Spectroscopy and dynamics of selected rotational levels in the B̃2A″ state of the vinoxy radical

The fluorescence lifetimes of single rotational states in the 81, 71 and 51 vibrational levels of the B̃2A″ electronic state in jet-cooled vinoxy radicals have been investigated following coherent excitation. The emission decays were found to be exponential and independent of the rotational quantum number J, and the observed quantum beats were due exclusively to hyperfine interactions. The dynamics of two regimes of radiationless processes (internal conversion with and without curve crossing) were explored and the electronic structure of the B̃2A″ state further characterised.