- Numerisches Verfahren (1) (remove)
- MAS NMR of Nuclei with Spin S=1/2 in Polycrystalline Powders: Experiments and Numerical Simulations (2004)
- The objective of this work is the examination of one-dimensional magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectra. These spectra serve as a source of spin-system parameters which are related to structural and conformational parameters. It is to show that all spin-system parameters can be derived in a robust and reliable manner. Further on it is investigated how experimental conditions can be optimised in order to determine parameters in a stepwise fashion and get best accuracy for the derived data. This work is dealing with dipolar coupled spin S = 1/2 systems in polycrystalline powdered samples. MAS is used in order to increase spectral resolution and achieve gain in signal-to-noise ratio. However, MAS also causes a substantial down scaling of the information content about the anisotropic interactions of a spin system. A technique to remedy this drawback, while keeping the advantages of MAS, is the use of pulse sequences that reintroduce ("recouple") anisotropic dipolar coupling interactions. To access the spin-system parameters encoded in the lineshapes of MAS NMR spectra an iterative fitting approach is applied. These procedures make numerically exact simulations mandatory and involve accurate calculations of the complete spin-system dynamics. As a consequence all spin-system parameters sensitively encoded in the spectral lineshapes can principally be extracted. Computation of numerically exact simulations can be quite demanding on hardware (CPU speed). The algorithmic implementation of the spin dynamics has significant impact on the time required to simulate a spectrum. Optimisation and clever design of such algorithms is crucial especially when considering the need for repeated simulations in the process of iterative fitting. Usually spin-system size and the complexity of the pulse sequence are the principal factors determining the computation time of a spectrum. The numerical strategy adopted here is applied to one- to four-spin systems where the limiting factor is less the size of the spin system but rather the spin-system characteristics themselves. Spin systems composed of one to four spins have been chosen such that a representative range of spin-system parameters is covered. A combination R² and DQF proved to build robust and reliable experiments making all spin-system parameters accessible to an iterative fitting approach in a usually stepwise manner. The numerical simulations used in this approach additionally can serve for optimising existing pulse sequences. This usually results in better experimental spectra due to a better prediction of optimum experimental setup parameters. Such pre-experiment simulations are especially useful when large CSA interactions are present in dipolar coupled spin systems, a scenario not amenable to a complete theoretical description. Numerically exact simulations can also be regarded as an additional way of designing new pulse sequences. However, there is a certain lack of insight in the physical mechanisms of a pulse sequence when obtained by numerical methods only. For the future it would be useful to improve further the techniques of NMR that give complete and accurate information about local structure. This includes dipolar recoupling experiments of improved selectivity like R²-DQF. But when aiming for the ability to handle larger dipolar coupled spin systems it would also be advantageous to exploit pulse sequences that completely suppress the influence of CSA interactions while maintaining/recoupling the information about dipolar interactions. Further it is important to vary the information content of the spectra, a task for which e.g. OMAS experiments could be used.