Mean first-passage times for solvated LiCN isomerization at intermediate to high temperatures
arXiv:2201.00868 · doi:10.1063/5.0065090
Abstract
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 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.
arXiv comment11 pages, 6 figures
References in corpus (5)
- Reaction Pathways Based on the Gradient of the Mean First-Passage Time
- Kramers turnover: from energy diffusion to spatial diffusion using metadynamics
- Influence of external driving on decays in the geometry of the LiCN isomerization
- Identifying Reaction Pathways in Phase Space via Asymptotic Trajectories
- Superscars in the LiNC=LiCN isomerization reaction