Electronic factors influencing the local and cooperative jahn-teller interactions in spinels with Copper(II) and Nickel(II)

M. Atanasov, U. Kesper, B. L. Ramakrishna, D. Reinen

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Abstract

Optical spectra and structural data of mixed crystals CuxZn1-xCr2O4, NixZn1-xCr2O4, and Cu1-xNixCr2O4 are reported. The optical results are used as a probe characterizing the d -contributions to the Cu-O bonds. The cooperative Jahn-Teller forces are analyzed, extending the statistical model by Wojtowicz to the tetrahedral sublattice. Thermodynamical and optical data are used to estimate the corresponding cooperative strain energies. A microscopic bonding model is proposed which is based on the bonding properties of the oxygen ligands with respect to Cu2+ due to the presence of the “contrapolarizing” Cr3+ cations. This concept makes it possible to understand the enhancement of the local Jahn-Teller distortions with increasing cooperativeness.

Original languageEnglish (US)
Pages (from-to)1-18
Number of pages18
JournalJournal of Solid State Chemistry
Volume105
Issue number1
DOIs
StatePublished - Jul 1993

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ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Ceramics and Composites
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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