Spectroscopic properties and electronic structures of 17-electron half-sandwich ruthenium acetylide complexes, [Ru(CCAr)(L2)Cp′]+ (Ar=phenyl, p-tolyl, 1-naphthyl, 9-anthryl; L2=(PPh3)2, Cp′=Cp; L2=dppe; Cp′=Cp∗)

A series of half-sandwich bis(phosphine) ruthenium acetylide complexes [Ru(C CAr)(L-2)Cp'] (Ar = phenyl, p-tolyl, 1-naphthyl, 9-anthryl; L2 = (PPh3)(2), Cp' = Cp; L-2 = dppe; Cp' = Cp*) have been examined using electrochemical and spectroelectrochemical methods. One-electron oxidation of these complexes gave the corresponding radical cations [Ru(C CAr)(L2)Cp'](+). Those cations based on Ru(dppe)Cp*, or which feature a para-tolyl acetylide substituent, are more chemically robust than examples featuring the Ru(PPh3)(2)Cp moiety, permitting good quality UV-Vis-NIR and IR spectroscopic data to be obtained using spectroelectrochemical methods. On the basis of TD DFT calculations, the low energy (NIR) absorption bands in the experimental electronic spectra for most of these radical cations are assigned to transitions between the beta-HOSO and beta-LUSO, both of which have appreciable metal d and ethynyl pi character. However, the large contribution from the anthryl moiety to the frontier orbitals of [Ru(C CC14H9)(L2)CP'](+) suggests compounds containing this moiety should be described as metal-stabilised anthryl radical cations.

Composite control of non-linear singularly perturbed systems: meeting a design objective

Using the integral manifold approach, a composite control—the sum of a fast control and a slow control—is derived for a particular class of non-linear singularly perturbed systems. The fast control is designed completely at the outset, thus ensuring the stability of the fast transients of the system and, furthermore, the existence of the integral manifold. A new method is then presented which simplifies the derivation of a slow control such that the singularly perturbed system meets a preselected design objective to within some specified order of accuracy. Though this approach is, by its very nature, ad hoc, the underlying procedure is easily extended to more general classes of singularly perturbed systems by way of three examples.

A three-regime model of speculative behaviour: modelling the evolution of the S&P 500 composite index

We examine whether a three-regime model that allows for dormant, explosive and collapsing speculative behaviour can explain the dynamics of the S&P 500. We extend existing models of speculative behaviour by including a third regime that allows a bubble to grow at a steady rate, and propose abnormal volume as an indicator of the probable time of bubble collapse. We also examine the financial usefulness of the three-regime model by studying a trading rule formed using inferences from it, whose use leads to higher Sharpe ratios and end of period wealth than from employing existing models or a buy-and-hold strategy.

New half-sandwich heterobimetallic CpMPt (M=Rh, Ir) dithiolato bridged complexes

Cationic heterobimetallic complexes 5–7 [(PPh3)2Pt(μ-edt)MClCp′)]BF4 (edt=−S(CH2)2S−; 5: M=Rh and Cp′=η5-C5H5; 6: M=Rh and Cp′=η5-C5Me5 and 7: M=Ir and Cp′=η5-C5Me5) were prepared by reaction of [Pt(edt)(PPh3)2] with [Cp′ClM(μ-Cl)2MClCp′] in THF in the presence of two equivalents of AgBF4. The crystalline structure of 5 was determined by X-ray diffraction methods. Cationic heterobimetallic complexes [(PPh3)2Pt(μ-S(CH2)2S)MClCp′)]BF4 (M=Rh, Ir) were prepared. The crystalline structure of [(PPh3)2Pt(μ-edt)RhClCp)]BF4 was determined by X-ray diffraction methods.

Dimensionalising on- and off-line brands' composite equity

This paper approaches the subject of brand equity measurement on and offline. The existing body of research knowledge on brand equity measurement has derived from classical contexts; however, the majority of today's brands prosper simultaneously online and offline. Since branding on the Web needs to address the unique characteristics of computer-mediated environments, it was posited that classical measures of brand equity were inadequate for this category of brands. Aaker's guidelines for building a brand equity measurement system were thus followed and his brand equity ten was employed as a point of departure. The main challenge was complementing traditional measures of brand equity with new measures pertinent to the Web. Following 16 semi-structured interviews with experts, ten additional measures were identified.

