Electronic Origin for Enhanced Nonlinear Optical Response of Complexes from Tetraalkylammonium Halide and Carbon Tetrabromide: Electrostatic Potentials of Intermolecular Donor–Acceptor Dyads
✍ Scribed by Wendan Cheng; Juan Shen; Dongsheng Wu; Xiaodong Li; Youzhao Lan; Feifei Li; Shuping Huang; Hao Zhang; Yajing Gong
- Publisher
- John Wiley and Sons
- Year
- 2006
- Tongue
- English
- Weight
- 333 KB
- Volume
- 12
- Category
- Article
- ISSN
- 0947-6539
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✦ Synopsis
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] ≅ [Et~4~I^−^⋅⋅⋅Br] > [Bu~4~Br^−^⋅⋅⋅Br]. The calculated second‐order susceptibilities of solid complexes are in an increasing order of [NEt~4~Cl⋅CBr~4~] < [NEt~4~Br⋅CBr~4~] ≅ [NEt~4~I⋅CBr~4~] < [NBu~4~Br⋅CBr~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.