Identification of paramagnetic centers in irradiated Sn-doped silicon dioxide by first-principles.

We present a first-principles investigation of Sn paramagnetic centers in Sn-doped vitreous silica based on calculations of the electron paramagnetic resonance (EPR) parameters. The present investigation provides evidence of an extended analogy between the family of Ge paramagnetic centers in Ge-doped silica and the family of Sn paramagnetic centers in Sn-doped silica for SnO2concentrations below phase separation. We infer, also keeping into account the larger spin-orbit coupling of Sn atoms with respect to Ge atoms, that a peculiar and highly distorted three-fold coordinated Sn center (i.e. the Sn forward-oriented configuration) should give rise to an orthorhombic EPR signal of which we suggest a fingerprint in the EPR spectra recorded by Chiodiniet al(2001Phys. Rev.B64073102). Given its structural analogy with theEα'and Ge(2) centers, we here name it as the 'Sn(2) center'. Moreover, we show that the single trapped electron at a SnO4tetrahedron constitutes a paramagnetic center responsible for the orthorhombic EPR signal reported in Chiodiniet al(1998Phys. Rev.B589615), confuting the early assignment to a distorted variant of the Sn-E' center. We hence relabel the latter orthorhombic EPR signal as the 'Sn(1) center' due to its analogy to the Ge(1) center in Ge-doped silica.

Advanced capabilities for materials modelling with Quantum ESPRESSO.

Quantum EXPRESSO is an integrated suite of open-source computer codes for quantum simulations of materials using state-of-the-art electronic-structure techniques, based on density-functional theory, density-functional perturbation theory, and many-body perturbation theory, within the plane-wave pseudopotential and projector-augmented-wave approaches. Quantum EXPRESSO owes its popularity to the wide variety of properties and processes it allows to simulate, to its performance on an increasingly broad array of hardware architectures, and to a community of researchers that rely on its capabilities as a core open-source development platform to implement their ideas. In this paper we describe recent extensions and improvements, covering new methodologies and property calculators, improved parallelization, code modularization, and extended interoperability both within the distribution and with external software.

Two-membered silicon rings on the dehydroxylated surface of silica

We present extensive modeling of the amorphous silica surface, aimed at connecting its structural and chemical features. beta-cristobalite surfaces are initially studied to model the hydroxylated surfaces. A model reconstruction of the (111) surface is used to define a path leading to the formation of two-membered silicon rings upon dehydroxylation. Subsequently, a realistic model of the amorphous dehydroxylated (dry) surface is produced, by full ab initio annealing of an initial model generated by classical simulation. The presence of surface two-membered silicon rings emerges naturally. A calculation of IR activity yields an associated peak doublet in agreement with experimental data.

Cognitive, psychological and psychiatric effects of ionizing radiation exposure.

Radiation exposure leads to an increased risk for cancer and, possibly, additional ill-defined non-cancer risk, including atherosclerotic, cardiovascular, cerebro-vascular and neurodegenerative effects. Studies of brain irradiation in animals and humans provide evidence of apoptosis, neuro-inflammation, loss of oligo-dendrocytes precursors and myelin sheaths, and irreversible damage to the neural stem compartment with long-term impairment of adult neurogenesis. With the present paper we aim to present a comprehensive review on brain effects of radiation exposure, with a special focus on its impact on cognitive processes and psychological functions, as well as on their possible role in the pathophysiology of different psychiatric disorders.

Peak effect versus skating in high-temperature nanofriction.

The physics of sliding nanofriction at high temperature near the substrate melting point, TM, is so far unexplored. We conducted simulations of hard tips sliding on a prototype non-melting surface, NaCl(100), revealing two distinct and opposite phenomena for ploughing and for grazing friction in this regime. We found a frictional drop close to TM for deep ploughing and wear, but on the contrary a frictional rise for grazing, wearless sliding. For both phenomena, we obtain a fresh microscopic understanding, relating the former to 'skating' through a local liquid cloud, and the latter to linear response properties of the free substrate surface. We argue that both phenomena occur more generally on surfaces other than NaCl and should be pursued experimentally. Most metals, in particular those possessing one or more close-packed non-melting surfaces, such as Pb, Al or Au(111), are likely to behave similarly.

Why are alkali halide surfaces not wetted by their own melt?

Alkali halide (100) crystal surfaces are anomalous, being very poorly wetted by their own melt at the triple point. We present extensive simulations for NaCl, followed by calculations of the solid-vapor, solid-liquid, and liquid-vapor free energies showing that solid NaCl(100) is a nonmelting surface, and that its full behavior can quantitatively be accounted for within a simple Born-Meyer-Huggins-Fumi-Tosi model potential. The incomplete wetting is traced to the conspiracy of three factors: surface anharmonicities stabilizing the solid surface; a large density jump causing bad liquid-solid adhesion; incipient NaCl molecular correlations destabilizing the liquid surface. The latter is pursued in detail, and it is shown that surface short-range charge order acts to raise the surface tension because incipient NaCl molecular formation anomalously reduces the surface entropy of liquid NaCl much below that of solid NaCl(100).

