Quantifying the effect of heavy-atom only augmented basis sets for the calculation of non-covalent interactions
Abstract
Truncating the basis set is a straightforward way of reducing the computational cost of a calculation, often done by augmenting only the non-hydrogen atoms with diffuse functions. Calculations of non-covalent interactions, which require large diffuse basis sets for quantitative results, regularly employ this truncation. Herein, we assess the validity of this basis set truncation across the A24 and S66 datasets and for case study examples at a range of interaction distances. For the majority of non-covalent interactions, we find that the heavy-atom-only augmented basis sets can be safely applied as a method of reducing computational cost. However, for aliphatic-aliphatic and π-aliphatic type dispersion interactions, we find that lower cardinal number basis sets with full augmentation for all atoms, including hydrogen, can provide similar or even more accurate results than higher cardinal number basis sets with partial augmentation. These results emphasize that increasing basis set size and computational cost does not necessarily improve accuracy; rather, the composition of a basis set is critical to achieving highly accurate and efficient computations.
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BibTeX
@misc{lambie2026quantifying,
title = {{Quantifying the effect of heavy-atom only augmented basis sets for the calculation of non-covalent interactions}},
author = {Stephanie Lambie and Ali Alavi},
howpublished = {arXiv},
year = {2026},
month = oct,
doi = {10.48550/arxiv.2610.32567},
eprint = {2610.32567},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2610.32567},
note = {CC BY 4.0},
}
RIS
TY - UNPB
TI - Quantifying the effect of heavy-atom only augmented basis sets for the calculation of non-covalent interactions
AU - Stephanie Lambie
AU - Ali Alavi
PY - 2026
DA - 2026/10/23
PB - arXiv
DO - 10.48550/arxiv.2610.32567
UR - https://arxiv.org/abs/2610.32567
AB - Truncating the basis set is a straightforward way of reducing the computational cost of a calculation, often done by augmenting only the non-hydrogen atoms with diffuse functions. Calculations of non-covalent interactions, which require large diffuse basis sets for quantitative results, regularly employ this truncation. Herein, we assess the validity of this basis set truncation across the A24 and S66 datasets and for case study examples at a range of interaction distances. For the majority of non-covalent interactions, we find that the heavy-atom-only augmented basis sets can be safely applied as a method of reducing computational cost. However, for aliphatic-aliphatic and π-aliphatic type dispersion interactions, we find that lower cardinal number basis sets with full augmentation for all atoms, including hydrogen, can provide similar or even more accurate results than higher cardinal number basis sets with partial augmentation. These results emphasize that increasing basis set size and computational cost does not necessarily improve accuracy; rather, the composition of a basis set is critical to achieving highly accurate and efficient computations.
ER -