Collect. Czech. Chem. Commun. 2003, 68, 405-422

Electronic States of Fe2S-/0/+

Olaf Hübner and Joachim Sauer*

Humboldt-Universität zu Berlin, Arbeitsgruppe Quantenchemie, Unter den Linden 6, D-10099 Berlin, Germany


The relative energies of a multitude of low-lying electronic states of Fe2S-/0/+ are determined by complete active space self-consistent field (CASSCF) calculations. The numerous states obtained are assigned to spin ladders. For selected states, dynamic correlation has been included by multireference configuration interaction (MRCI) and the structures of some high-spin states have been optimized by CASSCF/MRCI. Comparison is made with structures obtained by density-functional theoretical calculations. The ground states of Fe2S-/0/+ are 10B2, 1A1 and 8A2, respectively, and the total splittings of the lowest-energy spin ladders are about 0.18, 0.07 and 0.13 eV, respectively. The spin ladders of Fe2S qualitatively reflect the picture of Heisenberg spin coupling. While both Fe2S- and Fe2S+ show an Fe-Fe distance of about 270 pm, that of Fe2S is about 100 pm longer. The calculated adiabatic electron affinity of Fe2S is 1.2 eV and the ionization energy 6.6 eV. An interpretation of the observed photoelectron spectrum of Fe2S- is given.

Keywords: Iron sulfur clusters; Electronic structure; Spin ladders; Multireference configuration interaction; Complete active space SCF; Ab initio calculations.

References: 52 live references.