Automated Identification of Relevant Frontier Orbitals for Chemical Compounds and Processes.
Automated Identification of Relevant Frontier Orbitals for Chemical Compounds and Processes.
复制标题
DOI：
10.2533/chimia.2017.170
复制
发表时间：
2017-02
期刊：
影响因子：
1.2
通讯作者：
C. Stein;M. Reiher
中科院分区：
文献类型：
--
作者：
C. Stein;M. Reiher
静态电子相关是具有多个（近）简并前沿轨道的分子的电子结构所固有的现象，需要量子化学的多构型方法来正确描述静态电子相关。在这里，我们回顾了这些前沿轨道的一个性质，即纠缠熵与静态电子相关的关系。作为轨道的一个子集，所谓的主动轨道空间是所有多构型方法的基本组成部分。我们建议自动选择这个活跃的轨道空间，否则这将是一个繁琐和容易出错的人工程序，基于纠缠措施。在此，我们对该方案进行了扩展，以证明它具有选择多个激发态和沿反应坐标的一致活动空间的能力。
Quantum-chemical multi-configurational methods are required for a proper description of static electron correlation, a phenomenon inherent to the electronic structure of molecules with multiple (near-)degenerate frontier orbitals. Here, we review how a property of these frontier orbitals, namely the entanglement entropy is related to static electron correlation. A subset of orbitals, the so-called active orbital space is an essential ingredient for all multi-configurational methods. We proposed an automated selection of this active orbital space, that would otherwise be a tedious and error prone manual procedure, based on entanglement measures. Here, we extend this scheme to demonstrate its capability for the selection of consistent active spaces for several excited states and along reaction coordinates.