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DOI: 10.1002/cphc.201300723
Quantifying the Nature of Lone Pair Domains
Martin Rahm* and Karl. O. Christe[a]
The lone pair lies at the heart of chemistry, and is often in
a conceptual respect the site of chemical reactivity. Here we
show how the analysis of the electron localization function
(ELF) can be improved upon by introducing intra-basin parti-
tioning. The high-ELF localization domain population (HELP), is
presented as a probe of the more chemically relevant and elec-
tron-localized regions of the ELF lone pair basin, and shown to
correlate with a range of physical properties and quantum me-
chanical constructs, such as the ESP, e and H + affinity, IP,
1. Introduction
The lone pair lies at the heart of chemistry, and is often in
a conceptual respect the site of chemical reactivity. Being an
archetypal example of a “fuzzy” chemical concept,[1] lone pairs
are routinely invoked to rationalize much and more, such as
Lewis acid–base interactions, nucleophilicity, and general reac-
tivity through “electron pushing” schemes, as well as molecular
geometry through the valence-shell electron-pair repulsion
(VSEPR) approach.[2] But how can lone pairs be characterized?
How are they different from each other, and how do they re-
flect the properties of a molecule? How do they change with
periods and groups of the periodic table?
Herein we introduce a descriptor obtained from a novel par-
titioning of the electron density that can connect the impor-
tant concept of the lone pair domain with observable molecu-
lar properties and commonly used theoretical quantities in
a quantitative and chemically meaningful way. An exhaustive
theoretical study, encompassing 45 XL13 main group mole-
cules (where X = N, P, As, Sb, Bi, O, S, Se, Te, Po, F, Cl, Br, I, At
and L = H, F and CH3), and eight highly coordinated (hyperva-
lent) fluorides (PF4 , AsF4 , SbF4 , BiF4 , BiF52, ClF3, BrF3 and
IF3.), offers validation for our approach and insight into the
nature of main-group lone pair domains. Finally, an organic
chemistry case (methyl methylcarbamate) is discussed in com-
parison with the highly explosive Bi(N3)52 double anion, exem-
plifying one of our main conclusions—that lone pair domains
are not created equal.
The concept of localized lone pairs originates from the clas-
sical (non-quantum mechanical) Lewis–Langmuir theory of
bonding.[3] Following the application of quantum mechanics to
[a] Dr. M. Rahm, Prof. K. O. Christe
Loker Hydrocarbon Research Institute and Department of Chemistry
University of Southern California, Los Angeles, CA 90089 (USA)
Fax: (+ 1) 213 740 6679
E-mail: rahm@usc.edu
Supporting Information for this article is available on the WWW under
http://dx.doi.org/10.1002/cphc.201300723.
 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
HOMO/LUMO energies, atomic charge, NBO lone pair orbitals,
and molecular geometry. A strong connection between topo-
logical density and orbital-based analysis of chemistry is intui-
tively expected, yet this is the first time that an average elec-
tron population, obtained by any localization method, can be
linked to properties of molecules. The application of HELP as
a descriptor of lone pair domains is predicted to be of general
use.
chemical bonding,[4–9] and the early realization that the Hamil-
tonian operator is invariant with respect to unitary transforma-
tion among molecular orbitals, a plethora of orbital localization
procedures were devised.[10–12] With modern use of valence
bond and hybrid orbitals (e.g. sp3) as successful tools to de-
scribe chemistry, the concept of localized electrons have
become commonplace in the minds of many chemists. Para-
doxically, the for most purposes equivalent and equally suc-
cessful delocalized description by molecular orbital (MO)
theory is also often used. The still ongoing localized–delocal-
ized “conflict” has deep historical, practical, and philosophical
roots,[13] and can be exemplified by the recent flurry of re-
sponses[14] following a suggestion to retire the hybrid
orbital.[15]
The quantum mechanical reason for pairing of electrons is
the Pauli exclusion principle, which dictates that any wavefunc-
tion must be antisymmetric with respect to the interchange of
any two electrons. Seminal work by Bader et al. showed that
the quantum mechanical requirement for electron localization
is the localization of an electrons’ Fermi hole density (the local
exclusion of same-spin density due to Pauli repulsion).[16, 17]
It was shown that near-complete localization only occurs for
core electrons, whereas molecular valence electrons are delo-
calized by nature, and generally only exhibit partial “pair con-
densation”.[16, 18] In light of this realization, which fits less well
with the traditional Lewis-picture, the successful VSEPR model
was adjusted and now relates to “electron pair domains”, in-
stead of localized pairs.[19]
We must stress that it is not the purpose of this work to
argue for or against the validity of any type of orbital descrip-
tion, and instead, we will side-step the issue by quoting Bader:
““The ability to define a set of doubly occupied localized
molecular orbitals does not imply physical localization of
the electrons into spatial pairs.” – R. W. F. Bader[17]
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Indeed, any set of orbitals, be they localized or canonical
(delocalized), are interchangeable in their description of the
electron density, 1(r). Because 1(r) is a real physical observable,
it is natural to analyze it for clues to bonding characteristics,
such as localization. However, and maybe contrary to popular
belief, 1(r) is typically a slowly decaying and quite featureless
function, without direct evidence of electron localization, for
example, lone pairs, except at nuclei. Instead, the second deri-
vate of 1(r), the Laplacian of the electron density r21(r), can
be analyzed. The Laplacian reveals subtle spatial variations in
the total density that are otherwise difficult to detect directly.
This is realized through the quantum theory of atoms in mole-
cules (QTAIM),[20] which has proven highly successful in analyz-
ing bonding in molecular and extended systems.[21, 22]
2. Identifying Lone Pair Domains: QTAIM and
ELF
QTAIM partitions molecules into atom-centered basins. The di-
viding surface between neighboring basins (atoms) is deter-
mined by the gradient field of the electron density, r1(r), that
is, by a surface corresponding to the minima in the electron
density between two atoms. The integration of 1(r) over each
such basin provides the Bader atomic charge, and the topolog-
ical analysis of 1(r) produce a set of critical points [where
r1(r) = 0] that can be local maxima, minima or saddle-points.
