583

ARTICLE
Chemical bonding in groups 10, 11, and 12 transition metal
homodimers — An electron density study
SeyedAbdolreza Sadjadi, Chérif F. Matta, and I.P. Hamilton
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Abstract: The properties of metal–metal bonding for transition metal homonuclear diatomics from groups 10, 11 and 12 are
studied within the framework of the quantum theory of atoms in molecules (QTAIM) at the coupled cluster CCSD and CCSD(T)
levels of theory. A novel approximate method developed by Keith and Frisch is used to augment electron densities calculated
with pseudopotentials with the missing relativistic core densities to obtain approximations to the total densities of the dimers.
The calculated delocalization indices for group 10 dimers are: Ni2 (1.6), Pd2 (0.44, an outlier in the group), and Pt2 (1.8); for group
11 dimers: Cu2 and Ag2 (1.01), and Au2 (1.13), all covalent bonds; for group 12: Zn2 (0.06), Cd2 (0.08), and Hg2 (0.09), all consistent
with weak van der Waals complexes. The picture of bonding obtained by examining the values of the electron density at the bond
critical points is consistent with the one obtained on the basis of these delocalization indices. A curious linear (instead of
exponential) dependence of the delocalization index on the electron density at the bond critical point is presented here as an
observation and will be investigated in more depth in later work. Several correlations between bond properties and bond
dissociation energies are also explored. It is found that, with the exception of the Ni2 dimer that exhibits considerable multi-
reference character, there are correlations between the calculated bond dissociation energies of the studied diatomics and
several bond critical point properties. These correlations are novel as they span a set of bonds between different pairs of
elements, while traditionally these correlations were reported for bonds between the same pair or elements but with different
substituents.
For personal use only.

Key words: topology of the electron density, chemical bonding in transition metals, quantum theory of atoms in molecules,
QTAIM, metal-metal bonding.

Résumé : Les propriétés des liaisons métal-métal pour les dimères homonucléaires des métaux de transition des groupes 10, 11
et 12 sont étudiés dans le cadre de la théorie quantique des atomes-dans-les-molécules (QTAIM) en faisant appel aux niveaux de
théorie CCSD et CCSD (T). Une nouvelle méthode développée par Keith et Frisch est utilisée pour augmenter des densités
électroniques calculées à l'entremise de pseudo potentiels avec les densités de cœur relativistes manquantes pour obtenir des
approximations aux densités totales des dimères. Les indices de délocalisation calculés pour les dimères du groupe 10 : Ni2 (1.6),
Pd2 (0.44, qui est en écart du reste du groupe) et Pt2 (1.8); pour les dimères du groupe 11 : Cu2 et Ag2 (1.01) et Au2 (1.13), toutes les
liaisons étant covalentes; et pour le groupe 12 : Zn2 (0.06), Cd2 (0.08) et Hg2 (0.09) indiquant de faibles liaisons du type van der
Waals. L'image qui émerge à propos de la nature de la liaison chimique obtenu en examinant les valeurs de la densité
électronique aux points critiques est complètement en accord avec celle obtenue sur la base des indices de délocalisation. Une
curieuse dépendance linéaire (au lieu d'exponentielle) de l'indice de délocalisation sur la densité électronique au point critique
est présenté ici comme une observation et sera enquêté en plus de profondeur dans un travail future. Plusieurs corrélations entre
les propriétés des liaisons chimiques et les énergies de leur dissociation sont aussi explorées. Il est constaté que, à l'exception du
dimer de Ni2, doté d'un caractère multiréférenciel considérable, il existe des corrélations entre les énergies de dissociation des
dimères étudiés et plusieurs des propriétés de leur point critiques de liaisons. Ces corrélations sont nouvelles car ils s'étendent
sur un ensemble de liaisons entre de paires d'éléments différentes, quand traditionnellement ces corrélations ont été trouvées
pour les liaisons entre une même paire d'élément, mais avec des substituents différents.

Mots-clés : la topologie de la densité électronique, la liaison chimique des métaux de transition, la théorie quantique des atomes
dans les molécules (QTAIM/TQADM), la liaison métal-métal.

Introduction
Transition metal dimers have been studied for a number of
years1 and continue to provide challenges for ab initio methods.
As noted by Yanagisawa, Tsuneda, and Hirao, nonhybrid density
functionals typically give accurate bond distances but overesti-
mate the bond dissociation energies, while hybrid density func-
tionals typically give accurate bond dissociation energies but
overestimate bond distances.2 There have been significant ad-
vances over the past decade, and using software packages such as
DeMon, density functional theory (DFT) calculations are now fea-
sible for clusters of up to 100 transition metal atoms.3 However,
standard ab initio methods (which are only feasible for small
clusters) can be more accurate,4 and we employ coupled cluster
CCSD and CCSD(T) calculations5–8 for our studies of bonding in
transition metal homonuclear diatomics. These calculations, es-
pecially when corrected to account for relativistic effects, are very

Received 21 December 2012. Accepted 9 February 2013.

