| Abstract: | The correlations among composition, structure, chemical bond and thermoelectric property of skutterudites CoSb3 and CeCo5Fe3Sb12 have been studied by using density function and discrete variation (DFT-DVM) method. Three models for this study were proposed and calculated by which the "rattling" pattern was described. Model 1 is with Ce in the center, model 2 is with Ce away the center and near to Sb, and model 3 is also with Ce away the center but near to Fe. The calculated results show that in model 3, the ionic bond is the strongest, but the covalent bond is the weakest. Due to the different changes between ionic and covalent bond, there is less difference in the stability among the models 1, 2 and 3. Therefore, these different models can exist at the same time, or can translate from one to another more easily. In other words, the "rattling" pattern has taken place. Unfilled model of CoSb3, without Ce and Fe, is called model 4. The covalent bond of Co-Sb or Fe-Sb in models 1, 2 and 3 is weaker than that of Co-Sb in model 4, as some electrical cloud of Sb takes part in the covalent bond of Ce-Sb in the filled models. The result is consistent with the experimental result that the thermal conductivity of CeCo5f e3Sb12 is lower than that of CoSb3, and the thermoelectric property of CeCo5Fe3Sb12 is superior to that of CoSb3. |
