Basis Set Superposition Errors Are Partly Basis Set Imbalances

Frank Jensen

doi:10.1021/acs.jctc.3c01156

Basis Set Superposition Errors Are Partly Basis Set Imbalances

^*Corresponding author af dette arbejde

Institut for Kemi

Publikation: Bidrag til tidsskrift/Konferencebidrag i tidsskrift /Bidrag til avis › Tidsskriftartikel › Forskning › peer review

6 Citationer (Scopus)

Abstract

When calculating fragment interaction energies by electronic structure methods employing medium-sized atom-centered basis sets, it is often observed that the effect is systematically overestimated. The common interpretation is that the systematic error arises because the basis set for the complex is more complete than for the isolated fragments, and this is denoted basis set superposition errors. It has been observed, however, that the interaction energy in some cases is underestimated, which defies the interpretation in terms of basis set completeness, and instead suggests that the effect partly is due to basis set imbalance. The imbalance can be removed by explicit optimization of the basis sets for each structure, and it is shown that this to a significant extent reduces the systematic overestimation attributed to basis set superposition error.

Originalsprog	Engelsk
Tidsskrift	Journal of Chemical Theory and Computation
Vol/bind	20
Nummer	2
Sider (fra-til)	767-774
Antal sider	8
ISSN	1549-9618
DOI	https://doi.org/10.1021/acs.jctc.3c01156
Status	Udgivet - 23 jan. 2024

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AB - When calculating fragment interaction energies by electronic structure methods employing medium-sized atom-centered basis sets, it is often observed that the effect is systematically overestimated. The common interpretation is that the systematic error arises because the basis set for the complex is more complete than for the isolated fragments, and this is denoted basis set superposition errors. It has been observed, however, that the interaction energy in some cases is underestimated, which defies the interpretation in terms of basis set completeness, and instead suggests that the effect partly is due to basis set imbalance. The imbalance can be removed by explicit optimization of the basis sets for each structure, and it is shown that this to a significant extent reduces the systematic overestimation attributed to basis set superposition error.

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Basis Set Superposition Errors Are Partly Basis Set Imbalances

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