Excited states of [formula omitted]: A comprehensive time-dependent relativistic density functional theory study

Abstract

The perrhenate anion, ReO4-, is taken as a showcase of heavy transition metal complexes, to examine the performance of time-dependent relativistic density functional linear response theory for electronic excitations, which is based on a newly proposed exact two-component Hamiltonian resulting from the symmetrized elimination of the small component. In total 30 scalar and 63 spinor excited states are investigated and the results are grossly in good agreement with those by the singles and doubles coupled-cluster linear response theory. It is found that only a few scalar states of 3T1 and 3T2 symmetries are split significantly by the spin–orbit coupling, whereas only those excited states involving the Rydberg-type virtual orbital are affected by the solvent effects. The nature of the optical absorption spectra is also highlighted.