Probing the ignored elimination channel of Br2 in the 248 nm photodissociation of 1,1-dibromoethylene by cavity ring-down absorption spectroscopy.

In the photodissociation of 1,1-C(2)H(2)Br(2) at 248 nm, the Br(2) elimination channel is probed by using cavity ring-down absorption spectroscopy (CRDS). In terms of spectral simulation, the vibrational population ratio of Br(2)(v = 1)/Br(2)(v = 0) is found to be 0.55+/-0.05, which indicates that the Br(2) fragment is vibrationally hot. The rotational population is thermally equilibrated with a Boltzmann temperature of 349+/-38 K. According to ab initio potential energy calculations, the obtained fragments are anticipated to result primarily from photodissociation of the ground electronic state that undergoes 1) H migration followed by three-center elimination, and 2) isomerization forming either trans- or cis-1,2-C(2)H(2)Br(2) from which Br(2) is eliminated. RRKM calculations predict that the Br(2) dissociation rates through the ground singlet state prevail over those through the triplet state. Measurements of temperature and Ar pressure dependence are examined to support the proposed pathway via internal conversion. The quantum yield for the Br(2) elimination reaction is determined to be 0.07+/-0.04. This result is smaller than that obtained in 1,2-C(2)H(2)Br(2), probably because the dissociation rates are slowed in the isomerization stage.