Metal-to-metal charge-transfer transitions: reliable excitation energies from ab initio calculations

Abstract

A computational strategy is presented to describe excited states, involving the transfer of an electron from one metallic site to a neighboring metal center, the so-called metal-to-metal charge-transfer (MMCT) states. An accurate ab initio treatment of these states in transition metal compounds is intrinsically difficult for both time-dependent density functional and wave function-based methods. The rather large dependence of the MMCT energies on the applied functional makes difficult to extract reliable estimates from density functional theory, while the standard multiconfigurational approach (complete active space SCF + second-order perturbation theory) leads to severe intruder state problems and unrealistic, negative energies. The analysis of the failure of the multiconfigurational approach shows that the state-average orbitals are biased toward the ground state and strongly deficient to describe the MMCT state. We propose a method to improve the orbitals by gradually approaching as much as possible the state-specific description of the MMCT state in the reference wave function for the second-order perturbation treatment of the dynamic electron correlation.