It is well established that an isolated benzene radical anion is not electronically stable. In the present study, we experimentally show that electron attachment to benzene clusters leads to weak albeit unequivocal occurrence of a C6H6 - moiety. We propose here-based on electronic structure calculation-that this moiety actually corresponds to linear structures formed by the opening of the benzene ring via electron attachment. The cluster environment is essential in this process since it quenches the internal energy released upon ring opening, which in the gas phase leads to further dissociation of this anion.

Institut für Ionenphysik und Angewandte Physik Universität Innsbruck Technikerstr 25 A 6020 Innsbruck Austria

Institute of Organic Chemistry and Biochemistry Czech Academy of Sciences Flemingovo nám 2 166 10 Prague 6 Czech Republic

J Heyrovský Institute of Physical Chemistry Czech Academy of Sciences Dolejškova 2155 3 182 23 Prague Czech Republic

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