Chemistry Publications
Document Type
Article
Publication Date
7-28-2022
Journal
The Journal of Physical Chemistry Letters
Volume
13
Issue
29
First Page
6839
Last Page
6844
URL with Digital Object Identifier
https://doi.org/10.1021/acs.jpclett.2c01827
Abstract
The notion of noninteracting v-representability is extended from electron densities to finite-dimensional linear subspaces of orbitals. Unlike electron densities, orbital subspaces can be tested for noninteracting v-representability using a transparent necessary condition: the subspace must be invariant under the action of some one-electron Kohn–Sham Hamiltonian. This condition allows one to determine in principle, and sometimes in practice, whether a given one-electron basis set can represent an N-electron density within the Kohn–Sham method and to find the corresponding Kohn–Sham effective potential v if it exists. If the occupied Kohn–Sham orbitals form linearly independent products, then their subspace is determined by the corresponding ground-state electron density. This means that the Kohn–Sham effective potential corresponding to certain finite-basis-set electron densities can be deduced from the basis set itself.
Notes
This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in The Journal of Physical Chemistry Letters, copyright © American Chemical Society after peer review. To access the final edited and published work see https://doi.org/10.1021/acs.jpclett.2c01827