The Reaction X + Cl2→XCl + Cl (X = Mu,H, D). II. Comparison of experimental data with theoretical results derived from a new potential energy surface

We consider experimental implications for the Mu + Cl₂, H + Cl₂, and D + Cl₂ reactions of the extended London—Eyring—Polanyi—Sato (LEPS) potential energy surface derived from experimental data in paper I. In the present calculations, it is necessary to make additional implicit and explicit assumptions concerning the three-dimensional (3D) nature of the potential surface, since the inversion procedure of paper I yields information only on the collinear (1D) part of the surface. We have performed accurate 1D quantum calculations of reaction probabilities, which are then transformed into 3D by an information theoretic 1D → 3D transformation incorporating a constraint to allow for angular momentum transfer effects in light+heavy—heavy atom reactions. This procedure implicitly accounts for the 3D nature of the potential surface. The calculated vibrational and vibrotational product distributions are in good agreement with those determined in thermal chemiluminescence experiments. The Sato parameters for the 1D surface also define a full 3D surface. This is used as an approximation to the true surface, and its properties are explored in 3D quasiclassical trajectory calculations. Comparison is made for the H and D reactions with available chemiluminescence, molecular beam and kinetic experimental data for differential and total reaction cross sections, energy disposal, rate coefficients and Arrhenius parameters. Some kinetic isotope effects in the Mu, H, and D reactions are discussed using vibrationally adiabatic theory. Comparison is also made with results from other calculations in the literature for the H + Cl₂ and D + Cl₂ reactions.