高等学校化学学报 ›› 2010, Vol. 31 ›› Issue (1): 125.

• 研究论文 • 上一篇    下一篇

H2CCC光谱性质的从头算研究

舒鑫, 赵增霞, 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:2009-02-24 出版日期:2010-01-10 发布日期:2010-01-10
  • 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.

ab initio Study on the Spectroscopy of H2CCC

SHU Xin, ZHAO Zeng-Xia, 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:2009-02-24 Online:2010-01-10 Published:2010-01-10
  • 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:

采用全活化空间自洽场方法(CASSCF)在C2v对称性和ANO-S基组水平下, 研究了H2CCC自由基及其阴阳离子的基态和低激发态性质. 为了进一步考虑动态电子相关效应, 采用多组态二级微扰理论(CASPT2)获得了更加精确的能量值. 计算得到X1A1 → 1A2, X1A1 → 1B1和X1A1 → 21A1在159.0, 216.5和476.4 kJ/mol处的激发可分别归因于π(b2)→π*(b1), n(a1)→π*(b1)和π(b1)→π*(b1)的跃迁, 理论波长与紫外吸收光谱得到的实验数据一致. 计算得到的电子亲和势与实验值也非常接近.

关键词: 亚丙二烯基; 多组态自洽场理论; 多组态二级微扰理论; 光电子能谱

Abstract:

Complete active space self-consistent field(CASSCF) calculations with ANO-S basis sets were performed for a few electronic states of propadienylidene, H2CCC, and its cation and anion in C2v symmetry. For all the calculated states, the accuracy of the total energies was improved by including dynamic electron correlation via the multiconfiguration second-order perturbation theory(CASPT2) method. The results suggest that the calculated transitions of X1A1 → 1A2, X1A1 → 1B1 and X1A1 → 21A1 at 159.0, 216.5 and 476.4 kJ/mol are attributed to π(b2)→π*(b1), n(a1)→π*(b1) and π(b1)→π*(b1) transition, respectively. The electron affinities were obtained in comparison with the photoelectron spectrum(PES) data. These above results are in agreement with the previous experimental data.

Key words: Propadienylidene; Completeactivespace selfconsistent field; Completeactive-space secondorder perturbation; Photoelectron spectroscopy

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