Combined Monte Carlo and quantum mechanics study of the solvatochromism of phenol in water. The origin of the blue shift of the lowest pi-pi* transition

A combined and sequential use of Monte Carlo simulations and quantum mechanical calculations is made to analyze the spectral shift of the lowest pi-pi* transition of phenol in water. The solute polarization is included using electrostatic embedded calculations at the MP2/aug-cc-pVDZ level giving a dipole moment of 2.25 D, corresponding to an increase of 76% compared to the calculated gas-phase value. Using statistically uncorrelated configurations sampled from the MC simulation,first-principle size-extensive calculations are performed to obtain the solvatochromic shift. Analysis is then made of the origin of the blue shift. Results both at the optimized geometry and in room-temperature liquid water show that hydrogen bonds of water with phenol promote a red shift when phenol is the proton-donor and a blue shift when phenol is the proton-acceptor. In the case of the optimized clusters the calculated shifts are in very good agreement with results obtained from mass-selected free jet expansion experiments. In the liquid case the contribution of the solute-solvent hydrogen bonds partially cancels and the total shift obtained is dominated by the contribution of the outer solvent water molecules. Our best result, including both inner and outer water molecules, is 570 +/- 35 cm(-1), in very good agreement with the small experimental shift of 460 cm(-1) for the absorption maximum.

Onset of pi(0) Suppression Studied in Cu plus Cu Collisions at root s(NN)=22.4, 62.4, and 200 GeV

Neutral pion transverse momentum (p(T)) spectra at midrapidity (|y| less than or similar to 0.35) were measured in Cu + Cu collisions at root s(NN) = 22.4, 62.4, and 200 GeV. Relative to pi(0) yields in p + p collisions scaled by the number of inelastic nucleon-nucleon collisions (N(coll)) the pi(0) yields for p(T) greater than or similar to 2 GeV/c in central Cu + Cu collisions are suppressed at 62.4 and 200 GeV whereas an enhancement is observed at 22.4 GeV. A comparison with a jet-quenching model suggests that final state parton energy loss dominates in central Cu + Cu collisions at 62.4 and 200 GeV, while the enhancement at 22.4 GeV is consistent with nuclear modifications in the initial state alone.

Dihadron azimuthal correlations in Au+Au collisions at root s(NN)=200 GeV

Azimuthal angle (Delta phi) correlations are presented for a broad range of transverse momentum (0.4 < p(T) < 10 GeV/c) and centrality (0-92%) selections for charged hadrons from dijets in Au+Au collisions at root s(NN) = 200 GeV. With increasing p(T), the away-side Delta phi distribution evolves from a broad and relatively flat shape to a concave shape, then to a convex shape. Comparisons with p + p data suggest that the away-side distribution can be divided into a partially suppressed ""head"" region centered at Delta phi similar to pi, and an enhanced ""shoulder"" region centered at Delta phi similar to pi +/- 1.1. The p(T) spectrum for the associated hadrons in the head region softens toward central collisions. The spectral slope for the shoulder region is independent of centrality and trigger p(T). The properties of the near-side distributions are also modified relative to those in p + p collisions, reflected by the broadening of the jet shape in Delta phi and Delta eta, and an enhancement of the per-trigger yield. However, these modifications seem to be limited to p(T)less than or similar to 4 GeV/c, above which both the hadron pair shape and per-trigger yield become similar to p + p collisions. These observations suggest that both the away- and near-side distributions contain a jet fragmentation component which dominates for p(T) greater than or similar to 5 GeV/c and a medium-induced component which is important for p(T) less than or similar to 4 GeV/c. We also quantify the role of jets at intermediate and low p(T) through the yield of jet-induced pairs in comparison with binary scaled p + p pair yield. The yield of jet-induced pairs is suppressed at high pair proxy energy (sum of the p(T) magnitudes of the two hadrons) and is enhanced at low pair proxy energy. The former is consistent with jet quenching; the latter is consistent with the enhancement of soft hadron pairs due to transport of lost energy to lower p(T).

