Spin–Orbit Couplings for Nonadiabatic Molecular Dynamics at the ΔSCF Level
- Momir Mališ*Momir Mališ*Email: [email protected] (M.M.).Department of Chemistry, University of Zürich, Winterthurerstrasse 190, 8057 Zürich, SwitzerlandMore by Momir Mališ
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- Eva VandaeleEva VandaeleDepartment of Chemistry, University of Zürich, Winterthurerstrasse 190, 8057 Zürich, SwitzerlandMore by Eva Vandaele
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- Sandra Luber*Sandra Luber*Email: [email protected] (S.L.).Department of Chemistry, University of Zürich, Winterthurerstrasse 190, 8057 Zürich, SwitzerlandMore by Sandra Luber
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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