Electronic absorption by Ti3+ ions and electron delocalization in synthetic blue rutile

Polarized absorption spectra, σ and π, in the spectral range 30000–400 cm⁻¹ (3.71–0.05 eV) were obtained on crystal slabs // [001] of deep blue rutile at various temperatures from 88 to 773 K. The rutile crystals were grown in Pt-capsules from carefully dried 99.999% TiO₂ rutile powder at 50 kbar/1500 °C using graphite heating cells in a belt-type apparatus. Impurities were below the detection limits of the electron microprobe (about 0.005 wt% for elements with Z≥13). The spectra are characterized by an unpolarized absorption edge at 24300 cm⁻¹, two weak and relatively narrow (Δν_1/2≈3500–4000 cm⁻¹), slightly σ-polarized bands ν₁ at 23500 cm⁻¹ and ν₂ at 18500 cm⁻¹, and a complex, strong band system in the NIR (near infra red) with sharp weak peaks in the region of the OH stretching fundamentals superimposed on the NIR system in the σ-spectra. The NIR band system and the UV edge produce an absorption minimum in both spectra, σ and π, at 21000 cm⁻¹, i.e. in the blue, which explains the colour of the crystals. Bands ν₁ and ν₂ are assigned to dd transitions to the Jahn-Teller split upper E_g state of octahedral Ti³⁺. The NIR band system can be fitted as a sum of three components. Two of them are partly π-polarized, nearly Gaussian bands, both with large half widths 6000–7000 cm⁻¹, ν₃ at 12000 cm^–1 and the most intense ν₄ at 6500 cm⁻¹. The third NIR band ν₅ of a mixed Lorentz-Gaussian shape with a maximum at 3000 cm⁻¹ forms a shoulder on the low-energy wing of ν₄. Energy positions, half band widths and temperature behaviour of these bands are consistent with a small polaron type of Ti³⁺Ti⁴⁺ charge transfer (CT). Polarization dependence of CT bands can be explained on the basis of the structural model of defect rutile by Bursill and Blanchin (1983) involving interstitial titanium. Two OH bands at 3322 and 3279 cm⁻¹ in σ-spectra show different stability during annealing, indicating two different positions of proton in the rutile structure, one of them probably connected with Ti³⁺ impurity. Total water concentration in blue rutile determined by IR spectroscopy is 0.10 wt-% OH. The EPR spectra measured in the temperature interval 20–295 K show the presence of an electron centre at temperatures above 100 K and Ti³⁺ ions in more than one structural position, but predominantly in compressed interstitial octahedral sites, at lower temperatures. These results are in good agreement with the conclusions based on the electronic absorption data. Received: 24 March 1997 / Revised, accepted: 14 October 1997     

The dispersion of fibrous amphiboles by glacial processes in the area surrounding Libby,Montana, USA

Mining operations began at a world-class vermiculite deposit at Vermiculite Mountain near Libby, Montana, circa 1920 and ended in 1990. Fibrous and asbestiform amphiboles intergrown with vermiculite ore are suspected to be a causative factor in an abnormally high number of cases of respiratory diseases in former mine and mill workers, and in residents of Libby. The question addressed in this report is whether some of the amphibole from Vermiculite Mountain could have been dispersed by Pleistocene glacial processes rather than by human activity after vermiculite mining began. The history of Pinedale glaciation in the Libby area provides a framework for estimating the presence and distribution of asbestiform amphiboles derived from Vermiculite Mountain and found in naturally occurring sediments of Glacial Lake Kootenai that underlie the Libby Valley area. There were two situations where sediments derived from Vermiculite Mountain were deposited into Glacial Lake Kootenai: (1) as lake-bottom sediments derived from meltwater flowing down Rainy Creek when the valley south of Vermiculite Mountain was free of ice but active ice still covered Vermiculite Mountain; and (2) as lake-bottom sediments eroded from the Rainy Creek outwash and re-deposited during a re-advance of the Purcell Trench Glacier lobe near Moyie Springs, Idaho.     

