Effect of media polarity on the photoisomerisation of substituted stilbene, azobenzene and imine chromophores

The influence of substituents and media polarity on the photoinducedE→Z geometrical isomerisation of the stilbene, azobenzene and N-benzylideneaniline chromophores has been compared and assessed. The efficiency of the process in all three systems is markedly dependent on the presence and characteristics of electron-donor and electron-acceptor substituents at the 4- and 4′-positions. The results are discussed in terms of relaxation of the E-excited singlet state. In the absence of a nitro substituent, relaxation to the S1 orthogonal state competes effectively with non-productive intramolecular electron transfer; in the presence of a nitro substituent, the T1 orthogonal state is formed from inter-system crossing. For systems with a 4-nitro and a 4′-electron-donor substituent, access to the triplet state is inhibited by polar solvents promoting formation of the inactive charge-transfer state from the S1 state, and no isomerisation is observed. Similar effects are observed in both solution and polymer films. Such variations in behaviour have important implications for the utilisation of the chromophores in nonlinear optical phenomena including photorefractivity.

Biaxial optical properties of thermotropic random copolyesters

The optical microstructures of thin sections of two liquid crystalline polymers are examined in the polarizing microscope. The polymers are random copolyesters based on hydroxybenzoic and hydroxynaphthoic acids (B-N), and hydroxybenzoic acid and ethylene terephthalate (B-ET). Sections cut from oriented samples, so as to include the extrusion direction, show microstructures in which there is no apparent preferred orientation of the axes describing the local optical anisotropy. The absence of preferred orientation in the microstructure, despite marked axial alignment of molecular chain segments as demonstrated by X-Ray diffraction, is interpreted in terms of the polymer having biaxial optical properties. The implication of optical biaxiality is that, although the mesophases are nematic, the orientation of the molecules is correlated about three (orthogonal) axes over distances greater than a micron. The structure is classified as a multiaxial nematic.

A study of COFDM in a terrestrial multipath environment

Coded orthogonal frequency division multiplexing (COFDM) has existed for many years but it was not until 1997 when the European Telecommunications Standards Institute proposed its use for the transmission of digital television through a terrestrial channel. Up to date, an assumption has been made concerning the resilience of COFDM in a multipath environment. This paper discusses this assumption, give results of a DVB-T compliant simulation and discuss the validity of this assumption based on the obtained results.

Feedback design for regularizing descriptor systems

This paper surveys numerical techniques for the regularization of descriptor (generalized state-space) systems by proportional and derivative feedback. We review generalizations of controllability and observability to descriptor systems along with definitions of regularity and index in terms of the Weierstraß canonical form. Three condensed forms display the controllability and observability properties of a descriptor system. The condensed forms are obtained through orthogonal equivalence transformations and rank decisions, so they may be computed by numerically stable algorithms. In addition, the condensed forms display whether a descriptor system is regularizable, i.e., when the system pencil can be made to be regular by derivative and/or proportional output feedback, and, if so, what index can be achieved. Also included is a a new characterization of descriptor systems that can be made to be regular with index 1 by proportional and derivative output feedback.

Numerical computation of an analytic singular value decomposition of a matrix valued function

This paper extends the singular value decomposition to a path of matricesE(t). An analytic singular value decomposition of a path of matricesE(t) is an analytic path of factorizationsE(t)=X(t)S(t)Y(t) T whereX(t) andY(t) are orthogonal andS(t) is diagonal. To maintain differentiability the diagonal entries ofS(t) are allowed to be either positive or negative and to appear in any order. This paper investigates existence and uniqueness of analytic SVD's and develops an algorithm for computing them. We show that a real analytic pathE(t) always admits a real analytic SVD, a full-rank, smooth pathE(t) with distinct singular values admits a smooth SVD. We derive a differential equation for the left factor, develop Euler-like and extrapolated Euler-like numerical methods for approximating an analytic SVD and prove that the Euler-like method converges.

Regularization of descriptor systems by output feedback

Conditions are given under which a descriptor, or generalized state-space system can be regularized by output feedback. It is shown that under these conditions, proportional and derivative output feedback controls can be constructed such that the closed-loop system is regular and has index at most one. This property ensures the solvability of the resulting system of dynamic-algebraic equations. A reduced form is given that allows the system properties as well as the feedback to be determined. The construction procedures used to establish the theory are based only on orthogonal matrix decompositions and can therefore be implemented in a numerically stable way.

Regularization of Descriptor Systems by Derivative and Proportional State Feedback

For linear multivariable time-invariant continuous or discrete-time singular systems it is customary to use a proportional feedback control in order to achieve a desired closed loop behaviour. Derivative feedback is rarely considered. This paper examines how derivative feedback in descriptor systems can be used to alter the structure of the system pencil under various controllability conditions. It is shown that derivative and proportional feedback controls can be constructed such that the closed loop system has a given form and is also regular and has index at most 1. This property ensures the solvability of the resulting system of dynamic-algebraic equations. The construction procedures used to establish the theory are based only on orthogonal matrix decompositions and can therefore be implemented in a numerically stable way. The problem of pole placement with derivative feedback alone and in combination with proportional state feedback is also investigated. A computational algorithm for improving the “conditioning” of the regularized closed loop system is derived.

Minimum norm regularization of descriptor systems by mixed output feedback

We study the regularization problem for linear, constant coefficient descriptor systems Ex' = Ax+Bu, y1 = Cx, y2 = Γx' by proportional and derivative mixed output feedback. Necessary and sufficient conditions are given, which guarantee that there exist output feedbacks such that the closed-loop system is regular, has index at most one and E+BGΓ has a desired rank, i.e., there is a desired number of differential and algebraic equations. To resolve the freedom in the choice of the feedback matrices we then discuss how to obtain the desired regularizing feedback of minimum norm and show that this approach leads to useful results in the sense of robustness only if the rank of E is decreased. Numerical procedures are derived to construct the desired feedback gains. These numerical procedures are based on orthogonal matrix transformations which can be implemented in a numerically stable way.

Radar scattering from ice aggregates using the horizontally aligned oblate spheroid approximation

The assumed relationship between ice particle mass and size is profoundly important in radar retrievals of ice clouds, but, for millimeter-wave radars, shape and preferred orientation are important as well. In this paper the authors first examine the consequences of the fact that the widely used ‘‘Brown and Francis’’ mass–size relationship has often been applied to maximumparticle dimension observed by aircraftDmax rather than to the mean of the particle dimensions in two orthogonal directions Dmean, which was originally used by Brown and Francis. Analysis of particle images reveals that Dmax ’ 1.25Dmean, and therefore, for clouds for which this mass–size relationship holds, the consequences are overestimates of ice water content by around 53% and of Rayleigh-scattering radar reflectivity factor by 3.7 dB. Simultaneous radar and aircraft measurements demonstrate that much better agreement in reflectivity factor is provided by using this mass–size relationship with Dmean. The authors then examine the importance of particle shape and fall orientation for millimeter-wave radars. Simultaneous radar measurements and aircraft calculations of differential reflectivity and dual-wavelength ratio are presented to demonstrate that ice particles may usually be treated as horizontally aligned oblate spheroids with an axial ratio of 0.6, consistent with them being aggregates. An accurate formula is presented for the backscatter cross section apparent to a vertically pointing millimeter-wave radar on the basis of a modified version of Rayleigh–Gans theory. It is then shown that the consequence of treating ice particles as Mie-scattering spheres is to substantially underestimate millimeter-wave reflectivity factor when millimeter-sized particles are present, which can lead to retrieved ice water content being overestimated by a factor of 4.h

On the drivers of inter-annual and decadal rainfall variability in Queensland, Australia

Queensland experiences considerable inter-annual and decadal rainfall variability, which impacts water-resource management, agriculture and infrastructure. To understand the mechanisms by which large-scale atmospheric and coupled air–sea processes drive these variations, empirical orthogonal teleconnection (EOT) analysis is applied to 1900–2010 seasonal Queensland rainfall. Fields from observations and the 20th Century Reanalysis are regressed onto the EOT timeseries to associate the EOTs with large-scale drivers. In winter, spring and summer the leading, state-wide EOTs are highly correlated with the El Nino–Southern Oscillation (ENSO); the Inter-decadal Pacific Oscillation modulates the summer ENSO teleconnection. In autumn, the leading EOT is associated with locally driven, late-season monsoon variations, while ENSO affects only tropical northern Queensland. Examining EOTs beyond the first, southeastern Queensland and the Cape York peninsula emerge as regions of coherent rainfall variability. In the southeast, rainfall anomalies respond to the strength and moisture content of onshore easterlies, controlled by Tasman Sea blocking. The summer EOT associated with onshore flow and blocking has been negative since 1970, consistent with the observed decline in rainfall along the heavily populated coast. The southeastern Queensland EOTs show considerable multi-decadal variability, which is independent of large-scale drivers. Summer rainfall in Cape York is associated with tropical-cyclone activity.

