.0019 0.0018 0.0017
01-H3 antibond 0.0005 0.0008 0.0009 0.0001 0.0003 0.0003
01-H4 anti bond 0.0005 0.0151 0.0234 0.0001 0.0075 0.0120
02-HS anti bond 0.0005 0.0008 0.0009 0.0001 0.0004 0.0006
02-H6 antibond 0.0005 0.0008 0.0009 0.0001 0.0004 0.0006

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 4070 A. E. Reed and F. Weinhold: Orbital analysis of near-Hartree-Fock water dimer

TABLE IV. Analysis of the H20 dimer interaction [cf. text allows a more complete description of the charge trans-
Eq. (2.3)J using the DHP minimal and PKC [431/21) basis sets fer because of the greater availability of unoccupied
at two different geometries (see Fig. 1), with four variants of
orbitals.
the NBO procedure. All energies are in kcal/mol. For R
=3.00, t:.E (DHP)=-5.705, t:.E(431/21) =-4.323. ForR=2.85, In the minimal baSis, about 98% of ~Ean is due to the
t:.E (DHP) = - 5. 987, t:.E (431/21) = - 4.007. O2 lone pair to 01H. anti bond interaction. As already
mentioned, the picture is more complicated at the ex-
Fixed
tended SCF level. In this case, when the OH anti bonds
LSL Fixed LSL WSW WSW
are removed from the baSiS, some of their occupancy
R=3.00'A can redistribute into the available Rydbergs, resulting
t:.E",,* in a slight energy stabilization that will diminish the
DHP -11.234 -11.535 - 9.251 -9.627
431/21 -10.804 - 9. 825 -7.945
apparent energy contribution of the antibonds. Simi-
-9.247
larly, if the OH antibonds are deleted from the basiS
t:.E w after all the Rydbergs have been deleted, their energy
DHP 5.529 5.830 3.546 3.922
contribution will be somewhat overestimated because
431/21 6.481 5.502 3.622 4.924
of the redistribution of part of the Rydberg occupancy
trbjH4 occupancy into the antibonds before they were deleted, ThUS, the
DHP 0.0169 0.0175 0.0144 0.0151 energy changes obtained when deleting various sets of
431/21 0.0114 0.0110 0.0076 0.0075 orbitals are not strictly additive. A rough estimate of
Charge transfer the contribution of each set of orbitals may be obtained
DHP 0.0165 0.0165 0.0137 0.0137 by interpolating between the two extreme deletion ener-
431/21 0.0101 0.0091 0.0077 0.0071 gies just mentioned, Thus, for R = 3. 00 A, with the
PKC [4, 3, 1/2, 1] baSiS, the charge delocalization ener-
R =2.85 'A
gy ~Eaa* of - 9. 25 kcal (fixed WSW method) is divided
t:.E w *
DHP -18.213 -18.634 -14.926 -15.451 as follows: - 6.00 kcal from OH anti bonds (about - 5.41
431/21 -17.368 -15.439 -12.693 -14.025 of this from the dominant 01H. antibond); - O. 89 kcal
from 0 1 Rydberg orbitalS of the acceptor monomer;
t:.E""
DHP 12.226 12.647 8.939 9.464 - 1. 34 kcal from O2 Rydberg orbitals of the donor mono-
431/21 13.361 11.432 8.686 10.018 mer; and - 1. 02 kcal from hydrogen Rydbergs (almost
entirely from H4).
*
trOjH4 occupancy
DHP 0.0265 0.0276 0.0223 0.0234 Two effects are included in AEaa *: intramolecular
431/21 0.0187 0.0174 0.0126 0.0120 charge transfer (repolarization within each monomer
Charge transfer accompanying dimer formation) and intermolecular
DHP 0.0259 0.0259 0.0213 0.0213 charge transfer. These effects can be separated by
431/21 0.0170 0.0147 0.0126 0.0110 zeroing specific blocks of the Fock matrix in the BO
basis, and reevaluating the total energy as described
in Section II C. The energy associated with charge trans-
fer from monomer A to monomer B, AEcT(A- B), is
cy, it will tend to give a somewhat larger estimate of found by zeroing the Fock matrix blocks connecting the
the charge transferred from O2 toward H4, We consider a orbitals of A (cores, lone pairs, bonds) with the u*
that the WSW procedure, which weights 0 and H orbitals orbitals of B (antibonds, Rydbergs). Similarly, AEcT(B
in proportion to their occupancy, should give an improved - A) is found by zeroing the as - aX blocks. The repo-
estimate of the charge transfer. As expected by this larization energy AERP is found by zeroing the u A - aX
argument, it can be seen in Table IV that the total charge and as - a~ blocks. The energies obtained in this way
transfer, the 01H4 antibond occupancy, and the delocali- are Slightly nonadditive (-104%), but can be used to
zation energy ~Eaa* are consistently larger for the LSL roughly decompose the total AEaa * as before. For R
than for the WSW procedures. Although the four esti- = 3. 00 A with the PKC baSiS, and using the fixed WSW
mates differ somewhat, they all point to a Significantly method, we estimate AEcT(donor- acceptor) = -7. 43
greater charge transfer contribution to H bonding than kcal, AEc T (acceptor - donor) = - O. 71 kcal, and AE BP
has been indicated by certain previous methods of an- =-1. 12 kcal. Thus, the total AEan = - 9.25 kcal, and
alysis (see Sec. IV). We conSider the fixed WSW re- approximately 88% of this can be called intermolecular
sults, which preserve the monomer orbitals as much as charge transfer energy.
