The coverage dependence of the infrared absorption of CO adsorbed to NaCl(100)

Abstract

CO adsorbed to NaCl(100) exhibits perhaps the weakest possible coupling between the adsorbate and solid. It is, therefore, an ideal system to observe the influence of adsorbate-adsorbate interactions on infrared absorption. In this work, we report polarized FTIR absorption spectra of CO/NaCl(100) as a function of coverage (0.02 ≤ θ ≤ 1 ML), where the coverage has been quantitatively determined by temperature-programmed desorption and molecular beam dosing. We extend a previous semi-empirical model designed to describe the screening of the local electric field due to dipole-dipole interactions in a CO monolayer. The extended model applies to sub-monolayer coverages and describes properly the electric field of the absorbed radiation at the vacuum-substrate interface. Fitting this model to coverage-dependent IR absorption data allows us to derive the vibrational and electronic polarizabilities [χv = 0.0435(14) Å3, χe = 3.30(36) Å3] and the integrated absorption cross section of 2.51(8) × 10-17 cm/molecule for an isolated CO molecule adsorbed at the NaCl (100) surface. The determined integrated absorption cross section is substantially smaller than that of gas phase CO.