Work Group Prof. Dr. F. Temps

Photodissociation of alkylnitrites

The photodissociation mechanism of methyl- and other alkylnitrites via the S1 state has been studied in great detail in the 1990s by theory, especially by the Schinke group. In principle, the reaction may proceed following a vibrationally adiabatic route (ΔvNO = 0) by tunneling across a small potential energy barrier or following a vibrationally nonadiabatic route(ΔvNO = -1). A clear interpretation of older experimental results obtained by Doppler spectroscopy of the NO fragment has, however, been hampered by uncertainty of the correct assignment of the vibrational band progression in the absorption spectrum of methylnitrite. Using velocity-mapped photofragment imaging, we are able to solve this problem without ambiguity in a very straightforward way.