2,745 research outputs found
Energy Level Alignment at Molecule-Metal Interfaces from an Optimally-Tuned Range-Separated Hybrid Functional
The alignment of the frontier orbital energies of an adsorbed molecule with
the substrate Fermi level at metal-organic interfaces is a fundamental
observable of significant practical importance in nanoscience and beyond.
Typical density functional theory calculations, especially those using local
and semi-local functionals, often underestimate level alignment leading to
inaccurate electronic structure and charge transport properties. In this work,
we develop a new fully self-consistent predictive scheme to accurately compute
level alignment at certain classes of complex heterogeneous molecule-metal
interfaces based on optimally-tuned range-separated hybrid functionals.
Starting from a highly accurate description of the gas-phase electronic
structure, our method by construction captures important nonlocal surface
polarization effects via tuning of the long-range screened exchange in a
range-separated hybrid in a non-empirical and system-specific manner. We
implement this functional in a plane-wave code and apply it to several
physisorbed and chemisorbed molecule-metal interface systems. Our results are
in quantitative agreement with experiments, both the level alignment and work
function changes. Our approach constitutes a new practical scheme for accurate
and efficient calculations of the electronic structure of molecule-metal
interfaces.Comment: 15 pages, 8 figure
Isomorphs in model molecular liquids
Isomorphs are curves in the phase diagram along which a number of static and
dynamic quantities are invariant in reduced units. A liquid has good isomorphs
if and only if it is strongly correlating, i.e., the equilibrium
virial/potential energy fluctuations are more than 90% correlated in the NVT
ensemble. This paper generalizes isomorphs to liquids composed of rigid
molecules and study the isomorphs of two systems of small rigid molecules, the
asymmetric dumbbell model and the Lewis-Wahnstrom OTP model. In particular, for
both systems we find that the isochoric heat capacity, the excess entropy, the
reduced molecular center-of-mass self part of the intermediate scattering
function, the reduced molecular center-of-mass radial distribution function to
a good approximation are invariant along an isomorph. In agreement with theory,
we also find that an instantaneous change of temperature and density from an
equilibrated state point to another isomorphic state point leads to no
relaxation. The isomorphs of the Lewis-Wahnstrom OTP model were found to be
more approximative than those of the asymmetric dumbbell model, which is
consistent with the OTP model being less strongly correlating. For both models
we find "master isomorphs", i.e., isomorphs have identical shape in the
virial/potential energy phase diagram.Comment: 20 page
Perception of nonnative tonal contrasts by Mandarin-English and English-Mandarin sequential bilinguals
This study examined the role of acquisition order and crosslinguistic similarity in influencing transfer at the initial stage of perceptually acquiring a tonal third language (L3). Perception of tones in Yoruba and Thai was tested in adult sequential bilinguals representing three different first (L1) and second language (L2) backgrounds: L1 Mandarin-L2 English (MEBs), L1 English-L2 Mandarin (EMBs), and L1 English-L2 intonational/non-tonal (EIBs). MEBs outperformed EMBs and EIBs in discriminating L3 tonal contrasts in both languages, while EMBs showed a small advantage over EIBs on Yoruba. All groups showed better overall discrimination in Thai than Yoruba, but group differences were more robust in Yoruba. MEBs’ and EMBs’ poor discrimination of certain L3 contrasts was further reflected in the L3 tones being perceived as similar to the same Mandarin tone; however, EIBs, with no knowledge of Mandarin, showed many of the same similarity judgments. These findings thus suggest that L1 tonal experience has a particularly facilitative effect in L3 tone perception, but there is also a facilitative effect of L2 tonal experience. Further, crosslinguistic perceptual similarity between L1/L2 and L3 tones, as well as acoustic similarity between different L3 tones, play a significant role at this early stage of L3 tone acquisition.Published versio
SGAS 143845.1+145407: A Big, Cool Starburst at Redshift 0.816
We present the discovery and a detailed multi-wavelength study of a
strongly-lensed luminous infrared galaxy at z=0.816. Unlike most known lensed
galaxies discovered at optical or near-infrared wavelengths this lensed source
is red, r-Ks = 3.9 [AB], which the data presented here demonstrate is due to
ongoing dusty star formation. The overall lensing magnification (a factor of
17) facilitates observations from the blue optical through to 500micron, fully
capturing both the stellar photospheric emission as well as the re-processed
thermal dust emission. We also present optical and near-IR spectroscopy. These
extensive data show that this lensed galaxy is in many ways typical of
IR-detected sources at z~1, with both a total luminosity and size in accordance
with other (albeit much less detailed) measurements in samples of galaxies
observed in deep fields with the Spitzer telescope. Its far-infrared spectral
energy distribution is well-fit by local templates that are an order of
magnitude less luminous than the lensed galaxy; local templates of comparable
luminosity are too hot to fit. Its size (D~7kpc) is much larger than local
luminous infrared galaxies, but in line with sizes observed for such galaxies
at z~1. The star formation appears uniform across this spatial scale. In this
source, the luminosity of which is typical of sources that dominate the cosmic
infrared background, we find that star formation is spatially extended and well
organised, quite unlike the compact merger-driven starbursts which are typical
for sources of this luminosity at z~0.Comment: 18 pages, 10 figure
F-spondin deficient mice have a high bone mass phenotype
