Predissociation dynamics of the A²⁺ state of SH radical: Fine-structure state distributions of the S(³P_J) products

Photo-predissociation of rovibrational levels of SH (A(2)Sigma(+), v ' = 0-6) is studied using the high-n Rydberg atom time-of-flight technique. Spin-orbit branching fractions of the S(P-3(J=2,1,0)) products are measured in the product translational energy distributions. The SH A(2)Sigma(+) v ' = 0 state predissociates predominantly via coupling to the (4)Sigma(-) repulsive state. As the vibrational level v ' increases, predissociation dynamics change drastically, with all three repulsive states ((4)Sigma(-), (2)Sigma(-), and (4)Pi) involved in the dissociation. Nonadiabatic interactions and quantum interferences among these dissociation pathways affect the fine-structure state distributions of the S(P-3(J=2,1,0)) products.