Valence and Rydberg excitations of 2-fluorotoluene in the 4.4–10.8 eV photoabsorption energy region

Funding Information: PASR acknowledges support from the Brazilian agency Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES). ASB and MHFB acknowledge support from the Brazilian agency Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq). PASR, ASB and MHFB also acknowledge Prof. Carlos de Carvalho for computational support at LFTC-DFis-UFPR and at LCPAD-UFPR. The authors wish to acknowledge the beam time at the ISA synchrotron, Aarhus University, Denmark. The research leading to this result has been supported by the project CALIPSOplus under the Grant Agreement 730872 from the EU Framework Programme for Research and Innovation HORIZON 2020. SK, AIL and PLV acknowledges the Portuguese National Funding Agency (FCT) through research grant CEFITEC (UIDB/00068/2020) . PLV also acknowledges his visiting professor position at Federal University of Paraná, Curitiba, Brazil. This contribution is also based upon work from the COST Action CA18212-Molecular Dynamics in the GAS phase (MD-GAS), supported by COST (European Cooperation in Science and Technology). Funding Information: PASR acknowledges support from the Brazilian agency Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES). ASB and MHFB acknowledge support from the Brazilian agency Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq). PASR, ASB and MHFB also acknowledge Prof. Carlos de Carvalho for computational support at LFTC-DFis-UFPR and at LCPAD-UFPR. The authors wish to acknowledge the beam time at the ISA synchrotron, Aarhus University, Denmark. The research leading to this result has been supported by the project CALIPSOplus under the Grant Agreement 730872 from the EU Framework Programme for Research and Innovation HORIZON 2020. SK, AIL and PLV acknowledges the Portuguese National Funding Agency (FCT) through research grant CEFITEC (UIDB/00068/2020). PLV also acknowledges his visiting professor position at Federal University of Paraná, Curitiba, Brazil. This contribution is also based upon work from the COST Action CA18212-Molecular Dynamics in the GAS phase (MD-GAS), supported by COST (European Cooperation in Science and Technology). Publisher Copyright: © 2023 The Author(s)The electronic state spectroscopy of 2-fluorotoluene in the gas phase has been investigated for the first time using high-resolution vacuum ultraviolet photoabsorption experiments in the 4.4–10.8 eV energy-range, with absolute cross-section measurements obtained. Additionally, we also present a novel set of ab initio calculations (vertical excitation energies and oscillator strengths) at two different levels of theory, equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) and time-dependent density functional theory (TD-DFT). These are used in the assignment of valence, mix valence-Rydberg and Rydberg transitions, with the associated vibronic series analysed. The measured absolute photoabsorption cross-sections have been used to calculate the photolysis lifetime of 2-fluorotoluene in the Earth's atmosphere.publishersversionpublishe

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