Using the laser photolysis/laser-induced fluorescence (LP/LIF) pump-pr
obe technique, the gas-phase photodissociation dynamics of room temper
ature HNCO was studied at a photolysis wavelength of 248 nm. H atoms p
roduced via HNCO+hv-->H(S-2)+NCO(X(2)II) were detected by vacuum-UV la
ser-induced fluorescence (VUY-LIF) at the Lyman-alpha transition. By m
eans of a calibration method - using H2S photolysis as a source of wel
l defined H atom concentrations - the absolute cross section for direc
t photolytic H atom formation was determined to be sigma(H)=(1.2+/-0.3
)x10(-21) cm(2) molecule(-1). From the H atom Doppler profiles, measur
ed under single-collision conditions, the fraction of the available en
ergy released as product translational energy was determined to be f(T
)(H+NCO)=(0.55+/-0.02). In addition, the second energetically accessib
le 'spin-forbidden' dissociation channel, HNCO+hv-->NH(X (3) Sigma(-))
+CO(X(1) Sigma(+)), was investigated. Our results show that at a wavel
ength of 248 nm, direct Il atom formation is the dominant dissociation
channel in the HNCO photolysis.