Accurate thermochemistry for transition metal complexes from first-

principles calculations
Nathan J. DeYonker, T. Gavin Williams, Adam E. Imel, Thomas R. Cundari, and Angela K. Wilson

Citation: J. Chem. Phys. 131, 024106 (2009); doi: 10.1063/1.3160667

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 THE JOURNAL OF CHEMICAL PHYSICS 131, 024106 共2009兲

Accurate thermochemistry for transition metal complexes

from first-principles calculations
Nathan J. DeYonker,a兲 T. Gavin Williams, Adam E. Imel, Thomas R. Cundari, and
Angela K. Wilson
Department of Chemistry, Center for Advanced Scientific Computing and Modeling (CASCaM),
University of North Texas, Denton, Texas 76203-5070, USA
共Received 16 April 2009; accepted 9 June 2009; published online 8 July 2009兲

The “correlation consistent Composite Approach” or ccCA is an ab initio model chemistry based on
the single reference MP2 level of theory. By adjusting the basis set and level of theory of the core
valence additive correction, ccCA is capable of reliable thermochemical predictions of inorganic and
organometallic transition metal-containing molecules, as well as achieving chemical accuracy on
main group species, with a mean absolute deviation of 0.89 kcal mol−1 against the 147 enthalpies
of formation in the G2/97 test set. For a set of 52 complexes containing elements Sc–Zn, ranging in
size from diatomics to Ni共PF3兲4 and Fe共C5H2兲2, ccCA on average predicts enthalpies of formation
to within ⫾3 kcal mol−1 of the experimental result with a mean absolute deviation of
2.85 kcal mol−1 and a root mean square deviation of 3.77 kcal mol−1. The ccCA methodology is a
significant step toward quantitative theoretical modeling of transition metal thermodynamics.
© 2009 American Institute of Physics. 关DOI: 10.1063/1.3160667兴

I. INTRODUCTION be to develop first principles computational techniques to

The energetic content of a material or the energetic bal-
ance of a chemical process is arguably the most important
physical factor in determining its suitability. For example,
explosives must detonate with sufficient energy to achieve
their intended purpose but must be stable enough to be safely
handled. Catalysts must be active enough to allow reactants
to swiftly traverse reaction coordinates to produce the many
products needed by our society—fuels, drugs, commodity
and bulk chemicals, etc.—but not so high in energy that they
react in unintended ways 共i.e., display low selectivity兲.
Societal progress has long been marked by the mastery
of metals. Among these, the d-block 共or transition兲 metals
occupy a pivotal position in numerous technical fields. These
include current technologies that form the foundation of
modern society 共e.g., the fixation of dinitrogen by iron cata-
lysts to make ammonia for fertilizers兲1,2 and necessary new
technologies 共e.g., photosplitting of water to produce
hydrogen3 or materials4 to more efficiently convert sunlight
to electricity兲. The past decades have seen a revolution in
how scientific research is conducted, whereby modeling and
simulation now complement the traditional pursuits of theory
and experiment. Despite rapid advances, modeling and simu-
lation of transition metal containing entities—at all scales
from molecular to device level—lag behind comparable
methods for nonmetal species, in large part due to the ability
of transition metals to stabilize many disparate chemical and
physical environments. It is, however, the same aptitude that
has made transition metals an important ally in technological
advancement. To the extent that modeling and simulation
will play an important role in identifying new materials and
processes for technological advances, an essential goal must
a兲
Electronic mail: ndeyonk@unt.edu.
calculate their energetic content reliably, accurately, and ef-
ficiently. Herein, we describe a methodology that provides a
substantial improvement in accuracy over previous MP2-
based techniques and in efficiency over coupled cluster-
based techniques, and achieves the aforementioned goals for
large, chemically relevant transition metal species without
resorting to ad hoc parameters.
A host of theoretical hurdles have thwarted efforts at
using single reference ab initio methods for quantitative tran-
sition metal computational chemistry. To name a few, these
include strongly interacting valence electrons, increased im-
portance of core-core and core-valence electron correlation, a
diversity of low-lying excited electronic states, and relativis-
tic effects. The evolution of density functional theory 共DFT兲,
electron pseudopotentials, and multireference techniques to
treat heavy element chemistry has resulted in many success-
ful and synergistic avenues between experimental and com-
putational chemistry. However, the aforementioned problems
with transition metals, exacerbated by the nonsystematic na-
ture of treating electron correlation via DFT5–8 and multiref-
erence methods9–13 mean that quantitative transition metal
共TM兲 thermochemistry remains a lofty goal.
There has been some success using single reference
coupled cluster theory to study inorganic chemical problems.
Nielsen and co-workers14–16 examined the enthalpies of for-
mation 共⌬H f 兲 for chromium compounds. Dixon and
co-authors17–20 used a coupled cluster-based model chemis-
try to examine binding and electronic excitation energies of
some transition metal oxides. Hyla-Kryspin and Grimme21
used spin-component scaled MP2 and MP3 methods to ob-
tain metal-carbonyl bond dissociation energies 共BDEs兲. Gen-
erally, however, the quality, quantity, and reliability of re-

