Synthesis of [Cu-2(Me-2[9]aneN(2)S)(2)(OH)(2)] (PF6)(2), a hydroxo-bridged copper(II) complex of N,N '-dimethyl-1-thia-4,7-diazacyclononane (Me-2[9]aneN(2)S). X-ray structural analysis, magnetic susceptibility, EPR and visible spectroscopy

The bis(mu-hydroxo) complex [Cu-2(Me-2[9]aneN(2)S)(2)(OH)(2)](PF6)(2) (Me-2[9]aneN(2)S = N,N'-dimethyl-1-thia-4,7-diazacyclononane) results after reaction of [Cu(Me-2[9]aneN(2)S)(MeCN)] (PF6) with dioxygen at -78 degrees C in acetonitrile. The complex has been characterized by X-ray crystallography: orthorhombic, space group Pnma, with a 18.710(3), b 16.758(2), c 9.593(2) Angstrom, and Z = 4. The structure refined to a final R value of 0.051. The complex contains two copper(II) ions bridged by two hydroxo groups with Cu ... Cu 2.866(1) Angstrom. The solid-state magnetic susceptibility study reveals ferromagnetic coupling, the fitting parameters being J = +46+/-5 cm(-1), g = 2.01+/-0.01 and theta = -0.58+/-0.03 K. The frozen-solution e.p.r. spectrum in dimethyl sulfoxide is characteristic of a monomeric copper(II) ion (g(parallel to) 2.300, g(perpendicular to) 2.063; A(parallel to) 156.2 x 10(-4) cm(-1), A(perpendicular to) 9.0 x 10(-4) cm(-1)) with an N2O2 donor set. Thioether coordination to the copper(II) in solution is supported by the presence of an intense absorption assigned to a sigma(S)-->Cu-II LMCT transition at c. 34000 cm(-1). The single-crystal spectrum of [Cu-2(Me-2[9]aneN(2)S)(2)(OH)(2)] (PF6)(2) (273 K) reveals d-->d transitions at 14500 and 18300 cm(-1) and a weak pi(S)-->Cu-II charge-transfer band at approximately 25000 cm(-1).

Visible and near-infrared luminescent Eu(3+) or Er(3+) doped laponite-derived xerogels and thick films: Structural and spectroscopic properties

Laponite-derived materials represent promising materials for optical applications. In this work, Eu(3+)- or Er(3+)-doped laponite xerogels and films were prepared from colloidal dispersion. Homogeneous, crack-free and transparent single layers were deposited on soda-lime substrates with a thickness of 10 mu m. Structural and spectroscopic properties were analyzed by thermal analyses, X-ray diffractometry, transmission electron microscopy, infrared spectroscopy, and luminescence spectroscopy. The addition of a rare earth ion to the laponite does not promote any changes in thermal stability or phase transition. Laponite clay was identified after annealing up to 500 degrees C, with a decrease in basal spacing when the annealing temperature is changed from 100 degrees C to 500 degrees C. Enstatite polymorphs and amorphous silicate phases were observed after heat treatment at 700 degrees C and 900 degrees C. Stationary and time-dependent luminescence spectra in the visible region for Eu(3+), and (5)D(0) lifetime are discussed in terms of thermal treatment and structural evolution. In the layered host, the Eu(3+) ions are distributed in many different local environments. However, Eu(3+) ions were found to occupy at least two symmetry sites, and the ions are preferentially incorporated into the crystalline enstatite for the materials annealed at 700 degrees C and 900 degrees C. A (5)D(0) lifetime of 1.3 ms and 3.1 ms was obtained for Eu(3+) ions in an amorphous silicate and crystalline MgSiO(3) local environment, respectively. Strong Er(3+) emission at the 1550 nm region was observed for the materials annealed at 900 degrees C, with a bandwidth of 44 nm. (C) 2008 Elsevier B.V. All rights reserved.

