Bian Xuezhi, Wu Yanze, Rawlinson Jonathan, Littlejohn Robert G, Subotnik Joseph E
Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.
Department of Mathematics, University of Manchester, Manchester M13 9PL, U.K.
J Phys Chem Lett. 2022 Aug 18;13(32):7398-7404. doi: 10.1021/acs.jpclett.2c01802. Epub 2022 Aug 4.
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.
核贝里曲率效应源于电子自旋简并，可导致非平凡的自旋相关（非绝热）核动力学。然而，目前的任何混合量子-经典方法，如最少开关表面跳跃法，都无法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跃（PSSH）方法来模拟单重态-三重态系间窜越动力学。我们表明，通过一个简单的赝绝热假设，PSSH算法可以捕捉到相关的贝里曲率效应，并对一个简单的单重态-三重态模型哈密顿量做出与精确量子动力学一致的预测。因此，这种方法代表了朝着同时模拟与系间窜越和自旋-晶格弛豫动力学相关的光化学和自旋过程迈出的重要一步。
