Pushing The Limits of Chemical Bonding

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Home > Volume 92 Issue 38 > Pushing The Limits Of Chemical Bonding
Volume 92 Issue 38 | pp. 10-13

Issue Date: September 22, 2014
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Pushing The Limits Of Chemical Bonding

Conference highlights how computational and experimental chemists are applying bonding models to more
complex systems
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By Stephen K. Ritter
Cheerios-Fed Fungi Yield Biofilm
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Department: Science & Technology
News Channels: Biological SCENE, Materials SCENE, Nano SCENE
Keywords: chemical bonding, valence bond, molecular orbital, hydrogen bond, computational chemistry
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NANOWHEEL
Chemists used the AdNDP theoretical model to calculate the bonding orbitals for TaB10 (left), an
observed gas-phase planar cluster.
Credit: Alexander Boldyrev
Chemical bonding is the heart of chemistry, according to Alexander I. Boldyrev, a

chemistry professor at Utah State University who spends his time thinking about how
molecules are put together. But it is still not well-defined. We need to develop the
breadth of the concept and make it as rigorous as we can, yet as simple as we can, so it
is more powerful and more useful.
BOND BUNDLES
This charge-density map depicts a cross
section of the interface between iron (red
atoms) and a metal-carbide additive (green
and black) in steel. The red and yellow
regions in the middle are the most
important in controlling interfacial strength.
Alloying elements that decrease the
number of electrons in the red region
improve the steels fracture resistance.
Credit: Courtesy of Mark Eberhart
Boldyrev put that challenge to a group of some 50 of the worlds leading experts on chemical bonding. The occasion was the
opening session of the International Conference on Chemical Bonding, which was held on the Hawaiian island of Kauai
during the final week of July. Its a meeting Boldyrev helped start last year to bring theoreticians, spectroscopists, and
experimentalists together to forget business as usual and think about branching further out into underexplored fields in bonding
such as biochemistry and materials science.
Chemists have developed many bonding models over the years in trying to comprehend the tussle between attractive and
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23/10/14 17:36
repulsive forces that hold atoms together in molecules. These models help researchers visualize changes in atomic and molecular
orbitals that give rise to the many types of bonds.
Armed with knowledge of bond energies and other parameters, chemists can better orchestrate chemical reactions, determine
how biomolecules respond to myriad chemical signals in the body, and monitor materials to see how they answer to external
forces such as light or an applied current or magnetic field.
The end goal, Boldyrev emphasized, is the ability to better understand chemical behavior and advance the design and synthesis of
chemicals and materials.
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H-BONDING REVEALED
NEGATIVE H-BOND
These calculated 2-D contour and 3-D overlap diagrams depict unexpected
FHOCO2 antielectrostatic hydrogen bonding.
Credit: Frank Weinhold
In 2013, researchers used atomic force microscopy to

see intricate details of intermolecular interactions of
8-hydroxyquinoline on a copper surface; C = gray, H =
white, O = red, N = blue.
Credit: Science
Wasting no time, Frank A. Weinhold of the University of Wisconsin, Madison, led off the conference by asking an oftenrepeated question: What is a hydrogen bond? Its a question fraught with controversy that Weinhold nevertheless feels
compelled to pursue.
H-bonds give water its room-temperature liquid properties, lower or raise energy barriers and thus speed or slow reactions, and
hold together the three-dimensional shapes of DNA, proteins, and synthetic materials such as some types of polymers. Better
understanding of these weak interactions could enable chemistsin particular those in pharmaceutical researchto use
H-bonding as a catalyst design tool or to design drugs for better interactions with their targets.
But current chemical bonding descriptions for H-bonds leave a lot to be desired, Weinhold believes. The dipole-dipole concepts
that fill current textbooks and are used for molecular dynamics simulations of H-bonding are inadequate, he said. Still, just
mentioning H-bonding raises the dander of many bonding specialists who cant agree on whether it is a true bonding phenomenon
or not. Weinhold would like to resolve the issue once and for all.
An H-bond is typically described as a weak electrostatic attraction
between an electronegative atom or a polar molecule and a
hydrogen atom that is covalently bonded to an electronegative atom,
typically oxygen or nitrogen. The interaction is not strong enough to
be considered a conventional covalent bond, but some scientists
contend that bonding models as well as spectroscopic evidence
indicate that H-bonds must contain some covalent character. Others
think it is purely an electrostatic interactionand not a bond at all.
To address this disparity, in 2011 a committee of the International
Union of Pure & Applied Chemistry proposed a broader definition
of H-bonding along with a set of criteria that can be used as

