Measurements of Rate Coefficients for Reactions of OH with Ethanol and Propan-2-ol at Very Low Temperatures.

The low temperature kinetics of the reactions of OH with ethanol and propan-2-ol have been studied using a pulsed Laval nozzle apparatus coupled with pulsed laser photolysis-laser-induced fluorescence (PLP-LIF) spectroscopy. The rate coefficients for both reactions have been found to increase significantly as the temperature is lowered, by approximately a factor of 18 between 293 and 54 K for ethanol, and by ∼10 between 298 and 88 K for OH + propan-2-ol. The pressure dependence of the rate coefficients provides evidence for two reaction channels: a zero pressure bimolecular abstraction channel leading to products and collisional stabilization of a weakly bound OH-alcohol complex. The presence of the abstraction channel at low temperatures is rationalized by a quantum mechanical tunneling mechanism, most likely through the barrier to hydrogen abstraction from the OH moiety on the alcohol

HO2 + NO2: Kinetics, Thermochemistry, and Evidence for a Bimolecular Product Channel

A master equation (ME) analysis of available experimental data has been carried out on the reaction HO2 + NO2 + M ⇋ HO2NO2 + M (1a)/(−1a). The analysis, based on the ME code MESMER, uses both the association and dissociation kinetic data from the literature, and provides improved thermochemistry on reaction 1a. Our preferred model assigns two low-frequency vibrations of HO2NO2 as hindered rotors and couples these to the external rotations. This model gives ΔrH°0(1a) = −93.9 ± 1.0 kJ mol–1, which implies that ΔfH°0 HO2NO2 = −42.0 ± 1.0 kJ mol–1 (uncertainties are 2σ). A significant contributor to the uncertainty derives from modeling the interaction between the internal and external rotors. Using this improved kinetics for reaction 1a/–1a, data at elevated temperatures, 353–423 K, which show no evidence of the expected equilibration, have been reanalyzed, indicating that an additional reaction is occurring that masks the equilibration. Based on a published ab initio study, this additional channel is assigned to the bimolecular reaction HO2 + NO2 → H–NO2 + O2 (1b); H–NO2 is nitryl hydride and has not previously been directly observed in experiments. The output of the master equation analysis has been parametrized and Troe expressions are provided for an improved description of k1a(p,T) and k–1a(p,T)

Structure and superconducting properties of ((Ln(1-x)Ln*(x) 1/2 (Ba(1-y)Sr(y) 1/3 Ce 1/6) 8Cu6O(z)

A variety of new oxide superconductors were prepared. The crystallographic structures of the oxides were all tetragonal and of the (Ln(+), Ce)4(Ln(+),Ba)4Cu6Oz (Ln(+) = Nd, Sm or Eu) type which had been previously discovered by Akimitsu et al. As the Sr content, y, increased when Ln = Ln(excited state) = Nd, the oxygen content, z, monotonically increased and the superconducting transition temperature, T(sub c), varied exhibiting a maximum. When z was controlled directly by means of high oxygen pressure sintering techniques, T(sub c) was changed accordingly. T(sub c's) of samples with different combinations of Ln and Ln(excited state) and different values of x and y were found to depend on the magnitude of the bond valence sum for a Cu atom located in the bottom plane of the Cu-O5 pyramid. Transport and magnetization measurements were carried out to investigate the magnetic field dependence of superconducting properties and to determine the phenomenological parameters. The Hall coefficients were positive below room temperature and varied yielding a maximum with respect to temperature

Low-temperature reactions: Tunnelling in space.

International audienceChemical reactions with activation barriers generally slow to a halt in the extreme cold of dense interstellar clouds. Low-temperature experiments on the reaction of OH with methanol have now shown that below 200 K there is a major acceleration in the rate that can only be explained by enhanced quantum mechanical tunnelling through the barrier

Recent Salmon Declines: A Result of Lost Feeding Opportunities Due to Bad Timing?

