Gaussian quadrature 4D-VAR

A new incremental four-dimensional variational (4D-Var) data assimilation algorithm is introduced. The algorithm does not require the computationally expensive integrations with the nonlinear model in the outer loops. Nonlinearity is accounted for by modifying the linearization trajectory of the observation operator based on integrations with the tangent linear (TL) model. This allows us to update the linearization trajectory of the observation operator in the inner loops at negligible computational cost. As a result the distinction between inner and outer loops is no longer necessary. The key idea on which the proposed 4D-Var method is based is that by using Gaussian quadrature it is possible to get an exact correspondence between the nonlinear time evolution of perturbations and the time evolution in the TL model. It is shown that J-point Gaussian quadrature can be used to derive the exact adjoint-based observation impact equations and furthermore that it is straightforward to account for the effect of multiple outer loops in these equations if the proposed 4D-Var method is used. The method is illustrated using a three-level quasi-geostrophic model and the Lorenz (1996) model.

PSO assisted NURB Neural Network Identification

A system identification algorithm is introduced for Hammerstein systems that are modelled using a non-uniform rational B-spline (NURB) neural network. The proposed algorithm consists of two successive stages. First the shaping parameters in NURB network are estimated using a particle swarm optimization (PSO) procedure. Then the remaining parameters are estimated by the method of the singular value decomposition (SVD). Numerical examples are utilized to demonstrate the efficacy of the proposed approach.

Prowess, the Nine Worthies and the Hundred Years War: the Prologues to the Chroniques of Jean Froissart and Enguerrand de Monstrelet

An analysis of the evolution of the image of chivalry in the successive redactions of the Prologue to Froissart's Chroniques, focussing on the figures of the Nine Worthies as models of behaviour for young noblemen. This is then compared and contrasted with the prologue written by his continuator, Enguerrand de Monstrelet, whose work betrays a shift in sensibilities that expresses itself, inter alia, by a near-total absence of the Worthies in his Chronique. Close textual analysis suggests that the two choniclers shared a comparable sense of disillusion, though expressed in different ways.

Solvent-dependent modulation of metal–metal electronic interactions in a dinuclear cyanoruthenate complex: a detailed electrochemical, spectroscopic and computational study

The dinuclear complex [{Ru(CN)4}2(μ-bppz)]4− shows a strongly solvent-dependent metal–metal electronic interaction which allows the mixed-valence state to be switched from class 2 to class 3 by changing solvent from water to CH2Cl2. In CH2Cl2 the separation between the successive Ru(II)/Ru(III) redox couples is 350 mVand the IVCT band (from the UV/Vis/NIR spectroelectrochemistry) is characteristic of a borderline class II/III or class III mixed valence state. In water, the redox separation is only 110 mVand the much broader IVCT transition is characteristic of a class II mixed-valence state. This is consistent with the observation that raising and lowering the energy of the d(π) orbitals in CH2Cl2 or water, respectively, will decrease or increase the energy gap to the LUMO of the bppz bridging ligand, which provides the delocalisation pathway via electron-transfer. IR spectroelectrochemistry could only be carried out successfully in CH2Cl2 and revealed class III mixed-valence behaviour on the fast IR timescale. In contrast to this, time-resolved IR spectroscopy showed that the MLCTexcited state, which is formulated as RuIII(bppz˙−)RuII and can therefore be considered as a mixed-valence Ru(II)/Ru(III) complex with an intermediate bridging radical anion ligand, is localised on the IR timescale with spectroscopically distinct Ru(II) and Ru(III) termini. This is because the necessary electron-transfer via the bppz ligand is more difficult because of the additional electron on bppz˙− which raises the orbital through which electron exchange occurs in energy. DFT calculations reproduce the electronic spectra of the complex in all three Ru(II)/Ru(II), Ru(II)/Ru(III) and Ru(III)/Ru(III) calculations in both water and CH2Cl2 well as long as an explicit allowance is made for the presence of water molecules hydrogen-bonded to the cyanides in the model used. They also reproduce the excited-state IR spectra of both [Ru(CN)4(μ-bppz)]2– and [{Ru(CN)4}2(μ-bppz)]4− very well in both solvents. The reorganization of the water solvent shell indicates a possible dynamical reason for the longer life time of the triplet state in water compared to CH2Cl2.

