Controlling tunnelling in methane loss from acetone ions by deuteration.
Energetic acetone cations decay by methane or methyl radical loss. Although the methane-loss barrier to form the ketene cation is higher and the activation entropy is lower, it has a significant branching ratio at low energies thanks to quantum tunnelling. H-atom tunnelling can be selectively quenched and the methane-loss channel suppressed quantitatively by deuteration.
Molecular Dynamics Group, Paul Scherrer Institute, Villigen 5232, Switzerland. andras.boedi@psi.ch.
Andras
A
Bodi
Department of Chemistry, University of North Carolina, Chapel Hill, NC 27517, USA.
Tomas
T
Baer
Department of Chemistry, Hiram College, Hiram, OH 44234, USA.
Nancy K
NK
Wells
Department of Chemistry, Hiram College, Hiram, OH 44234, USA.
Daniel
D
Fakhoury
Department of Chemistry, Hiram College, Hiram, OH 44234, USA.
David
D
Klecyngier
Department of Chemistry, Hiram College, Hiram, OH 44234, USA.
James P
JP
Kercher