Bian Xuezhi, Wu Yanze, Teh Hung-Hsuan, Subotnik Joseph E
Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.
J Chem Theory Comput. 2022 Apr 12;18(4):2075-2090. doi: 10.1021/acs.jctc.1c01103. Epub 2022 Mar 9.
We present a preliminary surface-hopping approach for modeling intersystem crossing (ISC) dynamics between four electronic states: one singlet and one (triply degenerate) triplet. In order to incorporate all Berry force effects, the algorithm requires that, when moving along an adiabatic surface associated with the triplet manifold, one must also keep track of a quasi-diabatic index (akin to a "" quantum number) for each trajectory. For a simple model problem, we find that a great deal of new physics can be captured by our algorithm, setting the stage for larger, more realistic (or perhaps even ab initio) simulations in the future.
我们提出了一种初步的表面跳跃方法，用于对四个电子态之间的系间窜越（ISC）动力学进行建模：一个单重态和一个（三重简并）三重态。为了纳入所有贝里力效应，该算法要求，当沿着与三重态流形相关的绝热表面移动时，对于每条轨迹，还必须跟踪一个准绝热指数（类似于一个“量子数”）。对于一个简单的模型问题，我们发现我们的算法可以捕捉到大量新的物理现象，为未来更大规模、更现实（甚至可能是从头算）的模拟奠定了基础。
