Quantum Monte Carlo study of small aluminum clusters Al-n (n=2-13)

Using fixed node diffusion quantum Monte Carlo (FN-DMC) simulations and density functional theory (DFT) within the generalized gradient approximations, we calculate the total energies of the relaxed and unrelaxed neutral, cationic, and anionic aluminum clusters, Al-n (n = 1-13). From the obtained total energies, we extract the ionization potential and electron detachment energy and compare with previous theoretical and experimental results. Our results for the electronic properties from both the FN-DMC and DFT calculations are in reasonably good agreement with the available experimental data. A comparison between the FN-DMC and DFT results reveals that their differences are a few tenths of electron volt for both the ionization potential and the electron detachment energy. We also observe two distinct behaviors in the electron correlation contribution to the total energies from smaller to larger clusters, which could be assigned to the structural transition of the clusters from planar to three-dimensional occurring at n = 4 to 5.

Encapsulation of small magnetic clusters in fullerene cages: A density functional theory investigation within van der Waals corrections

The encapsulation of magnetic transition-metal (TM) clusters inside carbon cages (fullerenes, nanotubes) has been of great interest due to the wide range of applications, which spread from medical sensors in magnetic resonance imaging to photonic crystals. Several theoretical studies have been reported; however, our atomistic understanding of the physical properties of encapsulated magnetic TM 3d clusters is far from satisfactory. In this work, we will report general trends, derived from density functional theory within the generalized gradient approximation proposed by Perdew, Burke, and Ernzerhof (PBE), for the encapsulation properties of the TMm@C-n (TM = Fe, Co, Ni; m = 2-6, n = 60,70,80,90) systems. Furthermore, to understand the role of the van der Waals corrections to the physical properties, we employed the empirical Grimme's correction (PBE + D2). We found that both PBE and PBE + D2 functionals yield almost the same geometric parameters, magnetic and electronic properties, however, PBE + D2 strongly enhances the encapsulation energy. We found that the center of mass of the TMm clusters is displaced towards the inside C-n surfaces, except for large TMm clusters (m = 5 and 6). For few cases, e. g., Co-4 and Fe-4, the encapsulation changes the putative lowest-energy structure compared to the isolated TMm clusters. We identified few physical parameters that play an important role in the sign and magnitude of the encapsulation energy, namely, cluster size, fullerene equatorial diameter, shape, curvature of the inside C-n surface, number of TM atoms that bind directly to the inside C-n surface, and the van der Waals correction. The total magnetic moment of encapsulated TMm clusters decreases compared with the isolated TMm clusters, which is expected due to the hybridization of the d-p states, and strongly depends on the size and shape of the fullerene cages.

Ethanol and Water Adsorption on Close-Packed 3d, 4d, and 5d Transition-Metal Surfaces: A Density Functional Theory Investigation with van der Waals Correction

Nowadays, there is a great interest in the economic success of direct ethanol fuel cells; however, our atomistic understanding of the designing of stable and low-cost catalysts for the steam reforming of ethanol is still far from satisfactory, in particular due to the large number of undesirable intermediates. In this study, we will report a first-principles investigation of the adsorption properties of ethanol and water at low coverage on close-packed transition-metal (TM) surfaces, namely, Fe(110), Co(0001), Ni(111), Cu(111), Ru(0001), Rh(111), Pd(111), Ag(111), Os(0001), Ir(111), Pt(111), and Au(111), employing density functional theory (DFT) calculations. We employed the generalized gradient approximation with the formulation proposed by Perdew, Burke, and Erzenholf (PBE) to the exchange correlation functional and the empirical correction proposed by S. Grimme (DFT+D3) for the van der Waals correction. We found that both adsorbates binds preferentially near or on the on top sites of the TM surfaces through the 0 atoms. The PBE adsorption energies of ethanol and water decreases almost linearly with the increased occupation of the 4d and 5d d-band, while there is a deviation for the 3d systems. The van der Waals correction affects the linear behavior and increases the adsorption energy for both adsorbates, which is expected as the van der Waals energy due to the correlation effects is strongly underestimated by DFT-PBE for weak interacting systems. The geometric parameters for water/TM are not affected by the van der Waals correction, i.e., both DFT and DFT+D3 yield an almost parallel orientation for water on the TM surfaces; however, DFT+D3 changes drastically the ethanol orientation. For example, DFT yields an almost perpendicular orientation of the C-C bond to the TM surface, while the C-C bond is almost parallel to the surface using DFT +D3 for all systems, except for ethanol/Fe(110). Thus, the van der Waals correction decreases the distance of the C atoms to the TM surfaces, which might contribute to break the C-C bond. The work function decreases upon the adsorption of ethanol and water, and both follow the same trends, however, with different magnitude (larger for ethanol/TM) due to the weak binding of water to the surface. The electron density increases mainly in the region between the topmost layer and the adsorbates, which explains the reduction of the substrate work function.

