The tetrahedral framework in glasses and melts — inferences from molecular orbital calculations and implications for structure,thermodynamics, and physical properties

Results of ab initio molecular orbital (MO) calculations provide a basis for the interpretation of structural and thermodynamic properties of crystals, glasses, and melts containing tetrahedrally coordinated Si, Al, and B. Calculated and experimental tetrahedral atom-oxygen (TO) bond lengths are in good agreement and the observed average SiO and AlO bond lengths remain relatively constant in crystalline, glassy, and molten materials. The TOT framework geometry, which determines the major structural features, is governed largely by the local constraints of the strong TO bonds and its major features are modeled well by ab initio calculations on small clusters. Observed bond lengths for non-framework cations are not always in agreement with calculated values, and reasons for this are discussed in the text. The flexibility of SiOSi, SiOAl, and AlOAl angles is in accord with easy glass formation in silicates and aluminosilicates. The stronger constraints on tetrahedral BOB and BOSi angles, as evidenced by much deeper and steeper calculated potential energy versus angle curves, suggest much greater difficulty in substituting tetrahedral B than Al for Si. This is supported by the pattern of immiscibility in borosilicate glasses, although the occurrence of boron in trigonal coordination is an added complication. The limitations on glass formation in oxysulfide and oxynitride systems may be related to the angular requirements of SiSSi and Si(NH)Si groups. Although the SiO and AlO bonds are the strongest ones in silicates and aluminosilicates, they are perturbed by other cations. Increasing perturbation and weakening of the framework occurs with increasing ability of the other atom to compete with Si or Al for bonding to oxygen, that is, with increasing cation field strength. The perturbation of TOT groups, as evidenced by TO bond lengthening predicted by MO calculations and observed in ordered crystalline aluminosilicates, increases in the series Ca, Mg and K, Na, Li. This perturbation correlates strongly with thermochemical mixing properties of glasses in the systems SiO₂-M ₁ ^n/n+ AlO₂ and SiO₂-M ⁿ⁺O _n/2 (M=Li, Na, K, Rb, Cs, and Mg, Ca, Sr, Ba, Pb), with tendencies toward immiscibility in these systems, and with systematics in vibrational spectra. Trends in physical properties, including viscosity at atmospheric and high pressure, can also be correlated.     

Applications of quantum mechanical potential surfaces to mineral physics calculations

Ab-Initio quantum mechanical calculations on molecular clusters are used to obtain potential surfaces for the SiO bond in silicates. These potential surfaces form the basis for extracting the key parameters in various commonly employed potential functions. Applications to the usual ionic model demonstates a close relation between the ab-initio derived ionic potential and those empirically dervied. The ionic model is then used to predict structures and elastic properties of orthosilicates and of the silica polymorphs. The deficiencies in the ionic model lead to the application of the quantum results to covalent models. These latter models are then used in theoretical calculations of the properties of silica polymorphs.     

A method for calculating fractional s-character for bonds of tetrahedral oxyanions in crystals

A method for calculating fractional s-character, f _s , for TO bonds has been devised to apply to TO₄ tetrahedral oxyanions in crystals. These f _s -values rank bond lengths with the better correlations obtained for T atoms associated with larger bond strengths and larger electronegativities. As a simple formula, it is found that 2cot²〈?〉₃ does a good job of estimating f _s where 〈?〉₃ is the triple angle average of the three angles common to a given bond.     

Critical point properties of electron density distributions for oxide molecules containing first and second row cations

