Gaussian basis sets for all-electron excited-state calculations of large molecules

Fuente: arXiv
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Main Authors: Pasquier, Rémi, Graml, Maximilian, Wilhelm, Jan
Format: Preprint
Published: 2025
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author Pasquier, Rémi
Graml, Maximilian
Wilhelm, Jan
author_facet Pasquier, Rémi
Graml, Maximilian
Wilhelm, Jan
contents We introduce a family of all-electron Gaussian basis sets, augmented MOLOPT, optimized for excited-state calculations on large molecules. We generate these basis sets by augmenting existing STO-3G, STO-6G, and MOLOPT basis sets optimized for ground state energy calculations. The augmented MOLOPT basis sets achieve fast convergence of $GW$ gaps and Bethe-Salpeter excitation energies, while maintaining low condition numbers of the overlap matrix to ensure numerical stability. For $GW$ HOMO-LUMO gaps, the double-zeta augmented MOLOPT basis yields a mean absolute deviation of 60 meV to the complete basis set limit. The basis set convergence for excitation energies from time-dependent density functional theory and the Bethe-Salpeter equation is similar. We use our smallest generated augmented MOLOPT basis (aug-SZV-MOLOPT-ae-mini) to demonstrate $GW$ calculations on nanographenes with 9224 atoms requiring only 34300 core hours of computational resources.
format Preprint
id arxiv_https___arxiv_org_abs_2508_12884
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Gaussian basis sets for all-electron excited-state calculations of large molecules
Pasquier, Rémi
Graml, Maximilian
Wilhelm, Jan
Chemical Physics
Materials Science
We introduce a family of all-electron Gaussian basis sets, augmented MOLOPT, optimized for excited-state calculations on large molecules. We generate these basis sets by augmenting existing STO-3G, STO-6G, and MOLOPT basis sets optimized for ground state energy calculations. The augmented MOLOPT basis sets achieve fast convergence of $GW$ gaps and Bethe-Salpeter excitation energies, while maintaining low condition numbers of the overlap matrix to ensure numerical stability. For $GW$ HOMO-LUMO gaps, the double-zeta augmented MOLOPT basis yields a mean absolute deviation of 60 meV to the complete basis set limit. The basis set convergence for excitation energies from time-dependent density functional theory and the Bethe-Salpeter equation is similar. We use our smallest generated augmented MOLOPT basis (aug-SZV-MOLOPT-ae-mini) to demonstrate $GW$ calculations on nanographenes with 9224 atoms requiring only 34300 core hours of computational resources.
title Gaussian basis sets for all-electron excited-state calculations of large molecules
topic Chemical Physics
Materials Science
url https://arxiv.org/abs/2508.12884