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Sample records for cowo4 tungstates first-principles

  1. Synchrotron-based far-infrared spectroscopy of nickel tungstate

    NASA Astrophysics Data System (ADS)

    Kalinko, A.; Kuzmin, A.; Roy, P.; Evarestov, R. A.

    2016-07-01

    Monoclinic antiferromagnetic NiWO4 was studied by far-infrared (30-600 cm-1) absorption spectroscopy in the temperature range of 5-300 K using the synchrotron radiation from SOLEIL source. Two isomorphous CoWO4 and ZnWO4 tungstates were investigated for comparison. The phonon contributions in the far-infrared range of tungstates were interpreted using the first-principles spin-polarized linear combination of atomic orbital calculations. No contributions from magnetic excitations were found in NiWO4 and CoWO4 below their Neel temperatures down to 5 K.

  2. Optical phonon modes and infrared dielectric properties of monoclinic CoWO4 microcrystals

    NASA Astrophysics Data System (ADS)

    Moreira, Roberto L.; Almeida, Rafael M.; Siqueira, Kisla P. F.; Abreu, Cintia G.; Dias, Anderson

    2016-02-01

    The phonon characteristics of CoWO4 microcrystals with monoclinic Wolframite structure were investigated by far-infrared (IR) and Raman spectroscopies. Near-normal spectra were taken for IR light polarization along the principal b-axis (A u modes) and along several angles within the ac-plane (B u modes). The IR spectra were analyzed with a generalized Drude-Lorentz model, and all predicted polar phonon modes were fully determined, including their symmetries, the dielectric Lorentz parameters and the non-orthogonal phonon polarizations for the B u modes. Anomalous dispersion and negative values for the real and imaginary parts of the off-diagonal components of the dielectric tensor functions were identified and discussed under the light of the varying phonon polarization directions (spread out in the ac-plane). The obtained static and background dielectric tensors gave an average permittivity of 16.1 (at microwave region), refractive indices along the principal dielectric axes of 2.22, 2.33 and 2.44 (at 1 μm), the optical axes, and an estimated value for the biaxial angle of the crystal. Polarized Raman spectra on appropriate scattering configurations revealed the 18 non-polar gerade phonons of CoWO4 crystals, with their correct symmetries attributed.

  3. Large-scale synthesis and photoluminescence of cobalt tungstate nanowires

    NASA Astrophysics Data System (ADS)

    Zhang, Cuiling; Guo, Donglin; Hu, Chenguo; Chen, Yanxue; Liu, Hong; Zhang, Hulin; Wang, Xue

    2013-01-01

    Single-crystalline wolframite-type monoclinic structure cobalt tungstate (CoWO4) nanowires were obtained by a solvothermal method at 180 °C for 24 h with a width of 20 nm and length of 200 to 400 nm. Besides the strong blue-green light emission at 10-250 K, we found much stronger and broader near-infrared emission ranging from 700-1000 nm at about 300 K under the excitation wavelength of 325 nm. The emission and the dependence of emission intensity on temperature are discussed by introducing the effect of Co vacancies. This near-infrared emission material might have potential applications in infrared detection or stealth technology.

  4. Culturing conceptions: From first principles

    NASA Astrophysics Data System (ADS)

    Roth, Wolff-Michael; Lee, Yew Jin; Hwang, Sungwon

    2008-07-01

    Over the past three decades, science educators have accumulated a vast amount of information on conceptions--variously defined as beliefs, ontologies, cognitive structures, mental models, or frameworks--that generally (at least initially) have been derived from interviews about certain topics. During the same time period, cultural studies has emerged as a field in which everyday social practices are interrogated with the objective to understand culture in all its complexity. Science educators have however yet to ask themselves what it would mean to consider the possession of conceptions as well as conceptual change from the perspective of cultural studies. The purpose of this article is thus to articulate in and through the analysis of an interview about natural phenomenon the first principles of such a cultural approach to scientific conceptions. Our bottom-up approach in fact leads us to develop the kind of analyses and theories that have become widespread in cultural studies. This promises to generate less presupposing and more parsimonious explanations of this core issue within science education than if conceptions are supposed to be structures inhabiting the human mind.

  5. Chamber Clearing First Principles Modeling

    SciTech Connect

    Loosmore, G

    2009-06-09

    LIFE fusion is designed to generate 37.5 MJ of energy per shot, at 13.3 Hz, for a total average fusion power of 500 MW. The energy from each shot is partitioned among neutrons ({approx}78%), x-rays ({approx}12%), and ions ({approx}10%). First wall heating is dominated by x-rays and debris because the neutron mean free path is much longer than the wall thickness. Ion implantation in the first wall also causes damage such as blistering if not prevented. To moderate the peak-pulse heating, the LIFE fusion chamber is filled with a gas (such as xenon) to reduce the peak-pulse heat load. The debris ions and majority of the x-rays stop in the gas, which re-radiates this energy over a longer timescale (allowing time for heat conduction to cool the first wall sufficiently to avoid damage). After a shot, because of the x-ray and ion deposition, the chamber fill gas is hot and turbulent and contains debris ions. The debris needs to be removed. The ions increase the gas density, may cluster or form aerosols, and can interfere with the propagation of the laser beams to the target for the next shot. Moreover, the tritium and high-Z hohlraum debris needs to be recovered for reuse. Additionally, the cryogenic target needs to survive transport through the gas mixture to the chamber center. Hence, it will be necessary to clear the chamber of the hot contaminated gas mixture and refill it with a cool, clean gas between shots. The refilling process may create density gradients that could interfere with beam propagation, so the fluid dynamics must be studied carefully. This paper describes an analytic modeling effort to study the clearing and refilling process for the LIFE fusion chamber. The models used here are derived from first principles and balances of mass and energy, with the intent of providing a first estimate of clearing rates, clearing times, fractional removal of ions, equilibrated chamber temperatures, and equilibrated ion concentrations for the chamber. These can be used

  6. Description of charge conjugation from first principles

    SciTech Connect

    Lujan-Peschard, C.; Napsuciale, M.

    2006-09-25

    We construct the charge conjugation operator as a unitary automorphism in the spinor space ((1/2), 0) + (0 (1/2)) from first principles. We calculate its eigenspinors and derive the equation of motion they satisfy. The mapping associated to charge conjugation is constructed from parity eigenstates which are considered as particle and antiparticle.

  7. Interface Structure Prediction from First-Principles

    SciTech Connect

    Zhao, Xin; Shu, Qiang; Nguyen, Manh Cuong; Wang, Yangang; Ji, Min; Xiang, Hongjun; Ho, Kai-Ming; Gong, Xingao; Wang, Cai-Zhuang

    2014-05-08

    Information about the atomic structures at solid–solid interfaces is crucial for understanding and predicting the performance of materials. Due to the complexity of the interfaces, it is very challenging to resolve their atomic structures using either experimental techniques or computer simulations. In this paper, we present an efficient first-principles computational method for interface structure prediction based on an adaptive genetic algorithm. This approach significantly reduces the computational cost, while retaining the accuracy of first-principles prediction. The method is applied to the investigation of both stoichiometric and nonstoichiometric SrTiO3 Σ3(112)[1¯10] grain boundaries with unit cell containing up to 200 atoms. Several novel low-energy structures are discovered, which provide fresh insights into the structure and stability of the grain boundaries.

  8. First-principles transversal DNA conductance deconstructed

    SciTech Connect

    Zhang, Xiaoguang; Krstic, Predrag; Zikic, Radomir; Wells, Jack C; Fuentes-Cabrera, Miguel A

    2006-01-01

    First-principles calculation of the transverse conductance across DNA fragments placed between gold nanoelectrodes, reveals that such conductance describes electron tunneling that depends critically on geometrical rather than electronic-structure properties. By factoring the first-principles result into two simple and approximately independent tunneling factors, we show that the conductances of the A, C, G, and T fragments differ only because of their sizes: the larger is the DNA base, the smaller is the distance that separates the electrode from the corresponding molecule, and the larger is its conductance. Because the geometrical factors are difficult to control in an experiment, the DC-current measurements across DNA may not be a convenient approach to DNA sequencing.

  9. First principles determination of dislocation properties.

    SciTech Connect

    Hamilton, John C.

    2003-12-01

    This report details the work accomplished on first principles determination of dislocation properties. It contains an introduction and three chapters detailing three major accomplishments. First, we have used first principle calculations to determine the shear strength of an aluminum twin boundary. We find it to be remarkably small ({approx}17 mJ/m{sup 2}). This unexpected result is explained and will likely pertain for many other grain boundaries. Second, we have proven that the conventional explanation for finite grain boundary facets is wrong for a particular aluminum grain boundary. Instead of finite facets being stabilized by grain boundary stress, we find them to originate from kinetic effects. Finally we report on a new application of the Frenkel-Kontorova model to understand reconstructions of (100) type surfaces. In addition to the commonly accepted formation of rectangular dislocation arrays, we find numerous other possible solutions to the model including hexagonal reconstructions and a clock-rotated structure.

  10. First principle thousand atom quantum dot calculations

    SciTech Connect

    Wang, Lin-Wang; Li, Jingbo

    2004-03-30

    A charge patching method and an idealized surface passivation are used to calculate the single electronic states of IV-IV, III-V, II-VI semiconductor quantum dots up to a thousand atoms. This approach scales linearly and has a 1000 fold speed-up compared to direct first principle methods with a cost of eigen energy error of about 20 meV. The calculated quantum dot band gaps are parametrized for future references.

  11. First principles semiclassical calculations of vibrational eigenfunctions.

    PubMed

    Ceotto, Michele; Valleau, Stéphanie; Tantardini, Gian Franco; Aspuru-Guzik, Alán

    2011-06-21

    Vibrational eigenfunctions are calculated on-the-fly using semiclassical methods in conjunction with ab initio density functional theory classical trajectories. Various semiclassical approximations based on the time-dependent representation of the eigenfunctions are tested on an analytical potential describing the chemisorption of CO on Cu(100). Then, first principles semiclassical vibrational eigenfunctions are calculated for the CO(2) molecule and its accuracy evaluated. The multiple coherent states initial value representations semiclassical method recently developed by us has shown with only six ab initio trajectories to evaluate eigenvalues and eigenfunctions at the accuracy level of thousands trajectory semiclassical initial value representation simulations. PMID:21837839

  12. First principles calculations for lithiated manganese oxides.

    SciTech Connect

    Prasad, R.

    1998-12-23

    First principles calculations within the local-spin-density-functional theory (LSDFF) framework are presented of densities of electronic states for MnO, LiMnO{sub 2} in the monoclinic and orthorhombic structures, cubic LiMn{sub 2}O{sub 4} spinel and {lambda}-MnO{sub 2} (delithiated spinel), all in antiferromagnetic spin configurations. The changes in energy spectra as the Mn oxidation state varies between 2+ and 4+ are illustrated. Preliminary calculations for Co-doped LiMnO{sub 2} are presented, and the destabilization of a monoclinic relative to a rhombohedral structure is discussed.

  13. First-Principles pH Theory

    NASA Astrophysics Data System (ADS)

    Kim, Yong-Hyun; Zhang, S. B.

    2006-03-01

    Despite being one of the most important macroscopic measures and a long history even before the quantum mechanics, the concept of pH has rarely been mentioned in microscopic theories, nor being incorporated computationally into first-principles theory of aqueous solutions. Here, we formulate a theory for the pH dependence of solution formation energy by introducing the proton chemical potential as the microscopic counterpart of pH in atomistic solution models. Within the theory, the general acid-base chemistry can be cast in a simple pictorial representation. We adopt density-functional molecular dynamics to demonstrate the usefulness of the method by studying a number of solution systems including water, small solute molecules such as NH3 and HCOOH, and more complex amino acids with several functional groups. For pure water, we calculated the auto- ionization constant to be 13.2 with a 95 % accuracy. For other solutes, the calculated dissociation constants, i.e., the so- called pKa, are also in reasonable agreement with experiments. Our first-principles pH theory can be readily applied to broad solution chemistry problems such as redox reactions.

  14. Iron diffusion from first principles calculations

    NASA Astrophysics Data System (ADS)

    Wann, E.; Ammann, M. W.; Vocadlo, L.; Wood, I. G.; Lord, O. T.; Brodholt, J. P.; Dobson, D. P.

    2013-12-01

    The cores of Earth and other terrestrial planets are made up largely of iron1 and it is therefore very important to understand iron's physical properties. Chemical diffusion is one such property and is central to many processes, such as crystal growth, and viscosity. Debate still surrounds the explanation for the seismologically observed anisotropy of the inner core2, and hypotheses include convection3, anisotropic growth4 and dendritic growth5, all of which depend on diffusion. In addition to this, the main deformation mechanism at the inner-outer core boundary is believed to be diffusion creep6. It is clear, therefore, that to gain a comprehensive understanding of the core, a thorough understanding of diffusion is necessary. The extremely high pressures and temperatures of the Earth's core make experiments at these conditions a challenge. Low-temperature and low-pressure experimental data must be extrapolated across a very wide gap to reach the relevant conditions, resulting in very poorly constrained values for diffusivity and viscosity. In addition to these dangers of extrapolation, preliminary results show that magnetisation plays a major role in the activation energies for diffusion at low pressures therefore creating a break down in homologous scaling to high pressures. First principles calculations provide a means of investigating diffusivity at core conditions, have already been shown to be in very good agreement with experiments7, and will certainly provide a better estimate for diffusivity than extrapolation. Here, we present first principles simulations of self-diffusion in solid iron for the FCC, BCC and HCP structures at core conditions in addition to low-temperature and low-pressure calculations relevant to experimental data. 1. Birch, F. Density and composition of mantle and core. Journal of Geophysical Research 69, 4377-4388 (1964). 2. Irving, J. C. E. & Deuss, A. Hemispherical structure in inner core velocity anisotropy. Journal of Geophysical

  15. First principles studies on anatase surfaces

    NASA Astrophysics Data System (ADS)

    Selcuk, Sencer

    TiO2 is one of the most widely studied metal oxides from both the fundamental and the technological points of view. A variety of applications have already been developed in the fields of energy production, environmental remediation, and electronics. Still, it is considered to have a high potential for further improvement and continues to be of great interest. This thesis describes our theoretical studies on the structural and electronic properties of anatase surfaces, and their (photo)chemical behavior. Recently much attention has been focused on anatase crystals synthesized by hydrofluoric acid assisted methods. These crystals exhibit a high percentage of {001} facets, generally considered to be highly reactive. We used first principles methods to investigate the structure of these facets, which is not yet well understood. Our results suggest that (001) surfaces exhibit the bulk-terminated structure when in contact with concentrated HF solutions. However, 1x4-reconstructed surfaces, as observed in UHV, become always more stable at the typical temperatures used to clean the as-prepared crystals in experiments. Since the reconstructed surfaces are only weakly reactive, we predict that synthetic anatase crystals with dominant {001} facets should not exhibit enhanced photocatalytic activity. Understanding how defects in solids interact with external electric fields is important for technological applications such as memristor devices. We studied the influence of an external electric field on the formation energies and diffusion barriers of the surface and the subsurface oxygen vacancies at the anatase (101) surface from first principles. Our results show that the applied field can have a significant influence on the relative stabilities of these defects, whereas the effect on the subsurface-to-surface defect migration is found to be relatively minor. Charge carriers play a key role in the transport properties and the surface chemistry of TiO2. Understanding their

  16. Numerical inductance calculations based on first principles.

    PubMed

    Shatz, Lisa F; Christensen, Craig W

    2014-01-01

    A method of calculating inductances based on first principles is presented, which has the advantage over the more popular simulators in that fundamental formulas are explicitly used so that a deeper understanding of the inductance calculation is obtained with no need for explicit discretization of the inductor. It also has the advantage over the traditional method of formulas or table lookups in that it can be used for a wider range of configurations. It relies on the use of fast computers with a sophisticated mathematical computing language such as Mathematica to perform the required integration numerically so that the researcher can focus on the physics of the inductance calculation and not on the numerical integration. PMID:25402467

  17. First-principles simulations of thiophene oligomers

    NASA Astrophysics Data System (ADS)

    Scherlis, Damian; Marzari, Nicola

    2003-03-01

    Conducting polymers, extensively investigated for their use in electronic and nanotechnology applications, have recently gained prominence for their possible use as molecular actuators in mechanical and bioengineering devices. We have focused our efforts on thiophene-based compounds, a class of materials that can be designed for high stress generation and large linear displacement (actuation strain), ideally outperforming mammalian muscle. Key features for the development of these materials are the microscopic binding properties of thiophene and thiophene oligomers stacks, where applied electric fields lead to oxidation and enhanced pi-pi bonding. We have completed the structural studies of neutral and charged oligothiophene dimers, in the search for efficient dimerization mechanisms. A comparison between different density-functional and quantum-chemistry approaches is critically presented, as are solvation effects, described in this work with a combination of first-principles molecular dynamics and a QM/MM approach for the solvating medium.

  18. Phonon-phonon interactions: First principles theory

    SciTech Connect

    Gibbons, T. M.; Bebek, M. B.; Kang, By.; Stanley, C. M.; Estreicher, S. K.

    2015-08-28

    We present the details of a method to perform molecular-dynamics (MD) simulations without thermostat and with very small temperature fluctuations ±ΔT starting with MD step 1. It involves preparing the supercell at the time t = 0 in physically correct microstates using the eigenvectors of the dynamical matrix. Each initial microstate corresponds to a different distribution of kinetic and potential energies for each vibrational mode (the total energy of each microstate is the same). Averaging the MD runs over many initial microstates further reduces ΔT. The electronic states are obtained using first-principles theory (density-functional theory in periodic supercells). Three applications are discussed: the lifetime and decay of vibrational excitations, the isotope dependence of thermal conductivities, and the flow of heat at an interface.

  19. Intrinsic ferroelectric switching from first principles

    NASA Astrophysics Data System (ADS)

    Liu, Shi; Grinberg, Ilya; Rappe, Andrew M.

    2016-06-01

    The existence of domain walls, which separate regions of different polarization, can influence the dielectric, piezoelectric, pyroelectric and electronic properties of ferroelectric materials. In particular, domain-wall motion is crucial for polarization switching, which is characterized by the hysteresis loop that is a signature feature of ferroelectric materials. Experimentally, the observed dynamics of polarization switching and domain-wall motion are usually explained as the behaviour of an elastic interface pinned by a random potential that is generated by defects, which appear to be strongly sample-dependent and affected by various elastic, microstructural and other extrinsic effects. Theoretically, connecting the zero-kelvin, first-principles-based, microscopic quantities of a sample with finite-temperature, macroscopic properties such as the coercive field is critical for material design and device performance; and the lack of such a connection has prevented the use of techniques based on ab initio calculations for high-throughput computational materials discovery. Here we use molecular dynamics simulations of 90° domain walls (separating domains with orthogonal polarization directions) in the ferroelectric material PbTiO3 to provide microscopic insights that enable the construction of a simple, universal, nucleation-and-growth-based analytical model that quantifies the dynamics of many types of domain walls in various ferroelectrics. We then predict the temperature and frequency dependence of hysteresis loops and coercive fields at finite temperatures from first principles. We find that, even in the absence of defects, the intrinsic temperature and field dependence of the domain-wall velocity can be described with a nonlinear creep-like region and a depinning-like region. Our model enables quantitative estimation of coercive fields, which agree well with experimental results for ceramics and thin films. This agreement between model and experiment suggests

  20. Intrinsic ferroelectric switching from first principles.

    PubMed

    Liu, Shi; Grinberg, Ilya; Rappe, Andrew M

    2016-06-16

    The existence of domain walls, which separate regions of different polarization, can influence the dielectric, piezoelectric, pyroelectric and electronic properties of ferroelectric materials. In particular, domain-wall motion is crucial for polarization switching, which is characterized by the hysteresis loop that is a signature feature of ferroelectric materials. Experimentally, the observed dynamics of polarization switching and domain-wall motion are usually explained as the behaviour of an elastic interface pinned by a random potential that is generated by defects, which appear to be strongly sample-dependent and affected by various elastic, microstructural and other extrinsic effects. Theoretically, connecting the zero-kelvin, first-principles-based, microscopic quantities of a sample with finite-temperature, macroscopic properties such as the coercive field is critical for material design and device performance; and the lack of such a connection has prevented the use of techniques based on ab initio calculations for high-throughput computational materials discovery. Here we use molecular dynamics simulations of 90° domain walls (separating domains with orthogonal polarization directions) in the ferroelectric material PbTiO3 to provide microscopic insights that enable the construction of a simple, universal, nucleation-and-growth-based analytical model that quantifies the dynamics of many types of domain walls in various ferroelectrics. We then predict the temperature and frequency dependence of hysteresis loops and coercive fields at finite temperatures from first principles. We find that, even in the absence of defects, the intrinsic temperature and field dependence of the domain-wall velocity can be described with a nonlinear creep-like region and a depinning-like region. Our model enables quantitative estimation of coercive fields, which agree well with experimental results for ceramics and thin films. This agreement between model and experiment suggests

  1. Safeguards First Principle Initiative (SFPI) Cost Model

    SciTech Connect

    Mary Alice Price

    2010-07-11

    The Nevada Test Site (NTS) began operating Material Control and Accountability (MC&A) under the Safeguards First Principle Initiative (SFPI), a risk-based and cost-effective program, in December 2006. The NTS SFPI Comprehensive Assessment of Safeguards Systems (COMPASS) Model is made up of specific elements (MC&A plan, graded safeguards, accounting systems, measurements, containment, surveillance, physical inventories, shipper/receiver differences, assessments/performance tests) and various sub-elements, which are each assigned effectiveness and contribution factors that when weighted and rated reflect the health of the MC&A program. The MC&A Cost Model, using an Excel workbook, calculates budget and/or actual costs using these same elements/sub-elements resulting in total costs and effectiveness costs per element/sub-element. These calculations allow management to identify how costs are distributed for each element/sub-element. The Cost Model, as part of the SFPI program review process, enables management to determine if spending is appropriate for each element/sub-element.

  2. First principle study of sodium decorated graphyne

    NASA Astrophysics Data System (ADS)

    Sarkar, Utpal; Bhattacharya, Barnali; Seriani, Nicola

    2015-11-01

    We present first-principles calculations of the electronic properties of Na-decorated graphyne. This structure of the graphyne family is a direct band gap semiconductor with a band gap of 0.44 eV in absence of sodium, but Na-decorated graphyne compounds are metallic, and can then be employed as carbon-based conductors. Metallization is due to charge donation from sodium to carbon. Pristine graphyne is more stable than Na-decorated graphyne, therefore is seems probable that, if this material should be employed as electrode in Na-ion batteries, it would lead to the formation of metallic sodium rather than well dispersed sodium ions. On the other side, this property might be useful if graphyne is employed in water desalination. Finally, the abrupt change from a semiconducting to a metallic state in presence of a small amount of sodium might be exploited in electronics, e.g. for the production of smooth metal-semiconductor interfaces through spatially selective deposition of sodium.

  3. First-principles calculations of novel materials

    NASA Astrophysics Data System (ADS)

    Sun, Jifeng

    Computational material simulation is becoming more and more important as a branch of material science. Depending on the scale of the systems, there are many simulation methods, i.e. first-principles calculation (or ab-initio), molecular dynamics, mesoscale methods and continuum methods. Among them, first-principles calculation, which involves density functional theory (DFT) and based on quantum mechanics, has become to be a reliable tool in condensed matter physics. DFT is a single-electron approximation in solving the many-body problems. Intrinsically speaking, both DFT and ab-initio belong to the first-principles calculation since the theoretical background of ab-initio is Hartree-Fock (HF) approximation and both are aimed at solving the Schrodinger equation of the many-body system using the self-consistent field (SCF) method and calculating the ground state properties. The difference is that DFT introduces parameters either from experiments or from other molecular dynamic (MD) calculations to approximate the expressions of the exchange-correlation terms. The exchange term is accurately calculated but the correlation term is neglected in HF. In this dissertation, DFT based first-principles calculations were performed for all the novel materials and interesting materials introduced. Specifically, the DFT theory together with the rationale behind related properties (e.g. electronic, optical, defect, thermoelectric, magnetic) are introduced in Chapter 2. Starting from Chapter 3 to Chapter 5, several representative materials were studied. In particular, a new semiconducting oxytelluride, Ba2TeO is studied in Chapter 3. Our calculations indicate a direct semiconducting character with a band gap value of 2.43 eV, which agrees well with the optical experiment (˜ 2.93 eV). Moreover, the optical and defects properties of Ba2TeO are also systematically investigated with a view to understanding its potential as an optoelectronic or transparent conducting material. We find

  4. First principles model of carbonate compaction creep

    NASA Astrophysics Data System (ADS)

    Keszthelyi, Daniel; Dysthe, Dag Kristian; Jamtveit, Bjørn

    2016-05-01

    Rocks under compressional stress conditions are subject to long-term creep deformation. From first principles we develop a simple micromechanical model of creep in rocks under compressional stress that combines microscopic fracturing and pressure solution. This model was then upscaled by a statistical mechanical approach to predict strain rate at core and reservoir scale. The model uses no fitting parameter and has few input parameters: effective stress, temperature, water saturation porosity, and material parameters. Material parameters are porosity, pore size distribution, Young's modulus, interfacial energy of wet calcite, the dissolution, and precipitation rates of calcite, and the diffusion rate of calcium carbonate, all of which are independently measurable without performing any type of deformation or creep test. Existing long-term creep experiments were used to test the model which successfully predicts the magnitude of the resulting strain rate under very different effective stress, temperature, and water saturation conditions. The model was used to predict the observed compaction of a producing chalk reservoir.

  5. Transition Metal Nitrides: A First Principles Study

    NASA Astrophysics Data System (ADS)

    Pathak, Ashish; Singh, A. K.

    2016-04-01

    The present work describes the structural stability and electronic and mechanical properties of transition metal nitrides (TmNs: B1 cubic structure (cF8, Fm ‾ overline 3 m)) using first principles density functional theory (DFT) within generalized gradient approximation (GGA). The lattice constant of TmNs increases with increasing the atomic radii of the transition metals. Stability of the TmNs decreases from IVB to VIB groups due to increase in formation energy/atom. The bonding characteristics of these nitrides have been explained based on electronic density of states and charge density. All the TmNs satisfy Born stability criteria in terms of elastic constants except CrN and MoN that do not exist in equilibrium binary phase diagrams. The groups IVB and V-VIB nitrides are associated with brittle and ductile behaviour based on G/B ratios, respectively. The estimated melting temperatures of these nitrides exhibit reasonably good agreement with calculated with B than those of the C11 for all nitrides.

  6. Methods for First-Principles Alloy Thermodynamics

    NASA Astrophysics Data System (ADS)

    van de Walle, Axel

    2013-11-01

    Traditional first-principles calculations excel at providing formation energies at absolute zero, but obtaining thermodynamic information at nonzero temperatures requires suitable sampling of all the excited states visited in thermodynamic equilibrium, which would be computationally prohibitive via brute-force quantum mechanical calculations alone. In the context of solid-state alloys, this issue can be addressed via the coarse-graining concept and the cluster expansion formalism. This process generates simple, effective Hamiltonians that accurately reproduce quantum mechanical calculation results and that can be used to efficiently sample configurational, vibrational, and electronic excitations and enable the prediction of thermodynamic properties at nonzero temperatures. Vibrational and electronic degrees of freedom are formally eliminated from the problem by writing the system's partition function in a nested form in which the inner sums can be readily evaluated to yield an effective Hamiltonian. The remaining outermost sum corresponds to atomic configurations and can be handled via Monte Carlo sampling driven by the resulting effective Hamiltonian, thereby delivering thermodynamic properties at nonzero temperatures. This article describes these techniques and their implementation in the alloy theoretic automated toolkit, an open-source software package. The methods are illustrated by applications to various alloy systems.

  7. THERMODYNAMIC MODELING AND FIRST-PRINCIPLES CALCULATIONS

    SciTech Connect

    Turchi, P; Abrikosov, I; Burton, B; Fries, S; Grimvall, G; Kaufman, L; Korzhavyi, P; Manga, R; Ohno, M; Pisch, A; Scott, A; Zhang, W

    2005-12-15

    The increased application of quantum mechanical-based methodologies to the study of alloy stability has required a re-assessment of the field. The focus is mainly on inorganic materials in the solid state. In a first part, after a brief overview of the so-called ab initio methods with their approximations, constraints, and limitations, recommendations are made for a good usage of first-principles codes with a set of qualifiers. Examples are given to illustrate the power and the limitations of ab initio codes. However, despite the ''success'' of these methodologies, thermodynamics of complex multi-component alloys, as used in engineering applications, requires a more versatile approach presently afforded within CALPHAD. Hence, in a second part, the links that presently exist between ab initio methodologies, experiments, and CALPHAD approach are examined with illustrations. Finally, the issues of dynamical instability and of the role of lattice vibrations that still constitute the subject of ample discussions within the CALPHAD community are revisited in the light of the current knowledge with a set of recommendations.

  8. First Principles Quantitative Modeling of Molecular Devices

    NASA Astrophysics Data System (ADS)

    Ning, Zhanyu

    In this thesis, we report theoretical investigations of nonlinear and nonequilibrium quantum electronic transport properties of molecular transport junctions from atomistic first principles. The aim is to seek not only qualitative but also quantitative understanding of the corresponding experimental data. At present, the challenges to quantitative theoretical work in molecular electronics include two most important questions: (i) what is the proper atomic model for the experimental devices? (ii) how to accurately determine quantum transport properties without any phenomenological parameters? Our research is centered on these questions. We have systematically calculated atomic structures of the molecular transport junctions by performing total energy structural relaxation using density functional theory (DFT). Our quantum transport calculations were carried out by implementing DFT within the framework of Keldysh non-equilibrium Green's functions (NEGF). The calculated data are directly compared with the corresponding experimental measurements. Our general conclusion is that quantitative comparison with experimental data can be made if the device contacts are correctly determined. We calculated properties of nonequilibrium spin injection from Ni contacts to octane-thiolate films which form a molecular spintronic system. The first principles results allow us to establish a clear physical picture of how spins are injected from the Ni contacts through the Ni-molecule linkage to the molecule, why tunnel magnetoresistance is rapidly reduced by the applied bias in an asymmetric manner, and to what extent ab initio transport theory can make quantitative comparisons to the corresponding experimental data. We found that extremely careful sampling of the two-dimensional Brillouin zone of the Ni surface is crucial for accurate results in such a spintronic system. We investigated the role of contact formation and its resulting structures to quantum transport in several molecular

  9. Transversity from First Principles in QCD

    SciTech Connect

    Brodsky, Stanley J.; /SLAC /Southern Denmark U., CP3-Origins

    2012-02-16

    Transversity observables, such as the T-odd Sivers single-spin asymmetry measured in deep inelastic lepton scattering on polarized protons and the distributions which are measured in deeply virtual Compton scattering, provide important constraints on the fundamental quark and gluon structure of the proton. In this talk I discuss the challenge of computing these observables from first principles; i.e.; quantum chromodynamics, itself. A key step is the determination of the frame-independent light-front wavefunctions (LFWFs) of hadrons - the QCD eigensolutions which are analogs of the Schroedinger wavefunctions of atomic physics. The lensing effects of initial-state and final-state interactions, acting on LFWFs with different orbital angular momentum, lead to T-odd transversity observables such as the Sivers, Collins, and Boer-Mulders distributions. The lensing effect also leads to leading-twist phenomena which break leading-twist factorization such as the breakdown of the Lam-Tung relation in Drell-Yan reactions. A similar rescattering mechanism also leads to diffractive deep inelastic scattering, as well as nuclear shadowing and non-universal antishadowing. It is thus important to distinguish 'static' structure functions, the probability distributions computed the target hadron's light-front wavefunctions, versus 'dynamical' structure functions which include the effects of initial- and final-state rescattering. I also discuss related effects such as the J = 0 fixed pole contribution which appears in the real part of the virtual Compton amplitude. AdS/QCD, together with 'Light-Front Holography', provides a simple Lorentz-invariant color-confining approximation to QCD which is successful in accounting for light-quark meson and baryon spectroscopy as well as hadronic LFWFs.

