Essay

Unicorns in the World of Chemical Bonding Models

GERNOT FRENKING, ANDREAS KRAPP

Fachbereich Chemie, Philipps-Universitat Marburg, Hans-Meerwein-Strasse,
D-35043 Marburg, Germany

Received 5 May 2006; Revised 3 July 2006; Accepted 11 July 2006

DOI 10.1002/jcc.20543
Published online 15 November 2006 in Wiley InterScience (www.interscience.wiley.com).

Abstract: The appearance and the signicance of heuristically developed bonding models are compared with the
phenomenon of unicorns in mythical saga. It is argued that classical bonding models played an essential role for the
development of the chemical science providing the language which is spoken in the territory of chemistry. The
advent and the further development of quantum chemistry demands some restrictions and boundary conditions for
classical chemical bonding models, which will continue to be integral parts of chemistry.
q 2006 Wiley Periodicals, Inc. J Comput Chem 28: 1524, 2007

Key words: bonding model; energy decomposition analysis; electrostatic interactions; unicorn

A unicorn is a mystical animal whose appearance is known
to everybody although nobody has ever seen one. Unicorns are
mythical creatures that appear in numerous fairy tales and saga
all over the world. They belong to the cultural heritage of many
Asian and European people, where unicorns play important roles
in fabulous legends that narrate the history of mankind and the
origin of life. There are Chinese, Japanese, Indian, Greek, Scan-
dinavian, and other cultural variants of unicorn stories dating
back up to 2800 years BC which all have something in common.
The unicorn appears as a creature which brings law and order,
health and good fortune, fame and satisfaction in an otherwise
chaotic and disordered world.1
There are many unicorns in the world of chemical bonding
models carrying quite different names: resonance, conjugation,
hyperconjugation, frontier orbitals, covalent bonding, donor-
acceptor bond, agostic interactions,
bonding, to name just a
few. A particularly ckle species is aromaticity, which is an
evergreen target for hard core unicorn hunters.2 Just as in mythi-
cal saga, unicorns bring law and order, health and good fortune,
fame and satisfaction to chemists who would otherwise be lost
in a pandemonium of experimental observations. Unicorns were
particularly important in the early days of chemistry when the
science evolved from its historical ancestor alchemy. Chemists
needed a classication system which helped them to identify
compounds and to understand and possibly predict the outcome
of chemical reactions. The atomic hypothesis and the discovery
of the chemical elements proved to be very helpful for the pur-
pose because it provided the building blocks which could be
used to construct the world of chemistry in terms of molecular
structures. As a result, chemistry nally evolved as the science
of understanding and manipulation of the material world on a
molecular scale.3
While the development of experimental chemistry in the 19th
century was a great success story which together with its scien-
tic progress paved the way for the build-up of a new and rap-
idly developing branch of industry, the theoretical side became
much less developed. This was not because of insufcient efforts
by the chemists. The physical laws which were known at that
time did not provide a theoretical basis for understanding the
strong attractive interactions between atoms yielding a chemical
bond. The appearance and denition of chemistry as a scientic
discipline has been signicantly inuenced by the fact that, his-
torically, the molecular understanding of the material world was
and still is far behind its experimental control.
Without possessing physical knowledge about the nature of
atoms and molecules and the forces acting between them, chem-
ists developed a set of working hypotheses and experimental
descriptions which enabled them to manipulate the material
world to an extent which was hitherto unknown. Guided by intu-
ition and experience, heuristic chemical models were suggested
to explain the experimental observations and to guide new
experiments. The models became more and more elaborate with
an increasing number of chemical compounds being synthesized.
Experimental results were used like in a neural network for
developing bonding models which proved to be very powerful
Correspondence to: G. Frenking; e-mail: frenking@chemie.uni-marburg.de
Contract/grant sponsor: Deutsche Forschungsgemeinschaft

q 2006 Wiley Periodicals, Inc.

