Photofragment translational spectroscopy of Ibr at 304 nm: Polarization dependence and dissociation dynamics

TitlePhotofragment translational spectroscopy of Ibr at 304 nm: Polarization dependence and dissociation dynamics
Publication TypeJournal Article
Year of Publication1995
AuthorsJung, K-W, Griffiths, JA, EL-Sayed, MA
JournalJournal of Chemical Physics
Date PublishedOct 22
ISBN Number0021-9606
Accession NumberWOS:A1995TA44100018

The photodissociation dynamics of IBr has been studied at 304 nm by state-selective photofragment translational spectroscopy. Velocity distributions, anisotropy parameters, and relative quantum yields are obtained for the ground I(P-2(3/2)) and spin-orbit excited state I*(P-2(1/2)) iodine atoms, which are produced from photodissociation of IBr at this wavelength. Two sharp velocity distributions observed for the I channel suggest the two dissociation pathways that correlate with ground-state iodine formation. Based on the expected translational energy release and the energy separation between the peaks, the two distributions have been assigned to dissociation of IBr to form I(P-2(3/2))+Br(P-2(3/2)) and I(P-2(3/2))+Br*(P-2(1/2)) with the former channel appearing at higher translational energy. The I* distribution shows one strong peak indicating that there is one dominant channel for formation of I* atoms at this wavelength which has been assigned to dissociation of IBr to form I*(P-2(1/2))+Br(P-2(3/2)) with a quantum yield of 0.1. The I* signal formed from the I*(P-2(1/2))+Br*(P-2(1/2)) dissociation channel is observed very weakly. The observed anisotropy parameter indicates that the I+Br* product (beta=-0.7) is formed mainly from the perpendicular (1) Pi(1)(2341)<--X transition while the I*+Br channel (beta=1.8) is formed predominantly from the parallel 3 Pi(0+)(2341)<--X transition followed by curve crossing to the (3) Sigma(0+)(-)(2422) State. The recoil energy dependence of the anisotropy parameter in the I atom produced in the I+Br channel shows a positive beta value above maximum of the peak recoil energy and a negative value below the peak maximum of the recoil energy distribution. These results are interpreted in terms of the presence of more than one path for the formation of I+Br photoproduct with opposite polarization for their absorbing transitions, most likely the (3) Pi(0+)(2341)<--X and the (3) Pi(1)(2341)<--X transitions. The possible excited state dynamics which give the observed results are discussed in terms of the previously proposed potential energy diagrams for IBr and ICl. (C) 1995 American Institute of Physics.