Two-dimensional exchange nuclear quadrupole resonance spectroscopy of molecular crystals

Abstract

A theoretical treatment of the 2D exchange NQR pulse sequence is presented and applied to the quantitative study of exchange processes in molecular crystals. It takes into account the off-resonance irradiation, which critically influences the spin dynamics. The response of a system of spins I = 3/2 in zero applied field, experiencing electric quadrupole couplings, to the three-pulse sequence is analysed. All the tools and mathematical expressions to predict the time evolution of the signal created by a pure NQR multipulse sequence are presented explicitly. The mixing dynamics by exchange and the expected cross-peak intensities as a function of the frequency offset have been derived. The theory is illustrated by a study of the optimization procedure, which is of crucial importance for the detection of the cross- and diagonalpeaks in a 2D exchange spectrum. The systems investigated here were hexachloroethane and tetrachloroethylene, which show threefold and twofold reorientational jumps about the carbon-carbon axis, respectively.