Document Type

Article

Publication Date

5-19-2021

Abstract

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.

Comments

This is a pre-copy-editing, author-produced PDF of an article accepted for publication in Journal of Chemical Physics, volume 154, in 2021 following peer review. This article may not exactly replicate the final published version. The definitive publisher-authenticated version is available online at https://doi.org/10.1063/5.0050683.

Copyright

American Institute of Physics

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