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  • Title: Ce4(P1-xSi x)3-z: a first example for the stabilization of the anti-Th3P4 type structure by substitution in the non-metal substructure.
    Author: Chizhov PS, Khasanova NR, Baitinger M, Schnelle W, Prots Y, Burkhardt U, Antipov EV, Grin Y.
    Journal: Inorg Chem; 2006 Sep 04; 45(18):7210-6. PubMed ID: 16933921.
    Abstract:
    A first rare-earth phosphide silicide Ce4(P(1-x)Si(x))(3-z) and its analogues with La, Pr, and Nd were synthesized and characterized. The compounds crystallize in the anti-Th3P4 structure type. The cerium compound shows a mixed occupation of the 12a site with Si and P and possesses a wide homogeneity range with respect to x and z variation. The electronic configuration of Ce, deduced from magnetic susceptibility and X-ray absorption spectroscopy data, remains 4f(1) (Ce3+) independently from x and z. The cerium valence and the phase stability region are discussed employing electronic band-structure calculation and chemical bonding analysis with electron localization function. Atomic interactions are shown to remain nearly unchanged, while the change of the excess electron concentration with P/Si substitution is considered to play the main role for the stabilization of the structural motif.
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