Unveiling hidden dynamic correlations in CASSCF correlation energies by Hartree-Fock nodes.

Abstract

We have recently introduced an original method for sharply partitioning the correlation energy into dynamic and non-dynamic contributions. This method is based on the node of the Hartree-Fock (HF) Slater determinant and the stochastic projector fixed-node diffusion Monte Carlo (FNDMC) method [Šulka et al., J. Chem. Theory Comput. 19, 8147 (2023)]. This approach addresses the challenge of dissecting correlation energy in quantum chemistry. Here, we present the first application of this technique to explore CASSCF correlation energy contributions in selected molecular systems such as BH, FH, F2, and H2-H2. The results show that correlation energies derived from the full-valence active space CASSCF method, often believed to describe mostly non-dynamic correlation effects, contain an extraneous, unwanted, system-dependent component that belongs to the dynamic correlation energy. The findings suggest that the new HF-node/FNDMC-based electron correlation energy decomposition method provides a useful complementary tool, enabling the detection of inherent challenges in distinguishing between dynamic and non-dynamic contributions to correlation energies within methods where precise dissection of these effects is not possible.