Modeling the Quality of Videos Displayed With Local Dimming Backlight at Different Peak White and Ambient Light Levels.

This paper investigates the impact of ambient light and peak white (maximum brightness of a display) on the perceived quality of videos displayed using local backlight dimming. Two subjective tests providing quality evaluations are presented and analyzed. The analyses of variance show significant interactions of the factors peak white and ambient light with the perceived quality. Therefore, we proceed to predict the subjective quality grades with objective measures. The rendering of the frames on liquid crystal displays with light emitting diodes backlight at various ambient light and peak white levels is computed using a model of the display. Widely used objective quality metrics are applied based on the rendering models of the videos to predict the subjective evaluations. As these predictions are not satisfying, three machine learning methods are applied: partial least square regression, elastic net, and support vector regression. The elastic net method obtains the best prediction accuracy with a spearman rank order correlation coefficient of 0.71, and two features are identified as having a major influence on the visual quality.

How Accurately Can Extended X-ray Absorption Spectra Be Predicted from First Principles? Implications for Modeling the Oxygen-Evolving Complex in Photosystem II.

First principle calculations of extended X-ray absorption fine structure (EXAFS) data have seen widespread use in bioinorganic chemistry, perhaps most notably for modeling the Mn4Ca site in the oxygen evolving complex (OEC) of photosystem II (PSII). The logic implied by the calculations rests on the assumption that it is possible to a priori predict an accurate EXAFS spectrum provided that the underlying geometric structure is correct. The present study investigates the extent to which this is possible using state of the art EXAFS theory. The FEFF program is used to evaluate the ability of a multiple scattering-based approach to directly calculate the EXAFS spectrum of crystallographically defined model complexes. The results of these parameter free predictions are compared with the more traditional approach of fitting FEFF calculated spectra to experimental data. A series of seven crystallographically characterized Mn monomers and dimers is used as a test set. The largest deviations between the FEFF calculated EXAFS spectra and the experimental EXAFS spectra arise from the amplitudes. The amplitude errors result from a combination of errors in calculated S0(2) and Debye-Waller values as well as uncertainties in background subtraction. Additional errors may be attributed to structural parameters, particularly in cases where reliable high-resolution crystal structures are not available. Based on these investigations, the strengths and weaknesses of using first-principle EXAFS calculations as a predictive tool are discussed. We demonstrate that a range of DFT optimized structures of the OEC may all be considered consistent with experimental EXAFS data and that caution must be exercised when using EXAFS data to obtain topological arrangements of complex clusters.

Modeling the subjective quality of highly contrasted videos displayed on LCD with local backlight dimming.

Local backlight dimming is a technology aiming at both saving energy and improving visual quality on television sets. As the rendition of the image is specified locally, the numerical signal corresponding to the displayed image needs to be computed through a model of the display. This simulated signal can then be used as input to objective quality metrics. The focus of this paper is on determining which characteristics of locally backlit displays influence quality assessment. A subjective experiment assessing the quality of highly contrasted videos displayed with various local backlight-dimming algorithms is set up. Subjective results are then compared with both objective measures and objective quality metrics using different display models. The first analysis indicates that the most significant objective features are temporal variations, power consumption (probably representing leakage), and a contrast measure. The second analysis shows that modeling of leakage is necessary for objective quality assessment of sequences displayed with local backlight dimming.

Study of liquid-liquid interfaces by an easily implemented localized NMR sequence.

To selectively extract heavy metals from solutions containing fission products, it is essential to optimize the liquid-liquid extraction processes. Such an objective requires improving the fundamental knowledge of the different mechanisms that are involved in these processes. In that respect, we propose a localized NMR sequence named LOCSY to assess the concentration profiles of different species involved in these processes. One of the goals of this sequence is to study the products as close as possible to the liquid-liquid interface with the help of a standard NMR spectrometer of chemistry labs. The one-dimensional spatial localization along the NMR tube is obtained by a discrete stepping of the frequency-selective excitation pulses under a pulsed field gradient. Specific data processing has been developed to obtain the 1D NMR spectra as a function of the vertical position in the NMR tube. The LOCSY sequence has been tested and evaluated on three different systems: (i) a cylindrical phantom inserted in the NMR tube containing 4-methylsalicylic acid solution, (ii) D(2)O/olive oil biphasic system, and (iii) the dissolution of solid saccharose in D(2)O. These examples illustrate potential applications of the LOCSY sequence, particularly the possibility to measure concentration profiles and to study phenomena such as diffusion, provided the dynamic range is compatible with NMR timescale and sensitivity.

Combined NMR and DFT studies for the absolute configuration elucidation of the spore photoproduct, a UV-induced DNA lesion.

By irradiation of bacterial spores under UV radiation, a photoproduct (SP) bearing a covalent methylene link between two adjacent thymines is formed in DNA. Because of the presence of an asymmetric carbon on the aglycone and of two possible orientations for the formation of the cross-link, four isomers could in principle be obtained. Currently, no conclusive structural information of this photoproduct is available. The structure of the isolated SPTpT dinucleotide was revisited in order to determine the type of cross-link and the absolute configuration of the C5a carbon. For this purpose, a study combining NMR spectroscopy and DFT calculations was pursued on the spore photoproduct of the dinucleoside TpT since its structure was previously shown to be identical to the one produced in DNA. A full characterization of SPTpT by NMR analyses was performed in D2O and DMSO. 2D NMR measurements (1H-13C, 1H-31P, COSY, NOESY, and ROESY) and DFT calculations (geometries optimization of R and S isomers and theoretical chemical shifts) lead us to conclude without ambiguity that the absolute configuration of the C5a carbon is R and that the methylene bridge of the photoproduct corresponds to the methyl group of the thymine located on the 3'-end of the dinucleoside monophosphate.

