Reference Energies for Double Excitations: Improvement and Extension.

Abstract

In the realm of photochemistry, the significance of double excitations (also known as doubly excited states), where two electrons are concurrently elevated to higher energy levels, lies in their involvement in key electronic transitions essential in light-induced chemical reactions as well as their challenging nature from the computational theoretical chemistry point of view. Based on state-of-the-art electronic structure methods (such as high-order coupled-cluster, selected configuration interaction, and multiconfigurational methods), we improve and expand our prior set of accurate reference excitation energies for electronic states exhibiting a substantial amount of double excitations [Loos et al. J. Chem. Theory Comput. 2019, 15, 1939]. This extended collection encompasses 47 electronic transitions across 26 molecular systems that we separate into two distinct subsets: (i) 28 "genuine" doubly excited states where the transitions almost exclusively involve doubly excited configurations and (ii) 19 "partial" doubly excited states which exhibit a more balanced character between singly and doubly excited configurations. For each subset, we assess the performance of high-order coupled-cluster (CC3, CCSDT, CC4, and CCSDTQ) and multiconfigurational methods (CASPT2, CASPT3, PC-NEVPT2, and SC-NEVPT2). Using as a probe the percentage of single excitations involved in a given transition (%T1) computed at the CC3 level, we also propose a simple correction that reduces the errors of CC3 by a factor of 3, for both sets of excitations. We hope that this more complete and diverse compilation of double excitations will help future developments of electronic excited-state methodologies.