The values of r21(r) and 1(r) at the different critical points,
and their positions in space, provide characteristics of the
bonding between atoms in molecules. The reader is kindly re-
ferred elsewhere for detailed reviews of QTAIM’s basics, details,
and many applications.[6, 20, 23]
The Laplacian of the electron density, r21(r), has been said
to provide the physical basis for the Lewis and VSEPR
models.[24, 25] Central to this claim lies its empirical track record
of reproducing the positions of formal lone pairs, and its physi-
cally solid foundation in the local virial theorem [Eq. (1)]:
r2 ðrÞ ¼ 2GðrÞ þ VðrÞ ð1Þ
where G(r) > 0 is the electronic kinetic energy density, and
V(r) < 0 is the electronic potential energy density. Positions in
space that are dominated by potential energy, that is, where
r21(r) < 0, are defined as locations of negative charge concen-
tration (CCs). In contrast, depletion of electron density occurs
at positions that are dominated by kinetic energy, that is,
where r21(r) > 0. Valence-shell charge concentrations (VSCCs)
are in other words QTAIM’s requirement for identification of
a lone pair domain.[17] With reference to the local virial theo-
rem, VSCCs have also been equated to Lewis bases.[17]
There are many methods for calculating electron localization,
and the number of electrons in a given volume of space.
These include the pioneering work of Artmann,[26] Lennard-
Jones,[9] Daudel et al.,[8, 27] Aslangul et al.,[28] Bader et al.,[16]
Becke and Edgecombe,[29] Savin et al.,[30] Silvi et al.,[31] Kohout
et al.[32, 33] and others.[10–12, 34–37] Many of these focus on mea-
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suring the Pauli repulsion, by means of the Fermi hole density
in various ways.
As a necessary complement to QTAIM we have in this work
utilized the popular electron localization function (ELF) of
Becke and Edgecombe.[29] ELF has many interpretations, all
which provide similar results.[17, 29, 38, 39] In principle, ELF mea-
sures the local excess of kinetic energy (or same-spin pair
probability, depending on definition) due to Pauli repulsion rel-
ative to a uniform electron gas of equal density.[5, 29, 40, 41] ELF, or
h(r), ranges from 1.0 in positions where the local Pauli repul-
sion is small relative to the uniform electron gas reference, and
where an electron is alone with respect to its same spin coun-
terpart, to 1=2 where the Pauli repulsion equals that of the uni-
formly distributed electron gas reference. For h(r) values below
1
=2 the Pauli repulsion relative to the reference is high, which
can be interpreted as positions of low localization where multi-
ple electrons contribute. In the case of a single-determinant
Kohn–Sham DFT wave function the close-shell formulation[40]
of ELF reads as Equation (2):
1
ELF ¼ hðrÞ ¼  2 ð2Þ
D
1þ Dh
where [Eqs. (3)–(5)]:
1X 1 jr1ðrÞj2
D¼ jri ðrÞj2  ð3Þ
2 i 8 1ðrÞ
3
Dh ¼ ð3p2 Þ2=3 1ðrÞ5=3 ð4Þ
10
X
1ðrÞ ¼ i
ji ðrÞj2 ð5Þ
with i being the Kohn–Sham orbital of electron i, D the kinet-
ic energy density required to satisfy the Pauli exclusion princi-
ple, and Dh the kinetic energy density of a homogeneous elec-
tron gas of identical electron density.
Local maxima in ELF, named attractors, are typically found at
the positions of formal bonding pairs, nuclei and lone pair do-
mains. In a manner closely related to QTAIM, ELF basins can be
constructed around each such attractor, by using the gradient
field of ELF, giving corresponding basin populations. ELF is in-
dependent of the type of orbitals used (e.g. localized or canon-
ical/delocalized) and can in principle be obtained from experi-
mental data. Most importantly, it accurately reproduces atomic
shell structures and occupations.[41] The latter is in contrast to
the Laplacian of the electron density, which, albeit being fun-
damentally connected to the atomic shell structure, has been
reported to fail in the case of several heavy elements.[21, 42–45]
The implementation of ELF, (and related methods) has reached
widespread use in the analysis of molecules and extended
systems.[5, 17, 32, 35–38, 46, 47]
One ELF study dedicated solely to lone pairs is that of Ches-
nut, who studied a series of first- and second-period hydrides.
It emphasizes that small changes in basin populations and the
positions of ELF lone pair maxima can provide insight into
weak intra- and intermolecular interactions.[48] Berski et al. have
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investigated how electron density is delocalized between ELF
basins in a series of H2X, H2C=X and XO2 (X = O, S, Se and Te)
compounds. The study suggests that lone pair electrons of O
and S primarily delocalize between pair domains, whereas the
heavier Se and Te exhibit lone pair delocalization with the core
region, indicating penetration of d-electrons of the outer core
with the valence shell.[49]
3. Defining the Lone Pair Domain
To the best of our knowledge there is no clear definition of the
degree of delocalization in a molecule, and there has been
little or no success in finding a connection between popula-
tions in a given region of space (originating from any localiza-
tion method) with any chemical observable.[36] Savin has point-
ed out that even though ELF can be interpreted as having
physical meaning, and being in conceptual agreement with
Lewis theory, ELF basins have no real physical significance.[39, 50]
It is argued that this is so because ELF is defined locally. The
physical interpretation of an average number of electrons (e.g.
one electron) in a non-infinitesimal volume of space (e.g.
a basin population) does not give the probability of finding
that number of electrons in this volume. This is because many
electrons contribute to the average population. For a thorough
discussion see Chamorro et al.[51] and Savin.[39, 50]
Nevertheless, one way to analyze ELF is examination of spa-
tial regions limited by a certain value, that is, by using isosurfa-
ces at which h(r) = f, and 0 < f < 1. This is commonly done for
visualization purposes, to clearly illustrate the separation into
different f-localization domains. However, the most commonly
used and reported f-localization domain population, is that of
the entire basin, typically limited only by the formal van der
Waals edge of the molecule where 1(r) = 0.001 e Bohr3, as de-
fined by Bader. Unfortunately such basins commonly exhibit
unphysical populations that exceed two electrons.[47] Ponec
and Chaves have addressed this problem by analyzing
domain-averaged Fermi holes.[52] They concluded that the ex-
planation lies in the determination of basin boundaries, and
contamination by electrons in neighboring domains.