  10. First principles investigation of substituted strontium hexaferrite

    NASA Astrophysics Data System (ADS)

    Dixit, Vivek

    This dissertation investigates how the magnetic properties of strontium hexaferrite change upon the substitution of foreign atoms at the Fe sites. Strontium hexaferrite, SrFe12O19, is a commonly used hard magnetic material and is produced in large quantities (around 500,000 tons per year). For different applications of strontium hexaferrite, its magnetic properties can be tuned by a proper substitution of the foreign atoms. Experimental screening for a proper substitution is a cost-intensive and time-consuming process, whereas computationally it can be done more efficiently. We used the 'density functional theory' a first principles based method to study substituted strontium hexaferrite. The site occupancies of the substituted atoms were estimated by calculating the substitution energies of different configurations. The formation probabilities of configurations were used to calculate the magnetic properties of substituted strontium hexaferrite. In the first study, Al-substituted strontium hexaferrite, SrFe12-x AlxO19 with x=0.5 and x=1.0 were investigated. It was found that at the annealing temperature the non-magnetic Al +3 ions preferentially replace Fe+3 ions from the 12 k and 2a sites. We found that the magnetization decreases and the magnetic anisotropy field increases as the fraction, x of the Al atoms increases. In the second study, SrFe12-xGaxO19 and SrFe12-xInxO19 with x=0.5 and x=1.0 were investigated. In the case of SrFe12-xGaxO19, the sites where Ga+3 ions prefer to enter are: 12 k, 2a, and 4f1. For SrFe12-xInxO19, In+3 ions most likely to occupy the 12k, 4f1 , and 4f2 sites. In both cases the magnetization was found to decrease slightly as the fraction of substituted atom increases. The magnetic anisotropy field increased for SrFe12-xGaxO 19, and decreased for SrFe12-xInxO19 as the concentration of substituted atoms increased. In the third study, 23 elements (M) were screened for their possible substitution in strontium hexaferrite, SrFe12-xMxO 19

  11. Time-dependent first-principles approaches to PV materials

    SciTech Connect

    Miyamoto, Yoshiyuki

    2013-12-10

    Computational scheme for designing photovoltaic (PV) materials is presented. First-principles electron dynamics of photo-excitation and subsequent electron-hole splitting is performed based on the time-dependent density functional theory. Photo-induced enhancement of dipole moment was observed in a polar crystal and a donor-acceptor molecular pair. These experiences will pave a way to design PV material from first-principles simulations.

  12. Materials Databases Infrastructure Constructed by First Principles Calculations: A Review

    SciTech Connect

    Lin, Lianshan

    2015-10-13

    The First Principles calculations, especially the calculation based on High-Throughput Density Functional Theory, have been widely accepted as the major tools in atom scale materials design. The emerging super computers, along with the powerful First Principles calculations, have accumulated hundreds of thousands of crystal and compound records. The exponential growing of computational materials information urges the development of the materials databases, which not only provide unlimited storage for the daily increasing data, but still keep the efficiency in data storage, management, query, presentation and manipulation. This review covers the most cutting edge materials databases in materials design, and their hot applications such as in fuel cells. By comparing the advantages and drawbacks of these high-throughput First Principles materials databases, the optimized computational framework can be identified to fit the needs of fuel cell applications. The further development of high-throughput DFT materials database, which in essence accelerates the materials innovation, is discussed in the summary as well.

  13. Force field development from first principles for materials design

    NASA Astrophysics Data System (ADS)

    Chan, Maria; Kinaci, Alper; Narayanan, Badri; Sen, Fatih; Gray, Stephen; Davis, Michael; Sankaranaryanan, Subramanian

    2015-03-01

    The ability to perform accurate calculations efficiently is crucial for computational materials design. In this talk, we will discuss a stream-lined approach to force field development using first principles density functional theory training data and machine learning algorithms. We will also discuss the validation of this approach on precious metal nanoparticles.

  14. Diagnosis: Reasoning from first principles and experiential knowledge

    NASA Technical Reports Server (NTRS)

    Williams, Linda J. F.; Lawler, Dennis G.

    1987-01-01

    Completeness, efficiency and autonomy are requirements for suture diagnostic reasoning systems. Methods for automating diagnostic reasoning systems include diagnosis from first principles (i.e., reasoning from a thorough description of structure and behavior) and diagnosis from experiential knowledge (i.e., reasoning from a set of examples obtained from experts). However, implementation of either as a single reasoning method fails to meet these requirements. The approach of combining reasoning from first principles and reasoning from experiential knowledge does address the requirements discussed above and can possibly ease some of the difficulties associated with knowledge acquisition by allowing developers to systematically enumerate a portion of the knowledge necessary to build the diagnosis program. The ability to enumerate knowledge systematically facilitates defining the program's scope, completeness, and competence and assists in bounding, controlling, and guiding the knowledge acquisition process.

  15. Hybrid first-principles/neural networks model for column flotation

    SciTech Connect

    Gupta, S.; Liu, P.H.; Svoronos, S.A.; Sharma, R.; Abdel-Khalek, N.A.; Cheng, Y.; El-Shall, H.

    1999-03-01

    A new model for phosphate column flotation is presented which for the first time relates the effects of operating variables such as frother concentration on column performance. This is a hybrid model that combines a first-principles model with artificial neural networks. The first-principles model is obtained from material balances on both phosphate particles and gangue (undesired material containing mostly silica). First-order rates of net attachment are assumed for both. Artificial neural networks relate the attachment rate constants to the operating variables. Experiments were conducted in a 6-in.-dia. (152-mm-dia.) laboratory column to provide data for neural network training and model validation. The model successfully predicts the effects of frother concentration, particle size, air flow rate and bubble diameter on grade and recovery.

  16. First principles molecular dynamics of molten NaCl

    NASA Astrophysics Data System (ADS)

    Galamba, N.; Costa Cabral, B. J.

    2007-03-01

    First principles Hellmann-Feynman molecular dynamics (HFMD) results for molten NaCl at a single state point are reported. The effect of induction forces on the structure and dynamics of the system is studied by comparison of the partial radial distribution functions and the velocity and force autocorrelation functions with those calculated from classical MD based on rigid-ion and shell-model potentials. The first principles results reproduce the main structural features of the molten salt observed experimentally, whereas they are incorrectly described by both rigid-ion and shell-model potentials. Moreover, HFMD Green-Kubo self-diffusion coefficients are in closer agreement with experimental data than those predicted by classical MD. A comprehensive discussion of MD results for molten NaCl based on different ab initio parametrized polarizable interionic potentials is also given.

  17. First-principles study of complex material systems

    NASA Astrophysics Data System (ADS)

    He, Lixin

    This thesis covers several topics concerning the study of complex materials systems by first-principles methods. It contains four chapters. A brief, introductory motivation of this work will be given in Chapter 1. In Chapter 2, I will give a short overview of the first-principles methods, including density-functional theory (DFT), planewave pseudopotential methods, and the Berry-phase theory of polarization in crystallines insulators. I then discuss in detail the locality and exponential decay properties of Wannier functions and of related quantities such as the density matrix, and their application in linear-scaling algorithms. In Chapter 3, I investigate the interaction of oxygen vacancies and 180° domain walls in tetragonal PbTiO3 using first-principles methods. Our calculations indicate that the oxygen vacancies have a lower formation energy in the domain wall than in the bulk, thereby confirming the tendency of these defects to migrate to, and pin, the domain walls. The pinning energies are reported for each of the three possible orientations of the original Ti--O--Ti bonds, and attempts to model the results with simple continuum models are discussed. CaCu3Ti4O12 (CCTO) has attracted a lot of attention recently because it was found to have an enormous dielectric response over a very wide temperature range. In Chapter 4, I study the electronic and lattice structure, and the lattice dynamical properties, of this system. Our first-principles calculations together with experimental results point towards an extrinsic mechanism as the origin of the unusual dielectric response.

  18. Understanding and Predicting Thiolated Gold Nanoclusters from First Principles

    SciTech Connect

    Jiang, Deen

    2010-01-01

    This is an exciting time for studying thiolated gold nanoclusters. Single crystal structures of Au{sub 102}(SR){sub 44} and Au{sub 25}(SR){sub 18}{sup -} (-SR being an organothiolate group) bring both surprises and excitement in this field. First principles density functional theory (DFT) simulations turn out to be an important tool to understand and predict thiolated gold nanoclusters. In this review, I summarize the progresses made by us and others in applying first principles DFT to thiolated gold nanoclusters, as inspired by the recent experiments. First, I will give some experimental background on synthesis of thiolated gold nanoclusters, followed by a description of the recent experimental breakthroughs. Then I will introduce the superatom complex concept as a way to understand the electronic structure of thiolated gold nanoclusters or smaller nanoparticles. Next, I will describe in detail how first principles DFT is used to understand the Au-thiolate interface, predict structures for Au{sub 38}(SR){sub 24}, screen good dopants for the Au{sub 25}(SR){sub 18}{sup -} cluster, design the smallest magic thiolated gold cluster, and demonstrate the need for the trimer protecting motif. I will conclude with a grand challenge: the real time monitoring of nucleation of thiolated gold nanoclusters.

  19. Materials Databases Infrastructure Constructed by First Principles Calculations: A Review

    DOE PAGESBeta

    Lin, Lianshan

    2015-10-13

    The First Principles calculations, especially the calculation based on High-Throughput Density Functional Theory, have been widely accepted as the major tools in atom scale materials design. The emerging super computers, along with the powerful First Principles calculations, have accumulated hundreds of thousands of crystal and compound records. The exponential growing of computational materials information urges the development of the materials databases, which not only provide unlimited storage for the daily increasing data, but still keep the efficiency in data storage, management, query, presentation and manipulation. This review covers the most cutting edge materials databases in materials design, and their hotmore » applications such as in fuel cells. By comparing the advantages and drawbacks of these high-throughput First Principles materials databases, the optimized computational framework can be identified to fit the needs of fuel cell applications. The further development of high-throughput DFT materials database, which in essence accelerates the materials innovation, is discussed in the summary as well.« less

  20. Evolutionary approach for determining first-principles hamiltonians

    NASA Astrophysics Data System (ADS)

    Hart, Gus L. W.; Blum, Volker; Walorski, Michael J.; Zunger, Alex

    2005-05-01

    Modern condensed-matter theory from first principles is highly successful when applied to materials of given structure-type or restricted unit-cell size. But this approach is limited where large cells or searches over millions of structure types become necessary. To treat these with first-principles accuracy, one 'coarse-grains' the many-particle Schrödinger equation into 'model hamiltonians' whose variables are configurational order parameters (atomic positions, spin and so on), connected by a few 'interaction parameters' obtained from a microscopic theory. But to construct a truly quantitative model hamiltonian, one must know just which types of interaction parameters to use, from possibly 106-108 alternative selections. Here we show how genetic algorithms, mimicking biological evolution ('survival of the fittest'), can be used to distil reliable model hamiltonian parameters from a database of first-principles calculations. We demonstrate this for a classic dilemma in solid-state physics, structural inorganic chemistry and metallurgy: how to predict the stable crystal structure of a compound given only its composition. The selection of leading parameters based on a genetic algorithm is general and easily applied to construct any other type of complex model hamiltonian from direct quantum-mechanical results.

  1. Evolutionary approach for determining first-principles hamiltonians.

    PubMed

    Hart, Gus L W; Blum, Volker; Walorski, Michael J; Zunger, Alex

    2005-05-01

    Modern condensed-matter theory from first principles is highly successful when applied to materials of given structure-type or restricted unit-cell size. But this approach is limited where large cells or searches over millions of structure types become necessary. To treat these with first-principles accuracy, one 'coarse-grains' the many-particle Schrodinger equation into 'model hamiltonians' whose variables are configurational order parameters (atomic positions, spin and so on), connected by a few 'interaction parameters' obtained from a microscopic theory. But to construct a truly quantitative model hamiltonian, one must know just which types of interaction parameters to use, from possibly 10(6)-10(8) alternative selections. Here we show how genetic algorithms, mimicking biological evolution ('survival of the fittest'), can be used to distil reliable model hamiltonian parameters from a database of first-principles calculations. We demonstrate this for a classic dilemma in solid-state physics, structural inorganic chemistry and metallurgy: how to predict the stable crystal structure of a compound given only its composition. The selection of leading parameters based on a genetic algorithm is general and easily applied to construct any other type of complex model hamiltonian from direct quantum-mechanical results. PMID:15834412

  2. Diffusion in thorium carbide: A first-principles study

    NASA Astrophysics Data System (ADS)

    Pérez Daroca, D.; Llois, A. M.; Mosca, H. O.

    2015-12-01

    The prediction of the behavior of Th compounds under irradiation is an important issue for the upcoming Generation-IV nuclear reactors. The study of self-diffusion and hetero-diffusion is a central key to fulfill this goal. As a first approach, we obtained, by means of first-principles methods, migration and activation energies of Th and C atoms self-diffusion and diffusion of He atoms in ThC. We also calculate diffusion coefficients as a function of temperature.

  3. Electromagnetic Response of ^{12}C: A First-Principles Calculation.

    PubMed

    Lovato, A; Gandolfi, S; Carlson, J; Pieper, Steven C; Schiavilla, R

    2016-08-19

    The longitudinal and transverse electromagnetic response functions of ^{12}C are computed in a "first-principles" Green's function Monte Carlo calculation, based on realistic two- and three-nucleon interactions and associated one- and two-body currents. We find excellent agreement between theory and experiment and, in particular, no evidence for the quenching of the measured versus calculated longitudinal response. This is further corroborated by a reanalysis of the Coulomb sum rule, in which the contributions from the low-lying J^{π}=2^{+}, 0_{2}^{+} (Hoyle), and 4^{+} states in ^{12}C are accounted for explicitly in evaluating the total inelastic strength. PMID:27588850

  4. First-Principles Study of Impurities in TlBr

    SciTech Connect

    Du, Mao-Hua

    2012-01-01

    TlBr is a promising semiconductor material for room-temperature radiation detection. Material purification has been the driver for the recent improvement in the TlBr detector performance, mainly reflected by the significant increase in the carrier mobility-lifetime product. This suggests that impurities have significant impact on the carrier transport in TlBr. In this paper, first-principles calculations are used to study the properties of a number of commonly observed impurities in TlBr. The impurity-induced gap states are presented and their effects on the carrier trapping are discussed.

  5. First-Principles Studies of Li Nucleation on Graphene.

    PubMed

    Liu, Mingjie; Kutana, Alex; Liu, Yuanyue; Yakobson, Boris I

    2014-04-01

    We study the Li clustering process on graphene and obtain the geometry, nucleation barrier, and electronic structure of the clusters using first-principles calculations. We estimate the concentration-dependent nucleation barrier for Li on graphene. While the nucleation occurs more readily with increasing Li concentration, possibly leading to the dendrite formation and failure of the Li-ion battery, the existence of the barrier delays nucleation and may allow Li storage on graphene. Our electronic structure and charge transfer analyses reveal how the fully ionized Li adatoms transform to metallic Li during the cluster growth on graphene. PMID:26274475

  6. First-principles theory of multipolar order in neptunium dioxide

    NASA Astrophysics Data System (ADS)

    Suzuki, M.-T.; Magnani, N.; Oppeneer, P. M.

    2010-12-01

    We provide a first-principles, materials-specific theory of multipolar order and superexchange in NpO2 by means of a noncollinear local-density approximation +U (LDA+U) method. Our calculations offer a precise microscopic description of the triple- q antiferro ordered phase in the absence of any dipolar moment. We find that, while the most common nondipolar degrees of freedom (e.g., electric quadrupoles and magnetic octupoles) are active in the ordered phase, both the usually neglected higher-order multipoles (electric hexadecapoles and magnetic triakontadipoles) have at least an equally significant effect.

  7. Derivation of instanton rate theory from first principles

    NASA Astrophysics Data System (ADS)

    Richardson, Jeremy O.

    2016-03-01

    Instanton rate theory is used to study tunneling events in a wide range of systems including low-temperature chemical reactions. Despite many successful applications, the method has never been obtained from first principles, relying instead on the "Im F" premise. In this paper, the same expression for the rate of barrier penetration at finite temperature is rederived from quantum scattering theory [W. H. Miller, S. D. Schwartz, and J. W. Tromp, J. Chem. Phys. 79, 4889 (1983)] using a semiclassical Green's function formalism. This justifies the instanton approach and provides a route to deriving the rate of other processes.

  8. Accurately Predicting Complex Reaction Kinetics from First Principles

    NASA Astrophysics Data System (ADS)

    Green, William

    Many important systems contain a multitude of reactive chemical species, some of which react on a timescale faster than collisional thermalization, i.e. they never achieve a Boltzmann energy distribution. Usually it is impossible to fully elucidate the processes by experiments alone. Here we report recent progress toward predicting the time-evolving composition of these systems a priori: how unexpected reactions can be discovered on the computer, how reaction rates are computed from first principles, and how the many individual reactions are efficiently combined into a predictive simulation for the whole system. Some experimental tests of the a priori predictions are also presented.

  9. Large impurity effects in rubrene crystals: First-principles calculations

    SciTech Connect

    Tsetseris, L.; Pantelides, Sokrates T.

    2008-01-01

    Carrier mobilities of rubrene films are among the highest values reported for any organic semiconductor. Here, we probe with first-principles calculations the sensitivity of rubrene crystals on impurities. We find that isolated oxygen impurities create distinct peaks in the electronic density of states consistent with observations of defect levels in rubrene and that increased O content changes the position and shape of rubrene energy bands significantly. We also establish a dual role of hydrogen as individual H species and H impurity pairs create and annihilate deep carrier traps, respectively. The results are relevant to the performance and reliability of rubrene-based devices.

  10. Electromagnetic Response of 12C: A First-Principles Calculation

    NASA Astrophysics Data System (ADS)

    Lovato, A.; Gandolfi, S.; Carlson, J.; Pieper, Steven C.; Schiavilla, R.

    2016-08-01

    The longitudinal and transverse electromagnetic response functions of 12C are computed in a "first-principles" Green's function Monte Carlo calculation, based on realistic two- and three-nucleon interactions and associated one- and two-body currents. We find excellent agreement between theory and experiment and, in particular, no evidence for the quenching of the measured versus calculated longitudinal response. This is further corroborated by a reanalysis of the Coulomb sum rule, in which the contributions from the low-lying Jπ=2+, 02+ (Hoyle), and 4+ states in 12 are accounted for explicitly in evaluating the total inelastic strength.

  11. Computation of Mössbauer isomer shifts from first principles

    NASA Astrophysics Data System (ADS)

    Zwanziger, J. W.

    2009-05-01

    Computation of the observables of a Mössbauer spectrum, primarily the isomer shift, from a first-principles approach is described. The framework used is density functional theory using the projector augmented wave formalism (DFT PAW), which enables efficient computation even of many-electron solids such as SnCl2. The proper PAW version of the isomer shift is derived and shown to be correct through comparison of computed shifts and experiment in a variety of compounds based on tin, germanium and zinc. The effects of pressure are considered as well as motional effects including the Lamb-Mössbauer factor and the second-order Doppler shift.

  12. Ethanol adsorption on the Si (111) surface: First principles study

    NASA Astrophysics Data System (ADS)

    Gavrilenko, Alexander V.; Bonner, Carl E.; Gavrilenko, Vladimir I.

    2012-03-01

    Equilibrium atomic configurations and electron energy structure of ethanol adsorbed on the Si (111) surface are studied by the first principles density functional theory. Geometry optimization is performed by the total energy minimization method. Equilibrium atomic geometries of ethanol, both undissociated and dissociated, on the Si (111) surface are found and analysed. Reaction pathways and predicted transition states are discussed in comparison with available experimental data in terms of the feasibility of the reactions occurring. Analysis of atom and orbital resolved projected density of states indicates substantial modifications of the Si surface valence and conduction electron bands due to the adsorption of ethanol affecting the electronic properties of the surface.

  13. Oxygen diffusion in hcp metals from first principles

    NASA Astrophysics Data System (ADS)

    Wu, Henry H.; Wisesa, Pandu; Trinkle, Dallas R.

    2016-07-01

    Oxygen interstitial site energies and migration barriers in 15 hexagonal close-packed (hcp) metals have been calculated with first-principles density functional theory. Multiple hcp systems show a preference for the hexahedral site over the tetrahedral site, as well as a stable crowdion site. More surprisingly, in more than half of the hcp systems, the oxygen does not choose the large octahedral interstitial as its ground state. We explain this result based on the effective valence of the metal from crystal-field splitting and the c /a ratio. Diffusion constants for oxygen in all 15 hcp systems are calculated from analytically derived diffusion equations and match available experimental data.

  14. Superconductivity of compressed solid argon from first principles

    NASA Astrophysics Data System (ADS)

    Ishikawa, Takahiro; Asano, Masamichi; Suzuki, Naoshi; Shimizu, Katsuya

    2015-02-01

    We present first-principles calculations on the superconductivity of solid argon under high pressure. Solid argon is found to take the double hexagonal close-packed structure in pressure range from 420 to 690 GPa, where an insulator-to-metal transition occurs at around 590 GPa. The crystal structure transforms into the hexagonal close-packed structure at 690 GPa and into the face-centered cubic structure at 2300 GPa. The superconducting critical temperature is gradually increased with the successive phase transitions and reaches the maximum value of 12 K at 2600 GPa due to the enhancement of the Fermi surface nesting.

  15. First Principles Phase Diagram Calculaions with the Maps Package

    NASA Astrophysics Data System (ADS)

    Burton, B. P.

    2003-12-01

    The MAPS, MIT ab initio software package (http://cms.northwestern.edu/Group.html) was used to perform first principles phase diagram calculations (FPPD) for the mineral systems: CaCO3}-MgCO{3; CdCO3}-MgCO{3; CaCO3}-MgCO{3; and NaCl-KCl. General characteristics of FPPD calculations will be reviewed and details of specific calculations will be discussed. Particular attention will be given to: the prediction of new stable ordered phases; metastable ordered phases; and the role of vibrational entropy in phase stability.

  16. First principles pseudopotential calculations on aluminum and aluminum alloys

    SciTech Connect

    Davenport, J.W.; Chetty, N.; Marr, R.B.; Narasimhan, S.; Pasciak, J.E.; Peierls, R.F.; Weinert, M.

    1993-12-31

    Recent advances in computational techniques have led to the possibility of performing first principles calculations of the energetics of alloy formation on systems involving several hundred atoms. This includes impurity concentrations in the 1% range as well as realistic models of disordered materials (including liquids), vacancies, and grain boundaries. The new techniques involve the use of soft, fully nonlocal pseudopotentials, iterative diagonalization, and parallel computing algorithms. This approach has been pioneered by Car and Parrinello. Here the authors give a review of recent results using parallel and serial algorithms on metallic systems including liquid aluminum and liquid sodium, and also new results on vacancies in aluminum and on aluminum-magnesium alloys.

  17. Rare-earth pnictides and chalcogenides from first-principles.

    PubMed

    Petit, L; Szotek, Z; Lüders, M; Svane, A

    2016-06-01

    This review tries to establish what is the current understanding of the rare-earth monopnictides and monochalcogenides from first principles. The rock salt structure is assumed for all the compounds in the calculations and wherever possible the electronic structure/properties of these compounds, as obtained from different ab initio methods, are compared and their relation to the experimental evidence is discussed. The established findings are summarised in a set of conclusions and provide outlook for future study and possible design of new materials. PMID:27165563

  18. First-Principles Study of LiPON Solid Electrolyte

    NASA Astrophysics Data System (ADS)

    Santosh, K. C.; Xiong, Ka; Cho, Kyeongjae

    2011-03-01

    There has been much interest in the thin-film solid electrolyte for solid state battery and ionics applications. LiPON is a representative material developed by Oak Ridge National Laboratory. In this work, we use first principles calculations based on the density functional theory to investigate the Li- ion migration mechanisms of LiPON family materials. We investigate atomic structures, electronic structures and defect formation energies of these materials. To determine the migration path of Li diffusion, the activation energies are calculated. This study helps us to understand fundamental mechanisms of Li-ion migration and to improve Li ion conductivity in the solid electrolytes.

  19. Rare-earth pnictides and chalcogenides from first-principles

    NASA Astrophysics Data System (ADS)

    Petit, L.; Szotek, Z.; Lüders, M.; Svane, A.

    2016-06-01

    This review tries to establish what is the current understanding of the rare-earth monopnictides and monochalcogenides from first principles. The rock salt structure is assumed for all the compounds in the calculations and wherever possible the electronic structure/properties of these compounds, as obtained from different ab initio methods, are compared and their relation to the experimental evidence is discussed. The established findings are summarised in a set of conclusions and provide outlook for future study and possible design of new materials.

  20. Collective modes in light nuclei from first principles.

    PubMed

    Dytrych, T; Launey, K D; Draayer, J P; Maris, P; Vary, J P; Saule, E; Catalyurek, U; Sosonkina, M; Langr, D; Caprio, M A

    2013-12-20

    Results for ab initio no-core shell model calculations in a symmetry-adapted SU(3)-based coupling scheme demonstrate that collective modes in light nuclei emerge from first principles. The low-lying states of 6Li, 8Be, and 6He are shown to exhibit orderly patterns that favor spatial configurations with strong quadrupole deformation and complementary low intrinsic spin values, a picture that is consistent with the nuclear symplectic model. The results also suggest a pragmatic path forward to accommodate deformation-driven collective features in ab initio analyses when they dominate the nuclear landscape. PMID:24483740

  1. First-principles studies of low tolerance factor perovskites

    NASA Astrophysics Data System (ADS)

    Kang, Sung Gu; Fennie, Craig J.

    2014-03-01

    Most perovskites form in the non-polar Pnma structure, however, materials found in the polar subgroup of this structure, e.g., space group Pna21, are rare. Here we study from first principles the structural and vibrational properties of twelve materials that span a wide range of tolerance factors (MgSnO3, ZnSnO3, MgTiO3, ZnTiO3, MgGeO3, ZnGeO3, CdSnO3, CaSnO3, CdTiO3, CaTiO3, CdGeO3, and CaGeO3) . We illustrate how low tolerance factor materials that have been artificially constrained to the Pnma structure do in fact display ferroelectric instabilities. Insight is gained by further studying the energetics for each material in the ilmenite, lithium niobate, and perovskite structures over a wide pressure range. Our first-principles results are shown to correlate with physical descriptors, such as tolerance factor, ionic radii, and electronegativity. The rationalized rules from our data analysis will guide to design the new ferroelectric/functional materials.

  2. Vanadate, molybdate and tungstate for orthomolecular medicine.

    PubMed

    Matsumoto, J

    1994-09-01

    Recent studies indicate that oxyanions, such as vanadate (V) or vanadyl (IV), cause insulin-like effects on rats by stimulating the insulin receptor tyrosine kinase. Tungstate (VI) and molybdate (VI) show the same effects on rat adipocytes and hepatocytes. Results of uncontrolled trials on volunteers accumulated in Japan also suggest that tungstate effectively regulates diabetes mellitus without detectable side effects. Since these oxyanions naturally exist in organisms, oxyanion therapy, the oral administration of vanadate, vanadyl, molybdate, or tungstate, can be considered to be orthomolecular medicine. Therefore, these oxyanions may provide a viable alternative to chemotherapy. Many diseases in addition to diabetes mellitus might also be treated since the implication of these results is that tyrosine kinases are involved in a variety of diseases. PMID:7815975

  3. First-Principles Informed Thermodynamics of CRUD Deposition

    NASA Astrophysics Data System (ADS)

    O'Brien, Christopher John

    The recent emphasis in the United States on developing abundant domestic sources of energy, together with an increasing awareness of the environmental hazards of fossil fuels, has led to a fresh look at the challenges of nuclear energy within the science and engineering community. One of these challenges is controlling the precipitation of porous oxide deposits onto the nuclear fuel rod cladding from the primary coolant during operation of pressurized light-water reactors (PWRs). These deposits, called CRUD (an acronym for Chalk River Unidentified Deposits), are a major concern to reactor operation because they reduce fuel lifetime and efficiency by reducing heat transfer to the coolant, promote corrosion, and depress neutron flux. This dissertation provides fundamental insights into the process by which CRUD is formed in PWRs by providing a framework linking the results of first-principles calculations to experimental data. The technique developed to facilitate the investigation is referred to as Density Functional Theory (DFT) referenced semi-empirical thermodynamics; It links 0K first-principles calculations with high temperature thermodynamics by redefining the reference chemical potentials of the constituent elements. The technique permits aqueous chemistry to be incorporated into thermodynamic calculations and allows for the prediction of temperature and pressure dependent free energies of materials that are experimentally inaccessible or have not yet been measured. The ability to extend accurate first-principles calculations to high temperatures and aqueous environments allows the stability of crystal surfaces, calculated with DFT techniques, to be predicted at conditions representative of an operating PWR. Accurate values of surface energies are used in fulfilling the principal goal of this dissertation, which is to investigate the aqueous thermodynamics of formation of nickel oxide (NiO) and nickel ferrite (NiFe 2O4) crystallites as representative CRUD

  4. Morphology Tuning of Strontium Tungstate Nanoparticles

    SciTech Connect

    Joseph, S.; George, T.; George, K. C.; Sunny, A. T.; Mathew, S.

    2007-08-22

    Strontium tungstate nanocrystals in two different morphologies are successfully synthesized by controlled precipitation in aqueous and in poly vinyl alcohol (PVA) medium. Structural characterizations are carried out by XRD and SEM. The average particle size calculated for the SrWO4 prepared in the two different solvents ranges 20-24 nm. The SEM pictures show that the surface morphologies of the SrWO4 nanoparticles in aqueous medium resemble mushroom and the SrWO4 nanoparticles in PVA medium resemble cauliflower. Investigations on the room temperature luminescent properties of the strontium tungstate nanoparticles prepared in aqueous and PVA medium shows strong emissions around 425 nm.

  5. First-principles study of point defects in thorium carbide

    NASA Astrophysics Data System (ADS)

    Pérez Daroca, D.; Jaroszewicz, S.; Llois, A. M.; Mosca, H. O.

    2014-11-01

    Thorium-based materials are currently being investigated in relation with their potential utilization in Generation-IV reactors as nuclear fuels. One of the most important issues to be studied is their behavior under irradiation. A first approach to this goal is the study of point defects. By means of first-principles calculations within the framework of density functional theory, we study the stability and formation energies of vacancies, interstitials and Frenkel pairs in thorium carbide. We find that C isolated vacancies are the most likely defects, while C interstitials are energetically favored as compared to Th ones. These kind of results for ThC, to the best authors' knowledge, have not been obtained previously, neither experimentally, nor theoretically. For this reason, we compare with results on other compounds with the same NaCl-type structure.

  6. First-principles semiclassical initial value representation molecular dynamics.

    PubMed

    Ceotto, Michele; Atahan, Sule; Shim, Sangwoo; Tantardini, Gian Franco; Aspuru-Guzik, Alán

    2009-05-28

    In this work, we explore the use of the semiclassical initial value representation (SC-IVR) method with first-principles electronic structure approaches to carry out classical molecular dynamics. The proposed approach can extract the vibrational power spectrum of carbon dioxide from a single trajectory providing numerical results that agree with experiment and quantum calculations. The computational demands of the method are comparable to those of classical single-trajectory calculations, while describing uniquely quantum features such as the zero-point energy and Fermi resonances. The method can also be used to identify symmetry properties of given vibrational peaks and investigate vibrational couplings by selected classical trajectories. The accuracy of the method degrades for the reproduction of anharmonic shifts for high-energy vibrational levels. PMID:19440613

  7. First-principles study of silicon nitride nanotubes

    NASA Astrophysics Data System (ADS)

    Gao, Guohua; Kang, Hong Seok

    2008-10-01

    We have made a first-principles calculation of the topological, geometric, and electronic structures of nitrogen-doped armchair and zigzag silicon carbide nanotubes, where we have assumed that all carbon atoms have been substituted by nitrogen atoms. The doping was found to be substantially easier than for analogous carbon nanotubes. In addition, the doping process is cooperative, leading us to theoretically predict the stable existence of silicon nitride nanotubes (SiNNTs). For (n,n) SiNNTs, all kinds of chiral indices n are possible. These armchair tubes are semiconductors with much smaller band gaps than those of corresponding silicon carbide nanotubes, and the gap decreases with the tube diameter. For (n,0) chirality, only even-numbered chiral indices (n=2l) are possible. These nanotubes are also semiconductors with band gaps larger than those of armchair SiNNTs of similar diameters.