S. Sadjadi. Department of Chemistry, Faculty of Science, University of Hong Kong, Hong Kong.
C.F. Matta. Department of Chemistry and Physics, Mount Saint Vincent University, Halifax, NS B3M 2J6, Canada; Department of Chemistry, Dalhousie University, Halifax,
NS B3H 4J3, Canada.
I.P. Hamilton. Department of Chemistry, Wilfrid Laurier University, 75 University Avenue West, Waterloo, ON N2L 3C5, Canada.
Corresponding authors: Chérif F. Matta (e-mail: cherif.matta@msvu.ca) and I.P. Hamilton (e-mail: ihamilton@wlu.ca).
This article is part of a Special Issue dedicated to Professor Dennis Salahub in recognition of his contributions to theoretical and computational chemistry.

Can. J. Chem. 91: 583–590 (2013) dx.doi.org/10.1139/cjc-2012-0549 Published at www.nrcresearchpress.com/cjc on 25 February 2013.
 584 Can. J. Chem. Vol. 91, 2013

accurate for both bond distances and bond dissociation energies, Table 1. Zero-point energy (ZPE) corrections and
with few exceptions, such as Ni2 that exhibits a significant multi- basis set superposition error (BSSE) correction
reference character. with the Boys–Bernardi counterpoise (CP) method
Using the calculated molecular electron densities, empirically for all dimers in this study.
corrected for relativistic effects (vide infra), we employ Bader's ZPE CP
|⌬Ecorr |
quantum theory of atoms in molecules (QTAIM) to examine cor- Dimer Method (kcal/mol) (kcal/mol)
relations between bond properties and bond dissociation energies
for nine transition metal homonuclear diatomics belonging to Ni2 CCSD 0.52 1.02
groups 10, 11, and 12. The analysis of the electron densities accord- Pd2 CCSD 0.15 0.40
CCSD(T) 0.17 0.54
ing to QTAIM has been shown to shed invaluable light on the
Pt2 CCSD 0.37 29.26
nature and characterization of chemical bonding.9–19 Recently,
CCSD(T) 0.35 26.26
we have studied metal–metal bonding in the coinage metal homo- Cu2 CCSD 0.36 0.72
nuclear diatomics from the perspective of the analysis of their
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CCSD(T) 0.38 0.98

molecular electron densities, specifically, via analysis of elec- Ag2 CCSD 0.27 0.58
tronic properties at the bond critical points and the integrated CCSD(T) 0.27 0.69
atomic basin properties.20 In this work, an almost perfectly linear Au2 CCSD 0.26 0.70
correlation (r = 1.000) is reported between the electron density at CCSD(T) 0.26 0.84
the bond critical point (BCP), ␳b, and bond dissociation energy Zn2 CCSD 0.02 0.08
(BDE) of Cu2, Ag2, and Au2.20 The idea of correlating ␳b with bond Cd2 CCSD 0.02 0.10
order, and hence bond strength, of a bond between the same pair CCSD(T) 0.03 0.15
of elements in a series of related compounds is not new;21,22 how- Hg2 CCSD 0.02 0.16
ever, in the case of the coinage metal dimers, this correlation was CCSD(T) 0.03 0.21
CP
established for a case where the bond in question is between Note: |⌬Ecorr | = magnitude of counterpoise correction;
CP
different pairs of elements,20 hence its novelty. Other correlations |⌬Ecorr| = |(EA ⫺ ECP CP CP
A ) ⫹ (EB ⫺ EB )|; for A2 molecules: |⌬Ecorr| =

between descriptors of the metal–metal bonding in the coinage |2EA ⫺ 2ECP A |. CCSD(T) values for Zn 2 are not shown because
metal dimers and their respective BDE were also reported.20 In calculations failed to converge due to high multi-
reference character of the ground electronic state.
order of decreasing correlation, the BDE linear correlation coeffi-
cients are with (i) curvature normal to the bond path ␭1,2 (r =
−0.996), (ii) total energy density at the BCP (Hb) (r = −0.987), and (iii)
For personal use only.

