Intrinsic and extrinsic precursors to adsorption: Coverage and temperature dependence of Kr adsorption on Pt(111)

Abstract

The kinetics of krypton adsorption on Pt(111) were investigated using supersonic molecular beam techniques. Krypton adsorbs at defects via an intrinsic precursor below a surface temperature of 85 K. The difference in activation energies for desorption and migration of a Kr atom on the terrace seeking a defect site is 10.7 kJ/mol, indicating that at 80 K, a Kr atom makes about 107 site hops before desorbing or finding a binding site. Below 60 K stable adsorption occurs on terraces, where the initial adsorption probability is independent of surface temperature. The activation energy for zero-order desorption from Pt(111) terraces is 12.9 kJ/mol; the activation energy for Kr migration on the terraces is then calculated to be ⩽2.2 kJ/mol. Krypton adsorption proceeds at nonzero coverages via an extrinsic precursor. The adsorption probability of Kr increases with self-coverage, and is described by the modified Kisliuk model [H. C. Kang, C. B. Mullins, and W. H. Weinberg, J. Chem. Phys. 92, 1397 (1990); C. R. Arumainayagam, M. C. McMaster, and R. J. Madix, J. Phys. Chem. 95, 2461 (1991)]. The Kr overlayer on terraces compresses between 60 and 42 K, then forms a second state before forming stable multilayers at 34 K.