  8. First-principles study of thermal properties of borophene.

    PubMed

    Sun, Hongyi; Li, Qingfang; Wan, X G

    2016-06-01

    Very recently, a new single-element two-dimensional (2D) material borophene was successfully grown on a silver surface under pristine ultrahigh vacuum conditions which attracts tremendous interest. In this paper, the lattice thermal conductivity, phonon lifetimes, thermal expansion and temperature dependent elastic moduli of borophene are systematically studied by using first-principles. Our simulations show that borophene possesses unique thermal properties. Strong phonon-phonon scattering is found in borophene, which results in its unexpectedly low lattice thermal conductivity. Thermal expansion coefficients along both the armchair and zigzag directions of borophene show impressive negative values. More strikingly, the elastic moduli are sizably strengthened as temperature increases, and the negative in-plane Poisson's ratios are found along both the armchair and zigzag directions at around 120 K. The mechanisms of these unique thermal properties are also discussed in this paper. PMID:27188523

  9. Thermodynamics of Magnetic Systems from First Principles: WL-LSMS

    SciTech Connect

    Eisenbach, Markus; Zhou, Chenggang; Nicholson, Don M; Brown, Greg; Larkin, Jeffrey M; Schulthess, Thomas C

    2010-01-01

    Density Functional calculations have proven to be a powerful tool to study the ground state of many materials. For finite temperatures the situation is less ideal and one is often forced to rely on models with parameters either fitted to zero temperature first principles calculations or experimental results. This approach is especially unsatisfacory in inhomogeneous systems, nano particles, or other systems where the model parameters could vary significantly from one site to another. Here we describe a possible solution to this problem by combining classical Monte Carlo calculations the Wang-Landau method in this case with a firs principles electronic structure calculation, specifically our locally selfconsistent multiple scallering code (LSMS). The combined code shows superb scaling behavior on massively parallel computers. The code sustained 1.836 Petaflop/s on 223232 cores of the Cray XT5 jaguar system at Oak Ridge.

  10. Modeling of Co overlayers on Pd (111) from first principles

    NASA Astrophysics Data System (ADS)

    Uba, S.; Uba, L.; Antonov, V. N.

    2007-04-01

    The electronic, magnetic and magneto-optical properties of Co overlayers on Pd (1 1 1) substrate have been investigated by ab initio band structure calculations within the spin-polarized relativistic linear muffin-thin orbitals (LMTO) method and supercell approach. The role of the Co-Pd interface structure, the number of the Co atomic layers ( n Co ), as well as the spin-orbit interaction and induced Pd spin polarization, in formation of magneto-optical response of the structures for [ n CoCo/Pd (1 1 1)] system is shown. The sign reversal of the polar Kerr rotation obtained theoretically with decreasing thickness of Co overlayers agrees well with experiment. We will demonstrate the effectiveness of the extended numeric modeling of magneto-optical properties from first principles.

  11. Defects in AIN/GaN Superlattice: First Principle Calculations.

    PubMed

    Rao, Xue; Wang, Ru-Zhi; Cao, Juexian; Yan, Hui

    2016-01-01

    In this paper we investigate the atomic configurations, electronic structure and formation energies of native point defects, (such as vacancies and self-interstitials), in an AIN/GaN superlattice (SL) constructed on a wurtzite structure along a [0001] growth direction. Comprehensive first-principle calculations based on the density functional theory (DFT) are used. Cation and anion vacancies in the neutral charge state are calculated. For the native defects, the results showed that the most favorable configurations are the cation vacancies at the interface of the SL, or the anion vacancies in the GaN wells. Considering the formation energies of different vacancies, the results show that the nitrogen vacancy has the lowest formation energy, indicating that they are significantly the most stable configuration, and thus should be expected to be the major defect in a AIN/GaN superlattice. PMID:27398499

  12. Hydrogen storage in LiH: A first principle study

    NASA Astrophysics Data System (ADS)

    Banger, Suman; Nayak, Vikas; Verma, U. P.

    2014-04-01

    First principles calculations have been performed on the Lithium hydride (LiH) using the full potential linearized augmented plane wave (FP-LAPW) method within the framework of density functional theory. We have extended our calculations for LiH+2H and LiH+6H in NaCl structure. The structural stability of three compounds have been studied. It is found that LiH with 6 added Hydrogen atoms is most stable. The obtained results for LiH are in good agreement with reported experimental data. Electronic structures of three compounds are also studied. Out of three the energy band gap in LiH is ˜3.0 eV and LiH+2H and LiH+6H are metallic.

  13. Two Dimensional Ice from First Principles: Structures and Phase Transitions.

    PubMed

    Chen, Ji; Schusteritsch, Georg; Pickard, Chris J; Salzmann, Christoph G; Michaelides, Angelos

    2016-01-15

    Despite relevance to disparate areas such as cloud microphysics and tribology, major gaps in the understanding of the structures and phase transitions of low-dimensional water ice remain. Here, we report a first principles study of confined 2D ice as a function of pressure. We find that at ambient pressure hexagonal and pentagonal monolayer structures are the two lowest enthalpy phases identified. Upon mild compression, the pentagonal structure becomes the most stable and persists up to ∼2  GPa, at which point the square and rhombic phases are stable. The square phase agrees with recent experimental observations of square ice confined within graphene sheets. This work provides a fresh perspective on 2D confined ice, highlighting the sensitivity of the structures observed to both the confining pressure and the width. PMID:26824547

  14. Adsorption of methylchloride on Si(100) from first principles

    NASA Astrophysics Data System (ADS)

    Romero, Aldo H.; Sbraccia, Carlo; Silvestrelli, Pier Luigi; Ancilotto, Francesco

    2003-07-01

    The chemisorption of methylchloride (CH3Cl) on Si(100) is studied from first principles. We find that, among a number of possible adsorption configurations, the lowest-energy structure is one in which the methylchloride molecule is dissociated into CH3 and Cl fragments which are bound to the two Si atoms of the same surface dimer. Our calculations show that dissociative chemisorption of methylchloride on Si(100) may proceed along different reaction paths characterized by different energy barriers that the system must overcome: some dissociation processes are mediated by a molecular precursor state and, at least in one case, we find that the dissociation process is nonactivated, in agreement with recent experimental findings. We have also generated, for many possible adsorption structures, theoretical scanning tunneling microscopy images which could facilitate the interpretation of experimental measurements.

  15. Auger recombination in sodium-iodide scintillators from first principles

    SciTech Connect

    McAllister, Andrew; Åberg, Daniel; Schleife, André; Kioupakis, Emmanouil

    2015-04-06

    Scintillator radiation detectors suffer from low energy resolution that has been attributed to non-linear light yield response to the energy of the incident gamma rays. Auger recombination is a key non-radiative recombination channel that scales with the third power of the excitation density and may play a role in the non-proportionality problem of scintillators. In this work, we study direct and phonon-assisted Auger recombination in NaI using first-principles calculations. Our results show that phonon-assisted Auger recombination, mediated primarily by short-range phonon scattering, dominates at room temperature. We discuss our findings in light of the much larger values obtained by numerical fits to z-scan experiments.

  16. First-principles study of 2D electride : Gadolinium carbide

    NASA Astrophysics Data System (ADS)

    Nandadasa, Chandani; Kim, Seong-Gon; Kim, Sungho; Kim, Sung Wng

    Electrides are an exclusive class of ionic compounds in which some electrons are occupying crystal voids instead of attaching to specific atoms or bonds. Using first-principles density functional theory calculations, we study structural, electronic and magnetic properties of Gd2C. The theoretically predicted structure of Gd2C is in good agreement with the available experimental data. Energy band diagram of Gd2C shows that they are crossing the Fermi level. Projected electronic density of states plots indicate that the interstitial sites are the main contributor to the density of states at the Fermi level. Charge of individual atoms including interstitial site are obtained using Bader analysis. Magnetic properties of Gd2C is determined from magnetization density plots. Work functions of Gd2C are determined for (001) and (100) surfaces with the technique of macroscopic average of electrostatic potential with the Fermi energy of bulk.

  17. Thermoelastic properties of α -iron from first-principles

    NASA Astrophysics Data System (ADS)

    Dragoni, Daniele; Ceresoli, Davide; Marzari, Nicola

    2015-03-01

    We calculate the thermomechanical properties of α -iron, and in particular its isothermal and adiabatic elastic constants, using first-principles total-energy and lattice-dynamics calculations, minimizing the quasiharmonic vibrational free energy under finite strain deformations. Particular care is made in the fitting procedure for the static and temperature-dependent contributions to the free energy, in discussing error propagation for the two contributions separately, and in the verification and validation of pseudopotential and all-electron calculations. We find that the zero-temperature mechanical properties are sensitive to the details of the calculation strategy employed, and common semilocal exchange-correlation functionals provide only fair to good agreement with experimental elastic constants, while their temperature dependence is in excellent agreement with experiments in a wide range of temperature almost up to the Curie transition.

  18. First-principles prediction of disordering tendencies in pyrochlore oxides

    NASA Astrophysics Data System (ADS)

    Jiang, Chao; Stanek, C. R.; Sickafus, K. E.; Uberuaga, B. P.

    2009-03-01

    Using first-principles calculations, we systematically predict the order-disorder energetics of series of zirconate (A2Zr2O7) , hafnate (A2Hf2O7) , titanate (A2Ti2O7) , and stannate (A2Sn2O7) pyrochlores. The disordered defect-fluorite structure is modeled using an 88-atom two-sublattice special quasirandom structure (SQS) that closely reproduces the most relevant near-neighbor intrasublattice and intersublattice pair-correlation functions of the random mixture. The order-disorder transition temperatures of these pyrochlores estimated from our SQS calculations show overall good agreement with existing experiments. We confirm previous studies suggesting that the bonding in pyrochlores is not purely ionic and thus electronic effects also play a role in determining their disordering tendencies. Our results have important consequences for numerous applications, including nuclear waste forms and fast ion conductors.

  19. First Principles Dynamics of Photoexcited DNA and RNA Bases

    SciTech Connect

    Hudock, Hanneli R.; Levine, Benjamin G.; Thompson, Alexis L.; Martinez, Todd J.

    2007-12-26

    The reaction dynamics of excited electronic states in nucleic acid bases is a key process in DNA photodamage. Recent ultrafast spectroscopy experiments have shown multi-component decays of excited uracil and thymine, tentatively assigned to nonadiabatic transitions involving multiple electronic states. Using both quantum chemistry and first principles quantum molecular dynamics methods we show that a true minimum on the bright S{sub 2} electronic state is responsible for the first step which occurs on a femtosecond timescale. Thus the observed femtosecond decay does not correspond to surface crossing as previously thought. We suggest that subsequent barrier crossing to the minimal energy S{sub 2}/S{sub 1} conical intersection is responsible for the picosecond decay.

  20. First-principles study of interface doping in ferroelectric junctions

    PubMed Central

    Wang, Pin-Zhi; Cai, Tian-Yi; Ju, Sheng; Wu, Yin-Zhong

    2016-01-01

    Effect of atomic monolayer insertion on the performance of ferroelectric tunneling junction is investigated in SrRuO3/BaTiO3/SrRuO3 heterostrucutures. Based on first-principles calculations, the atomic displacement, orbital occupancy, and ferroelectric polarization are studied. It is found that the ferroelectricity is enhanced when a (AlO2)− monolayer is inserted between the electrode SRO and the barrier BTO, where the relatively high mobility of doped holes effectively screen ferroelectric polarization. On the other hand, for the case of (LaO)+ inserted layer, the doped electrons resides at the both sides of middle ferroelectric barrier, making the ferroelectricity unfavorable. Our findings provide an alternative avenue to improve the performance of ferroelectric tunneling junctions. PMID:27063704

  1. Helium diffusion in olivine based on first principles calculations

    NASA Astrophysics Data System (ADS)

    Wang, Kai; Brodholt, John; Lu, Xiancai

    2015-05-01

    As a key trace element involved in mantle evolution, the transport properties of helium in the mantle are important for understanding the thermal and chemical evolution of the Earth. However, the mobility of helium in the mantle is still unclear due to the scarcity of measured diffusion data from minerals under mantle conditions. In this study, we used first principles calculations based on density functional theory to calculate the absolute diffusion coefficients of the helium in olivine. Using the climbing images nudged elastic band method, we defined the diffusion pathways, the activation energies (Ea), and the prefactors. Our results demonstrate that the diffusion of helium has moderate anisotropy. The directionally dependent diffusion of helium in olivine can be written in Arrhenius form as follows.

  2. Electromagnetic response of C12 : A first-principles calculation

    DOE PAGESBeta

    Lovato, A.; Gandolfi, S.; Carlson, J.; Pieper, Steven C.; Schiavilla, R.

    2016-08-15

    Here, the longitudinal and transverse electromagnetic response functions ofmore » $$^{12}$$C are computed in a ``first-principles'' Green's function Monte Carlo calculation, based on realistic two- and three-nucleon interactions and associated one- and two-body currents. We find excellent agreement between theory and experiment and, in particular, no evidence for the quenching of measured versus calculated longitudinal response. This is further corroborated by a re-analysis of the Coulomb sum rule, in which the contributions from the low-lying $$J^\\pi\\,$$=$$\\, 2^+$$, $0^+$ (Hoyle), and $4^+$ states in $$^{12}$$C are accounted for explicitly in evaluating the total inelastic strength.« less

  3. First-principles study of hydrogen in perfect tungsten crystal

    NASA Astrophysics Data System (ADS)

    Xu, Jingcheng; Zhao, Jijun

    2009-09-01

    Tungsten-based materials are used as the first wall materials in ITER. Hydrogen impurities were introduced via bombarding with the reaction plasma, which are important for the behavior and stability of the tungsten wall. Using the first-principles density functional theory and planewave pseudopotential technique, we have simulated the behaviors of hydrogen atoms inside the perfect tungsten bcc lattice. The binding energies for different interstitial sites were compared to determine the optimal trapping site for the hydrogen atom inside the tungsten lattice. The diffusion barriers for hydrogen atom between nearby trapping sites and the interaction between two interstitial hydrogen atoms were also calculated. The implication of our theoretical results on the hydrogen diffusion and accumulation behavior was discussed.

  4. First-principles modeling hydrogenation of bilayered boron nitride

    NASA Astrophysics Data System (ADS)

    Jing, Wang; Peng, Zhang; Xiang-Mei, Duan

    2016-05-01

    We have investigated the structural and electronic characteristics of hydrogenated boron-nitride bilayer (H–BNBN–H) using first-principles calculations. The results show that hydrogenation can significantly reduce the energy gap of the BN–BN into the visible-light region. Interestingly, the electric field induced by the interface dipoles helps to promote the formation of well-separated electron–hole pairs, as demonstrated by the charge distribution of the VBM and CBM. Moreover, the applied bias voltage on the vertical direction of the bilayer could modulate the band gap, resulting in transition from semiconductor to metal. We conclude that H–BNBN–H could improve the solar energy conversion efficiency, which may provide a new way for tuning the electronic devices to meet different environments and demands. Project supported by the National Natural Science Foundation of China (Grant No. 11574167).

  5. Vibrational and Thermophysical Properties of PETN from First Principles

    NASA Astrophysics Data System (ADS)

    Gonzalez, Joseph; Landerville, Aaron; Oleynik, Ivan

    2015-06-01

    Thermophysical properties are urgently sought as input for meso- and continuum-scale modeling of energetic materials (EMs). However, empirical data in this regard are often limited to specific pressures and temperatures. Such modeling of EMs can be greatly improved by inclusion of thermophysical properties over a wide range of pressures and temperatures, provided such data could be reliably obtained from theory. We demonstrate such a capability by calculating the equation of state, heat capacities, coefficients of thermal expansion, and Gruneissen parameters for pentaerythritol tetranitrate (PETN) using first-principles density functional theory, which includes proper description of van der Waals interactions and zero-point and thermal free energy contributions to pressure, the latter being calculated using the quasi-harmonic approximation. Further, we investigate the evolution of the vibration spectrum of PETN as a function of pressure.

  6. High pressure polyhydrides of molybdenum: A first-principles study

    NASA Astrophysics Data System (ADS)

    Feng, Xiaolei; Zhang, Jurong; Liu, Hanyu; Iitaka, Toshiaki; Yin, Ketao; Wang, Hui

    2016-07-01

    We present results from first-principles calculations on molybdenum polyhydrides under pressure. In addition to the experimental ε-phase of MoH, we find several novel structures of MoH2 and MoH3 at pressures below 100 GPa. A hexagonal structure of MoH2 becomes stable with respect to decomposition into MoH and H2 above 9 GPa, and transforms into an orthorhombic structure at 24 GPa, which remains stable up to 100 GPa. MoH3 is unstable relative to decomposition into MoH and H2 over the whole pressure range studied. Electronic structure calculations reveal that molybdenum polyhydrides are metallic under pressure.

  7. Ziegler Natta heterogeneous catalysis by first principles computer experiments

    NASA Astrophysics Data System (ADS)

    Boero, M.; Parrinello, M.; Terakura, K.

    1999-09-01

    In this work we present a first attempt to study the polymerization process of ethylene in a realistic Ziegler-Natta heterogeneous system by means of first principles molecular dynamics. In particular, we simulate, in a very unbiased way, both the deposition of the catalyst TiCl 4 on the (110) active surface of a solid MgCl 2 support and the polymer chain formation. By using a constrained molecular dynamics approach, we work out the energetics and the reaction pathway of the polymerization process as it occurs in a laboratory or an industrial plant. The good agreement of the results of our simulations with the available experimental data indicates that these kinds of simulations can be used as a skilful approach to study the details of the reaction mechanism which are not accessible to experimental probes. This offers a tool to improve the production and/or to design reactants and products for practical use.

  8. First principles electron transport simulations in the Kondo regime

    NASA Astrophysics Data System (ADS)

    Rungger, Ivan; Radonjic, Milos; Appelt, Wilhelm; Chioncel, Liviu; Droghetti, Andrea

    When magnetic atoms, molecules or thin films are brought into contact with metals the electron-electron interaction leads to the appearance of the correlated Kondo state at low temperatures. In this talk we will present results for the electronic structure and conductance in the Kondo regime of recent STM and break junction experiments for stable radical molecules, which correspond to spin half molecular magnets. We will outline the methodological approach to evaluate the conductance of such systems from first principles, as implemented in the Smeagol electron transport code. The method combines the density functional theory (DFT) with Anderson impurity solvers within the continuum time quantum Monte Carlo (CTQMC) and numerical renormalization group (NRG) approaches.

  9. First principles modeling of grain boundaries in CdTe

    NASA Astrophysics Data System (ADS)

    Chan, Maria K. Y.; Sen, Fatih; Buurma, Christopher; Paulauskas, Tadas; Sun, Ce; Kim, Moon; Klie, Robert

    The role of extended defects is of significant interest for semiconductors, especially photovoltaics since energy conversion efficiencies are often affected by such defects. In particular, grain boundaries in CdTe photovoltaics are enigmatic since the achievable efficiencies of CdTe photovoltaics are higher in polycrystalline devices as compared to single crystalline devices. Yet, despite recent advances, the efficiency of poly-CdTe devices are still substantially below the theoretical maximum. We carry out an atomistic-level study using Scanning Transmission Electron Microscopy (STEM), together with first principles density functional theory (DFT) modeling, in order to understand the properties of specific bicrystals, i.e. artificial grain boundaries, constructed using wafer bonding. We discuss examples of bicrystals, including some involving large scale DFT calculations, and trends in defect and electronic properties. This work was funded by DOE SunShot BRIDGE program.

  10. First principle study of manganese doped cadmium sulphide sheet

    SciTech Connect

    Kumar, Sanjeev; Kumar, Ashok; Ahluwalia, P. K.

    2014-04-24

    First-principle electronic structure calculations for cadmium sulphide (CdS) sheet in hexagonal phase, with Manganese substitution and addition, as well as including the Cd defects, are investigated. The lattice constants calculated for CdS sheet agrees fairly well with results reported for thin films experimentally. The calculations of total spin density of states and partial density of states in different cases shows substantial magnetic dipole moments acquired by the sheet. A magnetic dipole moment 5.00612 μ{sub B} and band gap of the order 1 eV are found when cadmium atom is replaced by Manganese. The magnetism acquired by the sheet makes it functionally important candidate in many applications.

  11. First principles pseudopotential calculations on aluminum and aluminum alloys

    SciTech Connect

    Davenport, J.W.; Chetty, N.; Marr, R.B.; Narasimhan, S.; Pasciak, J.E.; Peierls, R.F.; Weinert, M.; Rahman, T.S.

    1994-12-31

    Recent advances in computational techniques have led to the possibility of performing first principles calculations of the energetics of alloy formation on systems involving several hundred atoms. This includes impurity concentrations in the 1% range as well as realistic models of disordered materials (including liquids), vacancies, and grain boundaries. The new techniques involve the use of soft, fully nonlocal pseudopotentials, iterative diagonalization, and parallel computing algorithms. This approach has been pioneered by Car and Parrinello. Here the authors give a review of recent results using parallel and serial algorithms by their group on metallic systems including liquid aluminum and liquid sodium, and also new results on vacancies in aluminum and on aluminum-magnesium alloys.

  12. Carbon-rich icosahedral boron carbide designed from first principles

    SciTech Connect

    Jay, Antoine; Vast, Nathalie; Sjakste, Jelena; Duparc, Olivier Hardouin

    2014-07-21

    The carbon-rich boron-carbide (B{sub 11}C)C-C has been designed from first principles within the density functional theory. With respect to the most common boron carbide at 20% carbon concentration B{sub 4}C, the structural modification consists in removing boron atoms from the chains linking (B{sub 11}C) icosahedra. With C-C instead of C-B-C chains, the formation of vacancies is shown to be hindered, leading to enhanced mechanical strength with respect to B{sub 4}C. The phonon frequencies and elastic constants turn out to prove the stability of the carbon-rich phase, and important fingerprints for its characterization have been identified.

  13. Electronic Stopping Power in LiF from First Principles

    SciTech Connect

    Pruneda, J. M.; Sanchez-Portal, D.; Artacho, Emilio

    2007-12-07

    Using time-dependent density-functional theory we calculate from first principles the rate of energy transfer from a moving proton or antiproton to the electrons of an insulating material, LiF. The behavior of the electronic stopping power versus projectile velocity displays an effective threshold velocity of {approx}0.2 a.u. for the proton, consistent with recent experimental observations, and also for the antiproton. The calculated proton/antiproton stopping-power ratio is {approx}2.4 at velocities slightly above the threshold (v{approx}0.4 a.u.), as compared to the experimental value of 2.1. The projectile energy loss mechanism is observed to be extremely local.

  14. Two Dimensional Ice from First Principles: Structures and Phase Transitions

    NASA Astrophysics Data System (ADS)

    Chen, Ji; Schusteritsch, Georg; Pickard, Chris J.; Salzmann, Christoph G.; Michaelides, Angelos

    2016-01-01

    Despite relevance to disparate areas such as cloud microphysics and tribology, major gaps in the understanding of the structures and phase transitions of low-dimensional water ice remain. Here, we report a first principles study of confined 2D ice as a function of pressure. We find that at ambient pressure hexagonal and pentagonal monolayer structures are the two lowest enthalpy phases identified. Upon mild compression, the pentagonal structure becomes the most stable and persists up to ˜2 GPa , at which point the square and rhombic phases are stable. The square phase agrees with recent experimental observations of square ice confined within graphene sheets. This work provides a fresh perspective on 2D confined ice, highlighting the sensitivity of the structures observed to both the confining pressure and the width.

  15. 2D ice from first principles: structures and phase transitions

    NASA Astrophysics Data System (ADS)

    Chen, Ji; Schusteritsch, Georg; Pickard, Chris J.; Salzmann, Christoph G.; Michaelides, Angelos

    Despite relevance to disparate areas such as cloud microphysics and tribology, major gaps in the understanding of the structures and phase transitions of low-dimensional water ice remain. Here we report a first principles study of confined 2D ice as a function of pressure. We find that at ambient pressure hexagonal and pentagonal monolayer structures are the two lowest enthalpy phases identified. Upon mild compression the pentagonal structure becomes the most stable and persists up to ca. 2 GPa at which point square and rhombic phases are stable. The square phase agrees with recent experimental observations of square ice confined within graphene sheets. We also find a double layer AA stacked square ice phase, which clarifies the difference between experimental observations and earlier force field simulations. This work provides a fresh perspective on 2D confined ice, highlighting the sensitivity of the structures observed to both the confining pressure and width.

  16. First-principles simulations of electrostatic interactions between dust grains

    SciTech Connect

    Itou, H. Amano, T.; Hoshino, M.

    2014-12-15

    We investigated the electrostatic interaction between two identical dust grains of an infinite mass immersed in homogeneous plasma by employing first-principles N-body simulations combined with the Ewald method. We specifically tested the possibility of an attractive force due to overlapping Debye spheres (ODSs), as was suggested by Resendes et al. [Phys. Lett. A 239, 181–186 (1998)]. Our simulation results demonstrate that the electrostatic interaction is repulsive and even stronger than the standard Yukawa potential. We showed that the measured electric field acting on the grain is highly consistent with a model electrostatic potential around a single isolated grain that takes into account a correction due to the orbital motion limited theory. Our result is qualitatively consistent with the counterargument suggested by Markes and Williams [Phys. Lett. A 278, 152–158 (2000)], indicating the absence of the ODS attractive force.

  17. First principles modeling of panchromatic dyes for solar cells applications.

    NASA Astrophysics Data System (ADS)

    di Felice, Rosa; Calzolari, Arrigo; Dong, Rui; Buongiorno Nardelli, Marco

    2013-03-01

    The state-of-the-art dye in Grätzel solar cells, N719, exhibits a total solar-to-electric conversion efficiency of 11.2%. However, it severely lacks absorption in the red and the near infrared regions of the electromagnetic spectrum, which represent more than 70% of the solar radiation spectrum. Using calculations from first principles in the time-dependent domain, we have studied the electronic and optical response of a novel class of panchromatic sensitizers that can harvest solar energy efficiently across the visible and near infrared regions, which have been recently synthesized [A. El-Shafei, M. Hussain, A. Atiq, A. Islam, and L. Han, J. Mater. Chem. 22, 24048 (2012)]. Our calculations show that, by tuning the properties of antenna groups, one can achieve a substantial improvement of the optical properties.

  18. NMR shifts for polycyclic aromatic hydrocarbons from first-principles

    SciTech Connect

    Thonhauser, Timo; Ceresoli, Davide; Marzari, Nicola N.

    2009-09-03

    We present first-principles, density-functional theory calculations of the NMR chemical shifts for polycyclic aromatic hydrocarbons, starting with benzene and increasing sizes up to the one- and two-dimensional infinite limits of graphene ribbons and sheets. Our calculations are performed using a combination of the recently developed theory of orbital magnetization in solids, and a novel approach to NMR calculations where chemical shifts are obtained from the derivative of the orbital magnetization with respect to a microscopic, localized magnetic dipole. Using these methods we study on equal footing the 1H and 13C shifts in benzene, pyrene, coronene, in naphthalene, anthracene, naphthacene, and pentacene, and finally in graphene, graphite, and an infinite graphene ribbon. Our results show very good agreement with experiments and allow us to characterize the trends for the chemical shifts as a function of system size.

  19. Hadron Phenomenology from First-Principle QCD Studies

    NASA Astrophysics Data System (ADS)

    Papavassiliou, Joannis

    2016-03-01

    The form of the kernel that controls the dynamics of the Bethe-Salpeter equations is essential for obtaining quantitatively accurate predictions for the observable properties of hadrons. In the present work we briefly review the basic physical concepts and field-theoretic techniques employed in a first-principle derivation of a universal (process-independent) component of this kernel. This "top-down" approach combines nonperturbative ingredients obtained from lattice simulations and Dyson-Schwinger equations, and furnishes a renormalization-group invariant quark-gluon interaction strength, which is in excellent agreement with the corresponding quantity obtained from a systematic "bottom-up" treatment, where bound-state data are fitted within a well-defined truncation scheme.

  20. Free-Carrier Absorption in Silicon from First Principles

    NASA Astrophysics Data System (ADS)

    Shi, Guangsha; Kioupakis, Emmanouil

    The absorption of light by free carriers in semiconductors such as silicon results in intraband electron or hole excitations, and competes with optical transitions across the band gap. Free-carrier absorption therefore reduces the efficiency of optoelectronic devices such as solar cells because it competes with the generation of electron-hole pairs. In this work, we use first-principles calculations based on density functional theory to investigate direct and phonon-assisted free-carrier absorption in silicon. We determine the free-carrier absorption coefficient as a function of carrier concentration and temperature and compare to experiment. We also identify the dominant phonon modes that contributing to phonon-assisted free-carrier absorption processes, and analyze the results to evaluate the impact of this loss mechanism on the efficiency of silicon solar cells. This research was supported by the National Science Foundation CAREER award through Grant No. DMR-1254314. Computational resources were provided by the DOE NERSC facility.

  1. Optimized Materials From First Principles Simulations: Are We There Yet?

    SciTech Connect

    Galli, G; Gygi, F

    2005-07-26

    In the past thirty years, the use of scientific computing has become pervasive in all disciplines: collection and interpretation of most experimental data is carried out using computers, and physical models in computable form, with various degrees of complexity and sophistication, are utilized in all fields of science. However, full prediction of physical and chemical phenomena based on the basic laws of Nature, using computer simulations, is a revolution still in the making, and it involves some formidable theoretical and computational challenges. We illustrate the progress and successes obtained in recent years in predicting fundamental properties of materials in condensed phases and at the nanoscale, using ab-initio, quantum simulations. We also discuss open issues related to the validation of the approximate, first principles theories used in large scale simulations, and the resulting complex interplay between computation and experiment. Finally, we describe some applications, with focus on nanostructures and liquids, both at ambient and under extreme conditions.

  2. First-Principles Dielectric Spectra of Silicon: THz through UV

    NASA Astrophysics Data System (ADS)

    Lawler, H. M.; Dalosto, S.; Levine, Z. H.; Shirley, E. L.; Rehr, J. J.

    2007-03-01

    We present an implementation of the GW-Bethe-Salpeter-equation approach to first-principles calculations of dielectric response based in part on input from the plane-wave, pseudopotential code ABINIT. This work, together with lattice dynamical calculations, aims to develop versatile codes capable of calculating dielectric spectra in insulators for the full spectral range from THz to the UV. Below the bandgap, lattice vibrations absorb light in the THz range. These spectra are generally composed of sharp infrared-active features (absent by symmetry in silicon); weak, temperature dependent continuum effects from IR-active-multiphonon state hybridization; and contributions to the macroscopic polarization directly from multiphonon states. Above the bandgap, density-functional band structures are taken as a starting point for the inclusion of many-body interactions within the GW-BSE approximation. Emphasis will be on treating the excitionic effects and non-zero-momentum application of the modern theory of polarization with ABINIT.

  3. Hadron Phenomenology from First-Principle QCD Studies

    NASA Astrophysics Data System (ADS)

    Papavassiliou, Joannis

    2016-06-01

    The form of the kernel that controls the dynamics of the Bethe-Salpeter equations is essential for obtaining quantitatively accurate predictions for the observable properties of hadrons. In the present work we briefly review the basic physical concepts and field-theoretic techniques employed in a first-principle derivation of a universal (process-independent) component of this kernel. This "top-down" approach combines nonperturbative ingredients obtained from lattice simulations and Dyson-Schwinger equations, and furnishes a renormalization-group invariant quark-gluon interaction strength, which is in excellent agreement with the corresponding quantity obtained from a systematic "bottom-up" treatment, where bound-state data are fitted within a well-defined truncation scheme.