old of 10−8 atomic units has been imposed on self-consistent field

logarithm of the delocalization index [log DI, or log ␦(A,B)] (r =
0.925).20 It is noteworthy to mention that ␳b9 and ␦(A,B) have both
been shown to correlate with the classical Lewis bond order.23,24
These statistics, however, include only 3 data points and, while
suggestive, are insufficient to claim general trends as we remark
in Ref. 20 The purpose of this paper is to explore the generality of
these preliminary findings by enlarging the molecular set to 9
metal dimers from groups 10, 11, and 12 (including the 3 coinage
metal atoms dimers that were considered previously). The results
reflect the fundamental role played by the molecular electron
density, a quantum mechanical observable, in the quantitative
description of bonding, even in the case of the bond dissociation
energy, an energy difference that depends on the energies of both
reactants and products.
Molecular set
The diatomics considered in this study are the group 10, 11, and
12 transition metal homonuclear dimers: Ni2, Pd2, Pt2, Cu2, Ag2,
Au2, Zn2, Cd2, and Hg2. The ground electronic state of each dimer
was established by geometry optimization for both singlet and
triplet states; the state exhibiting the lowest energy was taken as
the ground electronic state. As discussed below, these species
exhibit a wide range of bonding, with bond dissociation energies
that are very large for the group 10 dimers and very small for the
group 12 dimers.
Computational details
Electronic structure calculations
Two sets of ab initio calculations have been carried out within
the Born–Oppenheimer and frozen-core approximations: (i) single
reference coupled cluster (CC) with single and double excitations
(CCSD) and (ii) CCSD with triple excitation correction CCSD(T). The
combination of the nonrelativistic CCSD and CCSD(T) Hamiltoni-
ans with the ECPnMDF pseudopotential (PP)25–28 and their corre-
sponding consistent aug-cc-pVTZ-PP(spdfg) basis set27–30 were
constructed within the pseudorelativistic framework to account
for both scalar relativistic and spin-orbit coupling effects between
the inner core electrons and the valence electrons. A tight thresh-
(SCF) density-matrix calculations. Thresholds of 1.5 × 10−5 and
4.0 × 10−5 hartree/bohr for residual maximum forces and residual
root-mean square forces on the nuclei, respectively, were imposed
on all energy minimizations. Frequency calculations via har-
monic oscillator approximation were subsequently performed to
obtain the zero point energy (ZPE).
The total number of electrons and the number of electrons that
have been replaced by the ECPnMDF pseudopotential for each
element (total/ECPnMDF) are: Ni = 28/10, Pd = 46/28, Pt = 78/60,
Cu = 29/10, Ag = 47/28, Au = 79/60, Zn = 30/10, Cd = 48/28, and
Hg = 80/60. Thus all electrons are replaced by the PP with the
exception of the outer 18, 19, and 20 electrons (which are treated
explicitly) for groups 10, 11, and 12, respectively. For each metal
atom in these groups, 8 of the remaining electrons are consis-
tently treated as core (outer core) and the rest as valence electrons
in our pseudorelativitic calculations. All calculated bond dissoci-
ation energies (BDE) were corrected for ZPE and for basis set su-
perposition error (BSSE) using Boys and Bernardi's counterpoise
approach (CP).31,32 The results of these two corrections (ZPE, and
BSSE-CP) are collected in Table 1.
Core-augmented pseudo-potential electron densities
Electron densities calculated using a pseudopotential, ␳PP, pres-
ent several problems for a topological analysis of the electron
density: (i) the lack of nuclear maxima and (ii) the appearance of
spurious topological features near the boundary of the core elec-
trons replaced by the pseudopotential. An elegant approximation
introduced by Keith and Frisch (KF) provides a practical resolution
of these problems.33
In the KF approximation,33 Douglass–Kroll–Hess two-component
(DKH2) scalar-relativistic34–37 all-electron DFT calculations were
performed on every atom of the periodic table (in the free neutral
ground state) using a very large basis set. Each core subshell con-
tribution (␳ss) to the total electron density (␳total) was separately
fitted to a linear combination of s-type (spherical) Gaussian func-
tions (␳ssfit). The total core electron density [␳total(core)] of a given
atom in a molecule is then approximated as:

