標題: Ab initio chemical kinetics for the ClOO+NO reaction: Effects of temperature and pressure on product branching formation
作者: Raghunath, P.
Lin, M. C.
應用化學系
Department of Applied Chemistry
公開日期: 1-一月-1970
摘要: "The kinetics and mechanism for the reaction of ClOO with NO have been investigated by ab initio molecular orbital theory calculations based on the CCSD(T)/6-311+G(3df)//PW91PW91/6-311+G(3df) method, employed to evaluate the energetics for the construction of potential energy surfaces and prediction of reaction rate constants. The results show that the reaction can produce two key low energy products ClNO + O-3(2) via the direct triplet abstraction path and ClO + NO2 via the association and decomposition mechanism through long-lived singlet pc-ClOONO and ClONO2 intermediates. The yield of ClNO + O-2 ((1)Delta) from any of the singlet intermediates was found to be negligible because of their high barriers and tight transition states. As both key reactions initially occur barrierlessly, their rate constants were evaluated with a canonical variational approach in our transition state theory and Rice-Ramspergen-Kassel-Marcus/master equation calculations. The rate constants for ClNO + O-3(2) and ClO + NO2 production from ClOO + NO can be given by 2.66 x 10(-16) T-1.91 exp(341/T) (200-700 K) and 1.48 x 10(-24) T-3.99 exp(1711/T) (200-600 K), respectively, independent of pressure below atmospheric pressure. The predicted total rate constant and the yields of ClNO and NO2 in the temperature range of 200-700 K at 10-760 Torr pressure are in close agreement with available experimental results. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4731883]"
URI: http://dx.doi.org/14315
http://hdl.handle.net/11536/16631
ISSN: 0021-9606
DOI: 14315
期刊: JOURNAL OF CHEMICAL PHYSICS
Volume: 137
Issue: 1
結束頁: 
顯示於類別:期刊論文


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  1. 000306142600028.pdf