High-spin chloro mononuclear MnIII complexes: a multifrequency high-field EPR study.

The isolation, structural characterization, and electronic properties of two six-coordinated chloromanganese (III) complexes, [Mn(terpy)(Cl)3] (1) and [Mn(Phterpy)(Cl)3] (2), are reported (terpy = 2,2':6'2"-terpyridine, Phterpy = 4'-phenyl-2,2':6',2"-terpyridine). These complexes complement a series of mononuclear azide and fluoride Mn(lll) complexes synthesized with neutral N-tridentate ligands, [Mn(L)(X)3] (X = F- or N3 and L = terpy or bpea [N,N-bis(2-pyridylmethyl)-ethylamine)], previously described. Similar to these previous complexes, 1 and 2 exhibit a Jahn-Teller distortion of the octahedron, characteristic of a high-spin Mn(III) complex (S = 2). The analysis of the crystallographic data shows that, in both cases, the manganese ion lies in the center of a distorted octahedron characterized by an elongation along the tetragonal axis. Their electronic properties were investigated by multifrequency EPR (190-475 GHz) performed in the solid state at different temperatures (5-15 K). This study confirms our previous results and further shows that: i) the sign of D is correlated with the nature of the tetragonal distortion; ii) the magnitude of D is not sensitive to the nature of the anions in our series of rhombic complexes, contrary to the porphyrinic systems; iii) the [E/D] values (0.124 for 1 and 0.085 for 2) are smaller compared to those found for the [Mn(L)(X)3] complexes (in the range of 0.146 to 0.234); and iv) the E term increases when the ligand-field strength of the equatorial ligands decreases.

Structural characterization and electronic properties determination by high-field and high-frequency EPR of a series of five-coordinated Mn(II) complexes.

The isolation, structural characterization, and electronic properties of a series of high-spin mononuclear five-coordinated Mn(II) complexes, [Mn(terpy)(X)(2)] (terpy = 2, 2':6',2' '-terpyridine; X = I(-) (1), Br(-) (2), Cl(-) (3), or SCN(-) (4)), are reported. The X-ray structures of the complexes reveal that the manganese ion lies in the center of a distorted trigonal bipyramid for complexes 1, 2, and 4, while complex 3 is better described as a distorted square pyramid. The electronic properties of 1-4 were investigated by high-field and high-frequency EPR spectroscopy (HF-EPR) performed between 5 and 30 K. The powder HF-EPR spectra have been recorded in high-field-limit conditions (95-285 GHz) (D << gbetaB). The spectra are thus simplified, allowing an easy interpretation of the experimental data and an accurate determination of the spin Hamiltonian parameters. The magnitude of D varies between 0.26 and 1.00 cm(-)(1) with the nature of the anionic ligand. Thanks to low-temperature EPR experiments, the sign of D was unambiguously determined. D is positive for the iodo and bromo complexes and negative for the chloro and thiocyano ones. A structural correlation is proposed. Each complex is characterized by a significant rhombicity with E/D values between 0.17 and 0.29, reflecting the distorted geometry observed around the manganese. Finally, we compared the spin Hamiltonian parameters of our five-coordinated complexes and those previously reported for other analogous series of dihalo four- and six-coordinated complexes. The effect of the coordination number and of the geometry of the Mn(II) complexes on the spin Hamiltonian parameters is discussed.

A high-frequency and high-field EPR study of new azide and fluoride mononuclear Mn(III) complexes.

The isolation, structural characterization and electronic properties of three new six-coordinated Mn(III) complexes, [Mn(bpea)(F)(3)] (1), [Mn(bpea)(N(3))(3)] (2), and [Mn(terpy)(F)(3)] (3) are reported (bpea = N,N-bis(2-pyridylmethyl)-ethylamine; terpy = 2,2':6',2' '-terpyridine). As for [Mn(terpy)(N(3))(3)] (4) (previously described by Limburg J.; Vrettos J. S.; Crabtree R. H.; Brudvig G. W.; de Paula J. C.; Hassan A.; Barra A-L.; Duboc-Toia C.; Collomb M-N. Inorg. Chem. 2001, 40, 1698), all these complexes exhibit a Jahn-Teller distortion of the octahedron characteristic of high-spin Mn(III) (S = 2). The analysis of the crystallographic data shows an elongation along the tetragonal axis of the octahedron for complexes 1 and 3, while complex 2 presents an unexpected compression. The electronic properties were investigated using a high-field and high-frequency EPR study performed between 5 and 15 K (190-575 GHz). The spin Hamiltonian parameters determined in solid state are in agreement with the geometry of the complexes observed in the crystal structures. A negative D value found for 1 and 3 is related to the elongated tetragonal distortion, whereas the positive D value determined for 2 is in accordance with a compressed octahedron. The high E/D values, in the range of 0.103 to 0.230 for all complexes, are correlated with the highly distorted geometry present around the Mn(III) ion. HF-EPR experiments were also performed on complex 1 in solution and show that the D value is the only spin Hamiltonian parameter which is slightly modified compared to the solid state (D = -3.67 cm(-1) in solid state; D = -3.95 cm(-1) in solution).