Physics Department of Trento University, Via Sommarive 14, 37123 Povo (Trento), Italy.
J Chem Phys. 2018 Aug 21;149(7):072336. doi: 10.1063/1.5027253.
Transition Path Theory (TPT) provides a rigorous framework to investigate the dynamics of rare thermally activated transitions. In this theory, a central role is played by the forward committor function (), which provides the ideal reaction coordinate. Furthermore, the reactive dynamics and kinetics are fully characterized in terms of two time-independent scalar and vector distributions. In this work, we develop a scheme which enables all these ingredients of TPT to be efficiently computed using the short non-equilibrium trajectories generated by means of a specific combination of enhanced path sampling techniques. In particular, first we further extend the recently introduced self-consistent path sampling algorithm in order to compute the committor (). Next, we show how this result can be exploited in order to define efficient algorithms which enable us to directly sample the transition path ensemble.
过渡态理论（TPT）为研究稀有热激活跃迁的动力学提供了一个严格的框架。在这个理论中，向前配分函数（）起着核心作用，它提供了理想的反应坐标。此外，反应动力学和反应速率完全由两个与时间无关的标量和向量分布来描述。在这项工作中，我们开发了一种方案，通过特定的增强路径采样技术的组合来生成短的非平衡轨迹，从而有效地计算 TPT 的所有这些成分。具体来说，首先我们进一步扩展了最近提出的自洽路径采样算法，以计算配分函数（）。接下来，我们展示了如何利用这个结果来定义有效的算法，使我们能够直接对跃迁路径集进行采样。