Model parameter optimization for site-dependent simulation of ground motion by simulated annealing: Re-evaluation of the Ashigara Valley prediction experiment

More than 40 groups from 10 different countries participated in a weak- and strong-motion prediction experiment at Ashigara Valley which required the blind prediction of time series, spectra and spectral ratios for selected and instrumented sedimentary sites with well-known geotechnical properties. The wide scatter of the results of this experiment have raised a number of questions as to how to model high-frequency ground motion in the presence of available geotechnical and geophysical data. Using a simulated annealing waveform inversion method, we have tried to optimize and automate the model construction for ID site-dependent ground-motion simulation. We found a whole set of successfull models which provide good waveform fit (r > 0.8) for the observed displacement records at site KS2 but also yield sufficiently accurate response spectra and peak value predictions for both surface and downhole site. This shows that ID models are fully adequate to model the site conditions at least for the weak motion data. The resulting successful layer models consistently show a slower, less dense, and slightly thicker low velocity coverage with stronger damping than the official geotechnical model. Furthermore, their statistical properties directly measure the sensitivity of the individual parameters for the simulations. The critical re-evaluation of our own prediction which was based on stochastic simulation shows that although this approach has its greatest merits in situations where little information is available, it can also be successfully applied to model individual records if sufficient care is taken to determine the source parameters. Simulated annealing waveform inversion has shown to be a powerful tool to optimize that process.     

Pressure- and temperature-effects on exchange-coupled-pair bands in electronic spectra of some oxygen-based iron-bearing minerals

The special properties of spin-allowed transitions of Fe²⁺, exchanged-coupled in pairs with Fe³⁺, (ECP-effect) are studied in single crystals of vivianite, phlogopite, biotite, elbaite and schörl under changing temperature and pressure in the ranges 79≤T[K]≤597 and 10^-4≤P[GPa]≤8. The two Fe²⁺ dd-transitions, known to be subject to ECP-effects, occur at 11000 to 14000 (II) and 8400 to 9150 cm^-1 (III), depending on the structural matrix. With pressure, band energies shift to higher values, while temperature has the opposite effect. Δv is nearly the same in all cases, decrease on temperature, and increase with pressure. Δα/ΔT or Δα/ΔP have similar values for bands II and III in all minerals studied. These observations are interpreted in terms of geometrical and vibrational changes of the octahedra, involved in the pair effects, on changing P and T. They clearly separate the ECP-bands from ordinary dd-transitions and also from IVCT-bands. A unique pressure effect in the spectral range of 17000 to 26000 cm^-1 was found in schörl: a band system that immensly gains intensity on pressure. Two explanations are suggested: (a) traces of Ti³⁺, exchange-coupled to Fe²⁺ show the above pressure effect typical of ECP, (b) there occurs pressureinduced reduction of Ti⁴⁺ in Y-positions, induced by Fe²⁺ in connected Y-octahedra, whereby OH in trans-configuration of Y-octahedra promote this process.     

Dynamic response of single-span beam bridges to a series of moving loads

The paper makes a contribution to the problem of a stream of loads crossing a single-span beam bridge. There are considered the basic load models, in the form of a stream of fixed amplitude forces, unsprung masses and viscoelastic oscillators. The matrix equations of motion of the system are formulated and discussed. The problem of dynamic stability and steady-state response of a bridge carrying a periodic stream of inertial loads is formulated and solved. The paper also includes a vibration study of a beam bridge subjected to a uniform stream of moving loads, of a limited or unlimited number of load cycles.     

