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bonding in terms of classical lone pairs and two-center bonds, as well as multi-center delocalized bonds.
DOI: 10.1039/c3cp50350j
demonstrate the versatility of the method by applying it to several systems featuring both localized and
Here we extend the domain of AdNDP to bulk materials and interfaces, yielding SSAdNDP. We
many-center chemical bonding, and varying in structural complexity: boron a-sheet, magnesium diboride
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I. Introduction
The lone pairs and two-centered bonds of Lewis structures form
the basis of our qualitative understanding of chemical bonding.
Due to their simplicity and wide applicability, Lewis structures
are widely used and taught throughout chemistry, in spite of
their known limitations in describing delocalized interactions.
Such limitations can be overcome by using molecular orbital
(MO) theory, which provides a more rigorous description of
molecules and forms the basic language of much of quantum
chemistry. However, the resulting canonical molecular orbitals
are, in general, delocalized over the whole molecule and thus
hard to interpret within the chemically intuitive framework of
Lewis theory. As a result, there is a need for techniques to
interpret MO calculation results within a localized bonding
perspective. While a wide variety of such techniques exist, only
a handful are also applicable to systems with periodic symmetry, specifically bulk and surface structures.
Among these existing approaches, delocalization (and corresponding localization) indices (LI/DI) provide one such quantitative
description of such multi-center bonding interactions.1,2 In this
a
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in bulk materials. LMO methods exploit the invariance of the
wavefunction under unitary transformation to localize the
orbitals under a given metric. However, no unique localization
criterion can be defined, and each yields slightly dierent
results and interpretations. Nonetheless, these techniques have
found wide utility in studying molecular systems and have been
extended to periodic systems via maximally localized Wannier
functions.12,13 Although one-, two-, and many-center bonding
are inherently treated on an equal footing, the resulting
localized orbitals are not rigorously related to bonds involving
specific atomic centers. Rather, orbitals are generally localized
to some region of space and then (frequently) interpreted in
terms of specific bonding interactions or lone pairs once
again, providing no direct mapping to the powerful, intuitive
(and often predictive) Lewis-like framework.
In contrast to the above methods, Natural Bond Orbital
(NBO) analysis1417 constructs an optimal Lewis-like representation of bonding based on the underlying electronic structure
calculation. The analysis is natural in that the bonding orbitals
are determined directly as eigenvectors of the systems density
matrix (or portions thereof). Basing the analysis in the density
matrix ensures a rigorous foundation for the orbitals identified.
While this limits the bonds to two-electron interactions, it allows
for the results to be interpreted within the classical Lewis picture
of electron pairing. Additionally, many electron bonding motifs,
such as three-center four-electron bonds, can be understood using
a resonance representation of two-electron bonds; for a detailed
discussion, see ref. 14. In NBO, lone pairs and bonds are
constructed as linear combinations of orthogonal hybrid orbitals
centered on atoms within the molecule. While traditionally
restricted to molecular systems, NBO was recently extended to
periodic systems, allowing for the analysis of chemical bonding in
bulk materials and interfaces.18
While, in principle, the NBO algorithm can be generalized to
many-centered bonding, the extension is nontrivial and existing implementations are limited to two- and three-centered
bonds. In some cases, this limitation can be partially circumvented by introducing the concept of multiple resonance structures via Natural Resonance Theory.1921 However, there is a
need for an analysis technique capable of explicitly identifying
multi-center bonding motifs alongside the traditional Lewis
structure elements of lone pairs and bonds, especially in
periodic systems where the number of potential resonance
structures grows rapidly. Adaptive Natural Density Partioning
(AdNDP) is an extension of NBO that oers a natural description of both localized (two-centered) and delocalized (manycentered) bonding.22 AdNDP has been successfully applied to a
variety of molecular systems, including: prototypical organic
aromatic compounds,23,24 metalloorganic and inorganic
complex compounds,25,26 pure and mixed boron clusters,2737
and gold nanoparticles.38,39
Here, we present an extension of AdNDP to periodic systems.
We demonstrate the scope of the newly developed solid
state AdNDP (SSAdNDP) by applying it to several representative
bulk systems featuring both traditional localized and manycenter bonds.
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II. Theory
We begin with a brief review of the standard AdNDP process as
applied to molecular systems; complete details can be found
elsewhere.22 AdNDP calculations begin with the real space
density matrix, PAO, expressed in a localized atomic orbital
(AO) basis set that is obtained from the underlying electronic
structure calculation. The density matrix is then transformed
into the Natural Atomic Orbital basis, PNAO, which is an orthogonal
atom-centered basis that is maximally occupied for the given
molecular environment. The details of this transformation are
given in ref. 16. The density matrix in this basis straightforwardly
provides atomic populations in what is known as Natural Population Analysis (NPA).16
Bonds are identified by analyzing various atomic subblocks
of PNAO. For a given number of centers, n, all possible n-tuples
are first enumerated. For each tuple, the corresponding n-atom
subblock of PNAO is extracted and the eigenvalues/eigenvectors
of this matrix are calculated. Each eigenvector with occupation
(eigenvalue) above some pre-determined threshold (usually near
two) is identified as an n-center two-electron bond. Contributions
from all identified n-center bonds are then removed from the
density matrix to prevent the double counting of their density in
higher-center bonds. The process is repeated for n + 1-center bonds
and iterated until all electron pairs have been accounted for. This
ascending structure guarantees that localized interactions are
properly identified. Note that selection of appropriate occupancy
cutos is extremely important, since the designation of n-center
bonds directly aects the classification of n + 1-center bonds.
The goal is to obtain the most localized bonds, with occupancy
near two and symmetry consistent with that of the system.