Signals for new spin-1 resonances in electroweak gauge boson pair production at the LHC

The mechanism of electroweak symmetry breaking ( EWSB) will be directly scrutinized soon at the CERN Large Hadron Collider. We analyze the LHC potential to look for new vector bosons associated with the EWSB sector, presenting a possible model independent approach to search for these new spin-1 resonances. We show that the analyses of the processes pp -> l(+)l(1-)E(T), l +/- jjE(T), l(1 +/-)l(+)l(-)E(T), l(+/-)jjE(T), and l(+)l(-) jj (with l, l' = e or mu and j = jet) have a large reach at the LHC and can lead to the discovery or exclusion of many EWSB scenarios such as Higgsless models.

Parton energy loss in heavy-ion collisions via direct-photon and charged-particle azimuthal correlations

Charged-particle spectra associated with direct photon (gamma(dir)) and pi(0) are measured in p + p and Au + Au collisions at center-of-mass energy root(S)(NN) = 200 GeV with the STAR detector at the Relativistic Heavy Ion Collider. A shower-shape analysis is used to partially discriminate between gamma(dir) and pi(0). Assuming no associated charged particles in the gamma(dir) direction ( near side) and small contribution from fragmentation photons (gamma(frag)), the associated charged-particle yields opposite to gamma(dir) (away side) are extracted. In central Au + Au collisions, the charged-particle yields at midrapidity (vertical bar eta vertical bar < 1) and high transverse momentum (3 < (assoc)(PT) < 16 GeV/c) associated with gamma(dir) and pi(0) (vertical bar eta vertical bar < 0.9, 8 < (trig)(PT) < 16 GeV/c) are suppressed by a factor of 3-5 compared with p + p collisions. The observed suppression of the associated charged particles is similar for gamma(dir) and pi(0) and independent of the gamma(dir) energy within uncertainties. These measurements indicate that, in the kinematic range covered and within our current experimental uncertainties, the parton energy loss shows no sensitivity to the parton initial energy, path length, or color charge.

Azimuthal di-hadron correlations in d plus Au and Au plus Au collisions at root s(NN)=200 GeV measured at the STAR detector

Yields, correlation shapes, and mean transverse momenta p(T) of charged particles associated with intermediate-to high-p(T) trigger particles (2.5 < p(T) < 10 GeV/c) in d + Au and Au + Au collisions at root s(NN) = 200 GeV are presented. For associated particles at higher p(T) greater than or similar to 2.5 GeV/c, narrow correlation peaks are seen in d + Au and Au + Au, indicating that the main production mechanism is jet fragmentation. At lower associated particle pT < 2 GeV/c, a large enhancement of the near- (Delta phi similar to 0) and away-side (Delta phi similar to pi) associated yields is found, together with a strong broadening of the away-side azimuthal distributions in Au + Au collisions compared to d + Au measurements, suggesting that other particle production mechanisms play a role. This is further supported by the observed significant softening of the away-side associated particle yield distribution at Delta phi similar to pi in central Au + Au collisions.

Longitudinal double-spin asymmetry and cross section for inclusive neutral pion production at midrapidity in polarized proton collisions at s=200 GeV

We report a measurement of the longitudinal double-spin asymmetry A(LL) and the differential cross section for inclusive pi(0) production at midrapidity in polarized proton collisions at s=200 GeV. The cross section was measured over a transverse momentum range of 1 < p(T)< 17 GeV/c and found to be in good agreement with a next-to-leading order perturbative QCD calculation. The longitudinal double-spin asymmetry was measured in the range of 3.7 < p(T)< 11 GeV/c and excludes a maximal positive gluon polarization in the proton. The mean transverse momentum fraction of pi(0)'s in their parent jets was found to be around 0.7 for electromagnetically triggered events.

