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An Ab initio determination of the rate constant for H 2 + CN → H + HCN
Author(s) -
Wagner Albert F.,
Bair Raymond A.
Publication year - 1986
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550180406
Subject(s) - chemistry , reaction rate constant , saddle point , ab initio , transition state theory , atmospheric temperature range , curvature , reaction rate , ab initio quantum chemistry methods , thermodynamics , computational chemistry , saddle , kinetics , molecule , physics , organic chemistry , geometry , quantum mechanics , catalysis , mathematics , mathematical optimization
The reactants, products, and saddle point for the reaction H 2 + CN → H + HCN have been studied by ab initio calculations. The computed structures, frequencies, and energetics are compared directly to available measurements and, indirectly, to experimental rateconstants. The theoretical rate constants used in the comparison are calculated with conventional transition state theory. By reduction of the computed reaction barrier to 4.1 kcal mol, −1 good agreement with experimental rate constants is obtained over a 3250‐K temperature range. This computed rate constant is well represented by the form 4.9 × 10 −18 T 2.45 e −1, 126/ T over the temperature range of 250 K–3500 K. Substantial reaction rate curvature is found due to low‐frequency bending modes at the saddle point. The results for this reaction are compared to other abstraction reactions involving H atom transfer to identify correlations between reaction exothermicity and both abstraction barriers and reaction rate curvature.