324 research outputs found

    Exciton bimolecular annihilation dynamics in supramolecular nanostructures of conjugated oligomers

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    We present femtosecond transient absorption measurements on π\pi-conjugated supramolecular assemblies in a high pump fluence regime. Oligo(\emph{p}-phenylenevinylene) monofunctionalized with ureido-\emph{s}-triazine (MOPV) self-assembles into chiral stacks in dodecane solution below 75^{\circ}C at a concentration of 4×1044\times 10^{-4} M. We observe exciton bimolecular annihilation in MOPV stacks at high excitation fluence, indicated by the fluence-dependent decay of 111^1Bu_{u}-exciton spectral signatures, and by the sub-linear fluence dependence of time- and wavelength-integrated photoluminescence (PL) intensity. These two characteristics are much less pronounced in MOPV solution where the phase equilibrium is shifted significantly away from supramolecular assembly, slightly below the transition temperature. A mesoscopic rate-equation model is applied to extract the bimolecular annihilation rate constant from the excitation fluence dependence of transient absorption and PL signals. The results demonstrate that the bimolecular annihilation rate is very high with a square-root dependence in time. The exciton annihilation results from a combination of fast exciton diffusion and resonance energy transfer. The supramolecular nanostructures studied here have electronic properties that are intermediate between molecular aggregates and polymeric semiconductors

    Spatial layout planning in sub-surface rail station design for effective fire evacuation

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    The London Underground network is a crucial part of the transportation system in one of only four ‘Alpha’ world cities. The other three – Paris, New York and Tokyo – also have such sub-surface railway transport systems that may benefit from this shape grammar station design process in a future research proposal. In London’s case, the passenger flow rates are the underlining factor in sizing infrastructure where passengers have access – it is therefore this criterion that provides the basis for the shape grammar formulation for the largest, oldest and one of the most complex underground systems in the world. The research aims to improve passenger fire evacuation times, with due cognisance of the growth of numbers using the system, and its present susceptibility to terrorist attacks taken into account. The proposed shape grammar approach will provide for generation of spatial layouts, based upon visual rules of shape recognition, replacement / union, their connectivity and spatial relationships. The paper concentrates on definition and implementation of novel shape grammar design rules that incorporate station planning design knowledge, and in particular also discusses designers’ fire risk assessment approach and related knowledge that is also needed to produce credible station design solutions. Development, to date, of the proposed artificially intelligent CAD environment is also described along with parallel theoretical research. The proposed CAD interface provides familiarity to the designer and avoids incompatibility issues regarding drawing exchange format between various software systems. The shape grammar layouts produced will be tested in SIMULEX, a commercially available evacuation package, and be compared against ‘traditionally’ designed layouts to demonstrate improvements of preliminary ‘reference’ designs, which follow the standard London Underground design process as a later stage of this research
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