Assessing a First-Principles Model of an Electrochemical Interface by Comparison with Experiment

In the dawn of green chemistry and the search for renewable energy sources, the importance of electrocatalysis has soared in recent years. In particular, electrocatalysis is the key technology for (water) electrolysis, fuel cells and electrosynthesis. Electrified interfaces are central in electrocatalysis, where the electrochemical potential determines the stability of adsorbed surface species and their reactivity.

Experimental characterization of these complex interfaces with atomic resolution is highly challenging. First-principles modeling could provide a link between the measurable quantities and an atomic scale understanding. However, such simulations are far from straightforward. Although approaches that include the effect of the potential and the electrolyte have been proposed, detailed validation has been scarce and ”indirect” since atomically resolved experimental studies of systems that can be convincingly simulated are scarce. We introduce here the adsorption of pyridine on Au(111) as a convenient and relevant model: the adsorption mode of pyridine switches as a function of the electrochemical potential. We demonstrate that the primitive surface charging model gives qualitatively correct results at a low complexity.

Assessing a First-Principles Model of an Electrochemical Interface by Comparison with Experiment
Stephan N. Steinmann and Philippe Sautet
J. Phys. Chem. C, 2016, 120 (10), pp 5619–5623.