论文标题
沿化学反应路径的相应活跃轨道空间
Corresponding Active Orbital Spaces along Chemical Reaction Paths
论文作者
论文摘要
用多配合的电子结构方法计算出的反应能量曲线的准确性并通过多引力扰动理论校正了沿反应路径选择的一致的活性轨道空间至关重要。但是，选择可以认为在不同分子结构中相对应的分子轨道一直具有挑战性。在这里，我们证明了如何以完全自动化的方式沿反应坐标始终选择活跃的轨道空间。该方法不需要反应物与产品之间的结构插值。取而代之的是，它来自直接轨道选择轨道映射Ansatz的协同作用，并结合了我们的全自动空间选择算法AutoCAS。我们证明了我们的算法，用于在电子基态以1五键的双键围绕1键键的均利碳碳键解离并旋转。但是，我们的算法也适用于电子激发的Born-Oppenheimer表面。
The accuracy of reaction energy profiles calculated with multi-configurational electronic structure methods and corrected by multi-reference perturbation theory depends crucially on consistent active orbital spaces selected along the reaction path. However, it has been challenging to choose molecular orbitals that can be considered corresponding in different molecular structures. Here, we demonstrate how active orbital spaces can be selected consistently along reaction coordinates in a fully automated way. The approach requires no structure interpolation between reactants and products. Instead, it emerges from a synergy of the Direct Orbital Selection orbital mapping ansatz combined with our fully automated active space selection algorithm autoCAS. We demonstrate our algorithm for the potential energy profile of the homolytic carbon-carbon bond dissociation and rotation around the double bond of 1-pentene in the electronic ground state. However, our algorithm also applies to electronically excited Born-Oppenheimer surfaces.
