@article{3ee39b18f046461f8b97b88b33cef36d,
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). (Graph Presented).",
keywords = "ABSORPTION CROSS-SECTIONS , GAUSSIAN-BASIS SETS , EXCITED-STATE , SPECTROSCOPY , SPECTRA , UV, BENZENE , PHOTOABSORPTION , TRANSITION , OXIDATION",
author = "C. Serralheiro and Denis Duflot and {Da Silva}, {F. Ferreira} and Hoffmann, {Soren Vronning} and Jones, {Nycola C.} and Mason, {Nigel J.} and Benilde Mendes and P. Lim{\~a}o-Vieira",
note = "info:eu-repo/grantAgreement/FCT/SFRH/SFRH%2FBSAB%2F105792%2F2014/PT# info:eu-repo/grantAgreement/FCT/3599-PPCDT/127212/PT# info:eu-repo/grantAgreement/FCT/5876/147412/PT# IF-FCT IF/00380/2014 F.F.d.S. and P.L.-V. acknowledge the Portuguese National Funding Agency FCT-MEC through researcher and sabbatical grants, IF-FCT IF/00380/2014 and SFRH/BSAB/105792/2014, as well as from the research grants PTDC/FIS-ATO/1832/2012 and UID/FIS/00068/2013. P.L.-V. acknowledges his visiting Professor position at The Open University, U.K., and together with NJ.M. the support from the British Council for the Portuguese-English joint collaboration. The authors wish to acknowledge the beam time at the ISA synchrotron at Aarhus University, Denmark. We also acknowledge the financial support provided by the European Commission through 13 Integrated Activity on Synchrotron and Free Electron Laser Science (IA-SFS), contract number RII3-CT-2004-506008, under the Research Infrastructure Action of the FP6 EC programme Structuring the European Research Area. D.D. acknowledges support from the CaPPA project (Chemical and Physical Properties of the Atmosphere), funded by the French National Research Agency (ANR) through the PIA (Programme d'Investissement d'Avenir) under Contract ANR-10-LABX-005. This work was performed using HPC resources from GENCI-CINES (Grant 2015-088620). The Centre de Ressources Informatiques (CRI) of the Universite of Lille also provided computing time.",
year = "2015",
month = aug,
day = "27",
doi = "10.1021/acs.jpca.5b05080",
language = "English",
volume = "119",
pages = "9059--9069",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "ACS - American Chemical Society",
number = "34",
}