Spectroscopy and dynamics of selected rotational levels in the B(2)A '' state of the vinoxy radical

The fluorescence lifetimes of single rotational states in the 8(1), 7(1) an d 5(1) vibrational levels of the (B) over tilde (2)A " electronic state in jet-cooled vinery radicals have been investigated following coherent excita tion. The emission decays were found to be exponential and independent of t he rotational quantum number J, and the observed quantum beats were due exc lusively to hyperfine interactions. The dynamics of two regimes of radiatio nless processes (internal conversion with and without curve crossing) were explored and the electronic structure of the (B) over tilde (2)A " state fu rther characterised. (C) 2000 Elsevier Science B.V. All rights reserved.