Mode specific dynamics in bond selective reaction O′(3P) + HOD → O′H plus OD/O′D plus OH

Taking advantage of bond selectivity and mode specificity has long been realized to control the outcome of chemical reactions. The mode-specific dynamics in the bond selective abstraction reaction O'(P-3) + HOD are investigated using a full-dimensional time-dependent quantum wave packet method. Integral cross sections and product branching ratios from several low-lying vibrational states of the reactant HOD are calculated on an accurate global potential energy surface describing the lowest triplet state of the HOOH system. Both the H-abstraction reaction and the D-abstraction reaction prefer the vibrational energy to the translational energy, satisfying the prediction of Polanyi rules for a late-barrier reaction. The observed strong bond selectivity can be rationalized by the sudden vector projection model as well. The bias to the D-abstraction channel for the reaction O'(P-3) + HOD from the reactant ground state can be partially attributed to the different mass combination in comparison to the H + HOD reaction, in which the H-abstraction channel is more favored. Published by AIP Publishing.