Constant Potential Thermodynamic Integration for Obtaining the Free Energy Profile of Electrochemical Reaction

In this work, we advanced an efficient free energy sampling method based on constrained ab initio molecular dynamics (cAIMD) with a fully explicit solvent layer to depict the electrochemical reaction process at constant surface charge density, named the "Constant-Potential Thermodynamic Integration (CPTI)" method. For automatically adjusting surface charge density at different states, we built an "on-the-fly" procedure which is capable of managing all the necessary steps during cAIMD simulations, including the system pre-equilibrium, surface charge density updating, and force sampling. We applied it to predict the potential-dependent free energy profiles of CO2 adsorption on a single-atom catalyst. The results show that our method can not only account for changes in electrostatic potential energy associated with potential but also consider the potential-induced solvation effects. Our approach enables the accurate simulation of electrochemical environment by presenting the complete solid–liquid interface and efficient computation of electrocatalytic reaction energetics based on a robust potential descriptor.