We determine the ionization potential (IP) and the electron affinity (EA) of liquid water together with the absolute redox level of the standard hydrogen electrode (SHE) by combining advanced electronic-structure calculations, ab initio molecular dynamics simulations, thermodynamic integration, and potential alignment at the water vacuum interface. The calculated SHE level lies at 4.56 eV below the vacuum level, close to the experimental reference of 4.44 eV inferred by Trasatti. The band edges are determined through a hybrid functional designed to reproduce the band gap achieved with highly accurate GW calculations. Our analysis yields IP = 9.7 eV and EA = 0.8 eV, consistent with both photoemission spectra of liquid water and thermodynamical data for the hydrated electron.

Absolute Energy Levels of Liquid Water

Ambrosio F;
2018-01-01

Abstract

We determine the ionization potential (IP) and the electron affinity (EA) of liquid water together with the absolute redox level of the standard hydrogen electrode (SHE) by combining advanced electronic-structure calculations, ab initio molecular dynamics simulations, thermodynamic integration, and potential alignment at the water vacuum interface. The calculated SHE level lies at 4.56 eV below the vacuum level, close to the experimental reference of 4.44 eV inferred by Trasatti. The band edges are determined through a hybrid functional designed to reproduce the band gap achieved with highly accurate GW calculations. Our analysis yields IP = 9.7 eV and EA = 0.8 eV, consistent with both photoemission spectra of liquid water and thermodynamical data for the hydrated electron.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11386/4783507
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