Chemistry Publications
Document Type
Article
Publication Date
11-28-2022
Journal
The Journal of Chemical Physics
Volume
157
Issue
20
First Page
204107
Last Page
204107
URL with Digital Object Identifier
https://doi.org/10.1063/5.0128508
Abstract
Harriman showed that within finite basis sets of one-electron functions that form linearly independent products (LIP), differential and integral operators can be represented exactly and unambiguously by multiplicative (local) potentials. Although almost no standard basis sets of quantum chemistry form LIPs in a numerical sense, occupied self-consistent field (SCF) orbitals routinely do so. Using minimal LIP basis sets of occupied SCF orbitals, we construct multiplicative potentials for electronic kinetic energy and exact exchange that reproduce the Hartree-Fock and Kohn-Sham Hamiltonian matrices and electron densities for atoms and molecules. The results highlight fundamental differences between local and nonlocal operators and suggest a practical possibility of developing exact kinetic energy functionals within finite basis sets by using effective local potentials.
