title: Unraveling the Complex Nature of the Hydrated Electron.
abstract: The structure of the hydrated electron, which is a key species in radiative processes in water, has remained elusive. The traditional cavity model has been questioned recently, but the newly suggested picture of an electron delocalized over a region of enhanced water density is controversial. Here, we present results from ab initio molecular dynamics simulations, where not only the excess electron but also the valence electrons of the surrounding water molecules are described quantum mechanically. Unlike in previous one-electron pseudopotential calculations, many-electron interactions are explicitly accounted for. The present approach allows for partitioning of the electron solvated in liquid water into contributions from an inner cavity, neighboring water molecules, and a diffuse tail. We demonstrate that all three of these contributions are sizable and, consequently, important, which underlines the complex nature of the hydrated electron and warns against oversimplified interpretations based on pseudopotential models.
authors: Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nám. 2, CZ-16610 Prague 6, Czech Republic.
authors: Frank
authors: F
authors: Uhlig
authors: Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nám. 2, CZ-16610 Prague 6, Czech Republic.
authors: Ondrej
authors: O
authors: Marsalek
authors: Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nám. 2, CZ-16610 Prague 6, Czech Republic.
authors: Pavel
authors: P
authors: Jungwirth
keywords: DFT; QM/MM; bulk; hydrated electron; ionization potentials; photoionization; water