A complete quantum mechanical study of chlorine photodissociation

A fully quantum mechanical dynamical calculation on the photodissociation of molecular chlorine is presented. The magnitudes and phases of all the relevant photofragment T-matrices have been calculated, making this study the computational equivalent of a "complete experiment," where all the possible parameters defining an experiment have been determined. The results are used to simulate cross-sections and angular momentum polarization information which may be compared with experimental data. The calculations rigorously confirm the currently accepted mechanism for the UV photodissociation of Cl(2), in which the majority of the products exit on the C(1)Π(1u) state, with non-adiabatic couplings to the A(3)Π(1u) and several other Ω = 1 states, and a small contribution from the B(3)Π state present at longer wavelengths.