evidence for H-bonds. And last year, researchers used atomic force
microscopy to capture stunning images of H-bonding for the
first time. The wispy lines of electron density between
8-hydroxyquinoline molecules on a copper surface lend credence to
a higher level of bonding.
For his part, Weinhold created a model for a surprising class of
H-bonded complexes between ions of like charge, something so
unthinkable that people havent looked for them before. These
anion-anion and cation-cation interactions exhibit the characteristics
of H-bonding despite the powerful opposing electrostatic forces,
Weinhold said. If H-bonds still occur in these complexes, he
reasoned, there must be some type of covalent interaction involved.
Weinhold used the Natural Bond Orbital analysis method he
developed to analyze potential energy curves for the ion-ion
interactions. Natural bond orbitals are designed orbitals with
properties intermediate to the atomic orbital properties of atoms and
the combined molecular orbitals of molecules. They are used to
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Bonding Nuggets
These digests highlight a selection of the research
presented during the International Conference on
Chemical Bonding.
C2 Stays Single
Thom H. Dunning Jr.
Pacific Northwest National Laboratory
Dunning related how generalized valence bond
theory, which draws on properties of both atomic
orbitals and molecular orbitals, provides a simple yet
richer description of bonding than molecular orbital
theory alone for diatomic molecules such as C2, N2,
and P2 and hypervalent molecules such as PF5 and
SF6. In C2, for example, Dunning explained that
bonding might best be viewed as only a single bond,
rather than involving multiple bonding as previous
models have suggested. The remaining six valence
electrons reside in the leftover carbon orbitals in a
high-spin coupled state.
B40 Fullerene
Lai-Sheng Wang
Brown University
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23/10/14 17:36
calculate the distribution of electron density and spot bonds in

molecules.
To test his idea, Weinhold calculated the interactions between
fluoride (F) and bicarbonate (HOCO2). It seems improbable, he
said, but short-range resonance-type covalent charge-transfer
interactions between the anions overcome the long-range
electrostatic opposition expected between ions of like charge. The
small net bond energy observed signifies that there is a bonding
interaction holding the atoms together. And the complex formed
satisfies all the accepted criteria for authentic H-bonding, Weinhold
said. Cation-cation H-bonded complexes, such as hydronium ion
with protonated aminomethanol, are also feasible.
These antielectrostatic H-bond complexes may finally put to rest the
Credit: Lai-Sheng Wang
superficial quasiclassical conceptions of H-bonding and other

resonance-type phenomena that have too long held sway in the
molecular and supramolecular sciences, Weinhold concluded.
Wang reviewed the progress his group has made

using computational studies supported by
Weinhold identifies, likely correctly, that H-bonds can exist between

anions, noted Martin P. Head-Gordon of the University of
photoelectron spectroscopy to analyze gas-phase

all-boron clusters. Molecules with up to 24 boron
California, Berkeley, who also studies H-bonding. The H-bonded

dianion complexes are not the overall (global) energy minimum,
which would represent infinitely separated anions, Head-Gordon
noted. But they do represent a local energy minimum that is trapped
from reaching complete dissociation by a large enough barrier so
that the H-bonded complexes could possibly be observed
experimentally.
atoms form planar species, after which larger