Change detection evokes a Simon-like effect

A change detection paradigm was used to estimate the role of explicit change detection in the generation of the irrelevant spatial stimulus coding underlying the Simon effect. In one condition, no blank was interposed between two successive displays, which produced efficient change detection. In another condition, the presence of a blank frame produced a robust change blindness effect, which is crucially assumed to occur as the consequence of impaired attentional orienting to the change location. The results showed a strong Simon-like effect under conditions of efficient change detection. By contrast, no Simon-like effect was observed under conditions of change blindness, namely when attention shifting towards the change location was hampered. Experiment 2 supported this pattern by showing that a Simon-like effect could be observed when the blank was present, but only when participants detected the change by means of a cue that was informative as to change location. Overall, our findings show that a Simon-like effect can only be observed under conditions of explicit change detection, likely because a shift of attention towards the change location has occurred.

Pulsatory andesite lava flow at Bagana Volcano

Using a time series of TerraSAR-X spaceborne radar images we have measured the pulsatory motion of an andesite lava flow over a 14-month period at Bagana volcano, Papua New Guinea. Between October 2010 and December 2011, lava flowed continuously down the western flank of the volcano forming a 3 km-long blocky lava flow with a channel, levees, overflows and branches. We captured four successive pulses of lava advancing down the channel system, the first such behaviour of an andesite flow to be recorded using radar. Each pulse had a volume of the order of 107 m3 emplaced over many weeks. The average extrusion rate estimated from the radar data was 0.92 ± 0.35 m3 s-1 , and varied between 0.3 and 1.8 m3 s-1, with higher rates occurring earlier in each pulse. This, together with observations of sulphur dioxide emissions, explosions and incandescence suggest a variable supply rate of magma through Bagana’s conduit as the most likely source of the pulsatory behaviour.

Social divisions in school participation and attainment in India: 1983-2004

This study documents the size and nature of “Hindu-Muslim” and “boy-girl” gaps in children’s school participation and attainments in India. Individual-level data from two successive rounds of the National Sample Survey suggest that considerable progress has been made in decreasing the Hindu-Muslim gap. Nonetheless, the gap remains sizable even after controlling for numerous socio-economic and parental covariates, and the Muslim educational disadvantage in India today is greater than that experienced by girls and Scheduled Caste Hindu children. A gender gap still appears within as well as between communities, though it is smaller within Muslim communities. While differences in gender and other demographic and socio-economic covariates have recently become more important in explaining the Hindu-Muslim gap, those differences altogether explain only 25 percent to 45 percent of the observed schooling gap.

Multivariate analysis of the dielectric response of materials modeled using networks of resistors and capacitors

We discuss the modeling of dielectric responses of electromagnetically excited networks which are composed of a mixture of capacitors and resistors. Such networks can be employed as lumped-parameter circuits to model the response of composite materials containing conductive and insulating grains. The dynamics of the excited network systems are studied using a state space model derived from a randomized incidence matrix. Time and frequency domain responses from synthetic data sets generated from state space models are analyzed for the purpose of estimating the fraction of capacitors in the network. Good results were obtained by using either the time-domain response to a pulse excitation or impedance data at selected frequencies. A chemometric framework based on a Successive Projections Algorithm (SPA) enables the construction of multiple linear regression (MLR) models which can efficiently determine the ratio of conductive to insulating components in composite material samples. The proposed method avoids restrictions commonly associated with Archie’s law, the application of percolation theory or Kohlrausch-Williams-Watts models and is applicable to experimental results generated by either time domain transient spectrometers or continuous-wave instruments. Furthermore, it is quite generic and applicable to tomography, acoustics as well as other spectroscopies such as nuclear magnetic resonance, electron paramagnetic resonance and, therefore, should be of general interest across the dielectrics community.

