Ce4(P1- x Si x )3- z :  A First Example for the Stabilization of the Anti-Th3P4 Type Structure by Substitution in the Non-Metal Substructure

• Published in: Inorganic chemistry 2006-09, Vol.45 (18), p.7210-7216
• Main Authors: Chizhov, Pavel S, Khasanova, Nellie R, Baitinger, Michael, Schnelle, Walter, Prots, Yuri, Burkhardt, Ulrich, Antipov, Evgeny V, Grin, Yuri
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic060726h

A first rare-earth phosphide silicide Ce4(P1 - 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.