CO-Induced Restructuring on Stepped Pt Surfaces: A Molecular Dynamics Study

The effects of plateau width and step-edge kinking on carbon monoxide (CO)-induced restructuring of platinum surfaces were explored using molecular dynamics (MD) simulations. Platinum crystals displaying four different vicinal surfaces [(321), (765), (112), and (557)] were constructed and exposed to partial coverages of carbon monoxide. Platinum–CO interactions were fit to recent experimental data and density functional theory (DFT) calculations, providing a classical interaction model that captures the atop binding preference on Pt. The differences in Pt–Pt binding strength between edge atoms on the various facets were found to play a significant role in step-edge wandering and reconstruction events. Because the mechanism for step doubling relies on a stochastic meeting of two wandering edges, the widths of the plateaus on the original surfaces were also found to play a role in these reconstructions. On the Pt(321) surfaces, the CO adsorbate was found to assist in reordering the kinked step edges into straight {100} edge segments.