Theoretical study of magnetism, structure and chemical order in transition-metal alloy clusters

Research on transition-metal nanoalloy clusters composed of a few atoms is fascinating by their unusual properties due to the interplay among the structure, chemical order and magnetism. Such nanoalloy clusters, can be used to construct nanometer devices for technological applications by manipulating their remarkable magnetic, chemical and optical properties. Determining the nanoscopic features exhibited by the magnetic alloy clusters signifies the need for a systematic global and local exploration of their potential-energy surface in order to identify all the relevant energetically low-lying magnetic isomers. In this thesis the sampling of the potential-energy surface has been performed by employing the state-of-the-art spin-polarized density-functional theory in combination with graph theory and the basin-hopping global optimization techniques. This combination is vital for a quantitative analysis of the quantum mechanical energetics. The first approach, i.e., spin-polarized density-functional theory together with the graph theory method, is applied to study the Fe$_m$Rh$_n$ and Co$_m$Pd$_n$ clusters having $N = m+n \leq 8$ atoms. We carried out a thorough and systematic sampling of the potential-energy surface by taking into account all possible initial cluster topologies, all different distributions of the two kinds of atoms within the cluster, the entire concentration range between the pure limits, and different initial magnetic configurations such as ferro- and anti-ferromagnetic coupling. The remarkable magnetic properties shown by FeRh and CoPd nanoclusters are attributed to the extremely reduced coordination number together with the charge transfer from 3$d$ to 4$d$ elements. The second approach, i.e., spin-polarized density-functional theory together with the basin-hopping method is applied to study the small Fe$_6$, Fe$_3$Rh$_3$ and Rh$_6$ and the larger Fe$_{13}$, Fe$_6$Rh$_7$ and Rh$_{13}$ clusters as illustrative benchmark systems. This method is able to identify the true ground-state structures of Fe$_6$ and Fe$_3$Rh$_3$ which were not obtained by using the first approach. However, both approaches predict a similar cluster for the ground-state of Rh$_6$. Moreover, the computational time taken by this approach is found to be significantly lower than the first approach. The ground-state structure of Fe$_{13}$ cluster is found to be an icosahedral structure, whereas Rh$_{13}$ and Fe$_6$Rh$_7$ isomers relax into cage-like and layered-like structures, respectively. All the clusters display a remarkable variety of structural and magnetic behaviors. It is observed that the isomers having similar shape with small distortion with respect to each other can exhibit quite different magnetic moments. This has been interpreted as a probable artifact of spin-rotational symmetry breaking introduced by the spin-polarized GGA. The possibility of combining the spin-polarized density-functional theory with some other global optimization techniques such as minima-hopping method could be the next step in this direction. This combination is expected to be an ideal sampling approach having the advantage of avoiding efficiently the search over irrelevant regions of the potential energy surface.

Second order Coriolis resonance in the v2, v5 Raman bands of CH3F

The vibration-rotation Raman spectrum of the ν2 and ν5 fundamentals of CH3F is reported, from 1320 to 1640 cm−1, with a resolution of about 0.3 cm−1. The Coriolis resonance between the two bands leads to many perturbation-allowed transitions. Where the resonance is still sufficiently weak that the quantum number K′ retains its meaning, perturbation-allowed transitions are observed for all values of ΔK from +4 to −4; in regions of strong resonance, however, we can only say that the observed transitions obey the selection rule Δ(k−l) = 0 or ±3. The spectrum has been analyzed by band contour simulation using a computer program based on exact diagonalization of the Hamiltonian within the ν2, ν5 vibrational levels, and improved vibration-rotation constants for these bands are reported. The relative magnitudes and relative sings of polarizability derivatives involved in these vibrations are also reported.

Low-order dynamical behavior in the martian atmosphere: Diagnosis of general circulation model results

The hypothesis of a low dimensional martian climate attractor is investigated by the application of the proper orthogonal decomposition (POD) to a simulation of martian atmospheric circulation using the UK Mars general circulation model (UK-MGCM). In this article we focus on a time series of the interval between autumn and winter in the northern hemisphere, when baroclinic activity is intense. The POD is a statistical technique that allows the attribution of total energy (TE) to particular structures embedded in the UK-MGCM time-evolving circulation. These structures are called empirical orthogonal functions (EOFs). Ordering the EOFs according to their associated energy content, we were able to determine the necessary number to account for a chosen amount of atmospheric TE. We show that for Mars a large fraction of TE is explained by just a few EOFs (with 90% TE in 23 EOFs), which apparently support the initial hypothesis. We also show that the resulting EOFs represent classical types of atmospheric motion, such as thermal tides and transient waves. Thus, POD is shown to be an efficient method for the identification of different classes of atmospheric modes. It also provides insight into the non-linear interaction of these modes.