Because the scale of ELF is arbitrarily set to range from zero
to one [Eq. (2)], it includes all electrons and thus covers all
quantities of electron localization in the molecule. Fortunately,
this arbitrariness is irrelevant for graphical representations and
qualitative analysis. However, because the populations of dif-
ferent basins can be virtually identical while being made up of
different amounts of low-ELF and high-ELF electrons, the classi-
cal definition makes it impossible to distinguish between them
by means of the population alone.
We note that by separating the basin populations into two
parts that covers predominantly high-ELF (localized), and pre-
dominately low-ELF (delocalized) electrons, we can approach
a chemically relevant measure of what are formally (in the
Lewis sense) lone pair domains. One natural definition of such
an intra-basin boundary is ELF’s original reference, the uniform
electron gas, which sets h(r) = 1=2 , that is, where [Eq. (6)]:
D ¼ Dh ð6Þ
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Allowing for h(r) < 1=2 , which is common practice, serves to
include large volumes where multiple electron pairs dominate.
These include regions between electron shells and diffuse
outer parts of molecules, which are arguably of less chemical
relevance, and whose accurate description are also highly
method- and basis-set-dependent.
Herein we therefore choose to define a descriptor of the
lone pair domain as the region of space encompassed by an
ELF f-localization domain, which is bound by [Eq. (7)]:
hðrÞ  1=2 ð7Þ
and [Eq. (8)]:
1ðrÞ ¼ 0:001 e Bohr3 ð8Þ
For the sake of comparison with normal ELF values, the aver-
age electron populations and volumes of such localization do-
mains will be called high ELF localization domain populations
and volumes (HELP and HELV). Thus, HELP is defined here as
the average number of electrons contained by an ELF f-locali-
zation domain, which is limited to local kinetic energy densities
due to Pauli repulsion that equal and exceed that of a homoge-
neous electron gas of identical electron density.
The truncation at the Van der Waals boundary has little
impact on the domain population. Instead it ensures a more
reliable measure of the domain’s volume (c.f. yellow line,
Figure 1), which otherwise could fluctuate significantly with
Figure 1. Graphical representation of the HELP domain of phosphine, which
contains 1.50 electrons. The yellow line illustrates the border of the HELP
domain, which is constructed from the HELP boundary condition h(r) = 1=2 ,
and the Van der Waals edge of the molecule, 1(r) = 0.001 e Bohr3.
the level of theory. As large, less chemically relevant volumes
are removed, the computational cost of the grid-based topo-
logical analysis is also significantly reduced.
The critical issue here is the application of basin partitioning.
This allows for quantification of that part of the basin that is
more chemically relevant, and better described by computa-
tional methods. The use of the homogeneous electron gas as
the limiting value for HELP is not necessarily the ideal choice
for intrabasin partitioning. Nevertheless, as will be shown
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below, this choice enables good correlation with a range of to ignore the shades of gray that de facto exist, in favor of
physical properties. Not only is the homogeneous electron gas fuzzy “lines-and-lobes” arguments. For example, it is obvious
a common reference state in solid-state physics, it also agrees to most that the lone pair domain of NH3 is fundamentally
well with the original construction of ELF. Both limiting values, chemically different from those of NF3 and BiF3, yet conceptu-
h(r) = 1.0 and 1=2 , have clear physical interpretations. At h(r) = ally many still describe such structures by drawing identical
1.0, the local kinetic energy density due to Pauli repulsion lone pair (Lewis) lobes. Such a simplified picture has led many
equals zero, at h(r) = 1=2 it equals that of a homogeneous elec- astray. For instance, X-ray photoemission spectroscopy and
tron gas of equal density. The problem with a more ambiguous theoretical studies have recently called for a revision of the
interpretation of h(r) < 1=2 , which occurs in normal ELF basins, lone pair model, which has since long erroneously been in-
is removed. Our approach of basin partitioning can be straight- voked to explain distortions in heavy main group metal
forwardly applied using other limiting values. Other functions oxides.[53]
for electron localizability, such as the reference free electron lo- Our topological analyses of the electron density show no
calizability indicator (ELI),[32] can also be used. evidence for lone pair domains (VSCCs) in the investigated
We wish to emphasize that the HELP methodology outlined main-group molecules HI, HAt, H2Te, H2Po, AsH3, SbH3, BiH3, IF,
above is based on the subdivision of a normalized localizability AtF, PoF2, SbF3, BiF3, SbF4 , BiF4 , CH3I, CH3At, Te(CH3)2,
scale (in principle, ELF, ELI or otherwise) into “high” and “low”. Po(CH3)2, Sb(CH3)2, Bi(CH3)2 or BiF52 (Table 1 and Tables S1 and
These are naturally subjective concepts. As it is unlikely that S2 in the Supporting Information). Continuous charge deple-
there will ever be a mathematical
proof separating “high” from
“low” one should not expect Table 1. Lone-pair-related properties for selected hydrides and fluorides (see the Supporting Information for
a physical reason for the exact full table).
high-to-low boundary condition.
Geometry[a] r21(r)[b] ESP[c] NBO HELP (HELV)
However, our definition has, in  [8] e Bohr 5
kcal mol1 s-character (%) e [Bohr3]
the case of the ELF scale, the ad-
NH3 1.012 (106.7) 2.392 39.8 23.4 1.78 (38)
vantage of being exactly defined PH3 1.411 (93.4) 0.282 16.1 53.6 1.50 (84)
to equal a physical reference AsH3 1.521 (92.3) >0 10.9 61.3 1.30 (84)
state. This enables for a more SbH3 1.707 (92.4) >0 7.5 64.5 1.11 (97)
comprehensible definition. BiH 3 1.779 (91.3) > 0 + 2.9 75.5 1.01 (74)
NF3 1.355 (102.0) 4.375 3.7 57.5 1.70 (24)
As pointed out by one review- PF3 1.565 (97.2) 0.392 + 3.1 70.8 1.20 (60)
er, some experimental chemists AsF3 1.707 (95.8) 0.012 + 21.3 78.6 0.97 (61)
might not appreciate how to SbF3 1.878 (94.3) >0 + 27.3 81.2 0.85 (78)
deal with a HELP value of less BiF 3 1.978 (94.6) > 0 + 51.2 89.0 0.75 (58)
BiF4 2.140 (90.0)[d] >0 58.9 90.0 0.57 (41)
than two, since it does not rep- BiF52 2.220 (89.0)[d] >0 59.6 93.3 0.36 (22)
resent a pair of electrons. In this
3
[a] Bond length (bond angle). [b] Laplacian at VSCC. [c] from 0.001 e Bohr isosurface. [d] Average BiF bond
light, we must stress that our
lengths and average angles between adjacent fluorines are shown for BiF4 (C2v, trigonal bipyramid) and BiF52
use of the term lone pair (C4v, distorted octahedron).
