ALBERT

Notes: Following the early Eocene collision of the Indian and Asian plates, intracontinental subduction occurred along the Main Central Thrust (MCT) zone in the High Himalaya. In the Kishtwar–Zanskar Himalaya, the MCT is a 2 km thick shear zone of high strain, distributed ductile deformation which emplaces the amphibolite facies High Himalayan Crystalline (HHC) unit south-westwards over the lower greenschist facies Lesser Himalaya. An inverted metamorphic field gradient, mapped from the first appearance of garnet, staurolite and kyanite index minerals, is coincident with the high strain zone. Petrography and garnet zoning profiles indicate that rocks in the lower MCT zone preserve a prograde assemblage, whereas rocks in the HHC unit show retrograde equilibration. Thermobarometric results derived using THERMOCALC indicate a P–T  increase of c. 180 °C and c. 400 MPa across the base of the MCT zone, which is a consequence of the syn- to postmetamorphic juxtaposition of M1 kyanite grade rocks of the HHC unit on a cooling path over biotite grade footwall rocks, which subsequently attain their peak (M2) during thrusting. Inclusion thermobarometry from the lower MCT zone reveals that M2 was accompanied by loading, and peak conditions of 537±38 °C and 860±120 MPa were attained. M1 kyanite assemblages in the HHC unit, which have not been overprinted by M2 fibrolitic sillimanite, were not significantly affected by M2, and conditions of equilibration are estimated as 742±53 °C and 960±180 MPa.There is no evidence for dissipative or downward conductive heating in the MCT zone. Instead, the primary control on the distribution of peak assemblages, represented by the index minerals, is postmetamorphic ductile thrusting in a downward propagating shear zone. Polymetamorphism and diachroneity of equilibration are also important controls on the thermal profile through the MCT zone and HHC unit.

Notes: Quantum mechanical calculations on the vibrational predissociation dynamics of NeBr2 in the B electronic state have been performed and the results compared with both experimental data and other computational studies. For vibrational levels with v≤20 we find that the vibrational state dependence of the predissociation lifetimes is in qualitative agreement with experimental measurements, as are the calculated Br2 fragment rotational distributions. For higher vibrational levels, the B←X excitation profiles are well represented by a sum of two Lorentzian line shapes. We attribute this result to the presence of long-lived resonances in the dissociative continuum that are reminiscent of long-lived dissociative trajectories in previous classical studies of NeBr2. © 2000 American Institute of Physics.

Notes: The electronic energy transfer pathways that occur following collisions between I2 in the E ion-pair electronic state (v=0, J=55) and He and Ar atoms have been determined. The nearby D, D′, and β ion-pair states are populated, but with relative branching ratios that vary with the rare gas collision partner. In He/I2 collisions, the D state is preferentially populated, while Ar/I2 collisions preferentially populate the β electronic state. Bimolecular rate constants and effective hard sphere collision cross sections have been determined for each channel; the cross sections range from 7.0±1.0 Å2 for populating the β state with Ar collisions to 0.9±0.2 Å2 for populating the D′ state with He collisions. For both rare gas collision partners, and all three final electronic states, low vibrational levels are populated, in rough accord with the relevant Franck–Condon factors. There is little propensity observed for population of vibrational levels that are in near resonance with the initially prepared level in the E state. © 2002 American Institute of Physics.

Notes: The mechanism of the reaction CH4+O(1D2)→CH3+OH was investigated by ultrafast, time-resolved and state-resolved experiments. In the ultrafast experiments, short ultraviolet pulses photolyzed ozone in the CH4⋅O3 van der Waals complex to produce O(1D2). The ensuing reaction with CH4 was monitored by measuring the appearance rate of OH(v=0,1;J,Ω,Λ) by laser-induced fluorescence, through the OH A←X transition, using short probe pulses. These spectrally broad pulses, centered between 307 and 316 nm, probe many different OH rovibrational states simultaneously. At each probe wavelength, both a fast and a slow rise time were evident in the fluorescence signal, and the ratio of the fast-to-slow signal varied with probe wavelength. The distribution of OH(v,J,Ω,Λ) states, Pobs(v,J,Ω,Λ), was determined by laser-induced fluorescence using a high-resolution, tunable dye laser. The Pobs(v,J,Ω,Λ) data and the time-resolved data were analyzed under the assumption that different formation times represent different reaction mechanisms and that each mechanism produces a characteristic rovibrational distribution. The state-resolved and the time-resolved data can be fit independently using a two-mechanism model: Pobs(v,J,Ω,Λ) can be decomposed into two components, and the appearance of OH can be fit by two exponential rise times. However, these independent analyses are not mutually consistent. The time-resolved and state-resolved data can be consistently fit using a three-mechanism model. The OH appearance signals, at all probe wavelengths, were fit with times τfast(approximate)0.2 ps, τinter(approximate)0.5 ps and τslow(approximate)5.4 ps. The slowest of these three is the rate for dissociation of a vibrationally excited methanol intermediate (CH3OH*) predicted by statistical theory after complete intramolecular energy redistribution following insertion of O(1D2) into CH4. The Pobs(v,J,Ω,Λ) was decomposed into three components, each with a linear surprisal, under the assumption that the mechanism producing OH at a statistical rate would be characterized by a statistical prior. Dissociation of a CH4O* intermediate before complete energy randomization was identified as producing OH at the intermediate rate and was associated with a population distribution with more rovibrational energy than the slow mechanism. The third mechanism produces OH promptly with a cold rovibrational distribution, indicative of a collinear abstraction mechanism. After these identifications were made, it was possible to predict the fraction of signal associated with each mechanism at different probe wavelengths in the ultrafast experiment, and the predictions proved consistent with measured appearance signals. This model also reconciles data from a variety of previous experiments. While this model is the simplest that is consistent with the data, it is not definitive for several reasons. First, the appearance signals measured in these experiments probe simultaneously many OH(v,J,Ω,Λ) states, which would tend to obfuscate differences in the appearance rate of specific rovibrational states. Second, only about half of the OH(v,J,Ω,Λ) states populated by this reaction could be probed by laser-induced fluorescence through the OH A←X band with our apparatus. Third, the cluster environment might influence the dynamics compared to the free bimolecular reaction.

