[M(N)X2]-(M=Ru，Os；X=S2C6H4，mnt)的电子结构和光谱性质的理论研究

Theoretical Studies of Electronic Structures and Spectroscopic Properties of [M(N)X_2]^-(M=Ru,Os;X=S_2C_6H_4,mnt)

利用密度泛函理论(DFT)中的B3LYP方法优化了氮化钌和氮化锇配合物[M(N)X2]-[M=Ru,Os;X=S2C6H4,mnt(maleonitriledithiolate)]的基态几何结构,得到的几何参数与实验结果吻合得很好.采用TD-DFT方法,得到了配合物在CH3CN溶液中的激发态电子结构和电子吸收光谱.利用SCRF方法中的CPCM模型来模拟溶剂化效应.研究结果表明,配合物1~4在CH3CN溶液中的吸收跃迁性质相似,低能吸收均被指认为LMCT和LLCT的混合跃迁,高能吸收均被指认为ILCT/LLCT跃迁.

Ruthenium （ Ⅵ） nitrido complexes and osmium （ VI ） nitride complexes [ M （ N ） X2 ] - （ M = Ru, Os; X = S2C6H4, mnt） were investigated theoretically to explore their electronic structures and spectroscopic properties. The ground-state geometry structures of complexes 1--4 were optimized by the DFT method （B3LYP）. The calculated geometry parameters are in agreement with experimental values. Absorption spectra for complexes 1--4 in CH3CN solution are predicted at the TD-DFT/B3LYP level. The solvent effects are seri- ously considered using the conductor-like polarizable continuum model （CPCM）. For complexes 1---4, in CH3CN solution, the low-energy absorptions have a mixed LMCT/LLCT character, while the high-energy absorptions are attributed to the ILCT/LLCT.