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Statistical modeling of sequential collision-induced dissociation thresholds.
MedLine Citation:
PMID:  17600415     Owner:  NLM     Status:  PubMed-not-MEDLINE    
Abstract/OtherAbstract:
Thermochemistry determined from careful analysis of the energy dependence of cross sections for collision-induced dissociation (CID) reactions has primarily come from the primary dissociation channel. Higher order dissociations generally have thresholds measured to be higher than the thermodynamic limit because of the unknown internal and kinetic energy distributions of the primary products. A model that utilizes statistical theories for energy-dependent unimolecular decomposition to estimate these energy distributions is proposed in this paper. This permits a straightforward modeling of the cross sections for both primary and secondary dissociation channels. The model developed here is used to analyze data for K+(NH3)x, x=2-5, complexes, chosen because the thermochemistry previously determined by threshold CID studies agrees well with values from theory and equilibrium high pressure mass spectrometry. The model is found to reproduce the cross sections with high fidelity and the threshold values for secondary processes are found to be in excellent agreement with literature values. Furthermore, relative thresholds for higher order dissociation processes appear to provide accurate thermodynamic information as well.
Authors:
P B Armentrout
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Publication Detail:
Type:  Journal Article    
Journal Detail:
Title:  The Journal of chemical physics     Volume:  126     ISSN:  0021-9606     ISO Abbreviation:  J Chem Phys     Publication Date:  2007 Jun 
Date Detail:
Created Date:  2007-06-29     Completed Date:  2007-08-21     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  0375360     Medline TA:  J Chem Phys     Country:  United States    
Other Details:
Languages:  eng     Pagination:  234302     Citation Subset:  -    
Affiliation:
Department of Chemistry, University of Utah, Salt Lake City, Utah 84112, USA. armentrout@chem.utah.edu
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