Rossby number expansions, slaving principles, and balance dynamics

We consider the problem of constructing balance dynamics for rapidly rotating fluid systems. It is argued that the conventional Rossby number expansion—namely expanding all variables in a series in Rossby number—is secular for all but the simplest flows. In particular, the higher-order terms in the expansion grow exponentially on average, and for moderate values of the Rossby number the expansion is, at best, useful only for times of the order of the doubling times of the instabilities of the underlying quasi-geostrophic dynamics. Similar arguments apply in a wide class of problems involving a small parameter and sufficiently complex zeroth-order dynamics. A modified procedure is proposed which involves expanding only the fast modes of the system; this is equivalent to an asymptotic approximation of the slaving relation that relates the fast modes to the slow modes. The procedure is systematic and thus capable, at least in principle, of being carried to any order—unlike procedures based on truncations. We apply the procedure to construct higher-order balance approximations of the shallow-water equations. At the lowest order quasi-geostrophy emerges. At the next order the system incorporates gradient-wind balance, although the balance relations themselves involve only linear inversions and hence are easily applied. There is a large class of reduced systems associated with various choices for the slow variables, but the simplest ones appear to be those based on potential vorticity.

Sparse polynomial approximation in positive order Sobolev spaces with bounded mixed derivatives and applications to elliptic problems with random loading

In the present paper we study the approximation of functions with bounded mixed derivatives by sparse tensor product polynomials in positive order tensor product Sobolev spaces. We introduce a new sparse polynomial approximation operator which exhibits optimal convergence properties in L2 and tensorized View the MathML source simultaneously on a standard k-dimensional cube. In the special case k=2 the suggested approximation operator is also optimal in L2 and tensorized H1 (without essential boundary conditions). This allows to construct an optimal sparse p-version FEM with sparse piecewise continuous polynomial splines, reducing the number of unknowns from O(p2), needed for the full tensor product computation, to View the MathML source, required for the suggested sparse technique, preserving the same optimal convergence rate in terms of p. We apply this result to an elliptic differential equation and an elliptic integral equation with random loading and compute the covariances of the solutions with View the MathML source unknowns. Several numerical examples support the theoretical estimates.

Centennial variations in sunspot number, open solar flux and streamer belt width: 1. correction of the sunspot number record since 1874

We analyse the widely-used international/ Zürich sunspot number record, R, with a view to quantifying a suspected calibration discontinuity around 1945 (which has been termed the “Waldmeier discontinuity” [Svalgaard, 2011]). We compare R against the composite sunspot group data from the Royal Greenwich Observatory (RGO) network and the Solar Optical Observing Network (SOON), using both the number of sunspot groups, N{sub}G{\sub}, and the total area of the sunspots, A{sub}G{\sub}. In addition, we compare R with the recently developed interdiurnal variability geomagnetic indices IDV and IDV(1d). In all four cases, linearity of the relationship with R is not assumed and care is taken to ensure that the relationship of each with R is the same before and after the putative calibration change. It is shown the probability that a correction is not needed is of order 10{sup}−8{\sup} and that R is indeed too low before 1945. The optimum correction to R for values before 1945 is found to be 11.6%, 11.7%, 10.3% and 7.9% using A{sub}G{\sub}, N{sub)G{\sub}, IDV, and IDV(1d), respectively. The optimum value obtained by combining the sunspot group data is 11.6% with an uncertainty range 8.1-14.8% at the 2σ level. The geomagnetic indices provide an independent yet less stringent test but do give values that fall within the 2σ uncertainty band with optimum values are slightly lower than from the sunspot group data. The probability of the correction needed being as large as 20%, as advocated by Svalgaard [2011], is shown to be 1.6 × 10{sup}−5{\sup}.

