title: Vibrationally induced charge transfer in a bimolecular model complex in vacuo.
abstract: We report vibrationally induced charge transfer from nitromethane anion to methyliodide in a molecular complex. Excitation of a CH stretching vibrational transition in either of the molecular constituents results in dissociative electron transfer to the CH3I molecule, resulting in I(-) product anions. Solvation of the pre-reactive complex with more than two Ar atoms leads to complete quenching of the reaction and can be used to estimate the barrier for this reaction. We discuss the results in the framework of electronic structure calculations and compare the intra-complex electron transfer with vibrationally mediated electron emission in bare nitromethane anion.
authors.affiliation: JILA and Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309, USA.
authors.forename: Benjamin J
authors.initials: BJ
authors.lastname: Knurr
authors.forename: Anne B
authors.initials: AB
authors.lastname: McCoy
authors.forename: J Mathias
authors.initials: JM
authors.lastname: Weber