卤代效应对乙酸胍非线性光学性质的影响

摘要针对具有应用价值的卤代乙酸胍（GXA）非线性光学（NLO）晶体研究不系统的问题，设计了系列三卤代和系列氯代的乙酸胍（GAc）体系，通过量子化学计算研究了系列GXA的结构、NLO性质和构效关系，探讨了卤代效应可能的影响机理。结果表明，卤代原子显著地改变了GXA分子构象，并通过不同方式参与强氢键作用来影响超分子堆积。卤代主要通过影响GXA分子的LUMO来改变其能隙（E_gap）。GXA的平均偶极矩（μ_total）和平均极化率<α>随卤原子数量以及半径的增大而增大。超极化率总体上相对于GAc降低，但影响复杂，其中，平均第1超极化率（β_total）随卤原子数量的增多而降低，平均第2超极化率（<γ>）则随卤原子的变大而显著增强。此外，并未发现E_gap与μ_total及<γ>之间存在明显的相关性。

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	李慧娜
	裴铁柱
	王奇
	谢闯

关键词：非线性光学晶体卤代效应乙酸胍量子化学计算

Abstract： Halogenated guanidium acetate (GXA)-based non-linear optical (NLO) crystals are promising in the application of NLO field. But the research on this series of NLO crystals remains non-systematic. In this work, a series of tri-halogenated (trifluoro-, trichloro-, and tribromo-) and chlorinated guanidine acetate (GAc) systems were investigated. The structure, NLO properties and structure-activity relationship of this series of GXAs were studied by quantum chemical calculation. The possible mechanism of the halogenation effect was discussed. The results show that halogenated atoms significantly affect the molecular conformation of GXA. They also originally change the supramolecular packing by participating in strong hydrogen bonding interactions in different modes. Halogenation adjusts the energy gap (E_gap) of GXA by affecting their molecular LUMO. The average dipole moment (μ_total) and average polarizability <α> of GXA increase with both increasing number of halogen atoms and enlarging halogen atoms. The hyperpolarizability properties generally decreases relative to GAc, but the effects are complex. The average first hyperpolarizability (β_total) decreases as the number of halogen atoms increases, while the average second hyperpolarizability (<γ>) raises with enlarging halogen atoms. In addition, no significant correlation among E_gap and μ_total and <γ> was found.

Keywords： nonlinear optical crystal； halogenation effect； guanidine acetate； quantum chemical calculation

Received 2020-03-01;

Fund:国家自然科学基金面上项目（21776204）。

Corresponding Authors: 谢闯,E-mail:acxie@tju.edu.cn。 Email: acxie@tju.edu.cn

About author: 李慧娜(1995-),女,硕士研究生,现从事工业结晶方面的研究。

引用本文:

李慧娜, 裴铁柱, 王奇, 谢闯.卤代效应对乙酸胍非线性光学性质的影响[J]. 化学工业与工程, 2020,37(5): 31-36

Li Huina, Pei Tiezhu, Wang Qi, Xie Chuang.Effect of Halogenation on the Nonlinear Optical Properties of Guanidine Acetate[J]. Chemcial Industry and Engineering, 2020,37(5): 31-36

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