Mapping the structural diversity of C60 carbon clusters and their infrared spectra

The current debate about the nature of the carbonaceous material carrying the infrared (IR) emission spectra of planetary and proto-planetary nebulae, including the broad plateaus, calls for further studies on the interplay between structure and spectroscopy of carbon-based compounds of astrophysical interest. The recent observation of C60 buckminsterfullerene in space suggests that carbon clusters of similar size may also be relevant. In the present work, broad statistical samples of C60 isomers were computationally determined without any bias using a reactive force field, their IR spectra being subsequently obtained following local optimization with the density-functional-based tight-binding theory. Structural analysis reveals four main structural families identified as cages, planar polycyclic aromatics, pretzels, and branched. Comparison with available astronomical spectra indicates that only the cage family could contribute to the plateau observed in the 6-9 micron region. The present framework shows great promise to explore and relate structural and spectroscopic features in more diverse and possibly hydrogenated carbonaceous compounds, in relation with astronomical observations

Size effect in the ionization energy of PAH clusters

We report the first experimental measurement of the near-threshold photo-ionization spectra of polycyclic aromatic hydrocarbon clusters made of pyrene C16H10 and coronene C24H12, obtained using imaging photoelectron photoion coincidence spectrometry with a VUV synchrotron beamline. The experimental results of the ionization energy are confronted to calculated ones obtained from simulations using dedicated electronic structure treatment for large ionized molecular clusters. Experiment and theory consistently find a decrease of the ionization energy with cluster size. The inclusion of temperature effects in the simulations leads to a lowering of this energy and to a quantitative agreement with the experiment. In the case of pyrene, both theory and experiment show a discontinuity in the IE trend for the hexamer

Blending of nanoscale and microscale in uniform large-area sculptured thin-film architectures

The combination of large thickness ($>3$ $\mu$m), large--area uniformity (75 mm diameter), high growth rate (up to 0.4 $\mu$m/min) in assemblies of complex--shaped nanowires on lithographically defined patterns has been achieved for the first time. The nanoscale and the microscale have thus been blended together in sculptured thin films with transverse architectures. SiO$_x$ ($x\approx 2$) nanowires were grown by electron--beam evaporation onto silicon substrates both with and without photoresist lines (1--D arrays) and checkerboard (2--D arrays) patterns. Atomic self--shadowing due to oblique--angle deposition enables the nanowires to grow continuously, to change direction abruptly, and to maintain constant cross--sectional diameter. The selective growth of nanowire assemblies on the top surfaces of both 1--D and 2--D arrays can be understood and predicted using simple geometrical shadowing equations.Comment: 17 pages, 9 figure

Formation and destruction of polycyclic aromatic hydrocarbon clusters in the interstellar medium

The competition between the formation and destruction of coronene clusters under interstellar conditions is investigated theoretically. The unimolecular nucleation of neutral clusters is simulated with an atomic model combining an explicit classical force field and a quantum tight-binding approach. Evaporation rates are calculated in the framework of the phase space theory and are inserted in an infrared emission model and compared with the growth rate constants. It is found that, in interstellar conditions, most collisions lead to cluster growth. The time evolution of small clusters (containing up to 312 carbon atoms) was specifically investigated under the physical conditions of the northern photodissociation region of NGC 7023. These clusters are found to be thermally photoevaporated much faster than they are reformed, thus providing an interpretation for the lowest limit of the interstellar cluster size distribution inferred from observations. The effects of ionizing the clusters and density heterogeneities are also considered. Based on our results, the possibility that PAH clusters could be formed in PDRs is critically discussed.Comment: 14 pages, 14 figures. Astronomy & Astrophysics, accepted for publicatio

