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Roles of cations, electronegativity difference, and anionic interlayer interactions in the metallic versus nonmetallic character of Zintl phases related to arsenic
Author(s) -
Alemany Pere,
Llunell Miquel,
Canadell Enric
Publication year - 2008
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.20989
Subject(s) - electronegativity , character (mathematics) , arsenic , metal , chemistry , density functional theory , electronic structure , chemical physics , conductivity , ion , crystallography , covalent bond , computational chemistry , inorganic chemistry , materials science , organic chemistry , geometry , mathematics
A first‐principles Density Functional Theory study of several layered solids structurally related to rhombohedral arsenic has been carried out. The electronic structures of rhombohedral arsenic, CaSi 2 , CaAl 2 Si 2 , KSnSb, and SrSn 2 As 2 are discussed in detail, emphasizing on the origins of their metallic or nonmetallic behaviours. It is found that all of these systems are metallic except KSnSb. Electronegativity differences between the elements in the anionic sublattice and/or direct interlayer interactions play the main role in controlling the conductivity behavior. CaSi 2 exhibits a peculiar feature since the cation directly influences the conductivity but is not essential for its appearance. Cation‐anion interactions are shown to have an important covalent contribution, but despite this fact and the metallic character found for most of these phases, the Zintl approach still provides a valid approximation to their electronic structure. © 2008 Wiley Periodicals, Inc. J Comput Chem 2008