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Density functional calculations in the generalized gradient approximation are used to study the transport properties of the clathrates Ba8Ga16Ge30, Sr8Ga16Ge30, Ba8Ga16Si30, and Ba8In16Sn30. The band structures of these clathrates indicate that they are all semiconductors. Seebeck coefficients, conductivities and Hall coefficients are calculated, to assess the effects of carrier concentration on the quantity S2σ/τ (where S is the Seebeck coefficient, σ is the conductivity, and τ the electron relaxation time) which is proportional to the thermoelectric power factor. In each compound we find that both p- and n-doping will significantly enhance the thermoelectric capabilities of these compounds. For p-doping, the power factors of all four clathrates are of comparable magnitude and have similar temperature dependence, while for n-doping we see significant variations from compound to compound. We estimate that room-temperature ZT values of 0.5 may be possible for optimally n-doped Sr8Ga16Ge30 or Ba8In16Sn30; a...

We use density functional calculations and single-crystal x-ray diffraction measurements to study structure and bonding in the solid state clathrates Ba8Ga16Ge30, Ba8Ga16Si30, Sr8Ga16Ge30, and Ba8In16Sn30. The structures calculated by minimizing the energy provided by the density functional theory agree well with those determined by x-ray scattering. The preferred stoichiometry is found to always have 8 group II, 16 group III, and 30 group IV elements. The resultant structures are shown to be substantially more stable than the constituent elements in their standard states at room temperature and pressure. Calculations show that the group III elements prefer to be located in the six rings of the structure and are distributed to avoid bonding to one another. Motion of the group II atom (the guest) within the cages is facile, with estimated frequencies for vibration ranging from 40 to 100 cm−1. While these results may suggest a weak guest-frame bond, we find that the binding energy is over 4 eV per guest. We...