The primary photodynamics of aqueous nitrate: formation of peroxynitrite

We have examined the photochemical reactions occurring after irradiation at 200 nm of the aqueous nitrate ion, NO3(-)(aq). Using femtosecond transient absorption spectroscopy over the range 194-388 nm, we have characterized the formation and subsequent relaxation of the primary photoproducts of nitrate photolysis. The dominant photoproduct is the cis-isomer of peroxynitrite, which accounts for 48% of the excited state molecules initially produced. A slightly smaller fraction, 44%, of the excited molecules return to the electronic ground state of NO3(-) and relax to the vibrational ground state in 2 ps. The remaining 8% of the molecules initially excited react via the *NO + *O2(-) or the NO- + O2 dissociation channels. Formation of NO2(-) and *NO2 is not observed, suggesting that the previous observations of these species in steady-state photolysis are caused by reactions occurring on a longer time scale.