Visible range plasmonic effect produced by aluminium nanoparticles embedded in amorphous silicon

We present results, obtained by means of an analytic study and a numerical simulation, about the resonant condition necessary to produce a Localized Surface Plasmonic Resonance (LSPR) effect at the surface of metal nanospheres embedded in an amorphous silicon matrix. The study is based on a Lorentz dispersive model for a-Si:H permittivity and a Drude model for the metals. Considering the absorption spectra of a-Si:H, the best choice for the metal nanoparticles appears to be aluminium, indium or magnesium. No difference has been observed when considering a-SiC:H. Finite-difference time-domain (FDTD) simulation of an Al nanosphere embedded into an amorphous silicon matrix shows an increased scattering radius and the presence of LSPR induced by the metal/semiconductor interaction under green light (560 nm) illumination. Further results include the effect of the nanoparticles shape (nano-ellipsoids) in controlling the wavelength suitable to produce LSPR. It has been shown that is possible to produce LSPR in the red part of the visible spectrum (the most critical for a-Si:H solar cells applications in terms of light absorption enhancement) with aluminium nano-ellipsoids. As an additional results we may conclude that the double Lorentz-Lorenz model for the optical functions of a-Si:H is numerically stable in 3D simulations and can be used safely in the FDTD algorithm. A further simulation study is directed to determine an optimal spatial distribution of Al nanoparticles, with variable shapes, capable to enhance light absorption in the red part of the visible spectrum, exploiting light trapping and plasmonic effects. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optical-geometrical effects on the photoluminescence spectra of Si nanocrystals embedded in SiO2

We demonstrate that thickness, optical constants, and details of the multilayer stack, together with the detection setting, strongly influence the photoluminescence spectra of Si nanocrystals embedded in SiO2. Due to multiple reflections of the visible light against the opaque silicon substrate, an interference pattern is built inside the oxide layer, which is responsible for the modifications in the measured spectra. This interference effect is complicated by the depth dependence of (i) the intensity of the excitation laser and (ii) the concentration of the emitting nanocrystals. These variations can give rise to apparent features in the recorded spectra, such as peak shifts, satellite shoulders, and even splittings, which can be mistaken as intrinsic material features. Thus, they can give rise to an erroneous attribution of optical bands or estimate of the average particle size, while they are only optical-geometrical artifacts. We have analyzed these effects as a function of material composition (Si excess fraction) and thickness, and also evaluated how the geometry of the detection setup affects the measurements. To correct the experimental photoluminescence spectra and extract the true spectral shape of the emission from Si nanocrystals, we have developed an algorithm based on a modulation function, which depends on both the multilayer sequence and the experimental configuration. This procedure can be easily extended to other heterogeneous systems.

Comparing the artificial neural network with parcial least squares for prediction of soil organic carbon and pH at different moisture content levels using visible and near-infrared spectroscopy

Visible and near infrared (vis-NIR) spectroscopy is widely used to detect soil properties. The objective of this study is to evaluate the combined effect of moisture content (MC) and the modeling algorithm on prediction of soil organic carbon (SOC) and pH. Partial least squares (PLS) and the Artificial neural network (ANN) for modeling of SOC and pH at different MC levels were compared in terms of efficiency in prediction of regression. A total of 270 soil samples were used. Before spectral measurement, dry soil samples were weighed to determine the amount of water to be added by weight to achieve the specified gravimetric MC levels of 5, 10, 15, 20, and 25 %. A fiber-optic vis-NIR spectrophotometer (350-2500 nm) was used to measure spectra of soil samples in the diffuse reflectance mode. Spectra preprocessing and PLS regression were carried using Unscrambler® software. Statistica® software was used for ANN modeling. The best prediction result for SOC was obtained using the ANN (RMSEP = 0.82 % and RPD = 4.23) for soil samples with 25 % MC. The best prediction results for pH were obtained with PLS for dry soil samples (RMSEP = 0.65 % and RPD = 1.68) and soil samples with 10 % MC (RMSEP = 0.61 % and RPD = 1.71). Whereas the ANN showed better performance for SOC prediction at all MC levels, PLS showed better predictive accuracy of pH at all MC levels except for 25 % MC. Therefore, based on the data set used in the current study, the ANN is recommended for the analyses of SOC at all MC levels, whereas PLS is recommended for the analysis of pH at MC levels below 20 %.

