Probing the electronic structure of bulk water at the molecular lengthscale with angle-resolved photoelectron spectroscopy

S. Gozem, R. Seidel, U. Hergenhahn, E. Lugovoy, B. Abel, B. Winter, A. I. Krylov, and S. E. Bradforth
J. Phys. Chem. Lett.  11, 5162 – 5170 (2020)

We report a combined experimental and theoretical study of bulk water photoionization. Angular distributions of photoelectrons produced by ionizing the valence band of neat water using X-ray radiation (250-750 eV) show a limited (~20 %) decrease in the beta anisotropy parameter compared to the gas phase, indicating that the electronic structure of the individual water molecules can be probed. By theoretical modeling using high-level electronic structure methods, we show that in a high-energy regime photoionization of bulk can be described as an incoherent superposition of individual molecules, in contrast to a low-energy regime where photoionization probes delocalized entangled states of molecular aggregates. The two regimes---low energy versus high energy---are defined as limiting cases where the de Broglie wavelength of the photoelectron is either larger or smaller than the intermolecular distance between water molecules, respectively.

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