8,340 research outputs found
Complexes of iron and cobalt with new tripodal amido-polyphosphine hybrid ligands
Divalent complexes of iron and cobalt with new, monoanionic tripodal amido-polyphosphine ligands have been thoroughly characterized, and XRD analysis reveals geometries that are distinct for this class of ligand
Using baseline-dependent window functions for data compression and field-of-interest shaping in radio interferometry
In radio interferometry, observed visibilities are intrinsically sampled at
some interval in time and frequency. Modern interferometers are capable of
producing data at very high time and frequency resolution; practical limits on
storage and computation costs require that some form of data compression be
imposed. The traditional form of compression is a simple averaging of the
visibilities over coarser time and frequency bins. This has an undesired side
effect: the resulting averaged visibilities "decorrelate", and do so
differently depending on the baseline length and averaging interval. This
translates into a non-trivial signature in the image domain known as
"smearing", which manifests itself as an attenuation in amplitude towards
off-centre sources. With the increasing fields of view and/or longer baselines
employed in modern and future instruments, the trade-off between data rate and
smearing becomes increasingly unfavourable. In this work we investigate
alternative approaches to low-loss data compression. We show that averaging of
the visibility data can be treated as a form of convolution by a boxcar-like
window function, and that by employing alternative baseline-dependent window
functions a more optimal interferometer smearing response may be induced. In
particular, we show improved amplitude response over a chosen field of
interest, and better attenuation of sources outside the field of interest. The
main cost of this technique is a reduction in nominal sensitivity; we
investigate the smearing vs. sensitivity trade-off, and show that in certain
regimes a favourable compromise can be achieved. We show the application of
this technique to simulated data from the Karl G. Jansky Very Large Array (VLA)
and the European Very-long-baseline interferometry Network (EVN)
Detecting Vanishing Dimensions Via Primordial Gravitational Wave Astronomy
Lower-dimensionality at higher energies has manifold theoretical advantages
as recently pointed out. Moreover, it appears that experimental evidence may
already exists for it - a statistically significant planar alignment of events
with energies higher than TeV has been observed in some earlier cosmic ray
experiments. We propose a robust and independent test for this new paradigm.
Since (2+1)-dimensional spacetimes have no gravitational degrees of freedom,
gravity waves cannot be produced in that epoch. This places a universal maximum
frequency at which primordial waves can propagate, marked by the transition
between dimensions. We show that this cut-off frequency may be accessible to
future gravitational wave detectors such as LISA.Comment: Somewhat expanded version with discussions that could not fit into
the PRL version; references adde
Thermal decomposition of RDX from reactive molecular dynamics
We use the recently developed reactive force field ReaxFF with molecular dynamics to study thermal induced chemistry in RDX [cyclic-[CH2N(NO2)]3] at various temperatures and densities. We find that the time evolution of the potential energy can be described reasonably well with a single exponential function from which we obtain an overall characteristic time of decomposition that increases with decreasing density and shows an Arrhenius temperature dependence. These characteristic timescales are in reasonable quantitative agreement with experimental measurements in a similar energetic material, HMX [cyclic-[CH2N(NO2)]4]. Our simulations show that the equilibrium population of CO and CO2 (as well as their time evolution) depend strongly of density: at low density almost all carbon atoms form CO molecules; as the density increases larger aggregates of carbon appear leading to a C deficient gas phase and the appearance of CO2 molecules. The equilibrium populations of N2 and H2O are more insensitive with respect to density and form in the early stages of the decomposition process with similar timescales
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Changes in alpine plant growth under future climate conditions
