All-electron relativistic computations on the low-lying electronic states, bond length, and vibrational frequency of CeF diatomic molecule with spin-orbit coupling effects,Journal of Computational Chemistry

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All-electron relativistic computations on the low-lying electronic states, bond length, and vibrational frequency of CeF diatomic molecule with spin-orbit coupling effects
Journal of Computational Chemistry ( IF 3.4 ) Pub Date : 2018-01-30 , DOI: 10.1002/jcc.25171
Yusuke Kondo ₁ , Masato Kobayashi ₂ , Tomoko Akama ₂ , Takeshi Noro ₂ , Tetsuya Taketsugu ₂

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Ab initio all‐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, the n‐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]4f15d16s1 and [Xe]4f15d2 configurations, 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.

中文翻译：

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

已经对 Ce+ 和 CeF 进行了从头算全电子计算，包括定量的电子相关性、标量相对论和自旋轨道耦合效应。首先，基于状态平均受限有源空间多构型自洽场（SA-RASSCF）和状态平均完整的 n 电子价态二阶多参考微扰理论（NEVPT2）和自旋轨道构型相互作用（SOCI）活动空间多构型自洽场（SA-CASSCF）波函数已被用于评估具有 [Xe]4f15d16s1 和 [Xe]4f15d2 构型的 Ce+ 的低能级，以测试几种全电子相对论基础的准确性套。结果表明，四重态和双重态的混合对于再现激发能量是必不可少的。然后，使用 Sapporo(-DKH3)-2012-QZP 基组进行 SA-RASSCF(CASSCF)/NEVPT2 + SOCI 计算以确定 CeF 低电子态的能级。计算出的激发能、键长和振动频率与可用的实验数据非常吻合。© 2018 Wiley Periodicals, Inc.

更新日期：2018-01-30

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