J. Phys. Chem.
1989, 93, 2997-2999
the high-spin states of (Ar core) 3d/v~14s1 and (Ar core)3dJV con-
figurations for Sc+, Ti+, V+, and Cr+. Note that at the SCF level
the energies of the two states are in the experimental order for
Cr+, Ti+, and Sc+ but not for V+, where the 5F (3d34s‘) state is
more stable. Therefore, we include the 5F V+ energies in Table
VII. Work2d·23·24 suggests that a reasonable calculation of the
relative energy of a first-row transition element or small molecule
containing such an element is possible if one at least includes the
differential electron correlation between the low-lying states of
different configurations of both the transition-metal and ligand
(23) Botch, B. H.; Dunning, Jr., T. H.; Harrison, J. F. J. Chem. Phys.
1981, 75, 3466.
(24) Walsh, S. P.; Bauschlicher, Jr., C. W. J. Chem. Phys. 1983, 78, 4597.
Ground-State Geometry of the (i}6-CeH6)V and (tj6-C6H6)V+ Half-Sandwich Complexes
by Local-Spin-Density Linear Combination of Atomic Orbitals Techniques
Saba M. Mattar* and William Hamilton
Department of Chemistry, University of New Brunswick, Bag Service No. 45222, Fredericton, New Brunswick,
Canada E3B 6E2 (Received: July 14, 1988; In Final Form: August 23, 1988)
The electronic structures of (tj6-C6H6)V and (t/6-C6H6)V+ have been computed by an LCAO method using two different
local density functionals. The neutral molecule and the cation are predicted to have stable bound ground states with an
optimal benzene-vanadium distance of 3.06 and 3.08 au, respectively. The dissociation energies required to separate the
V and C6H6 are found to be in the range of 5.25-3.05 eV. They are of the same order of magnitude as those predicted from
thermodynamic data.
In the past few years, molecular beam experiments have been
reported where various metal atoms or metal dimers and organic
ligands have resulted in benzene-metal products.1·2 These ex-
periments provide us with dissociation energies and heats of
formation of the fundamental interactions between the metal atoms
and the C6H6 moiety. The beam experiments produce complexes
that are short-lived due to their high reactivity. It is desirable
to have complementary theoretical computations that confirm/
predict the equilibrium geometries and binding energies of these
products. These computations would also illustrate the struc-
ture-bonding relationships of these complexes. Ab initio electronic
structure computations of such molecules, using large basis sets
and including electron-electron correlation effects, are very scarce
because of the large expense in computer time and costs.
Recently, the study of the 550-nm absorption band formed by
the co-condensation of V atoms with C6H6/Ar mixtures, at 12
K, led to the discovery of the matrix-isolated (tj6-C6H6)V half-
sandwich complex.3,4 Its structure was confirmed by electron
paramagnetic resonance (EPR), infrared, and UV-visible spec-
troscopies. A self-consistent-field scattered wave (SCF-SW)
computation of its electronic structure, using the Xa approxi-
4
mation, was also performed The geometry was assumed to be
that of bis(benzene)vanadium5 with one C6H6 ring removed.4
There are no reports to date of the existence of (??6-C6H6)V in
the gas phase.
It is important to understand the electronic structure, bonding,
and properties of (?j6-C6H6)V because the V atom has a naked
(1) Hettich, R. L.; Freiser, B. S. J. Am. Chem. Soc. 1985,107, 6222-6226.
(2) Whetten, R. L.; Cox, D. M.; Trevor, D. J.; Kaldor, A. Surf. Sci. 1985,
156, 8.
(3) Andrews, . P.; Huber, . X.; Mattar, S. M.; McIntosh, D. F.; Ozin,
G. A. J. Am. Chem. Soc. 1983, 105, 6170-6172.
(4) Andrews, . P.; Mattar, S. M.; Ozin, G. A. J. Phys. Chem. 1986, 90,
744-753.
