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The pyrochlore structure exhibits myriad technologically relevant properties including superconductivity, ferroelectricity, and frustrated magnetism. There has been a wealth of research on the structural and compositional intricacies of these compounds. However, there exist few design principles in regard to the intentional manipulation of the chemistry and structure for desired functionality. Here we will describe drivers of polarity on the pyrochlore structure through a combination of structural, computational, and physical characterization techniques. The main focus will be on the use of total scattering to establish structure-property relationships in these systems.