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化学学报
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化学学报 ›› 2005, Vol. 63 ›› Issue (24): 2199-2204. 上一篇    下一篇

研究论文

平面四方金属苯配合物的非线性光学性质的从头算研究

丁涪江*，何云清，刘柳斜，赵可清   

  1. (四川师范大学化学学院 成都 610066)
  • 投稿日期:2005-01-20 修回日期:2005-08-10 发布日期:2005-12-28
  • 通讯作者: 丁涪江

Ab initio Study on the Nonlinear Optical Properties of Square-planar Phenyl Metal Complex

DING Fu-Jiang*, HE Yun-Qing, LIU Liu-Xie, ZHAO Ke-Qing   

  1. (Department of Chemistry, Sichuan Normal University, Chengdu 610066)
  • Received:2005-01-20 Revised:2005-08-10 Published:2005-12-28
  • Contact: DING Fu-Jiang

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被引次数

38 | 13

反位平面四方型过渡金属有机配合物[XM(PEt3)2-C6H4-R] (M＝Pd, Pt; X＝Br, I; R＝NO2, CHO), 已被测定有较高的非线性光学系数. 本工作采用从头算方法对该配合物的结构和非线性光学性质进行研究. 构型在MP2/Lanl2DZ水平优化. 对基组进行慎重选择后, 认为应该在赝势价分裂基Lanl2DZ的基础上添加弥散函数和极化函数. 弥散函数按几何级数规则增加, 极化函数的指数应取低一个角量子数的基函数中最弥散的两个函数的指数的比例中项. 本工作的SCF水平计算表明苯的对位取代基R的吸电子能力越强, 金属对位配体X的电负性越强, 则配合物的超极化率越大.

关键词: 金属有机配合物, 非线性光学性质, 基组, 从头算

Some square-planar phenyl metal complexes [XM(PEt3)2-C6H4-R] (M＝Pd, Pt, X＝Br, I, R＝NO2, CHO) were reported to possess rather large hyperpolarizabilities. This series of complexes have been studied by ab initio method. An extending Lanl2DZ basis set was used in calculations, which is augmented with one diffuse function in each shell with their exponents determined from the even-tempered sequences. Only one polarization function has been augmented for each atom and its exponent determined from the exponents of most two diffuse functions of outermost occupied shell of the definite atom, the square root of their product. According to our RHF/extending-Lanl2DZ calculations, the trans influence of X was more evident with the bromo ligand than iodo ligand for β. The importance of electrowithdrawing substituent R was also evident, and β values were found to be increased with electrowithdrawing strength, leading to the higher values of the nitro derivatives.

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