Measurement of D* mesons in jets from p plus p collisions at root s=200 GeV

We report the measurement of charged D* mesons in inclusive jets produced in proton-proton collisions at a center-of-mass energy root s = 200 GeV with the STAR experiment at the Relativistic Heavy Ion Collider. For D* mesons with fractional momenta 0.2< z< 0.5 in inclusive jets with 11.5 GeV mean transverse energy, the production rate is found to be N(D*(+) + D*(-))/N(jet) = 0.015 +/- 0.008(stat) +/- 0.007(sys). This rate is consistent with perturbative QCD evaluation of gluon splitting into a pair of charm quarks and subsequent hadronization.

Flow injection analysis of paracetamol using a biomimetic sensor as a sensitive and selective amperometric detector

This work describes the coupling of a biomimetic sensor to a flow injection system for the sensitive determination of paracetamol. The sensor was prepared as previously described in the literature (M. D. P. T. Sotomayor, A. Sigoli, M. R. V. Lanza, A. A. Tanaka and L. T. Kubota, J. Braz. Chem. Soc., 2008, 19, 734) by modifying a glassy carbon electrode surface with a Nafion (R) membrane doped with iron tetrapyridinoporphyrazine (FeTPyPz), a biomimetic catalyst of the P450 enzyme. The performance of the sensor for paracetamol detection was investigated and optimized in a flow injection system (FIA) using a wall jet electrochemical cell. Under optimized conditions a wide linear response range (1.0 x 10(-5) to 5.0 x 10(-2) mol L(-1)) was obtained, with a sensitivity of 2579 (+/- 129) mu A L mu mol(-1). The detection and quantification limits of the sensor for paracetamol in the FIA system were 1.0 and 3.5 mu mol L(-1), respectively. The analytical frequency was 51 samples h(-1), and over a period of five days (320 determinations) the biosensor maintained practically the same response. The system was successfully applied to paracetamol quantification in seven pharmaceutical formulations and in water samples from six rivers in Sao Paulo State, Brazil.

Air uptake along the lower nappe of a spillway aerator

Air concentration measurements performed along the lower nappe of a bottom aerator through the impact and downstream flow regions permitted the calculation of air entrainment along the jet length. The air uptake was also measured in the air supply conduit. It was shown that integration of the concentration profiles along the jet overestimates the air uptake measured in the air supply conduit. Corrective procedures were developed by adapting the concept of entrained and entrapped air, in which the latter is re-circulated in the cavity, but both are measured by air concentration probes.

Effect of nitrogen on the corrosion-erosion synergism in an austenitic stainless steel

High temperature gas nitrided AISI 304L austenitic stainless steel containing 0.55 wt% N in solid solution, was corrosion, erosion and corrosion-erosion tested in a jet-like device, using slurry composed of 3.5% NaCl and quartz particles. Scanning electron microscopy analysis of the damaged surfaces, mass loss measurements and electrochemical test results were used to understand the effect of nitrogen on the degradation mechanisms. Increasing the nitrogen content improved the corrosion, erosion and corrosion-erosion resistance of the AISI 304L austenitic stainless steel. Smoother wear mark contours observed on the nitrided surfaces indicate a positive effect of nitrogen on the reduction of the corrosion-erosion synergism. (C) 2011 Elsevier Ltd. All rights reserved.

EROSION-CORROSION SYNERGISM OF AN AISI 410 MARTENSITIC STAINLESS STEEL

In this work, the behavior of an AISI 410 martensitic stainless steel under corrosion-erosion conditions is evaluated. Quenched and tempered samples were used for the wear test, using a low velocity jet-like device connected to a potentiostat. Potentiodynamic polarization curves were obtained with the electrolyte in static state, with flow conditions and under corrosion-erosion, adding quartz particles to the electrolyte. In addition, mass loss measurements under erosion and corrosion-erosion conditions were carried out. The topography of the surfaces was examined after the wear tests, using optical and scanning electron microscopy. This information, together with the results of mass losses and the electrochemical tests were used to establish the degradation mechanisms of the stainless steels under different testing conditions. The results showed that synergism is a significant part of the degradation process of this steel (66.5%) and that the mass removal process of steel was controlled by corrosion assisted by erosion.

