Effects of applied voltage on water at a gold electrode interface fromab initiomolecular dynamics

Zachary K. Goldsmith, Marcos F. Calegari Andrade, Annabella Selloni

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33 Scopus citations


Electrode-water interfaces under voltage bias demonstrate anomalous electrostatic and structural properties that are influential in their catalytic and technological applications. Mean-field and empirical models of the electrical double layer (EDL) that forms in response to an applied potential do not capture the heterogeneity that polarizable, liquid-phase water molecules engender. To illustrate the inhomogeneous nature of the electrochemical interface, Born-Oppenheimerab initiomolecular dynamics calculations of electrified Au(111) slabs interfaced with liquid water were performed using a combined explicit-implicit solvent approach. The excess charges localized on the model electrode were held constant and the electrode potentials were computed at frequent simulation times. The electrode potential in each trajectory fluctuated with changes in the atomic structure, and the trajectory-averaged potentials converged and yielded a physically reasonable differential capacitance for the system. The effects of the average applied voltages, both positive and negative, on the structural, hydrogen bonding, dynamical, and vibrational properties of water were characterized and compared to literature where applicable. Controlled-potential simulations of the interfacial solvent dynamics provide a framework for further investigation of more complex or reactive species in the EDL and broadly for understanding electrochemical interfacesin situ.

Original languageEnglish (US)
Pages (from-to)5865-5873
Number of pages9
JournalChemical Science
Issue number16
StatePublished - Apr 28 2021

All Science Journal Classification (ASJC) codes

  • General Chemistry


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