Implicit solvent models are a computationally efficient method of representing solid/liquid interfaces, which are prevalent in electrocatalysis, energy storage and materials science. However, electronic structure changes induced by the dielectric continuum at the metallic surface are not fully understood. To address this, we compare implicit and explicit water models for the Pt(111)/water interface using ab initio molecular dynamics (AIMD) simulations and Poisson-Boltzmann continuum solvation within large scale density functional theory calculations. We show that the work function of the Pt surface immersed in implicit solvent can be parametrized in terms of the electronic structure changes for an equilibrated AIMD simulation of the Pt(111)/H2O interface. We further compare the geometry and charge density based dielectric cavitation methods for the adsorption of phenol on Pt(111), and demonstrate that the parametrization of dielectric cavities for individual molecules is key to obtaining accurate enthalpy changes under aqueous conditions. In addition, we show that electronic structure changes induced by both solvent models follow largely similar trends in terms of density difference profiles and d-band projected density of states. We therefore demonstrate the ability of the implicit solvent model to capture the main electronic effects of aqueous solvent on the metallic surface, which will allow computationally efficient simulations of interfacial processes.

Comparison of implicit and explicit solvent models on metal surfaces: Pt(111)/water interface

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.