Toward an accurate ab initio estimation of compressibility and thermal expansion of diamond in the [0, 3000 K] temperature and [0, 30 GPa] pressures ranges, at the hybrid HF/DFT theoretical level

The isothermal bulk modulus, together with its temperature dependence, and the thermal expansion of diamond at various pressures were calculated from first principles in the [0, 30 GPa] and [0, 3000 K] pressure and temperature ranges, within the limits of the quasi-harmonic approximation (QHA). The hybrid HF/DFT functional employed (WC1LYP) proved to be particularly effective in providing a very close agreement between the calculated and the available experimental data. In particular, the bulk modulus at 300 K was estimated to be 444.6 GPa (K' = 3.60); at the same temperature, the (volume) thermal expansion coefficient was 3.19×10-6 K-1. To the authors’ knowledge, among the theoretical papers devoted to the subject, the present one provides the most accurate thermo-elastic data in high-pressure and temperature ranges. Such data can confidently be used in the determination of the pressure of formation using the “elastic method” for minerals found as inclusions in diamonds (recently applied on different minerals included in diamonds), thus shedding light upon the genesis of diamonds in the Earth’s upper mantle

The (100), (111) and (110) surfaces of diamond: an ab initio B3LYP study

We present an accurate ab initio study of the structure and surface energy of the low-index (100),(111) and (110) diamond faces, by using the hybrid Hartree-Fock/Density Functional B3LYPHamiltonian and a localized all-electron Gaussian-type basis set. A 2D periodic slab model has been adopted, for which convergence on both structural and energetic parameters has been thoroughly investigated. For all the three surfaces, possible relaxations and reconstructions have been considered; a detailed geometrical characterization is provided for the most stable structure of each orientation. Surface energy is discussed for all the investigated faces

The IR vibrational properties of six members of the garnet family: A quantum mechanical ab initio study

The IR vibrational properties and the corresponding reflectance spectra of the six most common members of the garnet family (pyrope Mg3Al2Si3O12, almandine Fe3Al2Si3O12, spessartine Mn3Al2Si3O12, grossular Ca3Al2Si3O12, uvarovite Ca3Cr2Si3O12, and andradite Ca3Fe2Si3O12) were simulated at the ab initio level with the CRYSTAL09 code by using a large all-electron Gaussian-type basis set and the B3LYP hybrid functional. The 17 IR active F1u transverse optical (TO) and longitudinal optical (LO) frequencies, the oscillator strengths, the high frequency and static dielectric constants, and the reflectance spectrum were computed. The agreement with experiments for the TO and LO peaks is always excellent, the mean absolute difference for the whole set of data (overall 178 peaks) being 5 cm−1. Oscillator strengths, calculated from the mass-weighted effective Born charges, are found in semi-quantitative agreement with the experimental data. The reflectance spectra, simulated through the classical dispersion relation, reproduce the experimental curves extremely well. The availability of the full set of simulated frequencies and intensities, obtained by using uniform computational tools (computer code, variational basis sets, density functional), permits the establishment of correlations between IR wavenumbers and structural features suggested, but only partially documented, in the past

On the use of symmetry in configurational analysis for the simulation of disordered solids

The starting point for a quantum mechanical investigation of disordered systems usually implies calculations on a limited subset of configurations, generated by defining either the composition of interest or a set of compositions ranging from one end member to another, within an appropriate supercell of the primitive cell of the pure compound. The way in which symmetry can be used in the identification of symmetry independent configurations (SICs) is discussed here. First, Pólya's enumeration theory is adopted to determine the number of SICs, in the case of both varying and fixed composition, for colors numbering two or higher. Then, De Bruijn's generalization is presented, which allows analysis of the case where the colors are symmetry related, e.g. spin up and down in magnetic systems. In spite of their efficiency in counting SICs, neither Pólya's nor De Bruijn's theory helps in solving the difficult problem of identifying the complete list of SICs. Representative SICs are obtained by adopting an orderly generation approach, based on lexicographic ordering, which offers the advantage of avoiding the (computationally expensive) analysis and storage of all the possible configurations. When the number of colors increases, this strategy can be combined with the surjective resolution principle, which permits the efficient generation of SICs of a problem in |R| colors starting from the ones obtained for the (|R| − 1)-colors case. The whole scheme is documented by means of three examples: the abstract case of a square with C4v symmetry and the real cases of the garnet and olivine mineral families

