Dataset Information

Exploratory Work in the Quaternary System of Ca?Eu?Cd?Sb: Synthesis, Crystal, and Electronic Structures of New Zintl Solid Solutions.

ABSTRACT: Investigation of the quaternary system, Ca?Eu?Cd?Sb, led to a discovery of the new solid solutions, Ca_1-xEu_xCd?Sb?, with the CaAl?Si? structure type (x ? 0.3?0.9, hP5, P 3 ¯ m1, a = 4.6632(5)?4.6934(3) Å, c = 7.630(1)?7.7062(7) Å), Ca_2-xEu_xCdSb? with the Yb?CdSb? type (x ? 0.6, oS20, Cmc2?, a = 4.646(2) Å, b = 17.733(7) Å, c = 7.283(3) Å), and Eu_11-xCa_xCd?Sb₁₂ with the Sr₁₁Cd?Sb₁₂ type (x ? 1, mS58, C2/m, a = 32.407(4) Å, b = 4.7248(5) Å, c = 12.377(1) Å, ? = 109.96(1)°). Systematic crystallographic studies of the Ca_1-xEu_xCd?Sb? series indicated expansion of the unit cell upon an increase in the Eu content, in accordance with a larger ionic radius of Eu²⁺ vs. Ca²⁺. The Ca_2-xEu_xCdSb? composition with x ? 0.6 adopts the non-centrosymmetric space group, Cmc2?, although the parent ternary phase, Ca?CdSb?, crystallizes in the centrosymmetric space group, Pnma. Two non-equivalent Ca sites in the layered crystal structure of Ca_2-xEu_xCdSb? get unevenly occupied by Eu, with a preference for the interlayer position, which offers a larger available volume. Similar size-driven preferred occupation is observed in the Eu_11-xCa_xCd?Sb₁₂ solid solution with x ? 1.

SUBMITTER: Ovchinnikov A

PROVIDER: S-EPMC6265713 | biostudies-literature | 2018 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Exploratory Work in the Quaternary System of Ca⁻Eu⁻Cd⁻Sb: Synthesis, Crystal, and Electronic Structures of New Zintl Solid Solutions.

Ovchinnikov Alexander A Darone Gregory M GM Saparov Bayrammurad B Bobev Svilen S

Materials (Basel, Switzerland) 20181031 11

Investigation of the quaternary system, Ca⁻Eu⁻Cd⁻Sb, led to a discovery of the new solid solutions, Ca1-xEuxCd₂Sb₂, with the CaAl₂Si₂ structure type (x ≈ 0.3⁻0.9, hP5, P 3 ¯ m1, a = 4.6632(5)⁻4.6934(3) Å, c = 7.630(1)⁻7.7062(7) Å), Ca2-xEuxCdSb₂ with the Yb₂CdSb₂ type (x ≈ 0.6, oS20, Cmc2₁, a = 4.646(2) Å, b = 17.733(7) Å, c = 7.283(3) Å), an ...[more]

PMID: 30384471

Similar Datasets

Project description:The recent application of concepts from condensed-matter physics to photoelectron spectroscopy (PES) of volatile, liquid-phase systems has enabled the measurement of electronic energetics of liquids on an absolute scale. Particularly, vertical ionization energies, VIEs, of liquid water and aqueous solutions, both in the bulk and at associated interfaces, can now be accurately, precisely, and routinely determined. These IEs are referenced to the local vacuum level, which is the appropriate quantity for condensed matter with associated surfaces, including liquids. In this work, we connect this newly accessible energy level to another important surface property, namely, the solution work function, eΦliq. We lay out the prerequisites for and unique challenges of determining eΦ of aqueous solutions and liquids in general. We demonstrate - for a model aqueous solution with a tetra-n-butylammonium iodide (TBAI) surfactant solute - that concentration-dependent work functions, associated with the surface dipoles generated by the segregated interfacial layer of TBA+ and I- ions, can be accurately measured under controlled conditions. We detail the nature of surface potentials, uniquely tied to the nature of the flowing-liquid sample, which must be eliminated or quantified to enable such measurements. This allows us to refer aqueous-phase spectra to the Fermi level and to quantitatively assign surfactant-concentration-dependent spectral shifts to competing work function and electronic-structure effects, where the latter are typically associated with solute-solvent interactions in the bulk of the solution which determine, e.g., chemical reactivity. The present work describes the extension of liquid-jet PES to quantitatively access concentration-dependent surface descriptors that have so far been restricted to solid-phase measurements. Correspondingly, these studies mark the beginning of a new era in the characterization of the interfacial electronic structure of aqueous solutions and liquids more generally.

Dataset Information

Exploratory Work in the Quaternary System of Ca?Eu?Cd?Sb: Synthesis, Crystal, and Electronic Structures of New Zintl Solid Solutions.

Publications

Exploratory Work in the Quaternary System of Ca⁻Eu⁻Cd⁻Sb: Synthesis, Crystal, and Electronic Structures of New Zintl Solid Solutions.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets