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

Merle, John Kenneth
http://rave.ohiolink.edu/etdc/view?acc_num=osu1126305456

Abstract Details

2005, Doctor of Philosophy, Ohio State University, 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 In each case, a hydrogen atom on the ethene and benzene has been replaced by a series of substituents.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.
Christopher Hadad (Advisor)
276 p.
atmospheric chemistry; combustion chemistry; computational chemistry; radical chemistry

Recommended Citations

Citations

  • Merle, J. K. (2005). Computational studies of gas-phase radical reactions with volatile organic compounds of relevance to combustion and atmospheric chemistry [Doctoral dissertation, Ohio State University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=osu1126305456

    APA Style (7th edition)

  • Merle, John. Computational studies of gas-phase radical reactions with volatile organic compounds of relevance to combustion and atmospheric chemistry. 2005. Ohio State University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=osu1126305456.

    MLA Style (8th edition)

  • Merle, John. "Computational studies of gas-phase radical reactions with volatile organic compounds of relevance to combustion and atmospheric chemistry." Doctoral dissertation, Ohio State University, 2005. http://rave.ohiolink.edu/etdc/view?acc_num=osu1126305456

    Chicago Manual of Style (17th edition)

osu1126305456
2,148
© 2005, all rights reserved.
This open access ETD is published by The Ohio State University and OhioLINK.