Pauling bond strength, bond length and electron density distribution

The power law regression equation, <R(M–O)> = 1.46(<ρ(r _c)>/r)^?0.19, relating the average experimental bond lengths, <R(M–O)>, to the average accumulation of the electron density at the bond critical point, <ρ(r _c)>, between bonded pairs of metal and oxygen atoms (r is the row number of the M atom), determined at ambient conditions for oxide crystals, is similar to the regression equation R(M–O) = 1.41(ρ(r _c)/r)^?0.21 determined for three perovskite crystals at pressures as high as 80 GPa. The pair are also comparable with the equation <R(M–O)> = 1.43(<s>/r)^?0.21 determined for oxide crystals at ambient conditions and <R(M–O)> = 1.39(<s>/r)^?0.22 determined for geometry-optimized hydroxyacid molecules that relate the geometry-optimized bond lengths to the average Pauling bond strength, <s>, for the M–O bonded interactions. On the basis of the correspondence between the equations relating <ρ(r _c)> and <s> with bond length, it seems plausible that the Pauling bond strength might serve a rough estimate of the accumulation of the electron density between M–O bonded pairs of atoms. Similar expressions, relating bond length and bond strength hold for fluoride, nitride and sulfide molecules and crystals. The similarity of the expressions for the crystals and molecules is compelling evidence that molecular and crystalline M–O bonded interactions are intrinsically related. The value of <ρ(r _c)> = r[(1.41)/<R(M–O)>]^4.76 determined for the average bond length for a given coordination polyhedron closely matches the Pauling’s electrostatic bond strength reaching each the coordinating anions of the coordinated polyhedron. Despite the relative simplicity of the expression, it appears to be more general in its application in that it holds for the bulk of the M–O bonded pairs of atoms of the periodic table.     

Advances in the state of the art for AUV inertial sensors andnavigation systems

This paper presents an overview of two new inertial systems that are now in production at the Guidance and Control Systems Division of Litton Systems, Inc. These units are small, lightweight, require little power, and are silent. Data are presented that show long-term performance as well as short-term attitude, position, and velocity reference data for the LN-100 system. Attitude, velocity, and body axis rate data are required for stabilization of such devices as laser line scanners and long baseline side-scan sonars. The relationship between the characteristics of these sensors and inertial type errors is explored. This analysis shows that it is not sufficient to specify the inertial system only in terms of its navigation CEP. The specification of the inertial unit must also be based on the needs of the sensor payload and include such considerations as short-term stability, the noise content, phase, and bandwidth of the stabilization reference     

The galactic infrared/submillimeter dust radiation

Summary The unprecedented quality of the IRAS data prompted a series of papers reinvestigating the origin of the galactic infrared/submillimeter radiation and the nature of the heating sources of the interstellar dust. The scope of this paper is to review the main results of these new studies. Sect. 1 contains a general introduction to the subject and an overview of the earlier work. In Sect. 2 and 3, we summarize our current knowledge on dust properties and on the interstellar radiation field. Then, we present the recent interpretations of the infrared emission of our Galaxy, which are based on the IRAS data: in Sect. 4 we present the results from the galactic disk; Sect. 5 covers the question of the contribution from small dust particles, and in Sect. 6 we describe the infrared radiation from the galactic center. The nature of the heating sources and the origin of the galactic infrared radiation is then discussed in Sect. 7. Finally, Sect. 8 presents a comparison of our Galaxy with external galaxies     

Water quality condition and trend in North Queensland waterways

The Queensland Environmental Protection Agency monitored water quality at 133 sites in North Queensland waterways between Cooktown and Bundaburg from 1992 to 2001. Condition of the waterways was rated by comparing recent data with the Queensland Water Quality Guidelines. Long-term trends were analysed using a censored regression technique that incorporates the effects of flow, temperature, seasonality and allows for long-term non-linear trends. Many sites were in good condition; those in poor condition were usually impacted by point source discharges; those in moderate condition were usually impacted by agricultural land use. There were no consistent long-term trends across the whole region. Recommendations for future programs include incorporating pressure indicators, ensuring high standards of quality assurance, including covariates such as rainfall in trend assessment and continuing programs over more than 10 years to allow detection of trends due to changes in land-use.     

ON THE THEORY OF HITCH-HIKING AS A SPATIAL STOCHASTIC PROCESS

Hitch-hiking has been ignored by traditional geography. In this article it is shown that ideas and techniques from the new geography yield substantial insights into its character as a spatial process.     