Variation des biomarqueurs dans le spectre visible non résolu de la Terre

L’évolution rapide des technologies de détection et de caractérisation des exoplanètes depuis le début des années 1990 permet de croire que de nouveaux instruments du type Terrestrial Planet Finder (TPF) pourront prendre les premiers spectres d’exoplanètes semblables à la Terre d’ici une ou deux décennies. Dans ce contexte, l’étude du spectre de la seule planète habitée connue, la Terre, est essentielle pour concevoir ces instruments et analyser leurs résultats. Cette recherche présente les spectres de la Terre dans le visible (390-900 nm), acquis lors de 8 nuits d’observation étalées sur plus d’un an. Ces spectres ont été obtenus en observant la lumière cendrée de la Lune avec le télescope de 1.6 m de l’Observatoire du Mont-Mégantic (OMM). La surface de la Lune réfléchissant de manière diffuse la lumière provenant d’une portion de la Terre, ces spectres sont non résolus spatialement. L’évolution de ces spectres en fonction de la lumière réfléchie à différentes phases de Terre est analogue à celle du spectre d’une exoplanète, dont la phase change selon sa position autour de l’étoile. L'eau, l'oxygène et l'ozone de l’atmosphère, détectés dans tous nos spectres, sont des biomarqueurs dont la présence suggère l’habitabilité de la planète et/ou la présence d’une activité biologique. Le Vegetation Red Edge (VRE), une autre biosignature spectrale, dû aux organismes photosynthétiques à la surface, est caractérisé par l’augmentation de la réflectivité autour de 700 nm. Pour les spectres de 5 nuits, cette augmentation a été évaluée entre -5 et 15% ±~5%, après que les contributions de la diffusion de Rayleigh, des aérosols et d’une large bande moléculaire de l’ozone aient été enlevées. Les valeurs mesurées sont cohérentes avec la présence de végétation dans la phase de la Terre contribuant au spectre, mais s’étendent sur une plage de variations plus large que celles trouvées dans la littérature (0-10%). Cela pourrait s’expliquer par des choix faits lors de la réduction des données et du calcul du VRE, ou encore par la présence d’autres éléments de surface ou de l’atmosphère dont la contribution spectrale autour de 700 nm serait variable.

Interchannel interactions and relaxation in the 2p auger spectra of Mg-like ions

Relativistic Auger rates for the 2p spectra of Mg-like ions have been calculated in the atomic range 13 < Z < 36. We used the multiconfiguration Dirac-Fock method but beyond a simple frozen-orbital approach we include also relaxation for the bound electrons and the interchannel interaction between the continuum states. Both effects may alter the individual transition rates remarkably. This is analysed for a few selected states within the isoelectronic sequence. Weak transitions within the 2p spectra can be changed by an order of magnitude because of the continuum coupling. The influence of both effects for higher-Z ions is reduced but still remain visible.

Vibrational overtone spectra of monofluoroacetylene: a preliminary report

High-resolution infrared and near-infrared spectra have been observed for more than 80 overtone bands of the HCCF molecule, including two CH stretching overtones in the visible region. Many of these have been analysed, and many more are in the course of analysis and will be reported later. All fundamentals have now been rotationally analysed and the equilibrium rotational constant determined. These data provide a testing ground for anharmonic force-field analyses, and they are discussed briefly in this connection.

Visible-near infrared spectroscopy sensor for predicting curd and whey composition during cheese processing

The potential of visible-near infrared spectra, obtained using a light backscatter sensor, in conjunction with chemometrics, to predict curd moisture and whey fat content in a cheese vat was examined. A three-factor (renneting temperature, calcium chloride, cutting time), central composite design was carried out in triplicate. Spectra (300–1,100 nm) of the product in the cheese vat were captured during syneresis using a prototype light backscatter sensor. Stirring followed upon cutting the gel, and samples of curd and whey were removed at 10 min intervals and analyzed for curd moisture and whey fat content. Spectral data were used to develop models for predicting curd moisture and whey fat contents using partial least squares regression. Subjecting the spectral data set to Jack-knifing improved the accuracy of the models. The whey fat models (R = 0.91, 0.95) and curd moisture model (R = 0.86, 0.89) provided good and approximate predictions, respectively. Visible-near infrared spectroscopy was found to have potential for the prediction of important syneresis indices in stirred cheese vats.

