Controlling the effects of pulse transients and RF inhomogeneity in phase-modulated multiple-pulse sequences for...

The effects of pulse imperfections and RF inhomogeneity on NMR spectra obtained with phase-modulated multiple-pulse NMR sequences are analyzed. The emphasis is on the combined effects of frequency offset, RF inhomogeneity, and pulse phase transients. To enable a theoretical description of the transients associated with phase changes under continuous RF irradiation, the nature of the transients is investigated in depth. As monitored in our 300 MHz spectrometer, they are found to be caused by linear elements of the RF circuitry. The validity of their representation as delta-function pulses and the significance of their decomposition into antisymmetric and symmetric components are discussed. A practical method for quantitative control of the antisymmetric phase transients is proposed. The linearity property allows the development of a theoretical description of the spin dynamics caused by the transients. This leads to a vector-Hamiltonian model for phase-modulated Lee-Goldburg experiments. It quantitatively predicts both the frequency shift and the line broadening caused by antisymmetric phase transients and their coupling with RF inhomogeneity. The model is shown to be equally applicable to frequency-switched Lee-Goldburg experiments. A noteworthy discovery is that for a given magnitude of the antisymmetric phase transients a frequency offset exists at which the inhomogeneity broadening is essentially canceled. This explains the common observation that for best resolution one side of resonance is preferred over the other. It also suggests a strategy for enhancing resolution without having to resort to severe sample volume restriction. Numerical calculations verified the theoretical predictions and allowed extension of the model to BLEW-12 and DUMBO-1. Experimental verification is presented. The deviations from theoretical predictions are discussed.