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H-1 relaxation dispersion in solutions of nitroxide radicals: Influence of electron spin relaxation
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för material- och miljökemi (MMK).
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2013 (engelsk)Inngår i: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 138, nr 12, s. 124506-Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

The work presents a theory of nuclear (H-1) spin-lattice relaxation dispersion for solutions of N-15 and N-14 radicals, including electron spin relaxation effects. The theory is a generalization of the approach presented by Kruk et al. [J. Chem. Phys. 137, 044512 (2012)]. The electron spin relaxation is attributed to the anisotropic part of the electron spin-nitrogen spin hyperfine interaction modulated by rotational dynamics of the paramagnetic molecule, and described by means of Redfield relaxation theory. The H-1 relaxation is caused by electron spin-proton spin dipole-dipole interactions which are modulated by relative translational motion of the solvent and solute molecules. The spectral density characterizing the translational dynamics is described by the force-free-hard-sphere model. The electronic relaxation influences the H-1 relaxation by contributing to the fluctuations of the inter-molecular dipolar interactions. The developed theory is tested against H-1 spin-lattice relaxation dispersion data for glycerol solutions of 4-oxo-TEMPO-d(16)-N-15 and 4-oxo-TEMPO-d(16)-N-14 covering the frequency range of 10 kHz-20 MHz. The studies are carried out as a function of temperature starting at 328 K and going down to 290 K. The theory gives a consistent overall interpretation of the experimental data for both N-14 and N-15 systems and explains the features of H-1 relaxation dispersion resulting from the electron spin relaxation.

sted, utgiver, år, opplag, sider
2013. Vol. 138, nr 12, s. 124506-
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URN: urn:nbn:se:su:diva-89912DOI: 10.1063/1.4795006ISI: 000316969500086OAI: oai:DiVA.org:su-89912DiVA, id: diva2:621522
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AuthorCount:6;

Tilgjengelig fra: 2013-05-15 Laget: 2013-05-15 Sist oppdatert: 2022-02-24bibliografisk kontrollert

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Kowalewski, Jozef

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