The gas-phase reaction between silylene and 2-butyne: kinetics, isotope studies, pressure dependence studies and quantum chemical calculations

Time-resolved kinetic studies of the reactions of silylene, SiH2, and dideutero-silylene, SiD2, generated by laser. ash photolysis of phenylsilane and phenylsilane-d(3), respectively, have been carried out to obtain rate coefficients for their bimolecular reactions with 2-butyne, CH3C CCH3. The reactions were studied in the gas phase over the pressure range 1-100 Torr in SF6 bath gas at five temperatures in the range 294-612 K. The second-order rate coefficients, obtained by extrapolation to the high pressure limits at each temperature, fitted the Arrhenius equations where the error limits are single standard deviations: log(k(H)(infinity)/cm(3) molecule(-1) s(-1)) = (-9.67 +/- 0.04) + (1.71 +/- 0.33) kJ mol(-1)/RTln10 log(k(D)(infinity)/cm(3) molecule(-1) s(-1)) = (-9.65 +/- 0.01) + (1.92 +/- 0.13) kJ mol(-1)/RTln10 Additionally, pressure-dependent rate coefficients for the reaction of SiH2 with 2-butyne in the presence of He (1-100 Torr) were obtained at 301, 429 and 613 K. Quantum chemical (ab initio) calculations of the SiC4H8 reaction system at the G3 level support the formation of 2,3-dimethylsilirene [cyclo-SiH2C(CH3)=C(CH3)-] as the sole end product. However, reversible formation of 2,3-dimethylvinylsilylene [CH3CH=C(CH3)SiH] is also an important process. The calculations also indicate the probable involvement of several other intermediates, and possible products. RRKM calculations are in reasonable agreement with the pressure dependences at an enthalpy value for 2,3-dimethylsilirene fairly close to that suggested by the ab initio calculations. The experimental isotope effects deviate significantly from those predicted by RRKM theory. The differences can be explained by an isotopic scrambling mechanism, involving H - D exchange between the hydrogens of the methyl groups and the D-atoms in the ring in 2,3-dimethylsilirene-1,1-d(2). A detailed mechanism involving several intermediate species, which is consistent with the G3 energy surface, is proposed to account for this.

Preliminary results on the non-thermal effects of 200-350 GHz radiation on the growth rate of S. cerevisiae cells in microcolonies

We report preliminary results from studies of biological effects induced by non-thermal levels of non-ionizing electromagnetic radiation. Exponentially growing Saccharomyces cerevisiae yeast cells grown on dry media were exposed to electromagnetic fields in the 200–350 GHz frequency range at low power density to observe possible non-thermal effects on the microcolony growth. Exposure to the electromagnetic field was conducted over 2.5 h. The data from exposure and control experiments were grouped into either large-, medium- or small-sized microcolonies to assist in the accurate assessment of growth. The three groups showed significant differences in growth between exposed and control microcolonies. A statistically significant enhanced growth rate was observed at 341 GHz. Growth rate was assessed every 30 min via time-lapse photography. Possible interaction mechanisms are discussed, taking into account Frohlich's hypothesis.

Operator performance evaluation of controlled depth of field in a stereographically displayed virtual environment

Retinal blurring resulting from the human eye's depth of focus has been shown to assist visual perception. Infinite focal depth within stereoscopically displayed virtual environments may cause undesirable effects, for instance, objects positioned at a distance in front of or behind the observer's fixation point will be perceived in sharp focus with large disparities thereby causing diplopia. Although published research on incorporation of synthetically generated Depth of Field (DoF) suggests that this might act as an enhancement to perceived image quality, no quantitative testimonies of perceptional performance gains exist. This may be due to the difficulty of dynamic generation of synthetic DoF where focal distance is actively linked to fixation distance. In this paper, such a system is described. A desktop stereographic display is used to project a virtual scene in which synthetically generated DoF is actively controlled from vergence-derived distance. A performance evaluation experiment on this system which involved subjects carrying out observations in a spatially complex virtual environment was undertaken. The virtual environment consisted of components interconnected by pipes on a distractive background. The subject was tasked with making an observation based on the connectivity of the components. The effects of focal depth variation in static and actively controlled focal distance conditions were investigated. The results and analysis are presented which show that performance gains may be achieved by addition of synthetic DoF. The merits of the application of synthetic DoF are discussed.

