title: Determining the geometry and magnetic parameters of fluorinated radicals by simulation of powder ESR spectra and DFT calculations: the case of the radical RCF2CF2* in nafion perfluorinated ionomers.
abstract: The ESR spectrum of the chain-end radical RCF2CF2* detected in Nafion perfluorinated membranes exposed to the photo-Fenton reagent was accurately simulated by an automatic fitting procedure, using as input the hyperfine coupling tensors of the two F alpha and two F beta nuclei as well as the corresponding directions of the principal values from density functional theory (DFT) calculations. An accurate fit was obtained only for different orientations of the hyperfine coupling tensors for the two F alpha nuclei, indicating a nonplanar structure about the C alpha radical center. The fitted isotropic hyperfine splittings for the two F beta nuclei in the Nafion radical, 24.9 and 27.5 G, are significantly larger than those for the chain-end radical in Teflon (15 G), implying different radical conformations in the two systems. The excellent fit indicated that the geometry and electronic structure of free radicals can be obtained not only from single-crystal ESR spectroscopy, but also, in certain cases, from powder spectra, by combination with data from DFT calculations. The optimized structures obtained by DFT calculations for the CF3CF2CF2CF2* or CF3OCF2CF2* radicals as models provided additional support for the pyramidal structure determined from the spectral fit. Comparison and analysis of calculated and fitted values for the hyperfine splittings of the two F beta nuclei suggested that the radical detected by ESR in Nafion is ROCF2CF2*, which originates from attack of oxygen radicals on the Nafion side chain. The combination of spectrum fitting and DFT is considered important in terms of understanding the hyperfine splittings from 19F nuclei and the different conformations of fluorinated chain-end-type radicals RCF2CF2* in different systems, and also for elucidating the mechanism of Nafion fragmentation when exposed to oxygen radicals in fuel cell conditions.
authors.affiliation: Department of Chemistry and Biochemistry, University of Detroit Mercy, 4001 West McNichols, Detroit, Michigan 48221, USA. alund@ifm.liu.se
authors.forename: Anders
authors.initials: A
authors.lastname: Lund
authors.forename: Lindsey D
authors.initials: LD
authors.lastname: Macomber
authors.forename: Marek
authors.initials: M
authors.lastname: Danilczuk
authors.forename: Jonathan E
authors.initials: JE
authors.lastname: Stevens
authors.forename: Shulamith
authors.initials: S
authors.lastname: Schlick