Evaluation of data for atmospheric models: master equation/RRKM calculations on the combination reaction, BrO+NO2 -> BrONO2, a conundrum

Experimental data for the title reaction were modeled using master equation (ME)/RRKM methods based on the Multiwell suite of programs. The starting point for the exercise was the empirical fitting provided by the NASA (Sander, S. P.; Finlayson-Pitts, B. J.; Friedl, R. R.; Golden, D. M.; Huie, R. E.; Kolb, C. E.; Kurylo, M. J.; Molina, M. J.; Moortgat, G. K.; Orkin, V. L.; Ravishankara, A. R. Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation Number 15; Jet Propulsion Laboratory: Pasadena, California, 2006)(1) and IUPAC (Atkinson, R.; Baulch, D. L.; Cox, R. A.: R. F. Hampson, J.; Kerr, J. A.; Rossi, M. J.; Troe, J. J. Phys. Chem. Ref. Data. 2000, 29, 167) 2 data evaluation panels, which represents the data in the experimental pressure ranges rather well. Despite the availability of quite reliable parameters for these calculations (molecular vibrational frequencies (Parthiban, S.; Lee, T. J. J. Chem. Phys. 2000, 113, 145)3 and a. value (Orlando, J. J.; Tyndall, G. S. J. Phys. Chem. 1996, 100,. 19398)4 of the bond dissociation energy, D-298(BrO-NO2) = 118 kJ mol(-1), corresponding to Delta H-0(circle) = 114.3 kJ mol(-1) at 0 K) and the use of RRKM/ME methods, fitting calculations to the reported data or the empirical equations was anything but straightforward. Using these molecular parameters resulted in a discrepancy between the calculations and the database of rate constants of a factor of ca. 4 at, or close to, the low-pressure limit. Agreement between calculation and experiment could be achieved in two ways, either by increasing Delta H-0(circle) to an unrealistically high value (149.3 kJ mol(-1)) or by increasing , the average energy transferred in a downward collision, to an unusually large value (> 5000 cm(-1)). The discrepancy could also be reduced by making all overall rotations fully active. The system was relatively insensitive to changing the moments of inertia in the transition state to increase the centrifugal effect. The possibility of involvement of BrOONO was tested and cannot account for the difficulties of fitting the data.

Condition number estimates for combined potential integral operators in acoustics and their boundary element discretisation

We consider the classical coupled, combined-field integral equation formulations for time-harmonic acoustic scattering by a sound soft bounded obstacle. In recent work, we have proved lower and upper bounds on the $L^2$ condition numbers for these formulations, and also on the norms of the classical acoustic single- and double-layer potential operators. These bounds to some extent make explicit the dependence of condition numbers on the wave number $k$, the geometry of the scatterer, and the coupling parameter. For example, with the usual choice of coupling parameter they show that, while the condition number grows like $k^{1/3}$ as $k\to\infty$, when the scatterer is a circle or sphere, it can grow as fast as $k^{7/5}$ for a class of `trapping' obstacles. In this paper we prove further bounds, sharpening and extending our previous results. In particular we show that there exist trapping obstacles for which the condition numbers grow as fast as $\exp(\gamma k)$, for some $\gamma>0$, as $k\to\infty$ through some sequence. This result depends on exponential localisation bounds on Laplace eigenfunctions in an ellipse that we prove in the appendix. We also clarify the correct choice of coupling parameter in 2D for low $k$. In the second part of the paper we focus on the boundary element discretisation of these operators. We discuss the extent to which the bounds on the continuous operators are also satisfied by their discrete counterparts and, via numerical experiments, we provide supporting evidence for some of the theoretical results, both quantitative and asymptotic, indicating further which of the upper and lower bounds may be sharper.

