Chemiluminescent (CL) reaction of bismuth with F2 has been studied in
a beam-gas arrangement under single-collision conditions. Time-of-flig
ht (TOF) measurements suggest that the Bi2 dimer is the major beam rea
ctant responsible for the observed CL. The bond dissociation energy of
BiF has been estimated by observing the short wavelength limit in the
B0+-X(1)0+ emission spectrum of BiF. The estimated lower bound of 3.7
+/- 0.1 eV is in good agreement with a recent determination of the bo
nd dissociation energy of BiF. The vibrational distributions of the CL
product states provide information on the potential energy surfaces g
overning the reaction.