skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Structural study of quasi-one-dimensional vanadium pyroxene LiVSi{sub 2}O{sub 6} single crystals

Abstract

Single crystals of quasi-one-dimensional vanadium pyroxene LiVSi{sub 2}O{sub 6} were synthesized and the crystal structures at 293 K and 113 K were studied using X-ray diffraction experiments. We found a structural phase transition from the room-temperature crystal structure with space group C2/c to a low-temperature structure with space group P2{sub 1}/c, resulting from a rotational displacement of SiO{sub 4} tetrahedra. The temperature dependence of magnetic susceptibility shows a broad maximum around 116 K, suggesting an opening of the Haldane gap expected for one-dimensional antiferromagnets with S=1. However, an antiferromagnetic long-range order was developed below 24 K, probably caused by a weak inter-chain magnetic coupling in the compound. - Graphical abstract: Low temperature crystal structure of LiVSi{sub 2}O{sub 6} and an orbital arrangement within the V-O zig-zag chain along the c-axis. - Highlights: • A low temperature structure of LiVSi{sub 2}O{sub 6} was determined by single crystal X-ray diffraction measurements. • The origin of the structural transition is a rotational displacement of SiO{sub 4} tetrahedra. • The uniform orbital overlap in the V-O zigzag chain makes the system a quasi one-dimensional antiferromagnet.

Authors:
 [1];  [2]; ;  [1]
  1. Department of Physics, Hokkaido University, Sapporo 060-0810 (Japan)
  2. National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan)
Publication Date:
OSTI Identifier:
22658175
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 246; Other Information: Copyright (c) 2016 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANTIFERROMAGNETISM; CRYSTALLIZATION; LITHIUM COMPOUNDS; MAGNETIC SUSCEPTIBILITY; MONOCLINIC LATTICES; MONOCRYSTALS; SILICATE MINERALS; SILICON OXIDES; SPACE GROUPS; TEMPERATURE DEPENDENCE; VANADIUM COMPOUNDS; X-RAY DIFFRACTION

