Descripción: We use ring-polymer-molecular-dynamics (RPMD) techniques and the semi-empirical q-TIP4P/F water model to investigate the relationship between hydrogen bond connectivity and the characteristics of nuclear position fluctuations, including explicit incorporation of quantum effects, for the energetically low lying isomers of the prototype cluster [H2O] 8 at T = 50 K and at 150 K. Our results reveal that tunneling and zero-point energy effects lead to sensible increments in the magnitudes of the fluctuations of intra and intermolecular distances. The degree of proton spatial delocalization is found to map logically with the hydrogen-bond connectivity pattern of the cluster. Dangling hydrogen bonds exhibit the largest extent of spatial delocalization and participate in shorter intramolecular O-H bonds. Combined effects from quantum and polarization fluctuations on the resulting individual dipole moments are also examined. From the dynamical side, we analyze the characteristics of the infrared absorption spectrum. The incorporation of nuclear quantum fluctuations promotes red shifts and sensible broadening relative to the classical profile, bringing the simulation results in much more satisfactory agreement with direct experimental information in the mid and high frequency range of the stretching band. While RPMD predictions overestimate the peak position of the low frequency shoulder, the overall agreement with that reported using an accurate, parameterized, many-body potential is reasonable, and far superior to that one obtains by implementing a partially adiabatic centroid molecular dynamics approach. Quantum effects on the collective dynamics, as reported by instantaneous normal modes, are also discussed. © 2013 AIP Publishing LLC.

Descripción: The photophysical behaviour of phloxine B adsorbed onto microcrystalline cellulose was evaluated by reflectance spectroscopy and laser induced time-resolved luminescence in the picosecond-nanosecond and microsecond- millisecond ranges. Analysis of the absorption spectral changes with concentration points to a small tendency of the dye to aggregate in the range of concentrations under study. Prompt fluorescence, phosphorescence and delayed fluorescence spectral decays were measured at room temperature and 77 K, without the need of sample degassing because cellulose protects triplet states from oxygen quenching. In all cases, spectral changes with time and lifetime distribution analysis were consistent with the dye coexisting in two different environments: dyes tightly entrapped between polymer chains in crystalline regions of cellulose showed longer fluorescence and phosphorescence lifetimes and more energetic triplet states, while dyes adsorbed in more amorphous regions of the support showed shorter lifetimes and less energetic triplet states. This behaviour is discussed in terms of the different dye-support interactions in both kinds of adsorption sites.

Descripción: Photoactive materials based on dye molecules incorporated into thin films or bulk solids are useful for applications as photosensitization, photocatalysis, solar cell sensitization and fluorescent labeling, among others. In most cases, high concentrations of dyes are desirable to maximize light absorption. Under these circumstances, the proximity of dye molecules leads to the formation of aggregates and statistical traps, which dissipate the excitation energy and lower the population of excited states. The search for enhancement of light collection, avoiding energy wasting requires accounting the photophysical parameters quantitatively, including the determination of quantum yields, complicated by the presence of light scattering when particulate materials are considered. In this work we summarize recent advances on the photophysics of dyes in light-scattering materials, with particular focus on the effect of dye concentration. We show how experimental reflectance, fluorescence and laser-induced optoacoustic spectroscopy data can be used together with theoretical models for the quantitative evaluation of inner filter effects, fluorescence and triplet formation quantum yields and energy transfer efficiencies. © 2013 The American Society of Photobiology.

Descripción: CO recombination kinetics has been investigated in the type II truncated hemoglobin from Thermobifida fusca (Tf-trHb) over more than 10 time decades (from 1 ps to ~100 ms) by combining femtosecond transient absorption, nanosecond laser flash photolysis and optoacoustic spectroscopy. Photolysis is followed by a rapid geminate recombination with a time constant of ~2 ns representing almost 60% of the overall reaction. An additional, small amplitude geminate recombination was identified at ~100 ns. Finally, CO pressure dependent measurements brought out the presence of two transient species in the second order rebinding phase, with time constants ranging from ~3 to ~100 ms. The available experimental evidence suggests that the two transients are due to the presence of two conformations which do not interconvert within the time frame of the experiment. Computational studies revealed that the plasticity of protein structure is able to define a branched pathway connecting the ligand binding site and the solvent. This allowed to build a kinetic model capable of describing the complete time course of the CO rebinding kinetics to Tf-trHb. © 2012 Marcelli et al.

Descripción: Aims.We investigate the morphology at low radio frequencies of the supernova remnant (SNR) IC 443 in detail and accurately establish its radio continuum spectral properties. Methods. We used the VLA in multiple configurations to produce high-resolution radio images of IC 443 at 74 and 330 MHz. From these data we produced the first sensitive, spatially resolved spectral analysis of the radio emission at long wavelengths. The changes with position in the radio spectral index were correlated with data in near infrared (NIR) from 2MASS, in gamma-rays from VERITAS, and with the molecular 12CO (J = 1-0) line emission. Results. The new image at 74 MHz has HPBW = 35′′ and rms = 30 mJy beam-1 and at 330 MHz HPBW = 17′′and rms = 1.7 mJy beam-1. The integrated flux densities for the whole SNR are S SNR 74MHz = 470 ± 51 Jy and S SNR 330MHz = 248 ± 15 Jy. Improved estimates of the integrated spectrum were derived taking a turnover into account to fit the lowest frequency measurements in the literature. Combining our measurements with existing data, we derive an integrated spectral index α 10700MHz 10MHz =-0.39 ± 0.01 with a free-free continuum optical depth at 330 MHz 330 ∼ 7 × 10 -4 (τ10 = 1.07); all measurements above ∼10 MHz are equally consistent with a power law spectrum. For the pulsar wind nebula associated with the compact source CXOU J061705.3+222127, we calculated S PWN 330MHz = 0.23±0.05 Jy, SPWN 1420MHz = 0.20±0.04 Jy, and α8460MHz 330MHz ∼ 0.0. Substantial variations are observed in spectral index between 74 and 330 MHz across IC 443. The flattest spectral components (-0.25 = a =-0.05) coincide with the brightest parts of the SNR along the eastern border, with an impressive agreement with ionic lines as observed in the 2MASS J and H bands. The diffuse interior of IC 443 has a spectrum steeper than found anywhere in the SNR (-0.85 = a =-0.6), while the southern ridge again has a flatter spectrum (a ∼-0.4). With the available statistics the VERITAS .-ray emission strikingly matches the CO distribution, but no clear evidence is found for a morphological correlation between the TeV distribution and radio emission. Conclusions. The excellent correspondence between the eastern radio flattest spectrum region and NIR ionic lines strongly suggests that the passage of a fast, dissociating J-type shock across the interacting molecular cloud dissociated the molecules and ionized the gas.We therefore conclude that thermal absorption at 74 MHz (τ74 up to ∼0.3) is responsible for the localized spectral index flattening observed along the eastern border of IC 443. Towards the interior of IC 443, the spectrum is consistent with those expected from linear diffusive shock acceleration, while the flatter spectrum in the southern ridge is a consequence of the strong shock/molecular cloud interaction. © 2011 ESO.