Double-hybrid density-functional theory with density-based basis-set correction

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Auteurs principaux: Znaïda, Aurore, Toulouse, Julien
Format: Preprint
Publié: 2025
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author Znaïda, Aurore
Toulouse, Julien
author_facet Znaïda, Aurore
Toulouse, Julien
contents We develop the theory justifying the application of the density-based basis-set correction (DBBSC) method to double-hybrid approximations in order to accelerate their basis convergence. We show that, for the oneparameter double hybrids based on the adiabatic connection, the exact dependence of the basis-set correction functional on the coupling-constant parameter $λ$ involves a uniform coordinate scaling by a factor 1/$λ$ of the density and of the basis functions. Neglecting this uniform coordinate scaling corresponds essentially to the recent work of Mester and K{á}llay [J. Phys. Chem. Lett. 16, 2136 (2025)] on the application of the DBBSC method to double-hybrid approximations. Test calculations on molecular atomization energies and reaction barrier heights confirm that the DBBSC method efficiently accelerates the basis convergence of double-hybrid approximations, and also show that neglecting the uniform coordinate scaling is a reasonable approximation.
format Preprint
id arxiv_https___arxiv_org_abs_2506_18612
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Double-hybrid density-functional theory with density-based basis-set correction
Znaïda, Aurore
Toulouse, Julien
Chemical Physics
We develop the theory justifying the application of the density-based basis-set correction (DBBSC) method to double-hybrid approximations in order to accelerate their basis convergence. We show that, for the oneparameter double hybrids based on the adiabatic connection, the exact dependence of the basis-set correction functional on the coupling-constant parameter $λ$ involves a uniform coordinate scaling by a factor 1/$λ$ of the density and of the basis functions. Neglecting this uniform coordinate scaling corresponds essentially to the recent work of Mester and K{á}llay [J. Phys. Chem. Lett. 16, 2136 (2025)] on the application of the DBBSC method to double-hybrid approximations. Test calculations on molecular atomization energies and reaction barrier heights confirm that the DBBSC method efficiently accelerates the basis convergence of double-hybrid approximations, and also show that neglecting the uniform coordinate scaling is a reasonable approximation.
title Double-hybrid density-functional theory with density-based basis-set correction
topic Chemical Physics
url https://arxiv.org/abs/2506.18612