F-spondin is a pericellular matrix protein upregulated in developing growth plate cartilage and articular cartilage during osteoarthritis. To address its function in bone and cartilage in vivo, we generated mice that were deficient for the F-spondin gene, Spon1. Spon1-/- mice were viable and developed normally to adulthood with no major skeletal abnormalities. At 6 months, femurs and tibiae of Spon1-/- mice exhibited increased bone mass, evidenced by histological staining and micro CT analyses, which persisted up to 12 months. In contrast, no major abnormalities were observed in articular cartilage at any age group. Immunohistochemical staining of femurs and tibiae revealed increased levels of periostin, alkaline phosphate and tartrate resistant acid phosphatase (TRAP) activity in the growth plate region of Spon1-/- mice, suggesting elevated bone synthesis and turnover. However, there were no differences in serum levels of TRAP, the bone resorption marker, CTX-1, or osteoclast differentiation potential between genotypes. Knockout mice also exhibited reduced levels of TGF-β1 in serum and cultured costal chondrocytes relative to wild type. This was accompanied by increased levels of the BMP-regulatory SMADs, P-SMAD1/5 in tibiae and chondrocytes. Our findings indicate a previously unrecognized role for Spon1 as a negative regulator of bone mass. We speculate that Spon1 deletion leads to a local and systemic reduction of TGF-β levels resulting in increased BMP signaling and increased bone deposition in adult mice. © 2014 Palmer et al
Cognitive conflicts in major depression : Between desired change and personal coherence
This is an open access article under the terms of the Creative Commons Attribution-NonCommercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposesThe notion of intrapsychic conflict has been present in psychopathology for more than a century within different theoretical orientations. However, internal conflicts have not received enough empirical attention, nor has their importance in depression been fully elaborated. This study is based on the notion of cognitive conflict, understood as implicative dilemma (ID), and on a new way of identifying these conflicts by means of the Repertory Grid Technique. Our aim was to explore the relevance of cognitive conflicts among depressive patientsPeer reviewedFinal Published versio
Patient and physician discordance of global disease assessment in juvenile dermatomyositis: Findings from the Childhood Arthritis & Rheumatology Research Alliance Legacy Registry
© 2020 The Author(s). Background: Global disease activity scores (gVAS) capture patient or family (PF) and physician (MD) assessments of disease. This study sought to measure discordance between PF and MD global activity scores in juvenile dermatomyositis (JDM), and determine factors associated with discordance. Methods: Patients with JDM were included from the Childhood Arthritis and Rheumatology Research Alliance (CARRA) Legacy Registry (N = 563). PF and MD gVAS were assessed for discordance, defined as a ≥ 2-point difference. Factors associated with discordant gVAS were compared in univariate analysis. Multivariable regression analysis was used to identify predictors of discordance. Results: Almost 40% (N = 219) of PF and MD gVAS were discordant. Among discordant scores, 68% of PF rated gVAS ≥2-points above MD, which was associated with calcinosis and lower quality of life and functional scores (p \u3c 0.01). MD gVAS rated ≥2-points above PF in 32%, which was associated with abnormal laboratory results, weakness, arthritis, rash and other skin changes, and current intravenous steroid treatment (p \u3c 0.01). In multivariate analysis, predictors for higher PF rating included calcinosis, lower quality of life and functional scores, while predictors for higher MD rating included rash, calcinosis, nailfold capillaroscopy changes, and current intravenous steroid treatment. Conclusions: Discordance between PF and MD gVAS was common in this JDM cohort. Overall, higher PF rating was associated with poorer patient reported outcome (PRO) scores, while higher MD rating was associated with poorer objective measures. This suggests PF and MD assessments of gVAS may be measuring different aspects of disease, highlighting the importance of integrating PROs into clinical practice and research
Identifying substitutional oxygen as a prolific point defect in monolayer transition metal dichalcogenides with experiment and theory
Chalcogen vacancies are considered to be the most abundant point defects in
two-dimensional (2D) transition-metal dichalcogenide (TMD) semiconductors, and
predicted to result in deep in-gap states (IGS). As a result, important
features in the optical response of 2D-TMDs have typically been attributed to
chalcogen vacancies, with indirect support from Transmission Electron
Microscopy (TEM) and Scanning Tunneling Microscopy (STM) images. However, TEM
imaging measurements do not provide direct access to the electronic structure
of individual defects; and while Scanning Tunneling Spectroscopy (STS) is a
direct probe of local electronic structure, the interpretation of the chemical
nature of atomically-resolved STM images of point defects in 2D-TMDs can be
ambiguous. As a result, the assignment of point defects as vacancies or
substitutional atoms of different kinds in 2D-TMDs, and their influence on
their electronic properties, has been inconsistent and lacks consensus. Here,
we combine low-temperature non-contact atomic force microscopy (nc-AFM), STS,
and state-of-the-art ab initio density functional theory (DFT) and GW
calculations to determine both the structure and electronic properties of the
most abundant individual chalcogen-site defects common to 2D-TMDs.
Surprisingly, we observe no IGS for any of the chalcogen defects probed. Our
results and analysis strongly suggest that the common chalcogen defects in our
2D-TMDs, prepared and measured in standard environments, are substitutional
oxygen rather than vacancies
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