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Natural Resonance Theory:


III. Chemical Applications

E. D. GLENDENING,* J. K. BADENHOOP,** and F. WEINHOLD


Theoretical Chemistry Institute and Department of Chemistry, University of Wisconsin, Madison,
Wisconsin 53706

Received 15 July 1997; accepted 1 November 1997

ABSTRACT: We describe quantitative numerical applications of the natural


resonance theory ŽNRT. to a variety of chemical bonding types, in order to
demonstrate the generality and practicality of the method for a wide range of
chemical systems. Illustrative applications are presented for 1. benzene and
polycyclic aromatics; 2. CO2 , formate, and related acyclic species; 3. ionic and
polar compounds; 4. coordinate covalent compounds and complexes; 5.
hypervalent and electron-deficient species; 6. noncovalent H-bonded complex;
and 7. a model Diels-Alder chemical reaction surface. The examples exhibit the
general harmony of NRT weightings with qualitative resonance-theoretic
concepts and illustrate how these concepts can be extended to many new types
of chemical phenomena at a quanitative ab initio level. Q 1998 John Wiley &
Sons, Inc. J Comput Chem 19: 628]646, 1998

Keywords: natural resonance theory; resonance theory; bonding; chemical

scribe quantitative ab initio NRT applications to a


Introduction variety of species in order to demonstrate the
generality and practicality of the NRT method for
a wide range of chemical systems and to test the

I n the two accompanying papers we presented


a ‘‘natural resonance theory’’ ŽNRT. algorithm
and the associated definitions of NRT bond order
consistency of NRT weightings with qualitative
Pauling-Wheland1, 2 resonance concepts.
Attempts to apply rigorously the Pauling-
and valency indices. In the present paper, we de- Wheland resonance theory were usually limited to
*Present address: Department of Chemistry, Indiana State the benzene molecule,3 the prototypical ‘‘reso-
University, Terre Haute, IN 47809 nance hybrid.’’ Even before the discovery of quan-
**Present address: Department of Math and Sciences, Po- tum theory, it was recognized that the unique
tomac State College of West Virginia, Keyser, WV 26726
properties of benzene Žespecially its high symme-
Correspondence to: F. Weinhold
See the Editor’s Note for the first paper in this series, p. 593, try and stability. are associated with delocalization
this issue. of electron-pair bonds from either of the two

Journal of Computational Chemistry, Vol. 19, No. 6, 628]646 (1998)


Q 1998 John Wiley & Sons, Inc. CCC 0192-8651 / 98 / 060628-19
NATURAL RESONANCE THEORY: III

´. formulas,
equivalent Lewis ŽKekule mized geometry, to demonstrate that the analysis
is independent of valence bond ŽVB.-type wave
functions.
. Ž 1.1.

6
6
The plan of the paper is as follows. The next
section describes classical cases of resonance in
cyclic aromatic benzenoid systems Žbenzene, naph-
The strongest Ž‘‘aromatic’’. forms of electronic thalene, anthracene, phenanthrene. and deriva-
delocalization are sometimes assumed to be re- tives Žtoluene, xylenes, benzyl cation.. We then
stricted to cyclic geometry and symmetry-equiv- describe CO2 , formate, and related strongly delo-
alent resonance structures, as in Ž1.1., but Žas rec- calized acyclic species ŽOCNH, HNCNH, allene,
ognized by Pauling and others 4 . similar strong formamide, HNO 2 , HONO.. Next we describe
resonance delocalization can occur in species that ionic bonding and ‘‘ionic-covalent resonance’’ in
are acyclic Že.g., CO2 , formate ion. or have unique the series X—F, X—CH 3 ŽX s Li, CH 3 , NH 2 , OH,
leading resonance structures Že.g., amide group, F., examining the transition between covalent and
naphthalene.. Moreover, the well-known instabil- ionic bonding limits. After this we describe coordi-
ity of cyclobutadiene w despite the superficial nate covalent bonding, including Lewis acid-base
‘‘analogy’’ to Ž1.1.x complexation ŽBF3 —NH 3 . and transition metal co-
ordination ŽNi—CO.. Later we describe ‘‘octet-
H H H H violating’’ examples of hypervalency ŽPCl 5 , SF6 ,
C C C C Ž 1.2. SF4 . and electron-deficient hypovalency ŽB 2 H 6 ,
6
6

BF3 , F2 CO, F2 N2 .. Following this discussion, the


C C C C next section describes noncovalent bonding, partic-
H H H H ularly H-bonded complexes Žwater dimer, cyclic
formamide dimer, FHFy, malonaldehyde., fol-
demonstrates that cyclic, symmetry-equivalent lowed by NRT analysis of the potential energy
structures can oppose Žrather than promote. reso- surface for a model Diels-Alder chemical reaction
nance stabilization. Thus, a comprehensive theory surface, including the ‘‘activated complex’’ transi-
of quantum-mechanical resonance should describe tion state. The final section presents a brief sum-
a wide range of electronic delocalization effects in mary and conclusions.
benzenoid and nonbenzenoid systems, with cyclic
or acyclic geometry and equivalent or inequivalent
resonance structures. Cyclic Aromatic Systems
Several examples of NRT applications to weakly
delocalized species Žwell represented by a conven- BENZENE AND BENZENE DERIVATIVES
tional Lewis structural formula. were presented in
A unique feature of benzenoid systems is the
the preceding two papers. In the present paper, we
cyclic pattern of conjugation allowing each local-
emphasize the applications to strongly delocalized
ized p bond to delocalize into two adjacent p *
or ‘‘anomalous’’ species whose properties cannot
antibonds in concerted counterrotating triple
be depicted by a conventional Lewis structural
cycles.
formula. Our goal is to present representative ex-
U
amples of NRT applications for a wide range of pAB ª p CD , p CD ª p UEF , p EF ª pAB
U
Ž 2.1a.
bonding types, rather than detailed discussion of
pAB ª p UEF , p EF ª p CD
U U
, p CD ª pAB Ž 2.1b.
individual species, providing a baseline for more
detailed future investigations. Furthermore, be- Such concerted donor-acceptor interactions are in-
cause the two preceding papers describe the nu- herently cooperative, so that each p ª p U interac-
merical stability and convergence of NRT analysis tion of benzene is strengthened relative to a corre-
with respect to improvements in theoretical level sponding interaction in, e.g., butadiene. In terms of
Žextensions of basis, inclusion of correlation effects, the resonance-theoretic mnemonic w cf. Ž4.3. in the
etc.., we shall not emphasize this aspect in the first paperx , the concerted sequence of 2-e delocal-
present work. Unless otherwise mentioned, all cal- izations Ž2.1a. or Ž2.1b. leads to the three-bond
culations were carried out with default NRT pro- shifts that convert one Kekule ´ structure to another.
gram options. We employ ab initio molecular or- The NRT program7 automatically searches for
bital ŽMO. wave functions at selected basis levels, 5 ´
Kekule-like NBO interaction patterns Ž2.1. when-
with either idealized Pople-Gordon6 or fully opti- ever strong delocalizations are encountered and

JOURNAL OF COMPUTATIONAL CHEMISTRY 629


GLENDENING ET AL.

adds the second Kekule ´ structure if necessary. showing the slight tendency to ‘‘fix’’ the Kekulé
Note that the cyclic conjugative patterns Ž2.1. can structure for which a double bond eclipses the
in principle occur even if the interacting bonds are in-plane methyl C—H bond.12 This leads to slightly
not linked by a sigma framework w as might occur, higher CC bond order for the 1,6 than for the 1,2
e.g., in the transition from localized ŽH 2 . 3 to delo- position Ž b 16 s 1.481, b 12 s 1.473., even in ideal-
calized ‘‘metallic’’ H 6 at high pressuresx ,8 so the ized PG geometry. When the ring geometry is
´
reference to a ‘‘Kekule-like’’ structure has only optimized, the bonds are found to be slightly dis-
topological significance. torted in the manner predicted by the bond indices
Table I shows the calculated ab initio NRT ˚ R12 s 1.3926 A
Ž R 16 s 1.3878 A, ˚ ..
weights for benzene ŽRHFr6-31G*rrPG level.. The Still more subtle bond-fixing ŽMills-Nixon13 .
NRT weights confirm the dominance of the lead- propensities can be seen in the dimethyl deriva-
ing Kekule ´ structures Ž1.1.. A slight admixture tives. For o-xylene, the calculated ŽRHFr6-31G*rr
Ž-0.01%. of dipolar ‘‘singly ionic’’ structures is PG. NRT weights of the two leading Kekule ´ struc-
associated with individual p i ª p jU interactions, tures for the preferred rotamer are
according to the standard resonance mnemonic.9
q q H H H H
i HH HH
q H H

