Vibrational Versus Electronic Isotropic Polarizability And First Hyperpolarizability Of A Series Of Cis - Ru (ii) - Bipyridine Complexes: A Non-empirical Investigation

摘要

Dipole moments, vibrational and electronic polarizabilities and first hyperpolarizabilities of a set of nine ruthenium (II) complexes, m-RuL_2L'_2 where L = 2,2'-bipyridine and L' = SCN~- (1), SeCN~- (2) or TeCN~- (3); L = (4,4'-dicarboxyH_2)-2,2'-bipyridine and L' = SCN~- (4), SeCN~- (5) or TeCN~- (6); L = [(4,4'-dicarboxy)-2,2'-bipyridine]~(-4) and L' = SCN~- (7), SeCN~- (8) or TeCN~- (9) have been evaluated at the non-empirical PBElPBE/LanL2DZ level. Complete optimizations of their geometrical structures have been made followed by frequency calculations. The order of magnitude and the qualitative variation of μ, Δ_α~e Δ_α~v, Δ_α~(tot), β_(vec)~e, β_(vec)~v and β_(vec)~(tot) in function of the ligands L and L' have also been made. The complexation effects on the vector first hyperpolarizabilities have been studied. The obtained results show that both contributions to β_(vec) are substantially affected by this complexation. The highest effect of complexation is recorded in the case of the complex 8. It has been found that the complexation factor Γ~e is less than 0.13 and for all the considered complexes is less than Γ~v. The individual normal modes contributions to the vibrational first hyperpolarizability show that only a bit of fundamental normal modes, with frequencies are smaller than 50 cm~(-1), contribute to more than 10% to β_(vec)~v.