Some empirical estimates of the H2 formation rate in photon-dominated regions

We combine recent ISO observations of the vibrational ground state lines of H2 towards Photon-Dominated Regions (PDRs) with observations of vibrationally excited states made with ground-based telescopes in order to constrain the formation rate of H2 on grain surfaces under the physical conditions in the layers responsible for H2 emission. We use steady state PDR models in order to examine the sensitivity of different H2 line ratios to the H2 formation rate Rf. We show that the ratio of the 0-0 S(3) to the 1-0 S(1) line increases with Rf but that one requires independent estimates of the radiation field incident upon the PDR and the density in order to infer Rf from the H2 line data. We confirm the earlier result of Habart et al. (2003) that the H2 formation rate in regions of moderate excitation such as Oph W, S140 and IC 63 is a factor of 5 times larger than the standard rate inferred from UV observations of diffuse clouds. On the other hand, towards regions of higher radiation field such as the Orion Bar and NGC 2023, we derive H2 formation rates consistent with the standard value. We find also a correlation between the H2 1-0 S(1) line and PAH emission suggesting that Rf scales with the PAH abundance. With the aim of explaining these results, we consider some empirical models of the H2 formation process. Here we consider both formation on big (a~0.1 microns) and small (a~10 Angstroms) grains by either direct recombination from the gas phase or recombination of physisorbed H atoms with atoms in a chemisorbed site. We conclude that indirect chemisorption is most promising in PDRs. Moreover small grains which dominate the total grain surface and spend most of their time at relatively low temperatures may be the most promising surface for forming H2 in PDRs.Comment: A&A in press, 16 pages, 5 figure

Minocycline-induced hypersensitivity syndrome presenting with meningitis and brain edema: a case report

<p/> <p>Background</p> <p>Hypersentivity Syndrome (HS) may be a life-threatening condition. It frequently presents with fever, rash, eosinophilia and systemic manifestations. Mortality can be as high as 10% and is primarily due to hepatic failure. We describe what we believe to be the first case of minocycline-induced HS with accompanying lymphocytic meningitis and cerebral edema reported in the literature.</p> <p>Case presentation</p> <p>A 31-year-old HIV-positive female of African origin presented with acute fever, lymphocytic meningitis, brain edema, rash, eosinophilia, and cytolytic hepatitis. She had been started on minocycline for inflammatory acne 21 days prior to the onset of symptoms. HS was diagnosed clinically and after exclusion of infectious causes. Minocycline was withdrawn and steroids were administered from the second day after presentation because of the severity of the symptoms. All signs resolved by the seventh day and steroids were tailed off over a period of 8 months.</p> <p>Conclusion</p> <p>Clinicians should maintain a high index of suspicion for serious adverse reactions to minocycline including lymphocytic meningitis and cerebral edema among HIV-positive patients, especially if they are of African origin. Safer alternatives should be considered for treatment of acne vulgaris. Early recognition of the symptoms and prompt withdrawal of the drug are important to improve the outcome.</p

Velocity Dispersion of Excited H2

We present a study of the high rotational bands (J > 2) of H2 toward 4 early type galactic stars: HD 73882, HD 192639, HD 206267, and HD 207538. In each case, the velocity dispersion - characterized by the spectrum fitting parameter b - increases with the level of excitation, a phenomenon that has previously been detected by the Copernicus and IMAPS observatories. In particular, we show with 4 sigma confidence that for HD 192639 it is not possible to fit all J levels with a single b value, and that higher b values are needed for the higher levels. The amplitude of the line broadening, which can be as high as 10 km s^-1, makes explanations such as inhomogeneous spatial distribution unlikely. We investigate a mechanism in which the broadening is due to the molecules that are rotationally excited through the excess energy acquired after their formation on a grain (H2-formation pumping). We show that different dispersions would be a natural consequence of this mechanism. We note however that such process would require a formation rate 10 times higher then what was inferred from other observations. In view of the difficulty to account for the velocity dispersion as thermal broadening (T would be around 10,000 K), we conclude then that we are most certainly observing some highly turbulent warm layer associated with the cold diffuse cloud. Embedded in a magnetic field, it could be responsible for the high quantities of CH+ measured in the cold neutral medium.Comment: accepted in Ap