Coherent view of crystal chemistry and ab initio analyses of Pb(II) and Bi(III) Lone Pair in square planar coordination

The stereochemistry of 6s2 (E) lone pair of divalent Pb and trivalent Bi (PbII and BiIII designated by M*) in structurally related PbO, PbFX (X= Cl, Br, I), BiOX (X= F, Cl, Br, I) and Bi2NbO5F is rationalized. The lone pair LP presence determined by its sphere of influence E, equal to those of oxygen or fluorine anions, was settled by its center then giving M*-E directions and distances. Detailed description of structural features of both elements in the title compounds characterized by [PbEO]n and [BiEO]n layers allowed to show the evolution of M*-E distance versus the changes with the square pyramidal SP coordination polyhedra. All are different, in red PbO one finds {PbEO4E4} square antiprism, a {[Bi.E]O4X4Xapical} monocapped square antiprism in PbFX and BiOX and {BiEO4F4}square antiprism in Bi2NbO5F. To analyze the crystal chemistry results, the electronic structures of these compounds were calculated within density functional theory DFT. Real space analyses of electron localization illustrate a full volume development of the lone pair on PbII within {PbEO4E4} in PbOE, {PbEF4X4} in PbFXE and Bi(III) within {BiEO4X4} square antiprisms, contrary to Bi(III) within {[Bi.E]O4F4Fapical} monocapped square antiprism. Larger hardness (larger bulk modules B0) and band gap characterize BiOF versus PbO due to the presence of F which brings antibonding Bi-F interactions oppositely to mainly bonding Bi-O. In PbFX and BiOX series there is a systematic decrease of B0 with the increasing volume following the nature and size of X which is decreasingly electronegative and increasingly large. The electronic densities of states mirror these effects through the relative energy position and relative electronegativities of F/X and O/X leading to decrease the band gap.Comment: 20 text pages/ 10 multifigures/large review article, J. Progress Solid State Chemistry, under production MAY 201

Crystal structure of LaTiO_3.41 under pressure

The crystal structure of the layered, perovskite-related LaTiO_3.41 (La_5Ti_5O_{17+\delta}) has been studied by synchrotron powder x-ray diffraction under hydrostatic pressure up to 27 GPa (T = 295 K). The ambient-pressure phase was found to remain stable up to 18 GPa. A sluggish, but reversible phase transition occurs in the range 18--24 GPa. The structural changes of the low-pressure phase are characterized by a pronounced anisotropy in the axis compressibilities, which are at a ratio of approximately 1:2:3 for the a, b, and c axes. Possible effects of pressure on the electronic properties of LaTiO_3.41 are discussed.Comment: 5 pages, 6 figure

National flood modelling for insurance purposes: using IFSAR for flood risk estimation in Europe

International audienceFlood risk poses a major problem for insurers and governments who ultimately pay the financial costs of losses resulting from flood events. Insurers therefore face the problem of how to assess their exposure to floods and how best to price the flood element of their insurance products. This paper looks at the insurance implications of recent flood events in Europe and the issues surrounding insurance of potential future events. In particular, the paper will focus on the flood risk information needs of insurers and how these can be met. The data requirements of national and regional flood models are addressed in the context of the accuracy of available data on property location. Terrain information is generally the weakest component of sophisticated flood models. Therefore, various sources of digital terrain models (DTM) are examined and discussed with consideration of the vertical and horizontal accuracy, the speed of acquisition, the costs and the comprehensiveness of the data. The NEXTMap DTM series from Intermap Technologies Inc. is proposed as a suitable DTM for flood risk identification and mapping, following its use in the UK. Its acquisition, processing and application is described and future plans discussed. Examples are included of the application of flood information to insurance property information and the potential benefits and advantages of using suitable hazard modelling data sources are detailed

NaV_2O_5 as a quarter-filled ladder compound

A new X-ray diffraction study of the one-dimensional spin-Peierls compound \alpha-NaV_2O_5 reveals a centrosymmetric (Pmmn) crystal structure with one type of V site, contrary to the previously postulated non-centrosymmetric P2_1mn structure with two types of V sites (V^{+4} and V^{+5}). Density functional calculations indicate that NaV_2O_5 is a quarter-filled ladder compound with the spins carried by V-O-V molecular orbitals on the rungs of the ladder. Estimates of the charge-transfer gap and the exchange coupling agree well with experiment and explain the insulating behavior of NaV_2O_5 and its magnetic properties.Comment: Final version for PRL, value of U correcte

