Time-resolved gas-phase kinetic and quantum chemical studies of the reaction of silylene with oxygen

Time-resolved kinetic studies of the reaction of silylene, SiH2, generated by laser flash photolysis of phenylsilane, have been carried out to obtain rate constants for its bimolecular reaction with O-2. The reaction was studied in the gas phase over the pressure range 1-100 Torr in SF6 bath gas, at five temperatures in the range 297-600 K. The second order rate constants at 10 Torr were fitted to the Arrhenius equation: log(k/cm(3) molecule(-1) s(-1)) = (-11.08 +/- 0.04) + (1.57 +/- 0.32 kJ mol(-1))/RT ln10 The decrease in rate constant values with increasing temperature, although systematic is very small. The rate constants showed slight increases in value with pressure at each temperature, but this was scarcely beyond experimental uncertainty. From estimates of Lennard-Jones collision rates, this reaction is occurring at ca. 1 in 20 collisions, almost independent of pressure and temperature. Ab initio calculations at the G3 level backed further by multi-configurational (MC) SCF calculations, augmented by second order perturbation theory (MRMP2), support a mechanism in which the initial adduct, H2SiOO, formed in the triplet state (T), undergoes intersystem crossing to the more stable singlet state (S) prior to further low energy isomerisation processes leading, via a sequence of steps, ultimately to dissociation products of which the lowest energy pair are H2O + SiO. The decomposition of the intermediate cyclo-siladioxirane, via O-O bond fission, plays an important role in the overall process. The bottleneck for the overall process appears to be the T -> S process in H2SiOO. This process has a small spin orbit coupling matrix element, consistent with an estimate of its rate constant of 1 x 10(9) s(-1) obtained with the aid of RRKM theory. This interpretation preserves the idea that, as in its reactions in general, SiH2 initially reacts at the encounter rate with O-2. The low values for the secondary reaction barriers on the potential energy surface account for the lack of an observed pressure dependence. Some comparisons are drawn with the reactions of CH2 + O-2 and SiCl2 + O-2

Population Monte Carlo algorithms

We give a cross-disciplinary survey on ``population'' Monte Carlo algorithms. In these algorithms, a set of ``walkers'' or ``particles'' is used as a representation of a high-dimensional vector. The computation is carried out by a random walk and split/deletion of these objects. The algorithms are developed in various fields in physics and statistical sciences and called by lots of different terms -- ``quantum Monte Carlo'', ``transfer-matrix Monte Carlo'', ``Monte Carlo filter (particle filter)'',``sequential Monte Carlo'' and ``PERM'' etc. Here we discuss them in a coherent framework. We also touch on related algorithms -- genetic algorithms and annealed importance sampling.Comment: Title is changed (Population-based Monte Carlo -> Population Monte Carlo). A number of small but important corrections and additions. References are also added. Original Version is read at 2000 Workshop on Information-Based Induction Sciences (July 17-18, 2000, Syuzenji, Shizuoka, Japan). No figure

Young star clusters in M31

In our study of M31's globular cluster system with MMT/Hectospec, we have obtained high-quality spectra of 85 clusters with ages less than 1 Gyr. With the exception of Hubble V, the young cluster in NGC 205, we find that these young clusters have kinematics and spatial distribution consistent with membership in M31's young disk. Preliminary estimates of the cluster masses and structural parameters, using spectroscopically derived ages and HST imaging, confirms earlier suggestions that M31 has clusters similar to the LMC's young populous clusters.Comment: 4 pages, 1 figure, contributed talk at "Galaxies in the Local Volume" conference in Sydney, July 200

Fast Non-Adiabatic Two Qubit Gates for the Kane Quantum Computer

In this paper we apply the canonical decomposition of two qubit unitaries to find pulse schemes to control the proposed Kane quantum computer. We explicitly find pulse sequences for the CNOT, swap, square root of swap and controlled Z rotations. We analyze the speed and fidelity of these gates, both of which compare favorably to existing schemes. The pulse sequences presented in this paper are theoretically faster, higher fidelity, and simpler than existing schemes. Any two qubit gate may be easily found and implemented using similar pulse sequences. Numerical simulation is used to verify the accuracy of each pulse scheme

Reddening law and interstellar dust properties along Magellanic sight-lines

This study establishes that SMC, LMC and Milky Way extinction curves obey the same extinction law which depends on the 2200A bump size and one parameter, and generalizes the Cardelli, Clayton and Mathis (1989) relationship. This suggests that extinction in all three galaxies is of the same nature. The role of linear reddening laws over all the visible/UV wavelength range, particularly important in the SMC but also present in the LMC and in the Milky Way, is also highlighted and discussed.Comment: accepted for publication in Astrophysics and Space Science. 16 pages, 12 figures. Some figures are colour plot

