Title: Corresponding Active Orbital Spaces along Chemical Reaction Paths Show Chinese title

Title: 化学反应路径上的对应活性轨道空间

Abstract: 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. Show Chinese abstract

Abstract: 使用多组态电子结构方法计算的反应能级曲线，并通过多参考微扰理论进行修正，其准确性关键取决于在反应路径上选择一致的活性轨道空间。 然而，选择在不同分子结构中可以被认为是对应的分子轨道一直是一个挑战。 在这里，我们展示了如何在反应坐标上以完全自动化的方式一致地选择活性轨道空间。 该方法不需要在反应物和产物之间进行结构插值。 相反，它源于直接轨道选择轨道映射假设与我们完全自动化的活性空间选择算法autoCAS之间的协同作用。 我们对碳-碳均裂键解离以及1-戊烯在电子基态下双键旋转的势能曲线进行了算法演示。 然而，我们的算法也适用于电子激发的Born-Oppenheimer表面。