Evaluating Thermal Corrections for Adsorption Processes at the Metal/Gas Interface

2019

International audience; Adsorption and desorption steps are key for active catalysts and rely on a subtle balance between enthalpic and entropic terms. While the enthalpic term is becoming ever more accurate through density functional development, the entropic term remains underrated and its precise determination a great challenge. In this work, we have performed extensive first principles thermodynamic integration (TI) simulations for the 1 adsorption of small (e.g., CO) to larger (e.g., phenol) molecules at metallic surfaces and compared their adsorption free energies to the values obtained by vertical, static statistical mechanics approximations to thermal corrections invoking three diff…