Living Long and Prosperous: Productive Intraligand Charge-Transfer States from a Rhenium(I) Terpyridine Photosensitizer with Enhanced Light Absorption

The ground- and excited-state properties of six rhenium(I) κ2N-tricarbonyl complexes with 4′-(4-substituted-phenyl)terpyridine ligands bearing substituents of different electron-donating abilities were evaluated. Significant modulation of the electrochemical potentials and a nearly 4-fold variation of the triplet metal-to-ligand charge-transfer (3MLCT) lifetimes were observed upon going from CN to OMe. With the more electron-donating NMe2 group, we observed in the κ2N complex the appearance of a very strong absorption band, red-shifted by ca. 100 nm with respect to the other complexes. This was accompanied by a dramatic enhancement of the excited-state lifetime (380 vs 1.5 ns), and a character change from 3MLCT to intraligand charge transfer (3ILCT), despite the remote location of the substituent. The dynamics and character of the excited states of all complexes were assigned by combining transient IR spectroscopy, IR spectroelectrochemistry, and (time-dependent) density functional theory calculations. Selected complexes were evaluated as photosensitizers for hydrogen production, with the κ2N-NMe2 complex resulting in a stable and efficient photocatalytic system reaching TONRe values of over 2100, representing the first application of the 3ILCT state of a rhenium(I) carbonyl complex in a stable photocatalytic system

Constraints on Lorentz Invariance Violation using INTEGRAL/IBIS observations of GRB041219A

One of the experimental tests of Lorentz invariance violation is to measure the helicity dependence of the propagation velocity of photons originating in distant cosmological obejcts. Using a recent determination of the distance of the Gamma-Ray Burst GRB 041219A, for which a high degree of polarization is observed in the prompt emission, we are able to improve by 4 orders of magnitude the existing constraint on Lorentz invariance violation, arising from the phenomenon of vacuum birefringence.Comment: 5 pages, 3 figures, accepted for publication as a Rapid Communication in Physical Review

Kinematics of the Outflow From The Young Star DG Tau B: Rotation in the vicinities of an optical jet

We present $^{12}$CO(2-1) line and 1300 $\mu$m continuum observations made with the Submillimeter Array (SMA) of the young star DG Tau B. We find, in the continuum observations, emission arising from the circumstellar disk surrounding DG Tau B. The $^{12}$CO(2-1) line observations, on the other hand, revealed emission associated with the disk and the asymmetric outflow related with this source. Velocity asymmetries about the flow axis are found over the entire length of the flow. The amplitude of the velocity differences is of the order of 1 -- 2 km s$^{-1}$ over distances of about 300 -- 400 AU. We interpret them as a result of outflow rotation. The sense of the outflow and disk rotation is the same. Infalling gas from a rotating molecular core cannot explain the observed velocity gradient within the flow. Magneto-centrifugal disk winds or photoevaporated disk winds can produce the observed rotational speeds if they are ejected from a keplerian disk at radii of several tens of AU. Nevertheless, these slow winds ejected from large radii are not very massive, and cannot account for the observed linear momentum and angular momentum rates of the molecular flow. Thus, the observed flow is probably entrained material from the parent cloud. DG Tau B is a good laboratory to model in detail the entrainment process and see if it can account for the observed angular momentum.Comment: Accepted to Ap

A general approach for robust integrated polarization rotators

Integrated polarization rotators suffer from very high sensitivity to fabrication errors. A polarization rotator scheme that substantially increases fabrication tolerances is proposed. In the proposed scheme, two tunable polarization phase shifters are used to connect three rotator waveguide sections. By means of properly setting the polarization phase shifters, fabrication errors are compensated and perfect polarization rotation is achieved. Analytical conditions are shown that determine the maximum deviation that can be corrected with the proposed scheme. A design example is discussed, where the thermo-optic effect is used to provide the required tunable polarization phase shifting. Calculated 40dB extinction ratio is shown in presence of fabrication errors that would yield a 4dB extinction ratio in the conventional approach. © (2013) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE). Downloading of the abstract is permitted for personal use only.The authors want to aknowledge Universidad de Málaga alaga, Campus de Excelencia Internacional Andalucia Tech for their support

Nano-Hall sensors with granular Co-C

We analyzed the performance of Hall sensors with different Co-C ratios, deposited directly in nano-structured form, using $Co_2(CO)_8$ gas molecules, by focused electron or ion beam induced deposition. Due to the enhanced inter-grain scattering in these granular wires, the Extraordinary Hall Effect can be increased by two orders of magnitude with respect to pure Co, up to a current sensitivity of $1 \Omega/T$. We show that the best magnetic field resolution at room temperature is obtained for Co ratios between 60% and 70% and is better than $1 \mu T/Hz^{1/2}$. For an active area of the sensor of $200 \times 200 nm^2$, the room temperature magnetic flux resolution is $\phi_{min} = 2\times10^{-5}\phi_0$, in the thermal noise frequency range, i.e. above 100 kHz.Comment: 5 pages, 4 figure

