title: Addition of water to Al5O4- determined by anion photoelectron spectroscopy and quantum chemical calculations.
abstract: The anion photoelectron spectra of Al5O4- and Al5O5H2- are presented and interpreted within the context of quantum chemical calculations on these species. Experimentally, the electron affinities of these two molecules are determined to be 3.50(5) eV and 3.10(10) eV for the bare and hydrated cluster, respectively. The spectra show at least three electronic transitions crowded into a 1 eV energy window. Calculations on Al5O4- predict a highly symmetric near-planar structure with a singlet ground state. The neutral structure calculated to be most structurally similar to the ground state structure of the anion is predicted to lie 0.15 eV above the ground state structure of the neutral. The lowest energy neutral isomer does not have significant Franck-Condon overlap with the ground state of the anion. Dissociative addition of water to Al5O4- is energetically favored over physisorption. The ground state structure for the Al5O4- +H(2)O product forms when water adds to the central Al atom in Al5O4- with -H migration to one of the neighboring O atoms. Again, the ground state structures for the anion and neutral are very different, and the PE spectrum represents transitions to a higher-lying neutral structure from the ground state anion structure.
authors.affiliation: Department of Chemistry, Indiana University, Bloomington, IN 47405-7102, USA.
authors.forename: Ujjal
authors.initials: U
authors.lastname: Das
authors.forename: Krishnan
authors.initials: K
authors.lastname: Raghavachari
authors.forename: Caroline Chick
authors.initials: CC
authors.lastname: Jarrold