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 Sadjadi et al. 585

Table 2. Total energies of singlet and triplet states and calculated bond lengths and bond dissociation energies for group 10, 11, and 12
homonuclear diatomics and their corresponding experimental values. (Calculations at the CCSD/ECPnMDF-aug-cc-pVTZ-PP and CCSD(T)/
ECPnMDF-aug-cc-pVTZ-PP levels of theory, with the unrestricted formulation applied for open-shell species).
|⌬Esinglet-triplet| ⌬(R-Rexp) BDE BDEEXP ⌬(BDE-BDEexp)
Diatomic 2S+1 E(total) (a.u.) (kcal/mol) R (Å) Rexp (Å) (Å) (kcal/mol) (kcal/mol) (kcal/mol)
Ni2
RCCSD 1 −337.89882 2.1086
UCCSD 3 −337.94285 27.6 2.0443 2.15456±0.0004a −0.1103 28.87 47.0896 (0.0461)a −18.22
RCCSD(T) 1 Not foundⴱⴱ
UCCSD(T) 3 Not foundⴱⴱ
Pd2
RCCSD 1 −253.92234 18.8 2.8006 0.32 5.26 23.752c −18.49
UCCSD 3 −253.89244 2.3052 2.48b
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RCCSD(T) 1 −253.96383 10.3 2.7443 0.26 7.37 −20.38

UCCSD(T) 3 −253.94738 2.3516
Pt2
RCCSD 1 −237.70174 2.3234
UCCSD 3 −237.73301 19.6 2.3026 2.33297±0.00044d −0.0304 118.76 73.3031c 45.46
RCCSD(T) 1 −237.76185 2.3637
UCCSD(T) 3 −237.78504 14.6 2.3199 −0.0131 127.83 54.53
Cu2
RCCSD 1 −393.33686 39.6 2.2412 0.0219 38.89 47.9f −9.01
UCCSD 3 −393.27374 4.0692 2.2193e
RCCSD(T) 1 −393.39233 43.9 2.2213 0.0020 44.04 −3.86
UCCSD(T) 3 −393.32233 2.6931
Ag2
RCCSD 1 −292.92371 32.6 2.5562 0.0259 32.34 37.8g −5.46
UCCSD 3 −292.87170 3.9492 2.5303g
RCCSD(T) 1 −292.96396 36.4 2.5454 0.0151 36.35 −1.45
UCCSD(T) 3 −292.90603 3.3066
For personal use only.

Au2
RCCSD 1 −270.35686 62.9 2.5055 0.0340 43.79 53.2i −9.41
UCCSD 3 −270.25668 2.4723 2.4715h
RCCSD(T) 1 −270.39952 2.5002 0.0287 48.43 −4.77
UCCSD(T) 3 Not foundⴱⴱ
Zn2
RCCSD 1 −452.91603 65.3 4.4194 0.01 0.19 0.6919j, 0.7977k, (0.7448)ⴱ −0.55
UCCSD 3 −452.81192 2.5186 4.19j,k, 4.62l, (4.41)ⴱ
RCCSD(T) 1 Not found
UCCSD(T) 3 −452.84807 2.5096
Cd2
RCCSD 1 −334.55446 63.3 4.4018 0.34 0.30 0.9378m −0.64
UCCSD 3 −334.45351 2.8213 3.78 (0.03)m, 4.07k,
4.33l, (4.06)ⴱ
RCCSD(T) 1 −334.59159 65.2 4.0664 0.01 0.54 −0.40
UCCSD(T) 3 −334.48774 2.8186
Hg2
RCCSD 1 −305.92087 93.3 4.0667 0.43 0.44 1.086o, 1.164q, (1.125)ⴱ −0.67
UCCSD 3 −305.77221 2.7491 3.605n, 3.69o,
3.63p, (3.64)ⴱ
RCCSD(T) 1 −305.95984 94.7 3.8515 0.21 0.72 −0.41
UCCSD(T) 3 −305.80892 2.7519
Note: (a) Ref. 51. (b) Ref. 59. (c) Ref. 55. (d) Ref. 52. (e) Ref. 45. (f) Ref. 46. (g) Ref. 60. (h) Ref. 61. (i) Ref. 62. (j) Ref. 63. (k) Ref. 48. (l) Ref. 64. (m) Ref. 65. (n) Ref. 66. (o) Ref. 67.
(p) Ref. 49. (q) Ref. 68.
ⴱAverage value of experimental bond lengths.

ⴱⴱThe single reference calculations failed due to highly multi-reference character of the electronic state at the given multiplicity and/or very shallow potential well

on the PES which did not satisfy the tight criteria applied to optimize the geometry.

