A density‐fitting implementation of the density‐based basis‐set correction method

Heßelmann, Andreas, Giner, Emmanuel, Reinhardt, Peter, Knowles, Peter J. ORCID: https://orcid.org/0000-0003-4657-6331, Werner, Hans‐Joachim and Toulouse, Julien 2024. A density‐fitting implementation of the density‐based basis‐set correction method. Journal of Computational Chemistry 10.1002/jcc.27325

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Abstract

This work reports an efficient density‐fitting implementation of the density‐based basis‐set correction (DBBSC) method in the molpro software. This method consists in correcting the energy calculated by a wave‐function method with a given basis set by an adapted basis‐set correction density functional incorporating the short‐range electron correlation effects missing in the basis set, resulting in an accelerated convergence to the complete‐basis‐set limit. Different basis‐set correction density‐functional approximations are explored and the complementary‐auxiliary‐basis‐set single‐excitation correction is added. The method is tested on a benchmark set of reaction energies at the second‐order Møller–Plesset (MP2) level and a comparison with the explicitly correlated MP2‐F12 method is provided. The results show that the DBBSC method greatly accelerates the basis convergence of MP2 reaction energies, without reaching the accuracy of the MP2‐F12 method but with a lower computational cost.

Item Type:	Article
Date Type:	Published Online
Status:	In Press
Schools:	Chemistry
Additional Information:	License information from Publisher: LICENSE 1: URL: http://creativecommons.org/licenses/by/4.0/
Publisher:	Wiley
ISSN:	0192-8651
Date of First Compliant Deposit:	14 February 2024
Date of Acceptance:	26 January 2024
Last Modified:	14 Feb 2024 10:00
URI:	https://orca.cardiff.ac.uk/id/eprint/166294

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