Dynamics of excess electronic charge in aliphatic ionic liquids containing the bis(trifluoromethylsulfonyl)amide anion

In a recent article (J. Am. Chem. Soc. 2011, 133, 20186) we investigated the initial spatial distribution of dry excess electrons in a series of room-temperature ionic liquids (RTILs). Perhaps unexpectedly, we found that in some alkylammonium-based systems the excess negative charge resided on anions and not on the positive cations. Following on these results, in the current paper we describe the time evolution of an excess electronic charge introduced in alkylammonium- and pyrrolidinium-based ionic liquids coupled with the bis(trifluoromethylsulfonyl)amide ([TfN]) anion. We find that on a 50 fs time scale an initially delocalized excess electron localizes on a single [TfN] anion which begins a fragmentation process. Low-energy transitions have a very different physical origin on the several femtoseconds time scale when compared to what occurs on the picosecond time scale. At time zero, these are intraband transitions of the excess electron. However after 40 fs when the excess electronic charge localizes on a single anion, these transitions disappear, and the spectrum is dominated by electron-transfer transitions between the fragments of the doubly charged breaking anion. © 2013 American Chemical Society.

A multiconfigurational time-dependent Hartree-Fock method for excited electronic states. II. Coulomb interaction effects in single conjugated polymer chains

Conjugated polymers have attracted considerable attention in the last few decades due to their potential for optoelectronic applications. A key step that needs optimisation is charge carrier separation following photoexcitation. To understand better the dynamics of the exciton prior to charge separation, we have performed simulations of the formation and dynamics of localised excitations in single conjugated polymer strands. We use a nonadiabatic molecular dynamics method which allows for the coupled evolution of the nuclear degrees of freedom and of multiconfigurational electronic wavefunctions. We show the relaxation of electron-hole pairs to form excitons and oppositely charged polaron pairs and discuss the modifications to the relaxation process predicted by the inclusion of the Coulomb interaction between the carriers. The issue of charge photogeneration in conjugated polymers in dilute solution is also addressed. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3600404]

The List_Tree - an innovative solution to customer portfolio representation

The scale of BT's operations necessitates the use of very large scale computing systems, and the storage and management of large volumes of data. Customer product portfolios are an important form of data which can be difficult to store in a space efficient way. The difficulties arise from the inherently structured form of product portfolios, and the fact that they change over time as customers add or remove products. This paper introduces a new data-modelling abstraction called the List_Tree. It has been designed specifically to support the efficient storage and manipulation of customer product portfolios, but may also prove useful in other applications with similar general requirements.

Impacts of compressed air energy storage plant on an electricity market with a large renewable energy portfolio

Renewable energy generation is expected to continue to increase globally due to renewable energy targets and obligations to reduce greenhouse gas emissions. Some renewable energy sources are variable power sources, for example wind, wave and solar. Energy storage technologies can manage the issues associated with variable renewable generation and align non-dispatchable renewable energy generation with load demands. Energy storage technologies can play different roles in each of the step of the electric power supply chain. Moreover, large scale energy storage systems can act as renewable energy integrators by smoothing the variability. Compressed air energy storage is one such technology. This paper examines the impacts of a compressed air energy storage facility in a pool based wholesale electricity market in a power system with a large renewable energy portfolio.

Covariance Averaging for Improved Estimation and Portfolio Allocation

We propose a new method for estimating the covariance matrix of a multivariate time series of nancial returns. The method is based on estimating sample covariances from overlapping windows of observations which are then appropriately weighted to obtain the nal covariance estimate. We extend the idea of (model) covariance averaging o ered in the covariance shrinkage approach by means of greater ease of use, exibility and robustness in averaging information over different data segments. The suggested approach does not su er from the curse of dimensionality and can be used without problems of either approximation or any demand for numerical optimization.

Electronic voting in the French legislative elections of 2012

This chapter presents an analysis of the unprecedented use of electronic voting by expatriates during the French 2012 legislative elections, when they elected their own representatives (referred to here as ‘deputies’), to the National Assembly in Paris for the first time, in 11 newly created overseas constituencies.
The study is presented within the broader perspective of electronic voting in France more generally, and in the historical context of extra-territorial voting by French expatriates. The authors discuss the main issues and controversies that arose during the 2012 elections, and in a final section analyse the results. The authors conclude by drawing attention to recent developments in electronic voting in France since the 2012 elections, which suggest that although there was much criticism expressed by experts of electronic voting as to the security and transparency of the system used, the official discourse that acclaimed the experience as a success, appears to have convinced its target audience.