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Polar-Covalent Bonding Beyond the Zintl Picture in Intermetallic Rare-Earth Germanides

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Freccero,  Riccardo
Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Grin,  Yuri
Juri Grin, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Wagner,  Frank R.
Frank Wagner, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Citation

Freccero, R., Solokha, P., De Negri, S., Saccone, A., Grin, Y., & Wagner, F. R. (2019). Polar-Covalent Bonding Beyond the Zintl Picture in Intermetallic Rare-Earth Germanides. Chemistry – A European Journal, 25, 6600-6612. doi:10.1002/chem.201900510.


Cite as: http://hdl.handle.net/21.11116/0000-0003-BC11-6
Abstract
A comparative chemical bonding analysis for the germanides La 2 MGe 6 (M=Li, Mg, Al, Zn, Cu, Ag, Pd) and Y 2 PdGe 6 is presented, together with the crystal structure determination for M=Li, Mg, Cu, Ag. The studied compounds adopt the two closely related structure types oS72-Ce 2 (Ga 0.1 Ge 0.9 ) 7 and mS36-La 2 AlGe 6 , containing zigzag chains and corrugated layers of Ge atoms bridged by M species, with La/Y atoms located in the biggest cavities. Chemical bonding was studied by means of the quantum chemical position-space techniques QTAIM (quantum theory of atoms in molecules), ELI-D (electron localizability indicator), and their basin intersections. The new penultimate shell correction (PSC0) method was introduced to adapt the ELI-D valence electron count to that expected from the periodic table of the elements. It plays a decisive role to balance the Ge−La polar-covalent interactions against the Ge−M ones. In spite of covalently bonded Ge partial structures formally obeying the Zintl electron count for M=Mg 2+ , Zn 2+ , all the compounds reveal noticeable deviations from the conceptual 8−N picture due to significant polar-covalent interactions of Ge with La and M ≠ Li, Mg atoms. For M=Li, Mg a formulation as a germanolanthanate M[La 2 Ge 6 ] is appropriate. Moreover, the relative Laplacian of ELI-D was discovered to reveal a chemically useful fine structure of the ELI-D distribution being related to polyatomic bonding features. With the aid of this new tool, a consistent picture of La/Y−M interactions for the title compounds was extracted. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim