Ab-initio electronic structure studies of mobility paths in fast-ion conductors-I. Results for MI4-3 clusters

J. I. McOmber, S. Topiol, Mark A Ratner, D. F. Shriver, J. W. Moskowitz

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

We report results of minimum-basis Pseudopotential Hartree-Fock studies of MI4-3 clusters (M = Na+, K+, Ag+, and Cu+), and of HgI4-2. The calculations are designed to characterize local-site effects on mobility paths in solid state electrolytes. We observe qualitatively correct behavior, with Ag+ predicted to be the most mobile ion. Quadrupolar polarizability of the metal ion, which is produced by s-d mixing, lowers the energy of trigonal transition state, thus accounting for the observation that quadrupole polarizable species are ideal mobile ions in close-packed halide frameworks. Mulliken populations show that there is considerable local covalency, so that electrostatic potential studies must be done very carefully. Expansion of the I4 tetrahedron lowers the barrier energy.

Original languageEnglish
Pages (from-to)447-453
Number of pages7
JournalJournal of Physics and Chemistry of Solids
Volume41
Issue number5
DOIs
Publication statusPublished - 1980

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Electronic structure
conductors
Ions
electronic structure
Energy barriers
tetrahedrons
Electrolytes
pseudopotentials
halides
Metal ions
Electrostatics
metal ions
ions
quadrupoles
electrolytes
electrostatics
solid state
expansion
energy

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Condensed Matter Physics

Cite this

Ab-initio electronic structure studies of mobility paths in fast-ion conductors-I. Results for MI4-3 clusters. / McOmber, J. I.; Topiol, S.; Ratner, Mark A; Shriver, D. F.; Moskowitz, J. W.

In: Journal of Physics and Chemistry of Solids, Vol. 41, No. 5, 1980, p. 447-453.

Research output: Contribution to journalArticle

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