Intermolecular multiple-quantum coherences and cross correlations in solution nuclear magnetic resonance

Abstract

It was recently reported that multiple-quantum NMR coherences could apparently be observed in water and other concentrated samples, in direct violation of established theory. These results were previously explained in a dressed-state framework as manifestations of the coupling between the spins and the coil (quantized radiation damping). Here we provide details of previously communicated experimental explorations of these effects [J. Chem. Phys. 96, 1659 (1992)], and we extend these results to multicomponent samples. We observe cross peaks between independent molecules in solution in two-dimensional experiments, including spectra with multiple-quantum coherence transfer echoes; we also demonstrate coherence transfer between solvent and (dilute) solute molecules. However, we show that these intermolecular cross peaks are induced by a mechanism which is local in nature, and thus radiation damping (either classical or quantized) cannot provide the bulk of the explanation for their occurrence. Simulations and analytical results show that the dipolar demagnetizing field can account for many of these surprising effects, although a complete picture must be more complex.