Reflection absorption infrared spectroscopy (RAIRS) was used to probe for vibrational bond-selectivity in the dissociative chemisorption of three partially deuterated methane isotopologues on a Pt(111) surface. While a combination of incident translational energy and thermal vibrational excitation produces a nearly statistical distribution of C-H and C-D bond cleavage products, we observe that laser excitation of an infrared active C-H stretch normal mode leads to highly selective dissociation of a C-H bond for CHD3, CH2D2, and CH3D. Our results show that vibrational energy redistribution between C-H and C-D stretch modes due to methane/surface interactions is negligible during the sub-picosecond collision time which indicates that vibrational bond-selectivity may be the rule rather than the exception in heterogeneous reactions of small polyatomic molecules.

Vibrationally bond-selected chemisorption of methane on Pt(111) studied by reflection absorption infrared spectroscopy

244th National Meeting (2012)

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