Shchepanovska Darya, Shannon Robin J, Curchod Basile F E, Glowacki David R
School of Chemistry, University of Bristol, Bristol BS8 1TS, U.K.
Department of Chemistry, Durham University, Durham DH1 3LE, U.K.
J Phys Chem A. 2021 Apr 29;125(16):3473-3488. doi: 10.1021/acs.jpca.1c01260. Epub 2021 Apr 21.
We propose and test an extension of the energy-grained master equation (EGME) for treating nonadiabatic (NA) hopping between different potential energy surfaces, which enables us to model the competition between stepwise collisional relaxation and kinetic processes which transfer population between different electronic states of the same spin symmetry. By incorporating Zhu-Nakamura theory into the EGME, we are able to treat NA passages beyond the simple Landau-Zener approximation, along with the corresponding treatments of zero-point energy and tunneling probability. To evaluate the performance of this NA-EGME approach, we carried out detailed studies of the UV photodynamics of the volatile organic compound C-hydroperoxy aldehyde (C-HPALD) using on-the-fly ab initio molecular dynamics and trajectory surface hopping. For this multichromophore molecule, we show that the EGME is able to capture important aspects of the dynamics, including kinetic timescales, and diabatic trapping. Such an approach provides a promising and efficient strategy for treating the long-time dynamics of photoexcited molecules in regimes which are difficult to capture using atomistic on-the-fly molecular dynamics.
我们提出并测试了能量粒主方程（EGME）的一种扩展，用于处理不同势能面之间的非绝热（NA）跃迁，这使我们能够对逐步碰撞弛豫与在相同自旋对称性的不同电子态之间转移布居的动力学过程之间的竞争进行建模。通过将朱 - 中村理论纳入EGME，我们能够处理超越简单朗道 - 齐纳近似的非绝热跃迁，以及相应的零点能量和隧穿概率处理。为了评估这种非绝热 - EGME方法的性能，我们使用实时从头算分子动力学和轨迹表面跳跃对挥发性有机化合物氢过氧醛（C - HPALD）的紫外光动力学进行了详细研究。对于这种多发色团分子，我们表明EGME能够捕捉动力学的重要方面，包括动力学时间尺度和非绝热俘获。这种方法为处理光激发分子在难以用实时原子分子动力学捕捉的区域中的长时间动力学提供了一种有前景且有效的策略。
