Molecular motion of a nickel-bis(dithiolato) complex in solution

The molecular motion of the planar bis(maleonitriledithiolato)nickel anion, Ni(mnt)(2)(-), has been studied as a function of temperature using electron spin resonance (ESR) in several polar solvents; they are ethyl alcohol, eugenol, dimethyl phthalate, tri-n-butyl phosphate, tris(2-ethyl-hexyl)phosphate, diglyme, and a dimethylformamide-chloroform mixed solvent. Calculated spectra in agreement with the experimental X-band spectra are obtained using axially symmetric reorientation when the long in-plane axis is the unique (parallel) axis of the rotational diffusion tensor with D parallel/D perpendicular = 3.0-4.0; D parallel and D perpendicular are the diffusion constants for reorientation about the parallel and perpendicular axes, respectively. The reorientational model required for the simulations is either in or close to the Brownian rotational diffusion limit. In the slow motional (low temperature) region, the spectra can be simulated using the glassy g values. As the temperature increases, however, agreement is obtained only if the intermediate g factor, g(y), for the non-axially symmetric Zeeman interaction increases while g(x), g(z), and the motional model remain unchanged; this scheme and others for which gx and g(z) are possibly temperature-dependent are discussed. The values of D perpendicular from the simulations are in general agreement with those from earlier analyses of the width of the central spectral feature. The simulations and width analyses indicate (as do electrochemical, conductivity, and vapor-phase osmometry data) that the paramagnetic species reorienting in solution has a shape similar to that of the Ni(mnt)(2)(-) ion.     

Isomerism of [64Cu-NOTA-Bn]-labeled radiotracers: separation of two complex isomers and determination of their interconversion energy barrier using ion pair chromatography

The model complex [(64)Cu((S)-p-NH(2)-Bn-NOTA)](-) ([(64)Cu]1) was used to study the isomerism of [(64)Cu-NOTA-Bn]-labeled radiotracers. Two complex isomers [(64)Cu]1a and [(64)Cu]1b, which were formed at a ratio of 1:9 during the complexation of [(64)Cu]Cu(2+) with (S)-p-NH(2)-Bn-NOTA, were separated using ion pair chromatography. To study the interconversion, the nonradioactive complex isomers Cu1a and Cu1b were separated and thermally treated at 90 °C in both ammonium acetate solution and deionized water. A faster interconversion rate was observed for both isomers with lower concentrations of ammonium ions. At the end of reaction, the thermodynamic Cu1a to Cu1b equilibrium ratio was 6:94. The particular energy barriers of the interconversion for Cu1a and Cu1b were 130 kJ mol(-1) and 140 kJ mol(-1). Spectrophotometric measurements with Cu1a and Cu1b revealed two isomers adopting different geometrical configurations.     

Risk minimising strategies for revenue management problems with target values

Consider a risk-averse decision maker in the setting of a single-leg dynamic revenue management problem with revenue controlled by limiting capacity for a fixed set of prices. Instead of focussing on maximising the expected revenue, the decision maker has the main objective of minimising the risk of failing to achieve a given target revenue. Interpreting the revenue management problem in the framework of finite Markov decision processes, we augment the state space of the risk-neutral problem definition and change the objective function to the probability of failing a certain specified target revenue. This enables us to obtain a dynamic programming solution that generates the policy minimising the risk of not attaining this target revenue. We compare this solution with recently proposed risk-sensitive policies in a numerical study and discuss advantages and limitations.     

Network revenue management with inventory-sensitive bid prices and customer choice

We develop an approximate dynamic programming approach to network revenue management models with customer choice that approximates the value function of the Markov decision process with a non-linear function which is separable across resource inventory levels. This approximation can exhibit significantly improved accuracy compared to currently available methods. It further allows for arbitrary aggregation of inventory units and thereby reduction of computational workload, yields upper bounds on the optimal expected revenue that are provably at least as tight as those obtained from previous approaches. Computational experiments for the multinomial logit choice model with distinct consideration sets show that policies derived from our approach can outperform some recently proposed alternatives, and we demonstrate how aggregation can be used to balance solution quality and runtime.     

Improved bid prices for choice-based network revenue management

One of the latest developments in network revenue management (RM) is the incorporation of customer purchase behavior via discrete choice models. Many authors presented control policies for the booking process that are expressed in terms of which combination of products to offer at a given point in time and given resource inventories. However, in many implemented RM systems—most notably in the hotel industry—bid price control is being used, and this entails the problem that the recommended combination of products as identified by these policies might not be representable through bid price control. If demand were independent from available product alternatives, an optimal choice of bid prices is to use the marginal value of capacity for each resource in the network. But under dependent demand, this is not necessarily the case. In fact, it seems that these bid prices are typically not restrictive enough and result in buy-down effects.We propose (1) a simple and fast heuristic that iteratively improves on an initial guess for the bid price vector; this first guess could be, for example, dynamic estimates of the marginal value of capacity. Moreover, (2) we demonstrate that using these dynamic marginal capacity values directly as bid prices can lead to significant revenue loss as compared to using our heuristic to improve them. Finally, (3) we investigate numerically how much revenue performance is lost due to the confinement to product combinations that can be represented by a bid price.The heuristic is not restricted to a particular choice model and can be combined with any method that provides us with estimates of the marginal values of capacity. In our numerical experiments, we test the heuristic on some popular networks examples taken from peer literature. We use a multinomial logit choice model which allows customers from different segments to have products in common that they consider to purchase. In most problem instances, our heuristic policy results in significant revenue gains over some currently available alternatives at low computational cost.     

Thermodynamically and variationally consistent cohesive zone models for large deformation

The thermodynamical and variational consistency of cohesive zone models is analyzed in the present contribution. Based on a naive application of the classical Coleman & Noll procedure, it is shown that the second law of thermodynamics is not fulfilled in general. This can even be seen, in case of hyperelastic interfaces. For guaranteeing thermomechanical consistency, additional surface stresses acting at the interface have to be introduced. Based on such findings, a thermomechanically consistent model including dissipative effects is proposed. This model possesses a natural variational structure. More precisely, all state variables can naturally and jointly be computed by minimizing an incrementally defined potential. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Study of radiation damage induced by 12 keV X‐rays in MOS structures built on high‐resistivity n‐type silicon

Imaging experiments at the European X‐ray Free Electron Laser (XFEL) require silicon pixel sensors with extraordinary performance specifications: doses of up to 1 GGy of 12 keV photons, up to 10⁵ 12 keV photons per 200 µm × 200 µm pixel arriving within less than 100 fs, and a time interval between XFEL pulses of 220 ns. To address these challenges, in particular the question of radiation damage, the properties of the SiO₂ layer and of the Si–SiO₂ interface, using MOS (metal‐oxide‐semiconductor) capacitors manufactured on high‐resistivity n‐type silicon irradiated to X‐ray doses between 10 kGy and 1 GGy, have been studied. Measurements of capacitance/conductance–voltage (C/G–V) at different frequencies, as well as of thermal dielectric relaxation current (TDRC), have been performed. The data can be described by a dose‐dependent oxide charge density and three dominant radiation‐induced interface states with Gaussian‐like energy distributions in the silicon band gap. It is found that the densities of the fixed oxide charges and of the three interface states increase up to dose values of approximately 10 MGy and then saturate or even decrease. The shapes and the frequency dependences of the C/G–V measurements can be quantitatively described by a simple model using the parameters extracted from the TDRC measurements.