Competitive partitioning of rotational energy in gas ensemble equilibration

A wide-ranging computational study of equilibration in binary mixtures of diatomic gases reveals the existence of competition between the constituent species for the orbital angular momentum and energy available on collision with the bath gas. The ensembles consist of a bath gas AB(v;j), and a highly excited minor component CD(v';j'), present in the ratio AB:CD = 10:1. Each ensemble contains 8000 molecules. Rotational temperatures (T(r)) are found to differ widely at equilibration with T(r)(AB)/T(r)(CD) varying from 2.74 to 0.92, indicating unequal partitioning of rotational energy and angular momentum between the two species. Unusually, low values of T(r) are found generally to be associated with diatomics of low reduced mass. To test effects of the equi-partition theorem on low T(r) we undertook calculations on HF(6;4) in N(2)(0;10) over the range 100-2000 K. No significant change in T(r)(N2)/T(r)(HF) was found. Two potential sources of rotational inequality are examined in detail. The first is possible asymmetry of -Δj and +Δj probabilities for molecules in mid- to high j states resulting from the quadratic dependence of rotational energy on j. The second is the efficiency of conversion of orbital angular momentum, generated on collision with bath gas molecules, into molecular rotation. Comparison of these two possible effects with computed T(r)(AB)/T(r)(CD) shows the efficiency factor to be an excellent predictor of partitioning between the two species. Our finding that T(r) values for molecules such as HF and OH are considerably lower than other modal temperatures suggests that the determination of gas ensemble temperatures from Boltzmann fits to rotational distributions of diatomics of low reduced mass may require a degree of caution

Kinetics and mechanism of the reaction between atomic chlorine and dimethyl selenide; comparison with the reaction between atomic chlorine and dimethyl sulfide

Dimethyl selenide is the most abundant gaseous selenium species in marine environments. In this work, the value of the rate coefficient for the gas-phase reaction between dimethyl selenide and Cl atoms has been determined for the first time. The value of the second-order rate coefficient obtained was (5.0±1.4)×10–10 cm3 molecule–1 s–1. The very fast nature of the reaction means that, when estimating the lifetime of dimethyl selenide in the atmosphere, loss due to reaction with Cl atoms should be considered along with loss due to reaction with O3 and with OH and NO3 radicals. Analysis of the available kinetic data suggests that at 760 Torr the dominant reaction pathway for the reaction of Cl atoms with dimethyl selenide will be the addition of Cl to the Se atom forming an adduct of the type CH3Se(Cl)CH3. Theoretical calculations, at the B3LYP/6-311++G(2df,p)//B3LYP/6-311++G(d,p) level of theory, show that at 298 K the value of rH for the formation of the adduct is –111.4 kJ mol–1. This value may be compared to –97.0 kJ mol–1, the value calculated for rH for the formation of the analogous sulfur adduct, CH3S(Cl)CH3, following the reaction between Cl atoms and dimethyl sulfide. Variational RRKM theory was used to predict the thermal decomposition rates of the two adducts back to starting materials. The estimated rate constant for the decomposition of the selenium adduct to the reactants is 5×10–5 s–1, compared to 0.02 s–1 in the case of the sulfur adduct. However, our calculations suggest that the CH3Se(Cl)CH3 adduct, which is initially formed highly excited, will not be stabilised under atmospheric conditions, but rather will decompose to yield CH3SeCl and CH3, a process that is calculated to be exothermic with respect to the initial reactants by 5.8 kJ mol–1. The formation of CH3SCl and CH3 from the sulfur adduct, on the other hand, is endothermic by 20.8 kJ mol–1 with respect to the initial reactants, and is thus not expected to occur