(5) The C6H6-V distance was that of (C6H6)2V taken from: Meutterties,
E. L.; Bleek, J. R.; Wucherer, E. J.; Albright, T. A. Chem. Rev. 1982, 82, 499.
0022-3654/89/2093-2997S01.50/0
2997
fragments. Because d-d radial correlation up to the singles and
doubles level is included in the MCSCF+1+2 calculations (all
occupied d orbitals are in the active space), the SCF+1+2 energies
are in the correct order for all the M+ states.
Comparison of our previous work with experiment has allowed
us to assess the absolute accuracy of our calculations.lc,d When
calculated from the MCSCF+1+2 wave functions, our £>„’s tend
to be 25% low. Thus, dissociation energies calculated from the
MCSCF+1+2 wave functions should be lower bounds and will
likely increase with calculations that include a more extensive level
of correlation. Bond lengths are expected to be more reliable than
our energetic predictions.
Registry No. ScN+, 119145-01-6; TiN+, 83018-06-8; VN+, 110207-
20-0; CrÑ+, 83017-97-4.
hemisphere to which the addition of other metal atoms or sta-
bilizing ligands (CO, CS, NO, C6H6, etc.) is possible. It is thus
an important reactive intermediate to be used in the synthesis of
a variety of organometallic complexes and clusters.
A fundamental question regarding (tj6-C6H6)V comes to mind:
is this molecule stable in the gas phase, or does it exist because
the C6H6 and V fragments are simply held together and isolated
by the matrix at 12 K? The answer may be obtained by computing
the total energy of the complex as a function of the benzene-
vanadium distance and searching for a geometry that displays a
bound ground state. In such a case the SCF-SW method is
inappropriate for geometry optimization because the change of
sphere radii with different geometries renders the comparison of
the total energies meaningless.
Here we report the geometry optimization and the electronic
structure of (t;6-C6H6)V using a local-spin-density linear com-
bination of atomic orbitals (LSD-LCAO) method that gives
accurate total energies.6 The electronic structure was computed
by using the Xa approximation (a = 0.7). In a separate treatment
the effects of electron exchange and correlation were introduced
using the interpolation formulas of Perdew and Zunger7 (PZ
approximation) that parametrize the exchange-correlation po-
tentials and energy densities of an electron gas as computed by
Ceperly and Alder.8
The 13s/7p/5d[4333/43/41+] basis set of Andzelm et al. for
V was used.9 This basis set is specifically designed for LSD-
LCAO computations. A 9s/3p[3s/2p] for carbon and a 3s[2s]
for hydrogen were employed for the C6H6 ring.10 The auxiliary
(6) (a) Dunlap, B. I.; Connolly, J. W. D.; Sabin, J. R. J. Chem. Phys. 1979,
71, 4993. (b) Lamson, S. H.; Messmer, R. P. Chem. Phys. Lett. 1983, 98,
72.
(7) Perdew, J. P.; Zunger, A. Phys. Rev. B 1981, 23, 5048.
(8) Ceperly, D. M.; Alder, B. J. Phys. Rev. Lett. 1980, 45, 566.
(9) Andzelm, J.; Radzio, E.; Salahub, D. R. J. Comput. Chem. 1985, 6,
520-532.
© 1989 American Chemical Society
2998 The Journal of Physical Chemistry, Vol. 93, No. 8, 1989
Figure 1. Total energy of (i;6-C6H6)V and (t¡6-C6H6)V+ ground states
as afunction of the vanadium-benzene ring distance, r. (a) (tj6-C6H6)V+
(Xa approximation); (b) (?j6-C6H6)V (Xa approximation); (c) (y6-
C6H6)V+ (PZ approximation); (d) (j;6-C6H6)V (PZ approximation).
basis sets for the charge density and exchange-correlation potential
were constructed according to the method of Dunlap.6 No attempt
was made to optimize the C6H6 geometry. To minimize basis set
superposition errors in computing the dissociation energy, the total
energies of the V atom and the C6H6 ring were computed sepa-
rately. The same C6„ symmetry adapted basis sets used for
(tj6-C6H6)V were also used for the C6H6 and V fragments. Ad-
ditional computational details are available from the authors upon
request.
