Surface hopping study of the photodissociation dynamics of ICN− and BrCN−

Abstract In this work the efficacy of semi-classical surface hopping approaches is investigated through studies of the photodissociation dynamics of BrCN −  and ICN − . BrCN −  provides a challenging situation for semi-classical approaches as excitation to the first bright state yields both Br −  + CN and Br ∗  + CN −  products. Further, this branching is highly sensitive to the amount of rotational energy in the CN 0/− fragment. The results of semi-classical and quantum mechanical descriptions of the dynamics are compared when the classical dynamics are propagated in an adiabatic and diabatic representation. The implications of the differences between the classical and quantum treatments of J = 0 are also explored.