Effective hamiltonian crystal field: Present status and applications to iron compounds

We review the basics of the Effective Hamiltonian Crystal Field (EHCF) method originally targeted for calculations of the intra-shell excitations in the d-shells of coordination compounds of the first row transition metal. The formalism employs in the concerted way the McWeeny's group-function approximation and the Lowdin partition technique. It is needed for description of the transition metal complexes with partially filled d-shells where the (static) electronic correlations are manifested. These features are particularly important for electron fillings close to “half shell” ones occurring, for example, in the Fe2+ and Fe3+ ions. Recently we extended this methodology to polynuclear coordination compounds to describe magnetic interactions of the effective spins residing in several open d-shells. This improves the accuracy from about 1000 cm−1 to that of about 100 cm−1, that is, eventually by an order of magnitude. This approach implemented in the MagAixTic package is applied here to a series of binuclear Fe(III) complexes featuring μ-oxygen superexchange pathways. The results of calculations are in a reasonable agreement with available experimental data and other theoretical studies of protonated bridges. Further we discuss the application of the EHCF to analysis of Mosbauer experiments performed on two organometallic solids: FeNCN and Fe(HNCN)2 and conjecture a new thermal effect in the latter material. © 2015 Wiley Periodicals, Inc.

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