Excited state hydrogen transfer dynamics in substituted phenols and their complexes with ammonia: pi pi*-pi sigma* energy gap propensity and ortho-substitution effect
| Autor: | Pino, G. A., Oldani, A. N., Marceca, E., Fujii, M., Ishiuchi, Shun-ichi, Miyazaki, M., Broquier, M., Dedonder, C., Jouvet, C. |
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| Přispěvatelé: | Instituto de Investigaciones en Físico Química [Córdoba] (INFIQC), Consejo Nacional de Investigaciones Científicas y Técnicas [Buenos Aires] (CONICET)-Facultad de Ciencias Químicas [Córdoba], Universidad Nacional de Córdoba [Argentina]-Universidad Nacional de Córdoba [Argentina], Instituto de Química Física de los Materiales, Medio Ambiente y Energía [Buenos Aires] (INQUIMAE), Consejo Nacional de Investigaciones Científicas y Técnicas [Buenos Aires] (CONICET)-Facultad de Ciencias Exactas y Naturales [Buenos Aires] (FCEyN), Universidad de Buenos Aires [Buenos Aires] (UBA)-Universidad de Buenos Aires [Buenos Aires] (UBA), Chemical Resources Laboratory and Integrated Research Institute, Tokyo Institute of Technology [Tokyo] (TITECH), Institut des Sciences Moléculaires d'Orsay (ISMO), Centre National de la Recherche Scientifique (CNRS)-Université Paris-Sud - Paris 11 (UP11), Centre Laser de l'Université Paris Sud (CLUPS), Université Paris-Sud - Paris 11 (UP11) |
| Jazyk: | angličtina |
| Rok vydání: | 2010 |
| Předmět: |
rotational isomers
General Physics and Astronomy h-atom elimination 010402 general chemistry 01 natural sciences ultraviolet photolysis 0103 physical sciences Molecule ion dip spectroscopy Physical and Theoretical Chemistry Spectroscopy photofragment translational spectroscopy 010304 chemical physics Chemistry Photodissociation Intermolecular force photodissociation dynamics Conical intersection phenol/ammonia clusters Internal conversion (chemistry) 0104 chemical sciences 3. Good health proton-transfer [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry Vibronic coupling molecular-orbital calculations Excited state near-uv photolysis Atomic physics |
| Zdroj: | Journal of Chemical Physics Journal of Chemical Physics, American Institute of Physics, 2010, 133 (12), pp.124313. ⟨10.1063/1.3480396⟩ |
| ISSN: | 0021-9606 1089-7690 |
| DOI: | 10.1063/1.3480396⟩ |
| Popis: | International audience; Lifetimes of the first electronic excited state (S(1)) of fluorine and methyl (o-, m-, and p-) substituted phenols and their complexes with one ammonia molecule have been measured for the 0(0) transition and for the intermolecular stretching σ(1) levels in complexes using picosecond pump-probe spectroscopy. Excitation energies to the S(1) (ππ*) and S(2) (πσ*) states are obtained by quantum chemical calculations at the MP2 and CC2 level using the aug-cc-pVDZ basis set for the ground-state and the S(1) optimized geometries. The observed lifetimes and the energy gaps between the ππ* and πσ* states show a good correlation, the lifetime being shorter for a smaller energy gap. This propensity suggests that the major dynamics in the excited state concerns an excited state hydrogen detachment or transfer (ESHD/T) promoted directly by a S(1)/S(2) conical intersection, rather than via internal conversion to the ground-state. A specific shortening of lifetime is found in the o-fluorophenol-ammonia complex and explained in terms of the vibronic coupling between the ππ* and πσ* states occurring through the out-of-plane distortion of the C-F bond. |
| Databáze: | OpenAIRE |
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