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Title: Hydrothermal synthesis, structure, and magnetic properties of Pu(SeO3)2

Abstract

The reaction between PuO2 and SeO2 under mild hydrothermal conditions results in the formation of Pu(SeO3)2 as brick-red prisms. This compound adopts the Ce(SeO3)2 structure type, and consists of one-dimensional chains of edge-sharing [PuO8] distorted bicapped trigonal prisms linked by [SeO3] units into a three-dimensional network. Crystallographic data: Pu(SeO3)2, monoclinic, space group P21/n, a 6.960(1) A , b 10.547(2) A , c 7.245(1) A , b 106.880(9)1, V 508.98(17) A 3, Z 4 (T 193 K), R(F) 2.92% for 83 parameters with 1140 re ections with I42s(I). Magnetic susceptibility data for Pu(SeO3)2 are linear from 35 to 320 K and yield an effective moment of 2.71(5) mB and a Weiss constant of -500(5) K.

Authors:
 [1];  [2];  [2];  [3];  [4];  [5]
  1. ORNL
  2. Argonne National Laboratory (ANL)
  3. University of South Alabama, Mobile
  4. Oak Ridge National Laboratory (ORNL)
  5. Auburn University, Auburn, Alabama
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1055151
DOE Contract Number:
DE-AC05-00OR22725
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 181; Journal Issue: 3
Country of Publication:
United States
Language:
English