The influence of Ga+^+-irradiation on the transport properties of mesoscopic conducting thin films

We studied the influence of 30keV Ga$^+$-ions -- commonly used in focused ion beam (FIB) devices -- on the transport properties of thin crystalline graphite flake, La$_{0.7}$Ca$_{0.3}$MnO$_3$ and Co thin films. The changes of the electrical resistance were measured in-situ during irradiation and also the temperature and magnetic field dependence before and after irradiation. Our results show that the transport properties of these materials strongly change at Ga$^+$ fluences much below those used for patterning and ion beam induced deposition (IBID), limiting seriously the use of FIB when the intrinsic properties of the materials of interest are of importance. We present a method that can be used to protect the sample as well as to produce selectively irradiation-induced changes.Comment: 14 pages, 11 figures, will be published in Nanotechnology 201

The HELLAS2XMM survey: XI. Unveiling the nature of X-ray Bright Optically Normal Galaxies

X-ray Bright Optically Normal Galaxies (XBONGs) constitute a small but not negligible fraction of hard X-ray selected sources in recent Chandra and XMM-Newton surveys. Even though several possibilities were proposed to explain why a relatively luminous hard X-ray source does not leave any significant signature of its presence in terms of optical emission lines, the nature of XBONGs is still subject of debate. We aim to a better understanding of their nature by means of a multiwavelength and morphological analysis of a small sample of these sources. Good-quality photometric near-infrared data (ISAAC/VLT) of four low-redshift (z=0.1-0.3) XBONGs, selected from the HELLAS2XMM survey, have been used to search for the presence of the putative nucleus, applying the surface-brightness decomposition technique through the least-squares fitting program GALFIT. The surface brightness decomposition allows us to reveal a nuclear point-like source, likely to be responsible of the X-ray emission, in two out of the four sources. The results indicate that moderate amounts of gas and dust, covering a large solid angle (possibly 4pi) at the nuclear source, combined with the low nuclear activity, may explain the lack of optical emission lines. The third XBONG is associated with an X-ray extended source and no nuclear excess is detected in the near infrared at the limits of our observations. The last source is associated to a close (d< 1 arcsec) double system and the fitting procedure cannot achieve a firm conclusion.Comment: 20 pages, 12 figures, A&A in pres

Design, Realization, and Characterization of Advanced Adhesives for Joining Ultra-Stable C/C Based Components

The aim of this work is to develop high-performance adhesives to join carbon fiber reinforced composites (C/C) for use in aerospace applications; in order to guarantee sound mechanical strength, a low coefficient of thermal expansion, and ease of application on large components. Several different adhesive formulations, based on phenolic or cyanate-ester resins (charged with the maximum experimentally feasible amount of carbon-based fillers), are developed and tested. The measurements of the lap shear strength at room temperature of the C/C joined by means of one phenolic and one cyanate ester-based resin demonstrates that these formulations are the most suitable for the given application. A complete characterization, by means of viscosimetry, dilatometry, and thermal gravimetric analysis, coupled with gas analysis by means of mass spectroscopy, confirms that the phenolic-based formulation is the most promising joining material. A nano-indenter is used to obtain its Young modulus and hardness, both inside the joint and as a bulk cured adhesive

Nanoinformatics: developing new computing applications for nanomedicine

Nanoinformatics has recently emerged to address the need of computing applications at the nano level. In this regard, the authors have participated in various initiatives to identify its concepts, foundations and challenges. While nanomaterials open up the possibility for developing new devices in many industrial and scientific areas, they also offer breakthrough perspectives for the prevention, diagnosis and treatment of diseases. In this paper, we analyze the different aspects of nanoinformatics and suggest five research topics to help catalyze new research and development in the area, particularly focused on nanomedicine. We also encompass the use of informatics to further the biological and clinical applications of basic research in nanoscience and nanotechnology, and the related concept of an extended ?nanotype? to coalesce information related to nanoparticles. We suggest how nanoinformatics could accelerate developments in nanomedicine, similarly to what happened with the Human Genome and other -omics projects, on issues like exchanging modeling and simulation methods and tools, linking toxicity information to clinical and personal databases or developing new approaches for scientific ontologies, among many others