556 research outputs found
Generarized Cubic Model for BaTiO-like Ferroelectric Substance
We propose an order-disorder type microscopic model for BaTiO-like
Ferroelectric Substance. Our model has three phase transitions and four phases.
The symmetry and directions of the polarizations of the ordered phases agree
with the experimental results of BaTiO. The intermediate phases in our
model are known as an incompletely ordered phase, which appears in a
generalized clock model.Comment: 6 pages, 4figure
Band-Engineered LaFeO-LaNiO Thin Film Interfaces for Electrocatalysis of Water
Transition metal oxides have generated significant interest for their
potential as catalysts for the oxygen evolution reaction (OER) in alkaline
environments. Iron and nickel-based perovskite oxides have proven particularly
promising, with catalytic over-potentials rivaling precious metal catalysts
when the alignment of the valence band relative to the OER reaction potential
is tuned through substitutional doping or alloying. Here we report that
engineering of band alignment in LaFeO/LaNiO (LFO/LNO)
heterostructures via interfacial doping yields greatly enhanced catalytic
performance. Using density functional theory modeling, we predict a 0.2 eV
valence band offset (VBO) between metallic LNO and semiconducting LFO that
significantly lowers the barrier for hole transport through LFO compared to the
intrinsic material and make LFO a p-type semiconductor. Experimental band
alignment measurements using in situ X-ray photoelectron spectroscopy of
epitaxial LFO/LNO heterostructures agree quite well with these predictions,
producing a measured VBO of 0.3(1) eV. OER catalytic measurements on the same
samples in alkaline solution show an increase in catalytic current density by a
factor of ~275 compared to LFO grown on n-type Nb-doped SrTiO. These
results demonstrate the power of tuning band alignments through interfacial
band engineering for improved catalyticComment: 13 pages, 5 figures; Supplemental info: 5 pages, 5 figure
Thickness Dependent OER Electrocatalysis of Epitaxial LaFeO Thin Films
Transition metal oxides have long been an area of interest for water
electrocatalysis through the oxygen evolution and oxygen reduction reactions.
Iron oxides, such as LaFeO, are particularly promising due to the
favorable energy alignment of the valence and conduction bands comprised of
Fe cations and the visible light band gap of such materials. In this
work, we examine the role of band alignment on the electrocatalytic oxygen
evolution reaction (OER) in the intrinsic semiconductor LaFeO by growing
epitaxial films of varying thicknesses on Nb-doped SrTiO. Using cyclic
voltammetry and electrochemical impedance spectroscopy, we find that there is a
strong thickness dependence on the efficiency of electrocatalysis for OER.
These measurements are understood based on interfacial band alignment in the
system as confirmed by layer-resolved electron energy loss spectroscopy and
electrochemical Mott-Schottky measurements. Our results demonstrate the
importance of band engineering for the rational design of thin film
electrocatalysts for renewable energy sources.Comment: 19 pages, 6 figures; authors Burton and Paudel contributed equally;
supplement: 11 pages, 7 figure
Testing the daytime oxidizing capacity of the troposphere: 1994 OH field campaign at the Izaña Observatory, Tenerife
A field campaign was carried out during May 1994 at the Izaña station, Tenerife. This campaign was part of the program Environment and Climate sponsored by the European Commission to study the influence of European emissions on the oxidizing capacity of a clean tropospheric environment. Daytime and also nighttime measurements were made, covering the OH as well as the NO3 chemistry. This paper presents the OH measurements taken with a multipass optical absorption spectrometer (MOAS) and discusses the daytime chemistry in a statistical and therefore more preliminary way. All relevant parameters influencing the OH concentration were monitored. From the data the two main contributions to the OH production can clearly be discerned and are given by the primary production following the ozone photolysis and the O(1D)-H2O reaction and by the catalytic reactions of NOx in the recycling process. The latter processes prove to contribute a dominant part to the OH concentration. The measurements of the nonmethane hydrocarbons (NMHC) especially of the biogenics, indicate a considerable influence of the NMHC on the absolute values of the OH concentration at Tenerife.This work has been financially supported by the European Commission (grant EV5V-CT93-0321), by the DFG, and by the Fonds der Chemischen Industrie, which is gratefully acknowledged
Public Good Overprovision by a Manipulative Provider
We study contracting between a public good provider and users with private valuations of the good. We show that, once the provider extracts the users' private information, she benefits from manipulating the collective information received from all users when communicating with them. We derive conditions under which such manipulation determines the direction of distortions in public good provision. If the provider is non-manipulative, the public good is always underprovided, whereas overprovision occurs with a manipulative provider. With overprovision, not only high-valuation users, but also low-valuation users may obtain positive rents—users may prefer facing a manipulative provider.Peer Reviewe
The Energetics of Li Off-Centering in KLiTaO; First Principles Calculations
KLiTaO (KLT) solid solutions exhibit a variety of
interesting physical phenomena related to large displacements of Li-ions from
ideal perovskite A-site positions. First-principles calculations for KLT
supercells were used to investigate these phenomena. Lattice dynamics
calculations for KLT exhibit a Li off-centering instability. The energetics of
Li-displacements for isolated Li-ions and for Li-Li pairs up to 4th neighbors
were calculated. Interactions between nearest neighbor Li-ions, in a Li-Li
pair, strongly favor ferroelectric alignment along the pair axis. Such Li-Li
pairs can be considered "seeds" for polar nanoclusters in KLT.
