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Approaching the basis set limit for DFT calculations using an environment-adapted minimal basis with perturbation theory: formulation, proof of concept, and a pilot implementation

Approaching the basis set limit for DFT calculations using an environment-adapted minimal basis with perturbation theory: formulation, proof of concept, and a pilot implementation
Approaching the basis set limit for DFT calculations using an environment-adapted minimal basis with perturbation theory: formulation, proof of concept, and a pilot implementation
Recently developed density functionals have good accuracy for both thermochemistry (TC) and non-covalent interactions (NC) if very large atomic orbital basis sets are used. To approach the basis set limit with potentially lower computational cost, a new self-consistent field (SCF) scheme is presented that employs minimal adaptive basis (MAB) functions. The MAB functions are optimized on each atomic site by minimizing a surrogate function. High accuracy is obtained by applying a perturbative correction (PC) to the MAB calculation, similar to dual basis approaches. Compared to exact SCF results, using this MAB-SCF?(PC) approach with the same large target basis set produces <0.15 kcal/mol root-mean-square deviations for most of the tested TC datasets, and <0.1 kcal/mol for most of the NC datasets. The performance of density functionals near the basis set limit can be even better reproduced. With further improvement to its implementation, MAB-SCF?(PC) is a promising lower-cost substitute for conventional large-basis calculations as a method to approach the basis set limit of modern density functionals.
0021-9606
1-18
Mao, Yuezhi
19117f2e-bd57-431d-ad0e-f36f4aa2187c
Horn, Paul R.
7b2d88e6-39c7-4f8c-bf11-26e273b02834
Mardirossian, Narbe
6dc65ee1-19a9-490e-83e6-6984a64bb7f9
Head-Gordon, Teresa
11febdf4-20fa-4abb-97a1-3305c6e81b09
Skylaris, Chris
8f593d13-3ace-4558-ba08-04e48211af61
Head-Gordon, Martin
f203c934-60ff-4c19-a2ff-b1f6ec2ad05a
Mao, Yuezhi
19117f2e-bd57-431d-ad0e-f36f4aa2187c
Horn, Paul R.
7b2d88e6-39c7-4f8c-bf11-26e273b02834
Mardirossian, Narbe
6dc65ee1-19a9-490e-83e6-6984a64bb7f9
Head-Gordon, Teresa
11febdf4-20fa-4abb-97a1-3305c6e81b09
Skylaris, Chris
8f593d13-3ace-4558-ba08-04e48211af61
Head-Gordon, Martin
f203c934-60ff-4c19-a2ff-b1f6ec2ad05a

Mao, Yuezhi, Horn, Paul R., Mardirossian, Narbe, Head-Gordon, Teresa, Skylaris, Chris and Head-Gordon, Martin (2016) Approaching the basis set limit for DFT calculations using an environment-adapted minimal basis with perturbation theory: formulation, proof of concept, and a pilot implementation. The Journal of Chemical Physics, 145 (4), 1-18. (doi:10.1063/1.4959125).

Record type: Article

Abstract

Recently developed density functionals have good accuracy for both thermochemistry (TC) and non-covalent interactions (NC) if very large atomic orbital basis sets are used. To approach the basis set limit with potentially lower computational cost, a new self-consistent field (SCF) scheme is presented that employs minimal adaptive basis (MAB) functions. The MAB functions are optimized on each atomic site by minimizing a surrogate function. High accuracy is obtained by applying a perturbative correction (PC) to the MAB calculation, similar to dual basis approaches. Compared to exact SCF results, using this MAB-SCF?(PC) approach with the same large target basis set produces <0.15 kcal/mol root-mean-square deviations for most of the tested TC datasets, and <0.1 kcal/mol for most of the NC datasets. The performance of density functionals near the basis set limit can be even better reproduced. With further improvement to its implementation, MAB-SCF?(PC) is a promising lower-cost substitute for conventional large-basis calculations as a method to approach the basis set limit of modern density functionals.

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Accepted/In Press date: 3 July 2016
e-pub ahead of print date: 27 July 2016
Organisations: Computational Systems Chemistry

Identifiers

Local EPrints ID: 401779
URI: http://eprints.soton.ac.uk/id/eprint/401779
ISSN: 0021-9606
PURE UUID: c30579ae-bcab-43cf-b79d-b5b31420e355
ORCID for Chris Skylaris: ORCID iD orcid.org/0000-0003-0258-3433

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Date deposited: 19 Oct 2016 15:51
Last modified: 15 Mar 2024 03:26

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Contributors

Author: Yuezhi Mao
Author: Paul R. Horn
Author: Narbe Mardirossian
Author: Teresa Head-Gordon
Author: Chris Skylaris ORCID iD
Author: Martin Head-Gordon

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