Abstract
Infrared spectra of 12CO+ 13CO mixtures adsorbed on polycrystalline platinum electrodes from 1 M H 2SO 4 solutions have been obtained by EMIRS electrochemically modulated infrared spectroscopy. The carbon-oxygen stretch spectra for variable 12CO/ 13CO ratios at constant saturation coverage and fixed 12CO/ 13CO ratios at high coverage show a single bipolar EMIRS band indicative of a highly coupled system. Lower coverage mixed isotopic samples with greater than 30% 13CO produced spectra with two bipolar bands. A simple three parameter model for calculation of infrared band contours was used to assess the effects from adsorbate-adsorbate coupling and from changes in the principal force constant. The different potential and coverage dependences of the position of the absorption band for the observed spectra show that the former is due entirely to a change in the principal force constant and the latter is caused by changes in the coupling.
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