Gas-Phase Retro-Diels-Alder Reactions of Cyclohexene, 1-Methylcyclohexene, and 4-Methylcyclohexene following Photoexcitation at 193 nm: A Velocity-Map Imaging Study

The Journal of Physical Chemistry. a
Sara H GardinerClaire Vallance

Abstract

We present the results of a velocity-map imaging study into the retro-Diels-Alder (RDA) reactions of cyclohexene, 1-methylcyclohexene, and 4-methylcyclohexene following photoexcitation at 193 nm. Universal detection of all neutral fragments via vacuum-ultraviolet photoionization at 118 nm allows imaging of both RDA fragments in all cases. Fragment kinetic energy distributions reveal contributions from both dissociative ionization and retro-Diels-Alder reaction of the respective parent molecules, yielding reaction products with a high degree of internal excitation. Together with the observed isotropic product angular distributions, this is consistent with a mechanism in which the RDA reaction occurs from high vibrational levels of the electronic ground state following internal conversion from a higher-lying state initially populated in the photoexcitation process, as predicted by frontier molecular orbital theory. Velocity-map images and total translational energy distributions for the RDA products of 1-methylcyclohexene and 4-methylcyclohexene are very similar to those for unsubstituted cyclohexene, indicating that methyl substitution either adjacent to or far from the double bond has little effect on the dynamics of the RDA pr...Continue Reading

References

Jul 19, 2001·Journal of the American Chemical Society·W FussS A Trushin
Oct 27, 2004·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Hans LischkaMichal Dallos
Jul 27, 2011·The Journal of Chemical Physics·W Scott HopkinsClaire Vallance
Jul 4, 2012·Proceedings of the National Academy of Sciences of the United States of America·Kersey BlackKendall N Houk
Jun 2, 2015·Physical Chemistry Chemical Physics : PCCP·Mohamad M Ahmad, Munirah M Al-Quaimi

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Citations

May 18, 2019·Chemical Communications : Chem Comm·Claire Vallance
Aug 4, 2021·The Journal of Chemical Physics·Shuai LiMarcos Dantus

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