Reiff Johannes, Feldmaier Matthias, Main Jörg, Hernandez Rigoberto
Institut für Theoretische Physik I, Universität Stuttgart, 70550 Stuttgart, Germany.
Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, USA.
Phys Rev E. 2021 Feb;103(2-1):022121. doi: 10.1103/PhysRevE.103.022121.
The framework of transition state theory (TST) provides a powerful way for analyzing the dynamics of physical and chemical reactions. While TST has already been successfully used to obtain reaction rates for systems with a single time-dependent saddle point, multiple driven saddles have proven challenging because of their fractal-like phase space structure. This paper presents the construction of an approximately recrossing-free dividing surface based on the normally hyperbolic invariant manifold in a time-dependent two-saddle model system. Based on this, multiple methods for obtaining instantaneous (time-resolved) decay rates of the underlying activated complex are presented and their results discussed.
过渡态理论（TST）的框架为分析物理和化学反应的动力学提供了一种强大的方法。虽然TST已成功用于获得具有单个时间依赖鞍点的系统的反应速率，但多个驱动鞍点因其类分形相空间结构而颇具挑战性。本文提出了基于含时双鞍点模型系统中的正常双曲不变流形构建近似无再穿越的分界面。在此基础上，提出了多种获取基础活化络合物瞬时（时间分辨）衰减率 的方法，并对其结果进行了讨论。