Adsorption of NO on the Rh-13, Pd-13, Ir-13, and Pt-13 Clusters: A Density Functional Theory Investigation

The adsorption of NO on transition-metal (TM) surfaces has been widely studied by experimental and theoretical techniques; however, our atomistic understanding of the interaction of nitrogen monoxide (NO) with small TM clusters is far from satisfactory, which compromises a deep understanding of real catalyst devices. In this study, we report a density functional theory study of the adsorption properties of NO on the TM13 (TM = Rh, Pd, Ir, Pt) clusters employing the projected augmented wave method. We found that the interaction of NO with TM13 is much more complex than that for NO/TM(111). In particular, for low symmetry TM13 clusters, there is a strong rearrangement of the electronic charge density upon NO adsorption and, as a consequence, the adsorption energy shows a very complex dependence even for adsorption sites with the same local effective coordination. We found a strong enhancement of the binding energy of NO to the TM13 clusters compared with the TM(111) surfaces, as the antibonding NO states are not occupied for NO/TM13, and the general relationship based on the d-band model between adsorption energy and the center of gravity of the occupied d-states does not hold for the studied TM13 clusters, in particular, for clusters with low symmetry. In contrast with the adsorption energy trends, the geometric NO/TM13 parameters and the vibrational N-O frequencies for different coordination sites follow the same trend as for the respective TM(111) surfaces, while the changes in the frequencies between different surfaces and TM13 clusters reflect the strong NO-TM13 interaction.

Sulfur Radicals as Tethers for the Adsorption of Aromatic Molecules on Silicon Surface

In this work we employ the state of the art pseudopotential method, within a generalized gradient approximation to the density functional theory, to investigate the adsorption process of benzenethiol and diphenyl disulfide with the silicon (001) surface. A direct comparison of different adsorption structures with Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) allow us to identify that benzenethiol and diphenyl disulfide dissociatively adsorb on the silicon surface. In addition, theoretically obtained data suggests that the C6H5SH:Si(001) presents a higher Schottky barrier height contact when compared to other similar aromatic molecules.

The T-2 phase in the Nb-Si-B system studied by ab initio calculations and synchrotron X-ray diffraction

The solid solution based on Nb5Si3 (Cr5B3 structure type, D8(l), tl32, 14/mcm, No140, a=6.5767 angstrom, c=11.8967 angstrom) in the Nb-Si-B system was studied from the structural and thermodynamic point of view both experimentally and by ab initio calculations. Rietveld refinement of powder X-ray synchrotron data allowed to determine the boron to silicon substitution mechanism and the structural parameters. Ab initio calculations of different ordered compounds and selected disordered alloys allowed to obtain in addition to the enthalpy of formation of the solution, substitution mechanism and structural parameters which are in excellent agreement with the experimental data. The stability of the phase is discussed. (C) 2012 Elsevier Inc. All rights reserved.

