New implementation of spin‐orbit coupling calculation on multi‐configuration electron correlation theory
New implementation of spin‐orbit coupling calculation on multi‐configuration electron correlation theory
复制标题
多构型电子关联理论自旋轨道耦合计算的新实现
DOI：
10.1002/qua.26772
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发表时间：
2021
影响因子：
2.2
通讯作者：
Bingbing Suo
中科院分区：
文献类型：
--
作者：
Qianlong Zhou;Bingbing Suo
为了同时处理相对论效应和电子关联，在多组态电子关联理论的基础上，结合无自旋精确二组分和自旋相关的一阶Douglas-Kroll-Hess哈密顿量和态相互作用(SI)方法计算了自旋-轨道耦合(SOC)。在这种方法中，SOC是从完整的活动空间自洽场计算中通过电子态上的SI来估计的，动态关联可以用高水平的多参考电子关联理论来计算。在图么群方法的框架下，给出了计算Gelfand态SOC矩阵元的工作方程。基准计算验证了实施的有效性。作为中试应用，通过SI方法与SOC的内缩多参考组态相互作用产生了合理的AUO基态的平衡键长和简谐振动频率，以及的跃迁能。
For treating both relativistic effect and electron correlation, the spin‐free exact two‐component and spin‐dependent first‐order Douglas–Kroll–Hess Hamiltonian and the state‐interaction (SI) method are combined to calculate the spin‐orbit coupling (SOC) on multi‐configuration electron correlation theory. In this method, SOC is evaluated via SI over electronic states from the complete active space self‐consistent field calculation, and dynamic correlation can be reckoned with the high‐level multi‐reference electron correlation theory. Work equations to calculate SOC matrix elements over Gelfand states in the framework of the graphic unitary group approach are presented. Benchmark calculations have verified the validity of the implementation. As a pilot application, the internally contracted multi‐reference configuration interaction with the inclusion of SOC via the SI approach produces reasonable equilibrium bond length and harmonic vibrational frequency of the ground state of AuO, as well as the transition energy of .