Source:http://linkedlifedata.com/resource/pubmed/id/15739193
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| Predicate | Object |
|---|---|
| rdf:type | |
| lifeskim:mentions | |
| pubmed:issue |
6
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| pubmed:dateCreated |
2005-3-10
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| pubmed:abstractText |
Several intermediates for the CH(3)SH + OH(*) --> CH(3)S(*) + H(2)O reaction were identified using MP2(full) 6-311+g(2df,p) ab initio calculations. An adduct, CH(3)S(H)OH(*), I, with electronic energy 13.63 kJ mol(-1) lower than the reactants, and a transition state, II(double dagger), located 5.14 kJ mol(-1) above I, are identified as the entrance channel for an addition-elimination reaction mechanism. After adding zero-point and thermal energies, DeltaH(r,298) ( degrees )(reactants --> I) = -4.85 kJ mol(-1) and DeltaH(298) (double dagger)(I --> II(double dagger)) = +0.10 kJ mol(-1), which indicates that the potential energy surface is broad and flat near the transition state. The calculated imaginary vibrational frequency of the transition state, 62i cm(-1), is also consistent with an addition-elimination mechanism. These calculations are consistent with experimental observations of the OH(*) + CH(3)SH reaction that favored an addition-elimination mechanism rather than direct hydrogen atom abstraction. An alternative reaction, CH(3)SH + OH(*) --> CH(3)SOH + H(*), with DeltaH(r,298) ( degrees ) = +56.94 kJ mol(-1) was also studied, leading to a determination of DeltaH(f,298) ( degrees )(CH(3)SOH) = -149.8 kJ mol(-1).
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| pubmed:language |
eng
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| pubmed:journal | |
| pubmed:status |
PubMed-not-MEDLINE
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| pubmed:month |
Apr
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| pubmed:issn |
0192-8651
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| pubmed:author | |
| pubmed:copyrightInfo |
(c) 2005 Wiley Periodicals, Inc.
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| pubmed:issnType |
Print
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| pubmed:day |
30
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| pubmed:volume |
26
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| pubmed:owner |
NLM
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| pubmed:authorsComplete |
Y
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| pubmed:pagination |
612-8
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| pubmed:year |
2005
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| pubmed:articleTitle |
The OH* + CH3SH reaction: support for an addition-elimination mechanism from ab initio calculations.
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| pubmed:affiliation |
Department of Chemistry, Mathematics and Physical Sciences, Saint Francis University, P.O. Box 600, Loretto, Pennsylvania 15940, USA. pmuino@francis.edu
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| pubmed:publicationType |
Journal Article
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