Atomic and ionic radii: a comparison with radii derived from electron density distributions

 The bonded radii of anions obtained in topological analyses of theoretical and experimental electron density distributions differ from atomic, ionic and crystal radii in that oxide-, fluoride-, nitride- and sulfide-anion radii are not constant for a given coordination number. They vary in a regular way with bond length and the electronegativity of the cation to which they are bonded, exhibiting radii close to atomic radii when bonded to a highly electronegative cation and radii close to ionic radii when bonded to a highly electropositive cation. The electron density distributions show that anions are not spherical but exhibit several different radii in different bonded directions. The bonded radii of cations correlate with ionic and atomic radii. But unlike ionic radii, the bonded radius of a cation shows a relatively small increase in value with an increase in coordination number. In contrast to atomic and ionic radii, the bonded radius of an ion in a crystal or molecule can be used as a reliable and well-defined estimate of its radius in the direction of its bonds. Received April 16, 1996 / Revised, accepted August 6, 1996     

The effect of tributyltin upon steroid titres in the female dogwhelk, Nucella lapillus, and the development of imposex

Exposure of female Nucella lapillus to tributyltin (TBT) in seawater at a concentration of 40 ng Sn/litre led to accumulation of TBT in the tissues, and an increase in penis length compared to control animals. Investigation of the steroid concentrations by radioimmunoassay revealed a significant increase in testosterone after 28 days exposure to TBT. No significant effect was noted upon the amounts of progesterone or estradiol-17β. When testosterone was injected into female N. lapillus in the absence of TBT, penis length was found to increase significantly. These observation suggest that there may be an association between the change in testosterone titre in response to exposure to TBT and the development of imposex in the dogwhelk.     

A CNDO/2 molecular orbital study of the silica polymorphs quartz,cristobalite, and coesite

CNDO/2 MO calculations on H₁₂Si₅O₁₆ clusters modeling silicate tetrahedral linkage in the silica polymorphs show total energy minima at bent SiOSi angles and a correlation between the Si-O bond lengths, d(Si-O), used in the calculation and the minimum energy value of the SiOSi angle. Calculations on hydrogen saturated Si₅O₁₆ clusters isolated from the structures of low quartz, low cristobalite and coesite which were adjusted by DLS methods so that all d(Si-O) equal 1.61 Å and all _L OSiO equal 109.47° yield Mulliken bond overlap populations, n(Si-O), and Si-O two-center energies, E(Si-O), which correlate with observed bond lengths; shorter bonds involve larger n(Si-O) values and more negative E(Si-O) values.

     

Volcanic ash soils in New Zealand

Ash and lapilli derived from Holocene and Late Pleistocene volcanic cruptions cover approximately half of the North Island of New Zealand. Deposits from 16 separate series of showers are recognised in the surface soils and areas with 3 inches and more of each ash bed have been mapped out during soil surveys. These and other shower deposits are also recognised and described in fossil soils. The effects of the volcanic ashes on soil properties are related to the thickness and frequency of deposition, to mineral composition, and to the period of exposure to soil formation. Soils formed from shower deposits of Holocene age are extensive and have characteristic properties of friability, fine granular structure, deep humic topsoils and slippery non-sticky clays. The clays are chiefly amorphous and responsible for the notable practical properties of free drainage, high moisture retention, low bulk density, and critical limits of stability under pressure. In New Zealand the development of these characteristies increases with time up to about 15,000 years and then decreases with the crystallisation of the clays to halloysite. Soils formed from Late Pleistocene volcanic ashes are high in halloysite clay and with increasing age resemble soils formed from marine sedimentary rocks. Differing degrees of development of the characteristics are shown in the soil classification. The soils from volcanic ash are widely used for crop, pasture or forestry production. More intensive permanent usage depends on more detailed knowledge of the materials which will be obtained through combined volcanological and pedological research.     

A molecular orbital study of bond length and angle variations in framework structures

Molecular orbital calculations on a variety of silicate and aluminosilicate molecules have been used to explore the bonding forces that govern tetrahedral bond length variations, r(TO), in framework silicates and aluminosilicates. Not only do the calculations provide insight into the variety of structural types and the substitution limits of one tetrahedral atom for another, but they also provide an understanding of the interrelationships among r(TO) and linkage factors, bond strength sum, coordination number, and angles within and between tetrahedra. A study of these interrelationships for a theoretical data set shows that r(SiO) and r(AlO) are linearly correlated with (1) p _o, the bond strength sum to a bridging oxygen, (2) f _s(O), the fractional s-character of a bridging oxygen, and (3) f _s (T), the fractional s-character of the T atom. In a multiple linear regression analysis of the data, 92% of the variation of r(SiO) and 99% of the variation of r(AlO) can be explained in terms of a linear dependence on p _o, f _s (O), and f _s (T). Analogous regression analyses completed for observed r(Al, SiO) bond length data from a number of silica polymorphs and ordered aluminosilicates account for more than 75% of the bond length variation. The lower percentage of bond length variation explained is ascribed in part to the random and systematic errors in the experimental data which have a negligible effect on the theoretical data. The modeling of more than 75% of the variation of r(Al, SiO) in the framework silicates using the same model used for silicate and aluminosilicate molecules strengthens the viewpoint that the bonding forces that govern the shapes of such molecules are quite similar to the forces that govern the shapes of chemically similar groups in solids. The different regression coefficients calculated for f _s (T) indicate that SiO and AlO bond length variations in framework structures should not be treated as a single population in estimating the average Al, Si content of a tetrahedral site.     