-
C C

-
ª ª Ž 2.2a.
C C
y Ž 2.4.
j y y H H
In terms of Pauling-Wheland ‘‘covalent-ionic reso-
nance,’’ this structure could be formally associated a. w 41.7%x b. w 40.8%x
with a long-bonded ‘‘Dewar structure’’ form
q and similarly, for m-xylene,

Ž 2.2b. H H H H
6
6

H H
-

-
y C C
but this association is unjustified and misleading.
The weight of actual Dewar structures in the NRT H H Ž 2.5.
expansion is negligibly small, apparently owing to C C
a type of numerical ‘‘redundancy’’ in the NRT - -
functional Žsee Appendix.. Table I shows that the HH HH
two Kekule ´ structures Žeach 45.8%. essentially a. w 43.2%x b. w 41.0%x
dominate the NRT expansion, leading to CC bond
orders Ž bCC s 1.494. in excellent agreement with and, for p-xylene,
the value Ž1 12 . expected from conventional reso-
nance concepts.10 H H H H
H H
-

It is interesting to examine the subtle effects of C C


substituents that lift the equivalence of the two
leading Kekule ´ structures and could only be dis-
cerned with a quantitative form of resonance the- . Ž 2.6.
ory. From the RHFr6-31G*rrPG wave function
for toluene, for example, the NRT weights of the C C
two leading 11 resonance structures are found to be H - H H - H
Žnumbers in brackets denote reference structure. H H
a. w 43.5%x b. w 41.2%x
H H H H
H H
-

C C Note that, in all these cases, the energetically pre-


ferred rotamer Žas shown. allows the in-plane
Ž 2.3. C—H bond of each methyl group to eclipse a p
bond of the more highly weighted Kekule ´ struc-
ture. Table II compares the calculated NRT bond
a. w 43.8%x b. w 42.6%x orders Žfor idealized PG geometry. with fully

630 VOL. 19, NO. 6


NATURAL RESONANCE THEORY: III

TABLE I.
Summary of NRT Analysis for RHF / 6-31G* Benzene (Pople-Gordon Geometry), Showing Leading Resonance
Structure Weightings [ wa ; with Degeneracies (Deg.)], Bond Orders ( b C C , b CH ), and Atomic Valencies
( VC , VH ), with Covalent and Ionic (Electrovalent) Contributions.

Structure a Deg. wa (%) Structure a Deg. wa (%)

H Hy

H C H 2 45.80 H C H 12 0.08
C C C C
C C C C+
H C H H C H
H H

H+ H
H C H 12 0.10 H C+ Hy 12 0.08
C C C C
Cy C C C
H C H H C H
H H

H
H C H+ 12 0.10 (78 others) 4.08
Cy C
C C
H C H
H
NRT bond order NRT valency
(cov) (ion)
Atom X b XC b XC b XC VX V X(cov) V X(ion)

C 1.4941 1.4842 0.0072 3.9706 3.7293 0.2414


H 0.9878 0.7608 0.2270 0.9878 0.7608 0.2270

optimized R CC values for the xylenes and other nance structures are11
benzene derivatives, showing that the actual ring
distortions are consistent with the calculated varia- CH 2 q CH 2 CH 2
tions in NRT weightings. Figure 1 shows the q
graphical correlation of R CC Žoptimized. with bCC .
ŽPG. for all the neutral aromatic ring bonds Žin-
cluding those discussed in the following subsec- q
tion., demonstrating the accuracy with which sub- a. w 16.2%x Ž 2 . b. w 11.6%x c. w 11.5%x Ž 2 .
tle variations of ring geometry w on the order of Ž 2.7.
O Ž10y3 A
˚ .x are predicted by quantitative NRT bond
orders. The calculated NRT bond orders predict quinoid-
As a further test we examine the benzyl cation, like ring distortion with significant double bond
which is expected to exhibit much stronger depar- character in the exocyclic CC bond, consistent with
tures from idealized benzene geometry. At the experimental findings.15 Table II includes compar-
RHFr6-31G*rrPG level,14 the leading NRT reso- isons of these bond orders with the optimized

JOURNAL OF COMPUTATIONAL CHEMISTRY 631


GLENDENING ET AL.

TABLE II.
Comparison of Calculated RHF / 6-31G* // PG NRT Bond Orders ( b CC , b CH ) and Optimized RHF / 6-31G* Bond
˚ ) for Benzene Derivatives [see (2.3) – (2.7)]: Benzene; Toluene; Benzyl Cation; o-, m-,
Lengths ( RCC , RCH; in A
and p-Xylene a

Benzene Toluene Benzyl cationb


(PG) (opt) (PG) (opt) (PG) (opt)
a b b ab Rab b ab Rab b ab Rab

C1 C2 1.4941 1.3862 1.4648 1.3926 1.2243 1.4365


C2 C3 1.4941 1.3862 1.4938 1.3830 1.5075 1.3621
C3 C4 1.4941 1.3862 1.4807 1.3875 1.3715 1.4030
C4 C5 1.4941 1.3862 1.4913 1.3829 1.3715 1.4030
C5 C6 1.4941 1.3862 1.4773 1.3879 1.5075 1.3621
C6 C1 1.4941 1.3862 1.4810 1.3878 1.2243 1.4365
C1 Cx — — 1.0081 1.5115 1.4867 1.3577
C2 H 0.9878 1.0756 0.9872 1.0769 0.9874 1.0747
C3 H 0.9878 1.0756 0.9879 1.0758 0.9878 1.0727
C4 H 0.9878 1.0756 0.9877 1.0754 0.9880 1.0752
C5 H 0.9878 1.0756 0.9879 1.0758 0.9878 1.0727
C6 H 0.9878 1.0756 0.9872 1.0763 0.9874 1.0747
Cx Hi — — 0.9975 1.0838 0.9982 1.0751
Cx Ho — — 0.9904 1.0860 — —

o-Xylene m-Xylene p-Xylene


(PG) (opt) (PG) (opt) (PG) (opt)
a b b ab Rab b ab Rab b ab Rab

C1 C2 1.4542 1.4012 1.4596 1.3949 1.4597 1.3944


C2 C3 1.4727 1.3874 1.4867 1.3841 1.4937 1.3796
C3 C4 1.4778 1.3866 1.4625 1.3946 1.4597 1.3944
C4 C5 1.4935 1.3809 1.4979 1.3792 1.4878 1.3839
C5 C6 1.4778 1.3866 1.4754 1.3895 1.4700 1.3900
C6 C1 1.4727 1.3874 1.4881 1.3841 1.4878 1.3840
C1 Cx 1.0076 1.5118 1.0082 1.5115 1.0080 1.5112
C 2, 3, 4 Cy 1.0076 1.5118 1.0082 1.5114 1.0080 1.5112
C2 H — — 0.9867 1.0776 0.9874 1.0771
C3 H 0.9873 1.0763 — — 0.9874 1.0771
C4 H 0.9878 1.0756 0.9872 1.0767 — —
C5 H 0.9878 1.0756 0.9880 1.0759 0.9874 1.0765
C6 H 0.9873 1.0763 0.9872 1.0761 0.9874 1.0764
Cx Hi 0.9977 1.0835 0.9976 1.0838 0.9975 1.0839
Cx Ho 0.9903 1.0863 0.9903 1.0860 0.9904 1.0861
Cy Hi 0.9977 1.0835 0.9976 1.0838 0.9975 1.0839
Cy Ho 0.9903 1.0863 0.9904 1.0860 0.9904 1.0861
a
Carbon atoms are labelled as shown below.
x
1 (o)
6 2
5 3
4 (m)
(p)

Hi , H o , respectively, denote in-plane and out-of-plane H atoms (with Hi cis to C 6 ), and C y denotes the second methyl carbon (C o ,
Cm , or Cp ) in the xylenes.
b
PG geometry.

632 VOL. 19, NO. 6


NATURAL RESONANCE THEORY: III

resonance stabilization energy from 1 to 10 kcalr


mol. to suppress the many structures associated
with weak sigma delocalization.
For naphthalene, the leading NRT weightings
are found to be

a. w 29.8%x Ž 2 . b. w 27.0%x
q q . Ž 2.8.

y
y
c. 1.5% Ž 4 . d. 1.1% Ž 4 .