Identification of fractional-order transfer functions using a step excitation

This brief proposes a new method for the identification of fractional order transfer functions based on the time response resulting from a single step excitation. The proposed method is applied to the identification of a three-dimensional RC network, which can be tailored in terms of topology and composition to emulate real time systems governed by fractional order dynamics. The results are in excellent agreement with the actual network response, yet the identification procedure only requires a small number of coefficients to be determined, demonstrating that the fractional order modelling approach leads to very parsimonious model formulations.

Analysis of the distribution of the number of bidders in construction contract auctions

The number of bidders, N, involved in a construction procurement auction is known to have an important effect on the value of the lowest bid and the mark-up applied by bidders. In practice, for example, it is important for a bidder to have a good estimate of N when bidding for a current contract. One approach, instigated by Friedman in 1956, is to make such an estimate by statistical analysis and modelling. Since then, however, finding a suitable model for N has been an enduring problem for researchers and, despite intensive research activity in the subsequent 30 years, little progress has been made, due principally to the absence of new ideas and perspectives. The debate is resumed by checking old assumptions, providing new evidence relating to concomitant variables and proposing a new model. In doing this and in order to ensure universality, a novel approach is developed and tested by using a unique set of 12 construction tender databases from four continents. This shows the new model provides a significant advancement on previous versions. Several new research questions are also posed and other approaches identified for future study.

Tests of sunspot number sequences: 1. Using ionosonde data

More than 70 years ago it was recognised that ionospheric F2-layer critical frequencies [foF2] had a strong relationship to sunspot number. Using historic datasets from the Slough and Washington ionosondes, we evaluate the best statistical fits of foF2 to sunspot numbers (at each Universal Time [UT] separately) in order to search for drifts and abrupt changes in the fit residuals over Solar Cycles 17-21. This test is carried out for the original composite of the Wolf/Zürich/International sunspot number [R], the new “backbone” group sunspot number [RBB] and the proposed “corrected sunspot number” [RC]. Polynomial fits are made both with and without allowance for the white-light facular area, which has been reported as being associated with cycle-to-cycle changes in the sunspot number - foF2 relationship. Over the interval studied here, R, RBB, and RC largely differ in their allowance for the “Waldmeier discontinuity” around 1945 (the correction factor for which for R, RBB and RC is, respectively, zero, effectively over 20 %, and explicitly 11.6 %). It is shown that for Solar Cycles 18-21, all three sunspot data sequences perform well, but that the fit residuals are lowest and most uniform for RBB. We here use foF2 for those UTs for which R, RBB, and RC all give correlations exceeding 0.99 for intervals both before and after the Waldmeier discontinuity. The error introduced by the Waldmeier discontinuity causes R to underestimate the fitted values based on the foF2 data for 1932-1945 but RBB overestimates them by almost the same factor, implying that the correction for the Waldmeier discontinuity inherent in RBB is too large by a factor of two. Fit residuals are smallest and most uniform for RC and the ionospheric data support the optimum discontinuity multiplicative correction factor derived from the independent Royal Greenwich Observatory (RGO) sunspot group data for the same interval.

Influence of organic fertilization on the number of culturable diazotrophic endophytic bacteria isolated from sugarcane

The numbers of culturable diazotrophic endophytic bacteria (CDEB) from roots stems and leaves of sugarcane submitted to organic inorganic or no fertilization were compared In order to determine the size of the N(2) fixing populations the Most Probable Number technique (MPN) was used The quantification of diazotrophic bacteria by using the acetylene reduction assay (ARA) was more accurate than observing the bacterial growth in the vials to confirm N(2) fixing capability the detection of gene nifH was performed on a sample of 105 Isolated bacteria The production of extracellular enzymes involved in the penetration of the plants by the bacteria was also studied The results showed that organic fertilization enhances the number of CDEB when compared with conventional fertilization used throughout the growing season The maximum number of bacteria was detected in the roots Roots and stems presented the greatest number of CDEB in the middle of the cropping season and in leaves numbers varied according to the treatment Using two pairs of primers and two different methods the nifH gene was found in 104 of the 105 tested isolates Larger amounts of pectinase were released by isolates from sugarcane treated with conventional fertilizers (66%) whereas larger amounts of cellulase were released by strains isolated from sugarcane treated with organic fertilizers (80%) (C) 2010 Elsevier Masson SAS All rights reserved

One-dimensional trapped atoms: critical coupling parameter and critical number of particles

In this paper we consider the case of a Bose gas in low dimension in order to illustrate the applicability of a method that allows us to construct analytical relations, valid for a broad range of coupling parameters, for a function which asymptotic expansions are known. The method is well suitable to investigate the problem of stability of a collection of Bose particles trapped in one- dimensional configuration for the case where the scattering length presents a negative value. The eigenvalues for this interacting quantum one-dimensional many particle system become negative when the interactions overcome the trapping energy and, in this case, the system becomes unstable. Here we calculate the critical coupling parameter and apply for the case of Lithium atoms obtaining the critical number of particles for the limit of stability.

