高等学校化学学报 ›› 2009, Vol. 30 ›› Issue (11): 2284.

• 研究论文 • 上一篇    下一篇

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

李明霞1,2, 周欣1, 张红星1, 付宏刚2, 孙家锺1   

  1. 1. 吉林大学理论化学研究所, 理论化学计算国家重点实验室, 长春 130023;
    2. 黑龙江大学功能无机材料化学省部共建重点实验室, 哈尔滨 150080
  • 收稿日期:2007-04-25 出版日期:2009-11-10 发布日期:2009-11-10
  • 通讯作者: 张红星, 男, 博士, 教授, 博士生导师, 主要从事发光材料、精确小分子激发态和生物大分子模拟计算化学理论研究. E-mail: zhanghx@mail.jlu.edu.cn
  • 基金资助:

    国家自然科学基金(批准号: 20173021, 20333050, 20573042)资助.

Theoretical Studies of Electronic Structures and Spectroscopic Properties of [M(N)X2]-(M=Ru, Os; X=S2C6H4, mnt)

LI Ming-Xia1,2, ZHOU Xin1, ZHANG Hong-Xing1*, FU Hong-Gang2, SUN Chia-Chung1   

  1. 1. State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China;
    2. Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education of the People′s Republic of China, Heilongjiang University, Harbin 150080, China
  • Received:2007-04-25 Online:2009-11-10 Published:2009-11-10
  • Contact: ZHANG Hong-Xing. E-mail: zhanghx@mail.jlu.edu.cn
  • Supported by:

    国家自然科学基金(批准号: 20173021, 20333050, 20573042)资助.

摘要:

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.

关键词: 氮化钌配合物; 氮化锇配合物; 吸收光谱; 密度泛函理论; 含时密度泛函理论

Abstract:

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 14 were optimized by the DFT method(B3LYP). The calculated geometry parameters are in agreement with experimental values. Absorption spectra for complexes 14 in CH3CN solution are predicted at the TD-DFT/B3LYP level. The solvent effects are seriously considered using the conductor-like polarizable continuum model(CPCM). For complexes 14, in CH3CN solution, the low-energy absorptions have a mixed LMCT/LLCT character, while the high-energy absorptions are attributed to the ILCT/LLCT.

Key words: Ru(Ⅵ) nitride complex; Os(Ⅵ) nitride complex; Absorption spectrum; Density functional theory; Time-dependent density functional theory

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