Planarity of para Hexaphenyl

URL:http://link.aps.org/doi/10.1103/PhysRevLett.82.3625 DOI:10.1103/PhysRevLett.82.3625We present experimental and theoretical findings on the geometry of polycrystalline para hexaphenyl via Raman scattering. The planarity of the molecule is affected by hydrostatic pressure and temperature. Our studies indicate that the potential energy curve which governs the torsional motion between neighboring phenyl rings is “W” shaped. We determine the activation energy to promote the molecule from a nonplanar to a planar state to be 0.04 eV, in good agreement with our quantum chemical calculations. From the relative intensities of the 1280cm-1 to the 1220cm-1 Raman modes we show that high pressure planarizes the molecules, modifying the “W”-shaped potential energy curve to a “U”-shaped one.We acknowledge the financial support from U.S. Army Grant No. DAAL03-92-0381, University of Missouri Research Board and Österreichische Nationalbank (Project No. 6608)

Current state of the art and use case description on geofencing for traffic management

This report is a result of a literature review and document gathering focused on geofence use cases specific for road traffic management. It presents geofence use cases that are trialled or to be trialled, implemented use cases, as well as conceptual and potential future use cases, showing for which type of transport they are used and how geofence zones are applied or to be applied. The report was conducted in the project GeoSence – Geofencing strategies for implementation in urban traffic management and planning. It is a Joint programme initiative (JPI) Urban Europe project funded by European Union´s Horizon 2020, under ERA-NET Cofund Urban Accessibility and Connectivity and gather project partners from Germany, Norway, Sweden and UK. The goal is to present the current state of art, and describe use cases, based on the working definition of geofencing in the project, where geofence is defined as a virtual geographically located boundary, statically or dynamically defined. The study shows that for implemented and real-traffic trial use case, geofencing has been applied within private car transport, shared micro-mobility, freight and logistics, public bus transportation and ridesourcing. For the future use cases, geofencing has been tested or conceptually developed also for automated vehicles and shared automated mobility, among others. The report summarises main use cases and find them to answering to especially four challenges in traffic management: safety, environment, efficiency, and tracking and data collection. Some of the use cases however answer to several of these challenges, such as differentiated road charging, and the use cases in micro-mobility. Further, the system and functionality of the trialled and/or implemented use cases, show different types of regulation geofence use cases can be used for, from informing, assisting, full enforcement, incentivising and penalisation. Guidelines and recommendations so far form national authorities show that the existence of joint regulation or guidelines for the use of geofencing for different use cases is low – with some exceptions. Digital representation of traffic regulation will be crucial for enabling geofencing

Metastable anions of dinitrobenzene: resonances for electron attachment and kinetic energy release

Attachment of free, low-energy electrons to dinitrobenzene (DNB) in the gas phase leads to DNB as well as several fragment anions. DNB, (DNB-H), (DNB-NO), (DNB-2NO), and (DNB-NO(2)) are found to undergo metastable (unimolecular) dissociation. A rich pattern of resonances in the yield of these metastable reactions versus electron energy is observed; some resonances are highly isomer-specific. Most metastable reactions are accompanied by large average kinetic energy releases (KER) that range from 0.5 to 1.32 eV, typical of complex rearrangement reactions, but (1,3-DNB-H)(-) features a resonance with a KER of only 0.06 eV for loss of NO. (1,3-DNB-NO)(-) offers a rare example of a sequential metastable reaction, namely, loss of NO followed by loss of CO to yield C(5)H(4)O(-) with a large KER of 1.32 eV. The G4(MP2) method is applied to compute adiabatic electron affinities and reaction energies for several of the observed metastable channels. (C) 2010 American Institute of Physics. [doi:10.1063/1.3514931

(Meta-)stable reconstructions of the diamond(111) surface: interplay between diamond- and graphite-like bonding

Off-lattice Grand Canonical Monte Carlo simulations of the clean diamond (111) surface, based on the effective many-body Brenner potential, yield the $(2\times1)$ Pandey reconstruction in agreement with \emph{ab-initio} calculations and predict the existence of new meta-stable states, very near in energy, with all surface atoms in three-fold graphite-like bonding. We believe that the long-standing debate on the structural and electronic properties of this surface could be solved by considering this type of carbon-specific configurations.Comment: 4 pages + 4 figures, Phys. Rev. B Rapid Comm., in press (15Apr00). For many additional details (animations, xyz files) see electronic supplement to this paper at http://www.sci.kun.nl/tvs/carbon/meta.htm

Conjugation-Length Dependence of Spin-Dependent Exciton Formation Rates in Pi-Conjugated Oligomers and Polymers

