The Simplest Possible Approach for Simulating S0- S1 Conical Intersections with DFT/TDDFT: Adding One Doubly Excited Configuration.
The Simplest Possible Approach for Simulating S0- S1 Conical Intersections with DFT/TDDFT: Adding One Doubly Excited Configuration.
复制标题
使用 DFT/TDDFT 模拟 S0-S1 圆锥形相交的最简单方法：添加一个双激励配置。
DOI：
10.1021/acs.jpclett.9b00981
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发表时间：
2019
期刊：
影响因子：
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通讯作者：
Joseph E. Subotnik
中科院分区：
文献类型：
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作者：
Hung;Joseph E. Subotnik
提出了一种简单的密度泛函理论/含时密度泛函理论（DFT/TDDFT）和组态相互作用的结合，以修正S 0- S1圆锥相交（CI）的不正确拓扑结构，并允许描述光诱导动力学中的成键和键断裂.建议的TDDFT-1D方法包括一个孤独的优化双激发配置除了DFT/TDDFT单激发态的背景下，一个大的配置相互作用的哈密顿量。乙烯和二苯乙烯的结果表明，这种anterior可以产生物理上有意义的势能面附近的S 0- S1避免交叉，而不改变垂直激发能远离相关的交叉点。我们还研究了著名的线性水的例子，以表明该算法计算正确的拓扑结构的S 0- S1 CI，并产生正确的几何相位。
A simple combination of density functional theory/time-dependent density functional theory (DFT/TDDFT) and configuration interaction is presented to fix the incorrect topology of the S0- S1 conical intersection (CI) and allow a description of bond making and bond breaking in photoinduced dynamics. The proposed TDDFT-1D method includes one lone optimized doubly excited configuration in addition to the DFT/TDDFT singly excited states within the context of a large configuration interaction Hamiltonian. Results for ethylene and stilbene are provided to demonstrate that this ansatz can yield physically meaningful potential energy surfaces near S0- S1 avoided crossings without changing the vertical excitation energies far from the relevant crossings. We also investigate the famous linear water example to show that the algorithm calculates the correct topology of the S0- S1 CI and yields the correct geometric phase.