Conformational Landscape and Torsion–Rotation–Vibration Effects in the Two Conformers of Methyl Vinyl Ketone, a Major Oxidation Product of Isoprene
| Autor: | Olena Zakharenko, Juan Ramón Avilés Moreno, Thérèse R. Huet, Roman A. Motiyenko |
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| Přispěvatelé: | Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS) |
| Rok vydání: | 2017 |
| Předmět: |
[PHYS.PHYS.PHYS-AO-PH]Physics [physics]/Physics [physics]/Atmospheric and Oceanic Physics [physics.ao-ph]
010304 chemical physics Infrared spectroscopy 010402 general chemistry Photochemistry 7. Clean energy 01 natural sciences 0104 chemical sciences [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry chemistry.chemical_compound [PHYS.QPHY]Physics [physics]/Quantum Physics [quant-ph] chemistry 13. Climate action Excited state 0103 physical sciences Methyl vinyl ketone Alkane stereochemistry Physical chemistry [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph] Physical and Theoretical Chemistry Ground state Conformational isomerism ComputingMilieux_MISCELLANEOUS Isoprene Methyl group |
| Zdroj: | Journal of Physical Chemistry A Journal of Physical Chemistry A, American Chemical Society, 2017, 121 (34), pp.6420-6428. ⟨10.1021/acs.jpca.7b06360⟩ Journal of Physical Chemistry A, 2017, 121 (34), pp.6420-6428. ⟨10.1021/acs.jpca.7b06360⟩ |
| ISSN: | 1520-5215 1089-5639 |
| DOI: | 10.1021/acs.jpca.7b06360 |
| Popis: | Methyl vinyl ketone is the second major oxidation product of isoprene, and as such an important volatile organic compound present in the troposphere. In the present study, quantum chemical calculations coupled to high-resolution millimeter-wave spectroscopy have been performed to characterize the ground and first excited vibrational states of the two stable conformers. Equilibrium structures, internal rotation barriers, and relative energies have been calculated at the MP2 and M062X levels of theory. Experimental molecular parameters have been obtained that model the rotational and torsional structures, including splitting patterns due to the internal rotation of the methyl group. For the most stable antiperiplanar (s-trans) conformer, the set of parameters obtained for the ground state should be useful to further model IR spectra up to room temperature. By combining theoretical and experimental data, we obtained a relative energy value of 164 ± 30 cm–1 in the gas phase between the more stable antiperipla... |
| Databáze: | OpenAIRE |
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