title: Excitation Energies from Real-Time Propagation of the Four-Component Dirac-Kohn-Sham Equation.
abstract: We report the first implementation of real-time time-dependent density functional theory (RT-TDDFT) at the relativistic four-component level of theory. In contrast to the perturbative linear-response TDDFT approach (LR-TDDFT), the RT-TDDFT approach performs an explicit time propagation of the Dirac-Kohn-Sham density matrix, offering the possibility to simulate molecular spectroscopies involving strong electromagnetic fields while, at the same time, treating relativistic scalar and spin-orbit corrections variationally. The implementation is based on the matrix representation of the Dirac-Coulomb Hamiltonian in the basis of restricted kinetically balanced Gaussian-type functions, exploiting the noncollinear Kramers unrestricted formalism implemented in the program ReSpect. We also present an analytic form for the delta-type impulse commonly used in RT-TDDFT calculations, as well as a dipole-weighted transition matrix analysis, facilitating the interpretation of spectral transitions in terms of ground-state molecular orbitals. The possibilities offered by the methodology are illustrated by investigating vertical excitation energies and oscillator strengths for ground-state to excited-state transitions in the Group 12 atoms and in heavy-element hydrides. The accuracy of the method is assessed by comparing the excitation energies obtained with earlier relativistic linear response TDDFT results and available experimental data.
authors.affiliation: The Centre for Theoretical and Computational Chemistry, Department of Chemistry, UiT, The Arctic University of Norway , Tromsø, Norway.
authors.forename: Michal
authors.initials: M
authors.lastname: Repisky
authors.affiliation: Department of Inorganic Chemistry, Faculty of Natural Sciences, Comenius University , Bratislava, Slovak Republic.
authors.forename: Lukas
authors.initials: L
authors.lastname: Konecny
authors.affiliation: The Centre for Theoretical and Computational Chemistry, Department of Chemistry, UiT, The Arctic University of Norway , Tromsø, Norway.
authors.forename: Marius
authors.initials: M
authors.lastname: Kadek
authors.affiliation: The Centre for Theoretical and Computational Chemistry, Department of Chemistry, UiT, The Arctic University of Norway , Tromsø, Norway.
authors.forename: Stanislav
authors.initials: S
authors.lastname: Komorovsky
authors.affiliation: Department of Inorganic Chemistry, Faculty of Natural Sciences, Comenius University , Bratislava, Slovak Republic.|Institute of Inorganic Chemistry, Slovak Academy of Sciences , Bratislava, Slovak Republic.
authors.forename: Olga L
authors.initials: OL
authors.lastname: Malkin
authors.affiliation: Institute of Inorganic Chemistry, Slovak Academy of Sciences , Bratislava, Slovak Republic.
authors.forename: Vladimir G
authors.initials: VG
authors.lastname: Malkin
authors.affiliation: The Centre for Theoretical and Computational Chemistry, Department of Chemistry, UiT, The Arctic University of Norway , Tromsø, Norway.
authors.forename: Kenneth
authors.initials: K
authors.lastname: Ruud