Deuterium relaxation of a partially oriented methyl group. II. Density matrix calculations of multiple quantum spin-echo linewidths

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Abstract

Redfield relaxation matrix elements are derived for the multiple quantum coherences of even order for a partially ordered CD3 group in terms of six spectral densities of motion characterizing quadrupolar relaxation. Effects of degeneracy and cross-relaxation during evolution are discussed, and strategies are developed for optimizing 2D-FT-MQSE experiments to obtain the maximum amount of accurate relaxation information.

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    Molecular reorientation in anisotropic media such as liquid crystals, described by the spectral densities of the motion of a molecule, Jq(ω), are usually estimated from a range of relaxation measurements. In quadrupolar systems, the relaxation of zero-, double-, triple- and higher-order coherences have been used to estimate the spectral densities of motion for small deuterated organic molecules (including CDCl3,70 D–C≡C–C≡N,71 CD2Cl2,72–74 and CD3–C≡N,75–77) dissolved in liquid crystalline solution. The relaxation of the 2Q and 3Q resonances of 23Na (I=3/2) and the 4Q and 5Q resonances of 17O (I=5/2) have also been measured in lyotropic liquid crystals.78

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