305 research outputs found
Silicon vacancy in SiC: A high-spin state defect
We report results from spin-polarized ab initio local spin-density calculations for the silicon vacancy (VSi) in 3C– and 2H–SiC in all its possible charge states. The calculated electronic structure for SiC reveals the presence of a stable spin-aligned electron-state t2 near the midgap. The neutral and doubly negative charge states of VSi in 3C–SiC are stabilized in a high-spin configuration with S=1 giving rise to a ground state, which is a many-electron orbital singlet 3T1. For the singly negative VSi, we find a high-spin ground-state4A2 with S=3/2. In the high-spin configuration, VSi preserves the Td symmetry. These results indicate that in neutral, singly, and doubly negative charge states a strong exchange coupling, which prefers parallel electron spins, overcomes the Jahn–Teller energy. In other charge states, the ground state of VSi has a low-spin configuration.Peer reviewe
A mixed ultrasoft/normconserved pseudopotential scheme
A variant of the Vanderbilt ultrasoft pseudopotential scheme, where the
normconservation is released for only one or a few angular channels, is
presented. Within this scheme some difficulties of the truly ultrasoft
pseudopotentials are overcome without sacrificing the pseudopotential softness.
i) Ghost states are easily avoided without including semicore shells. ii) The
ultrasoft pseudo-charge-augmentation functions can be made more soft. iii) The
number of nonlocal operators is reduced. The scheme will be most useful for
transition metals, and the feasibility and accuracy of the scheme is
demonstrated for the 4d transition metal rhodium.Comment: 4 pages, 2 figure
Prediction of Ferromagnetic Ground State of NaCl-type FeN
Ab-initio results for structural and electronic properties of NaCl-type FeN
are presented in a framework of plane-wave and ultrasoft pseudopotentials.
Competition among different magnetic ordering is examined. We find the
ferromagnetic phase stable overall. Stabilization over the unpolarized phase is
obtained by splitting one flat t_2g-type band crossing the Fermi energy. A
comparison with CrN is considered. We find large differences in the properties
of the two systems that can be addressed to the smaller ionicity and
magnetization of FeN.Comment: 5 pages, 4 figures, twocolumn latex style Sentence changed in Section
III line 1
Active site manipulation in MoS2 cluster electrocatalysts by transition metal doping
The development of non-platinum group metal catalysts for the hydrogen evolution reaction (HER) in water electrolyser devices is essential for their widespread and sustainable deployment. In recent years, molybdenum disulfide (MoS2) catalysts have received significant attention as they not only exhibit good electrocatalytic HER activity but also, crucially, acid-stability. However, further performance enhancement is required for these materials to be competitive with Pt and to that end transition metal doping of MoS2 has been explored as a route to further increasing its catalytic activity. In this work, cluster beam deposition was employed to produce controlled cobalt-doped MoS2 clusters (MoS2–Co). We demonstrate that, in contrast to previous observations of performance enhancement in MoS2 resulting from nickel doping (MoS2–Ni), the introduction of Co has a detrimental effect on HER activity. The contrasting behaviours of Ni and Co doping are rationalized by density functional theory (DFT) calculations, which suggest that HER-active surface vacancies are deactivated by combination with Co dopant atoms, whilst their activity is retained, or even partially enhanced, by combination with Ni dopant atoms. Furthermore, the adatom dopant–vacancy combination kinetics appear to be more than three orders of magnitude faster in MoS2–Co than for MoS2–Ni. These findings highlight a fundamental difference in the influence of transition metal dopants on the HER performance of MoS2 electrocatalysts and stress the importance of considering surface atomic defects when predicting their behaviour
Pretreatment resistin levels are associated with erosive disease in early rheumatoid arthritis treated with disease-modifying anti-rheumatic drugs and infliximab
Objective: Resistin is an adipocytokine related to insulin resistance and inflammation. We investigated whether resistin is associated with disease activity and inflammation in disease-modifying anti-rheumatic drug (DMARD)-naive rheumatoid arthritis (RA) patients, whether it has predictive value for radiological disease progression, and whether tumour necrosis factor-alpha (TNF-alpha) is involved in these effects. Method: Ninety-nine patients with early, DMARD-naive RA participated in the NEO-RACo study. Patients were treated for the first 4 weeks with a combination of methotrexate, sulfasalazine, hydroxychloroquine, and prednisolone (FIN-RACo treatment). Thereafter, they were randomized to receive either infliximab or placebo added to the combination for 6 months. Patients were followed for 5 years. Disease activity was evaluated using the Disease Activity Score based on 28-joint count-erythrocyte sedimentation rate, radiographs were scored with the modified Sharp-van der Heijde method, and plasma resistin concentrations were measured by immunoassay. Human THP-1 macrophages were used in the in vitro studies. Results: A high resistin level at baseline was associated with active inflammatory disease and predicted more rapid radiological progression during 5 year follow-up. Adding infliximab to the DMARD combination delayed radiological progression and overcame the poor predictive value of resistin. Resistin increased TNF-alpha production in human macrophages, indicating a possible connection between resistin and TNF-alpha. Conclusion: The results suggest that high resistin concentration may be a useful marker to distinguish patients with an increased risk of erosive disease in early active RA, and that adding TNF-alpha antagonist to the traditional DMARD combination may delay radiological progression of the disease in these patients.Peer reviewe
