Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 13, Issue 10, Pages 4494-4499Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c0cp02429e
Keywords
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Funding
- EPSRC [EP/E011187, EP/H003401]
- Leverhulme Trust
- Royal Society
- University of Warwick
- EPSRC [EP/H003401/1, EP/E011187/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/E011187/1, EP/H003401/1] Funding Source: researchfish
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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, CH(3) 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 pi sigma* states in the excited state dynamics of anisole as compared to the hydride counterpart (phenol), providing strong evidence to suggest that only CH(3) fragments eliminated with high kinetic energy are due to direct dissociation involving a (1)pi sigma* state. These measurements also suggest that indirect mechanisms such as statistical unimolecular decay could be contributing to the dynamics at much longer times.
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