. .k)
The lth bond thus obtained for a given tuple (ij. . .k), |h(ij.
i,
l
a
can be thought of as a linear combination of hybrids, |Zl i, on
each center, a, contained in the tuple, with some coecients cl,a.
E ij:::k
X
ij:::k
cl;a Zal ;
hl
a
where
collection of all NAO functions
in the
on center a. In AdNDP, unlike
the NBO procedure, the hybrids on a given center in dierent
bonds are not rigorously orthogonal. Although this leads to a slight
overestimation of bond occupancies, relaxing the orthogonality
requirement maintains the symmetry of the obtained bonds
and ensures that, for a given n, the results are independent of
the order in which the tuples are searched.
II.1.
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P00;NAO
ii
6
6 0s;NAO
6P
6 ji
6
6
6
:::
4
0t;NAO
Pki
P0s;NAO
ij
:::
P00;NAO
jj
:::
:::
:::
:::
:::
P00;NAO
kk
0st;NAO
Pkj
P0t;NAO
ik
0ts;NAO
Pjk
3
7
7
7
7
7:
7
7
5
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ij...k
P~0r;NAO
P0r;NAO
Nl
cl;i cl;j jnil ihnjl j:
ij
ij
Fig. 1
Boron a-sheet
The a-sheet is the most stable all-boron planar structure predicted computationally thus far.5156 Its peculiar geometrical
structure of alternating centered hexagons and vacancies has
attracted significant interest.5760
A PW DFT calculation was performed on the geometry of the
predicted lattice structure51 using an 11 11 1 k-point grid.
The cc-pVTZ AO basis set61 was used to represent the projected
PW density.
We utilize SSAdNDP in conjunction with a general (nondirected) search to elucidate the bonding in the boron sheet.
The resulting chemical bonding pattern is presented in Fig. 1b.
There are 8 boron atoms and 24 valence electrons per unit cell,
thus we anticipate 12 two-electron bonds. Six three-center twoelectron (3c2e) s-type bonds with occupation number (ON) of
1.9 |e| were found on every boron triangle bordering a vacant
hexagon. Three 4c2e s bonds were revealed in the rhombi
connecting two centered hexagons. Thus nine electron pairs
(a) Structure and (b) SSAdNDP chemical bonding pattern of boron a-sheet. The unit cell is shown in black.
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were found via general search over three and four centers,
leaving three more to be accounted for. A further general search
became computationally demanding, and frequently yielded
bonding motifs that were not commensurate with the symmetry of the underlying lattice. Presumably, linear (resonance)
combinations of such symmetry-breaking bonding motifs commensurate with the lattice symmetry could be generated. However, such a complex resonance representative is not easily
interpretable within a simple Lewis-like framework. Therefore,
a user-directed search was utilized to probe the next smallest
tuple which maintains the symmetry of the system a six-center
fragment over the hexagonal hole. We found a p-bond with
a ON = 1.5 |e| over this hexagonal vacancy. Similarly, two 7c2e
p-bonds were found via directed search over each centered
hexagon in the unit cell with ON = 1.6 |e|.
The bonding motifs found in SSAdNDP are in qualitative
agreement with those obtained in a previous molecular AdNDP
study performed using cluster models.58 The clusters multicenter p-bonds had higher ONs (1.72 for the 6c2e bond and
1.97 |e| for the 7c2e bonds), which is probably due to the less
accurate treatment of boundary conditions. Quantitative comparison
is further obscured by the use of a hybrid functional in the
cluster study and the charged nature of the clusters.
IV.2.
Magnesium diboride
Fig. 2 (a) Structure, (b) SSAdNDP chemical bonding pattern and (c) alternative
8c2e p bond representation of the 6c2e p bond in magnesium diboride. The
unit cell is shown in black.
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Fig. 3
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(a) Structure, (b) SSAdNDP chemical bonding pattern for the Na8BaSn6 Zintl phase. The unit cell is shown in black.
V. Conclusions
Solid State Adaptive Natural Density Partitioning (SSAdNDP)
yields a localized and inherently chemical representation
of bonding in terms of localized Lewis-type lone pairs and
two-center bonds as well as delocalized (multi-center) bonds in
periodic systems. Our extension of AdNDP to periodic systems
via SSAdNDP allows us to elucidate the bonding in bulk
materials and interfaces in a natural, chemically-intuitive fashion, yielding insight into the fundamental origins of their
structure, properties, and reactivity.
We have applied this newly developed method to several
representative systems, featuring both localized and delocalized bonding. In the all-boron a-sheet, SSAdNDP reveals not
only prototypical boron 3c2e s bonds, but also additional,
unexpected bonding: three 4c2e s bonds, one 6c2e and two
7c2e p bonds per 8 atom unit cell. Analysis of MgB2 reveals a
graphene-like electronic structure of the boron sheet, with
three 2c2e s-bonds and one delocalized p-bond. The latter is
perturbed by the neighboring Mg layers and as such can be
represented as either a 6c2e or an 8c2e bond. For Na8BaSn6
SSAdNDP reveals a cyclopentadienyl anion like structure, with
three delocalized p-bonds on each Sn five-membered ring. The
resulting chemical bonding patterns are consistent with symmetry and chemical intuition, providing a useful interpretation
of chemical bonding in complex systems.
We anticipate that SSAdNDP will be as helpful in analyzing
both localized and multi-center chemical bonding in solids,
providing a powerful compliment to standard Natural Bond
Orbital analysis in circumstances where non-classical manycenter bonding may play a crucial role.
Acknowledgements
The authors acknowledge partial support of this research
from the National Science Foundation (CHE-1057746, AIB),
the donors of the American Chemical Society Petroleum
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