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Evaluation of data for atmospheric models: Master Equation/RRKM calculations on the combination reaction ClO + NO 2 → ClONO 2 , a recurring issue
Author(s) -
Golden David M.
Publication year - 2009
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.20432
Subject(s) - chemistry , master equation , dissociation (chemistry) , thermodynamics , rrkm theory , reaction rate constant , bond dissociation energy , computational chemistry , kinetic energy , kinetics , quantum mechanics , physics , quantum
Experimental data for the title reaction have been modeled using Master Equation/RRKM methods based on the Multiwell suite of programs. The starting point for the exercise was the empirical fitting provided by the NASA and IUPAC data evaluation panels, which represent the data in the experimental pressure ranges rather well. Despite the availability of quite reliable parameters for these calculations (molecular vibrational frequencies and a value of the bond dissociation energy of ClONO 2 , DH 298 (ClONO 2 ) = 26.5 kcal mol −1 , corresponding to Δ H 0 0 = 25.35 kcal mol −1 at 0 K) and use of RRKM/Master Equation methods, fitting calculations to the reported data was anything but straightforward. Using these molecular parameters resulted in a discrepancy between the calculations and the database of rate constants of a factor of ca 4 at, or close to, the low‐pressure limit. © 2009 Wiley Periodicals, Inc. Int J Chem Kinet 41: 573–581, 2009