On the Kohn--Sham density response in a localized basis set

Abstract

We construct the Kohn--Sham density response function $χ_{0}$ in a previously described basis of the space of orbital products. The calculational complexity of our construction is $O(N^{2}N_ω)$ for a molecule of $N$ atoms and in a spectroscopic window of $N_ω$ frequency points. As a first application, we use $χ_{0}$ to calculate molecular spectra from the Petersilka--Gossmann--Gross equation. With $χ_{0}$ as input, we obtain correct spectra with an extra computational effort that grows also as $O(N^2 N_ω)$ and, therefore, less steeply in $N$ than the $O(N^{3})$ complexity of solving Casida's equations. Our construction should be useful for the study of excitons in molecular physics and in related areas where $χ_{0}$ is a crucial ingredient.