Edward Dixon

Mn(I) in an Extended Oxide: The Synthesis and Characterization of La1–xCaxMnO2+δ (0.6 ≤ x ≤ 1)

Reduction of La(1-x)Ca(x)MnO(3) (0.6 ≤ x ≤ 1) perovskite phases with sodium hydride yields materials of composition La(1-x)Ca(x)MnO(2+δ). The calcium-rich phases (x = 0.9, 1) adopt (La(0.9)Ca(0.1))(0.5)Mn(0.5)O disordered rocksalt structures. However local structure analysis using reverse Monte Carlo refinement of models against pair distribution functions obtained from neutron total scattering data reveals lanthanum-rich La(1-x)Ca(x)MnO(2+δ) (x = 0.6, 0.67, 0.7) phases adopt disordered structures consisting of an intergrowth of sheets of MnO(6) octahedra and sheets of MnO(4) tetrahedra. X-ray absorption data confirm the presence of Mn(I) centers in La(1-x)Ca(x)MnO(2+δ) phases with x < 1. Low-temperature neutron diffraction data reveal La(1-x)Ca(x)MnO(2+δ) (x = 0.6, 0.67, 0.7) phases become antiferromagnetically ordered at low temperature.

The topotactic reduction of Sr3Fe2O5Cl2-square planar Fe(II) in an extended oxyhalide.

The topotactic reduction of the oxychloride Sr(3)Fe(2)O(5)Cl(2) with LiH results in the formation of Sr(3)Fe(2)O(4)Cl(2). Neutron powder diffraction data show that Sr(3)Fe(2)O(4)Cl(2) adopts a body-centered tetragonal crystal structure (I4/mmm, a = 4.008(1) Å, c = 22.653(1) Å at 388 K) with anion vacancies located within the SrO layer of the phase. This leads to a structure consisting of infinite sheets of corner-sharing Fe(II)O(4) square planes. Variable-temperature neutron diffraction data show that Sr(3)Fe(2)O(4)Cl(2) adopts G-type antiferromagnetic order below T(N) ∼ 378(10) K with an ordered moment of 2.81(9) μ(B) per iron center at 5 K consistent with the presence of high-spin Fe(II). The observed structural and chemical selectivity of the reduction reaction is discussed. The contrast between the structure of Sr(3)Fe(2)O(4)Cl(2) and the isoelectronic all-oxide analogue (Sr(3)Fe(2)O(5)) suggests that by careful selection of substrate phases, the topotactic reduction of complex transition metal oxychlorides can lead to the preparation of novel anion-deficient phases with unique transition metal-oxygen sublattices which cannot be prepared via the reduction of all-oxide substrates.

Suppression of magnetic order in Sr3Fe2O4Cl2 by Fe-site substitution by cobalt.

The low-temperature topotactic reduction of Sr(3)Fe(2-x)Co(x)O(5)Cl(2) oxychloride phases with LiH allows the preparation of phases of composition Sr(3)Fe(2-x)Co(x)O(4)Cl(2) (0 ≤ x ≤ 1). The reduced phases adopt body-centered tetragonal structures which are isostructural with Sr(3)Fe(2)O(4)Cl(2) and contain square-planar (Fe/Co)O(4) centers connected into apex-linked sheets, analogous to the CuO(2) sheets present in superconducting cuprate phases. As the cobalt concentration in Sr(3)Fe(2-x)Co(x)O(4)Cl(2) is increased the antiferromagnetic order of the Sr(3)Fe(2)O(4)Cl(2) host phase is suppressed, ultimately leading to spin-glass behavior, at low temperature, in Sr(3)Fe(2-x)Co(x)O(4)Cl(2) phases with x ≥ 0.8. The limited influence of cobalt substitution on the reactions which form the Sr(3)Fe(2-x)Co(x)O(4)Cl(2) phases is discussed and contrasted to that of the related SrFeO(3-δ)-SrFeO(2) system.

Reverse Monte Carlo study of Cu—O bond distortions in YBa2Cu3O6.9

Abstract A combination of neutron total scattering measäurement and reverse Monte Carlo (RMC) refinement is applied to the study of apical Cu—O bond distortions in the high-Tc superconductor YBa2Cu3O6.93. We show that the average structure is not consistent with a split-site model for the corresponding Cu and O positions, but that the local structure nevertheless reveals the existence of two separate apical Cu—O bond lengths. Using G(r) data obtained from a variety of Qmax values we show that this result is independent of the data treatment methodology. We also find that the resulting ‘short’ and ‘long’ Cu—O bond lengths agree well with the results of previous äEXAFS studies. The existence of bimodal apical Cu—O bond distributions in the context of a single-site average structure model is interpreted in terms of correlated displacements of the Cu and O atoms. We investigate the possibility of clustering of short apical Cu—O bonds within our RMC configurations.

Structures and magnetism of La_{1-x}Sr_{x}MnO_{3-(0.5+x)/2} ( 0.67\leq x\leq1 ) phases

Topotactic reduction of La1–xSrxMnO3 (0.67 ≤ x ≤ 1) phases with sodium hydride yields a series of isoelectronic materials of composition La1–xSrxMnO3–(0.5+x)/2. Lanthanum rich members of the series (0.67 ≤ x ≤ 0.83) adopt anion deficient perovskite structures with a 6-layer -OTOOT′O- stacking sequence of sheets of octahedra/square-based pyramids (O) and sheets of tetrahedra (T). The strontium rich members of the series (0.83 ≤ x ≤ 1) incorporate “step defects” into this 6-layer structure in which the OTOOT′O stacking sequence is converted into either OOTOOT′ or TOOT′OO at a defect plane which runs perpendicular to the [201] lattice plane. The step defects appear to provide a mechanism to relieve lattice strain and accommodate additional anion deficiency in phases with x > 0.83. Magnetization and neutron diffraction data indicate La1–xSrxMnO3–(0.5+x)/2 phases adopt antiferromagnetically ordered states at low-temperature in which the ordered arrangement of magnetic spins is incommensurate with the crystallo...