Ionization Energy of Liquid Water Revisited

The ionization energy of liquid water is one of its most fundamental properties, an important benchmark for first-principles electronic-structure calculations and a crucial reference in the growing field of liquid-phase photoelectron spectroscopy. Despite this significance, a consensus on its value appears to be missing in the literature. Therefore, we use a monochromatized high-harmonic light source to perform detailed measurements of the ionization energy of liquid water in the presence of a tunable bias voltage applied to the liquid jet. Our results suggest that this simple method is sufficient to simultaneously compensate the effects of the streaming potential and that of the vacuum-level offset between the liquid and the photoelectron spectrometer. Our measurements yield corrected values of the vertical and adiabatic ionization energies of the 1b₁ band of bulk liquid water of 11.67(15) and 10.12(15) eV, respectively. Our method is broadly applicable and is likely to result in corrections to the measured ionization energies of solvated species as well.