Collisional parameters of H2O lines: effects of vibration

A complex semiclassical model for the calculation of line widths and shifts of H₂O broadened by N₂, derived from the Robert and Bonamy approach, is tested by comparisons with measurements for selected transitions in various vibrational bands. The lines retained, which involve rotational states with Kc=J or J−1 have been chosen for two reasons. The first is that they show large variations of the widths with J and thus enable a severe test of the model. The second is that, as explained in this paper, they are well-suited for the study of the effects of vibration on the collisional parameters. The measured values have been extracted from an updated version of a database built years ago (JQSRT 52 (1994) 481) that contains all available measurements. Comparisons between experimental and calculated widths and shifts at room temperature illustrate the quality of the model and clearly demonstrate, for the first time, that there is a vibrational dependence of the broadening. Values of collisional parameters are first studied in fundamental bands. This shows that the theoretical approach accounts for most of the dependence of broadening and shifting on rotational quantum numbers: the variations of γ, which reach a factor of nearly 20 from low to high J values, are correctly accounted for by the model as are some specific features of the shifts δ. Analysis confirms that the bending and stretching vibrations have significantly different effects on δ, due to the vibrational dependence of the intermolecular potential. On the other hand, differences on the widths are rather small with slightly smaller broadening for lines of the bending band. Calculations show that there is a spectroscopic effect, due to the larger rotational constant A in the v₂=1 state. Calculations made for overtone bands involving numerous quanta of the stretching vibration are then presented. They predict that a significant dependence of the width should be observed for high J lines due to the effect of vibration on the interaction potential. This is confirmed by comparisons with measurements for lines involving a change of three and four quanta of stretching vibration.     

Methods for implementing the stream boundary condition in DSMC computations

In the direct simulation Monte‐Carlo (DSMC) method for simulating rarefied gas flows, the velocities of simulator particles that cross a simulation boundary and enter the simulation space are typically generated using the acceptance–rejection procedure that samples the velocities from a truncated theoretical velocity distribution that excludes low and high velocities. This paper analyses an alternative technique, where the velocities of entering particles are obtained by extending the simulation procedures to a region adjacent to the simulation space, and considering the movement of particles generated within that region during the simulation time step. The alternative method may be considered as a form of acceptance–rejection procedure, and permits the generation of all possible velocities, although the population of high velocities is depleted with respect to the theoretical distribution. Nevertheless, this is an improvement over the standard acceptance–rejection method. Previous implementations of the alternative method gave a number flux lower than the theoretical number required. Two methods for obtaining the correct number flux are presented. For upstream boundaries in high‐speed flows, the alternative method is more computationally efficient than the acceptance–rejection method. However, for downstream boundaries, the alternative method is extremely inefficient. The alternative method, with the correct theoretical number flux, should therefore be used in DSMC computations in favour of the acceptance–rejection method for upstream boundaries in high‐speed flows. Copyright © 2003 John Wiley & Sons, Ltd.     

Facile modifications of a polyimide via chloromethylation. I. Novel synthesis of a new photosensitive polyimide

A soluble aromatic polyimide was chloromethylated via a reaction with chloromethyl methyl ether in the presence of tin(IV) chloride to produce a new starting material for the modification of aromatic polyimides. The chemical structure of the resulting polymer was confirmed by ¹H NMR and Fourier transform infrared spectroscopy. The maximum number of chloromethyl groups per repeat unit was 1.81. The chloromethylated polyimide was stable up to 250 °C and soluble in both chloroform and tetrahydrofuran. So that its utilization for further modification could be demonstrated, cinnamic acid was reacted with the formed polyimide, and it produced a new photosensitive polyimide with a cinnamoyl side chain. The photosensitivity of the resulting polyimide was investigated with ultraviolet spectroscopic methods. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 22–29, 2003     

Critical Point Theorems and Applications to Differential Equations

This paper contains a generalization of the well-known Palais-Smale and Cerami compactness conditions. The compactness condition introduced is used to prove some general existence theorems for critical points. Some applications are given to differential equations.     

The study of the influence of uniaxial stress on impurity complexes in silicon

The influence of external uniaxial stress on the different indium-donor complexes in silicon has been studied using the perturbed γ –γ angular correlation (PAC) method. Such effect of an applied stress is detected by means of the probe atoms situated at different complexes in the sample. The current results showed that the responses of the probes in an extrinsic silicon samples are found to be dissimilar for the same value of stress. Such change in the local environments of the probe atoms could be associated with the various strain field created by the implantations of varied size of impurities. The phosphorous implantation in silicon has even lead to the complete absence of observable effect of the applied stress suggesting significant lose of the elasticity of the sample.     

Lithium heptadecafluorooctanesulfonate catalyzed Mannich-type and aza-Diels-Alder reactions in supercritical carbon dioxide

The Mannich-type reaction of imines with (1-methoxy-2-methylpropenyloxy)trimethylsilane and aza-Diels-Alder reaction of imines with Danishefsky's diene can be carried out in scCO₂ in the presence of lithium heptadecafluorooctanesulfonate which offer a way to synthesize β-amino carbonyl compounds and nitrogen-containing six-membered ring compounds under environmentally benign conditions.     

Electron spin lifetimes in Hg0.78Cd0.22 Te and InSb

We have made direct pump–probe measurements of spin lifetimes in long wavelength narrow-gap semiconductors at wavelengths between 4 and 10 μm and from 4 to 300 K. In particular, we measure remarkably long spin lifetimes, τ_s300 ps, even at 300 K for epilayers of degenerate n-type InSb. In this material the mobility is approximately constant between 77 and 300 K, and we find that τ_s is approximately constant in this temperature range. In order to determine the dominant spin relaxation mechanism we have investigated the temperature dependence of τ_s in non-degenerate lightly n-type Hg_0.78Cd_0.22Te of approximately the same band gap as InSb, and find that τ_s varies from 356 ps at 150 K to 24 ps at 300 K. Our results, both in magnitude and temperature dependence of τ_s, imply that the Elliott–Yafet model dominates in these materials.     

Negative luminescence from mid-wave infrared HgCdTe diode arrays

A self-referencing, optical modulation technique was used to measure the negative luminescence efficiencies of an array of mid-wave infrared HgCdTe photodiodes with cutoff wavelength 4.6 μm as a function of sample temperature. The internal efficiency at a wavelength of 4 μm was 93% at 295 K, and nearly independent of temperature in the 240–300 K range. This corresponds to an apparent temperature reduction >50 K at room temperature and >30 K at 240 K. Moreover, the reverse-bias saturation current density was only 0.13 A/cm². The measured transmission and emission spectra were simulated using empirical HgCdTe absorption formulas from the literature.