Unwritten law in Hobbesian political thought

In Hobbesian terminology, ‘unwritten laws’ are natural laws enforced within a polity, by a non-sovereign judge, without some previous public promulgation. This article discusses the idea in the light of successive Hobbesian accounts of ‘law’ and ‘obligation’. Between De Cive and Leviathan, Hobbes dropped the idea that natural law is strictly speaking law, but he continued to believe unwritten laws must form a part of any legal system. He was unable to explain how such a law could claim a legal status. His loyalty to the notion, in spite of all the trouble that it caused, is a sign of his belief that moral knowledge is readily accessible to all.

Ternary erbium chromium sulfides : structural relationships and magnetic properties

Single crystals of four erbium-chromium sulfides have been grown by chemical vapor transport using iodine as the transporting agent. Single-crystal X-ray diffraction reveals that in Er(3)CrS(6) octahedral sites are occupied exclusively by Cr(3+) cations, leading to one-dimensional CrS(4)(5-) chains of edge-sharing octahedra, while in Er(2)CrS(4), Er(3+), and Cr(2+) cations occupy the available octahedral sites in an ordered manner. By contrast, in Er(6)Cr(2)S(11) and Er(4)CrS(7), Er(3+) and Cr(2+) ions are disordered over the octahedral sites. In Er(2)CrS(4), Er(6)Cr(2)S(11), and Er(4)CrS(7), the network of octahedra generates an anionic framework constructed from M(2)S(5) slabs of varying thickness, linked by one-dimensional octahedral chains. This suggests that these three phases belong to a series in which the anionic framework may be described by the general formula [M(2n+1)S(4n+3)](x-), with charge balancing provided by Er(3+) cations located in sites of high-coordination number within one-dimensional channels defined by the framework. Er(4)CrS(7), Er(6)Cr(2)S(11), and Er(2)CrS(4) may thus be considered as the n = 1, 2, and infinity members of this series. While Er(4)CrS(7) is paramagnetic, successive magnetic transitions associated with ordering of the chromium and erbium sub-lattices are observed on cooling Er(3)CrS(6) (T(C)(Cr) = 30 K; T(C)(Er) = 11 K) and Er(2)CrS(4) (T(N)(Cr) = 42 K, T(N)(Er) = 10 K) whereas Er(6)Cr(2)S(11) exhibits ordering of the chromium sub-lattice only (T(N) = 11.4 K).

(PDF, 406 KB) On L3 acquisition and phonological permeability: a new test case for debates on the mental representation of non-native phonological systems

The goal of this article is to make an epistemological and theoretical contribution to the nascent field of third language (L3) acquisition and show how examining L3 development can offer a unique view into longstanding debates within L2 acquisition theory. We offer the Phonological Permeability Hypothesis (PPH), which maintains that examining the development of an L3/Ln phonological system and its effects on a previously acquired L2 phonological system can inform contemporary debates regarding the mental constitution of postcritical period adult phonological acquisition. We discuss the predictions and functional significance of the PPH for adult SLA and multilingualism studies, detailing a methodology that examines the effects of acquiring Brazilian Portuguese on the Spanish phonological systems learned before and after the so-called critical period (i.e., comparing simultaneous versus successive adult English-Spanish bilinguals learning Brazilian Portuguese as an L3).

Primary evolving networks and the comparative analysis of robust and fragile structures

In this paper we consider the structure of dynamically evolving networks modelling information and activity moving across a large set of vertices. We adopt the communicability concept that generalizes that of centrality which is defined for static networks. We define the primary network structure within the whole as comprising of the most influential vertices (both as senders and receivers of dynamically sequenced activity). We present a methodology based on successive vertex knockouts, up to a very small fraction of the whole primary network,that can characterize the nature of the primary network as being either relatively robust and lattice-like (with redundancies built in) or relatively fragile and tree-like (with sensitivities and few redundancies). We apply these ideas to the analysis of evolving networks derived from fMRI scans of resting human brains. We show that the estimation of performance parameters via the structure tests of the corresponding primary networks is subject to less variability than that observed across a very large population of such scans. Hence the differences within the population are significant.

