Abstract
The role of tropylium ion (Tr +) versus benzylium ion (Bz +) formation by H loss from toluene radical cation (TOL +) was studied by time-resolved photoionization mass spectrometry, by ab initio calculations and by RRKM-QET. Tr + is not formed at its thermochemical threshold owing to the presence of a reverse activation energy for the reaction leading from the cycloheptatrien radical cation (CHT +) to Tr + + H. The critical energies required to form Bz + and Tr + from TOL + are very close, being 2.18 and 2.11 eV, respectively. The computational results are in excellent agreement with experiments regarding appearance energies, heats of formation and Tr +/Bz + abundance ratios as a function of energy.
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