644 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
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
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
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
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
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
The order parameter-entropy relation in some universal classes: experimental evidence
The asymptotic behaviour near phase transitions can be suitably characterized
by the scaling of with , where is
the excess entropy and is the order parameter. As is obtained by
integration of the experimental excess specific heat of the transition , it displays little experimental noise so that the curve versus is better constrained than, say,
versus . The behaviour of for different
universality classes is presented and compared. In all cases, it clearly
deviates from being a constant. The determination of this function can then be
an effective method to distinguish asymptotic critical behaviour. For
comparison, experimental data for three very different systems, Rb2CoF4,
Rb2ZnCl4 and SrTiO3, are analysed under this approach. In SrTiO3, the function
does not deviate within experimental resolution from a straight
line so that, although Q can be fitted with a non mean-field exponent, the data
can be explained by a classical Landau mean-field behaviour. In contrast, the
behaviour of for the antiferromagnetic transition in Rb2CoF4 and
the normal-incommensurate phase transition in Rb2ZCl4 is fully consistent with
the asymptotic critical behaviour of the universality class corresponding to
each case. This analysis supports, therefore, the claim that incommensurate
phase transitions in general, and the ABX compounds in particular, in
contrast with most structural phase transitions, have critical regions large
enough to be observable.Comment: 13 pp. 9 ff. 2 tab. RevTeX. Submitted to J. Phys.: Cond. Matte
Advances in ab-initio theory of Multiferroics. Materials and mechanisms: modelling and understanding
Within the broad class of multiferroics (compounds showing a coexistence of
magnetism and ferroelectricity), we focus on the subclass of "improper
electronic ferroelectrics", i.e. correlated materials where electronic degrees
of freedom (such as spin, charge or orbital) drive ferroelectricity. In
particular, in spin-induced ferroelectrics, there is not only a {\em
coexistence} of the two intriguing magnetic and dipolar orders; rather, there
is such an intimate link that one drives the other, suggesting a giant
magnetoelectric coupling. Via first-principles approaches based on density
functional theory, we review the microscopic mechanisms at the basis of
multiferroicity in several compounds, ranging from transition metal oxides to
organic multiferroics (MFs) to organic-inorganic hybrids (i.e. metal-organic
frameworks, MOFs)Comment: 22 pages, 9 figure
Hypermethioninaemia due to methionine adenosyltransferase I/III (MAT I/III) deficiency: diagnosis in an expanded neonatal screening programme
The Expanded Newborn Screening Program (MS/MS) in the region of Galicia (NW Spain) was initiated in 2000 and includes the measurement of methionine levels in dried blood spots. Between June 2000 and June 2007, 140 818 newborns were analysed, and six cases of persistent hypermethioninaemia were detected: one homocystinuria due to cystathionine β-synthase (CβS) deficiency, and five methionine adenosyltransferase I/III (MAT I/III) deficiencies. The five cases of MAT I/III deficiency represent an incidence of 1/28 163 newborns. In these five patients, methionine levels in dried blood spots ranged from 50 to 147 μmol/L. At confirmation of the persistence of the hypermethioninaemia in a subsequent plasma sample, plasma methionine concentrations were moderately elevated in 4 of the 5 patients (mean 256 μmol/L), while total homocysteine (tHcy) was normal; the remaining patient showed plasma methionine of 573 μmol/L and tHcy of 22.8 μmol/L. All five patients were heterozygous for the same dominant mutation, R264H in the MAT1A gene. With a diet not exceeding recommended protein requirements for their age, all patients maintained methionine levels below 300 μmol/L. Currently, with a mean of 2.5 years since diagnosis, the patients are asymptomatic and show developmental quotients within the normal range. Our results show a rather high frequency of hypermethioninaemia due to MAT I/III deficiency in the Galician neonatal population, indicating a need for further studies to evaluate the impact of persistent isolated hypermethioninaemia in neonatal screening programmes
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