Full-Dimensional Quantum Dynamical Studies of the Cl + HOD → HCl/DCl + OD/OH Reaction: Bond Selectivity and Isotopic Branching Ratio

Full-dimensional quantum dynamical calculations are carried out to study the mode specificity, bond selectivity, and isotopic branching ratio of the Cl + HOD reaction on an accurate global potential energy surface. Total reaction cross sections have been computed for several low-lying vibrational states of HOD. Our results confirm the experimental observed vibrationally promoted bond cleavage, in which the breaking of the OH(OD) bond is strongly enhanced by the OH(OD) excitation. These results are rationalized by the recently proposed sudden vector projection model. In addition, the OH/OD branching ratio as a function of energy is investigated and rationalized by a reorientation effect.MOE (Min. of Education, S’pore)Published versio