Polarization modulation infrared reflection absorption spectroscopy at elevated pressures: CO adsorption on Pd(111) at atmospheric pressures
Journal of Physical Chemistry B, ISSN: 1089-5647, Vol: 106, Issue: 36, Page: 9367-9371
2002
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Article Description
CO adsorption on a Pd(111) single-crystal surface was investigated using in situ polarization modulation infrared reflection absorption spectroscopy (PM-IRAS) within the pressure range 10-800 mbar. The coverage-dependent CO overlayer structures found on the Pd(111) surface are identical throughout this pressure regime, that is, no new surface species at elevated pressures or adsorbate-induced substrate reconstructions were observed. The transition from an adsorbate superstructure dominated by bridged-bound CO to an adsorbate overlayer having 3-fold/atop CO sites was followed by varying the adsorbate pressure over 9 orders of magnitude. The derived phase diagram indicates an apparent activation energy of 44.35 ± 1.63 kJ/mol for the bridged-to-3-fold-hollow/atop transition. A comparison between these data and recent sum frequency generation (SFG) results is made.
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