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Surface-Charge Dependent Orientation of Water at the Interface of a Gold Electrode: A Cluster Study

Gianluca Fazio , Gotthard Seifert , Mathias Rapacioli , Nathalie Tarrat and Jan-Ole Joswig EMAIL logo


A gold/water interface has been investigated with the DFT-based self-consistent-charge density-functional tight-binding (SCC-DFTB) method using a cluster model. Born–Oppenheimer molecular-dynamics simulations for mono-, bi-, and trilayers of water on the surface of a Au55 cluster have been computed. We have demonstrated the applicability of this method to the study of the structural and dynamical properties of the gold/water-multilayer interface. The results of the simulations clearly show the charge-dependent orientation and the corresponding polarization of the water sphere around the gold cluster. However, it was also shown that this polarization is restricted almost only to the first solvation shell. This illustrates the rather short-range screening behavior of water. The present study builds the basis for further investigations of metal/electrolyte interfaces on a reliable atomistic level, avoiding the problems of spurious artifacts in models using periodic boundary conditions.

Dedicated to:

Prof. Alexander Eychmüller on the occasion of his 60th birthday.


On the occasion of his 60th birthday, GS and JOJ acknowledge a long-term fruitful collaboration and friendship with their colleague Alexander Eychmüller. JOJ enjoyed especially their joint participation in the LVB project (project number 18/59/74/95/127/130-133/135). Furthermore, the authors acknowledge computational time by the Zentrum für Informationsdienste und Hochleistungsrechnen (ZIH) at TU Dresden for project TransPheMat.


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Received: 2018-01-30
Accepted: 2018-02-07
Published Online: 2018-03-02
Published in Print: 2018-08-28

©2018 Walter de Gruyter GmbH, Berlin/Boston

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