Ab initio studies of isomerization and dissociation reactions of peroxyacetyl nitrate (PAN)

The complex potential energy surface for the unimolecular isomerization and decomposition of peroxyacetyl nitrate (PAN, CH3C(O)OONO2), including 11 isomers, 45 interconversion transition states and 18 major dissociation products, is probed theoretically at the G2MP2//B3LYP/6-311G(2d,2p) level of theory. The geometries and relative energies for various stationary points are determined. Based on the calculated G2MP2 potential energy surface, the possible unimolecular decomposition mechanism of PAN is proposed. It is shown that the most feasible decomposition channels of PAN are those leading to 2CH3C(O)OO + NO2, 2CH3C(O)O + 2NO3, and 2CH3 + CO2 + 2NO3, respectively. Among them, the formations of the products of the first two channels are produced by the homolytic O-N and O-O bond ruptures of PAN with the bond dissociation energies of 32.3 and 33.9 kcal/mol, respectively, while the last one is initiated by the concerted C-C and O-O bond fissions via a barrier of 36.5 kcal/mol. Our results suggest that besides the first two decomposition pathways which have been reported by the literature, the last concerted bond fission dissociation channel via a well-defined transition state is also feasible, which has been confirmed by using CBS-Q and CBS-QB3 methods. Therefore, PAN dissociation occurs mainly via the homolytic O-N or O-O bond ruptures or via the concerted C-C and O-O bond fissions while the first channel is more favorable than the last two channels.