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J. Vogt, Helmut Weiss
Physisorption of Small Molecules on Single Crystal Alkali Halide Surfaces: CO and N2 Adsorbed on KCl(100)
The adsorption of CO and N2 on KCl(100) single crystal cleavage planes has been investigated by means of low energy electron diffraction (LEED) at primary currents in the nA range as well as polarization infrared spectroscopy (PIRS) in transmittance geometry. These isoelectronic adsorbates behave very similarly, and three different adsorption phases can be distinguished as a function of surface coverage for both of them. Initially a (1×1) structure is observed and assigned to a commensurate monolayer with one molecule per KCl ion pair. The CO infrared spectrum of this ‘phase I’ is characterized by a doublet absorption of the CO stretching vibration, which is discussed in the context of a correlation field splitting. The lack of superstructure diffraction peaks is attributed to a high degree of orientational disorder in this phase. From LEED adsorption isotherms the isosteric heat of adsorption of N2 has been determined to be 11±3 kJ mol−1. Upon increase in coverage by 50% ‘phase II’ is formed which exhibits a large number of additional diffraction spots. It is assigned to a bilayer in which the second layer is only half filled. Based on the LEED experiments a structure model is proposed in which the second layer is characterized by growth in rows along the [210] direction and a high degree of roughness in the perpendicular direction. This model can explain all experimentally observed main features. Finally upon further exposure formation of three-dimensional solid is observed, which proceeds via Stransky–Krastanov growth of crystalline 3D clusters with the structure of the low-temperature cubic α-phase. A simulation of the CO cluster infrared spectra within the dipole–dipole coupling approach can reproduce all major observed vibrational features.
Zeitschrift für Physikalische Chemie, Oldenbourg Wissenschaftsverlag
Print ISSN: 0942-9352
Volume: 218, 08/2004
Pages: 973 - 995