Tracking cavity formation in electron solvation: insights from x‑ray spectroscopy and theory

We present time-resolved X-ray absorption spectra of ionized liquid water and demonstrate that OH radicals, H3O+ ions, and solvated electrons all leave distinct X-ray-spectroscopic signatures. Particularly, this allows us to characterize the electron solvation process through a tool that focuses on...

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Bibliographic Details
Main Authors: Moros, Arturo Sopena, Li, Shuai, Li, Kai, Doumy, Gilles, Southworth, Stephen H., Otolski, Christopher, Schaller, Richard D., Kumagai, Yoshiaki, Rubensson, Jan-Erik, Simon, Marc, Dakovski, Georgi, Kunnus, Kristjan, Robinson, Joseph S., Hampton, Christina Y., Hoffman, David J., Koralek, Jake, Loh, Zhi-Heng, Santra, Robin, Inhester, Ludger, Young, Linda
Other Authors: School of Chemistry, Chemical Engineering and Biotechnology
Format: Journal Article
Language:English
Published: 2024
Subjects:
Online Access:https://hdl.handle.net/10356/179940
Description
Summary:We present time-resolved X-ray absorption spectra of ionized liquid water and demonstrate that OH radicals, H3O+ ions, and solvated electrons all leave distinct X-ray-spectroscopic signatures. Particularly, this allows us to characterize the electron solvation process through a tool that focuses on the electronic response of oxygen atoms in the immediate vicinity of a solvated electron. Our experimental results, supported by ab initio calculations, confirm the formation of a cavity in which the solvated electron is trapped. We show that the solvation dynamics are governed by the magnitude of the random structural fluctuations present in water. As a consequence, the solvation time is highly sensitive to temperature and to the specific way the electron is injected into water.