molecules start forming 3-D structures. For example,
Wang and his colleagues recently discovered B40,
an unprecedented all-boron fullerene-like cage
molecule, which is a potential semiconducting

material.
Two-Prong Analysis
But Head-Gordon took friendly exception to Weinholds argument
that the possible existence of these ionic H-bonds shows the
essential irrelevance of electrostatic contributions to H-bonding. He
also disagreed that Weinholds results should lead to skeptical
reassessment of energy decomposition analysis of H-bonding, a
method Head-Gordon uses that offers partial support to the
electrostatic view.
The fact that like charges repel explains the overall minimum where
there is no H-bond, Head-Gordon added. But in my view it does not
necessarily mean electrostatics are inessential. In fact, good energy
decomposition analysis methods, which split complex bonding
interactions up into permanent and induced electrostatics,
dispersion, and charge-transfer contributions, can provide support for
or contradict Weinholds assertion about electrostatics, Head-Gordon
told C&EN.
Helmut Schwarz
Technical University of Berlin
By combining computational chemistry and mass
spectrometry, Schwarz has been breaking new
ground in understanding the activation sites of
heterogeneous catalysts in gas-phase reactions.
Mass spectrometry on isolated species provides a
means of probing the energetics and kinetics of
reactions in an unperturbed environment, which is
typically not possible in solution-phase reactions.
The approach allowed Schwarz to study the role of
electron density in intermediates of metal-mediated
CC bond formation, and oxygen-centered radicals
in CH activation.
Phase-Switch Bonding
Weinholds view that electrostatics are also not relevant for types of
H-bonding beyond those found in ion-ion interactions is still open for
debate, Head-Gordon suggested. On the basis of his own research,
Head-Gordon thinks H-bonding typically has contributions from both
charge transfer and electrostatics, with the relative importance of
each varying, depending on details of the system. It will be
fascinating to see where this goes over the next few years, he said.
As debate about H-bonding continued off-line, other chemists took
the floor to discuss advancing the synergy between electronic
structure calculations and studying the properties of catalytic
surfaces and solid-state materials.
3 de 7
Matthias Wuttig
RWTH Aachen University, Germany
Phase-change materials such as Ge2Sb2Te5 rapidly
switch between amorphous and crystalline states,
changing their optical and electrical properties and
making them useful for optical data storage. Wuttig
showed that the crystalline state is characterized by
resonant, directional covalent bonding rather than
delocalized bonding as in the amorphous state. This
information can be used to create phase diagram
treasure maps for selecting alloy compositions in
the design of new phase-change materials.
Chemical bonding theory traditionally has been in the realm of

molecular chemistry, especially organic chemistry, conference
cofounder Anastassia N. Alexandrova of UCLA told C&EN. But
Sturdy Microalloys
that topic is perhaps considered archaic and long since done.
California Institute of Technology
Meanwhile, materials scientists have typically used either

macroscopic qualitative descriptors or nondescriptive electronic band
structure concepts and not benefited from the rationale and design
principles that arise from traditional bonding theory, Alexandrova
explained. Applying bonding theory to solid-state materials has been
underexplored. But even as capable models have become available,
By studying the multicentered bonding in borons

many polymorphs, Goddard has been able to design
boron alloys with carbon, oxygen, and other
elements. For example, B4C is a known material
William A. Goddard
that is very hard. But its also very brittle, which

prevents its use in engineering applications.
Goddard described how his team has used
23/10/14 17:36
they are not garnering much attention. Breaking this stagnation is

one of the conferences goals, she said.
computational methods to explore the mechanism of

the structural deformation that leads to B4Cs
brittleness. The researchers are designing
To set an example, Alexandrovas group is collaborating with Mark
microalloys with improved properties by further
Saeys at Ghent University, in Belgium, to study the chemistry of
adding hydrogen, silicon, or nitrogen atoms, with
unexpected square-planar carbon species that form on cobalt
silicon looking the most promising.
catalyst surfaces treated with synthesis gas. The tetracoordinated

carbon takes on the square-planar geometry as opposed to the
typical tetrahedral structure, and the aromaticity of Co4C building
Whats the Highest Oxidation