Figure lb,d shows that both LSD-LCAO computations lead
to a 2A, ground state with a minimum occurring around 3.06 au.
As the V-ring separation is increased to 10.0 au, we essentially
recovér the V and C6H6 fragments. The shapes of these curves
indicate that the (i?6-C6H6)V is definitely a stable bound molecule
at cryogenic temperatures. We also predict that it is possible to
detect this molecule, once formed, in the gas phase using molecular
beam spectroscopy. Its short lifetime, when not isolated, may be
attributed to the reactivity of the V moiety. We are presently
investigating, by matrix-isolation and by LSD-LCAO computa-
tions, the reaction pathways that lead to the addition of CO and
NO ligands to (t?6-C6H6)V.
The existence of a bound state for (j)6-C6H6)V is in accordance
with our previous EPR observations for this molecule.3,4 The EPR
spectra show seven well-resolved lines on every V hyperfine res-
onance. This implies that the C6H6 ring is freely rotating with
respect to the external applied magnetic field and is not hindered
by the matrix. This situation would be unlikely if the matrix were
totally responsible for holding the V and C6H6 together.
It is satisfying to find that the structure and bonding pictures
obtained from the Xa SCF-SW4 and the LSD-LCAO compu-
tations, shown in Figure 2, are essentially the same. In addition,
the V-ring distance, predicted here, is not much different from
that assumed in the previous calculation.4,5 Furthermore, the
effects of the synergic donation and back-donation mechanisms,
occurring between the C6H6 pz orbitals and the V 3d orbitals, are
at a maximum at the predicted benzene-vanadium equilibrium
distance.
The dissociation energy is estimated to be 3.77 eV from the
Xa computation and 4.26 eV by including the effects of electron
correlation. The exchange-correlation method of computation
generally predicts excellent equilibrium distances for dimers but
(10) Binkley, J. S.; Pople, J. A.; Hehre, W. J. J. Am. Chem. Soc. 1980,
102, 939.
Mattar and Hamilton
Figure 2. Ground-state one-electron MO energy diagrams for C6H6,
(?j6-C6H6)V, and the V atom computed with C&, symmetry adapted basis
sets. The highest occupied MO’s are 4e,4 for C6H6, 10a,1 for (y6-
C6H6)V, and 6a,1, 3e,2, and le22 for V. In the case of (tj6-C6H6)V the
benzene-vanadium distance is 3.06 au.
tends to overestimate their binding energies.11,12 Hence, the bond
dissociation energy for this molecule may be as low as 3.00 eV.
Skinner13 has estimated the V-benzene bond dissociation energy,
from the thermodynamic data on dibenzene-vanadium,14 to be
3.04 eV (70.00 kcal/mol). This is in the same range as our present
computed values.
The (tj6-C6H6)V+ ion is very similar to (tj6-C6H6)V, and its
experimental bond dissociation energy is found to be 2.68 eV1 (62.0
kcal/mol). Consequently, it is a good example for comparison
of the experimental and computed bond dissociation energies. We
have repeated all the previous computations for the corresponding
(t)6-C6H6)V+ ion. Figure la,c shows (?;6-C6H6)V+ energy curves
that are similar to Figure lb,d. The equilibrium 'A, V-benzene
distance is essentially the same (3.08 au). The bond dissociation
energy for the ion is 5.25 eV (Xa) and could be as low as 3.75
eV by using exchange-correlation effects. Thus, the experimental
and predicted values differ by 1.07 eV (24 kcal/mol). These
results indicate that the computed bond dissociation energies are
reasonable. However, they are definitely overestimated, as pre-
viously found for dimers. The incorporation of nonlocal spin
density corrections to compensate for the overestimation of binding
energies15,16 in our program is presently under way.