On the generalized eigenvalue problem for the Rossby wave vertical velocity in the presence of mean flow and topography

In a series of papers, Killworth and Blundell have proposed to study the effects of a background mean flow and topography on Rossby wave propagation by means of a generalized eigenvalue problem formulated in terms of the vertical velocity, obtained from a linearization of the primitive equations of motion. However, it has been known for a number of years that this eigenvalue problem contains an error, which Killworth was prevented from correcting himself by his unfortunate passing and whose correction is therefore taken up in this note. Here, the author shows in the context of quasigeostrophic (QG) theory that the error can ulti- mately be traced to the fact that the eigenvalue problem for the vertical velocity is fundamentally a non- linear one (the eigenvalue appears both in the numerator and denominator), unlike that for the pressure. The reason that this nonlinear term is lacking in the Killworth and Blundell theory comes from neglecting the depth dependence of a depth-dependent term. This nonlinear term is shown on idealized examples to alter significantly the Rossby wave dispersion relation in the high-wavenumber regime but is otherwise irrelevant in the long-wave limit, in which case the eigenvalue problems for the vertical velocity and pressure are both linear. In the general dispersive case, however, one should first solve the generalized eigenvalue problem for the pressure vertical structure and, if needed, diagnose the vertical velocity vertical structure from the latter.

Synthesis of prebiotic galactooligosaccharides from lactose using bifidobacterial β-galactosidase (BbgIV) immobilised on DEAE-Cellulose, Q-Sepharose and amino-ethyl agarose

The bifidobacterial β-galactosidase BbgIV was immobilised on DEAE-Cellulose and Q-Sepharose via ionic binding and on amino-ethyl- and glyoxal-agarose via covalent attachment, and was then used to catalyse the synthesis of galactooligosaccharides (GOS). The immobilisation yield exceeded 90 % using ionic binding, while it was low using aminoethyl agarose (25 – 28 %) and very low using glyoxal agarose (< 3 %). This was due to the mild conditions and absence of chemical reagents in ionic binding, compared to covalent attachment. The maximum GOS yield obtained using DEAE-Cellulose and Q-Sepharose was similar to that obtained using free BbgIV (49 – 53 %), indicating the absence of diffusion limitation and mass transfer issues. For amino-ethyl agarose, however, the GOS yield obtained was lower (42 – 44 %) compared to that obtained using free BbgIV. All the supports tried significantly (P < 0.05) increased the BbgIV operational stability and the GOS synthesis productivity up to 55 °C. Besides, six successive GOS synthesis batches were performed using BbgIV immobilised on Q-Sepharose; all resulted in similar GOS yields, indicating the possibility of developing a robust synthesis process. Overall, the GOS synthesis operation performance using BbgIV was improved by immobilising the enzyme onto solid supports, in particular on Q-Sepharose

Following the creation of active gold nanocatalysts from phosphine-stabilized molecular clusters

The phosphine-stabilised gold cluster [Au6(Ph2P-o-tolyl)6](NO3)2 is converted into an active nanocatalyst for the oxidation of benzyl alcohol through low-temperature peroxide-assisted removal of the phosphines, avoiding the high-temperature calcination process. The process was monitored using in-situ X-ray absorption spectroscopy, which revealed that after a certain period of the reaction with tertiary butyl hydrogen peroxide, the phosphine ligands are removed to form nanoparticles of gold which matches with the induction period seen in the catalytic reaction. Density functional theory calculations show that the energies required to remove the ligands from the [Au6Ln]2+ increase significantly with successive removal steps, suggesting that the process does not occur at once but sequentially. The calculations also reveal that ligand removal is accompanied by dramatic re-arrangements in the topology of the cluster core.