title: Toluene Valence and Rydberg Excitations as Studied by ab initio Calculations and Vacuum Ultraviolet (VUV) Synchrotron Radiation.
abstract: The electronic spectroscopy of isolated toluene in the gas phase has been investigated using high-resolution photoabsorption spectroscopy in the 4.0-10.8 eV energy range, with absolute cross-section measurements derived. We present the first set of ab initio calculations (vertical energies and oscillator strengths), which we use in the assignment of valence and Rydberg transitions of the toluene molecule. The spectrum reveals several new features not previously reported in the literature, with particular relevance to 7.989 and 8.958 eV, which are here tentatively assigned to the π*(17a') ← σ(15a') and 1π*(10a″) ← 1π(14a') transitions, respectively. The measured absolute photoabsorption cross sections have been used to calculate the photolysis lifetime of toluene in the upper stratosphere (20-50 km).
authors.affiliation: Laboratório de Colisões Atómicas e Moleculares, CEFITEC, Departamento de Física, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa , 2829-516 Caparica, Portugal.|Centro de Engenharia Mecânica e Sustentabilidade de Recursos (MEtRICs), Departamento de Ciências e Tecnologia da Biomassa, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa , 2829-516 Caparica, Portugal.
authors.forename: C
authors.initials: C
authors.lastname: Serralheiro
authors.affiliation: Laboratoire de Physique des Lasers, Atomes et Molécules (PhLAM), UMR CNRS 8523, Université de Lille , F-59655 Villeneuve d'Ascq Cedex, France.
authors.forename: D
authors.initials: D
authors.lastname: Duflot
authors.affiliation: Laboratório de Colisões Atómicas e Moleculares, CEFITEC, Departamento de Física, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa , 2829-516 Caparica, Portugal.
authors.forename: F Ferreira
authors.initials: FF
authors.lastname: da Silva
authors.affiliation: ISA, Department of Physics and Astronomy, Aarhus University , Ny Munkegade 120, DK-8000, Aarhus C, Denmark.
authors.forename: S V
authors.initials: SV
authors.lastname: Hoffmann
authors.affiliation: ISA, Department of Physics and Astronomy, Aarhus University , Ny Munkegade 120, DK-8000, Aarhus C, Denmark.
authors.forename: N C
authors.initials: NC
authors.lastname: Jones
authors.affiliation: Department of Physical Sciences, The Open University , Walton Hall, Milton Keynes, MK7 6AA, U.K.
authors.forename: N J
authors.initials: NJ
authors.lastname: Mason
authors.affiliation: Centro de Engenharia Mecânica e Sustentabilidade de Recursos (MEtRICs), Departamento de Ciências e Tecnologia da Biomassa, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa , 2829-516 Caparica, Portugal.
authors.forename: B
authors.initials: B
authors.lastname: Mendes
authors.affiliation: Laboratório de Colisões Atómicas e Moleculares, CEFITEC, Departamento de Física, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa , 2829-516 Caparica, Portugal.|Department of Physical Sciences, The Open University , Walton Hall, Milton Keynes, MK7 6AA, U.K.
authors.forename: P
authors.initials: P
authors.lastname: Limão-Vieira
mesh_terms: D065638:Absorption, Radiation; D001272:Atmosphere; D004583:Electrons; D010782:Photolysis; D011789:Quantum Theory; D013056:Spectrophotometry, Ultraviolet; D017356:Synchrotrons; D014050:Toluene / Q000737:chemistry*; D014466:Ultraviolet Rays; D014618:Vacuum
chemical_list: D014050:Toluene