Laser-induced fluorescence (LIF) excitation and emission spectra and f
luorescence lifetimes of jet-cooled 4-aminobenzonitrile (4-ABN) are re
ported. The dispersed fluorescence following excitation of transitions
in the medium and high excess energy region in the S1 manifold are ex
amined. Strong Fermi resonances between the I-0(2) (0(0)0 + 807 cm-1)
and 1(0)1 (0(0)0 + 815 cm-1) bands are observed. The inversion mode do
minates in most dispersed fluorescence spectra, confirming the importa
nce of the fluxional amino group in 4-ABN. Broad and unstructured emis
sion in this region is observed for 4-ABN under jet conditions, which
may be associated with intramolecular vibrational redistribution (IVR)
. The relatively low onset of IVR in 4-ABN is attributed mainly to the
activity of the fluxional amino group.