title: Does the hydrated electron occupy a cavity?
abstract: Since the discovery of the hydrated electron more than 40 years ago, a general consensus has emerged that the hydrated electron occupies a quasispherical cavity in liquid water. We simulated the electronic structure and dynamics of the hydrated electron using a rigorously derived pseudopotential to treat the electron-water interaction, which incorporates attractive oxygen and repulsive hydrogen features that have not been included in previous pseudopotentials. What emerged was a hydrated electron that did not reside in a cavity but instead occupied a approximately 1-nanometer-diameter region of enhanced water density. Both the calculated ground-state absorption spectrum and the excited-state spectral dynamics after simulated photoexcitation of this noncavity hydrated electron showed excellent agreement with experiment. The relaxation pathway involves a rapid internal conversion followed by slow ground-state cooling, the opposite of the mechanism implicated by simulations in which the hydrated electron occupies a cavity.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA 90095-1569, USA. Ross.Larsen@nrel.gov
authors.forename: Ross E
authors.initials: RE
authors.lastname: Larsen
authors.forename: William J
authors.initials: WJ
authors.lastname: Glover
authors.forename: Benjamin J
authors.initials: BJ
authors.lastname: Schwartz