Magnetic and Electronic Properties in Rattling Systems, an Experimental and Theoretical Study

The search for heat regenerators is currently very important due to the amount of wasted heat produced in different human activities. Thermoelectric materials have emerged as a possible solution to the world?s demand and reuse of energy. Recent advances have included the development of materials with tailored phonon properties, including localized "rattling" oscillator modes. In addition a number of interesting physical properties have emerged in rattling systems. This dissertation reports a study of several such systems, experimentally and computationally. Experiments performed include XRD, electron micro-probe, electrical and thermal conductivity, Seebeck coefficient measurements, dc magnetization, dc susceptibility and NMR. In the computational side several ab-initio models have been considered to understand the structural, vibrational and magnetic properties observed in these compounds.

Among the studied compounds, the Fe-Al-Zn materials showed interesting magnetic properties combined with anomalous vibrational behavior in a chain geometry. Computational results indicated that the moment is affected by Fe antisites, but also the neighbor configuration contributes to it.

Al-V-La is an example of a classical Einstein oscillator material. These properties are related to the existence of loose atoms inside the material. A purely computational study on these materials denoted the existence of two weakly bonded sites.

The clathrate structural results from first-principles considerations elucidated the preferred structural configurations in several clathrates. This included Ba-Cu-Ge clathrates, where it was confirmed that the compound follows the Zintl electron counting balance. Also the bonding inside these materials was studied to address the binding of the local-oscillator atoms within the material.

For Ba-Ga-Sn clathrates an unusual dimorphism was studied, with both of the two different types of structures investigated. For type-I Ba8Ga16Sn30 the preferred configuration was obtained from NMR lineshape simulations and energy considerations. For the type-VIII Ba8Ga16Sn30 the experimental thermoelectric properties were analyzed in conjunction with computational modeling.

Finally in Ba-Al-Ge clathrates the local environments, preferred configuration and vacancy formation were clarified. This included an extensive experimental and computational study on Ba8AlxGe46-x-y2(box)y systems. The different local Al environments were elucidated, with the location of vacancies influencing the surroundings. Also the correlation between the Al substitution and number of vacancies was studied.