Simultaneous bridge-localized and mixed-valence character in diruthenium radical cations featuring diethynylaromatic bridging ligands

A series of bimetallic ruthenium complexes [{Ru(dppe)Cp*}2(μ-C≡CArC≡C)] featuring diethynylaromatic bridging ligands (Ar = 1,4-phenylene, 1,4-naphthylene, 9,10-anthrylene) have been prepared and some representative molecular structures determined. A combination of UV–vis–NIR and IR spectroelectrochemical methods and density functional theory (DFT) have been used to demonstrate that one-electron oxidation of compounds [{Ru(dppe)Cp*}2(μ-C≡CArC≡C)](HC≡CArC≡CH = 1,4-diethynylbenzene; 1,4-diethynyl-2,5-dimethoxybenzene; 1,4-diethynylnaphthalene; 9,10-diethynylanthracene) yields solutions containing radical cations that exhibit characteristics of both oxidation of the diethynylaromatic portion of the bridge, and a mixed-valence state. The simultaneous population of bridge-oxidized and mixed-valence states is likely related to a number of factors, including orientation of the plane of the aromatic portion of the bridging ligand with respect to the metal d-orbitals of appropriate π-symmetry.

The Dirichlet-to-Neumann map for the elliptic sine Gordon

We analyse the Dirichlet problem for the elliptic sine Gordon equation in the upper half plane. We express the solution $q(x,y)$ in terms of a Riemann-Hilbert problem whose jump matrix is uniquely defined by a certain function $b(\la)$, $\la\in\R$, explicitly expressed in terms of the given Dirichlet data $g_0(x)=q(x,0)$ and the unknown Neumann boundary value $g_1(x)=q_y(x,0)$, where $g_0(x)$ and $g_1(x)$ are related via the global relation $\{b(\la)=0$, $\la\geq 0\}$. Furthermore, we show that the latter relation can be used to characterise the Dirichlet to Neumann map, i.e. to express $g_1(x)$ in terms of $g_0(x)$. It appears that this provides the first case that such a map is explicitly characterised for a nonlinear integrable {\em elliptic} PDE, as opposed to an {\em evolution} PDE.

Self, role and character: developing a professional identity as a drama teacher

The paper reports on research into what may have influenced trainees on four post-graduate teacher training courses in England to become specialist drama teachers rather than pursue careers in the world of professional entertainment. In doing so it raises questions regarding the value of considering teaching as a performing art. The paper goes on to explore how drama trainees regard an understanding of performance, and an ability to both use and demonstrate performance techniques, as integral to their role as subject specialists. The subsequent discussion examines how a drama teacher’s professional identity may be seen as being made up of the three inter-connected elements, self, role and character. Thus, while all teaching may be considered to involve some elements of performativity , this paper suggests that, for the drama specialist, an understanding of what constitutes ‘performance’ has a particular importance. One conclusion drawn from the research is that recognising the place of performance in their practice may result in experienced teachers of drama regarding themselves as artists whose art is teaching drama; another is that recognising the different ways in which adopting a role may involve performance could be of value to all teachers and teacher educators.

On the strong uniqueness of some finite dimensional Dirichlet operators

We prove essential self-adjointness of a class of Dirichlet operators in ℝn using the hyperbolic equation approach. This method allows one to prove essential self-adjointness under minimal conditions on the logarithmic derivative of the density and a condition of Muckenhoupt type on the density itself.

Scattering by rough surfaces: the Dirichlet problem for the Helmholtz equation in a non-locally perturbed half-plane

We consider the Dirichlet boundary value problem for the Helmholtz equation in a non-locally perturbed half-plane, this problem arising in electromagnetic scattering by one-dimensional rough, perfectly conducting surfaces. We propose a new boundary integral equation formulation for this problem, utilizing the Green's function for an impedance half-plane in place of the standard fundamental solution. We show, at least for surfaces not differing too much from the flat boundary, that the integral equation is uniquely solvable in the space of bounded and continuous functions, and hence that, for a variety of incident fields including an incident plane wave, the boundary value problem for the scattered field has a unique solution satisfying the limiting absorption principle. Finally, a result of continuous dependence of the solution on the boundary shape is obtained.

(Re)enchanting geography? The nature of being critical and the character of critique in human geography

Enchantment is a term frequently used by human geographers to express delight, wonder or that which cannot be simply explained. However, it is a concept that has yet to be subject to sustained critique, specifically how it can be used to progress geographic thought and praxis. This paper makes sense of, and space for, the unintelligibility of enchantment in order to encourage a less repressed, more cheerful way of engaging with the geographies of the world. We track back through our disciplinary heritage to explore how geographers have employed enchantment as a force through which the world inspires affective attachment. We review the terrain of the debate surrounding recent geographical engagements with enchantment, focusing on the nature of being critical and the character of critique in human geography, offering a new ‘enchanted’ stance to our geographical endeavours. We argue that the moment of enchantment has not passed with the current challenging climate; if anything, it is more pressing.

