Detailed study of the direct numerical observation of the Kramers turnover in the LiNC?LiCN isomerization rate

摘要

According to Kramers, rates of molecular process are expected to follow a rise and fall from low friction (at little to no interaction with the environment) to high friction (at typical liquid densities and above). This so-called Kramers turnover was recently observed and delineated in the case of the LiNC?LiCN isomerization reaction in the presence of an argon bath [P. García-Müller, R. Hernandez, R. M. Benito, and F. Borondo, Phys. Rev. Lett. 101, 178302 (2008)]10.1103/PhysRevLett.101.178302. The rates were obtained using direct molecular dynamics of an all-atom representation and the Langevin dynamics of a projected representation. We now provide further evidence that the forward and backward rates are indeed exhibiting the turnover. The rates are also seen to agree remarkably well with the Pollak-Grabert-H?nggi rate formulas in regimes satisfying the theory underlying assumptions. At higher temperatures, when the theory is expected to fail, the solvated LiCN isomerization continues to exhibit activated dynamics following the turnover.