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Automatic purpose-driven basis set truncation for time-dependent Hartree–Fock and density-functional theory


Han, Ruocheng; Mattiat, Johann; Luber, Sandra (2023). Automatic purpose-driven basis set truncation for time-dependent Hartree–Fock and density-functional theory. Nature Communications, 14(1):106.

Abstract

Real-time time-dependent density-functional theory (RT-TDDFT) and linear response time-dependent density-functional theory (LR-TDDFT) are two important approaches to simulate electronic spectra. However, the basis sets used in such calculations are usually the ones designed mainly for electronic ground state calculations. In this work, we propose a systematic and robust scheme to truncate the atomic orbital (AO) basis set employed in TDDFT and TD Hartree–Fock (TDHF) calculations. The truncated bases are tested for both LR- and RT-TDDFT as well as RT-TDHF approaches, and provide an acceleration up to an order of magnitude while the shifts of excitation energies of interest are generally within 0.2 eV. The procedure only requires one extra RT calculation with 1% of the total propagation time and a simple modification on basis set file, which allows an instant application in any quantum chemistry package supporting RT-/LR-TDDFT calculations. Aside from the reduced computational effort, this approach also offers valuable insight into the effect of different basis functions on computed electronic excitations and further ideas on the design of basis sets for special purposes.

Abstract

Real-time time-dependent density-functional theory (RT-TDDFT) and linear response time-dependent density-functional theory (LR-TDDFT) are two important approaches to simulate electronic spectra. However, the basis sets used in such calculations are usually the ones designed mainly for electronic ground state calculations. In this work, we propose a systematic and robust scheme to truncate the atomic orbital (AO) basis set employed in TDDFT and TD Hartree–Fock (TDHF) calculations. The truncated bases are tested for both LR- and RT-TDDFT as well as RT-TDHF approaches, and provide an acceleration up to an order of magnitude while the shifts of excitation energies of interest are generally within 0.2 eV. The procedure only requires one extra RT calculation with 1% of the total propagation time and a simple modification on basis set file, which allows an instant application in any quantum chemistry package supporting RT-/LR-TDDFT calculations. Aside from the reduced computational effort, this approach also offers valuable insight into the effect of different basis functions on computed electronic excitations and further ideas on the design of basis sets for special purposes.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
08 Research Priority Programs > Solar Light to Chemical Energy Conversion
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > General Chemistry
Life Sciences > General Biochemistry, Genetics and Molecular Biology
Health Sciences > Multidisciplinary
Physical Sciences > General Physics and Astronomy
Uncontrolled Keywords:General Physics and Astronomy, General Biochemistry, Genetics and Molecular Biology, General Chemistry, Multidisciplinary
Language:English
Date:6 January 2023
Deposited On:20 Feb 2024 08:53
Last Modified:29 Jun 2024 01:40
Publisher:Nature Publishing Group
ISSN:2041-1723
OA Status:Gold
Free access at:Publisher DOI. An embargo period may apply.
Publisher DOI:https://doi.org/10.1038/s41467-022-35694-4
PubMed ID:36609507
Project Information:
  • : FunderSNSF
  • : Grant ID170667
  • : Project TitleIn Silico Investigation and Design of Bio-inspired Catalysts for Water Splitting
  • Content: Published Version
  • Language: English
  • Licence: Creative Commons: Attribution 4.0 International (CC BY 4.0)