Generalization of Intrinsic Orbitals to Kramers-Paired Quaternion Spinors, Molecular Fragments, and Valence Virtual Spinors
Generalization of Intrinsic Orbitals to Kramers-Paired Quaternion Spinors, Molecular Fragments, and Valence Virtual Spinors
复制标题
将本征轨道推广到克莱默配对的四元数旋量、分子片段和价虚拟旋量
DOI：
10.1021/acs.jctc.0c00964
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发表时间：
2011
影响因子：
5.5
通讯作者：
Visscher, Lucas
中科院分区：
文献类型：
--
作者：
Senjean, Bruno;Sen, Souloke;Repisky, Michal;Knizia, Gerald;Visscher, Lucas
分子轨道的定域化在化学键（和反键）的表示和平均场近似以外的定域相关处理中具有重要意义。本文推广了内禀原子轨道和成键轨道[G. Knizia，J. Chem. Theory Comput.2013，9，11，4834-4843]到使用复数和四元数旋量的相对论应用，以及到分子碎片而不是仅原子碎片。通过执行奇异值分解，我们展示了如何本地化价虚拟轨道可以表示在这个内在的最小基础。我们展示了我们的方法，从简单的情况下，如苯，丙烯酸和二茂铁分子的系统越来越复杂，然后演示使用分子片段和包含相对论效应的复合物含有重元素，如碲，铱，和<$。上述方案被实施到与几个不同的量子化学包接口的独立程序中。
Localization of molecular orbitals finds its importance in the representation of chemical bonding (and antibonding) and in the local correlation treatments beyond mean-field approximation. In this paper, we generalize the intrinsic atomic and bonding orbitals [G. Knizia,J. Chem. Theory Comput.2013,9, 11, 4834–4843] to relativistic applications using complex and quaternion spinors, as well as to molecular fragments instead of atomic fragments only. By performing a singular value decomposition, we show how localized valence virtual orbitals can be expressed on this intrinsic minimal basis. We demonstrate our method on systems of increasing complexity, starting from simple cases such as benzene, acrylic acid, and ferrocene molecules, and then demonstrate the use of molecular fragments and inclusion of relativistic effects for complexes containing heavy elements such as tellurium, iridium, and astatine. The aforementioned scheme is implemented into a standalone program interfaced with several different quantum chemistry packages.