The microscopic diffusion processes of NO molecules on Pt(997) at low coverage were investigated using time-resolved infrared reflection absorption spectroscopy (TR-IRAS). When NO molecules adsorb on Pt(997) at low temperature, each molecule transiently migrates on the surface from the first impact point to a possible adsorption site. At 11 K, the molecules are trapped at four adsorption sites on Pt(997): the on-top sites on the (111) terrace (OT), the hollow sites on the (111) terrace (HT), the bridge sites at the step (BS) and the hollow sites at the step downstream (HS). Based on the initial population ratio for these sites, the mean lateral displacement by transient migration is estimated to be 4.1 Å. By heating the surface to 45 K, the HS species migrate up to the BS sites; the migration barrier is roughly estimated to be 120 meV. In the temperature range from 70 to 77 K, TR-IRAS measurements were carried out to observe the site change of OT species to the adjacent HT sites at isothermal conditions; the activation barrier and the preexponential factor are estimated to be 200 meV and 2.0× 1011 s-1, respectively. In the temperature range from 100 to 110 K, the HT species migrate across the terrace and finally reach the BS sites. The activation barrier between the HT sites and the preexponential factor are estimated to be 290 meV and 6.5× 1011 s-1, respectively, from the TR-IRAS data together with kinetic Monte Carlo simulations. On the whole, the quantitative microscopic picture of NO migration on Pt(997) has been established.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry