ArticleThe journal of physical chemistry. A2014
EPR line shifts and line shape changes due to Heisenberg spin exchange and dipole-dipole interactions of nitroxide free radicals in liquids: 9. An alternative method to separate the effects of the two interactions employing ¹⁵N and ¹⁴N.
Article in The journal of physical chemistry. A, 2014. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 3 papers.
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3 citing papers in PubMed.
- Continuous Diffusion Model for Concentration Dependence of Nitroxide EPR Parameters in Normal and Supercooled Water.The journal of physical chemistry. B · 2017Article
- EPR Line Shifts and Line Shape Changes Due to Spin Exchange Between Nitroxide Free Radicals in Liquids 10. Spin-Exchange Frequencies of the Order of the Nitrogen Hyperfine Interaction: A Hypothesis.Applied magnetic resonance · 2017Article
- Enhancement of Paramagnetic Relaxation by Photoexcited Gold Nanorods.Scientific reports · 2016Article
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Abstract
A method to separate the effects of Heisenberg spin exchange (HSE) and dipole-dipole (DD) interactions on EPR spectra of nitroxide spin probes in solution by employing (15)N and (14)N nitroxide spin probes in parallel experiments is developed theoretically and tested experimentally. Comprehensive EPR measurements are reported of 4-oxo-2,2,6,6-tetramethylpiperidine-d16;1-(15)N-1-oxyl (perdeuterated (15)N Tempone; 15pDT), in 70 wt % aqueous glycerol as functions of concentration and temperature. The method, termed the relative broadening constant method (RBCM), is demonstrated by using the present results together with those in the literature that employed perdeuterated (14)N Tempone (14pDT) under identical conditions. In principle, the separation of DD and HSE is dependent on the model of diffusion and molecular-kinetic parameters; however, within present day experimental uncertainties, the RBCM method turns out to be insensitive to the model. The earlier methods to separate DD and HSE by measuring the dispersion component introduced by the two interactions shows general agreement with the RBCM; however, there are discrepancies larger than estimated uncertainties due to random errors. Thus, further support is found for Salikhov's recent theory of the effects of DD and HSE on EPR spectra (Appl. Magn. Reson. 2010, 38, 237); however, detailed confirmation is still lacking. The RBCM affords a possible approach to separate HSE and DD in spectra complicated by slow motion and/or overlap with other resonance lines, allowing the method to be used in situations more complicated than low-viscosity simple liquids.
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