Xu Jiabo, Shi Zhecun, Wang Linjun
Key Laboratory of Excited-State Materials of Zhejiang Province, Department of Chemistry, Zhejiang University, Hangzhou 310058, China.
J Chem Theory Comput. 2024 Mar 26;20(6):2349-2361. doi: 10.1021/acs.jctc.4c00137. Epub 2024 Mar 15.
Proper construction of the density matrix based on surface hopping trajectories remains a difficult problem. Due to the well-known overcoherence in traditional surface hopping simulations, the electronic wave function cannot be used directly. In this work, we propose a consistent density matrix construction method, which takes the advantage of occupation of active states to rescale the coherence calculated by wave functions and ensures the intrinsic consistency of the density matrix. This new trajectory analysis method can be used for both Tully's fewest switches surface hopping (FSSH) and our recently proposed branching corrected surface hopping (BCSH). As benchmarked in both one- and two-dimensional standard scattering models, the new approach combined with BCSH trajectories achieves highly accurate time-dependent spatial distributions of adiabatic populations and coherence compared to exact quantum results.
基于表面跳跃轨迹正确构建密度矩阵仍然是一个难题。由于传统表面跳跃模拟中众所周知的过度相干性，电子波函数不能直接使用。在这项工作中，我们提出了一种一致的密度矩阵构建方法，该方法利用活性态的占据情况来重新调整由波函数计算出的相干性，并确保密度矩阵的内在一致性。这种新的轨迹分析方法可用于塔利的最少开关表面跳跃（FSSH）和我们最近提出的分支校正表面跳跃（BCSH）。在一维和二维标准散射模型中作为基准测试，与精确量子结果相比，新方法与BCSH轨迹相结合可实现绝热布居和相干性的高精度时间相关空间分布。
