Natural transition orbitals for complex two‐component excited state calculations
Natural transition orbitals for complex two‐component excited state calculations
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DOI：
10.1002/jcc.26196
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发表时间：
2020-03
影响因子：
3
通讯作者：
Joseph M. Kasper;Xiaosong Li
中科院分区：
文献类型：
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作者：
Joseph M. Kasper;Xiaosong Li
虽然自然跃迁轨道（NTO）方法允许在传统的轨道图中观察来自时间相关的Hartree - Fock和密度泛函理论的电子激发，由于自旋组分的混合和自旋翻转跃迁在时间相关的GHF/GKS中固有的包含，向多组分分子轨道（如在相对论双组分方法或广义Hartree - Fock （GHF）或广义Kohn - Sham （GKS）中使用的方法）的扩展就不那么直接了。除了简要讨论可视化双分量复轨道的实际方面外，还提出了单分量nto到双分量框架的扩展。与单组分模拟不同，该方法明确地描述了自旋，并经常得到具有几个重要轨道对的解。该方法是通过计算汞原子和CrO2Cl2配合物。
While the natural transition orbital (NTO) method has allowed electronic excitations from time‐dependent Hartree‐Fock and density functional theory to be viewed in a traditional orbital picture, the extension to multicomponent molecular orbitals such as those used in relativistic two‐component methods or generalized Hartree‐Fock (GHF) or generalized Kohn‐Sham (GKS) is less straightforward due to mixing of spin‐components and the inherent inclusion of spin‐flip transitions in time‐dependent GHF/GKS. An extension of single‐component NTOs to the two‐component framework is presented, in addition to a brief discussion of the practical aspects of visualizing two‐component complex orbitals. Unlike the single‐component analog, the method explicitly describes the spin and frequently obtains solutions with several significant orbital pairs. The method is presented using calculations on a mercury atom and a CrO2Cl2 complex.