Identifying the local structural units in LaBaMnO and BaYFeO through the neutron pair distribution function.

Neutron pair distribution function data are used to investigate the local structures of two oxygen deficient perovskites with simple cubic crystal structures. LaBaMnO is found to have alternating layers of MnO octahedra and MnO tetrahedra, making it similar to other members of the LaBaMnO series with smaller x values which have brownmillerite crystal structures. Our fitting results suggest that LaBaMnO is not locally similar to any one brownmillerite structure type but instead has a variety of intra-layer and inter-layer relationships. We propose that this could be due to short range segregation of the much differently sized La and Ba cations, which creates significantly different inter-layer distances. BaYFeO is found not to have a brownmillerite-type local structure but rather seems to consist of structural units which are similar to BaYFeO, an earlier member of the BaYFeO series. The PDF analysis shows that there are never neighboring Y atoms and that the O vacancies lie exclusively between Fe atoms, such that Y is always octahedrally coordinated. The PDF also suggests that there are more tetrahedral Fe than expected, which could be due to the presence of terminal O atoms in Fe centered dimeric units, similar to what is found in BaYFeO.