Difference of p– d hybridization in noble metal halides

• Published in: Solid state ionics Vol. 139; no. 3; pp. 249 - 254
• Main Authors: Ono, S., Kobayashi, M., Iyetomi, H., Tomoyose, T.
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 01.02.2001; Elsevier Science
• Subjects: Activation energy; Condensed matter: electronic structure, electrical, magnetic, and optical properties; Electron density of states and band structure of crystalline solids; Electron states; Exact sciences and technology; Ionic conductivity; LCAO; Noble metal halides; Other inorganic compounds; Physics; p– d hybridization; Superionic conductors; p– d hybridization; Activation energy; Noble metal halides; LCAO; Ionic conductivity; Superionic conductors; Band structure; Polarizability; Transition element compounds; Theoretical study; Binary compounds; Hybridization; Transition elements Halides; Ionicity; LCAO method; Ionic bonds
• ISSN: 0167-2738; 1872-7689
• DOI: 10.1016/S0167-2738(00)00824-9

The band calculations of noble metal halides are studied to reveal the high ionic conductivity of Ag + and Cu + in noble metal halides using the linear combination of atomic orbitals (LCAO) theory. It is found that the d states of Ag + are much more weakly coupled with the p states of halogen ions, while those of Cu + are much more strongly coupled with the p bands. The strength of p– d hybridization is discussed in relation to the activation energy for the ionic conduction. It is shown that the high ionic conductivity of AgX (X=halogen) primarily stems from the combination of the deformability of the d shell and the weakness of p– d hybridization.