Export citation

Export citation

Choose format for download:

Download Citation

    Local geometries and stabilities of Cu+ centers in alkali halides

    M. Flórez, M. A. Blanco, Víctor Luaña, and L. Pueyo

    • Departamento de Química Física y Analítica, Universidad de Oviedo, 33006-Oviedo, Spain

    Phys. Rev. B 49, 69 – Published 1 January, 1994

    DOI: https://doi.org/10.1103/PhysRevB.49.69

    Abstract

    The local geometry, energy stabilization, and pseudolocal t1u vibration mode of the Cu+ impurity in the alkali halide crystals have been investigated with the ab initio perturbed ion cluster-in-the-lattice methodology. The electronic structure of different clusters, containing up to 179 ions, has been computed for nine Cu:AX systems (A=Li,Na,K;X=F,Cl,Br). The calculations clearly show that the nearest-neighbor relaxations induced by impurity substitution are essentially determined by the substituted cation, the anion playing a rather minor role. In contrast with predictions deducible from empirical ionic radii, we find negligible or very small relaxations for Cu:LiX systems, and inward relaxations of about -0.1 Å for Cu:NaX systems [in very good agreement with recent extended x-ray absorption fine-structure (EXAFS) measurements on Cu:NaCl]. For the Cu:KX family we found inward relaxations as large as -0.3 Å. The stabilization energy associated to the substitution reaction turns out to range from -0.2 to -1.8 eV, with a remarkable dependence upon the substituted cation. The t1u frequencies, computed without including the intershell coupling, decrease with increasing cationic size, showing a trend that agrees with the experimental data reported by McClure for Cu:LiCl, Cu:NaF, and Cu:NaCl. Our methodology, in its present form, does not reproduce the off-center equilibrium position of the Cu+ ion observed in Cu:NaBr, Cu:KCl, and Cu:KBr.

    Authorization Required

    We need you to provide your credentials before accessing this content.

    References (Subscription Required)

    Outline

    Information

    Sign In to Your Journals Account

    Filter

    Filter

    Article Lookup

    Enter a citation