Spin-orbit relativistic long-range corrected time-dependent density functional theory for investigating spin-forbidden transitions in photochemical reactions
- Advanced Science Institute, RIKEN, Wako 351-0198 (Japan)
A long-range corrected (LC) time-dependent density functional theory (TDDFT) incorporating relativistic effects with spin-orbit couplings is presented. The relativistic effects are based on the two-component zeroth-order regular approximation Hamiltonian. Before calculating the electronic excitations, we calculated the ionization potentials (IPs) of alkaline metal, alkaline-earth metal, group 12 transition metal, and rare gas atoms as the minus orbital (spinor) energies on the basis of Koopmans' theorem. We found that both long-range exchange and spin-orbit coupling effects are required to obtain Koopmans' IPs, i.e., the orbital (spinor) energies, quantitatively in DFT calculations even for first-row transition metals and systems containing large short-range exchange effects. We then calculated the valence excitations of group 12 transition metal atoms and the Rydberg excitations of rare gas atoms using spin-orbit relativistic LC-TDDFT. We found that the long-range exchange and spin-orbit coupling effects significantly contribute to the electronic spectra of even light atoms if the atoms have low-lying excitations between orbital spinors of quite different electron distributions.
- OSTI ID:
- 22038790
- Journal Information:
- Journal of Chemical Physics, Vol. 135, Issue 22; Other Information: (c) 2011 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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