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

Dietrich Foerster (1) , Peter Koval

1 CPMOH - Centre de physique moléculaire optique et hertzienne

We construct the Kohn--Sham density response function $\chi_{0}$ in a previously described basis of the space of orbital products. The calculational complexity of our construction is $O(N^{2}N_{\omega})$ for a molecule of $N$ atoms and in a spectroscopic window of $N_{\omega}$ frequency points. As a first application, we use $\chi_{0}$ to calculate molecular spectra from the Petersilka--Gossmann--Gross equation. With $\chi_{0}$ as input, we obtain correct spectra with an extra computational effort that grows also as $O(N^2 N_{\omega})$ 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 $\chi_{0}$ is a crucial ingredient.

Keywords: Noninteracting Kohn-Sham response

Domains: Other [cond-mat.other]; Chemical Physics [physics.chem-ph]

Dietrich Foerster, Peter Koval. On the Kohn--Sham density response in a localized basis set. Journal of Chemical Physics, 2009, 131 (4), pp.044103. ⟨10.1063/1.3179755⟩. ⟨hal-00378987⟩