Excited states of OsO4: A comprehensive time-dependent relativistic density functional theory study.

A large number of scalar as well as spinor excited states of OsO4, in the experimentally accessible energy range of 3–11 eV, have been captured by time-dependent relativistic density functional linear response theory based on an exact two-component Hamiltonian resulting from the symmetrized elimination of the small component. The results are grossly in good agreement with those by the singles and doubles coupled-cluster linear response theory in conjunction with relativistic effective core potentials. The simulated-excitation spectrum is also in line with the available experiment. Furthermore, combined with detailed analysis of the excited states, the nature of the observed optical transitions is clearly elucidated. It is found that a few scalar states of 3T1 and 3T2 symmetries are split significantly by the spin-orbit coupling. The possible source for the substantial spin-orbit splittings of ligand molecular orbitals is carefully examined, leading to a new interpretation on the primary valence photoelectron ionization spectrum of OsO4. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010 [ABSTRACT FROM AUTHOR]