Ab Initio Models for Electron Tunnelling Between Transition Metal Complexes. Final Report

摘要

Electron transfer matrix elements are calculated and analyzed for several pairs of transition metal complexes of the type ML sub 62+ -ML sub 63+ , chosen so as to allow a comparison of t/sub 2g/( pi ) vs e/sub g/(sigma) transfer (M = Fe, Co, and Ru), and NH sub 3 vs H sub 2 O ligands, based on an apex-to-apex orientation of the reactant complexes. The magnitude of the calculated matrix elements, which span the range from non-adiabatic to strongly adiabatic coupling, are found to exhibit a pronounced dependence on transfer type (e/sub g/ > t/sub 2g/) and ligand type (NH sub 3 > H sub 2 O), an effect which is correlated with the degree of mixing of the metal and ligand orbitals, using a simple LCAO-type analysis of the ab initio molecular orbitals. (ERA citation 11:038490)