In conclusion, the LCAO-LSD results predict that (tj6-C6H6)V
has a bound ground state similar to the experimentally observed
(p6-C6H6)V+ ion. The V atom and the C6H6 fragment are not
simply held together by the rare gas matrix at cryogenic tem-
peratures. The detection of (i?6-C6H6)V in the gas phase is
probably difficult due to its high reactivity. The bond dissociation
energies computed for these two molecules seem reasonable but
slightly larger than expected. This is due to the local density
(11) Baykara, N. A.; McMaster, B. N.; Salahub, D. R. Mol. Phys. 1984,
52, 891.
(12) Baykara, N. A.; Salahub, D. R. Surf. Sci. 1985, 156, 605.
(13) Skinner, H. In Advances in Organometallic Chemistry·, Stone, F. G.
A., West, R., Eds.; Academic Press: New York, 1964; Vol. 2, pp 49-114.
(14) Fischer, E. O.; Reckziegel, A. Chem. Ber. 1961, 94, 258.
(15) Becke, A. J. Chem. Phys. 1986, 84, 4525.
(16) Ziegler, T.; Tschinke, V.; Becke, A. J. Am. Chem. Soc. 1987, 109,
1351.
 J. Phys. Chem. 1989, 93, 2999-3011 2999

functional approximation used in the computations. There are
very few computations for arene-metal complexes that are of
sufficient quality to predict their bond and total energies accu-
rately. In order to determine whether the LCAO-LSD method
can generally predict these properties, more computations on a
whole series of arene-metal compounds must be performed and
compared with accurate experimental data.
Acknowledgment. Saba M. Mattar acknowledges the financial
assistance from the Natural Science and Engineering Research
Council of Canada, the University of New Brunswick Research
Fund, and the allocation of computer time from the Computer
Center of the University of New Brunswick.
Registry No. (i/6-C6H6)V, 61332-91-0; (i76-C6H6)V+, 102307-49-3.

Magnetic Circular Dichroism and Absorption Spectrum of Zinc Phthalocyanine in an

Argon Matrix between 14 700 and 74 000 cm"1

Thomas C. VanCott/ Janna L. Rose/ G. Christian Misener/ 8 Bryce E. Williamson,*1

+
Andreas E. Schrimpf/11 Michael E. Boyle/1 and Paul N, Schatz*
The Chemistry Department, University of Virginia, Charlottesville, Virginia 22901, and The Chemistry
Department, University of Canterbury, Christchurch 1, New Zealand (Received: July 14, 1988;
In Final Form: September 26, 1988)

The magnetic circular dichroism (MCD) and absorption spectra of zinc phthalocyanine (ZnPc) isolated in an Ar matrix
have been studied over the range 14700-74000 cm"1. Synchrotron radiation, from the electron storage ring at the Synchrotron
Radiation Center, Madison, WI, was used for energies above 33 000 cm"1. The spectra are well resolved, and the MCD
permits the determination of excited-state magnetic moments. There is strong evidence that the Pc rings are preferentially
oriented with the molecular planes parallel to the deposition window. The data can be reasonably correlated with the old
Peel calculation of Henriksson et al., but there is a compelling need for a new calculation that extends to higher energy and
includes extensive configuration interaction.

