Abstract
The lineshape of the carbon-oxygen stretching vibration for CO chemisorbed at the two-fold bridge sites and on top sites of Ni(111) has been measured over the temperature range 80 to 300 K with infrared reflection absorption spectroscopy. The bridge bonded CO undergoes pronounced broadening at higher temperatures while the terminally bonded CO is only slightly broadened. The results are interpreted according to a recent vibrational dephasing model developed for condensed phase molecules. In this model the dephasing is brought about by rapid energy exchange between low frequency modes of the substrate and low frequency modes of the molecule which are anharmonically coupled to the high frequency band being studied.
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