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Derivation of spin-orbit couplings in collinear linear-response TDDFT: A rigorous formulation

de Carvalho, Felipe Franco; Curchod, Basile F.E.; Penfold, Thomas J.; Tavernelli, Ivano

Derivation of spin-orbit couplings in collinear linear-response TDDFT: A rigorous formulation Thumbnail


Authors

Felipe Franco de Carvalho

Thomas J. Penfold

Ivano Tavernelli



Abstract

Using an approach based upon a set of auxiliary many-electron wavefunctions we present a rigorous derivation of spin-orbit coupling (SOC) within the framework of linear-response time-dependent density functional theory (LR-TDDFT). Our method is based on a perturbative correction of the non-relativistic collinear TDDFT equations using a Breit-Pauli spin-orbit Hamiltonian. The derivation, which is performed within both the Casida and Sternheimer formulations of LR-TDDFT, is valid for any basis set. The requirement of spin noncollinearity for the treatment of spin-flip transitions is also discussed and a possible alternative solution for the description of these transitions in the collinear case is also proposed. Our results are validated by computing the SOC matrix elements between singlet and triplet states of two molecules, formaldehyde and acetone. In both cases, we find excellent agreement with benchmark calculations performed with a high level correlated wavefunction method.

Citation

de Carvalho, F. F., Curchod, B. F., Penfold, T. J., & Tavernelli, I. (2014). Derivation of spin-orbit couplings in collinear linear-response TDDFT: A rigorous formulation. The Journal of Chemical Physics, 140(14), Article 144103. https://doi.org/10.1063/1.4870010

Journal Article Type Article
Acceptance Date Mar 19, 2014
Online Publication Date Apr 9, 2014
Publication Date Apr 9, 2014
Deposit Date Nov 6, 2017
Publicly Available Date Mar 28, 2024
Journal Journal of Chemical Physics
Print ISSN 0021-9606
Electronic ISSN 1089-7690
Publisher American Institute of Physics
Peer Reviewed Peer Reviewed
Volume 140
Issue 14
Article Number 144103
DOI https://doi.org/10.1063/1.4870010

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Copyright Statement
© 2014 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in The Journal of Chemical Physics 140, 144103 (2014) and may be found at https://doi.org/10.1063/1.4870010




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