高等学校化学学报 ›› 2009, Vol. 30 ›› Issue (9): 1839.

• 研究论文 • 上一篇    下一篇

卤代氰基卡宾自由基XCCN(X=F,Cl,Br)的理论研究

赵增霞, 侯春园, 张红星, 孙家锺   

  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
  • 收稿日期:2008-09-02 出版日期:2009-09-10 发布日期:2009-09-10
  • 通讯作者: 张红星, 男, 博士, 教授, 博士生导师, 主要从事量子化学研究. E-mail: zhanghx@mail.jlu.edu.cn
  • 基金资助:

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

Theoretical Investigation on Halocyanocarbene XCCN(X=F, Cl, Br)

ZHAO Zeng-Xia, HOU Chun-Yuan, ZHANG Hong-Xing*, SUN Chia-Chung   

  1. State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China
  • Received:2008-09-02 Online:2009-09-10 Published:2009-09-10
  • Contact: ZHANG Hong-Xing. E-mail: zhanghx@mail.jlu.edu.cn
  • Supported by:

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

摘要:

Cs对称性和ANO-S基组下, 使用全活化空间自洽场方法(CASSCF), 研究了卤代氰基卡宾自由基及其阴离子的低能电子激发态性质. 为了进一步考虑电子的动态相关效应,采用多组态二级微扰理论(CASPT2)获得更加精确的能量值. 计算结果表明, XCCN的基态是三重态. 单重态和三重态的能隙差ΔES-T(kJ/mol): 7.4(FCCN)<13.4(ClCCN)<16.6(BrCCN). 计算得到, XCCN(X=F, Cl, Br)最低垂直激发能分别为408.3, 385.4和 345.2 kJ/mol, 这归因于π(a′) →nxy 的电子跃迁; XCCN的电子亲和势分别为235.7, 233.0和 237.2 kJ/mol, 与HCCN相比, 其电子亲和势变大.

关键词: 卤代氰基卡宾; 多组态自洽场理论; 多组态二级微扰理论; 单重态; 三重态

Abstract:

Complete the calculations by means of the active space self-consistent field method(CASSCF) with ANO-S basis sets was performed on the ground and low-lying electronic excited states of halocyanocarbene XCCN and their anions, with X=F, Cl and Br. Our results show that XCCN have triplet X 3A″ neutral ground states and the singlet-triplet energy gaps ΔES-T(kJ/mol) follow this order: 7.4(FCCN)<13.4(ClCCN)<16.6(BrCCN). The calculated most intensive vertical excitation energies of X3A″→23A″ transitions for FCCN, ClCCN, and BrCCN at 408.3, 385.4 and 345.2 kJ/mol, respectively, are mainly attributed to the π(a′)→nxy transitions. The adiabatic electron affinities for XCCN are found to be 235.7, 233.0 and 237.2 kJ/mol, respectively. Compared with the results of HCCN, the electron affinities are enhanced.

Key words: Halocyanocarbene; Complete-active-space self-consistent field; Complete-active-space second-order perturbation; Singlet state; Triplet state

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