The reaction of HO2NO2 （peroxynitric acid, PNA） with OH was studied by the hybrid density functional B3LYP and CBS-QB3 methods. Based on the calculated potential energy surface, five reaction channels, H20＋NO2＋O2, HOOH＋NO3, NO2＋HO3H, HO2＋HONO2 and HO2＋HOONO, were examined in detail. The major reaction channel is PNA＋OH→M1→TS1→H2O＋NO2＋O2. Taking a pre-equilibrium approximation and using the CBS-QB3 energies, the theoretical rate constant of this channel was calculated as 1.13×10-12 cm^3/（molecule s） at 300 K, in agreement with the experimental result. Comparison between reactions of HOONO2＋OH and HONO2＋OH was carried out. For HOR＋OH reactions, the total rate constants increase from R=NO2 to R=ONO2, which is consistent with experimental measurements.
Yan TianTian-jing HeLi HeFan-chen LiuDong-ming Chen