16 Frenking and Krapp Vol. 28, No. 1 Journal of Computational Chemistry
for designing new experiments. This was all done before the
laws of quantum theory were formulated.
The development of heuristic bonding models in chemistry
culminated in the epochal contribution of Lewis.4 His formula-
tion of the chemical bonds in terms of electron pairs and the
rules which he suggested for understanding molecular structures
have shaped chemical bonding models in a way which consti-
tutes still now, 90 years after the rst publication, the basis for
teaching molecular structure and reactivity. It should be men-
tioned that, as a counterpart to the formulation of the covalent
bond by Lewis, a theoretical model of the ionic bond was intro-
duced in the same year by Kossel.5 An outline of the most im-
portant ideas of Lewis is presented and discussed in this issue in
the essay by Shaik.6 It is important to realize that the work of
Lewis appeared before quantum theory provided new physical
laws for electrostatic interactions which were necessary to
understand chemical bonding in terms of elementary physics.
This was nally done in 1927 when Heitler and London7
described the interatomic interactions in H2 in terms of the
newly formulated quantum theory of Heisenberg and Schro-
dinger. It was the rst time that a picture of the chemical bond-
ing was presented which was in agreement with basic laws of
physics. But the year 1927 saw also the Nobel Prize in chemis-
try awarded to Heinrich Wieland for his pioneer ndings about
the constituents of the bile acids and related substances.8 Figure
1 shows the fundamental difference between chemistry and
physics in describing chemical bonding in 1927 which still
exists today. Note that the research about the rather complicated
compounds which was awarded a Nobel Prize was carried out
by Wieland using unicorns as essential ingredients for planning
and explaining experiments. He and his fellow chemists had no
knowledge about the quantum theoretical nature of the chemical
bond.
The model of the chemical bond in terms of electron pairs
which was used by Wieland is still familiar to present day
chemists. It is used in all textbooks of chemistry and it is clearly
the most powerful model for describing chemical phenomena. In
essence, the model consists of only a few simple symbols (a dot
for an atom identied by its chemical symbol and straight lines
for assigning chemical bonds) and a set of empirical rules which
in the hands of an experienced chemist possess an unprece-
dented explanatory and predictive efcacy in explaining molecu-
lar structures and reactivity. Much of the rules and the under-
standing of the electron-pair bonding goes back to the work of
Lewis.4 He recognized that the electron-pair model does not
agree with classical electrostatic laws. Lewis was bold enough
to suggest in 1916 that the law which describes the electric
forces that are responsible for a chemical bond must be different
from Coulombs formulation of electrostatic interactions.4a This
amazing intuition was conrmed by Heitler and London in
1927.7 Pauling later showed that the electron-pair interpretation
of the chemical bond introduced by Lewis can be put on quan-
tum theoretical grounds.9 It is astounding that in nearly 80 years
of quantum chemistry, which undoubtly contributed in its own
way to modern chemistry, the Lewis bonding model has been
complemented but not replaced.
Heitler and London were the rst who applied quantum
theory for investigating chemical bonding using a method which
Journal of Computational Chemistry
was later named VB (valence bond) theory. An alternative
method which proved to be very powerful for qualitative and
quantitative studies of the chemical bond is MO (molecular
orbital) theory which was shortly afterwards developed by Hund,
Mulliken, Huckel, Lennard-Jones, et al.10 Both methods gave
birth to a multitude of new unicorns with some of them still
being alive in present-day bonding models.
In his essay about the Lewis legacy, Shaik argues that chemi-
cal bonding is a traditional chemical territory.6 We want to add
that the afore mentioned unicorns are integral parts of the chem-
ical language which is spoken in this territory, and that the
chemical formula are the alphabet which is used to write down
the language. Inspection of the scientic literature shows that
discussion about molecular structures, chemical reactions, and
bonding situation uses expressions which are characteristic for
the communication among chemists. This holds true even for
most publications which report about quantum chemical studies
of molecules and chemical reactions. In many theoretical papers
there are attempts to connect the calculated data with classical
bonding models. This is in line with the statement which was
made by Coulson in his famous after-dinner speech in 1952
when he addressed his fellow theoreticians who were occupied
with calculating accurate data: Give us insight, not numbers.11
But this is not an easy task!
The physical description of the chemical bond given by Hei-
tler and London had the advantage over the intuitive chemical
bonding models that it was derived from fundamental laws of
physics. The problem was that the physical picture of a chemical
bond in terms of the complicated wave function did not appeal
at all to the imagination of chemists who were used to living
with unicorns. The heuristic chemical bonding models were easy
to write and they had proven to be very helpful as classication
system and as predictive tools for experimental chemistry.
Chemists had become so intimate with their unicorns that they
attained the status of real living beings. This made it very dif-
cult until today to introduce new concepts which do not agree
with the unicorn world. The interpretation of C was a central
topic of controversial discussions in physics but chemists largely
ignored the new ndings which were not appealing to human
senses. This was so, even though the quantum theoretical descrip-
tion of the chemical bond, soon after its introduction by Heitler
and London, solved long-standing problems such as explaining
the triplet ground state of O212 and the stability of aromatic com-
pounds (inclusive predicting new aromatic species).13
It is useful to point out the essential nding of Heitler and
London (HL) about chemical bonding because it is still not cor-
rectly described in many textbooks.14 Figure 2 has been taken
from the original publication of HL.7 The calculation of the
bond energy in H2 using classical laws of electrostatic interac-
tion between charges (r) gives only a weak energy minimum
of *10 kcal/mol at a too long H

