A combined theoretical and experimental study of the dissociation of benzene cation

Article abstract of DOI:10.1063/1.464670

Variational Rice-Ramsperger-Kassel-Marcus (RRKM) theory calculations of the energy and angular momentum dependence of the rate constant for the dissociation of C6H6⁺ into C6H5⁺ and an H atom are reported.In these variational calculations both the definition of the reaction coordinate and its value are independently optimized.A model potential-energy surface which interpolates between a Morse potential at short range and an ion-induced dipole potential at long range is employed in these variational calculations.The fully optimized variational results indicate that the transition state for this dissociation occurs at separation distances of about 3-4 Angstroem and that the available phase space in the transition state is typically a factor of 5 lower than the predicted by phase space theory.Experimental measurements were made of the time-resolved product ion intensity resulting from the laser-induced dissociation of a thermal (ca. 375 K) distribution of benzene cations.An ion cyclotron resonance trap was used over a range of photolysis wavelengths from 266 to 285 nm.The observed time dependences in the product ion signals are a result of both dissociative and radiative relaxation processes with a deconvolution procedure yielding estimated dissociation rate constants. Satisfactory agreement between the theoretical and experimental results, including the previous experimental results of Neusser and co-workers is obtained for an assumed dissociation energy of 3.88 eV to the lowest triplet state of C6H5⁺.

Full text of DOI:10.1063/1.464670

A combined theoretical and experimental study of the dissociation of benzene
cation
Stephen J. Klippenstein, James D. Faulk, and Robert C. Dunbar
Citation: The Journal of Chemical Physics 98, 243 (1993); doi: 10.1063/1.464670
View online: http://dx.doi.org/10.1063/1.464670
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/98/1?ver=pdfcov
Published by the AIP Publishing
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