Note that the high weight of the nondegenerate


resonance structure Ž2.8b. implies a significantly
FIGURE 1. NRT bond order]bond length correlation higher degree of pi bond fixation in naphthalene
for neutral aromatic ring CC bonds of Table II, comparing
˚) to than in benzene. Table III compares the calculated
bond orders of idealized geometry (all RCC = 1.40 A
the fully optimized bond lengths: benzene (dot), toluene NRT bond orders Žfor the idealized PG geometry
(circles), o-xylene (crosses), m-xylene (squares), and with all CC bonds fixed at 1.40 A ˚ . to fully opti-
p-xylene (triangles). mized CC bond lengths, which are seen to exhibit
the expected pattern of distortions. Graphical rep-
resentations of these correlations are displayed in
Figure 2.
bond lengths,16 showing the correlation with the We also consider two fused three-ring C 14 H 10
actual distortions. isomers, anthracene and phenanthrene, at the
Whereas the p i ª p jU interactions of benzene RHFr3-21GrrPG level. For anthracene, the lead-
and other aromatics give rise to strong stabilizing ing NRT structures are found to be
delocalizations and alternative resonance struc-
tures, the corresponding delocalizations in cyclo-
butadiene Ž1.2. are wholly absent. This is due to
the fact that the near-rectangular geometry of a
hypothetical closed-shell cyclobutadiene molecule a. w 27.5%x Ž 2 . b. w 15.3%x Ž 2 .
necessarily puts the localized p and p * orbitals in q . Ž 2.9.
q
a nearly parallel arrangement, so that the nodal
plane of the antibonding p * leads to effective
y
cancellation of p i ] p jU overlap Žand Fock matrix y
element, etc... Hence, the alternative resonance c. 3.4% Ž 2 . d. 0.8% Ž 4 .
structure shown in Ž1.2. gains no weighting in the
NRT expansion, and the cyclobutadiene molecule Similarly, NRT analysis for phenanthrene gives
gains none of the conjugative delocalization that
usually stabilizes species with adjacent double
bonds.

POLYCYCLIC AROMATICS a. w 22.3%x Ž 2 . b. w 17.9%x


Ž 2.10.
We also briefly illustrate application of the NRT
method to polycyclic aromatic systems Žall calcu-
lated at the split valence RHFr3-21GrrPG level..
For these examples we set NRTTHR s 10 Ži.e.,
increase the threshold for estimated second-order c. w 10.6%x d. w 9.0%x

JOURNAL OF COMPUTATIONAL CHEMISTRY 633


GLENDENING ET AL.

TABLE III.
Comparison of Calculated RHF / 3-21G // PG NRT Bond Orders ( bij(PG) ) and Optimized RHF / 3-21G Bond
˚ ) for Ci —C j Bonds of Naphthalene, Anthracene, and Phenanthrene [See Eq. (2.8) ] (2.10)],
Lengths ( Rij(opt ), in A
with the Atom Numberings Shown Below.a
9 10
8 1 8 9 1
7 9 2 7 13 11 2 8 14 11 1
6 10 3 6 14 12 3 7 13 12 2
5 4 5 10 4
6 5 4 3
Naphthalene Anthracene Phenanthrene
i j b ij(PG) Rij(opt) b ij(PG) Rij(opt) b ij(PG) Rij(opt)

1 2 1.6441 1.3569 1.6996 1.3645 1.5892 1.3646


1 9 1.3218 1.4186 — — — —
2 3 1.3368 1.4143 1.2881 1.4301 1.3941 1.3998
9 10 1.3279 1.4086 — — 1.7479 1.3370
1 11 — — 1.2907 1.4343 1.3770 1.4063
9 11 — — 1.4620 1.3874 — —
11 12 — — 1.2354 1.4243 1.3811 1.4036
3 4 — — — — 1.5890 1.3667
4 12 — — — — 1.3929 1.4086
10 11 — — — — 1.2216 1.4389
12 13 — — — — 1.2036 1.4604
a
Note that the CC, CH bonds of polycyclic aromatics are all assumed equal to corresponding benzene values (1.40 A, ˚ 1.08 A
˚) in
(P G)
idealized PG geometry, so that the calculated b ab values reflect intrinsic electronic differences rather than variations in bond
lengths.

straints of ring geometry.. Figure 2 exhibits the


graphical bond order]bond length correlation for
the polycyclic aromatics over the full range of CC
variation from near-single to near-double bond
character. The NRT results appear to be in satisfac-
tory overall harmony with qualitative resonance-
theoretic concepts of organic chemistry,17 but the
NRT weightings bring out many subtleties of reso-
nance delocalization that would not be apparent in
the qualitative framework.

Carbon Dioxide, Formate Ion, and


Related Acyclic Species
CO 2 AND RELATED SPECIES
A particularly interesting type of acyclic strong
delocalization is exhibited by the carbon dioxide
FIGURE 2. Similar to Figure 1, for polycyclic aromatics molecule, which Pauling judged to have equal
of Table III: naphthalene (circles), anthracene (squares), resonance contributions from the double-bonded
and phenanthrene (triangles). and triple-bonded forms.18 In the nominal Lewis
¨ C O:
representation Ž :O ¨ ., there are strong n O
U
with lesser contributions from many ionic struc- ª p CO delocalizations in the orthogonal pi sys-
tures. Table III includes comparisons of Židealized tems of each of the two Ždegenerate. NBO Lewis
PG. NRT bond orders with optimized CC bond structures. In excellent accordance with Pauling’s
lengths for all these species, showing the overall description are comparable NRT contributions
pattern of agreement Ždespite the severe con- ŽRHFr6-31G*rrPG level. from double- and

634 VOL. 19, NO. 6


NATURAL RESONANCE THEORY: III

triple-bonded resonance structures,9 FORMATE ION AND RELATED SPECIES

y
It is also interesting to consider the general
O C O O C Oq . A B C ¨ ‘‘keto-enol’’ resonance motif,
Ž 3.1.
a. w 49.5%x b. w 25.0%x Ž 2 .
A B ¨
C ¨y
A B Cq Ž 3.4.

6
6
The resonance-weighted NRT bond orders Ž bCO s
2.000. essentially coincide with classical structural as exemplified by formate ion ŽHCOOy. , for-
mamide ŽH 2 NCHO., nitrous acid ŽHONO.,
formulas, even though NBO analysis indicates that
U HNOO, and other species. We describe NRT appli-
strong n O ª p CO delocalizations Žeach estimated
cations to several such systems at the geometry-
at 199 kcalrmol by second-order perturbation the-
optimized RHFr6-31 q G* level of theory.
ory. make each CO bond quite unlike that of, e.g.,
The formate ion itself is a classic case of strong,
formaldehyde.
symmetric delocalization, with equivalent leading
The strong n ª p * delocalizations can be suc-
NRT structures
cessively removed by ‘‘protonating’’ each lone pair
and decreasing nuclear charge to preserve neutral- O Oy Oy O
ity in the isovalent sequence O C O ,
HN C O . . . H 2 C C CH 2 . Each such re- C C
Ž 3.5.
placement diminishes the weight of a triple-bonded H H
form Žarising from n ª p * delocalization.. The a. w 46.4%x b. w 46.4%x
first of these ‘‘partially localized’’ analogs,
HN C O , has NRT weightings
and equal CO bond orders Ž bCO s 1.524. of signifi-
cant ionic character Ž bCO
Žion.
s 0.689, bCO
Žcov.
s 0.835..20
H H H An analogous neutral pattern is seen in HNO 2 ,
y q
N C O N C Oq N C Oy
a. w 49.7%x b. w 24.4%x c. w 22.1%x O Oy Oy O
Ž 3.2. Nq Nq
Ž 3.6.
H H
reflecting the ‘‘symmetry breaking’’ of the two a. w 47.0%x b. w 47.0%x
orthogonal pi systems. The next member,
HN C NH , has a twisted symmetric Ž S2 . with similar NO bond orders Ž b NO s 1.518. and
NO s 1.226, b NO s 0.296 .
even higher ionicity Ž b Žion. Žcov.
structure with NRT weightings reflecting still .
higher pi localization, The corresponding nonsymmetric pattern is ex-
emplified by the amide group 21 of formamide,
H H which has leading NRT structures
y
N C N N C Nq H H
-

H H
O N Oy Nq
a. w 76.9%x b. 8.2%
Ž 3.3. C H C H Ž 3.7.
H
q H H
N C Ny .
a. w 65.8%x b. w 28.4%x
-

H
c. 8.2% with distinct CO and CN bond orders Ž bCO s 1.744,
bCN s 1.289. and degrees of ionicity Ž bCO
Žion.
s 0.715,
Finally in allene, in which the last of the n ª p * bCO s 1.029; bCN s 0.508, bCN s 0.781.. Simi-
Žcov. Žion. Žcov.

delocalizations is removed, only the nominal larly, the NRT weightings for HONO
double-bonded resonance structure has significant
weighting Ž91.9%.. Thus, the NRT weightings19 O O H Oy Oq H
exhibit the expected successive degrees of localiza- N N Ž 3.8.
tion of the pi system in this isovalent sequence. a. w 87.1%x b. 7.2%

JOURNAL OF COMPUTATIONAL CHEMISTRY 635


GLENDENING ET AL.

result in nonsymmetric NRT bond orders Žproton- XF , 0 for X s Li to covalent e.g., b XF s 0,


1, b Žcov. . Ž Žion.

ated b NO s 1.042, free b NO s 1.968., reflecting the b XF s 1 for X s F.. The NRT ionic and covalent
Žcov.

still greater dominance of the leading resonance bond orders are seen to vary smoothly in the
structure.19 The greater weighting of the dipolar manner expected from empirical electronegativity
structure in formamide Ž3.7b. than in HONO Ž3.8b. differences.
can be attributed to the better donor ŽLewis base. It is noteworthy that Žexcept for X s Li. the
character of n N vs. n O Ži.e., greater electropositiv- methyl C—X bonds exhibit slight partial double
ity of N. and better acceptor ŽLewis acid. character bond character, of the type expected to give rise to
U
of p CO vs. p UNO Ži.e., greater CO electronegativity torsional barriers. The resonance structures respon-
difference polarizing the pi antibond toward the sible for partial C s X character are associated
U
central atom., leading to stronger n N ª p CO than with hyperconjugative s ª s * Žor n ª s *. inter-
U
n O ª p NO NBO delocalizations. Thus, the relative actions that were previously identified 23 as the
NRT weights in Ž3.7. and Ž3.8. seem to be in principal origin of barriers to internal rotation in
agreement with expected chemical trends. ethane-like molecules. Weak resonance delocaliza-
tion of the form

Ionic Bonding and ‘‘Ionic-Covalent H Hq


Resonance’’
C X C X Ž 4.2.