Bistability of the thermohaline circulation identified through comprehensive 2-parameter sweeps of an efficient climate model

The effect of changes in zonal and meridional atmospheric moisture transports on Atlantic overturning is investigated. Zonal transports are considered in terms of net moisture export from the Atlantic sector. Meridional transports are related to the vigour of the global hydrological cycle. The equilibrium thermohaline circulation (THC) simulated with an efficient climate model is strongly dependent on two key parameters that control these transports: an anomaly in the specified Atlantic–Pacific moisture flux (F_a) and atmospheric moisture diffusivity (K_q). In a large ensemble of spinup experiments, the values of F_a and K_q are varied by small increments across wide ranges, to identify sharp transitions of equilibrium THC strength in a 2-parameter space (between Conveyor On and Off states). Final states from this ensemble of simulations are then used as the initial states for further such ensembles. Large differences in THC strength between ensembles, for identical combinations of F_a and K_q, reveal the co-existence of two stable THC states (Conveyor On and Off)—i.e. a bistable regime. In further sensitivity experiments, the model is forced with small, temporary freshwater perturbations to the mid-latitude North Atlantic, to establish the minimum perturbation necessary for irreversible THC collapse in this bistable regime. A threshold is identified in terms of the forcing duration required. The model THC, in a Conveyor On state, irreversibly collapses to a Conveyor Off state under additional freshwater forcing of just 0.1 Sv applied for around 100 years. The irreversible collapse is primarily due to a positive feedback associated with suppressed convection and reduced surface heat loss in the sinking region. Increased atmosphere-to-ocean freshwater flux, under a collapsed Conveyor, plays a secondary role.     

A modeling of the structure and favorable H-docking sites and defects for the high-pressure silica polymorph stishovite

Employing first-principles methods, the docking sites for H were determined and H, Al, and vacancy defects were modeled with an infinite periodic array of super unit cells each consisting of 27 contiguous symmetry nonequivalent unit cells of the crystal structure of stishovite. A geometry optimization of the super-cell structure reproduces the observed bulk structure within the experimental error when P1 translational symmetry was assumed and an array of infinite extent was generated. A mapping of the valence electrons for the structure displays mushroom-shaped isosurfaces on the O atom, one on each side of the plane of the OSi₃ triangle in the nonbonded region. An H atom, placed in a cell near the center of the super cell, was found to dock upon geometry optimization at a distance of 1.69 Å from the O atom with the OH vector oriented nearly perpendicular to the plane of the triangle such that the OH vector makes a angle of 91° with respect to [001]. However, an optimization of a super cell with an Al atom replacing Si and an H atom placed nearby in a centrally located cell resulted in an OH distance of 1.02 Å with the OH vector oriented perpendicular to [001] as observed in infrared studies. The geometry-optimized position of the H atom was found to be in close agreement with that (0.44, 0.12, 0.0) determined in an earlier study of the theoretical electron density distribution. The docking of the H atom at this site was found to be 330 kJ mol^–1 more stable than a docking of the atom just off the shared OO edge of the octahedra as determined for rutile. A geometry optimization of a super cell with a missing Si generated a vacant octahedra that is 20% larger than that of the SiO₆ octahedra. The valence electron density distribution displayed by the two-coordinate O atoms that coordinate the vacant octahedral site is very similar to those displayed by the bent SiOSi angles in coesite. The internal distortions induced by the defect were found to diminish rather rapidly with distance, with the structure annealing to that observed in the bulk crystal to within about three coordination spheres.     

Ouachita, Appalachian, and Ancestral Rockies deformations recorded in mesoscale structures on the foreland Ozark plateaus

Mesoscale structures in Paleozoic rocks of the Ozark plateaus reveal four Pennsylvanian deformation episodes in midcontinent North America. The two earliest episodes can be assigned to progressive northwestward docking of the Ouachita terrane with North America. Early extensional structures (Event 1) indicate a northwest/southeast maximum horizontal stress (Hmax) during Early Pennsylvanian Ouachita terrane advance. Event 2 extensional and strike-slip structures indicate Hmax across the Ozark plateaus that varies systematically from north-northwest/south-southeast in the south to northeast/southwest in the north. This suggests development of a slip-line deformation field in response to minor northeastward lateral escape of lithospheric blocks away from the northwestward-moving Ouachita terrane's leading edge, which acted as an indenter in western Arkansas, southeastern Oklahoma, and Texas. Younger contractional and strike-slip structures of Event 3 indicate northeast/southwest Hmax across the entire Ozark plateaus, and deformation orientation and intensity are not readily assigned to Ouachita foreland deformation and may be related to Middle Pennsylvanian Ancestral Rockies contractional deformation. Finally, Event 4 contractional structures indicate northwest/southeast Hmax consistent with southern Appalachian late stage convergence.Deformation episodes are localized along basement fault zones, particularly at major bends, suggesting minor restraining-bend uplifts along strike-slip faults. Geometries of conjugate normal fault and hybrid shear joint arrays indicate localized areas of high differential stress consistent with basement block uplift at these bends. High-angle faults reactivated in a reverse sense and bedding-parallel veins suggest tensile minimum stresses and pore fluid pressures exceeding lithostatic stress, consistent with brine pulses driven into the midcontinent during Late Paleozoic orogeny (as proposed by other authors).