  4. Structural instabilities in strontium titanate from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Lasota, Christopher Andrew

    For some time now, first-principles calculation methods have proven to be an effective tool for investigating the physics of condensed matter systems. The additional use of density functional theory (DFT) and the local density approximation (LDA) has permitted even complex materials to be studied on desktop workstations with remarkable success. The incorporation of linear response theory into these methods has extended their power, allowing investigation of important dynamical properties. Contained within the following pages are the results of a first-principles study of SrTiO3. This transition metal oxide is often grouped with ferroelectric materials, due to its similar composition and perovskite structure. Although it behaves as if it were to become ferroelectric, it fails to do so, even at the lowest temperatures. Using the LAPW method for bulk materials, the ground-state equilibrium properties for the cubic phase were found. Additional linear response calculations produced the phonon frequencies throughout the Brillouin zone. Imaginary values for these frequencies revealed two distinct regions of reciprocal space corresponding to structural instabilities of the ferroelectric (FE) and antiferrodistortive (AFD) types. A cell-doubling AFD transition to tetragonal structure is observed experimentally, so subsequent calculations were continued in this phase. Total energy calculations were performed for both FE and AFD distortions in this new phase, and it was found that the AFD instability is enhanced with decreasing lattice parameter, while the FE instability is diminished. Furthermore, these calculations suggest that this material is marginally stable against FE distortions, even at the 105 K volume.

  5. Synthesis procedure optimization and characterization of europium (III) tungstate nanoparticles

    NASA Astrophysics Data System (ADS)

    Rahimi-Nasrabadi, Mehdi; Pourmortazavi, Seied Mahdi; Ganjali, Mohammad Reza; Reza Banan, Ali; Ahmadi, Farhad

    2014-09-01

    Taguchi robust design as a statistical method was applied for the optimization of process parameters in order to tunable, facile and fast synthesis of europium (III) tungstate nanoparticles. Europium (III) tungstate nanoparticles were synthesized by a chemical precipitation reaction involving direct addition of europium ion aqueous solution to the tungstate reagent solved in an aqueous medium. Effects of some synthesis procedure variables on the particle size of europium (III) tungstate nanoparticles were studied. Analysis of variance showed the importance of controlling tungstate concentration, cation feeding flow rate and temperature during preparation of europium (III) tungstate nanoparticles by the proposed chemical precipitation reaction. Finally, europium (III) tungstate nanoparticles were synthesized at the optimum conditions of the proposed method. The morphology and chemical composition of the prepared nano-material were characterized by means of X-ray diffraction, scanning electron microscopy, transmission electron microscopy, FT-IR spectroscopy and fluorescence.

  6. First-Principles and Semi-Empirical Studies of Microclusters.

    NASA Astrophysics Data System (ADS)

    Chang, Audrey Young-Zee

    The structural, electronic and magnetic properties of clusters have been a subject of intense investigation in recent years, due to many advancements in theoretical and experimental techniques. Since the bonding of atoms in clusters is often different from in bulk, clusters may assume different shapes and structures as the size varies. They therefore provide a model for understanding the transition and structural formation of bulk materials. In this dissertation, two different approaches for pursuing cluster study are carried out: one is based on a realistic but semi-empirical method, the other is more of a first-principles type of calculation. In the first part, the implementation and application of a dynamics simulated annealing scheme, introduced by Car and Parrinello, to a semi-empirical tight-binding model for studying the silicon clusters is presented. In searching for the ground state structures, Langevin molecular dynamics is employed to allow relaxation of the nuclei. For small silicon clusters, Si_{n} (n <= 10), a preference of close-packed structure with binding energies depending on the size are found. Relatively stable structures are observed for clusters of size 4, 6 and 7 which are in accordance with the experimentally found "magic number". In the second part, the study of transition-metal chromium clusters via a first-principles, all-electron, linear combination of Gaussian orbitals method is presented. Transition -metal elements are characterized by having contracted valence d-orbitals containing up to ten electrons, which make them a highly correlated system. The many-electron effects attributed to interactions among these electrons are manifested rather dramatically through the observed magnetic ordering. In this study, the magnetic and structural properties of chromium clusters, (Cr_{n} n <= 9), are investigated based on density functional theory. In bulk, the bcc chromium crystal has a weak antiferromagnetic coupling due to Fermi surfaces

  7. First Principles Studies of ABO3 Perovskite Surfaces and Nanostructures

    NASA Astrophysics Data System (ADS)

    Pilania, Ghanshyam

    Perovskite-type complex oxides, with general formula ABO 3, constitute one of the most prominent classes of metal oxides which finds key applications in diverse technological fields. In recent years, properties of perovskites at reduced dimensions have aroused considerable interest. However, a complete atomic-level understanding of various phenomena is yet to emerge. To fully exploit the materials opportunities provided by nano-structured perovskites, it is important to characterize and understand their bulk and near-surface electronic structure along with the electric, magnetic, elastic and chemical properties of these materials in the nano-regime, where surface and interface effects naturally play a dominant role. In this thesis, state-of-the-art first principles computations are employed to systematically study properties of one- and two-dimensional perovskite systems which are of direct technological significance. Specifically, our bifocal study targets (1) polarization behavior and dielectric response of ABO3 ferroelectric nanowires, and (2) oxygen chemistry relevant for catalytic properties of ABO3 surfaces. In the first strand, we identify presence of novel closure or vortex-like polarization domains in PbTIO3 and BaTiO3 ferroelectric nanowires and explore ways to control the polarization configurations by means of strain and surface chemistry in these prototypical model systems. The intrinsic tendency towards vortex polarization at reduced dimensions and the underlying driving forces are discussed and previously unknown strain induced phase transitions are identified. Furthermore, to compute the dielectric permittivity of nanostructures, a new multiscale model is developed and applied to the PbTiO3 nanowires with conventional and vortex-like polarization configurations. The second part of the work undertaken in this thesis is comprised of a number of ab initio surface studies, targeted to investigate the effects of surface terminations, prevailing chemical

  8. First-Principles Investigation of the Electronic Properties of Interfaces

    NASA Astrophysics Data System (ADS)

    Lucking, Michael C.

    Modern technology depends on the interfaces between materials. Nanomaterials and 2D systems are also promising for future energy and electronics applications. The much larger surface to volume ration of these systems compared to their bulk counterparts makes the interface properties even more important. Understanding the properties of interfaces is vital for technological advancement. First-principles calculations utilizing Density Functional Theory (DFT) can be applied to interfaces and nanostructures to improve the understanding of these systems. I have used these methods to investigate several systems with energy and electronics applications. Several aspects of solar water splitting have been examined, leading to a method of calculating redox levels as well as alignments for amorphous materials. A derailed understanding of the hole transfer reaction on surfaces has also been developed, as well as an understanding of band edge engineering in the promising photocatalyst CoO. In the field if electronics, edge engineering possibilities have been discovered in MoS2, also leading to a general electron counting method that is widely applicable. The nature of the insulating state as well as a model for the transition to the superconducting state has been proposed in (Li,Fe)OHFeSe. The interface between STO and FeSe has also been investigated and the issues are discussed.

  9. A First-Principle Kinetic Theory of Meteor Plasma Formation

    NASA Astrophysics Data System (ADS)

    Dimant, Yakov; Oppenheim, Meers

    2015-11-01

    Every second millions of tiny meteoroids hit the Earth from space, vast majority too small to observe visually. However, radars detect the plasma they generate and use the collected data to characterize the incoming meteoroids and the atmosphere in which they disintegrate. This diagnostics requires a detailed quantitative understanding of formation of the meteor plasma. Fast-descending meteoroids become detectable to radars after they heat due to collisions with atmospheric molecules sufficiently and start ablating. The ablated material then collides into atmospheric molecules and forms plasma around the meteoroid. Reflection of radar pulses from this plasma produces a localized signal called a head echo. Using first principles, we have developed a consistent collisional kinetic theory of the near-meteoroid plasma. This theory shows that the meteoroid plasma develops over a length-scale close to the ion mean free path with a non-Maxwellian velocity distribution. The spatial distribution of the plasma density shows significant deviations from a Gaussian law usually employed in head-echo modeling. This analytical model will serve as a basis for more accurate quantitative interpretation of the head echo radar measurements. Work supported by NSF Grant 1244842.

  10. Predicted boron-carbide compounds: a first-principles study.

    PubMed

    Wang, De Yu; Yan, Qian; Wang, Bing; Wang, Yuan Xu; Yang, Jueming; Yang, Gui

    2014-06-14

    By using developed particle swarm optimization algorithm on crystal structural prediction, we have explored the possible crystal structures of B-C system. Their structures, stability, elastic properties, electronic structure, and chemical bonding have been investigated by first-principles calculations with density functional theory. The results show that all the predicted structures are mechanically and dynamically stable. An analysis of calculated enthalpy with pressure indicates that increasing of boron content will increase the stability of boron carbides under low pressure. Moreover, the boron carbides with rich carbon content become more stable under high pressure. The negative formation energy of predicted B5C indicates its high stability. The density of states of B5C show that it is p-type semiconducting. The calculated theoretical Vickers hardnesses of B-C exceed 40 GPa except B4C, BC, and BC4, indicating they are potential superhard materials. An analysis of Debye temperature and electronic localization function provides further understanding chemical and physical properties of boron carbide. PMID:24929411

  11. Predicted boron-carbide compounds: A first-principles study

    NASA Astrophysics Data System (ADS)

    Wang, De Yu; Yan, Qian; Wang, Bing; Wang, Yuan Xu; Yang, Jueming; Yang, Gui

    2014-06-01

    By using developed particle swarm optimization algorithm on crystal structural prediction, we have explored the possible crystal structures of B-C system. Their structures, stability, elastic properties, electronic structure, and chemical bonding have been investigated by first-principles calculations with density functional theory. The results show that all the predicted structures are mechanically and dynamically stable. An analysis of calculated enthalpy with pressure indicates that increasing of boron content will increase the stability of boron carbides under low pressure. Moreover, the boron carbides with rich carbon content become more stable under high pressure. The negative formation energy of predicted B5C indicates its high stability. The density of states of B5C show that it is p-type semiconducting. The calculated theoretical Vickers hardnesses of B-C exceed 40 GPa except B4C, BC, and BC4, indicating they are potential superhard materials. An analysis of Debye temperature and electronic localization function provides further understanding chemical and physical properties of boron carbide.

  12. Predicted boron-carbide compounds: A first-principles study

    SciTech Connect

    Wang, De Yu; Yan, Qian; Wang, Bing; Wang, Yuan Xu Yang, Jueming; Yang, Gui

    2014-06-14

    By using developed particle swarm optimization algorithm on crystal structural prediction, we have explored the possible crystal structures of B-C system. Their structures, stability, elastic properties, electronic structure, and chemical bonding have been investigated by first-principles calculations with density functional theory. The results show that all the predicted structures are mechanically and dynamically stable. An analysis of calculated enthalpy with pressure indicates that increasing of boron content will increase the stability of boron carbides under low pressure. Moreover, the boron carbides with rich carbon content become more stable under high pressure. The negative formation energy of predicted B{sub 5}C indicates its high stability. The density of states of B{sub 5}C show that it is p-type semiconducting. The calculated theoretical Vickers hardnesses of B-C exceed 40 GPa except B{sub 4}C, BC, and BC{sub 4}, indicating they are potential superhard materials. An analysis of Debye temperature and electronic localization function provides further understanding chemical and physical properties of boron carbide.

  13. First Principles Modelling of Oxygen Impurities in UN Nuclear Fuels

    SciTech Connect

    Kotomin, Eugene Alexej; Mastrikov, Yuri A.

    2008-07-15

    We report results of first principles VASP supercell calculations of O impurity in UN fuels placed either at an interstitial tetrahedral position or as a substitution for a host N ion. In the latter case O perfectly fits into N site producing no lattice distortion. Such the O substitutional impurity only slightly affects the formation energies of U and N vacancies nearby. In both interstitial and substitutional positions O atom attracts the additional electron density and transforms into the negatively charged ion. Oxygen incorporation into pre-existing N vacancy is energetically more favourable than into the interstitial position. The O impurities produce an additional peak at the low energy side of N contribution to the DOS calculated for uranium mononitride which could be used for the O identification by means of the UPS spectroscopy. We compare also the DOS calculated for UN and hypothetical isostructural UO. Both O solution and incorporation energies are negative, indicating that O penetration into UN fuel is the energetically favourable. The migration energy of the interstitial O ion is estimated as 2.8 eV.

  14. Ions in solutions: Determining their polarizabilities from first-principles

    NASA Astrophysics Data System (ADS)

    Molina, John J.; Lectez, Sébastien; Tazi, Sami; Salanne, Mathieu; Dufrêche, Jean-François; Roques, Jérôme; Simoni, Eric; Madden, Paul A.; Turq, Pierre

    2011-01-01

    Dipole polarizabilities of a series of ions in aqueous solutions are computed from first-principles. The procedure is based on the study of the linear response of the maximally localized Wannier functions to an applied external field, within density functional theory. For most monoatomic cations (Li ^+, Na ^+, K ^+, Rb ^+, Mg ^{2+}, Ca ^{2+} and Sr ^{2+}) the computed polarizabilities are the same as in the gas phase. For Cs ^+ and a series of anions (F ^-, Cl ^-, Br ^- and I ^-), environmental effects are observed, which reduce the polarizabilities in aqueous solutions with respect to their gas phase values. The polarizabilities of H ^+_(aq), OH ^-_(aq) have also been determined along an ab initio molecular dynamics simulation. We observe that the polarizability of a molecule instantaneously switches upon proton transfer events. Finally, we also computed the polarizability tensor in the case of a strongly anisotropic molecular ion, UO _2^{2+}. The results of these calculations will be useful in building interaction potentials that include polarization effects.

  15. First-principles study of hydrogen storage materials

    NASA Astrophysics Data System (ADS)

    Ma, Zhu

    2008-10-01

    In this thesis, we use first-principles calculations to study the structural, electronic, and thermal properties of several complex hydrides. We investigate structural and electronic properties of Na-Li alanates. Although Na alanate can reversibly store H with Ti catalyst, its weight capacity needs to be improved. This can be accomplished by partial replacement of Na with lighter elements. We explore the structures of possible Na-Li alloy alanates, and study their phase stability. We also study the structural and thermal properties of Li/Mg/Li-Mg Amides/Imides. Current experimental results give a disordered model about the structure of Li-Mg Imide, in which the positions of Li and Mg are not specified. In addition the model gives a controversial composition stoichiometry. We try to resolve this controversy by searching for low-energy ordered phases. In the last part, we study the structural, energetic, and electronic properties of the La-Mg-Pd-H system. This quaternary system is another example of hydrogenation-induced metal-nonmetal transition without major reconstruction of metal host structure, and it is also with partial reversible H capacity. Experiment gives partially disordered H occupancy on two Wyckoff positions. Our calculation explains the structural and bonding characteristics observed in experiment.

  16. First principle active neutron coincidence counting measurements of uranium oxide

    NASA Astrophysics Data System (ADS)

    Goddard, Braden; Charlton, William; Peerani, Paolo

    2014-03-01

    Uranium is present in most nuclear fuel cycle facilities ranging from uranium mines, enrichment plants, fuel fabrication facilities, nuclear reactors, and reprocessing plants. The isotopic, chemical, and geometric composition of uranium can vary significantly between these facilities, depending on the application and type of facility. Examples of this variation are: enrichments varying from depleted (~0.2 wt% 235U) to high enriched (>20 wt% 235U); compositions consisting of U3O8, UO2, UF6, metallic, and ceramic forms; geometries ranging from plates, cans, and rods; and masses which can range from a 500 kg fuel assembly down to a few grams fuel pellet. Since 235U is a fissile material, it is routinely safeguarded in these facilities. Current techniques for quantifying the 235U mass in a sample include neutron coincidence counting. One of the main disadvantages of this technique is that it requires a known standard of representative geometry and composition for calibration, which opens up a pathway for potential erroneous declarations by the State and reduces the effectiveness of safeguards. In order to address this weakness, the authors have developed a neutron coincidence counting technique which uses the first principle point-model developed by Boehnel instead of the "known standard" method. This technique was primarily tested through simulations of 1000 g U3O8 samples using the Monte Carlo N-Particle eXtended (MCNPX) code. The results of these simulations showed good agreement between the simulated and exact 235U sample masses.

  17. First principles molecular dynamics study of filled ice hydrogen hydrate.

    PubMed

    Zhang, Jingyun; Kuo, Jer-Lai; Iitaka, Toshiaki

    2012-08-28

    We investigated structural changes, phase diagram, and vibrational properties of hydrogen hydrate in filled-ice phase C(2) by using first principles molecular dynamics simulation. It was found that the experimentally reported "cubic" structure is unstable at low temperature and/or high pressure: The "cubic" structure reflects the symmetry at high (room) temperature where the hydrogen bond network is disordered and the hydrogen molecules are orientationally disordered due to thermal rotation. In this sense, the "cubic" symmetry would definitely be lowered at low temperature where the hydrogen bond network and the hydrogen molecules are expected to be ordered. At room temperature and below 30 GPa, it is the thermal effects that play an essential role in stabilizing the structure in "cubic" symmetry. Above 60 GPa, the hydrogen bonds in the framework would be symmetrized and the hydrogen bond order-disorder transition would disappear. These results also suggest the phase behavior of other filled-ice hydrates. In the case of rare gas hydrate, there would be no guest molecules' rotation-nonrotation transition since the guest molecules keep their spherical symmetry at any temperature. On the contrary methane hydrate MH-III would show complex transitions due to the lower symmetry of the guest molecule. These results would encourage further experimental studies, especially nuclear magnetic resonance spectroscopy and neutron scattering, on the phases of filled-ice hydrates at high pressures and/or low temperatures. PMID:22938248

  18. First principles molecular dynamics study of filled ice hydrogen hydrate

    NASA Astrophysics Data System (ADS)

    Zhang, Jingyun; Kuo, Jer-Lai; Iitaka, Toshiaki

    2012-08-01

    We investigated structural changes, phase diagram, and vibrational properties of hydrogen hydrate in filled-ice phase C2 by using first principles molecular dynamics simulation. It was found that the experimentally reported "cubic" structure is unstable at low temperature and/or high pressure: The "cubic" structure reflects the symmetry at high (room) temperature where the hydrogen bond network is disordered and the hydrogen molecules are orientationally disordered due to thermal rotation. In this sense, the "cubic" symmetry would definitely be lowered at low temperature where the hydrogen bond network and the hydrogen molecules are expected to be ordered. At room temperature and below 30 GPa, it is the thermal effects that play an essential role in stabilizing the structure in "cubic" symmetry. Above 60 GPa, the hydrogen bonds in the framework would be symmetrized and the hydrogen bond order-disorder transition would disappear. These results also suggest the phase behavior of other filled-ice hydrates. In the case of rare gas hydrate, there would be no guest molecules' rotation-nonrotation transition since the guest molecules keep their spherical symmetry at any temperature. On the contrary methane hydrate MH-III would show complex transitions due to the lower symmetry of the guest molecule. These results would encourage further experimental studies, especially nuclear magnetic resonance spectroscopy and neutron scattering, on the phases of filled-ice hydrates at high pressures and/or low temperatures.

  19. First-principles prediction of disordering tendencies in complex oxides

    SciTech Connect

    Jiang, Chao; Stanek, Christopher R; Sickafus, Kurt E; Uberuaga, Blas P

    2008-01-01

    The disordering tendencies of a series of zirconate (A{sub 2}Zr{sub 2}O{sub 7}) , hafnate (A{sub 2}Hf{sub 2}O{sub 7}), titanate (A{sub 2}Ti{sub 2}O{sub 7}), and stannate (A{sub 2} Sn{sub 2}O{sub 7}) pyrochlores are predicted in this study using first-principles total energy calculations. To model the disordered (A{sub 1/2}B{sub 1/2})(O{sub 7/8}/V{sub 1/8}){sub 2} fluorite structure, we have developed an 88-atom two-sublattice special quasirandom structure (SQS) that closely reproduces the most important near-neighbor intra-sublattice and inter-sublattice pair correlation functions of the random alloy. From the calculated disordering energies, the order-disorder transition temperatures of those pyrochlores are further predicted and our results agree well with the existing experimental phase diagrams. It is clearly demonstrated that both size and electronic effects play an important role in determining the disordering tendencies of pyrochlore compounds.

  20. First principles based mean field model for oxygen reduction reaction.

    PubMed

    Jinnouchi, Ryosuke; Kodama, Kensaku; Hatanaka, Tatsuya; Morimoto, Yu

    2011-12-21

    A first principles-based mean field model was developed for the oxygen reduction reaction (ORR) taking account of the coverage- and material-dependent reversible potentials of the elementary steps. This model was applied to the simulation of single crystal surfaces of Pt, Pt alloy and Pt core-shell catalysts under Ar and O(2) atmospheres. The results are consistent with those shown by past experimental and theoretical studies on surface coverages under Ar atmosphere, the shape of the current-voltage curve for the ORR on Pt(111) and the material-dependence of the ORR activity. This model suggests that the oxygen associative pathway including HO(2)(ads) formation is the main pathway on Pt(111), and that the rate determining step (RDS) is the removal step of O(ads) on Pt(111). This RDS is accelerated on several highly active Pt alloys and core-shell surfaces, and this acceleration decreases the reaction intermediate O(ads). The increase in the partial pressure of O(2)(g) increases the surface coverage with O(ads) and OH(ads), and this coverage increase reduces the apparent reaction order with respect to the partial pressure to less than unity. This model shows details on how the reaction pathway, RDS, surface coverages, Tafel slope, reaction order and material-dependent activity are interrelated. PMID:22064886

  1. Dissolved carbon in extreme conditions characterized by first principles simulations

    NASA Astrophysics Data System (ADS)

    Pan, Ding; Galli, Giulia

    One key component to understanding carbon transport in the Earth interior is the determination of the molecular species formed when carbon bearing materials are dissolved in water at extreme conditions. We used first principles molecular dynamics to investigate oxidized carbon in water at high pressure (P) and high temperature (T), up to the conditions of the Earth's upper mantle. Contrary to popular geochemistry models assuming that CO2 is the major carbon species present in water, we found that most of the dissolved carbon at 10 GPa and 1000 K is in the form of solvated CO32- and HCO3-anions. We also found that ion pairing between alkali metal cations and CO32- or HCO3-anions is greatly affected by P-T conditions, decreasing with pressure along an isotherm. Our study shows that it is crucial to take into account the specific molecular structure of water under extreme conditions and the changes in hydrogen bonding occurring at high P and T, in order to predict chemical reactions in dissolved carbon. Our findings also shed light on possible reduction mechanisms of CO2 when it is geologically stored, depending on the availability of water. The work is supported by the Sloan Foundation through the Deep Carbon Observatory.

  2. Properties of nanoscale dielectrics from first principles computations

    NASA Astrophysics Data System (ADS)

    Shi, Ning

    In recent years, dielectric materials of nanoscale dimensions have aroused considerable interest. We mention two examples. First, in the semiconductor industry, in order to keep pace with Moore's law scaling, the thickness of gate oxide dielectric material is reaching nanoscale dimensions. Second, the high energy density capacitor industry is currently considering dielectric composites with a polymer host matrix filled with inorganic dielectric nanoparticles or polarizable organic molecules. The driving force for the former application is high dielectric constants (or high-k), and those for the latter are high-k and/or high dielectric breakdown strengths. Thus, it is important to characterize the electronic and dielectric properties of materials in the nano-regime, where surface and interface effects naturally play a dominant role. The primary goal of this work is to determine the extent to which such surface/interface effects modify the dielectric constants, band edges, and dielectric breakdown strengths of systems with at least one of their dimensions in the nano-regime. Towards that end, we have developed new computational methodologies at the first principles (density functional) level of theory. These methods have then been applied to several relevant and critical nanoscale systems, including Si:SiO2 and Si:HfO2 heterojunctions, and polymeric composites containing Cu-phthalocyanine and SiO2 nanoparticles.

  3. Electrostatic engineering of strained ferroelectric perovskites from first principles

    NASA Astrophysics Data System (ADS)

    Cazorla, Claudio; Stengel, Massimiliano

    2015-12-01

    Design of novel artificial materials based on ferroelectric perovskites relies on the basic principles of electrostatic coupling and in-plane lattice matching. These rules state that the out-of-plane component of the electric displacement field and the in-plane components of the strain are preserved across a layered superlattice, provided that certain growth conditions are respected. Intense research is currently directed at optimizing materials functionalities based on these guidelines, often with remarkable success. Such principles, however, are of limited practical use unless one disposes of reliable data on how a given material behaves under arbitrary electrical and mechanical boundary conditions. Here we demonstrate, by focusing on the prototypical ferroelectrics PbTiO3 and BiFeO3 as test cases, how such information can be calculated from first principles in a systematic and efficient way. In particular, we construct a series of two-dimensional maps that describe the behavior of either compound (e.g., concerning the ferroelectric polarization and antiferrodistortive instabilities) at any conceivable choice of the in-plane lattice parameter, a , and out-of-plane electric displacement, D . In addition to being of immediate practical applicability to superlattice design, our results bring new insight into the complex interplay of competing degrees of freedom in perovskite materials and reveal some notable instances where the behavior of these materials depart from what naively is expected.

  4. Oxygen transport in ceria: a first-principles study

    NASA Astrophysics Data System (ADS)

    Sergei, Simak

    2012-02-01

    Ceria (CeO2) is an important material for environmentally benign applications, ranging from solid-oxide fuel cells (SOFC) to oxygen storage [1-2]. The key characteristic needed to be improved is the mobility of oxygen ions. Optimization of ionic transport in ceria has been the topic of many studies. In particular, it has been discovered how the ionic conductivity in ceria might be improved by choosing the proper kind and concentration of dopants [3]. In this presentation we will approach the problem from a different direction by adjusting structural parameters of ceria via the change of external conditions. A systematic first-principles study of the energy landscape and kinetics of reduced ceria as a function of external parameters reveals a physically transparent way to improve oxygen transport in ceria. [4pt] [1] N. Skorodumova, S. Simak, B. Lundqvist, I. Abrikosov, and B. Johansson, Physical Review Letters 89, 14 (2002). [0pt] [2] A. Trovarelli, in Catalysis by Ceria and related materials (Imperial College Press, London, 2002). [0pt] [3] D. A. Andersson, S. I. Simak, N. V. Skorodumova, I. A.Abrikosov, and B. Johansson, Proceedings of the National Academy of Sciences of the United States of America 103, 3518 (2006).

  5. First principles calculations for modern ceramic science and engineering

    NASA Astrophysics Data System (ADS)

    Tanaka, Isao; Oba, Fumiyasu

    2008-02-01

    The free energy of compounds can be theoretically obtained as a function of temperature, pressure and chemical potentials by a combination of a first principles method including phonon calculations and statistical approaches using cluster expansion and Monte Carlo simulations. The information is quite useful in ceramic science and engineering since experimental data are not abundantly available. As an example of phonon calculations, results for graphite in comparison to diamond are presented. The free energy difference among polymorphs of Ga2O3 is shown as a function of temperature as well. Theoretical calculations of x-ray absorption near edge structures (XANES) and electron energy loss near edge structures (ELNES) are also demonstrated. Proper inclusion of the core-hole effect is mandatory in the calculation. For 3d transition element L2,3 XANES/ELNES, a configuration interaction approach to take account of the correlation among the core-hole and the excited electron satisfactorily reproduces experimental spectra. As an example, results for Mn-doped ZnO are shown.

  6. First-principles Simulations and the Criticality of Calving Glaciers

    NASA Astrophysics Data System (ADS)

    Vallot, D.; Åström, J. A.; Schäfer, M.; Welty, E.; O'Neel, S.; Bartholomaus, T. C.; Liu, Y.; Riikilä, T.; Zwinger, T.; Timonen, J.; Moore, J.

    2014-12-01

    The algoritm of a first principles calving-simulation computer-code is outlined and demonstrated. The code is particle-based and uses Newtonian dynamics to simulate ice-fracture, motion and calving. The code can simulate real-size glacier but is only able to simualte individual calving events within a few tens of minutes in duration. The code couples to the Elmer/Ice ice flow-simulation code: Elmer is employed to produce various glacier geomteries, which are then tested for stability using the particle code. In this way it is possible to pin-point the location of calving fronts. The particle simulation code and field observations are engaged to investigate the criticality of calving glaciers. The calving mass and inter-event waiting times both have power-law distributions with the same critical exponents as found for Abelian sand-pile models. This indicate that calving glaciers share characteristics with Self-Organized Critical systems (SOC). This would explain why many glacier found in nature may become unstable as a result of even minor changes in their environment. An SOC calving glacier at the critical point will display so large fluctuations in calving rate that it will render the concept 'average calving rate' more or less useless. I.e. 'average calving rate' will depend on measurement time and always have fluctuaions in the range of 100% more or less independent of the averaging time.

  7. First-principles calculations of gated adatoms on graphene

    NASA Astrophysics Data System (ADS)

    Chan, Kevin T.; Lee, Hoonkyung; Cohen, Marvin L.

    2011-03-01

    The two-dimensional surface of graphene is well-suited for adsorption of adatoms or molecules. The application of a gate voltage can be used to precisely control the electron concentration of the adsorbate-graphene system. Such control over electronic properties of adsorbates on graphene might have useful applications in areas such as catalysis and hydrogen storage. In this work, the gating of a variety of adatoms adsorbed on graphene is studied using first-principles calculations. We compute the projected density of states, local electrostatic potential, and charge density of the adatom-graphene system as a function of gate voltage. We demonstrate that adatoms on graphene can be ionized by gating, and that the ionization causes a sharp change in the electrostatic potential. Additional interesting features of our results are also discussed. This work was supported by NSF Grant No. DMR10-1006184 and DOE under Contract No. DE-AC02-05CH11231. Computational resources were provided by the IT Division at LBNL.

  8. The Effects of Relativity on First-Principles Calculations

    NASA Astrophysics Data System (ADS)

    Semi, T.; Mattsson, A. E.; Wills, J. M.

    2011-06-01

    The construction of the equation of state for a given material is of central importance to its characterization. Hugoniots can be calculated using Density Functional Theory (DFT), and DFT points compared to available experimental results. By evaluating the accuracy in a relevant phase space, confidence is gained in the DFT method. This bolsters the dependability of DFT data in phase spaces in which experiment may be difficult or impossible to perform, and verifies its usefulness. The equation of state is comprised of the cold curve and thermal electronic and ionic terms. We discuss differences in the cold curve of Ce produced by first principles calculations using the Scalar Dirac equation with variational spin-orbit coupling treatment and that generated by the full relativistic formulation, both with the same DFT functionals. The relativistic effects of f-electrons in systems like Ce are expected to be of a magnitude substantial enough to be consequential to the description of these structures. ``Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.''

  9. First-principles investigation of graphene-metal interfaces

    NASA Astrophysics Data System (ADS)

    Ross, Andrew; Adamska, Lyudmyla; Lin, You; Oleynik, Ivan

    2011-03-01

    Epitaxial growth of graphene on Ni(111) substrates is one promising method of large-scale, high-quality graphene wafer production, due to the small lattice mismatch between these two materials. We present results of first-principles density functional theory (DFT) investigation of thestructural, electronic, and magnetic properties of graphene/Ni(111) interfaces relevant to experimental studies of graphene growth on nickel substrates. DFT calculations were performed to identify the favored interface geometries and binding sites for different interface configurations. Additional adlayers of Ni and Cu were either adsorbed on top of the graphene/metal interface, or placed between the graphene and substrate to model processes of metal intercalation. It was also found that the interaction between graphene/Ni(111) and the top Cu adlayer is much weaker compared to that for Ni adlayer. The atomic, electronic, and magnetic properties of these interfaces, including induced magnetic moments in graphene/Ni(111) and Cu,Ni/graphene/Ni(111) systems are also discussed. This work was supported by NSF REU supplement to the award CCF-0726842.

  10. Electronic structure and ionicity of actinide oxides from first principles

    NASA Astrophysics Data System (ADS)

    Petit, L.; Svane, A.; Szotek, Z.; Temmerman, W. M.; Stocks, G. M.

