675 research outputs found
Compositional uniformity, domain patterning and the mechanism underlying nano-chessboard arrays
We propose that systems exhibiting compositional patterning at the nanoscale,
so far assumed to be due to some kind of ordered phase segregation, can be
understood instead in terms of coherent, single phase ordering of minority
motifs, caused by some constrained drive for uniformity. The essential features
of this type of arrangements can be reproduced using a superspace construction
typical of uniformity-driven orderings, which only requires the knowledge of
the modulation vectors observed in the diffraction patterns. The idea is
discussed in terms of a simple two dimensional lattice-gas model that simulates
a binary system in which the dilution of the minority component is favored.
This simple model already exhibits a hierarchy of arrangements similar to the
experimentally observed nano-chessboard and nano-diamond patterns, which are
described as occupational modulated structures with two independent modulation
wave vectors and simple step-like occupation modulation functions.Comment: Preprint. 11 pages, 11 figure
Large ferroelectric polarization in the new double perovskite NaLaMnWO induced by non-polar instabilities
Based on density functional theory calculations and group theoretical
analysis, we have studied NaLaMnWO compound which has been recently
synthesized [Phys. Rev. B 79, 224428 (2009)] and belongs to the family of double perovskites. At low temperature, the structure has
monoclinic symmetry, with layered ordering of the Na and La ions and
rocksalt ordering of Mn and W ions. The Mn atoms show an antiferromagnetic
(AFM) collinear spin ordering, and the compound has been reported as a
potential multiferroic. By comparing the low symmetry structure with a parent
phase of symmetry, two distortion modes are found dominant. They
correspond to MnO and WO octahedron \textit{tilt} modes, often
found in many simple perovskites. While in the latter these common tilting
instabilities yield non-polar phases, in NaLaMnWO the additional presence
of the - cation ordering is sufficient to make these rigid unit modes
as a source of the ferroelectricity. Through a trilinear coupling with the two
unstable tilting modes, a significant polar distortion is induced, although the
system has no intrinsic polar instability. The calculated electric polarization
resulting from this polar distortion is as large as 16 . Despite its secondary character, this polarization is coupled with
the dominant tilting modes and its switching is bound to produce the switching
of one of two tilts, enhancing in this way a possible interaction with the
magnetic ordering. The transformation of common non-polar purely steric
instabilities into sources of ferroelectricity through a controlled
modification of the parent structure, as done here by the cation ordering, is a
phenomenon to be further explored.Comment: Physical Chemistry Chemical physics (in press
Magnetic superspace groups and symmetry constraints in incommensurate magnetic phases
Although superspace formalism has become the standard approach for the
analysis of structurally modulated crystals, it has remained during the last
thirty years almost unexplored as a practical tool to deal with magnetic
incommensurate structures. This situation has recently changed with the
development of new computer tools for magnetic phases based on this formalism.
In this context we show here that, as in the case of nonmagnetic incommensurate
systems, the concept of superspace symmetry provides a simple, efficient and
systematic way to characterize the symmetry and rationalize the structural and
physical properties of incommensurate magnetic materials. The method introduces
significant advantages over the most commonly employed method of representation
analysis for the description of the magnetic structure of a crystal. But, more
importantly, in contrast with that method, it consistently yields and
classifies all degrees of freedom of the system. The knowledge of the
superspace group of an incommensurate magnetic material allows to predict its
crystal tensor properties and to rationalize its phase diagram, previous to any
appeal to microscopic models or mechanisms. This is especially relevant when
the properties of incommensurate multiferroics are being studied. We present
first a summary of the superspace method under a very practical viewpoint
particularized to magnetic modulations. Its relation with the usual
representation analysis is then analyzed in detail, with the derivation of
important general rules for magnetic modulations with a single propagation
vector. The power and efficiency of the formalism is illustrated with various
selected examples, including some multiferroic materials
First-principles study of the ferroelastic phase transition in CaCl_2
First-principles density-functional calculations within the local-density
approximation and the pseudopotential approach are used to study and
characterize the ferroelastic phase transition in calcium chloride (CaCl_2). In
accord with experiment, the energy map of CaCl_2 has the typical features of a
pseudoproper ferroelastic with an optical instability as ultimate origin of the
