PNNL

Abstract

The proper description of electron transfer (ET) processes in mixed-valence compounds poses a significant challenge for commonly used theoretical approaches. In this paper we analyze the 12A2 and 22A2 potential energy surfaces of the Spiro cation which is a frequently used model to study ET processes. We compare and contrast the results obtained with three different methods: Multireference Perturbation Theory, Equation-of-Motion Coupled Cluster Theory, Time-Dependent Density Functional Theory. We demonstrate that the proper inclusion of dynamical correlation effects plays a crucial role in the description of an avoided crossing between potential energy surfaces. We also find that proper balancing of the ground- and excited-state correlation effects is especially challenging in the vicinity of the 12A2 and 22A2 avoided crossing region.