    2010-01-01

    The ground-state electronic structures of the actinide oxides AO , A2O3 , and AO2 ( A=U , Np, Pu, Am, Cm, Bk, and Cf) are determined from first-principles calculations, using the self-interaction corrected local spin-density approximation. Emphasis is put on the degree of f -electron localization, which for AO2 and A2O3 is found to follow the stoichiometry, namely, corresponding to A4+ ions in the dioxide and A3+ ions in the sesquioxides. In contrast, the A2+ ionic configuration is not favorable in the monoxides, which therefore become metallic. The energetics of the oxidation and reduction in the actinide dioxides is discussed, and it is found that the dioxide is the most stable oxide for the actinides from Np onward. Our study reveals a strong link between preferred oxidation number and degree of localization which is confirmed by comparing to the ground-state configurations of the corresponding lanthanide oxides. The ionic nature of the actinide oxides emerges from the fact that only those compounds will form where the calculated ground-state valency agrees with the nominal valency expected from a simple charge counting.

  11. Incorporation of water in pyrope: a first principles study

    NASA Astrophysics Data System (ADS)

    Manga, V. R.; Mookherjee, M.; Muralidharan, K.

    2014-12-01

    Pyrope (Mg3Al2Si3O12) rich garnet is the most important secondary mineral phase with volume fractions ranging between 20 % in the shallow upper mantle to 40 % in the lower part of upper mantle. The volume fractions of garnet in subducted oceanic crusts are as high as 80 %. However, our understanding of the incorporation of water in garnet as proton defect is rather limited. Experimental studies conducted at pressures and temperatures relevant to the deep lower mantle have resulted in wide range of water contents ranging between 0 wt % to ~ 0.8 wt %. In a pyriolyte composition representative of the upper mantle, unlike olivine (Mg2SiO4), which remains largely iso-chemical upon compression, garnet undergoes solid solution with pyroxene (MgSiO3) and as a result there is a continuous evolution of the chemistry of garnet as a function of pressure. This complicates the analysis of proton defects using conventional thermodynamics expressing water solubility as a function of water fugacity, oxide activity, and activation volume. To circumvent this issue, we use first principles simulations to explore the relative energetics of the formation of protons in Mg, Al, and Si sites. Preliminary results at ambient conditions indicate positive enthalpy changes for the proton defects in all the sites, with silicon site being the most favorable. We intend to explore the effect of pressure and temperature on the defect formation energies. Acknowledgement- MM is supported by the US National Science Foundation grant (EAR-1250477).

  12. First-principles design of organo-Sn polymeric dielectrics

    NASA Astrophysics Data System (ADS)

    Tran, Huan; Kumar, Arun; Wang, Chenchen; Baldwin, Aaron; Ma, Rui; Sotzing, Gregory; Ramprasad, Rampi

    2014-03-01

    Following on from recent computation-based suggestions that Sn-containing polymers may be promising dielectrics, one of them, poly (dimethyltin glutarate) (pDMTG), has been synthesized. The measured dielectric constant of pDMTG is ɛ ~= 7 . 4 , significantly higher than the current standard material used for high-energy-density applications, namely, polypropylene (ɛ ~= 2 . 2). By performing first-principles calculations at the level of density functional theory and using the minima-hopping method to predict the stable structures (given that just the composition is provided), we propose four structural models of pDMTG. Based on these models, various physical properties of pDMTG, e.g., dielectric constant, infrared spectra and refractive index, are determined to closely agree with experimental data. The calculated band gap of pDMTG is high (Eg ~= 6 . 1 eV), implying that pDMTG is a promising candidate for high-energy-density materials. The strategy that has lead to the synthesis and understanding of pDMTG shows that density functional theory is a powerful method to study and design new materials. Our work is supported by the Office of Naval Research through the Multidisciplinary University Research Initiative (MURI).

  13. First-principles study of liquid and amorphous metals

    NASA Astrophysics Data System (ADS)

    Ganesh, Panchapakesan

    Computer simulations using state of the art First-Principles ab-initio methods enable us to probe the structural features of novel materials like liquid metals and metallic glass forming alloys, both in their supercooled liquid state as well as in their quenched amorphous forms where available. The ab-initio nature of the calculations enable us to capture the chemical identity realistically at the atomistic level without any free parameters. The results show that even though elemental liquid metals like face-centered cubic (FCC) Cu and body-centered cubic (BCC) Fe (and W) have similar atomic structure at high temperature, which is also similar to jammed packing of hard-spheres, they differ quite appreciably even with slight supercooling. This difference enables us to further supercool Fe and W to a much greater degree than Cu. The origin of this difference between elemental metals with different crystalline ground states can be understood based on concepts of geometric frustration. Further, the role played by atoms of different sizes in controlling the geometric frustration in glass forming alloys has been investigated. Studies of Silicon in its supercooled regime have been made to investigate the existence of a possible structural transition. Attempts to clarify if the structural transition could be a thermodynamic phase transition have been made and changes in electronic properties accompanying this structural change have been studied.

  14. First-Principle Characterization for Singlet Fission Couplings.

    PubMed

    Yang, Chou-Hsun; Hsu, Chao-Ping

    2015-05-21

    The electronic coupling for singlet fission, an important parameter for determining the rate, has been found to be too small unless charge-transfer (CT) components were introduced in the diabatic states, mostly through perturbation or a model Hamiltonian. In the present work, the fragment spin difference (FSD) scheme was generalized to calculate the singlet fission coupling. The largest coupling strength obtained was 14.8 meV for two pentacenes in a crystal structure, or 33.7 meV for a transition-state structure, which yielded a singlet fission lifetime of 239 or 37 fs, generally consistent with experimental results (80 fs). Test results with other polyacene molecules are similar. We found that the charge on one fragment in the S1 diabatic state correlates well with FSD coupling, indicating the importance of the CT component. The FSD approach is a useful first-principle method for singlet fission coupling, without the need to include the CT component explicitly. PMID:26263271

  15. First principles Tafel kinetics of methanol oxidation on Pt(111)

    NASA Astrophysics Data System (ADS)

    Fang, Ya-Hui; Liu, Zhi-Pan

    2015-01-01

    Electrocatalytic methanol oxidation is of fundamental importance in electrochemistry and also a key reaction in direct methanol fuel cell. To resolve the kinetics at the atomic level, this work investigates the potential-dependent reaction kinetics of methanol oxidation on Pt(111) using the first principles periodic continuum solvation model based on modified-Poisson-Boltzmann equation (CM-MPB), focusing on the initial dehydrogenation elementary steps. A theoretical model to predict Tafel kinetics (current vs potential) is established by considering that the rate-determining step of methanol oxidation (to CO) is the first Csbnd H bond breaking (CH3OH(aq) → CH2OH* + H*) according to the computed free energy profile. The first Csbnd H bond breaking reaction needs to overcome a large entropy loss during methanol approaching to the surface and replacing the adsorbed water molecules. While no apparent charge transfer is involved in this elementary step, the charge transfer coefficient of the reaction is calculated to be 0.36, an unconventional value for charge transfer reactions, and the Tafel slope is deduced to be 166 mV. The results show that the metal/adsorbate interaction and the solvation environment play important roles on influencing the Tafel kinetics. The knowledge learned from the potential-dependent kinetics of methanol oxidation can be applied in general for understanding the electrocatalytic reactions of organic molecules at the solid-liquid interface.

  16. Thermal conductivity of silicene from first-principles

    SciTech Connect

    Xie, Han; Bao, Hua E-mail: hua.bao@sjtu.edu.cn; Hu, Ming E-mail: hua.bao@sjtu.edu.cn

    2014-03-31

    Silicene, as a graphene-like two-dimensional material, now receives exceptional attention of a wide community of scientists and engineers beyond graphene. Despite extensive study on its electric property, little research has been done to accurately calculate the phonon transport of silicene so far. In this paper, thermal conductivity of monolayer silicene is predicted from first-principles method. At 300 K, the thermal conductivity of monolayer silicene is found to be 9.4 W/mK and much smaller than bulk silicon. The contributions from in-plane and out-of-plane vibrations to thermal conductivity are quantified, and the out-of-plane vibration contributes less than 10% of the overall thermal conductivity, which is different from the results of the similar studies on graphene. The difference is explained by the presence of small buckling, which breaks the reflectional symmetry of the structure. The flexural modes are thus not purely out-of-plane vibration and have strong scattering with other modes.

  17. First-principles pressure-temperature phase diagrams in metals

    SciTech Connect

    Moriarty, J.A.

    1993-07-01

    Using interatomic potentials derived from first-principles generalized pseudopotential theory, finite-temperature phase transitions in both simple and transition metals can be studied through a combination of analytic statistical methods and molecular-dynamics simulation. In the prototype simple metal-Mg, where volume and pair forces adequately describe the energetics, a complete and accurate phase diagram has thereby been obtained to 60 GPa. A rapidly temperature-dependent hcp-bcc phase line is predicted which ends in a triple point on the melting curve near 4 GPa. In central transition metals such as Mo or Fe, on the other hand, the energetics are complicated by d-state interactions which give rise to both many-body angular forces and enhanced electron-thermal contributions. We have made a detailed study of these phenomena and their impact on melting in the prototype case of Mo and a full melting curve to 2 Mbar has been obtained. In the case of Fe, we are examining the high-pressure phase diagram and the question of whether or not there exists a high-pressure, high-temperature solid bcc phase, as has been speculated. To date, we have shown that the bcc structure is both thermodynamically and mechanically unstable at high pressure and zero temperature, with a large and increasing bcc-hcp energy difference under compression.

  18. Safeguards First Principles Initiative at the Nevada Test Site

    SciTech Connect

    Geneva Johnson

    2007-07-08

    The Material Control and Accountability (MC&A) program at the Nevada Test Site (NTS) was selected as a test bed for the Safeguards First Principles Initiative (SFPI). The implementation of the SFPI is evaluated using the system effectiveness model and the program is managed under an approved MC&A Plan. The effectiveness model consists of an evaluation of the critical elements necessary to detect, deter, and/or prevent the theft or diversion of Special Nuclear Material (SNM). The modeled results indicate that the MC&A program established under this variance is still effective, without creating unacceptable risk. Extensive performance testing is conducted through the duration of the pilot to ensure the protection system is effective and no material is at an unacceptable risk. The pilot was conducted from January 1, 2007, through May 30, 2007. This paper will discuss the following activities in association with SFPI: 1. Development of Timeline 2. Crosswalk of DOE Order and SFPI 3. Peer Review 4. Deviation 5. MC&A Plan and Procedure changes 6. Changes implemented at NTS 7. Training 8. Performance Test

  19. First principles calculation of finite temperature magnetism in Ni

    NASA Astrophysics Data System (ADS)

    Eisenbach, Markus; Yin, Junqi; Nicholson, Don M.; Li, Ying Wai

    2013-03-01

    We harnesses the computational power of massively parallel computers to calculate finite temperature magnetic properties by combining classical Monte-Carlo calculations with our first principles multiple scattering electronic structure code (LSMS) for constrained magnetic states. Our previous calculations of Fe and Fe3 C [J. Appl. Phys. 109, 07E138 (2011)] only considered fluctuations in the local moment directions. Recent advances, both in the understanding of the Wang-Landau method used in our calculations [Phys. Rev. E 84, 065702(R) (2011)] and more powerful computing resources have enabled us to investigate Ni where the fluctuation in the magnitude of the local magnetic moments is of importance equal to their directional fluctuations. Here we will present our recent results for Ni that axpands our method to an even wider class of 3d element based ferromagnets. This research was sponsored by the Offices of Basic Energy Science (M.E. and D.M.N) and the Office of Advanced Computing Research (J.Y. and Y.W.L) of the US Department of Energy. This research used resources of the Oak Ridge Leadership Computing Facility at Oak Ridge National Laboratory, which is supported by the Office of Science of the Department of Energy under contract DE-AC05-00OR22725.

  20. Designing substrates for silicene and germanene: First-principles calculations

    NASA Astrophysics Data System (ADS)

    Chen, M. X.; Zhong, Z.; Weinert, M.

    2016-08-01

    We propose a guideline for exploring substrates that stabilize the monolayer honeycomb structure of silicene and germanene while simultaneously preserving the Dirac states: in addition to having a strong binding energy to the monolayer, a suitable substrate should be a large-gap semiconductor with a proper work function such that the Dirac point lies in the gap and far from the substrate states when their bands align. We illustrate our idea by performing first-principles calculations for silicene and germanene on the Al-terminated (0001) surface of Al2O3 . The overlaid monolayers on Al-terminated Al2O3 (0001) retain the main structural profile of the low-buckled honeycomb structure via a binding energy comparable to the one between silicene and Ag(111). An unfolded band structure derived from the k -projection method reveals that a gapped Dirac cone is formed at the K point due to the structural distortion and the interaction with the substrate. The gaps of 0.4 and 0.3 eV, respectively, for the supported silicene and germanene suggest that they may have potential applications in nanoelectronics.

  1. Semiconducting Graphene on Silicon from First-Principles Calculations.

    PubMed

    Dang, Xuejie; Dong, Huilong; Wang, Lu; Zhao, Yanfei; Guo, Zhenyu; Hou, Tingjun; Li, Youyong; Lee, Shuit-Tong

    2015-08-25

    Graphene is a semimetal with zero band gap, which makes it impossible to turn electric conduction off below a certain limit. Transformation of graphene into a semiconductor has attracted wide attention. Owing to compatibility with Si technology, graphene adsorbed on a Si substrate is particularly attractive for future applications. However, to date there is little theoretical work on band gap engineering in graphene and its integration with Si technology. Employing first-principles calculations, we study the electronic properties of monolayer and bilayer graphene adsorbed on clean and hydrogen (H)-passivated Si (111)/Si (100) surfaces. Our calculation shows that the interaction between monolayer graphene and a H-passivated Si surface is weak, with the band gap remaining negligible. For bilayer graphene adsorbed onto a H-passivated Si surface, the band gap opens up to 108 meV owing to asymmetry introduction. In contrast, the interaction between graphene and a clean Si surface is strong, leading to formation of chemical bonds and a large band gap of 272 meV. Our results provide guidance for device designs based on integrating graphene with Si technology. PMID:26213346

  2. Transport Properties of Nanoscale Materials by First-principles Calculations

    NASA Astrophysics Data System (ADS)

    Mizuseki, Hiroshi; Belosludov, Rodion V.; Lee, S.-U.; Kawazoe, Yoshiyuki

    2009-03-01

    Molecular devices are potential candidates for the next step towards nanoelectronic technology. Our group has covered a wide range of nanoscale wires, which have potential application in molecular electronics using first-principles calculations and nonequilibrium Green's function formalism [1]. Our target materials are supramolecular enamel wires (covered wires) [2], connection between organic molecules and metal electrodes, self-assembled nanowires on silicon surface [3], porphyrin [4], phthalocyanine, metallocene [5], fused-ring thiophene molecules, length dependence of conductance in alkanedithiols and so on. Namely, we have investigated a relationship of the energy levels of delocalized frontier orbitals (HOMO and LUMO) and Fermi level of metal electrodes and estimate the electronic transport properties through atomic and molecular wires using Green's function approach. References [1] http://www-lab.imr.edu/˜mizuseki/nanowire.html [2] R. V. Belosludov, A. A. Farajian, H. Baba, H. Mizuseki, and Y. Kawazoe, Jpn. J. Appl. Phys., 44, 2823 (2005). [3] R. V. Belosludov, A. A. Farajian, H. Mizuseki, K. Miki, and Y. Kawazoe, Phys. Rev. B, 75, 113411 (2007). [4] S.-U. Lee, R. V. Belosludov, H. Mizuseki, and Y. Kawazoe, Small 4 (2008) 962. [5] S.-U Lee, R. V. Belosludov, H. Mizuseki, and Y. Kawazoe, J. Phys. Chem. C. 111 (2007) 15397.

  3. First principles statistical mechanics of alloys and magnetism

    NASA Astrophysics Data System (ADS)

    Eisenbach, Markus; Khan, Suffian N.; Li, Ying Wai

    Modern high performance computing resources are enabling the exploration of the statistical physics of phase spaces with increasing size and higher fidelity of the Hamiltonian of the systems. For selected systems, this now allows the combination of Density Functional based first principles calculations with classical Monte Carlo methods for parameter free, predictive thermodynamics of materials. We combine our locally selfconsistent real space multiple scattering method for solving the Kohn-Sham equation with Wang-Landau Monte-Carlo calculations (WL-LSMS). In the past we have applied this method to the calculation of Curie temperatures in magnetic materials. Here we will present direct calculations of the chemical order - disorder transitions in alloys. We present our calculated transition temperature for the chemical ordering in CuZn and the temperature dependence of the short-range order parameter and specific heat. Finally we will present the extension of the WL-LSMS method to magnetic alloys, thus allowing the investigation of the interplay of magnetism, structure and chemical order in ferrous alloys. This research was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Science and Engineering Division and it used Oak Ridge Leadership Computing Facility resources at Oak Ridge National Laboratory.

  4. First principle investigation of isolated vacancy in (111) diamond surface

    NASA Astrophysics Data System (ADS)

    Hu, Wenhao; Flatté, Michael

    As the simplest intrinsic defect, isolated vacancy has been studied intensively theoretically and experimentally in diamond's bulk phase. Nevertheless, its correspondence in surface phase still lacks people's attention. Nitrogen vacancy center has become the most ideal candidates for solid states computing due to its long coherence time at room temperature. Resembling NV center, the isolated vacancy on surface exhibits a similar ambient potential and the same 3-fold rotational symmetry due to the asymmetry of surface, which implies a similar character in them. In our work, the isolated vacancy in clean and hydrogen terminated (111) surface of diamond are investigated from first principle perspective. Full potential LAPW method implemented in WIEN2K is exploited under GGA approximation. To evaluated the surface effect, the defect depth from topmost layer to fifth subsurface are considered with different slab thickness. By checking the spin density distribution and electronic structure, the hydrogen vacancy in H-terminated surface exhibit a spin-1/2 center with a 0/-1 transition level located in the middle of band gap. The -1/-2 transition level of carbon vacancy in the subsurface approaches the 0/-1 transition level implying the potential stability of spin-1 center. The work was supported by an AFOSR MURI.

  5. Realtime capable first principle based modelling of tokamak turbulent transport

    NASA Astrophysics Data System (ADS)

    Citrin, Jonathan; Breton, Sarah; Felici, Federico; Imbeaux, Frederic; Redondo, Juan; Aniel, Thierry; Artaud, Jean-Francois; Baiocchi, Benedetta; Bourdelle, Clarisse; Camenen, Yann; Garcia, Jeronimo

    2015-11-01

    Transport in the tokamak core is dominated by turbulence driven by plasma microinstabilities. When calculating turbulent fluxes, maintaining both a first-principle-based model and computational tractability is a strong constraint. We present a pathway to circumvent this constraint by emulating quasilinear gyrokinetic transport code output through a nonlinear regression using multilayer perceptron neural networks. This recovers the original code output, while accelerating the computing time by five orders of magnitude, allowing realtime applications. A proof-of-principle is presented based on the QuaLiKiz quasilinear transport model, using a training set of five input dimensions, relevant for ITG turbulence. The model is implemented in the RAPTOR real-time capable tokamak simulator, and simulates a 300s ITER discharge in 10s. Progress in generalizing the emulation to include 12 input dimensions is presented. This opens up new possibilities for interpretation of present-day experiments, scenario preparation and open-loop optimization, realtime controller design, realtime discharge supervision, and closed-loop trajectory optimization.

  6. First-principles prediction of a native ferroelectric metal

    NASA Astrophysics Data System (ADS)

    Iniguez, Jorge; Filippetti, Alessio; Fiorentini, Vincenzo; Ricci, Francesco; Delugas, Pietro

    The possibility that metals may support ferroelectricity is an intriguing open issue. Over the years, various compounds have been referred to as ferroelectric metals, including non-centrosymmetric metals as well as ferroelectrics whose polar distortion survives moderate metallicity induced by doping or proximity. Yet, we think none of these systems embodies a truly ferroelectric metal with native switchable polarization and native metallicity coexisting in a single phase. Here we report a first-principles prediction of such a material. We show that the layered perovskite Bi5Ti5O17 has a non-zero density of states at the Fermi level and metal-like conductivity, as well as a spontaneous polarization in zero field. Further, we predict that the polarization of Bi5Ti5O17 is switchable both in principle (the material complies with the sufficient symmetry requirements) and in practice (in spite of being a metal, Bi5Ti5O17 can sustain a sizable potential drop along the polar direction, as needed to revert its polarization by application of an electric bias). Our results also reveal striking behaviors - such as the self screening mechanism at work in thin Bi5Ti5O17 layers - emerging from the intimate interplay between polar distortions and free carriers in such an exotic material. Supported by MIUR-PRIN, Fondazione Banco di Sardegna, FNR Luxembourg, MINECO-Spain, CINECA-ISCRA and CESGA.

  7. First-principles stability study of clathrate hydrates under pressure

    NASA Astrophysics Data System (ADS)

    Thonhauser, Timo; Li, Qi; Kolb, Brian

    2010-03-01

    We present a first-principles DFT study of the structural stability of clathrate hydrates under pressure. These materials form under high pressure and low temperature and consist of polyhedral water cages that form an ice-like framework of hydrogen bonds. Clathrate hydrates can be filled with guest molecules such as methane or molecular hydrogen, in which case these materials and their stability are of interest for energy-storage solutions. Since the interactions between the water molecules themselves---but also between the water molecules and the guest molecules---is at least partly determined by van der Waals forces, we utilize the recently developed self-consistent van der Waals density functional vdW-DF (T. Thonhauser, V.R. Cooper, S. Li, A. Puzder, P. Hyldgaard, and D.C. Langreth, Phys. Rev. B 76, 125112 (2007)). For our simulations we consider the empty host lattice, as well as the host lattice filled with methane and molecular hydrogen, for pressures up to 1 GPa. Our results show that the system undergoes phase transitions from structure I to structure II and finally to structure H, in good agreement with experiment.

  8. First principles molecular dynamics without self-consistent field optimization

    SciTech Connect

    Souvatzis, Petros; Niklasson, Anders M. N.

    2014-01-28

    We present a first principles molecular dynamics approach that is based on time-reversible extended Lagrangian Born-Oppenheimer molecular dynamics [A. M. N. Niklasson, Phys. Rev. Lett. 100, 123004 (2008)] in the limit of vanishing self-consistent field optimization. The optimization-free dynamics keeps the computational cost to a minimum and typically provides molecular trajectories that closely follow the exact Born-Oppenheimer potential energy surface. Only one single diagonalization and Hamiltonian (or Fockian) construction are required in each integration time step. The proposed dynamics is derived for a general free-energy potential surface valid at finite electronic temperatures within hybrid density functional theory. Even in the event of irregular functional behavior that may cause a dynamical instability, the optimization-free limit represents a natural starting guess for force calculations that may require a more elaborate iterative electronic ground state optimization. Our optimization-free dynamics thus represents a flexible theoretical framework for a broad and general class of ab initio molecular dynamics simulations.

  9. First principles simulations of fluid water: The radial distribution functions

    NASA Astrophysics Data System (ADS)

    Ortega, José; Lewis, James P.; Sankey, Otto F.

    1997-03-01

    We apply a recently developed first principles but simplified molecular dynamics method to the simulation of water at different conditions. The computational simplicity of this method allows its application to systems containing a significant number of molecules, yet still taking explicitly into account the quantum electronic structure of the system. In the present work we simulate a system of 216 H2O molecules with periodic boundary conditions at two different densities (ρ=1.0 g/cm3 and ρ=0.72 g/cm3 and temperatures ranging from ˜300 K to ˜580 K. The effect of density and temperature on the structure of water is analyzed by means of the partial radial distribution functions gOO, gOH and gHH . We find an important reduction of the hydrogen-bond peak for water at the supercritical conditions ρ= 0.72 g/cm3, T=580 K, in good agreement with recent experimental results.

  10. Auger recombination in InN from first principles

    NASA Astrophysics Data System (ADS)

    McAllister, Andrew; Kioupakis, Emmanouil

    Group-III Nitride materials are used in numerous electronic and optoelectronic devices including solid-state lighting, energy conversion, sensor technologies, and high-power electronics. Indium nitride in particular is interesting for fast electronics and optoelectronics in the infrared. Auger recombination is a non-radiative carrier recombination process that would limit the efficiency of these devices. The small band gap (0.7 eV) and the high intrinsic free-electron concentrations in InN possibly make Auger recombination particularly important in this material. We used first-principles computational methods to determine the Auger recombination rates in InN. Our results suggest that direct Auger recombination is dominant in this material and that phonon-assisted Auger processes are not as important as in wider-gap nitrides such as GaN. This research was supported by the National Science Foundation CAREER award through Grant No. DMR-1254314. Computational resources were provided by the DOE NERSC facility.

  11. Gypsum under pressure: A first-principles study

    NASA Astrophysics Data System (ADS)

    Giacomazzi, Luigi; Scandolo, Sandro

    2010-02-01

    We investigate by means of first-principles methods the structural response of gypsum (CaSO4ṡ2H2O) to pressures within and above the stability range of gypsum-I (P≤4GPa) . Structural and vibrational properties calculated for gypsum-I are in excellent agreement with experimental data. Compression within gypsum-I takes place predominantly through a reduction in the volume of the CaO8 polyhedra and through a distortion of the hydrogen bonds. The distance between CaSO4 layers becomes increasingly incompressible, indicating a mechanical limit to the packing of water molecules between the layers. We find that a structure with collapsed interlayer distances becomes more stable than gypsum-I above about 5 GPa. The collapse is concomitant with a rearrangement of the hydrogen-bond network of the water molecules. Comparison of the vibrational spectra calculated for this structure with experimental data taken above 5 GPa supports the validity of our model for the high-pressure phase of gypsum.

  12. Monolayer II-VI semiconductors: A first-principles prediction

    NASA Astrophysics Data System (ADS)

    Zheng, Hui; Li, Xian-Bin; Chen, Nian-Ke; Xie, Sheng-Yi; Tian, Wei Quan; Chen, Yuanping; Xia, Hong; Zhang, S. B.; Sun, Hong-Bo

    2015-09-01

    A systematic study of 32 honeycomb monolayer II-VI semiconductors is carried out by first-principles methods. While none of the two-dimensional (2D) structures can be energetically stable, it appears that BeO, MgO, CaO, ZnO, CdO, CaS, SrS, SrSe, BaTe, and HgTe honeycomb monolayers have a good dynamic stability. The stability of the five oxides is consistent with the work published by Zhuang et al. [Appl. Phys. Lett. 103, 212102 (2013), 10.1063/1.4831972]. The rest of the compounds in the form of honeycomb are dynamically unstable, revealed by phonon calculations. In addition, according to the molecular dynamic (MD) simulation evolution from these unstable candidates, we also find two extra monolayers dynamically stable, which are tetragonal BaS [P 4 /n m m (129 ) ] and orthorhombic HgS [P 21/m (11 ) ] . The honeycomb monolayers exist in the form of either a planar perfect honeycomb or a low-buckled 2D layer, all of which possess a band gap and most of them are in the ultraviolet region. Interestingly, the dynamically stable SrSe has a gap near visible light, and displays exotic electronic properties with a flat top of the valence band, and hence has a strong spin polarization upon hole doping. The honeycomb HgTe has recently been reported to achieve a topological nontrivial phase under appropriate in-plane tensile strain and spin-orbital coupling (SOC) [J. Li et al., arXiv:1412.2528]. Some II-VI partners with less than 5 % lattice mismatch may be used to design novel 2D heterojunction devices. If synthesized, potential applications of these 2D II-VI families could include optoelectronics, spintronics, and strong correlated electronics.

  13. Risk reduction and the privatization option: First principles

    SciTech Connect

    Bjornstad, D.J.; Jones, D.W.; Russell, M.; Cummings, R.C.; Valdez, G.; Duemmer, C.L.

    1997-06-25

    The Department of Energy`s Office of Environmental Restoration and Waste Management (EM) faces a challenging mission. To increase efficiency, EM is undertaking a number of highly innovative initiatives--two of which are of particular importance to the present study. One is the 2006 Plan, a planning and budgeting process that seeks to convert the clean-up program from a temporally and fiscally open-ended endeavor to a strictly bounded one, with firm commitments over a decade-long horizon. The second is a major overhauling of the management and contracting practices that define the relationship between the Department and the private sector, aimed at cost reduction by increasing firms` responsibilities and profit opportunities and reducing DOE`s direct participation in management practices and decisions. The goal of this paper is to provide an independent perspective on how EM should create new management practices to deal with private sector partners that are motivated by financial incentives. It seeks to ground this perspective in real world concerns--the background of the clean-up effort, the very difficult technical challenges it faces, the very real threats to environment, health and safety that have now been juxtaposed with financial drivers, and the constraints imposed by government`s unique business practices and public responsibilities. The approach is to raise issues through application of first principles. The paper is targeted at the EM policy officer who must implement the joint visions of the 2006 plan and privatization within the context of the tradeoff between terminal risk reduction and interim risk management.

  14. A first-principles theoretical approach to heterogeneous nanocatalysis.

    PubMed

    Negreiros, Fabio R; Aprà, Edoardo; Barcaro, Giovanni; Sementa, Luca; Vajda, Stefan; Fortunelli, Alessandro

    2012-02-21

    A theoretical approach to heterogeneous catalysis by sub-nanometre supported metal clusters and alloys is presented and discussed. Its goal is to perform a computational sampling of the reaction paths in nanocatalysis via a global search in the phase space of structures and stoichiometry combined with filtering which takes into account the given experimental conditions (catalytically relevant temperature and reactant pressure), and corresponds to an incremental exploration of the disconnectivity diagram of the system. The approach is implemented and applied to the study of propylene partial oxidation by Ag(3) supported on MgO(100). First-principles density-functional theory calculations coupled with a Reactive Global Optimization algorithm are performed, finding that: (1) the presence of an oxide support drastically changes the potential energy landscape of the system with respect to the gas phase, favoring configurations which interact positively with the electrostatic field generated by the surface; (2) the reaction energy barriers for the various mechanisms are crucial in the competition between thermodynamically and kinetically favored reaction products; (3) a topological database of structures and saddle points is produced which has general validity and can serve for future studies or for deriving general trends; (4) the MgO(100) surface captures some major features of the effect of an oxide support and appears to be a good model of a simple oxide substrate; (5) strong cooperative effects are found in the co-adsorption of O(2) and other ligands on small metal clusters. The proposed approach appears as a viable route to advance the role of predictive computational science in the field of heterogeneous nanocatalysis. PMID:22057595

  15. First principles characterization of silicate sites in clay surfaces.

    PubMed

    Alvim, Raphael S; Miranda, Caetano R

    2015-02-21

    Aluminosilicate clays like Montmorillonite (MMT) and Muscovite Mica (MT) have siloxane cavities on the basal plane. The hydroxyl groups localized in these cavities and van der Waals (vdW) forces contribute significantly to adsorption processes. However, the basal sites are found to be difficult to characterize experimentally. Here, (001) surfaces of MMT and MT clays were investigated using first-principles calculations to understand how these silicate surface sites are influenced by hydroxyl groups and the effective role of inner layer vdW interactions. Based on density-functional theory (DFT) within the generalized gradient approximation (GGA), different types of exchange-correlation functionals were tested to check the effect of vdW dispersion correction. Noncontact atomic force microscopy (nc-AFM), X-ray absorption spectroscopy (XAS) in the near-edge region and solid-state nuclear magnetic resonance (SS-NMR) spectroscopy were simulated. In both clays, the oxygen surface sites are directly affected by the intralayer interaction through hydroxyl groups. Our results indicated that the chemical environment of the hydroxyl groups is distinct in the MMT and MT structures. The vdW correction was essential for a better description of the surface oxygen sites and correctly describes the similarity between both clays. Particularly, the bulk apical oxygen sites in the MT structure are less influenced by vdW interaction. Compared to MMT, the silicon surface sites of MT are more sensitive to the intralayer changes in Si-Oapical-Al and with less effect of the hydroxyl groups. These results provide a clear understanding of influence of the siloxane cavity on the oxygen and silicon surface sites in aluminosilicates. PMID:25592132

  16. First principles modeling of nonlinear incidence rates in seasonal epidemics.

    PubMed

    Ponciano, José M; Capistrán, Marcos A

    2011-02-01

    In this paper we used a general stochastic processes framework to derive from first principles the incidence rate function that characterizes epidemic models. We investigate a particular case, the Liu-Hethcote-van den Driessche's (LHD) incidence rate function, which results from modeling the number of successful transmission encounters as a pure birth process. This derivation also takes into account heterogeneity in the population with regard to the per individual transmission probability. We adjusted a deterministic SIRS model with both the classical and the LHD incidence rate functions to time series of the number of children infected with syncytial respiratory virus in Banjul, Gambia and Turku, Finland. We also adjusted a deterministic SEIR model with both incidence rate functions to the famous measles data sets from the UK cities of London and Birmingham. Two lines of evidence supported our conclusion that the model with the LHD incidence rate may very well be a better description of the seasonal epidemic processes studied here. First, our model was repeatedly selected as best according to two different information criteria and two different likelihood formulations. The second line of evidence is qualitative in nature: contrary to what the SIRS model with classical incidence rate predicts, the solution of the deterministic SIRS model with LHD incidence rate will reach either the disease free equilibrium or the endemic equilibrium depending on the initial conditions. These findings along with computer intensive simulations of the models' Poincaré map with environmental stochasticity contributed to attain a clear separation of the roles of the environmental forcing and the mechanics of the disease transmission in shaping seasonal epidemics dynamics. PMID:21379320

  17. First-principles studies of Ni-Ta intermetallic compounds

    SciTech Connect

    Zhou Yi; Wen Bin; Ma Yunqing; Melnik, Roderick; Liu Xingjun

    2012-03-15

    The structural properties, heats of formation, elastic properties, and electronic structures of Ni-Ta intermetallic compounds are investigated in detail based on density functional theory. Our results indicate that all Ni-Ta intermetallic compounds calculated here are mechanically stable except for P21/m-Ni{sub 3}Ta and hc-NiTa{sub 2}. Furthermore, we found that Pmmn-Ni{sub 3}Ta is the ground state stable phase of Ni{sub 3}Ta polymorphs. The polycrystalline elastic modulus has been deduced by using the Voigt-Reuss-Hill approximation. All Ni-Ta intermetallic compounds in our study, except for NiTa, are ductile materials by corresponding G/K values and poisson's ratio. The calculated heats of formation demonstrated that Ni{sub 2}Ta are thermodynamically unstable. Our results also indicated that all Ni-Ta intermetallic compounds analyzed here are conductors. The density of state demonstrated the structure stability increases with the Ta concentration. - Graphical abstract: Mechanical properties and formation heats of Ni-Ta intermetallic compounds are discussed in detail in this paper. Highlights: Black-Right-Pointing-Pointer Ni-Ta intermetallic compounds are investigated by first principle calculations. Black-Right-Pointing-Pointer P21/m-Ni{sub 3}Ta and hc-NiTa{sub 2} are mechanically unstable phases. Black-Right-Pointing-Pointer Pmmn-Ni{sub 3}Ta is ground stable phase of Ni{sub 3}Ta polymorphs. Black-Right-Pointing-Pointer All Ni-Ta intermetallic compounds are conducting materials.

