高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

HO2自由基电子激发态的理论研究

李步通1, 魏子章1, 潘清江2, 张红星1, 孙家锺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. 黑龙江大学化学化工与材料学院, 哈尔滨150080
  • 收稿日期:2005-12-31 修回日期:1900-01-01 出版日期:2006-11-10 发布日期:2006-11-10
  • 通讯作者: 张红星

A Theoretical Study of Excited States of HO2 Radical

LI Bu-Tong1, WEI Zi-Zhang1, PAN Qing-Jiang2, ZHANG Hong-Xing1, SUN Chia-Chung1   

    1. State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University 130023, China;
    2. College of Chemistry, Chemical Engineering and Materials, Heilongjiang University, Harbin 150080, China
  • Received:2005-12-31 Revised:1900-01-01 Online:2006-11-10 Published:2006-11-10
  • Contact: ZHANG Hong-Xing

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摘要： 采用CASPT2/CASSCF方法对HO2自由基进行统计算, 优化了三个电子态的稳定点几何构型, 得到详细的频率数据. 利用垂直激发计算确定了3个里德堡态、11个价电子态的电子结构以及在三种理论水平上(CASSCF, SS-CASPT2和MS-CASPT2)的能量信息. 计算中使用了ANO-L和ANO-L+基组, 验证了已知实验数据的同时, 通过与其它理论计算结果的对比, 揭示了应用弥散轨道系数对于该体系激发态研究的重要性.

关键词: 电子激发态, CASPT2, 里德堡态, HO2自由基

Abstract: CASSCF and CASPT2 calculations on the HO2 radical were performed in atom natural orbital basis sets(ANO-L and ANO-L+). The geometries for three electronic states are optimized at CASSCF level and the energies of these electronic states were located adiabatically at CASSCF, SS-CASPT2 and MS-CASPT2 level. The first excited energy were simulated as 0.779 eV vertically and 0.921 eV adiabatically. These data are consistent with those of the experimental values 0.74—0.88 eV, compared to the vertical energy of 1.12 eV from literature. Three Rydberg states and eleven valence excited states are located vertically in CASSCF, SS-CASPT2 and MS-CASPT2 levels. The lowest four low-lying electronic states are 12A', 22A' and 32A' in the order of energy which disagreed with the former confirmed order X2A', A2A" and B2A'. Through discussing the discrepancies in detail the important significance of the dispersion orbital for the title molecule are confirmed.

Key words: Electronic excitation state, CASPT2, Rydberg states, HO2 radical

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