Probing the Threshold to H Atom Transfer Along a Hydrogen-Bonded Ammonia Wire
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- 5 December 2003
- journal article
- other
- Published by American Association for the Advancement of Science (AAAS) in Science
- Vol. 302 (5651) , 1736-1739
- https://doi.org/10.1126/science.1091708
Abstract
We characterized the entrance channel, reaction threshold, and mechanism of an excited-state H atom transfer reaction along a unidirectionally hydrogen-bonded “wire” –O–H···NH3···NH3···NH3···N. Excitation of supersonically cooled 7-hydroxyquinoline·(NH3)3 to its vibrationless S1 state produces no reaction, whereas excitation of ammonia-wire vibrations induces H atom transfer with a reaction threshold ≈ 200 wave numbers. Further translocation steps along the wire produce the S1 state 7-ketoquinoline·(NH3)3 tautomer. Ab initio calculations show that proton and electron movement along the wire are closely coupled. The rate-controlling S1 state barriers arise from crossings of a ππ* with a Rydberg-type πσ* state.Keywords
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