Guest-Framework Interaction in Type I Inorganic Clathrates with Promising Thermoelectric Properties: On the Ionic versus Neutral Nature of the Alkaline-Earth Metal Guest A in A8Ga16Ge30 (A=Sr, Ba)

Periodic density functional calculations using pseudopotentials and a local basis set were performed on the type I clathrates A8Ga16Ge30 (A=Sr, Ba). Both are known to show promising thermoelectric properties. Ab initio wave functions were analyzed within the framework of the quantum theory of atoms in molecules. This enabled us to analyze both the charge transfer and bonding properties of the clathrate from a rigorous quantum mechanical viewpoint. The Ba and Sr centers were found to be largely ionic (charge: ca. +1.7 e) both in the smaller 20‐atom and in the larger 24‐atom cages, consistent with a Zintl‐phase view of these type I clathrates. The assertion that the Sr atoms in the different cages have similar oxidation states is shown to be consistent with multiwavelength diffraction experiments on Sr8Ga16Ge30; while the assertion of ionicity of the Sr center is supported by the observation that the adsorption edge lies close to that previously found in the Sr K‐edge XANES spectra of Sr(OH)2⋅8 H2O. As such, this work contradicts previous experimental and theoretical studies that claim that the guest atoms are neutral. We show that the discrepancy is related to the definitions used for electron transfer. Definitions based on electron displacement (rearrangement) in space, as in previous works, do not account for the variation in shape and volume of the atomic catchment regions upon change in the number and average locations of the particles in the system. Eventually, such definitions lead to underestimation of charge transfer. The large binding energy found in earlier work for Ba and Sr in these materials is found to be consistent with a simple picture of charge transfer from the guest to the frame. Preliminary investigations on a clathrate of perfect stoichiometry appear to rule out any important relationship between the observed increase in the thermoelectric figure of merit with increasing external pressure and host–guest charge transfer. Guest neutrality refuted: Recent claims of near charge neutrality of the guest metal atoms in A8Ga16Ge30 (A=Sr,Ba) clathrates (see picture) are contradicted by the present ab initio study, which used periodical DFT calculations and atoms in molecules analysis. This work demonstrates that the guest atoms are almost completely ionized and confirm that they act as charge donors in these clathrates, which show promising thermoelectric properties. Thus, this theoretical picture is fully consistent with the Zintl‐phase view th