高等学校化学学报

高等学校化学学报 ›› 2013, Vol. 34 ›› Issue (9): 2184.doi: 10.7503/cjcu20130250

• 物理化学 • 上一篇    下一篇

超碱金属复合物Al7X0/-(X=F,Cl,Br,I)的结构及非线性光学性质的理论研究

肖文敏1,2, 麻娜娜1, 马腾颖1, 张婷1, 颜力楷1, 苏忠民1   

  1. 1. 东北师范大学化学学院, 功能材料化学研究所, 长春 130024;
    2. 赤峰学院化学化工学院, 赤峰 024000
  • 收稿日期:2013-03-18 出版日期:2013-09-10 发布日期:2013-08-30
  • 作者简介:颜力楷,女,博士,教授,博士生导师,主要从事量子力学研究.E-mail:yanlk924@nenu.edu.cn苏忠民,男,博士,教授,博士生导师,主要从事功能材料和量子力学研究.E-mail:zmsu@nenu.edu.cn
  • 基金资助:

    国家自然科学基金(批准号:21073030,21131001)资助.

Theoretical Studies on Structures and Nonlinear Optical Properties of Superalkali Compounds Al7X0/-(X=F, Cl, Br, I)

XIAO Wen-Min1,2, MA Na-Na1, MA Teng-Ying1, ZHANG Ting1, YAN Li-Kai1, SU Zhong-Min1   

  1. 1. Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, China;
    2. Department of Chemistry and Chemical Engineerin, Chifeng University, Chifeng 024000, China
  • Received:2013-03-18 Online:2013-09-10 Published:2013-08-30

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摘要：

采用密度泛函理论(DFT)方法研究了一系列超碱金属复合物Al7X0/-(X=F, Cl, Br, I)的几何结构及二阶非线性光学(NLO)性质. 结果表明, 不同卤素的连接对Al0/-7簇的几何构型影响均很小. 计算得到Al7X和Al7X-体系的垂直电离能(VIE)均低于Cs原子的第一电离势(IP=3.90 eV), 表明这些体系具有超碱金属的性质, 可称其为超碱金属. 此外, 采用CAM-B3LYP, M06-2X和PBE0等3种泛函计算了该体系的非线性光学性质, 结果显示, 上述体系均具有较大的第一超极化率(β0), 其中Al7I-的β0值为21679 a. u., 是已知超碱金属复合物BLi6F(11459 a. u.) 的1.9倍. 值得注意的是, 该类体系的第一超极化率随着卤素电负性的减小而增大, 即Al7F0/-7Cl0/-7Br0/-7I0/-, 与其垂直电离能具有相同的变化规律.

关键词: 密度泛函理论, 非线性光学性质, 超碱金属, 第一超极化率

Abstract:

The structures and nonlinear optical(NLO) properties of a series of superalkali compounds, Al7X0/-(X=F, Cl, Br, I) were investigated by the means of density functional theory(DFT) calculations. The results indicate that the halogens have little influence on the geometry of the compounds. The present results indicate that Al7X and Al7X- can be considered as superalkali duo to that the calculated vertical ionization energies(VIEs) are all lower than the ionization potential of Cs atom(IP=3.90 eV). In addition, three functionals(CAM-B3LYP, M06-2X and PBE0) were employed to calculate the NLO properties of these species. The results show that these compounds own large first hyperpolarizabilities(β0), with the largest β0 values of 21679 a. u. for Al7I-, which is 1.9 times of that of BLi6F(11459 a. u.). Furthermore, it is worth noting that the values of β0 are increased with the decrease of the electronegativity of the halogens for this type of compounds(Al7F0/- 7Cl0/-7Br0/-7I0/-), which exhibit the same variations as the vertical ionization energies.

Key words: Density functional theory, Nonlinear optical property, Superalkali, First hyperpolarizability

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