Chen, LiUeta, HirokazuBisson, RégisBeck, Rainer D.2012-02-272012-02-272012-02-27201210.1039/C2FD20007Dhttps://infoscience.epfl.ch/handle/20.500.14299/78103WOS:000309137600015Reflection 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.text::journal::journal article::research article