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化学学报
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化学学报 ›› 2006, Vol. 64 ›› Issue (19): 2003-2007. 上一篇    下一篇

研究论文

平面四方金属苯配合物的二阶超极化率的量子化学计算

丁涪江*, 赵可清   

  1. (四川师范大学化学学院 成都 610066)
  • 投稿日期:2005-12-02 修回日期:2006-03-24 发布日期:2006-10-14
  • 通讯作者: 丁涪江

Quantum Chemistry Calculations of the Second Hyperpolarizabilities of Square-planar Metal Aromatics

DING Fu-Jiang*; ZHAO Ke-Qing   

  1. (Department of Chemistry, Sichuan Normal University, Chengdu 610066)
  • Received:2005-12-02 Revised:2006-03-24 Published:2006-10-14
  • Contact: DING Fu-Jiang

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788

被引次数

18 | 5

反位平面四方型过渡金属有机配合物[XM(PEt3)2-C6H4-A] (M＝Pd, Pt; X＝Br, I; A＝NO2, CHO), 具有较高的二阶超极化率. 采用从头算方法对该配合物的二阶超极化率进行了研究. 构型在MP2/Lanl2DZ水平优化. 基组采用赝势价分裂基Lanl2DZ添加弥散函数和极化函数. HF水平计算(个别情况用MP2计算验证)表明, 苯的对位取代基A的吸电子能力越强, 金属对位配体X的供电子能力越强, 则配合物的二阶超极化率越大.

关键词: 金属有机化合物, 二阶非线性超极化率, 基组, 从头算

Some square-planar metal benzene derivative [XM(PEt3)2-C6H4-A] (M＝Pd, Pt; X＝Br, I; A＝NO2, CHO) were reported to possess rather large second hyperpolarizabilities. The series of compounds have been studied by using ab initio method. An extending Lanl2DZ basis set was used in calculations. According to our RHF/extending-Lanl2DZ calculations, the trans influence of X is evident with the iodo ligand better than bromo ligand for γ. The importance of benzene acceptor (A) is also evident, γ values were found to be increased with increase of acceptor strength, giving the higher values for the nitro derivatives.

Key words: metal complex, second hyperpolarizability, basis set, ab initio