English

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

Chemical Physics 2025-12-15 v2 Materials Science

Abstract

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 GWGW gaps and Bethe-Salpeter excitation energies, while maintaining low condition numbers of the overlap matrix to ensure numerical stability. For GWGW 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 GWGW calculations on nanographenes with 9224 atoms requiring only 34300 core hours of computational resources.

Keywords

Cite

@article{arxiv.2508.12884,
  title  = {Gaussian basis sets for all-electron excited-state calculations of large molecules},
  author = {Rémi Pasquier and Maximilian Graml and Jan Wilhelm},
  journal= {arXiv preprint arXiv:2508.12884},
  year   = {2025}
}

Comments

24 pages, 9 figures, 1 anciliary file (167 pages, 3 figures)