The global distribution of phytoplankton size spectrum and size classes from their light-absorption spectra derived from satellite data

The absorption spectra of phytoplankton in the visible domain hold implicit information on the phytoplankton community structure. Here we use this information to retrieve quantitative information on phytoplankton size structure by developing a novel method to compute the exponent of an assumed power-law for their particle-size spectrum. This quantity, in combination with total chlorophyll-a concentration, can be used to estimate the fractional concentration of chlorophyll in any arbitrarily-defined size class of phytoplankton. We further define and derive expressions for two distinct measures of cell size of mixed populations, namely, the average spherical diameter of a bio-optically equivalent homogeneous population of cells of equal size, and the average equivalent spherical diameter of a population of cells that follow a power-law particle-size distribution. The method relies on measurements of two quantities of a phytoplankton sample: the concentration of chlorophyll-a, which is an operational index of phytoplankton biomass, and the total absorption coefficient of phytoplankton in the red peak of visible spectrum at 676 nm. A sensitivity analysis confirms that the relative errors in the estimates of the exponent of particle size spectra are reasonably low. The exponents of phytoplankton size spectra, estimated for a large set of in situ data from a variety of oceanic environments (~ 2400 samples), are within a reasonable range; and the estimated fractions of chlorophyll in pico-, nano- and micro-phytoplankton are generally consistent with those obtained by an independent, indirect method based on diagnostic pigments determined using high-performance liquid chromatography. The estimates of cell size for in situ samples dominated by different phytoplankton types (diatoms, prymnesiophytes, Prochlorococcus, other cyanobacteria and green algae) yield nominal sizes consistent with the taxonomic classification. To estimate the same quantities from satellite-derived ocean-colour data, we combine our method with algorithms for obtaining inherent optical properties from remote sensing. The spatial distribution of the size-spectrum exponent and the chlorophyll fractions of pico-, nano- and micro-phytoplankton estimated from satellite remote sensing are in agreement with the current understanding of the biogeography of phytoplankton functional types in the global oceans. This study contributes to our understanding of the distribution and time evolution of phytoplankton size structure in the global oceans.

Remote Spectroscopy in the Visible Using Fibers on the Optical Internet Network

The work presented here demonstrates the feasibility of using the single-mode fibers of an optical Internet network to deliver visible light between separate laboratories as a way to perform remote spectroscopy in the visible for teaching purposes. The coupling of a broadband light source into the single-mode fiber (SMF) and the characterization of optical losses as a function of the wavelength are discussed. Sample spectra were measured with a portable spectrometer controlled by an acquisition program developed with the LabVIEW software that allows the data to be collected and analyzed.

Visible and near-infrared luminescent Eu3+ or Er3+ doped laponite-derived xerogels and thick films: Structural and spectroscopic properties

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Visible emission from Er-doped SnO2 thin films deposited by sol-gel

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Visible PL phenomenon at room temperature in disordered structure of SrWO4 powder

The SrWO4 (SWO) powders were synthesized by the polymeric precursor method and annealed at different temperatures. The SWO structure was obtained by X-ray diffraction and the corresponding photoluminescence (PL) spectra was measured. The PL results reveal that the structural order-disorder degree in the SWO lattice influences in the PL emission intensity. Only the structurally order-disordered samples present broad and intense PL band in the visible range. To understand the origin of this phenomenon, we performed quantum-mechanical calculations with crystalline and order-disordered SWO periodic models. Their electronic structures were analyzed in terms of band structure. The appearance of localized levels in the band gap of the order-disordered structure was evidenced and is a favorable condition for the intense PL to occur.

Conditions giving rise to intense visible room temperature photoluminescence in SrWO4 thin films: the role of disorder

The nature of intense visible photoluminescence at room temperature of SrWO4 (SWO) non-crystalline thin films is discussed in the light of experimental results and theoretical calculations. The SWO thin films were synthesized by the polymeric precursors method. Their structural properties have been obtained by X-ray diffraction data and the corresponding photoluminescence (PL) spectra have been measured. The UV-vis optical spectra measurements suggest the creation of localized states in the disordered structure. The photoluminescence measurements reveal that the PL changes with the degree of disorder in the SWO thin film. To understand the origin of visible PL at room temperature in disordered SWO, we performed quantum-mechanical calculations on crystalline and disordered SWO periodic models. Their electronic structures are analyzed in terms of DOS, hand dispersion and charge densities. We used DFT method with the hybrid non-local B3LYP approximation. The polarization induced by the symmetry break and the existence of localized levels favors the creation of trapped holes and electrons, giving origin to the room temperature photoluminescence phenomenon in the SWO thin films. (c) 2004 Elsevier B.V. All rights reserved.