[1] ␳total(core) ≈ 兺
core
␳ssfit
The KF density so obtained thus incorporates scalar relativistic
effects in an approximate manner. The resulting approximate den-
sity is well-behaved, and all spurious critical points and pathological
subshells
features in the topology and topography of the density are removed,
The total (all-electron) molecular electron density is then ap- as demonstrated in the recent literature.20,33,38 The last equality in
proximated as: eq. [2] expresses the approximate electron densities analyzed in this

关 共 兲兴
paper as well as in our previous work.20
[2] ␳total ⫽ 兺
all atoms
␳total(core) ⫹ ␳PP ≈ 兺 兺
all atoms core
␳ssfit ⫹ ␳PP All electronic structure calculations in this paper were per-
formed using Gaussian 09-Rev.B0139 and all QTAIM calculations
subshells were performed using AIMAll.40
The Muller approximation41 to the two-electron density matrix
where, in the first two summations, “all atoms” means all atoms in terms of natural orbitals of the one-electron density matrix has
for which the core has been replaced by a PP. been used by AIMAll40 to calculate electronic delocalization prop-

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 586 Can. J. Chem. Vol. 91, 2013

Table 3. Bond properties calculated at the CCSD/ECPnMDF-aug-cc-pVTZ-PP level of theory, with the unrestricted formulation applied for
open-shell species.
Group Species 2S+1 BDE Bond length ␦(A,B) ␳b ⵜ2␳b ␭1,2 ␭3 Vb Gb Hb
10 Ni2 3 28.9 2.0443 1.579 0.099 0.372 −0.110 0.592 −0.189 0.140 −0.049
10 Pd2 1 5.3 2.8006 0.439 0.035 0.097 −0.029 0.156 −0.038 0.031 −0.007
10 Pt2 3 118.8 2.3026 1.781 0.130 0.384 −0.128 0.640 −0.228 0.162 −0.066
11 Cu2 1 38.9 2.2412 1.014 0.063 0.146 −0.058 0.262 −0.079 0.058 −0.022
11 Ag2 1 32.3 2.5562 1.013 0.055 0.152 −0.045 0.243 −0.066 0.052 −0.014
11 Au2 1 43.8 2.5055 1.125 0.083 0.192 −0.074 0.341 −0.108 0.078 −0.030
12 Zn2 1 0.2 4.4194 0.057 0.002 0.003 −0.001 0.005 0.000 0.001 0.000
12 Cd2 1 0.3 4.4018 0.083 0.003 0.004 −0.001 0.006 −0.001 0.001 0.000
12 Hg2 1 0.4 4.0667 0.090 0.005 0.010 −0.002 0.015 −0.002 0.002 0.000
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Note: Dimensioned quantities are all in atomic units (a.u.) except bond lengths which are in Å. The subscript b signifies that the value is reported at the “bond
critical point”; ␦(A,B) is the delocalization index between atoms A and B; ␭n is the nth curvature of the electron density at the BCP where by convention |␭1| ≥ |␭2|; and
Vb, Gb, and Hb are the potential, gradient kinetic, and total energy densities at the BCP, respectively. Hb = Vb + Gb. The bond ellipticity, defined by ␧ = ␭1/␭2 − 1, is zero
for all these dimers that possess cylindrical symmetry (C∞-axis).

Table 4. Atomic properties calculated by numerical integration over atomic basins at the CCSD/ECPnMDF-aug-cc-pVTZ-PP level of theory, with
the unrestricted formulation applied for open-shell species.
Vol(⍀), Error
Diatomic N(⍀)a LI(⍀)a %loc(⍀)a 0.001a E(⍀)b ␮(⍀) 兺
⍀
E(⍀) (kcal/mol)
Ni2 18.000 17.219 95.66 250.170 −168.971102 0.333 −337.942203 0.41
Pd2 18.000 17.781 98.78 254.849 −126.961113 0.046 −253.922225 0.07
Pt2 18.000 17.109 95.05 292.433 −118.865524 0.286 −237.731051 1.23
Cu2 19.000 18.493 97.33 241.914 −196.668335 0.258 −393.336669 0.12
Ag2 19.000 18.493 97.33 282.114 −146.461704 0.287 −292.923710 0.00
Au2 19.000 18.437 97.04 285.031 −135.178061 0.233 −270.356859 0.00
Zn2 20.000 19.971 99.86 319.017 −226.458017 0.027 −452.916034 0.00
Cd2 20.000 19.958 99.79 368.526 −167.277232 0.044 −334.554465 −0.00
For personal use only.

