Imaging NO elimination in the infrared multiphoton dissociation of nitroalkanes and alkyl nitrites

Highlights: • IRMPD of C2, C3 and C4 nitroalkanes and alkyl nitrites is studied. • DC slice imaging is used as state-resolved probe of NO product. • Trends in translational energy are correlated to NO J level for nitro systems. • Distinct behavior is seen for C4 systems vs. C2 and C3. • Roaming-mediated isomerization is suggested as the mechanism for C2 and C3 case. We present a DC slice imaging study of the decomposition of C2, C3 and C4 nitroalkanes and alkyl nitrites, focusing on the NO elimination channel, possibly a minor pathway. Infrared multiphoton dissociation (IRMPD) is used to induce dissociation on the ground electronic state under collisionless conditions. The channels that produced NO as a product were studied and compared among the target molecules to gain a better understanding of the isomerization of the nitroalkanes prior to dissociation. Trends in the total translational energy and NO rotational temperatures obtained from the images are discussed.