(domain) is meant to consolidate
the HELP approach with the ter-
minology used by most chem-
ists. HELP refers to the region of space where there is formally tion [r21(r) > 0] is seen from the nuclei and outwards. Whereas
(in the Lewis sense) a single localized pair of electrons. Because the elements At, Po, Bi and Sb show no evidence of VSCCs at
there is no unique way of defining individual lone pair elec- all, Te, As and I are borderline, and occasionally show areas of
trons, the term lone pair remains an interpretation and not minute charge concentration (where 0.002 > r21(r) >
a property of the wave function. As mentioned above, the 0.020 e Bohr5). Absolute signs of such small values are un-
HELP values do not necessarily arise from a single pair of elec- certain. However, r21(r) at detected VSCCs consistently shows
trons, but from contributions of many electrons. Because elec- an exponential decrease down the periodic table. For example,
trons can be delocalized over different parts of a molecule H2O (4.788), H2S (0.531), H2Se (0.021) or NF3 (4.375), PF3
HELP can by construction deviate significantly from 2.0. There- (0.392) and AsF3 (0.012).
in lies its strength, for where the classical rationale is a black- We can conclude that the heavier nuclei exhibit extremely
and-white picture of two electrons, HELP introduces quantifia- shallow electron densities in their formal lone pair domains,
ble shades of grey. and show little or no proof of lone pair localization by means
of QTAIM analysis. This is in good agreement with earlier work
on the shell structure of heavy atoms and ions[42–45] and heavy
4. Properties of Lone Pair Domains
metalmetal and metalligand bonds,[21] and clearly demon-
There are many reasons to reflect on the different characteris- strates a distinct difference in the nature of lone pair domains
tics of lone pair domains across the periodic table. First and between lighter and heavier elements. This unfortunately im-
foremost it is obstructive to the progress of chemical science plies that the Laplacian of the electron density, r21(r), does

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not provide a physical basis for classical Lewis theory and the
VSEPR model of molecular geometry, in the case of heavy
atom main-group compounds.
Because the lone-pair concept is central to rationalizing
chemistry, any successful descriptor thereof can reasonably be
expected to correlate with a number of chemical properties
and quantum mechanical observables, such as:
1. Electrostatic surface potential
2. Atomic charges of the parent atoms
3. s-character of NBO lone pair orbitals
4. HOMO/LUMO energies
5. Proton affinity
6. Electron affinity (vertical and adiabatic)
7. Ionization potential (adiabatic)
8. Molecular geometry (bond lengths and angles).
Except for clear connections (r2 > 0.95) with ELF attractor po-
sitions and densities (many of which were previously known,
see the Supporting Information, for example Figures S1 and
S3), neither of the VSCC characteristics r21(r) or 1(r) show any
reasonable correlation to the above-mentioned quantities.
Consequently they are deemed poor choices as descriptors of
lone pair.
As expected, no meaningful correlations were found be-
tween normal ELF basin populations, which vary seemingly
randomly between 1.9 and 2.6 for all neutrals, with any of the
investigated quantities (Tables S1–S2). The ELF maxima, h(r), at
lone pair attractor positions were similarly found to vary be-
tween 0.85 and 0.99, without showing any meaningful trends.
The electron density, 1(r), at ELF maxima does on occasion cor-
relate well with electron affinity, however the extent of correla-
tion varies significantly between structure and ligand types.
Having established these conceptual problems with both
QTAIM and ELF with respect to quantifying lone pair domains,
the remainder of this work is focused on the validity of HELP
and HELV, defined previously.
Encouragingly, and in stark contrast to the populations of
normal ELF basins, we note that HELP correlates qualitatively
(and negatively) with its corresponding volume (HELV, all neu-
trals: r2 = 0.586). This is to be expected as increasingly delocal-
ized electrons reside in larger volumes that both include the
lone pair domain, as well as other parts of the molecule.
The average electron concentration defined as HELP/HELV is
found to correlate strongly with 1(r) at VSCCs (r2 = 0.937, Fig-
ure S2). HELP/HELV is also found to follow r21(r) at VSCCs for
all compounds were the latter is observable (r2 = 0.875,
Figure 2).
In validating the use of HELP as a descriptor of lone pair do-
mains we can demonstrate clear interrelations with all of the
previously mentioned eight lone-pair-related quantities. Natu-
rally, perfect linear correlation with HELP should not be expect-
ed, as the investigated properties measure many different as-
pects of the molecular reality. In other words, they are not
themselves all perfectly linearly dependent on each other.
Table 1 exemplifies how HELP and HELV can quantify intui-
tive concepts such as size and diffusiveness of lone pair do-
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Figure 2. Electron concentration (HELP/HELV) of lone pair domains correlates
with the Laplacian of the electron density, r21(r), at detectable VSCCs.
mains and relate them to other measures, such as geometry,
electrostatic and orbital analyses. Detailed accounts of all re-
sults are given in the Supporting Information.
