title: On the nature and origin of dicationic, charge-separated species formed in liquid water on X-ray irradiation.
abstract: To understand the yield and patterns of damage in aqueous condensed matter, including biological systems, it is essential to identify the initial products subsequent to the interaction of high-energy radiation with liquid water. Until now, the observation of several fast reactions induced by energetic particles in water was not possible on their characteristic timescales. Therefore, some of the reaction intermediates involved, particularly those that require nuclear motion, were not considered when describing radiation chemistry. Here, through a combined experimental and theoretical study, we elucidate the ultrafast proton dynamics in the first few femtoseconds after X-ray core-level ionization of liquid water. We show through isotope analysis of the Auger spectra that proton-transfer dynamics occur on the same timescale as electron autoionization. Proton transfer leads to the formation of a Zundel-type intermediate [HO*···H···H2O](+), which further ionizes to form a so-far unnoticed type of dicationic charge-separated species with high internal energy. We call the process proton-transfer mediated charge separation.
authors.affiliation: Helmholtz-Zentrum Berlin für Materialien und Energie, and Berlin Electron Storage Ring Society for Synchrotron Radiation, 12489 Berlin, Germany.
authors.forename: Stephan
authors.initials: S
authors.lastname: Thürmer
authors.forename: Milan
authors.initials: M
authors.lastname: Ončák
authors.forename: Niklas
authors.initials: N
authors.lastname: Ottosson
authors.forename: Robert
authors.initials: R
authors.lastname: Seidel
authors.forename: Uwe
authors.initials: U
authors.lastname: Hergenhahn
authors.forename: Stephen E
authors.initials: SE
authors.lastname: Bradforth
authors.forename: Petr
authors.initials: P
authors.lastname: Slavíček
authors.forename: Bernd
authors.initials: B
authors.lastname: Winter
mesh_terms: D002413:Cations, Divalent / Q000737:chemistry*; D011522:Protons; D014867:Water / Q000737:chemistry*; D014965:X-Rays
chemical_list: D002413:Cations, Divalent; D011522:Protons; D014867:Water