Dynamic and Nondynamic Electron Correlation Energy Decomposition Based on the Node of the Hartree–Fock Slater Determinant

• Published in: Journal of chemical theory and computation Vol. 19; no. 22; pp. 8147 - 8155
• Main Authors: Šulka, Martin, Šulková, Katarína, Jurečka, Petr, Dubecký, Matúš
• Format: Journal Article
• Language: English
• Published: Washington American Chemical Society 28.11.2023
• Subjects: Boundary conditions; Correlation; Energy; Hartree approximation; Nodes; Quantum chemistry; Wave functions
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/acs.jctc.3c00828

Distinguishing between dynamic and nondynamic electron correlation energy is a fundamental concept in quantum chemistry. It can be challenging to make a clear distinction between the two types of correlation energy or to determine their actual contributions in specific cases using wave function theory. This is because both single-reference and multireference methods cover both types of correlation energy to some extent. Fixed-node diffusion quantum Monte Carlo (FNDMC) accurately covers dynamic correlations, but it is limited in overall accuracy by the node of the trial wave function. We introduce a methodology for partitioning an exact electron correlation energy into its dynamic and nondynamic components. This is accomplished by restricting a ground-state solution from sharing its node with a spin-restricted Hartree–Fock Slater determinant. The FNDMC method is used as a tool to conveniently project out a lowest-energy state obeying such a boundary condition. The proposed approach provides an unambiguous and useful procedure for separating electron correlation energy, as demonstrated on multiple systems, including the He atom, bond breaking of H2, the parametric H2–H2 system, the Be–Ne atomic series with low- and high-spin states for C, N, and O atoms, and small molecules such as BH, HF, and CO at both equilibrium and elongated configurations, respectively.