Methylidyne Adsorption on Pt(211) Probed by Reflection Absorption Infrared Spectroscopy (RAIRS).

Methylidyne, CH(ads), adsorbed on a Pt(211) surface and its interaction with chemisorbed hydrogen atoms was studied by reflection absorption infrared spectroscopy (RAIRS). Methylidyne was formed on Pt(211) by methane dissociation from a molecular beam followed by thermal decomposition of the methane dissociation products. CH(ads) was detected by RAIRS via its symmetric C-H stretch vibration resulting in three discrete absorption peaks in the region of 2950-2970 cm. While the frequencies of the three C-H stretch peaks remain fixed, their relative intensities depend on the H(ads) co-coverage. This differs markedly from what was observed previously for the RAIR spectra of CH(ads) adsorbed on Pt(111) by the group of Trenary, who observed a single C-H stretch peak, which showed a continuous blue shift with increasing H(ads) coverage. Based on our experimental results and density functional theory (DFT) calculations, we propose that the three discrete absorption peaks on Pt(211) are due to the adsorption of methylidyne on the steps of Pt(211) forming one-dimensional rows of adsorbates. Depending on the H(ads) coverage, the CH(ads) species on the step sites can have either zero, one, or two neighboring H(ads) atoms, leading to three different vibrational C-H stretch frequencies and a reversible shift in relative peak intensity depending on the H(ads) coverage.