The distribution of the ring current: Cluster observations

Extending previous studies, a full-circle investigation of the ring current has been made using Cluster 4-spacecraft observations near perigee, at times when the Cluster array had relatively small separations and nearly regular tetrahedral configurations, and when the Dst index was greater than −30 nT (non-storm conditions). These observations result in direct estimations of the near equatorial current density at all magnetic local times (MLT) for the first time and with sufficient accuracy, for the following observations. The results confirm that the ring current flows westward and show that the in situ average measured current density (sampled in the radial range accessed by Cluster 4–4.5RE) is asymmetric in MLT, ranging from 9 to 27 nAm−2. The direction of current is shown to be very well ordered for the whole range of MLT. Both of these results are in line with previous studies on partial ring extent. The magnitude of the current density, however, reveals a distinct asymmetry: growing from 10 to 27 nAm−2 as azimuth reduces from about 12:00MLT to 03:00 and falling from 20 to 10 nAm−2 less steadily as azimuth reduces from 24:00 to 12:00MLT. This result has not been reported before and we suggest it could reflect a number of effects. Firstly, we argue it is consistent with the operation of region-2 field aligned-currents (FACs), which are expected to flow upward into the ring current around 09:00MLT and downward out of the ring current around 14:00MLT. Secondly, we note that it is also consistent with a possible asymmetry in the radial distribution profile of current density (resulting in higher peak at 4– 4.5RE). We note that part of the enhanced current could reflect an increase in the mean AE activity (during the periods in which Cluster samples those MLT).

The dependence of contrail formation on the weather pattern and altitude in the North Atlantic

Aircraft flying through cold ice-supersaturated air produce persistent contrails which contribute to the climate impact of aviation. Here, we demonstrate the importance of the weather situation, together with the route and altitude of the aircraft through this, on estimating contrail coverage. The results have implications for determining the climate impact of contrails as well as potential mitigation strategies. Twenty-one years of re-analysis data are used to produce a climatological assessment of conditions favorable for persistent contrail formation between 200 and 300 hPa over the north Atlantic in winter. The seasonal-mean frequency of cold ice-supersaturated regions is highest near 300 hPa, and decreases with altitude. The frequency of occurrence of ice-supersaturated regions varies with large-scale weather pattern; the most common locations are over Greenland, on the southern side of the jet stream and around the northern edge of high pressure ridges. Assuming aircraft take a great circle route, as opposed to a more realistic time-optimal route, is likely to lead to an error in the estimated contrail coverage, which can exceed 50% for westbound north Atlantic flights. The probability of contrail formation can increase or decrease with height, depending on the weather pattern, indicating that the generic suggestion that flying higher leads to fewer contrails is not robust.

Lorrie Moore: Mo(o)re than an interim assessment

Lorrie Moore has long shed the image of the precocious talent who won the Seventeen story prize with her first submission as a nineteen-year-old undergraduate, but there is still a sense that her best work may be yet to come. In that respect, this mini special issue represents by no means the final word on Moore, but rather an interim assessment of a career that is already substantial and that promises much more to come. Together these three essays (and introduction) offer a coherent and striking exploration of Moore's work that develops new directions for future criticism and will help cement her growing reputation as one of the most original and distinctive contemporary writers. They sometimes circle around the same stories, even the same quotations, reading them in a variety of frames and picking up (and at) the nuances of Moore's sustained wordplay and careful documenting of space, of identity, of gender. Thus these essays work together rather than separately, layering over multiple understandings of Moore's incisive American literature.

Roll of the rhythmic component in the proactive control of a human hand

In terms of evolution, the strategy of catching prey would have been an important part of survival in a constantly changing environment. A prediction mechanism would have developed to compensate for any delay in the sensory-motor system. In a previous study, “proactive control” was found, in which the motion of the hands preceded the virtual moving target. These results implied that the positive phase shift of the hand motion represents the proactive nature of the visual-motor control system, which attempts to minimize the brief error in the hand motion when the target changes position unexpectedly. In our study, a visual target moves in circle (13 cm diameter) on a computer screen, and each subject is asked to keep track of the target’s motion by the motion of a cursor. As the frequency of the target increases, a rhythmic component was found in the velocity of the cursor in spite of the fact that the velocity of the target was constant. The generation of a rhythmic component cannot be explained simply as a feedback mechanism for the phase shifts of the target and cursor in a sensory-motor system. Therefore, it implies that the rhythmic component was generated to predict the velocity of the target, which is a feed-forward mechanism in the sensory-motor system. Here, we discuss the generation of the rhythmic component and its roll in the feed-forward mechanism.