H distance. Equations (1)(3)
in Scheme 1 show the basic ansatz of the classical approach.
Equations (4)(9) give the new quantum theoretical approach.
The pivotal difference to the classical ansatz is that the wave
functions C and not the charges (r) of the hydrogen atoms
must be added (or subtracted) in order to get an accurate
description of the wave function and thus, of the electronic
charge of H2. The two quantities C and (r) are related by
DOI 10.1002/jcc
 Unicorns in the World of Chemical Bonding Models 17

Figure 1. Representation of the chemical bond in 1927: (a) in chemistry; (b) in physics. The chemical
formula in (a) shows an example for the bile acids which have been studied in the Nobel Prize work
of Heinrich Wieland (Ref. 8). The mathematical formulas in (b) have been reproduced from the publi-
cation of Heitler and London (Ref. 7). The energy curves of E and E are shown in Figure 2.

Journal of Computational Chemistry DOI 10.1002/jcc

18 Frenking and Krapp Vol. 28, No. 1 Journal of Computational Chemistry
Figure 2. Potential energy curves for the interaction between two
neutral hydrogen atoms given by the classical electrostatic interac-
tion (E11) and by the quantum theoretical expressions E (homoopo-
lare Anziehung) and E (elastische Reexion). Reproduced from
Ref. 7, with permission from Springer.
eq. (4), which requests that the wave function C must be squared
in order to obtain the electronic charge (r). It means that the
sign information of C is not found anymore in (r). Woodward
and Hoffmann15 and Fukui16 showed that the sign of the wave-
function given by the molecular orbitals determines the reaction
course of many chemical reactions. This led to the genesis of
new unicorns like HOMO and LUMO which proved to be very
helpful for understanding and predicting chemical reactions, par-
ticularly pericyclic reactions.17
Equation (6) shows that there is a new quantity which shows
up when the wavefunction rather than the charges of the atoms
are added (or subtracted in case of C). The new term
6C(Ha)C(Hb) called interference or resonance gives an
accumulation of charge when the sign is positive, or a depletion
of charge when the sign is negative. The unicorn covalent
bonding is strongly associated with the interference of the
wave function. Many textbooks are saying that chemical bond-
ing is a result of the accumulation of density in the binding
region.14 This is a deceptive statement, because the origin for
the charge accumulation is not given. It is also misleading
because it gives the incorrect impression that it is sufcient to
consider the electronic charge of the interacting species for
understanding chemical bonding. Figure 2 shows that the two
hydrogen atoms may interact in two very different ways, i.e. in
a bonding or antibonding fashion. The bonding comes from the
spin-pairing arrangement of the atoms which yields a covalent
bond. The information about the two different possibilities
is given only by C but not by (r). The charge distribution (r)
is the result but not the origin of the bond formation which
Journal of Computational Chemistry
can only become fully understood when the wave function is
considered.
An important contribution to the understanding of the physical
mechanism of the chemical bond was made by Ruedenberg.18 This
author showed that the kinetic energy plays a paradoxical role in
the chemical bond formation in H2 and H 2 . According to the virial
theorem, the kinetic energy T and the potential energy V of a mole-
cule at equilibrium are related as E V
2T. It seems logical
that the energy lowering upon formation of a chemical bond is
driven by a decrease of V and an increase of T. Ruedenberg has
shown that it is actually a decrease of T which accompanies the
charge accumulation in the bonding region, and that the increase
of T comes from the intraatomic compression of charge in the nal
stadium of the bond formation.18
While the wavefunction C is recognized as the fundamental
quantity for understanding the chemical bond, it is premature to
conclude that a quasiclassical18a treatment of the interatomic inter-
actions in terms of classical electrostatic laws using eq. (4) from
Scheme 1 does not yield a strong chemical bond. It has been
pointed out already in 1968 by Hirshfeld that the very weak quasi-
classical attraction in H2 is atypical for diatomic molecules.19
Spackman and Maslen published in 1984 the results of quasiclassi-
cal interaction energies in 147 diatomic molecules which were cal-
culated through integration over the undisturbed spherically sym-
metric charge distributions of the atoms.20 The interaction energy
was found to be strongly attractive in all molecules except H2. A
striking example is N2 whose bond was also recently analyzed by
us. The quasiclassical interaction energy of dinitrogen given by
eq. (2) of the classical ansatz for dinitrogen was calculated to be

