Polarity-extended 8 − Neff rule for semiconducting main-group compounds with the TiNiSi-type of crystal structure

Abstract

Application of chemical bonding analysis in position-space techniques based on combined topological analysis of the electron density and electron-localizability indicator distributions has recently led to the formulation of a polarity-extended 8 − N^eff rule for consistent inclusion of quantum chemically obtained polar-covalent bonding data into the classical 8 − N scheme for main-group compounds. Previous application of this scheme to semiconducting main-group compounds of the cubic MgAgAs type of structure with 8 valence electrons per formula unit (8 ve per f.u.) has shown a covalent bonding tendency preferring one zinc blende type partial structure over the other one, which seems to corroborate the classical Lewis picture of maximally four covalent bonds per main-group element. In contrast to the MgAgAs type, the orthorhombic TiNiSi type of structure displays a much higher geometrical flexibility to incorporate different kinds of metal atoms. The analysis of polar-covalent bonding in semiconducting 8 ve per f.u. containing main-group compounds AA′E of this structure type reveals a transition to non-Lewis type bonding scenarios of species E with up to ten polar-covalently bonded metal atoms. This kind of situation is consistently included into the extended 8 − N^eff type bonding scheme. A systematic increase of partially covalent bonding from chalcogenides E¹⁶ to the tetrelides E¹⁴ is found, summing up to as much as 2 covalent bonds E¹⁴–A and E¹⁴–A′, and correspondingly remaining 4 lone pair type electrons on species E¹⁴. The familiar notion of this structure type consisting of a ‘[NiSi]’-type framework with ‘Ti’-type atoms filling the voids cannot be supported for the compounds investigated.