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024106-2 DeYonker et al.
search involving high-accuracy calculation of transition
metal thermodynamic properties greatly lag behind that of
their main group counterparts.
Ab initio methods should ideally be calibrated against a
set of well-established experimental energetic quantities
and/or the most sophisticated theoretical results that are tech-
nologically possible. While there are enormous test sets for
main group/organic energetic quantities,22–24 the same cannot
be said for inorganic molecules. In part, appropriate compari-
son of transition metal-containing molecules with experi-
mental values contained in popular thermochemical compen-
dia is problematic because the uncertainties 共when these are
even reported兲 in transition metal thermochemical quantities
are often significantly larger than those for main group spe-
cies, certainly outside of the usual definition of “chemical
accuracy” 共i.e., ⫾1 kcal/mol兲, and in extreme cases literature
values 关cf. the ⌬H f共g兲 of titanocene dichloride, Ti共C5H5兲2Cl2,
listed in the NIST webbook兴25 can differ by over
70 kcal mol−1. The largest sets of transition metal thermody-
namic data available so far are from DFT studies by Furche
and Perdew,7 Rinaldo et al.,26 and Riley and Merz.6 Except
for the Riley and Merz study, most comparisons of experi-
mental and theoretical data have focused on DFT perfor-
mance on TM dissociation energies. The Riley and Merz
study contains the largest number of enthalpies of formation
benchmarked so far. However, all 12 of the density function-
als investigated, including the functional that performed the
best 共TPSS1KCIS兲, showed inconsistent performance from
the early to middle to late elements in the 3d block.6
Another major impediment for quantitative transition
metal thermochemistry has been the lack of high-quality ba-
sis sets. While basis sets have been created for elements
Sc–Zn,27–30 the TM basis sets that would allow systematic
convergence of thermochemical properties with respect to
increasing basis set size simply did not exist until recently,
when Peterson and Balabanov31,32 expanded the suite of cor-
relation consistent basis sets to include elements Sc–Zn.
A focus of the research in our laboratories has been the
development of the correlation consistent Composite Ap-
proach 共ccCA兲, an efficient MP2-based model chemistry that
uses correlation consistent basis sets. Tested against a variety
of main group energetic properties, ccCA has been shown to
be comparable to the most accurate formulations of the MP4-
based G3 methods 共G3X兲 and improved accuracy versus the
MP2-based G4 variant 关G4共MP2兲兴.33 Where MP2-based
model chemistries and even some coupled cluster-based
model chemistries have failed, ccCA has been able to be
used to reliably compute energies and thermodynamic prop-
erties, viz., alkali and alkaline earth metal oxides and
hydroxides,34,35 hypervalent inorganics,36 sulfur-containing
molecules with substantial multireference character,37 and
heavy p-block molecules.38
It is worth noting that the most recent formulation of
ccCA contains no empirical parameters. Even the harmonic
vibrational scale factor in ccCA, used to account for anhar-
monic vibrational effects, is calibrated based on theoretical
zero-point energies 共ZPEs兲. Comparatively, the G3 methods
have a “high level correction” or HLC utilizing four opti-
mized energy corrections, and G4 methods contain six.
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J. Chem. Phys. 131, 024106 共2009兲
While the newest hybrid metaexchange DFT functionals de-
veloped by Truhlar and co-worker39 have a mean absolute
deviation 共MAD兲 in calculated versus experimental energet-
ics of 5.6– 5.7 kcal mol−1 for 48 different metal-bonding
situations, these functionals may contain more than a dozen
optimized parameters.
While developing ccCA, we sought a HLC-free ap-
proach with the target of a uniform ab initio recipe for com-
puting accurate and efficient energies across the entire peri-
odic table without utilization of large basis set coupled
cluster computations. In earlier work, DeYonker et al.40 used
ccCA to compute enthalpies of formation for 18 small
transition-metal-containing molecules and compared them to
an accurate coupled-cluster based model chemistry 关CBS-
CCSD共T兲兴. Agreement between ccCA and CBS-CCSD共T兲
was satisfactory. Over a subset of eight enthalpies of forma-
tion for which the latter was computationally feasible, the
ccCA MAD was 3.4 versus 3.1 kcal mol−1 for CBS-
CCSD共T兲. Our laboratories sought a target “transition metal
chemical accuracy” of ⫾3.0 kcal mol−1, this choice reflect-
ing the aforementioned increased uncertainties vis-à-vis TM
thermochemistry.
However, as the “ccCA-TM” method was further tested
on larger inorganic complexes, serious problems emerged.
For example, the ccCA-predicted enthalpy of formation for
Ni共CO兲4 was in error by 30– 100 kcal mol−1 when using
various ccCA schemes. For the CBS-CCSD共T兲 model chem-
istry, the error was only 5.5 kcal mol−1 from the experimen-
tal value of −144⫾ 2.5 kcal mol−1. Upon further investiga-
tion, it was discovered that the MP2-based additive
correction for core-valence and core-core electron correlation
was quickly deteriorating in quality with increasing molecu-
lar size. By improving the treatment of correlation for the
core-valence ccCA step from MP2 to MP3 or CCSD, vastly
improved results were found for carbonyl complexes and
larger molecules such as ferrocene. However, the computa-
tion of core-valence electron interactions became the bottle-
neck of the ccCA algorithm and greatly increased the com-
putational requirements. Because the ccCA methodology is
not based on semiempirical parameters, it is possible to in-
vestigate changes to the level of theory and basis set used in
the core-valence term. In this manuscript, we propose a
modification of ccCA based on improved physics rather than
ad hoc parameters that retains chemical accuracy for main
group molecules, as well as predicts accurate enthalpies of
formation for smaller inorganic radicals and larger inorganic
and organometallic species.
II. METHODS
There are five major technical modifications to the new
ccCA-TM model chemistry versus that previously
reported.33,36,40 First, equilibrium geometries and harmonic
vibrational frequencies are computed using the B3LYP/cc-
pVTZ level of theory. Second, for single point energies, all
computations utilize the Douglas–Kroll basis sets and em-
ploy the spin-free, one-electron Douglas–Kroll–Hess
Hamiltonian.41,42 Third, the basis set level for the additive
correction accounting for core valence correlation effects is
024106-3 Thermochemistry for inorganic complexes J. Chem. Phys. 131, 024106 共2009兲

