The nitrate radical is a key atmospheric oxidant, with visible excitation leading to both NO and NO2 photochemical products that is strongly wavelength dependent. Recent experimental results have shown that dissociation to NO+O2 occurs exclusively via roaming dynamics, and that this roaming appears to occur both on the �dark� D1 state and on the ground D0 state, with distinct product state distributions for each. We have undertaken infrared multiphoton dissociation studies using high-resolution DC slice imaging to explore the contributions from each of these pathways starting from the ground electronic state rather than the electronically excited state as in the work reported to-date. The results clearly show both dissociation channels occur even for ground state excitation, but the high translational energy component associated with the D1 dissociation pathway is considerably reduced relative to the case of electronic excitation.

Imaging infrared multiphoton dissociation of the nitrate radical: Disentangling ground and excited state roaming

248th National Meeting (2014)

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