title: Spectroscopic studies of the Ã-X̃ electronic spectrum of the β-hydroxyethylperoxy radical: structure and dynamics.
abstract: The jet-cooled Ã-X̃ near IR origin band spectra of the G(1)G(2)G(3) conformer of four β-hydroxyethylperoxy isotopologues, β-HEP (HOCH(2)CH(2)OO), β-DHEP (DOCH(2)CH(2)OO), β-HEP-d(4) (HOCD(2)CD(2)OO), and β-DHEP-d(4) (DOCD(2)CD(2)OO), have been recorded by a cavity ringdown spectrometer with a laser source linewidth of ~70 MHz. The spectra of all four isotopologues have been analyzed and successfully simulated with an evolutionary algorithm, confirming the cyclic structure of the molecule responsible for the observed origin band. The analysis also provides experimental Ã and X̃ state rotational constants and the orientation of the transition dipole moment in the inertial axis system; these quantities are compared to results from electronic structure calculations. The observed, broad linewidth (Δν > 2 GHz) is attributed to a shortened lifetime of the Ã state associated with dynamics along the reaction path for hydrogen transfer from the OH to OO group.
authors.affiliation: Laser Spectroscopy Facility, Department of Chemistry, The Ohio State University, 120 W. 18th Avenue, Columbus, Ohio 43210, USA. mingchen@chemistry.ohio-state.edu
authors.forename: Ming-Wei
authors.initials: MW
authors.lastname: Chen
authors.forename: Gabriel M P
authors.initials: GM
authors.lastname: Just
authors.forename: Terrance
authors.initials: T
authors.lastname: Codd
authors.forename: Terry A
authors.initials: TA
authors.lastname: Miller