Communication: Rigorous quantum dynamics of O + O2 exchange reactions on an ab initio potential energy surface substantiate the negative temperature dependence of rate coefficients

Abstract

The kinetics and dynamics of several O + O2 isotope exchange reactions have been investigated on a recently determined accurate global O 3 potential energy surface using a time-dependent wave packet method. The agreement between calculated and measured rate coefficients is significantly improved over previous work. More importantly, the experimentally observed negative temperature dependence of the rate coefficients is for the first time rigorously reproduced theoretically. This negative temperature dependence can be attributed to the absence in the new potential energy surface of a submerged "reef" structure, which was present in all previous potential energy surfaces. In addition, contributions of rotational excited states of the diatomic reactant further accentuate the negative temperature dependence. © 2014 AIP Publishing LLC.