Tuning of redox potential and visible absorption band of ruthenium(II) complexes of (benzimidazolyl) derivatives: synthesis, characterization, spectroscopic and redox properties, X-ray structures and DFT calculations

Six ruthenium(II) complexes have been prepared using the tridentate ligands 2,6-bis(benzimidazolyl) pyridine and bis(2-benzimidazolyl methyl) amine and having 2,2'-bipyridine, 2,2':6',2 ''-terpyridine, PPh3, MeCN and chloride as coligands. The crystal structures of three of the complexes trans-[Ru(bbpH(2))(PPh3)(2)(CH3CN)I(ClO4)(2) center dot 2H(2)O (2), [Ru(bbpH(2))(bpy)Cl]ClO4 (3) and [Ru(bbpH(2))(terpy)](ClO4)(2) (4) are also reported. The complexes show visible region absorption at 402-517 nm, indicating that it is possible to tune the visible region absorption by varying the ancillary ligand. Luminescence behavior of the complexes has been studied both at RT and at liquid nitrogen temperature (LNT). Luminescence of the complexes is found to be insensitive to the presence of dioxygen. Two of the complexes [Ru(bbpH(2))(bpy)Cl]ClO4 (3) and [Ru(bbpH(2))(terpy]ClO4)(2) (4) show RT emission in the NIR region, having lifetime, quantum yield and radiative constant values suitable for their application as NIR emitter in the solid state devices. The DFT calculations on these two complexes indicate that the metal t(2g) electrons are appreciably delocalized over the ligand backbone. (C) 2006 Elsevier B.V. All rights reserved.

Perceptual compensation for reverberation in speech identification: effects of single-band, multiple-band and wideband noise contexts

Perceptual effects of room reverberation on a "sir" or "stir" test-word can be observed when the level of reverberation in the word is increased, while the reverberation in a surrounding 'context I utterance remains at a minimal level. The result is that listeners make more "sit" identifications. When the context's reverberation is also increased, to approach the level in the test word, extrinsic perceptual compensation is observed, so that the number of listeners' "sir" identifications reduces to a value similar to that found with minimal reverberation. Thus far, compensation effects have only been observed with speech or speech-like contexts in which the short-term spectrum changes as the speaker's articulators move. The results reported here show that some noise contexts with static short-term spectra can also give rise to compensation. From these experiments it would appear that compensation requires a context with a temporal envelope that fluctuates to some extent, so that parts of it resemble offsets. These findings are consistent with a rather general kind of perceptual compensation mechanism; one that is informed by the 'tails' that reverberation adds at offsets. Other results reported here show that narrow-band contexts do not bring about compensation, even when their temporal-envelopes are the same as those of the more effective wideband contexts. These results suggest that compensation is confined to the frequency range occupied by the context, and that in a wideband sound it might operate in a 'band by band' manner.

Room reflections and constancy in speech-like sounds: within-band effects

The experiment asks whether constancy in hearing precedes or follows grouping. Listeners heard speech-like sounds comprising 8 auditory-filter shaped noise-bands that had temporal envelopes corresponding to those arising in these filters when a speech message is played. The „context‟ words in the message were “next you‟ll get _to click on”, into which a “sir” or “stir” test word was inserted. These test words were from an 11-step continuum that was formed by amplitude modulation. Listeners identified the test words appropriately and quite consistently, even though they had the „robotic‟ quality typical of this type of 8-band speech. The speech-like effects of these sounds appears to be a consequence of auditory grouping. Constancy was assessed by comparing the influence of room reflections on the test word across conditions where the context had either the same level of reflections, or where it had a much lower level. Constancy effects were obtained with these 8-band sounds, but only in „matched‟ conditions, where the room reflections were in the same bands in both the context and the test word. This was not the case in a comparison „mismatched‟ condition, and here, no constancy effects were found. It would appear that this type of constancy in hearing precedes the across-channel grouping whose effects are so apparent in these sounds. This result is discussed in terms of the ubiquity of grouping across different levels of representation.

