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research article

Ab initio study of water dissociation on a charged Pd(111) surface

Fidanyan, Karen
•
Liu, Guoyuan  
•
Rossi, Mariana
March 7, 2023
Journal Of Chemical Physics

The interactions between molecules and electrode surfaces play a key role in electrochemical processes and are a subject of extensive research, both experimental and theoretical. In this paper, we address the water dissociation reaction on a Pd(111) electrode surface, modeled as a slab embedded in an external electric field. We aim at unraveling the relationship between surface charge and zero-point energy in aiding or hindering this reaction. We calculate the energy barriers with dispersion-corrected density-functional theory and an efficient parallel implementation of the nudged-elastic-band method. We show that the lowest dissociation barrier and consequently the highest reaction rate take place when the field reaches a strength where two different geometries of the water molecule in the reactant state are equally stable. The zero-point energy contributions to this reaction, on the other hand, remain nearly constant across a wide range of electric field strengths, despite significant changes in the reactant state. Interestingly, we show that the application of electric fields that induce a negative charge on the surface can make nuclear tunneling more significant for these reactions.

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Type
research article
DOI
10.1063/5.0139082
Web of Science ID

WOS:000942108500021

Author(s)
Fidanyan, Karen
Liu, Guoyuan  
Rossi, Mariana
Date Issued

2023-03-07

Published in
Journal Of Chemical Physics
Volume

158

Issue

9

Article Number

094707

Subjects

Chemistry, Physical

•

Physics, Atomic, Molecular & Chemical

•

Chemistry

•

Physics

•

molecular-dynamics simulation

•

bias

•

chemistry

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

Available on Infoscience
March 27, 2023
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/196484
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