possible during dimer formation, to provide the best (We did not attempt to further decompose the "bonds
estimates of the four sets. only" term AEaa , as in Ref. 17. Such a decomposition
The results from the DHP minimal basis and the PKC seems to depend much more strongly on the choice of
extended basis compare favorably. When one allows for basis. )
the fact that the total ~E in the DHP basis is larger than
in the PKC basis by 1. 38 kcal/mol at R = 3. 00 A and by
C. Comparison with previous NBO results
1. 98 kcal/mol at R =2.85 A, the values of ~Eaa * agree
within about 1 kcal/mol. The superposition error in the The previous ab initio NBO study of the H20 dimer 17
smaller basis is certainly much larger, resulting in a used idealized tetrahedral monomer geometry and tilt
larger apparent charge transfer. The large basis set angle. For the DHP baSiS, with R =2.85 A and e = 54. 73°,

J. Chern. Phys., Vol. 78, Part II, No.6, 15 March 1983

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 A. E. Reed and F. Weinhold: Orbital analysis of near-Hartree-Fock water dimer
AEfIfI * was found to be -19.69 kcal and the 01H4 anti bond
occupancy was O. 0303, using the LSL procedure. For
the PKC basis set at the same distance (but with (J =0°
and experimental monomer geometry) the comparable
LSL results are AEaa* =- 17.37 and 01H4 antibond oc-
cupancy =0. 0187. For completeness, we also recal-
culated these quantities for a DHP dimer with experi-
mental monomer geometries and (J =0° at R =2.85 A,
obtaining the results AEaa * = -18.21 kcal and 01H4 anti-
bond occupancy =O. 0265. Thus, the extended basis
PKC value for AEaa * is rather similar to that obtained
with much smaller basis set, if similar R values are
chosen. Table III also shows that the occupancy changes
in DHP and PKC calculations are quite parallel in their
dependence on distance.
IV. DISCUSSION
The present work supports the conclusions of an ear-
lier analysis, 17 which showed the crucial role of inter-
molecular charge transfer in determining the strength
and equilibrium length of the hydrogen bond in the water
dimer. Without the stabilization due to charge-transfer
delocalization into antibond and Rydberg orbitals (espe-
cially the 01H 4 anti bond), we estimate that the interac-
tion between two water molecules would be repulsive
by 3-5 kcal/mol at R = 3.00 A, a distance that is prob-
ably slightly greater than the equilibrium H-bond
length. 2s
Our analysis suggests that the principal contributions
to H-bond formation in the PKC water dimer are:
(i) Approximately 8.1 kcal/mol charge-transfer sta-
bilization, of which about 5.4 kcal is due to the n-()"~IH4
interaction, and the remainder principally to donation
into Rydberg orbitals of 0 1 and H4• A small portion
(0.7 kcal) can be associated with "back donation" from
the 0IH4 bond into Rydberg orbitals on O2 ,
(ii) Approximately 1. 1 kcal/mol stabilization associ-
ated with internal repolarization within each monomer
as the dimer forms.
(iii) A net repulsive bonds only term AEaa , represent-
ing the net effect of the (electrostatic plus sterlc) in-
teractions between fixed monomers constrained to have
doubly occupied bond orbitals, characteristic of the
isolated monomers, at all separations.
