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On the measurement of intermolecular heteronuclear cross relaxation rates in ionic liquids
journal contribution
posted on 2018-05-21, 00:00 authored by Pierre-Alexandre Martin, Elodie Salager, Maria ForsythMaria Forsyth, Luke O'DellLuke O'Dell, Michaël DeschampsThe HOESY (Heteronuclear Overhauser Effect SpectroscopY) NMR experiment is commonly used to study interactions and structuring in ionic liquids (ILs) via the measurement of the cross relaxation rate σ between two spins. In the intermolecular case, σ is proportional to r-n, where r is the internuclear distance and n can vary between 1 and 6 depending on the frequency of the nuclei and their dynamics, thus σ can potentially provide detailed information on the liquid phase structure. However, in HOESY studies of ILs only relative values for σ are typically reported, making comparisons between different samples difficult. Herein we discuss the quantitative measurement of intermolecular cross relaxation rates based on the normalisation of HOESY signal intensities to the nuclear Boltzmann polarisation, demonstrated for 7Li-1H spin pairs in a lithium-containing pyrrolidinum-based ionic liquid electrolyte. We also use a simple model based on diffusing hard spheres for interpreting these quantities in terms of a distance of closest approach.
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Journal
Physical chemistry chemical physicsVolume
20Issue
19Pagination
13357 - 13364Publisher
Royal Society of ChemistryLocation
Cambridge, Eng.Publisher DOI
eISSN
1463-9084Language
engPublication classification
C1 Refereed article in a scholarly journalCopyright notice
2018, the Owner SocietiesUsage metrics
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HOESY (Heteronuclear Overhauser Effect SpectroscopY)ionic liquids (ILs)Science & TechnologyPhysical SciencesChemistry, PhysicalPhysics, Atomic, Molecular & ChemicalChemistryPhysicsOVERHAUSER EFFECT MEASUREMENTSNOE NMR-SPECTROSCOPYSURFACTANT SYSTEMSPHYSICOCHEMICAL PROPERTIESELECTROLYTESSALTSELECTROCHEMISTRYCOORDINATIONDIFFUSIONMIXTURES
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