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Electronic Structure of Metallloporphyrins. Ab Initio CI Calculations

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Quantum Chemistry: The Challenge of Transition Metals and Coordination Chemistry

Part of the book series: NATO ASI Series ((ASIC,volume 176))

Abstract

Ab initio configuration interaction (CI) calculations are reported for different electronic configurations of the two model iront II) porphyrin complexes, the four-coordinate FeP molecule and its dioxygen complex FePO2, in order to assign the ground state configurations. For FeP (in an intermediate spin state S=l) the calculations predict a 3A2g ground state configuration. For FePO2 an analysis of the results suggests a singlet ground state of Fe(II)-O2 structure having some Fe(III) (d5)-O2 character. Several low-lying triplet and singlet states are also found for the FePO2 system. The electron deformation density maps computed from the CI wavefunctions for the 3A2g and 3Eg states of the FeP system are discussed, in connection with the grouna state assignment.

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Authors and Affiliations

  1. E.R. n° 139 du C.N.R.S. Institut Le Bel, Université Louis Pasteur, 4, rue Blaise Pascal, 67000, Strasbourg, France

    M.-M. Rohmer

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  1. M.-M. Rohmer
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  1. Centre National de la Recherche Scientifique, Strasbourg, France

    A. Veillard

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© 1986 D. Reidel Publishing Company

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Rohmer, MM. (1986). Electronic Structure of Metallloporphyrins. Ab Initio CI Calculations. In: Veillard, A. (eds) Quantum Chemistry: The Challenge of Transition Metals and Coordination Chemistry. NATO ASI Series, vol 176. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-4656-9_27

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  • DOI: https://doi.org/10.1007/978-94-009-4656-9_27

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-90-277-2237-9

  • Online ISBN: 978-94-009-4656-9

  • eBook Packages: Springer Book Archive

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