The Reaction Cl + NO2 ClONO and ClNO2
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- 作者：David M. Golden
- 刊名：Journal of Physical Chemistry A
- 出版年：2007
- 出版时间：July 26, 2007
- 年：2007
- 卷：111
- 期：29
- 页码：6772 - 6780
- 全文大小：211K
- 年卷期：v.111,no.29(July 26, 2007)
- ISSN：1520-5215
文摘
The extant data (see Int. J. Chem. Kinet. 1984, 16, 1311; Int. J. Chem. Kinet. 1988, 20, 811; and J. Phys.Chem. 1996, 100, 4019)1-3 for the reaction of Cl atoms with NO2 has been examined and compared withcalculated values using RRKM/ME methods through the use of the coded suite "Multiwell" (see Int. J. Chem.Kinet. 2001, 33, 232; MultiWell-2.08 Software; University of Michigan: Ann Arbor, MI, 2007; http://aoss.engin.umich.edu/multiwell/)4,5 and ab initio quantum calculations in the literature (see J. Phys. Chem.1994, 98, 111; J. Phys. Chem. A 2005, 109, 4736; and Chemphyschem 2004, 5, 1864).6-8 The data are in, orvery near, the low-pressure limit and therefore sensitive to the density of states of the excited ClONO andClNO2 molecules as well as collisional energy transfer, centrifugal effects, and anharmonicity corrections.The data were underpredicted by a factor of 2.6 using accepted prescriptions for centrifugal corrections,collision frequency, and ignoring anharmonicity. The data could be fit by either making all rotational degreesof freedom active or artificially increasing the collision frequency, or maybe some of each. This last couldalso be complemented or supplemented by a multiplicative factor ascribed to anharmonicity.