Quantum saturation and condensation of excitons in Cu2_2O: a theoretical study

Recent experiments on high density excitons in Cu$_2$O provide evidence for degenerate quantum statistics and Bose-Einstein condensation of this nearly ideal gas. We model the time dependence of this bosonic system including exciton decay mechanisms, energy exchange with phonons, and interconversion between ortho (triplet-state) and para (singlet-state) excitons, using parameters for the excitonic decay, the coupling to acoustic and low-lying optical phonons, Auger recombination, and ortho-para interconversion derived from experiment. The single adjustable parameter in our model is the optical-phonon cooling rate for Auger and laser-produced hot excitons. We show that the orthoexcitons move along the phase boundary without crossing it (i.e., exhibit a ``quantum saturation''), as a consequence of the balance of entropy changes due to cooling of excitons by phonons and heating by the non-radiative Auger two-exciton recombination process. The Auger annihilation rate for para-para collisions is much smaller than that for ortho-para and ortho-ortho collisions, explaining why, under the given experimental conditions, the paraexcitons condense while the orthoexcitons fail to do so.Comment: Revised to improve clarity and physical content 18 pages, revtex, figures available from G. Kavoulakis, Physics Department, University of Illinois, Urban

Present Effects of Past Wildfires on Leaf Litter Breakdown in Stream Ecosystems

We investigated the present effects from a 10-year-old wildfire on leaf litter breakdown rates in 3 headwater streams in central Idaho. These systems experienced a massive debris flow one year after the fire. Based on soil instability and burn patterns, we identified 3 stream conditions: unburned, burned only, and burned/scoured. We placed leaf bags containing willow leaves (Salix sp.) in each stream type and removed bags at various time intervals until all bags were collected 100 days after their introduction. Leaf material was dried and weighed, and decay rate coefficients were calculated. Macroinvertebrates colonizing the bags were enumerated and identified, and selected taxa were placed into trophic groups. We found that the unburned stream had the fastest leaf litter breakdown rate, the lowest level of incident light reaching the stream, and the largest amount of benthic organic matter. The burned/scoured stream was nearly opposite in all respects. Numbers of 2 detritivore invertebrate taxa, Serratella tibialis and Zapada oregonensis, were highest in the unburned stream but lowest in the burned/scoured stream. A third taxon, Baetis sp., showed the opposite relationship. Presence of predatory invertebrates did not affect detritivore abundance or leaf decay rate in the bags. Our research suggests that recovery response variables of some stream systems may not have returned to prefire levels even a decade after the initial wildfire. In this study, the recovery of our streams appears to be connected to the return of the riparian zone, though fire-induced debris flows may slow or alter final recovery of the stream system

Zn Diffusion and α-Fe(Zn) Layer Growth During Annealing of Zn-Coated B Steel

Direct hot press forming of Zn-coated 22MnB5 steels is impeded by micro-cracks that occur in the substrate due to the presence of Zn during the forming process. A study was therefore undertaken to quantify concentration of Zn across the α-Fe(Zn) coating and on grain boundaries in the α-Fe(Zn) layer and the underlying γ-Fe(Zn) substrate after isothermal annealing of Zn-coated 22MnB5 at 1173 K (900 °C) and to link the Zn distribution to the amount and type of micro-cracks observed in deformed samples. Finite difference model was developed to describe Zn diffusion and the growth of the α-Fe(Zn) layer. The penetration of Zn into the γ-Fe(Zn) substrate after 600 seconds annealing at 1173 K (900 °C) through bulk diffusion is estimated to be 3 μm, and the diffusion depth of Zn on the γ-Fe(Zn) grain boundaries is estimated to be 6 μm, which is significantly shorter than the maximum length (15 to 50 μm) of the micro-cracks formed in the severely stressed conditions, indicating that the Zn diffusion into the γ-Fe(Zn) from the α-Fe(Zn) during annealing is not correlated to the depth of micro-cracks. On the other hand, the maximum amount of Zn present in α-Fe(Zn) layer decreases with annealing time as the layer grows and Zn oxidizes, and the amount of Zn-enriched areas inside the α-Fe(Zn) layer is reduced leading to reduced length of cracking. Solid-Metal-Induced Embrittlement mechanism is proposed to explain the benefit of extended annealing on reduced depth of micro-crack penetration into the γ-Fe(Zn) substrate