Ab initio and Direct Quasiclassical Trajectory Study of the F + CH₄ → HF + CH₃ and F + C₂H₆ → HF + C₂H₅ Reactions

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dc.contributor.authorWeiss, Paulaen
dc.contributor.committeechairTroya, Diegoen
dc.contributor.committeememberCrawford, T. Danielen
dc.contributor.committeememberGandour, Richard D.en
dc.contributor.committeememberMorris, John R.en
dc.contributor.committeememberValeyev, Eduard Faritovichen
dc.contributor.departmentChemistryen
dc.date.accessioned2014-03-14T20:46:31Zen
dc.date.adate2007-10-15en
dc.date.available2014-03-14T20:46:31Zen
dc.date.issued2007-09-25en
dc.date.rdate2007-10-15en
dc.date.sdate2007-10-09en
dc.description.abstractThe reparametization of semiempirical Hamiltonians is an emerging method used in direct dynamics studies. The use of semiempirical Hamiltonians in direct dynamics studies diminishes the computational cost of trajectory calculations and negates the need for an analytical potential energy surface when performing reaction dynamics studies. The reparametization of semiempirical Hamiltonians increases the agreement with experiment and high level ab initio theory. We have chosen to create one set of new parameters that apply to two related reactions, F + CH₄ → HF + CH₃ and F + C₂H₆ → HF + C₂H₅. We have performed an electronic structure study for these reactions. The ab initio data obtained from the electronic structure study is then used as the reference for a reparametization of the PM3 Hamiltonian. The reparametization has improved the ab initio and PM3 reaction energy and potential energy surface scan agreement. This new set of parameters for PM3 (SRP-PM3) is used to perform a direct quasiclassical trajectory study of the reactions. The vibrational and rotational HF distributions calculated using SRP-PM3 are compared with experiments. We have observed an improvement in the agreement with experimental vibrational distributions but have seen no change in the rotational distributions.en
dc.description.degreeMaster of Scienceen
dc.identifier.otheretd-10092007-111213en
dc.identifier.sourceurlhttp://scholar.lib.vt.edu/theses/available/etd-10092007-111213/en
dc.identifier.urihttp://hdl.handle.net/10919/35340en
dc.publisherVirginia Techen
dc.relation.haspartPWThesis.pdfen
dc.rightsIn Copyrighten
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/en
dc.subjectpotential energy surfaceen
dc.subjectdirect dynamicsen
dc.subjectspecific reaction parameter semiempirical Hamiltonen
dc.subjectquasiclassical trajectory studyen
dc.titleAb initio and Direct Quasiclassical Trajectory Study of the F + CH₄ → HF + CH₃ and F + C₂H₆ → HF + C₂H₅ Reactionsen
dc.typeThesisen
thesis.degree.disciplineChemistryen
thesis.degree.grantorVirginia Polytechnic Institute and State Universityen
thesis.degree.levelmastersen
thesis.degree.nameMaster of Scienceen
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