Statistical evaporation of rotating clusters. II. Angular momentum distribution

The change in the angular momentum of an atomic cluster following evaporation is investigated using rigorous phase space theory and molecular dynamics simulations, with an aim at the possible rotational cooling and heating effects. Influences of the shape of the interaction potential, anharmonicity of the vibrational density of states (DOS), and the initial distribution of excitation energies are systematically studied on the example of the Lennard-Jones cluster LJ_14. For this system, the predictions of PST are in quantitative agreement with the results of the simulations, provided that the correct forms for the vibrational density of states and the interaction potential are used. The harmonic approximation to the DOS is used to obtain explicit forms for the angular momentum distribution in larger clusters. These are seen to undergo preferential cooling when thermally excited, and preferential heating when subject to a strong vibrational excitation.Comment: 10 pages, 7 figure

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

Statistical evaporation of rotating clusters. IV. Alignment effects in the dissociation of nonspherical clusters

Unimolecular evaporation in rotating, non-spherical atomic clusters is investigated using Phase Space Theory in its orbiting transition state version. The distributions of the total kinetic energy release epsilon_tr and the rotational angular momentum J_r are calculated for oblate top and prolate top main products with an arbitrary degree of deformation. The orientation of the angular momentum of the product cluster with respect to the cluster symmetry axis has also been obtained. This statistical approach is tested in the case of the small 8-atom Lennard-Jones cluster, for which comparison with extensive molecular dynamics simulations is presented. The role of the cluster shape has been systematically studied for larger, model clusters in the harmonic approximation for the vibrational densities of states. We find that the type of deformation (prolate vs. oblate) plays little role on the distributions and averages of epsilon_tr and J_r except at low initial angular momentum. However, alignment effects between the product angular momentum and the symmetry axis are found to be significant, and maximum at some degree of oblateness. The effects of deformation on the rotational cooling and heating effects are also illustrated.Comment: 15 pages, 9 figure

Second moment closure analysis of the backstep flow database

A Second Moment Closure computation (SMC) is compared in detail with the Direct Numerical Simulation (DNS) data of Le and Moin for the backstep flow at Re = 5,000 in an attempt to understand why the intensity of the backflow and, consequently, the friction coefficient in the recirculation bubble are severely underestimated. The data show that this recirculation bubble is far from being laminar except in the very near wall layer. A novel 'differential a priori' procedure was used, in which the full transport equation for one isolated component of the Reynolds stress tensor was solved using DNS data as input. Conclusions are then different from what would have been deduced by comparing a full simulation to a DNS. One cause of discrepancy was traced back to insufficient transfer of energy to the normal stress by pressure strain, but was not cured. A significant finding, confirmed by the DNS data in the core region of a channel flow, is that the coefficient that controls destruction of dissipation, C epsilon(sub 2), should be decreased by a factor of 2 when production is vanishing. This is also the case in the recirculation bubble, and a new formulation has cured 25% of the backflow discrepancy

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

Molecular hydrogen formation on grain surfaces

We reconsider H2 formation on grain surfaces. We develop a rate equation model which takes into account the presence of both physisorbed and chemisorbed sites on the surface, including quantum mechanical tunnelling and thermal diffusion. In this study, we took into consideration the uncertainties on the characteristics of graphitic surfaces. We calculate the H2 formation efficiency with the Langmuir Hinshelwood and Eley Rideal mechanisms, and discuss the importance of these mechanisms for a wide range of grain and gas temperatures. We also develop a Monte Carlo simulation to calculate the H2 formation efficiency and compare the results to our rate equation models. Our results are the following: (1) Depending on the barrier against chemisorption, we predict the efficiency of H2 formation for a wide range of grain and gas temperatures. (2) The Eley-Rideal mechanism has an impact on the H2 formation efficiency at high grain and gas temperatures. (3) The fact that we consider chemisorption in our model makes the rate equation and Monte Carlo approaches equivalent.Comment: in "Light, dust and chemical evolution", Journal of Physics: Conference Serie

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

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