Perceptual constancy, reverberation, and grouping: within-band effects

Perceptual constancy effects are observed when differing amounts of reverberation are applied to a context sentence and a test‐word embedded in it. Adding reverberation to members of a “sir”‐“stir” test‐word continuum causes temporal‐envelope distortion, which has the effect of eliciting more sir responses from listeners. If the same amount of reverberation is also applied to the context sentence, the number of sir responses decreases again, indicating an “extrinsic” compensation for the effects of reverberation. Such a mechanism would effect perceptual constancy of phonetic perception when temporal envelopes vary in reverberation. This experiment asks whether such effects precede or follow grouping. Eight auditory‐filter shaped noise‐bands were modulated with the temporal envelopes that arise when speech is played through these filters. The resulting “gestalt” percept is the appropriate speech rather than the sound of noise‐bands, presumably due to across‐channel “grouping.” These sounds were played to listeners in “matched” conditions, where reverberation was present in the same bands in both context and test‐word, and in “mismatched” conditions, where the bands in which reverberation was added differed between context and test‐word. Constancy effects were obtained in matched conditions, but not in mismatched conditions, indicating that this type of constancy in hearing precedes across‐channel grouping.

Unusually high differential attenuation at C band: Results from a two-year analysis of the French Trappes polarimetric radar data

The differential phase (ΦDP) measured by polarimetric radars is recognized to be a very good indicator of the path integrated by rain. Moreover, if a linear relationship is assumed between the specific differential phase (KDP) and the specific attenuation (AH) and specific differential attenuation (ADP), then attenuation can easily be corrected. The coefficients of proportionality, γH and γDP, are, however, known to be dependent in rain upon drop temperature, drop shapes, drop size distribution, and the presence of large drops causing Mie scattering. In this paper, the authors extensively apply a physically based method, often referred to as the “Smyth and Illingworth constraint,” which uses the constraint that the value of the differential reflectivity ZDR on the far side of the storm should be low to retrieve the γDP coefficient. More than 30 convective episodes observed by the French operational C-band polarimetric Trappes radar during two summers (2005 and 2006) are used to document the variability of γDP with respect to the intrinsic three-dimensional characteristics of the attenuating cells. The Smyth and Illingworth constraint could be applied to only 20% of all attenuated rays of the 2-yr dataset so it cannot be considered the unique solution for attenuation correction in an operational setting but is useful for characterizing the properties of the strongly attenuating cells. The range of variation of γDP is shown to be extremely large, with minimal, maximal, and mean values being, respectively, equal to 0.01, 0.11, and 0.025 dB °−1. Coefficient γDP appears to be almost linearly correlated with the horizontal reflectivity (ZH), differential reflectivity (ZDR), and specific differential phase (KDP) and correlation coefficient (ρHV) of the attenuating cells. The temperature effect is negligible with respect to that of the microphysical properties of the attenuating cells. Unusually large values of γDP, above 0.06 dB °−1, often referred to as “hot spots,” are reported for 15%—a nonnegligible figure—of the rays presenting a significant total differential phase shift (ΔϕDP > 30°). The corresponding strongly attenuating cells are shown to have extremely high ZDR (above 4 dB) and ZH (above 55 dBZ), very low ρHV (below 0.94), and high KDP (above 4° km−1). Analysis of 4 yr of observed raindrop spectra does not reproduce such low values of ρHV, suggesting that (wet) ice is likely to be present in the precipitation medium and responsible for the attenuation and high phase shifts. Furthermore, if melting ice is responsible for the high phase shifts, this suggests that KDP may not be uniquely related to rainfall rate but can result from the presence of wet ice. This hypothesis is supported by the analysis of the vertical profiles of horizontal reflectivity and the values of conventional probability of hail indexes.

Evaluation of two "integrated" polarimetric Quantitative Precipitation Estimation (QPE) algorithms at C-band