Platinum-Based Nanoalloys PtnTM55-n (TM=Co, Rh, Au): A Density Functional Theory Investigation

Structural and electronic properties of the PtnTM55-n (TM = Co, Rh, Au) nanoalloys are investigated using density functional theory within the generalized gradient approximation and employing the all-electron projected augmented wave method. For TM = Co and Rh, the excess energy, which measures the relative energy stability of the nanoalloys, is negative for all Pt compositions. We found that the excess energy has similar values for a wide range of Pt compositions, i.e., n = 20-42 and n = 28-42 for Co and Rh, respectively, with the core shell icosahedron-like configuration (n = 42) being slightly more stable for both Co and Rh systems because of the larger release of the strain energy due to the smaller atomic size of the Co and Rh atoms. For TM = Au, the excess energy is positive for all compositions, except for n = 13, which is energetically favorable due to the formation of the core-shell structure (Pt in the core and Au atoms at the surface). Thus, our calculations confirm that the formation of core-shell structures plays an important role to increase the stability of nanoalloys. The center of gravity of the occupied d-states changes almost linearly as a function of the Pt composition, and hence, based on the d-band model, the magnitude of the adsorption energy of an adsorbate can be tuned by changing the Pt composition. The magnetic moments of PtnCo55-n decrease almost linearly as a function of the Pt composition; however, the same does not hold for PtRh and PtAu. We found an enhancement of the magnetic moments of PtRh by a few times by increasing Pt composition, which we explain by the compression effects induced by the large size of the Pt atoms compared with the Rh atoms.

Study of the vertical transport in p-doped superlattices based on group III-V semiconductors

The electrical conductivity σ has been calculated for p-doped GaAs/Al0.3Ga0.7As and cubic GaN/Al0.3Ga0.7N thin superlattices (SLs). The calculations are done within a self-consistent approach to the k → ⋅ p → theory by means of a full six-band Luttinger-Kohn Hamiltonian, together with the Poisson equation in a plane wave representation, including exchange correlation effects within the local density approximation. It was also assumed that transport in the SL occurs through extended minibands states for each carrier, and the conductivity is calculated at zero temperature and in low-field ohmic limits by the quasi-chemical Boltzmann kinetic equation. It was shown that the particular minibands structure of the p-doped SLs leads to a plateau-like behavior in the conductivity as a function of the donor concentration and/or the Fermi level energy. In addition, it is shown that the Coulomb and exchange-correlation effects play an important role in these systems, since they determine the bending potential.

First principles calculations for vacancies and antisites in PbSe and PbTe: bulk and nanowire.

The energetic stability and the electronic properties of vacancies (VX) and antisites (XY) in PbSe and PbTe are investigated. PbSe and PbTe are narrow band gap semiconductors and have the potential to be used in infrared detectors, laser, and diodes. They are also of special interest for thermoelectric devices (TE). The calculations are based in the Density Functional Theory (DFT) and the General Gradient Approximation (GGA) for the exchange-correlation term, as implemented in the VASP code. The core and valence electrons are described by the Projected Augmented Wave (PAW) and the Plane Wave (PW) methods, respectively. The defects are studied in the bulk and nanowire (NW) system. Our results show that intrinsec defects (vacancies and antisites) in PbTe have lower formation energies in the NW as compared to the bulk and present a trend in migrate to the surface of the NW. For the PbSe we obtain similar results when compare the formation energy for the bulk and NW. However, the Pb vacancy and the antisites are more stable in the core of the NW. The intrinsec defects are shallow defects for the bulk system. For both PbSe and PbTe VPb is a shallow acceptor defect and VSe and VT e are shallow donor defects for the PbSe and PbTe, respectively. Similar electronic properties are observed for the antisites. For the Pb in the anion site we obtain an n-type semiconductor for both PbSe and PbTe, SeP b is a p-type for the PbSe, and T eP b is a n-type for PbTe. Due the quantum con¯nement effects present in the NW (the band gap open), these defects have different electronic properties for the NW as compared to the bulk. Now these defects give rise to electronic levels in the band gap of the PbTe NW and the VT e present a metallic character. For the PbSe NW a p-type and a n-type semiconductor is obtained for the VP b and P bSe, respectively. On the other hand, deep electronic levels are present in the band gap for the VSe and SePb. These results show that due an enhanced in the electronic density of states (DOS) near the Fermi energy, the defective PbSe and PbTe are candidates for efficient TE devices.