 Minimum energy geometries and electron density distributions, ϱ(r), for ∼40 polyatomic oxide molecules containing first and second row M-cations have been calculated at the Hartree-Fock level with a 6-311++G** basis set. The nature of the bonded interactions in these molecules is examined in terms of the relative electronegativities, χ _M , of the M-cations and the properties of the electron density distribution, ϱ(r _c ), evaluated at the bond critical points, r _c , along each MO bond. As ϱ(r _c ) and the Laplacian of ϱ(r _c ) increase, χ _M increases indicating an increase in the covalent character of the bonded interactions between M and O. The ratios of the curvatures of ϱ(r _c ) indicate that the NO bond is predominantly covalent, that the CO and SO bonds are of intermediate type and that the remaining MO bonds are indicated to be predominantly ionic in character. A comparison of the critical point properties of ϱ(r _c ) and χ _M indicates that the minimum energy MO bond length is an important determinate of the properties of ϱ(r _c ) and the character of the MO bonds. On the other hand, values of the local energy density, H(r _c ), indicate that the LiO, BeO, NaO, MgO and AlO bonds are predominantly ionic and that the BO, CO, NO, SiO, PO and SO bonds are predominantly covalent in character. The χ _M -values provided by the properties of ϱ(r _c ) indicate that the covalent component of a bond increases with decreasing bond length, coordination number and increasing bond strength. Each MO bond seems to represent a unique entity and to possess a distinct set of ϱ(r _c ) properties, the distinction being greater for the more electronegative cations. The bonded radius of the oxide ion, r _b (O), and the χ _M -values determined from ϱ(r _c ) correlate with values determined from promolecule electron density distributions. In addition, r _b (O) and χ _M -values determined from experimental electron density distributions for crystals correlate with values determined from procrystal electron density distributions. The number of critical points and bond paths are modeled rather faithfully by procrystal and promolecule electron density distributions, despite the neglect of the binding forces in their constructions. Received: October 15, 1996/Revised, accepted: February 10, 1997     

A study of the bonded interactions in nitride molecules in terms of bond critical point properties and relative electronegativities

Bond critical point properties calculated for the MN bonds in a number of geometry optimized nitride molecules containing first- and second-row M cations are compared with those calculated for a number of oxide molecules. As reported for the oxides, the value of the electron density, ρ(r _c ), at the bond critical points, r _c , increases with decreasing bond length while for the more electronegative cations, the local energy density, H(r _c ) decreases nonlinearly in value as the relative electronegativities of the M-cations, χ _M , tend to increase. In the majority of cases, χ_M, |λ₁|/λ₃ and ∇²ρ(r _c ) increase with decreasing minimum energy bond lengths. The bond lengths adopted by the molecules are indicated to be an important determinant of the critical point properties of the electron density distributions. The relative electronegativities derived from the electron density distributions of the nitrides agree with those derived for the oxides and Pauling’s electronegativities to within ∼5%, on average. Received: 3 February 1997 / Revised, accepted: 11 July 1997     

Accumulation of muds and metals in the Hudson River estuary turbidity maximum

 In the Hudson River estuary, fine mud and toxic metals are enriched in the upstream turbidity maximum. The mechanisms causing the enrichment were assessed through the analysis of suspended-sediment concentration (SSC) (bottom and surface), particle size, and trace metal distributions. Bottom SSCs varied across the study area by a factor of ten, and the turbidity maximum activity was observed in between kilometers 45 and 80. The particle-size analysis defined two accumulation modes: <4.65 and >22.1 μm. The ratio of the fine-to-coarse mode increased from 1.75 to 2.75 in the turbidity maximum. The fine mud concentration (55–60%) in the turbidity maximum was found to have a high correlation (r=0.98;p<0.005) with the concentration of <2-μm particles. A conceptual model was derived in order to understand the possible mechanisms by which fine mud (and specifically <2-μm particles) is concentrated. The two dominant size modes were analyzed for toxic metals. The upstream tributaries are major sources of metals compared to point sources at downstream locations. In the turbidity maximum, Cd, Cu, Zn, and Pb are significantly enriched compared to average shale metal values and ERM toxicity guidelines by 580, 42, 10, 16 and 12, 7, 2.4, 1.4 times, respectively. Decreasing metal concentrations downstream of the turbidity maximum imply that Haverstraw Bay acts as temporary storage for fine particles and enriched metals. It is demonstrated in this study that toxic metals are enriched in Haverstraw Bay due to the mud accumulation. The high levels of toxic metals in the sediments of the Hudson River estuary are a major concern because human activities (dredging and river traffic) cause resuspension of sediments and can change the mobility patterns of bioavailable contaminants. Received: 4 June 1997 · Accepted: 9 September 1997     

