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化学学报
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化学学报 ›› 2010, Vol. 68 ›› Issue (08): 733-738. 上一篇    下一篇

研究论文

13顶点金属碳硼烷结构和非线性光学性质的DFT研究

麻娜娜，仇永清*，孙世玲，樊敏，苏忠民   

  1. (东北师范大学化学学院 功能材料化学研究所 长春 130024)
  • 投稿日期:2009-09-09 修回日期:2009-11-11 发布日期:2009-12-30
  • 通讯作者: 仇永清 E-mail:qiuyq466@nenu.edu.cn

Density Functional Theory Study on Structure and Nonlinear Optical Properties of 13-Vertex Metallacarborane

MA Na-Na, CHOU Yong-Qing, SUN Shi-Ling, FAN Min, SU Zhong-Min   

  1. (Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024)
  • Received:2009-09-09 Revised:2009-11-11 Published:2009-12-30
  • Contact: Qiu Yong-Qing E-mail:qiuyq466@nenu.edu.cn

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被引次数

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采用量子化学密度泛函理论(DFT) B3LYP/6-31G(d)方法, 对4,1,6-MC2B10H1213顶点金属碳硼烷几何构型进行优化, 结合有限场(FF)方法计算了它们的极化率和二阶非线性光学(NLO)系数. 结果表明, 十个13顶点金属碳硼烷分子中1a～6a的二阶NLO系数与其构型纵向扩张呈现相同的规律. 分子的前线分子轨道能级差越小, 其二阶NLO系数越大. 对于不同自旋态的同种金属碳硼烷分子, 其偶极矩值为高自旋态大于相应的低自旋态, 极化率和二阶NLO系数与自旋多重度没有一致的对应规律, 自旋多重度对NLO性质影响不大.

关键词: 13顶点金属碳硼烷, 几何结构, 二阶NLO系数, DFT

Density functional theory (DFT) B3LYP method based on the 6-31G(d) level were employed to optimize the structures of 13-vertex metallacarborane 4,1,6-MC2B10H12. The polarizability and second-order nonlinear optical (NLO) coefficients were calculated by means of finite-field (FF) method. The results show that the second-order NLO coefficients of 1a～6a molecules have identical change with their configurations. In all metallacarboranes, the smaller the frontier molecular orbital energy gap is, the larger the second-order NLO coefficient is. For the homogeneous metallacarborane of different spin states, the dipole moments of high-spin state are larger than that of low-spin state, however, the polarizability and second-order NLO coefficient have not direct relationships with spin multiplicity. Therefore, the spin state has a little influence on NLO properties.

Key words: 13-vertex metallacarborane, geometrical structure, second-order NLO coefficient, DFT