title: The kinetic method as a structural diagnostic tool: ionized alpha-diketones as loosely one-electron bonded diacylium ion dimers.
abstract: The kinetic method is used to corroborate the description of ground state ionized alpha-diketones as loosely electron-bonded acylium ion dimers: R(1)-C=O(+)---e(-)---(+)O=C-R(2). The abundance ratio of both the acylium ion fragments R(1)CO(+) and R(2)CO(+) (summed to those of their respective secondary fragments) formed upon low energy (5 eV) collision-induced dissociation of several ionized alpha-diketones is found to correlate linearly with the ionization energies (IEs) of the corresponding R(1)CO(.) and R(2)CO(.) 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 alpha-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 alpha-diketones as loosely electron-bonded diacylium ion dimers.
authors.affiliation: State University of Campinas - UNICAMP, Institute of Chemistry CP6154, 13083-970 Campinas, SP Brazil.
authors.forename: Eduardo C
authors.initials: EC
authors.lastname: Meurer
authors.forename: Fabio C
authors.initials: FC
authors.lastname: Gozzo
authors.forename: R
authors.initials: R
authors.lastname: Augusti
authors.forename: Marcos N
authors.initials: MN
authors.lastname: Eberlin