Theoretical studies of product polarization and state distributions of the H+HCl reaction

The angular momentum polarization and rotational state distributions of the H-2 and HCl products from the H + HCl reaction are calculated at a relative translational energy of 1.6 eV by using quasiclassical trajectories on two potential energy surfaces, one from G3 surface [T.C. Allison et al., J. Phys. Chem. 100 (1996) 13575], and the other from BW2 surface [W. Bian, H.-J. Werner, J. Chem. Phys. 112 (2000) 220]. Product rotational distributions obtained on the G3 potential energy surface (PES) are much closer to the experimental results (P.M. Aker et al., J. Chem. Phys. 90 (1989) 4795; J. Chem. Phys. 90 (1989) 4809) than the distributions calculated on the BW2 PES. The distributions of P(phi(r)) for the H-2 and HCl products obtained on the G3 PES are similar, whereas the rotational alignment effect of the H-2 product is stronger than that of the HCl product. In contrast to the polarization distributions obtained on the G3 PES, the rotational alignment effect of the two products calculated on the BW2 PES is similar. However, the abstraction reaction is dominated by out-of-plane mechanisms, while the exchange reaction is dominated by in-plane mechanisms. The significant difference of the product rotational polarization obtained on the G3 and BW2 PESs implies that the studies of the dynamical stereochemistry can provide a sensitive test for the accuracy of the PES. (C) 2002 Elsevier Science B.V. All rights reserved.

Application of static and dynamic enclosures for determining dimethyl sulfide and carbonyl sulfide exchange in Sphagnum peatlands: Implications for the magnitude and direction of flux

A static enclosure method was applied to determine the exchange of dimethyl sulfide (DMS) and carbonyl sulfide (OCS) between the surface of Sphagnum peatlands and the atmosphere. Measurements were performed concurrently with dynamic (flow through) enclosure measurements with sulfur-free air used as sweep gas. This latter technique has been used to acquire the majority of available data on the exchange of S gases between the atmosphere and the continental surfaces and has been criticized because it is thought to overestimate the true flux of gases by disrupting natural S gas gradients. DMS emission rates determined by both methods were not statistically different between 4 and >400 nmol m−2 h−1, indicating that previous data on emissions of at least DMS are probably valid. However, the increase in DMS in static enclosures was not linear, indicating the potential for a negative feedback of enclosure DMS concentrations on efflux. The dynamic enclosure method measured positive OCS flux rates (emission) at all sites, while data using static enclosures indicated that OCS was consumed from the atmosphere at these same sites at rates of 3.7 to 55 nmol m−2 h−1. Measurements using both enclosure techniques at a site devoid of vegetation showed that peat was a source of both DMS and OCS. However, the rate of OCS efflux from decomposing peat was more than counterbalanced by OCS consumption by vegetation, including Sphagnum mosses, and net OCS uptake occurred at all sites. We propose that all wetlands are net sinks for OCS.

Real-Time Study of Genomic DNA Structural Changes upon Interaction with Small Molecules Using Dual-Polarization Interferometry

The structural changes of genomic DNA upon interaction with small molecules have been studied in real time using dual-polarization interferometry (DPI). Native or thermally denatured DNA was immobilized on the silicon oxynitride surface via a preadsorbed poly(ethylenimine) (PEI) layer. The mass loading was similar for both types of DNA, however, native DNA formed a looser and thicker layer due to its rigidity, unlike the more flexible denatured DNA, which mixed with PEI to form a denser and thinner layer. Ethidium bromide (EtBr), a classical intercalator, induced the large thickness decrease and density increase of native DNA (double-stranded), but a slight increase in both the thickness and density of denatured DNA (partial single-stranded).

Constructing Thin Polythiophene Film Composed of Aligned Lamellae via Controlled Solvent Vapor Treatment

Thin poly(3-butylthiophene) (P3BT) film composed of aligned lamellae attached to the edge of the original film has been achieved via a controlled solvent vapor treatment (C-SVT) method. The polarized optical microscopy operated at both single-polarization and cross-polarization modes has been used to investigate the alignment of the fiber-like lamellae. A numerical simulation method is used to quantitatively calculate angle distributions of the lamellae deviated from the film growth direction. Prepatterned P3BT film edge acts as nuclei which densely initialize subsequent crystal growth by exhausting the materials transported from the partially dissolved film. The growth of new film upon crystallization is actually a self-healing process where the two-dimensional geometric confinement is mainly responsible for this parallel alignment of P3BT crystals. The solvent vapor pressure should be carefully chosen so as to induce crystal growth but avoid liquid instability which will destroy the continuity of the film.

INFLUENCE OF THE OHMIC POLARIZATION EFFECT ON THIN-LAYER SPECTROELECTROCHEMISTRY

The influence of thin-layer resistance in cyclic voltammetry was studied in detail. Under the experimental conditions, a linear relationship between the peak-peak potential difference and the product of the peak current and the resistance was obtained and

Improving Ship Detection with Polarimetric SAR based on Convolution between Co-polarization Channels

The convolution between co-polarization amplitude only data is studied to improve ship detection performance. The different statistical behaviors of ships and surrounding ocean are characterized a by two-dimensional convolution function (2D-CF) between different polarization channels. The convolution value of the ocean decreases relative to initial data, while that of ships increases. Therefore the contrast of ships to ocean is increased. The opposite variation trend of ocean and ships can distinguish the high intensity ocean clutter from ships' signatures. The new criterion can generally avoid mistaken detection by a constant false alarm rate detector. Our new ship detector is compared with other polarimetric approaches, and the results confirm the robustness of the proposed method.

Validation of RADARSAT-2 fully polarimetric SAR measurements of ocean surface waves

C band RADARSAT-2 fully polarimetric (fine quad-polarization mode, HH+VV+HV+VH) synthetic aperture radar (SAR) images are used to validate ocean surface waves measurements using the polarimetric SAR wave retrieval algorithm, without estimating the complex hydrodynamic modulation transfer function, even under large radar incidence angles. The linearly polarized radar backscatter cross sections (RBCS) are first calculated with the copolarization (HH, VV) and cross-polarization (HV, VH) RBCS and the polarization orientation angle. Subsequently, in the azimuth direction, the vertically and linearly polarized RBCS are used to measure the wave slopes. In the range direction, we combine horizontally and vertically polarized RBCS to estimate wave slopes. Taken together, wave slope spectra can be derived using estimated wave slopes in azimuth and range directions. Wave parameters extracted from the resultant wave slope spectra are validated with colocated National Data Buoy Center (NDBC) buoy measurements (wave periods, wavelengths, wave directions, and significant wave heights) and are shown to be in good agreement.

Estimation of Pose and Illuminant Direction for Face Processing

In this paper three problems related to the analysis of facial images are addressed: the illuminant direction, the compensation of illumination effects and, finally, the recovery of the pose of the face, restricted to in-depth rotations. The solutions proposed for these problems rely on the use of computer graphics techniques to provide images of faces under different illumination and pose, starting from a database of frontal views under frontal illumination.