Finite element models of coseismic deformation due to the 2009 L'Aquila (Italy) and 2008 Wenchuan(China) earthquakes

The topic of my Ph.D. thesis is the finite element modeling of coseismic deformation imaged by DInSAR and GPS data. I developed a method to calculate synthetic Green functions with finite element models (FEMs) and then use linear inversion methods to determine the slip distribution on the fault plane. The method is applied to the 2009 L’Aquila Earthquake (Italy) and to the 2008 Wenchuan earthquake (China). I focus on the influence of rheological features of the earth's crust by implementing seismic tomographic data and the influence of topography by implementing Digital Elevation Models (DEM) layers on the FEMs. Results for the L’Aquila earthquake highlight the non-negligible influence of the medium structure: homogeneous and heterogeneous models show discrepancies up to 20% in the fault slip distribution values. Furthermore, in the heterogeneous models a new area of slip appears above the hypocenter. Regarding the 2008 Wenchuan earthquake, the very steep topographic relief of Longmen Shan Range is implemented in my FE model. A large number of DEM layers corresponding to East China is used to achieve the complete coverage of the FE model. My objective was to explore the influence of the topography on the retrieved coseismic slip distribution. The inversion results reveals significant differences between the flat and topographic model. Thus, the flat models frequently adopted are inappropriate to represent the earth surface topographic features and especially in the case of the 2008 Wenchuan earthquake.

Ab-initio determination of x-ray absorption near edge structure (xanes) spectra in an ultrasoft and norm conserving pseudopotentials scheme

X-ray absorption spectroscopy (XAS) is a powerful means of investigation of structural and electronic properties in condensed -matter physics. Analysis of the near edge part of the XAS spectrum, the so – called X-ray Absorption Near Edge Structure (XANES), can typically provide the following information on the photoexcited atom: - Oxidation state and coordination environment. - Speciation of transition metal compounds. - Conduction band DOS projected on the excited atomic species (PDOS). Analysis of XANES spectra is greatly aided by simulations; in the most common scheme the multiple scattering framework is used with the muffin tin approximation for the scattering potential and the spectral simulation is based on a hypothetical, reference structure. This approach has the advantage of requiring relatively little computing power but in many cases the assumed structure is quite different from the actual system measured and the muffin tin approximation is not adequate for low symmetry structures or highly directional bonds. It is therefore very interesting and justified to develop alternative methods. In one approach, the spectral simulation is based on atomic coordinates obtained from a DFT (Density Functional Theory) optimized structure. In another approach, which is the object of this thesis, the XANES spectrum is calculated directly based on an ab – initio DFT calculation of the atomic and electronic structure. This method takes full advantage of the real many-electron final wavefunction that can be computed with DFT algorithms that include a core-hole in the absorbing atom to compute the final cross section. To calculate the many-electron final wavefunction the Projector Augmented Wave method (PAW) is used. In this scheme, the absorption cross section is written in function of several contributions as the many-electrons function of the finale state; it is calculated starting from pseudo-wavefunction and performing a reconstruction of the real-wavefunction by using a transform operator which contains some parameters, called partial waves and projector waves. The aim of my thesis is to apply and test the PAW methodology to the calculation of the XANES cross section. I have focused on iron and silicon structures and on some biological molecules target (myoglobin and cytochrome c). Finally other inorganic and biological systems could be taken into account for future applications of this methodology, which could become an important improvement with respect to the multiscattering approach.

Effectiveness of a nondestructive evaluation technique for assessing standing timber quality

The research presented in this thesis was conducted to further the development of the stress wave method of nondestructively assessing the quality of wood in standing trees. The specific objective of this research was to examine, in the field, use of two stress wave nondestructive assessment techniques. The first technique examined utilizes a laboratory-built measurement system consisting of commercially available accelerometers and a digital storage oscilloscope. The second technique uses a commercially available tool that incorporates several technologies to determine speed of stress wave propagation in standing trees. Field measurements using both techniques were conducted on sixty red pine trees in south-central Wisconsin and 115 ponderosa pine trees in western Idaho. After in-situ measurements were taken, thirty tested red pine trees were felled and a 15-foot-long butt log was obtained from each tree, while all tested ponderosa pine trees were felled and an 8 1/2 -foot-long butt log was obtained, respectively. The butt logs were sent to the USDA Forest Products Laboratory and nondestructively tested using a resonance stress wave technique. Strong correlative relationships were observed between stress wave values obtained from both field measurement techniques. Excellent relationships were also observed between standing tree and log speed-of-sound values.

