Physics
Scientific paper
Jun 2011
adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2011mss..confema01c&link_type=abstract
"International Symposium On Molecular Spectroscopy, 66th Meeting, Held 20-24 June, 2011 at Ohio State University. http://molspec
Physics
Plenary
Scientific paper
The HOCO radical plays a crucial role as the intermediate in the reaction of OH + CO → H + CO_2, yet significant questions regarding its detailed dynamics remain. Through photoelectron and photoelectron-photofragment coincidence spectroscopy on cold HOCO^- and DOCO^- anions, we have gained new insight into the dynamics of the strongly bound HOCO system. Photoelectron spectra probing the lower region of the deep HOCO well reveal structured spectra that are supported by Franck-Condon simulations, and allow for the reassignment of the electron affinities for both cis- and trans- isomers. Higher in the well, where tunneling from HOCO to H + CO_2 becomes relevant, energy-resolved tunneling lifetimes are inverted to obtain a model barrier to formation of H + CO_2 that is consistent with experimental internal energy distributions. Tunneling lifetimes at the top of the barrier indicate that tunneling can play an important role in this elementary reaction.
Continetti Robert E.
Harding Michael E.
Johnson Christopher J.
Poad Berwyck L. J.
Stanton John F.
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