225 research outputs found
Ab Initio Evidence for the Formation of Impurity d(3z^2-r^2) Holes in Doped La_{2-x}Sr_xCuO_4
Using the spin unrestricted Becke-3-Lee-Yang-Parr density functional, we
computed the electronic structure of explicitly doped La_{2-x}Sr_xCuO_4 (x =
0.125, 0.25, and 0.5). At each doping level, an impurity hole band is formed
within the undoped insulating gap. This band is well-localized to CuO_6
octahedra adjacent to the Sr impurities. The nature of the impurity hole is
A_{1g} in symmetry, formed primarily from the z^2 orbital on the Cu and p_z
orbitals on the apical O's. There is a strong triplet coupling of this hole
with the intrinsic B_{1g} Cu x^2-y^2/O1 p_{sigma} hole on the same site.
Optimization of the c coordinate of the apical O's in the doped CuO_6
octahedron lead to an asymmetric anti-Jahn-Teller distortion of the O2 atoms
toward the central Cu. In particular, the O2 atom between the Cu and Sr is
displaced 0.26 A while the O2 atom between the Cu and La is displaced 0.10 A.
Contrary to expectations, investigation of a 0.1 A enhanced Jahn-Teller
distortion of this octahedron does not force formation of an x^2-y^2 hole, but
instead leads to migration of the z^2 hole to the four other CuO_6 octahedra
surrounding the Sr impurity. This latter observation offers a simple
explanation for the bifurcation of the Sr-O2 distance revealed in x-ray
absorption fine structure data.Comment: Submitted to Phys. Rev. B. See http://www.firstprinciples.com for
more informatio
Mathematical programming modelling tools for resource-poor countries and organisations
In recent years, powerful mathematical modelling languages have enabled Operational Research practitioners to rapidly develop prototype tools capable of modelling complex managerial decisions such as staff shift scheduling, or production and supply chain planning. However, such tools have often required expensive commercial optimisation solvers that are sometimes beyond the financial reach of small companies and organisations, particularly in the low-income and emerging economies. Fortunately, the worldwide scope of the internet has put powerful free optimisation tools within the reach of anyone with a modest PC and even a slow internet connection. This article will present examples showing just how beneficial such an approach can be for resource-poor organisations
Threshold electronic structure at the oxygen K edge of 3d transition metal oxides: a configuration interaction approach
It has been generally accepted that the threshold structure observed in the
oxygen K edge X-ray absorption spectrum in 3d transition metal oxides
represents the electronic structure of the 3d transition metal. There is,
however, no consensus about the correct description. We present an
interpretation, which includes both ground state hybridization and electron
correlation. It is based on a configuration interaction cluster calculation
using a MO6 cluster. The oxygen K edge spectrum is calculated by annihilating a
ligand hole in the ground state and is compared to calculations representing
inverse photoemission experiments in which a 3d transition metal electron is
added. Clear differences are observed related to the amount of ligand hole
created in the ground state. Two "rules" connected to this are discussed.
Comparison with experimental data of some early transition metal compounds is
made and shows that this simple cluster approach explains the experimental
features quite well.Comment: 10 pages, submitted to Phys. Rev. B, tried to make a better PS file
The Antiferromagnetic Band Structure of La2CuO4 Revisited
Using the Becke-3-LYP functional, we have performed band structure
calculations on the high temperature superconductor parent compound, La2CuO4.
Under the restricted spin formalism (rho(alpha) equal to rho(beta)), the
R-B3LYP band structure agrees well with the standard LDA band structure. It is
metallic with a single Cu x2-y2/O p(sigma) band crossing the Fermi level. Under
the unrestricted spin formalism (rho(alpha) not equal to rho(beta)), the UB3LYP
band structure has a spin polarized antiferromagnetic solution with a band gap
of 2.0 eV, agreeing well with experiment. This state is 1.0 eV (per formula
unit) lower than that calculated from the R-B3LYP. The apparent high energy of
the spin restricted state is attributed to an overestimate of on-site Coulomb
repulsion which is corrected in the unrestricted spin calculations. The
stabilization of the total energy with spin polarization arises primarily from
the stabilization of the x2-y2 band, such that the character of the eigenstates
at the top of the valence band in the antiferromagnetic state becomes a strong
mixture of Cu x2-y2/O p(sigma) and Cu z2/O' p(z). Since the Hohenberg-Kohn
theorem requires the spin restricted and spin unrestricted calculations give
exactly the same ground state energy and total density for the exact
functionals, this large disparity in energy reflects the inadequacy of current
functionals for describing the cuprates. This calls into question the use of
band structures based on current restricted spin density functionals (including
LDA) as a basis for single band theories of superconductivity in these
materials.Comment: 13 pages, 8 figures, to appear in Phys. Rev. B, for more information
see http://www.firstprinciples.co
Further Optimizations of CSIDH: A Systematic Approach to Efficient Strategies, Permutations, and Bound Vectors
