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research article

Reactivity and energy level of a localized hole in liquid water

Ambrosio, Francesco  
•
Pasquarello, Alfredo  
December 28, 2018
Physical Chemistry Chemical Physics

We study the reactivity and the energy level associated with the reduction of the H2O+ radical cation in liquid water by combining ab initio molecular dynamics simulations at the hybrid functional level, a grand-canonical formulation of solutes in aqueous solution, and nudge-elastic-band calculations. We demonstrate that this extremely oxidative solute promptly dissociates and calculate an energy barrier for the reaction of 0.06 eV, consistent with the short measured lifetimes. We calculate the energy level related to the H2O+/H2O redox couple with respect to the vacuum level and to the computational standard hydrogen electrode (SHE), using the thermodynamic integration method. This energy level is found to lie at 3.8 +/- 0.1 eV above the SHE level, in remarkable agreement with a previous estimate based on thermodynamical data. The implications of the present results for the mechanism of water splitting at the heterogenous semiconductor-water interface are discussed.

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Type
research article
DOI
10.1039/c8cp03682a
Web of Science ID

WOS:000453231100017

Author(s)
Ambrosio, Francesco  
Pasquarello, Alfredo  
Date Issued

2018-12-28

Published in
Physical Chemistry Chemical Physics
Volume

20

Issue

48

Start page

30281

End page

30289

Subjects

Chemistry, Physical

•

Physics, Atomic, Molecular & Chemical

•

Chemistry

•

Physics

•

density-functional approximations

•

hydrated electron

•

ionized water

•

dynamics

•

clusters

•

proton

•

spectroscopy

•

alignment

•

exchange

•

polarons

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
CSEA  
Available on Infoscience
December 29, 2018
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/153263
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