Development of a high performance parallel computing platform and its use in the study of nanostructures : clusters, sheets and tubes .

Small clusters of gallium oxide, technologically important high temperature ceramic, together with interaction of nucleic acid bases with graphene and small-diameter carbon nanotube are focus of first principles calculations in this work. A high performance parallel computing platform is also developed to perform these calculations at Michigan Tech. First principles calculations are based on density functional theory employing either local density or gradient-corrected approximation together with plane wave and gaussian basis sets. The bulk Ga2O3 is known to be a very good candidate for fabricating electronic devices that operate at high temperatures. To explore the properties of Ga2O3 at nonoscale, we have performed a systematic theoretical study on the small polyatomic gallium oxide clusters. The calculated results find that all lowest energy isomers of GamOn clusters are dominated by the Ga-O bonds over the metal-metal or the oxygen-oxygen bonds. Analysis of atomic charges suggest the clusters to be highly ionic similar to the case of bulk Ga2O3. In the study of sequential oxidation of these slusters starting from Ga2O, it is found that the most stable isomers display up to four different backbones of constituent atoms. Furthermore, the predicted configuration of the ground state of Ga2O is recently confirmed by the experimental result of Neumark's group. Guided by the results of calculations the study of gallium oxide clusters, performance related challenge of computational simulations, of producing high performance computers/platforms, has been addressed. Several engineering aspects were thoroughly studied during the design, development and implementation of the high performance parallel computing platform, rama, at Michigan Tech. In an attempt to stay true to the principles of Beowulf revolutioni, the rama cluster was extensively customized to make it easy to understand, and use - for administrators as well as end-users. Following the results of benchmark calculations and to keep up with the complexity of systems under study, rama has been expanded to a total of sixty four processors. Interest in the non-covalent intereaction of DNA with carbon nanotubes has steadily increased during past several years. This hybrid system, at the junction of the biological regime and the nanomaterials world, possesses features which make it very attractive for a wide range of applicatioins. Using the in-house computational power available, we have studied details of the interaction between nucleic acid bases with graphene sheet as well as high-curvature small-diameter carbon nanotube. The calculated trend in the binding energies strongly suggests that the polarizability of the base molecules determines the interaction strength of the nucleic acid bases with graphene. When comparing the results obtained here for physisorption on the small diameter nanotube considered with those from the study on graphene, it is observed that the interaction strength of nucleic acid bases is smaller for the tube. Thus, these results show that the effect of introducing curvature is to reduce the binding energy. The binding energies for the two extreme cases of negligible curvature (i.e. flat graphene sheet) and of very high curvature (i.e. small diameter nanotube) may be considered as upper and lower bounds. This finding represents an important step towards a better understanding of experimentally observed sequence-dependent interaction of DNA with Carbon nanotubes.