6
6
The description of ionic and polar compounds H Hy
presents a peculiar difficulty in Pauling-Wheland
resonance theory, insofar as it was necessary to
can therefore be considered as the resonance-
attribute ‘‘covalent’’ and ‘‘ionic’’ resonance struc-
theoretic counterpart of the s ª s * ‘‘charge trans-
tures to molecules that were conventionally de-
fer’’ picture.24 The somewhat surprising ionic con-
scribed by a single Lewis structure formula. This
tribution to CC bonding in ethane Ž bCC Žion.
s 0.019,
difficulty stems from the fact that the Heitler-
London VB pair function describes homopolar corresponding to about 2% ionic character. can
bonds Ž‘‘pure covalent’’ bonding., so that bond also be attributed to the dipolar hyperconjugative
polarity must be represented with ‘‘ionic-covalent structures in Ž4.2..
resonance.’’22 No such difficulty arises in the Table IV also shows the variations in NRT cova-
NBOrNRT formalism; each two-center polar bond lency Ž VFŽcov., VCŽcov. ., electrovalency Ž VFŽion., VCŽion. .,
Že.g., sAB s cA hA q c B h B . can vary continuously and total atomic valency Ž VF , VC . for F and C
between homopolar Ž cA s c B . and ionic Ž cA s 0 or atoms. Consistent with standard valence concepts,
c B s 0. limits within the framework of a single fluorine is found to be essentially ‘‘univalent’’
localized Lewis structure formula. Ž V F s 1.00 " 0.02. and carbon ‘‘tetravalent’’ Ž VC s
To illustrate the distinctive treatment of ionic or 4.000 " 0.004. in all these compounds. The cova-
polar covalent bonding in the NRT framework, we lency of F Žor C. is found to vary steadily with the
consider two series of molecules, F—X Žor C—X. electronegativity difference in the
expected way. Thus, the NRT description of ionic
and polar compounds bypasses the problematic
X—F
5
X—CH 3 X s Li, CH 3 , NH 2 , OH, F. 4.1
Ž . ‘‘ionic-covalent resonance’’ of Pauling-Wheland
theory but achieves very satisfactory agreement
with intuitive electronegativity and valency con-
As expected, these are all well described by a cepts that underlie Pauling’s classic description of
single NRT structure Ž)99%.. Table IV displays chemical bonding.4
the calculated X—F and X—C bond orders
Ž b XF , b XC ., as well as their ionic Ž b Žion.
XF , b XC
Žion. .
and
covalent Ž b XF , b XC . components, at the RHFr6-
Žcov. Žcov.

31G*rrPG level. Coordinate Covalent Bonding: Lewis


As Table IV shows, the formal X—F or X—C Acid]Base and Organometallic
bond order is always close to unity Ž1.01 " 0.01., Complexes
corresponding to the nominal single bond of the
coventional Lewis structure. However, the bond Coordinate covalency Ž‘‘dative’’ or ‘‘donor-
type ranges from nearly pure ionic Že.g., b Žion. XF , acceptor’’ bonding. represents a pervasive bonding

636 VOL. 19, NO. 6


NATURAL RESONANCE THEORY: III

TABLE IV.
Variations in NRT Bond Order and Atomic Valency [and Their Covalent and Ionic Contributions: VF(co v ) = C F ,
VF(ion) = E F ; See Eq. (2.12) in the Preceding Paper] in a Series of X—F and X—CH3 Compounds (X = Li,
CH3 , NH 2 , OH, F), Evaluated at RHF / 6-31G* // PG Level (Except for X = Li, Where Geometry Was Optimized).

X—F compounds X—CH3 compounds


NRT bond order (X—F) NRT atomic valency (F) NRT bond order (X—C) NRT atomic valency (C)
X bXF b (c
XF
ov)
b (io
XF
n)
% Ionic VF VF(c o v ) VF(io n ) bXC b (c
XC
ov)
b (io
XC
n)
% Ionic VC VC(c o v ) VC(io n )

Li 1.000 0.026 0.974 97.4 1.000 0.026 0.974 1.000 0.135 0.865 86.5 4.000 1.388 2.613
CH3 1.019 0.526 0.493 48.4 1.019 0.526 0.493 1.019 1.000 0.019 1.9 4.000 3.346 0.654
NH 2 1.006 0.691 0.315 31.3 1.006 0.691 0.315 1.023 0.801 0.222 21.7 4.000 3.181 0.819
OH 1.000 0.836 0.163 16.3 1.000 0.836 0.163 1.022 0.645 0.377 36.9 4.000 3.060 0.940
F 1.000 1.000 0.000 0.0 1.000 1.000 0.000 1.019 0.507 0.493 48.4 3.996 2.970 1.026

motif in many inorganic and organometallic double zeta ECP basis.,26 with equilibrium bond
species.25 Formation of a coordinate bond between ˚ and R CO s 1.1483 A.
lengths R NiC s 1.7696 A ˚ NRT
a Lewis base ‘‘donor’’ and Lewis acid ‘‘acceptor’’ analysis of this wave function leads to the reso-
leads to a special type of polar covalency whose nance weightings
NRT description resembles that of ionic and strong
polar covalent bonding, as discussed in the preced- Ni C O: Ni C O: ¨ Ni :C O:¨
ing section. .
a. w 87.4%x b. 12.4% c. 0.2%
To illustrate the application of NRT to coordi- Ž 5.2.
nate complexes, we consider the prototype Lewis
acid]base adduct BF3 ??? NH 3 Žgeometry opti-
mized RHFr6-31G* level., whose leading NRT With respect to Ni and CO precursors, structure
weightings are shown below. Ž5.2a. is due to carbonyl lone pair donation into
unfilled Ni valence orbitals and Ž5.2b. to p back-
U
F H F H Fy H bonding from metal d into unfilled carbonyl p CO
H H H orbitals. Note that Ž5.2c. represents the carbonyl
-
-
-

B N B :N B Nq moiety as double bonded Žformally, ‘‘octet violat-


F - F - F -
F H F H F H ing’’ at C., rather than the usual triple-bond ‘‘free’’
a. w 35.8%x b. w 14.9%x c. w 12.3%x Ž 3 . CO. The calculated NRT bond orders indicate that
Ž 5.1. the coordinate NiC bond Žwith b NiC s 1.122. has
high polarity Ž86.1% ionic character., and the car-
bonyl bond order Ž bCO s 2.874. is significantly re-
The coordinate B ??? N bond is found to have total duced from its value in free CO. These NRT
bond order b BN s 0.803 of high polarity Ž b Žion.
BN s weightings and bond orders appear to be in good
0.589.. Note that formation of the final acid]base overall agreement with conventional concepts of
adduct from its isolated Lewis base Ž:NH 3 . and bonding in Werner-type complexes.27
Lewis acid ŽBF3 . precursors involves promotion of
the B—N bonded resonance structure Ž5.1a. from a
minor secondary structure at large separation to
the leading reference structure at equilibrium, so ‘‘Octet Rule-Violating’’ Hypervalent
the NRT weightings will exhibit a ‘‘discontinuity’’ and Hypovalent Bonding
Žof the type described in the preceding paper. at
some intermediate distance unless both structures The NRT structures of most stable compounds
Ž5.1a, b. are stipulated as reference structures for appear to conform well to the Lewis octet rule.
all R Žcf. penultimate section.. However, NRT analysis can also be applied to
As a second example, we consider the nickel species exhibiting formal surplus Ž‘‘hypervalency’’.
carbonyl complex, NiCO. The wave function was or deficiency Ž‘‘hypovalency’’. of valence electron
taken to be of RHFrLANL1DZ form ŽHay-Wadt pairs. In the former case, the NRT program can

