QUEST#4X: An Extension of QUEST#4 for Benchmarking Multireference Wave Function Methods.

Abstract

Given a number of data sets for evaluating the performance of single reference methods for the low-lying excited states of closed-shell molecules, a comprehensive data set for assessing the performance of multireference methods for the low-lying excited states of open-shell systems is still lacking. For this reason, we propose an extension (QUEST#4X) of the radical subset of QUEST#4 (J. Chem. Theory Comput. 2020, 16, 3720) to cover 110 doublet and 39 quartet excited states. Near-exact results obtained by iterative configuration interaction with selection and second-order perturbation correction (iCIPT2) are taken as benchmark to calibrate static-dynamic-static configuration interaction (SDSCI) and static-dynamic-static second-order perturbation theory (SDSPT2), which are minimal MRCI and CI-like perturbation theory, respectively. It is found that SDSCI is very close in accuracy to internally contracted multireference configuration interaction with singles and doubles (ic-MRCISD), although its computational cost is just that of one iteration of the latter. Unlike most variants of MRPT2, SDSPT2 treats single and multiple states in the same way and performs similarly to multistate n-electron valence second-order perturbation theory (MS-NEVPT2). These findings put SDSCI and SDSPT2 on a firm basis.