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中国物理学会期刊

SiN自由基X2+, A2和B2+ 电子态的光谱常数研究

CSTR: 32037.14.aps.62.013105

A study on spectroscopic parameters of X2+, A2 and B2+ low-lying electronic states of SiN radical

CSTR: 32037.14.aps.62.013105
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  • 采用内收缩多参考组态相互作用(MRCI)方法, 结合价态范围内的最大相关一致基aug-cc-pV6Z, 计算了SiN自由基X2+, A2 和B2+电子态的势能曲线. 采用Davidson修正来避免由于MRCI方法本身的大小一致性缺陷产生的误差. 为了提高计算精度, 进一步考虑了相对论修正和核价相关修正对势能曲线的影响. 本文的相对论修正是利用二阶Douglas-Kroll 哈密顿近似在cc-pV5Z基组水平进行的; 同时核价相关修正是在cc-pCV5Z基组水平进行的. 对这些势能曲线进行拟合, 得到各种水平下三个电子态的光谱常数(Te, Re, e, exe, e和Be), 并详细分析了Davidson修正、相对论修正和核价相关修正对光谱常数的影响. 与其他理论结果和实验数据进行比较, 可知本文的结果更精确、更完整.

     

    The potential energy curves (PECs) of X2+, A2 and B2+ low-lying electronic states of SiN radical are investigated using the highly accurate valence internally contracted multireference configuration interaction (MRCI) approach combining the full valence complete active space self-consistent field method. In the present calculations, the basis sets used are correlation-consistent basis sets, aug-cc-pV6Z. The PECs determined by the MRCI calculations are corrected for size-extensivity errors by means of the Davidson modification (MRCI +Q). To obtain more reliable results, effects of the core-valence correlation and relativistic correction on the PECs are taken into account. The core-valence correlation correction is carried out with the cc-pCV5Z basis set The way to consider the relativistic correction is to use the second-order Douglas-Kroll Hamiltonian approximation, and the correction is performed at the level of cc-pV5Z basis set. With these PECs, the spectroscopic parameters are determined. A comparison with the experimental data shows that the present spectroscopic parameters are more accurate than the previous calculations.

     

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