The effects of the RAW filter on the climatology and forecast skill of the SPEEDY model

In a recent study, Williams introduced a simple modification to the widely used Robert–Asselin (RA) filter for numerical integration. The main purpose of the Robert–Asselin–Williams (RAW) filter is to avoid the undesired numerical damping of the RA filter and to increase the accuracy. In the present paper, the effects of the modification are comprehensively evaluated in the Simplified Parameterizations, Primitive Equation Dynamics (SPEEDY) atmospheric general circulation model. First, the authors search for significant changes in the monthly climatology due to the introduction of the new filter. After testing both at the local level and at the field level, no significant changes are found, which is advantageous in the sense that the new scheme does not require a retuning of the parameterized model physics. Second, the authors examine whether the new filter improves the skill of short- and medium-term forecasts. January 1982 data from the NCEP–NCAR reanalysis are used to evaluate the forecast skill. Improvements are found in all the model variables (except the relative humidity, which is hardly changed). The improvements increase with lead time and are especially evident in medium-range forecasts (96–144 h). For example, in tropical surface pressure predictions, 5-day forecasts made using the RAW filter have approximately the same skill as 4-day forecasts made using the RA filter. The results of this work are encouraging for the implementation of the RAW filter in other models currently using the RA filter.

Effects of polydispersity on the order-disorder transition of diblock copolymer melts

The effect of polydispersity on an AB diblock copolymer melt is investigated using latticebased Monte Carlo simulations. We consider melts of symmetric composition, where the B blocks are monodisperse and the A blocks are polydisperse with a Schultz-Zimm distribution. In agreement with experiment and self-consistent field theory (SCFT), we find that polydispersity causes a significant increase in domain size. It also induces a transition from flat to curved interfaces, with the polydisperse blocks residing on the inside of the interfacial curvature. Most importantly, the simulations show a relatively small shift in the order-disorder transition (ODT) in agreement with experiment, whereas SCFT incorrectly predicts a sizable shift towards higher temperatures.

Spatial and temporal effects of free-air CO2 enrichment (POPFACE) on leaf growth, cell expansion and cell production in a closed canopy of poplar

Leaf expansion in the fast-growing tree,Populus × euramericana was stimulated by elevated [CO2] in a closed-canopy forest plantation, exposed using a free air CO2 enrichment technique enabling long-term experimentation in field conditions. The effects of elevated [CO2] over time were characterized and related to the leaf plastochron index (LPI), and showed that leaf expansion was stimulated at very early (LPI, 0–3) and late (LPI, 6–8) stages in development. Early and late effects of elevated [CO2] were largely the result of increased cell expansion and increased cell production, respectively. Spatial effects of elevated [CO2] were also marked and increased final leaf size resulted from an effect on leaf area, but not leaf length, demonstrating changed leaf shape in response to [CO2]. Leaves exhibited a basipetal gradient of leaf development, investigated by defining seven interveinal areas, with growth ceasing first at the leaf tip. Interestingly, and in contrast to other reports, no spatial differences in epidermal cell size were apparent across the lamina, whereas a clear basipetal gradient in cell production rate was found. These data suggest that the rate and timing of cell production was more important in determining leaf shape, given the constant cell size across the leaf lamina. The effect of elevated [CO2] imposed on this developmental gradient suggested that leaf cell production continued longer in elevated [CO2] and that basal increases in cell production rate were also more important than altered cell expansion for increased final leaf size and altered leaf shape in elevated [CO2].

π-dimerization of pleiadiene radical cations at low temperatures revealed by UV–vis spectroelectrochemistry and quantum theory

One-electron oxidation of the non-alternant polycyclic aromatic hydrocarbon pleiadiene and related cyclohepta[ c,d]pyrene and cyclohepta[c,d]fluoranthene in THF produces corresponding radical cations detectable in the temperature range of 293–263 K only on the subsecond time scale of cyclic voltammetry. Although the EPR-active red-coloured pleiadiene radical cation is stable according to the literature in concentrated sulfuric acid, spectroelectrochemical measurements reported in this study provide convincing evidence for its facile conversion into the green-coloured, formally closed shell and, hence, EPRsilent π-bound dimer dication stable in THF at 253 K. The unexpected formation of the thermally unstable dimeric product featuring a characteristic intense low-energy absorption band at 673 nm (1.84 eV; logεmax=4.0) is substantiated by ab initio calculations on the parent pleiadiene molecule and the PF6 − salts of the corresponding radical cation and dimer dication. The latter is stabilized with respect to the radical cation by 14.40 kcal mol−1 (DFT B3LYP) [37.64 kcal mol−1 (CASPT2/DFT B3LYP)]. An excellent match has been obtained between the experimental and TDDFT- calculated UV–vis spectra of the PF6 − salt of the pleiadiene dimer dication, considering solvent (THF) effects.