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实验发现金属钌的某些配合物具有大的非线性光学性能 .我们的理论研究表明金属钌配合物[Ru(NH3 ) 4LDLA]n + (n =2 ,3;LD,LA=吡啶衍生物配体 )的非线性光学性能取决于推电子基团LD 的给电子能力以及拉电子基团LA 的受电子能力 ,LD 和LA 的推拉电子能力越强越有利于提高配合物的二阶非线性光学系数 β,因此带正电荷的LA 能大幅度提高 β值 .虽然增加共轭体系的长度有利于提高 β值 ,但在Ru的配体中 ,吡啶环间或吡啶环与苯环间不一定要保持共面也会有大的β值 .DFT和abinitio方法的计算结果对比表明 ,对于含过渡金属Ru的化合物 ,在HF水平上难以得到满意的结论 ,由从头算有限场方法计算得到的 β值偏小 ,而用TDDFT方法能得到可与实验值符合较好的结果 .
Some complexes of metal ruthenium have been found to have large nonlinear optical properties. Our theoretical studies show that the metal ruthenium complex [Ru (NH3) 4LDLA] n + (n = 2, 3; LD, LA = The nonlinear optical properties of LD are dependent on the electron donating ability of the electron donating group LD and the electron accepting ability of the electron withdrawing group LA. The stronger the push-pull electron capacities of LD and LA are, the better the second-order nonlinear optical properties Coefficient β, so positively charged LA can greatly increase the value of β.Although the increase in the length of the conjugated system is conducive to improving the β value, but in the Ru ligand, pyridine ring or between the benzene ring and pyridine ring does not have to be maintained Coplanar will also have a large value of β.Comparison of the calculated results of the DFT and abinitio methods shows that it is difficult to obtain a satisfactory conclusion at the level of HF for compounds containing transition metal Ru and the β value calculated from the ab initio finite field method Small, and TDDFT method can be obtained with the experimental value in line with good results.