Litcius/Paper detail

Tracking Cavity Formation in Electron Solvation: Insights from X-ray Spectroscopy and Theory

Arturo Sopena, Shuai Li, Kai Ming Li, Gilles Doumy, S. H. Southworth, Christopher Otolski, Richard D. Schaller, Yoshiaki Kumagai, Jan‐Erik Rubensson, M. Simon, Georgi L. Dakovski, Kristjan Kunnus, Joseph S. Robinson, Christina Y. Hampton, David J. Hoffman, J. D. Koralek, Zhi-Heng Loh, Robin Santra, Ludger Inhester, Linda Young

2024Journal of the American Chemical Society17 citationsDOIOpen Access PDF

Abstract

High Resolution Image Download MS PowerPoint Slide We present time-resolved X-ray absorption spectra of ionized liquid water and demonstrate that OH radicals, H 3 O + 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.

Topics & Concepts

SolvationSolvated electronChemistrySolvation shellIonizationElectronChemical physicsAtomic physicsIonAb initio quantum chemistry methodsSpectroscopyElectron spectroscopyElectron localization functionAbsorption spectroscopyImplicit solvationMolecular physicsPhysical chemistryMoleculeRadiolysisAqueous solutionPhysicsQuantum mechanicsOrganic chemistrySpectroscopy and Quantum Chemical StudiesElectrochemical Analysis and ApplicationsPhotochemistry and Electron Transfer Studies