4.1. The Electrostatic Surface Potential (ESP)
The electrostatic potential V(r) is a physical observable that can
be obtained by diffraction experiments,[54] as well as by com-
putations. It is rigorously defined by Equation (9):
Z
X ZA 1ðr0 Þdr0
VðrÞ ¼  ð9Þ
A jR  r j
A jr 0  rj
When calculated at the surface of a molecule (ESP) it pro-
vides a direct mapping of the surfaces’ electrostatic interac-
tions to adjacent positive point charges. The electrostatic po-
tential and ESPs have many known relations to macroscopic
physical properties, such as heats of fusion, surface tension
and crystal densities.[55] It has also been found useful in pre-
dicting the directionality of many non-covalent interactions,[56]
such as hydrogen[57] and halogen bonding.[58]
Electrostatic interactions are perhaps the most intuitive
property of a lone pair domain, and are hence essential for
evaluating a lone pair descriptor. Herein we report the local
ESP maxima/minima found in the lone pair position of XL3-
type molecules (Table 1 and Figure 3). XL12 molecules are not
addressed as the positions of their ESP maxima/minima vary
significantly with period. As expected, ESP was found to relate
well to proton affinity within XL3-type molecules (r2 = 0.818,
Figure S11).
Figure 3 illustrates a clear correlation between ESP and HELP,
which is especially obvious within each ligand case [XH3, XF3
and X(CH3)3 series: r2 = 0.928, 0.773 and 0.890, respectively].
Qualitative agreement is also seen when all ligand types are
combined (r2 = 0.591).
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Figure 3. Electrostatic surface potential (kcal mol1, 0.001 e Bohr3 isosurface)
of XL3-type molecules shows qualitative agreement with HELP (shown in
black).
4.2. Atomic Charge
Despite not being a physical observable per se, few would
doubt the descriptive power of atomic charges, which are fun-
damentally connected to how we rationalize chemistry. Atomic
charges can be obtained in many ways, for example, through
partitioning of occupied molecular orbitals. One popular and
straightforward way to do so is the Mulliken method.[59]
Despite certain drawbacks such as a large basis-set depend-
ence, Mayer has argued that Mulliken’s is the only population
analysis that is completely consistent with the internal mathe-
matical structure of the theory of atom-centered basis func-
tions.[60] We observe a strikingly good agreement between
such atomic charges and HELP when large and correlation-con-
sistent basis sets are used (Figure 5). Natural population analy-
sis (NPA)[61] describes each atomic species as nearly as possible
in terms of its natural minimal basis orbitals. Because of this
NPA shows much less dependence on basis set when com-
pared to Mulliken charges. This can pose a problem in the
case of heavier atoms, which exhibit more complex non-Lewis-
like electronic structures, including close lying formally unoccu-
pied d- and f-shells. We find that NPA charges correlate, albeit
less well, with HELP. Attempts to correlate with Bader (QTAIM)
charges was abandoned due to only sporadic correlation with
HELP as well as complete ionized descriptions in some cases,
which is clearly unphysical (Figure S21).
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Figure 4. Atomic charge (Mulliken) correlates strongly with HELP. a) XL1
series, b) XL2 series, c) XL3 series. Dashed lines highlights correlation between
ligand types in periods 3–6. Lone diamond is N(CH3)3, which falls slightly off-
line.
Figure 4 illustrates the agreement with classic chemical ra-
tionale, for example, explaining how electron-withdrawing li-
gands (such as F) act to decrease the nucleophilicity of the
lone-pair bearing element, whereas electron-donating ligands
(such as H and Me) act in the opposite way. Linear decreases
of HELP down the periodic table for each structural type reflect
the strong relationship also expected from electron configura-
tion arguments (and qualitatively from electronegativity).
Excellent agreement is noted between Mulliken atomic
charge and electron affinity within each structural type. Quali-
tative agreements are furthermore seen with several other mo-
lecular properties, such as ESP and proton affinity (Tables S1–
S2).
4.3. Natural Bond Orbital (NBO) Analysis
NBO population analysis[7, 61] is in widespread use by theoretical
chemists. NBO is by construction biased against a delocalized
description of electrons, and constructs localized hybrid bond
and lone pair orbitals, which can be viewed as being in better
conceptual agreement with classical Lewis theory. As such,
NBO lone pair orbitals can act as one measure of the lone pair
domain. The hybrid orbital description is undoubtedly a power-
ful tool when applied to light elements. Unfortunately, the
analogy with Lewis theory becomes increasingly approximate
for the heavier main group elements, which have valence
shells in closer proximity to filled and unfilled d- and f-shells.
Because of this the analysis of hypervalent molecules (which at
least formally break the octet rule) is less straightforward.
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NBO analysis constructs lone pair orbitals by maximizing the

occupancy of orthonormal natural atomic orbitals. For in-
stance, one lone pair of H2O is described by a pure p-orbital
on oxygen, whereas the second is explained as a 50/50 mix be-
tween s- and p-orbitals. Averaging of water’s NBO lone pairs
thus results in an s-character of 25 % (or sp3). Because ELF is in
principle orbital-independent, electrons corresponding to the
s-character in the NBO description can be shared between the
core ELF domain and the lone pair domain (how much will
depend on the nodal behavior of the s-orbital in question),
whereas p-character will predominantly be attributed to the
lone pair domains. If we assume that all s-character is attribut-
ed to the core domain, we are left with  1.50 electrons per
lone pair domain. If the s-character is instead equally shared
between core and lone pair domain, then  1.75 electrons can
be attributed to the latter. In light of this, it is encouraging
that HELP values for period two elements (N, O and F) range
between 1.61–1.87, with an average of 1.77.
Because all investigated XL13 molecules are conceptually of
sp3-type we have averaged the s-character of their NBO lone
pair orbitals, for direct comparison with HELP. As is well
known, NBO analysis constructs lone pair orbitals with increas-
ing s-character down the periodic table. For instance, the lone
Figure 5. s-character of NBO lone pair orbitals shows strong correlation to
pair orbital of NH3 is attributed 23 % s-character, whilst (follow-
HELP. a) XL1 series, b) XL2 series, c) XL3 series.
ing a linear decrease) the one in BiH3 is attributed 76 % s-char-
acter (Table 1). In this study we calculate an average s-charac-
ter of 52 % for period six. Following the above argument, this shows excellent correlation with HELP (Figures S15–S17). The
should equal a lone pair domain population of  1.00 elec- exceptions are the O(CH3)2–Po(CH3)2 and NF3–BiF3 series, which
trons. Indeed, the average HELP value for period six is 1.08 exhibit shallow dependencies. Figure 6 illustrates the signifi-
electrons. cant differences in HOMO and LUMO energies and dispositions
Overall, s-character, as determined by NBO methodology, for NH3 and BiF3, a difference also reflected in their HELP
tracks HELP well within each XL13 family, and excellently values.
down the periodic table for a given ligand and structure type
(Figure 5). The average HELP and NBO values for each period
4.5. Proton Affinity (PA)
also show excellent general correlation (r2 = 0.968, Figure S9).