We have verified that these estimates are reasonably
insensitive to the details of forming the bond orbitals,
including a more refined orthogonalization procedure
which further incorporates the occupancy weighting that
underlies the entire NRO approach. The PKC estimates
are generally in line with values derived (at the same
R value) from smaller basis sets and less realistic geom-
etry for the water dimer. However, for the shorter
H- bond lengths characteristic of liquid and ice condensed
phases, 25 it should be expected that the magnitudes of
the charge transfer stabilization and steric repulsion
are both appreciably greater, since both depend expo-
nentially on distance R. Of course, the cooperativity
of H bonding, and associated strengthening of the charge
transfer interaction, is itself a natural consequence of
J. Chem. Phys., Vol. 78, Part II, No.6, 15 March 1983
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4071
the charge transfer process, since the occupancy gained
by the "acceptor" monomer of a dimer in turn makes
this monomer more suitable as a "donor" for trimer
formation, and so on.
However, the present results are in disagreement
with some previous hydrogen bond analyses based on the
method of Kltaura and Morokuma (KM).28 USing a 4-31G
basis set with (J =60°, KM obtain charge transfer ener-
gies of - 2.11 and - 2. 78 kcal/mol at R = 2.98 and 2.78
A, respectively.
The origin of this discrepancy lies in the treatment
of the intermolecular overlap. In order to define charge
transfer, one first partitions the total AO space into the
orthogonal subspaces associated with each species, so
that electron occupancy can be divided between them.
In the NBO procedure this is done explicitly by the LSL
or WSW 27 orthogonalization, incorporating all the oc-
cupied NAOs (the natural minimal baSiS, NMB, of each
atom) in the dimer. Any remaining orbitals are Schmidt
orthogonalized to the NMB set. When the orthonormal
NAOs are transformed to orthonormal NBOs, the space
spanned by the nearly doubly occupied core, lone pair,
and bond (in-phase) orbitals, plus the corresponding
out-oj-phase antibonding oratals, is very nearly the
space that is spanned by the NMB, the core plus valence
shell space of the constituent atoms. ThUS, the NMB
is mapped into cores, lone pairs, bonds, and anti bonds .
Note that the antibonds are not Schmidt orthogonalized
to orbitals of the other monomer, but are treated sym-
metrically with the other BOs arising out of the valence
shells of constituent atoms.
By contrast, the partitioning of the AO space in the
KM decomposition is carried out implicitly, based on
anti symmetrization of the product of nonorthogonal oc-
cupied MOs. In effect, the virtual MO space of each
monomer is Schmidt orthogonalized to the occupied MO
space of the other monomer. Since ~he anti bonds have
low occupancy, they will be almost entirely contained
in the virtual monomer MO space. Consider the over-
lap between the in-plane lone pair on O2 (which is almost
entirely in the occupied MO space of the donor monomer
because of its near double occupancy) and the 0IH4 anti-
bond. After the implicit Schmidt orthogonalizatlon, al-
most all of the overlap has been awarded to the O2 lone
pair, so that it Significantly penetrates the region around
the acceptor monomer. A large fraction of the elec-
troniC charge which originally overlaps the antibond of
the acceptor is prevented from belng transferred into
this anti bond because the antibond is being effectively
Schmidt orthogonalized to the occupied donor orbitals.
Thus, it is no surprise that the KM decompostition con-
sistently leads to a much smaller estimate of charge
transfer. In effect, the KM procedure employs symmet-
ric orthogonalizatlon for only a portion of the atomic
NMB space (i, e., 10 of the 14 dimenSions for the water
dimer), whereas the remaining portions of the NMB
space are subjected to Schmidt orthogonalization. 28
This leads to a major difference in the estimate of the
charge transferred between these subspaces in hydrogen
bonding.
Our results lend support to the general notion devel-
 4072 A. E. Reed and F. Weinhold: Orbital analysis of near-Hartree-Fock water dimer
oped by Klemperer and co-workers 5 of the important
role of charge transfer orbital interactions in the sta-
bility and structure of vdW molecules. In the present
work we have shown that small amounts of charge trans-
fer (0.01 electrons or less) into anti bonding orbitals
can result in quite appreciable stabilization of a hydro-
gen-bonded complex. This has obvious relevance to the
bonding in many vdW molecules. Charge transfer ef-
fects, even if not significantly stronger than dispersion
interactions, may exert a considerable influence on
equilibrium vdW geometries, since they will often be
more directionally dependent.