313 kcal/mol attractive which is more than the bond dissociation
energy (calculated value De 241 kcal/mol, experimental value
De 229 kcal/mol)!21 While H2 is a good example to demonstrate
the importance of resonance, it is also deceptive because covalent
bonds of the heavier atoms often possess strong contributions from
the quasiclassical attraction between the atomic charges . This
comes from the electronic charges whose interactions can not be
described with a pointcharge model when the atoms come closer
to each other. The deviation of the quasiclassical interaction
between electrons from Coulombs law can lead to signicant
attraction between neutral atoms. This has been explained and dis-
cussed in the literature.15,22
The above reasoning suggests that there are two terms which
can be identied as useful unicorns for explaining a chemical
bond A

B. These are the quasiclassical electrostatic interaction
between nuclear and electronic charges q of A and B and the
resonance term C(A)C(B). It is tempting to identify the two
terms with the two types of chemical bonds which were already
distinguished by Lewis as polar and non-polar bonds illustrated
by potassium chloride and methane, respectively.4 In modern lan-
guage these are ionic and covalent bonds. Most chemists would
probably agree with the assignment. But as mentioned above, the
quasiclassical attraction can also be very strong in bonds which
are considered as purely covalent. There are even covalently
bonded molecules which would not be stable without quasiclassi-
cal attraction. The energy decomposition analysis of chemical
bonds in nonpolar molecules showed that the interatomic attrac-
tion in N2 which comes from the quantum theoretical resonance
of the wavefunction is stronger (
730 kcal/mol) than the quasi-
DOI 10.1002/jcc
 Unicorns in the World of Chemical Bonding Models 19

Scheme 1

classical attraction (
313 kcal/mol), but the former attraction is
compensated by strong Pauli repulsion (802 kcal/mol) which is
a third important term for understanding chemical bonding.21
Pauli repulsion is a quantum theoretical phenomenon which does
not play a role in H2 but it becomes very important for most
other molecules. Thus, the quantum theoretical terms which are
the reason for the strong chemical bond in H2 are actually repul-
sive in N2!
The quantum theoretical postulate named after Wolfgang Pauli
requires that any two electrons must have at least one quantum
number which is different from each other, i.e. a proper wave
function must be antisymmetric with respect to the exchange of
(space and spin) coordinates. This has a dramatic effect on the
potential energy curve for the interaction between two electrons.
Figure 3 shows three different curves for e-e interactions.
One curve (solid line) gives the classical electrostatic repul-
sion which is calculated using Coulombs law for point charges.
The second curve (dotted line) gives the quasiclassical repulsion
between two electrons in 1s hydrogen orbitals ( 1.0) given
by eq. (1):
Z

Ee-e quasiclassical 1  2 =r12 d1 d2 : (1)
It becomes obvious that the e-e repulsion at distances r < 2 A is
less than what is calculated from Coulombs law. We want to