TABLE I. Formulation of the previously recommended ccCA for main group atoms vs the more “pan-periodic” formulation used in this study. For atoms
Na–Ar, cc-pV共X + d兲Z basis sets are always used with ccCA.

ccCAa ccCA-TM

Optimization B3LYP cc-pVTZ B3LYP cc-pVTZ

Harmonic frequencies B3LYP cc-pVTZ scaled by 0.989 B3LYP cc-pVTZ scaled by 0.989
HF CBS HF aug-cc-pVTZ HF aug-cc-pVTZ-DK
HF aug-cc-pVQZ HF aug-cc-pVQZ-DK
HF CBS fit E共n兲 = EHF-CBS + B exp共−1.63n兲 E共n兲 = EHF-CBS + B exp共−1.63n兲
MP2 CBS MP2 aug-cc-pVDZ MP2 aug-cc-pVDZ-DK
MP2 aug-cc-pVTZ MP2 aug-cc-pVTZ-DK
MP2 aug-cc-pVQZ MP2 aug-cc-pVQZ-DK
MP2 CBS fit “P ” = E共x兲 = ECBS + B exp关−共x − 1兲兴 + C exp关−共x − 1兲2兴 “P ” = E共x兲 = ECBS + B exp关−共x − 1兲兴 + C exp关−共x − 1兲2兴
B
“S3 ” = E共lmax兲 = ECBS +
共lmax兲3
“PS3 ” = 1 / 2ⴱ共“P ” + “ S3”兲
⌬共CC兲 CCSD共T兲 cc-pVTZ CCSD共T兲 cc-pVTZ-DK
⫺ MP2 cc-pVTZ ⫺MP2 cc-pVTZ-DK
⌬共CV兲 MP2共FC1兲 aug-cc-pCVTZ CCSD共T,FC1兲 aug-cc-pCVDZ-DK
⫺ MP2 aug-cc-pVTZ ⫺CCSD共T兲 aug-cc-pCVDZ-DK
⌬共DK兲 MP2 cc-pVTZ-DK Folded into all energy calculations
⫺ MP2 cc-pVTZ
⌬共SO兲 Experimental atomic values Experimental atomic values
FOCI Stuttgart ECP for molecules
a
From Ref. 33.

computed using basis sets of double-zeta quality, but the
wave function is computed using CCSD共T兲. Fourth, a small
basis set CCSD共T兲 computation is performed to avoid double
counting the extra basis polarization in the core-valence ad-
ditive correction. Overall, the core valence additive correc-
tion is
⌬E共CV兲 = E关CCSD共T,FC1兲/aug-cc-pCVDZ-DK兴
− E关CCSD共T,valence兲/aug-cc-pCVDZ-DK兴.
In the usual notation, “FC1” indicates that all electrons of
first-row atoms are correlated, all electrons of atoms Na–Ar
are correlated except the 1s orbitals, and all electrons of
atoms K–Kr are correlated except the 1s2s2p orbitals, i.e.,
the inner noble gas core molecular orbitals remain frozen.
Fifth, molecular spin-orbit coupling energy corrections are
computed using Stuttgart “small-core” effective core poten-
tials 共ECP10MDF兲 for TM elements43 and cc-pVTZ basis
sets for main group elements.44 Table I shows the additive
corrections of the new ccCA formulation compared to that in
Ref. 33. All computations employing an unrestricted Hartree-
Fock 共UHF兲 reference were performed using GAUSSIAN 03,45
while all computations employing a restricted open shell
Hartree-Fock 共ROHF兲 reference wave function were per-
formed using MOLPRO 2006.1.46
III. RESULTS
To assess the modified ccCA method against a set of
transition metal-containing species, it is first necessary to
reexamine the performance for main group species. A pri-
mary ethos of ccCA is to develop a chemically accurate com-

TABLE II. MSDs and MADs 共in kcal mol−1兲 of ccCA against the G2/97 enthalpies of formation.

UHF ccCA-PS3 UHF ccCA-TM ROHF ccCA-TM

MSDs
Enthalpies of formation 共147兲 0.20 0.08 ⫺0.24
Nonhydrogens 共34兲 0.20 0.27 ⫺0.27
Hydrocarbons 共22兲 ⫺0.25 ⫺0.77 ⫺1.16
Substituted hydrocarbons 共47兲 0.52 0.31 ⫺0.17
Inorganic hydrides 共15兲 0.99 1.12 0.95
Radicals 共29兲 ⫺0.38 ⫺0.40 ⫺0.24

MADs
Enthalpies of formation 共147兲 0.81 0.91 0.89
Nonhydrogens 共34兲 0.86 0.80 0.92
Hydrocarbons 共22兲 0.75 1.03 1.22
Substituted hydrocarbons 共47兲 0.83 0.92 0.80
Inorganic hydrides 共15兲 0.99 1.12 0.95
Radicals 共29兲 0.68 0.84 0.72

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024106-4 DeYonker et al. J. Chem. Phys. 131, 024106 共2009兲

TABLE III. Deviations of ten enthalpies of formation from initial ccCA transition metal benchmark set using ccCA and the CBS-CCSD共T兲 model chemistry
described in Ref. 40. All units are in kcal mol−1.

