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ESR lineshape and H-1 spin-lattice relaxation dispersion in propylene glycol solutions of nitroxide radicals - Joint analysis
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2013 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 139, no 24, 244502- p.Article in journal (Refereed) Published
Abstract [en]

Electron Spin Resonance (ESR) spectroscopy and Nuclear Magnetic Relaxation Dispersion (NMRD) experiments are reported for propylene glycol solutions of the nitroxide radical: 4-oxo-TEMPO-d(16) containing N-15 and N-14 isotopes. The NMRD experiments refer to H-1 spin-lattice relaxation measurements in a broad frequency range (10 kHz-20 MHz). A joint analysis of the ESR and NMRD data is performed. The ESR lineshapes give access to the nitrogen hyperfine tensor components and the rotational correlation time of the paramagnetic molecule. The NMRD data are interpreted in terms of the theory of paramagnetic relaxation enhancement in solutions of nitroxide radicals, recently presented by Kruk et al. [J. Chem. Phys. 138, 124506 (2013)]. The theory includes the effect of the electron spin relaxation on the H-1 relaxation of the solvent. The H-1 relaxation is caused by dipole-dipole interactions between the electron spin of the radical and the proton spins of the solvent molecules. These interactions are modulated by three dynamic processes: relative translational dynamics of the involved molecules, molecular rotation, and electron spin relaxation. The sensitivity to rotation originates from the non-central positions of the interacting spin in the molecules. The electronic relaxation is assumed to stem from the electron spin-nitrogen spin hyperfine coupling, modulated by rotation of the radical molecule. For the interpretation of the NMRD data, we use the nitrogen hyperfine coupling tensor obtained from ESR and fit the other relevant parameters. The consistency of the unified analysis of ESR and NMRD, evaluated by the agreement between the rotational correlation times obtained from ESR and NMRD, respectively, and the agreement of the translation diffusion coefficients with literature values obtained for pure propylene glycol, is demonstrated to be satisfactory.

Place, publisher, year, edition, pages
2013. Vol. 139, no 24, 244502- p.
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Atom and Molecular Physics and Optics
Identifiers
URN: urn:nbn:se:su:diva-100386DOI: 10.1063/1.4850635ISI: 000329191800028OAI: oai:DiVA.org:su-100386DiVA: diva2:693411
Note

AuthorCount:10;

Funding agencies:

Polish Ministry of Science and Higher Education N N202 105936; Swedish Research Council 613-2011-3311; M. Smoluchowski Krakow scientific consortium  

Available from: 2014-02-04 Created: 2014-02-03 Last updated: 2017-12-06Bibliographically approved

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