Quasiclassical trajectory calculations of the HO2 + NO reaction on a global potential energy surface.
We report quasiclassical trajectory calculations of the HO(2) + NO reaction using a new full dimensional, singlet potential energy surface (PES) which is a fit to more than 67 000 energies obtained with density functional theory-B3LYP/6-311G(d,p)-calculations. The PES is invariant with respect to permutation of like nuclei and describes all isomers of HOONO, HONO(2), saddle points connecting them and the OH + NO(2), HO(2) + NO channels. Quasiclassical trajectory calculations of cross-sections for the HO(2) + NO to form HOONO, HONO(2) and OH + NO(2) are done using this PES, for reactants in the ground vibrational state and rotational states sampled from a 300 K Boltzmann distribution. Trajectory calculations illustrate the pathway that HO(2) + NO takes to the energized HOONO complex, which dissociates to products OH + NO(2), reactants HO(2) + NO, or isomerizes to HONO(2). The association cross sections are used to obtain rate constants for formation of HOONO and HONO(2) in the high-pressure limit, and formation of products OH + NO(2) in the low-pressure limit.
Chen
Chao
C
Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, GA 30322, USA.
Shepler
Benjamin C
BC
Braams
Bastiaan J
BJ
Bowman
Joel M
JM