We investigated the photodissociation of HNO3 within the first (300 nm) and the third (200 nm) absorption band. The relevant S1 and S3 potential energy surfaces were calculated by taking into account the N-O single bond and N=O “double” bond distances. The striking feature of the dynamical analysis is a bifurcation of the wave packet on the S3 surface which explains the branching into the two
reaction pathways with the products OH+NO2 and O+HONO found in experiments. Dissociation on the S1 surface is predicted to proceed along a single channel leading to OH+NO2, both in their electronic ground states.