421 research outputs found
Frustrated square lattice with spatial anisotropy: crystal structure and magnetic properties of PbZnVO(PO4)2
Crystal structure and magnetic properties of the layered vanadium phosphate
PbZnVO(PO4)2 are studied using x-ray powder diffraction, magnetization and
specific heat measurements, as well as band structure calculations. The
compound resembles AA'VO(PO4)2 vanadium phosphates and fits to the extended
frustrated square lattice model with the couplings J(1), J(1)' between
nearest-neighbors and J(2), J(2)' between next-nearest-neighbors. The
temperature dependence of the magnetization yields estimates of averaged
nearest-neighbor and next-nearest-neighbor couplings, J(1) ~ -5.2 K and J(2) ~
10.0 K, respectively. The effective frustration ratio alpha=J(2)/J(1) amounts
to -1.9 and suggests columnar antiferromagnetic ordering in PbZnVO(PO4)2.
Specific heat data support the estimates of J(1) and J(2) and indicate a likely
magnetic ordering transition at 3.9 K. However, the averaged couplings
underestimate the saturation field, thus pointing to the spatial anisotropy of
the nearest-neighbor interactions. Band structure calculations confirm the
identification of ferromagnetic J(1), J(1)' and antiferromagnetic J(2), J(2)'
in PbZnVO(PO4)2 and yield J(1)'-J(1) ~ 1.1 K in excellent agreement with the
experimental value of 1.1 K, deduced from the difference between the expected
and experimentally measured saturation fields. Based on the comparison of
layered vanadium phosphates with different metal cations, we show that a
moderate spatial anisotropy of the frustrated square lattice has minor
influence on the thermodynamic properties of the model. We discuss relevant
geometrical parameters, controlling the exchange interactions in these
compounds, and propose a new route towards strongly frustrated square lattice
materials.Comment: 14 pages, 9 figures, 5 table
(CuCl)LaTa2O7 and quantum phase transition in the (CuX)LaM2O7 family (X = Cl, Br; M = Nb, Ta)
We apply neutron diffraction, high-resolution synchrotron x-ray diffraction,
magnetization measurements, electronic structure calculations, and quantum
Monte-Carlo simulations to unravel the structure and magnetism of
(CuCl)LaTa2O7. Despite the pseudo-tetragonal crystallographic unit cell, this
compound features an orthorhombic superstructure, similar to the Nb-containing
(CuX)LaNb2O7 with X = Cl and Br. The spin lattice entails dimers formed by the
antiferromagnetic fourth-neighbor coupling J4, as well as a large number of
nonequivalent interdimer couplings quantified by an effective exchange
parameter Jeff. In (CuCl)LaTa2O7, the interdimer couplings are sufficiently
strong to induce the long-range magnetic order with the Neel temperature TN~7 K
and the ordered magnetic moment of 0.53 mu_B, as measured with neutron
diffraction. This magnetic behavior can be accounted for by Jeff/J4~1.6 and
J4~16 K. We further propose a general magnetic phase diagram for the
(CuCl)LaNb2O7-type compounds, and explain the transition from the gapped
spin-singlet (dimer) ground state in (CuCl)LaNb2O7 to the long-range
antiferromagnetic order in (CuCl)LaTa2O7 and (CuBr)LaNb2O7 by an increase in
the magnitude of the interdimer couplings Jeff/J_4, with the (CuCl)LaM2O7 (M =
Nb, Ta) compounds lying on different sides of the quantum critical point that
separates the singlet and long-range-ordered magnetic ground states.Comment: 13 pages, 13 figures, 4 tables + Supplementary informatio
Interplay of atomic displacements in the quantum magnet (CuCl)LaNb2O7
We report on the crystal structure of the quantum magnet (CuCl)LaNb2O7 that
was controversially described with respect to its structural organization and
magnetic behavior. Using high-resolution synchrotron powder x-ray diffraction,
electron diffraction, transmission electron microscopy, and band structure
calculations, we solve the room-temperature structure of this compound
[alpha-(CuCl)LaNb2O7] and find two high-temperature polymorphs. The
gamma-(CuCl)LaNb2O7 phase, stable above 640K, is tetragonal with a(sub) = 3.889
A, c(sub) = 11.738 A, and the space group P4/mmm. In the gamma-(CuCl)LaNb2O7
structure, the Cu and Cl atoms are randomly displaced from the special
positions along the {100} directions. The beta-phase [a(sub) x 2a(sub) x
c(sub), space group Pbmm] and the alpha-phase [2a(sub) x 2a(sub) x c(sub),
space group Pbam] are stable between 640 K and 500 K and below 500 K,
respectively. The structural changes at 500 K and 640 K are identified as
order-disorder phase transitions. The displacement of the Cl atoms is frozen
upon the gamma --> beta transformation, while a cooperative tilting of the NbO6
octahedra in the alpha-phase further eliminates the disorder of the Cu atoms.
