In this article, we propose general criteria to construct optimal atomic centered basis sets in quantum chemistry. We focus in particular on two criteria, one based on the ground-state one-body density matrix of the system and the other based on the ground-state energy. The performance of these two criteria are then numerically tested and compared on a parametrized eigenvalue problem, which corresponds to a one-dimensional toy version of the ground-state dissociation of a diatomic molecule.
Cite
@article{arxiv.2207.12190,
title = {On basis set optimisation in quantum chemistry},
author = {Eric Cancès and Geneviève Dusson and Gaspard Kemlin and Laurent Vidal},
journal= {arXiv preprint arXiv:2207.12190},
year = {2023}
}