The hypervalent XF4 series shows surprisingly good correla- Proton affinity describes the gas-phase propensity of a mole-
tion (r2 = 0.972), whereas ClF3, BrF3 and IF3 do not. cule to form a chemical bond with a free proton, at the site of
the formal lone pair domain. Contrary to other non-invasive
measures of lone pair character, the addition of a proton can
4.4. HOMO and LUMO Energies
severely affect bonding and overall molecular structure. Not
Canonical (delocalized) HOMO and LUMO Kohn–Sham (KS) DFT surprisingly, proton affinity correlates strongly with ESP. Where-
orbitals are frequently used to rationalize many aspects of as XL3 molecules show clear correlation with HELP, the XL2
chemistry.[62] They have known relations to ionization poten- family shows flat or no dependencies, and XL1 show negative
tials, and are by necessity linked to the classical lone pair con- correlations (Figure S12).
cept. Unfortunately this link is not always obvious, primarily
due to their delocalized nature.
4.6. Electron Affinity (EA)
Whereas the KS-LUMO orbital of a single molecule formally
represents an excited state, the most energetically important Electron affinity is an intrinsic property of molecules that di-
interaction between interacting species typically occurs rectly reflects the propensity to accept free electrons. EAs can
through HOMO!LUMO overlap. Therefore, the KS-LUMO orbi- be obtained experimentally, for example, by negative ion pho-
tal can be considered the primary electron accepting orbital in toelectron spectroscopy, as well as computationally. EAs are
an intermolecular Lewis acid–base interaction. We note excel- naturally dependent on a molecule’s ability to delocalize
lent correlation between LUMO energies and HELP (Fig- charge, and consequently on molecular size (which is related
ures S15–S17). The exception is the O(CH3)2–Po(CH3)2 series, to both the molecular volume and number of nuclear charges).
which shows only moderate (r2 = 0.75) correlation. Because of its dependence on delocalization capability, EA can
The HOMO orbital, which is the primary electron donating be expected to also correlate with a measure of lone pair elec-
orbital in an intermolecular Lewis acid–base interaction, also trons, or localization thereof.

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Figure 6. HOMO and LUMO orbitals (0.02 a.u. isosurface) of NH3 and BiF3
(top) and LUMO–HELP dependence for trihydrides and trifluorides (bottom).
In ab initio Hartree–Fock theory the EA directly corresponds
to the LUMO energy. This is not necessarily true for DFT.
However, given that our KS-LUMO energies show excellent cor-
relation to HELP (vide supra), it is fortunate we can also note
good correlation between EA and HELP within each structural
type, going down the periodic table (Figure S22). However, be-
cause several of our calculated EAs are negative, correspond-
ing to a case where limitations in the basis set artificially force
an electron to remain close to the molecule, these values
should be interpreted with caution (or set to zero). For a more
detailed discussion, see the Supporting Information.
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4.7. Ionization Potential (IP)
The removal of the highest energy electron necessarily corre-
lates strongly with the HOMO energy in any compound (r2 =
0.948, Figure S13). The canonical HOMO orbital is often highly
delocalized, and the extent to which the HOMO (or IP) corre-
lates with HELP should therefore depend on the HOMO-HELV
spatial overlap. With this in mind it is reasonable that the
IP/HELP-correlation is poorest for the larger XL3 molecules,
whereas the smaller XL12 molecules shows clearer relations
within each group of the periodic table (Figure 7).
Figure 7. Adiabatic ionization potential correlates well with HELP within
each group of the periodic [except for the NF3–BiF3 and N(CH3)3–Bi(CH3)3
series, which show no dependence]. a) XL1 series, b) XL2 series, c) XL3 series.
4.8. Molecular Geometry
The lone pair concept is often central to how we rationalize
geometries of molecules, for example, through VSEPR ration-
ale. Arguments of “steric activity” of lone pairs typically refer to
notions such as “diffusiveness”, or size, of a lone pair domain.
As these notions are difficult to quantify, discussions on steric
activity necessarily revolve around the a priori assumption of
a lone pair affecting structure, and resulting in the observed
geometry.[63]
HELP/HELV (i.e. electron concentration) provides an approxi-
mate measure of lone pair domain diffusivity, and we note ex-
cellent correlation between this measure and ligand angles for
hydrides (r2 = 0.996 and 0.975 for the H2O and NH3 series, re-
spectively, Figure S14). Good correlation (r2 > 0.99) between
bond angles and HELP for fluoride and isoelectronic methyl
substitution was only found when the second period was plot-
ted as having perfect trigonal (1208) bond angles. This may be
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a reflection of steric effects induced by the larger F and CH3 li-
gands, compared to H, but is also likely due to the less flexible
electron configuration of N and O, compared to their heavier
analogues.
Both normal ELF and HELV volumes show a reasonable cor-
relation to ligand bond lengths, within each structure and
ligand type. The deviation from linearity typically occurs for
the lone pair domains of period six elements in which
a volume contraction relative period five is seen. This effect
likely stems from the increased nuclear potential introduced
by the fourteen protons of the lanthanides. However, it is also
possible this is a computational artifact that could be mitigat-
ed with an even better description of the outermost electrons.
Encouragingly, HELP correlates strongly with the lengths of
bonds adjacent to the lone pair domain (Figure 8 and Table 1).
This is expected from a descriptor of lone pair domains, since
shorter bonds generally should correspond to increased locali-
zation of bonding pairs. This, in turn, should coincide with in-
creased localization of the lone pairs due to increased Pauli
repulsion.
Figure 8. High HELP coincides with shorter bond lengths adjacent to the
lone pair domain.
