The atomistic description of the electrolyte at the electrode-electrolyte interface (EEI)

Advances in theory and methods of quantum mechanics and in supercomputers are making it practical to consider first principles (de novo) predictions of the mechanisms of complex catalytic reactions. We will highlight some recent advances in such methodologies including: QM Metadynamics calcns. of free energies of electrocatalysis at operational temp. and potential. Grand canonical QM calcns. of electrochem. catalysis at const. potential (instead of const. nos. of electrons) which we will illustrate with recent applications to catalytic systems selected from: The reaction mechanism for the Electrocatalytic oxygen redn. reaction on Pt(111) and Pt alloys. Reaction mechanisms Crit. potentials for CO_2 redn. on (100) and (111) Cu surfaces to form ethanol and ethylene. The reaction mechanism for the Electrocatalytic oxygen evolution reaction (OER). In particular, we will ext. from the simulations the predicted XPS chem. shifts and the OH vibrational frequencies for the species in the electrolyte that might be compared to future exptl. measurements to understand the nature of the electrode-electrolyte interface (EEI)