物理化学学报 >> 2012, Vol. 28 >> Issue (03): 555-560.doi: 10.3866/PKU.WHXB201112212

理论与计算化学 上一篇    下一篇

碱金属化物M+aza222M′- (M, M′=Li, Na, K)的结构及非线性光学性质

樊丽涛, 李莹, 吴迪, 李志儒, 孙家钟   

  1. 吉林大学理论化学研究所, 理论化学计算国家重点实验室, 长春 130023
  • 收稿日期:2011-10-12 修回日期:2011-12-11 发布日期:2012-02-23
  • 通讯作者: 吴迪 E-mail:wud@mail.jlu.edu.cn
  • 基金资助:

    国家自然科学基金(21043003, 21173095)资助项目

Structures and Nonlinear Optical Properties of the Alkalides M+aza222M′- (M, M′=Li, Na, K)

FAN Li-Tao, LI Ying, WU Di, LI Zhi-Ru, SUN Chia-Chung   

  1. State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, P. R. China
  • Received:2011-10-12 Revised:2011-12-11 Published:2012-02-23
  • Contact: WU Di E-mail:wud@mail.jlu.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21043003, 21173095).

摘要: 采用密度泛函理论(DFT)B3LYP 方法得到具有有机穴状配体的碱金属化物M+aza222M′- (M, M′=Li,Na, K)的几何结构. 并使用了BHandHLYP方法计算了此体系的非线性光学(NLO)性质. 结果表明: 该体系具有很大的一阶超极化率(β0), 对于Li+aza222K-体系, β0值达到1.0×106 a.u.; 体系的β0值及配体aza222 内外的碱金属之间距离与碱金属的原子序数均存在着依赖关系. 通过与其它碱金属化物的β0值对比发现, aza222 配体能够显著增大碱金属化物的一阶超极化率.

关键词: 密度泛函理论, 非线性光学, 碱金属化物, 一阶超极化率, 穴状配体

Abstract: Using density functional theory with the B3LYP functional, the optimized structures of the organic alkalides M+ aza222M′- (M, M′ =Li, Na, K, and aza222=Azacryptand[2.2.2]) were calculated. The nonlinear optical (NLO) properties of these species were calculated by the BHandHLYP method. The results indicate that the M+aza222M′- alkalides exhibit very large first hyperpolarizabilities (β0) up to 1.0×106 a.u. (for M=Li, M′ =K). Both the first hyperpolarizabilities and the M-M′ distances of M+aza222M′- were found to depend on the atomic number of the alkali metal atom M(M′). By comparing the β0 values of various organic alkalides, aza222 was found to be preferable to the previously investigated complexants in enhancing the first hyperpolarizabilities of alkalides.

Key words: Density functional theory, Nonlinear optics, Alkalide, First hyperpolarizability, Cryptand complexant

MSC2000: 

  • O641