  18. A digitally reconstructed radiograph algorithm calculated from first principles

    SciTech Connect

    Staub, David; Murphy, Martin J.

    2013-01-15

    Purpose: To develop an algorithm for computing realistic digitally reconstructed radiographs (DRRs) that match real cone-beam CT (CBCT) projections with no artificial adjustments. Methods: The authors used measured attenuation data from cone-beam CT projection radiographs of different materials to obtain a function to convert CT number to linear attenuation coefficient (LAC). The effects of scatter, beam hardening, and veiling glare were first removed from the attenuation data. Using this conversion function the authors calculated the line integral of LAC through a CT along rays connecting the radiation source and detector pixels with a ray-tracing algorithm, producing raw DRRs. The effects of scatter, beam hardening, and veiling glare were then included in the DRRs through postprocessing. Results: The authors compared actual CBCT projections to DRRs produced with all corrections (scatter, beam hardening, and veiling glare) and to uncorrected DRRs. Algorithm accuracy was assessed through visual comparison of projections and DRRs, pixel intensity comparisons, intensity histogram comparisons, and correlation plots of DRR-to-projection pixel intensities. In general, the fully corrected algorithm provided a small but nontrivial improvement in accuracy over the uncorrected algorithm. The authors also investigated both measurement- and computation-based methods for determining the beam hardening correction, and found the computation-based method to be superior, as it accounted for nonuniform bowtie filter thickness. The authors benchmarked the algorithm for speed and found that it produced DRRs in about 0.35 s for full detector and CT resolution at a ray step-size of 0.5 mm. Conclusions: The authors have demonstrated a DRR algorithm calculated from first principles that accounts for scatter, beam hardening, and veiling glare in order to produce accurate DRRs. The algorithm is computationally efficient, making it a good candidate for iterative CT reconstruction techniques

  19. Magnetic Properties of Ni(2+)(aq) from First Principles.

    PubMed

    Mareš, Jiří; Liimatainen, Helmi; Pennanen, Teemu O; Vaara, Juha

    2011-10-11

    The aqueous solution of the Ni(2+) ion was investigated using a first principles molecular dynamics (FPMD) simulation based on periodic density-functional theory (DFT) calculations. Statistical averages of the magnetic properties corresponding to the triplet spin state of the ion, the hyperfine coupling, g and zero-field splitting tensors, as well as the resulting paramagnetic nuclear magnetic resonance (pNMR) shielding terms were calculated using DFT from instantaneous simulation snapshots extracted from the FPMD trajectory. We report comprehensive tests of the reliability of systematically selected DFT functionals for the properties. The isotropic nuclear shielding of the (17)O nuclei can be obtained with good predictive power. The accuracy of the calculated (1)H shieldings is limited by the fact that the spin-density on the proton sites is not reproduced reliably with the tested functionals, rendering the dominant Fermi contact isotropic shielding term less well-defined. On the other hand, the dominant spin-dipole term of the shielding anisotropy, which gives a practically vanishing isotropic contribution, can be obtained with good reliability for both the (1)H and (17)O nuclei. The anisotropic shielding tensor can be thus utilized reliably in the calculation of Curie-type paramagnetic relaxation. We discuss the evolution of the pNMR properties through the first and second solvation shells of the ion, toward the bulk solvent. The magnetic properties of the dominant, six-coordinated solution are compared to those of the metastable, 5-fold coordinated intermediate occurring in the dissociative exchange process. PMID:26598159

  20. First-principles investigation of hydrous post-perovskite

    NASA Astrophysics Data System (ADS)

    Townsend, Joshua P.; Tsuchiya, Jun; Bina, Craig R.; Jacobsen, Steven D.

    2015-07-01

    A stable, hydrogen-defect structure of post-perovskite (hy-ppv, Mg1-xSiH2xO3) has been determined by first-principles calculations of the vibrational and elastic properties up to 150 GPa. Among three potential hy-ppv structures analyzed, one was found to be stable at pressures relevant to the lower-mantle D″ region. Hydrogen has a pronounced effect on the elastic properties of post-perovskite due to magnesium defects associated with hydration, including a reduction of the zero-pressure bulk (K0) and shear (G0) moduli by 5% and 8%, respectively, for a structure containing ∼1 wt.% H2O. However, with increasing pressure the moduli of hy-ppv increase significantly relative to ppv, resulting in a structure that is only 1% slower in bulk compressional velocity and 2.5% slower in shear-wave velocity than ppv at 120 GPa. In contrast, the reduction of certain anisotropic elastic constants (Cij) in hy-ppv increases with pressure (notably, C55, C66, and C23), indicating that hydration generally increases elastic anisotropy in hy-ppv at D″ pressures. Calculated infrared absorption spectra show two O-H stretching bands at ∼3500 cm-1 that shift with pressure to lower wavenumber by about 2 cm-1/GPa. At 120 GPa the hydrogen bonds in hy-ppv are still asymmetric. The stability of a hy-ppv structure containing 1-2 wt.% H2O at D″ pressures implies that post-perovskite may be a host for recycled or primordial hydrogen near the Earth's core-mantle boundary.

  1. Atomistic models of hydrogenated amorphous silicon nitride from first principles

    NASA Astrophysics Data System (ADS)

    Jarolimek, K.; de Groot, R. A.; de Wijs, G. A.; Zeman, M.

    2010-11-01

    We present a theoretical study of hydrogenated amorphous silicon nitride (a-SiNx:H) , with equal concentrations of Si and N atoms (x=1) , for two considerably different densities (2.0 and 3.0g/cm3 ). Densities and hydrogen concentration were chosen according to experimental data. Using first-principles molecular-dynamics within density-functional theory the models were generated by cooling from the liquid. Where both models have a short-range order resembling that of crystalline Si3N4 because of their different densities and hydrogen concentrations they show marked differences at longer length scales. The low-density nitride forms a percolating network of voids with the internal surfaces passivated by hydrogen. Although some voids are still present for the high-density nitride, this material has a much denser and uniform space filling. The structure factors reveal some tendency for the nonstoichiometric high-density nitride to phase separate into nitrogen rich and poor areas. For our slowest cooling rate (0.023 K/fs) we obtain models with a modest number of defect states, where the low (high) density nitride favors undercoordinated (overcoordinated) defects. Analysis of the structural defects and electronic density of states shows that there is no direct one-to-one correspondence between the structural defects and states in the gap. There are several structural defects that do not contribute to in-gap states and there are in-gap states that do only have little to no contributions from (atoms in) structural defects. Finally an estimation of the size and cooling rate effects on the amorphous network is reported.

  2. Properties of ferroelectric ultrathin films from first principles

    NASA Astrophysics Data System (ADS)

    Bin-Omran, Saad

    First-principles-based methods are used to determine the response of polarization to epitaxial strain in films made of BaTiO3 (BT) and Pb(Zr0.5Ti0.5)O3 (PZT). Unlike in BT films, the strength of this response as well as its sign dramatically depend on the film's thickness and electrical boundary conditions in PZT films. A phenomenological model provides a rationale for these findings. Moreover, we reveal the effect of the depolarizing field on the paraelectric-to-ferroelectric phase transition in BaTiO3 and PZT ultrathin films. We found that with decreasing the beta screening parameter (i.e., when increasing the depolarizing field) (i) the Curie temperature, Tc, linearly decreases; (ii) the dielectric maximum epsilonmax increases; (iii) the phase transition becomes less diffuse. Furthermore, we investigate the effect of mechanical boundary conditions on the paraelectric-to-ferroelectric phase transition in BaTiO3 and PZT ultrathin films. It is predicted that (i) the phase transition temperature (Tc) increases due to the applied compressive strain; (ii) the epitaxial strain decreases the dielectric maximum epsilon max at any given value of the screening parameter beta; (iii) the diffusive character of the transition is larger in compressive films than in freestanding systems at a fixed beta. Also, we reveal that the nature of all paraelectric-to-ferroelectric phase transitions in the BaTiO3 and PZT ultrathin films (that are under different electric and mechanical boundary conditions) is of second-order.

  3. Transport and first-principles study of novel thermoelectric materials

    NASA Astrophysics Data System (ADS)

    Chi, Hang

    Thermoelectric materials can recover waste industrial heat and convert it to electricity as well as provide efficient local cooling of electronic devices. The efficiency of such environmentally responsible and exceptionally reliable solid state energy conversion is determined by the dimensionless figure-of-merit ZT = alpha2 sigmaT/kappa, where alpha is the Seebeck coefficient, sigma is the electrical conductivity, kappa is the thermal conductivity, and T is the absolute temperature. The goal of the thesis is to (i) illustrate the physics to achieve high ZT of advanced thermoelectric materials and (ii) explore fundamental structure and transport properties in novel condensed matter systems, via an approach combining comprehensive experimental techniques and state-of-the-art first-principles simulation methods. Thermo-galvanomagnetic transport coefficients are derived from Onsager's reciprocal relations and evaluated via solving Boltzmann transport equation using Fermi-Dirac statistics, under the relaxation time approximation. Such understanding provides insights on enhancing ZT through two physically intuitive and very effective routes: (i) improving power factor PF = alpha2sigma; and (ii) reducing thermal conductivity kappa, as demonstrated in the cases of Mg2Si1-xSnx solid solution and Ge/Te double substituted skutterudites CoSb3(1-x)Ge1.5x Te1.5x, respectively. Motivated by recent theoretical predictions of enhanced thermoelectric performance in highly mismatched alloys, ZnTe:N molecular beam epitaxy (MBE) films deposited on GaAs (100) substrates are carefully examined, which leads to a surprising discovery of significant phonon-drag thermopower (reaching 1-2 mV/K-1) at ~13 K. Further systematic study in Bi2Te3 MBE thin films grown on sapphire (0001) and/or BaF2 (111) substrates, reveal that the peak of phonon drag can be tuned by the choice of substrates with different Debye temperatures. Moreover, the detailed transport and structure studies of Bi2-xTl xTe3

  4. Doping of rhenium disulfide monolayers: a systematic first principles study.

    PubMed

    Çakır, Deniz; Sahin, Hasan; Peeters, François M

    2014-08-21

    The absence of a direct-to-indirect band gap transition in ReS2 when going from the monolayer to bulk makes it special among the other semiconducting transition metal dichalcogenides. The functionalization of this promising layered material emerges as a necessity for the next generation technological applications. Here, the structural, electronic, and magnetic properties of substitutionally doped ReS2 monolayers at either the S or Re site were systematically studied by using first principles density functional calculations. We found that substitutional doping of ReS2 depends sensitively on the growth conditions of ReS2. Among the large number of non-metallic atoms, namely H, B, C, Se, Te, F, Br, Cl, As, P, and N, we identified the most promising candidates for n-type and p-type doping of ReS2. While Cl is an ideal candidate for n-type doping, P appears to be the most promising candidate for p-type doping of the ReS2 monolayer. We also investigated the doping of ReS2 with metal atoms, namely Mo, W, Ti, V, Cr, Co, Fe, Mn, Ni, Cu, Nb, Zn, Ru, Os and Pt. Mo, Nb, Ti, and V atoms are found to be easily incorporated in a single layer of ReS2 as substitutional impurities at the Re site for all growth conditions considered in this work. Tuning chemical potentials of dopant atoms energetically makes it possible to dope ReS2 with Fe, Co, Cr, Mn, W, Ru, and Os at the Re site. We observe a robust trend for the magnetic moments when substituting a Re atom with metal atoms such that depending on the electronic configuration of dopant atoms, the net magnetic moment of the doped ReS2 becomes either 0 or 1 μB. Among the metallic dopants, Mo is the best candidate for p-type doping of ReS2 owing to its favorable energetics and promising electronic properties. PMID:25001566

  5. First Principles Modeling of Bimolecular Reactions with Diffusion

    NASA Astrophysics Data System (ADS)

    Hansen, S. K.; Scher, H.; Berkowitz, B.

    2013-12-01

    We consider three approaches to modeling A + B → C irreversible reactions in natural media: 1) a discretized diffusion-reaction equation (DRE), 2) a particle tracking (PT) scheme in which reaction occurs if and only if an A and B particle pair are within a fixed distance, r (the "reaction radius"), and 3) a PT scheme using an alternative to the fixed reaction radius: a collocation probability distribution derived directly from first principles. Each approach has advantages. In some cases a discretized DRE may be the most computationally efficient method. For PT simulations, robust codes exist based on use of a fixed reaction radius. And finally, collocation probabilities may be derived directly from the Fick's Law constant, D, which is a well-established property for most species. In each approach, a single parameter governs the 'promiscuity' of the reaction (i.e. the thermodynamic favorability of reaction, predicated on the particles being locally well mixed). For the DRE, fixed-reaction-radius PT, and collocation-based PT, these parameters are, respectively: a second-order decay rate, r, and D. We established a number of new results enhancing these approaches and relating them to each other (and to nature). In particular, a thought experiment concerning a simple system in which the predictions of each approach can be computed analytically was used to derive formulas establishing a universal one-to-one correspondence among each of the governing parameters. We thus showed the conditions for equivalence of the three approaches, and grounded both the DRE approach and the fixed-radius PT approach in the Fick's Law D. We further showed that the existing collocation-based PT theory is based on a probability distribution that is only correct for infinitesimally small times, but which can be modified to be accurate for larger times by means of continuous time random walk analysis and first-passage probability distributions. Finally, we employed a novel mathematical

  6. ABINIT: First-principles approach to material and nanosystem properties

    NASA Astrophysics Data System (ADS)

    Gonze, X.; Amadon, B.; Anglade, P.-M.; Beuken, J.-M.; Bottin, F.; Boulanger, P.; Bruneval, F.; Caliste, D.; Caracas, R.; Côté, M.; Deutsch, T.; Genovese, L.; Ghosez, Ph.; Giantomassi, M.; Goedecker, S.; Hamann, D. R.; Hermet, P.; Jollet, F.; Jomard, G.; Leroux, S.; Mancini, M.; Mazevet, S.; Oliveira, M. J. T.; Onida, G.; Pouillon, Y.; Rangel, T.; Rignanese, G.-M.; Sangalli, D.; Shaltaf, R.; Torrent, M.; Verstraete, M. J.; Zerah, G.; Zwanziger, J. W.

    2009-12-01

    ABINIT [ http://www.abinit.org] allows one to study, from first-principles, systems made of electrons and nuclei (e.g. periodic solids, molecules, nanostructures, etc.), on the basis of Density-Functional Theory (DFT) and Many-Body Perturbation Theory. Beyond the computation of the total energy, charge density and electronic structure of such systems, ABINIT also implements many dynamical, dielectric, thermodynamical, mechanical, or electronic properties, at different levels of approximation. The present paper provides an exhaustive account of the capabilities of ABINIT. It should be helpful to scientists that are not familiarized with ABINIT, as well as to already regular users. First, we give a broad overview of ABINIT, including the list of the capabilities and how to access them. Then, we present in more details the recent, advanced, developments of ABINIT, with adequate references to the underlying theory, as well as the relevant input variables, tests and, if available, ABINIT tutorials. Program summaryProgram title: ABINIT Catalogue identifier: AEEU_v1_0 Distribution format: tar.gz Journal reference: Comput. Phys. Comm. Programming language: Fortran95, PERL scripts, Python scripts Computer: All systems with a Fortran95 compiler Operating system: All systems with a Fortran95 compiler Has the code been vectorized or parallelized?: Sequential, or parallel with proven speed-up up to one thousand processors. RAM: Ranges from a few Mbytes to several hundred Gbytes, depending on the input file. Classification: 7.3, 7.8 External routines: (all optional) BigDFT [1], ETSF IO [2], libxc [3], NetCDF [4], MPI [5], Wannier90 [6] Nature of problem: This package has the purpose of computing accurately material and nanostructure properties: electronic structure, bond lengths, bond angles, primitive cell size, cohesive energy, dielectric properties, vibrational properties, elastic properties, optical properties, magnetic properties, non-linear couplings, electronic and

  7. Electron Exchange and Conduction in Nontronite from First-Principles

    SciTech Connect

    Alexandrov, Vitali Y.; Neumann, Anke; Scherer, Michelle; Rosso, Kevin M.

    2013-01-11

    Fe-bearing clay minerals serve as an important source and sink for electrons in redox reactions in various subsurface geochemical environments, and electron transfer (ET) properties of the Fe2+/Fe3+ redox couple play a decisive role in a variety of physicochemical processes involving clays. Here, we apply first-principles calculations using both periodic GGA+U planewave and Hartree-Fock molecular-cluster frameworks in conjuction with small polaron hopping approach and Marcus electron transfer theory to examine electron exchange mobilities in an Fe-rich smectite, taking nontronite as a case study. GGA+U calculations of the activation barrier for small-polaron migration provide rates of electron hopping that agree very well with values deduced from variable temperature Mössbauer data (M. V. Schaefer, et. al., Environ. Sci. Technol. 45, 540, (2011)), indicating a surprisingly fast electron mobility at room temperature. Based on molecular cluster calculations, we show that the state with tetrahedral Fe2+ ion in the nontronite lattice is about 0.9 eV higher than the one with octahedral Fe2+. Also, evaluation of the ET rates for the Fe2+/Fe3+ electron hopping in tetrahedral (TS) and octahedral sheets (OS), as well as across the sheets (TS–OS) shows that the dominant contribution to the bulk electronic conductivity should come from the ET within the OS. Deprotonation of structural OH groups mediating ET between the Fe ions in the OS is found to decrease the internal reorganization energy and to increase the magnitude of the electronic coupling matrix element, whereas protonation (to OH2 groups) has the opposite effect. Overall, our calculations suggest that the major factors affecting ET rates are the nature and structure of the nearest-neighbor local environment and the degree of covalency of the bonds between Fe and ligands mediating electron hops. The generally higher reorganization energy and weaker electronic coupling found in Fe-bearing clay minerals leads to

  8. First-principles modelling of materials: From polythiophene to phosphorene

    NASA Astrophysics Data System (ADS)

    Ziletti, Angelo

    As a result of the computing power provided by the current technology, computational methods now play an important role in modeling and designing materials at the nanoscale. The focus of this dissertation is two-fold: first, new computational methods to model nanoscale transport are introduced, then state-of-the-art tools based on density functional theory are employed to explore the properties of phosphorene, a novel low dimensional material with great potential for applications in nanotechnology. A Wannier function description of the electron density is combined with a generalized Slater-Koster interpolation technique, enabling the introduction of a new computational method for constructing first-principles model Hamiltonians for electron and hole transport that maintain the density functional theory accuracy at a fraction of the computational cost. As a proof of concept, this new approach is applied to model polythiophene, a polymer ubiquitous in organic photovoltaic devices. A new low dimensional material, phosphorene - a single layer of black phosphorous - the phosphorous analogue of graphene was first isolated in early 2014 and has attracted considerable attention. It is a semiconductor with a sizable band gap, which makes it a perfect candidate for ultrathin transistors. Multi-layer phosphorene transistors have already achieved the highest hole mobility of any two-dimensional material apart from graphene. Phosphorene is prone to oxidation, which can lead to degradation of electrical properties, and eventually structural breakdown. The calculations reported here are some of the first to explore this oxidation and reveal that different types of oxygen defects are readily introduced in the phosphorene lattice, creating electron traps in some situations. These traps are responsible for the non-ambipolar behavior observed by experimental collaborators in air-exposed few-layer black phosphorus devices. Calculation results predict that air exposure of phosphorene

  9. First principles investigation of Fe and Al bearing phase H

    NASA Astrophysics Data System (ADS)

    Tsuchiya, J.; Tsuchiya, T.

    2015-12-01

    exploration of these hydrous phases, such as the spin transition of Fe in phase H and the possibility of further phase transition of this new hydrous mineral using first principles calculation techniques and discuss the possible effects of this hydrous phase at the bottom of lower mantle.

  10. Electrosynthesis and characterization of zinc tungstate nanoparticles

    NASA Astrophysics Data System (ADS)

    Rahimi-Nasrabadi, Mehdi; Pourmortazavi, Seied Mahdi; Ganjali, Mohammad Reza; Hajimirsadeghi, Seiedeh Somayyeh; Zahedi, Mir Mahdi

    2013-09-01

    Zinc tungstate nanoparticles with different sizes are produced through an electrolysis process including a zinc plate anode in sodium tungstate solution. The shape and size of the product was found to be controlled by varying reaction parameters such as electrolysis voltage, stirring rate of electrolyte solution and temperature. The morphological (SEM) characterization analysis was performed on the product and UV-Vis spectrophotometry and FT-IR spectroscopy was utilized to characterize the electrodeposited nanoparticles. Study of the particle size of the product versus the electrolysis voltage showed that, increasing the voltage from 4 to 8 V, led to the particle size of zinc tungstate to decrease, but further increasing the voltage from 8 to 12 V, the particle size of the produced particles increased. The size and shape of the product was also found to be dependent on the stirring rate and temperature of the electrolyte solution. X-ray diffraction (XRD), scanning electron microscopy (SEM), FT-IR spectroscopy, and photoluminescence, were used to study the structure as well as composition of the nano-material prepared under optimum conditions.

  11. Modeling of compositionally graded barium strontium titanate from first principles

    NASA Astrophysics Data System (ADS)

    Walizer, Laura Elizabeth

    Barium Strontium Titanate (BaxSr1-xTiO 3 or BST) is a Perovskite alloy of interest for both technological and intellectual reasons. Its ferroelectric and piezoelectric properties make it useful in a variety of electric components such as transducers and actuators, and BST in particular is a material of interest for the development of a ferroelectric RAM for computers.(1) The inclusion of SrTiO3, an incipient ferroelectric, and the fact that the properties of a BST system depend strongly on its relative composition of BaTiO3 (BT) and SrTiO3 (ST), make also this a material of high interest. (2) Compositionally graded systems are of further interest (see e.g., Refs. (3), (4), (5) and references therein), partly because their compositional grading leads to a built-in polarization gradient. Due to this, these systems could act as transcapacitors, devices which act as charge amplifiers in much the same way that transistors act as current amplifiers.(3), (4) Here, compositionally graded BST systems were modeled using a first-principles derived effective Hamiltonian method within Monte-Carlo simulation. (6) The graded systems under consideration had an average Ba composition of 70%. These systems were modeled under stress-free conditions, as well as, under epitaxial strain due to a SrTiO3 substrate. Both the degree of grading and the thickness of the layers were varied. The investigation revealed that graded BST systems behaved differently from bulk BST systems in several ways. First, some graded BST systems possessed both monodomain states qualitatively similar to those found in bulk systems (except that the polarization exhibited a "wave" behavior inside the graded systems), and also states with domain striping. Where this occurred, the monodomain state was lower in energy, and was therefore the ground-state, but the striped domain state was found to be metastable, representing a local energy minimum. Analyzing unstrained compositionally graded systems layer by layer

  12. Application of First Principles Ni-Cd and Ni-H2 Battery Models to Spacecraft Operations

    NASA Technical Reports Server (NTRS)

    Timmerman, Paul; Bugga, Ratnakumar; DiStefano, Salvador

    1997-01-01

    The conclusions of the application of first principles model to spacecraft operations are: the first principles of Bi-phasic electrode presented model provides an explanation for many behaviors on voltage fading on LEO cycling.

  13. Coarse Grained Approach to First Principles Modeling of Radiation Cascade in Large Fe Supercells

    NASA Astrophysics Data System (ADS)

    Odbadrakh, Kh; Nicholson, D. M.; Rusanu, A.; Samolyuk, G. D.; Stoller, R. E.; Zhang, X.-G.; Stocks, G. M.

    2012-12-01

    Classical Molecular Dynamics (MD) simulations characterizing dislocations and radiation damage typically treat 105-107 atoms. First principles techniques employed to understand systems at an atomistic level are not practical for such large systems consisting of millions of atoms. We present an efficient coarse grained (CG) approach to calculate local electronic and magnetic properties of large MD-generated structures from the first principles. Local atomic magnetic moments in crystalline Fe are perturbed by the presence of radiation generated vacancies and interstitials. The effects are most pronounced near the defect cores and decay slowly as the strain field of the defects decrease with distance. We develop the CG technique based on the Locally Self-consistent Multiple Scattering (LSMS) method that exploits the near-sightedness of the electron Green function. The atomic positions were determined by MD with an embedded atom force field. The local moments in the neighborhood of the defect cores are calculated with first-principles based on full local structure information. Atoms in the rest of the system are modeled by representative atoms with approximated properties. The calculations result in local moments near the defect centers with first-principles accuracy, while capturing coarse-grained details of local moments at greater length scales. This CG approach makes these large scale structures amenable to first principles study.

  14. 40 CFR 721.9840 - Tungstate (W12(OH)2O386-) hexasodium (9CI).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Tungstate (W12(OH)2O386-) hexasodium... Specific Chemical Substances § 721.9840 Tungstate (W12(OH)2O386-) hexasodium (9CI). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as tungstate...

  15. 40 CFR 721.9840 - Tungstate (W12(OH)2O386-) hexasodium (9CI).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Tungstate (W12(OH)2O386-) hexasodium... Specific Chemical Substances § 721.9840 Tungstate (W12(OH)2O386-) hexasodium (9CI). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as tungstate...

  16. Tuning the architecture and properties of microstructured yttrium tungstate oxide hydroxide and lanthanum tungstate.

    PubMed

    Kaczmarek, Anna M; Liu, Ying-Ya; Van der Voort, Pascal; Van Deun, Rik

    2013-04-21

    In this paper, various microstructures of yttrium and lanthanum tungstates were synthesized under hydrothermal conditions, at pH 5, in a ligand-free environment, and in the presence of a dioctyl sodium sulfosuccinate (DSS) surfactant. It was observed that the shape of the nanobuilding blocks, and therefore the architecture of the microstructures, could be tuned by controlling the reaction conditions, such as the source of the rare earth, the amount of a surfactant and the reaction time. X-ray powder diffraction (XRD), elemental analysis, scanning electron microscopy (SEM), and N2 adsorption were employed to characterize the obtained products. The photoluminescent properties of Eu(3+) and Dy(3+) doped tungstate materials were investigated. Luminescence measurements showed an efficient charge transfer from the WO4(2-) groups to Eu(3+) and Dy(3+) ions. It was found that under UV excitation the Dy(3+) doped Y(WO3)2(OH)3 and La2(WO4)3 precursors exhibit white emission. PMID:23426044

  17. Research on regularized mean-variance portfolio selection strategy with modified Roy safety-first principle.

    PubMed

    Atta Mills, Ebenezer Fiifi Emire; Yan, Dawen; Yu, Bo; Wei, Xinyuan

    2016-01-01

    We propose a consolidated risk measure based on variance and the safety-first principle in a mean-risk portfolio optimization framework. The safety-first principle to financial portfolio selection strategy is modified and improved. Our proposed models are subjected to norm regularization to seek near-optimal stable and sparse portfolios. We compare the cumulative wealth of our preferred proposed model to a benchmark, S&P 500 index for the same period. Our proposed portfolio strategies have better out-of-sample performance than the selected alternative portfolio rules in literature and control the downside risk of the portfolio returns. PMID:27386363

  18. Data set for diffusion coefficients of alloying elements in dilute Mg alloys from first-principles

    PubMed Central

    Zhou, Bi-Cheng; Shang, Shun-Li; Wang, Yi; Liu, Zi-Kui

    2015-01-01

    Diffusion coefficients of alloying elements in Mg are critical for the development of new Mg alloys for lightweight applications. Here we present the data set of the temperature-dependent dilute tracer diffusion coefficients for 47 substitutional alloying elements in hexagonal closed packed (hcp) Mg calculated from first-principles calculations based on density functional theory (DFT) by combining transition state theory and an 8-frequency model. Benchmark for the DFT calculations and systematic comparison with experimental diffusion data are also presented. The data set refers to “Diffusion coefficients of alloying elements in dilute Mg alloys: A comprehensive first-principles study” by Zhou et al. [1]. PMID:26702419

  19. First Principles Calculations for X-ray Resonant Spectra and Elastic Properties

    SciTech Connect

    Yongbin Lee

    2006-05-01

    In this thesis, we discuss applications of first principles methods to x-ray resonant spectra and elastic properties calculation. We start with brief reviews about theoretical background of first principles methods, such as density functional theory, local density approximation (LDA), LDA+U, and the linear augmented plane wave (LAPW) method to solve Kohn-Sham equations. After that we discuss x-ray resonant scattering (XRMS), x-ray magnetic circular dichroism (XMCD) and the branching problem in the heavy rare earths Ledges. In the last chapter we discuss the elastic properties of the second hardest material AlMgB{sub 14}.

  20. Integration of first-principles methods and crystallographic database searches for new ferroelectrics: Strategies and explorations

    SciTech Connect

    Bennett, Joseph W.; Rabe, Karin M.

    2012-11-15

    In this concept paper, the development of strategies for the integration of first-principles methods with crystallographic database mining for the discovery and design of novel ferroelectric materials is discussed, drawing on the results and experience derived from exploratory investigations on three different systems: (1) the double perovskite Sr(Sb{sub 1/2}Mn{sub 1/2})O{sub 3} as a candidate semiconducting ferroelectric; (2) polar derivatives of schafarzikite MSb{sub 2}O{sub 4}; and (3) ferroelectric semiconductors with formula M{sub 2}P{sub 2}(S,Se){sub 6}. A variety of avenues for further research and investigation are suggested, including automated structure type classification, low-symmetry improper ferroelectrics, and high-throughput first-principles searches for additional representatives of structural families with desirable functional properties. - Graphical abstract: Integration of first-principles methods with crystallographic database mining, for the discovery and design of novel ferroelectric materials, could potentially lead to new classes of multifunctional materials. Highlights: Black-Right-Pointing-Pointer Integration of first-principles methods and database mining. Black-Right-Pointing-Pointer Minor structural families with desirable functional properties. Black-Right-Pointing-Pointer Survey of polar entries in the Inorganic Crystal Structural Database.