The low-temperature alpha-(CuCl)LaNb2O7 structure thus combines the two types
of the atomic displacements that interfere due to the bonding between the Cu
atoms and the apical oxygens of the NbO6 octahedra. The precise structural
information resolves the controversy between the previous computation-based
models and provides the long-sought input for understanding the magnetic
properties of (CuCl)LaNb2O7.Comment: 12 pages, 10 figures, 5 tables; crystallographic information (cif
files) include
Spiral ground state against ferroelectricity in the frustrated magnet BiMnFe2O6
The spiral magnetic structure and underlying spin lattice of BiMnFe2O6 are
investigated by low-temperature neutron powder diffraction and density
functional theory band structure calculations. In spite of the random
distribution of the Mn3+ and Fe3+ cations, this compound undergoes a transition
into an incommensurate antiferromagnetically ordered state below TN ~ 220 K.
The magnetic structure is characterized by the propagation vector k=[0,beta,0]
with beta ~ 0.14 and the P22_12_11'(0 \beta 0)0s0s magnetic superspace
symmetry. It comprises antiferromagnetic helixes propagating along the b-axis.
The magnetic moments lie in the ac plane and rotate about pi*(1+beta) ~ 204.8
deg angle between the adjacent magnetic atoms along b. The spiral magnetic
structure arises from the peculiar frustrated arrangement of exchange couplings
in the ab plane. The antiferromagnetic coupling along the c-axis leads to the
cancellation of electric polarization, and results in the lack of
ferroelectricity in BiMnFe2O6.Comment: 11 pages, 8 figures, 8 table
Sodium-Vanadium Bronze Na9V14O35: An Electrode Material for Na-Ion Batteries
Na9V14O35 (η-NaxV2O5) has been synthesized via solid-state reaction in an evacuated sealed silica ampoule and tested as electroactive material for Na-ion batteries. According to powder X-ray diffraction, electron diffraction and atomic resolution scanning transmission electron microscopy, Na9V14O35 adopts a monoclinic structure consisting of layers of corner- and edge-sharing VO5 tetragonal pyramids and VO4 tetrahedra with Na cations positioned between the layers, and can be considered as sodium vanadium(IV,V) oxovanadate Na9V104.1+O19(V5+O4)4. Behavior of Na9V14O35 as a positive and negative electrode in Na half-cells was investigated by galvanostatic cycling against metallic Na, synchrotron powder X-ray diffraction and electron energy loss spectroscopy. Being charged to 4.6 V vs. Na+/Na, almost 3 Na can be extracted per Na9V14O35 formula, resulting in electrochemical capacity of ~60 mAh gâ1. Upon discharge below 1 V, Na9V14O35 uptakes sodium up to Na:V = 1:1 ratio that is accompanied by drastic elongation of the separation between the layers of the VO4 tetrahedra and VO5 tetragonal pyramids and volume increase of about 31%. Below 0.25 V, the ordered layered Na9V14O35 structure transforms into a rock-salt type disordered structure and ultimately into amorphous products of a conversion reaction at 0.1 V. The discharge capacity of 490 mAh gâ1 delivered at first cycle due to the conversion reaction fades with the number of charge-discharge cycles
Energy transfer in Eu3+ doped scheelites : use as thermographic phosphor
In this paper the luminescence of the scheelite-based CaGd2(1-x)Eu2x(WO4)4 solid solutions is investigated as a function of the Eu content and temperature. All phosphors show intense red luminescence due to the 5D0 â 7F2 transition in Eu3+, along with other transitions from the 5D1 and 5D0 excited states. For high Eu3+ concentrations the intensity ratio of the emission originating from the 5D1 and 5D0 levels has a non-conventional temperature dependence, which could be explained by a phonon-assisted cross-relaxation process. It is demonstrated that this intensity ratio can be used as a measure of temperature with high spatial resolution, allowing the use of these scheelites as thermographic phosphor. The main disadvantage of many thermographic phosphors, a decreasing signal for increasing temperature, is absent
Cubic lead perovskite PbMoO3 with anomalous metallic behavior
A previously unreported Pb-based perovskite PbMoO is obtained by
high-pressure and high-temperature synthesis. This material crystallizes in the
cubic structure at room temperature, making it distinct from
typical Pb-based perovskite oxides with a structural distortion. PbMoO
exhibits a metallic behavior down to 0.1 K with an unusual -sub linear
dependence of the electrical resistivity. Moreover, a large specific heat is
observed at low temperatures accompanied by a peak in around 10 K, in
marked contrast to the isostructural metallic system SrMoO. These transport
and thermal properties for PbMoO, taking into account anomalously large Pb
atomic displacements detected through diffraction experiments, are attributed
to a low-energy vibrational mode, associated with incoherent off-centering of
lone pair Pb cations. We discuss the unusual behavior of the electrical
resistivity in terms of a polaron-like conduction, mediated by the strong
coupling between conduction electrons and optical phonons of the local
low-energy vibrational mode.Comment: 5 pages, 5 figure
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