Journal of Computational Chemistry DOI 10.1002/jcc

20 Frenking and Krapp Vol. 28, No. 1 Journal of Computational Chemistry
Figure 3. Calculated interaction energies between electrons as a
function of their distance r12. (a) Repulsion between two electrons
calculated classically DEelstat(classical) q1  q2/r12 (solid line);
quasiclassical repulsion between two electrons in 1s orbitals DEelstat
$ 1  2/r12 d 1d 2 (dotted line); Pauli repulsion between two
electrons with the same spin in 1s orbitals DEPauli (dashed line).
emphasize that the curve for the quasiclassical repulsion
between electrons signicantly depends on the shape and the
size of the occupied orbitals.22b The third curve (dashed line)
gives the repulsive energy which comes from the antisymmetr-
isation of the product wave function C1C2 where C1 and C2 are
1s hydrogen orbitals which are occupied with electrons possessing
the same spin. Note that, in the bonding region between 1 and 2
A, the curve for the Pauli repulsion increases much more sharply
than the quasiclassical electron repulsion. This is in the same
region where the two curves for the electron-electron repulsion
describing the classical and the quantum theoretical behavior
begin to diverge. Moreover, as mentioned above (see also the
curve for E11 in Fig. 2), the overall electrostatic interaction in
molecules in the bonding region is attractive. The crucial term
which is responsible for repulsive interactions in chemical bonds
except in two-electron systems such as H2 is the Pauli repulsion.
The three terms (a) quasiclassical electrostatic interaction, (b) res-
onance, and (c) Pauli repulsion give a complete picture of the
Journal of Computational Chemistry
interatomic interactions which yield a chemical bond. The parti-
tioning of the binding interactions into the three expressions thus
yields useful unicorns for discussing chemical bonding.
The important role of the quasiclassical electrostatic attrac-
tion in chemical bonds of heavier main group atoms which have
valence p orbitals can be demonstrated by calculating the elec-
tronelectron and nuclearelectron interactions in a ctitious
diatomic molecule E2 where the atom E has the nuclear charge
Z 1 and the two electrons are either in 2s or in 2p orbitals.
Figure 4a gives the calculated curves for the e-e repulsion using
eq. (1). The curves show the behavior of the e-e repulsion when
both electrons are in 2s, 2p(), or in 2p(
) orbitals. Here we dis-
cuss only the situation when both electrons are in the same type
of orbitals. The curves for the interaction between electrons in
unlike orbitals are shown and discussed in Ref. 22b.
The curves in Fig. 4a show that the 2p()-2p() repulsion
(blue dotted line) is always larger than the 2s-2s repulsion (red
line) at any nite distance. The former repulsion is even stronger
than what is calculated by Coulombs law for point charges
(black line) at distances >*1.9 A. The curve for the 2p(
)-
2p(
) interaction (blue dashed line) on the other hand shows
weaker repulsion than all other terms at distances r >*1.0 A.
At this distance it crosses the 2s-2s curve and it converges to
the same value as the 2p()-2p() repulsion when r 0 A. Note
that the 2s and 2p orbitals converge to different values for the
electron repulsion.
Z

EN-e quasiclassical
q1 2 =r12 d2 : (2)
Figure 4b gives the curves for the quasiclassical attraction between
a nucleus N with the point charge q 1 and an electron in a 2s
or 2p orbital which are calculated using eq. (2). The curves for the
N-2p() (blue dotted line) and N-2p(
) attraction (blue dashed
line) converge toward the same value at r 0 A but the shape of
the curves are quite different. The N-2p() attraction is stronger
than the N-2p(
) attraction and the N-2s attraction (red line) at any
nite distance. While the other nuclear-electron curves exhibit a
steady increase of the attraction at shorter distances, the N-2p()
attraction attains a maximum value at r *0.5 A but then it
decreases and nally approaches the same value as the N-2p(
)
attraction when r 0 A. The curve for the point-charge model
(black line) shows larger attraction than the N-2p(
) and N-2s
attraction at nite distances while the N-2p() attraction is stronger
than the classical interaction at distances r > *1.1 A. Figure 4c
displays the curves which give the sum of the e-e, N-e, and N-N
interactions. It becomes obvious that the potential energy curve
has only a rather small energy minimum when the electrons are in
2s orbitals (red line). The situation is similar to the H2 molecule
where the electrons are in 1s orbitals (see the curve E11 in Fig. 2). The
quasiclassical potential energy curve is even purely repulsive when
the electrons are in 2p(
) orbitals (blue dashed line), i.e. when the
electrons form a
bond. However, the curve for a 2p()-2p() 
bond (blue dotted line) exhibits a deep energy minimum of nearly
100 kcal/mol at r *1.1 A. This means that nonpolar covalent
bonds between atoms which have occupied p() orbitals should
have strong bonding contributions from quasiclassical electrostatic
attraction. This is further discussed below.
DOI 10.1002/jcc
 Unicorns in the World of Chemical Bonding Models 21