State?
blocks drives formation of nanocluster islands on the catalyst surface
Jun Li
that facilitate the reaction.
Tsinghua University, China
In industrial reactions, catalyst surfaces often undergo massive

reconstructions as the catalytic sites form and re-form via
self-organization. Saeys and Alexandrova, in partnership with Shell,
[+]Enlarge
are now able to understand the unusual bonding leading to surface

reconstruction of commercial cobalt catalysts. This bonding insight
could lead to improved catalyst stability and selectivity in the FischerTropsch synthesis of fuels and chemicals.
In another example of analyzing structure-property relationships in
materials, Mark E. Eberhart of Colorado School of Mines
described the versatility of charge-density analysis based on an
extended form of the Bader Atoms in Molecules theory of molecular
structure.
Through calculations, Eberhart is able to glue together the electronic
parameters of sets of atoms into an extended framework and create
charge-density maps. The topology of these maps provides chemical
information, with peaks (atoms), valleys (nonbonding areas), and
ridges (bonding areas) illustrating where bonds exist and how
reactive these bonds might be.
To demonstrate how the process works, Eberhart described an
analysis of high-strength steel alloyed with dispersions of titanium
carbide to determine the propensity of metal-carbide interfaces
in the material to fracture and fail. The topologies enable

Eberharts team to determine optimum positions in the materials
lattice where inserting other metals such as nickel would alter the
number of electrons in specific regions and thereby allow them to
improve the adhesive properties of the alloys. This capability will be
particularly beneficial in solids, Eberhart said, where the nature of
charge-density evolution associated with even simple processes,
such as fracturing, is understudied.
Yet another bonding model discussed at the conference is Adaptive
Credit: Inorg. Chem.
Oxidation state is a central concept in chemistry, and

the question of highest possible oxidation state has
long been a controversial topic. For elements in
neutral compounds, the highest state is thought to
be 8+, which occurs in some transition-metal
compounds, such as RuO4. Li showed through
new calculations that, despite their f electron

shell, such high oxidation states are not stable in
actinides. Because of mass-driven relativistic effects
leading to contracted 5f electron shells, actinides
such as plutonium tend to form superoxo (O2)
rather than oxo (O2) complexes and max out at an
oxidation state of 5+, such as in PuO4.
Enzyme Metal Mysteries

Crystal E. Valdez
University of California, Los Angeles
Natural Density Partitioning (AdNDP), which was developed by

Utah States Boldyrev and his colleagues. An extension of
Weinholds Natural Bond Orbital approach, AdNDP is geared toward
preserving the classical Lewis two-center, two-electron bonding
picture as much as possible. But it relies extensively on
multicentered, two-electron delocalized bonding.
[+]Enlarge
When analyzing a molecule, the researchers first localize electron

pairs in two-center bonds or as lone pairs on single atoms. They then
place the remaining electron pairs in multicentered bonds localized
on the fewest atoms possible, which could be as many as all the
atoms in the system. In doing so, the method invokes both and
aromatic and antiaromatic bonding.

For me, a chemical bond is no longer an electron pair sitting
between two atoms, Boldyrev said. It is more simply a two-electron
blob that can connect two, three, five, or more atoms. We allow the
pairs to run over whatever part of the molecule they want to occupy.
Beyond common molecules, this approach is proving useful for
determining the bonding in metal clusters and molecular systems
that are too complex for traditional bonding models. For example,
Boldyrevs team has used AdNDP to obtain bonding patterns in
all-boron naphthalene (B162), inorganic complexes such as
4 de 7
Credit: J. Phys. Chem. B
When it comes to designing catalysts, chemists

