高等学校化学学报

高等学校化学学报

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FONO2低能激发态和光电子谱的理论研究

魏子章1, 李步通1, 潘清江2, 张红星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:2006-03-31 修回日期:1900-01-01 出版日期:2008-03-10 发布日期:2008-03-10
  • 通讯作者: 张红星

Theoretical Study on the Low-lying Electronic States and Ionization Spectra of Fluorine Nitrate

WEI Zi-Zhang1, LI Bu-Tong1, PAN Qing-Jiang2, ZHANG Hong-Xing1*   

    1. State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China;
    2. School of Chemistry and Material Science, Heilongjiang University, Harbin 150080, China
  • Received:2006-03-31 Revised:1900-01-01 Online:2008-03-10 Published:2008-03-10
  • Contact: ZHANG Hong-Xing

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摘要： 采用CASSCF方法和ANO-S基组计算了FONO2分子及其阳离子的低能激发态, 并采用CASPT2方法进行能量校正. 预测了在低能激发态时FONO2分子的几何结构发生了很大变化, 从基态的平面构型转变为空间的几何构型. 然而在阳离子中没有发生相似的几何构型改变. 此外, 在分子的基态几何构型下, 设计并计算了相应阳离子的垂直离子势, 对分子的光电子谱给出了详细的解释.

关键词: 硝酸氟, 离子化势, 激发态, CASSCF, CASPT2

Abstract: Using the complete active space self-consistent field(CASSCF) method with the atomic natural orbital(ANO) basis set, we studied the ground state and low-lying excited states of fluorine nitrate and its cation. The stable geometry of ground state was the planar structure with the Cs symmetry, but the stable structures of excited states were changed to the nonplanar structure. However, the similar change of the cation geometry was not observed. Furthermore, the vertical ionization potential of the fluorine nitrate molecular was studied on the basis of the optimized geometry of the ground state. Taking the dynamic correlation effects into account, we used the second-order perturbation(CASPT2) method to obtain more reliable energies. The assignment of the first two bands is in an excellent agreement with the experimental data and the theoretical results, but in the higher energy region, the different assignments were completed bass of the CASPT2 results.

Key words: Fluorine nitrate, Ionization potential, Excited state, CASSCF, CASPT2

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