Ab initio Quantum and ab initio Molecular Dynamics of the Dissociative Adsorption of Hydrogen on Pd(100)

The dissociative adsorption of hydrogen on Pd(100) has been studied by ab initio quantum dynamics and ab initio molecular dynamics calculations. Treating all hydrogen degrees of freedom as dynamical coordinates implies a high dimensionality and requires statistical averages over thousands of trajectories. An efficient and accurate treatment of such extensive statistics is achieved in two steps: In a first step we evaluate the ab initio potential energy surface (PES) and determine an analytical representation. Then, in an independent second step dynamical calculations are performed on the analytical representation of the PES. Thus the dissociation dynamics is investigated without any crucial assumption except for the Born-Oppenheimer approximation which is anyhow employed when density-functional theory calculations are performed. The ab initio molecular dynamics is compared to detailed quantum dynamical calculations on exactly the same ab initio PES. The occurence of quantum oscillations in the sticking probability as a function of kinetic energy is addressed. They turn out to be very sensitive to the symmetry of the initial conditions. At low kinetic energies sticking is dominated by the steering effect which is illustrated using classical trajectories. The steering effects depends on the kinetic energy, but not on the mass of the molecules. Zero-point effects lead to strong differences between quantum and classical calculations of the sticking probability. The dependence of the sticking probability on the angle of incidence is analysed; it is found to be in good agreement with experimental data. The results show that the determination of the potential energy surface combined with high-dimensional dynamical calculations, in which all relevant degrees of freedon are taken into account, leads to a detailed understanding of the dissociation dynamics of hydrogen at a transition metal surface.Comment: 15 pages, 9 figures, subm. to Phys. Rev.

N-type graphene induced by dissociative H-2 adsorption at room temperature

Studies of the interaction between hydrogen and graphene have been increasingly required due to the indispensable modulation of the electronic structure of graphene for device applications and the possibility of using graphene as a hydrogen storage material. Here, we report on the behaviour of molecular hydrogen on graphene using the gate voltage-dependent resistance of single-, bi-, and multi-layer graphene sheets as a function of H-2 gas pressure up to 24 bar from 300 K to 345 K. Upon H-2 exposure, the charge neutrality point shifts toward the negative gate voltage region, indicating n-type doping, and distinct Raman signature changes, increases in the interlayer distance of multi-layer graphene, and a decrease in the d-spacing occur, as determined by TEM. These results demonstrate the occurrence of dissociative H-2 adsorption due to the existence of vacancy defects on graphene.open12

The neuropathology of autism: defects of neurogenesis and neuronal migration, and dysplastic changes

Autism is characterized by a broad spectrum of clinical manifestations including qualitative impairments in social interactions and communication, and repetitive and stereotyped patterns of behavior. Abnormal acceleration of brain growth in early childhood, signs of slower growth of neurons, and minicolumn developmental abnormalities suggest multiregional alterations. The aim of this study was to detect the patterns of focal qualitative developmental defects and to identify brain regions that are prone to developmental alterations in autism. Formalin-fixed brain hemispheres of 13 autistic (4–60 years of age) and 14 age-matched control subjects were embedded in celloidin and cut into 200-μm-thick coronal sections, which were stained with cresyl violet and used for neuropathological evaluation. Thickening of the subependymal cell layer in two brains and subependymal nodular dysplasia in one brain is indicative of active neurogenesis in two autistic children. Subcortical, periventricular, hippocampal and cerebellar heterotopias detected in the brains of four autistic subjects (31%) reflect abnormal neuronal migration. Multifocal cerebral dysplasia resulted in local distortion of the cytoarchitecture of the neocortex in four brains (31%), of the entorhinal cortex in two brains (15%), of the cornu Ammonis in four brains and of the dentate gyrus in two brains. Cerebellar flocculonodular dysplasia detected in six subjects (46%), focal dysplasia in the vermis in one case, and hypoplasia in one subject indicate local failure of cerebellar development in 62% of autistic subjects. Detection of flocculonodular dysplasia in only one control subject and of a broad spectrum of focal qualitative neuropathological developmental changes in 12 of 13 examined brains of autistic subjects (92%) reflects multiregional dysregulation of neurogenesis, neuronal migration and maturation in autism, which may contribute to the heterogeneity of the clinical phenotype

Ferromagnetic nanostructures of oxygen on Ag(111)

First principles calculations were performed to investigate the robustness of oxygen adsorbed structures that show ferromagnetic properties. These ferromagnetic properties are induced by ferromagnetic superexchange interactions and Ruderman-Kittel-Kasuya-Yosida (RKKY) interactions. Such ferromagnetic oxygen adsorbed structures appear only in the case of coverages higher than 0.5 ML, because the ferromagnetic superexchange interactions and RKKY interactions are appreciable between O-O only for short distances. In this work, we focused on single oxygen atom diffusion parallel and perpendicular to Ag(111) surfaces. The in-plane diffusion could induce associative desorption, which reduces the oxygen coverage. On the other hand, diffusion to the subsurface could quench the magnetic moment. These diffusion paths have effective diffusion barriers of 0.78 eV. Thus, such diffusion rarely occurs in low temperature regions