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2〉 for a Kohn-Sham wave function should not be expected to be equal to S(S + 1): Pople, J. A.; Gill, P. M. W.; Handy, N. C. Int. J. Quantum Chem. 1995, 56, 303. See also: Wang, J.; Becke, A. D.; Smith, V. H., Jr. J. Chem. Phys. 1995, 102, 3477.
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Basis sets were obtained from the Extensible Computational Chemistry Environment Basis Set Database, Version 1.0, as developed and distributed by the Molecular Science Computing Facility, Environmental and Molecular Sciences Laboratory, which is part of the Pacific Northwest Laboratory, P.O. Box 999, Richland, WA 99352, and funded by the U.S. Department of Energy. The Pacific Northwest Laboratory is a multiprogram laboratory operated by Battelle Memorial Institute for the U.S. Department of Energy under Contract DE-AC06-76RLO 1830. Contact David Feller, Karen Schuchardt, or Don Jones for further information.
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3743142478
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note
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Calculation of contact charge densities using Gaussian 98 required a small modification to Link 601 so that the Fermi contact integrals were contracted with the charge density rather than the spin density.
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48
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3743069045
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note
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For all molecules, we designate the xz plane as the mirror plane of symmetry, with the z axis being essentially normal to both rings. Saillard et al. found an A′ SOMO by DFT for all three of these molecules.
-
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49
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3743110172
-
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note
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6) specifically checked that switching the occupancy of the A′ and A″ orbitals did not lower the energy. This supports the belief that the wave function is not that of an electronically excited state. For all three molecules the SOMO-LUMO gap in the spin-up manifold was calculated to be 0.5-0.6 eV using BP86 and 2.9-3.2 eV with the hybrid functionals. Increasing the size of the basis set on iron by decontracting the most diffuse s, p, and d functions did not lead to a different occupation of the frontier orbitals.
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AIM quantities were calculated using the PROMEGA algorithm of the AIMPAC package (Biegler-Konig, F. W.; Bader, R. F. W.; Tang, T. H. J. Comput. Chem. 1982, 3, 317-328; available from http://www.chemistry.mcmaster.ca/aimpac) and the wave function information in the .wfn file output by Gaussian 98 ("output = wfn"). The .wfn file was modified so that it included either the a spin orbitals or the β spin orbitals. PROMEGA then calculated the α and β atomic charges for Fe separately. The total atomic charge was obtained by adding these quantities, and the spin density was obtained by subtraction. Because the PROMEGA algorithm is very slow and because AIMPAC calculates AIM properties for only one atom per run, we only calculated the charge and spin for the iron atom.
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