Time-dependent density functional theory description of on-site electron repulsion and ligand field effects in the optical spectrum of hexaaquoruthenium(II) in solution.
Time-dependent density functional theory (TDDFT) and density functional-based molecular dynamics were used to simulate the finite temperature t(2g)5 e(g) <-- t(2g)6 absorption band of the Ru2+ hexahydrate coordination complex in aqueous solution. The (1)T1 <-- (1)A1 and (1)T2 <-- (1)A1 molecular term splitting of this transition, which is not accounted for by the Kohn-Sham excitation spectrum, is shown to be satisfactorily reproduced by TDDFT at the BLYP/ALDA level of theory. Comparison to the spectrum of the Ru2+ (H2O)6 complex in vacuo computed by similar density functional classical molecular dynamics methods leads to the observation that bulk solvation has a negligible effect on the position and the shape of the absorption profile.
Bernasconi
Leonardo
L
Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK.
Sprik
Michiel
M