The first hyperpolarizability (β) of [Ru II -(NH 3 ) 5 (4-AcPhQ)] 3+ and of its oxidized form [Ru III -(NH 3 ) 5 (4-AcPhQ)] 4+ , previously synthesized and characterized by Coe and co-workers by means of hyper-Rayleigh scattering measurements, has been calculated using time-dependent density functional theory and analyzed resorting to the summation-over-states scheme. Besides confirming a β contrast of at least one order of magnitude, calculations point out the key role of the metal-to-ligand charge transfer state, which is responsible for the larger β response of the reduced Ru(II) form. Results also evidence the small contribution to β of the higher-energy intra-ligand charge transfer excited states, as well as the small changes of the depolarization ratio upon oxidation.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry