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Spin–Orbit Couplings for Nonadiabatic Molecular Dynamics at the ΔSCF Level


Mališ, Momir; Vandaele, Eva; Luber, Sandra (2022). Spin–Orbit Couplings for Nonadiabatic Molecular Dynamics at the ΔSCF Level. Journal of Chemical Theory and Computation, 18(7):4082-4094.

Abstract

A procedure for the calculation of spin–orbit coupling (SOC) at the delta self-consistent field (ΔSCF) level of theory is presented. Singlet and triplet excited electronic states obtained with the ΔSCF method are expanded into a linear combination of singly excited Slater determinants composed of ground electronic state Kohn–Sham orbitals. This alleviates the nonorthogonality between excited and ground electronic states and introduces a framework, similar to the auxiliary wave function at the time-dependent density functional theory (TD-DFT) level, for the calculation of observables. The ΔSCF observables of the formaldehyde system were compared to reference TD-DFT values. Our procedure gives all components (energies, gradients, nonadiabatic couplings, and SOC terms) at the ΔSCF level of theory for conducting efficient, full-atomistic nonadiabatic molecular dynamics with intersystem crossing, particularly in condensed phase systems.

Abstract

A procedure for the calculation of spin–orbit coupling (SOC) at the delta self-consistent field (ΔSCF) level of theory is presented. Singlet and triplet excited electronic states obtained with the ΔSCF method are expanded into a linear combination of singly excited Slater determinants composed of ground electronic state Kohn–Sham orbitals. This alleviates the nonorthogonality between excited and ground electronic states and introduces a framework, similar to the auxiliary wave function at the time-dependent density functional theory (TD-DFT) level, for the calculation of observables. The ΔSCF observables of the formaldehyde system were compared to reference TD-DFT values. Our procedure gives all components (energies, gradients, nonadiabatic couplings, and SOC terms) at the ΔSCF level of theory for conducting efficient, full-atomistic nonadiabatic molecular dynamics with intersystem crossing, particularly in condensed phase systems.

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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 > Computer Science Applications
Physical Sciences > Physical and Theoretical Chemistry
Uncontrolled Keywords:Physical and Theoretical Chemistry, Computer Science Applications
Language:English
Date:12 July 2022
Deposited On:05 Jan 2023 13:09
Last Modified:28 Apr 2024 01:42
Publisher:American Chemical Society (ACS)
ISSN:1549-9618
OA Status:Green
Publisher DOI:https://doi.org/10.1021/acs.jctc.1c01046
Project Information:
  • : FunderSwiss National Science Foundation
  • : Grant IDPP00P2 170667
  • : Project Title
  • Content: Accepted Version