  Adsorption and dissociation of hydrocarbons on metallic surfaces represent
crucial steps to carburization of metal. Here, we use density functional theory
total energy calculations with the climbing-image nudged elastic band method to
estimate the adsorption energies and dissociation barriers for different CO
coverages with surface supercells of different sizes. For the absorption of CO,
the contribution from van der Waals interaction in the computation of
adsorption parameters is found important in small systems with high
CO-coverages. The dissociation process involves carbon insertion into the Fe
surface causing a lattice deformation that requires a larger surface system for
unrestricted relaxation. We show that, in larger surface systems associated
with dilute CO-coverages, the dissociation barrier is significantly decreased.
The elastic deformation of the surface is generic and can potentially
applicable for all similar metal-hydrocarbon reactions and therefore a dilute
coverage is necessary for the simulation of these reactions as isolated
processes.
