title: From a localized H3O radical to a delocalized H3O+···e- solvent-separated pair by sequential hydration.
abstract: The impact of microhydration on the electronic structure and reactivity of the H(3)O moiety is investigated by ab initio calculations. In the gas phase, H(3)O is a radical with spin density localized on its hydrogen end, which is only kinetically stable and readily decomposes into a water molecule and a hydrogen atom. When solvated by a single water molecule, H(3)O preserves to a large extent its radical character, however, two water molecules are already capable to shift most of the spin density to the solvent. With three solvating water molecules this shift is practically completed and the system is best described as a solvent-separated pair of a hydronium cation and a hydrated electron. The electronic structure of this system and its proton transfer reactivity leading to formation of a hydrogen atom already resemble those of a proton-electron pair in bulk water.
authors.affiliation: Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic and Center for Biomolecules and Complex Molecular Systems, Flemingovo nám. 2, 16610 Prague 6, Czech Republic.
authors.forename: Frank
authors.initials: F
authors.lastname: Uhlig
authors.forename: Ondrej
authors.initials: O
authors.lastname: Marsalek
authors.forename: Pavel
authors.initials: P
authors.lastname: Jungwirth