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

Lookup NU author(s): Professor Thomas Penfold

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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.

Publication metadata

Author(s): Franco de Carvalho F, Curchod BFE, Penfold TJ, Tavernelli I

Publication type: Article

Publication status: Published

Journal: Journal of Chemical Physics

Year: 2014

Volume: 140

Print publication date: 01/04/2014

Online publication date: 09/04/2014

Acceptance date: 19/03/2014

ISSN (print): 0021-9606

ISSN (electronic): 1089-7690

Publisher: American Institute of Physics

URL: http://dx.doi.org/10.1063/1.4870010

DOI: 10.1063/1.4870010

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