The Kinetic Method As A Structural Diagnostic Tool: Ionized α-diketones As Loosely One-electron Bonded Diacylium Ion Dimers

dc.creatorMeurer E.C.
dc.creatorGozzo F.C.
dc.creatorAugusti R.
dc.creatorEberlin M.N.
dc.date2003
dc.date2015-06-30T17:31:01Z
dc.date2015-11-26T14:10:01Z
dc.date2015-06-30T17:31:01Z
dc.date2015-11-26T14:10:01Z
dc.date.accessioned2018-03-28T21:10:39Z
dc.date.available2018-03-28T21:10:39Z
dc.identifier
dc.identifierEuropean Journal Of Mass Spectrometry. , v. 9, n. 4, p. 295 - 304, 2003.
dc.identifier14690667
dc.identifier10.1255/ejms.563
dc.identifierhttp://www.scopus.com/inward/record.url?eid=2-s2.0-0141784858&partnerID=40&md5=c3c5b24ae0bf5cd083f6f88210e3fe32
dc.identifierhttp://www.repositorio.unicamp.br/handle/REPOSIP/102408
dc.identifierhttp://repositorio.unicamp.br/jspui/handle/REPOSIP/102408
dc.identifier2-s2.0-0141784858
dc.identifier.urihttp://repositorioslatinoamericanos.uchile.cl/handle/2250/1241400
dc.descriptionThe kinetic method is used to corroborate the description of ground state ionized α-diketones as loosely electron-bonded acylium ion dimers: R 1-C=O+ - e- - +O=C-R2. The abundance ratio of both the acylium ion fragments R1CO + and R2CO+ (summed to those of their respective secondary fragments) formed upon low energy (5 eV) collision-induced dissociation of several ionized α-diketones is found to correlate linearly with the ionization energies (IEs) of the corresponding R 1CO• and R2CO• free radicals as predicted by density functional theory calculations at the B3LYP/6-311++G(d,p) level. However, when these abundances are taken from 70 eV electron ionization mass spectra, lower and sometimes inverted ratios (2,3-pentanedione and 2,3-hexanedione) are observed. Inverted ratios are also observed via charge-exchange mass spectrometry/mass spectrometry (MS/MS) experiments for ionized 2,3-pentanodione formed with relatively high internal energies. Ionized α-diketones are found to display an effective temperature of 1705 K, which indicates an intermediate loosely-bonded nature. B3LYP/6-311++G(d,p) optimized geometries and charge and spin densities also corroborate the description of ground state ionized α-diketones as loosely electron-bonded diacylium ion dimers.
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dc.languageen
dc.publisher
dc.relationEuropean Journal of Mass Spectrometry
dc.rightsfechado
dc.sourceScopus
dc.titleThe Kinetic Method As A Structural Diagnostic Tool: Ionized α-diketones As Loosely One-electron Bonded Diacylium Ion Dimers
dc.typeArtículos de revistas


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