Better cross hedges with composite hedging? Hedging equity portfolios using financial and commodity futures

Unless a direct hedge is available, cross hedging must be used. In such circumstances portfolio theory implies that a composite hedge (the use of two or more hedging instruments to hedge a single spot position) will be beneficial. The study and use of composite hedging has been neglected; possibly because it requires the estimation of two or more hedge ratios. This paper demonstrates a statistically significant increase in out-of-sample effectiveness from the composite hedging of the Amex Oil Index using S&P500 and New York Mercantile Exchange crude oil futures. This conclusion is robust to the technique used to estimate the hedge ratios, and to allowance for transactions costs, dividends and the maturity of the futures contracts.

Testing of fibre composite leaf spring for heavy axle loads

This paper presents the results of quasi-static and dynamic testing of glass fiber-reinforced polyester leaf suspension for rail freight vehicles named Euroleaf. The principal elements of the suspension's design and manufacturing process are initially summarized. Comparison between quasi-static tests and finite element predictions are then presented. The Euroleaf suspension have been mounted on a tipper wagon and tested dynamically at tare and full load on a purpose-built shaker rig. A shaker rig dynamic testing methodology has been pioneered for rail vehicles, which follows closely road vehicle suspension dynamic testing methodology. The use and evaluation of this methodology have demonstrated that the Euroleaf suspension is dynamically much softer than steel suspensions even though it is statically much stiffer. As a consequence, the suspension dynamic loading at laden loading conditions is reduced compared to the most advanced steel leaf suspension over shaker rig track tests.

Composite control of non-linear singularly perturbed systems: a geometric approach

Using a geometric approach, a composite control—the sum of a slow control and a fast control—is derived for a general class of non-linear singularly perturbed systems. A new and simpler method of composite control design is proposed whereby the fast control is completely designed at the outset. The slow control is then free to be chosen such that the slow integral manifold of the original system approximates a desired design manifold to within any specified order of ε accuracy.

Composite control of non-linear singularly perturbed systems: a geometric approach

Using a geometric approach, a composite control—the sum of a slow control and a fast control—is derived for a general class of non-linear singularly perturbed systems. A new and simpler method of composite control design is proposed whereby the fast control is completely designed at the outset. The slow control is then free to be chosen such that the slow integral manifold of the original system approximates a desired design manifold to within any specified order of ε accuracy.

Redox-active, dinuclear sandwich compounds [Cp*Fe(μ-L)FeCp*] (L = naphthalene and anthracene)

Although there has been much interest in the chemistry of bimetallic transition metal complexes, compounds with naphthalene or anthracene as bridging ligands are still rare. In this article, we describe the synthesis of the homodinuclear iron complexes [Cp*Fe(μ-η4:η4-L)FeCp*] (1: L = C10H8, 2: L = C14H10; Cp* = η5-C5Me5). The complexes were characterized by 1H and 13C{1H} NMR, UV/Vis, and 57Fe Mössbauer spectroscopy, and their molecular structures were determined by X-ray crystallography. Both complexes are diamagnetic as a result of the strong magnetic coupling of the 17e FeI centers mediated by the polyarene bridge. An analysisof the redox behavior of 1 and 2 by cyclic voltammetry andUV/Vis spectroelectrochemistry shows that the complexes can be oxidized reversibly in two well-separated one-electron steps to the monocation [Cp*Fe(μ-L)FeCp*]+ and the dication [Cp*Fe(μ-L)FeCp*]2+. The reduction to the monoanion [Cp*Fe(μ-L)FeCp*]– was also observed.

