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JAMES T. MUCKERMAN, Chemistry Department, Brookhaven National Laboratory, Upton, NY 11973-5000.
Despite widespread interest in the electronic structure and spectra of transition-metal complexes such as the starting and intermediate species of redox catalysts for water oxidation or hydrogen production, theoretical predictions of their electronic spectra generally come only from time-dependent density functional theory (TD-DFT) and are limited to one-electron excitations. Here we compare the results of TD-DFT to those of multi-reference configuration-interaction calculations for predicting the electronic spectra of some model and actual transition-metal-containing catalysts. Of particular interest are complexes with redox-active ligands that complicate the assignment of formal oxidation states, and complexes containing second- and third-transition-series metals.