Abstract
Multireference configuration interaction (MRCI//6-31G**) ab initio calculations show that the barrier for hydrogen scrambling in the benzene radical cation is about 50 kcal mol−1. Once the internal energy is sufficient for a 1,2-hydrogen shift, the moving hydrogen can go to any position in the ring. The barrier for carbon scrambling via an isomerization to the fulvene structure is about 17 kcal mol−1 higher than that for hydrogen scrambling. Both of these values are far below the dissociation limit.
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van der Hartcor, W.J. Ab initio calculations on 1,2-hydrogen shifts in the benzene radical cation and on carbon scrambling via an isomerization to the fulvene structure. J Am Soc Mass Spectrom 6, 513–515 (1995). https://doi.org/10.1016/1044-0305(95)00202-O
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DOI: https://doi.org/10.1016/1044-0305(95)00202-O