Adaptive Carrier Tracking for Mars to Earth Communications During Entry, Descent, and Landing

We propose a robust and low complexity scheme to estimate and track carrier frequency from signals traveling under low signal-to-noise ratio (SNR) conditions in highly nonstationary channels. These scenarios arise in planetary exploration missions subject to high dynamics, such as the Mars exploration rover missions. The method comprises a bank of adaptive linear predictors (ALP) supervised by a convex combiner that dynamically aggregates the individual predictors. The adaptive combination is able to outperform the best individual estimator in the set, which leads to a universal scheme for frequency estimation and tracking. A simple technique for bias compensation considerably improves the ALP performance. It is also shown that retrieval of frequency content by a fast Fourier transform (FFT)-search method, instead of only inspecting the angle of a particular root of the error predictor filter, enhances performance, particularly at very low SNR levels. Simple techniques that enforce frequency continuity improve further the overall performance. In summary we illustrate by extensive simulations that adaptive linear prediction methods render a robust and competitive frequency tracking technique.

Free-Surface Aeration and Momentum Exchange at a Bottom Outlet

This study aims to provide some new understanding of the air-water flow properties in high-velocity water jets discharging past an abrupt drop. Such a setup has been little studied to date despite the relevance to bottom outlets. Downstream of the step brink, the free-jet entrains air at both upper and lower air-water interfaces, as well as along the sides. An air-water shear layer develops at the lower nappe interface. At the lower nappe, the velocity redistribution was successfully modelled and the velocity field was found to be similar to that in two-dimensional wake flow. The results highlighted further two distinct flow regions. Close to the brink (Wex < 5000), the flow was dominated by momentum transfer. Further downstream (Wex > 5000), a strong competition between air bubble diffusion and momentum exchanges took place.

Turbulence in Hydraulic Jumps: Experimental Measurements

A hydraulic jump is the transition from a supercritical open channel flow to a subcritical regime. It is characterised by a highly turbulent flow with macro-scale vortices, some kinetic energy dissipation and a bubbly two-phase flow structure. New air-water flow measurements were performed in hydraulic jump flows for a range of inflow Froude numbers. The experiments were conducted in a large-size facility using two types of phase-detection intrusive probes: i.e., single-tip and double-tip conductivity probes. These were complemented by some measurements of free-surface fluctuations using ultrasonic displacement meters. The present study was focused on the turbulence characteristics of hydraulic jumps with partially-developed inflow conditions. The void fraction measurements showed the presence of an advective diffusion shear layer in which the void fractions profiles matched closely an analytical solution of the advective diffusion equation for air bubbles. The present results highlighted some influence of the inflow Froude number onto the air bubble entrainment process. At the largest Froude numbers, the advected air bubbles were more thoroughly dispersed vertically, and larger amount of air bubbles were detected in the turbulent shear layer. In the air-water mixing layer, the maximum void fraction and bubble count rate data showed some longitudinal decay function in the flow direction. Such trends were previously reported in the literature. The measurements of interfacial velocity and turbulence level distributions provided new information on the turbulent velocity field in the highly-aerated shear region. The present data suggested some longitudinal decay of the turbulence intensity. The velocity profiles tended to follow a wall jet flow pattern. The air–water turbulent time and length scales were deduced from some auto- and cross-correlation analyses based upon the method of CHANSON (2006,2007). The results provided the integral turbulent time and length scales of the eddy structures advecting the air bubbles in the developing shear layer. The experimental data showed that the auto-correlation time scale Txx was larger than the transverse cross-correlation time scale Txz. The integral turbulence length scale Lxz was a function of the inflow conditions, of the streamwise position (x-x1)/d1 and vertical elevation y/d1. Herein the dimensionless integral turbulent length scale Lxz/d1 was closely related to the inflow depth: i.e., Lxz/d1 = 0.2 to 0.8, with Lxz increasing towards the free-surface. The free-surface fluctuations measurements showed large turbulent fluctuations that reflected the dynamic, unsteady structure of the hydraulic jumps. A linear relationship was found between the normalized maximum free-surface fluctuation and the inflow Froude number.