Wolf, Canis lupus, Behavior in Areas of Frequent Human Activity

We report incidental observations of Wolves (Canis lupus) tolerating human activity in central Wisconsin. Three monitored packs raised pups in close proximity to varying levels of human activity. Wolf pups were raised <350m from rearing pens of the endangered Whooping Crane (Grus americana), which saw daily human activity. One pack used cornfields as rendezvous sites within 175 m of a maintenance shed visited regularly by workers. Another pack centered their activities along a well-traveled state highway using both the verge and the road center for activity. Aerial locations of 10 yearling and adult dispersing Wolves were plotted to evalute human densities in natal territories relative to dispersal and post-dispersal territories. Township densities (mean = 9.02 humans/km2, SE = 4.015) and residential densities (mean = 5.59 housing units/km2, SE = 2.12 ) in natal pack territories were significantly greater (P <.01) for dispersal and post-dispersal township densities (mean = 43.98 humans/km2, SE =7.37) and residence densities (mean = 23.12 housing units/km2, SE =3.49). Furthermore, a pup negotiated the densely populated region of northern Illinois and dispersed from central Wisconsin to east-central Indiana, a distance of at least 690 km. As Wolves live in closer proximity to humans, living in areas of higher township and residential densities, they can be expected to be more habituated to people, increasing the probability of human/Wolf conflicts

On the Weak-Wind Problem in Massive Stars: X-ray Spectra Reveal a Massive Hot Wind in \mu\ Columbae

\mu\ Columbae is a prototypical weak-wind O-star for which we have obtained a high-resolution X-ray spectrum with the Chandra LETG/ACIS-S instrument and a low resolution spectrum with Suzaku. This allows us, for the first time, to investigate the role of X-rays on the wind structure in a bona fide weak-wind system and to determine whether there actually is a massive, hot wind. The X-ray emission measure indicates that the outflow is an order of magnitude greater than that derived from UV lines and is commensurate with the nominal wind-luminosity relationship for O-stars. Therefore, the ``weak-wind problem''---identified from cool wind UV/optical spectra---is largely resolved by accounting for the hot wind seen in X-rays. From X-ray line profiles, Doppler shifts, and relative strengths, we find that this weak-wind star is typical of other late O dwarfs. The X-ray spectra do not suggest a magnetically confined plasma---the spectrum is soft and lines are broadened; Suzaku spectra confirm the lack of emission above 2 keV. Nor do the relative line shifts and widths suggest any wind decoupling by ions. The He-like triplets indicate that the bulk of the X-ray emission is formed rather close to the star, within 5 stellar radii. Our results challenge the idea that some OB stars are ``weak-wind'' stars that deviate from the standard wind-luminosity relationship. The wind is not weak, but it is hot and its bulk is only detectable in X-rays.Comment: Accepted for publication in ApJ Letter

A Nova Web Application for Population Viability and Sustainable Harvesting Analyses

Population viability analyses are used to assess the probability that a particular population of individuals will persist as a self-reproducing, ecologically viable entity for a specified period of time. Such models are typically cast as Markov processes that may inter alia include demographic structure (e.g. age, stage, sex), ecological processes through the incorporation of density-dependent reproduction or survival functions, viability thresholds that trigger remedial interventions when breached (e.g. removal of individuals to protect environments), metapopulation structure, stocking, harvesting or translocations of the population. These models can also be used to assess the impacts of harvesting strategies when they include population removal options. Here we present a general Nova modeling framework that integrates all of the above features and generates distributions of outcomes through repeated simulations. The framework incorporates the most relevant ecosystem structures, including metapopulation structure with associated connectivity and movement parameters, age/stage class structure with population-specific life history data, demographic and environmental stochasticity components, and management interventions including off-take, translocation, and stocking components. The NOVA PVA model is available as a responsively configured web application that can be run locally in a browser or on high performance computing systems controlled by a browser-based dashboard. In this talk the structure of the model will be discussed and the operation of the web application will be demonstrated

What We Share Is Who We Are and What We Do: How Emotional Intimacy Shapes Organizational Identification and Collaborative Behaviors

Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/155930/1/apps12208_am.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/155930/2/apps12208.pd