Notes: The collision-induced electronic energy transfer that occurs when I2 in the E(0g+) ion-pair electronic state collides with ground electronic state I2 has been investigated. We prepare I2 in single rotational levels in v=0 of the E state using two-color double resonance laser excitation. The resulting emission spectrum shows that the nearby (ΔTe=−385 cm−1) D(0u+) electronic state is populated. The cross section for collision-induced E→D energy transfer is found to be 18±3 Å2. A range of D state vibrational levels are populated, consistent with a model in which overlap between the initial and final vibrational wave functions is important, but modulated by propensities for small vibrational energy gaps and those energy gaps that are closely matched to the v=0→v=1 energy separation in the I2(X) collision partner. © 2001 American Institute of Physics.

Notes: X-ray magnetic circular dichroism studies of magnetic 3d transition-metal samples require the recording of high-quality absorption scans in high magnetic fields using circularly polarized soft X-rays of energies in the range 0.5–1 keV. Normally this is performed by electron yield measurements in vacuum. This technique is rendered problematic by the influence of the high magnetic field on the motion of the electrons emitted. Detection of the fluorescent X-rays avoids this problem and eases the constraints of sample preparation and environment. However, the specifications required for a successful X-ray detector are severe, requiring an insensitivity to magnetic fields up to 4 T (for hysteresis curve measurements), a large dynamic range, detection of soft X-rays with good efficiency and signal to noise and containment of the detector structure within a space of a few cm3. Such a detector has been developed using gas microstrip technology and tests show that these requirements can be met.

Notes: Abstract  Sinkhole collapse is one of the main limitations on the development of karst areas, especially where bedrock is covered by unconsolidated material. Studies of sinkhole formation have shown that sinkholes are likely to develop in cutter (enlarged joint) zones as a result of subterranean erosion by flowing groundwater. Because of the irregular distribution of pinnacles and cutters on the bedrock surface, uncertainties arise when "hit-or-miss" borehole drilling is used to locate potential collapse sites. A high-resolution geophysical technique capable of depicting the details of the bedrock surface is essential for guiding the drilling program. Dipole-dipole electrical resistivity tomography (ERT) was used to map the bedrock surface at a site in southern Indiana where limestone is covered by about 9 m of clayey soils. Forty-nine transects were conducted over an area of approximately 42,037 m2. The electrode spacing was 3 m. The length of the transects varied from 81 to 249 m. The tomographs were interpreted with the aid of soil borings. The repeatability of ERT was evaluated by comparing the rock surface elevations interpreted from pairs of transects where they crossed each other. The average difference was 2.4 m, with a maximum of 10 m. The discrepancy between interpreted bedrock-surface elevations for a transect intersection may be caused by variations in the subsurface geology normal to the transect. Averaging the elevation data interpreted from different transects improved the ERT results. A bedrock surface map was generated using only the averaged elevation data at the transect junctions. The accuracy of the map was further evaluated using data from four exploratory boreholes. The average difference between interpreted and actual bedrock surface-elevations was less than 0.4 m. The map shows two large troughs in the limestone surface: one coinciding with an existing sinkhole basin, while the other is in alignment with a small topographic valley. Because sinkholes were observed at the same elevation interval in similar valleys in the vicinity, the delineated trough may have implications for future land use at the site.

Notes: Abstract It has previously been shown that it is possible to differentiate between squamous and columnar epithelia in rat and resected human tissues using an impedance probe to makein vitro measurements. This probe can be passed down an endoscope allowing measurements to be made in patients. However, the probe emerges parallel to the oesophageal wall, with little room to manoeuvre. The conditions of control required to give reliable readings have been investigated. The importance of pressure applied and the angle of approach to the oesophagus was assessed. Pressures in the range 26.6 Pa to 46.3 kPa and angles in the range 15–90 degrees were considered. Inin vitro studies it was observed that it was possible to obtain consistent readings with pressures greater than 2.9 kPa and with angles greater than 15 degrees between the probe and the oesophagus. These conditions can be achievedin vivo, and readings obtained from twelve patients are shown (45 readings on normal squamous, 34 on Barrett's oesophagus and 22 on stomach). At low frequencies (9.6–153.2 kHz), a Mann-Whitney test shows a significant difference (p〈0.001) when comparing the means from squamous and columnar, and also when readings from Barrett's and normal gastric epithelia are compared (p〈0.001).