Ab initio kinetics for decomposition/isomerization reactions of C 2H5O radicals

Zhen Feng Xu; Kun Xu; Ming-Chang Lin

doi:10.1002/cphc.200800719

Ab initio kinetics for decomposition/isomerization reactions of C ₂H₅O radicals

Zhen Feng Xu, Kun Xu, Ming-Chang Lin

Department of Applied Chemistry

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

43 Scopus citations

Abstract

The ground-state potential energy surface of the C₂H ₅O system, including the decomposition and isomerization of the ethoxy (CH₃CH₂O), 1-hydroxyethyl (CH₃CHOH), and 2-hydroxyethyl (CH₂CH₂OH) radicals, is computed by the modified Gaussian-2 (G2M) and CCSD(T)/6-311 +G(3df,2p) methods by using the geometries optimized at the B3LYP/6-311 + G(3df,2p) level of theory. These detailed reaction pathways are used to calculate the rate constants for the unimolecular isomerization and decomposition reactions of the three radicals by the microcanonical transition-state theory and Rice-Ramsperger-Kassel-Marcus (RRKM) theory in the temperature range of 200-3000 K at varying pressures of He and other diluents. The predicted rate constants are in reasonable agreement with the available experimental data, in addition, the predicted heats of formation of the three isomeric radicals are compared with available experimental and theoretical values.

Original language	English
Pages (from-to)	972-982
Number of pages	11
Journal	ChemPhysChem
Volume	10
Issue number	6
DOIs	https://doi.org/10.1002/cphc.200800719
State	Published - 14 Apr 2009

Keywords

Ab initio calculations
Isomerization
Kinetics
Radical reactions
Transition states

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title = "Ab initio kinetics for decomposition/isomerization reactions of C 2H5O radicals",

abstract = "The ground-state potential energy surface of the C2H 5O system, including the decomposition and isomerization of the ethoxy (CH3CH2O), 1-hydroxyethyl (CH3CHOH), and 2-hydroxyethyl (CH2CH2OH) radicals, is computed by the modified Gaussian-2 (G2M) and CCSD(T)/6-311 +G(3df,2p) methods by using the geometries optimized at the B3LYP/6-311 + G(3df,2p) level of theory. These detailed reaction pathways are used to calculate the rate constants for the unimolecular isomerization and decomposition reactions of the three radicals by the microcanonical transition-state theory and Rice-Ramsperger-Kassel-Marcus (RRKM) theory in the temperature range of 200-3000 K at varying pressures of He and other diluents. The predicted rate constants are in reasonable agreement with the available experimental data, in addition, the predicted heats of formation of the three isomeric radicals are compared with available experimental and theoretical values.",

keywords = "Ab initio calculations, Isomerization, Kinetics, Radical reactions, Transition states",

author = "Xu, {Zhen Feng} and Kun Xu and Ming-Chang Lin",

year = "2009",

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doi = "10.1002/cphc.200800719",

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T1 - Ab initio kinetics for decomposition/isomerization reactions of C 2H5O radicals

AU - Xu, Zhen Feng

AU - Xu, Kun

AU - Lin, Ming-Chang

PY - 2009/4/14

Y1 - 2009/4/14

N2 - The ground-state potential energy surface of the C2H 5O system, including the decomposition and isomerization of the ethoxy (CH3CH2O), 1-hydroxyethyl (CH3CHOH), and 2-hydroxyethyl (CH2CH2OH) radicals, is computed by the modified Gaussian-2 (G2M) and CCSD(T)/6-311 +G(3df,2p) methods by using the geometries optimized at the B3LYP/6-311 + G(3df,2p) level of theory. These detailed reaction pathways are used to calculate the rate constants for the unimolecular isomerization and decomposition reactions of the three radicals by the microcanonical transition-state theory and Rice-Ramsperger-Kassel-Marcus (RRKM) theory in the temperature range of 200-3000 K at varying pressures of He and other diluents. The predicted rate constants are in reasonable agreement with the available experimental data, in addition, the predicted heats of formation of the three isomeric radicals are compared with available experimental and theoretical values.

AB - The ground-state potential energy surface of the C2H 5O system, including the decomposition and isomerization of the ethoxy (CH3CH2O), 1-hydroxyethyl (CH3CHOH), and 2-hydroxyethyl (CH2CH2OH) radicals, is computed by the modified Gaussian-2 (G2M) and CCSD(T)/6-311 +G(3df,2p) methods by using the geometries optimized at the B3LYP/6-311 + G(3df,2p) level of theory. These detailed reaction pathways are used to calculate the rate constants for the unimolecular isomerization and decomposition reactions of the three radicals by the microcanonical transition-state theory and Rice-Ramsperger-Kassel-Marcus (RRKM) theory in the temperature range of 200-3000 K at varying pressures of He and other diluents. The predicted rate constants are in reasonable agreement with the available experimental data, in addition, the predicted heats of formation of the three isomeric radicals are compared with available experimental and theoretical values.

KW - Ab initio calculations

KW - Isomerization

KW - Kinetics

KW - Radical reactions

KW - Transition states

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DO - 10.1002/cphc.200800719

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SN - 1439-4235

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SP - 972

EP - 982

JO - ChemPhysChem

JF - ChemPhysChem

IS - 6

ER -

Ab initio kinetics for decomposition/isomerization reactions of C ₂H₅O radicals

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