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Local approaches for electric dipole moments in periodic systems and their application to real-time time-dependent density functional theory


Schreder, Lukas; Luber, Sandra (2021). Local approaches for electric dipole moments in periodic systems and their application to real-time time-dependent density functional theory. Journal of Chemical Physics, 155(13):134116.

Abstract

Within periodic boundary conditions, the traditional quantum mechanical position operator is ill-defined, necessitating the use of alternative methods, most commonly the Berry phase formulation in the modern theory of polarization. Since any information about local properties is lost in this change of framework, the Berry phase formulation can only determine the total electric polarization of a system. Previous approaches toward recovering local electric dipole moments have been based on applying the conventional dipole moment operator to the centers of maximally localized Wannier functions (MLWFs). Recently, another approach to local electric dipole moments has been demonstrated in the field of subsystem density functional theory (DFT) embedding. We demonstrate in this work that this approach, aside from its use in ground state DFT-based molecular dynamics, can also be applied to obtain electric dipole moments during real-time propagated time-dependent DFT (RT-TDDFT). Moreover, we present an analogous approach to obtain local electric dipole moments from MLWFs, which enables subsystem analysis in cases where DFT embedding is not applicable. The techniques were implemented in the quantum chemistry software CP2K for the mixed Gaussian and plane wave method and applied to cis-diimide and water in the gas phase, cis-diimide in aqueous solution, and a liquid mixture of dimethyl carbonate and ethylene carbonate to obtain absorption and infrared spectra decomposed into localized subsystem contributions.

Abstract

Within periodic boundary conditions, the traditional quantum mechanical position operator is ill-defined, necessitating the use of alternative methods, most commonly the Berry phase formulation in the modern theory of polarization. Since any information about local properties is lost in this change of framework, the Berry phase formulation can only determine the total electric polarization of a system. Previous approaches toward recovering local electric dipole moments have been based on applying the conventional dipole moment operator to the centers of maximally localized Wannier functions (MLWFs). Recently, another approach to local electric dipole moments has been demonstrated in the field of subsystem density functional theory (DFT) embedding. We demonstrate in this work that this approach, aside from its use in ground state DFT-based molecular dynamics, can also be applied to obtain electric dipole moments during real-time propagated time-dependent DFT (RT-TDDFT). Moreover, we present an analogous approach to obtain local electric dipole moments from MLWFs, which enables subsystem analysis in cases where DFT embedding is not applicable. The techniques were implemented in the quantum chemistry software CP2K for the mixed Gaussian and plane wave method and applied to cis-diimide and water in the gas phase, cis-diimide in aqueous solution, and a liquid mixture of dimethyl carbonate and ethylene carbonate to obtain absorption and infrared spectra decomposed into localized subsystem contributions.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > General Physics and Astronomy
Physical Sciences > Physical and Theoretical Chemistry
Uncontrolled Keywords:Physical and Theoretical Chemistry, General Physics and Astronomy
Language:English
Date:7 October 2021
Deposited On:11 Feb 2022 15:48
Last Modified:26 Jun 2024 01:52
Publisher:American Institute of Physics
ISSN:0021-9606
Additional Information:The following article appeared in the Journal of Chemical Physics and may be found at https://doi.org/10.1063/5.0058793.
OA Status:Green
Publisher DOI:https://doi.org/10.1063/5.0058793
PubMed ID:34624999
Project Information:
  • : FunderSNSF
  • : Grant IDPP00P2_170667
  • : Project TitleIn Silico Investigation and Design of Bio-inspired Catalysts for Water Splitting
  • Content: Accepted Version
  • Language: English
  • Content: Published Version
  • Language: English