JOURNAL OF COMPUTATIONAL CHEMISTRY 637


GLENDENING ET AL.

recognize hypervalency if the number of formal lated NRT covalency Ž VSŽcov. s 1.564. is actually
electron pairs of a candidate structure exceeds the less than expected for a nominal ‘‘divalent’’ ele-
valence shell dimensionality, and multireference ment Žand far less than the apparent ‘‘hexava-
weighting Žif required. is then carried out in the lency’’ of a superficial line formula.. With respect
full NAO basis rather than the restricted valence to the charge distributions as well as the relative
space. We briefly present numerical examples for unimportance of d-orbital participation, the NRT
each of these exceptional bonding types. results are quite consistent with the NBO analysis
presented by Reed,29 showing the close connection
between these descriptions.
‘‘HYPERVALENT’’ SPECIES As a final example, we consider SF4 Ž‘‘sawhorse’’
A classical example of hypervalency is ‘‘penta- geometry, C 2v .. At the geometry-optimized
valent’’ PCl 5 , in which P appears to be surrounded RHFr6-31G* level, the two sets of SF bonds are
by five valence electron pairs.28 NRT analysis of inequivalent, leading to the five reference struc-
the geometry-optimized RHFr6-31G* wave func- tures shown below.
tion for this species gives the six reference struc-
tures shown below. F ¨S F F ¨Sq Fy F ¨Sq F
- - -
F F F F F Fy
Cly Cl Cl
Cl Cl Cl a. w 21.1%x b. w 19.8%x Ž 2 . c. w 14.0%x Ž 2 .
Pq Cl P Cl Pq Cly Ž 6.3.
-

Cl
-

Cl Cl
Cl Cl Cl
a. w 18.1%x Ž 2 . b. w 12.4%x c. w 10.2%x Ž 3 . The near-collinear SF bonds have lower total b SF
Ž0.772 vs. 0.820. but higher b Žion.
SF
Ž0.534 vs. 0.489.
Ž 6.1.
than do the two transverse bonds, consistent with
an ionic picture of linear three-center hypervalent
Each PCl bond w with b PCl s 0.744 Ž ax . and 0.849 bonds28 Žalso applicable to the bonding in SF629 ..
Ž eq .x is of rather high ionic character w 41.1% Ž ax ., Although leading structure Ž6.3a. is formally hy-
34.2% Ž eq .x . As is shown in Ž6.1., five of the lead- pervalent, the other four reference structures
ing resonance structures Žaccounting for about 67% Žaccounting for about 67% of the NRT expansion.
of the NRT expansion. are found to obey the octet are not, and neither the sulfur total valency Ž VS s
rule, and the calculated atomic valency of phos- 3.184. nor the covalency Ž VSŽion. s 1.138. suggests
phorus Ž VP s 4.036, VPŽcov. s 2.554. appears only the five valence electron pairs that might be naively
slightly exceptional. Evidently, the high ionic char- inferred from a line formula. Further aspects of
acter of P—Cl bonding permits high coordination hypervalency in relation to NRT weightings and
number to phosphorus within the constraint of the natural charge distributions are discussed else-
octet rule. where.31
Another classical example of apparent hyperva-
lency is given by sulfur hexafluoride, SF6 .29 At the
RHFr6-31G* geometry-optimized level, SF6 gives ‘‘HYPOVALENT’’ (ELECTRON-DEFICIENT)
rise to the 16Ž!. reference structures shown below: SPECIES
A classical example of electron-deficient bond-
F F Fy ing is diborane, 32 B 2 H 6 , which leads Žat
Fy F F geometry-optimized RHFr6-31G* level. to the
F S 2q
Fy F S F F S 2q F NRT weightings shown below.
, Ž 6.2.
-
-

F F
-

F y
F F F
a. w 6.3%x Ž 12. b. w 5.4%x w 3.5%x Ž 3 . H H H H H H
By Bq B B
H Ž 6.4.
-

H
-

H H H H
only one of which wŽ 6.2b., approximately 5%x is
formally hypervalent.30 The formal SF bond orders w x
a. 25.1% 2 Ž . b. w 24.3%x Ž 2 .
are all equal Ž b SF s 0.680. and of high polarity
SF s 0.419 . Although the total atomic valency
Ž b Žion. . In the NRT representation, the bridging BH bonds
of sulfur Ž VS s 4.080. is rather unusual, the calcu- have significantly lower bond order Ž b BH s 0.500.

638 VOL. 19, NO. 6


NATURAL RESONANCE THEORY: III

BH s 0.221 than do the


and higher polarity Ž b Žion. NF s 0.176 . Thus, these isoelectronic AXF2
0.742, b Žion.
. .
‘‘ordinary’’ flanking BH bonds Ž b BH s 0.995, b Žion.
BH species illustrate the progressive change in AX
s 0.024.. Note that this molecule is well described bonding from ‘‘single’’ ŽA s B, X s F. to ‘‘double’’
by a single NBO structure with two three-center ŽA s C, X s 0. to ‘‘triple’’ ŽA s X s N., in accor-
B H B bonds, and the NRT weightings and dance with conventional Lewis structure models.
bond orders from Ž6.4. are crudely consistent with
Pauling’s standard resonance-theoretic treatment
of three-center bridge bonds.33 The calculated NRT Noncovalent Bonding: H-Bonded
atomic valency of boron Ž VB s 2.943. is in excel- Complexes
lent agreement with the empirical trivalency of
Group III elements. The topic of ‘‘noncovalent’’ hydrogen bonding
A still simpler type of hypovalency is repre- is of special interest for resonance theory. Pauling 34
sented by the Lewis acid BF3 w cf. Ž5.1.x , whose NRT originally judged that the H-bond was esentially of
representation Žgeometry-optimized RHFr6-31G* pure electrostatic rather than ‘‘partial divalent’’
level. has leading structures character Žas had been suggested by Lewis 35 ..
However, Sidgwick 36 applied the theory of reso-
F Fq nance to H bonding, and Coulson37 concluded that
resonance effects were the leading contributions to
B By . Ž 6.5.
F F F H bond attraction. The controversy regarding
F
whether H bonding is primarily of ‘‘electrostatic’’
a. w 76.1%x b. 5.2% Ž 3 .
or ‘‘resonance’’ Žpartial covalent. nature has con-
tinued unabated.38 Although the original reso-
The dipolar structures in Ž6.5. lead to B—F bonds nance picture of A—H ??? B hydrogen bonding
with partial double-bond character Ž b BF s 1.050. w cf. Ž3.4.x
BF s 0.774 . The total natural
and high ionicity Ž b Žion. .
valency of boron Ž VB s 3.150. is seen to be primar- A H :B A: y H Bq Ž 7.1.

6
6
ily of electrovalent origin Ž VBŽion. s 2.201., and the
leading resonance structure Ž6.5a. is indeed of was developed by Sidgwick Žrather than Pauling
‘‘octet-violating’’ form. and Wheland., we can compare NRT applications
It is interesting to compare BF3 with the isoelec- with this conventional Pauling-Wheland-like reso-
tronic species F2 CO and F2 NN Žat the same nance description.
RHFr6-31G* level.. The leading NRT structures of We first consider the elementary example of the
F2 CO are found to be water dimer, ŽH 2 O. 2 , at the optimized RHFr6-31
q G* level. NRT analysis leads to the leading
O Oq Oy resonance structures

C C C , Ž 6.6. H H
F F F Fy F Fq H H
-

a. w 51.0%x b. w 18.9%x Ž 2 . c. 2.6% Ž 2 . O H O Oy Hq O


. Ž 7.2.
H H
with bond orders Ž bCO s 2.335, bCF s 0.821. of rel- a. w 98.1%x b. 1.9%
atively high ionic character Ž bCO
Žion.
s 1.046, bCF
Žion.
s
0.441 ., having somewhat higher b CO than Consistent with Ž7.1., the NRT expansion predicts
formaldehyde Ž2.045.. The corresponding NRT rep- appreciable O ??? H bond order Ž bOH s 0.019.. The
resentation of F2 NN is appearance of the ‘‘ion pair’’ contribution Ž7.2b. is
consistent with the suggestion of significant
Ny N ‘‘charge transfer’’ character of the H-bonded com-
plex.39
Nq Nq , Ž 6.7. The H-bonded complex Fy ??? HF demonstrates
F F F Fy another aspect of intermolecular resonance delo-
a. w 46.4%x b. w 23.4%x Ž 2 . calization, in that the resonating contributions
analogous to Ž7.1. are symmetrically related,
with increased NN triple-bond character Ž b NN s
NN s 0.808 and weaker NF bonds b NF s F—H Fy Fy H—F, Ž7.3.
6

