title: Theoretical and infrared spectroscopic investigation of the O(2) (-).benzene and O(4) (-).benzene complexes.
abstract: The infrared spectra of the O(2) (-).benzene and O(4) (-).benzene complexes are determined by means of Ar predissociation spectroscopy. Several transitions due to CH stretch fundamentals and various combination bands are observed in the 2700-3100 cm(-1) region. The experimental results are interpreted with the aid of electronic structure calculations. A comparison of the calculated and experimental spectra reveals that the spectrum of O(2) (-).benzene most likely arises from an isomer where the superoxide molecule binds preferentially to one CH group of benzene. In contrast, the spectrum of O(4) (-).benzene yields a CH pattern remarkably similar to that displayed by the C(2nu) X(-).benzene (X=halogen) complexes, consistent with a structure with two CH groups equally involved in the bonding. The lower energy vibrational fundamental transitions of the O(4) (-) anion are recovered with a slight redshift in the O(4) (-).benzene spectrum, establishing that this charge-delocalized dimer ion retains its identity upon complexation.
authors.affiliation: JILA, NIST, and Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309, USA.
authors.forename: Holger
authors.initials: H
authors.lastname: Schneider
authors.forename: J Mathias
authors.initials: JM
authors.lastname: Weber
authors.forename: Evgeniy M
authors.initials: EM
authors.lastname: Myshakin
authors.forename: Kenneth D
authors.initials: KD
authors.lastname: Jordan
authors.forename: Joseph
authors.initials: J
authors.lastname: Bopp
authors.forename: Tobias
authors.initials: T
authors.lastname: Herden
authors.forename: Mark A
authors.initials: MA
authors.lastname: Johnson