Old UHF ROHF Old UHF ROHF-TM

CBS-CCSD共T兲 ccCA-S4 共Q5兲 ccCA-TM ccCA-TM CBS-CCSD共T兲 ccCA-S4 共Q5兲 ccCA-TM ccCA
Expt. ⌬H f ⌬H f ⌬H f ⌬H f deviation deviation deviation deviation

TiF2 −164.5⫾ 10 ⫺131.0 ⫺138.0 ⫺130.5 ⫺132.7 ⫺33.5 ⫺26.5 ⫺34.0 ⫺31.8
TiF3 −284⫾ 10 ⫺259.7 ⫺267.1 ⫺260.4 ⫺265.6 ⫺24.3 ⫺16.9 ⫺23.6 ⫺18.4
VO 31.8⫾ 2 32.3 27.7 38.0 32.8 ⫺0.5 4.1 ⫺6.2 ⫺1.0
VO2 −41.6⫾ 3.3 ⫺38.4 ⫺44.6 ⫺30.3 ⫺39.8 ⫺3.2 3.0 ⫺11.3 ⫺1.8
CrO3 −77.3⫾ 1.0 ⫺63.3 ⫺82.0 ⫺69.3 ⫺69.3 ⫺14.0 4.7 ⫺8.0 ⫺8.0
FeCl2 −31.7⫾ 0.2 ⫺32.1 ⫺35.2 ⫺22.1 ⫺32.5 0.4 3.5 ⫺9.6 0.8
CoCl3 −39.1⫾ 2.5 ⫺35.7 ⫺35.0 ⫺38.3 ⫺34.6 ⫺3.4 ⫺4.1 ⫺0.8 ⫺4.5
NiCl2 −17.4⫾ 1.6 ⫺14.6 ⫺18.4 ⫺14.1 ⫺14.1 ⫺2.8 1.0 ⫺3.3 ⫺3.3
CuF −3.1⫾ 2.0 2.3 ⫺3.0 0.2 0.3 ⫺5.4 ⫺0.1 ⫺3.3 ⫺3.4
CuF2 −63.8⫾ 3.0 ⫺64.7 ⫺59.8 ⫺61.9 ⫺67.3 0.9 ⫺4.1 ⫺1.9 3.5
Ni共PF3兲4 −953.4⫾ 2.4 ⫺1034.4 ⫺957.7 ⫺957.0 81.0 4.3 3.6
Cr共CO兲6 −240⫾ 1.1 ⫺269.7 ⫺238.7 ⫺237.8 29.7 ⫺1.3 ⫺2.2
Mn共CO兲5Cl −219.5⫾ 3.1 ⫺253.8 ⫺218.3 ⫺217.4 34.3 ⫺1.2 ⫺2.1
Fe共CO兲5 −173.0⫾ 1.6 ⫺221.7 ⫺179.6 ⫺179.1 48.7 6.6 6.1
Ni共CO兲4 −144⫾ 2.5 ⫺136.7a ⫺189.6 ⫺143.4 143.3 ⫺7.4 45.6 ⫺0.6 ⫺0.7
Fe共C5H5兲2 57.9⫾ 0.6 30.2 55.0 55.7 27.7 2.9 2.2

MSD all 14.48 ⫺5.71 ⫺3.81

MSD w/o
larger
species 3.56 ⫺8.59 ⫺3.54 ⫺10.20 ⫺6.79
MSD w/o
TiFx 1.95 ⫺3.50 1.00 ⫺5.55 ⫺2.21
MSD w/o
TiFx and
CrO3 2.09 ⫺2.01 0.47 ⫺5.20 ⫺1.38
Standard deviation
w/o TiFx and
CrO3 2.31 3.42 3.98 2.78

MAD all 20.94 7.43 5.84

MAD w/o
larger
species 8.84 6.79 10.20 7.65
MAD w/o
TiFx 3.82 3.06 5.55 3.29
MAD w/o TiFx and
CrO3 2.37 2.83 5.20 2.62
a
For the CBS-CCSD共T兲 computations on Ni共CO兲4, cc-pVxZ basis sets were used in the CBS extrapolations instead of aug-cc-pVxZ sets.

posite ab initio method that is pan periodic, whereby one
formulation results in acceptable accuracy for molecules
across the entire periodic table. Table II shows the original
recommended formulation of ccCA 共denoted as ccCA-PS3兲
compared to the new formula using both unrestricted and
restricted Hartree–Fock wave functions for open-shell atoms
and molecules 共UHF ccCA-TM and ROHF ccCA-TM, re-
spectively兲 and their performance against the 147 main
group enthalpies of formation contained in the G2/97 train-
ing set.47 While there is a slight decrease in overall accuracy,
the new ccCA-TM methods show little systematic bias and
the performance is still within the boundaries of main group
chemical accuracy. The ROHF-ccCA-TM method has a
mean signed deviation 共MSD兲 of −0.24 kcal mol−1 and a
MAD of 0.89 kcal mol−1 compared to a MSD of
0.20 kcal mol−1 and MAD of 0.81 kcal mol−1 for the previ-
ous formulation 共UHF-based ccCA-PS3兲.
In our initial study of TM thermochemistry,40 ten enthal-
pies of formation were compared using both ccCA and a
CBS-CCSD共T兲 based model chemistry. In the previous work,
the enthalpies of formation of five carbonyl-containing com-
plexes and ferrocene were computed using ccCA-S4 共Q5兲.
The average error for these six larger molecules was
+44.5 kcal mol−1. For the smaller molecules, Table III
shows the deviations of the ten small TM-containing mol-
ecules from our initial investigation using the “old”
ccCA-TM method 关共ccCA-S4 共Q5兲兴 and the new ccCA-TM
method, again the latter with both UHF and ROHF reference
wave functions. Six out of ten of the CBS-CCSD共T兲 values
are within two times the experimentally quoted uncertainties.
Previously, the enthalpies of formation for TiF2, TiF3, and
CrO3 were recognized as being significant outliers and theo-
retical results cast significant doubt on the quality of the
literature values.40 In the case of CuF, although the value

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024106-5 Thermochemistry for inorganic complexes J. Chem. Phys. 131, 024106 共2009兲

TABLE IV. Listing of molecules in the ccCA-TM test set along with ground electronic states used to compute
energies.

