High resolution ion imaging study of BrCl photolysis in the wavelength range 330–570 nm

The photodissociation of jet-cooled BrCl molecules has been investigated at many different excitation wavelengths in the range 330–570 nm by velocity map imaging of the ground state Br and ground and spin–orbit excited Cl atom products. Image analysis confirms literature values for the energies of the ground, Br(2P3/2)+Cl(2P3/2), and first excited [Br(2P3/2)+Cl(2P1/2)] dissociation asymptotes, and provides measures of the electronic branching into these two active product channels, and the recoil anisotropy of each set of products, as a function of parent vibrational level (v″⩽2) and excitation wavelength. The availability of such experimental data allows mapping of the partial cross-sections for parallel (i.e., ΔΩ=0) and perpendicular (i.e., ΔΩ=±1) absorption as a function of excitation energy, and thus deconvolution of the room temperature parent absorption spectrum into contributions associated with excitation to the A 3Π(1), B 3Π(0+), and C 1Π(1) excited states of BrCl. This analysis of the continuous absorption spectrum of BrCl, when considered in conjuction with existing spectroscopic data for the ground electronic state and for the bound levels supported by the B state potential, allows determination of key regions of the potential energy curves for, and transition moments to, each of these three excited states. Further wave packet calculations, which reproduce the experimentally measured wavelength dependent product channel branching ratios and product recoil anisotropies very well, serve to validate the excited state potential energy functions so derived and allow estimation of the strength (∼80 cm−1) of the coupling between the bound (B) and dissociative (Y) diabatic states of 0+ symmetry.