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Probing the Electronic Structure of Bulk Water at the Molecular Lengthscale with Angle-Resolved Photoelectron Spectroscopy

preprint
revised on 19.05.2020 and posted on 20.05.2020 by Samer Gozem, Robert Seidel, Uwe Hergenhahn, Evgeny Lugovoy, Bernd Abel, Bernd Winter, Anna I. Krylov, Stephen E. Bradforth
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 (<30 %) 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. The comparison of the measured and computed anisotropies reveals that at high kinetic energies the observed reduction in beta is mostly due to scattering rather than rehybridization due to solvation.

Funding

Spectroscopy and Dynamics at the Gas-Liquid Interface (SDynG-LI)

Deutsche Forschungsgemeinschaft

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Army Research Office grant W911NF-16-1-0232

National Science Foundation Grant CHE-130146

ACS Petroleum Research Fund 60837-DNI6

Deutsche Forschungsgemeinschaft Emmy Noether Young Investigator SE 2253/3-1

History

Email Address of Submitting Author

sgozem@gsu.edu

Institution

Georgia State University

Country

United States

ORCID For Submitting Author

0000-0002-6429-2853

Declaration of Conflict of Interest

A.I.K. is the President and a part-owner of Q-Chem, Inc.

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