Klemperer and co-workers 5 have pOinted out that
dispersion interactions would lead to the expectation
that a rare gas atom should generally bind to a linear
molecule in a collinear fashion, since the parallel po-
larizability of a linear molecule is greater than its per-
pendicular polarizability. However, the geometry of
Ar' .• OCS is T shaped, leading these workers to sug-
gest that the weak bond is a donor-acceptor or general-
ized Lewis acid-Lewis base interaction. They proposed
that Ar ... OCS is a 7T* acceptor complex, whereas the
linear structures Ar··· HCI, Ar··· HF, Ar'" CIF, and
Kr ... CIF are (1* acceptor complexes. In each case the
inert gas acts as a weak Lewis base. As in the H-bonded
water dimer, the internuclear distances in these four
linear (1* systems are all Significantly shorter (by 0.4-
0.5 A.) than would be predicted from van der Waals radii.
Our results lend strong support to the claSSification of
H20' .. H20 as a (1* complex.
Flygare and co-workers 6 carried out a detailed study
of Xe' .• HCI based on the 131Xe nuclear quadrupole cou-
pling constant, and found that most or all of the nonzero
electric field gradient at the 131Xe nucleus could be ac-
counted for by the Sternheimer shielding effect. Their
analysis leads to an estimate of the charge transfer from
Xe to HCI of 0.0004 electrons or less. Thus, charge
transfer, if present, is probably very small in this com-
plex.
However, charge transfer almost certainly plays an
important role in the hydrogen bonded complexes of
HCN, CO, C2H2, C 2H4 and C3H6 with various hydrogen
halides that have been studied by Flygare and co-
workers. 9 Indeed, by measuring 14N nuclear quadrupole
coupling constants these workers found evidence for
very Significant intramolecular charge transfer of 0.02
electrons in NCCN' .. HF and 0.03 electrons in N2 ..• HF
from the outer nitrogen to the inner (hydrogen bonded)
nitrogen. 7,8
Other experimentalists have pOinted out the inadequacy
of simple electrostatic models and/or the apparent im-
portance of charge transfer in hydrogen bonding. Mail-
lard et al. 29 found it necessary to introduce a" charge
transfer parameter" T C T to account for IR vibrational
intensity changes in H- bonded complexes, and Allavena
et al. 30 have recently given independent theoretical evi-
dence for this parameter. Viswanathan and Dyke 31 have
recently analyzed the structure of the H-bonded com-
plex H2S· .. HF, and concluded that "the structure of
H2S' HF cannot be explained by simple electrostatic
J. Chem. Phys., Vol. 78, Part II, No.6, 15 March 1983
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models." The earlier conclusions of Pimentel and Mc-
Clellan32 also should be cited in this regard.
Our results suggest that the analysis of accurate ab
initio wave functions can be essentially reconciled with
such concluSions, and indeed, that the language of
intermolecular n-(1* interactions aptly describes the
principal contribution to H-bond stability. It is hoped
that the reconciliation of the results of accurate ab
initio calculations with a simple, intuitive model of H-
bond formation may further stimulate the fruitful inter-
play between theoretical and experimental studies of
weak intermolecular interactions.
ACKNOWLEDGM ENTS
We thank Professor Dan Chipman for providing STO
denSity matrices for the Rosenberg-Shavitt wave func-
tions. The support of NSF Grant CHE80-23004 is grate-
fully acknowledged.
IT. R. Dyke, B. J. Howard, and W. Klemperer, J. Chem.
Phys. 56, 2242 (1972); E. W. Kaiser, ibid. 53, 1686 (1970).
2T • J. Balle and W. H. Flygare, Rev. Sci. Instrum. 52, 33
(1981); E. J. Campbell, L. W. Buxton, T. J. Balle, and W.
H. Flygare, J. Chem. Phys. 74, 813 (1981)_
3G. E_ Ewing, Can. J. Phys. 54, 487 (1976).
4T • A. Dixon, C. H. Joyner, F. A. Baiocchi, andW. Klem-
perer, J. Chem. Phys. 74, 6539 (1981), and references
therein: C. H. Joyner, T. A. Dixon, F. A. Baiocchi, and W.
Klemperer, ibid. 75, 5285 (1981).
5S• J. Harris, K. C. Janda, S. E. NOVick, and W. Klemperer,
J. Chem. Phys. 63, 881 (1975).
6M. R. Keenan, L. W. Buxton, E. J. Campbell, T. J. Balle,
and W. H. Flygare, J. Chem. Phys. 73, 3523 (1980).
lA. C. Legon, P. D. Soper, and W. H. Flygare, J. Chem.
Phys. 74, 4936 (1981).
8p • D. Soper, A. C. Legon, W. G. Read, and W. H. Flygare,
J. Chem. Phys. 76, 292 (1982).
9J. A. Shea and W. H. Flygare, J. Chem. Phys. 76, 4857
(1982) •
lOB. L. Blaney and G. E. Ewing, Annu. Rev. Phys. Chem. 27,
553 (1976),
l1 H• Lischka, Chem. Phys. Lett. 66, 108 (1979).
