Cross-Correlation Effects Involving Curie Spin Relaxation in Methyl Groups

Abstract

Cross-correlation effects arising in methyl protons due to the simultaneous presence of dipole–dipole, chemical shift anisotropy, and Curie spin relaxation mechanisms in paramagnetic systems are analyzed. We assess the potential of obtaining structural constraints from the cross-correlation of Curie spin relaxation with dipolar relaxation mechanisms among methyl proton spins. By theoretical analysis and numerical simulations we characterize the transfer functions describing the interconversion processes of different ranks of multispin order. The time dependence of these processes contains a new type of structural information, the orientation of the methyl C3-axis with respect to the electron center. Experimental confirmation is found for selected methyl groups in low spin Fe3+ sperm whale myoglobin.