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.

Solvated molecular dynamics of LiCN isomerization: All-atom argon solvent versus a generalized Langevin bath.

The reaction rate rises and falls with increasing density or friction when a molecule is activated by collisions with the solvent particles. This so-called Kramers turnover has recently been observed in the isomerization reaction of LiCN in an argon bath. In this paper, we demonstrate by direct comparison with those results that a reduced-dimensional (generalized) Langevin description gives rise to similar reaction dynamics as the corresponding (computationally expensive) full molecular dynamics calculations.

The role of the CN vibration in the activated dynamics of LiNC<−>LiCN isomerization in an argon solvent at high temperatures.

The isomerization between CN-Li and Li-CN in an argon bath provides a paradigmatic example of a reaction in a solvent with tunable coupling. In previous work, we found that the rates exhibited a turnover with the density of the argon bath in the limit that the CN bond was held fixed [P. L.