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simultaneously. The (h
6-Aniline)Cr(CO)3 complex was sublimed
from a right angled tube which was electrically heated to 50 ꢂC. The
sample deposition was monitored using either UV/vis. or infrared
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5.3. Computational details
DFT methods were used in all calculations presented here. These
employed a three parameter hybrid functional (B3) [50], and the
LeeeYangeParr correlation functional (LYP) i.e. the B3LYP func-
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calculations. All calculations were performed using the Gaussian 03
package [51], using HP dual Xeon processor workstations. It is
known that the B3LYP functional tends to underestimate the
energy of high spin states relative to low spin states [43,52].
Consequently, Reiher has proposed that a reduction in the exact
exchange parameter from 0.2 to 0.15 provides a more reliable
estimate of the energy difference between spin states in organo-
metallic systems and called this modified functional B3LYP*. For
estimates of the energy difference between the singlet and triplet
species, the B3LYP* functional was used. These model chemistries
represent a compromise between accuracy in measuring energy
differences between species with different multiplicities and the
computational cost in the large number of optimisation cycles to
map the singlet or especially the triplet surfaces. Initial geometries
were obtained from molecular mechanics calculations and the final
geometries of species located at local energy minima were opti-
mized using tight convergence criteria. Zero point energy correc-
tions were applied to species at stationary points. A listing of
internal parameters is provided in the supporting information.
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Acknowledegments
[51] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheese-
man, J.J.A. Montgomery, T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S.
Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A.
Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa,
M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox, H.
P. Hratchian, J.B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O.
Yazyev, A.J. Austin, R. Cammi, C.J. Pomelli, W. Ochterski, P.Y. Ayala, K. Moro-
kuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S. Dapprich, A.
D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B.
Foresman, J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J. Cioslowski, B.B. Stefanov,
G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.L. Martin, D.J. Fox, T. Keith, M.A.
Al-Laham, C.Y. Peng, A. Nanayakkara, M. Challacombe, P.M.W. Gill, B. Johnson,
W. Chen, M.W. Wong, C. Gonzalez, J.A. Pople, Gaussian 03, Gaussian, Inc.,
Wallingford CT, 2004.
CL wishes to thank DCU for the award of a Senior Research
Fellowship to support this work.
Appendix. Supplementary data
Supplementary data associated with this article can be found, in
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