Alpine shrub- and grasslands are shaped by extreme climatic conditions such as a long-lasting snow cover and a short vegetation period. Such ecosystems are expected to be highly sensitive to global environmental change. Prolonged growing seasons and shifts in temperature and precipitation are likely to affect plant phenology and growth. In a unique experiment, climatology and plant growth was monitored for almost a decade at 17 snow meteorological stations in different alpine regions along the Swiss Alps. Regression analyses revealed highly significant correlations between mean air temperature in May/June and snow melt out, onset of plant growth, and plant height. These correlations were used to project plant growth phenology for future climate conditions based on the gridded output of a set of regional climate models runs. Melt out and onset of growth were projected to occur on average 17 days earlier by the end of the century than in the control period from 1971–2000 under the future climate conditions of the low resolution climate model ensemble. Plant height and biomass production were expected to increase by 77% and 45%, respectively. The earlier melt out and onset of growth will probably cause a considerable shift towards higher growing plants and thus increased biomass. Our results represent the first quantitative and spatially explicit estimates of climate change impacts on future growing season length and the respective productivity of alpine plant communities in the Swiss Alps
Changes in alpine plant growth under future climate conditions
Alpine shrub- and grasslands are shaped by extreme climatic conditions such as a long-lasting snow cover and a short vegetation period. Such ecosystems are expected to be highly sensitive to global environmental change. Prolonged growing seasons and shifts in temperature and precipitation are likely to affect plant phenology and growth. In a unique experiment, climatology and plant growth was monitored for almost a decade at 17 snow meteorological stations in different alpine regions along the Swiss Alps. Regression analyses revealed highly significant correlations between mean air temperature in May/June and snow melt out, onset of plant growth, and plant height. These correlations were used to project plant growth phenology for future climate conditions based on the gridded output of a set of regional climate models runs. Melt out and onset of growth were projected to occur on average 17 days earlier by the end of the century than in the control period from 1971–2000 under the future climate conditions of the low resolution climate model ensemble. Plant height and biomass production were expected to increase by 77% and 45%, respectively. The earlier melt out and onset of growth will probably cause a considerable shift towards higher growing plants and thus increased biomass. Our results represent the first quantitative and spatially explicit estimates of climate change impacts on future growing season length and the respective productivity of alpine plant communities in the Swiss Alps
Fe(I)-Mediated Reductive Cleavage and Coupling of CO_2:  An Fe^(II)(μ-O,μ-CO)Fe^(II) Core
THF solutions of a new iron(I) source, [PhBP^(CH2_Cy_3)]Fe ([PhBP^(CH_2Cy_3)] = [PhBP(CH_2P(CH_2Cy)_2)_3]-), effect the reductive cleavage of CO_2 via O-atom transfer at ambient temperature. The dominant reaction pathway is bimetallic and leads to the formation of a structurally unprecedented diiron Fe^(II)(ÎĽ-O)(ÎĽ-CO)Fe^(II) core. X-ray data are also available to suggest that bimetallic reductive CO_2 coupling to generate oxalate occurs as a minor reaction pathway. These initial observations forecast a diverse reaction landscape between CO_2 and iron(I) synthons
CO_2 reduction by Fe(I): solvent control of C-O cleavage versus C-C coupling
This manuscript explores the product distribution of the reaction of carbon dioxide with reactive iron(I)
complexes supported by tris(phosphino)borate ligands, [PhBP^R_3]- ([PhBP^R_3]- =[PhB(CH_2PR_2)_3]-; R = CH_2Cy,Ph, ^iPr, mter; mter = 3,5-meta-terphenyl). Our studies reveal an interesting and unexpected role for the
solvent medium with respect to the course of the CO_2 activation reaction. For instance, exposure of
methylcyclohexane (MeCy) solutions of [PhBP^(CH_2Cy)_3 ]Fe(PR’_3) to CO_2 yields the partial decarbonylation product
{[PhBP^(CH_2Cy)_3 ]Fe}_2(µ-O)(µ-CO). When the reaction is instead carried out in benzene or THF, reductive coupling of CO_2 occurs to give the bridging oxalate species {[PhBP^(CH_2Cy_3 ]Fe}_2(µ- κOO’: κOO’-oxalato).
Reaction studies aimed at understanding this solvent effect are presented, and suggest that the product
profile is ultimately determined by the ability of the solvent to coordinate the iron center. When more
sterically encumbering auxiliary ligands are employed to support the iron(I) center (i.e., [PhBP^(Ph)_3]- and [PhBP^(iPr)_3 ]-), complete decarbonylation is observed to afford structurally unusual diiron(II) products of the
type {[PhBP^R_3]Fe}_2(µ-O). A mechanistic hypothesis that is consistent with the collection of results described is offered, and suggests that reductive coupling of CO_2 likely occurs from an electronically saturated
“Fe^(II)–CO_2-” species
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