Photochemistry of NH₂NO₂ and implications for chemistry in the atmosphere

Recent studies have indicated that nitramide (NH₂NO₂) may be formed more plentifully in the atmosphere than previously thought, while also being a missing source of the greenhouse gas nitrous oxide (N₂O) via catalyzed isomerization. To validate the importance of NH₂NO₂ in the Earth's atmosphere, the ground and first electronic excited states of NH₂NO₂ were characterized and its photochemistry was investigated using multireference and coupled cluster methods. NH₂NO₂ is non-planar and of singlet multiplicity in the ground state while exhibiting large out-of-plane rotation in the triplet first excited state. One-dimensional cuts of the adiabatic potential energy surface calculated using the MRCI+Q method show low-lying singlet electronic states with minima in their potential along the N-N and N-O bond coordinates. Due to vertical excitation energies in the 225-180 nm region, photochemical processes will not compete in the troposphere, causing N₂O production to be the predicted major removal process of NH₂NO₂. In the upper atmosphere, photodissociation to form NH₂NO + O (³P) is suggested to be a major photochemical removal pathway.