Ground state Ground state Ground state

ScO 2
⌺+ MnCl 7
⌺+ NiCl 2
⌸
ScF 1
⌺+ MnCl2 6
⌺+ NiCl2 3
⌺−g
ScF3 1
A⬘1 MnF ⌺
7 +
NiF2 ⌺g
3 −

ScCl3 1
A1 MnS ⌺
6 +
Ni共CO兲4 1
A1
Mn共CO兲5Cl 1
A1 Ni共PF3兲4 1
A1
TiO 3
⌬ Mn共CO兲5 2
A1
1
TiO2 A1
TiF2 3
⌬g FeCl 6
⌬ CuO 2
⌸
TiF3 2
A⬘1 FeCl2 5
⌬g CuF 1
⌺+
TiCl2 3
⌬g FeCl3 6
A⬘1 CuF2 2
兺g
TiF4 1
A1 FeCO ⌺
3 −
CuCl ⌺
1 +

Fe共CO兲2 兺g
3 −
Cu2 ⌺
1 +

VO 4
⌺− Fe共CO兲3 3
⌬2 CuH ⌺
1 +
2 3
VO2 A1 Fe共CO兲4 B1
VF5 1
A⬘1 Fe共CO兲5 1
A⬘1 Zn共CH3兲2 1
A1
VCl 5
⌬ Fe共C5H5兲2 1
A1g Zn共CH2CH3兲2 1
Ag
Fe共C5H5兲 1
A⬘ Zn共CH2CH2CH3兲2 1
A
CrO3 1
A1 ZnCl ⌺
2 +

CrCl 6
⌺+ CoCl3 5
A1 ZnCl2 兺g
1 +

Cr共CO兲3 1
A1 CoCl2 3
⌬g ZnH ⌺
2 +

Cr共CO兲4 1
A1 CoF2 4
⌬g
1 1
Cr共CO兲5 A1 Co共CO兲4H A1
1 2
Cr共CO兲6 A1g Co共CO兲4 A1

from the Yungman compendium48 has smaller error bars,
both the CBS-CCSD共T兲 and ccCA results are within the error
bars of the JANAF value 共1.1⫾ 3 kcal mol−1兲. After remov-
ing TiF2, TiF3, and CrO3 from this test set the MSDs of the
CBS-CCSD共T兲 and ROHF ccCA are ⫺2.01 and
−1.38 kcal mol−1, respectively. The MSD of the old ccCA
enthalpies for this subset has the smallest magnitude versus
the new formulations, but deviations in the original ccCA
method were usually of opposite sign to the CBS-CCSD共T兲
values. The agreement of ROHF ccCA-TM and CBS-
CCSD共T兲 MSDs suggests a more favorable comparison. The
MADs of CBS-CCSD共T兲 and ROHF ccCA-TM are 2.37 and
2.62 kcal mol−1, and these two methods are more reliable
than the previous formulation of ccCA for transition metals.
Because of the test set used in the initial ccCA-TM paper, it
was difficult to make a clear distinction between the perfor-
mance of ccCA-S4 共Q5兲 and the newer UHF- and ROHF-
based ccCA-TM model chemistry for smaller radical inor-
ganic species. However, the large positive deviations of the
larger classical inorganic complexes are evidence of system-
atic error, which is eliminated by incorporating a more so-
phisticated treatment of core-valence electron correlation.
In light of these positive results, enthalpies of formation
were computed using UHF and ROHF-based modified ccCA
methods for a larger set of 58 transition metal-containing
molecules. This training set includes larger carbonyl-
containing species such as Ni共CO兲4, Mn共CO兲5Cl, and
Cr共CO兲6, for which the previous version of ccCA for transi-
tion metals gave poor result deviations from experiment on
the order of several dozen kcal mol−1. Molecules containing
elements from Sc–Zn are represented, with the majority of
molecules in the test set being halogenated species and car-
bonyl species, due to the relative amount of reliable thermo-
chemical data in existence for these ligand families. Table IV
lists the molecules contained in our overall test set along
with the electronic ground states used in our computations.
Table V lists the MSDs and MADs for the test set. Experi-
mental values for the enthalpies of formation used in our
study, along with atomic ccCA energies, deviations, and
atomic/molecular spin-orbit corrections are in the supple-
mentary material.49
As an example, Fig. 1 shows the effect of ccCA additive
corrections upon Ni共CO兲4 for the previous ccCA implemen-
tation from Ref. 40 关ccCA-S4 共Q5兲兴 compared to the current

TABLE V. MSDs and MADs 共in kcal mol−1兲 of various ccCA-TM test sets.

