Kinetic Monte Carlo modeling of reaction-induced phase separation in Au/Ni(111) surface alloy

Kinetic Monte Carlo (KMC) simulations of Au–Ni phase separation in Au/Ni(111) surface alloy during nickel carbonyl formation reaction were performed at room temperature by taking into account realistic rates of Au and Ni adatom diffusion and CO adsorption and desorption, while keeping the rate of nickel carbonyl formation reaction as a free parameter. We also obtained pair and three-body interaction constants between Au and Ni adatoms using the ab initio calculations and demonstrated that their proper choice is crucial for understanding the Au–Ni separation process. Three regimes with qualitatively different Ni–CO reaction propagation kinetics in Au/Ni(111) surface alloy were found by varying the constants of trio-triangle interactions within the limits of their accuracy. The sensitivity of the proposed model to interaction parameters leads to the regimes that differ by step flow rate, Au islands formation mechanism (channel-type or homogenous flow), Au island contamination level by Ni impurities and reaction damping tendency at the reaction front. Nucleation of nickel-free Au islands was observed for a homogeneous step flow pattern, and the corresponding step flow rate is in a good quantitative agreement with existing experimental data.