Bond-specific chemistry: OD:OH product ratios for the reactions H+HOD(100) and H+HOD(001)

Abstract
From laser‐induced fluorescence measurements, the OD:OH product branching ratio is determined to be greater than 25:1 for the reaction H+HOD(001) and less than 1:8 for the reaction H+HOD(100). Fast H atoms are generated by the photolysis of HI at 266 nm and the HOD is excited to a specific vibronic state using an optical parametric oscillator. Here HOD(001) and HOD(100) correspond to O–H and O–D local‐mode stretch fundamentals, respectively. Within our signal‐to‐noise level, reaction occurs exclusively with the extended hydrogen atom of HOD in each case.