Computational studies of gas-phase radical reactions with volatile organic compounds of relevance to combustion and atmospheric chemistry

Bibliographic Details
Main Author:	Merle, John Kenneth
Language:	English
Published:	The Ohio State University / OhioLINK 2005
Subjects:	atmospheric chemistry combustion chemistry computational chemistry radical chemistry
Online Access:	http://rave.ohiolink.edu/etdc/view?acc_num=osu1126305456

id	ndltd-OhioLink-oai-etd.ohiolink.edu-osu1126305456
record_format	oai_dc
spelling	ndltd-OhioLink-oai-etd.ohiolink.edu-osu11263054562021-08-03T05:50:17Z Computational studies of gas-phase radical reactions with volatile organic compounds of relevance to combustion and atmospheric chemistry Merle, John Kenneth atmospheric chemistry combustion chemistry computational chemistry radical chemistry Density functional theory was utilized to determine whether the addition of oxygen to 2-oxepinoxy radical followed by unimolecular decomposition results in the formation of experimentally detected products for oxidative combustion of benzene. At temperatures between 500-750 K, the formation of peroxyoxepinone radicals and their decomposition pathways and products are competitive with those for the unimolecular decomposition of 2-oxepinoxy radical. The conformational distribution and unimolecular decomposition pathways for n-propylperoxy radical have been generated via ab initio and DFT methods. The study indicates that important bimolecular products could be derived from two 1,4-H transfer mechanisms available at T less than 500 K. Substituent effects on the bond dissociation enthalpies and hydroxyl radical addition reactions for a series of mono-substituted ethenes and benzenes have been studied using density functional theory. In each case, a hydrogen atom on the ethene and benzene has been replaced by a series of substituents. BDEs for the cis ethene and ortho benzene C-H bonds are shown to correlate well with the charge localized on the substituent of the parent molecule. When barrier heights are compared with the adiabatic ionization energies, a good correlation is obtained. The C-H bond dissociation energies and H-atom abstraction and radical addition reactions of hydrogen atom and hydroxyl radical with a series of PAHs have been studied using density functional theory. We have calculated detailed thermochemical and kinetic data for the reaction of acrolein with hydroxyl radical over an expanded temperature range of 200-2000 K, for comparison and extension of the current experimental temperature range of 243-372 K. Transition state theory was used to determine the rate coefficients. Our best estimate of the rate coefficients at the high-pressure limit for the reaction of acrolein with hydroxyl radical has been made using the mPW1K PES. We have calculated the stationary points for H-atom abstraction reactions of dimethyl ether and tetrahydrofuran by OH radical via ab initio and DFT methods. From these energy surfaces conventional transition state theory rate coefficients were generated. The mPW1K rate coefficients from 200 to 2000 K have been fit to a 3-parameter Arrhenius expression. 2005-10-10 English text The Ohio State University / OhioLINK http://rave.ohiolink.edu/etdc/view?acc_num=osu1126305456 http://rave.ohiolink.edu/etdc/view?acc_num=osu1126305456 unrestricted This thesis or dissertation is protected by copyright: all rights reserved. It may not be copied or redistributed beyond the terms of applicable copyright laws.
collection	NDLTD
language	English
sources	NDLTD
topic	atmospheric chemistry combustion chemistry computational chemistry radical chemistry
spellingShingle	atmospheric chemistry combustion chemistry computational chemistry radical chemistry Merle, John Kenneth Computational studies of gas-phase radical reactions with volatile organic compounds of relevance to combustion and atmospheric chemistry
author	Merle, John Kenneth
author_facet	Merle, John Kenneth
author_sort	Merle, John Kenneth
title	Computational studies of gas-phase radical reactions with volatile organic compounds of relevance to combustion and atmospheric chemistry
title_short	Computational studies of gas-phase radical reactions with volatile organic compounds of relevance to combustion and atmospheric chemistry
title_full	Computational studies of gas-phase radical reactions with volatile organic compounds of relevance to combustion and atmospheric chemistry
title_fullStr	Computational studies of gas-phase radical reactions with volatile organic compounds of relevance to combustion and atmospheric chemistry
title_full_unstemmed	Computational studies of gas-phase radical reactions with volatile organic compounds of relevance to combustion and atmospheric chemistry
title_sort	computational studies of gas-phase radical reactions with volatile organic compounds of relevance to combustion and atmospheric chemistry
publisher	The Ohio State University / OhioLINK
publishDate	2005
url	http://rave.ohiolink.edu/etdc/view?acc_num=osu1126305456
work_keys_str_mv	AT merlejohnkenneth computationalstudiesofgasphaseradicalreactionswithvolatileorganiccompoundsofrelevancetocombustionandatmosphericchemistry
_version_	1719426352481828864

Computational studies of gas-phase radical reactions with volatile organic compounds of relevance to combustion and atmospheric chemistry

Similar Items