Transition Orbital Projection Approach for Excited State Tracking
Transition Orbital Projection Approach for Excited State Tracking
复制标题
用于激发态跟踪的跃迁轨道投影方法
DOI：
10.1063/5.0081207
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发表时间：
2022
影响因子：
4.4
通讯作者：
Wei Li
中科院分区：
文献类型：
--
作者：
Jiahui Du;Yixuan Ma;Jing Ma;Shuhua Li;Wei Li
定量比较不同电子激发态（ES）之间的特征是势能面（PES）研究和激发态碎裂方法中的一项重要任务。然而，在复杂和高度退化系统的比较方面，它仍然是一个具有挑战性的问题。在此，我们提出了一个过渡轨道投影（TOP）的方法来计算不同的ES的相似性的基础上的配置向量的两种类型的过渡密度。它充分考虑了相位、空穴-粒子双射性、轨道排列和位形系数的符号等四个重要问题。基于TOP状态跟踪的激励状态优化算法在几个高对称系统中表现出了很好的鲁棒性，这些系统很难用传统的状态跟踪方法来描述。TOP态跟踪方法有望广泛应用于光化学反应的光电子能谱、非绝热态的ES分子动力学跟踪以及大体系局域激发的碎裂方法。
Quantitively comparing the features between different electronic excited states (ESs) is a crucial task in both potential energy surface (PES) studies and excited-state fragmentation approaches. However, it is still a challenging problem in regard to the comparison of complex and highly degenerate systems. Herein, we present a transition orbital projection (TOP) method to calculate the similarity of different ESs based on the configuration vectors of two types of transition densities. It fully considers four significant problems, including phase, hole-particle bijectivity, orbital permutation, and sign of configuration coefficients. TOP state-tracking-based excited-state optimization shows high robustness in several high-symmetric systems, which are difficult to describe with traditional state-tracking approaches. The TOP state-tracking method is expected to be widely applied to the PES of photochemical reactions, ES molecular dynamics to track the diabatic states, and fragmentation approaches for local excitation of large systems.