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• W2020271352 abstract "Quasiequilibrium theory has been applied to the parent ion fragmentation of benzene. Assuming uniform excitation energy transfer in the fragmentation threshold region and applicability of the step-function photoionization threshold law, it is possible to calculate fragment photoionization threshold curves in good agreement with experiment. It is concluded that the unimolecular decomposition occurs via two independent pairs of competing reactions. One pair of reactions leads to the formation of C6H5+ and C6H4+, and involves the benzene ion ground state. The other pair of reactions, leading to C4H4+ and C3H3+ involves the first excited state of C6H6+ lying 2.25 eV above the ground state, or an open chain isomer having a similar heat of formation. At threshold the C6H5+ ion has a phenyl ion structure, the C3H3+ ion a cyclopropenyl ion structure and the C4H4+ ion may have a cyclobutene ion structure. A heat of formation of ∼100 kcal/mol is derived for the benzyne molecule, in good agreement with semi-empirical estimates. Kinetic shift effects on the fragmentation thresholds are found to be important. Some difficulties are encountered in the comparison of relative abundances of parent ion metastable transitions to the relative abundances of the daughter ions near threshold. The calculated energy dependence of the unimolecular rate of formation of C4H4+ ion is in good agreement with experiment. However, the weak energy dependence of the rate of formation of C6H5+ found experimentally cannot be explained. Suggestions for further work are outlined." @default.
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• W2020271352 date "1973-06-01" @default.
• W2020271352 modified "2023-09-27" @default.
• W2020271352 title "Interpretation of photoionization thresholds:quasiequilibrium theory and the fragmentation of benzene" @default.
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• W2020271352 doi "https://doi.org/10.1016/0020-7381(73)80012-9" @default.
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