Stochastic simulation of catalytic surface reactions in the fast diffusion limit

The master equation of a lattice gas reaction tracks the probability of visiting all spatial configurations. The large number of unique spatial configurations on a lattice renders master equation simulations infeasible for even small lattices. In this work, a reduced master equation is derived for the probability distribution of the coverages in the infinite diffusion limit. This derivation justifies the widely used assumption that the adlayer is in equilibrium for the current coverages and temperature when all reactants are highly mobile. Given the reduced master equation, two novel and efficient simulation methods of lattice gas reactions in the infinite diffusion limit are derived. The first method involves solving the reduced master equation directly for small lattices, which is intractable in configuration space. The second method involves reducing the master equation further in the large lattice limit to a set of differential equations that tracks only the species coverages. Solution of the reduced master equation and differential equations requires information that can be obtained through short, diffusion-only kinetic Monte Carlo simulation runs at each coverage. These simulations need to be run only once because the data can be stored and used for simulations with any set of kinetic parameters, gas-phase concentrations, and initial conditions. An idealized CO oxidation reaction mechanism with strong lateral interactions is used as an example system for demonstrating the reduced master equation and deterministic simulation techniques

Two classes of quasi-steady-state model reductions for stochastic kinetics

The quasi-steady-state approximation (QSSA) is a model reduction technique used to remove highly reactive species from deterministic models of reaction mechanisms. In many reaction networks the highly reactive intermediates (QSSA species) have populations small enough to require a stochastic representation. In this work we apply singular perturbation analysis to remove the QSSA species from the chemical master equation for two classes of problems. The first class occurs in reaction networks where all the species have small populations and the QSSA species sample zero the majority of the time. The perturbation analysis provides a reduced master equation in which the highly reactive species can sample only zero, and are effectively removed from the model. The reduced master equation can be sampled with the Gillespie algorithm. This first stochastic QSSA reduction is applied to several example reaction mechanisms (including Michaelis-Menten kinetics) [Biochem. Z. 49, 333 (1913)]. A general framework for applying the first QSSA reduction technique to new reaction mechanisms is derived. The second class of QSSA model reductions is derived for reaction networks where non-QSSA species have large populations and QSSA species numbers are small and stochastic. We derive this second QSSA reduction from a combination of singular perturbation analysis and the Omega expansion. In some cases the reduced mechanisms and reaction rates from these two stochastic QSSA models and the classical deterministic QSSA reduction are equivalent; however, this is not usually the case

Mid-infrared selection of quasar-2s in Spitzer's First Look Survey

We present early results from the spectroscopic follow-up of a sample of candidate obscured AGN selected in the mid-infrared from the Spitzer First Look Survey. Our selection allows a direct comparison of the numbers of obscured and unobscured AGN at a given luminosity for the first time, and shows that the ratio of obscured to unobscured AGN at infrared luminosities corresponding to low luminosity quasars is ~1:1 at z~0.5. Most of our optically-faint candidate obscured AGN have the high-ionization, narrow-line spectra expected from type-2 AGN. A composite spectrum shows evidence for Balmer absorption lines, indicating recent star-formation activity in the host galaxies. There is tentative evidence for a decrease in the obscured AGN fraction with increasing AGN luminosity.Comment: To appear in the proceedings of the workshop "Multiband approach to AGN" Bonn October 2004 in Memorie della Societa Astronomica Italian

Near-Infrared Observations of Powerful High-Redshift Radio Galaxies: 4C 40.36 and 4C 39.37

We present near-infrared imaging and spectroscopic observations of two FR II high-redshift radio galaxies (HzRGs), 4C 40.36 (z=2.3) and 4C 39.37 (z=3.2), obtained with the Hubble, Keck, and Hale Telescopes. High resolution images were taken with filters both in and out of strong emission lines, and together with the spectroscopic data, the properties of the line and continuum emissions were carefully analyzed. Our analysis of 4C 40.36 and 4C 39.37 shows that strong emission lines (e.g., [O III] 5007 A and H alpha+[N II]) contribute to the broad-band fluxes much more significantly than previously estimated (80% vs. 20-40%), and that when the continuum sources are imaged through line-free filters, they show an extremely compact morphology with a high surface brightness. If we use the R^1/4-law parametrization, their effective radii (r(e)) are only 2-3 kpc while their restframe B-band surface brightnesses at r(e) are I(B) ~ 18 mag/arcsec^2. Compared with z ~ 1 3CR radio galaxies, the former is x3-5 smaller, while the latter is 1-1.5 mag brighter than what is predicted from the I(B)-r(e) correlation. Although exponential profiles produce equally good fits for 4C 40.36 and 4C 39.37, this clearly indicates that with respect to the z~1 3CR radio galaxies, the light distribution of these two HzRGs is much more centrally concentrated. Spectroscopically, 4C 40.36 shows a flat (fnu=const) continuum while 4C 39.37 shows a spectrum as red as that of a local giant elliptical galaxy. Although this difference may be explained in terms of a varying degree of star formation, the similarities of their surface brightness profiles and the submillimeter detection of 4C 39.37 might suggest that the intrinsic spectra is equally blue (young stars or an AGN), and that the difference is the amount of reddening.Comment: 30 pages, 6 tables, 10 figures; Accepted for publication in Astronomical Journa