Citation Formats

Ishii, Yuto, Matsushita, Yoshitaka, Oda, Migaku, and Yoshida, Hiroyuki. Structural study of quasi-one-dimensional vanadium pyroxene LiVSi{sub 2}O{sub 6} single crystals. United States: N. p., 2017. Web. doi:10.1016/J.JSSC.2016.11.012.
Ishii, Yuto, Matsushita, Yoshitaka, Oda, Migaku, & Yoshida, Hiroyuki. Structural study of quasi-one-dimensional vanadium pyroxene LiVSi{sub 2}O{sub 6} single crystals. United States. doi:10.1016/J.JSSC.2016.11.012.
Ishii, Yuto, Matsushita, Yoshitaka, Oda, Migaku, and Yoshida, Hiroyuki. Wed . "Structural study of quasi-one-dimensional vanadium pyroxene LiVSi{sub 2}O{sub 6} single crystals". United States. doi:10.1016/J.JSSC.2016.11.012.
@article{osti_22658175,
title = {Structural study of quasi-one-dimensional vanadium pyroxene LiVSi{sub 2}O{sub 6} single crystals},
author = {Ishii, Yuto and Matsushita, Yoshitaka and Oda, Migaku and Yoshida, Hiroyuki},
abstractNote = {Single crystals of quasi-one-dimensional vanadium pyroxene LiVSi{sub 2}O{sub 6} were synthesized and the crystal structures at 293 K and 113 K were studied using X-ray diffraction experiments. We found a structural phase transition from the room-temperature crystal structure with space group C2/c to a low-temperature structure with space group P2{sub 1}/c, resulting from a rotational displacement of SiO{sub 4} tetrahedra. The temperature dependence of magnetic susceptibility shows a broad maximum around 116 K, suggesting an opening of the Haldane gap expected for one-dimensional antiferromagnets with S=1. However, an antiferromagnetic long-range order was developed below 24 K, probably caused by a weak inter-chain magnetic coupling in the compound. - Graphical abstract: Low temperature crystal structure of LiVSi{sub 2}O{sub 6} and an orbital arrangement within the V-O zig-zag chain along the c-axis. - Highlights: • A low temperature structure of LiVSi{sub 2}O{sub 6} was determined by single crystal X-ray diffraction measurements. • The origin of the structural transition is a rotational displacement of SiO{sub 4} tetrahedra. • The uniform orbital overlap in the V-O zigzag chain makes the system a quasi one-dimensional antiferromagnet.},
doi = {10.1016/J.JSSC.2016.11.012},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 246,
place = {United States},
year = {Wed Feb 15 00:00:00 EST 2017},
month = {Wed Feb 15 00:00:00 EST 2017}
}
  • Nanostructured cobalt vanadium oxide (V{sub 2}O{sub 5}) xerogels spread onto crystalline Si substrates were synthesized via peroxovanadate sol gel route. The resulting products were characterized by distinct experimental techniques. The surface morphology and the nanostructure of xerogels correlate with Co concentration. The decrease of the structural coherence length is followed by the formation of a loose network of nanopores when the concentration of intercalated species was greater than 4 at% of Co. The efficiency of the synthesis route also drops with the increase of Co concentration. The interaction between the Co(OH{sub 2}){sub 6}{sup 2+} cations and the (H{sub 2}V{sub 10}O{submore » 28}){sup 4−} anions during the synthesis was suggested as a possible explanation for the incomplete condensation of the V{sub 2}O{sub 5} gel. Finally the experimental results points for the intercalation of Co between the bilayers of the V{sub 2}O{sub 5}. In this scenario two possible preferential occupation sites for the metallic atoms in the framework of the xerogel were proposed. - Graphical abstract: Quasi-one-dimensional nanostructured cobalt (Co) intercalated vanadium oxide (V{sub 2}O{sub 5}) nanoribbons synthesized by peroxovanadate sol gel route. - Highlights: • Nanostructured cobalt V{sub 2}O{sub 5} gel spread onto c{sub S}i were synthesized via peroxovanadate sol gel route. • The micro and nanostructure correlates with the cobalt content. • The efficiency of the synthesis route shows to be also dependent of Co content. • The experimental results points for the intercalation of Co between the bilayers of the V{sub 2}O{sub 5} xerogel.« less
