dc.creator Castleberry, Vanessa A. en_US dc.creator Dee, S. Jason en_US dc.creator Villarroel, Otsmar J. en_US dc.creator Laboren, Ivanna E. en_US dc.creator Frey, Sarah E. en_US dc.creator Bellert, Darrin J. en_US dc.date.accessioned 2009-07-29T12:52:18Z dc.date.available 2009-07-29T12:52:18Z dc.date.issued 2009 en_US dc.identifier 2009-FB-05 en_US dc.identifier.uri http://hdl.handle.net/1811/38199 dc.description Author Institution: Department of Chemistry and Biochemistry, Baylor University, Waco, Texas, 76798 en_US dc.description.abstract A unique application of a custom fabricated photodissociation spectrometer permits the determination of thermodynamic properties (activation energies), reaction rates, and mechanistic details of bare metal cation mediated C-C $\sigma$-bond activation in the gas phase. Specifically, the products and rates resulting from the unimolecular decomposition of the Ni$^+$Acetone (Ni$^+$Ac) adduct are monitored after absorption of a known amount of energy. The three dissociative products which are observed in high yield are Ni$^+$, Ni$^+$CO, and CH3CO$^+$. The latter two fragment ions result from the activation of a C-C $\sigma$-bond. It was found that minimally 14 000 cm$^{-1}$ of energy must be deposited into the adduct ion to induce C-C bond breakage. Preliminary results for the Ni$^+$ activation of the C-C $\sigma$-bond of acetone indicate that there are (at least) two low energy reaction coordinates leading to C-C bond breakage. The lower energy pathway emerges from the doublet ground state with an upper limit to the activation energy of 14 000 cm$^{-1}$ and reaction rate $\approx$0.14 molecules/$\mu$s. The higher energy path is assumed to be along the quartet reaction coordinate with a minimum activation energy of 18 800 cm$^{-1}$ (relative to the ground state) and a slightly slower reaction rate. en_US dc.language.iso English en_US dc.publisher Ohio State University en_US dc.title ENERGY AND RATE DETERMINATIONS TO ACTIVATE THE C-C $\sigma$-BOND OF ACETONE BY GASEOUS $NI^+$ en_US dc.type Article en_US
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