often look to enzymes as models. But enzymes dont
always work efficiently outside their cellular
environment, so chemists often tweak enzymes to
make artificial versions with the appropriate metal
charge and size, coordination geometry, and redox
potentials needed for chemical reactions. Valdez
described using a new approach, quantum
23/10/14 17:36
Tc3Cl92, and gold nanoclusters. Boldyrevs group has also
mechanics/discrete molecular dynamics
developed an AdNDP version for extended molecular
(QM/DMD) simulations, to explore what makes a
structures in bulk materials and used it to analyze the bonding
difference when switching one metal for another in
in graphene, all-boron planar sheets, MgB2 with alternating
metalloproteins. In two related natural amide
magnesium and boron layers, and intercalated inorganic materials
hydrolases (one shown) different metalszinc

versus nickelare used to catalyze similar reactions
such as Na8BaSn6.
proceeding through identical mechanisms.

I believe this is a method that eventually will enable us to draw
structures of solids by hand based on their formula, as we do now for
Predicting Crystal Structures
organic molecules, UCLAs Alexandrova speculated. From there,
Artem R. Oganov
we might eventually arrive to the intuitive interpretation of chemical
Stony Brook University, SUNY
reactivity and other properties of solid materials.

That is exactly where Boldyrev hopes the method will lead. Like
[+]Enlarge
physicists who want a unified theory to explain all matter, we

chemists would like a unified bonding theory that works seamlessly
for solids, gases, and solutions and helps explain the behavior of
organic and inorganic compounds, biomolecules, and
nanomaterials, Boldyrev said.
Chemists currently must solve structural problems for different types
of compounds by sifting through and choosing among different
models, he explained. The Lewis electron-pair model is simple, easy
to understand, and teach, Boldyrev said. However, it quickly runs
into problems if we go beyond simple molecules. What is the Lewis
structure for the tetrahedral Au20 cluster, the molecular
Credit: Artem Oganov
TaBnanowheel, or the FeSMo cluster that serves as the cofactor of

nitrogenase?
Molecular orbitals can be obtained for any chemical compound,
Boldyrev continued. But they are delocalized over the whole
molecule, which is not always descriptive of the actual bonding, and
get very complicated as the number of electrons in the system
increases.
Weinholds Natural Bond Orbital method, Baders Atoms in
Molecules approach, and the AdNDP model are all headed toward a
unified model, Boldyrev thinks. For example, Boldyrev has
successfully used AdNDP to decode the bonding in Au20 and
TaB10, though his group hasnt yet resolved the bonding in the
nitrogenase cofactor. But it should only be a matter of time before
bonding models evolve to tackle that problem as well as more
complex ones.
Researchers have long wished for the ability to

predict crystal structures of materials before they are
synthesized, which could significantly accelerate
chemical discoveries. Oganov described a
computational tool he developed to fulfill that wish.
Called USPEX, the method includes an evolutionary
algorithm to search through multidimensional energy
landscapes at different temperatures and pressures
to find stable combinations of selected elements.
Oganovs group has used USPEX to predict a new
phase of boron (-B) and an insulating and optically
transparent form of sodium, among other materials.
The researchers have prepared some of the
materials, including salt with unusual ratios of
sodium and chloride, such as NaCl3 shown.
That makes Boldyrev optimistic about the future of his field. I dont
think chemists are abandoning the concept of chemical bonding anytime soon.
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23/10/14 17:36
C&EN asked chemists who spend most of their time working with and thinking about chemical bonding to answer this question:
What do you think a chemical bond is in reality? The chemists were prompted to consider how they might describe a chemical bond
to a nonchemist, to a nonscientist, or to a family member. They were also asked to consider how a chemical bond impacts our daily
lives. Add your thoughts on the chemical bond in the comments below.
Anthony J. Arduengo III

