Direct ab initio dynamics studies of the reactions of HNO with H and OH radicals

Abstract

Ab initio calculations using the UMP2 and UQCISD methods with correlation consistent double-zeta and triple-zeta basis sets were applied to study the reactions of HNO with H and OH radicals. The classical energy barrier for the abstraction H+HNO→H2+NO is 0.5 kcal/mol. The reaction path of OH+HNO is: OH+HNO→HNO(OH)-complex→TS→NO(H2O)- complex→H2O+NO with no energy barrier relative to OH+HNO entrance channel. Canonical and microcanonical variational transition state theory calculations were carried out for these reactions (200-2500 K) and compared with available experimental kinetic data. © 2004 Elsevier B.V. All rights reserved.