Ab initio molecular dynamics simulations of the gas-phase reaction of hydroxyl radical with nitrogen dioxide radical

Abstract

The reaction between the hydroxyl radical and the nitrogen dioxide radical in the gas phase has been studied with ab initio molecular dynamics simulations based on density functional theory. Nitric acid HONO 2 and cis– cis peroxynitrous acid ONOOH are formed spontaneously, whereas for the formation of the corresponding trans– perp conformer of peroxynitrous acid, a barrier is observed. The relative energetics of the different conformers of ONOOH are in good agreement with MP2 results. The same holds for the structural properties, except for the N–O single bond which turns out to be highly sensitive to the exchange-correlation functional and is generally overestimated.