Wind forced circulation and sediment disturbance in a temperate lake

Meteorological forcing on the surface of a lake can generate mixing and transport processes that alter water quality. This study examined how meteorological forcing affected water currents in Lake Rotorua—a large, shallow, temperate, polymictic lake—during a period of sustained vertical mixing and strong winds. Acoustic Doppler current profiler (ADCP) measurements were recorded at two sites and a hydrodynamic model (ELCOM) was used to simulate water movement over the period of ADCP measurements. Model simulations show circulation patterns in Lake Rotorua are strongly influenced by the topography of the lake and, to a lesser extent, the catchment, with little variation in currents with depth during winter mixing. Northeasterly winds produced a clockwise circulation around the mid-lake island with a second anticlockwise gyre between the island and the western shore. This circulation pattern is consistent with topographic gyres found in other large lakes. A shift to a weaker southwesterly wind caused these circulation patterns to reverse direction over a period of c. 6?h, with a weak secondary gyre also occurring within the main anticlockwise circulation. The effect of this circulation pattern on the resuspension of sediment and thus potential in-lake phosphorus control strategies is considered.     

Effects of tributyltin (TBT) exposure on the reproduction and embryonic development of the bivalve Scrobicularia plana

Field and laboratory work was carried out during the summers of 1990 and 1991 on bivalves Scrobicularia plana from sites moderately-affected and relatively-unaffected by tributyltin (TBT) contamination (i.e. a mean concentration in clam tissues of 0.4 and 0.02 μg Sn g⁻¹ dry wt, respectively). Standard cultures after artificial fertilizations with broodstock of either site did not result in dissimilar survival of embryos nor in larvae of different quality at the time of hatching. Static 48 h toxicity tests on S. plana embryos showed that an EC₅₀ of less than the nominal 250 ng Sn litre⁻¹ (a range of 178–198 ng Sn litre⁻¹, as analysed) can be set for TBT independently of the origin of broodstock. The results are discussed in relation to the reported disappearance of S. plana throughout northern Europe and the simultaneous presence of toxic levels of butyltin. It is concluded that TBT has probably reduced the recruitment into some UK clam populations by preventing the successful development of a significant proportion of their embryos.     

Potential protonation sites in the Al<Subscript>2</Subscript>SiO<Subscript>5</Subscript> polymorphs based on polarized FTIR spectroscopy and properties of the electron density distribution

Potential protonation sites for, kyanite, sillimanite, and andalusite, located in a mapping of the (3, −3) critical points displayed by their L(r) = −∇²ρ(r) distributions, are compared with polarized single-crystal FTIR spectra of kyanite and sillimanite determined earlier and with andalusite measured in this study. For andalusite, seven peaks were observed when the electric vector, E, is parallel to [100]: four intense ones at 3,440, 3,460, 3,526, and 3,597 cm⁻¹ and three weaker ones at 3,480, 3,520, and 3,653 cm⁻¹. Six peaks, three intense ones at 3,440, 3,460, and 3,526 cm⁻¹ and three weaker ones at 3,480, 3,520, and 3,653 cm⁻¹ when E parallels [010]. No peaks were observed when E is parallel to [001]. The concentration of water in andalusite varies between 110 and 168 ppm by weight % H₂O. Polarized FTIR spectra indicate that the OH vector is parallel to (001) in andalusite and sillimanite and in kyanite. Examination of the L(r) (3, −3) critical points in comparison with the polarized FTIR indicates that H prefers to bond to the oxygen atoms O1 and O2 in andalusite and O2 and O4 in sillimanite which correspond to the underbonded oxygen atoms and those with the largest L(r) maxima. In kyanite, comparison of the FTIR spectrum and the critical points indicates that H will preferentially bond to the two 4-coordinated O2 and O6 atoms.