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.
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