title: High-resolution photoabsorption spectrum of jet-cooled propyne.
abstract: The absolute photoabsorption cross section of propyne was recorded between 62,000 and 88,000 cm(-1) by using the vacuum-ultraviolet, Fourier-transform spectrometer at the Synchrotron Soleil. This cross section spans the region including the lowest Rydberg bands and extends above the Franck-Condon envelope for ionization to the ground electronic state of the propyne cation, X̃(+). Room-temperature spectra were recorded in a flowing cell at 0.9 cm(-1) resolution, and jet-cooled spectra were recorded at 1.8 cm(-1) resolution and a rotational temperature of ~100 K. The reduced widths of the rotational band envelopes in the latter spectra reveal new structure and simplify a number of assignments. Although nf Rydberg series have not been assigned previously in the photoabsorption spectrum of propyne, arguments are presented for their potential importance, and the assignment of one nf series is proposed. As expected from previous photoelectron spectra, Rydberg series are also observed above the adiabatic ionization threshold that converge to the v3(+) = 1 and 2 levels of the C≡C stretching vibration.
authors.affiliation: Laboratorium für Physikalische Chemie, ETH Zürich, 8093 Zürich, Switzerland.
authors.forename: U
authors.initials: U
authors.lastname: Jacovella
authors.affiliation: STFC, Daresbury Laboratory, Daresbury, Warrington, Cheshire WA4 4AD, United Kingdom.
authors.forename: D M P
authors.initials: DM
authors.lastname: Holland
authors.affiliation: Institut des Sciences Moléculaires d'Orsay, UMR 8214, CNRS & Univ. Paris-Sud, F-91405 Orsay, France.
authors.forename: S
authors.initials: S
authors.lastname: Boyé-Péronne
authors.affiliation: Synchrotron Soleil, L'Orme des Merisiers, F-91192 Gif-sur-Yvette, France.
authors.forename: D
authors.initials: D
authors.lastname: Joyeux
authors.affiliation: Synchrotron Soleil, L'Orme des Merisiers, F-91192 Gif-sur-Yvette, France.
authors.forename: L E
authors.initials: LE
authors.lastname: Archer
authors.affiliation: Synchrotron Soleil, L'Orme des Merisiers, F-91192 Gif-sur-Yvette, France.
authors.forename: N
authors.initials: N
authors.lastname: de Oliveira
authors.affiliation: Synchrotron Soleil, L'Orme des Merisiers, F-91192 Gif-sur-Yvette, France.
authors.forename: L
authors.initials: L
authors.lastname: Nahon
authors.affiliation: Department of Chemistry, Texas A&M University, College Station, Texas 77843, USA.
authors.forename: R R
authors.initials: RR
authors.lastname: Lucchese
authors.affiliation: Argonne National Laboratory, Argonne, Illinois 60439, USA.
authors.forename: Hong
authors.initials: H
authors.lastname: Xu
authors.affiliation: Argonne National Laboratory, Argonne, Illinois 60439, USA.
authors.forename: S T
authors.initials: ST
authors.lastname: Pratt