Master equation methods for multiple well systems: application to the 1-,2-pentyl system.

The master equation (ME) provides a powerful technique for modeling reactions that involve at least one potential energy well. It can be widely applied to reactions with several connected energy wells and multiple product channels. The application of the technique is reviewed by reference to the H + SO(2) reaction, where phenomenological rate constants for use, for example, in a combustion model can be extracted through an analysis of the eigenvalues and eigenvectors of the collision matrix, M, that describes formation of the adducts HSO(2) and HOSO from the source H + SO(2), collisional energy transfer in the adduct wells and reaction via the product channel (sink) OH + SO.

The acidity of tert-butyl alcohol in near- and supercritical water: a polarizable continuum approach.

We use a polarizable continuum approach to study the acidity of tert-butyl alcohol in water at ambient, near-critical, and supercritical conditions. In the most straightforward calculation, the bare ionic species (the tert-butoxy anion and the hydronium cation) are placed in cavities surrounded by a dielectric continuum, using a dielectric constant corresponding to the state point. A second method is first to solvate these ions with a small number of explicit water molecules and then surround this cluster with the dielectric.