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Influence of Alkoxy Groups on the Photoinduced Dynamics of Organic Molecules Exemplified on Alkyl Vinyl Ethers
Stockholm University, Faculty of Science, Department of Physics.
Stockholm University, Faculty of Science, Department of Physics.
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Number of Authors: 7
2015 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 119, no 45, 11105-11112 p.Article in journal (Refereed) Published
Abstract [en]

A series of different alkyl vinyl ethers is investigated to decipher the possible reaction channels upon photoexcitation to the pi 3s-Rydberg and the pi pi*-valence state at 200 nm using time-resolved photoelectron spectroscopy and on-the-fly time-dependent density functional theory dynamics simulations. The results indicate two possible relaxation pathways: (1) a radiationless decay through the pi pi*-state back to the ground state via torsion of the C=C double bond, in accordance with the dynamics found in ethylene; and (2) a fast dissociation of the C-O bond between the alkyl and the vinoxy group in the pi sigma*-state. The latter state can be accessed only after excitation to the pi 3s-Rydberg state (quantum yield of similar to 50% according to the dynamics simulations). Additionally, the excited state barrier leading to formation of a vinyl radical was found to be too high to be crossed. These results indicate that the dynamics of ethers crucially depend on the excitation wavelength and that the pi sigma*-state constitutes an important competitive reaction channel that leads to dissociation of the molecules.

Place, publisher, year, edition, pages
2015. Vol. 119, no 45, 11105-11112 p.
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Chemical Sciences Physical Sciences
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URN: urn:nbn:se:su:diva-124174DOI: 10.1021/acs.jpca.5b06592ISI: 000364435300008PubMedID: 26490385OAI: oai:DiVA.org:su-124174DiVA: diva2:885982
Available from: 2015-12-21 Created: 2015-12-15 Last updated: 2015-12-21Bibliographically approved

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Schalk, OliverGeng, TingThomas, Richard D.Hansson, Tony
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