Two so-called “integrated” polarimetric rate estimation techniques, ZPHI (Testud et al., 2000) and ZZDR (Illingworth and Thompson, 2005), are evaluated using 12 episodes of the year 2005 observed by the French C-band operational Trappes radar, located near Paris. The term “integrated” means that the concentration parameter of the drop size distribution is assumed to be constant over some area and the algorithms retrieve it using the polarimetric variables in that area. The evaluation is carried out in ideal conditions (no partial beam blocking, no ground-clutter contamination, no bright band contamination, a posteriori calibration of the radar variables ZH and ZDR) using hourly rain gauges located at distances less than 60 km from the radar. Also included in the comparison, for the sake of benchmarking, is a conventional Z = 282R1.66 estimator, with and without attenuation correction and with and without adjustment by rain gauges as currently done operationally at Météo France. Under those ideal conditions, the two polarimetric algorithms, which rely solely on radar data, appear to perform as well if not better, pending on the measurements conditions (attenuation, rain rates, …), than the conventional algorithms, even when the latter take into account rain gauges through the adjustment scheme. ZZDR with attenuation correction is the best estimator for hourly rain gauge accumulations lower than 5 mm h−1 and ZPHI is the best one above that threshold. A perturbation analysis has been conducted to assess the sensitivity of the various estimators with respect to biases on ZH and ZDR, taking into account the typical accuracy and stability that can be reasonably achieved with modern operational radars these days (1 dB on ZH and 0.2 dB on ZDR). A +1 dB positive bias on ZH (radar too hot) results in a +14% overestimation of the rain rate with the conventional estimator used in this study (Z = 282R^1.66), a -19% underestimation with ZPHI and a +23% overestimation with ZZDR. Additionally, a +0.2 dB positive bias on ZDR results in a typical rain rate under- estimation of 15% by ZZDR.

Building a tropical-extratropical cloud band metbot

An automated cloud band identification procedure is developed that captures the meteorology of such events over southern Africa. This “metbot” is built upon a connected component labelling method that enables blob detection in various atmospheric fields. Outgoing longwave radiation is used to flag candidate cloud band days by thresholding the data and requiring detected blobs to have sufficient latitudinal extent and exhibit positive tilt. The Laplacian operator is used on gridded reanalysis variables to highlight other features of meteorological interest. The ability of this methodology to capture the significant meteorology and rainfall of these synoptic systems is tested in a case study. Usefulness of the metbot in understanding event to event similarities of meteorological features is demonstrated, highlighting features previous studies have noted as key ingredients to cloud band development in the region. Moreover, this allows the presentation of a composite cloud band life cycle for southern Africa events. The potential of metbot to study multiscale interactions is discussed, emphasising its key strength: the ability to retain details of extreme and infrequent events. It automatically builds a database that is ideal for research questions focused on the influence of intraseasonal to interannual variability processes on synoptic events. Application of the method to convergence zone studies and atmospheric river descriptions is suggested. In conclusion, a relation-building metbot can retain details that are often lost with object-based methods but are crucial in case studies. Capturing and summarising these details may be necessary to develop deeper process-level understanding of multiscale interactions.

Radar bright band correction using the linear depolarisation ratio

The enhanced radar return associated with melting snow, ‘the bright band’, can lead to large overestimates of rain rates. Most correction schemes rely on fitting the radar observations to a vertical profile of reflectivity (VPR) which includes the bright band enhancement. Observations show that the VPR is very variable in space and time; large enhancements occur for melting snow, but none for the melting graupel in embedded convection. Applying a bright band VPR correction to a region of embedded convection will lead to a severe underestimate of rainfall. We revive an earlier suggestion that high values of the linear depolarisation ratio (LDR) are an excellent means of detecting when bright band contamination is occurring and that the value of LDR may be used to correct the value of Z in the bright band.

Band gap control via tuning of inversion degree in CdIn2S4 spinel

Based on theoretical arguments we propose a possible route for controlling the band-gap in the promising photovoltaic material CdIn2S4. Our ab initio calculations show that the experimental degree of inversion in this spinel (fraction of tetrahedral sites occupied by In) corresponds approximately to the equilibrium value given by the minimum of the theoretical inversion free energy at a typical synthesis temperature. Modification of this temperature, or of the cooling rate after synthesis, is then expected to change the inversion degree, which in turn sensitively tunes the electronic band-gap of the solid, as shown here by Heyd-Scuseria-Ernzerhof screened hybrid functional calculations.

The potential of 1 h refractivity changes from an operational C-band magnetron-based radar for numerical weather prediction validation and data assimilation