Late-Holocene changes in character and behaviour of land-terminating glaciers on James Ross Island, Antarctica

Virtually no information is available on the response of land-terminating Antarctic Peninsula glaciers to climate change on a centennial timescale. This paper analyses the topography, geomorphology and sedimentology of prominent moraines on James Ross Island, Antarctica, to determine geometric changes and to interpret glacier behaviour. The moraines are very likely due to a late-Holocene phase of advance and featured (1) shearing and thrusting within the snout, (2) shearing and deformation of basal sediment, (3) more supraglacial debris than at present and (4) short distances of sediment transport. Retreat of ∼100 m and thinning of 15–20 m has produced a loss of 0.1 km3 of ice. The pattern of surface lowering is asymmetric. These geometrical changes are suggested most simply to be due to a net negative mass balance caused by a drier climate. Comparisons of the moraines with the current glaciological surface structure of the glaciers permits speculation of a transition from a polythermal to a cold-based thermal regime. Small land-terminating glaciers in the northern Antarctic Peninsula region could be cooling despite a warming climate.

Integrated visual vocabulary in latent Dirichlet allocation-based scene classification for IKONOS image

Scene classification based on latent Dirichlet allocation (LDA) is a more general modeling method known as a bag of visual words, in which the construction of a visual vocabulary is a crucial quantization process to ensure success of the classification. A framework is developed using the following new aspects: Gaussian mixture clustering for the quantization process, the use of an integrated visual vocabulary (IVV), which is built as the union of all centroids obtained from the separate quantization process of each class, and the usage of some features, including edge orientation histogram, CIELab color moments, and gray-level co-occurrence matrix (GLCM). The experiments are conducted on IKONOS images with six semantic classes (tree, grassland, residential, commercial/industrial, road, and water). The results show that the use of an IVV increases the overall accuracy (OA) by 11 to 12% and 6% when it is implemented on the selected and all features, respectively. The selected features of CIELab color moments and GLCM provide a better OA than the implementation over CIELab color moment or GLCM as individuals. The latter increases the OA by only ∼2 to 3%. Moreover, the results show that the OA of LDA outperforms the OA of C4.5 and naive Bayes tree by ∼20%. © 2014 Society of Photo-Optical Instrumentation Engineers (SPIE) [DOI: 10.1117/1.JRS.8.083690]

Bridge-localized HOMO-binding character of divinylanthracene-bridged dinuclear ruthenium carbonyl complexes: spectroscopic, spectroelectrochemical, and computational studies

The electronic properties of four divinylanthracene-bridged diruthenium carbonyl complexes [{RuCl(CO)(PMe3)3}2(μ[BOND]CH[DOUBLE BOND]CHArCH[DOUBLE BOND]CH)] (Ar=9,10-anthracene (1), 1,5-anthracene (2), 2,6-anthracene (3), 1,8-anthracene (4)) obtained by molecular spectroscopic methods (IR, UV/Vis/near-IR, and EPR spectroscopy) and DFT calculations are reported. IR spectroelectrochemical studies have revealed that these complexes are first oxidized at the noninnocent bridging ligand, which is in line with the very small ν(C[TRIPLE BOND]O) wavenumber shift that accompanies this process and also supported by DFT calculations. Because of poor conjugation in complex 1, except oxidized 1+, the electronic absorption spectra of complexes 2+, 3+, and 4+ all display the characteristic near-IR band envelopes that have been deconvoluted into three Gaussian sub-bands. Two of the sub-bands belong mainly to metal-to-ligand charge-transfer (MLCT) transitions according to results from time-dependent DFT calculations. EPR spectroscopy of chemically generated 1+–4+ proves largely ligand-centered spin density, again in accordance with IR spectra and DFT calculations results.

The multidimensional character of accounting numbers

This paper takes as its motivation debates surrounding the multiplicity of functions of accounting information. We are in particular interested in the existential function of accounting numbers and argue that numerical signs having discursive possibilities may acquire new meanings through reframing. Drawing on Goffman’s (1974) frame analysis and Vollmer’s (2007) work on three-dimensional character of numerical signs, we explore the ways in which numbers can go through instantaneous transformations and tell a new kind of story. In our analysis, we look at the main historical developments and current controversies surrounding accounting practice with a specific focus on scandals involving numerical signs as moments where our understandings and the discursive function of previously inoffensive signs shifts through a collective involvement. We map the purpose and usefulness of Vollmer’s three-dimensional framework in the analysis of selected financial accounting practices and scandals as examples of instances where numbers are reframed to suddenly perform a different existential function in context of their calculative and symptomatic dimensions.

Toeplitz operators on Dirichlet-Besov spaces

We study Toeplitz operators on the Besov spaces in the case of the open unit disk. We prove that a symbol satisfying a weak Lipschitz type condition induces a bounded Toeplitz operator. Such symbols do not need to be bounded functions or have continuous extensions to the boundary of the open unit disk. We discuss the problem of the existence of nontrivial compact Toeplitz operators, and also consider Fredholm properties and prove an index formula.