Barrier height titration by tunable photoionization combined with chemical monitoring: Unimolecular keto/enol tautomerization of the acetamide cation radical

D. Schröder (1) , J. Loos (1) , R. Thissen (2) , O. Dutuit (2) , Philippe Mourgues (3) , Henri E. Audier (3) , C. Lifshitz (4) , H. Schwarz (1)

1 Institut für Chemie
2 LCPO - Laboratoire de Chimie Physique D'Orsay
3 DCMR - Laboratoire des mécanismes réactionnels
4 Department of Physical Chemistry

By using a new "titration" technique, the activation barrier for the strictly unimolecular 1,3-hydrogen migration 1*+ ? 2*+ has been determined (0.74 ± 0.06 eV; see reaction profile). With this technique the internal energy of 1*+ is controlled by variable photoionization of acetamide and the chemistry of the resulting enol ion 2*+ is then probed by structure- specific ion - molecule reactions.

D. Schröder, J. Loos, R. Thissen, O. Dutuit, Philippe Mourgues, et al.. Barrier height titration by tunable photoionization combined with chemical monitoring: Unimolecular keto/enol tautomerization of the acetamide cation radical. Angewandte Chemie International Edition, 2002, 41 (15), pp.2748-2751. ⟨10.1002/1521-3773(20020802)41:15<2748::AID-ANIE2748>3.0.CO;2-V⟩. ⟨hal-00918088⟩