Magnetic reconstruction at (001) CaMnO surface
The Mn-terminated (001) surface of the stable anti-ferromagnetic insulating
phase of cubic perovskite CaMnO is found to undergo a magnetic
reconstruction consisting on a spin-flip process at surface: each Mn spin at
the surface flips to pair with that of Mn in the subsurface layer. In spite of
very little Mn-O charge transfer at surface, the surface behavior is driven by
the states due to charge redistribution. These
results, based on local spin density theory, give a double exchange like
coupling that is driven by character, not additional charge, and may have
relevance to CMR materials.Comment: 4 pages, 5 figures reference added Fig. 3 modified. Caption of Fig. 5
modifie
Double exchange-driven spin pairing at the (001) surface of manganites
The (001) surface of La_{1-x}Ca_xMnO_3 system in various magnetic orderings
is studied by first principle calculations. A general occurrence is that z^2
dangling bond charge -- which is ``invisible'' in the formal valence picture --
is promoted to the bulk gap/Fermi level region. This drives a
double-exchange-like process that serves to align the surface Mn spin with its
subsurface neighbor, regardless of the bulk magnetic order. For heavy doping,
the locally ``ferromagnetic'' coupling is very strong and the moment enhanced
by as much as 30% over the bulk value.Comment: 6 pages, 4 figure
Ab initio simulations of liquid NaSn alloys: Zintl anions and network formation
Using the Car-Parrinello technique, ab initio molecular dynamics simulations
are performed for liquid NaSn alloys in five different compositions (20, 40,
50, 57 and 80 % sodium). The obtained structure factors agree well with the
data from neutron scattering experiments. The measured prepeak in the structure
factor is reproduced qualitatively for most compositions. The calculated and
measured positions of all peaks show the same trend as function of the
composition.\\ The dynamic simulations also yield information about the
formation and stability of Sn clusters (Zintl anions) in the liquid. In our
simulations of compositions with 50 and 57 % sodium we observe the formation of
networks of tin atoms. Thus, isolated tin clusters are not stable in such
liquids. For the composition with 20 % tin only isolated atoms or dimers of tin
appear, ``octet compounds'' of one Sn atom surrounded by 4 Na atoms are not
observed.Comment: 12 pages, Latex, 3 Figures on reques
Thermal diffusion of supersonic solitons in an anharmonic chain of atoms
We study the non-equilibrium diffusion dynamics of supersonic lattice
solitons in a classical chain of atoms with nearest-neighbor interactions
coupled to a heat bath. As a specific example we choose an interaction with
cubic anharmonicity. The coupling between the system and a thermal bath with a
given temperature is made by adding noise, delta-correlated in time and space,
and damping to the set of discrete equations of motion. Working in the
continuum limit and changing to the sound velocity frame we derive a
Korteweg-de Vries equation with noise and damping. We apply a collective
coordinate approach which yields two stochastic ODEs which are solved
approximately by a perturbation analysis. This finally yields analytical
expressions for the variances of the soliton position and velocity. We perform
Langevin dynamics simulations for the original discrete system which fully
confirm the predictions of our analytical calculations, namely noise-induced
superdiffusive behavior which scales with the temperature and depends strongly
on the initial soliton velocity. A normal diffusion behavior is observed for
very low-energy solitons where the noise-induced phonons also make a
significant contribution to the soliton diffusion.Comment: Submitted to PRE. Changes made: New simulations with a different
method of soliton detection. The results and conclusions are not different
from previous version. New appendixes containing information about the system
energy and soliton profile
Ewald methods for polarizable surfaces with application to hydroxylation and hydrogen bonding on the (012) and (001) surfaces of alpha-Fe2O3
We present a clear and rigorous derivation of the Ewald-like method for
calculation of the electrostatic energy of the systems infinitely periodic in
two-dimensions and of finite size in the third dimension (slabs) which is
significantly faster than existing methods. Molecular dynamics simulations
using the transferable/polarizable model by Rustad et al. were applied to study
the surface relaxation of the nonhydroxylated, hydroxylated, and solvated
surfaces of alpha-Fe2O3 (hematite). We find that our nonhydroxylated structures
and energies are in good agreement with previous LDA calculations on
alpha-alumina by Manassidis et al. [Surf. Sci. Lett. 285, L517, 1993]. Using
the results of molecular dynamics simulations of solvated interfaces, we define
end-member hydroxylated-hydrated states for the surfaces which are used in
energy minimization calculations. We find that hydration has a small effect on
the surface structure, but that hydroxylation has a significant effect. Our
calculations, both for gas-phase and solution-phase adsorption, predict a
greater amount of hydroxylation for the (012) surface than for the (001)
surface. Our simulations also indicate the presence of four-fold coordinated
iron ions on the (001) surface.Comment: 23 pages, REVTeX (LaTeX), 8 figures not included, e-mail to
[email protected], paper accepted in Surface Scienc
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