Hg2 20.000 19.955 99.78 338.321 −152.960446 0.044 −305.920892 −0.01

aN(⍀) = total number of electrons in basin ⍀, excluding the ECP electrons; LI(⍀) = electron localization index; %loc(⍀) = percent localization = [LI(⍀)/N(⍀)] ×

100; Vol(⍀) 0.001 = atomic volume calculated up to the isodensity surface of ␳ = 0.001 a.u., i.e., the van der Waals surface.
bVirial-based total basin energy corrected by the molecular virial ratio. The last column (error) is the difference between the total energy obtained directly

from the electronic structure calculation and twice the atomic energy obtained by numerical integration, and hence, is a measure of the quality of the atomic
integration.

erties. Core electrons modeled by the ECP are not included in the
calculation of the DIs. In general, DIs calculated with the Muller
approximation41 (and which includes the effects of electron Cou-
lombic correlation, approximately) are generally lower, often sig-
nificantly, than their Hartree–Fock counterparts as Coulombic
correlation disrupts electron pairing.42
Results and discussions
Electronic ground states
Considering the highly multiconfigurational character of some
of the transition metal diatomics (in particular Ni2)43 and the
significant effect of spin-orbit coupling on the ground electronic
structure of these dimers,44 it is necessary to establish the reliabil-
ity of the wavefunction in predicting the molecular properties
prior to a detailed topological analysis of the ensuing electron
densities.
The calculated CCSD and CCSD(T) total energies and their cor-
responding optimized internuclear distances (R) together with
experimental internuclear distances (Rexp) are collected in Table 2.
For the group 11 and 12 dimers it may be seen that the singlet
states are lower in energy (more stable) than the triplet states,
with energy gaps greater than 30 kcal/mol (1 cal = 4.184 J). This
prediction of singlet electronic ground states for group 11 and 12
dimers is consistent with the spectroscopically determined ground
states.45–50
In contrast, the electronic ground states for Ni2 and Pt2 are
predicted to be triplet at both the CCSD and CCSD(T) levels,
although spectroscopic experiments have suggested a mixture
of singlet and triplet states for Ni251 and a singlet state for
Pt2.52,53
The electronic ground state for Pd2 is predicted to be singlet,
but the electronic ground state of this dimer has been determined
as 3 兺 u⫹ by photoelectron spectroscopy.54,55 This discrepancy
between the theoretically and experimentally determined
ground states for the group 10 dimers may be examined in
future work.
In Table 2 the experimental bond lengths and bond dissociation
energies are listed along with those calculated at the theoretical
electronic ground states. Table 2 also lists the differences (⌬) be-
tween theory and experiment for the bond dissociation energies.
The similar ⌬ values indicate that the CCSD and CCSD(T) results
are consistent, and from this consistency it may be inferred that
information about the bonding from CCSD should be of almost
the same quality as that from CCSD(T). This is important because
at the time of writing the coupled cluster relaxed density matrix
can only be obtained from the CCSD wavefunctions.
Correlation between bond dissociation energy (BDE) and
bond properties
A linear correlation between BDE and ␳b values was previously
reported for coinage metal dimers, where in all cases the bonding
was characterized by p2␳b > 0, Hb < 0 and ␦(A,B) ≈ 1.0 at the MP2
level.20 Here we examine this correlation at the CCSD level and
extend our study to the group 10 and 12 dimers.
CCSD(T) calculations at the complete basis set limit and exper-
imental measurements (see BDE values in Table 2) provide con-
vincing evidence that group 12 dimers are all of the van der Waals
type.56 In contrast, recent ab initio calculations and subsequent
population analyses of 3d and 4d transition metal dimers with