  1. First principles study of structural, electronic and magnetic properties of magnesium

    NASA Astrophysics Data System (ADS)

    Abdel Rahim, G. P.; Rodríguez M, J. A.; Moreno-Armenta, M. G.

    2016-02-01

    We investigated the structural, electronic, and magnetic properties of Mg, in the CS (simple cubic), NiAs (Nickel arsenide), FCC (rock-salt), R (Rhombohedral), Diamond and WZ (wurtzite) phases. Calculations were performed using the first-principles pseudo-potential method within the framework of spin-density functional theory (DFT).

  2. In situ growth of epitaxial cerium tungstate (100) thin films.

    PubMed

    Skála, Tomáš; Tsud, Nataliya; Orti, Miguel Ángel Niño; Menteş, Tevfik Onur; Locatelli, Andrea; Prince, Kevin Charles; Matolín, Vladimír

    2011-04-21

    The deposition of ceria on a preoxidized W(110) crystal at 870 K has been studied in situ by photoelectron spectroscopy and low-energy electron diffraction. Formation of an epitaxial layer of crystalline cerium tungstate Ce(6)WO(12)(100), with the metals in the Ce(3+) and W(6+) chemical states, has been observed. The interface between the tungsten substrate and the tungstate film consists of WO suboxide. At thicknesses above 0.89 nm, cerium dioxide grows on the surface of Ce(6)WO(12), favoured by the limited diffusion of tungsten from the substrate. PMID:21399780

  3. Synthesis of potassium tungstate micro-walls by thermal evaporation

    NASA Astrophysics Data System (ADS)

    Hong, Kunquan; Xie, Maohai; Hu, Rong; Wu, Huasheng

    2006-09-01

    We report the synthesis of potassium tungstate (K 2W 3O 10) micro-walls by a simple method of thermal evaporation. Using tungsten powder, tungsten oxide powder and potassium iodide as the source materials and tungsten plate as the substrate, K 2W 3O 10 micro-walls with thicknesses ranging from 400 nm to 2 μm, lengths up to hundreds of micrometers and heights up to tens of micrometers are obtained on a large scale. The possible mechanism for the formation of these tungstate micro-walls is discussed.

  4. Equation of state for technetium from X-ray diffraction and first-principle calculations

    NASA Astrophysics Data System (ADS)

    Mast, Daniel S.; Kim, Eunja; Siska, Emily M.; Poineau, Frederic; Czerwinski, Kenneth R.; Lavina, Barbara; Forster, Paul M.

    2016-08-01

    The ambient temperature equation of state (EoS) of technetium metal has been measured by X-ray diffraction. The metal was compressed using a diamond anvil cell and using a 4:1 methanol-ethanol pressure transmitting medium. The maximum pressure achieved, as determined from the gold pressureEquation of state for technetium from X-ray diffraction and first-principle calculations scale, was 67 GPa. The compression data shows that the HCP phase of technetium is stable up to 67 GPa. The compression curve of technetium was also calculated using first-principles total-energy calculations. Utilizing a number of fitting strategies to compare the experimental and theoretical data it is determined that the Vinet equation of state with an ambient isothermal bulk modulus of B0T=288 GPa and a first pressure derivative of B‧=5.9(2) best represent the compression behavior of technetium metal.

  5. First-Principles Studies of the Excited States of Chromophore Monomers and Dimers

    NASA Astrophysics Data System (ADS)

    Hamed, Samia; Sharifzadeh, Sahar; Neaton, Jeffrey

    2015-03-01

    Elucidation of the energy transfer mechanism in natural photosynthetic systems remains an exciting challenge. Through the careful analysis of excited states on individual chromophores and dimers - and the predictive first-principles methods used to compute them - we are building towards an understanding of the nature of excitation transfer among arrays of chromophores embedded in protein environments. Excitation energies, transition dipoles, and natural transition orbitals for the important low-lying singlet and triplet states of experimentally-relevant chromophores are obtained from first-principles time-dependent density functional theory (TDDFT) and many body perturbation theory. The effect of the Tamm-Dancoff approximation and the performance of several exchange-correlation functionals, including an optimally-tuned range-separated hybrid, are evaluated with TDDFT, and compared to MBPT calculations and experiments. This work has been supported by the DOE; computational resources have been provided by NERSC.

  6. Lack of support for adaptive superstructure NiPt7 : Experiment and first-principles calculations

    NASA Astrophysics Data System (ADS)

    Schönfeld, B.; Engelke, M.; Ruban, A. V.

    2009-02-01

    Order and effective interaction parameters on the Pt-rich side of solid Ni-Pt alloys have been investigated by experimental and first-principles theoretical techniques. Diffuse x-ray scattering was taken from single-crystalline Ni-87.8at.%Pt aged at 603 K to set up a state of thermal equilibrium. From the separated short-range order scattering, effective pair interaction parameters were determined. These experimentally deduced values do not produce the suggested NiPt7 superstructure at lower temperatures. Instead of that, phase separation into NiPt3 regions with L12 structure and a Pt-rich matrix is observed in Monte Carlo simulations and supported by x-ray scattering of Ni-75.2at.%Pt . First-principles calculations at 0 K also show that the suggested NiPt7 phase is unstable against decomposition into NiPt3 and Pt.

  7. Redox condition in molten salts and solute behavior: A first-principles molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Nam, Hyo On; Morgan, Dane

    2015-10-01

    Molten salts technology is of significant interest for nuclear, solar, and other energy systems. In this work, first-principles molecular dynamics (FPMD) was used to model the solute behavior in eutectic LiCl-KCl and FLiBe (Li2BeF4) melts at 773 K and 973 K, respectively. The thermo-kinetic properties for solute systems such as the redox potential, solute diffusion coefficients and structural information surrounding the solute were predicted from FPMD modeling and the calculated properties are generally in agreement with the experiments. In particular, we formulate an approach to model redox energetics vs. chlorine (or fluorine) potential from first-principles approaches. This study develops approaches for, and demonstrates the capabilities of, FPMD to model solute properties in molten salts.

  8. Large-Scale First-Principles Molecular Dynamics Simulations with Electrostatic Embedding: Application to Acetylcholinesterase Catalysis

    DOE PAGESBeta

    Fattebert, Jean-Luc; Lau, Edmond Y.; Bennion, Brian J.; Huang, Patrick; Lightstone, Felice C.

    2015-10-22

    Enzymes are complicated solvated systems that typically require many atoms to simulate their function with any degree of accuracy. We have recently developed numerical techniques for large scale First-Principles molecular dynamics simulations and applied them to study the enzymatic reaction catalyzed by acetylcholinesterase. We carried out Density functional theory calculations for a quantum mechanical (QM) sub- system consisting of 612 atoms with an O(N) complexity finite-difference approach. The QM sub-system is embedded inside an external potential field representing the electrostatic effect due to the environment. We obtained finite temperature sampling by First-Principles molecular dynamics for the acylation reaction of acetylcholinemore » catalyzed by acetylcholinesterase. Our calculations shows two energies barriers along the reaction coordinate for the enzyme catalyzed acylation of acetylcholine. In conclusion, the second barrier (8.5 kcal/mole) is rate-limiting for the acylation reaction and in good agreement with experiment.« less

  9. Structure of the (111) surface of bismuth: LEED analysis and first-principles calculations

    SciTech Connect

    Moenig, H.; Wells, J.; Hofmann, Ph.; Sun, J.; Pohl, K.; Koroteev, Yu.M.; Bihlmayer, G.; Chulkov, E.V.

    2005-08-15

    The surface structure of Bi(111) was investigated by low-energy electron diffraction (LEED) intensity analysis for temperatures between 140 and 313 K and by first-principles calculations. The diffraction pattern reveals a (1x1) surface structure and LEED intensity versus energy simulations confirm that the crystal is terminated with a Bi bilayer. Excellent agreement is obtained between the calculated and measured diffraction intensities in the whole temperature range. The first interlayer spacing shows no significant relaxation at any temperature while the second interlayer spacing expands slightly. The Debye temperatures deduced from the optimized atomic vibrational amplitudes for the two topmost layers are found to be significantly lower than in the bulk. The experimental results for the relaxations agree well with those of our first-principles calculation.

  10. First principles study of the Young's modulus of Si <001> nanowires

    SciTech Connect

    Lee, B; Rudd, R E

    2006-07-03

    We report the results of first-principles calculations of the Young's modulus and other mechanical properties of hydrogen-passivated Si <001> nanowires. The nanowires are taken to have predominantly {l_brace}100{r_brace} surfaces, with small {l_brace}110{r_brace} facets according to the Wulff shape. The Young's modulus, the equilibrium length and the constrained residual stress of a series of prismatic beams of differing sizes is found to have a size dependence that scales like the surface area to volume ratio for all but the smallest beam. The results are compared with two different models (and the results of classical atomistic calculations based on an empirical potential). We discuss the physics of the hydrogen interactions on the surface and the charge density variations within the beam that may account for the discrepancies of the models and the first principles results.

  11. Intrinsic buckling strength of graphene: First-principles density functional theory calculations

    NASA Astrophysics Data System (ADS)

    Kumar, Sandeep; Hembram, K. P. S. S.; Waghmare, Umesh V.

    2010-09-01

    How graphene, an atomically thin two-dimensional crystal, explores the third spatial dimension by buckling under compression is not yet understood. Knowledge of graphene’s buckling strength, the load at which it transforms from planar to buckled form, is a key to ensure mechanical stability of graphene-based nanoelectronic and nanocomposite devices. Here, we establish using first-principles theoretical analysis that graphene has an intrinsic rigidity against buckling, and it manifests in a weakly linear component in the dispersion of graphene’s flexural acoustic mode, which is believed to be quadratic. Contrary to the expectation from the elastic plate theory, we predict within continuum analysis that a graphene monolayer of macroscopic size buckles at a nonzero critical compressive strain at T=0K , and demonstrate it numerically from first principles. The origin of this rigidity is traced to the coupling between structural and electronic degrees of freedom arising from curvature-induced overlap between π orbitals in graphene.

  12. Magnetically induced phonon splitting in A Cr2O4 spinels from first principles

    NASA Astrophysics Data System (ADS)

    Wysocki, Aleksander L.; Birol, Turan

    2016-04-01

    We study the magnetically-induced phonon splitting in cubic A Cr2O4 (A =Mg , Zn, Cd) spinels from first principles and demonstrate that the sign of the splitting, which is experimentally observed to be opposite in CdCr2O4 compared to ZnCr2O4 and MgCr2O4 , is determined solely by the particular magnetic ordering pattern observed in these compounds. We further show that this interaction between magnetism and phonon frequencies can be fully described by the previously proposed spin-phonon coupling model [C. J. Fennie and K. M. Rabe, Phys. Rev. Lett. 96, 205505 (2006)], 10.1103/PhysRevLett.96.205505 that includes only the nearest neighbor exchange. Using this model with materials specific parameters calculated from first principles, we provide additional insights into the physics of spin-phonon coupling in this intriguing family of compounds.

  13. Conformational structures of a decapeptide validated by first principles calculations and cold ion spectroscopy.

    PubMed

    Roy, Tapta Kanchan; Kopysov, Vladimir; Nagornova, Natalia S; Rizzo, Thomas R; Boyarkin, Oleg V; Gerber, R Benny

    2015-05-18

    Calculated structures of the two most stable conformers of a protonated decapeptide gramicidin S in the gas phase have been validated by comparing the vibrational spectra, calculated from first- principles and measured in a wide spectral range using infrared (IR)-UV double resonance cold ion spectroscopy. All the 522 vibrational modes of each conformer were calculated quantum mechanically and compared with the experiment without any recourse to an empirical scaling. The study demonstrates that first-principles calculations, when accounting for vibrational anharmonicity, can reproduce high-resolution experimental spectra well enough for validating structures of molecules as large as of 200 atoms. The validated accurate structures of the peptide may serve as templates for in silico drug design and absolute calibration of ion mobility measurements. PMID:25721337

  14. First-Principles Atomic Force Microscopy Image Simulations with Density Embedding Theory.

    PubMed

    Sakai, Yuki; Lee, Alex J; Chelikowsky, James R

    2016-05-11

    We present an efficient first-principles method for simulating noncontact atomic force microscopy (nc-AFM) images using a "frozen density" embedding theory. Frozen density embedding theory enables one to efficiently compute the tip-sample interaction by considering a sample as a frozen external field. This method reduces the extensive computational load of first-principles AFM simulations by avoiding consideration of the entire tip-sample system and focusing on the tip alone. We demonstrate that our simulation with frozen density embedding theory accurately reproduces full density functional theory simulations of freestanding hydrocarbon molecules while the computational time is significantly reduced. Our method also captures the electronic effect of a Cu(111) substrate on the AFM image of pentacene and reproduces the experimental AFM image of Cu2N on a Cu(100) surface. This approach is applicable for theoretical imaging applications on large molecules, two-dimensional materials, and materials surfaces. PMID:27050710

  15. First-principles study of extensive dopants in wurtzite ZnO

    NASA Astrophysics Data System (ADS)

    Huang, Gui-Yang; Wang, Chong-Yu; Wang, Jian-Tao

    2010-01-01

    Based on comprehensive calculations of the transition energy levels for extensive dopant substitutional (H, Li, Na, K, Ag, B, Al, Ga, In, N, P, As, Sb, Bi, F, Cl, Br, I), we illustrate and check the validity of the first-principle calculations based on GGA and GGA+ U correction method. The results indicate that there still exist large limits for quantitative correct results of first-principle calculations. Nevertheless, some qualitative useful information can be obtained by such calculations. Based on our calculation results, LiZn, NaZn, KZn, NZn and AgZn have the shallowest transition energy level (0/1-) for p-type doping, from shallow to deep.

  16. Elastic and thermodynamic properties of Fe3Ga from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Lin, Ya-Ning; Li, Lin-Ling; Yan, Xiang-Hong; Zhang, Ya-Ping; Zhang, Dong-yun; Zhang, Peng

    2016-03-01

    First-principles calculations within the framework of density functional theory (DFT) are performed to investigate the elastic and thermodynamic properties of DO3-type Fe3Ga alloy. The obtained lattice constants and the bulk modulus are in good agreement with available experimental data. In terms of the calculated formation energy and Poisson's ratio, the Fe3Ga alloy is mechanically stable and exhibit a negative Poisson's ratio of -0.81 along the <110> direction. The thermodynamic properties such as the Gibbs free energy, thermal expansion, and the specific heat are obtained by the first-principles phonon calculations with the quasiharmonic approximation method. The predicted coefficient of linear thermal expansion and specific heat may provide a helpful reference for experimental work.

  17. Lattice Anharmonicity and Thermal Conductivity from Compressive Sensing of First-Principles Calculations

    SciTech Connect

    Zhou, Fei; Nielson, Weston; Xia, Yi; Ozolins, Vidvuds

    2014-10-27

    First-principles prediction of lattice thermal conductivity KL of strongly anharmonic crystals is a long-standing challenge in solid state physics. Using recent advances in information science, we propose a systematic and rigorous approach to this problem, compressive sensing lattice dynamics (CSLD). Compressive sensing is used to select the physically important terms in the lattice dynamics model and determine their values in one shot. Non-intuitively, high accuracy is achieved when the model is trained on first-principles forces in quasi-random atomic configurations. The method is demonstrated for Si, NaCl, and Cu12Sb4S13, an earth-abundant thermoelectric with strong phononphonon interactions that limit the room-temperature KL to values near the amorphous limit.

  18. Lattice Anharmonicity and Thermal Conductivity from Compressive Sensing of First-Principles Calculations

    SciTech Connect

    Zhou, Fei; Nielson, Weston; Xia, Yi; Ozoliņš, Vidvuds

    2014-10-01

    First-principles prediction of lattice thermal conductivity κL of strongly anharmonic crystals is a long-standing challenge in solid-state physics. Making use of recent advances in information science, we propose a systematic and rigorous approach to this problem, compressive sensing lattice dynamics. Compressive sensing is used to select the physically important terms in the lattice dynamics model and determine their values in one shot. Nonintuitively, high accuracy is achieved when the model is trained on first-principles forces in quasirandom atomic configurations. The method is demonstrated for Si, NaCl, and Cu12Sb4S13, an earth-abundant thermoelectric with strong phonon-phonon interactions that limit the room-temperature κL to values near the amorphous limit.

  19. New Optical Evaluation Approach for Parabolic Trough Collectors: First-Principle OPTical Intercept Calculation

    SciTech Connect

    Zhu, G.; Lewandowski, A.

    2012-11-01

    A new analytical method -- First-principle OPTical Intercept Calculation (FirstOPTIC) -- is presented here for optical evaluation of trough collectors. It employs first-principle optical treatment of collector optical error sources and derives analytical mathematical formulae to calculate the intercept factor of a trough collector. A suite of MATLAB code is developed for FirstOPTIC and validated against theoretical/numerical solutions and ray-tracing results. It is shown that FirstOPTIC can provide fast and accurate calculation of intercept factors of trough collectors. The method makes it possible to carry out fast evaluation of trough collectors for design purposes. The FirstOPTIC techniques and analysis may be naturally extended to other types of CSP technologies such as linear-Fresnel collectors and central-receiver towers.

  20. First-principles analysis of anharmonic nuclear motion and thermal transport in thermoelectric materials

    NASA Astrophysics Data System (ADS)

    Tadano, Terumasa; Tsuneyuki, Shinji

    2015-12-01

    We show a first-principles approach for analyzing anharmonic properties of lattice vibrations in solids. We firstly extract harmonic and anharmonic force constants from accurate first-principles calculations based on the density functional theory. Using the many-body perturbation theory of phonons, we then estimate the phonon scattering probability due to anharmonic phonon-phonon interactions. We show the validity of the approach by computing the lattice thermal conductivity of Si, a typical covalent semiconductor, and selected thermoelectric materials PbTe and Bi2Te3 based on the Boltzmann transport equation. We also show that the phonon lifetime and the lattice thermal conductivity of the high-temperature phase of SrTiO3 can be estimated by employing the perturbation theory on top of the solution of the self-consistent phonon equation.

  1. Lattice Anharmonicity and Thermal Conductivity from Compressive Sensing of First-Principles Calculations

    DOE PAGESBeta

    Zhou, Fei; Nielson, Weston; Xia, Yi; Ozolins, Vidvuds

    2014-10-27

    First-principles prediction of lattice thermal conductivity KL of strongly anharmonic crystals is a long-standing challenge in solid state physics. Using recent advances in information science, we propose a systematic and rigorous approach to this problem, compressive sensing lattice dynamics (CSLD). Compressive sensing is used to select the physically important terms in the lattice dynamics model and determine their values in one shot. Non-intuitively, high accuracy is achieved when the model is trained on first-principles forces in quasi-random atomic configurations. The method is demonstrated for Si, NaCl, and Cu12Sb4S13, an earth-abundant thermoelectric with strong phononphonon interactions that limit the room-temperature KLmore » to values near the amorphous limit.« less

  2. First-principles analysis of anharmonic nuclear motion and thermal transport in thermoelectric materials

    SciTech Connect

    Tadano, Terumasa; Tsuneyuki, Shinji

    2015-12-31

    We show a first-principles approach for analyzing anharmonic properties of lattice vibrations in solids. We firstly extract harmonic and anharmonic force constants from accurate first-principles calculations based on the density functional theory. Using the many-body perturbation theory of phonons, we then estimate the phonon scattering probability due to anharmonic phonon-phonon interactions. We show the validity of the approach by computing the lattice thermal conductivity of Si, a typical covalent semiconductor, and selected thermoelectric materials PbTe and Bi{sub 2}Te{sub 3} based on the Boltzmann transport equation. We also show that the phonon lifetime and the lattice thermal conductivity of the high-temperature phase of SrTiO{sub 3} can be estimated by employing the perturbation theory on top of the solution of the self-consistent phonon equation.

  3. Dispersion correction derived from first principles for density functional theory and Hartree-Fock theory.

    PubMed

    Guidez, Emilie B; Gordon, Mark S

    2015-03-12

    The modeling of dispersion interactions in density functional theory (DFT) is commonly performed using an energy correction that involves empirically fitted parameters for all atom pairs of the system investigated. In this study, the first-principles-derived dispersion energy from the effective fragment potential (EFP) method is implemented for the density functional theory (DFT-D(EFP)) and Hartree-Fock (HF-D(EFP)) energies. Overall, DFT-D(EFP) performs similarly to the semiempirical DFT-D corrections for the test cases investigated in this work. HF-D(EFP) tends to underestimate binding energies and overestimate intermolecular equilibrium distances, relative to coupled cluster theory, most likely due to incomplete accounting for electron correlation. Overall, this first-principles dispersion correction yields results that are in good agreement with coupled-cluster calculations at a low computational cost. PMID:25651435

  4. Large-Scale First-Principles Molecular Dynamics Simulations with Electrostatic Embedding: Application to Acetylcholinesterase Catalysis

    SciTech Connect

    Fattebert, Jean-Luc; Lau, Edmond Y.; Bennion, Brian J.; Huang, Patrick; Lightstone, Felice C.

    2015-10-22

    Enzymes are complicated solvated systems that typically require many atoms to simulate their function with any degree of accuracy. We have recently developed numerical techniques for large scale First-Principles molecular dynamics simulations and applied them to study the enzymatic reaction catalyzed by acetylcholinesterase. We carried out Density functional theory calculations for a quantum mechanical (QM) sub- system consisting of 612 atoms with an O(N) complexity finite-difference approach. The QM sub-system is embedded inside an external potential field representing the electrostatic effect due to the environment. We obtained finite temperature sampling by First-Principles molecular dynamics for the acylation reaction of acetylcholine catalyzed by acetylcholinesterase. Our calculations shows two energies barriers along the reaction coordinate for the enzyme catalyzed acylation of acetylcholine. In conclusion, the second barrier (8.5 kcal/mole) is rate-limiting for the acylation reaction and in good agreement with experiment.

  5. First-principle optimal local pseudopotentials construction via optimized effective potential method

    NASA Astrophysics Data System (ADS)

    Mi, Wenhui; Zhang, Shoutao; Wang, Yanchao; Ma, Yanming; Miao, Maosheng

    2016-04-01

    The local pseudopotential (LPP) is an important component of orbital-free density functional theory, a promising large-scale simulation method that can maintain information on a material's electron state. The LPP is usually extracted from solid-state density functional theory calculations, thereby it is difficult to assess its transferability to cases involving very different chemical environments. Here, we reveal a fundamental relation between the first-principles norm-conserving pseudopotential (NCPP) and the LPP. On the basis of this relationship, we demonstrate that the LPP can be constructed optimally from the NCPP for a large number of elements using the optimized effective potential method. Specially, our method provides a unified scheme for constructing and assessing the LPP within the framework of first-principles pseudopotentials. Our practice reveals that the existence of a valid LPP with high transferability may strongly depend on the element.

  6. Grain growth in U-7Mo alloy: A combined first-principles and phase field study

    NASA Astrophysics Data System (ADS)

    Mei, Zhi-Gang; Liang, Linyun; Kim, Yeon Soo; Wiencek, Tom; O'Hare, Edward; Yacout, Abdellatif M.; Hofman, Gerard; Anitescu, Mihai

    2016-05-01

    Grain size is an important factor in controlling the swelling behavior in irradiated U-Mo dispersion fuels. Increasing the grain size in U-Mo fuel particles by heat treatment is believed to delay the fuel swelling at high fission density. In this work, a multiscale simulation approach combining first-principles calculation and phase field modeling is used to investigate the grain growth behavior in U-7Mo alloy. The density functional theory based first-principles calculations were used to predict the material properties of U-7Mo alloy. The obtained grain boundary energies were then adopted as an input parameter for mesoscale phase field simulations. The effects of annealing temperature, annealing time and initial grain structures of fuel particles on the grain growth in U-7Mo alloy were examined. The predicted grain growth rate compares well with the empirical correlation derived from experiments.

  7. Harmonic phonon theory for calculating thermal conductivity spectrum from first-principles dispersion relations

    NASA Astrophysics Data System (ADS)

    Shiga, Takuma; Aketo, Daisuke; Feng, Lei; Shiomi, Junichiro

    2016-05-01

    In recent years, nanostructuring of dielectric and semiconducting crystals has enhanced controllability of their thermal conductivity. To carry out computational materials search for nanostructured materials with desirable thermal conductivity, a key property is the thermal conductivity spectrum of the original single crystal, which determines the appropriate length scale of nanostructures and mutual adaptability of different kinds of nanostructures. Although the first-principles phonon transport calculations have become accessible, the anharmonic lattice dynamics calculations are still expensive to scan many materials. To this end, we have developed an empirical model that describes the thermal conductivity spectrum in terms only of harmonic phonon properties and bulk thermal conductivity. The model was tested for several crystals with different structures and thermal conductivities, and was confirmed to reproduce the overall profiles of thermal conductivity spectra and their accumulation functions obtained by the first-principles anharmonic calculations.

  8. Spin-state transition induced half metallicity in a cobaltate from first principles

    NASA Astrophysics Data System (ADS)

    Ou, Xuedong; Fan, Fengren; Li, Zhengwei; Wang, Hongbo; Wu, Hua

    2016-02-01

    Half metal is a promising spintronic material. Here, we explore, using first principles calculations, a spin-state transition induced half metallicity in a layered cobaltate via a physical or chemical pressure. Our exemplary first principles study shows that the layered cobaltate Sr2CoO3F would undergo a transition, under a pressure of 5.4 GPa, from a high-spin antiferromagnetic insulator to an intermediate-spin ferromagnetic half-metal. The former phase is associated with a superexchange in a Mott insulator, and the latter one is due to a broad band formation and a kinetic energy gain of the partially occupied eg orbital. Note that the above transition could also be induced by a chemical pressure via doping in (Sr1-xCax)2CoO3F (x > 0.3). This work suggests that a cobaltate would be of a particular interest if stabilized into an intermediate-spin state.

  9. First-Principles Momentum-Dependent Local Ansatz Wavefunction and Momentum Distribution Function Bands of Iron

    NASA Astrophysics Data System (ADS)

    Kakehashi, Yoshiro; Chandra, Sumal

    2016-04-01

    We have developed a first-principles local ansatz wavefunction approach with momentum-dependent variational parameters on the basis of the tight-binding LDA+U Hamiltonian. The theory goes beyond the first-principles Gutzwiller approach and quantitatively describes correlated electron systems. Using the theory, we find that the momentum distribution function (MDF) bands of paramagnetic bcc Fe along high-symmetry lines show a large deviation from the Fermi-Dirac function for the d electrons with eg symmetry and yield the momentum-dependent mass enhancement factors. The calculated average mass enhancement m*/m = 1.65 is consistent with low-temperature specific heat data as well as recent angle-resolved photoemission spectroscopy (ARPES) data.

  10. Ballistic phonon thermal conductance in graphene nano-ribbon: First-principles calculations

    SciTech Connect

    Nakamura, Jun; Tomita, Hiroki

    2013-12-04

    Ballistic phonon thermal conductances for graphene nanoribbons are investigated using first-principles calculations with the density functional perturbation theory and the Landauer theory. The phonon thermal conductance per unit width for GNR is larger than that for graphene and increases with decreasing ribbon width. The normalized thermal conductances with regard to a thermal quantum for GNRs are higher than those for the single-walled carbon nanotube that have circumferential lengths corresponding to the width of GNR.

  11. Dissociative chemisorption of methylsilane and methylchloride on the Si(1 0 0) surface from first principles

    NASA Astrophysics Data System (ADS)

    Silvestrelli, Pier Luigi; Sbraccia, Carlo; Romero, Aldo H.; Ancilotto, Francesco

    2003-06-01

    The chemisorption process of methylsilane and methylchloride on the Si(1 0 0) surface is studied from first principles. Both the molecules are found to chemisorb dissociatively. The most stable adsorption structures are described. Moreover, the detailed adsorption processes are investigated by considering different possible reaction paths and evaluating the corresponding energy barriers that the molecules must overcome to dissociatively chemisorb on Si(1 0 0). Our results are compared with recent experimental observations.

  12. Stiffness of Diphenylalanine-Based Molecular Solids from First Principles Calculations

    NASA Astrophysics Data System (ADS)

    Azuri, Ido; Hod, Oded; Gazit, Ehud; Kronik, Leeor

    2013-03-01

    Diphenylalanine-based peptide nanotubes were found to be unexpectedly stiff, with a Young modulus of 19 GPa. Here, we calculate the Young modulus from first principles, using density functional theory with dispersive corrections. This allows us to show that at least half of the stiffness of the material comes from dispersive interactions and to identify the nature of the interactions that contribute most to the stiffness. This presents a general strategy for the analysis of bioinspired functional materials.

  13. First-principles Study of Electronic and Dielectric Properties of Polyoxymethylene

    NASA Astrophysics Data System (ADS)

    Sreepad, H. R.; Hembram, K. P. S. S.; Waghmare, Umesh V.

    2011-07-01

    The structure of orthorhombic Polyoxymethylene has been simulated using first-principles. Its structural parameters have been studied. Calculation of Electronic Density of States in the material shows that the material is an insulator with a band gap of 3.51 eV. Phonon frequencies and dielectric constant have been computed. Effect of change in volume of unit cell on the value of dielectric constant has been studied.

  14. First principles predictions of intrinsic defects in aluminum arsenide, AlAs : numerical supplement.

    SciTech Connect

    Schultz, Peter Andrew

    2012-04-01

    This Report presents numerical tables summarizing properties of intrinsic defects in aluminum arsenide, AlAs, as computed by density functional theory. This Report serves as a numerical supplement to the results published in: P.A. Schultz, 'First principles predictions of intrinsic defects in Aluminum Arsenide, AlAs', Materials Research Society Symposia Proceedings 1370 (2011; SAND2011-2436C), and intended for use as reference tables for a defect physics package in device models.

  15. Coupling multiscale phenomena in systems with mobile chemical species through first principles coarse graining

    NASA Astrophysics Data System (ADS)

    van der Ven, Anton

    2004-03-01

    Many multiscale solid state phenomena involve the transport of chemical species over large distances. This is true of crack growth in corrosive environments as well as diffusional phase transformations. Often these phenomena occur over time scales that are too long for a direct atomistic simulation. Instead continuum methods that draw on phenomenological kinetic parameters such as diffusion coefficients or thermodynamic response functions such as informed cohesive zone models are necessary. A link between first principles atomistic methods and macroscopic kinetic parameters or response functions can be made with statistical mechanical coarse-graining techniques. For multicomponent crystalline solids, this involves integrating out fast degrees of freedom to generate a coarse-grained first-principles lattice model Hamiltonian that is suited for calculating both thermodynamic and kinetic properties, the latter with the help of Green-Kubo methods. We illustrate this approach by describing (i) a first principles calculation of diffusion coefficients in non-dilute alloys, essential input for continuum simulations of diffusional phase transformations and (ii) a first principles derivation of a cohesive zone model in the presence of highly mobile impurities. Cohesive zone models are used to describe the response of a solid ahead of the crack tip in continuum simulations of crack growth. We will show that for some systems, stress induced phase transformations can occur along the cohesive zone above a critical impurity chemical potential. The stress-induced transformation is accompanied by a saturation of the cohesive zone region with impurities and leads to a dramatic reduction of critical stress for decohesion.