As the timing of spring productivity blooms in near-shore areas advances due to warming trends in global climate, the selection pressures on out-migrating salmon smolts are shifting. Species and stocks that leave natal streams earlier may be favoured over later-migrating fish. The low post-release survival of hatchery fish during recent years may be in part due to static release times that do not take the timing of plankton blooms into account. This study examined the effects of release time on the migratory behaviour and survival of wild and hatchery-reared coho salmon (Oncorhynchus kisutch) using acoustic and coded-wire telemetry. Plankton monitoring and near-shore seining were also conducted to determine which habitat and food sources were favoured. Acoustic tags (n = 140) and coded-wire tags (n = 266,692) were implanted into coho salmon smolts at the Seymour and Quinsam Rivers, in British Columbia, Canada. Differences between wild and hatchery fish, and early and late releases were examined during the entire lifecycle. Physiological sampling was also carried out on 30 fish from each release group. The smolt-to-adult survival of coho salmon released during periods of high marine productivity was 1.5- to 3-fold greater than those released both before and after, and the fish's degree of smoltification affected their downstream migration time and duration of stay in the estuary. Therefore, hatchery managers should consider having smolts fully developed and ready for release during the peak of the near-shore plankton blooms. Monitoring chlorophyll a levels and water temperature early in the spring could provide a forecast of the timing of these blooms, giving hatcheries time to adjust their release schedule

ALMA observations of the multiplanet system 61 Vir: What lies outside super-Earth systems?

A decade of surveys has hinted at a possible higher occurrence rate of debris discs in systems hosting low mass planets. This could be due to common favourable forming conditions for rocky planets close in and planetesimals at large radii. In this paper we present the first resolved millimetre study of the debris disc in the 4.6 Gyr old multiplanet system 61 Vir, combining ALMA and JCMT data at 0.86 mm. We fit the data using a parametric disc model, finding that the disc of planetesimals extends from 30 AU to at least 150 AU, with a surface density distribution of millimetre sized grains with a power law slope of 0.1$^{+1.1}_{-0.8}$. We also present a numerical collisional model that can predict the evolution of the surface density of millimetre grains for a given primordial disc, finding that it does not necessarily have the same radial profile as the total mass surface density (as previous studies suggested for the optical depth), with the former being flatter. Finally, we find that if the planetesimal disc was stirred at 150 AU by an additional unseen planet, that planet should be more massive than 10 M$_{\oplus}$ and lie between 10-20 AU. Lower planet masses and semi-major axes down to 4 AU are possible for eccentricities $\gg$ 0.1.This paper makes use of the following ALMA data: ADS/JAO.ALMA#2013.1.00359.S. ALMA is a partnership of ESO (representing its member states), NSF (USA) and NINS (Japan), together with NRC (Canada) and NSC and ASIAA (Taiwan) and KASI (Republic of Korea), in cooperation with the Republic of Chile. The Joint ALMA Observatory is operated by ESO, AUI/NRAO and NAOJ. MCW, LM and AS acknowledge the support of the European Union through ERC grant number 279973. GMK is supported by the Royal Society as a Royal Society University Research Fellow. AS is partially supported by funding from the Center for Exoplanets and Habitable Worlds. The Center for Exoplanets and Habitable Worlds is supported by the Pennsylvania State University, the Eberly College of Science and the Pennsylvania Space Grant Consortium

Exploring human-guided strategies for reaction network exploration: Interactive molecular dynamics in virtual reality as a tool for citizen scientists

The emerging fields of citizen science and gamification reformulate scientific problems as games or puzzles to be solved. Through engaging the wider non-scientific community, significant breakthroughs may be made by analyzing citizen-gathered data. In parallel, recent advances in virtual reality (VR) technology are increasingly being used within a scientific context and the burgeoning field of interactive molecular dynamics in VR (iMD-VR) allows users to interact with dynamical chemistry simulations in real time. Here, we demonstrate the utility of iMD-VR as a medium for gamification of chemistry research tasks. An iMD-VR "game"was designed to encourage users to explore the reactivity of a particular chemical system, and a cohort of 18 participants was recruited to playtest this game as part of a user study. The reaction game encouraged users to experiment with making chemical reactions between a propyne molecule and an OH radical, and "molecular snapshots"from each game session were then compiled and used to map out reaction pathways. The reaction network generated by users was compared to existing literature networks demonstrating that users in VR capture almost all the important reaction pathways. Further comparisons between humans and an algorithmic method for guiding molecular dynamics show that through using citizen science to explore these kinds of chemical problems, new approaches and strategies start to emerge