Citation Formats

Bray, Travis H, Skanthakumar, S, Soderholm, L., Sykora, Richard E., Haire, Richard G., and Albrecht-Schmitt, Thomas E.. Hydrothermal synthesis, structure, and magnetic properties of Pu(SeO3)2. United States: N. p., 2007. Web.
Bray, Travis H, Skanthakumar, S, Soderholm, L., Sykora, Richard E., Haire, Richard G., & Albrecht-Schmitt, Thomas E.. Hydrothermal synthesis, structure, and magnetic properties of Pu(SeO3)2. United States.
Bray, Travis H, Skanthakumar, S, Soderholm, L., Sykora, Richard E., Haire, Richard G., and Albrecht-Schmitt, Thomas E.. Mon . "Hydrothermal synthesis, structure, and magnetic properties of Pu(SeO3)2". United States. doi:.
@article{osti_1055151,
title = {Hydrothermal synthesis, structure, and magnetic properties of Pu(SeO3)2},
author = {Bray, Travis H and Skanthakumar, S and Soderholm, L. and Sykora, Richard E. and Haire, Richard G. and Albrecht-Schmitt, Thomas E.},
abstractNote = {The reaction between PuO2 and SeO2 under mild hydrothermal conditions results in the formation of Pu(SeO3)2 as brick-red prisms. This compound adopts the Ce(SeO3)2 structure type, and consists of one-dimensional chains of edge-sharing [PuO8] distorted bicapped trigonal prisms linked by [SeO3] units into a three-dimensional network. Crystallographic data: Pu(SeO3)2, monoclinic, space group P21/n, a 6.960(1) A , b 10.547(2) A , c 7.245(1) A , b 106.880(9)1, V 508.98(17) A 3, Z 4 (T 193 K), R(F) 2.92% for 83 parameters with 1140 re ections with I42s(I). Magnetic susceptibility data for Pu(SeO3)2 are linear from 35 to 320 K and yield an effective moment of 2.71(5) mB and a Weiss constant of -500(5) K.},
doi = {},
journal = {Journal of Solid State Chemistry},
number = 3,
volume = 181,
place = {United States},
year = {Mon Jan 01 00:00:00 EST 2007},
month = {Mon Jan 01 00:00:00 EST 2007}
}
  • The reaction between PuO{sub 2} and SeO{sub 2} under mild hydrothermal conditions results in the formation of Pu(SeO{sub 3}){sub 2} as brick-red prisms. This compound adopts the Ce(SeO{sub 3}){sub 2} structure type, and consists of one-dimensional chains of edge-sharing [PuO{sub 8}] distorted bicapped trigonal prisms linked by [SeO{sub 3}] units into a three-dimensional network. Crystallographic data: Pu(SeO{sub 3}){sub 2}, monoclinic, space group P2{sub 1}/n, a=6.960(1) A, b=10.547(2) A, c=7.245(1) A, {beta}=106.880(9){sup o}, V=508.98(17) A{sup 3}, Z=4 (T=193 K), R(F)=2.92% for 83 parameters with 1140 reflections with I>2{sigma}(I). Magnetic susceptibility data for Pu(SeO{sub 3}){sub 2} are linear from 35 to 320more » K and yield an effective moment of 2.71(5) {mu}{sub B} and a Weiss constant of -500(5) K. - Graphical abstract: A depiction of the three-dimensional structure of Pu(SeO{sub 3}){sub 2} formed from the interconnection of one-dimensional chains of edge-sharing PuO{sub 8} dodecahedra by selenite anions.« less
  • A new manganese(II) phosphate templated by ethylenediamine, (C{sub 2}H{sub 10}N{sub 2})[Mn{sub 2}(HPO{sub 4}){sub 3}(H{sub 2}O)], has been prepared by hydrothermal synthesis and characterized by single-crystal diffraction data and spectroscopic and magnetic techniques. The compound crystallizes in the monoclinic space group P2{sub 1}/n with a = 21.961(7), b = 9.345(1), c = 6.639(2) {angstrom}; {beta} = 91.06(2){degree}; V = 1362.3(6) {angstrom}{sup 3}; and Z = 4. The structure consists of anionic sheets of formula [Mn{sub 2}(HPO{sub 4}){sub 3}]{sup 2-}, being the charge compensated by ethylendiammonium cations. The sheets are constructed by edge-sharing MnO{sub 6} octahedra, MnO{sub 5} trigonal bipyramids, and hydrogenmore » phosphate tetrahedra. Within a layer, the edge-sharing octahedra and the trigonal bipyramids are linked in an alternating way, forming zigzag chains along the [001] direction. The ethylenediammonium cations and the water molecules are located in the interlayer space. The compound has been characterized by IR spectroscopy. A study of the compound by luminescence and diffuse reflectance spectroscopies is carried out. The Dq and Racah parameters have been calculated for Mn(II) ions in octahedral sites. The EST spectra at different temperatures of the compound show isotropic signals, with a g value that remains unchanged with variation in temperature. The intensity and the line width of the ESR signals increase continuously from room temperature to 4.2 K. Magnetic measurements from room temperature to 1.8 K indicate the presence of antiferromagnetic interactions. A value of J/k = {minus}0.75 K for the exchange parameter has been calculated by fitting the experimental magnetic data to a triangular lattice antiferromagnet of S = 5/2 spins.« less
  • The [M{sub x}{sup II}M{sub 2.5-x}{sup III}(H{sub 2}O){sub 2}(HP{sup III}O{sub 3}){sub y}(P{sup V}O{sub 4}){sub 2-y}F; M=Fe (1), x=2.08, y=1.58; M=Co (2), x=2.5, y=2; Ni (3), x=2.5, y=2] compounds have been synthesized using mild hydrothermal conditions at 170 deg. C during five days. Single-crystals of (1) and (2), and polycrystalline sample of (3) were obtained. These isostructural compounds crystallize in the orthorhombic system, space group Aba2, with a=9.9598(2), b=18.8149(4) and c=8.5751(2) A for (1), a=9.9142(7), b=18.570(1) and c=8.4920(5) A for (2) and a=9.8038(2), b=18.2453(2) and c=8.4106(1) A for (3), with Z=8 in the three phases. An X-ray diffraction study reveals that themore » crystal structure is composed of a three-dimensional skeleton formed by [MO{sub 5}F] and [MO{sub 4}F{sub 2}] (M=Fe, Co and Ni) octahedra and [HPO{sub 3}] tetrahedra, partially substituted by [PO{sub 4}] tetrahedra in phase (1). The IR spectra show the vibrational modes of the water molecules and those of the (HPO{sub 3}){sup 2-} tetrahedral oxoanions. The thermal study indicates that the limit of thermal stability of these phases is 195 deg. C for (1) and 315 deg. C for (2) and (3). The electronic absorption spectroscopy shows the characteristic bands of the Fe(II), Co(II) and Ni(II) high-spin cations in slightly distorted octahedral geometry. Magnetic measurements indicate the existence of global antiferromagnetic interactions between the metallic centers with a ferromagnetic transition in the three compounds at 28, 14 and 21 K for (1), (2) and (3), respectively. Compound (1) exhibits a hysteresis loop with remnant magnetization and coercive field values of 0.72 emu/mol and 880 Oe, respectively. - Abstract: Polyhedral view of the crystal structure of the [M{sub x}{sup II}M{sub 2.5-x}{sup III}(H{sub 2}O){sub 2}(HP{sup III}O{sub 3}){sub y}(P{sup IV}O{sub 4}){sub 2-y}F; M=Fe, x=2.08, y=1.58; M=Co, Ni, x=2.5, y=2] compounds showing the sheets along the [001] direction.« 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
  • The reaction of NpO{sub 2} with SeO{sub 2} in the presence of CsCl at 180 {sup o}C results in the formation of Np(NpO{sub 2}){sub 2}(SeO{sub 3}){sub 3} (1). The structure of 1 consists of three crystallographically unique Np centers with three different coordination environments in two different oxidation states. Np(1) is found in a neptunyl(V), ONpO{sup +}, unit that is further ligated in the equatorial plane by three chelating SeO{sub 3}{sup 2-} anions to create a hexagonal bipyramidal NpO{sub 8} unit. A second neptunyl(V) cation also occurs for Np(2); it is bound by four bridging selenite anions and by themore » oxo atom from the Np(1) neptunyl cation to form a pentagonal bipyramidal, NpO{sub 7}, unit. The third neptunium center, Np(3), which contains Np(IV), is found in a distorted NpO{sub 8} dodecahedron. Np(3) is bound by five bridging selenite anions and by three neptunyl units via cation-cation interactions. The NpO{sub 7} pentagonal bipyramids and NpO{sub 8} hexagonal bipyramids share both corners and edges. Both of these polyhedra share corners via cation-cation interactions with the NpO{sub 8} dodecahedra creating a three-dimensional structure with small channels that house the stereochemically active lone pair of electrons on the selenite anions. Magnetic susceptibility data follow Curie-Weiss behavior over the entire temperature range measured (5 {<=} T {<=} 320 K). The effective moment, {mu}{sub eff} = 2.28 {mu}{sub B}, which represents an average over the three crystallographically inequivalent Np atoms, is within the expected range of values. There is no evidence of long-range ordering of the Np moments at temperatures down to 5 K, consistent with the negligible Weiss constant determined from fitting the susceptibility data. Crystallographic data: 1, orthorhombic, space group Pbca, a = 10.6216(5), b = 11.9695(6), and c = 17.8084(8) {angstrom} and Z = 8 (T = 193 K).« less