title: Electronic origin for enhanced nonlinear optical response of complexes from tetraalkylammonium halide and carbon tetrabromide: electrostatic potentials of intermolecular donor-acceptor dyads.
abstract: Electronic origin for nonresonant enhancement of nonlinear optical response in the complexes formed from tetraalkylammonium halide and carbon tetrabromide is provided in view of electrostatic potentials of intermolecular donor (halide ion)-acceptor (CBr(4)). The calculated electrostatic potentials of donor-acceptor range from -4.83 to -7.70 kcal mol(-1) and show a decreasing order of [Et(4)Cl(-)Br] > [Et(4)Br(-)Br] congruent with [Et(4)I(-)Br] > [Bu(4)Br(-)Br]. The calculated second-order susceptibilities of solid complexes are in an increasing order of [NEt(4)ClCBr(4)] < [NEt(4)BrCBr(4)] congruent with [NEt(4)ICBr(4)] < [NBu(4)BrCBr(4)C(3)H(6)O]. It has been shown that the donor/acceptor dyads make the exclusive contribution to nonlinear optical response. A large size of halide or tetraalkylammonium ion results in a small electrostatic potential and large nonlinear optical response in these charge-transfer complexes. It indicates that a small supermolecular interaction will create a large nonlinear optical response, and it gives a clue to design the molecular complexes with large non-linear optical susceptibility.
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, The Chinese Academy of Sciences, Fuzhou, Fujian 350002, P.R. China.
authors.forename: Wendan
authors.initials: W
authors.lastname: Cheng
authors.forename: Juan
authors.initials: J
authors.lastname: Shen
authors.forename: Dongsheng
authors.initials: D
authors.lastname: Wu
authors.forename: Xiaodong
authors.initials: X
authors.lastname: Li
authors.forename: Youzhao
authors.initials: Y
authors.lastname: Lan
authors.forename: Feifei
authors.initials: F
authors.lastname: Li
authors.forename: Shuping
authors.initials: S
authors.lastname: Huang
authors.forename: Hao
authors.initials: H
authors.lastname: Zhang
authors.forename: Yajing
authors.initials: Y
authors.lastname: Gong
mesh_terms: D000588:Amines / Q000737:chemistry*; D006842:Hydrocarbons, Brominated / Q000737:chemistry*; D008958:Models, Molecular; D055672:Static Electricity
chemical_list: D000588:Amines; D006842:Hydrocarbons, Brominated; C031387:carbon tetrabromide