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Projeto de investigação
European Light Sources Activities - Synchrotrons and Free Electron Lasers
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On the electronic structure of methyl butyrate and methyl valerate
Publication . Śmiałek, Małgorzata A.; Duflot, Denis; Jones, Nykola C.; Hoffmann, Søren Vrønning; Zuin, Lucia; Macdonald, Michael; Mason, Nigel J.; Limão-Vieira, Paulo; DF – Departamento de Física; CeFITec – Centro de Física e Investigação Tecnológica; Springer
Abstract: We present novel results of the analysis of the electronic structure of two aliphatic esters: methyl butyrate and methyl valerate. High-resolution photoabsorption spectra were collected and analyzed over the energy range 4.0–10.8 eV and showed for both the molecules not only a clear band of the HOMO to LUMO transition, but also vibronic structure associated with the first Rydberg-valence transition. Photoelectron spectra recorded from 9 to over 28 eV revealed many ionization states with the first adiabatic ionization energies found to be 9.977 eV and 9.959 eV for methyl butyrate and methyl valerate, respectively. Ab initio calculations have been performed in order to help assign the photoabsorption and photoelectron features. Photolysis life times in the atmosphere were calculated revealing that photolysis is not competitive over hydroxyl radical scavenging in the process of removal of these esters from the atmosphere. Graphical abstract: [Figure not available: see fulltext.]
Cyclohexane Vibronic States
Publication . Bandeira, Edvaldo; Barbosa, Alessandra S.; Jones, Nykola C.; Hoffmann, Søren V.; Bettega, Márcio H. F.; Limão-Vieira, Paulo; DF – Departamento de Física; CeFITec – Centro de Física e Investigação Tecnológica; MDPI - Multidisciplinary Digital Publishing Institute
In this work, we provide results from a joint experimental and theoretical study of the vibronic features of cyclohexane (C6H12) in the photon energy range of 6.8–10.8 eV (182–115 nm). The high-resolution vacuum ultraviolet (VUV) photoabsorption measurements, together with quantum chemical calculations at the time-dependent density functional theory (TDDFT) level, have helped to assign the major electronic excitations to mixed valence–Rydberg and Rydberg transitions. The C6H12 photoabsorption spectrum shows fine structure which has been assigned to CH2 scissoring, ′3(1), CH2 rocking, ′4(1), C–C stretching, ′5(1), and CCC bending/CC torsion, ′24(), modes. Molecular structure calculations at the DFT level for the neutral and cationic electronic ground-states have shown the relevant structural changes that are operative in the higher-lying electronic states. Photolysis lifetimes in the Earth’s atmosphere are shown to be irrelevant, while the main atmospheric sink mechanism is the reaction with the •OH radical. Potential energy curves have been obtained at the TDDFT level of theory, showing the relevance of interchange character mainly involving the CH2 scissoring, ′3(1), and CH2 rocking, ′4(1), modes, while Jahn–Teller distortion yields weak vibronic coupling involving the non-totally symmetric CCC bending/CC torsion, ′24(), mode.
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Entidade financiadora
European Commission
Programa de financiamento
FP7
Número da atribuição
226716