Evaluation of a boundary integral representation for the conformal mapping of the unit disk onto a simply-connected domain

A representation of the conformal mapping g of the interior or exterior of the unit circle onto a simply-connected domain Ω as a boundary integral in terms ofƒ|∂Ω is obtained, whereƒ :=g -l. A product integration scheme for the approximation of the boundary integral is described and analysed. An ill-conditioning problem related to the domain geometry is discussed. Numerical examples confirm the conclusions of this discussion and support the analysis of the quadrature scheme.

A self-similar expansion model for use in solar wind transient propogation studies

Since the advent of wide-angle imaging of the inner heliosphere, a plethora of techniques have been developed to investigate the three-dimensional structure and kinematics of solar wind transients, such as coronal mass ejections, from their signatures in single- and multi-spacecraft imaging observations. These techniques, which range from the highly complex and computationally intensive to methods based on simple curve fitting, all have their inherent advantages and limitations. In the analysis of single-spacecraft imaging observations, much use has been made of the fixed φ fitting (FPF) and harmonic mean fitting (HMF) techniques, in which the solar wind transient is considered to be a radially propagating point source (fixed φ, FP, model) and a radially expanding circle anchored at Sun centre (harmonic mean, HM, model), respectively. Initially, we compare the radial speeds and propagation directions derived from application of the FPF and HMF techniques to a large set of STEREO/Heliospheric Imager (HI) observations. As the geometries on which these two techniques are founded constitute extreme descriptions of solar wind transients in terms of their extent along the line of sight, we describe a single-spacecraft fitting technique based on a more generalized model for which the FP and HM geometries form the limiting cases. In addition to providing estimates of a transient’s speed and propagation direction, the self-similar expansion fitting (SSEF) technique provides, in theory, the capability to estimate the transient’s angular extent in the plane orthogonal to the field of view. Using the HI observations, and also by performing a Monte Carlo simulation, we assess the potential of the SSEF technique.

Bootstrap prediction intervals for autoregressive time series

The calculation of interval forecasts for highly persistent autoregressive (AR) time series based on the bootstrap is considered. Three methods are considered for countering the small-sample bias of least-squares estimation for processes which have roots close to the unit circle: a bootstrap bias-corrected OLS estimator; the use of the Roy–Fuller estimator in place of OLS; and the use of the Andrews–Chen estimator in place of OLS. All three methods of bias correction yield superior results to the bootstrap in the absence of bias correction. Of the three correction methods, the bootstrap prediction intervals based on the Roy–Fuller estimator are generally superior to the other two. The small-sample performance of bootstrap prediction intervals based on the Roy–Fuller estimator are investigated when the order of the AR model is unknown, and has to be determined using an information criterion.

The absent body: representations of dying early modern women in a selection of seventeenth-century diaries

This article seeks to explore the absence of the body in the depiction of dying women in a selection of seventeenth-century diaries. It considers the cultural forces that made this absence inevitable, and the means by which the physical body was replaced in death by a spiritual presence. The elevation of a dying woman from physical carer to spiritual nurturer in the days before death ensured that gender codes were not broken. The centrality of the body of the dying woman, within a female circle of care and support, was paradoxically juxtaposed with an effacement of the body in descriptions of a good death. In death, a woman might achieve the stillness, silence and compliance so essential to perfect early modern womanhood, and retrospective diary entries can achieve this ideal by replacing the body with images that deflect from the essential physicality of the woman.