Molecular Dynamics of the Electrochemical Interface and the Double Layer

Revealing Elusive Intermediates of Platinum Cathodic Corrosion through DFT Simulations

“…The standard theoretical framework to analyze reactions at electrochemical interfaces does not involve explicit consideration of applied bias potential. For example, the common approach in first-principles computational electrochemistry , is to compute the total energy of the system assuming the values of U SHE = 0 V and pH = 0 for the electrode potential and solution pH, respectively, and then introduce a posteriori corrections as where Δ G 0 is the total energy of the system at U = 0 V and pH = 0, k B is the Boltzmann constant, T is the temperature, and a H + is the activity of the protons. However, the electronic-structure properties of interfacial species depend on applied bias potential as it determines the amount of excess charge at the interface.…”

“…However, the electronic-structure properties of interfacial species depend on applied bias potential as it determines the amount of excess charge at the interface. Also, the overall structure of the electrical double layer and solvation of reaction intermediates at the interface are functions of electrode potential. − An ideal approach would be to perform constant-potential calculations similar to experimental conditions. Despite several proposed computational schemes, ,− at present there is no universally accepted grand-canonical theoretical framework for controlling the electrode potential in first-principles simulations.…”