No. of Average of MSD MAD MSD MAD

Test set molecules uncertainties UHF UHF ROHF ROHF

Overall 共set I兲 58 2.67 ⫺3.89 5.99 ⫺2.50 4.78

w/o TiFx and CrO3 共set II兲 55 2.43 ⫺2.91 5.13 ⫺1.58 3.98
w/o CrCOx FeC5H5 共set III兲 51 2.17 ⫺2.69 4.40 ⫺1.24 3.20
w/JANAF CrO3 and Ricca Fe共CO兲x 共set IV兲 52 2.22 ⫺2.58 4.17 ⫺1.15 2.85

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024106-6 DeYonker et al.
FIG. 1. Contributions of additive corrections to the enthalpy of formation of
Ni共CO兲4 共in kcal mol−1兲 using methodology from Ref. 40 关ccCA-S4共Q5兲兴 vs
new ccCA-TM with ROHF reference.
implementation 共ROHF ccCA-TM兲. A complete basis set
treatment at the MP2 level of theory is not sufficient for
accurate thermochemistry, as the MP2 CBS ⌬H f values are
off from experiment by 203– 244 kcal mol−1. For both
implementations, a treatment of extended electron correla-
tion 关via the CCSD共T兲 cc-pVTZ computation兴 contributes
almost 190 kcal mol−1 to the enthalpy of formation. How-
ever, the ccCA-S4 共Q5兲 core-valence addition correction
overcorrects at the MP2 aug-cc-pCVTZ level of theory, con-
tributing 37.0 kcal mol−1 to the ⌬H f versus only
9.2 kcal mol−1 using CCSD共T兲 aug-cc-pCVDZ in the new
ccCA implementation. Enthalpies of formation using the new
ROHF ccCA-TM are too low, but corrected accordingly via
ZPE and 共in the case of closed shell carbonyl and metal-
locene complexes兲 atomic spin-orbit corrections. Once all of
the additive corrections are included, the ⌬H f value of
Ni共CO兲4 is within the experimental error bars of
⫾2.5 kcal mol−1. The trends shown in Fig. 1 are general for
the larger molecules in our test set; emphasis on the treat-
ment of electron correlation rather than basis set size is cru-
cial for appropriate consideration of core-core and core-
valence correlation.
In the complete set of 58 molecules 共set I兲, the ROHF
ccCA-TM shows significant bias with a MSD of
−2.50 kcal mol−1 and a large mean absolute error with a
MAD of 4.78 kcal mol−1. The performance of UHF-based
ccCA-TM 共with a MAD of 5.99 kcal mol−1兲 is worse than
the results obtained using a ROHF reference wave function
for set I and all subsequent pruned test sets. Clearly spin
contamination is more pronounced for many transition metal
species. For example, the difference between the UHF and
ROHF enthalpies of formation for VO2 is 9.5 and
25.7 kcal mol−1 for CuO. A ROHF reference wave function
is therefore recommended for inorganic studies and all sub-
sequent discussion will focus on ROHF ccCA-TM results.
As the test set is slightly pruned 共vida infra), the statistical
differences between ROHF and UHF based ccCA-TM will
become more apparent.
Set I includes some previously discussed outliers, TiF2,
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J. Chem. Phys. 131, 024106 共2009兲
FIG. 2. Scatter plot of experimental vs theoretical ROHF ccCA-TM enthal-
pies of formation for the 52 molecules in set IV 共in kcal mol−1兲.
TiF3, and CrO3 from our first ccCA-TM study. The ROHF
ccCA-TM deviations from reported experimental values for
TiF2 and TiF3 are ⫺31.8 and −18.4 kcal mol−1, respectively.
These two enthalpies both depend on an enthalpy of subli-
mation for TiF3 determined experimentally by Zmbov and
Margrave.50 On the other hand, the experimental value for
TiF4, which is obviously not reliant on TiF3 vapor pressure
measurements, has a much more precise experimental value.
The ROHF ccCA-TM deviation of the TiF4 enthalpy is only
3.1 kcal mol−1. When the enthalpies of TiF2, TiF3, and CrO3
are removed 共set II兲, the MSD of ROHF ccCA-TM is
−1.58 kcal mol−1 and the MAD of ROHF ccCA-TM is
3.98 kcal mol−1. Further refining the set, we have removed
the tabulated values of Cr共CO兲x, x = 3 – 5. These values are
from a review by Simoes posted on the NIST webbook25
using the JANAF literature value of Cr共CO兲6, which is
22 kcal mol−1 higher than the recommended value from the
Yungman compendium 共and also ⬃20 kcal mol−1 higher
than the ROHF ccCA-TM value兲. Also, the NIST webbook
value of the FeC5H5 enthalpy of formation does not include
references justifying the specific recommended value.25 Due
to controversy in the free cyclopentadienyl ⌬H f value and
the rather large multireference character of the sextet ground
state of FeC5H5 radical, we have also removed this value
from our test set. When these four molecules are removed
from the test set 共set III兲, the error of ROHF ccCA-TM de-
creases substantially with a MSD of −1.24 kcal mol−1 and a
MAD of 3.20 kcal mol−1.
By adopting the JANAF value for CrO3, which has a
larger uncertainty but agrees very well with CBS-CCSD共T兲
and ccCA values, and by using theoretical CBS-CCSD共T兲
values obtained by Ricca51 for Fe共CO兲x, x = 1 – 4, a final sub-
set of 52 molecules 共set IV兲 is created. The MSD for ROHF
ccCA-TM is −1.15 kcal mol−1 with a MAD of
2.85 kcal mol−1 and a root mean square deviation of
3.77 kcal mol−1. This MAD is near the average of the ex-
perimental uncertainties 共2.22 kcal mol−1兲 in set IV. Al-
though this is a rough statistical metric, it shows that the
ROHF ccCA-TM model is already at the threshold of mean-
