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dc.contributor.authorMosley, Jonathan David
dc.date.accessioned2015-04-10T04:30:11Z
dc.date.available2015-04-10T04:30:11Z
dc.date.issued2014-08
dc.identifier.othermosley_jonathan_d_201408_phd
dc.identifier.urihttp://purl.galileo.usg.edu/uga_etd/mosley_jonathan_d_201408_phd
dc.identifier.urihttp://hdl.handle.net/10724/31247
dc.description.abstractSmall organic cations of the form [Cn,Hm]+ (carbocations) and [Cx,Hy,O]+ (carboxonium ions) are produced in a molecular beam via electrical discharge in a pulsed nozzle source. Size-selected ions are investigated using infrared laser photodissociation spectroscopy in the fingerprint region (600-2150 cm-1) and the C−H and O−H stretching region (2400-3800 cm-1). Quantum chemistry is used to predict structures and frequencies to aid assignment of the infrared spectra. We attempted to produce and characterize the infamous 2-norbornyl carbocation [C7,H11] + in the gas phase. Spectral analysis reveals that a previously unanticipated rearrangement occurs. [C7,H9]+ is produced from norbornene, and an unusual structural isomer of the well-known protonated toluene is found. The mass 31 cation [C,H3,O]+ exists in two structural configurations, protonated formaldehyde and the triplet methoxy cation. Cation analogs to formaldehyde [C,H2,O]+ and methanol [C,H4,O]+ both have radically different structural isomers. [C2,H3,O]+ can exist as the remarkably stable acetyl cation, or as its more energetic protonated ketene isomer, depending on the complex reaction pathways involved in the ion source.
dc.languageeng
dc.publisheruga
dc.rightspublic
dc.subjectIon infrared spectroscopy
dc.subjectCarbocations
dc.subjectCarboxonium ions
dc.titleInfrared photodissociation spectroscopy of small organic cations
dc.typeDissertation
dc.description.degreePhD
dc.description.departmentChemistry
dc.description.majorChemistry
dc.description.advisorMichael Duncan
dc.description.committeeMichael Duncan
dc.description.committeePaul Schleyer
dc.description.committeeGary Douberly


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