Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 7, Issue 7, Pages 1507-1513Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/b502051d
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Recent advances in threshold photoelectron photoion coincidence (TPEPICO) make possible the analysis of several parallel and sequential dissociations of energy selected ions. The use of velocity focusing optics for the simultaneous collection of threshold and energetic electrons not only improves the resolution, but also permits subtraction of coincidences associated with hot'' electrons, thereby yielding TPEPICO data with no contamination from hot'' electrons. The data analysis takes into account the thermal energy distribution of the sample and uses statistical theory rate constants and energy partitioning in dissociation reactions to model the time of flight distributions and the breakdown diagram. Examples include CH(2)BrCl and P(C(2)H(5))(3). Of particular interest is the ability to extract error limits for rate constants and dissociation energies.
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