Jump to main content
Jump to site search

Issue 48, 2018
Previous Article Next Article

Reactivity and energy level of a localized hole in liquid water

Author affiliations

Abstract

We study the reactivity and the energy level associated with the reduction of the H2+ 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 H2+/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.

Graphical abstract: Reactivity and energy level of a localized hole in liquid water

Back to tab navigation

Publication details

The article was received on 11 Jun 2018, accepted on 14 Nov 2018 and first published on 22 Nov 2018


Article type: Paper
DOI: 10.1039/C8CP03682A
Citation: Phys. Chem. Chem. Phys., 2018,20, 30281-30289
  •   Request permissions

    Reactivity and energy level of a localized hole in liquid water

    F. Ambrosio and A. Pasquarello, Phys. Chem. Chem. Phys., 2018, 20, 30281
    DOI: 10.1039/C8CP03682A

Search articles by author

Spotlight

Advertisements