Multiple-Well, multiple-path unimolecular reaction systems. I. MultiWell computer program suite

Abstract

Unimolecular reaction systems in which multiple isomers undergo simultaneous reactions via multiple decomposition reactions and multiple isomerization reactions are of fundamental interest in chemical kinetics. The computer program suite described here can be used to treat such coupled systems, including the effects of collisional energy transfer (weak collisions). The program suite consists of MultiWell, which solves the internal energy master equation for complex unimolecular reactions systems; DenSum, which calculates sums and densities of states by an exact-count method; MomInert, which calculates external principal moments of inertia and internal rotation reduced moments of inertia; and Thermo, which calculates equilibrium constants and other thermodynamics quantities. MultiWell utilizes a hybrid master equation approach, which performs like an energy-grained master equation at low energies and a continuum master equation in the vibrational quasicontinuum. An adaptation of Gillespie's exact stochastic method is used for the solution. The codes are designed for ease of use. Details are presented of various methods for treating weak collisions with virtually any desired collision step-size distribution and for utilizing RRKM theory for specific unimolecular rate constants. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 232–245, 2001