Figure 4. Calculated attraction and repulsion between two charged species with the electron in a 2s or
2p orbital. (a) Electronelectron repulsion: classical repulsion between two point charges DEelstat(classi-
cal) q1  q2/r12 (black full line); quasiclassical repulsion between two electrons DEelstat $ 1  2/
r12 d 1d 2 in orbitals: 2s-2s (red full line); 2p()-2p() (blue dotted line); 2p(
)-2p(
) (blue dashed line).
(b) Nuclearelectron attraction: classical attraction between two point charges DEelstat(classical)
q1
 q2/r12 (black full line); quasiclassical attraction DEelstat
q1 $ 2/r12 d 2 for: N-2s (red solid line); N-
2p() (blue dotted line); N-2p(
) (blue dashed line). (c) Sum of the quasiclassical attractive and repulsive
interactions in a model two-electron diatomic molecule with nuclear point charges Z 1. The electrons
are in 2s orbitals (red solid line); 2p() orbitals (blue dotted line); 2p(
) orbitals (blue dashed line). [Color
gure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

What inuence did quantum chemistry exert on the appear-
ance of unicorns in the world of chemical bonding models? Ex-
amination of present day chemistry textbooks shows that chemical
bonding is explained using a combination of classical heuristic
bonding models with quantum chemical reasonings. The latter are
often given as ad-hoc explanations which are derived from vari-
ous partitioning schemes and arbitrary denitions of quantum
chemical terms which can lead to conicting explanations. Two
pertinent examples are the controversies about the explanation for
the staggered equilibrium conformation of ethane and the question
about the triple bond character of heavy atom homologues of
alkynes.23 An alternative view which has been strongly advocated
by Findlay24 and more recently by Cortes-Guzman and Bader25
calls for abandoning the historical chemical models which do not
come out of the fundamental principles of quantum mechanics.
The heuristic chemical approaches which he discarded as obsolete
should be replaced by new approaches which strictly follow rigor-
ous fundamental principles. Slaters position has been called The
View from Physics as opposed to The View from Chemistry
for which the name of Charles Coulson is standing.23 Coulson
demanded that the role of quantum chemistry should be to help
understanding the classical chemical concepts and to show what
their essential features are in chemical behavior.26
The latter philosophy has been adopted by Roald Hoffmann
who made a great impact on chemical bonding models by pav-
ing the way for using MO models like the Woodward-Hoffman
rules and his later work until today.15,17 New symbols were
added to the standard alphabet of chemical bonding models
like the famous green/blue
orbital sketches.15 New unicorns
were borne from MO theory like through-bond and through-
space interactions27 and hard and soft acids and bases.28 There
is a gap, however, between the approximate MO models and
the physical mechanism of the bond formation which needs an
accurate quantum mechanical treatment of the molecule. Such
a gap is no longer acceptable at the present time when mole-
cules with up to *100 atoms of the entire periodic system,
including very heavy atoms that need relativistic methods, can
be calculated with chemical accuracy competing with experi-
mental investigations. In our view, ve conditions should be
fullled by a chemical bonding model that is acceptable in
2006:
1. It should be derived from accurate quantum chemical calcu-
lations.
2. The terms which are used for describing the chemical bond
must be mathematically unambiguously dened.

