��-dimerization of pleiadiene radical cations at low temperatures revealed by UV���vis spectroelectrochemistry and quantum theory

One-electron oxidation of the non-alternant polycyclic aromatic hydrocarbon pleiadiene and related cyclohepta[ c,d]pyrene and cyclohepta[c,d]fluoranthene in THF produces corresponding radical cations detectable in the temperature range of 293���263 K only on the subsecond time scale of cyclic voltammetry. Although the EPR-active red-coloured pleiadiene radical cation is stable according to the literature in concentrated sulfuric acid, spectroelectrochemical measurements reported in this study provide convincing evidence for its facile conversion into the green-coloured, formally closed shell and, hence, EPRsilent ��-bound dimer dication stable in THF at 253 K. The unexpected formation of the thermally unstable dimeric product featuring a characteristic intense low-energy absorption band at 673 nm (1.84 eV; log��max=4.0) is substantiated by ab initio calculations on the parent pleiadiene molecule and the PF6 ��� salts of the corresponding radical cation and dimer dication. The latter is stabilized with respect to the radical cation by 14.40 kcal mol���1 (DFT B3LYP) [37.64 kcal mol���1 (CASPT2/DFT B3LYP)]. An excellent match has been obtained between the experimental and TDDFT- calculated UV���vis spectra of the PF6 ��� salt of the pleiadiene dimer dication, considering solvent (THF) effects.

A new source of suprathermal O+ions near the dayside polar cap boundary

A new dayside source of O+ ions for the polar magnetosphere is described, and a statistical survey presented of upward flows of O+ ions using 2 years of data from the retarding ion mass spectrometer (RIMS) experiment on board DE 1, at geocentric distances below 3 RE and invariant latitudes above 40��. The flows are classified according to their spin angle distributions. It is believed that the spacecraft potential near perigee is generally less than +2 V, in which case the entire O+ population at energies below about 60 eV is sampled. Examples are given of field-aligned flow and of transversely accelerated ���core��� O+ ions; in the latter events a large fraction of the total O+ ion population has been transversely accelerated, and in some extreme cases all the observed ions (of all ion species) have been accelerated, and no residual cold population is observed (���toroidal��� distributions). However, by far the most common type of O+ upflow seen by DE RIMS lies near the dayside polar cap boundary (particularly in the prenoon sector) and displays an asymmetric spin angle distribution. In such events the ions carry an upward heat flux, and strong upflow of all species is present (H+, He+, O+, O++, and N+ have all been observed with energies up to about 30 eV, but with the majority of ions below about 2 eV); hence, these have been termed upwelling ion events. The upwelling ions are embedded in larger regions of classical light ion polar wind and are persistently found under the following conditions: at geocentric distances greater than 1.4 RE; at all Kp in summer, but only at high Kp in winter. Low-energy conical ions (<30 eV) are only found near the equatorial edge of the events, the latitude of which moves equatorward with increasing Kp and is highly correlated with the location of field-aligned currents. The RIMS data are fully consistent with a ���mass spectrometer effect,��� whereby light ions and the more energetic O+ ions flow into the lobes and mantle and hence the far-tail plasma sheet, but lower-energy O+ is swept across the polar cap by the convection electric field, potentially acting as a source for the nightside auroral acceleration regions. The occurrence probability of upwelling ion events, as compared to those of low-altitude transversely accelerated core ions and of field-aligned flow, suggests this could be the dominant mechanism for supplying the nightside auroral acceleration region, and subsequently the ring current and near-earth plasma sheet, with ionospheric O+ ions. It is shown that the total rate of O+ outflow in upwelling ion events (greater than 10^25 s^{���1}) is sufficient for the region near the dayside polar cap boundary to be an important ionospheric heavy ion source.

Intersections of Jane Jacobs��� conditions for diversity and low-carbon urban systems: a look at four global cities

Countless cities are rapidly developing across the globe, pressing the need for clear urban planning and design recommendations geared towards sustainability. This article examines the intersections of Jane Jacobs��� four conditions for diversity with low-carbon and low-energy use urban systems in four cities around the world: Lyon (France), Chicago (United-States), Kolkata (India), and Singapore (Singapore). After reviewing Jacobs��� four conditions for diversity, we introduce the four cities and describe their historical development context. We then present a framework to study the cities along three dimensions: population and density, infrastructure development/use, and climate and landscape. These cities differ in many respects and their analysis is instructive for many other cities around the globe. Jacobs��� conditions are present in all of them, manifested in different ways and to varying degrees. Overall we find that the adoption of Jacobs' conditions seems to align well with concepts of low-carbon urban systems, with their focus on walkability, transit-oriented design, and more efficient land use (i.e., smaller unit sizes). Transportation sector emissions seems to demonstrate a stronger influence from the presence of Jacobs' conditions, while the link was less pronounced in the building sector. Kolkata, a low-income, developing world city, seems to possess many of Jacobs' conditions, while exhibiting low per capita emissions - maintaining both of these during its economic expansion will take careful consideration. Greenhouse gas mitigation, however, is inherently an in situ problem and the first task must therefore be to gain local knowledge of an area before developing strategies to lower its carbon footprint.

The atomic structure of low-index surfaces of the intermetallic compound InPd

The intermetallic compound InPd (CsCl type of crystal structure with a broad compositional range) is considered as a candidate catalyst for the steam reforming of methanol. Single crystals of this phase have been grown to study the structure of its three low-index surfaces under ultra-high vacuum conditions, using low energy electron diffraction (LEED), X-ray photoemission spectroscopy (XPS), and scanning tunneling microscopy (STM). During surface preparation, preferential sputtering leads to a depletion of In within the top few layers for all three surfaces. The near-surface regions remain slightly Pd-rich until annealing to ���580 K. A transition occurs between 580 and 660 K where In segregates towards the surface and the near-surface regions become slightly In-rich above ���660 K. This transition is accompanied by a sharpening of LEED patterns and formation of flat step-terrace morphology, as observed by STM. Several superstructures have been identified for the different surfaces associated with this process. Annealing to higher temperatures (���750 K) leads to faceting via thermal etching as shown for the (110) surface, with a bulk In composition close to the In-rich limit of the existence domain of the cubic phase. The Pd-rich InPd(111) is found to be consistent with a Pd-terminated bulk truncation model as shown by dynamical LEED analysis while, after annealing at higher temperature, the In-rich InPd(111) is consistent with an In-terminated bulk truncation, in agreement with density functional theory (DFT) calculations of the relative surface energies. More complex surface structures are observed for the (100) surface. Additionally, individual grains of a polycrystalline sample are characterized by micro-spot XPS and LEED as well as low-energy electron microscopy. Results from both individual grains and ���global��� measurements are interpreted based on comparison to our single crystals findings, DFT calculations and previous literature.