Issue 31, 2021

Accurate vertical ionization energy and work function determinations of liquid water and aqueous solutions


The absolute-scale electronic energetics of liquid water and aqueous solutions, both in the bulk and at associated interfaces, are the central determiners of water-based chemistry. However, such information is generally experimentally inaccessible. Here we demonstrate that a refined implementation of the liquid microjet photoelectron spectroscopy (PES) technique can be adopted to address this. Implementing concepts from condensed matter physics, we establish novel all-liquid-phase vacuum and equilibrated solution–metal-electrode Fermi level referencing procedures. This enables the precise and accurate determination of previously elusive water solvent and solute vertical ionization energies, VIEs. Notably, this includes quantification of solute-induced perturbations of water's electronic energetics and VIE definition on an absolute and universal chemical potential scale. Defining and applying these procedures over a broad range of ionization energies, we accurately and respectively determine the VIE and oxidative stability of liquid water as 11.33 ± 0.03 eV and 6.60 ± 0.08 eV with respect to its liquid-vacuum-interface potential and Fermi level. Combining our referencing schemes, we accurately determine the work function of liquid water as 4.73 ± 0.09 eV. Further, applying our novel approach to a pair of exemplary aqueous solutions, we extract absolute VIEs of aqueous iodide anions, reaffirm the robustness of liquid water's electronic structure to high bulk salt concentrations (2 M sodium iodide), and quantify reference-level dependent reductions of water's VIE and a 0.48 ± 0.13 eV contraction of the solution's work function upon partial hydration of a known surfactant (25 mM tetrabutylammonium iodide). Our combined experimental accomplishments mark a major advance in our ability to quantify electronic–structure interactions and chemical reactivity in liquid water, which now explicitly extends to the measurement of absolute-scale bulk and interfacial solution energetics, including those of relevance to aqueous electrochemical processes.

Graphical abstract: Accurate vertical ionization energy and work function determinations of liquid water and aqueous solutions

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Article information

Article type
Edge Article
04 Apr 2021
02 Jul 2021
First published
02 Jul 2021
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2021,12, 10558-10582

Accurate vertical ionization energy and work function determinations of liquid water and aqueous solutions

S. Thürmer, S. Malerz, F. Trinter, U. Hergenhahn, C. Lee, D. M. Neumark, G. Meijer, B. Winter and I. Wilkinson, Chem. Sci., 2021, 12, 10558 DOI: 10.1039/D1SC01908B

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