Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2012-12-01

Monomer- and polymer radicals of vinyl compounds: EPR and DFT studies of geometric and electronic structures in the adsorbed state.

Anders Lund, Marek Danilczuk

Index: Spectrochim. Acta. A. Mol. Biomol. Spectrosc. 98 , 367-77, (2012)

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Abstract

Electron paramagnetic resonance (EPR) spectroscopy was applied to study the paramagnetic species formed from styrene, 1,1-diphenylethylene, α-methylstyrene, β-methylstyrene and methylmethacrylate adsorbed on amorphous silica gel after γ-irradiation at 77K. Radicals formed by the hydrogen atom addition at the vinyl group of the monomers were observed in all samples. The hydrogen atoms were shown to originate to a large extent from the adsorbent by using silica gel with deuterated silanol groups. An EPR spectrum assigned to a propagating radical was observed at increased temperature for samples containing methylmethacrylate (MMA). The structures of the adsorption complexes, the respective hyperfine splitting constants and the adsorption energies were calculated by applying DFT quantum chemical methods. The reaction between an MMA molecule and the MMA radical and the structure of the propagating radical was modeled. The calculated hyperfine splitting constants for all radicals confirmed the assignment of the experimental spectra.Copyright © 2012 Elsevier B.V. All rights reserved.