5. HELP in Rationalizing Chemistry
By probing only the most chemically relevant and electron-lo-
calized regions of space, largely independent of the level of
theory, HELP represents a robust theoretical construct likely to
lend aid in a range of chemical problems. Its strong relation to
atomic charge is especially promising, since until now ELF-like
methods have not allowed for meaningful measurements of
charge. To exemplify the successful capture of the chemical dif-
ferences between lone pair domains on light and heavy atoms,
we compare the urethane linkage in methyl methylcarbamate
(Figure 9) to the highly explosive bismuth penta-azide dianion,
Bi(N3)52 (Figure 10), which has recently been prepared in our
laboratory.[64]
In agreement with chemical intuition all the lone pair do-
mains on the nitrogen and oxygen atoms of methyl methylcar-
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Figure 9. Visualized characteristics of lone pair domains in methyl methyl
carbamate: a) ELF lone pair basins visualized by a h(r) = 0.85 isosurface
(gold) are shown together with Mulliken atomic charges. b) Lewis structure
showing HELP values for the lone pair domains. c) Intra-molecular correla-
tion between atomic charges of lone-pair-bearing elements and HELP (solid
red line), and correlation when HELP value of carbonyl oxygen is modified
to equal 2.0 (dashed grey line). d) HOMO (0.01 a.u. isosurface). e) ESP plotted
on constant 0.001 a.u. electron density contour (blue = + 40.0 kcal mol1,
green = 0.0 kcal mol1, red = 40.0 kcal mol1). f) Laplacian of the electron
density in the plane of the molecule [r21(r) > 0: blue, r21(r)  2: green,
r21(r) < 4: red]. g) ELF in the plane of the molecule [h(r) < 0.3: blue,
0.3 < h(r) < 0.6: green, 0.6 < h(r) < 1.0: red).
bamate can act as Lewis bases. Partial localization of electrons
in the lone pair domains is confirmed by the presence of
VSCCs (where r21(r) < 0, Figure 9 f). HELP values correlate ex-
cellently with the atomic charges of the lone-pair-bearing ele-
ments (Figures 9 a–c), and increase in the order: amine <
ether < carbonyl, a trend also followed by local ESP maxima
(Figure 9 e). The HELP values for the carbonyl lone pair do-
mains are the only ones found to exceed 2.0, a fact that can
be explained by significant electron resonance delocalization,
or increased electron contamination from neighboring do-
mains. We note that a perfect correlation with atomic charges
is obtained if the carbonyl HELP value is set equal to 2.0
(Figure 9 c).
Bi(N3)52 is a telling example of a highly coordinated (hyper-
valent) main-group compound with one formally strongly steri-
cally active lone pair domain. The HELP value for the bismuth
lone pair domain is 0.81, thus predicting a character intermedi-
ate between those of SbF3 (0.85) and BiF3 (0.75, Table 1). This
value implies that in stark contrast to lone pair domains resid-
ing on lighter elements, which typically show HELP values
> 1.5, the lone pair domain in Bi(N3)52 is a region relatively de-
ficient of electron density, with low levels of electron localiza-
tion. Theoretical proof of local charge depletion is shown in
Figures 10 a–h. The ESP shows a decreased negative potential
in the lone pair domain (Figure 10 e). The atomic charge of bis-
muth is large and positive (Figure 10 a). The LUMO orbital,
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Figure 10. Visualized characteristics of the Bi(N3)52 lone pair domain. a) ELF
lone pair basins visualized with h(r) = 0.85/0.80 isosurfaces (gold/transparent)
together with bismuth Mulliken atomic charge. b) Lewis structure showing
HELP value of the lone pair domain. c) HOMO, (0.001 a.u. isosurface).
d) LUMO (0.001 a.u. isosurface). e) ESP plotted on constant 0.001 a.u. elec-
tron density contour (blue = 113 kcal mol1, red = 151 kcal mol1). f) Lapla-
cian of the electron density in the Bi(N3)3–lone-pair plane [r21(r) > 0: blue,
r21(r)  2: green, r21(r) < 4: red). g) ELF in the in the Bi(N3)3–lone-pair
plane [h(r) < 0.3: blue, 0.3 < h(r) < 0.6: green, 0.6 < h(r) < 1.0: red]. h) ELF in
the in the NBiN plane of the bipy···Bi(N3)52 adduct.
which is the electron-accepting orbital in a bimolecular Lewis
acid–base interaction is prominent in the lone pair domain
(Figure 10 d). Finally, QTAIM’s requirement for a VSCC (lone
pair domain) is not met. The Laplacian of the electron density
shows continuous charge depletion from the bismuth core
region and outwards (Figure 10 f). The low HELP value corre-
lates with, and thus captures, all of the above properties, and
explains how the addition of bipyrridine (a Lewis base) can
result in a strong adduct with bismuth, replacing the sterically
active lone pair domain.[64] In the resulting pseudo-pentagonal
bipyramidal structure, the lone pair domain vanishes
(Figure 10h).
The still widespread use of the lone pair concept in success-
fully rationalizing much of chemistry lends credence to the
usefulness of the HELP methodology, which enables quantifica-
tion of lone pair domains from a density-based and orbital-in-
dependent analysis. Its wider applicability and predictive func-
tions will be the subject of forthcoming research.
6. Conclusions
The lone pair concept is of fundamental importance for the ra-
tionalization of most chemistry. This work has demonstrated
how the nature of lone pair domains, for example, their locali-
zation, size, electrostatic and reactive properties, vary greatly
throughout the main groups. Most importantly, we have de-
fined and demonstrated how lone pair domains can be quanti-
fied and compared in a chemically meaningful way.
We can conclude that the direct topological analysis of the
electron density and its second derivative cannot detect lone
pairs in several heavy main group elements. This implies that
such an approach is lacking in providing a complete physical
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basis for classical Lewis theory or the VSEPR model of molecu-
lar geometry.
The average electron population within any volume of
space, such as a lone pair domain, is the result of partitioning
the total electron density of a molecule, which is a physical ob-
servable. The problem lies in the definition of that volume.
Herein we have shown how the ELF’s classical and arbitrary
definition of a lone pair basin can reach physical relevance by
the introduction of an intrabasin boundary, set to equal the
ELF value for a homogeneous electron gas of equal density.
