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.
| Original language | English |
|---|---|
| Pages (from-to) | R7-R11 |
| Journal | International Journal of Mass Spectrometry and Ion Processes |
| Volume | 125 |
| Issue number | 1 |
| DOIs | |
| State | Published - 24 May 1993 |
Keywords
- Ab initio calculations
- Benzylium
- RRKM-QET
- Time-resolved photoionization mass spectrometry
- Toluene
- Tropylium
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