2.473, b Žion.
6

. Ž

JOURNAL OF COMPUTATIONAL CHEMISTRY 639


GLENDENING ET AL.

and the equilibrium geometry is symmetric Ž D`h ., the resonance contributions in Ž7.2. and Ž7.3. ap-
suggesting the analogy with CO2 , formate ion, and pear to differ in degree, but not in type.
other cases of symmetric strong delocalization. As Another interesting aspect of intermolecular H
expected, the NRT expansion for this species bond resonance is its ability to couple to intramolec-
ŽRHFr6-31G* level. is dominated Ž50.0% each. by ular resonance delocalization. This can be illus-
the two structures in Ž7.3., and both partial FH trated with the example of the formamide dimer,
bonds Ž b FH s 0.500. have significant covalent ŽNH 2 CHO. 2 , cyclically H bonded. At the same
FH s 0.106 and ionic
Ž b Žcov. . FH s 0.394 bonding
Ž b Žion. . RHFr6-31 q G* level used for formamide w cf.
character. As with other symmetric and unsym- Ž3.7.x , the NRT expansion for the cyclic dimer has
metric examples discussed in previous sections, the leading terms

H H O H H H O H
N C Nq C
C N C N
H O H H H Oy H H
a. w 38.8%x b. w 18.7%x Ž 2 .
Ž 7.4.
y H q
H H O H H O H
Nq C Ny C
C Nq C N .
y
H O H H H O H H
c. 8.3% d. 1.1%

In addition to the leading H-bonded structure mized RHFr6-31 q G* level., for which the lead-
Ž7.4d., other structures appear in which H-bonding ing NRT structures are
U
is coupled to the n N ª p CO delocalization Žtotall-
ing about 3.3%., giving rise to appreciable bond H H H Oq H
order Ž bO ? ? ? H s 0.027. in each H bond. As ex- O O N y
C
pected, dipolar amide resonance structures Ž7.4b,
c. are the leading delocalizations, but it is note- C C C N
worthy that their relative weighting is significantly H C H H O H H
greater than that in the monomer. The calculated C
dimer bond orders bCN s 1.307 and bCO s 1.718 H -
Žcf. bCN s 1.292 and bCO s 1.744 for the monomer. H H
also reflect the enhanced amide resonance. From a. w 75.3%x b. 7.5%
such comparisons one can recognize that amide H H
delocalization is significantly strengthened by Oy O Oq O
dimer formation, i.e., that H bond formation
couples with, and enhances, amide resonance Žand C Cq C C
H C H y C H
vice versa.. Such coupling effects can be antici- H
pated from the donor-acceptor character of H C C
bonding.38, 39 H - H -
Finally, we consider the case of intramolecular H H H H H
bonding in methylated malonaldehyde40 Žopti- c. 6.0% d. 2.3%

640 VOL. 19, NO. 6


NATURAL RESONANCE THEORY: III

H H model are idealized with respect to actual Diels-


Oq O Oq Oy Alder reactions, the calculated reaction energy
profile ŽFig. 3a. shows the expected qualitative
C C C C .
features, with the separated reactant state at the
H Cy H H C H Ž 7.5. left Žethylene q butadiene, initially at s R s 3.0 A˚.
C C leading to the final product state at the right Žequi-
H - H - librium cyclohexene, at s P s 1.4324 A ˚ ., separ-
H H H H
ated by an activated ‘‘transition state’’ Žat s ‡ s
e. 1.7% f. 1.3% ˚ ..
2.0945 A
To compare the weightings of reactant-like Ž w R .
Structures Ž7.5b, c. are associated with expected pi and product-like Ž w P . resonance structures across
U U
conjugation Žp CO ª p CC , p CC ª p CO . and Ž7.5d, the entire reaction coordinate, we stipulate Žwith
e. with weaker sigma conjugation around the car- the $NRTSTR keylist. that these two resonance
U U
bonyl group Ž n O ª sCH , n O ª sCC ., whereas Ž7.5f. structures be considered as reference structures at
is the expected H bonding resonance, analogous to all s Ždespite the small weight of w R in the P
that found previously w e.g., Ž7.2b.x in the inter- region and vice versa.. Figure 3b shows the calcu-
molecular case. As with Ž7.4., one would expect lated NRT values of w R and w P along the reaction
that p-conjugative and H bond resonance would coordinate. As expected, the R structure domi-
be coupled Žand mutually enhanced. as the proton nates Ž w R s 87.03%, w P - 0.01%. in the reactant-
shifts from one oxygen toward the other. w Note, well region near s R s 3.0 A,˚ whereas the P struc-
however, that even a symmetrically bridged ture dominates Ž w P s 88.05%, w R - 0.01%. in the
O ??? H ??? O species will exhibit slight differences
product-well region near s P . As one approaches
between the weightings for the two ‘‘equivalent’’
the transition state ŽTS. region from either side, the
Ž O H O l O H O . tautomeric forms, ow-
weightings w RŽ s . and w P Ž s . of the two resonance
ing to methyl-eclipsing effects analogous to those
structures gradually approach equality, until they
in Ž2.3. ] Ž2.6..x Quantitative aspects of the well-
cross Ž w R s w P . near the TS. We may designate
known ‘‘proton hopping’’41 dynamics of malon- ‡
the crossing point s N at which
aldehyde and related species should be reflected in
the NRT weightings.
‡ .
wRŽ sN s w P Ž sN
‡ . Ž 8.2.

as the ‘‘natural transition state’’ ŽNTS., to distin-


Chemical Transformation on a
guish it from the corresponding point Ž s ‡ . at the
Potential Energy Surface: Reactant,
top of the energy barrier w where the NRT weight-
Product, and Transition Species ings are found to be w RŽ s ‡ . s 48.4%, w P Ž s ‡ . s
31.3%x . In the present case, the NTS is found to
As a final example, we consider the NRT repre- ˚ differing only slightly
occur near s N ‡
s 2.078 A,
sentation of a model Diels-Alder chemical reac- ‡
from s . On physical and chemical grounds, the
tion,
approximation s N ‡
, s ‡ would be expected to hold
true for many chemical reactions.
Figure 3c shows the corresponding variations of
q ª , Ž 8.1.
NRT bond orders for the four distinct CC bonds
Žin conventional cyclohexene numbering, b 12 , b 23 ,
to illustrate the use of user-selected reference b 34 , b45 .. Consistent with the expected chemical
structures to compare widely differing reactant picture, these evolve continuously from the
Ž R . and product Ž P . systems. We employ a model Ž1, 2, 0, 2. pattern of the reactant structure to the
reaction coordinate Ž s . corresponding to the dis- Ž2, 1, 1, 1. pattern of the product structure, with an
tance from the ethylene CC midpoint to the point approximate Ž1.5, 1.5, 0.5, 1.5. pattern at the TS. Al-
midway between the terminal C atoms of cis- though the quantitative values of the NRT bond
butadiene in constrained Cs symmetry. For each orders and weightings will be altered in higher
value of s, the remaining bond distances and an- level treatments of the reaction profile Žparticu-
gles were optimized Ž Cs constrained. at the larly, inclusion of correlation effects., the chemi-
RHFr3-21G level. Although several aspects of this cally reasonable variations shown in Figure 3a]c

JOURNAL OF COMPUTATIONAL CHEMISTRY 641


GLENDENING ET AL.

FIGURE 3. (a) Reaction energy profile for model Diels-Alder reaction,

q ª ,

calculated at RHF / 3-21G level (see text for geometry and definition of reaction coordinate s ). (b) NRT resonance
weights for reactant ( wR ; triangles) and product ( wP; squares) resonance structures along the model Diels-Alder
reaction coordinate. (c) Natural bond order b AB along the reaction coordinate, showing the evolution from reactant
(butadiene plus ethylene) to product (cyclohexene) bond patterns. Bond numbering corresponds to cyclohexene
labelling (e.g., b12 is the final cyclohexene double bond and b 45 the initial ethylene double bond).

are expected to be preserved at higher theoretical and bCC are highly correlated and appear to lie
levels. along a universal smooth curve. The nonlinear
Figure 4 compares the NRT bond orders to ‘‘kinks’’ of this curve are consistent with the ex-
optimized CC bond lengths for all points along the pectation w cf. Ž3.9. in the preceding paperx that a
Diels-Alder reaction coordinate. The values of R CC bond order]bond length curve cannot be globally

642 VOL. 19, NO. 6


NATURAL RESONANCE THEORY: III

including Gaussian 9X,44 GAMESS,45 and others.