Synthesis and Electronic Structure of Dissymmetrical, Naphthalene-Bridged Sandwich Complexes [Cp′Fe(μ‑C10H8)MCp*]x (x = 0, +1; M =Fe, Ru; Cp′ = η5‑C5H2‑1,2,4‑tBu3; Cp* = η5‑C5Me5)

The dissymmetrical naphthalene-bridged complexes [Cp′Fe(μ-C10H8)FeCp*] (3; Cp* = η5-C5Me5, Cp′ = η5-C5H2-1,2,4-tBu3) and [Cp′Fe(μ-C10H8)RuCp*] (4) were synthesized via a one-pot procedure from FeCl2(thf)1.5, Cp′K, KC10H8, and [Cp* FeCl(tmeda)] (tmeda = N,N,N′,N′- tetramethylethylenediamine) or [Cp*RuCl]4, respectively. The symmetrically substituted iron ruthenium complex [Cp*Fe(μ-C10H8)RuCp*] (5) bearing two Cp* ligands was prepared as a reference compound. Compounds 3−5 are diamagnetic and display similar molecular structures, where the metal atoms are coordinated to opposite sides of the bridging naphthalene molecule. Cyclic voltammetry and UV/vis spectroelectrochemistry studies revealed that neutral 3−5 can be oxidized to monocations 3+−5+ and dications 32+−52+. The chemical oxidation of 3 and 4 with [Cp2Fe]PF6 afforded the paramagnetic hexafluorophosphate salts [Cp′Fe(μ-C10H8)FeCp*]PF6 ([3]PF6) and [Cp′Fe(μ-C10H8)RuCp*]PF6 ([4]PF6), which were characterized by various spectroscopic techniques, including EPR and 57Fe Mössbauer spectroscopy. The molecular structure of [4]PF6 was determined by X-ray crystallography. DFT calculations support the structural and spectroscopic data and determine the compositions of frontier molecular orbitals in the investigated complexes. The effects of substituting Cp* with Cp′ and Fe with Ru on the electronic structures and the structural and spectroscopic properties are analyzed.

Reconstruction of geomagnetic activity and near-Earth interplanetary conditions over the past 167 yr – Part 1: A new geomagnetic data composite

We present a new composite of geomagnetic activity which is designed to be as homogeneous in its construction as possible. This is done by only combining data that, by virtue of the locations of the source observatories used, have similar responses to solar wind and IMF (interplanetary magnetic field) variations. This will enable us (in Part 2, Lockwood et al., 2013a) to use the new index to reconstruct the interplanetary magnetic field, B, back to 1846 with a full analysis of errors. Allowance is made for the effects of secular change in the geomagnetic field. The composite uses interdiurnal variation data from Helsinki for 1845–1890 (inclusive) and 1893–1896 and from Eskdalemuir from 1911 to the present. The gaps are filled using data from the Potsdam (1891–1892 and 1897–1907) and the nearby Seddin observatories (1908–1910) and intercalibration achieved using the Potsdam–Seddin sequence. The new index is termed IDV(1d) because it employs many of the principles of the IDV index derived by Svalgaard and Cliver (2010), inspired by the u index of Bartels (1932); however, we revert to using one-day (1d) means, as employed by Bartels, because the use of near-midnight values in IDV introduces contamination by the substorm current wedge auroral electrojet, giving noise and a dependence on solar wind speed that varies with latitude. The composite is compared with independent, early data from European-sector stations, Greenwich, St Petersburg, Parc St Maur, and Ekaterinburg, as well as the composite u index, compiled from 2–6 stations by Bartels, and the IDV index of Svalgaard and Cliver. Agreement is found to be extremely good in all cases, except two. Firstly, the Greenwich data are shown to have gradually degraded in quality until new instrumentation was installed in 1915. Secondly, we infer that the Bartels u index is increasingly unreliable before about 1886 and overestimates the solar cycle amplitude between 1872 and 1883 and this is amplified in the proxy data used before 1872. This is therefore also true of the IDV index which makes direct use of the u index values.

Non-steady state heat conduction in composite walls

The problem of heat conduction in one-dimensional piecewise homogeneous composite materials is examined by providing an explicit solution of the one-dimensional heat equation in each domain. The location of the interfaces is known, but neither temperature nor heat flux are prescribed there. Instead, the physical assumptions of their continuity at the interfaces are the only conditions imposed. The problem of two semi-infinite domains and that of two finite-sized domains are examined in detail. We indicate also how to extend the solution method to the setting of one finite-sized domain surrounded on both sides by semi-infinite domains, and on that of three finite-sized domains.