Arsenate Incorporation in Gypsum Probed by Neutron, X-ray Scattering and Density Functional Theory Modeling

International audienceThe ability of gypsum, a common sulfate mineral, to host arsenic atoms in its crystalline structure, is demonstrated through experimental structural studies of the solid solutions formed upon synthetic coprecipitation of gypsum (CaSO4 ·2H2O) and arsenic. Neutron and X-ray diffraction methods show an enlargement of the gypsum unit cell proportional to the concentration of arsenic in the solids and to the pH solution value. The substitution of sulfate ions (SO42-) by arsenate ions is shown to be more likely under alkaline conditions, where the HAsO42- species predominates. A theoretical Density Functional Theory model of the arsenicdoped gypsum structure reproduces the experimental volume expansion. Extended X-ray Absorption Fine Structure (EXAFS) measurements of the local structure around the arsenic atom in the coprecipitated solids confirm solid state substitution and allow some refinement of the local structure, corroborating the theoretical structure found in the simulations. The charge redistribution within the structure upon substitutions of either the protonated or the unprotonated arsenate species studied by means of Mulliken Population Analyses demonstrates an increase in the covalency in the interaction between Ca2+ and AsO4 3-, whereas the interaction between Ca2+ and HAsO4 2- remains predominantly ionic

The dynamics of pattern matching in camouflaging cuttlefish

Many cephalopods escape detection using camouflage. This behaviour relies on a visual assessment of the surroundings, on an interpretation of visual-texture statistics and on matching these statistics using millions of skin chromatophores that are controlled by motoneurons located in the brain. Analysis of cuttlefish images proposed that camouflage patterns are low dimensional and categorizable into three pattern classes, built from a small repertoire of components. Behavioural experiments also indicated that, although camouflage requires vision, its execution does not require feedback, suggesting that motion within skin-pattern space is stereotyped and lacks the possibility of correction. Here, using quantitative methods, we studied camouflage in the cuttlefish Sepia officinalis as behavioural motion towards background matching in skin-pattern space. An analysis of hundreds of thousands of images over natural and artificial backgrounds revealed that the space of skin patterns is high-dimensional and that pattern matching is not stereotyped-each search meanders through skin-pattern space, decelerating and accelerating repeatedly before stabilizing. Chromatophores could be grouped into pattern components on the basis of their covariation during camouflaging. These components varied in shapes and sizes, and overlay one another. However, their identities varied even across transitions between identical skin-pattern pairs, indicating flexibility of implementation and absence of stereotypy. Components could also be differentiated by their sensitivity to spatial frequency. Finally, we compared camouflage to blanching, a skin-lightening reaction to threatening stimuli. Pattern motion during blanching was direct and fast, consistent with open-loop motion in low-dimensional pattern space, in contrast to that observed during camouflage.journal articl

Tracing Hardware Monitors in the GR712RC Multicore Platform: Challenges and Lessons Learnt from a Space Case Study

The demand for increased computing performance is driving industry in critical-embedded systems (CES) domains, e.g. space, towards the use of multicores processors. Multicores, however, pose several challenges that must be addressed before their safe adoption in critical embedded domains. One of the prominent challenges is software timing analysis, a fundamental step in the verification and validation process. Monitoring and profiling solutions, traditionally used for debugging and optimization, are increasingly exploited for software timing in multicores. In particular, hardware event monitors related to requests to shared hardware resources are building block to assess and restraining multicore interference. Modern timing analysis techniques build on event monitors to track and control the contention tasks can generate each other in a multicore platform. In this paper we look into the hardware profiling problem from an industrial perspective and address both methodological and practical problems when monitoring a multicore application. We assess pros and cons of several profiling and tracing solutions, showing that several aspects need to be taken into account while considering the appropriate mechanism to collect and extract the profiling information from a multicore COTS platform. We address the profiling problem on a representative COTS platform for the aerospace domain to find that the availability of directly-accessible hardware counters is not a given, and it may be necessary to the develop specific tools that capture the needs of both the user’s and the timing analysis technique requirements. We report challenges in developing an event monitor tracing tool that works for bare-metal and RTEMS configurations and show the accuracy of the developed tool-set in profiling a real aerospace application. We also show how the profiling tools can be exploited, together with handcrafted benchmarks, to characterize the application behavior in terms of multicore timing interference.This work has been partially supported by a collaboration agreement between Thales Research and the Barcelona Supercomputing Center, and the European Research Council (ERC) under the EU’s Horizon 2020 research and innovation programme (grant agreement No. 772773). MINECO partially supported Jaume Abella under Ramon y Cajal postdoctoral fellowship (RYC2013-14717).Peer ReviewedPostprint (published version