No abstract

We predict the structures and detailed energetics for the dissociative adsorption of NH3 to form NH2 and H adsorbed on a single Si dimer on the Si(100)-2 × 1 surface at the MRSDCI (multireference single and double excitation configuration interaction) level of theory. We predict that this dissociation involves two steps:  (i) barrierless molecular chemisorption of NH3 followed by (ii) activated N−H bond cleavage of NH3(a) to form NH2(a) + H(a). While the second step involves a barrier, its relatively small height renders the overall reaction barrierless. The extremely high adsorption exothermicity (∼75 kcal/mol) results in a very high desorption barrier. These results can explain the experimentally determined high sticking probability of NH3, the observation of NH3(a) at low temperatures, and the observed stability of NH2(a) and H(a) on the Si(100) surface up to ∼600 K. Additionally, our CASSCF level (complete active space self-consistent-field) calculated geometries for the dissociatively adsorbed species agree with structures proposed to explain experimental data.

We present complete active space self-consistent field (CASSCF) ab initio molecular dynamics (AIMD) simulations of the preparation of the metastable species vinylidene, and its subsequent, highly exothermic isomerization to acetylene, via electron removal from vinylidene anion (D(2)C=C(-) --> D(2)C=C: --> DC triple bond CD). After equilibrating vinylidene anion-d(2) at either 600 +/- 300 K (slightly below the isomerization barrier) or 1440 K +/- 720 K (just above the isomerization barrier), we remove an electron to form a vibrationally excited singlet vinylidene-d(2) and follow its dynamical evolution for 1.0 ps. Remarkably, we find that none of the vinylidenes equilibrated at 600 K and only 20% of the vinylidenes equilibrated at 1440 K isomerized, suggesting average lifetimes >1 ps for vibrationally excited vinylidene-d(2). Since the anion and neutral vinylidene are structurally similar, and yet extremely different geometrically from the isomerization transition state (TS), neutral vinylidene is not formed near the TS so that it must live until it has sufficient instantaneous kinetic energy in the correct vibrational mode(s). The origin of the delay is explained via both orbital rearrangement and intramolecular vibrational energy redistribution (IVR) effects. Unique signatures of the isomerization dynamics are revealed in the anharmonic vibrational frequencies extracted from the AIMD, which should be observable by ultrafast vibrational spectroscopy and in fact are consistent with currently available experimental spectra. Most interestingly, of those trajectories that did isomerize, every one of them violated conventional transition-state theory by recrossing back to vinylidene multiple times, against conventional notions that expect highly exothermic reactions to be irreversible. The dynamical motion responsible for the multiple barrier recrossings involves strong mode-coupling between the vinylidene CD(2) rock and a local acetylene DCC bend mode that has been recently observed experimentally. The multiple barrier recrossings can be used, via a generalized definition of lifetime, to reconcile extremely disparate experimental estimates of vinylidene's lifetime (differing by at least 6 orders of magnitude). Last, a caveat: These results are constrained by the approximations inherent in the simulation (classical nuclear motion, neglect of rotation-vibration coupling, and restriction to C(s) symmetry); refinement of these predictions may be necessary when more exact simulations someday become feasible.

Direct estimation of Lagrangian turbulence statistics is essential for the proper modeling of dispersion and transport in highly obstructed canopy flows. However, Lagrangian flow measurements demand very high rates of data acquisition, resulting in bottlenecks that prevented the estimation of Lagrangian statistics in canopy flows hitherto. We report on a new extension to the 3D Particle Tracking Velocimetry (3D-PTV) method, featuring real-time particle segmentation that outputs centroids and sizes of tracer particles and performed on dedicated hardware during high-speed digital video acquisition from multiple cameras. The proposed extension results in four orders of magnitude reduction in data transfer rate that enables to perform substantially longer experimental runs, facilitating measurements of convergent statistics. The extended method is demonstrated through an experimental wind tunnel investigation of the Lagrangian statistics in a heterogeneous canopy flow. We observe that acceleration statistics are affected by the mean shear at the top of the canopy layer and that Lagrangian particle dispersion at small scales is dominated by turbulence in the wake of the roughness elements. This approach enables to overcome major shortcomings from Eulerian-based measurements which rely on assumptions such as the Taylor’s frozen turbulence hypothesis, which is known to fail in highly turbulent flows.

Lumpy skin disease virus (LSDV) is an infectious, arthropod-borne virus that affects mostly cattle. Solitary outbreaks have occurred in Israel in 1989 and 2006. In both years, the outbreaks occurred parallel to a severe outbreak in Egypt, and LSDV was hypothesized to be transmitted from Egypt to Israel via long-distance dispersal (LDD) of infected vectors by wind. The aim of this study was to identify possible events of such transport. At the first stage, we identified the relevant synoptic systems that allowed wind transport from Egypt to Israel during the 3 months preceding each outbreak. Three-dimensional backwards Lagrangian trajectories were calculated from the receptor sites in Israel for each occurrence of such relevant synoptic system. The analysis revealed several events in which atmospheric connection routes between the affected locations in Egypt and Israel were established. Specifically, during the 1989, Damietta and Port Said stand out as likely sources for the outbreak in Israel. In 2006, different locations acted simultaneously as potential sources of the outbreak in Israel. These locations were situated in the Nile delta, the Suez Canal and in northern Sinai. The analysis pointed out Sharav low and Shallow Cyprus low to the North to be the most likely systems to enable windborne transport from Egypt to Israel. These findings are of high importance for the analysis of the risk of transmission of vectorborne viruses in the eastern Mediterranean region.