Local and average structures and magnetic properties of of Sr2FeMnO5+y, y = 0.0, 0.5. comparisons with Ca2FeMnO5 and the effect of the A-site cation Ramezanipour, Farshid; Greedan, John E.; Siewenie, Joan; Proffen, Th.; Ryan, Dominic H.; Grosvenor, Andrew P.; Donaberger, Ronald L.Contact us / Contactez nous: nparc.cisti@nrc-cnrc.gc.ca. Oxygen-deficient perovskites can have a variety of structures depending on different factors including the degree of anion deficiency and the composition. In this article, the focus is on oxygen-deficient perovskites with the formula A 2 BB 0 O 5+x . The oxygen vacancies can order to form the brownmillerite structure in which the B cations are octahedrally coordinated, forming corner-sharing layers, and the B 0 cations are tetrahedrally coordinated, forming corner-sharing chains. (Figure 1). This longrange vacancy ordering results in a supercell that generally has dimensions with respect to the cubic perovskite cell constant, a p , of a br â 2 1/2 a p , b br â 4a p , and c br â 2 1/2 a p . A number of different space group symmetries are observed, depending on subtle differences in the ordering of the tetrahedral chains within the unit cell. The chains can show either a right-handed (R) or lefthanded (L) orientation and the correlation between the intraand interlayer chain orientations and the resulting space groups are summarized in ABSTRACT: Sr 2 FeMnO 5+y was synthesized under two different conditions, in air and in argon, both of which resulted in a cubic, Pm3m, structure with no long-range ordering of oxygen vacancies. The unit cell constants were found to be a 0 = 3.89328(1) Ă
for argon (y = 0.0) and a 0 = 3.83075(3) Ă
for air (y = 0.5). In contrast, Ca 2 FeMnO 5 retains long-range brownmillerite oxygen vacancy ordering for either air or argon synthesis. Remarkably, Sr 2 FeMnO 5.0 oxidizes spontaneously in air at room temperature. A neutron pair distribution function (NPDF) study of Sr 2 FeMnO 5.0 (Ar) showed evidence for local, brownmillerite-like ordering of oxygen vacancies for short distances up to 5 Ă
. M⏠ossbauer spectroscopy results indicate more than one Fe site for Sr 2 FeMnO 5+y (Ar and air), consistent with the noncubic local structure found by NPDF analysis. The isomer shifts and quadrupole splittings in both air-and argon-synthesized materials are consistent with the 3+ oxidation state for Fe in sites with coordination number four or five. This is confirmed by an L-edge XANES study. Mn is almost entirely in the 3+ state for Sr 2 FeMnO 5.0 (Ar), whereas Mn 4+ is predominantly present for Sr 2 FeMnO 5.5 (air). Magnetic susceptibility data show zero-fieldcooled/field-cooled (ZFC/FC) divergences near 50 K for the Ar sample and 25 K for the air sample, whereas Ca 2 FeMnO 5 is longrange G-type antiferromagnetically ordered at 407(2) K. Hyperfine magnetic splitting, observed in temperature-dependent M⏠ossbauer measurements, indicates short-range magnetic correlations that persist up to 150 K for Sr 2 FeMnO 5.0 (Ar) and 100 K for Sr 2 FeMnO 5.5 (air), well above the ZF...