12G• H. F. Diercksen, W. P. Kramer, and B. O. Roos, Theor.
Chim. Acta (Berlin) 36, 249 (1975), and references therein.
13p. A. Kollman, in Applicatians of Electronic Structure Theory
edited by H. F. Schaefer (Plenum, New York, 1977), p. 109.
14H• Popkie, H. Kistenmacher, and E. Clementi, J. Chem.
Phys. 59, 1325 (1973).
15T. R. Dyke and J. S. Muenter, J. Chem. Phys. 60, 2929
(1974).
16J. P. Foster and F. Weinhold, J. Am. Chem. Soc. 102, 7211
(1980): A. B. Rives and F. Weinhold, Int. J. Quantum Chem.
Symp. 14, 201 (1980).
17R • B. Weinstock, Ph. D. thesis, University Wisconsin-
Madison, University 1981: R. B. Weinstock and F. Weinhold,
University of Wisconsin Theoretical Chemistry Institute
Report WIS-TCI-661, 1981 (submitted).
18R• B. Weinstock, A. E. Reed, and F. Weinhold (in prepara-
tion).
19 E • Clementi and H. Popkie, J. Chem. Phys. 57, 1077 (1972).
20B. C. Carlson and J. M. Keller, Phys. Rev. 105, 102 (1957),
21The truncated Fock matrix is diagonalized to form a new den-
sity matrix, and this is used to evaluate the SCF energy in
a single cycle. This method is not strictly self-consistent.
However, if a complete SCF calculation is done in the trun-
 A. E. Reed and F. Weinhold: Orbital analysis of near-Hartree-Fock water dimer 4073

cated BO basis after a full integral transformation, it has
been previously shown (Ref. 17) that the deletion energies
change by less than 0.1 kcal in the water dimer.
22 B • J. Rosenberg and I. Shavitt, J. Chem. Phys. 63, 2162
(1975).
23B. J. Rosenberg and I. Shavitt, O.S. U. -T .C.G. Technical
Report No. 103, The Ohio state University, 1975. The SCF
MOs, overlap matrix, and CI density matrices were kindly
supplied to us on cards by Professor D. M. Chipman, Univer-
sity of Notre Dame.
24R • Dftchfield, W. J. Hehre, and J. A. Pople, J. Chem.
Phys. 52, 5001 (1970).
25The crystal distance between oxygen atoms in hexagonal ice
is known to be 2.75 A [W. C. Hamilton and J. A. Ibers, Hy-
drogen Banding in Solids (Benjamin, New York, 1968)).
Microwave spectra give an equilibrium geometry of the water
dimer in the gas phase with R = 2.98 ± 0.04 A and 8 =60 ± 10"
(Ref. 15). Diercksen et al. (Ref. 12) have carried out an ex-
tensive SCF-CI theoretical study of the water dimer geometry.
With a [5,4,1/3,1) basis, their SCF and CI (single + double ex-
citations, frozen core) monomer energies were -76.0520 and
-76.2665 a. u. ,respectively. For the optimum SCF dimer
geometry, R = 2. 994 A, 8 = 41. ff, M = - 5. 14 kcal/mol. With
CI, R =2. 924 A, 8 =42.4, M =-6.05 kcal/mol.
26K. Kitaura and K. Morokuma, Int. J. Quantum Chem. 10,
325 (19761; see also H. Umeyama and K. Morokuma, J. Am.
Chem. Soc. 99, 1316 (1977) for an extensive study of hydro-
gen bonding.
27For purposes of comparison with the KM procedure, the LSL
or WSW orthogonalizations are practically equivalent.
28It follows by the general Carlson-Keller theorem (Ref. 20)
that the KM atomic subs paces must have less resemblance
(in the least-squares sense) to the original nonorthogonal
atomic subs paces than do the symmetrically orthogonalized
ones we have employed. This theorem provides the basic
justification for the partitioning we have adopted. Some num-
erical illustrations of the consequences of the KM unsym-
metrical treatment are given in Appendix A of Ref. 17.
29D. Maillard, A. Schriver, J. P. Perchard, and C. Girardet,
J. Chem. Phys. 71, 517 (1979).
30M. Allavena, B. Silvi, and J. Cipriani, J. Chem. Phys. 76,
4573 (1982).
31 R • Viswanathan and T. R. Dyke, J. Chem. Phys. 77, 1166
(1982).
32G • C. Pimentel and A. L. McClellan, The Hydrogen Band
(Freeman, San Francisco, 1960), see especially pp. 233 and
241.

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