1H chemical shielding anisotropies from polycrystalline powders using MSHOT-3 based CRAMPS

It is demonstrated that combined rotation and multiple-pulse spectroscopy (CRAMPS) based on MSHOT-3 homonuclear multiple-pulse decoupling represents a powerful method for determination of 1H chemical shielding anisotropies from polycrystalline powders. By virtue of high-order dipolar decoupling, large spectral width, resonance offset stability, and the absence of artifacts fromtilted-axis precession, MSHOT-3-based CRAMPS enables straightforward sampling of high-quality spectra. Comparison with explicit calculations, taking the effect of the multiple-pulse sequence into account, shows that the spectra may be simulated and iteratively fitted using standard software for the calculation of magic-angle spinning spectra influenced by chemical shielding anisotropy with the shielding interaction reduced by the scaling factor of the MSHOT-3 decoupling sequence. The method is demonstrated by experimental determination of 1H chemical shielding anisotropies for adipic acid, Ca(OH)2, malonic acid, and KHSO4. The data are compared with those determined previously from single-crystal NMR studies. Copyright 1998 Academic Press.

Unitary control in quantum ensembles: maximizing signal intensity in coherent spectroscopy

Experiments in coherent magnetic resonance, microwave, and optical spectroscopy control quantum-mechanical ensembles by guiding them from initial states toward target states by unitary transformation. Often, the coherences detected as signals are represented by a non-Hermitian operator. Hence, spectroscopic experiments, such as those used in nuclear magnetic resonance, correspond to unitary transformations between operators that in general are not Hermitian. A gradient-based systematic procedure for optimizing these transformations is described that finds the largest projection of a transformed initial operator onto the target operator and, thus, the maximum spectroscopic signal. This method can also be used in applied mathematics and control theory.

REPULSION, A Novel Approach to Efficient Powder Averaging in Solid-State NMR

A novel approach to efficient powder averaging in magnetic resonance is presented. The method relies on a simple numerical procedure which based on a random set of crystallite orientations through simulation of fictive intercrystallite repulsive forces iteratively determines a set of orientations uniformly distributed over the unit sphere. The so-called REPULSION partition scheme is compared to earlier methods with respect to the distribution of crystallite orientations, solid angles, and powder averaging efficiency. It is demonstrated that powder averaging using REPULSION converges faster than previous methods with respect to the number of crystallite orientations involved in the averaging. This feature renders REPULSION particularly attractive for calculation of magic-angle-spinning solid-state NMR spectra using a minimum of crystallite orientations. For numerical simulation of powder spectra, the reduced number of required crystallite orientations translates into shorter computation times and simulations less prone to systematic errors induced by finite sets of nonuniformly distributed crystallite orientations.