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 Sadjadi et al.
Fig. 1. Correlation of BDE vs ␳b for homoatomic transition metal dimers. (a) Group 10. (b) Group 11. (c) Group 12. (d) All dimers pooled
together. (e) All dimers pooled together excluding Ni2. (Result of CCSD/ECPnMDF-aug-cc-pVTZ-PP calculations, with the unrestricted
formulation applied for open-shell species).
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For personal use only.
unfilled (n-1)d orbitals, such as Cr, W, and Mo, provide evidence of
multiple bonds.57
Bond properties for the group 10 and 12 dimers and the corre-
sponding atomic properties are presented in Tables 3 and 4, re-
spectively, all at the CCSD level. It may be seen that the bonding
for the group 10 dimers is characterized by p2␳b > 0 and Hb < 0,
indicating a location of the BCP in the valence shell charge deple-
tion region together with a high contribution of potential energy
density (Vb) at this point (Table 3). These characteristics of bonding
are very similar to those previously reported for group 11
dimers.20
In contrast, a marked distinction between group 10 and group 11
dimers is afforded by the values of the delocalization index (DI).
The values of the DI for group 10 dimers are substantially different
than the corresponding values for group 11 dimers. The large
values of ␦(Ni,Ni) = 1.579 and ␦(Pt,Pt) = 1.781 (for Ni2 and Pt2, re-
spectively) indicate considerable electron sharing in excess of
1½ electrons between the metal atoms; these values are equal to
the number of electrons shared in the bonding, since there is no
charge transfer in these dimers. We note in passing that a classical
double bond nature of the Pt–Pt bond has been suggested on the
basis of a comparison of the rotational constant values of Pt2 with
those of Au2.52 On the other hand, ␦(Pd,Pd) = 0.439 for Pd2, a
bonding clearly different than its two congeners Ni and Pt. The
587
much lower DI linking the two Pd atoms is consistent with a much
lower ␳b between these atoms (␳b = 0.035 a.u.), compared with a ␳b
of 0.099 and 0.130 a.u. for Ni2 and Pt2, respectively. It is important
to underscore that all the studied features of metal bonding re-
ported previously for the coinage metal dimers at the MP2 level
are reproduced at the CCSD level qualitatively and quantitatively
within reasonable accuracy (Tables 3 and 4).20
The QTAIM bonding descriptors calculated for group 12 dimers
(Table 3) are consistent with and provide support to the picture of
weakly bound dimers that emerged from experimental evidence
as described above.56 The bonding in this group is characterized
by very small values of ␳b (0.002 to 0.005 a.u.), p2␳b > 0, ␦(A,B) < 0.1,
and negative Hb of magnitudes less than 0.0005 a.u.
Studies of the Laplacian of the electron density for group 11 and
12 dimers have shown that the metal–metal bonding for transi-
tion metals is distinguished from that for main-group metals by a
large valence shell charge depletion zone (VSCD). This zone be-
comes larger from top to bottom in these groups, and in particular
both Hg2 and Au2 show very large (and diffuse) VSCDs.58 Thus,
each of the three groups of transition metals chosen in this study
is representative of one of the three fundamental types of bond-
ing, i.e., DI > 1.5 for group 10 (with the exception of Pd2), DI < 1.0
for group 11, and weak van der Waals type bonding with DI < 0.1
for group 12.
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 588
Fig. 2. Correlation of BDE with common QTAIM bond properties for all studied homoatomic transition metal dimers of the three groups
pooled together (the data points for Ni2 are shaded in gray). (a) DI [␦(A,B)]. (b) p2␳b. (c) ␭1,2. (d) ␭3. (e) Vb. (f) Hb. (Result of CCSD/ECPnMDF-aug-cc-
pVTZ-PP calculations, with the unrestricted formulation applied for open-shell species.)
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For personal use only.
Plots of BDE versus ␳b are shown in Fig. 1 for group 10, 11, and 12
dimers. It may be seen that the BDE–␳b plots for the group 11
(Fig. 1b) and 12 (Fig. 1c) dimers are close to linear (r = 0.94 and 0.99,
respectively). The BDE–␳b plot for the group 10 dimers (Fig. 1a)
shows the largest deviation from linearity (r = 0.86) as well as the
largest standard deviation. This large deviation is most probably
due to the multireference character of Ni2 and appears to indicate
that this particular dimer is not well represented by the level of
calculation in this work.
The observation of a linear correlation within each group (10, 11,
and 12) suggests that all of these dimers may lie on one general
BDE–␳b line. Pooling all calculated BDEs versus the corresponding
␳b values for all dimers in Fig. 1d clearly has a general linear trend,
with the Ni2 constituting the most noticeable outlier. The linear
correlation coefficient of the regression line in Fig. 1d is 0.876,
slightly higher than that for group 10. In Fig. 1d, the calculated
BDE values versus ␳b values for all dimers are replotted after the
omission of Ni2, which results in a significant improvement of the
linear correlation (r = 0.953). Substitution of the experimental
BDE value for Ni2 yields a value of ␳b = 0.067 a.u., a prediction to be
tested with future multireference calculations.
To provide a more complete picture of metal–metal bonding for
group 10, 11, and 12 transition metal homonuclear diatomics, the
correlation of BDE with other bonding indices (␦(A,B), p2␳b, ␭1,2,
Can. J. Chem. Vol. 91, 2013
