Linked Life Data

19242961

Source:http://linkedlifedata.com/resource/pubmed/id/19242961

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PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
14
pubmed:dateCreated
2009-8-31
pubmed:abstractText
A direct dynamics study was carried out for the multichannel reaction of CH(3)NHNH(2) with OH radical. Two stable Conformers (I, II) of CH(3)NHNH(2) are identified by the rotation of the -CH(3) group. For each conformer, five hydrogen-abstraction channels are found. The reaction mechanisms of product radicals (CH(3)NNH(2) and CH(3)NHNH) with OH radical are also investigated theoretically. The electronic structure information on the potential energy surface is obtained at the B3LYP/6-311G(d,p) level and the energetics along the reaction path is refined by the BMC-CCSD method. Hydrogen-bonded complexes are presented at both the reactant and product sides of the five channels, indicating that the reaction may proceed via an indirect mechanism. The influence of the basis set superposition error (BSSE) on the energies of all the complexes is discussed by means of the CBS-QB3 method. The rate constants of CH(3)NHNH(2) + OH are calculated using canonical variational transition-state theory with the small-curvature tunneling correction (CVT/SCT) in the temperature range of 200-1000 K. Slightly negative temperature dependence of rate constant is found in the temperature range from 200 to 345 K. The agreement between the theoretical and experimental results is good. It is shown that for Conformer I, hydrogen-abstraction from -NH- position is the primary pathway at low temperature; the hydrogen-abstraction from -NH(2) is a competitive pathway as the temperature increases. A similar case can be concluded for Conformer II. The overall rate constant is evaluated by considering the weight factors of each conformer from the Boltzmann distribution function, and the three-term Arrhenius expressions are fitted to be k(T) = 1.6 x 10(-24)T(4.03)exp (1411.5/T) cm(3) molecule(-1) s(-1) between 200-1000 K.
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Nov
pubmed:issn
1096-987X
pubmed:author
pubmed:copyrightInfo
2009 Wiley Periodicals, Inc.
pubmed:issnType
Electronic
pubmed:day
15
pubmed:volume
30
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
2194-204
pubmed:meshHeading
pubmed:year
2009
pubmed:articleTitle
CH3NHNH2 + OH reaction: mechanism and dynamics studies.
pubmed:affiliation
Institute of Theoretical Chemistry, State Key Laboratory of Theoretical and Computational Chemistry, Jilin University, Changchun 130023, People's Republic of China.
pubmed:publicationType
Journal Article