ingful accuracy for transition metal complexes. The maxi-
mum errors in set IV are both open-shell unsaturated carbo-
nyl systems: Mn共CO兲5 and Co共CO兲4 with deviations of
⫺11.2 and −10.1 kcal mol−1, respectively. The enthalpy of
024106-7 Thermochemistry for inorganic complexes
FIG. 3. Histogram of signed deviations for set IV 共in kcal mol−1兲.
formation of Mn共CO兲5 is another potentially controversial
molecule in our test set. The NIST webbook value has a
larger uncertainty 共−171⫾ 5.3 kcal mol−1兲 共Ref. 25兲 but
agrees much better with the ccCA value 共with a deviation of
only −2.8 kcal mol−1兲. However, this molecule shows sig-
nificant spin contamination with an 具S2典 value of 0.26 higher
than the optimal doublet value. In the absence of either clear
information about the origin of the NIST literature values or
coupled-cluster based theoretical values, further study is war-
ranted to resolve major discrepancies between literature val-
ues and ccCA. Overall, however, the new ccCA performs
extremely well for large TM-containing systems. For ex-
ample, the MAD for 16 molecules in set IV that contain
more than five atoms is only 3.39 kcal mol−1.
Figure 2 shows the scatter of experimental versus theo-
retical values for test set IV. With an R2 value of 0.999 and a
nearly linear slope, ROHF ccCA-TM is a reliable predictor
of gas phase enthalpies of formation without significant sys-
tematic error. For the 52 molecules in set IV, 29 molecules in
our test set are within the transition metal chemical accuracy
of ⫾3.0 kcal mol−1 using ccCA, with 16 of those enthalpies
of formation within the chemical accuracy of
⫾1.0 kcal mol−1 from the experimental value. Figure 3
shows the histogram of signed deviations for set IV. Most of
the errors cluster either very close to the experimental value
or deviate in the range of −6.0 – − 2.0 kcal mol−1 from the
experimental values. To further break down the enthalpies of
formation in our training set, Fig. 4 shows the MADs for
each of the ten 3d elements. Unlike the inconsistencies seen
in DFT benchmarking, ccCA is better than or near transition
metal chemical accuracy when computing enthalpies of for-
mation from Ti–Zn. The performance on the four scandium-
FIG. 4. MADs of set IV categorized by TM element 共in kcal mol−1兲.
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J. Chem. Phys. 131, 024106 共2009兲
FIG. 5. MADs of set IV 共in kcal mol−1兲 categorized by metal-ligand bond-
ing type.
containing molecules in our test set is slightly worse with a
MAD of 4.25 kcal mol−1. Looking at trends in chemical
bonding 共Fig. 5兲, all bonding categories are also within the
transition metal chemical accuracy, except for the carbonyls,
owing to the large errors in Co共CO兲4 and Mn共CO兲5. With a
MAD of 2.70 kcal mol−1 for the eight metal-oxide bonds
and a MAD of 1.93 kcal mol−1 for the four organometallic
species in our test set, ccCA shows promising capabilities in
the regimes of combustion and catalysis research for 3d met-
als.
In Table VI, carbonyl BDEs are given using ccCA. Re-
sults are compared to DFT computations performed by
Furche and Perdew7 as well as CCSD共T兲-based calculations
performed by Ricca and Bauschlicher.52 These BDEs are
known to provide an extremely stringent test of computa-
tional methods, as FeCO and FeCp are known to have high
multireference character. For instance, Ricca and Bauschli-
cher showed that CCSD共T兲 and multireference configuration
interaction methods generally give the wrong electronic
ground state for FeCO.52 The delicate balance between dy-
namical and nondynamical electron correlation in this mol-
ecule is akin to the difficulties encountered in applying
CCSD共T兲 and MRCISD methods to investigate FeCN and
FeNC.53 For the first four carbonyl dissociations of Fe共CO兲5,
ccCA performs very well and is within or very close to being
within the range of experimental uncertainty. However, the
dissociation of excited state FeCO to Fe+ CO shows the
same difficulties that previous theoretical studies have
highlighted.51,52 The ccCA method also predicts an incorrect
ground electronic state 共 5⌺−兲 for FeCO, compared to the ex-
perimental observation of Leopold and co-worker 共 3⌺−兲.54
The first CO dissociation of Cr共CO兲6 is only
−4.2 kcal mol−1 from the experimental value of 39⫾ 3,
while the third CO dissociation is in error by 37 kcal mol−1
Note that the recommended literature value of the Cr共CO兲6
→ Cr共CO兲3 + 3CO reaction uses the questionable value of the
Cr共CO兲6 enthalpy of formation in the NIST webbook.25
Since all species involved in this reaction are closed shell, it
is likely that the ccCA value is much closer to the true value.
BDEs for ferrocene are also listed in Table VI. The dis-
sociation of 1/2 molar equivalent of ferrocene to cyclopenta-
dienyl radical and half a molar equivalent of iron atom de-
viates from experiment by −5.7 kcal mol−1. However, the
024106-8 DeYonker et al.
TABLE VI. Dissociation energies 共in kcal mol−1兲 for various carbonyl and ferrocene reactions.
ROHF ccCA-TM
Fe共CO兲5 → Fe共CO兲4 + CO