In the present paper, we have emphasized NRT
applications in the framework of ab initio molecu-
lar orbital theory in order to demonstrate the prac-
ticality of NRT analysis for the most widely used
quantum chemical methods and its independence
from VB-type wave functions.
The results presented here illustrate the NRT
description for a wide variety of chemical species:
cyclic and acyclic; neutral and charged; symmetric
and nonsymmetric; and hypervalent, hypovalent,
normal covalent, ionic, coordinate covalent, and
noncovalent bonding types. Emphasis has been
placed on some classical applications of resonance
theory Žbenzene, CO2 , amide group, carboxylate
ion, etc.. as well as nonconventional applications
to subtle bond fixing ŽMills-Nixon., torsional, H
bonding, and conjugative coupling effects. The for-
FIGURE 4. NRT bond order]bond length correlation mer applications serve to demonstrate the broad
for CC bond variations along the model Diels-Alder consistency of NRT analysis with conventional
reaction coordinate (cf. Fig. 3a]c). Pauling-Wheland concepts Ždespite important dif-
ferences, e.g., in the treatment of ‘‘ionic-covalent
resonance’’.. The latter serve to illustrate the many
linear. Nevertheless, there are conspicuous broad extensions and refinements of resonance-theoretic
regions Že.g., centered about bCC s 0.5, 1.5. where reasoning that become feasible in the quantitative
a linear bond order]bond length assumption is NRT framework. We have also demonstrated the
apparently well justified. The global NRT bond applicability of NRT analysis to the continuous
order]bond length curve 42 of Figure 4 is therefore chemical transformations of a model Diels-Alder
qualitatively consistent with empirical Pauling- reaction, relating the transition state to the compet-
Wheland correlations, but the quantitative form of
ing reactant and product resonance structures. Our
this curve should considerably extend the predic-
emphasis throughout has been on sampling a broad
tive power of such correlations.
range of NRT applications, rather than investigat-
ing particular systems in detail. We believe that
these examples provide a useful baseline for future
Summary and Conclusions NRT investigations of a wide variety of organic,
inorganic, and biochemical systems.
The natural resonance theory ŽNRT. method Resonance theory once represented the most
provides a new, quantitative tool to express the
dominant influence in theoretical chemistry. We
chemical content of numerical wave functions in
believe it can once again play an active, crea-
the familiar and intuitive language of resonance
tive role in modern chemistry, infused with a
theory. Unlike classical Pauling-Wheland theory,
new degree of quantitative ab initio rigor and
the NRT method makes no reference to ‘‘ valence
generality.
bond,’’ multiconfigurational, or other specialized
form of wave function. Rather, it employs only the
information contained in the first-order reduced
density matrix and is therefore applicable to any Appendix
ab initio or semiempirical quantum chemical proce-
dure Žincluding variational, Møller-Plesset pertur- The minimum of the NRT variational functional
bative, and density functional methods. for which w eq. Ž4.7. in the first accompanying paperx can be
a density matrix is available. The NRT method has derived exactly for the elementary case of the
been implemented as a general-purpose program7 benzene pi system in a minimal basis Že.g.,
Žembedded in the general Natural Bond Orbital ¨
Huckel-type . framework, where the pi MOs are
analysis package 43 that can be attached to a wide determined by symmetry. When these MOs are
variety of modern electronic structure systems, transformed to a basis of localized bond Žp i . and

JOURNAL OF COMPUTATIONAL CHEMISTRY 643


GLENDENING ET AL.

antibond Žp iU . NBOs Ži s 1, 2, 3., it is readily shown by the NSF grant CHE-9007850 are gratefully
that the p i and p iU occupancies qi s ²p i < G ˆ <p i :, acknowledged.
qUi s ²p iU < G
ˆ <p iU : are given by

q1 s q2 s q3 s 1 23 , qU1 s qU2 s qU3 s 13 . Ž A1. References


For the usual covalent resonance structures 1. L. Pauling, in A. R. Todd Žed.., Perspectives in Organic
w Kekule
´ structures K Žreference., K9; Dewar struc- Chemistry, Wiley Interscience, New York, 1956.
tures D1, D2, D3x , one can readily write out the 2. G. W. Wheland, Resonance in Organic Chemistry, John Wiley
table of occupancies qi a of p i and p iU NBOs as and Sons, New York, 1955.
shown below. 3. L. Pauling and F. W. Wheland, J. Chem. Phys., 1, 362 Ž1933.;
H. Eyring, J. Walter, and G. E. Kimball, Quantum Chemistry,
Wiley, New York, 1944, pp. 249]254.
NBO K K9 D1 D2 D3 true
4. L. Pauling, The Nature of the Chemical Bond, 3rd ed., Cornell
p 1U 0 1 1 1 0 1
3 University Press, Ithaca, NY, 1960.
p U2 0 1 1 0 1 1
3
5. For an authoritative description of standard ab initio com-
p U3 0 1 0 1 1 1
3
putational methods and basis set designations referred to
herein, see W. J. Hehre, L. Radom, P. v. R. Schleyer, and J.
p1 2 1 2 2 0 1 2
3 A. Pople, Ab Initio Molecular Orbital Theory, Wiley, New
p2 2 1 2 0 2 1 2
3
York, 1986.
p3 2 1 0 2 2 1 2
3
6. J. A. Pople and M. S. Gordon, J. Am. Chem. Soc., 89, 4253
Ž1967..
7. F. Weinhold, NBO 4.0 Program Manual, University of Wis-
If we choose the weights of the three Dewar struc- consin Theoretical Chemistry Institute, Madison, 1994, Sect.
tures to be identical Ž w D ., the differences B.8; J. K. Badenhoop, Ph. D. Thesis, University of Wisconsin,
Madison, 1994.
qi y Ý wa qi a 8. E. D. Glendening, R. Faust, A. Streitwieser, K. P. C. Voll-
a hardt, and F. Weinhold, J. Am. Chem. Soc., 115, 10952
Ž1993..
are seen to be 9. Throughout this paper, ‘‘formal charge’’ labels are attached
to assist in specifying the complete Lewis structure for
1
3 y w K 9 y 2 w D , for each p iU Ž A2. cases that may otherwise be ambiguous. We typically omit
specification of lone pairs unless highlighted in the discus-
1 23 y 2 w K y w K 9 y 4w D , for each p i . Ž A3. sion. Note that ‘‘formal charges’’ are purely a notational
device, only loosely connected to the physical charge distri-
With the normalization condition w K q w K 9 q bution as described, e.g., by natural population analysis.
3w D s 1, one can eliminate w K from ŽA3. to see Note also that when two electronically distinct ‘‘structures’’
Žcorresponding, in the case of CO2 , to the two twisted
that ŽA2. and ŽA3. are equivalent. Thus, there are orientations of orthogonal pi bonds. map onto a single
two independent unknowns to satisfy a single con- Lewis diagram, as in Ž3.1a., the diagram is labelled with
dition ŽA2., and the variational minimum their combined weight Ž49.7%.. However, multiple equiva-
dŽ w K 9 , w K , w D . s 0 Žcorresponding to f Ž w . s 1. is lent Lewis diagrams are specified by giving the calculated
achieved for any values of w K 9 , w D satisfying ŽA2.. weighting for one member of the set, followed by the
multiplicity in parentheses, as for the two equivalent
In particular, the weights w K s 23 and w K 9 s 13 for triple-bonded structures Ž3.1b..
the two Kekule ´ structures reproduce the benzene 10. Strong resonance mixing is also observed for non-D6h
pi occupancies ŽA1. exactly, with no contribution geometries that break the symmetry equivalence of the two
from Dewar structures Ž w D s 0.. Kekule´ structures in Ž1.1.. In contrast, for the cyclobutadi-
ene ‘‘analog’’ Ž1.2., there is no resonance mixing of the two
structures in geometries that differ even infinitesimally
from D4h symmetry Žcorresponding to the fact that p ª p *
Acknowledgments NBO delocalizations are rigorously absent in this case; see
below..
We thank Prof. J. C. Weisshaar for many discus- 11. For brevity’s sake, in the following, we display only the
sions relating to benzyl cation and aromatic methyl leading resonance structure contributions, showing all ref-
rotors, Dr. Jens Abildgaard for suggesting the ex- erence structures w bracketedx and, in some cases, the few
most important secondary structures. Although the weights
ample of malonaldehyde, and Prof. Paul v.R.
of neglected structures are generally significantly smaller
Schleyer for many helpful critical suggestions. A than those displayed, their cumulative contribution can be
grant of RSr6000 computers from the IBM Corpo- appreciable, as, e.g., in Ž2.7.. Additional details of neglected
ration and other computational support provided structures are available from the authors.

