摘要
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.
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 Lan12DZ 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-Lan12DZ calculations, the trans influence of X was more evident with the bromo ligand than iodo ligand for ft. 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.
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
2005年第24期2199-2204,共6页
Acta Chimica Sinica
基金
国家自然科学基金(No.50473062)
四川省教育厅重点课题(No.2003A087)资助项目.