Refractivity changes (ΔN) derived from radar ground clutter returns serve as a proxy for near-surface humidity changes (1 N unit ≡ 1% relative humidity at 20 °C). Previous studies have indicated that better humidity observations should improve forecasts of convection initiation. A preliminary assessment of the potential of refractivity retrievals from an operational magnetron-based C-band radar is presented. The increased phase noise at shorter wavelengths, exacerbated by the unknown position of the target within the 300 m gate, make it difficult to obtain absolute refractivity values, so we consider the information in 1 h changes. These have been derived to a range of 30 km with a spatial resolution of ∼4 km; the consistency of the individual estimates (within each 4 km × 4 km area) indicates that ΔN errors are about 1 N unit, in agreement with in situ observations. Measurements from an instrumented tower on summer days show that the 1 h refractivity changes up to a height of 100 m remain well correlated with near-surface values. The analysis of refractivity as represented in the operational Met Office Unified Model at 1.5, 4 and 12 km grid lengths demonstrates that, as model resolution increases, the spatial scales of the refractivity structures improve. It is shown that the magnitude of refractivity changes is progressively underestimated at larger grid lengths during summer. However, the daily time series of 1 h refractivity changes reveal that, whereas the radar-derived values are very well correlated with the in situ observations, the high-resolution model runs have little skill in getting the right values of ΔN in the right place at the right time. This suggests that the assimilation of these radar refractivity observations could benefit forecasts of the initiation of convection.

Spin polarization, orbital occupation and band gap opening in vanadium dioxide: the effect of screened Hartree–Fock exchange

The metal–insulator transition of VO2 so far has evaded an accurate description by density functional theory. The screened hybrid functional of Heyd, Scuseria and Ernzerhof leads to reasonable solutions for both the low-temperature monoclinic and high-temperature rutile phases only if spin polarization is excluded from the calculations. We explore whether a satisfactory agreement with experiment can be achieved by tuning the fraction of Hartree Fock exchange (a) in the density functional. It is found that two branches of locally stable solutions exist for the rutile phase for 12:5% 6 a 6 20%. One is metallic and has the correct stability as compared to the monoclinic phase, the other is insulating with lower energy than the metallic branch. We discuss these observations based on the V 3d orbital occupations and conclude that a ¼ 10% is the best possible choice for spin-polarized VO2 calculations.

Coupling between gamma-band power and cerebral blood volume during recurrent acute neocortical seizures

Characterization of neural and hemodynamic biomarkers of epileptic activity that can be measured using noninvasive techniques is fundamental to the accurate identification of the epileptogenic zone (EZ) in the clinical setting. Recently, oscillations at gamma-band frequencies and above (N30 Hz) have been suggested to provide valuable localizing information of the EZ and track cortical activation associated with epileptogenic processes. Although a tight coupling between gamma-band activity and hemodynamic-based signals has been consistently demonstrated in non-pathological conditions, very little is known about whether such a relationship is maintained in epilepsy and the laminar etiology of these signals. Confirmation of this relationship may elucidate the underpinnings of perfusion-based signals in epilepsy and the potential value of localizing the EZ using hemodynamic correlates of pathological rhythms. Here, we use concurrent multi-depth electrophysiology and 2- dimensional optical imaging spectroscopy to examine the coupling between multi-band neural activity and cerebral blood volume (CBV) during recurrent acute focal neocortical seizures in the urethane-anesthetized rat. We show a powerful correlation between gamma-band power (25–90 Hz) and CBV across cortical laminae, in particular layer 5, and a close association between gamma measures and multi-unit activity (MUA). Our findings provide insights into the laminar electrophysiological basis of perfusion-based imaging signals in the epileptic state and may have implications for further research using non-invasive multi-modal techniques to localize epileptogenic tissue

Application of two-dimensional wavelet transform in near-shore X-band radar images

Among existing remote sensing applications, land-based X-band radar is an effective technique to monitor the wave fields, and spatial wave information could be obtained from the radar images. Two-dimensional Fourier Transform (2-D FT) is the common algorithm to derive the spectra of radar images. However, the wave field in the nearshore area is highly non-homogeneous due to wave refraction, shoaling, and other coastal mechanisms. When applied in nearshore radar images, 2-D FT would lead to ambiguity of wave characteristics in wave number domain. In this article, we introduce two-dimensional Wavelet Transform (2-D WT) to capture the non-homogeneity of wave fields from nearshore radar images. The results show that wave number spectra by 2-D WT at six parallel space locations in the given image clearly present the shoaling of nearshore waves. Wave number of the peak wave energy is increasing along the inshore direction, and dominant direction of the spectra changes from South South West (SSW) to West South West (WSW). To verify the results of 2-D WT, wave shoaling in radar images is calculated based on dispersion relation. The theoretical calculation results agree with the results of 2-D WT on the whole. The encouraging performance of 2-D WT indicates its strong capability of revealing the non-homogeneity of wave fields in nearshore X-band radar images.