Pseudolikelihood equations for Potts MRF model parameter estimation on higher order neighborhood systems

This letter presents pseudolikelihood equations for the estimation of the Potts Markov random field model parameter on higher order neighborhood systems. The derived equation for second-order systems is a significantly reduced version of a recent result found in the literature (from 67 to 22 terms). Also, with the proposed method, a completely original equation for Potts model parameter estimation in third-order systems was obtained. These equations allow the modeling of less restrictive contextual systems for a large number of applications in a computationally feasible way. Experiments with both simulated and real remote sensing images provided good results.

Acetylation of cellulose in LiCl-N,N-dimethylacetamide: first report on the correlation between the reaction efficiency and the aggregation number of dissolved cellulose

The acylation of three cellulose samples by acetic anhydride, Ac(2)O, in the solvent system LiCl/N,N-dimethylacetamide, DMAc (4 h, 110 A degrees C), has been revisited in order to investigate the dependence of the reaction efficiency on the structural characteristics of cellulose, and its aggregation in solution. The cellulose samples employed included microcrystalline, MCC; mercerized cotton linters, M-cotton, and mercerized sisal, M-sisal. The reaction efficiency expresses the relationship between the degree of substitution, DS, of the ester obtained, and the molar ratio Ac(2)O/AGU (anhydroglucose unit of the biopolymer); 100% efficiency means obtaining DS = 3 at Ac(2)O/AGU = 3. For all celluloses, the dependence of DS on Ac(2)O/AGU is described by an exponential decay equation: DS = DS(o) - Ae(-[(Ac2O/AGU)/B]); (A) and (B) are regression coefficients, and DS(o) is the calculated maximum degree of substitution, achieved under the conditions of each experiment. Values of (B) are clearly dependent on the cellulose employed: B((M-cotton)) > B((M-sisal)) > B((MCC)); they correlate qualitatively with the degree of polymerization of cellulose, and linearly with the aggregation number, N(agg), of the dissolved biopolymer, as calculated from static light scattering measurements: (B) = 1.709 + 0.034 N(agg). To our knowledge, this is the first report on the latter correlation; it shows the importance of the physical state of dissolved cellulose, and serves to explain, in part, the need to use distinct reaction conditions for MCC and fibrous celluloses, in particular Ac(2)O/AGU, time, temperature.

Dinoponera lucida Emery (Formicidae : Ponerinae): the highest number of chromosomes known in Hymenoptera

We report the remarkable karyotype of Dinoponera lucida, a Brazilian endemic ponerine ant. Its chromosome number is 2n=106, most of the chromosomes are acrocentric and of very small size, and the karyotype formula is 88A+18M. A chromosome pair of the AM(t) type is reported. This is the largest number of chromosomes reported for the Hymenoptera order until now.

Number Processing and Calculation in Brazilian Children Aged 7-12 Years

Numerical cognition is based on two components - number processing and calculation. Its development is influenced by biological, cognitive, educational, and cultural factors. The objectives of the present study were to: i) assess number processing and calculation in Brazilian children aged 7-12 years from public schools using the Zareki-R (Battery of neuropsychological tests for number processing and calculation in children, Revised; von Aster & Dellatolas, 2006) in order to obtain normative data for Portuguese speakers; ii) identify how environment, age, and gender influences the development of these mathematical skills; iii) investigate the construct validity of the Zareki-R by the contrast with the Arithmetic subtest of WISC-III. The sample included 172 children, both genders, divided in two groups: urban (N= 119) and rural (N= 53) assessed by the Zareki-R. Rural children presented lower scores in one aspect of number processing; children aged 7-8 years demonstrated an inferior global score than older; boys presented a superior performance in both number processing and calculation. Construct validity of Zareki-R was demonstrated by high to moderate correlations with Arithmetic subtest of WISC-III. The Zareki-R therefore is a suitable instrument to assess the development of mathematical skills, which is influenced by factors such as environment, age, and gender.