Hoyer Chad E, Li Xiaosong
Department of Chemistry, University of Washington, Seattle, Washington 98195, USA.
J Chem Phys. 2020 Sep 7;153(9):094113. doi: 10.1063/5.0012433.
In this work, we present a relativistic quantum embedding formalism capable of variationally treating relativistic effects, including scalar-relativity and spin-orbit coupling. We extend density functional theory (DFT)-in-DFT projection-based quantum embedding to a relativistic two-component formalism, where the full spin magnetization vector form is retained throughout the embedding treatment. To benchmark various relativistic embedding schemes, spin-orbit splitting of the nominally t valence manifold of W(CO), exchange coupling of [(HN)Cr(OH)Cr(NH)], and the dissociation potential curve of WF are investigated. The relativistic embedding formalism introduced in this work is well suited for efficient modeling of open-shell systems containing late transition metal, lanthanide, and actinide molecular complexes.
在这项工作中，我们提出了一种相对论量子嵌入形式体系，它能够变分处理相对论效应，包括标量相对论和自旋 - 轨道耦合。我们将基于密度泛函理论（DFT）的DFT投影量子嵌入扩展到相对论双组分形式体系，其中在整个嵌入处理过程中保留了完整的自旋磁化矢量形式。为了对各种相对论嵌入方案进行基准测试，研究了W(CO)名义上的t价轨道的自旋 - 轨道分裂、[(HN)Cr(OH)Cr(NH)]的交换耦合以及WF的解离势曲线。本文引入的相对论嵌入形式体系非常适合对包含晚期过渡金属、镧系和锕系分子配合物的开壳层体系进行高效建模。