  16. First-principles calculations of thermal, electrical, and thermoelectric transport properties of semiconductors

    NASA Astrophysics Data System (ADS)

    Zhou, Jiawei; Liao, Bolin; Chen, Gang

    2016-04-01

    The transport properties of semiconductors are key to the performance of many solid-state devices (transistors, data storage, thermoelectric cooling and power generation devices, etc). An understanding of the transport details can lead to material designs with better performances. In recent years simulation tools based on first-principles calculations have been greatly improved, being able to obtain the fundamental ground-state properties of materials (such as band structure and phonon dispersion) accurately. Accordingly, methods have been developed to calculate the transport properties based on an ab initio approach. In this review we focus on the thermal, electrical, and thermoelectric transport properties of semiconductors, which represent the basic transport characteristics of the two degrees of freedom in solids—electronic and lattice degrees of freedom. Starting from the coupled electron-phonon Boltzmann transport equations, we illustrate different scattering mechanisms that change the transport features and review the first-principles approaches that solve the transport equations. We then present the first-principles results on the thermal and electrical transport properties of semiconductors. The discussions are grouped based on different scattering mechanisms including phonon-phonon scattering, phonon scattering by equilibrium electrons, carrier scattering by equilibrium phonons, carrier scattering by polar optical phonons, scatterings due to impurities, alloying and doping, and the phonon drag effect. We show how the first-principles methods allow one to investigate transport properties with unprecedented detail and also offer new insights into the electron and phonon transport. The current status of the simulation is mentioned when appropriate and some of the future directions are also discussed.

  17. High-temperature properties of thorium dioxide: A first-principles molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Nakamura, Hiroki; Machida, Masahiko

    2016-09-01

    Thorium has been considered a potential nuclear fuel for decades. To develop evaluation method for high-temperature properties of thorium dioxide as a candidate nuclear fuel, we perform first-principles molecular dynamics. The calculated enthalpy and thermal expansion agree well with the observed data. The Bredig transition temperature also coincides with experiments. Our results indicate that this method can provide reliable data of thermal properties of nuclear fuels.

  18. Excited state dynamics in pyrrole water clusters: First-principles simulation

    NASA Astrophysics Data System (ADS)

    Frank, Irmgard; Damianos, Konstantina

    2008-01-01

    The excited state dynamics in pyrrole-water clusters is investigated using restricted open-shell Kohn-Sham theory. While the isolated pyrrole molecule dissociates in the excited state, no dissociation is observed in the presence of water molecules. Instead an electron is transferred to water and moves as solvated electron between the water molecules. The results are compared to data obtained from other first-principles and ab initio calculations.

  19. Dynamic first principles model of a complete reversible fuel cell system

    NASA Astrophysics Data System (ADS)

    Brown, Tim M.; Brouwer, Jacob; Samuelsen, G. Scott; Holcomb, Franklin H.; King, Joel

    A dynamic model of a discrete reversible fuel cell (RFC) system has been developed in a Matlab Simulink ® environment. The model incorporates first principles dynamic component models of a proton exchange membrane (PEM) fuel cell, a PEM electrolyzer, a metal hydride hydrogen storage tank, and a cooling system radiator, as well as empirical models of balance of plant components. Dynamic simulations show unique charging and discharging control issues and highlight factors contributing to overall system efficiency.

  20. Anisotropic dielectric functions of (0001) sapphire from spectroscopic ellipsometry and first-principles study

    NASA Astrophysics Data System (ADS)

    Yang, J. Y.; Zhang, W. J.; Liu, L. H.

    2015-09-01

    This work aims at understanding and predicting the high-temperature anisotropic dielectric functions of (0001) sapphire over the entire infrared-visible-ultraviolet spectrum via the state-of-the-art infrared variable angle spectroscopic ellipsometry (IR-VASE) and first-principles method without empirical parameters. Upon measuring the high-symmetry orientation of c-plane surface, the IR-VASE determines the anisotropic infrared dielectric functions of (0001) sapphire for wavelengths ranging from 10 to 25 μm and temperatures from 300 to 573 K. As ellipsometry experiments indicate, the maxima of ordinary infrared dielectric functions consistently decrease and shift to longer wavelength as temperature increases. By fitting ellipsometry data with the Lorentz oscillator model, the Lorentz parameters, e.g., oscillator strength, resonance frequency and broadening parameter, for infrared-active phonon modes are obtained to interpret the temperature effect. Moreover, the calculated vibration frequencies at varying temperatures by the first-principles method coincide with the positions of infrared absorption peaks, indicating that infrared optical absorption mainly arises from the coupling of incident photon with lattice vibration. In the visible-ultraviolet spectral range, the first-principles and lattice dynamics methods are combined to understand the temperature effect on dielectric functions of (0001) sapphire. This method reproduces the essential feature of previous room-temperature reflectivity experiments and detects the slight change of dielectric functions as temperature increases. The convincing results enable us to predict the high-temperature visible-ultraviolet dielectric functions of (0001) sapphire by the first-principles method.

  1. First-principles study of He point-defects in HCP rare-earth metals

    SciTech Connect

    Li, Yang; Chen, Ru; Peng, SM; Long, XG; Wu, Z.; Gao, Fei; Zu, Xiaotao

    2011-05-01

    He defect properties in Sc, Y, Gd, Tb, Dy, Ho, Er and Lu were studied using first-principles calculations based on density functional theory. The results indicate that the formation energy of an interstitial He atom is smaller than that of a substitutional He atom in all hcp rare-earth metals considered. Furthermore, the tetrahedral interstitial position is more favorable than an octahedral position for He defects. The results are compared with those from bcc and fcc metals.

  2. Accelerated materials design of fast oxygen ionic conductors based on first principles calculations

    NASA Astrophysics Data System (ADS)

    He, Xingfeng; Mo, Yifei

    Over the past decades, significant research efforts have been dedicated to seeking fast oxygen ion conductor materials, which have important technological applications in electrochemical devices such as solid oxide fuel cells, oxygen separation membranes, and sensors. Recently, Na0.5Bi0.5TiO3 (NBT) was reported as a new family of fast oxygen ionic conductor. We will present our first principles computation study aims to understand the O diffusion mechanisms in the NBT material and to design this material with enhanced oxygen ionic conductivity. Using the NBT materials as an example, we demonstrate the computation capability to evaluate the phase stability, chemical stability, and ionic diffusion of the ionic conductor materials. We reveal the effects of local atomistic configurations and dopants on oxygen diffusion and identify the intrinsic limiting factors in increasing the ionic conductivity of the NBT materials. Novel doping strategies were predicted and demonstrated by the first principles calculations. In particular, the K doped NBT compound achieved good phase stability and an order of magnitude increase in oxygen ionic conductivity of up to 0.1 S cm-1 at 900 K compared to the experimental Mg doped compositions. Our results provide new avenues for the future design of the NBT materials and demonstrate the accelerated design of new ionic conductor materials based on first principles techniques. This computation methodology and workflow can be applied to the materials design of any (e.g. Li +, Na +) fast ion-conducting materials.

  3. Effects of interlayer screening and temperature on dielectric functions of graphene by first-principles

    NASA Astrophysics Data System (ADS)

    Yang, J. Y.; Liu, L. H.

    2016-07-01

    The dielectric functions of few-layer graphene and the related temperature dependence are investigated from the atomic scale using first-principles calculations. Compared with ellipsometry experiments in the spectral range of 190-2500 nm, the normalized optical constants of mono-layer graphene demonstrate good agreement and further validate first-principles calculations. To interpret dielectric function of mono-layer graphene, the electronic band structure and density of states are analyzed. By comparing dielectric functions of mono-, bi-, and tri-layer graphene, it shows that interlayer screening strengthens intraband transition and greatly enhances the absorption peak located around 1 eV. The strengthened optical absorption is intrinsically caused by the increasing electron states near the Fermi level. To investigate temperature effect, the first-principles calculations and lattice dynamics are combined. The lattice vibration enhances parallel optical absorption peak around 1 eV and induces redshift. Moreover, it is observed that the van der Waals force plays a key role in keeping the interlayer distance stable during dynamics simulations.

  4. First-Principles Petascale Simulations for Predicting Deflagration to Detonation Transition in Hydrogen-Oxygen Mixtures

    SciTech Connect

    Khokhlov, Alexei; Austin, Joanna

    2015-03-02

    Hydrogen has emerged as an important fuel across a range of industries as a means of achieving energy independence and to reduce emissions. DDT and the resulting detonation waves in hydrogen-oxygen can have especially catastrophic consequences in a variety of industrial and energy producing settings related to hydrogen. First-principles numerical simulations of flame acceleration and DDT are required for an in-depth understanding of the phenomena and facilitating design of safe hydrogen systems. The goals of this project were (1) to develop first-principles petascale reactive flow Navier-Stokes simulation code for predicting gaseous high-speed combustion and detonation (HSCD) phenomena and (2) demonstrate feasibility of first-principles simulations of rapid flame acceleration and deflagrationto- detonation transition (DDT) in stoichiometric hydrogen-oxygen mixture (2H2 + O2). The goals of the project have been accomplished. We have developed a novel numerical simulation code, named HSCD, for performing first-principles direct numerical simulations of high-speed hydrogen combustion. We carried out a series of validating numerical simulations of inert and reactive shock reflection experiments in shock tubes. We then performed a pilot numerical simulation of flame acceleration in a long pipe. The simulation showed the transition of the rapidly accelerating flame into a detonation. The DDT simulations were performed using BG/Q Mira at the Argonne National Laboratiory, currently the fourth fastest super-computer in the world. The HSCD is currently being actively used on BG/QMira for a systematic study of the DDT processes using computational resources provided through the 2014-2016 INCITE allocation ”First-principles simulations of high-speed combustion and detonation.” While the project was focused on hydrogen-oxygen and on DDT, with appropriate modifications of the input physics (reaction kinetics, transport coefficients, equation of state) the code has a much

  5. EDITORIAL: Challenges for first-principles based properties of defects in semiconductors and oxides Challenges for first-principles based properties of defects in semiconductors and oxides

    NASA Astrophysics Data System (ADS)

    2009-12-01

    First-principles methods based on density functional theory (DFT) have been the mainstay of theoretical studies of the properties of semiconductor and oxide materials. Despite the tremendous successes of the past few decades, significant challenges remain in adapting these methods for predictive simulations that are quantitatively useful in predicting device behavior. Recent advances in computational capabilities, and improved theoretical methods taking advantage of ever more powerful computer hardware, offer the possibility that computational modeling may finally fulfill the long-sought goal of truly predictive simulations for defect properties. The exciting prospect of using modelling as `virtual experiments' to obtain quantitatively accurate predictions of semiconductor behavior seems tantalizingly close, but challenges still remain, which is evident in the many divergent approaches adopted for the modelling and simulation of various aspects of defect behavior. This special issue consists of papers describing different approaches to the study of defects, and the challenges that remain from the perspective of leading scientists in the field. It includes contributions on the theoretical and computational issues of using density functional methods for defect calculations [Nieminen], treatments to account for finite computational cell effects in periodic defect supercell calculations using analytical constructions [Lany and Zunger], or cell-size extrapolation techniques [Castleton et al], or instead using embedded cluster calculations to model charge-trapping defects [Shluger et al]. This issue also includes a description of the computation of g-tensor and hyperfine splitting for defect centers [Valentin and Pacchione], computation of vibrational properties of impurities from dynamical DFT calculations [Estreicher et al], and the use of DFT supercell calculations to predict charge transition energy levels of intrinsic defects in GaAs [Schultz and von Lilienfeld

  6. A first-principles methodology for diffusion coefficients in metals and dilute alloys

    NASA Astrophysics Data System (ADS)

    Mantina, Manjeera

    This work is a study exploring the extent of suitability of static first-principles calculations for studying diffusion in metallic systems. Specifically, vacancy-mediated volume diffusion in pure elements and alloys with dilute concentration of impurities is studied. A novel procedure is discovered for predicting diffusion coefficients that overcomes the shortcomings of the well-known transition state theory, by Vineyard. The procedure that evolves from Eyring's reaction rate theory yields accurate diffusivity results that include anharmonic effects within the quasi-harmonic approximation. Alongside, the procedure is straightforward in its application within the conventional harmonic approximation, from the results of static first-principles calculations. To prove the extensibility of the procedure, diffusivities have been computed for a variety of systems. Over a wide temperature range, the calculated self-diffusion and impurity diffusion coefficients using local density approximation (LDA) of density functional theory (DFT) are seen to be in excellent match with experimental data. Self-diffusion coefficients have been calculated for: (i) fcc Al, Cu, Ni and Ag (ii) bcc W and Mo (v) hcp Mg, Ti and Zn. Impurity diffusion coefficients have been computed for: (i) Mg, Si, Cu, Li, Ag, Mo and 3d transition elements in fcc Al (ii) Mo, Ta in bcc W and Nb, Ta and W in bcc Mo (iii) Sn and Cd in hcp Mg and Al in hcp Ti. It is also an observation from this work, that LDA does not require surface correction for yielding energetics of vacancy-containing system in good comparison with experiments, unlike generalized gradient approximation (GGA). It is known that first-principles' energy minimization procedures based on electronic interactions are suited for metallic systems wherein the valence electrons are freely moving. In this thesis, research has been extended to study suitability of first-principles calculations within LDA/GGA including the localization parameter U, for Al

  7. First-principles simulation of Raman spectra and structural properties of quartz up to 5 GPa

    NASA Astrophysics Data System (ADS)

    Liu, Lei; Lv, Chao-Jia; Zhuang, Chun-Qiang; Yi, Li; Liu, Hong; Du, Jian-Guo

    2015-12-01

    The crystal structure and Raman spectra of quartz are calculated by using first-principles method in a pressure range from 0 to 5 GPa. The results show that the lattice constants (a, c, and V) decrease with increasing pressure and the a-axis is more compressible than the c axis. The Si-O bond distance decreases with increasing pressure, which is in contrast to experimental results reported by Hazen et al. [Hazen R M, Finger L W, Hemley R J and Mao H K 1989 Solid State Communications 725 507-511], and Glinnemann et al. [Glinnemann J, King H E Jr, Schulz H, Hahn T, La Placa S J and Dacol F 1992 Z. Kristallogr. 198 177-212]. The most striking changes are of inter-tetrahedral O-O distances and Si-O-Si angles. The volume of the tetrahedron decreased by 0.9% (from 0 to 5 GPa), which suggests that it is relatively rigid. Vibrational models of the quartz modes are identified by visualizing the associated atomic motions. Raman vibrations are mainly controlled by the deformation of the tetrahedron and the changes in the Si-O-Si bonds. Vibrational directions and intensities of atoms in all Raman modes just show little deviations when pressure increases from 0 to 5 GPa. The pressure derivatives (dνi/dP) of the 12 Raman frequencies are obtained at 0 GPa-5 GPa. The calculated results show that first-principles methods can well describe the high-pressure structural properties and Raman spectra of quartz. The combination of first-principles simulations of the Raman frequencies of minerals and Raman spectroscopy experiments is a useful tool for exploring the stress conditions within the Earth. Project supported by the Key Laboratory of Earthquake Prediction, Institute of Earthquake Science, China Earthquake Administration (CEA) (Grant No. 2012IES010201) and the National Natural Science Foundation of China (Grant Nos. 41174071 and 41373060).

  8. First principles calculation of the effect of Coulomb collisions in partially ionized gases

    SciTech Connect

    Donkó, Z.

    2014-04-15

    Coulomb collisions, at appreciable ratios (η) of the electron to the neutral particle density, influence significantly the electron kinetics in particle swarms and in plasmas of gas discharges. This paper introduces a combination of Molecular Dynamics and Monte Carlo simulation techniques, to provide a novel, approximation-free, first principles calculation method for the velocity distribution function of electrons, and related swarm characteristics, at arbitrary η. Simulation results are presented for electrons in argon gas, for density ratios between zero and 10{sup −1}, representing the limits of a negligible electron density and an almost complete Maxwellization of the velocity distribution function, respectively.

  9. Emergence of Simple Patterns in Complex Atomic Nuclei from First Principles

    NASA Astrophysics Data System (ADS)

    Dytrych, T.; Launey, K. D.; Draayer, J. P.; Maris, P.; Vary, J. P.; Langr, D.; Oberhuber, T.

    2015-09-01

    We study the structure of low-lying states in 6Li, 6He, 8Be, 8B, 12C, and 16O, using ab initio symmetry-adapted no-core shell model. The results of our study demonstrate that collective modes in light nuclei emerge from first principles. We investigate the impact of the symmetry-adapted model space on spectroscopic properties and, in the case of the ground state of 6Li, on elastic electron scattering charge form factor. The results confirm that only a small symmetry-adapted subspace of the complete model space is needed to accurately reproduce complete-space observables and the form factor momentum dependence.

  10. First-principles study on the electronic and optical properties of cubic ABX3 halide perovskites

    NASA Astrophysics Data System (ADS)

    Lang, Li; Yang, Ji-Hui; Liu, Heng-Rui; Xiang, H. J.; Gong, X. G.

    2014-01-01

    The electronic properties of ABX3 type compounds in the cubic phase are systematically studied using the first-principles calculations. The chemical trend of their properties as A or B or X varies is fully investigated. The optical properties of the ABX3 compounds are also investigated. Our calculations show that taking into account the spin-orbit coupling effect is crucial for predicting the accurate band gap of these halide perovskites. We predict that CH3NH3SnBr3 is a promising material for solar cells absorber with a perfect band gap and good optical absorption.

  11. Multiple coherent states for first-principles semiclassical initial value representation molecular dynamics.

    PubMed

    Ceotto, Michele; Atahan, Sule; Tantardini, Gian Franco; Aspuru-Guzik, Alán

    2009-06-21

    A multiple coherent states implementation of the semiclassical approximation is introduced and employed to obtain the power spectra with a few classical trajectories. The method is integrated with the time-averaging semiclassical initial value representation to successfully reproduce anharmonicity and Fermi resonance splittings at a level of accuracy comparable to semiclassical simulations of thousands of trajectories. The method is tested on two different model systems with analytical potentials and implemented in conjunction with the first-principles molecular dynamics scheme to obtain the power spectrum for the carbon dioxide molecule. PMID:19548717

  12. First-Principles Study on β-SiC/BNNT Core/shell Nanocable

    NASA Astrophysics Data System (ADS)

    Zou, X. C.; Ouyang, J.; Wu, M. S.; Liu, G.; Lei, X. L.; Ouyang, C. Y.; Xu, B.

    2013-09-01

    In this paper, we studied the structural and electronic properties of core/shell nanocables composed of cubic silicon carbide nanowires (β-SiCNW) and boron nitride nanotubes (BNNT) using first-principles pseudopotential plane wave method within density functional theory. Our results show that the β-SiC/BNNT heterojunction structures are metallic, which primarily originates from the contributions of the BNNTs and the surfaces of SiCNWs. The BNNTs exhibit metallic characters after the SiC nanowires are inserted. The transition of the BNNTs is attributed to the charge transfer between BNNTs and SiCNWs.

  13. Crystal Structure Prediction from First Principles: The Crystal Structures of Glycine

    PubMed Central

    Lund, Albert M.; Pagola, Gabriel I.; Orendt, Anita M.; Ferraro, Marta B.; Facelli, Julio C.

    2015-01-01

    Here we present the results of our unbiased searches of glycine polymorphs obtained using the Genetic Algorithms search implemented in Modified Genetic Algorithm for Crystals coupled with the local optimization and energy evaluation provided by Quantum Espresso. We demonstrate that it is possible to predict the crystal structures of a biomedical molecule using solely first principles calculations. We were able to find all the ambient pressure stable glycine polymorphs, which are found in the same energetic ordering as observed experimentally and the agreement between the experimental and predicted structures is of such accuracy that the two are visually almost indistinguishable. PMID:25843964

  14. First Principles Calculations of Oxygen Adsorption on the UN(001) Surface

    SciTech Connect

    Zhukovskii, Yuri F.; Bocharov, Dmitry; Kotomin, Eugene Alexej; Evarestov, Robert; Bandura, A. V.

    2009-01-01

    Fabrication, handling and disposal of nuclear fuel materials require comprehensive knowledge of their surface morphology and reactivity. Due to unavoidable contact with air components (even at low partial pressures), UN samples contain considerable amount of oxygen impurities affecting fuel properties. In this study we focus on reactivity of the energetically most stable (001) substrate of uranium nitride towards the atomic oxygen as one of initial stages for further UN oxidation. The basic properties of O atoms adsorbed on the UN(001) surface are simulated here combining the two first principles calculation methods based on the plane wave basis set and that of the localized orbitals.

  15. First-principles Study of Hydrogen depassivation of Mg acceptor by Be in GaN

    NASA Astrophysics Data System (ADS)

    Zhang, Qiming; Wang, Xiao; Wang, Chihsiang

    2010-03-01

    The process of hydrogen depassivation of the acceptor by can convert the as-grown high-resistivity -doped into a - conducting material. A first-principles study on the process will be presented. The formation energies of various complex of impurities and point defects have been calculated and compared. The diffusion barriers of the hydrogen atom in the doped GaN have been obtained by the Nudge-Elastic-Band method. The results explain successfully the experimental observation that the hole concentration has been significantly enhanced in a Be-implanted Mg-doped GaN.

  16. First-principles study on bottom-up fabrication process of atomically precise graphene nanoribbons

    NASA Astrophysics Data System (ADS)

    Kaneko, Tomoaki; Tajima, Nobuo; Ohno, Takahisa

    2016-06-01

    We investigate the energetics of a polyanthracene formation in the bottom-up fabrication of atomically precise graphene nanoribbons on Au(111) using first-principles calculations based on the density functional theory. We show that the structure of precursor molecules plays a decisive role in the C–C coupling reaction. The reaction energy of the dimerization of anthracene dimers is a larger negative value than that of the dimerization of anthracene monomers, suggesting that the precursor molecule used in experiments has a favorable structure for graphene nanoribbon fabrication.

  17. First-principles study of lithium adsorption and diffusion on graphene: the effects of strain

    NASA Astrophysics Data System (ADS)

    Hao, Feng; Chen, Xi

    2015-10-01

    Large strain is produced within graphene sheets, which serve as a critical component in lithium-ion batteries, due to the expansion of the electrodes. First-principles calculations are therefore employed to investigate the interaction of Li with strained single-layer graphene. It is found that tensile strain enhances Li binding on graphene and significantly reduces the formation energy of divacancies. In addition, Li diffusion through graphene with defects is facilitated by tensile strain, whereas diffusion parallel to the plane of pristine graphene is slightly hindered.

  18. First-Principles Molecular Dynamics Calculations of the Equation of State for Tantalum

    PubMed Central

    Ono, Shigeaki

    2009-01-01

    The equation of state of tantalum (Ta) has been investigated to 100 GPa and 3,000 K using the first-principles molecular dynamics method. A large volume dependence of the thermal pressure of Ta was revealed from the analysis of our data. A significant temperature dependence of the calculated effective Grüneisen parameters was confirmed at high pressures. This indicates that the conventional approach to analyze thermal properties using the Mie-Grüneisen approximation is likely to have a significant uncertainty in determining the equation of state for Ta, and that an intrinsic anharmonicity should be considered to analyze the equation of state. PMID:20057949

  19. First-principles study of water adsorption on α-SiO2 [110] surface

    NASA Astrophysics Data System (ADS)

    Mankad, Venu; Jha, Prafulla K.

    2016-08-01

    We have investigated the structural and electronic properties of water molecule adsorbed silicon dioxide (α-SiO2) [110] surface and analyzed the influence of water molecule on its energetics, structure and elctronic propertes using density functional theory based first principles calculations. The inhomogeneous topology of the α-SiO2 clean surface promotes a total charge density displacement on the adsorbed water molecule and giving rise to electron-rich as well as hole-rich region. The electronic charge transfer from a α-SiO2 to the water molecule occurs upon the formation of a partially occupied level laying above conduction band level.

  20. First principles study of structural, electronic and mechanical properties of alkali nitride-KN

    SciTech Connect

    Murugan, A.; Rajeswarapalanichamy, R. Santhosh, M.; Iyakutti, K.

    2015-06-24

    The structural, electronic and elastic properties of alkali- metal nitride (KN) is investigated by the first principles calculations based on density functional theory as implemented in Vienna ab-initio simulation package. At ambient pressure KN is stable in the ferromagnetic state with NaCl structure. The calculated lattice parameters are in good agreement with the available results. The electronic structure reveals that the KN is half metallic ferromagnet at normal pressure. A pressure-induced structural phase transition from NaCl to ZB phase is observed in KN. Half metallicity and ferromagnetism is maintained at all pressures.

  1. First-principles theory of electron-spin fluctuation coupling and superconducting instabilities in iron selenide

    NASA Astrophysics Data System (ADS)

    Lischner, Johannes; Bazhirov, Timur; MacDonald, Allan H.; Cohen, Marvin L.; Louie, Steven G.

    2015-01-01

    We present first-principles calculations of the coupling of quasiparticles to spin fluctuations in iron selenide and discuss which types of superconducting instabilities this coupling gives rise to. We find that strong antiferromagnetic stripe-phase spin fluctuations lead to large coupling constants for superconducting gaps with s± symmetry, but these coupling constants are significantly reduced by other spin fluctuations with small wave vectors. An accurate description of this competition and an inclusion of band-structure and Stoner parameter renormalization effects lead to a value of the coupling constant for an s±-symmetric gap which can produce a superconducting transition temperature consistent with experimental measurements.

  2. Lithium intercalation and diffusion in TiO2 nanotubes: a first-principles investigation.

    PubMed

    Liang, Ke; Chen, Xue; Guo, Zhenyu; Hou, Tingjun; Zhang, Xiaohong; Li, Youyong

    2016-09-21

    Titanium dioxide nanotubes have attracted considerable attention because of their excellent photoelectric and electrochemical performance in lithium-ion batteries (LIBs). Precise intercalation sites and controllable diffusion paths are very important for the structures and transport properties of TiO2 nanotubes. Based on first-principles calculations, herein, we discuss these parameters. The results indicate that TiO2 nanotubes with 2-coordinate oxygen vacancies could effectively improve the immigration ability of Li ions. The effective diffusion barriers (0.53 eV) between the outer and inner surfaces suggest a potential material for application in Li-ion barriers. PMID:27533347

  3. A comparative first-principles study of structural and electronic properties among memantine, amantadine and rimantadine

    NASA Astrophysics Data System (ADS)

    Middleton, Kirsten; Zhang, G. P.; Nichols, Michael R.; George, Thomas F.

    2012-05-01

    Memantine, amantadine and rimantadine are structurally derived from the same diamondoid, adamantane. These derivatives demonstrate therapeutic efficacy in human diseases: memantine for Alzheimer's disease and amantadine and rimantadine for influenza. In order to better understand some of the properties that distinguish these three compounds, we conduct first-principles calculations on their structure and electronic properties. Our results indicate that protonation has a significant effect on the dipole moment, where the dipole moment in protonated memantine is over eight times larger than in the deprotonated form.

  4. Spin Polarization Properties of Na Doped Meridianal Tris(8-Hydroxyquinoline) Aluminum Studied by First Principles Calculations

    NASA Astrophysics Data System (ADS)

    Ren, Jun-Feng; Yuan, Xiao-Bo; Hu, Gui-Chao

    2014-04-01

    We theoretically investigate the electronic structure and spin polarization properties of Na-doped meridianal tris(8-hydroxyquinoline) aluminum (Alq3) by first principles calculations. It is found that the spin density is distributed mainly in the Alq3 part in the Alq3:Na complex. Electron charge transfer takes place from the Na atom to the Alq3 molecule, which induces asymmetric changing of the molecule bond lengths, thus the spin density distribution becomes asymmetric. Spin polarization of the complex originates from the preferable filling of the spin-split nitrogen and carbon p-orbitals because of the different bond length changes of the Alq3 molecule upon Na doping.

  5. Truncated spherical-wave basis set for first-principles pseudopotential calculations

    NASA Astrophysics Data System (ADS)

    Monserrat, B.; Haynes, P. D.

    2010-11-01

    Analytic results for two- and three-centre integrals are derived for the truncated spherical-wave basis set designed for first-principles pseudopotential calculations within density-functional theory. These allow the overlap, kinetic energy and non-local pseudopotential matrix elements to be calculated efficiently and accurately. In particular, the scaling of the computational effort with maximum angular momentum component is dramatically improved and the projection method takes full account of the discontinuities in the basis functions arising from their localization within spherical regions.

  6. Band gap engineering of early transition-metal-doped anatase TiO₂: first principles calculations.

    PubMed

    Li, C; Zhao, Y F; Gong, Y Y; Wang, T; Sun, C Q

    2014-10-21

    The thermal stability and electronic structures of anatase TiO2 doped with early transition metals (TM) (group III-B = Sc, Y and La; group IV-B = Zr and Hf; group V-B = V, Nb and Ta) have been studied using first principles calculations. It was found that all doped systems are thermodynamically stable, and their band gaps were reduced by 1-1.3 eV compared to pure TiO2. Doping with transition metals affects the strength of the hybrid orbital of TM-O bonding, and the band gap increases approximately linearly with the MP value of TM-O bonding. PMID:25183457

  7. First-principles calculation of the structural stability of 6d transition metals

    SciTech Connect

    Oestlin, A.; Vitos, L.

    2011-09-15

    The phase stability of the 6d transition metals (elements 103-111) is investigated using first-principles electronic-structure calculations. Comparison with the lighter transition metals reveals that the structural sequence trend is broken at the end of the 6d series. To account for this anomalous behavior, the effect of relativity on the lattice stability is scrutinized, taking different approximations into consideration. It is found that the mass-velocity and Darwin terms give important contributions to the electronic structure, leading to changes in the interstitial charge density and, thus, in the structural energy difference.

  8. Impact of first-principles properties of deuterium–tritium on inertial confinement fusion target designs

    DOE PAGESBeta

    Hu, S. X.; Goncharov, V. N.; Boehly, T. R.; McCrory, R. L.; Skupsky, S.; Collins, L. A.; Kress, J. D.; Militizer, B.

    2015-04-20

    In this study, a comprehensive knowledge of the properties of high-energy-density plasmas is crucial to understanding and designing low-adiabat, inertial confinement fusion (ICF) implosions through hydrodynamic simulations. Warm-dense-matter (WDM) conditions are routinely accessed by low-adiabat ICF implosions, in which strong coupling and electron degeneracy often play an important role in determining the properties of warm dense plasmas. The WDM properties of deuterium–tritium (DT) mixtures and ablator materials, such as the equation of state, thermal conductivity, opacity, and stopping power, were usually estimated by models in hydro-codes used for ICF simulations. In these models, many-body and quantum effects were only approximatelymore » taken into account in the WMD regime. Moreover, the self-consistency among these models was often missing. To examine the accuracy of these models, we have systematically calculated the static, transport, and optical properties of warm dense DT plasmas, using first-principles (FP) methods over a wide range of densities and temperatures that cover the ICF “path” to ignition. These FP methods include the path-integral Monte Carlo (PIMC) and quantum-molecular dynamics (QMD) simulations, which treat electrons with many-body quantum theory. The first-principles equation-of-state table, thermal conductivities (KQMD), and first principles opacity table of DT have been self-consistently derived from the combined PIMC and QMD calculations. They have been compared with the typical models, and their effects to ICF simulations have been separately examined in previous publications. In this paper, we focus on their combined effects to ICF implosions through hydro-simulations using these FP-based properties of DT in comparison with the usual model simulations. We found that the predictions of ICF neutron yield could change by up to a factor of –2.5; the lower the adiabat of DT capsules, the more variations in hydro

  9. First principles study of photoelectron spectra of Cu{sub {ital n}}{sup {minus}} clusters

    SciTech Connect

    Massobrio, C.; Pasquarello, A.; Car, R.

    1995-09-11

    We have determined equilibrium geometries and electronic properties of neutral and anionic Cu{sub {ital n}} ({ital n}=2,9) clusters by means of first principles calculations in which {ital s} and {ital d} electrons are treated on equal footing. We find that the calculated electronic density of states is inadequate to interpret photoelectron spectra of Cu{sub {ital n}}{sup {minus}} clusters. We obtain good agreement between calculated excitation energies and experimental spectra when we include final states effects.

  10. First-principles study of electronic structures of graphene on Y2O3

    NASA Astrophysics Data System (ADS)

    Kaneko, Tomoaki; Ohno, Takahisa

    2016-06-01

    We investigate the structures, stability and electronic properties of graphene adsorbed on Y2O3(111) using first-principles calculations based on density functional theories. When the interface of Y2O3(111) is terminated by an Y-layer, graphene is chemisorbed on Y2O3, resulting in the strong modification of electronic band structures. When the Y2O3(111) surface is terminated with O atoms and extra O atoms, on the other hand, graphene is physisorbed on Y2O3(111). Therefore, an O-rich environment is preferable for the graphene and Y2O3 interface.