title: The near-IR spectrum of NO(X̃(2)Π)-Ne detected through excitation into the Ã-state continuum: A joint experimental and theoretical study.
abstract: We present new measurements of the near IR spectrum of NO-Ne in the region of the first NO overtone transition. The IR absorption is detected by exciting the vibrationally excited complex to the Ã-state dissociation continuum. The resulting NO(A) fragment is subsequently ionized in the same laser pulse. Spectra of the two lowest bands, A and B, are recorded. The spectra are compared with calculated spectra based on bound states derived from a new set of high level ab initio potential energy surfaces (PESs). For the calculation, the PESs are used with either fixed NO intermolecular distance or averaged for the vibrational states of NO (X̃, v = 0 or 2). Spectra based on the new PESs reproduce the experimental spectra better than theoretical spectra based on the older PESs of M. H. Alexander et al. [J. Chem. Phys. 114, 5588 (2001)]. Especially, spectra based on the two different vibrationally averaged PESs show a marked improvement in comparison to the one based on the fixed internuclear NO-distance. A fitted set of spectroscopic constants allows to reproduce most of the finer details of the measured spectra. Monitoring simultaneously the NO fragment ion and the parent ion channels while scanning the UV wavelength through the NO A-X hot-band region enabled us to confirm the NO-Ne Ã-state dissociation limit of 44233 ± 5 cm(-1). These measurements also confirm the absence of a structured NO-Ne spectrum involving the Ã-state.
authors.affiliation: Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742-2021, USA.
authors.forename: J
authors.initials: J
authors.lastname: Kłos
authors.affiliation: Department of Physics and Astronomy, The University of Georgia, Athens, Georgia 30602-2451, USA.
authors.forename: S G
authors.initials: SG
authors.lastname: Zhang
authors.affiliation: Department of Physics and Astronomy, The University of Georgia, Athens, Georgia 30602-2451, USA.
authors.forename: H
authors.initials: H
authors.lastname: Meyer