Advanced Photodetectors for Hyperspectroscopy and Other Applications

Hyperspectroscopy is a new method of surface image taking, providing simultaneously high position and spectral resolutions which allow one to make some conclusions about chemical compositions of the surfaces. We are now studying applications of the hyperspctroscopic technique to be used for medicine. This may allow one to develop early diagnostics of some illnesses, as for example, skin cancer. For image taking advanced MCPs are currently used, sensitive in the spectral interval of 450-850 nm. One of the aims of this work is to extend the hyperspectrocpic method to the UV region of spectra: 185-280 nm. For this we have developed and successfully tested innovative 1D and 2D UV sealed photosensitive gaseous detectors with resistive electrodes. These detectors are superior MCPs due to the very low rate of noise pulses and thus due to the high signal to noise ratio. Other important features of these detectors are that they have excellent position resolutions - 30 micron in digital form, are vibration stable and are spark protected. The first results from the application of these detectors for spectroscopy, hyperspectroscopy and the flame detection are presented.Comment: Presented at the IEEE Nuclear Science Syposium, Puerto Rico, October 200

Dry deposition of nitrogen compounds (NO 2 , HNO 3 , NH 3 ), sulfur dioxide and ozone in west and central African ecosystems using the inferential method

Abstract. This work is part of the IDAF program (IGAC-DEBITS-AFRICA) and is based on the long-term monitoring of gas concentrations (1998–2007) established at seven remote sites representative of major African ecosystems. Dry deposition fluxes were estimated by the inferential method using on the one hand surface measurements of gas concentrations (NO2, HNO3, NH3, SO2 and O3) and on the other hand modeled exchange rates. Dry deposition velocities (Vd) were calculated using the big-leaf model of Zhang et al. (2003b). The bidirectional approach is used for NH3 surface–atmosphere exchange (Zhang et al., 2010). Surface and meteorological conditions specific to IDAF sites have been used in the models of deposition. The seasonal and annual mean variations of gaseous dry deposition fluxes (NO2, HNO3, NH3, O3 and SO2) are analyzed. Along the latitudinal transect of ecosystems, the annual mean dry deposition fluxes of nitrogen compounds range from −0.4 to −0.8 kg N ha−1 yr−1 for NO2, from −0.7 to −1.0 kg N ha−1 yr−1 for HNO3 and from −0.7 to −8.3 kg N ha−1 yr−1 for NH3 over the study period (1998–2007). The total nitrogen dry deposition flux (NO2+HNO3+NH3) is more important in forests (−10 kg N ha−1 yr−1) than in wet and dry savannas (−1.6 to −3.9 kg N ha−1 yr−1). The annual mean dry deposition fluxes of ozone range between −11 and −19 kg ha−1 yr−1 in dry and wet savannas, and −11 and −13 kg ha−1 yr−1 in forests. Lowest O3 dry deposition fluxes in forests are correlated to low measured O3 concentrations, lower by a factor of 2–3, compared to other ecosystems. Along the ecosystem transect, the annual mean of SO2 dry deposition fluxes presents low values and a small variability (−0.5 to −1 kg S ha−1 yr−1). No specific trend in the interannual variability of these gaseous dry deposition fluxes is observed over the study period

Magneto-Dielectric Effect in the S = 1/2 Quasi-Two Dimensional Antiferromagnet K2V3O8

We report the optical and magneto-optical properties of K2V3O8, an S=1/2 quasi-two-dimensional Heisenberg antiferromagnet. Local spin density approximation electronic structure calculations are used to assign the observed excitations and analyze the field dependent features. Two large magneto-optical effects, centered at ~1.19 and 2.5 eV, are attributed to field-induced changes in the V 4+ d to d on-site excitations due to modification of the local crystal field environment of the VO5 square pyramids with applied magnetic field. Taken together, the evidence for a soft lattice, the presence of vibrational fine structure on the sharp 1.19 eV magneto-optical feature,and the fact that these optical excitations are due to transitions from a nearly pure spin polarized V d state to hybridized states involving both V and O, suggest that the magneto-dielectric effect in K2V3O8 is driven by strong lattice coupling.Comment: Zipped file containing 8 pages, 12 figures, in press PR