论文标题
在中间至高温下溶剂化的LICN异构化的平均第一邮编时间
Mean first-passage times for solvated LiCN isomerization at intermediate to high temperatures
论文作者
论文摘要
自克莱默（Kramers）早期理论以来，已经使用随机动力学构建了粒子在溶剂中的行为。化学反应中的粒子在稀释的溶剂中反应较慢，因为通过碰撞缺乏能量转移。在非常致密的溶剂中再次掉落之前，随着密度的增加，磁通量反应速率持续上升。在本文中观察到这种Kramers的周转率在langevin Dynamics和平均第一学期时间（MFPTS）的linc $ \ rightleftharpoons $ LICN异构化（MFPTS）的中等温度和高温下观察到。它与较低温度下的Pollak-Grabert-Hänggi（PGH）反应率非常吻合。此外，我们在高温下发现了反应速率的平方根行为，并直接比较了中等温度和高温方案中的方法。所有这些都表明PGH和MFPT方法的准确性增加了范围。
The behavior of a particle in a solvent has been framed using stochastic dynamics since the early theory of Kramers. A particle in a chemical reaction reacts slower in a diluted solvent because of the lack of energy transfer via collisions. The flux-over-population reaction rate constant rises with increasing density before falling again for very dense solvents. This Kramers turnover is observed in this paper at intermediate and high temperatures in the backward reaction of the LiNC $\rightleftharpoons$ LiCN isomerization via Langevin dynamics and mean first-passage times (MFPTs). It is in good agreement with the Pollak-Grabert-Hänggi (PGH) reaction rates at lower temperatures. Furthermore, we find a square root behavior of the reaction rate at high temperatures and have made direct comparisons of the methods in the intermediate- and high- temperature regimes; all suggesting increased ranges in accuracy of both the PGH and MFPT approaches.
