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 language | English |
|---|---|
| Pages (from-to) | 447-453 |
| Number of pages | 7 |
| Journal | Journal of Physics and Chemistry of Solids |
| Volume | 41 |
| Issue number | 5 |
| DOIs | |
| Publication status | Published - 1980 |
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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 journal › Article
}
TY - JOUR
T1 - Ab-initio electronic structure studies of mobility paths in fast-ion conductors-I. Results for MI4-3 clusters
AU - McOmber, J. I.
AU - Topiol, S.
AU - Ratner, Mark A
AU - Shriver, D. F.
AU - Moskowitz, J. W.
PY - 1980
Y1 - 1980
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=0003476014&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0003476014&partnerID=8YFLogxK
U2 - 10.1016/0022-3697(80)90173-0
DO - 10.1016/0022-3697(80)90173-0
M3 - Article
AN - SCOPUS:0003476014
VL - 41
SP - 447
EP - 453
JO - Journal of Physics and Chemistry of Solids
JF - Journal of Physics and Chemistry of Solids
SN - 0022-3697
IS - 5
ER -