Modeling Spin-Dependent Nonadiabatic Dynamics with Electronic Degeneracy: A Phase-Space Surface-Hopping Method
Modeling Spin-Dependent Nonadiabatic Dynamics with Electronic Degeneracy: A Phase-Space Surface-Hopping Method
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DOI：
10.1021/acs.jpclett.2c01802
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发表时间：
2022-08-04
影响因子：
5.7
通讯作者：
Subotnik, Joseph E.
中科院分区：
文献类型：
--
作者：
Bian, Xuezhi;Wu, Yanze;Subotnik, Joseph E.
核浆果曲率效应产生于电子自旋简并，可导致非平凡的自旋依赖（非绝热）核动力学。然而，目前任何混合量子经典方法（如最小开关表面跳变）都不能完全捕捉到这种效应。在这项工作中，我们提出了一种相空间表面跳变（PSSH）方法来模拟单重态-三重态系统间交叉动力学。我们证明了在一个简单的伪非绝热分析中，PSSH算法可以捕获相关的Berry曲率效应，并对简单的单重态-三重态模型哈密顿量做出符合精确量子动力学的预测。因此，这种方法代表了模拟光化学和自旋过程同时进行的重要一步，因为与系统间交叉和自旋晶格弛豫动力学有关。
Nuclear Berry curvature effects emerge from electronic spin degeneracy and can lead to nontrivial spin-dependent (nonadiabatic) nuclear dynamics. However, such effects are not captured fully by any current mixed quantum-classical method such as fewest-switches surface hopping. In this work, we present a phase-space surface-hopping (PSSH) approach to simulate singlet-triplet intersystem crossing dynamics. We show that with a simple pseudodiabatic ansatz, a PSSH algorithm can capture the relevant Berry curvature effects and make predictions in agreement with exact quantum dynamics for a simple singlet-triplet model Hamiltonian. Thus, this approach represents an important step toward simulating photochemical and spin processes concomitantly, as relevant to intersystem crossing and spin- lattice relaxation dynamics.