Reduced order models for industrial thermo-fluid problems

A new method is presented to generate reduced order models (ROMs) in Fluid Dynamics problems of industrial interest. The method is based on the expansion of the flow variables in a Proper Orthogonal Decomposition (POD) basis, calculated from a limited number of snapshots, which are obtained via Computational Fluid Dynamics (CFD). Then, the POD-mode amplitudes are calculated as minimizers of a properly defined overall residual of the equations and boundary conditions. The method includes various ingredients that are new in this field. The residual can be calculated using only a limited number of points in the flow field, which can be scattered either all over the whole computational domain or over a smaller projection window. The resulting ROM is both computationally efficient(reconstructed flow fields require, in cases that do not present shock waves, less than 1 % of the time needed to compute a full CFD solution) and flexible(the projection window can avoid regions of large localized CFD errors).Also, for problems related with aerodynamics, POD modes are obtained from a set of snapshots calculated by a CFD method based on the compressible Navier Stokes equations and a turbulence model (which further more includes some unphysical stabilizing terms that are included for purely numerical reasons), but projection onto the POD manifold is made using the inviscid Euler equations, which makes the method independent of the CFD scheme. In addition, shock waves are treated specifically in the POD description, to avoid the need of using a too large number of snapshots. Various definitions of the residual are also discussed, along with the number and distribution of snapshots, the number of retained modes, and the effect of CFD errors. The method is checked and discussed on several test problems that describe (i) heat transfer in the recirculation region downstream of a backwards facing step, (ii) the flow past a two-dimensional airfoil in both the subsonic and transonic regimes, and (iii) the flow past a three-dimensional horizontal tail plane. The method is both efficient and numerically robust in the sense that the computational effort is quite small compared to CFD and results are both reasonably accurate and largely insensitive to the definition of the residual, to CFD errors, and to the CFD method itself, which may contain artificial stabilizing terms. Thus, the method is amenable for practical engineering applications. Resumen Se presenta un nuevo método para generar modelos de orden reducido (ROMs) aplicado a problemas fluidodinámicos de interés industrial. El nuevo método se basa en la expansión de las variables fluidas en una base POD, calculada a partir de un cierto número de snapshots, los cuales se han obtenido gracias a simulaciones numéricas (CFD). A continuación, las amplitudes de los modos POD se calculan minimizando un residual global adecuadamente definido que combina las ecuaciones y las condiciones de contorno. El método incluye varios ingredientes que son nuevos en este campo de estudio. El residual puede calcularse utilizando únicamente un número limitado de puntos del campo fluido. Estos puntos puede encontrarse dispersos a lo largo del dominio computacional completo o sobre una ventana de proyección. El modelo ROM obtenido es tanto computacionalmente eficiente (en aquellos casos que no presentan ondas de choque reconstruir los campos fluidos requiere menos del 1% del tiempo necesario para calcular una solución CFD) como flexible (la ventana de proyección puede escogerse de forma que evite contener regiones con errores en la solución CFD localizados y grandes). Además, en problemas aerodinámicos, los modos POD se obtienen de un conjunto de snapshots calculados utilizando un código CFD basado en la versión compresible de las ecuaciones de Navier Stokes y un modelo de turbulencia (el cual puede incluir algunos términos estabilizadores sin sentido físico que se añaden por razones puramente numéricas), aunque la proyección en la variedad POD se hace utilizando las ecuaciones de Euler, lo que hace al método independiente del esquema utilizado en el código CFD. Además, las ondas de choque se tratan específicamente en la descripción POD para evitar la necesidad de utilizar un número demasiado grande de snapshots. Varias definiciones del residual se discuten, así como el número y distribución de los snapshots,el número de modos retenidos y el efecto de los errores debidos al CFD. El método se comprueba y discute para varios problemas de evaluación que describen (i) la transferencia de calor en la región de recirculación aguas abajo de un escalón, (ii) el flujo alrededor de un perfil bidimensional en regímenes subsónico y transónico y (iii) el flujo alrededor de un estabilizador horizontal tridimensional. El método es tanto eficiente como numéricamente robusto en el sentido de que el esfuerzo computacional es muy pequeño comparado con el requerido por el CFD y los resultados son razonablemente precisos y muy insensibles a la definición del residual, los errores debidos al CFD y al método CFD en sí mismo, el cual puede contener términos estabilizadores artificiales. Por lo tanto, el método puede utilizarse en aplicaciones prácticas de ingeniería.

In situ acoustic methods to estimate the physical and mechanical aging of oriented strand board

Following the success achieved in previous research projects usin non-destructive methods to estimate the physical and mechanical aging of particle and fibre boards, this paper studies the relationships between aging, physical and mechanical changes, using non-destructive measurements of oriented strand board (OSB). 184 pieces of OSB board from a French source were tested to analyze its actual physical and mechanical properties. The same properties were estimated using acoustic non-destructive methods (ultrasound and stress wave velocity) during a physical laboratory aging test. Measurements were recorded of propagation wave velocity with the sensors aligned, edge to edge, and forming an angle of 45 degrees, with both sensors on the same face of the board. This is because aligned measures are not possible on site. The velocity results are always higher in 45 degree measurements. Given the results of statistical analysis, it can be concluded that there is a strong relationship between acoustic measurements and the decline in physical and mechanical properties of the panels due to aging. The authors propose several models to estimate the physical and mechanical properties of board, as well as their degree of aging. The best results are obtained using ultrasound, although the difference in comparison with the stress wave method is not very significant. A reliable prediction of the degree of deterioration (aging) of board is presented.