Chemistry Publications
Document Type
Article
Publication Date
10-11-2022
Journal
Journal of Chemical Theory and Computation
Volume
18
Issue
10
First Page
6092
Last Page
6098
URL with Digital Object Identifier
https://doi.org/10.1021/acs.jctc.2c00655
Abstract
Within a basis set of one-electron functions that form linearly independent products (LIPs), it is always possible to construct a unique local (multiplicative) real-space potential that is precisely equivalent to an arbitrary given operator. Although standard basis sets of quantum chemistry rarely form LIPs in a numerical sense, occupied and low-lying virtual canonical Kohn–Sham orbitals often do so, at least for small atoms and molecules. Using these principles, we construct atomic and molecular exchange–correlation potentials from their matrix representations in LIP basis sets of occupied canonical Kohn–Sham orbitals. The reconstructions are found to imitate the original potentials in a consistent but exaggerated way. Since the original and reconstructed potentials produce the same ground-state electron density and energy within the associated LIP basis set, the procedure may be regarded as a rigorous solution to the Kohn–Sham inversion problem within the subspace spanned by the occupied Kohn–Sham orbitals.
Notes
This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in Journal of Chemical Theory and Computation, copyright © American Chemical Society after peer review. To access the final edited and published work see https://doi.org/10.1021/acs.jctc.2c00655