First‐Principles Microkinetic Models for Crowded Surfaces

Abstract Catalytic reactions such as hydrogenations often occur on crowded surfaces. First‐principles microkinetic models are typically based on low‐coverage DFT calculations and therefore fail to capture the effect of the high coverage on the reaction energies and reaction kinetics, resulting in low turn‐over frequencies and incorrect selectivities. We discuss several approaches to incorporate realistic surface coverages in first‐principles microkinetic models.