Molecular dynamics study of an isomerizing triatomic in solution

The kinetics and equilibrium constant of an isomerizing triatomic in solution were studied, by computer simulation, for various potential barriers, force constants and solvents. It was found that variation in the shape of the barrier to isomerization and in the bending force constant could dramatically affect the isomer lifetimes even though barrier heights (of the bare potential) remained unchanged. The results could be quantitatively accounted for in terms of the potential of mean force and qualitatively explained in terms of the solvents’ tendency to reduce the solutes’ volume.