PNNL

Abstract

Recently a theory of vapor-to-liquid phase nucleation was developed that was based on the kinetics of cluster formation and decomposition. The new method used variational transition state theory (VTST) to obtain the evaporation and condensa-tion rate constants needed in the kinetic model of nucleation. VTST provides a means to systematically improve estimates for rate constants involved in the nucleation process. In the current work we perform dynamical simulations of the condensation process, estimating the effective reactive cross-section using a definition of a cluster that is determined from VTST. These calculations allow us to characterize dynamical corrections to the VTST rate constants. We find that for water cluster sizes rang-ing from 10-40 waters, VTST estimates of the condensation and evaporation rate constants using a spherical dividing surface require dynamical corrections that are approximately a factor of two.