title: Solvent and intermolecular effects on first hyperpolarizabilities of organometallic tungsten-carbonyl complexes, a TDDFT study.
abstract: The first hyperpolarizability of two tungsten-carbonyl complexes, tungsten pentacarbonyl pyridine and tungsten pentacarbonyl trans-1,2-bis(4-pyridyl)-ethylene, has been studied by the high-level TDDFT method. The consideration of the solvent effect and intermolecular pi-pi weak interaction in the calculations quantitatively improve the final result of both the electronic excitations and the first hyperpolarizabilities. By using the orbital decomposition scheme (J. Phys. Chem. A 2006, 110, 1014-1021), the NLO mechanisms of these two complexes have been ascribed to the dominant contribution from the metal-to-ligand charge transfer, with HOMO --> LUMO character, and the indispensable contribution from the intraligand charge transfer as well. A supplementary formula has been proposed to implement the orbital-pair transition analysis. This study reports the significant influences of solvation and intermolecular interactions on the first hyperpolarizabilities of organometallic NLO chromophores.
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, People's Republic of China.
authors.forename: Qiaohong
authors.initials: Q
authors.lastname: Li
authors.forename: Rongjian
authors.initials: R
authors.lastname: Sa
authors.forename: Caiping
authors.initials: C
authors.lastname: Liu
authors.forename: Kechen
authors.initials: K
authors.lastname: Wu