␭3, Vb, and Hb = Vb + Gb) is now examined (Table 3 and Fig. 2).
Figure 2 shows that the bond dissociation energies of all dimers
except Ni2 (the only clear outlier) exhibit close to linear functional
dependence with respect to each of the studied bonding descrip-
tors.
The correlation between BDE and DI is of particular interest,
since the delocalization index is correlated to the classical bond
order, particularly in molecules with no charge transfer across the
studied bond. Data in Table 3 can be fitted to the relationship
proposed by Matta and Hernández:24
[3] ln[␦(A,B)] ⫽ a(␳b ⫺ b) ⫽ a␳b ⫺ c
where a, b, and c are fitting parameters, a having dimensions of
reciprocal electron density and b having those of the density. This
relation between the DI and ␳b, originally proposed for carbon–
carbon bonds, has been found to also apply for the metal–metal
bonding in the three coinage metal dimers.20 Fig. 3 shows direct
relation between ␦(A,B) and ␳b, which in the case of the studied
dimers exhibits no obvious curvature as expected from the expo-
nential dependence, ␦(A,B) = exp[a(␳b − b)], a curious feature pre-
sented here as an observation.
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 Sadjadi et al.
Fig. 4. BDE plotted against the natural logarithm of the DI (ln[␦(A,B)]) for homoatomic transition metal dimers. (a) Group 10. (b) Group 11.
(c) Group 12. (d) All dimers pooled together but excluding Ni2. (Result of CCSD/ECPnMDF-aug-cc-pVTZ-PP calculations, with the unrestricted
formulation applied for open-shell species.)
Can. J. Chem. Downloaded from www.nrcresearchpress.com by George Mason University on 06/24/13
For personal use only.
Fig. 3. Plot of the DI (␦(A,B)) as a function of ␳b for all homoatomic
transition metal dimers including Ni2. (Result of CCSD/ECPnMDF-
aug-cc-pVTZ-PP calculations, with the unrestricted formulation
applied for open-shell species.)
The BDE–␦(A,B) correlation plots are shown in Fig. 4a–4c for
group 10, 11, and 12 dimers. The linear correlation coefficients r for
the group 10 and 11 dimers are significantly less than 1.00 (r = 0.76
and 0.82, respectively) in view of the marked curvature of the
functional dependence of BDE on the logarithm of the delocaliza-
tion index. The value of r for the coinage metal dimers, 0.826, is
lower than that previously reported at the MP2 level (r = 0.925)
reflecting the almost equal DI values for Cu2 and Ag2 at the CCSD
level of theory.20 The linear correlation coefficient for the group
12 dimers is closer to unity (r = 0.905). Figure 4d depicts the calcu-
lated BDE versus DI values for all dimers except Ni2. The linear
correlation coefficient for this plot is significantly less than unity
(r = 0.774) and much lower than that for the corresponding BDE–␳b
plot (r = 0.95) in Fig. 1e.
These results are consistent with previous work that has shown
that BDE is correlated with ␳b in almost linear fashion (in compar-
589
ison with several other common QTAIM bonding indices), despite
the fact that in this work the bonds included in the statistics are
different in nature and do not share a common element.
Conclusions
We have employed coupled cluster CCSD and CCSD(T) calcula-
tions with the frozen-core approximation in combination with
recently developed pseudopotential-based correlation consistent
basis sets, followed by relativistic core augmentation, to obtain
electron densities for nine group 10, 11, and 12 transition metal
homonuclear diatomics. Using the calculated electron densities,
Bader's quantum theory of atoms in molecules (QTAIM) has been
used to calculate the bond and atomic basin properties of these
dimers. Features of metal–metal bonding observed previously for
coinage metal dimers (specifically, Hb < 0 and p2␳b > 0) were also
observed for group 10 and 12 dimers. The calculated ␳b and ␦(A,B)
values show that the nature of the metal–metal bonding in these
three groups of transition metal dimers is markedly different. In
traditional chemistry language, dimers are characterized by par-
tial and multiple bonds for group 10, by single bonds for group 11,
and by van der Waals interactions for group 12, a picture consis-
tent with our calculations.
In spite of the fundamental differences in metal–metal bond-
ing, we have shown that for all transition metal dimers (with the
exception of Ni2 that exhibits considerable multireference char-
acter) there is a linear correlation between the strength of the
metal–metal bond and the value of the electron density at the
bond critical point (and also with several other QTAIM bonding
descriptors). This correlation has previously been established for
bonding between the same pair of elements in a series of related
compounds. We have established this correlation for bonding be-
tween different pairs of elements. Whether this correlation is con-
fined to certain transition metal dimers or is general for all
diatomics (homo and hetero, metal and non-metal) remains an
open question.
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 590
Acknowledgements
The authors dedicate this paper to Professor Denis Salahub.
This research was conducted using the HKU Information Technol-
ogy Services Research Computing Facilities and Mount Saint Vin-
cent University computer cluster and has been supported
financially by Hong Kong UGC Special Equipment Grant (SEG
HKU09), Natural Sciences and Engineering Research Council of
Canada (NSERC), Canada Foundation for Innovation (CFI), and
Mount Saint Vincent University.
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