H3o/h2do + H/d Reactions: Observation of the Rotational Effect in the Temperature Dependence (postprint)

Thermal rate coefficients for the title reactions computed using a quasi-classical trajectory method on an accurate global potential energy surface fitted to ∼81,000 high-level ab initio points are compared with experimental values measured between 100 and 600 K using a variable temperature selected ion flow tube instrument. Excellent agreement is found across the entire temperature range, showing a subtle, but unusual temperature dependence of the rate coefficients. For both reactions the temperature dependence has a maximum around 350 K, which is a result of H2O + rotations increasing the reactivity, while kinetic energy is decreasing the reactivity. A strong isotope effect is found, although the calculations slightly overestimate the kinetic isotope effect. The good experiment−theory agreement not only validates the accuracy of the potential energy surface but also provides more accurate kinetic data over a large temperature range.