Anthony J. Arduengo III, University of Alabama, studies the chemistry of compounds with abnormal valency
and bonding arrangements and discovered the first isolable Nheterocyclic carbene.
Humankind's ability to understand and transform matter through chemistry is as much the reason for the
success of our species as the opposable thumb and language. Whether this chemistry was mastering
combustion (fire) to release chemically stored energy (breaking and making bonds) to provide heat and
light at will, or whether one chooses a suitable material (wood or stone, for example) to construct durable
housing, tools, and devices to serve the interest of the human community, it's all chemistry. When it comes
to describing a chemical bond, I worry about being constrained by semantics, so I tend to have a rather
broad view. I've often thought about applying a definition that is energy relatedthat is, a chemical bond
must have a dissociation energy greater that X kcal/mol. But I'm not sure what constructive purpose such a
definition would serve, and I can see how it might constrain creative thought. You certainly don't want to
ever get me started talking about valency or aromaticity. I'd as soon discuss the number of angels on a
pinhead. Strangely, I'm much more comfortable discussing unusual valency, which seems to imply that I
have some preconceived notion of what valence isI don't, but I'm happy to accept the usual historical
definitions and claim all exceptions as "unusual." But when talking to a layman, I have no problem in stating
that a chemical bond is what holds materials (chemicals) together and gives them their properties.
Chemical & Engineering News

ISSN 0009-2347
Copyright 2014 American Chemical Society
Comments
Prof. C. Ramakrishnan (September 23, 2014 5:19 AM)
How about a valid universally acceptable and non-controversial parameter based criteria (such as distance, angles, orientation
etc.,) for identifying hydrogen bonds in crystallographically solved biomolecular structures, small or big?
Reply
Frank Weinhold (October 6, 2014 4:15 PM)

Following C&ENs recent coverage (Sept. 22, p. 10) of our work on anti-electrostatic H-bonding [F. Weinhold and R. A. Klein,
Angew. Chem. Int. Ed. 2014, DOI: 10.1002/ange.201405812), we were kindly informed by Profs. Ibon Alkorta (Madrid, Spain) and
Steven R. Kass (Minneapolis) of earlier experimental[1,2] and theoretical[3,4] works pertaining to doubly-ionic H-bonded species
in the gas phase that are peripherally related to our work. These works involve somewhat different species (such as large peptide
clusters) and different theoretical focus than the central What is H-bonding? question of our work, but should be recognized
(along with crystallographic evidence on bicarbonate dimer[5] previously noted) as relevant to attempted experimental and
theoretical detection and characterization of paradoxical anti-electrostatic (or electrostatics-defying3) H-bond species that
6 de 7
23/10/14 17:36
challenge current empirical modeling and pedagogy.

Frank Weinhold and Roger A. Klein
[1]S. W. Lee, J. L. Beauchamp, J. Am. Soc. Mass Spectrom. 1999, 10, 347-351.
[2]L. Feketeova, R. A. J. OHair, Chem. Commun. 2008, 4942-4944.
[3]S. R. Kass, J. Am. Chem. Soc. 2005, 127, 13098-19099; A. Shokri, M. Ramezani, A. Fattahi, S. R. Kass, J. Phys. Chem. A,
2013, 117, 9252-9258.
[4]I. Mata, I. Alkorta, E. Molins, E. Espinosa, ChemPhysChem 2012, 13, 1421-1424.
[5]D. Braga, F. Grepioni, J. J. Novoa, Chem. Commun. 1998, 1959-1960. See also ensuing discussions: T. Steiner, Chem.
Commun. 1999, 2299-2300; M. Mascal, C. E. Marjo, A. J. Blake, Chem. Commun. 2000, 1591-1592; P. Macchi, B. B. Iversen, A.
Sironi, B. C. Chakoumakos, F. K. Larsen, Angew. Chem. Int. Ed. 2000, 39, 2719-2721.
Reply
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Pushing The Limits of Chemical Bonding

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Volume 92 Issue 38 | pp. 10-13