SDSPT2s: SDSPT2 with Selection

As an approximation to SDSCI [static-dynamic-static (SDS) configuration interaction (CI), a minimal MRCI; Theor. Chem. Acc. 133, 1481 (2014)], SDSPT2 [Mol. Phys. 115, 2696 (2017)] is a CI-like multireference (MR) second-order perturbation theory (PT2) that treats single and multiple roots on an equal footing. This feature permits the use of configuration selection over a large complete active space (CAS) P to end up with a much reduced reference space P̃, which is connected only with a portion (Q̃₁) of the full first-order interacting space Q connected to P. The effective interacting Q̃ space can further be truncated by an integral-based cutoff threshold. With marginal loss of accuracy, the selection-truncation procedure, along with an efficient evaluation and storage of internal contraction coefficients, renders SDSPT2s (SDSPT2 with selection) applicable to systems that cannot be handled by the parent CAS-based SDSPT2, as demonstrated by several challenging showcases.