Physics of solid and liquid alkali halide surfaces near the melting point.

This paper presents a broad theoretical and simulation study of the high-temperature behavior of crystalline alkali halide surfaces typified by NaCl(100), of the liquid NaCl surface near freezing, and of the very unusual partial wetting of the solid surface by the melt. Simulations are conducted using two-body rigid-ion Born-Mayer-Huggins-Fumi-Tosi (BMHFT) potentials, with full treatment of long-range Coulomb forces. After a preliminary check of the description of bulk NaCl provided by these potentials, which seems generally good even at the melting point, we carry out a new investigation of solid and liquid surfaces. Solid NaCl(100) is found in this model to be very anharmonic and yet exceptionally stable when hot. It is predicted by a thermodynamic integration calculation of the surface free energy that NaCl(100) should be a well-ordered, nonmelting surface, metastable even well above the melting point. By contrast, the simulated liquid NaCl surface is found to exhibit large thermal fluctuations and no layering order. In spite of that, it is shown to possess a relatively large surface free energy. The latter is traced to a surface entropy deficit, reflecting some kind of surface short-range order. We show that the surface short-range order is most likely caused by the continuous transition of the bulk ionic melt into the vapor, made of NaCl molecules and dimers rather than of single ions. Finally, the solid-liquid interface free energy is derived through Young's equation from direct simulation of partial wetting of NaCl(100) by a liquid droplet. The resulting interface free energy is large, in line with the conspicuous solid-liquid 27% density difference. A partial wetting angle near 50 degrees close to the experimental value of 48 degrees is obtained in the process. It is concluded that three elements, namely, the exceptional anharmonic stability of the solid (100) surface, the molecular short-range order at the liquid surface, and the costly solid-liquid interface, all conspire to cause the anomalously poor wetting of the (100) surface by its own melt in the BMHFT model of NaCl-and most likely also in real alkali halide surfaces.

Trapping of excitons at chemical defects in polyethylene.

In a previous paper we studied an injected electron-hole pair in crystalline polyethylene (PE) and found that the exciton becomes weakly self-trapped in a narrow interchain pocket comprised between two gauche defects. Despite the large energy stored in the trapped excitation, there did not appear to be a direct nonradiative channel for electron-hole recombination. Actual polyethylene systems of practical use are, however, neither crystalline nor pure. To understand the fate of an electron-hole pair in the impure case, we studied by ab initio simulations the evolution of an exciton trapped on three common chemical defects found in polyethylene: a grafted carbonyl (C=O); an intrachain vinyl group (C=C); a grafted carboxyl (COOH). Ab initio simulations lead to predict three different outcomes: trapping, nonradiative recombination, and homolitic bond-breaking, respectively. This suggests that extrinsic self-trapping of electron-hole pairs over chemical defects inside the quasicrystalline fraction of PE could be relevant for electrical damage in high-voltage cables.

Femur fracture induces site-specific changes in T-cell immunity.

BACKGROUND: Trauma is associated with altered host defense and susceptibility to infection, in part due to cytokine dysregulation and altered T-cell immunity. The gut-associated lymphoid tissue (GALT) provides a defense against infection and contributes to the process of mucosal healing by T-cell activation and cytokine production. OBJECTIVE: To determine whether femur fracture induces alterations in Peyer's patch and splenic T-cell phenotype, proliferative response, and cytokine expression following traumatic injury. METHODS: Mice underwent femur fracture or sham procedure and, 48 h later, lymphocytes were isolated from spleen and Peyer's patches. Lymphocytes were cultured, and lipopolysaccharide (10 microg/ml) was added in some cultures. Cells and supernatant were harvested at 48 h. Proliferation was analyzed by [3H]thymidine, and interleukin-10 (IL-10) protein was measured by ELISA in the culture supernatant. T-cell phenotype was determined by flow cytometry. RESULTS: Femur fracture induced a significant increase in proliferative response in Peyer's patch immunocytes. In contrast, no significant differences were identified in splenocyte proliferative response 48 h after femur fracture injury. Femur fracture induced a significant decrease in IL-10 protein expression of both splenocytes and Peyer's patches. Femur fracture also induced a significant increase in the fraction of CD3(+), CD4(+), and T-cell receptor-alpha beta Peyer's patch immunocytes, whereas splenocytes demonstrated no significant phenotypic change. CONCLUSION: Femur fracture is associated with significant alterations in Peyer's patch but not splenic T-cell phenotype and proliferative response early (48 h) after injury. Changes in the GALT immune response may contribute to intestinal mucosal dysfunction and increased susceptibility to gut-derived sepsis after traumatic injury.