Sensitive Limits on the Water Abundance in Cold Low Mass Molecular Cores

We present SWAS observations of water vapor in two cold star-less clouds, B68 and Core D in rho Ophiuchus. Sensitive non-detections of the 1(10)-1(01) transition of o-H2O are reported for each source. Both molecular cores have been previously examined by detailed observations that have characterized the physical structure. Using these rather well defined physical properties and a Monte-Carlo radiation transfer model we have removed one of the largest uncertainties from the abundance calculation and set the lowest water abundance limit to date in cold low-mass molecular cores. These limits are < 3 x 10^{-8} (relative to H2) and < 8 x 10^{-9} in B68 and rho Oph D, respectively. Such low abundances confirm the general lack of ortho-water vapor in cold (T < 20 K) cores. Provided that the ortho/para ratio of water is not near zero, these limits are well below theoretical predictions and appear to support the suggestion that most of the water in dense low-mass cores is frozen onto the surfaces of cold dust grains.Comment: 12 pages, 3 figures, accepted by Astrophysical Journal Letter

Molecular ions in L1544. I. Kinematics

We have mapped the dense dark core L1544 in H13CO+(1-0), DCO+(2-1), DCO+(3-2), N2H+(1-0), NTH+(3-2), N2D+(2-1), N2D+(3-2), C18O(1-0), and C17O(1-0) using the IRAM 30-m telescope. We have obtained supplementary observations of HC18O+(1-0), HC17O+(1-0), and D13CO+(2-1). Many of the observed maps show a general correlation with the distribution of dust continuum emission in contrast to C18O(1-0) and C17O(1-0) which give clear evidence for depletion of CO at positions close to the continuum peak. In particular N2D+(2-1) and (3-2) and to a lesser extent N2H+(1-0) appear to be excellent tracers of the dust continuum. We find that the tracers of high density gas (in particular N2D+) show a velocity gradient along the minor axis of the L1544 core and that there is evidence for larger linewidths close to the dust emission peak. We interpret this using the model of the L1544 proposed by Ciolek & Basu (2000) and by comparing the observed velocities with those expected on the basis of their model. The results show reasonable agreement between observations and model in that the velocity gradient along the minor axis and the line broadening toward the center of L1544 are predicted by the model. This is evidence in favour of the idea that amipolar diffusion across field lines is one of the basic processes leading to gravitational collapse. However, line widths are significantly narrower than observed and are better reproduced by the Myers & Zweibel (2001) model which considers the quasistatic vertical contraction of a layer due to dissipation of its Alfvenic turbulence, indicating the importance of this process for cores in the verge of forming a star.Comment: 24 pages, 9 figures, to be published in Ap

Silicon isotopic abundance toward evolved stars and its application for presolar grains

Galactic chemical evolution (GCE) is important for understanding the composition of the present-day interstellar medium (ISM) and of our solar system. In this paper, we aim to track the GCE by using the 29Si/30Si ratios in evolved stars and tentatively relate this to presolar grain composition. We used the APEX telescope to detect thermal SiO isotopologue emission toward four oxygen-rich M-type stars. Together with the data retrieved from the Herschel science archive and from the literature, we were able to obtain the 29Si/30Si ratios for a total of 15 evolved stars inferred from their optically thin 29SiO and 30SiO emission. These stars cover a range of masses and ages, and because they do not significantly alter 29Si/30Si during their lifetimes, they provide excellent probes of the ISM metallicity (or 29Si/30Si ratio) as a function of time. The 29Si/30Si ratios inferred from the thermal SiO emission tend to be lower toward low-mass oxygen-rich stars (e.g., down to about unity for W Hya), and close to an interstellar or solar value of 1.5 for the higher-mass carbon star IRC+10216 and two red supergiants. There is a tentative correlation between the 29Si/30Si ratios and the mass-loss rates of evolved stars, where we take the mass-loss rate as a proxy for the initial stellar mass or current stellar age. This is consistent with the different abundance ratios found in presolar grains. We found that older objects (up to possibly 10 Gyr old) in our sample trace a previous, lower 29Si/30Si value of about 1. Material with this isotopic ratio is present in two subclasses of presolar grains, providing independent evidence of the lower ratio. Therefore, the 29Si/30Si ratio derived from the SiO emission of evolved stars is a useful diagnostic tool for the study of the GCE and presolar grains.Comment: 7 pages, 4 figure

Undergraduate work placements: an analysis of the effects on career progression

Combining work experience with degree-level study is seen as a key differentiator for securing employment upon graduation in a competitive employment market. The positive benefits of sandwich courses, where up to twelve months is spent working in industry, are widely acknowledged in academic literature though data analysis tends to focus on cohorts in single subject areas with course-based factors possibly influencing outcomes. This paper explores the benefits of work placements on a cross-cohort basis with an institutional level study empirically analysing over three academic years the outcomes for placement students in comparison to non-placement students. The study found that completing a sandwich work placement is associated with improved academic performance in the final year of study. Placement students are also more likely to secure appropriate graduate-level work and higher starting salaries upon completion of their degree in comparison to non-placement students

Limitations of focussing on homophobic, biphobic and transphobic ‘bullying’ to understand and address LGBT young people’s experiences within and beyond school

This paper presents new empirical data that highlight how a focus on ‘bullying’ is too limited and narrow when thinking about homophobia, biphobia and transphobia that young people may experience. The paper draws on two recent studies with young lesbian, gay, bisexual and trans participants, which each identified issues and experiences not readily captured within dominant bullying discourses and understandings. Findings are examined within three sections: beyond ‘bullying’, questioning inevitability, and (in)appropriate responses. In conclusion, I set out some implications and suggestions for the development of practice and future research concerning homophobia, biphobia and transphobia in youth settings