Correcting Implicit Solvation at Metal/Water Interfaces Through the Incorporation of Competitive Water Adsorption

04 July 2024, Version 3
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Conventional continuum solvation models are ubiquitous in computational catalysis, including for describing metal/water interfaces which are relevant to both solution-phase heterogeneous catalysis and electrocatalysis. Nonetheless, we find that such continuum models qualitative fail to describe both the adsorption free energy and conformational preference for many organic molecules at such interfaces, largely due to the failure of continuum models to incorporate the role of competitive water adsorption. We develop a simple phenomenological model that accounts for competitive water adsorption and show that the model, when used in conjunction with continuum solvation, provides a dramatic improvement in the description of both adsorption and conformational preference. The model is also extended to additionally incorporate the influence of applied potential at the electrode surface, thus facilitating computationally efficient applications to scenarios including electrocatalysis.

Keywords

electrocatalysis
Adsorption
Implicit solvation
QM/MM
Explicit solvation

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