Journal of Computational Chemistry DOI 10.1002/jcc

22 Frenking and Krapp Vol. 28, No. 1 Journal of Computational Chemistry

3. The dened terms yield numerical results that must not sig- Table 1. Energy Decomposition Analysis of the CarbonCarbon Bonds
nicantly change at different levels of theory. in Ethane, Ethene, and Ethyne at BP86/TZ2P.
4. The terms must be interpretable in a plausible way.
5. The terms should be useful for explaining chemical phenom- C2H6 C2H4 C2H2
ena such as structure and reactivity with a wide range of
applicability for electronic ground and exctited states. Sym D3d D2h D?h
DEint
114.8
191.1
280.0
DEPauli 201.6 281.9 255.4
It is clear that conditions 4 and 5 are the most critical ones
DEelstata
130.9 (41.4%)
181.6 (38.4%)
147.5 (27.6%)
because the interpretation of the terms is subject to some arbitra- DEorba
185.5 (58.6%)
291.4 (61.6%)
387.9 (72.4%)
riness. We think, however, that the sheer complexity of chemical DEb
175.5 (94.6%)
212.2 (72.8%)
215.5 (55.6%)
phenomena demands denitions and interpretations that are help- DE
b
10.0 (5.4%)
79.2 (27.2%)
172.4 (44.4%)
ful as classication schemes, for designing new experiments and DEprep 21.7 12.9 32.8
for qualitatively predicting their outcome. The difference to clas- De 93.1 178.2 247.2
sical heuristic models is that the latter are based on assumptions D0c 83.4 (89.9 6 0.5) 168.3 (175.4 6 2) 238.7 (230.9 6 2)
and correlations with experimental observations that may or may
not be justied. Useful quantities like covalent bonding or multi- Energy values in kcal/mol.
a
ple bonding would not be so controversial anymore if agreement The % age values in parentheses give the contribution to the total
attractive interactions DEelstat DEorb.
is reached for a denition which fullls the above requirements. b
The % age values in parentheses give the contribution to the orbital
Our reasoning is in the spirit of Ruedenberg who wrote in his interactions DEorb.
article The physical nature of the chemical bond: c
Experimental values have been taken from Ref. 33.
Many of these interpretations certainly are not physical
in an operational sense, i.e. they have no direct relation-
ship to specic experimental observations. They are how-
possible to dene multiple bonding character in molecules which
ever physical in the sense that they try to provide a
have mirror symmetry. Examples for EDA calculations of chem-
complete set of physical pictures which furnish a correct
ical bonds are given in Table1 which shows the data for the
facsimile of the mathematical workings of the Schro-
C

C bonds in ethane, ethene, and ethyne.
dinger equation.18a
The EDA data give a quantitative estimate of the
bonding
In other words, unicorns may become tamed by demanding contribution in ethene (27.2%) and ethyne (44.4%) which agrees
that their behavior does not violate physical laws, but they with the general expectation which comes from classical bond-
should not be doomed to extinction because they are not object ing models. The small
contribution to the C

C single bond
of physical reality. in ethane (5.4%) gives the hyperconjugation and the relaxation
One approach which fulls (One referee pointed out that the of the
orbitals of the methyl fragments after bond formation.
EDA results do not fulll condition 1 because the calculations The data also show that the quasiclassical contribution to the
are performed using DFT methods which are aficted with the carboncarbon bonds which comes from the DEelstat term is
electron self-interaction error (SIC). This is true, but there are rather large. The percentage share of DEelstat to the attractive
presently no accurate DFT methods available which are free of interactions is between 27.6% and 41.4%. Note that the absolute
SIC.) the above conditions is the energy decomposition analysis value of the electrostatic attraction in ethane (
130.9 kcal/mol)
(EDA) which was developed by Morokuma29 and Ziegler and is larger than the total interaction energy (
114.8 kcal/mol).
Rauk30 and then modied in the program ADF.22,31 It has been The large contribution of DEelstat to nonpolar bonds becomes
used by us in systematic studies of the chemical bond in transi- obvious from Fig. 5 which shows the EDA results for N2 at dif-
tion-metal compounds and in main group molecules.32 The EDA ferent NN distances. The p() orbitals of the nitrogen atoms in
uses those three unicorns which are mentioned above as central the 4S ground state are singly occupied. According to the above
terms for the classication of a chemical bond: (a) quasiclassical discussion a strong contribution from quasiclassical attraction to
electrostatic interaction DEelstat, (b) resonance interaction DEorb, the NN bonding should be found. Figure 5 shows that the
and (c) Pauli repulsion DEPauli. Since the resonance is calculated curve for the electrostatic attraction has indeed a deep minimum
through the relaxation of the orbitals the term is called orbital with a maximum value of *450 kcal/mol at the very short bond
interaction. The three terms are calculated in a well-dened three- lengths of *0.85 A. The clearly longer equilibrium distance of
step procedure where a chemical bond A