Polarized electronic absorption spectra of synthetic (Mg,Fe)-orthopyroxenes,ferrosilite and Fe3+-bearing ferrosilite

The assignment of spin-allowed Fe²⁺-bands in orthopyroxene electronic absorption spectra is revised by studying synthetic bronzite (Mg_0.8 Fe_0.2)₂Si₂O₆, hypersthene (Mg_0.5 Fe_0.5)₂Si₂O₆ and ferrosilite (Fe₂Si₂O₆). Reheating of bronzite and hypersthene single crystals causes a redistribution of the Fe²⁺-ions over the M1 and M2 octahedra, which was determined by Mössbauer spectroscopy and correlated to the intensity change of the spin-allowed Fe²⁺ d-d bands in the polarized absorption spectra. The 11000 cm^-1 band is caused by Fe²⁺ in M1 (⁵B_2g→⁵A_1g) and Fe²⁺ in M2 (⁵A₁→⁵A₁), the 8500 cm^-1 band by Fe²⁺ in M1 (⁵B_2g→⁵B_1g) and the 5000 cm^-1 band by Fe²⁺ in M2 octahedra (⁵A₁→⁵B₁). The Fe²⁺-Fe³⁺ charge transfer band is identified at 12500cm^-1 in the spectra of synthetic Fe³⁺ -Al bearing ferrosilite. This band shows a strong γ-polarization and therefore is caused by Fe²⁺ -Fe³⁺-ions in edge-sharing octahedra.     

High Angular Resolution Study of the Ion and Neutral Spectra as a Probe of the Magnetic Field Structure

We present the observations and analysis of the spectral linewidths of neutral and ion species across the DR21(OH) core to investigate the cyclotron interaction as a probe of magnetic fields. It has been suggested that under average interstellar field strengths the cyclotron interaction between ions and magnetic fields is strong enough to narrow the linewidth and suppress the line wings in the ion spectra. We have obtained high spatial resolution spectral line images of H¹³CN and H¹³CO⁺ at 3 mm in DR21(OH) with the Millimeter Array of the Owens Valley Radio Observatory. Our results show that in the eastern parts of the DR21(OH) core the spectral linewidth of the ions is narrower than that of the neutrals. We use our results, along with the existing Zeeman and dust/CO polarization data on small scales, to derive the 3D magnetic field structure. We obtain a field strength of 0.44 ± 0.12 mG with inclination of 36° to the line of sight, directed toward the observer, and a position angle of ?75° in the plane of the sky.     

Exploratory seismic site response surveys in a complex geologic area: a case study from Mt. Etna volcano (southern Italy)

A preliminary study targeting to evaluate the local seismic response was performed in the eastern flank of Mt. Etna (southern Italy) using ambient noise measurements. The obtained spectral ratios were subdivided through cluster analysis into different classes of fundamental frequency permitting to draw an iso-frequency contour map. The analysis set into evidence the extreme heterogeneity of lava sequences, which makes difficult to identify a single seismic bedrock formation. Another important outcome, concerning the local seismic effects in terms of frequency and azimuth, is the important role played by the fracture fields associated with the main structural systems of the area. The existence of two zones with strong directional effects striking WNW–ESE and NW–SE, nearly orthogonal to the orientation of the main fracture fields, corroborate such hypothesis.

     

Effects of hyperons on the vibrations of neutron stars

We calculate the effects of hyperons and resonance particles on the vibrations of neutron stars. Vibrating neutron stars can store large amounts of energy in their vibrations; the interaction of the vibrations with the atmosphere would produce electromagnetic radiation. If any process damps out the vibrations rapidly on an astronomical time scale ( 1000 years) then vibrating neutron stars are not likely to be found. Previous work indicates that radiation by a neutrino URCA process (N+NP+N+e ^–+ ) does not rapidly damp many of the neutron star models. Some neutron stars are predicted to contain massive baryons; here we study thermal damping by nonequilibrium reactions involving these baryons.During vibrations the thermodynamic equilibrium state is changed and particle reactions attempt to restore equilibrium. If the reaction rates per particle are very rapid or slow compared to the frequency of vibration the system follows almost the same pressure-volume curve through both parts of the gas cycle, and very little work is done. In the intermediate case, when reaction rates are comparable to the frequency, damping is rapid.We find that the reaction rates for weak interactions such asN+NP+^– (the ^– is the first hyperon to appear with increasing density in degenerate neutron star matter) are of the right magnitude to cause rapid damping. If there is a hyperon region in the star then it cannot sustain vibrations. We also consider the much faster (and hence less important) processN+NP+^–.