Vibrational versus electronic isotropic polarizability and first hyperpolarizability of a series of cis – Ru (II) – bipyridine complexes: A non-empirical investigation
Affiliations: [a] Laboratoire de Physico-Chimie Théorique et Chimie Informatique faculty of chemistry USTHB university, Algiers, Algeria | [b] Department of Chemistry, UMMTO university, Tizi-ouzou, Algeria | [c] Laboratoire d'Electrochimie et de Chimie Analytique, CNRS UMR 7575, Ecole Nationale Supérieure de Chimie de Paris, Paris Cedex 05, France
Correspondence:
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Corresponding author. Laboratoire de Physico-Chimie Théorique et Chimie Informatique faculty of chemistry USTHB university, Algiers 16111, Algeria. E-mail: [email protected].
Abstract: Dipole moments, vibrational and electronic polarizabilities and first hyperpolarizabilities of a set of nine ruthenium (II) complexes, cis-RuL2L′2 where L = 2,2’-bipyridine and L′ = SCN− (1), SeCN− (2) or TeCN− (3); L = (4,4’-dicarboxyH2)-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 PBE1PBE/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, Δαe, Δαv, Δαtot, βvece, βvecv and ηvectot 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 βvec 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 Γe is less than 0.13 and for all the considered complexes is less than Γv. 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 βvecv.
