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Abstract
Much of the information contained within solidstate nuclear magnetic resonance (NMR) spectra remains unexploited because of the challenges in obtaining highresolution spectra and the difficulty in assigning those spectra. Recent advances that enable researchers to accurately and efficiently determine NMR parameters in periodic systems have revolutionized the application of density functional theory (DFT) calculations in solidstate NMR spectroscopy. These advances are particularly useful for experimentalists. The use of firstprinciples calculations aids in both the interpretation and assignment of the complex spectral line shapes observed for solids. Furthermore, calculations provide a method for evaluating potential structural models against experimental data for materials with poorly characterized structures. Determining the structure of wellordered, periodic crystalline solids can be straightforward using methods that exploit Bragg diffraction. However, the deviations from periodicity, such as compositional, positional, or temporal disorder, often produce the physical properties (such as ferroelectricity or ionic conductivity) that may be of commercial interest. With its sensitivity to the atomicscale environment, NMR provides a potentially useful tool for studying disordered materials, and the combination of experiment with firstprinciples calculations offers a particularly attractive approach. In this Account, we discuss some of the issues associated with the practical implementation of firstprinciples calculations of NMR parameters in solids. We then use two key examples to illustrate the structural insights that researchers can obtain when applying such calculations to disordered inorganic materials. First, we describe an investigation of cation disorder in Y2Ti(2x)Sn(x)O7 pyrochlore ceramics using (89)Y and (119)Sn NMR. Researchers have proposed that these materials could serve as host phases for the encapsulation of lanthanide and actinidebearing radioactive waste. In a second example, we discuss how (17)O NMR can be used to probe the dynamic disorder of H in hydroxylhumite minerals (nMg2SiO4·Mg(OH)2), and how (19)F NMR can be used to understand F substitution in these systems. The combination of firstprinciples calculations and multinuclear NMR spectroscopy facilitates the investigation of local structure, disorder, and dynamics in solids. We expect that applications will undoubtedly become more widespread with further advances in computational and experimental methods. Insight into the atomicscale environment is a crucial first step in understanding the structureproperty relationships in solids, and it enables the efficient design of future materials for a range of end uses.
Original language  English 

Pages (fromto)  19641974 
Number of pages  11 
Journal  Accounts of Chemical Research 
Volume  46 
Issue number  9 
Early online date  12 Feb 2013 
DOIs  
Publication status  Published  17 Sept 2013 
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Dive into the research topics of 'Exploiting periodic firstprinciples calculations in NMR spectroscopy of disordered solids'. Together they form a unique fingerprint.Projects
 1 Finished

Computer Project NMR Crystallography: Collaborative Computer Project: NMR Crystallography
1/10/11 → 31/03/15
Project: Standard