How Much Interfacial Electrochemistry Can Be Understood Without Orbitals?

Electronic orbitals are a foundational concept in modern approaches to interfacial electrochemistry. While they are essential in many cases, the high computational cost of finding them could hinder the proper understanding of important practical problems. Therefore, a legitimate question is what aspects of interfacial electrochemistry can be understood without involving orbitals. Motivated by this question, I will start my talk with a few examples where orbitals are considered not to be of primary importance. Afterward, I will outline a theoretical model for interfacial electrochemistry that combines an orbital-free theory of electrons and a statistical field theory of the liquid solution. A benchmark of the model against experimental data on a model system will be presented. Finally, the calibrated model will be extended to electrochemical interfaces at rough electrodes and supported nanoparticle catalysts.