Electrostriction, local oxygen relaxation, coupling to the KT soft-mode, and
interactions with neighboring Li-ions all enhance the polarization from Li
off-centering. Calculated hopping barriers for isolated Li-ions and for nearest
neighbor Li-Li pairs are in good agreement with Arrhenius fits to experimental
dielectric data.Comment: 14 pages including 10 figures. To Physical Review B. Replaced after
corrections due to referees' remark
Quantitative Genetic Effects of Bottlenecks: Experimental Evidence from a Wild Plant Species, Nigella degenii
Understanding the genetic consequences of changes in population size is fundamental in a variety of contexts, such as adaptation and conservation biology. In the study presented here, we have performed a replicated experiment with the plant Nigella degenii to explore the quantitative genetic effects of a single-founder bottleneck. In agreement with additive theory, the bottleneck reduced the mean (co)variance within lines and caused stochastic, line-specific changes in the genetic (co)variance structure. However, a significant portion of the (co)variance structure was conserved, and 2 characters—leaf and flower (sepal) size—turned out to be positively correlated in all data sets, indicating a potential for correlated evolution in these characters, even after a severe bottleneck. The hierarchical partitioning of genetic variance for flower size was in good agreement with predictions from additive theory, whereas the remaining characters showed an excess of within-line variance and a deficiency of among-line variance. The latter discrepancies were most likely a result of selection, given the small proportion of lines (23%) that remained viable until the end of the experiment. Our results suggest that bottlenecked populations of N. degenii generally have a lower adaptive potential than the ancestral population but also highlight the idiosyncratic nature of bottleneck effects
Polarization Dependence of Born Effective Charge and Dielectric Constant in KNbO
The Born effective charge Z^{*} and dielectric tensor \epsilon_{\infty} of
KNbO_3 are found to be very sensitive to the atomic geometry, changing by as
much as 27% between the paraelectric cubic and ferroelectric tetragonal and
rhombohedral phases. Subtracting the bare ionic contribution reveals changes of
the dynamic component of Z^{*} as large as 50%, for atomic displacements that
are typically only a few percent of the lattice constant. Z^{*},
\epsilon_{\infty} and all phonon frequencies at the Brillouin zone center were
calculated using the {\it ab initio} linearized augmented plane-wave linear
response method with respect to the reference cubic, experimental tetragonal,
and theoretically determined rhombohedral ground state structures. The ground
state rhombohedral structure of KNbO_3 was determined by minimizing the forces
on the relaxed atoms. By contrast with the cubic structure, all zone center
phonon modes of the rhombohedral structure are stable and their frequencies are
in good agreement with experiment. In the tetragonal phase, one of the soft
zone center modes in the cubic phase is stablized. In view of the small atomic
displacements involved in the ferroelectric transitions, it is evident that not
only the soft mode frequencies but also the Born effective charge and
dielectric constants are very sensitive to the atomic geometry.Comment: 26 pages, revtex, no figures; to appear in Phys. Rev. B15 (Oct.),
199
Cirsium species show disparity in patterns of genetic variation at their range-edge, despite similar patterns of reproduction and isolation
Genetic variation was assessed across the UK geographical range of Cirsium acaule and Cirsium heterophyllum. A decline in genetic diversity and increase in population divergence approaching the range edge of these species was predicted based on parallel declines in population density and seed production reported seperately. Patterns were compared with UK populations of the widespread Cirsium arvense.Populations were sampled along a latitudinal transect in the UK and genetic variation
assessed using microsatellite markers. Cirsium acaule
shows strong isolation by distance, a significant decline in diversity and an increase in divergence among range-edge populations. Geographical structure is also evident in
C. arvense, whereas no such patterns are seen in C.heterophyllum. There is a major disparity between patterns of genetic variation in C. acaule and
C. heterophyllum despite very similar patterns in seed production and population isolation in these species. This suggests it may be misleading to make assumptions
about the geographical structure of genetic variation within species based solely on the present-day reproduction and distribution of populations
Comparison of the Electronic Structures and Energetics of Ferroelectric LiNbO3 and LiTaO3
This paper explains the origin of the ferroelectric instability in LiNbO3 and
LiTaO3 and compares the electronic structures and energetics of the two
materials.Comment: 31 pages, 11 Postscript figure
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