UV-spectrum and photodecomposition of peroxynitrous acid in the troposphere

The UV spectrum of peroxynitrous acid, HOONO, was computed at the B3LYP/AVTZ and MCSCF/AVTZ levels using the fewest switches surface hopping algorithm. Due to large-amplitude vibrational motions of this molecule, the maxima in the simulated spectra are displaced from the positions of vertical excitations. The three lowest excited electronic singlet states, which are all repulsive, can be reached by UV absorption. The photolysis products are determined, and the photolysis rate constant is provided for the first time. We found that near the tropopause the photolysis rate constant J approximate to 6 x 10-4 s-1, exceeds that for thermal decomposition by two orders of magnitude. The photolysis lifetime is about 30 minutes. Thus, photolysis is an important process and should be included in atmospheric models. Photolysis of HOONO is more rapid than thermal decomposition.

Automated summary

The UV spectrum of peroxynitrous acid, HOONO, was calculated and the photolysis process was found to be important and fast compared to thermal decomposition. It is recommended to include photolysis in atmospheric models.