phase transition. This unstable optic mode is close to a pure rigid unit mode
of the framework of chlorine atoms and has a negative Gruneisen parameter. The
ab-initio ground state agrees fairly well with the experimental low temperature
structure extrapolated at 0K. The calculated energy map around the ground state
is interpreted as an extrapolated Landau free-energy and is successfully used
to explain some of the observed thermal properties. Higher-order anharmonic
couplings between the strain and the unstable optic mode, proposed in previous
literature as important terms to explain the soft-phonon temperature behavior,
are shown to be irrelevant for this purpose. The LAPW method is shown to
reproduce the plane-wave results in CaCl_2 within the precision of the
calculations, and is used to analyze the relative stability of different phases
in CaCl_2 and the chemically similar compound SrCl_2.Comment: 9 pages, 6 figures, uses RevTeX
High-temperature phase transitions in SrBi_2Ta_2O_9 film: a study by THz spectroscopy
Time-domain THz transmission experiment was performed on a film deposited on sapphire substrate. Temperatures between 300
and 923 K were investigated and complex permittivity spectra of the film were
determined. The lowest frequency optic phonon near 28 cm reveals a slow
monotonic decrease in frequency on heating with no significant anomaly near the
phase transitions. We show that the dielectric anomaly near the ferroelectric
phase transition can be explained by slowing down of a relaxational mode,
observed in the THz spectra. A second harmonic generation signal observed in a
single crystal confirms a loss of center of symmetry in the ferroelectric phase
and a presence of polar clusters in the intermediate ferroelastic phase.Comment: subm. to J. Phys.: Condens. Matte
A neutron diffraction study and mode analysis of compounds of the system La<sub>1−x</sub>Sr<sub>x</sub>FeO<sub>3−x</sub>F<sub>x</sub> (x=1, 0.8, 0.5, 0.2) and an investigation of their magnetic properties
AbstractWe report here a detailed study of the system La1−xSrxFeO3−xFx, by neutron powder diffraction- and magnetic-measurements. All the compounds are robust antiferromagnetics with ordering temperatures well above room temperature. Magnetic moments are shown to align parallel to the c-axis. FC-ZFC measurements indicate a small canting of the magnetic moments, resulting in a ferromagnetic component with a maximum for La0.5Sr0.5FeO2.5F0.5. We show that the system exhibits a composition-driven transition from a phase, for low fluorination levels (x≤0.5), with Pnma symmetry and the usual system of octahedral tiltings, to a phase with space group Imma for higher fluorine contents, where a correlated distortion of the oxygen octahedra plays a significant role. The consistency of the structural models, with respect to the expected continuity of the amplitudes of the different distortion modes and the invariance of their internal form, was monitored through the symmetry mode decomposition of the structures
Unexpected phase transition sequence in the ferroelectric Bi4Ti3O12
Authors thank Dr George Carins for experimental assistance. Y.-Y.G thanks the China Scholarships Council and the University of St Andrews for a studentship.The high-temperature phase behaviour of the ferroelectric layered perovskite Bi4Ti3O12 has been re-examined by high-resolution powder neutron diffraction. Previous studies, both experimental and theoretical, had suggested conflicting structural models and phase transition sequences, exacerbated by the complex interplay of several competing structural instabilities. Here, we confirm that Bi4Ti3O12 undergoes two separate structural transitions from the aristotype tetragonal phase (space group I4/mmm) to the ambient temperature ferroelectric phase (confirmed as monoclinic, B1a1). An unusual, and previously unconsidered, intermediate paraelectric phase is suggested to exist above TC, with tetragonal symmetry, space group P4/mbm. This phase is peculiar in displaying a unique type of octahedral tilting, in which the triple perovskite blocks of the layered structure alternate between tilted and untilted. This is rationalised in terms of the bonding requirements of the Bi3+ cations within the perovskite blocks.Publisher PDFPeer reviewe
Phonons from neutron powder diffraction
The spherically averaged structure function \soq obtained from pulsed
neutron powder diffraction contains both elastic and inelastic scattering via
an integral over energy. The Fourier transformation of \soq to real space, as
is done in the pair density function (PDF) analysis, regularizes the data, i.e.
it accentuates the diffuse scattering. We present a technique which enables the
extraction of off-center phonon information from powder diffraction experiments
by comparing the experimental PDF with theoretical calculations based on
standard interatomic potentials and the crystal symmetry. This procedure
(dynamics from powder diffraction(DPD)) has been successfully implemented for
two systems, a simple metal, fcc Ni, and an ionic crystal, CaF. Although
computationally intensive, this data analysis allows for a phonon based
modeling of the PDF, and additionally provides off-center phonon information
from powder neutron diffraction
- …