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Time-resolved velocity map imaging of methyl elimination from photoexcited anisole

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Hadden, David J., Williams, C. A. (Craig A.), Roberts, Gareth M. and Stavros, Vasilios G.. (2011) Time-resolved velocity map imaging of methyl elimination from photoexcited anisole. Physical Chemistry Chemical Physics, Vol.13 (No.10). pp. 4494-4499. ISSN 1463-9076

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Official URL: http://dx.doi.org/10.1039/C0CP02429E

Abstract

To date, H-atom elimination from heteroaromatic molecules following UV excitation has been extensively studied, with the focus on key biological molecules such as chromophores of DNA bases and amino acids. Extending these studies to look at elimination of other non-hydride photoproducts is essential in creating a more complete picture of the photochemistry of these biomolecules in the gas-phase. To this effect, CH3 elimination in anisole has been studied using time resolved velocity map imaging (TR-VMI) for the first time, providing both time and energy information on the dynamics following photoexcitation at 200 nm. The extra dimension of energy afforded by these measurements has enabled us to address the role of πσ* states in the excited state dynamics of anisole as compared to the hydride counterpart (phenol), providing strong evidence to suggest that only CH3 fragments eliminated with high kinetic energy are due to direct dissociation involving a 1πσ* state. These measurements also suggest that indirect mechanisms such as statistical unimolecular decay could be contributing to the dynamics at much longer times.

Item Type:	Journal Article
Subjects:	Q Science > QD Chemistry
Divisions:	Faculty of Science > Chemistry
Library of Congress Subject Headings (LCSH):	Heterocyclic compounds, Photochemistry, Methyl groups, Elimination reactions
Journal or Publication Title:	Physical Chemistry Chemical Physics
Publisher:	Royal Society of Chemistry
ISSN:	1463-9076
Date:	2011
Volume:	Vol.13
Number:	No.10
Page Range:	pp. 4494-4499
Identification Number:	10.1039/c0cp02429e
Status:	Peer Reviewed
Access rights to Published version:	Restricted or Subscription Access
Funder:	Royal Society (Great Britain), Engineering and Physical Sciences Research Council (EPSRC), Leverhulme Trust (LT), University of Warwick
Grant number:	EP/E011187 (EPSRC), EP/H003401 (EPSRC)
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URI:	http://wrap.warwick.ac.uk/id/eprint/37078