We compare electrochemical simulation techniques based on grand canonical modifications to electronic structure methods and capacitor-based approaches, highlighting their basic thermodynamic equivalence, the cases of its breakdown and assumptions among the approaches.

Abstract

First principles-based computational and theoretical methods are constantly evolving trying to overcome the many obstacles towards a comprehensive understanding of electrochemical processes on an atomistic level. One of the major challenges has been the determination of reaction energetics under a constant potential. Here, a theoretical framework was proposed applying standard electronic structure methods and extrapolating to the infinite-cell size limit where reactions do not alter the potential. Today, electronically grand canonical modifications to electronic structure methods, holding the potential constant by varying the number of electrons in a finite simulation cell, become increasingly popular. In this perspective, we show that these two schemes are thermodynamically equivalent. Further, we link these methods to capacitive models of the interface, in the limit that the capacitance of the charging components (whether continuum or atomistic) are equal and invariant along the reaction pathway.

We benchmark the three approaches with an example of alkali cation adsorption on Pt(111) showing that all three approaches converge in the cases of Li, Na and K. For Cs, however, strong deviation from the ideal conditions leads to a spread in the respective results. We discuss the latter by highlighting the cases of broken equivalence and assumptions among the approaches.