Back to Search
Start Over
Polarity-extended 8 − Neff rule for semiconducting main-group compounds with the TiNiSi-type of crystal structure.
- Source :
-
Dalton Transactions: An International Journal of Inorganic Chemistry . 6/28/2023, Vol. 52 Issue 24, p8222-8236. 15p. - Publication Year :
- 2023
-
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 − Neff 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 − Neff 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. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 14779226
- Volume :
- 52
- Issue :
- 24
- Database :
- Academic Search Index
- Journal :
- Dalton Transactions: An International Journal of Inorganic Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 164393987
- Full Text :
- https://doi.org/10.1039/d3dt00621b