B is analyzed in terms r(NN) 1.102 A comes from the onset of the Pauli repulsion.
of instantaneous interactions between the frozen fragments A and The power of the EDA has been demonstrated by its applica-
B. The sum of the three terms DEelstat DEorb DEPauli gives tion to controversial topics such as the multiple-bond character
the interaction energy DEint. The bond dissociation energy De is in (CO)4Fe-GaCp*34 and the strength of the conjugation and
given (with opposite sign) by the sum of DEint and the prepara- hyperconjugation in 1,3-butaydiyne and related compounds.35
tion energy of the fragments A and B from their equilibrium New answers to the questions why CO has a higher bond disso-
structure to the geometry in A

B. Further details are given in ciation energy than N221 and why F2 has a weaker bond than
the literature.22,31 Cl232b have been given which are in agreement with the physical
The EDA makes it possible to dene covalent (orbital) and mechanism of the bond formation. The EDA was also used to
classical electrostatic contributions to a chemical bond. It is also give an explanation for the unusual structures which are exhib-

Journal of Computational Chemistry DOI 10.1002/jcc

 Unicorns in the World of Chemical Bonding Models 23

Figure 5. Energy contributions DEelstat, DEPauli, and DEorb to the total interaction energy DEint in N2
as a function of NN interatomic distance. [Color gure can be viewed in the online issue, which is
available at www.interscience.wiley.com.]

ited by the heavier group-14 analogous of acetylene E2H2 (E
Si
Pb).36 The EDA is but one example of a chemical bonding
model which fullls the above ve requirements. It serves as a
bridge between the heuristic bonding models of classical chemis-
try and quantum chemical insight into the chemical bond. Like
other models it has its strength and its weakness which indicate
the scope and the limitation of the approach.
One critical point of the EDA is the fact that the polarization
of the fragment charges is not explicitly considered. In the origi-
nal Morokuma scheme29 the orbital mixing is divided into the
intra-fragment excitation (polarization) and the inter-fragment
term (charge transfer). This has been criticized, because the
terms do not properly converge with the extension of basis set.37
The EDA avoids the problem which means that the polarization
is included in the orbital interaction term.
Another critical point of the EDA is the choice of the inter-
acting fragments which are used for analyzing a chemical bond.
The choice of the fragments is in most cases trivial when nonpo-
lar bonds are analysed,21b but for polar bonds it can be difcult
to choose proper fragments. Since the results of the EDA
strongly depend on the choice of the fragments it is important to
recognize that the particular data and thus the interpretation are
valid only with respect to the chosen fragments. For example,
the EDA results for the Li

CH3 bond differ signicantly when
either neutral fragments Li and CH3 or charged fragments Li
and CH3
are employed.38 An alternative energy decomposition
analysis which avoids this problem has recently been introduced
by Pendas.39 It uses the atomic basins dened by the topological
analysis of the electronic charge40 as interacting fragments.
Since the latter do not overlap the results of the energy partition-
ing necessarily differ a lot from the EDA results. Future studies
will show the merits of this and other approaches.
There is a future for unicorns in chemistry even after quan-
tum theory has been introduced, because the territory of chemi-
cal bonding requires a simple language which is spoken and
understood in the different communities of experimental chemis-
try. Quantum chemistry has imposed some restrictions to den-
ing unicorn species, but the essential features of the heuristic
bonding models will survive the attack even of their most noto-
rious hunters who fail to recognize the difference between chem-
istry and physics.
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DOI 10.1002/jcc