Mean first-passage times for solvated LiCN isomerization at intermediate to high temperatures.

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.

Influence of external driving on decays in the geometry of the LiCN isomerization.

The framework of transition state theory relies on the determination of a geometric structure identifying reactivity. It replaces the laborious exercise of following many trajectories for a long time to provide chemical reaction rates and pathways. In this paper, recent advances in constructing this geometry even in time-dependent systems are applied to the LiCN ⇌ LiNC isomerization reaction driven by an external field. We obtain decay rates of the reactant population close to the transition state by exploiting local properties of the dynamics of trajectories in and close to it. We find that the external driving has a large influence on these decay rates when compared to the non-driven isomerization reaction. This, in turn, provides renewed evidence for the possibility of controlling chemical reactions, like this one, through external time-dependent fields.

Newtonian versus special-relativistic statistical predictions for low-speed scattering.

The statistical predictions of Newtonian and special-relativistic mechanics, which are calculated from an initially Gaussian ensemble of trajectories, are compared for a low-speed scattering system. The comparisons are focused on the mean dwell time, transmission and reflection coefficients, and the position and momentum means and standard deviations. We find that the statistical predictions of the two theories do not always agree as conventionally expected. The predictions are close if the scattering is non-chaotic but they are radically different if the scattering is chaotic and the initial ensemble is well localized in phase space. Our result indicates that for low-speed chaotic scattering, special-relativistic mechanics must be used, instead of the standard practice of using Newtonian mechanics, to obtain empirically-correct statistical predictions from an initially well-localized Gaussian ensemble.