论文标题

模拟自旋轨道耦合与准代代的N-电子价扰动理论

Simulating Spin-Orbit Coupling With Quasidegenerate N-Electron Valence Perturbation Theory

论文作者

Majumder, Rajat, Sokolov, Alexander Yu.

论文摘要

我们介绍了完全内部收缩的二阶准代环境N-电子价扰动理论(SO-QDNEVPT2)中自旋轨道耦合效应的第一个实现。 SO-QDNEVPT2方法实现了将静态电子相关性的描述与动态相关性和自旋轨道耦合的有效处理相结合的地面和激发态能量和振荡器强度的计算。除了SO-QDNEVPT2外,还具有在两组分Breit-Pauli Hamiltonian级别对单身和两体旋转轨道相互作用的完整描述外,我们的实现还采用了一种简化的方法,它利用了旋转轨道均值均值场近似值(SOMF-QDNEVPT2)。测试了第14组和16组Hydrides,3D和4D过渡金属离子以及两种actacinide二氧化物(Neptunyl和Plutonyl dications)的精度。使用SO-QDNEVPT2和SOMF-QDNEVPT2计算的第14组和16组分子的零场分裂与可用的实验数据非常吻合。对于3D过渡金属离子,SO-QDNEVPT2方法比SOMF-QDNEVPT2明显更准确,而对于4D离子,没有观察到两种方法的性能的实质性差异。最后,我们证明,对于actacinide二氧化物,SO-QDNEVPT2和SOMF-QDNEVPT2的结果与这些系统先前理论研究的数据非常吻合。总体而言,我们的结果表明,SO-QDNEVPT2和SOMF-QDNEVPT2是有望使用相对较低的计算成本处理旋转轨道耦合的多余方法。

We present the first implementation of spin-orbit coupling effects in fully internally contracted second-order quasidegenerate N-electron valence perturbation theory (SO-QDNEVPT2). The SO-QDNEVPT2 approach enables the computations of ground- and excited-state energies and oscillator strengths combining the description of static electron correlation with an efficient treatment of dynamic correlation and spin-orbit coupling. In addition to SO-QDNEVPT2 with the full description of one- and two-body spin-orbit interactions at the level of two-component Breit-Pauli Hamiltonian, our implementation also features a simplified approach that takes advantage of spin-orbit mean-field approximation (SOMF-QDNEVPT2). The accuracy of these methods is tested for the group 14 and 16 hydrides, 3d and 4d transition metal ions, and two actinide dioxides (neptunyl and plutonyl dications). The zero-field splittings of group 14 and 16 molecules computed using SO-QDNEVPT2 and SOMF-QDNEVPT2 are in a good agreement with the available experimental data. For the 3d transition metal ions, the SO-QDNEVPT2 method is significantly more accurate than SOMF-QDNEVPT2, while no substantial difference in the performance of two methods is observed for the 4d ions. Finally, we demonstrate that for the actinide dioxides the results of SO-QDNEVPT2 and SOMF-QDNEVPT2 are in a good agreement with the data from previous theoretical studies of these systems. Overall, our results demonstrate that SO-QDNEVPT2 and SOMF-QDNEVPT2 are promising multireference methods for treating spin-orbit coupling with a relatively low computational cost.

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