Online Parameter Identification for Traffic Simulation via Lagrangian Sensing

This paper deals with parameter identification for traffic models. We present a method to estimate model parameters based on Lagrangian measurement data that can be used for online traffic simulation. In the context of Lagrangian sensing the sensor placement is reduced to the optimum choice of measurement vehicles currently moving with the traffic flow. Identifiability is investigated using the Fisher Information Matrix (FIM). Simulation results are presented and validated via simulation based on a car-following-model. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

A dispersed fluorescence and ab initio investigation of the X2B1 and A2A1 electronic states of the PH2 molecule

In this work, the X2B1 and A2A1 electronic states of the phosphino (PH2) free radical have been studied by dispersed fluorescence and ab initio methods. PH2 molecules were produced in a molecular free-jet apparatus by laser vaporizing a silicon rod in the presence of phosphine (PH3) gas diluted in helium. The laser-induced fluorescence, from the excited A2A1 electronic state down to the ground electronic state, was dispersed and analyzed. Ten (upsilon1upsilon2upsilon3) vibrationally excited levels of the ground electronic state, with upsilon1 < or = 2, upsilon2 < or = 6, and upsilon3 = 0, have been observed. Ab initio potential-energy surfaces for the X2B1 and A2A1 electronic states have been calculated at 210 points. These two states correlate with a 2Pi(u) state at linearity and they interact by the Renner-Teller coupling and spin-orbit coupling. Using the ab initio potential-energy surfaces with our RENNER computer program system, the vibronic structure and relative intensities of the A2A1 --> X2B1 emission band system have been calculated in order to corroborate the experimental assignments.     

Endohedral condensation and higher exohedral coverage of Kr on open single-walled carbon nanotubes at 77 K

An isotherm quasi-discontinuity, or a near-vertical step, at 177 microTorr indicative of Kr condensation inside open single-walled carbon nanotubes (SWNT) has been observed at 77 K. The isotherm shows double adsorption-branch structure attributed to the existence of two endohedral phases of confined Kr. Three well-pronounced steps corresponding to the formation of various exohedral phases are present in the high-density (low-pressure) branch. The desorption branch exhibits three rounded steps assigned to higher order exohedral coverage.     

Quantitative photochemistry of Cp'Pt(CH(3))(3) (Cp' = eta(5)-C(5)H(4)CH(3)) in solution: a highly efficient organometallic photoinitiator for hydrosilylation

The quantitative photochemistry of the platinum organometallic complex, Cp'Pt(CH(3))(3) (Cp' = eta(5)-C(5)H(4)CH(3)), has been investigated in methylcyclohexane and n-pentane solutions at 293 K following UV irradiation into the lowest lying absorption bands. Absolute photochemical quantum efficiency (phi(cr)) results obtained for Cp'Pt(CH(3))(3) at 313 and 366 nm reveal that the system very effectively photoreacts with phi(cr) = 0.34-0.41 in these solvents and 0.79-0.85 when 53 mM Et(3)SiH is incorporated. These photoefficiencies indicate that the quantitative photochemistry is 2 orders of magnitude higher than previously recognized. The application of Cp'Pt(CH(3))(3) as an effective photoinitiator for hydrosilylation reactions involving vinyl/hydride silicone mixtures is demonstrated.     

Quantitative energy dispersive X-ray microanalysis of electron beam-sensitive alloyed nanoparticles.

An energy dispersive X-ray spectrometry (EDXS) method is developed to evaluate the composition of alloyed nanoparticles (NPs) where one of the alloying elements is removed under the electron beam during microanalysis with a transmission electron microscope (TEM). The method is demonstrated for alloyed Au-Ag NPs of a diameter ranging from 6 to 20 nm produced by laser evaporation of a water-suspended Ag-Au powder mixture of varying composition. Series of EDXS spectra are recorded for 30 NPs from samples with five different Ag:Au ratios revealing Ag depletion from NPs during electron irradiation. By studying the evolution of NPs composition as a function of dose, the initial Ag content for each NP is extrapolated. The rate of Ag depletion is discussed in terms of sputtering and knock-on damage. On average, approximately one Ag atom is lost from the NP for each Ag L X-ray detected. To assess the limitations of microanalysis in these sensitive nanoscale structures, the concept of detectability limit is adapted to our method. This benchmark is then evaluated for Ag in Au-Ag NPs of various sizes and acquisition times. This study should be regarded as a guide for the design of analytical TEM measurements of beam-sensitive NPs.