Earthquake early warning scenarios at critical facilities in the Eastern Caribbean

A feasibility study of an earthquake early warning (EEW) system was conducted for the Eastern Caribbean region using scenario earthquakes, corresponding to the maximum credible earthquakes and to the earthquakes associated with a return period of 475 years. Broadband synthetic seismograms were produced at selected critical facilities, where there is potential interest in the installation of an EEW system. The expected damage was derived from the synthetic seismograms and compared with the lead-time determined for both a regional and on-site EEW configuration. Next, the Virtual Seismologist EEW algorithm, as included in SeisComP3, was tested. Additional broadband synthetic seismograms were produced for the stations in the Eastern Caribbean seismic networks in order to simulate the real time behaviour of the seismic networks during the occurrence of the synthetic earthquakes and to assess the predictive capacity of the selected ground motion prediction equation. Expected peak ground parameters and lead-times at the critical facilities constitute the major outcome of the study.     

Observing programmes for the Carlsberg Automatic Meridian Circle

At the Carlsberg Automatic Meridian Circle on La Palma an observing programme of 72500 stars is in progress. The observing conditions are discussed and a status report is presented as well as some plans for future programmes. A special effort is made for stars between vis. mag. 11 _m ^. 0 and 12 _m ^. 0 in a general net as well as in radio source fields. Some of these sources will be observed with the Danish 1.5m telescope on La Silla. Also discussed are fundamental programmes and large astrophysical programmes.     

Analysis of a numerical solution to the one-dimensional stochastic convection equation

Under certain conditions the concentration and flux of a substance moving in a stochastic flow field are described by the stochastic convection equation. A numerical method for solving the one-dimensional problem is studied here. The differential operator is replaced by a discrete linear operator based on finite differences. The resulting system of stochastic equations is then replaced by a system of equations whose solution is the mean concentration or mean flux. This final system is analysed and conditions for a stable numerical solution are obtained. Finally, numerical examples are given and are compared to an approximate analytical solution to the stochastic convection equation.     

A mapping of the electron localization function for earth materials

The electron localization function, ELF, generated for a number of geometry-optimized earth materials, provides a graphical representation of the spatial localization of the probability electron density distribution as embodied in domains ascribed to localized bond and lone pair electrons. The lone pair domains, displayed by the silica polymorphs quartz, coesite and cristobalite, are typically banana-shaped and oriented perpendicular to the plane of the SiOSi angle at ~0.60 Å from the O atom on the reflex side of the angle. With decreasing angle, the domains increase in magnitude, indicating an increase in the nucleophilic character of the O atom, rendering it more susceptible to potential electrophilic attack. The Laplacian isosurface maps of the experimental and theoretical electron density distribution for coesite substantiates the increase in the size of the domain with decreasing angle. Bond pair domains are displayed along each of the SiO bond vectors as discrete concave hemispherically-shaped domains at ~0.70 Å from the O atom. For more closed-shell ionic bonded interactions, the bond and lone pair domains are often coalesced, resulting in concave hemispherical toroidal-shaped domains with local maxima centered along the bond vectors. As the shared covalent character of the bonded interactions increases, the bond and lone pair domains are better developed as discrete domains. ELF isosurface maps generated for the earth materials tremolite, diopside, talc and dickite display banana-shaped lone pair domains associated with the bridging O atoms of SiOSi angles and concave hemispherical toroidal bond pair domains associated with the nonbridging ones. The lone pair domains in dickite and talc provide a basis for understanding the bonded interactions between the adjacent neutral layers. Maps were also generated for beryl, cordierite, quartz, low albite, forsterite, wadeite, åkermanite, pectolite, periclase, hurlbutite, thortveitite and vanthoffite. Strategies are reviewed for finding potential H docking sites in the silica polymorphs and related materials. As observed in an earlier study, the ELF is capable of generating bond and lone pair domains that are similar in number and arrangement to those provided by Laplacian and deformation electron density distributions. The formation of the bond and lone pair domains in the silica polymorphs and the progressive decrease in the SiO length as the value of the electron density at the bond critical point increases indicates that the SiO bonded interaction has a substantial component of covalent character.     

Effects of Temporal Discretization on Turbulence Statistics and Spectra in Numerically Simulated Convective Boundary Layers

Six state-of-the-art large-eddy simulation codes were compared in Fedorovich et al. (Preprints, 16th American Meteorological Society Symposium on Boundary Layers and Turbulence, 2004b) for three airflow configurations in order to better understand the effect of wind shear on entrainment dynamics in the convective boundary layer CBL). One such code was the University of Oklahoma large-eddy simulation (LES) code, which at the time employed a second-order leapfrog time-advancement scheme with the Asselin filter. In subsequent years, the code has been updated to use a third-order Runge–Kutta (RK3) time-advancement scheme. This study investigates what effect the upgrade from the leapfrog scheme to RK3 scheme has on turbulence statistics in the CBL differently affected by mean wind shear, also in relation to predictions by other LES codes that participated in the considered comparison exercise. In addition, the effect of changing the Courant number within the RK3 scheme is investigated by invoking the turbulence spectral analysis. Results indicate that low-order flow statistics obtained with the RK3 scheme generally match their counterparts from simulations with the leapfrog scheme rather closely. CBL growth rates due to entrainment in the shear-free case were also similar using both timestepping schemes. It was found, however, that care should be given to the choice of the Courant number value when running LES with the RK3 scheme in the sheared CBL setting. The advantages of the largest possible (based on the stability criterion) Courant number were negated by degrading the energy distribution across the turbulence spectrum. While mean profiles and low-order turbulence statistics were largely unaffected, the entrainment rate was over-predicted compared to that reported in the original code-comparison study.