Ab initio study on the kinetics and mechanisms for O3 reactions with HO2 and HNO

Z. F. Xu; Ming-Chang Lin

doi:10.1016/j.cplett.2007.04.005

Ab initio study on the kinetics and mechanisms for O₃ reactions with HO₂ and HNO

Z. F. Xu, Ming-Chang Lin^*

^*Corresponding author for this work

Department of Applied Chemistry

Research output: Contribution to journal › Article › peer-review

40 Scopus citations

Abstract

The reactions of O₃ with HO₂ and HNO have been studied at the G2M//BH&HLYP/6-311++G(2df,2p) level of theory. Both reactions can occur by H-abstraction by O₃ and O-abstraction by HXO (X = O and N). The barriers for H-abstraction reactions were found to be lower and take place via the O₃⋯HXO van der Waals complexes with 2.5 kcal/mol stability for O₃⋯HO₂ and 1.3 kcal/mol for O₃⋯HNO. The rate constants predicted for the H-abstraction processes in the temperature range 150-1000 K given in cm³ molecule^-1 s^-1 can be represented by k₁ = 6.34 × 10^-30 T^5.37 exp(885/T) for the former and k₂ = 3.36 × 10^-24 T^3.59 exp(397/T) for the latter reaction, which is 3-5 times faster than the former between 150 and 500 K. The predicted rate constant and product branching ratio for the HO₂ + O₃ reaction are in close agreement with experimental data. The heat of formation of HO₃ was estimated to be 7.4 ± 1.0 kcal/mol, HO₃ was predicted to fragment with 0.7 kcal/mol barrier.

Original language	English
Pages (from-to)	12-18
Number of pages	7
Journal	Chemical Physics Letters
Volume	440
Issue number	1-3
DOIs	https://doi.org/10.1016/j.cplett.2007.04.005
State	Published - 25 May 2007

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title = "Ab initio study on the kinetics and mechanisms for O3 reactions with HO2 and HNO",

abstract = "The reactions of O3 with HO2 and HNO have been studied at the G2M//BH&HLYP/6-311++G(2df,2p) level of theory. Both reactions can occur by H-abstraction by O3 and O-abstraction by HXO (X = O and N). The barriers for H-abstraction reactions were found to be lower and take place via the O3⋯HXO van der Waals complexes with 2.5 kcal/mol stability for O3⋯HO2 and 1.3 kcal/mol for O3⋯HNO. The rate constants predicted for the H-abstraction processes in the temperature range 150-1000 K given in cm3 molecule-1 s-1 can be represented by k1 = 6.34 × 10-30 T5.37 exp(885/T) for the former and k2 = 3.36 × 10-24 T3.59 exp(397/T) for the latter reaction, which is 3-5 times faster than the former between 150 and 500 K. The predicted rate constant and product branching ratio for the HO2 + O3 reaction are in close agreement with experimental data. The heat of formation of HO3 was estimated to be 7.4 ± 1.0 kcal/mol, HO3 was predicted to fragment with 0.7 kcal/mol barrier.",

author = "Xu, {Z. F.} and Ming-Chang Lin",

year = "2007",

month = may,

day = "25",

doi = "10.1016/j.cplett.2007.04.005",

language = "English",

volume = "440",

pages = "12--18",

journal = "Chemical Physics Letters",

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T1 - Ab initio study on the kinetics and mechanisms for O3 reactions with HO2 and HNO

AU - Xu, Z. F.

AU - Lin, Ming-Chang

PY - 2007/5/25

Y1 - 2007/5/25

N2 - The reactions of O3 with HO2 and HNO have been studied at the G2M//BH&HLYP/6-311++G(2df,2p) level of theory. Both reactions can occur by H-abstraction by O3 and O-abstraction by HXO (X = O and N). The barriers for H-abstraction reactions were found to be lower and take place via the O3⋯HXO van der Waals complexes with 2.5 kcal/mol stability for O3⋯HO2 and 1.3 kcal/mol for O3⋯HNO. The rate constants predicted for the H-abstraction processes in the temperature range 150-1000 K given in cm3 molecule-1 s-1 can be represented by k1 = 6.34 × 10-30 T5.37 exp(885/T) for the former and k2 = 3.36 × 10-24 T3.59 exp(397/T) for the latter reaction, which is 3-5 times faster than the former between 150 and 500 K. The predicted rate constant and product branching ratio for the HO2 + O3 reaction are in close agreement with experimental data. The heat of formation of HO3 was estimated to be 7.4 ± 1.0 kcal/mol, HO3 was predicted to fragment with 0.7 kcal/mol barrier.

AB - The reactions of O3 with HO2 and HNO have been studied at the G2M//BH&HLYP/6-311++G(2df,2p) level of theory. Both reactions can occur by H-abstraction by O3 and O-abstraction by HXO (X = O and N). The barriers for H-abstraction reactions were found to be lower and take place via the O3⋯HXO van der Waals complexes with 2.5 kcal/mol stability for O3⋯HO2 and 1.3 kcal/mol for O3⋯HNO. The rate constants predicted for the H-abstraction processes in the temperature range 150-1000 K given in cm3 molecule-1 s-1 can be represented by k1 = 6.34 × 10-30 T5.37 exp(885/T) for the former and k2 = 3.36 × 10-24 T3.59 exp(397/T) for the latter reaction, which is 3-5 times faster than the former between 150 and 500 K. The predicted rate constant and product branching ratio for the HO2 + O3 reaction are in close agreement with experimental data. The heat of formation of HO3 was estimated to be 7.4 ± 1.0 kcal/mol, HO3 was predicted to fragment with 0.7 kcal/mol barrier.

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SP - 12

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JO - Chemical Physics Letters

JF - Chemical Physics Letters

IS - 1-3

ER -

Ab initio study on the kinetics and mechanisms for O₃ reactions with HO₂ and HNO

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