I. Introduction
The phthalocyanines (Pc) are molecules with many interesting
and useful properties. Nyokong et al.1 have recently summarized
some of these properties and given a review of the relevant
spectroscopic literature. A comprehensive review can also be found
in the dissertation of Misener.2
Despite considerable work, the ultraviolet (UV) and vacuum
ultraviolet spectra of Pc’s remain poorly understood. To assign
such spectra with confidence, it is necessary to have a clear
knowledge of the total number of transitions as well as the energy
and excited-state symmetry of each individual transition, infor-
mation that would normally require sharp-band spectra of oriented
samples. Most spectra of Pc’s that have been reported previously
are of randomly oriented samples and show broad bands. Bajema
et al.,3 Bondybey and English,4 and Huang et al.5 have dem-678’6
onstrated that very much sharper spectra can be obtained from
dilute matrices at low temperatures. The later workers,4"6 using
selective excitation techniques, were able to resolve extensive
vibronic structure association with the lowest energy —ir*
transition.
al.1 recently presented a detailed spectral analysis,
Nyokong et
over the region ~11 600-43 000 cm"1, of ZnPc(L) and the ir-
cation-radical species, ZnPc(L)+, in solution, where L is an axially
coordinated cyanide, imidazole, or pyridine ligand. To determine
the excited-state symmetries, they measured the magnetic circular
dichroism (MCD) as well as the absorption spectra; the presence
of ^4-terms in the MCD is a clear indication of excited-state
degeneracy.7 These workers suggested assignments on the basis
of extensive band envelope deconvolution of the absorption and
f
University of Virginia.
•University of Canterbury.
* Present address: Environmental
Technologies Group, 1400 Taylor Ave.,
PO Box 9840, Baltimore, MD 21284.
1 Present address: Code Naval
6123, Research Laboratory, Washington,
D.C. 20375-5000.
1
Present address: Fachbereich Physik der Philipps Universitát, Marburg,
Federal Republic of Germany.
MCD spectra. (We compare our results with those of Nyokong
et al. in section VII.)
In this work we report the MCD and absorption spectra of ZnPc
in an argon matrix (ZnPc/Ar) at ~5 K. This approach combines
the advantage of MCD in determining excited-state symmetries
with the sharper bands that are a consequence of low temperature
and isolation of the chromophore in an “inert” medium. It has
the additional advantage that the host material remains trans-
parent well into the vacuum-UV so that the range of investigation
is not restricted by solvent absorption. As an unexpected bonus,
we have found considerable evidence that the guest molecules
assume a preferred orientation in the matrix, which allows the
extraction of additional information concerning the excited-state
symmetries.
ZnPc is well suited for a study that emphasizes the spectroscopy
of the Pc2" ligand. The central Zn2+ ion has a d10 configuration,
so ligand-to-metal charge-transfer and d-d transitions should not
complicate the spectra. The crystal structure of 0-ZnPC shows
the molecules to be centrosymmetric and, geometrically, almost
within experimental error of DAh symmetry.8 Deviations from
4-fold symmetry are important to a detailed analysis of the MCD,
since molecules with 2-fold or lower symmetry can have no de-
generate states and thus cannot show “true” terms.7 However,
if the deviations are small, it remains a useful and valid ap-
(1) Nyokong, T.; Gasyna, Z.; Stillman, M. J. Inorg. Chem. 1987, 26,
1087-1095, and references therein.
(2) Misener, G. C. Ph.D. Thesis, University of Virginia, Charlottesville,
VA, 1987, and references therein.
(3) Bajema, L.; Gouterman, M.; Meyer, B. J. Mol. Spectrosc. 1968, 27,
225-235.
(4) Bondybey, V. E.; English, J. H. J. Am. Chem. Soc. 1979, 101,
3446-3450.
(5) Huang, T. H.; Reickhoff, K. E.; Voigt, E. M. J. Chem. Phys. 1982,
77, 3424-3441.
(6) Huang, T. H.; Rieckhoff, K. E.; Voigt, E. M. J. Phys. Chem. 1981,
85, 3322-3326.
(7) Piepho, S. B.; Schatz, P. N. Group Theory in Spectroscopy with Ap-
plications to Magnetic Circular Dichroism; Wiley: New York, 1983.
(8) Scheldt, W. R.; Dow, W. J. Am. Chem. Soc. 1977, 99, 1101-1104.

0022-3654/89/2093-2999501.50/0 © 1989 American Chemical Society