CSIDH is a recent post-quantum key establishment protocol based on constructing isogenies between supersingular elliptic curves. Several recent works give constant-time implementations of CSIDH along with some optimizations of the ideal class group action evaluation algorithm, including the SIMBA technique of Meyer et al. and the two-point method of Onuki et al. A recent work of Cervantes-Vazquez et al. details a number of improvements to the works of Meyer et al. and Onuki et al. Several of these optimizations---in particular, the choice of ordering of the primes, the choice of SIMBA partition and strategies, and the choice of bound vector which defines the secret keyspace---have been made in an ad hoc fashion, and so while they yield performance improvements it has not been clear whether these choices could be improved upon, or how to do so. In this work we present a framework for improving these optimizations using (respectively) linear programming, dynamic programming, and convex programming techniques. Our framework is applicable to any CSIDH security level, to all currently-proposed paradigms for computing the class group action, and to any choice of model for the underlying curves. Using our framework we find improved parameter sets for the two major methods of computing the group action: in the case of the implementation of Meyer et al. we obtain a 12.77% speedup without applying the further optimizations proposed by Cervantes-Vazquez et al., while for that of Cervantes-Vazquez et al. under the two-point method we obtain a speedup of 5.06%, giving the fastest constant-time implementation of CSIDH to date
Insights into the function of silver as an oxidation catalyst by ab initio, atomistic thermodynamics
To help understand the high activity of silver as an oxidation catalyst,
e.g., for the oxidation of ethylene to epoxide and the dehydrogenation of
methanol to formaldehyde, the interaction and stability of oxygen species at
the Ag(111) surface has been studied for a wide range of coverages. Through
calculation of the free energy, as obtained from density-functional theory and
taking into account the temperature and pressure via the oxygen chemical
potential, we obtain the phase diagram of O/Ag(111). Our results reveal that a
thin surface-oxide structure is most stable for the temperature and pressure
range of ethylene epoxidation and we propose it (and possibly other similar
structures) contains the species actuating the catalysis. For higher
temperatures, low coverages of chemisorbed oxygen are most stable, which could
also play a role in oxidation reactions. For temperatures greater than about
775 K there are no stable oxygen species, except for the possibility of O atoms
adsorbed at under-coordinated surface sites Our calculations rule out thicker
oxide-like structures, as well as bulk dissolved oxygen and molecular
ozone-like species, as playing a role in the oxidation reactions.Comment: 15 pages including 9 figures, Related publications can be found at
http://www.fhi-berlin.mpg.de/th/paper.htm
Contribution of the first K-homology domain of poly(C)-binding protein 1 to its affinity and specificity for C-rich oligonucleotides
Poly-C-binding proteins are triple KH (hnRNP K homology) domain proteins with specificity for single stranded C-rich RNA and DNA. They play diverse roles in the regulation of protein expression at both transcriptional and translational levels. Here, we analyse the contributions of individual αCP1 KH domains to binding C-rich oligonucleotides using biophysical and structural methods. Using surface plasmon resonance (SPR), we demonstrate that KH1 makes the most stable interactions with both RNA and DNA, KH3 binds with intermediate affinity and KH2 only interacts detectibly with DNA. The crystal structure of KH1 bound to a 5′-CCCTCCCT-3′ DNA sequence shows a 2:1 protein:DNA stoichiometry and demonstrates a molecular arrangement of KH domains bound to immediately adjacent oligonucleotide target sites. SPR experiments, with a series of poly-C-sequences reveals that cytosine is preferred at all four positions in the oligonucleotide binding cleft and that a C-tetrad binds KH1 with 10 times higher affinity than a C-triplet. The basis for this high affinity interaction is finally detailed with the structure determination of a KH1.W.C54S mutant bound to 5′-ACCCCA-3′ DNA sequence. Together, these data establish the lead role of KH1 in oligonucleotide binding by αCP1 and reveal the molecular basis of its specificity for a C-rich tetrad
Familial history of diabetes and clinical characteristics in Greek subjects with type 2 diabetes
<p>Abstract</p> <p>Background</p> <p>A lot of studies have showed an excess maternal transmission of type 2 diabetes (T2D). The aim, therefore, of the present study was to estimate the prevalence of familial history of T2D in Greek patients, and to evaluate its potential effect on the patient's metabolic control and the presence of diabetic complications.</p> <p>Methods</p> <p>A total of 1,473 T2D patients were recruited. Those with diabetic mothers, diabetic fathers, diabetic relatives other than parents and no known diabetic relatives, were considered separately.</p> <p>Results</p> <p>The prevalence of diabetes in the mother, the father and relatives other than parents, was 27.7, 11.0 and 10.7%, respectively. Patients with paternal diabetes had a higher prevalence of hypertension (64.8 vs. 57.1%, P = 0.05) and lower LDL-cholesterol levels (115.12 ± 39.76 vs. 127.13 ± 46.53 mg/dl, P = 0.006) than patients with diabetes in the mother. Patients with familial diabetes were significantly younger (P < 0.001), with lower age at diabetes diagnosis (P < 0.001) than those without diabetic relatives. Patients with a diabetic parent had higher body mass index (BMI) (31.22 ± 5.87 vs. 30.67 ± 5.35 Kg/m<sup>2</sup>, P = 0.08), higher prevalence of dyslipidemia (49.8 vs. 44.6%, P = 0.06) and retinopathy (17.9 vs. 14.5%, P = 0.08) compared with patients with no diabetic relatives. No difference in the degree of metabolic control and the prevalence of chronic complications were observed.</p> <p>Conclusion</p> <p>The present study showed an excess maternal transmission of T2D in a sample of Greek diabetic patients. However, no different influence was found between maternal and paternal diabetes on the clinical characteristics of diabetic patients except for LDL-cholesterol levels and presence of hypertension. The presence of a family history of diabetes resulted to an early onset of the disease to the offspring.</p
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