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

TL;DR

This paper develops an efficient method to construct the Kohn--Sham density response function in a localized basis, enabling faster molecular spectra calculations and potential applications in exciton studies.

Contribution

It introduces a computationally efficient approach to build the Kohn--Sham density response function with complexity scaling as $O(N^{2}N_{ ext{omega}})$, improving over traditional methods.

Findings

Successfully calculated molecular spectra using the new $oldsymbol{ ext{chi}_0}$ construction.

Achieved spectral results with computational effort growing as $O(N^{2}N_{ ext{omega}})$.

Demonstrated potential for studying excitons in molecular physics.

Abstract

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.