644 VOL. 19, NO. 6


NATURAL RESONANCE THEORY: III

12. K.-T. Lu, G. C. Eiden, J. K. Badenhoop, F. Weinhold, and 27. See, e.g., F. A. Cotton and G. Wilkinson, Advanced Inorganic
J. C. Weisshaar, in, T. Baer, C. Ng, and I. Powis Žeds.., Chemistry, Wiley, New York, 1962, pp. 614]617.
Current Topics in Ion Chemistry and Physics, Vol. IV: Highly 28. R. E. Rundle, Rec. Chem. Progr., 23, 195 Ž1962.; K. S. Pitzer,
Resolved Laser Photoionization and Photoelectron Studies, Wi- Science, 139, 414 Ž1963.; J. I. Musher, Angew. Chem. 81, 68
ley, New York, 1994. Ž1969..
13. W. H. Mills and I. G. Nixon, J. Chem. Soc., 1930, 2510 Ž1930.;
29. A. E. Reed and F. Weinhold, J. Am. Chem. Soc., 108, 3586
reference 4, pp. 201]202.
Ž1986..
14. As the idealized ‘‘PG-like’’ geometry for this species, we
used the idealized geometry of neutral toluene, with the 30. Structure Ž6.2b. is associated with d bonding, as evidenced
methyl group replaced by a planar trigonal CH 2 group by the fact that this structure is absent in the corresponding
˚ R CC s 1.52 A
Ž R CH s 1.09 A, ˚ .. RHFr6-31G calculation where d orbitals are lacking.
15. G. C. Eiden, F. Weinhold, and J. C. Weisshaar, J. Chem. 31. L. Suidan, J. K. Badenhoop, E. D. Glendening, and F. Wein-
Phys., 95, 8665 Ž1991.. hold, J. Chem. Educ., 72, 583 Ž1995..
16. In optimized geometry, the quinone-like structure Ž2.7b. 32. G. N. Lewis, J. Chem. Phys., 1, 17 Ž1933.; W. N. Lipscomb,
becomes more highly weighted Ž w b s 16.9%. than either J. Chem. Phys., 22, 985 Ž1954.; D. S. Jones and W. N.
Kekule ´ structure Ž wa s 9.9% each., with polar structures Lipcomb, Acta Crystallogr. 26, 196 Ž1970.; W. N. Lipscomb,
Ž2.7c. intermediate Ž wc s 14.1% each., further accentuating Boron Hydrides, W. A. Benjamin, New York, 1963, Chapters
the quinone-like NRT description Ž b1x s 1.5966, b12 s 2, 3.
1.1563, b 23 s 1.5419, b 34 s 1.3376..
33. See, e.g., reference 4, p. 369. Pauling considers three types
17. See, e.g., R. T. Morrison and R. N. Boyd, Organic Chemistry, of BB-bonded structures Ž‘‘C, D, E’’. in addition to those
3rd ed., Allyn & Bacon: Boston, 1973, p. 989. Ž‘‘A, B’’. of the NRT expansion, with uncertain relative
18. See reference 4, pp. 267]269. weightings Žvarious estimates are presented that differ by a
19. Note, however, that more quantitative comparisons of two factor of three.. The NRT bond order Ž b BB s 0.0102. shows
systems should be based on a common number of compara- no evidence for significant metal]metal bonding.
ble reference structures. w For example, Ž3.2. can be com- 34. L. Pauling, Proc. Natl. Acad. Sci. USA, 14, 359 Ž1928.;
pared directly with Ž3.1., but not with Ž3.3.; the latter J. Am. Chem. Soc., 53, 1367 Ž1931..
involves a smaller set of reference structures.x The $NRTSTR
keylist can be used to stipulate a comparable set of refer- 35. G. N. Lewis, Valence and the Structure of Atoms and Molecules,
ence structures Žsee, e.g., the examples in the penultimate Chemical Catalog Co.: New York, 1923, especially the sec-
text section. when the default reference structures for two tion ‘‘Bivalent Hydrogen.’’ Lewis dot structures for water
molecules are dissimilar. dimer and FHFy Žexpressing the partial sharing of electron
pairs with two atoms. were included in the first discussions
20. In the Pauling-Wheland ‘‘covalent-ionic resonance’’ formal-
of H bonding: M. L. Huggins, Thesis, University of Califor-
ism, each structure in Ž3.5. would therefore correspond to
nia, Berkeley, 1919; W. M. Latimer and W. H. Rodebush, J.
significant contributions from more highly ionic structures,
Am. Chem. Soc., 42, 1419 Ž1920..
such as
36. N. V. Sidgwick, The Electronic Theory of Valency, Clarendon
Oy Oy Press, Oxford, 1927.
Cq .
37. C. A. Coulson, Research, 10, 149 Ž1957..
H 38. A. E. Reed, L. A. Curtiss, and F. Weinhold, Chem. Rev., 88,
899 Ž1988..
21. A more comprehensive discussion of the important topic of
resonance in amides and related groups is reserved for a 39. A. E. Reed and F. Weinhold, J. Chem. Phys., 78, 4066 Ž1983.;
forthcoming paper. L. A. Curtiss, D. J. Pochatko, A. E. Reed, and F. Weinhold,
J. Chem. Phys., 82, 2679 Ž1985.; A. E. Reed, F. Weinhold,
22. See, e.g., C. A. Coulson, Valence, Oxford University Press:
London, 1961, pp. 128]138; reference 4, Section 3.1; L. A. Curtiss, and D. Pochatko, J. Chem. Phys., 84, 5687
Ž1986.; P. Seiler, G. R. Weisman, E. D. Glendening, F.
J. Braunstein and W. T. Simpson, J. Chem. Phys. 23, 176
Ž1955.. The notion of a fundamental dichotomy between Weinhold, V. B. Johnson, and J. D. Dunitz, Angew. Chem.
Ž Engl. Ed.., 26, 1175 Ž1987..
ionic and covalent ‘‘types’’ Žespoused by Langmuir, Sidg-
wick, and Sugden. was opposed by Lewis, Mulliken, and 40. T. Chiavassa, P. Roubin, L. Pizzala, P. Verlaque, A. Al-
others; see the general historical discussion in Jensen Žrefer- louche, and F. Marinelli, J. Phys. Chem., 96, 10659 Ž1992.;
ence 25., pp. 74]77. Z. Latajka and S. Scheiner, J. Phys. Chem., 96, 9764 Ž1992..
23. T. K. Brunck and F. Weinhold, J. Am. Chem. Soc., 101, 1700 41. Z. K. Smedarchina and W. Siebrand, J. Mol. Struct., 297, 207
Ž1979.; A. E. Reed and F. Weinhold, Isr. J. Chem., 31, 277 Ž1993.; S. J. Formosinho and L. G. Arnaut, J. Photochem.
Ž1991.. Photobiol., A75, 21 Ž1993.; E. B. Wilson and Z. Smith, Acc.
24. In Pauling-Wheland theory, the origins of internal rotation Chem. Res., 20, 257 Ž1987., and references therein.
barriers were not linked to resonance interactions such as 42. Of course, bAB vs. RAB curves differ quantitatively for
Ž4.2., but instead were attributed to d- and f-orbital contri-
different A—B bond types. In particular, there is no `
a priori
butions to bonding hybrids Žreference 4, pp. 130]134.. reason to assume that bond length changes for C—C bonds
25. W. B. Jensen, The Lewis Acid]Base Concepts, Wiley, New are equal to those of, e.g., C—O or C—N bonds for com-
York, 1980; H. A. Bent, Chem. Rev., 68, 587 Ž1968.; see also parable bond order changes. It is also known that A—B
references 27 and 36. bond lengths depend significantly on hybridization w viz.,
26. P. J. Hay and W. R. Wadt, J. Chem. Phys., 82, 270 Ž1985.. CŽsp 3 . —H vs. CŽsp 2 . —Hx , atomic charge, ring geometry

JOURNAL OF COMPUTATIONAL CHEMISTRY 645


GLENDENING ET AL.

constraints, and other factors not directly related to reso- M. A. Robb, E. S. Repogle, R. Gomperts, J. L. Andres,
nance delocalization, and thus not reflected in bond order K. Raghavachari, J. S. Binkley, C. Gonzalez, R. L. Martin,
variations. D. J. Fox, D. J. Defrees, J. Baker, J. J. P. Stewart, and J. A.
43. E. D. Glendening, A. E. Reed, J. E. Carpenter, and Pople, Gaussian 92, Revision A, Gaussian, Inc., Pittsburgh,
F. Weinhold, QCPE Bull., 10, 58 Ž1990.; NBO 3.0 Program 1992.
Manual, University of Wisconsin Theoretical Chemistry In- 45. GAMESS version March 1992: M. W. Schmidt, K. K.
stitute Technical Note WIS-TCI-756, Madison, 1990. Baldridge, J. A. Boatz, J. H. Jensen, S. Koseki, M. S. Gordon,
44. M. J. Frisch, G. W. Trucks, M. Head-Gordon, P. M. W. Gill, K. A. Nguyen, T. L. Windus, and S. T. Elbert, QCPE Bull.,
M. W. Wong, J. B. Foresman, B. G. Johnson, H. B. Schlegel, 10, 52 Ž1990..

646 VOL. 19, NO. 6