Transition metal complexes with open d-shell in semiempirical context. Application to analysis of Mössbauer data on spin–active iron(II) compounds

Abstract

With use of cumulants of two-electron density matrices semiempirical methods are analyzed from a point of view of their suitability to describe qualitative features of electronic correlation important for calculation of electronic structure of the transition metal complexes (TMC). It is shown that traditional semiempirical methods relying upon the Hartree–Fock–Roothaan form of the trial wave function suffer from a structural deficiency not allowing them to distinguish the energies of the atomic multiplets of the TMCs' d-shells. On the other hand, the effective Hamiltonian of the crystal field (EHCF) previously proposed by the authors is shown to be suitable for further parameterization and has been successfully applied for calculations on polyatomic TMCs. Here we describe in details its recent modifications performed in relation to the SINDO/1 parameterization scheme and present the results of the calculations on spin-active Fe(II) complexes with nitrogen-containing polydentate ligands in relation with interpretation of the Mössbauer measurements performed on these complexes.