We have measured the ratio, r = $\sigma_S/\sigma_T$ of the formation cross section, $\sigma$ of singlet ($\sigma_S$) and triplet ($\sigma_T$) excitons from oppositely charged polarons in a large variety of $\pi$-conjugated oligomer and polymer films, using the photoinduced absorption and optically detected magnetic resonance spectroscopies. The ratio r is directly related to the singlet exciton yield, which in turn determines the maximum electroluminescence quantum efficiency in organic light emitting diodes (OLED). We discovered that r increases with the conjugation length, CL; in fact a universal dependence exists in which $r^{-1}$ depends linearly on $CL^{-1}$, irrespective of the chain backbone structure. These results indicate that $\pi$-conjugated polymers have a clear advantage over small molecules in OLED applications.Comment: 5 pages, 4 figure

Geometry-Dependent Electronic Properties of Highly Fluorescent Conjugated Molecules

URL:http://link.aps.org/doi/10.1103/PhysRevLett.85.2388 DOI:10.1103/PhysRevLett.85.2388We present a combined experimental/theoretical study of the electronic properties of conjugated para- phenylene type molecules under high pressure up to 80 kbar. Pressure is used as a tool to vary the molecular geometry and intermolecular interaction. The influence of the latter two on singlet and triplet excitons as well as polarons is monitored via optical spectroscopy. We have performed band structure calculations for the planar poly(para-phenylene) and calculated the dielectric function. By varying the intermolecular distances and the length of the polymer repeat unit the observed pressure effects can be explained.Supported by the University of Missouri Research Board, OeNB Project No. 6608, the vector-computer facilities at the University of Graz

On the static and dynamic properties of flax and Cordenka epoxy composites

Fibre reinforced composites have excellent specific properties and are widely sought after by engineers seeking to reduce mass. However, end of life disposal is a significant problem and so research into more sustainable natural fibre composites is extremely topical. This paper examines the applicability of natural fibre composites for high performance structural applications. Woven flax and regenerated cellulose (Cordenka) textiles were pre-impregnated with commercially available epoxy resins and consolidated into test laminates in an autoclave to determine their static (compressive, tensile, flexural) and dynamic (energy absorption) properties. The range of compressive strengths was 77.5–299.6 MPa. Tensile strengths ranged from 63 to 92.6 MPa and interlaminar shear strength (ILSS) from 10.7 to 23.3 MPa. Specific energy absorption (SEA) varied between 21.2–34.2 kJ/kg. Biotex flax combined with MTM49 resin matched the SEA of T300 carbon fibre using the same resin system and layup. This work has demonstrated that natural fibre composites have significant scope for use in structural applications but additional work is required on fibre to matrix bonding in order to maximise their properties whilst remaining an environmentally credible option

Endogenous cholinergic inputs and local circuit mechanisms govern the phasic mesolimbic dopamine response to nicotine

Nicotine exerts its reinforcing action by stimulating nicotinic acetylcholine receptors (nAChRs) and boosting dopamine (DA) output from the ventral tegmental area (VTA). Recent data have led to a debate about the principal pathway of nicotine action: direct stimulation of the DAergic cells through nAChR activation, or disinhibition mediated through desensitization of nAChRs on GABAergic interneurons. We use a computational model of the VTA circuitry and nAChR function to shed light on this issue. Our model illustrates that the α4β2-containing nAChRs either on DA or GABA cells can mediate the acute effects of nicotine. We account for in vitro as well as in vivo data, and predict the conditions necessary for either direct stimulation or disinhibition to be at the origin of DA activity increases. We propose key experiments to disentangle the contribution of both mechanisms. We show that the rate of endogenous acetylcholine input crucially determines the evoked DA response for both mechanisms. Together our results delineate the mechanisms by which the VTA mediates the acute rewarding properties of nicotine and suggest an acetylcholine dependence hypothesis for nicotine reinforcement.Peer reviewe

State based model of long-term potentiation and synaptic tagging and capture

Recent data indicate that plasticity protocols have not only synapse-specific but also more widespread effects. In particular, in synaptic tagging and capture (STC), tagged synapses can capture plasticity-related proteins, synthesized in response to strong stimulation of other synapses. This leads to long-lasting modification of only weakly stimulated synapses. Here we present a biophysical model of synaptic plasticity in the hippocampus that incorporates several key results from experiments on STC. The model specifies a set of physical states in which a synapse can exist, together with transition rates that are affected by high- and low-frequency stimulation protocols. In contrast to most standard plasticity models, the model exhibits both early- and late-phase LTP/D, de-potentiation, and STC. As such, it provides a useful starting point for further theoretical work on the role of STC in learning and memory