INFRARED-SPECTRUM OF A CHEMISORBED MOLECULE - COMPUTATIONAL ASPECTS, ANALYSIS OF EXPERIMENTAL-DATA FOR ETHYLIDYNE ON PT(111)

A microscopic model is presented for anharmonic vibrations of ethylidyne, = CCH3, chemisorbed on the Pt(111) surface. The model includes 24 vibrational modes of the adsorbate and of the solid. A quantum-mechanical calculation based on second-order perturbation theory is used to interpret experimental data on vibrations of = CCH3/Pt(111) and = CCD3/Pt(111). The measured temperature dependence of the CC infrared fundamental and of the umbrella mode fundamental can be accounted for by anharmonic coupling between the CC stretch and the three PtPt stretch coordinates at the base of the adsorbate. Line shapes calculated using classical molecular dynamics disagree significantly with quantum-mechanical results, the apparent reason being overestimation of vibrational energy transfer in the classical calculation. A semiclassical approximation is suggested, in which all the high frequency adsorbate modes except the infrared absorbing mode are frozen; the remaining modes are treated by classical mechanics. The semiclassical calculation agrees much better with the quantum-mechanical results, and can be extended to higher dimension in a straightforward fashion.