Toward accurate and efficient dynamic computational strategy for heterogeneous catalysis: Temperature-dependent thermodynamics and kinetics for the chemisorbed on-surface CO

Computational tools on top of first principle calculations have played an indispensable role in revealing the molecular details, thermodynamics, and kinetics in catalytic reactions. Here we proposed a highly efficient dynamic strategy for the calculation of thermodynamic and kinetic properties in heterogeneous catalysis on the basis of efficient potential energy surface (PES) and MD simulations. Taking CO adsorbate on Ru(0001) surface as the illustrative model system, we demonstrated the PES-based MD can efficiently generate reliable two-dimensional potential-of-mean-force (PMF) surfaces in a wide range of temperatures, and thus temperature-dependent thermodynamic properties can be obtained in a comprehensive investigation on the whole PMF surface. Moreover, MD offers an effective way to describe the surface kinetics such as adsorbate on-surface movement, which goes beyond the most popular static approach based on free energy barrier and transition state theory (TST). We further revealed that the dynamic strategy significantly improves the predictions of both thermodynamic and kinetic properties as compared to the popular ideal statistic mechanics approaches such as harmonic analysis and TST. It is expected that this accurate yet efficient dynamic strategy can be powerful in understanding mechanisms and reactivity of a catalytic surface system, and further guides the rational design of heterogeneous catalysts.