What is the Exchange Repulsion Energy? Insight by Partitioning into Physically Meaningful Contributions.

ABSTRACT: It is shown that the exchange repulsion energy, E_xr, can be rationalized by partitioning the respective energy expression for two systems with Hartree-Fock orbitals into physically meaningful contributions. A division of E_xr into a positive kinetic and a negative potential part is possible, but these contributions correlate only poorly with the actual exchange repulsion energy. A more meaningful partitioning is derived, where all kinetic energy contributions are collected in a term that vanishes for exact Hartree-Fock orbitals due to their stationarity conditions. The remaining terms can be distinguished into an exchange integral contribution as well as contributions to the repulsion energy with two, three and four orbital indices. The forms, relationships and absolut

SUBMITTER: Henrichsmeyer J 

PROVIDER: S-EPMC11878756 | biostudies-literature | 2025 Mar

REPOSITORIES: biostudies-literature