PHOTODISSOCIATION OF CBRCL3 AT 193 NM BY TRANSLATIONAL SPECTROSCOPY

The photodissociation of CBrCl3 at 193 nm has been studied by translat ional spectroscopy. Two major dissociation channels, (1) CBrCl3-->CCl3 +Br and (2) CBrCl3-->CBrCl3+Cl, are detected with product translationa l energies of 17 and 22 kcal/mol, respectively. The relative yield of (1):(2) is calculated to be 7:3. The primary product, CBrCl2, which is internally excited, undergoes unimolecular decay to form the CCl2+Br products. From the derived values of the anisotropy parameter beta, we conclude that these processes take place rapidly after excitation via an A(1)<--A(1) transition, with the transition moment aligned paralle l to the threefold axis. Results obtained for these two primary pathwa ys and other minor processes are discussed in terms of a simple direct dissociation mechanism. (C) 1995 American Institute of Physics.