Chercher pour or chercher après: arguing the case for contact-induced linguistic innovation in different varieties of French

This paper provides evidence for the claim made in Baetens Beardsmore (1971) that the grammatical collocation "chercher après" «to look for», which is very frequent in Brussels French, is the result of transfer from the contact language, Brussels Dutch. A detailed quantitative analysis of this construction in different varieties of French which have more or less contact with a Germanic language was made to investigate the likelihood of influence from the Germanic substrate. The differences between the meaning of "chercher" and "chercher après" are also analysed in some depth, to find out whether or not the particle is redundant. According to Trudgill (2004) redundant constructions are more often found in contact situations involving long-term, stable contact and child bilingualism. The particle "après" was found to add a particular shade of meaning to "chercher", and is thus not redundant. Therefore no evidence could be obtained from the current data for Trudgill’s (2004) claim.

A neurofuzzy classifier for two class problems

A neurofuzzy classifier identification algorithm is introduced for two class problems. The initial fuzzy base construction is based on fuzzy clustering utilizing a Gaussian mixture model (GMM) and the analysis of covariance (ANOVA) decomposition. The expectation maximization (EM) algorithm is applied to determine the parameters of the fuzzy membership functions. Then neurofuzzy model is identified via the supervised subspace orthogonal least square (OLS) algorithm. Finally a logistic regression model is applied to produce the class probability. The effectiveness of the proposed neurofuzzy classifier has been demonstrated using a real data set.

A mechanism for Atlantic multidecadal variability in the Kiel Climate Model

Atlantic Multidecadal Variability (AMV) is investigated in a millennial control simulation with the Kiel Climate Model (KCM), a coupled atmosphere–ocean–sea ice model. An oscillatory mode with approximately 60 years period and characteristics similar to observations is identified with the aid of three-dimensional temperature and salinity joint empirical orthogonal function analysis. The mode explains 30 % of variability on centennial and shorter timescales in the upper 2,000 m of the North Atlantic. It is associated with changes in the Atlantic Meridional Overturning Circulation (AMOC) of ±1–2 Sv and Atlantic Sea Surface Temperature (SST) of ±0.2 °C. AMV in KCM results from an out-of-phase interaction between horizontal and vertical ocean circulation, coupled through Irminger Sea convection. Wintertime convection in this region is mainly controlled by salinity anomalies transported by the Subpolar Gyre (SPG). Increased (decreased) dense water formation in this region leads to a stronger (weaker) AMOC after 15 years, and this in turn leads to a weaker (stronger) SPG after another 15 years. The key role of salinity variations in the subpolar North Atlantic for AMV is confirmed in a 1,000 year long simulation with salinity restored to model climatology: No low frequency variations in convection are simulated, and the 60 year mode of variability is absent.

Preferred orientation in an angled intercalation site of a chloro-substituted lambda- [Ru(TAP)2(dppz)]2+ complex bound to d(TCGGCGCCGA)2

The crystal structure of the ruthenium DNA ‘light-switch’ complex -[Ru(TAP)2(11-Cl-dppz)]2+ (TAP = tetraazaphenanthrene, dppz = dipyrido[3,2-a':2',3'-c]phenazine)) bound to the oligonucleotide duplex d(TCGGCGCCGA)2 is reported. The synthesis of the racemic ruthenium complex is described for the first time, and the racemate was used in this study. The crystal structure, at atomic resolution (1.0 Å), shows one ligand as a wedge in the minor groove, resulting in the 51 kinking of the double helix, as with the parent lambda-[Ru(TAP)2(dppz)]2+. Each complex binds to one duplex by intercalation of the dppz ligand and also by semi-intercalation of one of the orthogonal TAP ligands into a second symmetrically equivalent duplex. The 11-Cl substituent binds with the major component (66%) oriented with the 11-chloro substituent on the purine side of the terminal step of the duplex.

Isomap nonlinear dimensionality reduction and bimodality of Asian monsoon convection

It is known that the empirical orthogonal function method is unable to detect possible nonlinear structure in climate data. Here, isometric feature mapping (Isomap), as a tool for nonlinear dimensionality reduction, is applied to 1958–2001 ERA-40 sea-level pressure anomalies to study nonlinearity of the Asian summer monsoon intraseasonal variability. Using the leading two Isomap time series, the probability density function is shown to be bimodal. A two-dimensional bivariate Gaussian mixture model is then applied to identify the monsoon phases, the obtained regimes representing enhanced and suppressed phases, respectively. The relationship with the large-scale seasonal mean monsoon indicates that the frequency of monsoon regime occurrence is significantly perturbed in agreement with conceptual ideas, with preference for enhanced convection on intraseasonal time scales during large-scale strong monsoons. Trend analysis suggests a shift in concentration of monsoon convection, with less emphasis on South Asia and more on the East China Sea.