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.
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.
authors.affiliation: Chemistry Department, Moscow State University, 119992 Moscow, Russia. chizhov@cpfs.mpg.de
authors.forename: Pavel S
authors.initials: PS
authors.lastname: Chizhov
authors.forename: Nellie R
authors.initials: NR
authors.lastname: Khasanova
authors.forename: Michael
authors.initials: M
authors.lastname: Baitinger
authors.forename: Walter
authors.initials: W
authors.lastname: Schnelle
authors.forename: Yuri
authors.initials: Y
authors.lastname: Prots
authors.forename: Ulrich
authors.initials: U
authors.lastname: Burkhardt
authors.forename: Evgeny V
authors.initials: EV
authors.lastname: Antipov
authors.forename: Yuri
authors.initials: Y
authors.lastname: Grin