All-electron relativistic computations on the low-lying electronic states, bond length, and vibrational frequency of CeF diatomic molecule with spin-orbit coupling effects
All-electron relativistic computations on the low-lying electronic states, bond length, and vibrational frequency of CeF diatomic molecule with spin-orbit coupling effects
复制标题
具有自旋轨道耦合效应的CeF双原子分子低位电子态、键长和振动频率的全电子相对论计算
DOI：
10.1002/jcc.25171
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发表时间：
2018
影响因子：
3
通讯作者：
Taketsugu Tetsuya
中科院分区：
文献类型：
--
作者：
Kondo Yusuke;Kobayashi Masato;Akama Tomoko;Noro Takeshi;Taketsugu Tetsuya
对Ce+和CeF进行了初始电子计算，包括电子相关性、标量相对论性和自旋轨道耦合效应。首先，基于状态平均受限主动空间多构型自洽场（SA‐RASSCF）和状态平均完全主动空间多构型自洽场（SA‐CASSCF）波函数，将电子价态二阶多参考摄动理论（NEVPT2）和自旋轨道组态相互作用（SOCI）应用于[Xe]4f15d16s1和[Xe]4f15d2构型的Ce+低空能级评价。测试几种全电子相对论基集的准确性。结果表明，四重态和重偶态的混合是再现激发能的必要条件。然后，利用Sapporo（‐DKH3）‐2012‐QZP基集进行SA‐RASSCF(CASSCF)/NEVPT2 + SOCI计算，确定了CeF低空电子态的能级。计算得到的激发能、键长和振动频率与实验数据吻合较好。©2018 Wiley期刊公司
Ab initioall‐electron computations have been carried out for Ce+and CeF, including the electron correlation, scalar relativistic, and spin–orbit coupling effects in a quantitative manner. First, then‐electron valence state second‐order multireference perturbation theory (NEVPT2) and spin–orbit configuration interaction (SOCI) based on the state‐averaged restricted active space multiconfigurational self‐consistent field (SA‐RASSCF) and state‐averaged complete active space multiconfigurational self‐consistent field (SA‐CASSCF) wavefunctions have been applied to evaluations of the low‐lying energy levels of Ce+with [Xe]4f15d16s1and [Xe]4f15d2configurations, to test the accuracy of several all‐electron relativistic basis sets. It is shown that the mixing of quartet and doublet states is essential to reproduce the excitation energies. Then, SA‐RASSCF(CASSCF)/NEVPT2 + SOCI computations with the Sapporo(‐DKH3)‐2012‐QZP basis set were carried out to determine the energy levels of the low‐lying electronic states of CeF. The calculated excitation energies, bond length, and vibrational frequency are shown to be in good agreement with the available experimental data. © 2018 Wiley Periodicals, Inc.