  • The hydrothermal syntheses, X-ray single-crystal structures, and some properties of Ba(VO){sub 2}(SeO{sub 3}){sub 2}(HSeO{sub 3}){sub 2} and Ba{sub 8}(VO){sub 6}(PO{sub 4}){sub 2}(HPO{sub 4}){sub 11}{center_dot}3H{sub 2}O are described. Ba(VO){sub 2}(SeO{sub 3}){sub 2}(HSeO{sub 3}){sub 2} contains a three-dimensional network of VO{sub 6} and (H)SeO{sub 3} polyhedra, linked via V-O-Se bonds. The Ba cation is 10-coordinate, the VO{sub 6} group contains a short vanadyl V{double_bond}O bond typical of V{sup IV}, and the (H)SeO{sub 3} groups are pyramidal. Magnetic susceptibility data are consistent with V{sup IV} and show paramagnetic behavior from 4 to 300 K. Crystal data for Ba(VO){sub 2}(SeO{sub 3}){sub 2}(HSeO{sub 3}){sub 2}:M{submore » r} = 781.06, monoclinic, space group P2{sub 1}/c (No. 14), a = 9.680(3) {angstrom}, b = 7.024(2) {angstrom}, c = 9.882(4) {angstrom}, {beta} = 116.42(3){degrees}, V = 601.75 {angstrom}{sup 3}, Z = 2, R = 3.89%, R{sub w} = 3.64% [1637 observed reflections with I > 3{sigma}(I)]. Ba{sub 8}(VO){sub 6}(PO{sub 4}){sub 2}(HPO{sub 4}){sub 11}{center_dot}3H{sub 2}O contains a complex network of VO{sub 6} and PO{sub 4}/HPO{sub 4} groups, which form two different types of one-dimensional chains: one chain contains fairly regular V{sup IV}O{sub 6} and (H)PO{sub 4} groups; the other is built up from distorted V{sup IV}O{sub 6} octahedra and (hydrogen) phosphate groups. 10- and 13-coordinate Ba{sup 2+} cations complete the structure, which shows antiferromagnetic ordering of the V{sup IV} centers at {approximately}20 K. Crystal data for Ba{sub 8}(VO){sub 6}(PO{sub 4}){sub 2}(HPO{sub 4}){sub 11}{center_dot}3H{sub 2}O: M{sub r} = 2800.05, monoclinic, space group C2/m (No. 12), a = 31.685(11) {angstrom}, b = 5.208(2) {angstrom}, c = 7.784(3) {angstrom}, {beta} = 90.59(3){degrees}, V = 1284.5(7) {angstrom}{sup 3}, Z = 1, R = 4.03%, and R{sub w} = 5.28% [1892 observed reflections with I > 3{sigma}(I)].« less
  • The hydrothermal reaction of Cs[sub 4]V[sub 2]O[sub 7], V, H[sub 3]PO[sub 4], H[sub 2]O, and Bu[sub 4]NBr in the molar ratio 4.5:1:41:3150:1 at 200[degrees]C for 48 hr yielded the red-brown cesium vanadium phosphate Cs[(V[sub 2]O[sub 3])(HPO[sub 4])[sub 2](H[sub 2]O)], a mixed-valence V(IV, V) species. The structure contains corner-sharing vanadium octahedra and phosphorus tetrahedra with unusual 1-D (-V[sup IV]-O-V[sup v]-O-)[infinity] chains formed from VO[sub 6] octahedra sharing opposite corners. These chains are connected through tridentate bridging (HPO[sub 4])[sup 2[minus]] units to produce a three-dimensional network. The Cs[sup +] cations occupy large channels formed from six vanadium octahedra and six phosphorus tetrahedra.more » At room temperature the material is paramagnetic with one unpaired spin per (-V[sup IV]-O-V[sup v]-O-) unit while complicated anti-ferromagentic ordering is observed below ca. 6 K. Crystal data: monoclinic, P2[sub 1]/n with a = 7.22(1), b = 18.56(1), c = 8.195(6) [angstrom], [beta] = 114.01(6)[degrees], Z = 4, d[sub calc] = 3.233 g cm[sup [minus]3]; structure solution and refinement based on 1088 reflections converged at R = 0.028.« less
  • Phase equilibria in the Y{sub 2}O{sub 3}-BaO-NiO system were studied in the temperature range 1,000-1,350{degree}C in air. In addition to previously reported compositions, the new phase Y{sub 2}BaNiO{sub 5} was identified. Conditions for synthesis and stability of Y{sub 2}BaNiO{sub 5} are reported, as well as the dependence of oxygen nonstoichiometry and lattice parameters on conditions of preparation. Single crystals were obtained by rf induction melting and the structure was refined by four circle x-ray diffraction. Y{sub 2}BaNiO{sub 5} is isomorphous with Nd{sub 2}BaNiO{sub 5} and consists of isolated, highly compressed chains of corner-shared NiO{sub 6} octahedra.
  • Single crystals of Bi[sub 2]V[sub 1[minus]x]Ge[sub x]O[sub 5.5[minus]x/2] (x = 0.2, 0.4, and 0.6) were grown by slow cooling of melts. Bismuth vanadate transforms from an orthorhombic to a tetragonal structure and subsequently to an orthorhombic system when the Ge[sup 4+] concentration was varied from x = 0.2 to x = 0.6. All of these compositions crystallized in polar space groups (Aba2, F4mm, and Fmm2 for x = 0.2, 0.4, and 0.6, respectively). The structures were fully determined by single crystal X-ray diffraction studies.