Fe共CO兲4 → Fe共CO兲3 + CO
Fe共CO兲3 → Fe共CO兲2 + CO
Fe共CO兲2 → FeCO+ CO
5
FeCO→ 5Fe + CO
Cr共CO兲6 → Cr共CO兲5 + CO
Cr共CO兲6 → Cr共CO兲3 + 3CO 136.9
1 / 2Fe共Cp兲2 → 1 / 2Fe+ Cp
Fe共Cp兲2 → Fe+ 2Cp 174.2
a
All DFT results are from Ref. 7.
b
Reference 57.
c
Reference 51.
d
Reference 52. Value in parenthesis is without ad hoc correction of experimental 3⌺− − 5⌺− energy splitting.
e
Reference 25.
f
Reference 58.
g
Values in parenthesis are BDEs utilizing corrected C5H5 enthalpy of formation from Ref. 56.
h
Reference 59.
literature value of this BDE comes via the usage of an en-
thalpy of formation for C5H5 radical of 58⫾ 2 kcal mol−1.55
This value has been recently revisited by Nunes et al.56 using
time-resolved photoacoustic calorimetry and a newly recom-
mended value of 64.8⫾ 2.0 kcal mol−1 was obtained 共in
agreement with the ROHF-ccCA-TM value of
65.4 kcal mol−1兲. Using this newly recommended value of
⌬H f 共C5H5兲 results in a ROHF-ccCA-TM value approxi-
mately within 1 – 2 kcal mol−1 of the experimental BDE for
ferrocene to iron+ cyclopentadienyl radical.
IV. CONCLUSIONS
By focusing on extrapolation to a complete basis set
limit, in tandem with flexible correlation consistent basis
sets, efficient MP2-based single reference wave function
methods can be employed to obtain quantitatively accurate
thermochemical values. Our improved version of the ccCA
has been created such that not only it achieves main group
chemical accuracy for the G2/97 enthalpies of formation
共with a MAD of 0.89 kcal mol−1 over a set of 147 mol-
ecules兲 but also exceeds transition metal chemical accuracy
for small transition metal-containing radicals as well as
larger carbonyl and organometallic complexes 共with a MAD
of 2.85 kcal mol−1 over a set of 52 molecules whose enthal-
pies of formation are reasonably well established兲. While
DFT studies have shown that certain functionals display an
erratic behavior when used to compute energetics of early
versus late transition metal containing species, ccCA is con-
sistently accurate for the entire 3d block. Unlike our first
reports, the quality of the present ccCA methodology does
not degrade when tested against molecules with fairly high
multireference character nor as a function of increasing mo-
lecular size. Generally, BDEs computed with ccCA are reli-
able. We have identified a few molecules for which the ex-
perimental gas phase enthalpies of formation should clearly
be revisited such as FeCO, TiF2, TiF3, and Cr共CO兲3, as well
as amounted increasing evidence for the adoption of certain
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J. Chem. Phys. 131, 024106 共2009兲
CCSD共T兲 B3LYP TPSSh Expt.
41.6 36.9 a
45.7 41.5⫾ 2 b
36.5 31.1 27.9⫾ 8.8 c
31.6 32.8 29.1⫾ 5.8 c
40.5 33.7 36.7⫾ 3.5 c
1.3 共2.2兲d 7.0 12.4 19.2 8.1⫾ 3.5 c
43.2 35.6 42 39⫾ 3 b
108.9 131.4 99⫾ 10 e
87.1 67.9 88 81.4⫾ 1 f 共88.2兲g
158.4h 共172兲g
thermochemical values, such as the “higher” enthalpy of for-
mation of cyclopentadienyl radical determined by Nunes et
al.56
Previous DFT benchmark studies highlight the pitfalls
and nonsystematic nature of choosing the “correct” func-
tional. Cognizance is necessary in utilization of DFT to pre-
dict energetic properties of open-shell and/or coordinatively
unsaturated inorganic molecules. The ccCA is reliable
enough to provide a guideline for the creation of improved
density functionals for TM thermochemistry when 共as is of-
ten the case兲 such data are sparse or nonexistent, and perhaps
will also help thermochemical research place the emphasis
back on wave function-based methods to resolve controver-
sial quantities and to instigate investigation of new chemical
problems in the realm of quantitative inorganic chemistry.
This research also highlights the need for a “gold-standard”
共but computationally feasible兲 methodology in TM thermo-
chemistry akin to CBS-CCSD共T兲 methods for important
chemical issues in which pertinent experimental/
computational data are conflicting. However, such large basis
set coupled cluster computations are a long way from being
tractable for molecules as large as Ni共PF3兲4 and beyond, but
still they represent a worthy computational goal.
ACKNOWLEDGMENTS
We would like to thank Professor Dave A. Dixon and
Professor Kirk A. Peterson for helpful discussions and K. A.
P. for providing unpublished cc-pCVDZ basis sets for Sc–
Zn. CASCaM is supported by a grant from the U.S. Depart-
ment of Energy 共Grant No. BER-08ER64603兲. This research
is also partially supported by the National Science Founda-
tion via CAREER Award Nos. CHE-0239555 and CHE-
0809762 共for A.K.W.兲 and by a grant from the United States
Department of Energy, Office of Basic Energy Sciences 共for
A.K.W. and T.R.C.兲 under Grant No. DE-FG02-03ER15387.
Computational resources were provided via the National Sci-
ence Foundation 共Grant Nos. CHE-0342824 and CHE-
0741936兲 and by the Teragrid Alliance under Grant No. TG-
CHE010021 共for A.K.W.兲 and utilized the NCSA IBM p690
024106-9 Thermochemistry for inorganic complexes J. Chem. Phys. 131, 024106 共2009兲

26
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