The average number of electrons in the resulting high-localiza-
tion domain is termed the high-ELF localization domain popu-
lation (HELP). A number of key molecular and atomic proper-
ties, such as the electrostatic surface potential, electron affinity,
proton affinity, ionization potential, HOMO and LUMO energies,
and nuclear charge show clear correlations to HELP. Correlation
with natural bond orbital analysis provides further support for
the usefulness of HELP as a useful probe of lone pair domains.
Strong general correlation has also been demonstrated be-
tween HELP and bond lengths neighboring the lone pair
domain.
Correlation does not automatically imply causality. However,
close relationships between many lone-pair related quantities
and HELP strongly indicate that they reflect different aspects
of the same physical reality. Such a clear connection between
topological density and orbital-based analysis of chemistry is
intuitively expected. Yet to the best of our knowledge, this is
the first time any average electron population, obtained by
any localization method, has shown quantifiable correlation
with physical properties of molecules. Our hope is therefore
that these results can help to consolidate the complementarity
of orbital-based and density-based analyses of chemistry.
Exploring decomposition of the HELP localization domain
into delocalized contributions from other domains, through
evaluation of the source function,[65] and localization indices,[66]
is left for future work. This is primarily due to the already
broad scope of this work, as well as questionable interpreta-
tions of the low-density regions outside the HELP volumes.
Because there is no unique way of defining individual lone pair
electrons, the term “lone pair” remains an interpretation and
not a property of the wave function. The HELP methodology is
straightforwardly applicable using other intrabasin boundaries,
and other ELF-related functions, such as the Electron Localiza-
bility Indicator (ELI). Further validation of HELP will be dis-
closed in the near future. This will include analysis of the rela-
tion between high- and low-ELF electrons, broader analytical
applications including bonding analysis, and predictive
functions.
In summary, ELF is known as a powerful tool for qualitative
bonding analysis. We suggest that its application should be ex-
panded to the direct quantification of a chemically meaningful
descriptor of the lone pair domain.
Computational Details
All molecular geometries were evaluated using the hybrid meta ex-
change–correlation density functional M06-2X[67] as implemented
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in Gaussian 09, Revision A.02.[68] M06-2X is a high-accuracy general-
purpose DFT functional, as demonstrated by extensive benchmark-
ing.[69] Control QTAIM and ELF calculations on the NH3–BiH3 series
was performed using the classical BP86[70] functional and the
B3LYP[71] hybrid functional, with close to identical results compared
to M06-2X.
Analytical frequency analysis ensured that considered structures
were proper minima on the potential energy surface. Period 1–3 el-
ements were described by the correlation-consistent cc-pwCVTZ
basis set,[72] while the cc-pwCVTZ-PP[73] basis set was employed for
the treatment of all period 4–6 elements. The latter includes
a small-core relativistic Stuttgart pseudopotential that accurately
recovers both scalar and spin–orbit relativistic effects of inner core
electrons of the heavier elements. In the case of bismuth, which is
one of the heaviest nuclei considered, its 23 outermost electrons
are treated by a (23s23p15d3f1g)/[7s6p5d3f1g] Gaussian contrac-
tion. The large basis set ensures a highly flexible description of the
valence and sub-valence space, and is necessary, since neglecting
d-subshells is known to produce artefacts in the ELF.[74]
Augmentation of our PP-based wave functions through inclusion
of relativistic B3LYP atomic core electron densities, as recently sug-
gested by Frisch et al.[75] has not been performed. To ensure that
no artifacts arose due to the use of pseudo-potentials we investi-
gated AsF3 with all-electron calculations using the Douglas–Kroll–
Hess second-order scalar relativistic Hamiltonian[76] at the
M06-2X/cc-pVTZ-DK[77] level. Comparisons were also made with all-
electron DKH-B3LYP calculations and Hartree–Fock theory. All cases
showed lone-pair-related properties closely matching the
M06-2X/cc-pwCVTZ-PP calculations. Hartree–Fock and Kohn–Sham
DFT reference calculations are expected to provide slightly differ-
ent treatments of the scalar fields 1(r) and h(r) due to missing cor-
relation energy in the former. However, ELF properties calculated
with Hartree–Fock and B3LYP is known to compare well with CISD,
CCSD-BB, and CASSCF multi-reference calculations in a range of
cases.[78] We also note good agreement with published Hartree–
Fock and B3LYP QTAIM results.[24, 79]
Generation and analyses of the electron density, its Laplacian and
ELF were performed over a 0.05 Bohr (0.026 ) resolution grid in
Dgrid version 4.6.[80] Initial boxes were extended by 4–6 Bohr in all
three dimension, until lone pair domains could be extended to
their 1(r) = 0.001 e Bohr3 and h(r) = 1=2 limiting values. Calculation
of the ELF was performed using the spin-polarized definition of
Kohout and Savin.[41]
Natural bond orbital (NBO) analyses were performed with NBO 3.1,
in Gaussian 09. Graphical representations were generated using
VMD 1.9.[81] and VESTA 3.1.[82] For more information see the Sup-
porting Information.
Acknowledgements
The Sweden–America Foundation, the Swedish Research Council
(VR), the National Science Foundation (NSF), the Office of Naval
Research (ONR), the Air Force Office of Scientific Research
(AFOSR), the Defense Threat Reduction Agency (DTRA), David A.
Dixon, Jerry Boatz, Wojciech Grochala, Sebastian Riedel and sev-
eral reviewers are thanked for valuable comments. Guillaume
Chabot is thanked for his proofreading. Tore Brinck is thanked for
his kind sharing of computational resources.
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www.chemphyschem.org
Keywords: electron density · electron localization function ·
lone pairs · quantum chemical topology · quantum theory of
atoms in molecules
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Received: August 5, 2013
Published online on && &&, 2013
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ARTICLES
Help, HELP! The first chemically rele- M. Rahm,* K. O. Christe
vant quantification of the lone pair
&& – &&
domain by quantum chemical topology
calculations is demonstrated. A novel Quantifying the Nature of Lone Pair
partitioning of the electron localization Domains
function is introduced. The complemen-
tarity of density- and orbital-based anal-
yses of chemistry is discussed. This mea-
sure of the lone pair domain correlates
well with a range of molecular and
atomic properties, and is predicted to
be of general use.

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