Journal ArticleDOI
Reaction of Ethylene with Hydroxyl Radicals: A Theoretical Study†
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Ab initio calculations of portions of the C2H5O potential energy surface critical to the title reaction are presented and it is found that a significant fraction of the total rate coefficient is due to the formation of vinyl alcohol above this temperature.Abstract:
Ab initio calculations of portions of the C2H5O potential energy surface critical to the title reaction are presented. These calculations are based on QCISD geometries and frequencies and RQCISD(T) energies extrapolated to the complete-basis-set limit. Rate coefficients for the reaction of C2H4 with OH are calculated using this surface and the two transition-state model of Greenwald and co-workers [J. Phys. Chem. A 2005, 109, 6031] for the association of OH with C2H4. The present calculations reproduce most of the experimental data, including the temperature and pressure dependence of the rate coefficients, with only a small (0.4 kcal/mol) adjustment to the energy barrier for direct hydrogen abstraction. We confirm the importance of this channel above 800 K and find that a significant fraction of the total rate coefficient (∼10%) is due to the formation of vinyl alcohol above this temperature. Calculations of the vinyl alcohol channel are consistent with the recent observation of this molecule in low-pres...read more
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A Hierarchical and Comparative Kinetic Modeling Study of C1 − C2 Hydrocarbon and Oxygenated Fuels
TL;DR: In this paper, a detailed chemical kinetic mechanism has been developed to describe the oxidation of small hydrocarbon and oxygenated hydrocarbon species, such as formaldehyde, methanol, acetaldehyde, and ethanol.
Journal ArticleDOI
Alcohol combustion chemistry
TL;DR: A detailed overview of recent results on alcohol combustion can be found in this paper, with a particular emphasis on butanols and other linear and branched members of the alcohol family, from methanol to hexanols.
Journal ArticleDOI
Kinetics of elementary reactions in low-temperature autoignition chemistry
TL;DR: In this article, a review concentrates on recent developments in the study of elementary reaction kinetics in relation to the modeling and prediction of low-temperature combustion and autoignition, with specific focus placed on the critical alkylperoxy and hydroperoxyalkyl reactions.
Journal ArticleDOI
Theoretical studies of atmospheric reaction mechanisms in the troposphere
TL;DR: This review describes recent results from quantum chemical and theoretical kinetic studies of relevance to atmospheric chemistry and examines the VOC oxidation initiation channels by OH, O(3), NO(3) and Cl, followed by the reactions of the alkyl, alkoxy,Alkylperoxy and Criegee intermediates active in the subsequent oxidation steps.
Journal ArticleDOI
The role of NNH in NO formation and control
TL;DR: In this paper, the NNH−O, NNH+O, NH+O2, and NH2−O2 potential energy surfaces were investigated for thermal de NOx and NNH mechanism for NO formation.
References
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Journal ArticleDOI
Density-functional exchange-energy approximation with correct asymptotic behavior.
TL;DR: This work reports a gradient-corrected exchange-energy functional, containing only one parameter, that fits the exact Hartree-Fock exchange energies of a wide variety of atomic systems with remarkable accuracy, surpassing the performance of previous functionals containing two parameters or more.
Journal ArticleDOI
Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
TL;DR: In this article, the unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio using DFT, MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set.
Book
The Properties of Gases and Liquids
TL;DR: In this article, the authors estimate physical properties of pure components and Mixtures and show that the properties of these components and mixtures are similar to those of ideal gases and liquids.
Chemical kinetics and photochemical data for use in stratospheric modeling
W. B. Demore,J. J. Margitan,Mario J. Molina,R. T. Watson,D. M. Golden,R. F. Hampson,Michael J. Kurylo,Carleton J. Howard,A. R. Ravishankara +8 more
TL;DR: As part of a series of evaluated sets, rate constants and photochemical cross sections compiled by the NASA Panel for Data Evaluation are provided in this article, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena.
Chemical kinetics and photochemical data for use in stratospheric modeling
W. B. Demore,Stanley P. Sander,D. M. Golden,R. F. Hampson,Michael J. Kurylo,Carleton J. Howard,A. R. Ravishankara,C. E. Kolb,Mario J. Molina +8 more
TL;DR: As part of a series of evaluated sets, rate constants and photochemical cross sections compiled by the NASA Panel for Data Evaluation are provided in this paper, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena.