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Sample records for first-principles theoretical spectroscopy

  1. Spectroscopy of organic semiconductors from first principles

    NASA Astrophysics Data System (ADS)

    Sharifzadeh, Sahar; Biller, Ariel; Kronik, Leeor; Neaton, Jeffery

    2011-03-01

    Advances in organic optoelectronic materials rely on an accurate understanding their spectroscopy, motivating the development of predictive theoretical methods that accurately describe the excited states of organic semiconductors. In this work, we use density functional theory and many-body perturbation theory (GW/BSE) to compute the electronic and optical properties of two well-studied organic semiconductors, pentacene and PTCDA. We carefully compare our calculations of the bulk density of states with available photoemission spectra, accounting for the role of finite temperature and surface effects in experiment, and examining the influence of our main approximations -- e.g. the GW starting point and the application of the generalized plasmon-pole model -- on the predicted electronic structure. Moreover, our predictions for the nature of the exciton and its binding energy are discussed and compared against optical absorption data. We acknowledge DOE, NSF, and BASF for financial support and NERSC for computational resources.

  2. 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

  3. First-principles interpretation of core-level spectroscopy of photoelectrochemical materials and processes

    NASA Astrophysics Data System (ADS)

    Pemmaraju, Sri Chaitanya Das; Prendergast, David

    2014-03-01

    We present two case studies of first-principles theoretical methods applied in conjunction with experimental core-level spectroscopy measurements to investigate the electronic structure and dynamical processes in molecular and interfacial systems relevant to photoelectrochemical (PEC) technologies. In the first, we study the core-level and valence spectroscopies of two zinc(II)-porphyrin based Donor-pi-Acceptor (D-p-A) dyes using the occupancy-constrained excited electron and core-hole (XCH) approach and time-dependent density functional theory (TDDFT) simulations. In the second, we use constrained DFT and TDDFT to interpret measured transient core-level shifts in time-resolved femtosecond x-ray photoelectron spectroscopy, investigating the dynamics of the electron injection process from a N3 dye molecule chemisorbed onto a ZnO substrate. These studies illustrate the utility of first-principles methods in guiding the design of better PEC materials. This work was performed at the Molecular Foundry, LBNL, supported by the Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.

  4. First-principles photoemission spectroscopy in DNA and RNA nucleobases from Koopmans-compliant functionals

    NASA Astrophysics Data System (ADS)

    Nguyen, Ngoc Linh; Borghi, Giovanni; Ferretti, Andrea; Marzari, Nicola

    The determination of spectral properties of the DNA and RNA nucleobases from first principles can provide theoretical interpretation for experimental data, but requires complex electronic-structure formulations that fall outside the domain of applicability of common approaches such as density-functional theory. In this work, we show that Koopmans-compliant functionals, constructed to enforce piecewise linearity in energy functionals with respect to fractional occupation-i.e., with respect to charged excitations-can predict not only frontier ionization potentials and electron affinities of the nucleobases with accuracy comparable or superior with that of many-body perturbation theory and high-accuracy quantum chemistry methods, but also the molecular photoemission spectra are shown to be in excellent agreement with experimental ultraviolet photoemsision spectroscopy data. The results highlight the role of Koopmans-compliant functionals as accurate and inexpensive quasiparticle approximations to the spectral potential, which transform DFT into a novel dynamical formalism where electronic properties, and not only total energies, can be correctly accounted for.

  5. 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

  6. Combining solid-state NMR spectroscopy with first-principles calculations - a guide to NMR crystallography.

    PubMed

    Ashbrook, Sharon E; McKay, David

    2016-06-01

    Recent advances in the application of first-principles calculations of NMR parameters to periodic systems have resulted in widespread interest in their use to support experimental measurement. Such calculations often play an important role in the emerging field of "NMR crystallography", where NMR spectroscopy is combined with techniques such as diffraction, to aid structure determination. Here, we discuss the current state-of-the-art for combining experiment and calculation in NMR spectroscopy, considering the basic theory behind the computational approaches and their practical application. We consider the issues associated with geometry optimisation and how the effects of temperature may be included in the calculation. The automated prediction of structural candidates and the treatment of disordered and dynamic solids are discussed. Finally, we consider the areas where further development is needed in this field and its potential future impact. PMID:27117884

  7. First-principles calculation of parameters of electron paramagnetic resonance spectroscopy in solids.

    PubMed

    Kadantsev, Eugene S; Ziegler, Tom

    2010-12-01

    The hyperfine A-tensor and Zeeman g-tensor parameterize the interaction of an 'effective' electron spin with the magnetic field due to the nuclear spin and the homogeneous external magnetic field, respectively. The A- and g-tensors are the quantities of primary interest in electron paramagnetic resonance (EPR) spectroscopy. In this paper, we review our work [E.S. Kadantsev, T. Ziegler, J. Phys. Chem. A 2008, 112, 4521; E. S. Kadantsev, T. Ziegler, J. Phys. Chem. A 2009, 113, 1327] on the calculation of these EPR parameters under periodic boundary conditions (PBC) from first-principles. Our methodology is based on the Kohn-Sham DFT (KS DFT), explicit usage of Bloch basis set made up of numerical and Slater-type atomic orbitals (NAOs/STOs), and is implemented in the 'full potential' program BAND. Our implementation does not rely on the frozen core approximation. The NAOs/STOs basis is well suited for the accurate representation of the electron density near the nuclei, a prerequisite for the calculation of highly accurate hyperfine parameters. In the case of g-tensor, our implementation is based on the method of Van Lenthe et al. [E. van Lenthe, P. E. S. Wormer, A. van der Avoird, J. Chem. Phys. 1997, 107, 2488] in which the spin-orbital coupling is taken into account variationally. We demonstrate the viability of our scheme by calculating EPR parameters of paramagnetic defects in solids. We consider the A-tensor of 'normal' and 'anomalous' muonium defect in IIIA-VA semiconductors as well as the S2 anion radical in KCl host crystal lattice. PMID:20821407

  8. First-principles core-level X-ray photoelectron spectroscopy calculation on arsenic defects in silicon crystal

    SciTech Connect

    Kishi, Hiroki; Miyazawa, Miki; Matsushima, Naoki; Yamauchi, Jun

    2014-02-21

    We investigate the X-ray photoelectron spectroscopy (XPS) binding energies of As 3d in Si for various defects in neutral and charged states by first-principles calculation. It is found that the complexes of a substitutional As and a vacancy in charged and neutral states explain the experimentally observed unknown peak very well.

  9. First-Principles Theoretical Investigation of Neutral Vacancy-Associated Muonium Center in Silicon

    NASA Astrophysics Data System (ADS)

    Li, Hong; Nandini Usha Roy, Alok; Sahoo, N.; Das, T. P.; Scheuermann, R.; Nagamine, K.

    2000-03-01

    First-principles Hartree-Fock Cluster investigation has been carried out on the vacancy associated center MuV in silicon (B. Beck Nielsen et al, Phys. Rev. Lett. \\underline79, 1507 (1997)) and V_H, its H counterpart (M. Schefzik et al, Sol. St. Comm. \\underline107, 395 (1998)), using the cluster Si_4H_12Mu involving muonium and the four silicon neighbors nearest to the vacancy. Lattice relaxation effects are included. Our results explain the observed non-axial symmetry through Jahn-Teller distortion and provide reasonable quantitative agreement with experimental hyperfine data. The influence of using larger clusters and vibrational motion of the muon is being studied and results will be reported.

  10. Theoretical studies of aluminum and aluminide alloys using CALPHAD and first-principles approach

    NASA Astrophysics Data System (ADS)

    Jiang, Chao

    Heat-treatable aluminum alloys have been widely used in the automobile and aerospace industries as structural materials due to their light weight and high strength. To study the age-hardening process in heat-treatable aluminum alloys, the Gibbs energies of the strengthening metastable phases, e.g. theta ' and theta″, are critical. However, those data are not included in the existing thermodynamic databases for aluminum alloys due to the semi-empirical nature of the CALPHAD approach. In the present study, the thermodynamics of the Al-Cu system, the pivotal age-hardening system, is remodeled using a combined CALPHAD and first-principles approach. The formation enthalpies and vibrational formation entropies of the stable and metastable phases in the Al-Cu system are provided by first-principles calculations. Special Quasirandom Structures (SQS's) are applied to model the substitutionally random fee and bee alloys. SQS's for binary bee alloys are developed and tested in the present study. Finally, a self-consistent thermodynamic description of the Al-Cu system including the two metastable theta″ and theta' phases is obtained. During welding of heat-treatable aluminum alloys, a detrimental phenomenon called constitutional liquation, i.e. the local eutectic melting of second-phase particles in a matrix at temperatures above the eutectic temperature but below the solidus of the alloy, may occur in the heat-affected zone (HAZ). In the present study, diffusion code DICTRA coupled with realistic thermodynamic and kinetic databases is used to simulate the constitutional liquation in the model Al-Cu system. The simulated results are in quantitative agreement with experiments. The critical heating rate to avoid constitutional liquation is also determined through computer simulations. Besides the heat-treatable aluminum alloys, intermetallic compounds based on transition metal aluminides, e.g. NiAl and FeAl, are also promising candidates for the next-generation of high

  11. Phase stability, elasticity, and theoretical strength of polonium from first principles

    NASA Astrophysics Data System (ADS)

    Legut, Dominik; Friák, Martin; Šob, Mojmír

    2010-06-01

    Employing full-potential linearized augmented plane-wave method, we investigate the stability of Po in its ground-state simple cubic structure (α-Po) with respect to the trigonal spiral structure exhibited by Se and Te and to the displacive phase transformations into either tetragonal or trigonal phases. The origin of the phase stability of α-Po is analyzed with the help of densities of states, electronic band structures, and total energies of competing higher-energy structures corresponding to selected stationary points of the total energy. The electronic structures and total energies are calculated both within the generalized gradient approximation and local-density approximation (LDA) to the exchange-correlation energy as well as with and without inclusion of the spin-orbit (SO) coupling. The total energies are displayed in contour plots as functions of selected structural parameters and atomic volume. It turns out that the LDA calculation with SO interaction incorporated provides best agreement with existing experimental data and that the simple cubic structure of α-Po is stabilized by relativistic effects of core electrons. High elastic anisotropy of α-Po is explained as a consequence of its simple cubic structure and is compared with elastic properties of other crystal structures. Finally, an uniaxial tensile test for loading along the [001] and [111] directions is simulated; the corresponding theoretical tensile strengths calculated within the LDA+SO approach amount to 4.2 GPa and 4.7 GPa, respectively, which are the lowest values predicted in an element so far. According to Pugh and Frantsevich criteria, α-Po is predicted to be ductile. Also a positive value of the Cauchy pressure confirms the metallic type of interatomic bonding.

  12. First-Principles Photoemission Spectroscopy of DNA and RNA Nucleobases from Koopmans-Compliant Functionals.

    PubMed

    Nguyen, Ngoc Linh; Borghi, Giovanni; Ferretti, Andrea; Marzari, Nicola

    2016-08-01

    The need to interpret ultraviolet photoemission data strongly motivates the refinement of first-principles techniques that are able to accurately predict spectral properties. In this work, we employ Koopmans-compliant functionals, constructed to enforce piecewise linearity in approximate density functionals, to calculate the structural and electronic properties of DNA and RNA nucleobases. Our results show that not only ionization potentials and electron affinities are accurately predicted with mean absolute errors of <0.1 eV, but also that calculated photoemission spectra are in excellent agreement with experimental ultraviolet photoemission spectra. In particular, the role and contribution of different tautomers to the photoemission spectra are highlighted and discussed in detail. The structural properties of nucleobases are also investigated, showing an improved description with respect to local and semilocal density-functional theory. Methodologically, our results further consolidate the role of Koopmans-compliant functionals in providing, through orbital-density-dependent potentials, accurate electronic and spectral properties. PMID:27267665

  13. First-principles study of phonon effects in x-ray absorption near-edge structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Nemausat, R.; Brouder, Ch; Gervais, Ch; Cabaret, D.

    2016-05-01

    Usually first-principles x-ray absorption near-edge structure (XANES) calculations are performed in the Born-Oppenheimer approximation assuming a static lattice, whereas the nuclear motion undoubtedly impacts XANES spectra notably at the K pre-edge of light elements in oxides. Here, an efficient method based on density-functional theory to account for quantum thermal fluctuations of nuclei is developed and is successfully applied to the K edge of corundum for temperatures up to 930 K. The zero-point motion influence is estimated. Comparison is made with previous theoretical approaches also developed to account for vibrations in XANES.

  14. Speciation of Aqueous Silica Using Raman Spectroscopy and First Principles Calculations

    NASA Astrophysics Data System (ADS)

    Hunt, J. D.; Kavner, A.; Schauble, E. A.; Manning, C. E.

    2007-12-01

    This study presents Raman spectra of high-pH silica solutions taken at ambient conditions with varying silica concentrations. Dissolved silica plays an important role in lithospheric fluid chemistry. Over the range of crustal temperatures and pressures, silica concentrations in quartz-saturated aqueous fluids vary sufficiently to allow for significant mass transport of silica via fluid-rock interaction. Polymerization of aqueous silica plays an important role in elevating dissolved SiO2 concentrations, and could afford silicate-melt-like or crystal-like sites into which otherwise insoluble elements such as titanium could substitute, leading to enhanced mobility for those elements. It would therefore be useful to understand what the independent effects of concentration, composition (pH and incorporation of other elements), pressure, and temperature are on silica polymerization. Raman spectra of silica solutions have previously been obtained [Ref. 1, 2], but those studies did not vary aqueous silica concentration at a fixed P and T. As a foundation for future studies of polymerization of aqueous silica at high P and T, we collected Raman spectra of high-pH silica solutions at ambient conditions with varying silica concentrations. Total silica concentration was varied while keeping pH, P, and T constant. First principles calculations of explicitly solvated silica monomers and dimers are used to interpret the experimental spectra. The spectra show that as total silica concentration increases, the ratio of silica in dimers to silica in monomers increases as well, shown by the ratio of the dimer peak height at 600 cm-1 to the monomer peak height at 780 cm-1. This has been thermodynamically predicted [Ref. 3], and has been indirectly observed in high P-T solubility measurements [Ref. 4], but ours is the first experiment to directly observe that this is the case while keeping temperature and pressure constant. These results are a promising first step towards hydrothermal

  15. Quasiparticle and optical spectroscopy of the organic semiconductors pentacene and PTCDA from first principles

    NASA Astrophysics Data System (ADS)

    Sharifzadeh, Sahar; Biller, Ariel; Kronik, Leeor; Neaton, Jeffrey B.

    2012-03-01

    The broad use of organic semiconductors for optoelectronic applications relies on quantitative understanding and control of their spectroscopic properties. Of paramount importance are the transport gap—the difference between ionization potential and electron affinity—and the exciton binding energy—inferred from the difference between the transport and optical absorption gaps. Transport gaps are commonly established via photoemission and inverse photoemission spectroscopy (PES/IPES). However, PES and IPES are surface-sensitive, average over a dynamic lattice, and are subject to extrinsic effects, leading to significant uncertainty in gaps. Here, we use density functional theory and many-body perturbation theory to calculate the spectroscopic properties of two prototypical organic semiconductors, pentacene, and 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA), quantitatively comparing with measured PES, IPES, and optical absorption spectra. For bulk pentacene and PTCDA, the computed transport gaps are 2.4 and 3.0 eV, and optical gaps are 1.7 and 2.1 eV, respectively. Computed bulk quasiparticle spectra are in excellent agreement with surface-sensitive photoemission measurements over several eV only if the measured gap is reduced by 0.6 eV for pentacene and 0.6-0.9 eV for PTCDA. We attribute this redshift to several physical effects, including incomplete charge screening at the surface, static and dynamical disorder, and experimental resolution. Optical gaps are in excellent agreement with experiment with solid-state exciton binding energies of ˜0.5 eV for both systems; for pentacene the exciton is delocalized over several molecules and exhibits significant charge transfer character. Our parameter-free calculations provide new interpretation of spectroscopic properties of organic semiconductors critical to optoelectronics.

  16. Tracking conformational dynamics of polypeptides by non-linear electronic spectroscopy of aromatic residues: a first principles simulation study

    PubMed Central

    Beccara, Silvio a; Rivalta, Ivan; Cerullo, Giulio

    2014-01-01

    The ability of non-linear electronic spectroscopy to track folding/unfolding processes of proteins in solution by monitoring aromatic interactions is investigated by first-principle simulations of two-dimensional (2D) electronic spectra of a model peptide. A dominant reaction pathway approach is employed to determine the unfolding pathway of a tetrapeptide, connecting the initial folded configuration with stacked aromatic side chains and the final unfolded state with distant non-interacting aromatic residues. π-stacking and excitonic coupling effects are included via ab-initio simulations based on multiconfigurational methods within a hybrid QM/MM scheme. We show that linear absorption spectroscopy in the ultraviolet (UV) is unable to resolve the unstacking dynamics characterized by the three-step process: T-shaped→twisted offset stacking→unstacking. Conversely, pump-probe spectroscopy can be used to resolve aromatic interactions by probing in the visible (Vis) the excited state absorptions (ESA) that involve charge transfer (CT) states. 2DUV spectroscopy offers the highest sensitivity to the unfolding process, providing the disentanglement of ESA signals belonging to different aromatic chromophores and high correlation between the conformational dynamics and the quartic splitting. PMID:25145908

  17. The effect of moisture on the structures and properties of lead halide perovskites: a first-principles theoretical investigation.

    PubMed

    Zhang, Lei; Ju, Ming-Gang; Liang, WanZhen

    2016-08-17

    With efficiencies exceeding 20% and low production costs, lead halide perovskite solar cells (PSCs) have become potential candidates for future commercial applications. However, there are serious concerns about their long-term stability and environmental friendliness, heavily related to their commercial viability. Herein, we present a theoretical investigation based on the ab initio molecular dynamics (AIMD) simulations and the first-principles density functional theory (DFT) calculations to investigate the effects of sunlight and moisture on the structures and properties of MAPbI3 perovskites. AIMD simulations have been performed to simulate the impact of a few water molecules on the structures of MAPbI3 surfaces terminated in three different ways. The evolution of geometric and electronic structures as well as the absorption spectra has been shown. It is found that the PbI2-terminated surface is the most stable while both the MAI-terminated and PbI2-defective surfaces undergo structural reconstruction, leading to the formation of hydrated compounds in a humid environment. The moisture-induced weakening of photoabsorption is closely related to the formation of hydrated species, and the hydrated crystals MAPbI3·H2O and MA4PbI6·2H2O scarcely absorb the visible light. The electronic excitation in the bare and water-absorbed MAPbI3 nanoparticles tends to weaken Pb-I bonds, especially those around water molecules, and the maximal decrease of photoexcitation-induced bond order can reach up to 20% in the excited state in which the water molecules are involved in the electronic excitation, indicating the accelerated decomposition of perovskites in the presence of sunlight and moisture. This work is valuable for understanding the mechanism of chemical or photochemical instability of MAPbI3 perovskites in the presence of moisture. PMID:27499005

  18. Two-Dimensional Electronic Spectroscopy of Benzene, Phenol, and Their Dimer: An Efficient First-Principles Simulation Protocol.

    PubMed

    Nenov, Artur; Mukamel, Shaul; Garavelli, Marco; Rivalta, Ivan

    2015-08-11

    First-principles simulations of two-dimensional electronic spectroscopy in the ultraviolet region (2DUV) require computationally demanding multiconfigurational approaches that can resolve doubly excited and charge transfer states, the spectroscopic fingerprints of coupled UV-active chromophores. Here, we propose an efficient approach to reduce the computational cost of accurate simulations of 2DUV spectra of benzene, phenol, and their dimer (i.e., the minimal models for studying electronic coupling of UV-chromophores in proteins). We first establish the multiconfigurational recipe with the highest accuracy by comparison with experimental data, providing reference gas-phase transition energies and dipole moments that can be used to construct exciton Hamiltonians involving high-lying excited states. We show that by reducing the active spaces and the number of configuration state functions within restricted active space schemes, the computational cost can be significantly decreased without loss of accuracy in predicting 2DUV spectra. The proposed recipe has been successfully tested on a realistic model proteic system in water. Accounting for line broadening due to thermal and solvent-induced fluctuations allows for direct comparison with experiments. PMID:26574458

  19. X-ray photoelectron spectroscopy analysis of boron defects in silicon crystal: A first-principles study

    NASA Astrophysics Data System (ADS)

    Yamauchi, Jun; Yoshimoto, Yoshihide; Suwa, Yuji

    2016-05-01

    We carried out a comprehensive study on the B 1s core-level X-ray photoelectron spectroscopy (XPS) binding energies and formation energies for boron defects in crystalline silicon by first-principles calculation with careful evaluation of the local potential boundary condition for the model system using the supercell corresponding to 1000 Si atoms. It is reconfirmed that the cubo-octahedral B12 cluster in silicon crystal is unstable and exists at the saddle point decaying to the icosahedral and S4 B12 clusters. The electrically active clusters without any postannealing of ion-implanted Si are identified as icosahedral B12 clusters. The experimentally proposed threefold coordinated B is also identified as a ⟨ 001 ⟩ B - Si defect. For an as-doped sample prepared by plasma doping, the calculated XPS spectra for complexes consisting of vacancies and substitutional B atoms are consistent with the experimental spectra. It is proposed that, assuming that the XPS peak at 187.1 eV is due to substitutional B (Bs), the experimental XPS peaks at 187.9 and 186.7 eV correspond to interstitial B at the H-site and ⟨ 001 ⟩ B - Si defects, respectively. In the annealed samples, the complex of Bs and interstitial Si near the T-site is proposed as a candidate for the experimental XPS peak at 188.3 eV.

  20. Mg-25 ultra-high field solid state NMR spectroscopy and first principles calculations of magnesium compounds.

    PubMed

    Pallister, Peter J; Moudrakovski, Igor L; Ripmeester, John A

    2009-12-28

    Due to sensitivity problems, (25)Mg remains a largely under-explored nucleus in solid state NMR spectroscopy. In this work at an ultrahigh magnetic field of 21.1 T, we have studied at natural abundance the (25)Mg solid state (SS) NMR spectra for a number of previously unreported magnesium compounds with known crystal structures. Some previously reported compounds have been revisited to clarify the spectra that were obtained at lower fields and were either not sufficiently resolved, or misinterpreted. First principles calculations of the (25)Mg SS NMR parameters have been carried out using plane wave basis sets and periodic boundary conditions (CASTEP) and the results are compared with experimental data. The calculations produce the (25)Mg absolute shielding scale and give us insight into the relationship between the NMR and structural parameters. At 21.1 T the effects of the quadrupolar interactions are reduced significantly and the sensitivity and accuracy in determining chemicals shifts and quadrupole coupling parameters improve dramatically. Although T(1) measurements were not performed explicitly, these proved to be longer than assumed in much of the previously reported work. We demonstrate that the chemical shift range of magnesium in diamagnetic compounds may approach 200 ppm. Most commonly, however, the observed shifts are between -15 and +25 ppm. Quadrupolar effects dominate the (25)Mg spectra of magnesium cations in non-cubic environments. The chemical shift anisotropy appears to be rather small and only in a few cases could the contribution of the CSA be detected reliably. A good correspondence between the calculated shielding constants and experimental chemical shifts was obtained, demonstrating the good potential of computational methods in spectroscopic assignments of solid state (25)Mg NMR spectroscopy. PMID:20024420

  1. Silver in geological fluids from in situ X-ray absorption spectroscopy and first-principles molecular dynamics

    NASA Astrophysics Data System (ADS)

    Pokrovski, Gleb S.; Roux, Jacques; Ferlat, Guillaume; Jonchiere, Romain; Seitsonen, Ari P.; Vuilleumier, Rodolphe; Hazemann, Jean-Louis

    2013-04-01

    The molecular structure and stability of species formed by silver in aqueous saline solutions typical of hydrothermal settings were quantified using in situ X-ray absorption spectroscopy (XAS) measurements, quantum-chemical modeling of near-edge absorption spectra (XANES) and extended fine structure spectra (EXAFS), and first-principles molecular dynamics (FPMD). Results show that in nitrate-bearing acidic solutions to at least 200 °C, silver speciation is dominated by the hydrated Ag+ cation surrounded by 4-6 water molecules in its nearest coordination shell with mean Ag-O distances of 2.32 ± 0.02 Å. In NaCl-bearing acidic aqueous solutions of total Cl concentration from 0.7 to 5.9 mol/kg H2O (m) at temperatures from 200 to 450 °C and pressures to 750 bar, the dominant species are the di-chloride complex AgCl2- with Ag-Cl distances of 2.40 ± 0.02 Å and Cl-Ag-Cl angle of 160 ± 10°, and the tri-chloride complex AgCl32- of a triangular structure and mean Ag-Cl distances of 2.60 ± 0.05 Å. With increasing temperature, the contribution of the tri-chloride species decreases from ˜50% of total dissolved Ag in the most concentrated solution (5.9m Cl) at 200 °C to less than 10-20% at supercritical temperatures for all investigated solutions, so that AgCl2- becomes by far the dominant Ag-bearing species at conditions typical of hydrothermal-magmatic fluids. Both di- and tri-chloride species exhibit outer-sphere interactions with the solvent as shown by the detection, using FPMD modeling, of H2O, Cl-, and Na+ at distances of 3-4 Å from the silver atom. The species fractions derived from XAS and FPMD analyses, and total AgCl(s) solubilities, measured in situ in this work from the absorption edge height of XAS spectra, are in accord with thermodynamic predictions using the stability constants of AgCl2- and AgCl32- from Akinfiev and Zotov (2001) and Zotov et al. (1995), respectively, which are based on extensive previous AgCl(s) solubility measurements. These data

  2. Nonequilibrium optical properties in semiconductors from first principles: A combined theoretical and experimental study of bulk silicon

    NASA Astrophysics Data System (ADS)

    Sangalli, Davide; Dal Conte, Stefano; Manzoni, Cristian; Cerullo, Giulio; Marini, Andrea

    2016-05-01

    The calculation of the equilibrium optical properties of bulk silicon by using the Bethe-Salpeter equation solved in the Kohn-Sham basis represents a cornerstone in the development of an ab-initio approach to the optical and electronic properties of materials. Nevertheless, calculations of the transient optical spectrum using the same efficient and successful scheme are scarce. We report, here, a joint theoretical and experimental study of the transient reflectivity spectrum of bulk silicon. Femtosecond transient reflectivity is compared to a parameter-free calculation based on the nonequilibrium Bethe-Salpeter equation. By providing an accurate description of the experimental results we disclose the different phenomena that determine the transient optical response of a semiconductor. We give a parameter-free interpretation of concepts such as bleaching, photoinduced absorption, and stimulated emission, beyond the Fermi golden rule. We also introduce the concept of optical gap renormalization, as a generalization of the known mechanism of band gap renormalization. The present scheme successfully describes the case of bulk silicon, showing its universality and accuracy.

  3. A First-Principles Theoretical Study on the Thermoelectric Properties of the Compound Cu5AlSn2S8

    NASA Astrophysics Data System (ADS)

    Li, Weijian; Zhou, Chenyi; Li, Liangliang

    2016-03-01

    A new compound of Cu5AlSn2S8, which contained earth-abundant and environment-friendly elements and had a diamond-like crystal structure, was designed, and its electronic structure and thermoelectric transport properties from 300 K to 700 K were investigated by first-principles calculations, Boltzmann transport equations, and a modified Slack's model. The largest power factors of Cu5AlSn2S8 at 700 K were 47.5 × 1010 W m-1 K-2 s-1 and 14.7 × 1010 W m-1 K-2 s-1 for p- and n-type semiconductors, respectively. The lattice thermal conductivity of Cu5AlSn2S8 was calculated with its shear modulus and isothermal bulk modulus, which were also obtained by first-principles calculations. The lattice thermal conductivity was 0.9-2.2 W m-1 K-1 from 300 K to 700 K, relatively low among thermoelectric compounds. This theoretical study showed that Cu5AlSn2S8 could be a potential thermoelectric material.

  4. A perfect wetting of Mg monolayer on Ag(111) under atomic scale investigation: First principles calculations, scanning tunneling microscopy, and Auger spectroscopy

    NASA Astrophysics Data System (ADS)

    Migaou, Amani; Sarpi, Brice; Guiltat, Mathilde; Payen, Kevin; Daineche, Rachid; Landa, Georges; Vizzini, Sébastien; Hémeryck, Anne

    2016-05-01

    First principles calculations, scanning tunneling microscopy, and Auger spectroscopy experiments of the adsorption of Mg on Ag(111) substrate are conducted. This detailed study reveals that an atomic scale controlled deposition of a metallic Mg monolayer perfectly wets the silver substrate without any alloy formation at the interface at room temperature. A liquid-like behavior of the Mg species on the Ag substrate is highlighted as no dot formation is observed when coverage increases. Finally a layer-by-layer growth mode of Mg on Ag(111) can be predicted, thanks to density functional theory calculations as observed experimentally.

  5. A perfect wetting of Mg monolayer on Ag(111) under atomic scale investigation: First principles calculations, scanning tunneling microscopy, and Auger spectroscopy.

    PubMed

    Migaou, Amani; Sarpi, Brice; Guiltat, Mathilde; Payen, Kevin; Daineche, Rachid; Landa, Georges; Vizzini, Sébastien; Hémeryck, Anne

    2016-05-21

    First principles calculations, scanning tunneling microscopy, and Auger spectroscopy experiments of the adsorption of Mg on Ag(111) substrate are conducted. This detailed study reveals that an atomic scale controlled deposition of a metallic Mg monolayer perfectly wets the silver substrate without any alloy formation at the interface at room temperature. A liquid-like behavior of the Mg species on the Ag substrate is highlighted as no dot formation is observed when coverage increases. Finally a layer-by-layer growth mode of Mg on Ag(111) can be predicted, thanks to density functional theory calculations as observed experimentally. PMID:27208966

  6. Theoretical oxidation state analysis of Ru-(bpy){sub 3}: Influence of water solvation and Hubbard correction in first-principles calculations

    SciTech Connect

    Reeves, Kyle G.; Kanai, Yosuke

    2014-07-14

    Oxidation state is a powerful concept that is widely used in chemistry and materials physics, although the concept itself is arguably ill-defined quantum mechanically. In this work, we present impartial comparison of four, well-recognized theoretical approaches based on Lowdin atomic orbital projection, Bader decomposition, maximally localized Wannier function, and occupation matrix diagonalization, for assessing how well transition metal oxidation states can be characterized. Here, we study a representative molecular complex, tris(bipyridine)ruthenium. We also consider the influence of water solvation through first-principles molecular dynamics as well as the improved electronic structure description for strongly correlated d-electrons by including Hubbard correction in density functional theory calculations.

  7. Theoretical oxidation state analysis of Ru-(bpy)3: Influence of water solvation and Hubbard correction in first-principles calculations

    NASA Astrophysics Data System (ADS)

    Reeves, Kyle G.; Kanai, Yosuke

    2014-07-01

    Oxidation state is a powerful concept that is widely used in chemistry and materials physics, although the concept itself is arguably ill-defined quantum mechanically. In this work, we present impartial comparison of four, well-recognized theoretical approaches based on Lowdin atomic orbital projection, Bader decomposition, maximally localized Wannier function, and occupation matrix diagonalization, for assessing how well transition metal oxidation states can be characterized. Here, we study a representative molecular complex, tris(bipyridine)ruthenium. We also consider the influence of water solvation through first-principles molecular dynamics as well as the improved electronic structure description for strongly correlated d-electrons by including Hubbard correction in density functional theory calculations.

  8. Structural transformation during Li/Na insertion and theoretical cyclic voltammetry of the δ-NH4V4O10 electrode: a first-principles study.

    PubMed

    Sarkar, Tanmay; Kumar, Parveen; Bharadwaj, Mridula Dixit; Waghmare, Umesh

    2016-04-14

    A double layer δ-NH4V4O10, due to its high energy storage capacity and excellent rate capability, is a very promising cathode material for Li-ion and Na-ion batteries for large-scale renewable energy storage in transportation and smart grids. While it possesses better stability, and higher ionic and electronic conductivity than the most widely explored V2O5, the mechanisms of its cyclability are yet to be understood. Here, we present a theoretical cyclic voltammetry as a tool based on first-principles calculations, and uncover structural transformations that occur during Li(+)/Na(+) insertion (x) into (Lix/Nax)NH4V4O10. Structural distortions associated with single-phase and multi-phase structural changes during the insertion of Li(+)/Na(+), identified through the analysis of voltage profile and theoretical cyclic voltammetry are in agreement with the reported experimental electrochemical measurements on δ-NH4V4O10. We obtain an insight into its electronic structure with a lower band gap that is responsible for the high rate capability of (Lix/Nax) δ-NH4V4O10. The scheme of theoretical cyclic voltammetry presented here will be useful for addressing issues of cyclability and energy rate in other electrode materials. PMID:26996324

  9. Structure, Bonding, and Stability of Mercury Complexes with Thiolate and Thioether Ligands from High-Resolution XANES Spectroscopy and First-Principles Calculations.

    PubMed

    Manceau, Alain; Lemouchi, Cyprien; Rovezzi, Mauro; Lanson, Martine; Glatzel, Pieter; Nagy, Kathryn L; Gautier-Luneau, Isabelle; Joly, Yves; Enescu, Mironel

    2015-12-21

    We present results obtained from high energy-resolution L3-edge XANES spectroscopy and first-principles calculations for the structure, bonding, and stability of mercury(II) complexes with thiolate and thioether ligands in crystalline compounds, aqueous solution, and macromolecular natural organic matter (NOM). Core-to-valence XANES features that vary in intensity differentiate with unprecedented sensitivity the number and identity of Hg ligands and the geometry of the ligand environment. Post-Hartree-Fock XANES calculations, coupled with natural population analysis, performed on MP2-optimized Hg[(SR)2···(RSR)n] complexes show that the shape, position, and number of electronic transitions observed at high energy-resolution are directly correlated to the Hg and S (l,m)-projected empty densities of states and occupations of the hybridized Hg 6s and 5d valence orbitals. Linear two-coordination, the most common coordination geometry in mercury chemistry, yields a sharp 2p to 6s + 5d electronic transition. This transition varies in intensity for Hg bonded to thiol groups in macromolecular NOM. The intensity variation is explained by contributions from next-nearest, low-charge, thioether-type RSR ligands at 3.0-3.3 Å from Hg. Thus, Hg in NOM has two strong bonds to thiol S and k additional weak Hg···S contacts, or 2 + k coordination. The calculated stabilization energy is -5 kcal/mol per RSR ligand. Detection of distant ligands beyond the first coordination shell requires precise measurement of, and comparison to, spectra of reference compounds as well as accurate calculation of spectra for representative molecular models. The combined experimental and theoretical approaches described here for Hg can be applied to other closed-shell atoms, such as Ag(I) and Au(I). To facilitate further calculation of XANES spectra, experimental data, a new crystallographic structure of a key mercury thioether complex, Cartesian coordinates of the computed models, and examples of

  10. Structures and chemical bonding of B3O3-/0 and B3O3H-/0: A combined photoelectron spectroscopy and first-principles theory study

    NASA Astrophysics Data System (ADS)

    Zhao, Li-Juan; Tian, Wen-Juan; Ou, Ting; Xu, Hong-Guang; Feng, Gang; Xu, Xi-Ling; Zhai, Hua-Jin; Li, Si-Dian; Zheng, Wei-Jun

    2016-03-01

    We present a combined photoelectron spectroscopy and first-principles theory study on the structural and electronic properties and chemical bonding of B3O3-/0 and B3O3H-/0 clusters. The concerted experimental and theoretical data show that the global-minimum structures of B3O3 and B3O3H neutrals are very different from those of their anionic counterparts. The B3O3- anion is characterized to possess a V-shaped OB-B-BO chain with overall C2v symmetry (1A), in which the central B atom interacts with two equivalent boronyl (B≡O) terminals via B-B single bonds as well as with one O atom via a B=O double bond. The B3O3H- anion has a Cs (2A) structure, containing an asymmetric OB-B-OBO zig-zag chain and a terminal H atom interacting with the central B atom. In contrast, the C2v (1a) global minimum of B3O3 neutral contains a rhombic B2O2 ring with one B atom bonded to a BO terminal and that of neutral B3O3H (2a) is also of C2v symmetry, which is readily constructed from C2v (1a) by attaching a H atom to the opposite side of the BO group. The H atom in B3O3H-/0 (2A and 2a) prefers to interact terminally with a B atom, rather than with O. Chemical bonding analyses reveal a three-center four-electron (3c-4e) π hyperbond in the B3O3H- (2A) cluster and a four-center four-electron (4c-4e) π bond (that is, the so-called o-bond) in B3O3 (1a) and B3O3H (2a) neutral clusters.

  11. Structures and chemical bonding of B3O3 (-/0) and B3O3H(-/0): A combined photoelectron spectroscopy and first-principles theory study.

    PubMed

    Zhao, Li-Juan; Tian, Wen-Juan; Ou, Ting; Xu, Hong-Guang; Feng, Gang; Xu, Xi-Ling; Zhai, Hua-Jin; Li, Si-Dian; Zheng, Wei-Jun

    2016-03-28

    We present a combined photoelectron spectroscopy and first-principles theory study on the structural and electronic properties and chemical bonding of B3O3 (-/0) and B3O3H(-/0) clusters. The concerted experimental and theoretical data show that the global-minimum structures of B3O3 and B3O3H neutrals are very different from those of their anionic counterparts. The B3O3 (-) anion is characterized to possess a V-shaped OB-B-BO chain with overall C2 v symmetry (1A), in which the central B atom interacts with two equivalent boronyl (B≡O) terminals via B-B single bonds as well as with one O atom via a B=O double bond. The B3O3H(-) anion has a Cs (2A) structure, containing an asymmetric OB-B-OBO zig-zag chain and a terminal H atom interacting with the central B atom. In contrast, the C2 v (1a) global minimum of B3O3 neutral contains a rhombic B2O2 ring with one B atom bonded to a BO terminal and that of neutral B3O3H (2a) is also of C2 v symmetry, which is readily constructed from C2 v (1a) by attaching a H atom to the opposite side of the BO group. The H atom in B3O3H(-/0) (2A and 2a) prefers to interact terminally with a B atom, rather than with O. Chemical bonding analyses reveal a three-center four-electron (3c-4e) π hyperbond in the B3O3H(-) (2A) cluster and a four-center four-electron (4c-4e) π bond (that is, the so-called o-bond) in B3O3 (1a) and B3O3H (2a) neutral clusters. PMID:27036442

  12. Soft modes and anharmonicity in H3[Co (CN )6] : Raman spectroscopy and first-principles calculations

    NASA Astrophysics Data System (ADS)

    Mishra, K. K.; Chandra, Sharat; Salke, Nilesh P.; Achary, S. N.; Tyagi, A. K.; Rao, Rekha

    2015-10-01

    In situ high-pressure Raman spectroscopy and ab initio calculations are carried out to investigate the phase stability and the thermal expansion behavior of H3[Co (CN )6] . Raman studies at high pressures in a diamond anvil cell identify soft phonons and phase instability at 2.3 GPa. Evidence of pressure-induced amorphization is found at 11 GPa. The phonon frequencies and eigenvectors obtained from ab initio calculation are used to complement the observed phonon spectra and for assignment of Raman modes. The computed eigenvector displacement patterns indicate that the soft modes correspond to the CN-librational vibrations (Eg mode) of the Co-CN-H-NC-Co linkages and their Grüneisen parameters are found to be negative, in agreement with our measured values. The thermal expansion coefficient (15.6 ×10-6K-1 ) calculated using our computed mode Grüneisen parameters is found to be in good agreement with the reported value (20 ×10-6K-1 ). Temperature-dependent phonon spectra down to 77 K are used to obtain the anharmonicities of different modes.

  13. Theoretical analysis of structure and formation energy of impurity-doped Mg2Si: Comparison of first-principles codes for material properties

    NASA Astrophysics Data System (ADS)

    Hirayama, Naomi; Iida, Tsutomu; Funashima, Hiroki; Morioka, Shunsuke; Sakamoto, Mariko; Nishio, Keishi; Kogo, Yasuo; Takanashi, Yoshifumi; Hamada, Noriaki

    2015-07-01

    We theoretically investigate the impurity doping effects on the structural parameters such as lattice constant, atomic positions, and site preferences of impurity dopants for Al-doped magnesium silicide (Mg2Si) crystal using the first-principles calculation methods. We present comparison between several codes: ABCAP, Quantum Espresso, and Machikaneyama2002 (Akai KKR), which are based on the full-potential linearized augmented plane-wave method, the pseudopotential method, and KKR/GGA Green’s function method, respectively. As a result, any codes used in the present study exhibit qualitative consistency both in the dependence of the lattice constants on the doping concentration and the energetic preference of the Al atom for the following sites; substitutional Si and Mg sites, and interstitial 4b site; in particular, ABCAP, which is based on the all-electron full-potential method, and Quantum Espresso, which is a code of the pseudopotential method, produce closely-resemble calculation results. We also discuss the effects of local atomic displacement owing to the presence of impurities to the structural parameters of a bulk. Using the analytical method considering the local atomic displacement, moreover, we evaluate the formation energy of Na- and B-doped systems as examples of p-type doping in order to examine the possilbility of realizing p-type Mg2Si.

  14. Anharmonic Theoretical Vibrational Spectroscopy of Polypeptides.

    PubMed

    Panek, Paweł T; Jacob, Christoph R

    2016-08-18

    Because of the size of polypeptides and proteins, the quantum-chemical prediction of their vibrational spectra presents an exceptionally challenging task. Here, we address one of these challenges, namely, the inclusion of anharmonicities. By performing the expansion of the potential energy surface in localized-mode coordinates instead of the normal-mode coordinates, it becomes possible to calculate anharmonic vibrational spectra of polypeptides efficiently and reliably. We apply this approach to calculate the infrared, Raman, and Raman optical activity spectra of helical alanine polypeptides consisting of up to 20 amino acids. We find that while anharmonicities do not alter the band shapes, simple scaling procedures cannot account for the different shifts found for the individual bands. This closes an important gap in theoretical vibrational spectroscopy by making it possible to quantify the anharmonic contributions and opens the door to a first-principles calculation of multidimensional vibrational spectra. PMID:27472016

  15. 5 f -Shell correlation effects in dioxides of light actinides studied by O 1s x-ray absorption and emission spectroscopies and first-principles calculations

    NASA Astrophysics Data System (ADS)

    Modin, A.; Suzuki, M.-T.; Vegelius, J.; Yun, Y.; Shuh, D. K.; Werme, L.; Nordgren, J.; Oppeneer, P. M.; Butorin, S. M.

    2015-08-01

    Soft x-ray emission and absorption spectroscopic data are reported for the O 1s region of a single crystal of UO2, a polycrystalline NpO2 sample, and a single crystal of PuO2. The experimental data are interpreted using first-principles correlated-electron calculations within the framework of the density functional theory with added Coulomb U interaction (DFT+U). A detailed analysis regarding the origin of different structures in the x-ray emission and x-ray absorption spectra is given and the effect of varying the intra-atomic Coulomb interaction-U for the 5 f electrons is investigated. Our data indicate that O 1s x-ray absorption and emission spectroscopies can, in combination with DFT+U calculations, successfully be used to study 5 f -shell Coulomb correlation effects in dioxides of light actinides. The values for the Coulomb U parameter in these dioxides are derived to be in the range of 4-5 eV.

  16. Probing silicon and aluminium chemical environments in silicate and aluminosilicate glasses by solid state NMR spectroscopy and accurate first-principles calculations

    NASA Astrophysics Data System (ADS)

    Gambuzzi, Elisa; Pedone, Alfonso; Menziani, Maria Cristina; Angeli, Frédéric; Caurant, Daniel; Charpentier, Thibault

    2014-01-01

    Silicon and aluminium chemical environments in silicate and aluminosilicate glasses with compositions 60SiO2·20Na2O·20CaO (CSN), 60SiO2·20Al2O3·20CaO (CAS), 78SiO2·11Al2O3·11Na2O (NAS) and 60SiO2·10Al2O3·10Na2O·20CaO (CASN) have been investigated by 27Al and 29Si solid state magic angle spinning (MAS) and multiple quantum MAS (MQMAS) nuclear magnetic resonance (NMR) experiments. To interpret the NMR data, first-principles calculations using density functional theory were performed on structural models of these glasses. These models were generated by Shell-model molecular dynamics (MD) simulations. The theoretical NMR parameters and spectra were computed using the gauge including projected augmented wave (GIPAW) method and spin-effective Hamiltonians, respectively. This synergetic computational-experimental approach offers a clear structural characterization of these glasses, particularly in terms of network polymerization, chemical disorder (i.e. Si and Al distribution in second coordination sphere) and modifier cation distributions. The relationships between the local structural environments and the 29Si and 27Al NMR parameters are highlighted, and show that: (i) the isotropic chemical shift of both 29Si and 27Al increases of about +5 ppm for each Al added in the second sphere and (ii) both the 27Al and 29Si isotropic chemical shifts linearly decrease with the reduction of the average Si/Al-O-T bond angle. Conversely, 27Al and 29Si NMR parameters are much less sensitive to the connectivity with triple bridging oxygen atoms, precluding their indirect detection from 27Al and 29Si NMR.

  17. First principles theoretical study of the hole-assisted conversion of CO to CO{sub 2} on the anatase TiO{sub 2}(101) surface

    SciTech Connect

    Wanbayor, Raina; Deak, Peter; Frauenheim, Thomas; Ruangpornvisuti, Vithaya

    2011-03-14

    First principles density functional theory calculations were carried out to investigate the adsorption and oxidation of CO on the positively charged (101) surface of anatase, as well as the desorption of CO{sub 2} from it. We find that the energy gain on adsorption covers the activation energy required for the oxidation, while the energy gain on the latter is sufficient for the desorption of CO{sub 2}, leaving an oxygen vacancy behind. Molecular dynamics simulations indicate that the process can be spontaneous at room temperature. The oxidation process described here happens only in the presence of the hole. The possibility of a photocatalytic cycle is discussed assuming electron scavenging by oxygen.

  18. Theoretical methods for ultrafast spectroscopy.

    PubMed

    Marquardt, Roberto

    2013-05-10

    Time-resolved spectroscopy in the femtosecond and attosecond time domain is a tool to unravel the dynamics of nuclear and electronic motion in molecular systems. Theoretical insight into the underlying physical processes is ideally gained by solving the time-dependent Schrödinger equation. In this work, methods currently used to solve this equation are reviewed in a compact presentation. These methods involve numerical representations of wavefunctions and operators, the calculation of time evolution operators, the setting up of the Hamiltonian operators and the types of coordinates to be used hereto. The advantages and disadvantages of some methods are discussed. PMID:23606322

  19. Surface enhanced vibrational spectroscopy and first-principles study of L-cysteine adsorption on noble trimetallic Au/Pt@Rh clusters.

    PubMed

    Loganathan, B; Chandraboss, V L; Senthilvelan, S; Karthikeyan, B

    2015-09-01

    The Rh shell of the Au/Pt/Rh trimetallic nanoparticles induces a wide variety of interesting surface reactions by allowing the adsorption of amino acids like L-cysteine (L-Cys). We present a snapshot of theoretical and experimental investigation of L-Cys adsorption on the surface of noble trimetallic Au/Pt@Rh colloidal nanocomposites. Density functional theoretical (DFT) investigations of L-Cys interaction with the Rhodium (Rh) shell of a trimetallic Au/Pt@Rh cluster in terms of geometry, binding energy (E(B)), binding site, energy gap (E(g)), electronic and spectral properties have been performed. L-Cys establishes a strong interaction with the Rh shell. It binds to Rh by the S1-site, which makes a stable L-Cys-Rh surface complex. DFT can be taken as a valuable tool to assign the vibrational spectra of the adsorption of L-Cys on trimetallic Au/Pt@Rh colloidal nanocomposites and mono-metallic Rh nanoparticles. Surface-enhanced infrared spectroscopy (SEIRS) with L-Cys on a Rh6 cluster surface has been simulated for the first time. Experimental information on the L-Cys-Rh surface complex is included to examine the interaction. The experimental spectral observations are in good agreement with the simulated DFT results. Characterization of the synthesized trimetallic Au/Pt@Rh colloidal nanocomposites has been done by high-resolution transmission electron microscopy (HR-TEM) with selected area electron diffraction (SAED) pattern, energy dispersive X-ray (EDX) spectroscopy, dynamic light scattering (DLS) measurements, zeta potential, zeta deviation analysis and UV-visible (UV-Vis) spectroscopic studies. PMID:25650352

  20. Observing spin excitations in 3 d transition-metal adatoms on Pt(111) with inelastic scanning tunneling spectroscopy: A first-principles perspective

    NASA Astrophysics Data System (ADS)

    Schweflinghaus, Benedikt; dos Santos Dias, Manuel; Lounis, Samir

    2016-01-01

    Spin excitations in atomic-scale nanostructures have been investigated with inelastic scanning tunneling spectroscopy, sometimes with conflicting results. In this work, we present a theoretical viewpoint on a recent experimental controversy regarding the spin excitations of Co adatoms on Pt(111). While one group [Balashov et al., Phys. Rev. Lett. 102, 257203 (2009), 10.1103/PhysRevLett.102.257203] claims to have detected them, another group reported their observation only after the hydrogenation of the Co adatom [Dubout et al., Phys. Rev. Lett. 114, 106807 (2015), 10.1103/PhysRevLett.114.106807]. Utilizing time-dependent density functional theory in combination with many-body perturbation theory, we demonstrate that, although inelastic spin excitations are possible for Cr, Mn, Fe, and Co adatoms, their efficiency differs. While the excitation signature is less pronounced for Mn and Co adatoms, it is larger for Cr and Fe adatoms. We find that the tunneling matrix elements or the tunneling cross-section related to the nature and symmetry of the relevant electronic states are more favorable for triggering the spin excitations in Fe than in Co. An enhancement of the tunneling and of the inelastic spectra is possible by attaching hydrogen to the adatom at the appropriate position.

  1. The ground state and electronic structure of Gd@C{sub 82}: A systematic theoretical investigation of first principle density functionals

    SciTech Connect

    Dai, Xing; Gao, Yang; Xin, Minsi; Wang, Zhigang; Zhou, Ruhong

    2014-12-28

    As a representative lanthanide endohedral metallofullerene, Gd@C{sub 82} has attracted a widespread attention among theorists and experimentalists ever since its first synthesis. Through comprehensive comparisons and discussions, as well as references to the latest high precision experiments, we evaluated the performance of different computational methods. Our results showed that the appropriate choice of the exchange-correlation functionals is the decisive factor to accurately predict both geometric and electronic structures for Gd@C{sub 82}. The electronic structure of the ground state and energy gap between the septet ground state and the nonet low-lying state obtained from pure density functional methods, such as PBE and PW91, are in good agreement with current experiment. Unlike pure functionals, the popularly used hybrid functionals in previous studies, such as B3LYP, could infer the qualitative correct ground state only when small basis set for C atoms is employed. Furthermore, we also highlighted that other geometric structures of Gd@C{sub 82} with the Gd staying at different positions are either not stable or with higher energies. This work should provide some useful references for various theoretical methodologies in further density functional studies on Gd@C{sub 82} and its derivatives in the future.

  2. Probing the local environment of substitutional Al^{3+} in goethite using X-ray absorption spectroscopy and first-principles calculations

    NASA Astrophysics Data System (ADS)

    Ducher, Manoj; Blanchard, Marc; Vantelon, Delphine; Nemausat, Ruidy; Cabaret, Delphine

    2016-03-01

    We present experimental and calculated Al K-edge X-ray absorption near-edge structure (XANES) spectra of aluminous goethite with 10-33 mol% of AlOOH and diaspore. Significant changes are observed experimentally in the near- and pre-edge regions with increasing Al concentration in goethite. First-principles calculations based on density functional theory (DFT) reproduce successfully the experimental trends. This permits to identify the electronic and structural parameters controlling the spectral features and to improve our knowledge of the local environment of {Al}^{3+} in the goethite-diaspore partial solid solution. In the near-edge region, the larger peak spacing in diaspore compared to Al-bearing goethite is related to the nature (Fe or Al) of the first cation neighbours around the absorbing Al atom (Al*). The intensity ratio of the two near-edge peaks, which decreases with Al concentration, is correlated with the average distance of the first cations around Al* and the distortion of the {AlO}_6 octahedron. Finally, the decrease in intensity of the pre-edge features with increasing Al concentration is due to the smaller number of Fe atoms in the local environment of Al since Al atoms tend to cluster. In addition, it is found that the pre-edge features of the Al K-edge XANES spectra enable to probe indirectly empty 3 d states of Fe. Energetic, structural and spectroscopic results suggest that for Al concentrations around 10 mol%, Al atoms can be considered as isolated, whereas above 25 mol%, Al clusters are more likely to occur.

  3. Atomic Description of the Interface between Silica and Alumina in Aluminosilicates through Dynamic Nuclear Polarization Surface-Enhanced NMR Spectroscopy and First-Principles Calculations

    PubMed Central

    2015-01-01

    Despite the widespread use of amorphous aluminosilicates (ASA) in various industrial catalysts, the nature of the interface between silica and alumina and the atomic structure of the catalytically active sites are still subject to debate. Here, by the use of dynamic nuclear polarization surface enhanced NMR spectroscopy (DNP SENS) and density functional theory (DFT) calculations, we show that on silica and alumina surfaces, molecular aluminum and silicon precursors are, respectively, preferentially grafted on sites that enable the formation of Al(IV) and Si(IV) interfacial sites. We also link the genesis of Brønsted acidity to the surface coverage of aluminum and silicon on silica and alumina, respectively. PMID:26244620

  4. Atomic Description of the Interface between Silica and Alumina in Aluminosilicates through Dynamic Nuclear Polarization Surface-Enhanced NMR Spectroscopy and First-Principles Calculations.

    PubMed

    Valla, Maxence; Rossini, Aaron J; Caillot, Maxime; Chizallet, Céline; Raybaud, Pascal; Digne, Mathieu; Chaumonnot, Alexandra; Lesage, Anne; Emsley, Lyndon; van Bokhoven, Jeroen A; Copéret, Christophe

    2015-08-26

    Despite the widespread use of amorphous aluminosilicates (ASA) in various industrial catalysts, the nature of the interface between silica and alumina and the atomic structure of the catalytically active sites are still subject to debate. Here, by the use of dynamic nuclear polarization surface enhanced NMR spectroscopy (DNP SENS) and density functional theory (DFT) calculations, we show that on silica and alumina surfaces, molecular aluminum and silicon precursors are, respectively, preferentially grafted on sites that enable the formation of Al(IV) and Si(IV) interfacial sites. We also link the genesis of Brønsted acidity to the surface coverage of aluminum and silicon on silica and alumina, respectively. PMID:26244620

  5. Polymorphism of resorcinol explored by complementary vibrational spectroscopy (FT-RS, THz-TDS, INS) and first-principles solid-state computations (plane-wave DFT).

    PubMed

    Drużbicki, Kacper; Mikuli, Edward; Pałka, Norbert; Zalewski, Sławomir; Ossowska-Chruściel, Mirosława D

    2015-01-29

    The polymorphism of resorcinol has been complementary studied by combining Raman, time-domain terahertz, and inelastic neutron scattering spectroscopy with modern solid-state density functional theory (DFT) calculations. The spectral differences, emerging from the temperature-induced structural phase transition, have been successfully interpreted with an emphasis on the low-wavenumber range. The given interpretation is based on the plane-wave DFT computations, providing an excellent overall reproduction of both wavenumbers and intensities and revealing the source of the observed spectral differences. The performance of the generalized gradient approximation (GGA) functionals in prediction of the structural parameters and the vibrational spectra of the normal-pressure polymorphs of resorcinol has been extensively examined. The results show that the standard Perdew, Burke, and Ernzerhof (PBE) approach along with its "hard" revised form tends to be superior if compared to the "soft" GGA approximation. PMID:25564699

  6. Electronic and optical properties of ceramic Sc2O3 and Y2O3: Compton spectroscopy and first principles calculations

    NASA Astrophysics Data System (ADS)

    Ahuja, Babu Lal; Sharma, Sonu; Heda, Narayan Lal; Tiwari, Shailja; Kumar, Kishor; Meena, Bhoor Singh; Bhatt, Samir

    2016-05-01

    We present the first-ever experimental Compton profiles (CPs) of Sc2O3 and Y2O3 using 740 GBq 137Cs Compton spectrometer. The experimental momentum densities have been compared with the theoretical CPs computed using linear combination of atomic orbitals (LCAO) within density functional theory (DFT). Further, the energy bands, density of states (DOS) and Mulliken's population (MP) data have been calculated using LCAO method with different exchange and correlation approximations. In addition, the energy bands, DOS, valence charge density (VCD), dielectric function, absorption coefficient and refractive index have also been computed using full potential linearized augmented plane wave (FP-LAPW) method with revised functional of Perdew-Becke-Ernzerhof for solids (PBEsol) and modified Becke Johnson (mBJ) approximations. Both the ab-initio calculations predict wide band gaps in Sc2O3 and Y2O3. The band gaps deduced from FP-LAPW (with mBJ) are found to be close to available experimental data. The VCD and MP data show more ionic character of Sc2O3 than Y2O3. The ceramic properties of both the sesquioxides are explained in terms of their electronic and optical properties.

  7. 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.

  8. 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

  9. Nature and structure of aluminum surface sites grafted on silica from a combination of high-field aluminum-27 solid-state NMR spectroscopy and first-principles calculations.

    PubMed

    Kerber, Rachel Nathaniel; Kermagoret, Anthony; Callens, Emmanuel; Florian, Pierre; Massiot, Dominique; Lesage, Anne; Copéret, Christophe; Delbecq, Françoise; Rozanska, Xavier; Sautet, Philippe

    2012-04-18

    The determination of the nature and structure of surface sites after chemical modification of large surface area oxides such as silica is a key point for many applications and challenging from a spectroscopic point of view. This has been, for instance, a long-standing problem for silica reacted with alkylaluminum compounds, a system typically studied as a model for a supported methylaluminoxane and aluminum cocatalyst. While (27)Al solid-state NMR spectroscopy would be a method of choice, it has been difficult to apply this technique because of large quadrupolar broadenings. Here, from a combined use of the highest stable field NMR instruments (17.6, 20.0, and 23.5 T) and ultrafast magic angle spinning (>60 kHz), high-quality spectra were obtained, allowing isotropic chemical shifts, quadrupolar couplings, and asymmetric parameters to be extracted. Combined with first-principles calculations, these NMR signatures were then assigned to actual structures of surface aluminum sites. For silica (here SBA-15) reacted with triethylaluminum, the surface sites are in fact mainly dinuclear Al species, grafted on the silica surface via either two terminal or two bridging siloxy ligands. Tetrahedral sites, resulting from the incorporation of Al inside the silica matrix, are also seen as minor species. No evidence for putative tri-coordinated Al atoms has been found. PMID:22440230

  10. 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

  11. Theoretical aspects of light meson spectroscopy

    SciTech Connect

    Barnes, T. |

    1995-12-31

    In this pedagogical review the authors discuss the theoretical understanding of light hadron spectroscopy in terms of QCD and the quark model. They begin with a summary of the known and surmised properties of QCD and confinement. Following this they review the nonrelativistic quark potential model for q{anti q} mesons and discuss the quarkonium spectrum and methods for identifying q{anti q} states. Finally, they review theoretical expectations for non-q{anti q} states (glueballs, hybrids and multiquark systems) and the status of experimental candidates for these states.

  12. Single molecule dissociation by tunneling electrons in NO-Co-Porphyrin complex on Au(111): A novel mechanics revealed by scanning tunneling spectroscopy and first-principles thermodynamic simulation

    NASA Astrophysics Data System (ADS)

    Chang, Yunhee; Kim, Howon; Lee, Eui-Sup; Jang, Won-Jun; Kim, Yong-Hyun; Kahng, Se-Jong

    2015-03-01

    To microscopically understand the mechanisms of electron-induced NO dissociations, we performed first-principles density-functional theory (DFT) calculations for NO-CoTPP on Au(111). We explain the scanning tunneling microscopy (STM) results that the dissociations of NO were induced by both positive and negative voltage pulses with threshold voltages, +0.68 V and 0.74 V, respectively, at 0.1 nA tunneling current, showing power law relations between tunneling current and dissociation yield. To evaluate first-principles thermodynamics of the NO dissociation, we considered not only adsorption-desorption energetics, zero-point energy, and vibrational free energy at experiment temperature from first-principles, but also the chemical potential of NO gas at the cryogenic ultra-high vacuum condition. Using first-principles thermodynamics for the NO dissociation, we argue that the dissociations are induced with inelastic electron tunneling through molecular orbital resonances.

  13. 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.

  14. 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

  15. 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

  16. Characterization of the Dynamics in the Protonic Conductor CsH2PO4 by 17O Solid-State NMR Spectroscopy and First-Principles Calculations: Correlating Phosphate and Protonic Motion

    PubMed Central

    2015-01-01

    17O NMR spectroscopy combined with first-principles calculations was employed to understand the local structure and dynamics of the phosphate ions and protons in the paraelectric phase of the proton conductor CsH2PO4. For the room-temperature structure, the results confirm that one proton (H1) is localized in an asymmetric H-bond (between O1 donor and O2 acceptor oxygen atoms), whereas the H2 proton undergoes rapid exchange between two sites in a hydrogen bond with a symmetric double potential well at a rate ≥107 Hz. Variable-temperature 17O NMR spectra recorded from 22 to 214 °C were interpreted by considering different models for the rotation of the phosphate anions. At least two distinct rate constants for rotations about four pseudo C3 axes of the phosphate ion were required in order to achieve good agreement with the experimental data. An activation energy of 0.21 ± 0.06 eV was observed for rotation about the P–O1 axis, with a higher activation energy of 0.50 ± 0.07 eV being obtained for rotation about the P–O2, P–O3d, and P–O3a axes, with the superscripts denoting, respectively, dynamic donor and acceptor oxygen atoms of the H-bond. The higher activation energy of the second process is most likely associated with the cost of breaking an O1–H1 bond. The activation energy of this process is slightly lower than that obtained from the 1H exchange process (0.70 ± 0.07 eV) (Kim, G.; Blanc, F.; Hu, Y.-Y.; Grey, C. P. J. Phys. Chem. C2013, 117, 6504−6515) associated with the translational motion of the protons. The relationship between proton jumps and phosphate rotation was analyzed in detail by considering uncorrelated motion, motion of individual PO4 ions and the four connected/H-bonded protons, and concerted motions of adjacent phosphate units, mediated by proton hops. We conclude that, while phosphate rotations aid proton motion, not all phosphate rotations result in proton jumps. PMID:25732257

  17. First-principles and angle-resolved photoemission study of lithium doped metallic black phosphorous

    NASA Astrophysics Data System (ADS)

    Sanna, A.; Fedorov, A. V.; Verbitskiy, N. I.; Fink, J.; Krellner, C.; Petaccia, L.; Chikina, A.; Usachov, D. Yu; Grüneis, A.; Profeta, G.

    2016-06-01

    First principles calculations demonstrate the metallization of phosphorene by means of Li doping filling the unoccupied antibonding p z states. The electron–phonon coupling in the metallic phase is strong enough to eventually lead to a superconducting phase at T c = 17 K for LiP8 stoichiometry. Using angle-resolved photoemission spectroscopy we confirm that the surface of black phosphorus can be chemically functionalized using Li atoms which donate their 2s electron to the conduction band. The combined theoretical and experimental study demonstrates the semiconductor-metal transition indicating a feasible way to induce a superconducting phase in phosphorene and few-layer black phosphorus.

  18. 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.

  19. 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

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. Excitons and Davydov splitting in sexithiophene from first-principles many-body Green's function theory

    NASA Astrophysics Data System (ADS)

    Leng, Xia; Yin, Huabing; Liang, Dongmei; Ma, Yuchen

    2015-09-01

    Organic semiconductors have promising and broad applications in optoelectronics. Understanding their electronic excited states is important to help us control their spectroscopic properties and performance of devices. There have been a large amount of experimental investigations on spectroscopies of organic semiconductors, but theoretical calculation from first principles on this respect is still limited. Here, we use density functional theory (DFT) and many-body Green's function theory, which includes the GW method and Bethe-Salpeter equation, to study the electronic excited-state properties and spectroscopies of one prototypical organic semiconductor, sexithiophene. The exciton energies of sexithiophene in both the gas and bulk crystalline phases are very sensitive to the exchange-correlation functionals used in DFT for ground-state structure relaxation. We investigated the influence of dynamical screening in the electron-hole interaction on exciton energies, which is found to be very pronounced for triplet excitons and has to be taken into account in first principles calculations. In the sexithiophene single crystal, the energy of the lowest triplet exciton is close to half the energy of the lowest singlet one. While lower-energy singlet and triplet excitons are intramolecular Frenkel excitons, higher-energy excitons are of intermolecular charge-transfer type. The calculated optical absorption spectra and Davydov splitting are in good agreement with experiments.

  7. 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.

  8. 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

  9. The dielectric properties of La(Mg0.5Ti0.5)O3 ceramics studied by Raman-scattering, infrared reflectivity spectroscopy, and first-principles calculations.

    PubMed

    Liu, Hsiang-Lin; Hsueh, Hung-Chung; Lin, I-Nan; Yang, Ming-Ti; Lee, Wei-Chung; Chen, Yi-Chun; Chia, Chia-Ta; Cheng, Hsiu-Fung

    2011-06-01

    La(Mg(0.5)Ti(0.5))O(3) (LMT) ceramics were prepared by either the solid-state reaction (LMT)(SS) or the citric-acid chemical method (LMT)(CA). A combination of Raman scattering, infrared reflectivity, and first-principles calculations was carried out to elucidate the correlation between lattice dynamics and the dielectric properties of these materials. Twelve Raman-active phonons are observed in both samples, displaying similar frequency positions. Interestingly, the A(g) phonon (g(11) mode) of (LMT)(SS) at about 717 cm(-1) involving the oxygen octahedron breathing vibrations demonstrates a narrower linewidth, suggesting its better crystallinity. Furthermore, an infrared-active u(2) phonon band due to the vibrations of O(I) and O(II) layers, which possesses the largest oscillator strength, exhibits stronger intensity for (LMT)(SS), as compared with those for (LMT)(CA). Additionally, the Q × f values (the product of dielectric Q values and measurement frequency) of (LMT)(SS) estimated from either microwave cavity or infrared spectroscopic measurements are larger than those of (LMT)(CA). These results indicate that the better coherence of lattice vibrations in (LMT)(SS) leads to its higher Q × f value, providing evidence for a strong connection between optical spectroscopic behavior and microwave dielectric characteristics in these materials. PMID:21576769

  10. 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.

  11. 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

  12. 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

  13. 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.

  14. 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.

  15. Theoretical Calculations of Atomic Data for Spectroscopy

    NASA Technical Reports Server (NTRS)

    Bautista, Manuel A.

    2000-01-01

    Several different approximations and techniques have been developed for the calculation of atomic structure, ionization, and excitation of atoms and ions. These techniques have been used to compute large amounts of spectroscopic data of various levels of accuracy. This paper presents a review of these theoretical methods to help non-experts in atomic physics to better understand the qualities and limitations of various data sources and assess how reliable are spectral models based on those data.

  16. Theoretical Sum Frequency Generation Spectroscopy of Peptides.

    PubMed

    Carr, Joshua K; Wang, Lu; Roy, Santanu; Skinner, James L

    2015-07-23

    Vibrational sum frequency generation (SFG) has become a very promising technique for the study of proteins at interfaces, and it has been applied to important systems such as anti-microbial peptides, ion channel proteins, and human islet amyloid polypeptide. Moreover, so-called "chiral" SFG techniques, which rely on polarization combinations that generate strong signals primarily for chiral molecules, have proven to be particularly discriminatory of protein secondary structure. In this work, we present a theoretical strategy for calculating protein amide I SFG spectra by combining line-shape theory with molecular dynamics simulations. We then apply this method to three model peptides, demonstrating the existence of a significant chiral SFG signal for peptides with chiral centers, and providing a framework for interpreting the results on the basis of the dependence of the SFG signal on the peptide orientation. We also examine the importance of dynamical and coupling effects. Finally, we suggest a simple method for determining a chromophore's orientation relative to the surface using ratios of experimental heterodyne-detected signals with different polarizations, and test this method using theoretical spectra. PMID:25203677

  17. Theoretical Sum Frequency Generation Spectroscopy of Peptides

    PubMed Central

    2015-01-01

    Vibrational sum frequency generation (SFG) has become a very promising technique for the study of proteins at interfaces, and it has been applied to important systems such as anti-microbial peptides, ion channel proteins, and human islet amyloid polypeptide. Moreover, so-called “chiral” SFG techniques, which rely on polarization combinations that generate strong signals primarily for chiral molecules, have proven to be particularly discriminatory of protein secondary structure. In this work, we present a theoretical strategy for calculating protein amide I SFG spectra by combining line-shape theory with molecular dynamics simulations. We then apply this method to three model peptides, demonstrating the existence of a significant chiral SFG signal for peptides with chiral centers, and providing a framework for interpreting the results on the basis of the dependence of the SFG signal on the peptide orientation. We also examine the importance of dynamical and coupling effects. Finally, we suggest a simple method for determining a chromophore’s orientation relative to the surface using ratios of experimental heterodyne-detected signals with different polarizations, and test this method using theoretical spectra. PMID:25203677

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. Towards Experimental Accuracy from the First Principles

    NASA Astrophysics Data System (ADS)

    Polyansky, O. L.; Lodi, L.; Tennyson, J.; Zobov, N. F.

    2013-06-01

    Producing ab initio ro-vibrational energy levels of small, gas-phase molecules with an accuracy of 0.10 cm^{-1} would constitute a significant step forward in theoretical spectroscopy and would place calculated line positions considerably closer to typical experimental accuracy. Such an accuracy has been recently achieved for the H_3^+ molecular ion for line positions up to 17 000 cm ^{-1}. However, since H_3^+ is a two-electron system, the electronic structure methods used in this study are not applicable to larger molecules. A major breakthrough was reported in ref., where an accuracy of 0.10 cm^{-1} was achieved ab initio for seven water isotopologues. Calculated vibrational and rotational energy levels up to 15 000 cm^{-1} and J=25 resulted in a standard deviation of 0.08 cm^{-1} with respect to accurate reference data. As far as line intensities are concerned, we have already achieved for water a typical accuracy of 1% which supersedes average experimental accuracy. Our results are being actively extended along two major directions. First, there are clear indications that our results for water can be improved to an accuracy of the order of 0.01 cm^{-1} by further, detailed ab initio studies. Such level of accuracy would already be competitive with experimental results in some situations. A second, major, direction of study is the extension of such a 0.1 cm^{-1} accuracy to molecules containg more electrons or more than one non-hydrogen atom, or both. As examples of such developments we will present new results for CO, HCN and H_2S, as well as preliminary results for NH_3 and CH_4. O.L. Polyansky, A. Alijah, N.F. Zobov, I.I. Mizus, R. Ovsyannikov, J. Tennyson, L. Lodi, T. Szidarovszky and A.G. Csaszar, Phil. Trans. Royal Soc. London A, {370}, 5014-5027 (2012). O.L. Polyansky, R.I. Ovsyannikov, A.A. Kyuberis, L. Lodi, J. Tennyson and N.F. Zobov, J. Phys. Chem. A, (in press). L. Lodi, J. Tennyson and O.L. Polyansky, J. Chem. Phys. {135}, 034113 (2011).

  4. Incorporation of Mn in AlxGa1 -xN probed by x-ray absorption and emission spectroscopy, high-resolution microscopy, x-ray diffraction, and first-principles calculations

    NASA Astrophysics Data System (ADS)

    Rovezzi, Mauro; Schlögelhofer, Wolfgang; Devillers, Thibaut; Szwacki, Nevill Gonzalez; Li, Tian; Adhikari, Rajdeep; Glatzel, Pieter; Bonanni, Alberta

    2015-09-01

    Synchrotron radiation x-ray absorption and emission spectroscopy techniques, complemented by high-resolution transmission electron microscopy methods and density functional theory calculations, are employed to investigate the effect of Mn in AlxGa1 -xN :Mn samples with an Al content up to 100%. The atomic and electronic structure of Mn is established together with its local environment and valence state. A dilute alloy without precipitation is obtained for AlxGa1 -xN :Mn with Al concentrations up to 82%, and the surfactant role of Mn in the epitaxial process is confirmed.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. First-principles and time-differential γ-γ perturbed-angular-correlation spectroscopy study of structural and electronic properties of Ta-doped TiO2 semiconductor

    NASA Astrophysics Data System (ADS)

    Darriba, G. N.; Errico, L. A.; Eversheim, P. D.; Fabricius, G.; Rentería, M.

    2009-03-01

    The, time-differential γ-γ perturbed-angular-correlation (TDPAC) technique using ion-implanted H181f(→T181a) tracers was applied to study the hyperfine interactions of T181a impurities in the rutile structure of TiO2 single crystals. The experiments were performed in air in the temperature range of 300-1273 K, allowing the electric-field-gradient (EFG) tensor characterization (in magnitude, asymmetry, and orientation) at T181a probe atoms located in defect-free cation sites of the structure. The measured EFG is parallel to the [001] crystal axis, as occurs at Ti sites, but normal to the EFG orientation observed at C111d impurities in TiO2 single crystals [L. A. Errico , Phys. Rev. Lett. 89, 055503 (2002)]. In addition, ab initio calculations were performed using the full-potential augmented plane wave plus local orbital method that allow us to treat the electronic structure of the doped system and the atomic relaxations induced by the Ta impurity in a fully self-consistent way. We considered different dilutions of the doped system (using the supercell approach) and studied the electronic properties and structural atomic relaxation dependence on the charge state of the impurity. The accuracy of the calculations and the excellent agreement of the predicted magnitude, asymmetry, and orientation of the EFG tensor with the experimental results enable us to infer the EFG sign, not accessible with conventional TDPAC experiments. The comparison of the measured EFG at Ta sites with experimental and ab initio theoretical results reported in the literature at Cd, Ta, and Ti sites in TiO2 allowed us to obtain a deeper insight on the role played by metal impurities in oxide semiconductors.

  18. Probing cation and vacancy ordering in the dry and hydrated yttrium-substituted BaSnO3 perovskite by NMR spectroscopy and first principles calculations: implications for proton mobility.

    PubMed

    Buannic, Lucienne; Blanc, Frédéric; Middlemiss, Derek S; Grey, Clare P

    2012-09-01

    Hydrated BaSn(1-x)Y(x)O(3-x/2) is a protonic conductor that, unlike many other related perovskites, shows high conductivity even at high substitution levels. A joint multinuclear NMR spectroscopy and density functional theory (total energy and GIPAW NMR calculations) investigation of BaSn(1-x)Y(x)O(3-x/2) (0.10 ≤ x ≤ 0.50) was performed to investigate cation ordering and the location of the oxygen vacancies in the dry material. The DFT energetics show that Y doping on the Sn site is favored over doping on the Ba site. The (119)Sn chemical shifts are sensitive to the number of neighboring Sn and Y cations, an experimental observation that is supported by the GIPAW calculations and that allows clustering to be monitored: Y substitution on the Sn sublattice is close to random up to x = 0.20, while at higher substitution levels, Y-O-Y linkages are avoided, leading, at x = 0.50, to strict Y-O-Sn alternation of B-site cations. These results are confirmed by the absence of a "Y-O-Y" (17)O resonance and supported by the (17)O NMR shift calculations. Although resonances due to six-coordinate Y cations were observed by (89)Y NMR, the agreement between the experimental and calculated shifts was poor. Five-coordinate Sn and Y sites (i.e., sites next to the vacancy) were observed by (119)Sn and (89)Y NMR, respectively, these sites disappearing on hydration. More five-coordinated Sn than five-coordinated Y sites are seen, even at x = 0.50, which is ascribed to the presence of residual Sn-O-Sn defects in the cation-ordered material and their ability to accommodate O vacancies. High-temperature (119)Sn NMR reveals that the O ions are mobile above 400 °C, oxygen mobility being required to hydrate these materials. The high protonic mobility, even in the high Y-content materials, is ascribed to the Y-O-Sn cation ordering, which prevents proton trapping on the more basic Y-O-Y sites. PMID:22691062

  19. Phase transitions in the system CaCO3 at high P and T determined by in situ vibrational spectroscopy in diamond anvil cells and first-principles simulations

    NASA Astrophysics Data System (ADS)

    Koch-Müller, Monika; Jahn, Sandro; Birkholz, Natalie; Ritter, Eglof; Schade, Ulrich

    2016-05-01

    The stability of the high-pressure CaCO3 calcite (cc)-related polymorphs was studied in experiments that were performed in conventional diamond anvil cells (DAC) at room temperature as a function of pressure up to 30 GPa as well as in internally heated diamond anvil cells (DAC-HT) at pressures and temperatures up to 20 GPa and 800 K. To probe structural changes, we used Raman and FTIR spectroscopy. For the latter, we applied conventional and synchrotron mid-infrared as well as synchrotron far-infrared radiation. Within the cc-III stability field (2.2-15 GPa at room temperature, e.g., Catalli and Williams in Phys Chem Miner 32(5-6):412-417, 2005), we observed in the Raman spectra consistently three different spectral patterns: Two patterns at pressures below and above 3.3 GPa were already described in Pippinger et al. (Phys Chem Miner 42(1):29-43, 2015) and assigned to the phase transition of cc-IIIb to cc-III at 3.3 GPa. In addition, we observed a clear change between 5 and 6 GPa that is independent of the starting material and the pressure path and time path of the experiments. This apparent change in the spectral pattern is only visible in the low-frequency range of the Raman spectra—not in the infrared spectra. Complementary electronic structure calculations confirm the existence of three distinct stability regions of cc-III-type phases at pressures up to about 15 GPa. By combining experimental and simulation data, we interpret the transition at 5-6 GPa as a re-appearance of the cc-IIIb phase. In all types of experiments, we confirmed the transition from cc-IIIb to cc-VI at about 15 GPa at room temperature. We found that temperature stabilizes cc-VI to lower pressure. The reaction cc-IIIb to cc-VI has a negative slope of -7.0 × 10-3 GPa K-1. Finally, we discuss the possibility of the dense cc-VI phase being more stable than aragonite at certain pressure and temperature conditions relevant to the Earth's mantle.

  20. Two-dimensional electronic spectroscopy using incoherent light: theoretical analysis.

    PubMed

    Turner, Daniel B; Howey, Dylan J; Sutor, Erika J; Hendrickson, Rebecca A; Gealy, M W; Ulness, Darin J

    2013-07-25

    Electronic energy transfer in photosynthesis occurs over a range of time scales and under a variety of intermolecular coupling conditions. Recent work has shown that electronic coupling between chromophores can lead to coherent oscillations in two-dimensional electronic spectroscopy measurements of pigment-protein complexes measured with femtosecond laser pulses. A persistent issue in the field is to reconcile the results of measurements performed using femtosecond laser pulses with physiological illumination conditions. Noisy-light spectroscopy can begin to address this question. In this work we present the theoretical analysis of incoherent two-dimensional electronic spectroscopy, I((4)) 2D ES. Simulations reveal diagonal peaks, cross peaks, and coherent oscillations similar to those observed in femtosecond two-dimensional electronic spectroscopy experiments. The results also expose fundamental differences between the femtosecond-pulse and noisy-light techniques; the differences lead to new challenges and new opportunities. PMID:23176195

  1. Shell Model in a First Principles Approach

    SciTech Connect

    Navratil, P; Nogga, A; Lloyd, R; Vary, J P; Ormand, W E; Barrett, B R

    2004-01-08

    We develop and apply an ab-initio approach to nuclear structure. Starting with the NN interaction, that fits two-body scattering and bound state data, and adding a theoretical NNN potential, we evaluate nuclear properties in a no-core approach. For presently feasible no-core model spaces, we evaluate an effective Hamiltonian in a cluster approach which is guaranteed to provide exact answers for sufficiently large model spaces and/or sufficiently large clusters. A number of recent applications are surveyed including an initial application to exotic multiquark systems.

  2. First principles study of hydroxyapatite surface.

    PubMed

    Slepko, Alexander; Demkov, Alexander A

    2013-07-28

    The biomineral hydroxyapatite (HA) [Ca10(PO4)6(OH)2] is the main mineral constituent of mammal bone. We report a theoretical investigation of the HA surface. We identify the low energy surface orientations and stoichiometry under a variety of chemical environments. The surface most stable in the physiologically relevant OH-rich environment is the OH-terminated (1000) surface. We calculate the work function of HA and relate it to the surface composition. For the lowest energy OH-terminated surface we find the work function of 5.1 eV, in close agreement with the experimentally reported range of 4.7 eV-5.1 eV [V. S. Bystrov, E. Paramonova, Y. Dekhtyar, A. Katashev, A. Karlov, N. Polyaka, A. V. Bystrova, A. Patmalnieks, and A. L. Kholkin, J. Phys.: Condens. Matter 23, 065302 (2011)]. PMID:23902010

  3. Excitons and Davydov splitting in sexithiophene from first-principles many-body Green’s function theory

    SciTech Connect

    Leng, Xia; Yin, Huabing; Liang, Dongmei; Ma, Yuchen

    2015-09-21

    Organic semiconductors have promising and broad applications in optoelectronics. Understanding their electronic excited states is important to help us control their spectroscopic properties and performance of devices. There have been a large amount of experimental investigations on spectroscopies of organic semiconductors, but theoretical calculation from first principles on this respect is still limited. Here, we use density functional theory (DFT) and many-body Green’s function theory, which includes the GW method and Bethe-Salpeter equation, to study the electronic excited-state properties and spectroscopies of one prototypical organic semiconductor, sexithiophene. The exciton energies of sexithiophene in both the gas and bulk crystalline phases are very sensitive to the exchange-correlation functionals used in DFT for ground-state structure relaxation. We investigated the influence of dynamical screening in the electron-hole interaction on exciton energies, which is found to be very pronounced for triplet excitons and has to be taken into account in first principles calculations. In the sexithiophene single crystal, the energy of the lowest triplet exciton is close to half the energy of the lowest singlet one. While lower-energy singlet and triplet excitons are intramolecular Frenkel excitons, higher-energy excitons are of intermolecular charge-transfer type. The calculated optical absorption spectra and Davydov splitting are in good agreement with experiments.

  4. 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.

  5. A first-principle calculation of the XANES spectrum of Cu2+ in water

    NASA Astrophysics Data System (ADS)

    La Penna, G.; Minicozzi, V.; Morante, S.; Rossi, G. C.; Stellato, F.

    2015-09-01

    The progress in high performance computing we are witnessing today offers the possibility of accurate electron density calculations of systems in realistic physico-chemical conditions. In this paper, we present a strategy aimed at performing a first-principle computation of the low energy part of the X-ray Absorption Spectroscopy (XAS) spectrum based on the density functional theory calculation of the electronic potential. To test its effectiveness, we apply the method to the computation of the X-ray absorption near edge structure part of the XAS spectrum in the paradigmatic, but simple case of Cu2+ in water. In order to keep into account the effect of the metal site structure fluctuations in determining the experimental signal, the theoretical spectrum is evaluated as the average over the computed spectra of a statistically significant number of simulated metal site configurations. The comparison of experimental data with theoretical calculations suggests that Cu2+ lives preferentially in a square-pyramidal geometry. The remarkable success of this approach in the interpretation of XAS data makes us optimistic about the possibility of extending the computational strategy we have outlined to the more interesting case of molecules of biological relevance bound to transition metal ions.

  6. A first-principle calculation of the XANES spectrum of Cu{sup 2+} in water

    SciTech Connect

    La Penna, G.; Minicozzi, V.; Morante, S.; Stellato, F.; Rossi, G. C.

    2015-09-28

    The progress in high performance computing we are witnessing today offers the possibility of accurate electron density calculations of systems in realistic physico-chemical conditions. In this paper, we present a strategy aimed at performing a first-principle computation of the low energy part of the X-ray Absorption Spectroscopy (XAS) spectrum based on the density functional theory calculation of the electronic potential. To test its effectiveness, we apply the method to the computation of the X-ray absorption near edge structure part of the XAS spectrum in the paradigmatic, but simple case of Cu{sup 2+} in water. In order to keep into account the effect of the metal site structure fluctuations in determining the experimental signal, the theoretical spectrum is evaluated as the average over the computed spectra of a statistically significant number of simulated metal site configurations. The comparison of experimental data with theoretical calculations suggests that Cu{sup 2+} lives preferentially in a square-pyramidal geometry. The remarkable success of this approach in the interpretation of XAS data makes us optimistic about the possibility of extending the computational strategy we have outlined to the more interesting case of molecules of biological relevance bound to transition metal ions.

  7. First principle computational and experimental studies of cathode materials for lithium ion rechargeable batteries

    NASA Astrophysics Data System (ADS)

    Saavedra Arias, Jose Javier

    We have studied the properties of spinel and layered cathode materials for Li ion rechargeable batteries. The analysis was done by first principle calculations, and experimental techniques to elucidate materials that can substitute the presently commercialized material, namely LiCoO 2. We have studied the influence of Ni substitution for Mn in spinel Li 2MnO4. To understand the effects of this substitution on the crystal structure and electronic properties, first principle DFT calculations were performed using VASP. The substitution was done systematically for up to 25% of Mn replacement by Ni in a super cell configuration. Furthermore, the influence of Ni substitution on lithium hoping pathways between the two stable Li positions was also studied by first principle calculations in LiMn 2-xNixO4. These calculations revealed that Ni substitution for Mn in LiMn2O4 indeed improved Li ion mobility. Thereafter, systematic experimental studies were performed on LiMn 2-xNixO4 (0spectroscopy. The electrochemical performance of LiMn2-xNi xO4 materials was evaluated in two electrode CR2032 type coin cell configuration with Li metal as anode and liquid electrolyte (1 M LiPF6 in EC:DMC=1:1 v/v). Our results showed significant enhancement in the electrochemical properties with 25% of Ni substitution in LiMn 2O4, which is in good agreement with the theoretical calculations. We also studied layered cathode materials both theoretically and experimentally. The First principle calculations in conjunction with alloy metal method were used to evaluate the average voltage and phase stability of LiMO2 (M=Co, Ni, Mn, W) systems. By formation energy analysis we established that LiNi0.8Co0.1Mn0.1O2 is a promising candidate cathode material. Single

  8. 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

  9. 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.

  10. 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.

  11. 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}.

  12. 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.

  13. 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

  14. 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.

  15. 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.

  16. 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

  17. 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.

  18. 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.

  19. 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

  20. 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

  1. 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

  2. Theoretical Modeling of Various Spectroscopies for Cuprates and Topological Insulators

    NASA Astrophysics Data System (ADS)

    Basak, Susmita

    structure, strong electron correlations (for cuprates) and spin-orbit coupling (for TIs) are included realistically in material-specific detail. Turning to the cuprates, in order to obtain a realistic description of various spectroscopies, one must include not only the effects of the matrix elements and the complexity of the crystal structure, but also of strong electronic correlations beyond the local density approximation (LDA)-based conventional picture, so that the physics of kinks, pseudogaps and superconductivity can be taken into account properly. In this connection, a self-consistent, intermediate coupling scheme informed by material-specific, first-principles band structures has been developed, where electron correlation effects beyond the LDA are incorporated via appropriate self-energy corrections to the electron and hole one-particle Green's functions. Here the antiferromagnetic (AFM) order is used as the simplest model of a competing order. A number of salient features of the resulting electronic spectrum and its energy, momentum and doping dependencies are in accord with experimental observations in electron as well as hole doped cuprates. This scheme thus provides a reasonable basis for undertaking a comprehensive, beyond-LDA level of modeling of various spectroscopies. The specific topics considered here are: (i) Origin of high-energy kink or the waterfall effect found in ARPES; (ii) Identification of the three energy scales observed in RIXS spectra as the pseudogap, charge transfer gap, and Mott gap; (iii) Evolution of the electron momentum densities with holedoping as seen in Compton scattering experiments. For three dimensional topological insulators, the ARPES and scanning tunneling microscopy (STM) spectra has been analyzed using a tight-binding model as well as a k · p model. The spin-orbit coupling, which is essential to produce the characteristic features of the surface states of a TI, is included realistically in the above models. In our

  3. 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.

  4. NMR characterization of hydrocarbon adsorption on calcite surfaces: A first principles study

    SciTech Connect

    Bevilaqua, Rochele C. A.; Miranda, Caetano R.; Rigo, Vagner A.; Veríssimo-Alves, Marcos

    2014-11-28

    The electronic and coordination environment of minerals surfaces, as calcite, are very difficult to characterize experimentally. This is mainly due to the fact that there are relatively few spectroscopic techniques able to detect Ca{sup 2+}. Since calcite is a major constituent of sedimentary rocks in oil reservoir, a more detailed characterization of the interaction between hydrocarbon molecules and mineral surfaces is highly desirable. Here we perform a first principles study on the adsorption of hydrocarbon molecules on calcite surface (CaCO{sub 3} (101{sup ¯}4)). The simulations were based on Density Functional Theory with Solid State Nuclear Magnetic Resonance (SS-NMR) calculations. The Gauge-Including Projector Augmented Wave method was used to compute mainly SS-NMR parameters for {sup 43}Ca, {sup 13}C, and {sup 17}O in calcite surface. It was possible to assign the peaks in the theoretical NMR spectra for all structures studied. Besides showing different chemical shifts for atoms located on different environments (bulk and surface) for calcite, the results also display changes on the chemical shift, mainly for Ca sites, when the hydrocarbon molecules are present. Even though the interaction of the benzene molecule with the calcite surface is weak, there is a clearly distinguishable displacement of the signal of the Ca sites over which the hydrocarbon molecule is located. A similar effect is also observed for hexane adsorption. Through NMR spectroscopy, we show that aromatic and alkane hydrocarbon molecules adsorbed on carbonate surfaces can be differentiated.

  5. NMR characterization of hydrocarbon adsorption on calcite surfaces: a first principles study.

    PubMed

    Bevilaqua, Rochele C A; Rigo, Vagner A; Veríssimo-Alves, Marcos; Miranda, Caetano R

    2014-11-28

    The electronic and coordination environment of minerals surfaces, as calcite, are very difficult to characterize experimentally. This is mainly due to the fact that there are relatively few spectroscopic techniques able to detect Ca(2+). Since calcite is a major constituent of sedimentary rocks in oil reservoir, a more detailed characterization of the interaction between hydrocarbon molecules and mineral surfaces is highly desirable. Here we perform a first principles study on the adsorption of hydrocarbon molecules on calcite surface (CaCO3 (101¯4)). The simulations were based on Density Functional Theory with Solid State Nuclear Magnetic Resonance (SS-NMR) calculations. The Gauge-Including Projector Augmented Wave method was used to compute mainly SS-NMR parameters for (43)Ca, (13)C, and (17)O in calcite surface. It was possible to assign the peaks in the theoretical NMR spectra for all structures studied. Besides showing different chemical shifts for atoms located on different environments (bulk and surface) for calcite, the results also display changes on the chemical shift, mainly for Ca sites, when the hydrocarbon molecules are present. Even though the interaction of the benzene molecule with the calcite surface is weak, there is a clearly distinguishable displacement of the signal of the Ca sites over which the hydrocarbon molecule is located. A similar effect is also observed for hexane adsorption. Through NMR spectroscopy, we show that aromatic and alkane hydrocarbon molecules adsorbed on carbonate surfaces can be differentiated. PMID:25429955

  6. NMR characterization of hydrocarbon adsorption on calcite surfaces: A first principles study

    NASA Astrophysics Data System (ADS)

    Bevilaqua, Rochele C. A.; Rigo, Vagner A.; Veríssimo-Alves, Marcos; Miranda, Caetano R.

    2014-11-01

    The electronic and coordination environment of minerals surfaces, as calcite, are very difficult to characterize experimentally. This is mainly due to the fact that there are relatively few spectroscopic techniques able to detect Ca2+. Since calcite is a major constituent of sedimentary rocks in oil reservoir, a more detailed characterization of the interaction between hydrocarbon molecules and mineral surfaces is highly desirable. Here we perform a first principles study on the adsorption of hydrocarbon molecules on calcite surface (CaCO3 ( {10bar 14} )). The simulations were based on Density Functional Theory with Solid State Nuclear Magnetic Resonance (SS-NMR) calculations. The Gauge-Including Projector Augmented Wave method was used to compute mainly SS-NMR parameters for 43Ca, 13C, and 17O in calcite surface. It was possible to assign the peaks in the theoretical NMR spectra for all structures studied. Besides showing different chemical shifts for atoms located on different environments (bulk and surface) for calcite, the results also display changes on the chemical shift, mainly for Ca sites, when the hydrocarbon molecules are present. Even though the interaction of the benzene molecule with the calcite surface is weak, there is a clearly distinguishable displacement of the signal of the Ca sites over which the hydrocarbon molecule is located. A similar effect is also observed for hexane adsorption. Through NMR spectroscopy, we show that aromatic and alkane hydrocarbon molecules adsorbed on carbonate surfaces can be differentiated.

  7. Composition-Dependent Phase Concentrations from First Principles: Simulating Combinatorial Libraries of Transition Metal Oxides

    NASA Astrophysics Data System (ADS)

    Li, Guo; Yan, Qimin; Zhou, Lan; Newhouse, Paul; Gregoire, John; Neaton, Jeffrey

    To identify material phases in experimental combinatorial libraries, we develop a theoretical model as a complementary approach to accelerate phase identification. In this approach, samples in a combinatorial library are simulated as mixtures in chemical equilibria. Each of these mixtures contains all the solid-state phases, which can possibly exist in the library. Using the total energies of these phases obtained in first-principle calculations, we calculate the Gibbs free energy changes in the corresponding chemical reactions, and subsequently evaluate the equilibrium concentrations of the phases in every sample according to the law of mass action. Furthermore, to test this approach, we simulate pseudobinary libraries MnxV1-xOy and CuxV1-xOy. Interestingly, we find that the composition-dependent phase concentrations calculated within our approach agree well with the experimental results measured with XRD spectroscopy. This work supported by DOE (the JCAP under Award Number DE-SC0004993 and the Molecular Foundry of LBNL), and computational resources provided by NERSC.

  8. 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.

  9. 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.

  10. 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

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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

  5. 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.

  6. 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

  7. Theoretical analysis of single molecule spectroscopy lineshapes of conjugated polymers

    NASA Astrophysics Data System (ADS)

    Devi, Murali

    Conjugated Polymers(CPs) exhibit a wide range of highly tunable optical properties. Quantitative and detailed understanding of the nature of excitons responsible for such a rich optical behavior has significant implications for better utilization of CPs for more efficient plastic solar cells and other novel optoelectronic devices. In general, samples of CPs are plagued with substantial inhomogeneous broadening due to various sources of disorder. Single molecule emission spectroscopy (SMES) offers a unique opportunity to investigate the energetics and dynamics of excitons and their interactions with phonon modes. The major subject of the present thesis is to analyze and understand room temperature SMES lineshapes for a particular CP, called poly(2,5-di-(2'-ethylhexyloxy)-1,4-phenylenevinylene) (DEH-PPV). A minimal quantum mechanical model of a two-level system coupled to a Brownian oscillator bath is utilized. The main objective is to identify the set of model parameters best fitting a SMES lineshape for each of about 200 samples of DEH-PPV, from which new insight into the nature of exciton-bath coupling can be gained. This project also entails developing a reliable computational methodology for quantum mechanical modeling of spectral lineshapes in general. Well-known optimization techniques such as gradient descent, genetic algorithms, and heuristic searches have been tested, employing an L2 measure between theoretical and experimental lineshapes for guiding the optimization. However, all of these tend to result in theoretical lineshapes qualitatively different from experimental ones. This is attributed to the ruggedness of the parameter space and inadequateness of the L2 measure. On the other hand, when the dynamic reduction of the original parameter space to a 2-parameter space through feature searching and visualization of the search space paths using directed acyclic graphs(DAGs), the qualitative nature of the fitting improved significantly. For a more

  8. Clean Ir(111) and Pt(111) electronic surface states: A first-principle fully relativistic investigation

    NASA Astrophysics Data System (ADS)

    Dal Corso, Andrea

    2015-07-01

    We present a first-principle investigation of the fully relativistic electronic surface states and resonances of clean Pt(111) and Ir(111) and compare them with those of Au(111). Our calculations are based on a recently introduced fully relativistic projector augmented-wave (PAW) approach that includes spin-orbit coupling and allows us to access both the relativistic energy splittings and the spin polarization of the surface states. The maps of the electronic structure of the two surfaces are critically discussed in comparison with previous calculations and with some of the available angle-resolved photoelectron spectroscopy data.

  9. First-Principles Framework to Compute Sum-Frequency Generation Vibrational Spectra of Semiconductors and Insulators

    NASA Astrophysics Data System (ADS)

    Wan, Quan; Galli, Giulia

    2015-12-01

    We present a first-principles framework to compute sum-frequency generation (SFG) vibrational spectra of semiconductors and insulators. The method is based on density functional theory and the use of maximally localized Wannier functions to compute the response to electric fields, and it includes the effect of electric field gradients at surfaces. In addition, it includes quadrupole contributions to SFG spectra, thus enabling the verification of the dipole approximation, whose validity determines the surface specificity of SFG spectroscopy. We compute the SFG spectra of ice Ih basal surfaces and identify which spectra components are affected by bulk contributions. Our results are in good agreement with experiments at low temperature.

  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 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.

  16. 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

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. 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

  4. 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.

  5. 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.

  6. 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

  7. 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.

  8. 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.

  9. Optical properties of Yb-doped LaB6 from first-principles calculation

    NASA Astrophysics Data System (ADS)

    Chao, Luomeng; Bao, Lihong; Wei, Wei; Tegus, O.

    2016-03-01

    The optical properties of Yb-doped LaB6 have been investigated by first-principles calculations within the framework of density functional theory. The results show that the Yb 4f states at near Fermi surface affect their optical properties and the Yb-doping leads to a reduction of the plasmon energy of LaB6, i.e. a redshift of the position of transmission peak in the visible-near infrared region. This study offers a theoretical prediction for the design and application of Yb-doped LaB6 as an optoelectronic material.

  10. 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.

  11. First-principles study of the electronic and molecular structure of protein nanotubes

    NASA Astrophysics Data System (ADS)

    Okamoto, Hajime; Takeda, Kyozaburo; Shiraishi, Kenji

    2001-09-01

    The electronic and molecular structures of protein nanotubes (PNT's) have been investigated theoretically by first-principles electronic structure calculations. The results have been discussed in comparison to those of the polypeptide open chains (POC's) and polypeptide closed rings (PCR's) in order to give a systematic understanding. Focusing on the intra-ring and inter-ring hydrogen bonds (HB's), we also investigate the PCR stacking mechanism. The present calculation reveals that PNT's are semiconductors and that an extra proton in the tube interior has the potential to be an electron acceptor.

  12. Spin Crossover in Ferropericlase From First-Principles Molecular Dynamics Simulations

    NASA Astrophysics Data System (ADS)

    Holmstrom, E.; Stixrude, L. P.

    2013-12-01

    Ferropericlase is believed to be the second-most abundant mineral of the lower mantle of the Earth. It is experimentally known that with increasing pressure, the iron ions in the mineral begin to collapse from a high-spin to low-spin state. This spin crossover looks certain to have geophysical effects, and hence a good theoretical understanding of the phenomenon is necessary. Using first-principles molecular dynamics simulations in conjunction with thermodynamic integration, we construct a phase diagram of the spin crossover as a function of pressure and temperature. In addition, we predict that the mineral loses its electrically insulating character within the lower mantle.

  13. First-principles investigation of high pressure Pbca phase of carbon mononitride

    NASA Astrophysics Data System (ADS)

    Wei, Qun; Zhang, Meiguang; Yan, Haiyan

    2016-09-01

    A theoretical investigations on the stability, mechanical and electronic properties of Pbca-CN was performed by using first principle calculations. According to our calculations, Pbca-CN exhibits a large elastic anisotropy. The further mechanical calculations demonstrated that Pbca-CN shows high elastic moduli. Young's modulus of Pbca-CN is found to reach a maximum along [001] direction and a minimum along [100] direction. The ideal tensile and shear strength at large strains of Pbca-CN are also examined. The ideal shear strength along the weakest (100)[010] slip system is about 20 GPa, which shows Pbca-CN is not an intrinsic superhard material.

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. 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

  19. 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.

  20. 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

  1. 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).

  2. 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.

  3. 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.

  4. 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

  5. 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.

  6. 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

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. 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.

  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. Vibrational signatures in the THz spectrum of 1,3-DNB: A first-principles and experimental study

    NASA Astrophysics Data System (ADS)

    Ahmed, Towfiq; Azad, Abul K.; Chellappa, Raja; Higginbotham-Duque, Amanda; Dattelbaum, Dana M.; Zhu, Jian-Xin; Moore, David; Graf, Matthias J.

    2016-05-01

    Understanding the fundamental processes of light-matter interaction is important for detection of explosives and other energetic materials, which are active in the infrared and terahertz (THz) region. We report a comprehensive study on electronic and vibrational lattice properties of structurally similar 1,3-dinitrobenzene (1,3-DNB) crystals through first-principles electronic structure calculations and THz spectroscopy measurements on polycrystalline samples. Starting from reported x-ray crystal structures, we use density-functional theory (DFT) with periodic boundary conditions to optimize the structures and perform linear response calculations of the vibrational properties at zero phonon momentum. The theoretically identified normal modes agree qualitatively with those obtained experimentally in a frequency range up to 2.5 THz and quantitatively at much higher frequencies. The latter frequencies are set by intra-molecular forces. Our results suggest that van der Waals dispersion forces need to be included to improve the agreement between theory and experiment in the THz region, which is dominated by intermolecular modes and sensitive to details in the DFT calculation. An improved comparison is needed to assess and distinguish between intra- and intermolecular vibrational modes characteristic of energetic materials.

  6. Characterization of the unoccupied and partially occupied states of TTF-TCNQ by XANES and first-principles calculations

    NASA Astrophysics Data System (ADS)

    Fraxedas, J.; Lee, Y. J.; Jiménez, I.; Gago, R.; Nieminen, R. M.; Ordejón, P.; Canadell, E.

    2003-11-01

    We report a combined experimental and theoretical study of the unoccupied electronic states of the neutral molecular organic materials TTF (tetrathiafulvalene) and TCNQ (7,7,8,8-tetracyano-p-quinodimethane) and of the one-dimensional metallic charge transfer salt TTF-TCNQ. The experimental density of states (DOS) is obtained by x-ray absorption near edge spectroscopy (XANES) with synchrotron light and the predicted DOS by means of first-principles density functional theory calculations. Most of the experimentally derived element-specific XANES features can be associated to molecular orbitals of defined symmetry. Because of the planar geometry of the TTF and TCNQ molecules and the polarization of the synchrotron light, the energy dependent σ or π character of the orbitals can be inferred from angular dependent XANES measurements. The present work represents the state of the art analysis of the XANES spectra of this type of materials and points out the need for additional work in order to elucidate the governing selection rules in the excitation process.

  7. Finite temperature effects on the X-ray absorption spectra of lithium compounds: first-principles interpretation of X-ray Raman measurements.

    PubMed

    Pascal, Tod A; Boesenberg, Ulrike; Kostecki, Robert; Richardson, Thomas J; Weng, Tsu-Chien; Sokaras, Dimosthenis; Nordlund, Dennis; McDermott, Eamon; Moewes, Alexander; Cabana, Jordi; Prendergast, David

    2014-01-21

    We elucidate the role of room-temperature-induced instantaneous structural distortions in the Li K-edge X-ray absorption spectra (XAS) of crystalline LiF, Li2SO4, Li2O, Li3N, and Li2CO3 using high resolution X-ray Raman spectroscopy (XRS) measurements and first-principles density functional theory calculations within the eXcited electron and Core Hole approach. Based on thermodynamic sampling via ab initio molecular dynamics simulations, we find calculated XAS in much better agreement with experiment than those computed using the rigid crystal structure alone. We show that local instantaneous distortion of the atomic lattice perturbs the symmetry of the Li 1s core-excited-state electronic structure, broadening spectral line-shapes and, in some cases, producing additional spectral features. The excellent agreement with high-resolution XRS measurements validates the accuracy of our first-principles approach to simulating XAS, and provides both accurate benchmarks for model compounds and a predictive theoretical capability for identification and characterization of multi-component systems, such as lithium-ion batteries, under working conditions. PMID:25669363

  8. Superconductivity in compressed sulfur hydride: Dependences on pressure, composition, and crystal structure from first principles

    NASA Astrophysics Data System (ADS)

    Akashi, Ryosuke

    The recent discovery of high-temperature superconductivity in sulfur hydride under extreme pressure has broken the long-standing record of superconducting transition temperature (Tc) in the Hg-cuprate. According to the isotope effect measurement and theoretical calculations, the superconducting transition is mainly ascribed to the conventional phonon-mediated pairing interaction. It is, however, not enough for understanding the high-Tc superconductivity in the sulfur hydride. To elucidate various possible effects on Tc with accuracy, we have analyzed Tc with first-principles methods without any empirical parameters. First, for various pressures and theoretically proposed crystal structures, we calculated Tc with the density functional theory for superconductors (SCDFT) to examine which structure(s) can explain experimentally measured Tc data [Akashi et al., PRB 91, 224513 (2015)]. We next solved the Eliashberg equations without introducing the renormalized Coulomb parameter mu*, which is the Green-function-based counterpart of the SCDFT, and evaluated the effects of rapidly varying electron density of states, atomic zero-point motion, and phonon anharmonic corrections on Tc [Sano et al., in preparation]. In the talk, we review these results and discuss the dominant factors for the Tc and their relation to the experimental results. We also report some crystal structures that we recently found with first-principles calculations, which could have a key role for the pressure-induced transformation to the high-Tc phase.

  9. 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).

  10. 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

  11. 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

  12. 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.

  13. 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.

  14. 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.''

  15. 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.

  16. 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.

  17. 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).

  18. 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).

  19. 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.

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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).

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. Theoretical ultra-fast spectroscopy in transition metal dichalcogenides

    NASA Astrophysics Data System (ADS)

    Molina-Sanchez, Alejandro; Sangalli, Davide; Marini, Andrea; Wirtz, Ludger

    Semiconducting 2D-materials like the transition metal dichalcogenides (TMDs) MoS2, MoSe2, WS2, WSe2 are promising alternatives to graphene for designing novel opto-electronic devices. The strong spin-orbit interaction along with the breaking of inversion symmetry in single-layer TMDs allow using the valley-index as a new quantum number. The practical use of valley physics depends on the lifetimes of valley-polarized excitons which are affected by scattering at phonons, impurities and by carrier-carrier interactions. The carrier dynamics can be monitored using ultra-fast spectroscopies such as pump-probe experiments. The carrier dynamics is simulated using non-equilibrium Green's function theory in an ab-initio framework. We include carrier relaxation through electron-phonon interaction. We obtain the transient absorption spectra of single-layer TMD and compare our simulations with recent pump-probe experiments

  5. Pressure-Induced Valence and Structural Changes in YbMn2Ge2-Inelastic X-ray Spectroscopy and Theoretical Investigations

    SciTech Connect

    Kumar, Ravhi S; Svane, A; Vaitheeswaran, G; Zhang, Y; Kanchana, V; Hofmann, M; Campbell, S J; Xiao, Yuming; Chow, P; Chen, Changfeng; Zhao, Yusheng; Cornelius, Andrew L

    2013-01-08

    The pressure-induced valence change of Yb in YbMn2Ge2 has been studied by high pressure inelastic X-ray emission and absorption spectroscopy in the partial fluorescence yield mode up to 30 GPa. The crystal structure of YbMn2Ge2 has been investigated by high pressure powder X-ray diffraction experiments up to 40 GPa. The experimental investigations have been complemented by first principles density functional theoretical calculations using the generalized gradient approximation with an evolutionary algorithm for structural determination. The Yb valence and magnetic structures have been calculated using the self-interaction corrected local spin density approximation. The X-ray emission results indicate a sharp increase of Yb valence from v = 2.42(2) to v = 2.75(3) around 1.35 GPa, and Yb reaches a near trivalent state (v = 2.95(3)) around 30 GPa. Further, a new monoclinic P1 type high pressure phase is found above 35 GPa; this structure is characterized by the Mn layer of the ambient (I4/mmm) structure transforming into a double layer. The theoretical calculations yield an effective valence of v = 2.48 at ambient pressure in agreement with experiment, although the pure trivalent state is attained theoretically at significantly higher pressures (above 40 GPa).

  6. First-principles study on oxidation of Ge and its interface electronic structures

    NASA Astrophysics Data System (ADS)

    Ono, Tomoya; Saito, Shoichiro; Iwase, Shigeru

    2016-08-01

    We review a series of first-principles studies on the defect generation mechanism and electronic structures of the Ge/GeO2 interface. Several experimental and theoretical studies proved that Si atoms at the Si/SiO2 interface are emitted to release interface stress. In contrast, total-energy calculation reveals that Ge atoms at the Ge/GeO2 interface are hardly emitted, resulting in the low trap density. Even if defects are generated, those at the Ge/GeO2 interface are found to behave differently from those at the Si/SiO2 interface. The states attributed to the dangling bonds at the Ge/GeO2 interface lie below the valence-band maximum of Ge, while those at the Si/SiO2 interface generate the defect state within the band gap of Si. First-principles electron-transport calculation elucidates that this characteristic behavior of the defect states is relevant to the difference in the leakage current through the Si/SiO2 and Ge/GeO2 interfaces.

  7. Waltzing of a helium pair in tungsten: Migration barrier and trajectory revealed from first-principles

    SciTech Connect

    Niu, J. G.; Zhan, Q.; Geng, W. T.

    2014-06-15

    Despite well documented first-principles theoretical determination of the low migration energy (0.06 eV) of a single He in tungsten, fully quantum mechanical calculations on the migration of a He pair still present a challenge due to the complexity of its trajectory. By identifying the six most stable configurations of the He pair in W and decomposing its motion into rotational, translational, and rotational-translational routines, we are able to determine its migration barrier and trajectory. Our density functional theory calculations demonstrate a He pair has three modes of motion: a close or open circular two-dimensional motion in (100) plane with an energy barrier of 0.30 eV, a snaking motion along [001] direction with a barrier of 0.30 eV, and a twisted-ladder motion along [010] direction with the two He swinging in the plane (100) and a barrier of 0.31 eV. The graceful associative movements of a He pair are related to the chemical-bonding-like He-He interaction being much stronger than its migration barrier in W. The excellent agreement with available experimental measurements (0.24–0.32 eV) on He migration makes our first-principles result a solid input to obtain accurate He-W interatomic potentials in molecular dynamics simulations.

  8. The Role of the Cluster Variation Method in the First Principles Calculation of Phase Diagrams

    NASA Astrophysics Data System (ADS)

    Sanchez, J. M.; Becker, J. D.

    The Cluster Variation Method (CVM) proposed by Professor Kikuchi to study cooperative phenomena in solids has played a major role in the development of phenomenological and first principles theories of phase equilibrium. The CVM provides an accurate and rigorous framework for the study of the configurational thermodynamics of alloys. As such, the method has been a powerful tool in the quest for insight into the main contributions to alloy phase stability and in the interpretation of complex and extensive experimental data. The early successes of the CVM have also been instrumental in the development of ab-initio methods for the reliable description of phase equilibrium and, in particular, of phase diagrams. These new developments have relied heavily on the CVM and on the theoretical ideas put forth over 40 years ago by Professor Kikuchi. Here, we review the use of the CVM in the first-principles computation of phase diagrams, and present results for the Zr-Nb system. The theory that emerges is one that incorporates the calculation of total energies in the local density approximation, configurational entropies using the CVM, and vibrational modes in the Debye-Grüneisen approximation.

  9. Atomistic modeling of amorphous silicon carbide: an approximate first-principles study in constrained solution space.

    PubMed

    Atta-Fynn, Raymond; Biswas, Parthapratim

    2009-07-01

    Localized basis ab initio molecular dynamics simulation within the density functional framework has been used to generate realistic configurations of amorphous silicon carbide (a-SiC). Our approach consists of constructing a set of smart initial configurations that conform to essential geometrical and structural aspects of the materials obtained from experimental data, which is subsequently driven via a first-principles force field to obtain the best solution in a reduced solution space. A combination of a priori information (primarily structural and topological) along with the ab initio optimization of the total energy makes it possible to model a large system size (1000 atoms) without compromising the quantum mechanical accuracy of the force field to describe the complex bonding chemistry of Si and C. The structural, electronic and vibrational properties of the models have been studied and compared to existing theoretical models and available data from experiments. We demonstrate that the approach is capable of producing large, realistic configurations of a-SiC from first-principles simulation that display its excellent structural and electronic properties. Our study reveals the presence of predominant short range order in the material originating from heteronuclear Si-C bonds with a coordination defect concentration as small as 5% and a chemical disorder parameter of about 8%. PMID:21828477

  10. Theoretical Modeling for the X-ray Spectroscopy of Iron-bearing MgSiO3 under High Pressure

    NASA Astrophysics Data System (ADS)

    Wang, X.; Tsuchiya, T.

    2012-12-01

    The behaviors of iron (Fe) in MgSiO3 perovskite, including valence state, spin state, and chemical environments, at high pressures are of fundamental importance for more detailed understanding the properties of the Earth's lower mantle. The pressure induced spin transition of Fe-bearing MgO and MgSiO3 are detected often by using high-resolution K-edge X-ray emission spectroscopy (XES) [1,2,3] and confirmed by theoretical simulations. [4,5] Since the Fe K-edge XES is associated to the 3p orbital, which is far from the valence orbitals (3d and 4s), it provides no information about its coordination environments. However, the Fe L-edge XES and X-ray absorption spectroscopy (XAS) can directly present the distribution and intensity of Fe-3d character. To identify both the spin states and the coordination environments of iron-bearing MgSiO3, we systematically investigate the L-edge XAS, XES and X-ray photoelectron (XPS) spectroscopy of Fe2+- and Fe3+-bearing MgSiO3 under high pressure by using the first-principles density functional method combined with the slater-transition method. Our results show that Fe2+ and Fe3+ can be distinguished easily by taking the XPS spectra. The spin transition of Fe2+ and Fe3+ can also be clearly certified by XAS and XES. Interestingly, the broadness of L-edge XES of Fe changes depending on the iron position, meaning that its coordination environment might also be distinguishable by using high-resolution XES measurements. Research supported by the Ehime University G-COE program and KAKENHI. [1] James Badro, Guillaume Fiquet, FranÇois Guyot, Jean-Pascal Rueff, Viktor V. Struzhkin, György VankÓ, and Giulio Monaco. Science 300, 789 (2003), [2] James Badro, Jean-Pascal Rueff, György VankÓ, Giulio Monaco, Guillaume Fiquet, and FranÇois Guyot, Science 305, 383 (2004), [3] Jung-Fu Lin, Viktor V. Struzhkin, Steven D. Jacobsen, Michael Y. Hu, Paul Chow, Jennifer Kung, Haozhe Liu, Ho-kwang Mao, and Gussell J. Hemley, Nature 436, 377 (2005). [4

  11. 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.

  12. 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

  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. 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

  15. 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.

  16. 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.

  17. 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.

  18. 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

  19. Time-resolved photoabsorption in finite systems: A first-principles NEGF approach

    NASA Astrophysics Data System (ADS)

    Perfetto, E.; Uimonen, A.-M.; van Leeuwen, R.; Stefanucci, G.

    2016-03-01

    We describe a first-principles NonEquilibrium Green's Function (NEGF) approach to time-resolved photoabsortion spectroscopy in atomic and nanoscale systems. The method is used to highlight a recently discovered dynamical correlation effect in the spectrum of a Krypton gas subject to a strong ionizing pump pulse. We propose a minimal model that captures the effect, and study the performance of time-local approximations versus time-nonlocal ones. In particular we implement the time-local Hartree-Fock and Markovian second Born (2B) approximation as well as the exact adiabatic approximation within the Time-Dependent Density Functional Theory framework. For the time-nonlocal approximation we instead use the 2B one. We provide enough convincing evidence for the fact that a proper description of the spectrum of an evolving admixture of ionizing atoms requires the simultaneous occurrence of correlation and memory effects.

  20. Experimental and first-principles study of ferromagnetism in Mn-doped zinc stannate nanowires

    SciTech Connect

    Deng Rui; Zhou Hang; Qin Jieming; Wan Yuchun; Jiang Dayong; Liang Qingcheng; Li Yongfeng; Wu, Tom; Yao Bin; Liu Lei

    2013-07-21

    Room temperature ferromagnetism was observed in Mn-doped zinc stannate (ZTO:Mn) nanowires, which were prepared by chemical vapor transport. Structural and magnetic properties and Mn chemical states of ZTO:Mn nanowires were investigated by X-ray diffraction, superconducting quantum interference device (SQUID) magnetometry and X-ray photoelectron spectroscopy. Manganese predominantly existed as Mn{sup 2+} and substituted for Zn (Mn{sub Zn}) in ZTO:Mn. This conclusion was supported by first-principles calculations. Mn{sub Zn} in ZTO:Mn had a lower formation energy than that of Mn substituted for Sn (Mn{sub Sn}). The nearest neighbor Mn{sub Zn} in ZTO stabilized ferromagnetic coupling. This observation supported the experimental results.

  1. Cobalt (hydro)oxide electrodes under electrochemical conditions: a first principle study

    NASA Astrophysics Data System (ADS)

    Chen, Jia; Selloni, Annabella

    2013-03-01

    There is currently much interest in photoelectrochemical water splitting as a promising pathway towards sustainable energy production. A major issue of such photoelectrochemical devices is the limited efficiency of the anode, where the oxygen evolution reaction (OER) takes place. Cobalt (hydro)oxides, particularly Co3O4 and Co(OH)2, have emerged as promising candidates for use as OER anode materials. Interestingly, recent in-situ Raman spectroscopy studies have shown that Co3O4 electrodes undergo progressive oxidation and transform into oxyhydroxide, CoO(OH), under electrochemical working conditions. (Journal of the American Chemical Society 133, 5587 (2011))Using first principle electronic structure calculations, we provide insight into these findings by presenting results on the structural, thermodynamic, and electronic properties of cobalt oxide, hydroxide and oxydroxide CoO(OH), and on their relative stabilities when in contact with water under external voltage.

  2. Mechanisms of molecular doping of graphene: A first-principles study

    NASA Astrophysics Data System (ADS)

    Saha, Srijan Kumar; Chandrakanth, Reddy Ch.; Krishnamurthy, H. R.; Waghmare, U. V.

    2009-10-01

    Doping graphene with electron donating or accepting molecules is an interesting approach to introduce carriers into it, analogous to electrochemical doping accomplished in graphene when used in a field-effect transistor. Here, we use first-principles density-functional theory to determine changes in the electronic-structure and vibrational properties of graphene that arise from the adsorption of aromatic molecules such as aniline and nitrobenzene. Identifying the roles of various mechanisms of chemical interaction between graphene and a molecule, we bring out the contrast between electrochemical and molecular doping of graphene. Our estimates of various contributions to shifts in the Raman-active modes of graphene with molecular doping are fundamental to the possible use of Raman spectroscopy in (a) characterization of the nature and concentration of carriers in graphene with molecular doping, and (b) graphene-based chemical sensors.

  3. Vibrational spectroscopy and theoretical studies on 2,4-dinitrophenylhydrazine

    NASA Astrophysics Data System (ADS)

    Chiş, V.; Filip, S.; Miclăuş, V.; Pîrnău, A.; Tănăselia, C.; Almăşan, V.; Vasilescu, M.

    2005-06-01

    In this work, we will report a combined experimental and theoretical study on molecular and vibrational structure of 2,4-dinitrophenylhydrazine. FT-IR, FT-IR/ATR and Raman spectra of normal and deuterated DNPH have been recorded and analyzed in order to get new insights into molecular structure and properties of this molecule, with particular emphasize on its intra- and intermolecular hydrogen bonds (HB's). For computational purposes we used density functional theory (DFT) methods, with B3LYP and BLYP exchange-correlation functionals, in conjunction with 6-31G(d) basis set. All experimental vibrational bands have been discussed and assigned to normal modes on the basis of DFT calculations and isotopic shifts and by comparison to other dinitro- substituted compounds [V. Chiş, Chem. Phys., 300 (2004) 1]. To aid in mode assignments, we based on the direct comparison between experimental and calculated spectra by considering both the frequency sequence and the intensity pattern of the experimental and computed vibrational bands. It is also shown that semiempirical AM1 method predicts geometrical parameters and vibrational frequencies related to the HB in a pleasant agreement with experiment, being surprisingly accurate from this perspective.

  4. Plasmon spectroscopy: Theoretical and numerical calculations, and optimization techniques

    NASA Astrophysics Data System (ADS)

    Rodríguez-Oliveros, Rogelio; Paniagua-Domínguez, Ramón; Sánchez-Gil, José A.; Macías, Demetrio

    2016-02-01

    We present an overview of recent advances in plasmonics, mainly concerning theoretical and numerical tools required for the rigorous determination of the spectral properties of complex-shape nanoparticles exhibiting strong localized surface plasmon resonances (LSPRs). Both quasistatic approaches and full electrodynamic methods are described, providing a thorough comparison of their numerical implementations. Special attention is paid to surface integral equation formulations, giving examples of their performance in complicated nanoparticle shapes of interest for their LSPR spectra. In this regard, complex (single) nanoparticle configurations (nanocrosses and nanorods) yield a hierarchy of multiple-order LSPR s with evidence of a rich symmetric or asymmetric (Fano-like) LSPR line shapes. In addition, means to address the design of complex geometries to retrieve LSPR spectra are commented on, with special interest in biologically inspired algorithms. Thewealth of LSPRbased applications are discussed in two choice examples, single-nanoparticle surface-enhanced Raman scattering (SERS) and optical heating, and multifrequency nanoantennas for fluorescence and nonlinear optics.

  5. First principles study on the electronic structures and stability of Cr 7C 3 type multi-component carbides

    NASA Astrophysics Data System (ADS)

    Xiao, B.; Feng, J.; Zhou, C. T.; Xing, J. D.; Xie, X. J.; Chen, Y. H.

    2008-06-01

    First principles calculations were conducted to investigate the stabilities of six multi-component carbides of Cr 7C 3 by calculating the cohesive energy and formation enthalpy of them. The theoretical predictions were compared with the experimental results and they were in agreement with each other. The electronic structures of the six carbides were also calculated in order to provide more information about the relationship between the stability and crystal compositions at atomic scale.

  6. A first principle study for the comparison of phonon dispersion of armchair carbon and silicon nanotubes

    SciTech Connect

    Chandel, Surjeet Kumar; Kumar, Arun; Bharti, Ankush; Sharma, Raman

    2015-05-15

    Using first principles density functional theoretical calculations, the present paper reports a systematic study of phonon dispersion curves in pristine carbon (CNT) and silicon nanotubes (SiNT) having chirality (6,6) in the armchair configuration. Some of the phonon modes are found to have negative frequencies which leads to instability of the systems under study. The number of phonon branches has been found to be thrice as much as the number of atoms. The frequency of the higher optical bands varies from 1690 to 1957 cm{sup −1} for CNT(6,6) while it is 596 to 658 cm{sup −1} for SiNT.

  7. First-Principles Investigation to Ionization of Argon Under Conditions Close to Typical Sonoluminescence Experiments

    PubMed Central

    Kang, Wei; Zhao, Shijun; Zhang, Shen; Zhang, Ping; Chen, Q. F.; He, Xian-Tu

    2016-01-01

    Mott effect, featured by a sharp increase of ionization, is one of the unique properties of partially ionized plasmas, and thus of great interest to astrophysics and inertial confinement fusion. Recent experiments of single bubble sonoluminescence (SBSL) revealed that strong ionization took place at a density two orders lower than usual theoretical expectation. We show from the perspective of electronic structures that the strong ionization is unlikely the result of Mott effect in a pure argon plasma. Instead, first-principles calculations suggest that other ion species from aqueous environments can energetically fit in the gap between the continuum and the top of occupied states of argon, making the Mott effect possible. These results would help to clarify the relationship between SBSL and Mott effect, and further to gain an better understanding of partially ionized plasmas. PMID:26853107

  8. Formation and annealing behaviors of qubit centers in 4H-SiC from first principles

    SciTech Connect

    Wang, Xiaopeng; Zhao, Mingwen Bu, Hongxia; He, Xiujie; Wang, Aizhu; Zhang, Hongyu

    2013-11-21

    Inspired by finding that the nitrogen-vacancy center in diamond is a qubit candidate, similar defects in silicon carbide (SiC) have drawn considerable interest. However, the generation and annealing behaviors of these defects remain unclear. Using first-principles calculations, we describe the equilibrium concentrations and annealing mechanisms based on the diffusion of silicon vacancies. The formation energies and energy barriers along different migration paths, which are responsible for the formation rates, stability, and concentrations of these defects, are investigated. The effects on these processes of charge states, annealing temperature, and crystal orientation are also discussed. These theoretical results are expected to be useful in achieving controllable generation of these defects in experiments.

  9. Isotope dependence of the vibrational lifetimes of light impurities in Si from first principles

    NASA Astrophysics Data System (ADS)

    West, D.; Estreicher, S. K.

    2007-02-01

    The vibrational lifetimes of a range of H-related defects and interstitial O (Oi) in Si, including isotopic substitutions, are calculated from first principles as a function of temperature. The theoretical approach is explained in detail. The vibrational lifetimes of highest-frequency local vibrational modes of HBC+ , D2* , HD* , DH* , HBC+ , DBC+ , HV•VH , DV•VH , DV•VD , IH2 , ID2 , and various O and Si isotopic combinations of Oi are predicted and the decay channels analyzed. We show that the complete vibrational spectrum of the defects must be known in order to predict vibrational lifetimes. We also show that the “frequency-gap law” is not always valid for high-frequency local vibrational modes.

  10. First principles DFT investigation of yttrium-doped graphene: Electronic structure and hydrogen storage

    SciTech Connect

    Desnavi, Sameerah; Chakraborty, Brahmananda; Ramaniah, Lavanya M.

    2014-04-24

    The electronic structure and hydrogen storage capability of Yttrium-doped grapheme has been theoretically investigated using first principles density functional theory (DFT). Yttrium atom prefers the hollow site of the hexagonal ring with a binding energy of 1.40 eV. Doping by Y makes the system metallic and magnetic with a magnetic moment of 2.11 μ{sub B}. Y decorated graphene can adsorb up to four hydrogen molecules with an average binding energy of 0.415 eV. All the hydrogen atoms are physisorbed with an average desorption temperature of 530.44 K. The Y atoms can be placed only in alternate hexagons, which imply a wt% of 6.17, close to the DoE criterion for hydrogen storage materials. Thus, this system is potential hydrogen storage medium with 100% recycling capability.

  11. First-Principles Definition and Measurement of Planetary Electromagnetic-Energy Budget

    NASA Technical Reports Server (NTRS)

    Mishchenko, Michael I.; Lock, James A.; Lacis, Andrew A.; Travis, Larry D.; Cairns, Brian

    2016-01-01

    The imperative to quantify the Earths electromagnetic-energy budget with an extremely high accuracy has been widely recognized but has never been formulated in the framework of fundamental physics. In this paper we give a first-principles definition of the planetary electromagnetic-energy budget using the Poynting- vector formalism and discuss how it can, in principle, be measured. Our derivation is based on an absolute minimum of theoretical assumptions, is free of outdated notions of phenomenological radiometry, and naturally leads to the conceptual formulation of an instrument called the double hemispherical cavity radiometer (DHCR). The practical measurement of the planetary energy budget would require flying a constellation of several dozen planet-orbiting satellites hosting identical well-calibrated DHCRs.

  12. First principle investigation of the electronic and thermoelectric properties of Mg2C

    NASA Astrophysics Data System (ADS)

    Kulwinder, Kaur; Ranjan, Kumar

    2016-02-01

    In this paper, electronic and thermoelectric properties of Mg2C are investigated by using first principle pseudo potential method based on density functional theory and Boltzmann transport equations. We calculate the lattice parameters, bulk modulus, band gap and thermoelectric properties (Seebeck coefficient, electrical conductivity, and thermal conductivity) of this material at different temperatures and compare them with available experimental and other theoretical data. The calculations show that Mg2C is indirect band semiconductor with a band gap of 0.75 eV. The negative value of Seebeck coefficient shows that the conduction is due to electrons. The electrical conductivity decreases with temperature and Power factor (PF) increases with temperature. The thermoelectric properties of Mg2C have been calculated in a temperature range of 100 K-1200 K. Kulwinder Kaur thanks Council of Scientific & Industrial Research (CSIR), India for providing fellowship.

  13. First-Principles Investigation to Ionization of Argon Under Conditions Close to Typical Sonoluminescence Experiments

    NASA Astrophysics Data System (ADS)

    Kang, Wei; Zhao, Shijun; Zhang, Shen; Zhang, Ping; Chen, Q. F.; He, Xian-Tu

    2016-02-01

    Mott effect, featured by a sharp increase of ionization, is one of the unique properties of partially ionized plasmas, and thus of great interest to astrophysics and inertial confinement fusion. Recent experiments of single bubble sonoluminescence (SBSL) revealed that strong ionization took place at a density two orders lower than usual theoretical expectation. We show from the perspective of electronic structures that the strong ionization is unlikely the result of Mott effect in a pure argon plasma. Instead, first-principles calculations suggest that other ion species from aqueous environments can energetically fit in the gap between the continuum and the top of occupied states of argon, making the Mott effect possible. These results would help to clarify the relationship between SBSL and Mott effect, and further to gain an better understanding of partially ionized plasmas.

  14. First-principles calculation of dielectric response in molecule-based materials.

    PubMed

    Heitzer, Henry M; Marks, Tobin J; Ratner, Mark A

    2013-07-01

    The dielectric properties of materials are of fundamental significance to many chemical processes and the functioning of numerous solid-state device technologies. While experimental methods for measuring bulk dielectric constants are well-established, far less is known, either experimentally or theoretically, about the origin of dielectric response at the molecular/multimolecular scale. In this contribution we report the implementation of an accurate first-principles approach to calculating the dielectric response of molecular systems. We assess the accuracy of the method by reproducing the experimental dielectric constants of several bulk π-electron materials and demonstrating the ability of the method to capture dielectric properties as a function of frequency and molecular orientation in representative arrays of substituted aromatic derivatives. The role of molecular alignment and packing density on dielectric response is also examined, showing that the local dielectric behavior of molecular assemblies can diverge significantly from that of the bulk material. PMID:23734640

  15. Structural predictions based on the compositions of cathodic materials by first-principles calculations

    NASA Astrophysics Data System (ADS)

    Li, Yang; Lian, Fang; Chen, Ning; Hao, Zhen-jia; Chou, Kuo-chih

    2015-05-01

    A first-principles method is applied to comparatively study the stability of lithium metal oxides with layered or spinel structures to predict the most energetically favorable structure for different compositions. The binding and reaction energies of the real or virtual layered LiMO2 and spinel LiM2O4 (M = Sc-Cu, Y-Ag, Mg-Sr, and Al-In) are calculated. The effect of element M on the structural stability, especially in the case of multiple-cation compounds, is discussed herein. The calculation results indicate that the phase stability depends on both the binding and reaction energies. The oxidation state of element M also plays a role in determining the dominant structure, i.e., layered or spinel phase. Moreover, calculation-based theoretical predictions of the phase stability of the doped materials agree with the previously reported experimental data.

  16. Discharge Reaction Mechanisms in Na/FeS2 Batteries: First-Principles Calculations

    NASA Astrophysics Data System (ADS)

    Momida, Hiroyoshi; Kitajou, Ayuko; Okada, Shigeto; Yamashita, Tomoki; Oguchi, Tamio

    2015-12-01

    We have studied microscopic discharge reaction mechanisms in Na/FeS2 batteries by first-principles calculations. The calculated Na-Fe-S phase diagram shows that the discharge reactions can proceed by converting 4Na and FeS2 into 2Na2S and Fe as a fully discharged state. As an intermediate discharge reaction, we find that NaxFeS2 (x ˜ 1.5) intermediate products can be generated in the cathode, giving two major plateaus in voltage-capacity curves. The calculated voltage-capacity characteristics and X-ray absorption spectra at S and Fe K-edges of Na-discharged FeS2 cathode materials are compared with experimental results, showing that theoretically determined reaction formulas can account for the experimental discharge reactions.

  17. First-principles study on phase transition and ferroelectricity in lithium niobate and tantalate

    SciTech Connect

    Toyoura, Kazuaki Ohta, Masataka; Nakamura, Atsutomo; Matsunaga, Katsuyuki

    2015-08-14

    The phase transitions and ferroelectricity of LiNbO{sub 3} and LiTaO{sub 3} have been investigated theoretically from first principles. The phonon analyses and the molecular dynamics simulations revealed that the ferroelectric phase transition is not conventional displacive type but order-disorder type with strong correlation between cation displacements. According to the evaluated potential energy surfaces around the paraelectric structures, the large difference in ferroelectricity between the two oxides results from the little difference in short-range interionic interaction between Nb-O and Ta-O. As the results of the crystal orbital overlap population analyses, the different short-range interaction originates from the difference in covalency between Nb4d-O2p and Ta5d-O2p orbitals, particularly d{sub xz}-p{sub x}/d{sub yz}-p{sub y} orbitals (π orbitals), from the electronic point of view.

  18. Thermoelectric properties of binary LnN (Ln=La and Lu): First principles study

    SciTech Connect

    Sreeparvathy, P. C.; Gudelli, Vijay Kumar; Kanchana, V.; Vaitheeswaran, G.; Svane, A.; Christensen, N. E.

    2015-06-24

    First principles density functional calculations were carried out to study the electronic structure and thermoelectric properties of LnN (Ln = La and Lu) using the full potential linearized augmented plane wave (FP-LAPW) method. The thermoelectric properties were calculated by solving the Boltzmann transport equation within the constant relaxation time approximation. The obtained lattice parameters are in good agreement with the available experimental and other theoretical results. The calculated band gaps using the Tran-Blaha modified Becke-Johnson potential (TB-mBJ), of both compounds are in good agreement with the available experimental values. Thermoelectric properties like thermopower (S), electrical conductivity scaled by relaxation time (σ/τ) and power-factor (S{sup 2}σ/τ) are calculated as functions of the carrier concentration and temperature for both compounds. The calculated thermoelectric properties are compared with the available experimental results of the similar material ScN.

  19. First-principles elastic stiffness of LaPO4 monazite

    NASA Astrophysics Data System (ADS)

    Wang, Jingyang; Zhou, Yanchun; Lin, Zhijun

    2005-08-01

    In this letter, the full set of elastic coefficients of LaPO4 monazite is presented based on the first-principles plane-wave pseudopotential total energy method. Mechanical parameters (bulk modulus, shear modulus, Young's moduli, and Poisson's ratio) are also presented and compared with experimental results for polycrystalline monazite. The responses of electronic structure and chemical bonds to a series of {010}⟨001⟩ shear strains are examined in order to study the mechanism of low shear strain resistance. The results show that small shear moduli originate from the inhomogeneous strengths of atomic bonds. For example, the weak La-O bonds accommodate the shear strain locally, while the PO4 tetrahedra are almost rigid. The theoretical elastic stiffness may be useful to understand the deformation mechanisms of LaPO4 monazite.

  20. First-Principles Investigation to Ionization of Argon Under Conditions Close to Typical Sonoluminescence Experiments.

    PubMed

    Kang, Wei; Zhao, Shijun; Zhang, Shen; Zhang, Ping; Chen, Q F; He, Xian-Tu

    2016-01-01

    Mott effect, featured by a sharp increase of ionization, is one of the unique properties of partially ionized plasmas, and thus of great interest to astrophysics and inertial confinement fusion. Recent experiments of single bubble sonoluminescence (SBSL) revealed that strong ionization took place at a density two orders lower than usual theoretical expectation. We show from the perspective of electronic structures that the strong ionization is unlikely the result of Mott effect in a pure argon plasma. Instead, first-principles calculations suggest that other ion species from aqueous environments can energetically fit in the gap between the continuum and the top of occupied states of argon, making the Mott effect possible. These results would help to clarify the relationship between SBSL and Mott effect, and further to gain an better understanding of partially ionized plasmas. PMID:26853107

  1. Thermoelectric properties of binary LnN (Ln=La and Lu): First principles study

    NASA Astrophysics Data System (ADS)

    Sreeparvathy P., C.; Gudelli, Vijay Kumar; Kanchana, V.; Vaitheeswaran, G.; Svane, A.; Christensen, N. E.

    2015-06-01

    First principles density functional calculations were carried out to study the electronic structure and thermoelectric properties of LnN (Ln = La and Lu) using the full potential linearized augmented plane wave (FP-LAPW) method. The thermoelectric properties were calculated by solving the Boltzmann transport equation within the constant relaxation time approximation. The obtained lattice parameters are in good agreement with the available experimental and other theoretical results. The calculated band gaps using the Tran-Blaha modified Becke-Johnson potential (TB-mBJ), of both compounds are in good agreement with the available experimental values. Thermoelectric properties like thermopower (S), electrical conductivity scaled by relaxation time (σ/τ) and power-factor (S2σ/τ) are calculated as functions of the carrier concentration and temperature for both compounds. The calculated thermoelectric properties are compared with the available experimental results of the similar material ScN.

  2. First-principles definition and measurement of planetary electromagnetic-energy budget.

    PubMed

    Mishchenko, Michael I; Lock, James A; Lacis, Andrew A; Travis, Larry D; Cairns, Brian

    2016-06-01

    The imperative to quantify the Earth's electromagnetic-energy budget with an extremely high accuracy has been widely recognized but has never been formulated in the framework of fundamental physics. In this paper we give a first-principles definition of the planetary electromagnetic-energy budget using the Poynting-vector formalism and discuss how it can, in principle, be measured. Our derivation is based on an absolute minimum of theoretical assumptions, is free of outdated notions of phenomenological radiometry, and naturally leads to the conceptual formulation of an instrument called the double hemispherical cavity radiometer (DHCR). The practical measurement of the planetary energy budget would require flying a constellation of several dozen planet-orbiting satellites hosting identical well-calibrated DHCRs. PMID:27409440

  3. Multilayer heterostructures of magnetic Heusler and binary compounds from first principles

    NASA Astrophysics Data System (ADS)

    Garoufalis, Christos; Galanakis, Iosif

    2016-03-01

    Employing first-principles state-of-the-art electronic structure calculations, we study a series of multilayer heterostructures composed of ferro/ferrimagnetic half-metallic Heusler compounds and binary compounds presenting perpendicular magnetic anisotropy. We relax these heterostructures and study both their electronic and magnetic properties. In most studied cases the Heusler spacer keeps a large value of spin-polarization at the Fermi level even for ultrathin films which attends the maximum value of 100% in the case of the Mn2VSi/MnSi multilayer. Our results pave the way both experimentally and theoretically towards the growth of such multilayer heterostructures and their incorporation in spintronic/magnetoelectronic devices.

  4. Experimental and first principle studies on electronic structure of BaTiO{sub 3}

    SciTech Connect

    Sagdeo, Archna Ghosh, Haranath Chakrabarti, Aparna Kamal, C. Ganguli, Tapas Deb, S. K.; Phase, D. M.

    2014-04-24

    We have carried out photoemission experiments to obtain valence band spectra of various crystallographic symmetries of BaTiO{sub 3} system which arise as a function of temperature. We also present results of a detailed first principle study of these symmetries of BaTiO{sub 3} using generalized gradient approximation for the exchange-correlation potential. Here we present theoretical results of density of states obtained from DFT based simulations to compare with the experimental valence band spectra. Further, we also perform calculations using post density functional approaches like GGA + U method as well as non-local hybrid exchange-correlation potentials like PBE0, B3LYP, HSE in order to understand the extent of effect of correlation on band gaps of different available crystallographic symmetries (5 in number) of BaTiO{sub 3}.

  5. Experimental and first principle studies on electronic structure of BaTiO3

    NASA Astrophysics Data System (ADS)

    Sagdeo, Archna; Ghosh, Haranath; Chakrabarti, Aparna; Kamal, C.; Ganguli, Tapas; Phase, D. M.; Deb, S. K.

    2014-04-01

    We have carried out photoemission experiments to obtain valence band spectra of various crystallographic symmetries of BaTiO3 system which arise as a function of temperature. We also present results of a detailed first principle study of these symmetries of BaTiO3 using generalized gradient approximation for the exchange-correlation potential. Here we present theoretical results of density of states obtained from DFT based simulations to compare with the experimental valence band spectra. Further, we also perform calculations using post density functional approaches like GGA + U method as well as non-local hybrid exchange-correlation potentials like PBE0, B3LYP, HSE in order to understand the extent of effect of correlation on band gaps of different available crystallographic symmetries (5 in number) of BaTiO3.

  6. Elastic and Thermal Properties of Silicon Compounds from First-Principles Calculations

    NASA Astrophysics Data System (ADS)

    Hou, Haijun; Zhu, H. J.; Cheng, W. H.; Xie, L. H.

    2016-07-01

    The structural and elastic properties of V-Si (V3Si, VSi2, V5Si3, and V6Si5) compounds are studied by using first-principles method. The calculated equilibrium lattice parameters and formation enthalpy are in good agreement with the available experimental data and other theoretical results. The calculated results indicate that the V-Si compounds are mechanically stable. Elastic properties including bulk modulus, shear modulus, Young's modulus, and Poisson's ratio are also obtained. The elastic anisotropies of V-Si compounds are investigated via the three-dimensional (3D) figures of directional dependences of reciprocals of Young's modulus. Finally, based on the quasi-harmonic Debye model, the internal energy, Helmholtz free energy, entropy, heat capacity, thermal expansion coefficient, Grüneisen parameter, and Debye temperature of V-Si compounds have been calculated.

  7. Anisotropic elastic properties of MB (M = Cr, Mo, W) monoborides: a first-principles investigation

    NASA Astrophysics Data System (ADS)

    Li, Run-Yue; Duan, Yong-Hua

    2016-04-01

    First principles calculations were performed to systematically investigate structure properties, phase stability and mechanical properties of MB (M = Cr, Mo, W) monoborides in orthorhombic and tetragonal structures. The results of equilibrium structures are in good agreement with other available theoretical and experimental data. The elastic properties, including bulk modulus B, shear modulus G, Young's modulus E and Poisson's ratio ν were calculated by the Voigt-Reuss-Hill approximation. All considered monoborides are mechanically stable. The results of elastic anisotropies show that elastic anisotropy of orthorhombic structure is larger than that of tetragonal structure. Moreover, the minimum thermal conductivities were also estimated using the Cahill's model, and the results indicate that the minimum thermal conductivities show a dependence on directions.

  8. Spin crossover in ferropericlase from first-principles molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Holmstrom, Eero; Stixrude, Lars

    2014-05-01

    Ferropericlase is the second-most abundant mineral of the lower mantle of the Earth. It is experimentally known that with increasing pressure, the iron ions in the mineral begin to collapse from a high-spin to low-spin state. This spin crossover alters various properties of the material, and hence a good theoretical understanding of the phenomenon is necessary. Using first-principles molecular dynamics simulations in conjunction with thermodynamic integration, we construct a phase diagram of the spin crossover as a function of pressure and temperature. In addition, we present the thermal equation of state of the mineral up to 140 GPa and 4000 K, and predict that the electrical conductivity of ferropericlase reaches semi-metallic values within the lower mantle.

  9. First-principles approach to investigate toroidal property of magnetoelectric multiferroic GaFeO3

    NASA Astrophysics Data System (ADS)

    Nie, Yung-mau

    2016-01-01

    A first-principles approach incorporating the concept of toroidal moments as a measure of the spin vortex is proposed and applied to simulate the toroidization of magnetoelectric multiferroic GaFeO3. The nature of space-inversion and time-reversal violations of ferrotoroidics is reproduced in the simulated magnetic structure of GaFeO3. For undoped GaFeO3, a toroidal moment of -22.38 μB Å per unit cell was obtained, which is the best theoretical estimate till date. Guided by the spin vortex free-energy minimization perturbed by an externally applied field, it was discovered that the minority spin markedly biases the whole toroidization. In summary, this approach not only calculates the toroidal moment but provides a way to understand the toroidal nature of magnetoelectric multiferroics.

  10. First-principles calculations for point defects in MAX phases Ti2AlN

    NASA Astrophysics Data System (ADS)

    Zhang, Yaowen; Yang, Shutong; Wang, Canglong

    2016-04-01

    This paper outlines general physical issues associated with performing computational numerical simulations of primary point defects in MAX phases Ti2AlN. First-principles solutions are possible due to the development of computational resources of software and hardware. The calculation accuracy is a good agreement with the experimental results. As an important application of our simulations, the results could provide a theoretical guidance for future experiments and application of Ti2AlN. For example, the N mono-vacancy is the most difficult to form. On the contrary, the mono-vacancy formation in Ti2AlN is energetically most favorable for the Al atom. The essence of the phenomena is explained by the calculated density of state (DOS).

  11. The structural, electronic and phonon behavior of CsPbI3: A first principles study

    NASA Astrophysics Data System (ADS)

    Bano, Amreen; Khare, Preeti; Parey, Vanshree; Shukla, Aarti; Gaur, N. K.

    2016-05-01

    Metal halide perovskites are optoelectronic materials that have attracted enormous attention as solar cells with power conversion efficiencies reaching 20%. The benefit of using hybrid compounds resides in their ability to combine the advantage of these two classes of compounds: the high mobility of inorganic materials and the ease of processing of organic materials. In spite of the growing attention of this new material, very little is known about the electronic and phonon properties of the inorganic part of this compounds. A theoretical study of structural, electronic and phonon properties of metal-halide cubic perovskite, CsPbI3 is presented, using first-principles calculations with planewave pseudopotential method as personified in PWSCF code. In this approach local density approximation (LDA) is used for exchange-correlation potential.

  12. First-Principles Study of Back Contact Effects on CdTe Thin Film Solar Cells

    SciTech Connect

    Du, Mao-Hua

    2009-01-01

    Forming a chemically stable low-resistance back contact for CdTe thin-film solar cells is critically important to the cell performance. This paper reports theoretical study of the effects of the back-contact material, Sb{sub 2}Te{sub 3}, on the performance of the CdTe solar cells. First-principles calculations show that Sb impurities in p-type CdTe are donors and can diffuse with low diffusion barrier. There properties are clearly detrimental to the solar-cell performance. The Sb segregation into the grain boundaries may be required to explain the good efficiencies for the CdTe solar cells with Sb{sub 2}Te{sub 3} back contacts.

  13. Stability of the hcp Ruthenium at high pressures from first principles

    SciTech Connect

    Lugovskoy, A. V. Belov, M. P.; Vekilov, Yu. Kh; Krasilnikov, O. M.

    2014-09-14

    The method of calculation of the elastic constants up to third order from the energy-strain relation under pressure for the hcp crystals is given and described in details. The method is applied to the hcp phase of Ruthenium. Elastic constants, lattice dynamics, and electronic structure are investigated in the pressure interval of 0–600 GPa by means of first principles calculations. The obtained parameters are in very good agreement with available experimental and theoretical data. No preconditions for phase transformation driven by mechanical or dynamical instabilities for hcp Ru were found in the investigated pressure range. The reason of stability at such high pressures is explained in the context of electronic structure peculiarities.

  14. First-principles study of B1 to B2 phase transition in PbS

    NASA Astrophysics Data System (ADS)

    Bhambhani, P.; Munjal, N.; Sharma, G.; Vyas, V.; Sharma, B. K.

    2012-07-01

    The high pressure structural phase transition in PbS has been studied by means of first-principles total energy calculations which are based on linear combination of atomic orbitals (LCAO) method within local density approximation (LDA). In the present study, the exchange scheme of Becke and correlation functional of von-Barth-Hedin (VBH) are employed. It is observed that more stable phase for PbS is NaCl type (B1) and PbS transforms to the CsCl type (B2) structure under high pressure (22.8 GPa). The calculated value of transition pressure (Pt) from B1 to B2 structure is found in good agreement with the earlier experimental and theoretical investigations.

  15. Solute/impurity diffusivities in bcc Fe: A first-principles study

    NASA Astrophysics Data System (ADS)

    Zhang, Chong; Fu, Jie; Li, Ruihuan; Zhang, Pengbo; Zhao, Jijun; Dong, Chuang

    2014-12-01

    Chinese low activation martensitic steel (CLAM) has been designed with decreased W content and increased Ta content to improve performance. We performed first-principles calculations to investigate the diffusion properties of solute element (Cr, W, Mn, V, Ta) and C diffusion with a nearby solute element inside bcc Fe. The self-diffusion coefficients and solute diffusion coefficients in Fe host were derived using the nine-frequency model. A relatively lower diffusivity was observed for W in paramagnetic state, implying enriched W concentration inside Fe host. The solute atom interacts strongly with C impurity, depending on the interatomic distance. According to our calculations, formation of Ta carbide precipitates is energetically preferred by trapping C impurity around Ta atom. Our theoretical results are helpful for investigating the evolution of microstructure of steels for engineering applications.

  16. 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

  17. 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

  18. 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

  19. 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

  20. 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

  1. Topological semimetals predicted from first-principles calculations.

    PubMed

    Weng, Hongming; Dai, Xi; Fang, Zhong

    2016-08-01

    We have given a summary on our theoretical predictions of three kinds of topological semimetals (TSMs), namely, Dirac semimetal (DSM), Weyl semimetal (WSM) and node-line semimetal (NLSM). TSMs are new states of quantum matter, which are different from topological insulators. They are characterized by the topological stability of the Fermi surface, whether it encloses band crossing points, i.e. Dirac cone-like energy nodes, or not. They are distinguished from each other by the degeneracy and momentum space distribution of the nodal points. To realize these intriguing topological quantum states is quite challenging and crucial to both fundamental science and future application. Na3Bi and Cd3As2 were theoretically predicted to be DSM in 2012 and 2013 respectively. Their experimental verification in 2014 have ignited intensive studies on TSMs. The subsequent theoretical prediction of a nonmagnetic WSM in the TaAs family stimulated a second wave and many experimental works were released out in 2015. In 2014, a kind of three dimensional crystal of carbon was proposed to be an NLSM due to negligible spin-orbit coupling and coexistence of time-reversal and inversion symmetry. Though the final experimental confirmation of NLSM is still missing, there have been several theoretical proposals, including Cu3PdN from us. In the final part, we have summarized the whole family of TSMs and their relationships. PMID:27269048

  2. Topological semimetals predicted from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Weng, Hongming; Dai, Xi; Fang, Zhong

    2016-08-01

    We have given a summary on our theoretical predictions of three kinds of topological semimetals (TSMs), namely, Dirac semimetal (DSM), Weyl semimetal (WSM) and node-line semimetal (NLSM). TSMs are new states of quantum matter, which are different from topological insulators. They are characterized by the topological stability of the Fermi surface, whether it encloses band crossing points, i.e. Dirac cone-like energy nodes, or not. They are distinguished from each other by the degeneracy and momentum space distribution of the nodal points. To realize these intriguing topological quantum states is quite challenging and crucial to both fundamental science and future application. Na3Bi and Cd3As2 were theoretically predicted to be DSM in 2012 and 2013 respectively. Their experimental verification in 2014 have ignited intensive studies on TSMs. The subsequent theoretical prediction of a nonmagnetic WSM in the TaAs family stimulated a second wave and many experimental works were released out in 2015. In 2014, a kind of three dimensional crystal of carbon was proposed to be an NLSM due to negligible spin–orbit coupling and coexistence of time-reversal and inversion symmetry. Though the final experimental confirmation of NLSM is still missing, there have been several theoretical proposals, including Cu3PdN from us. In the final part, we have summarized the whole family of TSMs and their relationships.

  3. 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

  4. Covalently Bound Tetracoordinated Organoborons are Superhalogens: A Combined Negative Ion Photoelectron Spectroscopy and Theoretical Study

    SciTech Connect

    Zhang, Jian; Yang, Ping; Sun, Zhenrong; Wang, Xue B.

    2014-09-18

    Molecular species with electron affinities (EAs) larger than that of the chlorine atom (3.6131 eV) are superhalogens. The corresponding negative ions, namely, superhalogen anions, are intrinsically very stable with high electron binding energies (EBEs), and widely exist as building blocks of bulk materials and ionic liquids. The most common superhalogen anions proposed and confirmed to date are either ionic salts or compact inorganic species. Herein we report a new class of superhalogen species, a series of tetracoordinated organoboron anions [BL4]– (L = phenyl (1), 4-fluorophenyl (2), 1-imidazolyl (3), L4 = H(pyrazolyl)3 (4)) with bulky organic ligands covalently bound to the central B atom. Negative ion photoelectron spectroscopy (NIPES) reveals all of these anions possessing EBEs higher than that of Cl- with the adiabatic / vertical detachment energy (ADE / VDE) of 4.44/4.8 (1), 4.78/5.2 (2), 5.08/5.4 (3), and 4.59/4.9 eV (4), respectively. First-principles calculations confirmed high EBEs of [BL4]– and predicted that these anions are thermodynamically stable against fragmentation. The unraveled superhalogen nature of these species provides a molecular basis to explain the wide-range applications of tetraphenylborate (TPB) (1) and trispyrazolylborate (Tp) (4) in many areas spanning from industrial waste treatment to soft material synthesis and organometallic chemistry

  5. Elasticity and Pressure-induced Phase Transition in Coesite from Experiments and First Principle Calculations

    NASA Astrophysics Data System (ADS)

    Chen, T.; Wang, X.; Qi, X.; Ma, M.; Xu, Z.; Li, B.

    2015-12-01

    Coesite (space group C2/c) is a high-pressure polymorph of quartz. The behavior of coesite under pressure has long been of interest due to its abundance in the Earth's crust and mantle, and its relative simple chemistry but rich polymorphisms under elevated pressure and/or temperature conditions. A most recent Raman spectroscopy study reported two pressure-induced phase transitions at ~23 (coesite-II) and ~35 GPa, respectively. To further understand the properties of these pressure-induced phase transitions, we conducted X-ray diffraction experiments starting with coesite powder in a diamond anvil cell up to 31 GPa, and performed first-principle calculations on coesite, coesite-II (space group P21/n), and stishovite at 0 K up to 45 GPa. X-ray diffraction data show the formation of coesite-II at pressures above 20 GPa, which is consistent with first principles calculations that the enthalpy of coesite-II becomes lower than that of coesite above 21.4 GPa. Coesite is very anisotropic with the a-axis twice more compressible than the b- and c-axis. By comparison, coesite-II is less anisotropic, with a similar compressibility in a-, b-, and c-axis. As analyzed by a third-order Eulerian finite strain equation of state, the bulk modulus of coesite at 21.4 GPa is 180.6 GPa, and that of coesite-II is 140.8 GPa, indicating that coesite-II is much more compressible than coesite. If coesite-coesite-II transition occurs in cold subduction zones, it will change the elasticity as well as anisotropic properties of the subducted MORB, due to the different compressional behavior between coesite and coesite-II.

  6. First principles calculations of interlayer exchange coupling in bcc Fe/Cu/Fe structures

    SciTech Connect

    Kowalewski, M.; Heninrich, B.; Schulthess, T.C.; Butler, W.H.

    1998-01-01

    The authors report on theoretical calculations of interlayer exchange coupling between two Fe layers separated by a modified Cu spacer. These calculations were motivated by experimental investigations of similar structures by the SFU group. The multilayer structures of interest have the general form: Fe/Cu(k)/Fe and Fe/Cu(m)/X(1)/Cu(n)/Fe where X indicates one AL (atomic layer) of foreign atoms X (Cr, Ag, or Fe) and k, m, n represent the number of atomic layers of Cu. The purpose of the experimental and theoretical work was to determine the effect of modifying the pure Cu spacer by replacing the central Cu atomic layer with the atomic layer of foreign atoms X. The first principles calculation were performed using the Layer Korringa-Kohn-Rostoker (LKKR) method. The theoretical thickness dependence of the exchange coupling between two semi-infinite Fe layers was calculated for pure Cu spacer thicknesses in the range of 0 < k < 16. The effect of the foreign atoms X on the exchange coupling was investigated using the structure with 9 AL Cu spacer as a reference sample. The calculated changes in the exchange coupling are in qualitative agreement with experiment.

  7. First-principles theory, coarse-grained models, and simulations of ferroelectrics.

    PubMed

    Waghmare, Umesh V

    2014-11-18

    CONSPECTUS: A ferroelectric crystal exhibits macroscopic electric dipole or polarization arising from spontaneous ordering of its atomic-scale dipoles that breaks inversion symmetry. Changes in applied pressure or electric field generate changes in electric polarization in a ferroelectric, defining its piezoelectric and dielectric properties, respectively, which make it useful as an electromechanical sensor and actuator in a number of applications. In addition, a characteristic of a ferroelectric is the presence of domains or states with different symmetry equivalent orientations of spontaneous polarization that are switchable with large enough applied electric field, a nonlinear property that makes it useful for applications in nonvolatile memory devices. Central to these properties of a ferroelectric are the phase transitions it undergoes as a function of temperature that involve lowering of the symmetry of its high temperature centrosymmetric paraelectric phase. Ferroelectricity arises from a delicate balance between short and long-range interatomic interactions, and hence the resulting properties are quite sensitive to chemistry, strains, and electric charges associated with its interface with substrate and electrodes. First-principles density functional theoretical (DFT) calculations have been very effective in capturing this and predicting material and environment specific properties of ferroelectrics, leading to fundamental insights into origins of ferroelectricity in oxides and chalcogenides uncovering a precise picture of electronic hybridization, topology, and mechanisms. However, use of DFT in molecular dynamics for detailed prediction of ferroelectric phase transitions and associated temperature dependent properties has been limited due to large length and time scales of the processes involved. To this end, it is quite appealing to start with input from DFT calculations and construct material-specific models that are realistic yet simple for use in

  8. First-principles calculation of ground and excited-state absorption spectra of ruby and alexandrite considering lattice relaxation

    NASA Astrophysics Data System (ADS)

    Watanabe, Shinta; Sasaki, Tomomi; Taniguchi, Rie; Ishii, Takugo; Ogasawara, Kazuyoshi

    2009-02-01

    We performed first-principles calculations of multiplet structures and the corresponding ground-state absorption and excited-state absorption spectra for ruby (Cr3+:α-Al2O3) and alexandrite (Cr3+:BeAl2O4) which included lattice relaxation. The lattice relaxation was estimated using the first-principles total energy and molecular-dynamics method of the CASTEP code. The multiplet structure and absorption spectra were calculated using the configuration-interaction method based on density-functional calculations. For both ruby and alexandrite, the theoretical absorption spectra, which were already in reasonable agreement with experimental spectra, were further improved by consideration of lattice relaxation. In the case of ruby, the peak positions and peak intensities were improved through the use of models with relaxations of 11 or more atoms. For alexandrite, the polarization dependence of the U band was significantly improved, even by a model with a relaxation of only seven atoms.

  9. First-principles elastic properties of (alpha)-Pu

    SciTech Connect

    Soderlind, P; Klepeis, J E

    2008-11-04

    Density-functional electronic structure calculations have been used to investigate the ambient pressure and low temperature elastic properties of the ground-state {alpha} phase of plutonium metal. The electronic structure and correlation effects are modeled within a fully relativistic anti-ferromagnetic treatment with a generalized gradient approximation for the electron exchange and correlation functionals. The 13 independent elastic constants, for the monoclinic {alpha}-Pu system, are calculated for the observed geometry. A comparison of the results with measured data from resonant ultrasound spectroscopy for a cast sample is made.

  10. First-principles elastic properties of (alpha)-Pu

    SciTech Connect

    Soderlind, P; Klepeis, J

    2009-02-18

    Density-functional electronic-structure calculations have been used to investigate the ambient pressure and low temperature elastic properties of the ground-state {alpha} phase of plutonium metal. The electronic structure and correlation effects are modeled within a fully relativistic antiferromagnetic treatment with a generalized gradient approximation for the electron exchange and correlation functional. The 13 independent elastic constants, for the monoclinic {alpha}-Pu system, are calculated for the observed geometry. A comparison of the results with measured data from recent resonant ultrasound spectroscopy for a cast sample is made.

  11. Strain sensitivity and superconducting properties of Nb3Sn from first principles calculations

    NASA Astrophysics Data System (ADS)

    De Marzi, G.; Morici, L.; Muzzi, L.; della Corte, A.; Buongiorno Nardelli, M.

    2013-04-01

    Using calculations from first principles based on density-functional theory we have studied the strain sensitivity of the A15 superconductor Nb3Sn. The Nb3Sn lattice cell was deformed in the same way as observed experimentally on multifilamentary, technological wires subject to loads applied along their axes. The phonon dispersion curves and electronic band structures along different high-symmetry directions in the Brillouin zone were calculated, at different levels of applied strain, ɛ, on both the compressive and the tensile side. Starting from the calculated averaged phonon frequencies and electron-phonon coupling, the superconducting characteristic critical temperature of the material, Tc, has been calculated by means of the Allen-Dynes modification of the McMillan formula. As a result, the characteristic bell-shaped Tc versus ɛ curve, with a maximum at zero intrinsic strain, and with a slight asymmetry between the tensile and compressive sides, has been obtained. These first-principle calculations thus show that the strain sensitivity of Nb3Sn has a microscopic and intrinsic origin, originating from shifts in the Nb3Sn critical surface. In addition, our computations show that variations of the superconducting properties of this compound are correlated to stress-induced changes in both the phononic and electronic properties. Finally, the strain function describing the strain sensitivity of Nb3Sn has been extracted from the computed Tc(ɛ) curve, and compared to experimental data from multifilamentary, composite wires. Both curves show the expected bell-shaped behavior, but the strain sensitivity of the wire is enhanced with respect to the theoretical predictions for bulk, perfectly binary and stoichiometric Nb3Sn. An understanding of the origin of this difference might open potential pathways towards improvement of the strain tolerance in such systems.

  12. Design and Characterization of Photoelectrodes from First Principles

    SciTech Connect

    Ogitsu, T; Wood, B; Choi, W; Huda, M; Wei, S

    2012-05-11

    Although significant performance improvements have been realized since the first demonstration of sunlight-driven water splitting in 1972, mainstream adoption of photoelectrochemical (PEC) cells remains limited by an absence of cost-effective electrodes that show simultaneously high conversion efficiency and good durability. Here we outline current and future efforts to use advanced theoretical techniques to guide the development of a durable, high-performance PEC electrode material. Working in close collaboration with experimental synthesis and characterization teams, we use a twofold approach focusing on: (1) rational design of novel high-performance electrode materials; and (2) characterization and optimization of the electrode-electrolyte interface.

  13. Deriving the nuclear shell model from first principles

    NASA Astrophysics Data System (ADS)

    Barrett, B. R.; Dikmen, E.; Lisetskiy, A. F.; Maris, P.; Shirokov, A. M.; Vary, J. P.

    2015-02-01

    A procedure for calculating microscopically the input for standard shell-model calculations, i.e., the core and single-particle energies plus the two-body effective model-space interactions, is presented and applied to nuclei at the start of the sd-shell. Calculations with the JISP16 and Idaho χEFT N3LO nucleon-nucleon interactions are performed and yield consistent results, which also are similar to phenomenological results in the sd-shell as well as with other theoretical calculations, utilizing other techniques. All results show only a weak A-dependence.

  14. First-principles study of Casimir repulsion in metamaterials.

    PubMed

    Yannopapas, Vassilios; Vitanov, Nikolay V

    2009-09-18

    We examine theoretically the Casimir effect between a metallic plate and several types of magnetic metamaterials in pursuit of Casimir repulsion, by employing a rigorous multiple-scattering theory for the Casimir effect. We first examine metamaterials in the form of two-dimensional lattices of inherently nonmagnetic spheres such as spheres made from materials possessing phonon-polariton and exciton-polariton resonances. Although such systems are magnetically active in infrared and optical regimes, the force between finite slabs of these materials and metallic slabs is plainly attractive since the effective electric permittivity is larger than the magnetic permeability for the studied spectrum. When lattices of magnetic spheres made from superparamagnetic composites are employed, we achieve not only Casimir repulsion but almost total suppression of the Casimir effect itself in the micrometer scale. PMID:19792414

  15. First-Principles Investigation of Li Intercalation Kinetics in Phospho-Olivines

    NASA Astrophysics Data System (ADS)

    Malik, Rahul

    This thesis focuses broadly on characterizing and understanding the Li intercalation mechanism in phospho-olivines, namely LiFePO 4 and Li(Fe,Mn)PO4, using first-principles calculations. Currently Li-ion battery technology is critically relied upon for the operation of electrified vehicles, but further improvements mainly in cathode performance are required to ensure widespread adoption, which in itself requires learning from existing commercial cathode chemistries. LiFePO4 is presently used in commercial Li-ion batteries, known for its rapid charge and discharge capability but with underwhelming energy density. This motivates the three central research efforts presented herein. First, we investigate the modified phase diagram and electrochemical properties of mixed olivines, such as Li(Fe,Mn)PO4, which offer improved theoretical energy density over LiFePO4 (due to the higher redox voltage associated with Mn2+/Mn3+). The Lix(Fe1-yMny)PO4 phase diagram is constructed by Monte Carlo simulation on a cluster expansion Hamiltonian parametrized by first-principles determined energies. Deviations from the equilibrium phase behavior and voltages of pure LiFePO4 and LiMnPO 4 are analyzed and discussed to good agreement with experimental observations. Second, we address why LiFePO4 exhibits superior rate performance strictly when the active particle size is brought down to the nano-scale. By considering the presence of immobile point defects residing in the 1D Li diffusion path, specifically by calculating from first principles both defect formation energies and Li migration barriers in the vicinity of likely defects, the Li diffusivity is recalculated and is found to strongly vary with particle size. At small particle sizes, the contribution from defects is small, and fast 1D Li diffusion is accessible. However, at larger particle sizes (microm scale and above) the contribution from defects is much larger. Not only is Li transport impeded, but it is also less anisotropic in

  16. Lattice dynamics and thermal conductivity of calcium fluoride via first-principles investigation

    NASA Astrophysics Data System (ADS)

    Qi, Yuan-Yuan; Zhang, Tian; Cheng, Yan; Chen, Xiang-Rong; Wei, Dong-Qing; Cai, Ling-Cang

    2016-03-01

    The lattice thermal conductivity of CaF2 is accurately computed from a first-principles theoretical approach based on an iterative solution of the Boltzmann transport equation. The second- and third-order interatomic force constants are generated from a real-space finite-difference supercell approach. Then, the force constants for both the second- and third-order potential interactions are used to calculate the lattice thermal conductivity and related physical quantities of CaF2 at temperatures ranging from 30 K to 1500 K. The obtained lattice thermal conductivity 8.6 W/(m.K) for CaF2 at room temperature agrees better with the experimental value than other theoretical data, demonstrating the promise of this parameter-free approach in providing precise descriptions of the lattice thermal conductivity of materials. The obtained dielectric parameters and phonon spectrum of CaF2 accord well with available data. Meanwhile, the temperature dependence curves of the lattice thermal conductivity, heat capacity, and phonon mean free path are presented.

  17. First principles effective electronic couplings for hole transfer in natural and size-expanded DNA

    PubMed Central

    Migliore, Agostino; Corni, Stefano; Varsano, Daniele; Klein, Michael L.; Di Felice, Rosa

    2009-01-01

    Hole transfer processes between base pairs in natural DNA and size-expanded DNA (xDNA) are studied and compared, by means of an accurate first principles evaluation of the effective electronic couplings (also known as transfer integrals), in order to assess the effect of the base augmentation on the efficiency of charge transport through double-stranded DNA. According to our results, the size expansion increases the average electronic coupling, and thus the CT rate, with potential implications in molecular biology and in the implementation of molecular nanoelectronics. Our analysis shows that the effect of the nucleobase expansion on the charge-transfer (CT) rate is sensitive to the sequence of base pairs. Furthermore, we find that conformational variability is an important factor for the modulation of the CT rate. From a theoretical point of view, this work offers a contribution to the CT chemistry in π-stacked arrays. Indeed, we compare our methodology against other standard computational frameworks that have been adopted to tackle the problem of CT in DNA, and unravel basic principles that should be accounted for in selecting an appropriate theoretical level. PMID:19537767

  18. First-principles theoretical studies of half-metallic ferromagnetism in CrTe

    NASA Astrophysics Data System (ADS)

    Liu, Y.; Bose, S. K.; Kudrnovský, J.

    2010-09-01

    Using full-potential linear augmented plane-wave method (FP-LAPW) we have studied the stability and electronic properties of the chalcogenide CrTe in three competing structures: rocksalt (RS), zinc blende (ZB), and the NiAs-type (NA) hexagonal. Although the ground state is of NA structure, RS and ZB are interesting in that these fcc-based structures, which can perhaps be grown on various semiconductor substrates, exhibit half-metallic (HM) phases above some critical values of the lattice parameter. We find that the NA structure is not HM at its equilibrium volume while both ZB and RS structures are. The RS structure is more stable than the ZB with an energy that is lower by 0.25 eV/atom. While confirming previous results on the HM phase in ZB structure, we provide hitherto unreported results on the HM RS phase, with a gap in the minority channel and a magnetic moment of 4.0μB/f.u. A comparison of total energies for the ferromagnetic (FM), nonmagnetic, and antiferromagnetic (AFM) configurations shows the lowest energy configuration to be FM for CrTe in all the three structures. The exchange interactions in the RS and ZB structures are studied for a wide range of the lattice parameter using the linear-response method and a mapping of the total energy to the classical Heisenberg model. These linear-response calculations are performed in the linear muffin-tin orbitals (LMTOs) basis, using the atomic sphere approximation (ASA). We have verified that the results of the electronic structure obtained via the LMTO-ASA method under local-density approximation (LDA) and LDA+U schemes are in close agreement with those obtained via the more accurate FP-LAPW method. The results show that the exchange interactions in the RS structure are much more short ranged than in the ZB structure. Hence, for the RS structure the exchange interactions are also studied by using a nearest- and next-nearest-neighbor (J1-J2) model and the energy differences between FM and two AFM states. These J1-J2 model results are obtained by using both the FP-LAPW and LMTO-ASA methods and compared with the linear-response results. The calculated Curie temperatures for the RS phase are consistently higher than those for the ZB phase.

  19. Photodesorption of diatomic molecules from surfaces: A theoretical approach based on first principles

    NASA Astrophysics Data System (ADS)

    Klüner, Thorsten

    2010-05-01

    Photodesorption of small molecules from surfaces is one of the most fundamental processes in surface photochemistry. Despite its apparent simplicity, a microscopic understanding beyond a qualitative picture still poses a true challenge for theory. While the dynamics of nuclear motion can be treated on various levels of sophistication, all approaches suffer from the lack of sufficiently accurate potential energy surfaces, in particular for electronically excited states involved in the desorption scenario. In the last decade, a systematic and accurate methodology has been developed which allows a reliable calculation of accurate ground and excited state potential energy surfaces (PES) for different adsorbate-substrate systems. These potential energy surfaces serve as a prerequisite for subsequent quantum dynamical wave packet calculations, which allow for a direct simulation of experimentally observable quantities such as quantum state resolved velocity distributions. In the first part of this review, we will focus on scalar properties of desorbing diatomic molecules from insulating surfaces, where we also present a recently developed strategy of obtaining accurate potential energy surfaces using quantum chemical approaches. In general, diatomic molecules on large band gap materials such as oxide surfaces are studied which allows the use of sufficiently large cluster models and accurate ab initio methods beyond density functional theory (DFT). In the second part, we will focus on the vectorial aspects of the dynamics of nuclear motion and present simulations of experimentally accessible observables such as velocity distributions, Doppler profiles and alignment parameters. For each system, the microscopic mechanism of photodesorption is elucidated. We will demonstrate that the driving force of surface photochemistry is strongly dependent on details of the electronic structure of the adsorbate-substrate systems. This implies that great caution is advisable if experimental results are interpreted using empirical or semi-empirical models.

  20. Nitrate isotope fractionations during biological nitrate reduction: Insights from first principles theoretical modeling

    NASA Astrophysics Data System (ADS)

    Guo, W.; Granger, J.; Sigman, D. M.

    2010-12-01

    Coupled fractionations of N and O isotopes during biological nitrate reduction provide important constraints on the marine nitrogen cycle at present and in the geologic past. Recent laboratory experiments with mono-cultures of nitrate-assimilative algae and plankton, and denitrifying bacteria demonstrate that N and O isotopic compositions of the residual nitrate co-vary linearly with a constant ratio (i.e., Δδ18O: Δδ15N) of ~1 or ~0.6 [1]. These systematic variations have been inferred to derive from the kinetic isotope fractionations associated with nitrate reductases. The isotope fractionation mechanisms at the enzymatic level, however, remain elusive. Here we present models of isotope fractionations accompanying the nitrate reduction (NO3-→NO2-) by three functional types of nitrate reductases, using techniques from ab initio, transition state and statistical thermodynamic theory. We consider three types of nitrate reductases: eukNR (eukaryotic assimilatory nitrate reductase), NAR (prokaryotic respiratory nitrate reductase) and Nap (prokaryotic periplasmic nitrate reductase). All are penta- or hexa-coordinated molybdo-enzymes, but bear considerable differences in protein geometry among functional types. Our models, based on the simplified structures of their active sites, predict N and O isotope effects (15ɛ and 18ɛ) ranging from 32.7 to 36.6‰ and from 33.5 to 34.8‰, respectively, at 300K with 18ɛ:15ɛ ratios of 0.9-1.1. The predicted amplitudes of N and O isotope fractionations are in the range measured for eukNR in vitro (~27‰, Karsh et al. in prep), and also correspond to the upper amplitudes observed for denitrifiers in vivo (~25‰, [1]). Moreover, the computed 18ɛ:15ɛ ratios corroborate the consistent relationships of ~1 observed experimentally for eukNR and the respiratory NAR. These findings indicate the enzymatic reduction is likely the rate-limiting step in most biological nitrate reductions. In addition, the predicted similarity of 18ɛ:15ɛ ratios among different nitrate reductases suggests that the nitrate isotope fractionations by nitrate reductases are governed by the kinetics of the O-N bond cleavage, which incurs negligible differences from variations in surrounding moieties at the active sites. However, our model similarly predicts a 15ɛ of 36.6‰ and 18ɛ:15ɛ of 0.9 for the auxiliary Nap, although it exhibits a 15ɛ of ~15‰ and 18ɛ:15ɛ of ~0.6 in vivo [1]. This discrepancy is suspected to arise from slower binding and release of NO3- from Nap, which could be partially rate-determining in this enzymatic catalysis, or from the assumptions of our modeled enzyme structures. By extending our above models to include the multiply-substituted (clumped) isotopologues, we predict that isotope fractionations during biological nitrate reduction decrease the proportion of 15N-18O bonds in the residual nitrate relative to their expected equilibrium abundances (~0.02‰ decrease for every 1‰ kinetic enrichment in nitrate δ15N). Future quantification of 15N-18O clumped isotope anomalies in natural nitrate may provide additional constraints on the nitrogen cycle in the ocean. Reference: [1] Granger et al. (2010) GCA, 74: 1030-1040.

  1. A Theoretical Study of Bulk and Surface Diffusion Processes for Semiconductor Materials Using First Principles Calculations

    NASA Astrophysics Data System (ADS)

    Roehl, Jason L.

    Diffusion of point defects on crystalline surfaces and in their bulk is an important and ubiquitous phenomenon affecting film quality, electronic properties and device functionality. A complete understanding of these diffusion processes enables one to predict and then control those processes. Such understanding includes knowledge of the structural, energetic and electronic properties of these native and non-native point defect diffusion processes. Direct experimental observation of the phenomenon is difficult and microscopic theories of diffusion mechanisms and pathways abound. Thus, knowing the nature of diffusion processes, of specific point defects in given materials, has been a challenging task for analytical theory as well as experiment. The recent advances in computing technology have been a catalyst for the rise of a third mode of investigation. The advent of tremendous computing power, breakthroughs in algorithmic development in computational applications of electronic density functional theory now enables direct computation of the diffusion process. This thesis demonstrates such a method applied to several different examples of point defect diffusion on the (001) surface of gallium arsenide (GaAs) and the bulk of cadmium telluride (CdTe) and cadmium sulfide (CdS). All results presented in this work are ab initio, total-energy pseudopotential calculations within the local density approximation to density-functional theory. Single particle wavefunctions were expanded in a plane-wave basis and reciprocal space k-point sampling was achieved by Monkhorst-Pack generated k-point grids. Both surface and bulk computations employed a supercell approach using periodic boundary conditions. Ga adatom adsorption and diffusion processes were studied on two reconstructions of the GaAs(001) surface including the c(4x4) and c(4x4)-heterodimer surface reconstructions. On the GaAs(001)- c(4x4) surface reconstruction, two distinct sets of minima and transition sites were discovered for a Ga adatom relaxing from heights of 3 and 0.5 A from the surface. These two sets show significant differences in the interaction of the Ga adatom with surface As dimers and an electronic signature of the differences in this interaction was identified. The energetic barriers to diffusion were computed between various adsorption sites. Diffusion profiles for native Cd and S, adatom and vacancy, and non-native interstitial adatoms of Te, Cu and Cl were investigated in bulk wurtzite CdS. The interstitial diffusion paths considered in this work were chosen parallel to c-axis as it represents the path encountered by defects diffusing from the CdTe layer. Because of the lattice mismatch between zinc-blende CdTe and hexagonal wurtzite CdS, the c-axis in CdS is normal to the CdTe interface. The global minimum and maximum energy positions in the bulk unit cell vary for different diffusing species. This results in a significant variation, in the bonding configurations and associated strain energies of different extrema positions along the diffusion paths for various defects. The diffusion barriers range from a low of 0.42 eV for an S interstitial to a high of 2.18 eV for a S vacancy. The computed 0.66 eV barrier for a Cu interstitial is in good agreement with experimental values in the range of 0.58 - 0.96 eV reported in the literature. There exists an electronic signature in the local density of states for the s- and d-states of the Cu interstitial at the global maximum and global minimum energy position. The work presented in this thesis is an investigation into diffusion processes for semiconductor bulk and surfaces. The work provides information about these processes at a level of control unavailable experimentally giving an elaborate description into physical and electronic properties associated with diffusion at its most basic level. Not only does this work provide information about GaAs, CdTe and CdS, it is intended to contribute to a foundation of knowledge that can be extended to other systems to expand our overall understanding into the diffusion process. (Abstract shortened by UMI.)

  2. Putting DFT to the Test: A First-Principles Study of Electronic, Magnetic, and Optical Properties of Co3O4

    NASA Astrophysics Data System (ADS)

    Singh, Vijay; Kosa, Monica; Majhi, Koushik; Major, Dan Thomas; Arie Zaban Collaboration, Prof.

    First-principles density functional theory (DFT) and a many-body Green's function method have been employed to elucidate the electronic, magnetic, and photonic properties of a spinel compound, Co3O4. Co3O4 is believed to be a strongly correlated material, where the on-site Coulomb interaction (U) on Co d orbitals is presumably important, although this view has recently been contested. The suggested optical band gap for this material ranges from 0.8 to 2.0 eV, depending on the type of experiments and theoretical treatment. Thus, the correlated nature of the Co d orbitals in Co3O4 and the extent of the band gap are still under debate, raising questions regarding the ability of DFT to correctly treat the electronic structure in this material. To resolve the above controversies, we have employed a range of theoretical methods, including pure DFT, DFT +U, and a range-separated exchange-correlation functional (HSE06) as well as many-body Green's function theory (i.e., the GW method). We compare the electronic structure and band gap of Co3O4 with available photoemission spectroscopy and optical band gap data and confirm a direct band gap of ca. 0.8 eV. Furthermore, we have also studied the optical properties of Co3O4 by calculating the imaginary part of the dielectric function (Im(ε)) , facilitating direct comparison with the measured optical absorption spectra.

  3. First-principles investigations of elastic stability and electronic structure of cubic platinum carbide under pressure

    NASA Astrophysics Data System (ADS)

    Sun, Xiao-Wei; Chen, Qi-Feng; Chen, Xiang-Rong; Cai, Ling-Cang; Jing, Fu-Qian

    2011-11-01

    The authors have presented a detailed investigation on the phase stabilities and electronic properties of ideal stoichiometric platinum carbide (PtC) in the rock-salt (RS) and zinc-blende (ZB) structures under high pressure. Theoretical calculations are performed using the first-principles pseudopotential density functional method, in which we employ the generalized gradient approximation (GGA) of the Perdew-Burke-Ernzerhof form and local density approximation (LDA) of Ceperly and Adler parameterized by Perdew and Zunger together with plane-wave basis sets for expanding the periodic electron density. Through a series of tests, such as the total energy as a function of volume, the Gibbs free energy as a function of pressure, the P-V equation of states, the elastic stabilities, and the electronic band structures of PtC with ZB and RS phases, we have confirmed that the recently synthesized compound PtC is crystallized in the ZB structure at zero pressure and that the RS structure is a high-pressure phase; the phase transition studied from the usual condition of equal enthalpies occurs at the pressures of 46.6 and 46.5 GPa for GGA and LDA calculations, respectively. Our conclusions are consistent with the theoretical prediction obtained from the full-potential linearized augmented plane-wave method, but are reversed with the DAC experimental results and other pseudopotential plane-wave theoretical results. Therefore, the experimental observation of the RS structure in PtC remains a puzzle, and our study indicates that further experimental and theoretical investigations need to be carried out to find the cause of the stability of the PtC.

  4. First-Principles Computation of Graphene's Phonon Anharmonicity

    NASA Astrophysics Data System (ADS)

    Kornbluth, Mordechai; Marianetti, Chris A.

    Here we use density-functional theory to compute an interatomic potential for graphene, including anharmonicities up to at least fourth order. We generate all group-theoretically allowed terms within a hexagon via the recently-developed slave mode expansion. This expands the potential in terms of the normal modes of overlapping hexagons, while obeying the space group symmetry and homogeneity of free space. We further introduce the notion of cooperative modes, which combine strain and q = 0 phonons to yield the same pure mode amplitude on each hexagon. Within the cooperative subspace, cooperative modes allow for arbitrarily-precise meshing to directly compute energies, or calculation of the anharmonic coefficients via finite-difference. We demonstrate the power of our approach in the context of strained graphene, which is known to have a novel strain-driven soft mode at the K-point. We identify the dominant anharmonic terms which drive the soft K mode, and study the role of finite temperatures using molecular dynamics and Monte-Carlo simulations.

  5. First-principles studies of Al-Ni intermetallic compounds

    SciTech Connect

    Shi Dongmin; Wen Bin; Melnik, Roderick; Yao Shan; Li Tingju

    2009-10-15

    The structural properties, heats of formation, elastic properties, and electronic structures of Al-Ni intermetallic compounds are analyzed here in detail by using density functional theory. Higher calculated absolute values of heats of formation indicate a very strong chemical interaction between Al and Ni for all Al-Ni intermetallic compounds. According to the computational single crystal elastic constants, all the Al-Ni intermetallic compounds considered here are mechanically stable. The polycrystalline elastic modulus and Poisson's ratio have been deduced by using Voigt, Reuss, and Hill (VRH) approximations, and the calculated ratio of shear modulus to bulk modulus indicated that AlNi, Al{sub 3}Ni, AlNi{sub 3} and Al{sub 3}Ni{sub 5} compounds are ductile materials, but Al{sub 4}Ni{sub 3} and Al{sub 3}Ni{sub 2} are brittle materials. With increasing Ni concentration, the bulk modulus of Al-Ni intermetallic compounds increases in a linear manner. The electronic energy band structures confirm that all Al-Ni intermetallic compounds are conductors. - Graphical abstract: Calculated bulk modulus compared to experimental and other theoretical values for the Al-Ni intermetallic compounds.

  6. First Principles NMR Study of Fluorapatite under Pressure

    PubMed Central

    Pavan, Barbara; Ceresoli, Davide; Tecklenburg, Mary M. J.; Fornari, Marco

    2012-01-01

    NMR is the technique of election to probe the local properties of materials. Herein we present the results of density functional theory (DFT) ab initio calculations of the NMR parameters for fluorapatite (FAp), a calcium orthophosphate mineral belonging to the apatite family, by using the GIPAW method [Pickard and Mauri, 2001]. Understanding the local effects of pressure on apatites is particularly relevant because of their important role in many solid state and biomedical applications. Apatites are open structures, which can undergo complex anisotropic deformations, and the response of NMR can elucidate the microscopic changes induced by an applied pressure. The computed NMR parameters proved to be in good agreement with the available experimental data. The structural evaluation of the material behavior under hydrostatic pressure (from −5 to +100 kbar) indicated a shrinkage of the diameter of the apatitic channel, and a strong correlation between NMR shielding and pressure, proving the sensitivity of this technique to even small changes in the chemical environment around the nuclei. This theoretical approach allows the exploration of all the different nuclei composing the material, thus providing a very useful guidance in the interpretation of experimental results, particularly valuable for the more challenging nuclei such as 43Ca and 17O. PMID:22770669

  7. First principle computation of biomolecule-ligand interaction

    NASA Astrophysics Data System (ADS)

    Chachiyo, Teepanis

    We have determined the calibration constants for the SDFT prediction of 57Fe Mossbauer parameters. The calibration constants are basis set and exchange-correlation functional specific. The basis set is 6-311G* whereas the exchange-correlation functional are UB3LYP, UBLYP, UBPW91, and UMPW1PW91. This method is used to predict the binding conformation of a dioxygen molecule to the P intermediate of methane monooxygenase whose experimental binding structure is presently unknown. When O2 binds to the diiron cluster in a mu-1,2-peroxo fashion, the associated theoretical Mossbauer parameters are in good agreement with the experimental values. An efficient method for locating minimum energy crossing points is introduced and tested on the phenyl cation. An agreement of the present method and previous works is satisfactory. The convergence rate obeys a logarithmic law and is verified on the phenyl cation. Due to its rapid convergence rate, the method is suitable for a large molecular system. As an application of the new methodology, the crossing points of the cation of [Fe(ptz)6](BF4) 2 were studied in order to identify the geometrical parameters of the spin crossing points between S=0 ↔ S=1, and S=1 ↔ S=2. The calculation shows that the transition from a singlet ground state to the triplet intermediate state is accompanied by almost 0.3A bond length elongation of the axial ligands. We have implemented an approximation scheme that allows one to study protein system such as a ligand-protein binding conformation and a protein active site geometry optimization. The scheme, named E-MFCC, is a significant improvement over the previous MFCC approximation originally put forth by Zhang et al. The geometry optimization of some small test systems utilizing the E-MFCC scheme introduces an error on the order of 10-2A as compared to the all-atom calculation.

  8. First-principles modeling of electromagnetic scattering by discrete and discretely heterogeneous random media

    NASA Astrophysics Data System (ADS)

    Mishchenko, Michael I.; Dlugach, Janna M.; Yurkin, Maxim A.; Bi, Lei; Cairns, Brian; Liu, Li; Panetta, R. Lee; Travis, Larry D.; Yang, Ping; Zakharova, Nadezhda T.

    2016-05-01

    the first-principles formalism enabling accurate calculations of monochromatic and quasi-monochromatic scattering by static and randomly varying multiparticle groups. We illustrate how this general framework can be coupled with state-of-the-art computer solvers of the Maxwell equations and applied to direct modeling of electromagnetic scattering by representative random multi-particle groups with arbitrary packing densities. This first-principles modeling yields general physical insights unavailable with phenomenological approaches. We discuss how the first-order-scattering approximation, the radiative transfer theory, and the theory of weak localization of electromagnetic waves can be derived as immediate corollaries of the Maxwell equations for very specific and well-defined kinds of particulate medium. These recent developments confirm the mesoscopic origin of the radiative transfer, weak localization, and effective-medium regimes and help evaluate the numerical accuracy of widely used approximate modeling methodologies.

  9. A first principles study of the acetylene-water interaction

    SciTech Connect

    Tzeli, Demeter; Mavridis, Aristides; Xantheas, Sotiris S.

    2000-04-08

    We present an extensive study of the stationary points on the acetylene-water (AW) ground-state potential energy surface (PES) aimed in establishing accurate energetics for the two different bonding scenarios that are considered. Those include arrangements in which water acts either as a proton acceptor from one of the acetylene hydrogen atoms or a proton donor to the triple bond. We used a hierarchy of theoretical methods to account for electron correlation [MP2 (second-order Moller-Plesset), MP4 (fourth-order Moller-Plesset), and CCSD(T) (coupled-cluster single double triple)] coupled with a series of increasing size augmented correlation consistent basis sets (aug-cc-pVnZ, n=2,3,4). We furthermore examined the effect of corrections due to basis set superposition error (BSSE). We found that those have a large effect in altering the qualitative features of the PES of the complex. They are responsible for producing a structure of higher (C{sub 2v}) symmetry for the global minimum. Zero-point energy (ZPE) corrections were found to increase the stability of the C{sub 2v} arrangement. For the global (water acceptor) minimum of C{sub 2v} symmetry our best estimates are {delta}E{sub e}=-2.87 kcal/mol ({delta}E{sub 0}=-2.04 kcal/mol) and a van der Waals distance of R{sub e}=2.190 Aa. The water donor arrangement lies 0.3 kcal/mol (0.5 kcal/mol including ZPE corrections) above the global minimum. The barrier for its isomerization to the global minimum is E{sub e}=0.18 kcal/mol; however, inclusion of BSSE- and ZPE-corrections destabilize the water donor arrangement suggesting that it can readily convert to the global minimum. We therefore conclude that there exists only one minimum on the PES in accordance with previous experimental observations. To this end, vibrational averaging and to a lesser extend proper description of intermolecular interactions (BSSE) were found to have a large effect in altering the qualitative features of the ground-state PES of the acetylene

  10. First-principles study of the covalently functionalized graphene

    NASA Astrophysics Data System (ADS)

    Jha, Sanjiv Kumar

    Theoretical investigations of nanoscale systems, such as functionalized graphene, present major challenges to conventional computational methods employed in quantum chemistry and solid state physics. The properties of graphene can be affected by chemical functionalization. The surface functionalization of graphene offers a promising way to increase the solubility and reactivity of graphene for use in nanocomposites and chemical sensors. Covalent functionalization is an efficient way to open band-gap in graphene for applications in nanoelectronics. We apply ab initio computational methods based on density functional theory to study the covalent functionalization of graphene with benzyne (C6H4), tetracyanoethylene oxide (TCNEO), and carboxyl (COOH) groups. Our calculations are carried out using the SIESTA and Quantum-ESPRESSO electronic structure codes combined with the generalized gradient (GGA) and local density approximations (LDA) for the exchange correlation functionals and norm-conserving Troullier-Martins pseudopotentials. Calculated binding energies, densities of states (DOS), band structures, and vibrational spectra of functionalized graphene are analyzed in comparison with the available experimental data. Our calculations show that the reactions of [2 + 2] and [2 + 4] cycloaddition of C6H4 to the surface of pristine graphene are exothermic, with binding energies of --0.73 eV and --0.58 eV, respectively. Calculated band structures indicate that the [2 + 2] and [2 + 4] attachments of benzyne results in opening small band gap in graphene. The study of graphene--TCNEO interactions suggests that the reaction of cycloaddition of TCNEO to the surface of pristine graphene is endothermic. On the other hand, the reaction of cycloaddition of TCNEO is found to be exothermic for the edge of an H-terminated graphene sheet. Simulated Raman and infrared spectra of graphene functionalized with TCNEO are consistent with experimental results. The Raman (non-resonant) and

  11. Effect of Pressure on Valence and Structural Properties of YbFe2Ge2 Heavy Fermion Compound A Combined Inelastic X-ray Spectroscopy, X-ray Diffraction, and Theoretical Investigation

    SciTech Connect

    Kumar, Ravhi S.; Svane, Axel; Vaitheeswaran, Ganapathy; Kanchana, Venkatakrishnan; Antonio, Daniel; Cornelius, Andrew L.; Bauer, Eric D.; Xiao, Yuming; Chow, Paul

    2015-10-19

    The crystal structure and the Yb valence of the YbFe2Ge2 heavy fermion compound was measured at room temperature and under high pressures using high-pressure powder X-ray diffraction and X-ray absorption spectroscopy via both partial fluorescence yield and resonant inelastic X-ray emission techniques. Furthermore, the measurements are complemented by first-principles density functional theoretical calculations using the self-interaction corrected local spin density approximation investigating in particular the magnetic structure and the Yb valence. While the ThCr2Si2-type tetragonal (I4/mmm) structure is stable up to 53 GPa, the X-ray emission results show an increase of the Yb valence from v = 2.72(2) at ambient pressure to v = 2.93(3) at ~9 GPa, where at low temperature a pressure-induced quantum critical state was reported.

  12. Effect of Pressure on Valence and Structural Properties of YbFe2Ge2 Heavy Fermion Compound--A Combined Inelastic X-ray Spectroscopy, X-ray Diffraction, and Theoretical Investigation.

    PubMed

    Kumar, Ravhi S; Svane, Axel; Vaitheeswaran, Ganapathy; Kanchana, Venkatakrishnan; Antonio, Daniel; Cornelius, Andrew L; Bauer, Eric D; Xiao, Yuming; Chow, Paul

    2015-11-01

    The crystal structure and the Yb valence of the YbFe2Ge2 heavy fermion compound was measured at room temperature and under high pressures using high-pressure powder X-ray diffraction and X-ray absorption spectroscopy via both partial fluorescence yield and resonant inelastic X-ray emission techniques. The measurements are complemented by first-principles density functional theoretical calculations using the self-interaction corrected local spin density approximation investigating in particular the magnetic structure and the Yb valence. While the ThCr2Si2-type tetragonal (I4/mmm) structure is stable up to 53 GPa, the X-ray emission results show an increase of the Yb valence from v = 2.72(2) at ambient pressure to v = 2.93(3) at ∼9 GPa, where at low temperature a pressure-induced quantum critical state was reported. PMID:26479903

  13. First-principles study of alloying effect of transition metals on He in titanium ditritide

    NASA Astrophysics Data System (ADS)

    Wu, Y. X.; Yang, R.; Zheng, H.; Wang, Y. M.

    2006-08-01

    Due to its inert reactivity with almost elements, 3He produced from tritium decay has extremely detrimental effects on the tritide. To refrain from this 3He-induced damage, an efficient way is to increase the stability of 3He in metal tritide by alloying. Using a first-principles discrete variational method in two cluster models, one for a low 3He concentration and the other for a high 3He concentration, the authors study the alloying effect of 3d and 4d transition metals on the stability of 3He in TiT 2 system. It is found that the preferring and metastable sites of 3He are affected by 3He concentration: 3He prefers to stay at original tetrahedral interstitial site when 3He concentration is low but moves to octahedral site when 3He concentration is high enough. A criterion of alloying effect is proposed, according to which Nb, Y, Zr, Pd, Ru, Tc, Rh, Cr, Mo and Ag are suggested to be the beneficial alloying elements for increasing the stability of 3He in the alloyed TiT 2 with a low 3He concentration and Y, Nb, Mo, Zr, Cr, Tc, Ru, Rh and Cu for that with a high 3He concentration. Our results of alloying effect are supported by the positron annihilation spectroscopy (PAS) measurements for He-implanted Ti, TiMoYAl and TiZrYAl films.

  14. Molybdenum Disulfide-Coated Lithium Vanadium Fluorophosphate Anode: Experiments and First-Principles Calculations.

    PubMed

    Liu, Zhaomeng; Peng, Wenjie; Xu, Zhenming; Shih, Kaimin; Wang, Jiexi; Wang, Zhixing; Lv, Xiaojun; Chen, Jiangan; Li, Xinhai

    2016-08-23

    To develop a new anode material to meet the increasing demands of lithium-ion battery, MoS2 is used for the first time to modify the C/LiVPO4 F anode to improve its lithium-storage performance between 3 and 0.01 V. Morphological observations reveal that the MoS2 -modified C/LiVPO4 F particles (M-LVPF) are wrapped by an amorphous carbon as interlayer and layered MoS2 as external surface. Charge-discharge tests show that M-LVPF delivers a high reversible capacity of 308 mAh g(-1) at 50 mA g(-1) . After 300 cycles at 1.0 A g(-1) , a capacity retention of 98.7 % is observed. Moreover, it exhibits high rate capability with a specific capacity of 199 mAh g(-1) at 1.6 A g(-1) . Electrochemical impedance spectroscopy tests indicate that the lithium-ion diffusion and charge-exchange reaction at the surface of M-LVPF are greatly enhanced. First-principles calculations for the MoS2 (001)/C/LiVPO4 F (010) system demonstrate that the absorption of MoS2 on C/LiVPO4 F is exothermic and spontaneous and that the electron transfer at the MoS2 -absorbed C/LiVPO4 F surface is enhanced. PMID:27376792

  15. First-principles simulations of charge storage at electrochemical interfaces in supercapacitors

    NASA Astrophysics Data System (ADS)

    Wood, Brandon

    2015-03-01

    Supercapacitors store charge via polarization at the electrode-electrolyte interface. Many models of interfacial charge storage focus on the formation of the electric double layer (EDL) in the electrolyte, but it is often assumed that in the electrode, a shift in the Fermi level is the only notable response to interface polarization. In reality, the presence of the interface impacts the fundamental properties of both the electrode and the electrolyte, often in complex and nontrivial ways that are difficult to capture using simple models. I will discuss how including an applied bias potential in first-principles simulations allows one to directly simulate the process of charge storage at the electrode-electrolyte interface, and thereby to unravel the interplay between the electrode and the electrolyte. I will show how these more complex treatments lead to improved descriptions of intrinsic quantum and EDL capacitance contributions in graphene-based supercapacitors, which can be used to suggest engineering strategies for improved electrode materials. I will also discuss how combining theory with in operando X-ray spectroscopy can give insights into nanoscale chemical changes and mesoscale morphological changes in electrodes during charging. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under contract DE-AC52-07NA27344.

  16. First principles study of Al/SrTiO3 interface formation

    NASA Astrophysics Data System (ADS)

    Hamze, Ali; Posadas, Agham; Kormondy, Kristy; Demkov, Alexander

    Two-dimensional electron gasses (2DEGs) at the interfaces of oxides have been the subject of much interest in recent years due to their relatively high carrier mobilities and potential for use in all-oxide devices. In particular, the γ-Al2O3 (γ-alumina)-SrTiO3 (STO) system has been the focus of much research. It exhibits a 2DEG at the interface with a carrier mobility ranging from 103-105 cm2V-1 s-1, depending on the thickness of the STO and how the γ-alumina film was grown. It is believed that Al atoms steal oxygen from the STO substrate at growth temperature and thus create a conductive channel in STO near the interface. We investigate the initial studies of the interface formation using density functional theory. The results of first principles calculations are compared with those of x-ray photoemission spectroscopy (XPS) performed in situ on thin Al films deposited on STO by molecular beam epitaxy. Analysis of the Al 2p XPS spectrum shows one layer of aluminum is fully oxidized during growth at 40°C and 4 layers of aluminum are fully oxidized during growth at 600°C. Furthermore, the Ti 2p XPS spectrum shows the titanium atoms are reduced, which is consistent with the presence of oxygen vacancies in STO.

  17. Investigation of structural stability and elastic properties of Zrh and Zrh{sub 2}: A first principles study

    SciTech Connect

    Kanagaprabha, S.; Rajeswarapalanichamy, R. Sudhapriyanga, G. Murugan, A. Santhosh, M.; Iyakutti, K.

    2014-04-24

    The electronic, structural and mechanical properties of ZrH and ZrH{sub 2} are investigated by means of first principles calculation based on density functional theory as implemented in VASP code with generalized gradient approximation. The calculated ground state properties are in good agreement with previous experimental and other theoretical results. Among the six crystallographic structures considered for ZrH, ZB phase is found to be the most stable phase, whereas ZrH{sub 2} is energetically stable in tetragonal structure at ambient condition. A structural phase transition from ZB→NaCl at a pressure 10 GPa is predicted for ZrH.

  18. First-principles calculation of optical absorption spectra in conjugated polymers: Role of electron-hole interaction

    SciTech Connect

    Rohlfing, Michael; Tiago, M.L.; Louie, Steven G.

    2000-03-20

    Experimental and theoretical studies have shown that excitonic effects play an important role in the optical properties of conjugated polymers. The optical absorption spectrum of trans-polyacetylene, for example, can be understood as completely dominated by the formation of exciton bound states. We review a recently developed first-principles method for computing the excitonic effects and optical spectrum, with no adjustable parameters. This theory is used to study the absorption spectrum of two conjugated polymers: trans-polyacetylene and poly-phenylene-vinylene(PPV).

  19. First-principles Studies of the Optical Properties of Eu doped Barium Halides: From Storage Phosphor to Bright Scintillator

    NASA Astrophysics Data System (ADS)

    Canning, Andrew; Medasani, Bharat; Del Ben, Mauro; Bizarri, Gregory

    The Eu doped Ba mixed halide family BaBrX (X=F,Cl,Br,I) changes from being a widely used X-ray Storage Phosphor (BaBrF:Eu) to one of the brightest know new gamma ray detector scintillators (BaBrI:Eu). To help understand these contrasting optical properties and guide in the design of new and improved scintillator detectors, in collaboration with experimental groups, we have performed first principles theoretical studies of these materials. In particular we have studied their electron and hole trapping mechanisms and how that can explain their very different optical properties.

  20. Optical second-harmonic spectra of Si(001) with H and Ge adatoms: First-principles theory and experiment

    SciTech Connect

    Gavrilenko, V. I.; Wu, R. Q.; Downer, M. C.; Ekerdt, J. G.; Lim, D.; Parkinson, P.

    2001-04-15

    We present calculated second-harmonic-generation (SHG) spectra of the Si(001) surface based on a first-principles description of eigenvalues and eigenvectors using ab initio pseudopotentials. We also present SHG spectra for Ge-covered Si(001). The theoretical results explain all essential features of recent experimental SHG spectra of the Si(001)-(2x1) surface with low coverages of hydrogen and/or germanium, which alter the E{sub 1} resonance in contrasting ways. The strong adatom specificity of the spectra results from redistribution of the adatom-related electronic states on the surface.

  1. Sn doped CdTe as candidate for intermediate-band solar cells: A first principles DFT+GW study

    NASA Astrophysics Data System (ADS)

    Flores, Mauricio A.; Menéndez-Proupin, Eduardo

    2016-05-01

    In this work, we investigate the electronic properties and defect formation energies of Sn doped CdTe combining first principles density-functional theory and many body GW calculations. Due to the Sn dopant, an isolated impurity band is formed in the middle of the forbidden band gap of CdTe allowing the absorption of sub-bandgap photons via an intermediate-band. Our results suggest CdTe:Sn as a promising candidate for the development of third-generation intermediate-band solar cells with theoretical efficiencies up to 63.2%.

  2. The European Theoretical Spectroscopy Facility: an illustration for the power of collective research

    NASA Astrophysics Data System (ADS)

    Reining, Lucia

    As researchers and citizens, we should contribute to facing the grand challenges of our epoch. It is important to work on problems such as climate change or limited ressources. However, maybe the biggest challenge is to find ways to unite our forces and develop models of collaborative problem solving. This is mandatory to deal with complex problems, and it can boost efficiency in any case. Code development is just one example where a constructive and well-organized collaboration can take us much further than individual attempts. On the background of this general idea, we will analyze the impact of the European Theoretical Spectroscopy Facility (ETSF, www.etsf.eu) on the day-to-day research of its members, on the theoretical and computational tools that are produced, and on a wider field of theoretical or experimental research. We will see that much can be learnt from this attempt to consider ideas in competition, with people in collaboration.

  3. First principle study of elastic and thermodynamic properties of FeB4 under high pressure

    NASA Astrophysics Data System (ADS)

    Zhang, Xinyu; Qin, Jiaqian; Ning, Jinliang; Sun, Xiaowei; Li, Xinting; Ma, Mingzhen; Liu, Riping

    2013-11-01

    The elastic properties, elastic anisotropy, and thermodynamic properties of the lately synthesized orthorhombic FeB4 at high pressures are investigated using first-principles density functional calculations. The calculated equilibrium parameters are in good agreement with the available experimental and theoretical data. The obtained normalized volume dependence of high pressure is consistent with the previous experimental data investigated using high-pressure synchrotron x-ray diffraction. The complete elastic tensors and crystal anisotropies of the FeB4 are also determined in the pressure range of 0-100 GPa. By the elastic stability criteria and vibrational frequencies, it is predicted that the orthorhombic FeB4 is stable up to 100 GPa. In addition, the calculated B/G ratio reveals that FeB4 possesses brittle nature in the range of pressure from 0 to 100 GPa. The calculated elastic anisotropic factors suggest that FeB4 is elastically anisotropic. By using quasi-harmonic Debye model, the compressibility, bulk modulus, the coefficient of thermal expansion, the heat capacity, and the Grüneisen parameter of FeB4 are successfully obtained in the present work.

  4. Electronic and optical properties of ultrathin silicon nanomembranes: A first-principles investigation

    NASA Astrophysics Data System (ADS)

    Jang, Woosun; Yoo, Su-Hyun; Soon, Aloysius

    2015-03-01

    Owing to its unique and exotic physical and chemical properties, there has been a lot of effort undertaken to explore and study ultrathin low-dimensional nanostructures (e.g. graphene and MoS2). Of late, two-dimensional (2D) nanomembranes of silicon - a well-known prototypical bulk semiconductor - have attracted much attention, and has found its potential in niche nanodevice applications e.g. field effect transistors (FET) and secondary battery anodes. In this work, after considering various nanomembranes of Si with varying thicknesses, we study geometric and electronic structures using first-principles density-functional theory calculations (and beyond). Here, we consider both bulk-terminated pristine Si nanomembranes as well as surface-reconstructed ones, as motivated by available experimental and theoretical reports. To understand the influence of growth conditions on these Si nanomembranes, we have also studied the role of surface-passivation (e.g. with O, H, and OH) on their electronic and optical properties. Namely, we carefully investigate their thickness-dependent electronic band structure (i.e. both their fundamental and optical band gap energies), so as to elucidate their intrinsic structure-property relations for designing future technologically important nanodevices.

  5. Calculation of the Vibrational Stark Effect Using a First-Principles QM/MM Approach

    PubMed Central

    Ringer, Ashley L.; MacKerell, Alexander D.

    2011-01-01

    The proper description of the electric environment of condensed phases is a critical challenge for force field methods. To test and validate the ability of the CHARMM additive force field to describe the electric environment in aqueous solution combined QM/MM calculations have been used to calculate the vibrational Stark effect (VSE). We utilized a first principles methodology using correlated electronic structure techniques to compute the Stark shift between the gas phase and solvent environments and between two different solvent environments of three VSE probes containing acetonitrile or fluorine functionalities which have been well-characterized experimentally. Reasonable agreement with the experimentally determined Stark shifts is obtained when the MM atoms are described by the CHARMM additive force field, though it is essential to employ an anharmonic correction in the frequency calculation. In addition, the electric field created by the solvent is computed along the CN bond and a theoretical Stark tuning rate is determined for acetonitrile and shown to be in satisfactory agreement with experiment. PMID:21423871

  6. Water confined in nanotubes and between graphene sheets: A first principle study

    SciTech Connect

    Cicero, G; Grossman, J C; Schwegler, E; Gygi, F; Galli, G

    2008-10-17

    Water confined at the nanoscale has been the focus of numerous experimental and theoretical investigations in recent years, y yet there is no consensus on such basic properties et as diffusion and the nature of hydrogen bonding (HB) under confinement. Unraveling these properties is important to understand fluid flow and transport at the nanoscale, and to shed light on the solvation of biomolecules. Here we report on a first principle, computational study focusing on water confined between prototypical non polar substrate, i.e. , single wall carbon nanotubes and graphene sheets, 1 to 2.5 nm apart. The results of our molecular dynamics simulations show the presence of a thin, interfacial liquid layer ({approx} 5 Angstroms) whose microscopic structure and thickness are independent of the distance between confining layers. The prop properties of the hydrogen bonded network are very similar to those of the bulk outside the interfacial region, even in the case of strong confinement , confinement. Our findings indicate that the perturbation induced by the presence of confining media is extremely local in liquid water, and we propose that many of the effects attributed to novel phases under confinement are determined by subtle electronic structure rearrangements occurring at the interface with the confining medium.

  7. Thermoelectric transport properties of warm dense molybdenum from first-principles simulations

    NASA Astrophysics Data System (ADS)

    French, Martin; Haill, Thomas; Desjarlais, Michael; Mattsson, Thomas

    2013-10-01

    Molybdenum, with its high melting point, significant electrical conductivity, and high material strength, is a technologically important material in general and has in particular recently been proposed as a driver material in high-pressure strength experiments on Sandia's Z-machine. To simulate and understand the processes in these experiments with magneto-hydrodynamic simulations, accurate models for the electrical and thermal conductivity are needed for a wide range of thermodynamic parameters. Here, we present novel results for the electrical and thermal conductivity of molybdenum in various states ranging from the solid to the dense plasma phase. The results were obtained with first-principles simulation techniques that combine density functional theory with molecular dynamics and linear response theory. We find good agreement between our theoretical results and available experimental data. Sandia National Laboratories is a multiprogram laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the US Department of Energy's National Nuclear Security Administration under Contract No. DE-AC04-94AL85000.

  8. Structural, elastic, and lattice dynamic stability of yttrium selenide (YSe) under pressure: A first principle study

    SciTech Connect

    Sahoo, B. D. Joshi, K. D.; Gupta, Satish C.

    2014-11-21

    Structural, elastic, and lattice dynamical stability of YSe has been investigated as a function of pressure through first principles electronic band structure calculations. The comparison of enthalpies of rocksalt type (B1) and CsCl type cubic (B2) structures determined as a function of pressure suggests that the B1 phase will transform to B2 structure at ∼32 (30 GPa at 300 K obtained from comparison of Gibbs free energy at 300 K). The transition is identified to be of first order in nature with a volume discontinuity of ∼6.2% at the transition pressure. Furthermore, the theoretically determined equation of state has been utilized to derive various physical quantities, such as zero pressure equilibrium volume, bulk modulus, and pressure derivative of bulk modulus. The single crystal elastic constants have been predicted at various pressures for both the B1 and B2 structures using the energy strain method. The activation barrier between B1 and B2 phases calculated at transition point is ∼19.7mRy/formula unit. Our lattice dynamic calculations show that both the B1 as well as B2 structures are lattice dynamically stable not only at ambient pressure but also at transition pressure. The B1 phase becomes lattice dynamically unstable at ∼112 GPa, i.e., much beyond the transition pressure. The effect of temperature on volume and bulk modulus of the YSe in B1 phase has also been examined.

  9. First-principles study of two-dimensional electride: Yttrium carbide

    NASA Astrophysics Data System (ADS)

    Nandadasa, Chandani; Kim, Sungho; Kim, Seong-Gon; Lee, Young; Kim, Sung

    2015-03-01

    Electrides are an exclusive class of ionic compounds in which electrons serve as anions. We have performed first-principles density functional theory (DFT) calculations to investigate the structural, electronic and magnetic properties of two-dimensional layered-structure yttrium carbide (Y2C). Generalized gradient approximation (GGA) with Projector Augmented Potentials (PAW) was used to obtain optimized lattice parameters, energy band structure, charge density and density of states (DOS) plots for Y2C. The theoretically predicted structure of Y2C is in good agreement with the experimental results. The band crossing the Fermi energy level proved that Y2C has metallic properties. Additionally projected electronic density of states profiles were obtained to identify the electronic contribution from Y, C and non-atomic orbital located in interstitial site. The results of these calculations indicate that the presence of trapped electrons within the Y2C interlayers. Furthermore, surface energies of Y-Y and Y-C were calculated and charge densities were plotted with these surfaces. Magnetization density plots were used to obtain magnetic properties.

  10. Tuning the electron transport of molecular junctions by chemically functionalizing anchoring groups: First-principles study

    NASA Astrophysics Data System (ADS)

    Tsukamoto, Shigeru; Caciuc, Vasile; Atodiresei, Nicolae; Blügel, Stefan

    2012-06-01

    In this first-principles study, we present density-functional calculations of the electronic structures and electron transport properties of organic molecular junctions with several anchoring groups containing atoms with different electronegativities, i.e., benzenediboronate (BDB), benzenedicarboxylate (BDC), and dinitrobenzene (DNB) molecular junctions sandwiched between two Cu(110) electrodes. The electronic-structure calculations exhibit a significant difference in the density of states not only at the anchoring groups but also at the aromatic rings of the molecular junctions, suggesting that the electron transport is specific for each system. Our transport calculations show that the BDB and DNB molecular junctions have finite electron transmissions at the zero-bias limit while the BDC molecular junction has a negligible electron transmission. Moreover, for the BDB and DNB systems, the electron transmission channels around the Fermi energy reveal fingerprint features, which provide specific functionalities for the molecular junctions. Therefore, our theoretical results demonstrate the possibility to precisely tune the electron transport properties of molecular junctions by engineering the anchoring groups at the single-atom level.

  11. First-principles investigation of hydrogen interaction with TiC precipitates in α -Fe

    NASA Astrophysics Data System (ADS)

    Di Stefano, Davide; Nazarov, Roman; Hickel, Tilmann; Neugebauer, Jörg; Mrovec, Matous; Elsässer, Christian

    2016-05-01

    A correct description of hydrogen diffusion and trapping is the prerequisite for an understanding of the phenomenon of hydrogen embrittlement. In this study, we carried out extensive first-principles calculations based on density functional theory to investigate the interaction of H with TiC precipitates that are assumed to be efficient trapping agents mitigating HE in advanced high-strength steels. We found that there exists a large variety of possible trapping sites for H associated with different types of interfaces between the TiC particle and the Fe matrix, with misfit dislocations and other defects at these interfaces, and with carbon vacancies in TiC. The most efficient trapping by more than 1 eV occurs at carbon vacancies in the interior of TiC particles. However, these traps are difficult to populate at ambient temperatures since the energy barrier for H entering the particles is high. H trapping at the semicoherent interfaces between the TiC particles and the Fe matrix is moderate, ranging from 0.3 to 0.5 eV. However, a sufficiently large concentration of the carbide particles can significantly reduce the amount of H segregated at dislocation cores in the Fe matrix. A systematic comparison of the obtained theoretical results with available experimental observations reveals a consistent picture of hydrogen trapping at the TiC particles that is expected to be qualitatively valid also for other carbide precipitates with the rock-salt crystal structure.

  12. First-Principles Theory of Momentum Dependent Local Ansatz Approach to Correlated Electron System

    NASA Astrophysics Data System (ADS)

    Chandra, Sumal; Kakehashi, Yoshiro

    2016-06-01

    We have extended the momentum-dependent local-ansatz (MLA) wavefunction method to the first-principles version using the tight-binding LDA+U Hamiltonian for the description of correlated electrons in the real system. The MLA reduces to the Rayleigh-Schrödinger perturbation theory in the weak correlation limit, and describes quantitatively the ground state and related low-energy excitations in solids. The theory has been applied to the paramagnetic Fe. The role of electron correlations on the energy, charge fluctuations, amplitude of local moment, momentum distribution functions, as well as the mass enhancement factor in Fe has been examined as a function of Coulomb interaction strength. It is shown that the inter-orbital charge-charge correlations between d electrons make a significant contribution to the correlation energy and charge fluctuations, while the intra-orbital and inter-orbital spin-spin correlations make a dominant contribution to the amplitude of local moment and the mass enhancement in Fe. Calculated partial mass enhancements are found to be 1.01, 1.01, and 3.33 for s, p, and d electrons, respectively. The averaged mass enhancement 1.65 is shown to be consistent with the experimental data as well as the recent results of theoretical calculations.

  13. Electrical contacts to monolayer black phosphorus: A first-principles investigation

    NASA Astrophysics Data System (ADS)

    Gong, Kui; Zhang, Lei; Ji, Wei; Guo, Hong

    2014-09-01

    We report first-principles theoretical investigations of possible metal contacts to monolayer black phosphorus (BP). By analyzing lattice geometry, five metal surfaces are found to have minimal lattice mismatch with BP: Cu(111), Zn(0001), In(110), Ta(110), and Nb(110). Further studies indicate Ta and Nb bond strongly with monolayer BP causing substantial bond distortions, but the combined Ta-BP and Nb-BP form good metal surfaces to contact a second layer BP. By analyzing the geometry, bonding, electronic structure, charge transfer, potential, and band bending, it is concluded that Cu(111) is the best candidate to form excellent Ohmic contact to monolayer BP. The other four metal surfaces or combined surfaces also provide viable structures to form metal/BP contacts, but they have Schottky character. Finally, the band bending property in the current-in-plane (CIP) structure where metal/BP is connected to a freestanding monolayer BP, is investigated. By both work function estimates and direct calculations of the two-probe CIP structure, we find that the freestanding BP channel is n type.

  14. Hydration thermodynamics of pyrochlore structured oxides from TG and first principles calculations.

    PubMed

    Bjørheim, Tor S; Besikiotis, Vasileios; Haugsrud, Reidar

    2012-11-21

    In this contribution we investigate trends in the defect chemistry and hydration thermodynamics of rare-earth pyrochlore structured oxides, RE(2)X(2)O(7) (RE = La-Lu and X = Ti, Sn, Zr and Ce). First principles density functional theory (DFT) calculations have been performed to elucidate trends in the general defect chemistry and hydration enthalpy for the above-mentioned series. Further, to justify the use of such theoretical methods, the hydration properties of selected compositions were studied by means of thermogravimetric measurements. Both DFT calculations and TG measurements indicate that the hydration enthalpy becomes less exothermic with decreasing radii of RE ions within the RE(2)X(2)O(7) series (X = Ti, Sn, Zr and Ce), while it is less dependent on the X site ion. The observed hydration trends are discussed in connection with trends in the stability of both protons and oxygen vacancies and changes in the electronic density of states and bonding environment through the series. Finally, the findings are discussed with respect to existing correlations for other binary and ternary oxides. PMID:23001186

  15. First-principles studies of functionalization and substitutional doping of graphene and carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Al-Aqtash, Nabil

    Theoretical studies of nanoscale systems, such as functionalized carbon nanotubes (CNTs) and graphene, present major challenges to computational methods employed in quantum chemistry and condensed matter physics. For this reason, accurate numerical calculations for functionalized CNTs and graphene require a direct quantum mechanical approach. This thesis presents first principles calculations using density functional theory (DFT) to study the structural and electronic properties of functionalized and doped graphene and CNTs. The calculations are performed using density-functional pseudopotential computational methods combined with the generalized gradient approximation (GGA) for the exchange-correlation functional. The structural optimization of graphene and CNTs is carried out by energy and force minimization. We investigate the chemical functionalization of graphene and CNTs with carboxyl (COOH) groups. The binding energies, equilibrium geometries, and the charge transfer of graphene sheets and CNTs are examined. We find that the attachment of COOH groups induces substantial structural changes in graphene and CNTs. Our calculations show that the binding of the COOH group is significantly stronger in the presence of surface defects. The properties of graphene and CNTs doped with boron (B) and nitrogen (N) atoms are also studied. The calculations confirm that B doping increases and N doping decreases the binding energy of COOH groups to both defect-free and defective graphene and CNTs. The interactions between B and N atoms doping graphene are examined. The B-B and N-N interactions are found to be repulsive, while the B-N interaction is found to be attractive.

  16. Exciton diffusion in disordered small molecules for organic photovoltaics: insights from first-principles simulations.

    PubMed

    Li, Z; Zhang, X; Lu, G

    2014-05-01

    Exciton diffusion in small molecules 3,6-bis(5-(benzofuran-2-yl)thiophen-2-yl)-2,5-bis(2-ethylhexyl)pyrrolo[3,4-c]pyrrole-1,4-dione [DPP(TBFu)2] is studied using first-principles simulations. We have examined dependence of exciton diffusion on structure disorder, temperature and exciton energy. We find that exciton diffusion length and diffusivity increase with structural order, temperature and the initial exciton energy. Compared to conjugated polymer poly(3-hexylthiophene) (P3HT), DPP(TBFu)2 small molecules exhibit a much higher exciton diffusivity, but a shorter lifetime. The exciton diffusion length in DPP(TBFu)2 is 50% longer than that in P3HT, yielding a higher exciton harvesting efficiency; the physical origin behind these differences is discussed. The time evolutions of exciton energy, electron-hole distance, and exciton localization are explored, and the widely speculated exciton diffusion mechanism is confirmed theoretically. The connection between exciton diffusion and carrier mobilities is also studied. Finally we point out the possibility to estimate exciton diffusivity by measuring carrier mobilities under AC electric fields. PMID:24759042

  17. First principles DFT study of dye-sensitized CdS quantum dots

    SciTech Connect

    Jain, Kalpna; Singh, Kh. S.; Kishor, Shyam; Josefesson, Ida; Odelius, Michael; Ramaniah, Lavanya M.

    2014-04-24

    Dye-sensitized quantum dots (QDs) are considered promising candidates for dye-sensitized solar cells. In order to maximize their efficiency, detailed theoretical studies are important. Here, we report a first principles density functional theory (DFT) investigation of experimentally realized dye - sensitized QD / ligand systems, viz., Cd{sub 16}S{sub 16}, capped with acetate molecules and a coumarin dye. The hybrid B3LYP functional and a 6−311+G(d,p)/LANL2dz basis set are used to study the geometric, energetic and electronic properties of these clusters. There is significant structural rearrangement in all the clusters studied - on the surface for the bare QD, and in the positions of the acetate / dye ligands for the ligated QDs. The density of states (DOS) of the bare QD shows states in the band gap, which disappear on surface passivation with the acetate molecules. Interestingly, in the dye-sensitised QD, the HOMO is found to be localized mainly on the dye molecule, while the LUMO is on the QD, as required for photo-induced electron injection from the dye to the QD.

  18. Thermodynamic ground state of MgB{sub 6} predicted from first principles structure search methods

    SciTech Connect

    Wang, Hui; Department of Physics and Engineering Physics, University of Saskatchewan, Saskatoon, Saskatchewan S7N 5E2 ; LeBlanc, K. A.; Gao, Bo; Yao, Yansun; Canadian Light Source, Saskatoon, Saskatchewan S7N 0X4

    2014-01-28

    Crystalline structures of magnesium hexaboride, MgB{sub 6}, were investigated using unbiased structure searching methods combined with first principles density functional calculations. An orthorhombic Cmcm structure was predicted as the thermodynamic ground state of MgB{sub 6}. The energy of the Cmcm structure is significantly lower than the theoretical MgB{sub 6} models previously considered based on a primitive cubic arrangement of boron octahedra. The Cmcm structure is stable against the decomposition to elemental magnesium and boron solids at atmospheric pressure and high pressures up to 18.3 GPa. A unique feature of the predicted Cmcm structure is that the boron atoms are clustered into two forms: localized B{sub 6} octahedra and extended B{sub ∞} ribbons. Within the boron ribbons, the electrons are delocalized and this leads to a metallic ground state with vanished electric dipoles. The present prediction is in contrast to the previous proposal that the crystalline MgB{sub 6} maintains a semiconducting state with permanent dipole moments. MgB{sub 6} is estimated to have much weaker electron-phonon coupling compared with that of MgB{sub 2}, and therefore it is not expected to be able to sustain superconductivity at high temperatures.

  19. Two-dimensional arsenic monolayer sheet predicted from first-principles

    NASA Astrophysics Data System (ADS)

    Pu, Chun-Ying; Ye, Xiao-Tao; Jiang, Hua-Long; Zhang, Fei-Wu; Lu, Zhi-Wen; He, Jun-Bao; Zhou, Da-Wei

    2015-03-01

    Using first-principles calculations, we investigate the two-dimensional arsenic nanosheet isolated from bulk gray arsenic. Its dynamical stability is confirmed by phonon calculations and molecular dynamics analyzing. The arsenic sheet is an indirect band gap semiconductor with a band gap of 2.21 eV in the hybrid HSE06 functional calculations. The valence band maximum (VBM) and the conduction band minimum (CBM) are mainly occupied by the 4p orbitals of arsenic atoms, which is consistent with the partial charge densities of VBM and CBM. The charge density of the VBM G point has the character of a π bond, which originates from p orbitals. Furthermore, tensile and compressive strains are applied in the armchair and zigzag directions, related to the tensile deformations of zigzag and armchair nanotubes, respectively. We find that the ultimate strain in zigzag deformation is 0.13, smaller than 0.18 of armchair deformation. The limit compressive stresses of single-layer arsenic along armchair and zigzag directions are -4.83 GPa and -4.76 GPa with corresponding strains of -0.15 and -0.14, respectively. Projected supported by the Henan Joint Funds of the National Natural Science Foundation of China (Grant Nos. U1304612 and U1404608), the National Natural Science Foundation of China (Grant Nos. 51374132 and 11404175), the Special Fund for Theoretical Physics of China (Grant No. 11247222), and Nanyang Normal University Science Foundation, China (Grant Nos. ZX2012018 and ZX2013019).

  20. Density functional studies: First principles and semi-emperical calculations of clusters and surfaces

    SciTech Connect

    Susan, S.

    1993-04-30

    Theoretical electronic structure techniques are used to analyze widely different systems from Si clusters to transition metal solids and surfaces. For the Si clusters, first principles density functional methods are used to investigate Si{sub N} for N=2-8. Goal is to understand the different types of bonding that can occur in such small clusters where the atomic coordination differs substantially from tetrahedral bonding; such uncoordinated structures can test approximate models of Si surfaces. For the transition metal systems, non-self-consistent electronic structure methods are used to understand the driving force for surface relaxations. In-depth analysis of results is presented and physical basis of surface relaxation within the theory is discussed. Limitations inherent in calculations of metal surface relaxation are addressed. Finally, in an effort to understand approximate methods, a novel non-self- consistent density functional electronic structure method is developed that is about 1000 times faster than more sophisticated methods; this method is tested for various systems including diatomics, mixed clusters, surfaces, and bulk lattices.

  1. Rare-earth vs. heavy metal pigments and their colors from first principles

    PubMed Central

    Tomczak, Jan M.; Pourovskii, Leonid V.; Vaugier, Loig; Georges, Antoine; Biermann, Silke

    2013-01-01

    Many inorganic pigments contain heavy metals hazardous to health and environment. Much attention has been devoted to the quest for nontoxic alternatives based on rare-earth elements. However, the computation of colors from first principles is a challenge to electronic structure methods, especially for materials with localized f-orbitals. Here, starting from atomic positions only, we compute the colors of the red pigment cerium fluorosulfide as well as mercury sulfide (classic vermilion). Our methodology uses many-body theories to compute the optical absorption combined with an intermediate length-scale modelization to assess how coloration depends on film thickness, pigment concentration, and granularity. We introduce a quantitative criterion for the performance of a pigment. While for mercury sulfide, this criterion is satisfied because of large transition matrix elements between wide bands, cerium fluorosulfide presents an alternative paradigm: the bright red color is shown to stem from the combined effect of the quasi-2D and the localized nature of states. Our work shows the power of modern computational methods, with implications for the theoretical design of materials with specific optical properties. PMID:23302689

  2. Core-level shifts in fcc random alloys: A first-principles approach

    NASA Astrophysics Data System (ADS)

    Olovsson, W.; Göransson, C.; Pourovskii, L. V.; Johansson, B.; Abrikosov, I. A.

    2005-08-01

    First-principles theoretical calculations of the core-level binding-energy shift (CLS) for eight binary face-centered-cubic (fcc) disordered alloys, CuPd, AgPd, CuNi, NiPd, CuAu, PdAu, CuPt, and NiPt, are carried out within density-functional theory (DFT) using the coherent potential approximation. The shifts of the Cu and Ni 2p3/2 , Ag and Pd 3d5/2 , and Pt and Au 4f7/2 core levels are calculated according to the complete screening picture, which includes both initial-state (core-electron energy eigenvalue) and final-state (core-hole screening) effects in the same scheme. The results are compared with available experimental data, and the agreement is shown to be good. The CLSs are analyzed in terms of initial- and final-state effects. We also compare the complete screening picture with the CLS obtained by the transition-state method, and find very good agreement between these two alternative approaches for the calculations within the DFT. In addition the sensitivity of the CLS to relativistic and magnetic effects is studied.

  3. Thermoelectric properties of AgSbTe₂ from first-principles calculations

    SciTech Connect

    Rezaei, Nafiseh; Akbarzadeh, Hadi; Hashemifar, S. Javad

    2014-09-14

    The structural, electronic, and transport properties of AgSbTe₂ are studied by using full-relativistic first-principles electronic structure calculation and semiclassical description of transport parameters. The results indicate that, within various exchange-correlation functionals, the cubic Fd3⁻m and trigonal R3⁻m structures of AgSbTe₂ are more stable than two other considered structures. The computed Seebeck coefficients at different values of the band gap and carrier concentration are accurately compared with the available experimental data to speculate a band gap of about 0.1–0.35 eV for AgSbTe₂ compound, in agreement with our calculated electronic structure within the hybrid HSE (Heyd-Scuseria-Ernzerhof) functional. By calculating the semiclassical Seebeck coefficient, electrical conductivity, and electronic part of thermal conductivity, we present the theoretical upper limit of the thermoelectric figure of merit of AgSbTe₂ as a function of temperature and carrier concentration.

  4. High pressure phase transformation in yttrium sulfide(YS): A first principle study

    SciTech Connect

    Sahoo, B. D. Joshi, K. D. Gupta, Satish C.

    2014-04-24

    First principles calculations have been carried out to analyze structural, elastic and dynamic stability, of YS under hydrostatic compression. The comparison of enthalpies of rocksalt type (B1) and CsCl type cubic (B2) structures determined as a function of compression suggests the B1→B2 transition at ∼ 49 GPa. Various physical quantities such as zero pressure equilibrium volume, bulk modulus, and pressure derivative of bulk modulus have been derived from the theoretically determined equation of state. The single crystal elastic constants derived from the energy strain method agree well with the experimental values. The activation barrier between B1 and B2 phases calculated at transition point is ∼ 17/mRy/formula unit. Our lattice dynamic calculations show that at ambient condition, the B1 phase is lattice dynamically stable and frequencies of phonon modes in different high symmetry directions of Brillouin zone agrees well with experimental values. The B2 phase also is dynamical stable at ambient condition as well as at ∼ 49 GPa, supporting our static lattice calculation.

  5. Thermoelectric properties of AgSbTe2 from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Rezaei, Nafiseh; Hashemifar, S. Javad; Akbarzadeh, Hadi

    2014-09-01

    The structural, electronic, and transport properties of AgSbTe2 are studied by using full-relativistic first-principles electronic structure calculation and semiclassical description of transport parameters. The results indicate that, within various exchange-correlation functionals, the cubic F d 3 ¯ m and trigonal R 3 ¯ m structures of AgSbTe2 are more stable than two other considered structures. The computed Seebeck coefficients at different values of the band gap and carrier concentration are accurately compared with the available experimental data to speculate a band gap of about 0.1-0.35 eV for AgSbTe2 compound, in agreement with our calculated electronic structure within the hybrid HSE (Heyd-Scuseria-Ernzerhof) functional. By calculating the semiclassical Seebeck coefficient, electrical conductivity, and electronic part of thermal conductivity, we present the theoretical upper limit of the thermoelectric figure of merit of AgSbTe2 as a function of temperature and carrier concentration.

  6. Body-centered superhard BC2N phases from first principles

    NASA Astrophysics Data System (ADS)

    Luo, Xiaoguang; Guo, Xiaoju; Xu, Bo; Wu, Qinghua; Hu, Qianku; Liu, Zhongyuan; He, Julong; Yu, Dongli; Tian, Yongjun; Wang, Hui-Tian

    2007-09-01

    Body-centered BC2N deduced from the unit cell of the recently predicted body-centered carbon [F. J. Ribeiro , Phys. Rev. B 74, 172101 (2006)] are studied with first-principles pseudopotential density functional method. The structural, electronic, and mechanical properties are investigated for 11 possible atomic configurations of body-centered BC2N . Our results show that the sp3 -bonded body-centered BC2N phases have lower density than the previously investigated sp3 -bonded zinc-blende BC2N , wurtzite BC2N , and chalcopyrite BC2N . The struc-A and struc-B composed of the maximum numbers of C-C and B-N bonds have the lowest total energy among the investigated body-centered BC2N structures. Their calculated bulk moduli are 305 and 309GPa , respectively. The theoretical Vickers hardness of the body-centered BC2N is over 60GPa , indicating that it is a potential superhard material with the hardness comparable to cubic boron nitride.

  7. Crystal Structures, Stabilities, Electronic Properties, and Hardness of MoB2: First-Principles Calculations.

    PubMed

    Ding, Li-Ping; Shao, Peng; Zhang, Fang-Hui; Lu, Cheng; Ding, Lei; Ning, Shu Ya; Huang, Xiao Fen

    2016-07-18

    On the basis of the first-principles techniques, we perform the structure prediction for MoB2. Accordingly, a new ground-state crystal structure WB2 (P63/mmc, 2 fu/cell) is uncovered. The experimental synthesized rhombohedral R3̅m and hexagonal AlB2, as well as theoretical predicted RuB2 structures, are no longer the most favorite structures. By analyzing the elastic constants, formation enthalpies, and phonon dispersion, we find that the WB2 phase is thermodynamically and mechanically stable. The high bulk modulus B, shear modulus G, low Poisson's ratio ν, and small B/G ratio are benefit to its low compressibility. When the pressure is 10 GPa, a phase transition is observed between the WB2-MoB2 and the rhombohedral R3̅m MoB2 phases. By analyzing the density of states and electron density, we find that the strong covalent is formed in MoB2 compounds, which contributes a great deal to its low compressibility. Furthermore, the low compressibility is also correlated with the local buckled structure. PMID:27387577

  8. Migrations of pentagon-heptagon defects in hexagonal boron nitride monolayer: the first-principles study.

    PubMed

    Wang, J; Li, S N; Liu, J B

    2015-04-16

    The first-principles calculations are employed to study the migrations of pentagon-heptagon (5-7) defects in hexagonal boron nitride monolayer (h-BN). A type of grain boundaries, consisted of 5-7 defects, is constructed on the basis of experimental observations. With the absorption of a pair of atoms, one 5-7 defect in the grain boundary migrates apart by one unit cell and afterward migrates again through the bond rotation. It is also found that the two migrations could be replaced by one single step when the pair of absorbed atoms is located at another specific site in the same heptagon. Energy barriers and reaction paths for the migrations of 5-7 defects in h-BN by the bond rotation are theoretically investigated by the standard nudged elastic band method and the generalized solid-state nudged elastic band method. To elucidate the difference between the bond rotation process of the 5-7 defects with N-N bonds and those with B-B bonds, a couple of typical 21.7° grain boundaries with either N-N or B-B bonds are investigated. It is shown that the energy barrier of the migration of defects with N-N bonds is lower than that with B-B bonds in this type of grain boundaries. PMID:25811102

  9. A comparative investigation of the behaviors of H in Au and Ag from first principles

    NASA Astrophysics Data System (ADS)

    Han, Quan-Fu; Zhou, Zhen-Yu; Ma, Yuming; Liu, Yue-Lin

    2016-05-01

    Hydrogen (H) is a common impurity in metals and has a significant effect on their purification, even at concentrations of only a few parts per million. Here we present a comparative analysis of the behaviors of H in Au and Ag based on first-principles calculations. In bulk Au and Ag, the results demonstrate that the tetrahedral position is energetically more stable for a single H atom than the octahedral site. The concentration of H dissolving in the interstitial sites as a function of temperature is calculated in both metals. To characterize the dynamic behaviors, in bulk Au and Ag we determine the theoretical diffusivity and permeation of H, which are in quantitative agreement with the experimental data. Further, we investigate the role of vacancy on the formation of the H n -vacancy (H n V) via a clustering reaction. One vacancy can accommodate up to 9 H atoms in Au and capture as many as 7 H atoms in Ag. The H2 molecule in the vacancy is energetically unstable in both metals. These research results will provide a very useful reference for the refinement of Ag/Au as noble metals in industry.

  10. Design of BAs-AlN monolayered honeycomb heterojunction structures: A first-principles study

    NASA Astrophysics Data System (ADS)

    Camacho-Mojica, Dulce C.; López-Urías, Florentino

    2016-04-01

    BAs and AlN are semiconductor materials with an indirect and direct gap respectively in the bulk phase. Recently, electronic calculations have demonstrated that a single-layer or few layers of BAs and AlN exhibit a graphite-like structure with interesting electronic properties. In this work, infinite sheets single-layer heterojunction structures based on alternated strips with honeycomb BAs and AlN layers are investigated using first-principles density functional theory calculations. Optimized geometries, density of states, band-gaps, formation energies, and wave functions are studied for different strip widths joined along zigzag and armchair edges. Results in optimized heterojunction geometries revealed that BAs narrow strips exhibit a corrugation effect due to a lattice mismatch. It was found that zigzag heterojunctions are more energetically favored than armchair heterojunctions. Furthermore, the formation energy presents a maximum at the point where the heterojunction becomes a planar structure. Electronic charge density results yielded a more ionic behavior in Alsbnd N bonds than the Bsbnd As bonds in accordance with monolayer results. It was observed that the conduction band minimum for both heterojunctions exhibit confined states located mainly at the entire AlN strips whereas the valence band maximum exhibits confined states located mainly at BAs strips. We expect that the present investigation will motivate more experimental and theoretical studies on new layered materials made of III-V semiconductors.

  11. First-principles calculations of transition metal solute interactions with hydrogen in tungsten

    NASA Astrophysics Data System (ADS)

    Kong, Xiang-Shan; Wu, Xuebang; Liu, C. S.; Fang, Q. F.; Hu, Q. M.; Chen, Jun-Ling; Luo, G.-N.

    2016-02-01

    We have performed systematic first-principles calculations to predict the interaction between transition metal (TM) solutes and hydrogen in the interstitial site as well as the vacancy in tungsten. We showed that the site preference of the hydrogen atom is significantly influenced by the solute atoms, which can be traced to the charge density perturbation in the vicinity of the solute atom. The solute-H interactions are mostly attractive except for Re, which can be well understood in terms of the competition between the chemical and elastic interactions. The chemical interaction dominates the solute-H interaction for the TM solutes with a large atomic volume and small electronegativity compared to tungsten, while the elastic interaction is primarily responsible for the solute-H interaction for the TM solutes with a small atomic volume and large electronegativity relative to tungsten. The presence of a hydrogen atom near the solute atom has a negative effect on the binding of other hydrogen atoms. The large positive binding energies among the solute, vacancy and hydrogen suggest that they would easily form a defect cluster in tungsten, where the solute-vacancy and vacancy-H interaction contribute greatly while the solute-H interaction contributes a little. Our result provides a sound theoretical explanation for recent experimental phenomena of hydrogen retention in the tungsten alloy and further recommends a suitable W-Re-Ta ternary alloy for possible plasma-facing materials (PFMs) including the consideration of the hydrogen retention.

  12. First-principles equations of state and elastic properties of seven metals

    NASA Astrophysics Data System (ADS)

    Bercegeay, C.; Bernard, S.

    2005-12-01

    We present a systematic comparison of first-principles zero-temperature equations of state and elastic constants of seven metals (aluminum, titanium, copper, tantalum, tungsten, platinum, and gold) with the most recent diamond-anvil-cell (DAC) experimental data, for pressures up to 150 GPa. Our calculations were performed within density functional theory, testing both the local density approximation (LDA) and the generalized gradient approximation (GGA) to the exchange-correlation term, and using several types of pseudopotentials. The obtained pressure-volume relationships show good agreement with DAC data: the difference between ab initio pressure and experiment is at most 5 GPa at 100-150 GPa except for Au and Pt. The equilibrium volumes V0 and bulk moduli K0 are determined within 1.5% and 6% of DAC data respectively. Experimental results are better reproduced with GGA for Al, Ti, Cu, Ta and W, but with LDA for Pt and Au, in agreement with previous theoretical studies. The predicted elastic constants are within 10% of experiment. For tantalum we have also calculated phonon spectra under pressure. They are in excellent agreement with experimental data: especially they accurately reproduced the inflexion on the longitudinal branch in the Γ -H direction, which is typical of the VB column (V, Nb, Ta).

  13. Formaldehyde molecule adsorption on the doped monolayer MoS2: A first-principles study

    NASA Astrophysics Data System (ADS)

    Ma, Dongwei; Ju, Weiwei; Li, Tingxian; Yang, Gui; He, Chaozheng; Ma, Benyuan; Tang, Yanan; Lu, Zhansheng; Yang, Zongxian

    2016-05-01

    Based on first-principles calculations, formaldehyde (H2CO) adsorption on the pristine monolayer MoS2 and that doped with Cl, P, or Si was theoretically studied to explore the potential of the MoS2 sheets as H2CO gas sensors. It is found that under Mo-rich conditions it is viable for Cl to be filled into the S vacancies acting as n-type dopant and for P and Si acting as p-type dopants. The results on the H2CO adsorption on the pristine and the Cl-doped monolayer MoS2 indicate that both are insensitive to H2CO. In contrast, H2CO exhibits strong adsorption on the P or Si-doped monolayer MoS2. And there are large electron transfer from the P or Si-doped monolayer MoS2 to the H2CO and obvious change in the electronic densities of states of both systems induced by the H2CO adsorption. These suggest that P and Si can be appropriate dopants filled into MoS2 sheets for detecting H2CO molecule.

  14. Water solubility in calcium aluminosilicate glasses investigated by first principles techniques

    SciTech Connect

    Bouyer, Frederic; Geneste, Gregory; Ispas, Simona; Kob, Walter; Ganster, Patrick

    2010-12-15

    First-principles techniques have been employed to study the reactivity of water into a calcium aluminosilicate glass. In addition to the well known hydrolysis reactions Si-O-Si+H{sub 2}O{yields}Si-OH+Si-OH and Si-O-Al+H{sub 2}O{yields}Si-OH+Al-OH, a peculiar mechanism is found, leading to the formation of an AlO{sub 3}-H{sub 2}O entity and the breaking of Al-O-Si bond. In the glass bulk, most of the hydrolysis reactions are endothermic. Only a few regular sites are found reactive (i.e. in association with an exothermic reaction), and in that case, the hydrolysis reaction leads to a decrease of the local disorder in the amorphous vitreous network. Afterwards, we suggest that ionic charge compensators transform into network modifiers when hydrolysis occurs, according to a global process firstly suggested by Burnham in 1975. Our theoretical computations provide a more general model of the first hydrolysis steps that could help to understand experimental data and water speciation in glasses. -- Graphical Abstract: Reactivity within glass bulk: structures obtained after hydrolyses reactions (endothermic and exothermic processes) and mechanisms involving Si-OH, Al-OH, Si-OH-Al groups within aluminosilicates glasses (through ab initio molecular dynamics): formation of the Si-OH-Al entity coupled with an H exchange-Frederic Bouyer and Gregory Geneste. Display Omitted

  15. First-principles investigation of solute-hydrogen interaction in a α-Ti solid solution

    NASA Astrophysics Data System (ADS)

    Hu, Q. M.; Xu, D. S.; Yang, R.; Li, D.; Wu, W. T.

    2002-08-01

    In this paper, a first-principles method is used to calculate the interaction energy between substitutional solute atoms and hydrogen in α-Ti. The results show that simple metal (SM) solute atoms are repulsive to H and therefore are detraps for H, whereas transition metal (TM) solute atoms, with smaller sizes than that of the host atoms, attract H and provide traps for H. The relationship between the interaction energy and lattice distortion as well as the electronic structure is investigated. The SM-H and TM-H interactions are dominated by different factors. The repulsive interaction between SM atoms and H is mainly due to the hybridization between the electrons of SM atoms and H when they are close to each other. The interaction between the TM solutes and H is attributable to the atomic size effect, and can be described satisfactorily by Matsumoto's strain field relaxation model. From the solute-H interaction energy and available measured terminal solubility of hydrogen (TSH), the relationship between the solute trapping of hydrogen and TSH in α-Ti is discussed. No coherent relationship is found between the theoretical hydrogen trapping effect and the experimental TSH in α-Ti alloys.

  16. First-principle study on the surface atomic relaxation properties of sphalerite

    NASA Astrophysics Data System (ADS)

    Liu, Jian; Wen, Shu-ming; Xian, Yong-jun; Bai, Shao-jun; Chen, Xiu-min

    2012-09-01

    The surface properties of sphalerite (ZnS) were theoretically investigated using first principle calculations based on the density functional theory (DFT). DFT results indicate that both the (110) and the (220) surfaces of sphalerite undergo surface atom relaxation after geometry optimization, which results in a considerable distortion of the surface region. In the normal direction, i.e., perpendicular to the surface, S atoms in the first surface layer move outward from the bulk ( d 1), whereas Zn atoms move toward the bulk ( d 2), forming an S-enriched surface. The values of these displacements are 0.003 nm for d 1 and 0.021 nm for d 2 on the (110) surface, and 0.002 nm for d 1 and 0.011 nm for d 2 on the (220) surface. Such a relaxation process is visually interpreted through the qualitative analysis of molecular mechanics. X-ray photoelectron spectroscopic (XPS) analysis provides the evidence for the S-enriched surface. A polysulphide (S{/n 2-}) surface layer with a binding energy of 163.21 eV is formed on the surface of sphalerite after its grinding under ambient atmosphere. This S-enriched surface and the S{/n 2-} surface layer have important influence on the flotation properties of sphalerite.

  17. A first-principles study of He, Xe, Kr and O incorporation in thorium carbide

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

    Thorium-based materials are currently being investigated in relation with their potential utilization in Generation-IV reactors as nuclear fuels. Understanding the incorporation of fission products and oxygen is very important to predict the behavior of nuclear fuels. A first approach to this goal is the study of the incorporation energies and stability of these elements in the material. By means of first-principles calculations within the framework of density functional theory, we calculate the incorporation energies of He, Xe, Kr and O atoms in Th and C vacancy sites, in tetrahedral interstitials and in Schottky defects along the <1 1 1> and <1 0 0> directions. We also analyze atomic displacements, volume modifications and Bader charges. This kind of results for ThC, to the best authors' knowledge, have not been obtained previously, neither experimentally, nor theoretically. This should deal as a starting point towards the study of the complex behavior of fission products in irradiated ThC.

  18. First-principles study of migration and diffusion mechanisms of helium in α-Be

    NASA Astrophysics Data System (ADS)

    Yang, Xiao-Yong; Lu, Yong; Li, Meng-Lei; Zhang, Ping

    2016-03-01

    The behavior of interstitial helium in α-Be has been studied with first-principles method. It is found that the most favored position for helium is the basal octahedral (BO) site, closely followed by the basal tetrahedral (BT) site, in agreement with previous predictions. The interaction energy between the helium and the neighborhood Be atoms and the deformation energy of α-Be matrix are calculated. The feasible minimum-energy pathways (MEP) of interstitial helium atoms in α-Be matrix and the corresponding atomic structures of the saddle points associated with the each MEP are investigated. The temperature-dependent diffusion coefficients have also been predicted. It is confirmed that the interstitial helium diffuses two-dimensionally at low temperatures; however, it can diffuse three-dimensionally at higher temperatures. Besides, the microscopic parameters in the pre-factor and activation energy of the diffusion coefficients are obtained. Both diffusion coefficients are higher than the available experiment data, which may attribute to the fact that under real condition the diffusion is not free, i.e. the actual α-Be matric has various defects and impurities which heavily affect the diffusion of helium. Therefore, our theoretical prediction is the upper bound for helium diffusion in α-Be matrix.

  19. Oxygen vacancies in amorphous-Ta2O5 from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Lee, Jihang; Kioupakis, Emmanouil; Lu, Wei

    Oxygen vacancies are thought to play a crucial role in the electrical and optical properties of tantalum pentoxide (Ta2O5) devices. Even though numerous experimental studies on oxygen vacancies in Ta2O5 exist, experimentally detected defects are ambiguously identified due to the absence of an accurate and conclusive theoretical analysis. We investigate oxygen vacancies in amorphous Ta2O5 with first-principles calculations based on hybrid density functional theory. The calculated thermodynamic and optical transition levels of stable oxygen vacancies are in good agreement with measured values from a variety of experimental methods, providing conclusive clues for the identification of the defect states observed in experiments. We determine the concentration of oxygen vacancies and their dominant oxidation state as a function of growth conditions. We analyze the characteristics of extra electrons introduced by donor-like oxygen vacancies, which include the formation of polarons. Our results provide insight into the fundamental properties of oxygen vacancies in Ta2O5, which is essential to controlling the properties of films and optimize the performance of devices. This research was supported by the AFOSR through MURI grant FA9550-12-1-0038 and the National Science Foundation CAREER award through Grant No. DMR-1254314. Computational resources were provided by the DOE NERSC facility.

  20. Pressure effect on elastic, lattice dynamic and superconducting behaviour of yttrium sulfide: A first principle study

    SciTech Connect

    Sahoo, B. D. Joshi, K. D.; Gupta, Satish C.

    2014-03-28

    First principles calculations have been carried out to analyze structural, elastic, and dynamic stability of yttrium sulphide (YS) under hydrostatic compression. The comparison of enthalpies of rocksalt type (B1) and CsCl type cubic (B2) structures determined as a function of compression suggests the B1 → B2 transition at ∼49 GPa (the same transition occurs at ∼48 GPa at 300 K). Various physical quantities such as zero pressure equilibrium volume, bulk modulus, and pressure derivative of bulk modulus have been derived from the theoretically determined equation of state. The single crystal elastic constants derived from the energy strain method agree well with the experimental values. The activation barrier between B1 and B2 phases calculated at transition point is ∼17/mRy/f.u. Our lattice dynamic calculations show that at ambient condition, the B1 phase is lattice dynamically stable, and frequencies of phonon modes in different high symmetry directions of Brillouin zone agrees well with experimental values. The B2 phase also is dynamical stable at ambient condition as well as at ∼49 GPa, supporting our static lattice calculation. The effect of temperature on volume and bulk modulus of the YS in B1 phase has also been examined. The superconducting temperature of ∼2.78 K determine at zero pressure agrees well with experimental data. The effect of pressure is found to suppress the superconducting nature of this material.

  1. Phase transition and elasticity of enstatite under pressure from experiments and first-principles studies

    NASA Astrophysics Data System (ADS)

    Li, Baosheng; Kung, Jennifer; Liu, Wei; Liebermann, Robert C.

    2014-03-01

    We have investigated the thermodynamic stability, crystal structure, elastic constants, and sound velocities of MgSiO3-enstatite using data from X-ray diffraction and ultrasonic measurements up to 16.8 GPa and first-principles calculations up to 30 GPa. The calculated enthalpies provide theoretical support for the phase transition from Pbca to P21/c between 9 and 14 GPa previously observed in natural orthoensatite and MgSiO3 enstatite. A density increase of 1.4-1.5% for the Pbca → P21/c transition is obtained from both first-principles and experimental studies. Elastic constants of Pbca, P21/c, C2/c, P21ca and Pbca-II are all calculated, and a softening in the shear constant C55 is predicted for Pbca and Pbca-II phases. C55 of Pbca is found to be closely correlated with the A-site SiO4 tetrahedra chain angle while C44 and C66 are correlated with the B-site chain angle. Pbca, P21/c and C2/c all exhibit similar volumetric compressibilities at all pressures. The calculated velocities of the P21/c phase at 12 GPa are equal to those of Pbca for P and 1.3% higher for S waves. The experimentally observed P and S wave velocity anomalies can be qualitatively described by the transformation from Pbca to P21/c; however, the magnitudes of the velocity decreases between 10 and 14 GPa remain to be verified by future single crystal data or polycrystalline measurements at high pressures. The predicted velocity jumps of 2.8% and 4.5% for P and S waves, respectively, between Pbca and C2/c in the pressure range of 5-12 GPa are in excellent agreement with the values of ∼3(1)% and ∼5(1)% obtained from the directly measured data, thereby making it a plausible candidate for the seismic X-discontinuity at depths of 250-300 km in the Earth’s upper mantle.

  2. First-principles investigation of vanadium isotope fractionation in solution and during adsorption

    NASA Astrophysics Data System (ADS)

    Wu, Fei; Qin, Tian; Li, Xuefang; Liu, Yun; Huang, Jen-How; Wu, Zhongqing; Huang, Fang

    2015-09-01

    Equilibrium fractionation factors of vanadium (V) isotopes among tri- (V(III)), tetra- (V(IV)) and penta-valent (V(V)) inorganic V species in aqueous system and during adsorption of V(V) to goethite are estimated using first-principles calculation. Our results highlight the dependence of V isotope fractionation on valence states and the chemical binding environment. The heavy V isotope (51V) is enriched in the main V species following a sequence of V(III) < V(IV) < V(V). According to our calculations, at 25 °C, the equilibrium isotope fractionation factor between [V5+O2(OH)2]- and [V4+O(H2O)5]2+ (ln ⁡α V (V)- V (IV)) is 3.9‰, and the equilibrium isotope fractionation factor between [V5+O2(OH)2]- and [V3+(OH)3(H2O)3] (ln ⁡α V (V)- V (III)) is 6.4‰. In addition, isotope fractionation between +5 valence species [V5+O2(OH)2]- and [V5+O2(H2O)4]+ is 1.5‰ at 25 °C, which is caused by their different bond lengths and coordination numbers (CN). Theoretical calculations also show that light V isotope (50V) is preferentially adsorbed on the surface of goethite. Our work reveals that V isotopes can be significantly fractionated in the Earth's surface environments due to redox reaction and mineral adsorption, indicating that V isotope data can be used to monitor toxic V(V) attenuation processes through reduction or adsorption in natural water systems. In addition, a simple mass balance model suggests that V isotope composition of seawater might vary with change of ambient oxygen levels. Thus our theoretical investigations imply a promising future for V isotopes as a potential new paleo-redox tracer.

  3. Deep levels in high resistivity GaN detected by thermally stimulated luminescence and first-principles calculations

    NASA Astrophysics Data System (ADS)

    Gai, Yanqin; Li, Jingbo; Hou, Qifeng; Wang, Xiaoliang; Xiao, Hongling; Wang, Cuimei; Li, Jinmin

    2009-08-01

    Thermally stimulated luminescence spectroscopy has been applied to study the deep centres in unintentionally doped high resistivity GaN epilayers grown by the metal organic chemical vapour deposition method on c-sapphire substrates. Two trap states with activation energies of 0.12 and 0.62 eV are evaluated from two luminescence peaks at 141.9 and 294.7 K in the luminescence curve. Our spectroscopy measurement, in combination with more accurate first-principles studies, provided insights into the microscopic origin of these levels. Our investigations suggest that the lower level at 0.12 eV might originate from CN, which behaves as a hole trap state; the deeper level at 0.62 eV can be correlated with VGa that corresponds to the yellow luminescence band observed in low-temperature photoluminescence spectra.

  4. Interpretation of the optical absorption spectrum of Co3O4 with normal spinel structure from first principles calculations

    NASA Astrophysics Data System (ADS)

    Lima, A. F.

    2014-01-01

    First principles calculations based on density functional theory have been employed to study the electronic, magnetic and optical properties of Co3O4 in a cubic normal spinel structure. Exchange and correlation effects between electrons were treated by a B3PW91 hybrid functional, which produced better results than others scheme, such as GGA+U or PBE0 hybrid functionals or mBJ semilocal potential. The work focuses on clarifying the nature of the optical absorption bands, which have motivated various theoretical and experimental works in the literature. The calculated optical absorption spectrum was compared with available experimental data. On the basis of this calculated electronic and magnetic structure, the optical absorption peaks (theoretical and experimental) could be satisfactorily explained in terms of d3d charge transfer transitions between both CO2+→CO2+ and CO3+→CO3+ ions. The calculations also predicted that the crystal field splittings at both octahedral and tetrahedral sites in the Co3O4 compound are of the same magnitude. First principles calculations were used to predict optical properties of Co3O4. Exchange-correlation electronic effects were treated by a B3PW91 hybrid functional. Calculated optical absorption spectrum was compared with experimental data. Optical absorption peaks could be satisfactorily explained.

  5. Structural studies of homoisoflavonoids: NMR spectroscopy, X-ray diffraction, and theoretical calculations

    NASA Astrophysics Data System (ADS)

    Sievänen, Elina; Toušek, Jaromír; Lunerová, Kamila; Marek, Jaromír; Jankovská, Dagmar; Dvorská, Margita; Marek, Radek

    2010-08-01

    In this article we present a detailed structural investigation for five homoisoflavonoids, molecules important from the pharmacological point of view. For studying the electron distribution as well as its influence on the physicochemical properties, NMR spectroscopy, X-ray diffraction, and theoretical calculations have been used. Nuclear magnetic shieldings obtained by using DFT calculations for optimized molecular geometries are correlated with the experimentally determined chemical shifts. The theoretical data are well in agreement with the experimental values. The single crystal X-ray structures of homoisoflavonoid derivatives 1, 3, and 4 have been solved. The molecular geometries and crystal packing determined by X-ray diffraction are used for characterizing the intermolecular interactions. Electron distribution is crucial for the stability of radicals and hence the antioxidant efficiency of flavonoid structures. The hydrogen bonding governs the formation of complexes of homoisoflavonoids with biological targets.

  6. Combined Raman spectroscopy and first-principles calculation for essential oil of Lemongrass

    NASA Astrophysics Data System (ADS)

    Faria, Rozilaine A. P. G.; Picanço, Nágela F. M.; Campo, Gladís S. D. L.; Faria, Jorge L. B.; Instituto de Física/UFMT Collaboration; Instituto Federal de Mato Grosso/IFMT Team

    2014-03-01

    The essential oils have increased food's industry interest by the presence of antioxidant and antimicrobial. Many of them have antimicrobial and antioxidant, antibacterial and antifungal activities. But, due to the concentrations required to be added in the food matrix, the sensory quality of the food is changed. The production and composition of essential oil extracted from plants depend on the plant-environment interactions, the harvest season, phenophase and physiological state of the vegetal. Cymbopogom citratus (Lemongrass) has a good yield in essential oil with neral (citral A), geranial (citral B) and myrcene, reaching 90% of the oil composition. In our experimental work, the essential oil of lemongrass was obtained by hydrodistillation in Clevenger apparatus for 4 hours. The compound was further analyzed by Raman scattering in a spectrometer HR 800, with excitation at 633nm, in the range 80-3400 cm-1. The spectrum obtained was compared with DFT calculations of molecules of the oil components. Our results show the vibrational signatures of the main functional groups and suggest a simple, but very useful, methodology to quantify the proportions of these components in the oil composition, showing good agreement with Raman data. CNPq/Capes/Fapemat.

  7. Microhydrated dihydrogen phosphate clusters probed by gas phase vibrational spectroscopy and first principles calculations

    SciTech Connect

    Sun, Shou -Tian; Jiang, Ling; Liu, J. W.; Heine, Nadja; Yacovitch, Tara I.; Wende, Torsten; Asmis, Knut R.; Neumark, Daniel M.; Liu, Zhi -Feng

    2015-06-05

    We report infrared multiple photon dissociation (IRMPD) spectra of cryogenically-cooled H2PO4-(H2O)n anions (n = 2–12) in the spectral range of the stretching and bending modes of the solute anion (600–1800 cm-1). The spectra cannot be fully understood using the standard technique of comparison to harmonic spectra of minimum-energy structures; a satisfactory assignment requires considering anharmonic effects as well as entropy-driven hydrogen bond network fluctuations. Aided by finite temperature ab initio molecular dynamics simulations, the observed changes in the position, width and intensity of the IRMPD bands with cluster size are related to the sequence of microsolvation. Due to stronger hydrogen bonding to the two terminal P=O groups, these are hydrated before the two P–OH groups. By n = 6, all four end groups are involved in the hydrogen bond network and by n = 12, the cluster spectra show similarities to the condensed phase spectrum of H2PO4-(aq). Our results reveal some of the microscopic details concerning the formation of the aqueous solvation environment around H2PO4-, provide ample testing grounds for the design of model solvation potentials for this biologically relevant anion, and support a new paradigm for the interpretation of IRMPD spectra of microhydrated ions.

  8. Microhydrated dihydrogen phosphate clusters probed by gas phase vibrational spectroscopy and first principles calculations.

    PubMed

    Sun, Shou-Tian; Jiang, Ling; Liu, J W; Heine, Nadja; Yacovitch, Tara I; Wende, Torsten; Asmis, Knut R; Neumark, Daniel M; Liu, Zhi-Feng

    2015-10-21

    We report infrared multiple photon dissociation (IRMPD) spectra of cryogenically-cooled H2PO4(-)(H2O)n anions (n = 2-12) in the spectral range of the stretching and bending modes of the solute anion (600-1800 cm(-1)). The spectra cannot be fully understood using the standard technique of comparison to harmonic spectra of minimum-energy structures; a satisfactory assignment requires considering anharmonic effects as well as entropy-driven hydrogen bond network fluctuations. Aided by finite temperature ab initio molecular dynamics simulations, the observed changes in the position, width and intensity of the IRMPD bands with cluster size are related to the sequence of microsolvation. Due to stronger hydrogen bonding to the two terminal P[double bond, length as m-dash]O groups, these are hydrated before the two P-OH groups. By n = 6, all four end groups are involved in the hydrogen bond network and by n = 12, the cluster spectra show similarities to the condensed phase spectrum of H2PO4(-)(aq). Our results reveal some of the microscopic details concerning the formation of the aqueous solvation environment around H2PO4(-), provide ample testing grounds for the design of model solvation potentials for this biologically relevant anion, and support a new paradigm for the interpretation of IRMPD spectra of microhydrated ions. PMID:26105043

  9. A "First Principles" Potential Energy Surface for Liquid Water from VRT Spectroscopy of Water Clusters

    SciTech Connect

    Goldman, N; Leforestier, C; Saykally, R J

    2004-05-25

    We present results of gas phase cluster and liquid water simulations from the recently determined VRT(ASP-W)III water dimer potential energy surface. VRT(ASP-W)III is shown to not only be a model of high ''spectroscopic'' accuracy for the water dimer, but also makes accurate predictions of vibrational ground-state properties for clusters up through the hexamer. Results of ambient liquid water simulations from VRT(ASP-W)III are compared to those from ab initio Molecular Dynamics, other potentials of ''spectroscopic'' accuracy, and to experiment. The results herein represent the first time that a ''spectroscopic'' potential surface is able to correctly model condensed phase properties of water.

  10. Electronic and optical response of zirconium sulphoselenides: Compton spectroscopy and first-principles calculations

    NASA Astrophysics Data System (ADS)

    Kumar, Kishor; Bhatt, Samir; Jani, A. R.; Ahuja, B. L.

    2015-12-01

    We present the first-ever experimental Compton profiles (CPs) of ZrSSe2 and ZrS1.5Se1.5 using 100 mCi 241Am Compton spectrometer. To analyze the experimental momentum densities, we have computed for the first-time the CPs, energy bands and density of states using linear combination of atomic orbitals (LCAO) method. To model the exchange and correlation effects within LCAO approach, we have considered Hartree-Fock (HF), density functional theory (DFT) with revised functional of Perdew-Becke-Ernzerhof (PBEsol) and hybridization of HF and DFT. Going beyond computation of electronic properties using LCAO method, we have also derived electronic and optical properties using the modified Becke-Johnson (mBJ) potential within full potential linearized augmented plane wave (FP-LAPW) method. There is notable decrease in the energy band gap on replacing S by Se atoms in ZrSSe2 to obtain ZrS1.5Se1.5 composition, which is mainly attributed to readjustment of Zr-4d, S-3p and Se-4p states. It is seen that the CPs based on hybridization of HF and DFT show a better agreement with the experimental profiles than those based on individual HF and DFT-GGA-PBEsol schemes. The optical properties computed using FP-LAPW-mBJ method unambiguously depict feasibility of using both the sulphoselenides in photovoltaics and also utility of ZrS1.5Se1.5 in the field of non-linear optics.

  11. Microhydrated dihydrogen phosphate clusters probed by gas phase vibrational spectroscopy and first principles calculations

    DOE PAGESBeta

    Sun, Shou -Tian; Jiang, Ling; Liu, J. W.; Heine, Nadja; Yacovitch, Tara I.; Wende, Torsten; Asmis, Knut R.; Neumark, Daniel M.; Liu, Zhi -Feng

    2015-06-05

    We report infrared multiple photon dissociation (IRMPD) spectra of cryogenically-cooled H2PO4-(H2O)n anions (n = 2–12) in the spectral range of the stretching and bending modes of the solute anion (600–1800 cm-1). The spectra cannot be fully understood using the standard technique of comparison to harmonic spectra of minimum-energy structures; a satisfactory assignment requires considering anharmonic effects as well as entropy-driven hydrogen bond network fluctuations. Aided by finite temperature ab initio molecular dynamics simulations, the observed changes in the position, width and intensity of the IRMPD bands with cluster size are related to the sequence of microsolvation. Due to stronger hydrogenmore » bonding to the two terminal P=O groups, these are hydrated before the two P–OH groups. By n = 6, all four end groups are involved in the hydrogen bond network and by n = 12, the cluster spectra show similarities to the condensed phase spectrum of H2PO4-(aq). Our results reveal some of the microscopic details concerning the formation of the aqueous solvation environment around H2PO4-, provide ample testing grounds for the design of model solvation potentials for this biologically relevant anion, and support a new paradigm for the interpretation of IRMPD spectra of microhydrated ions.« less

  12. Molecular Theory of Detonation Initiation: Insight from First Principles Modeling of the Decomposition Mechanisms of Organic Nitro Energetic Materials.

    PubMed

    Tsyshevsky, Roman V; Sharia, Onise; Kuklja, Maija M

    2016-01-01

    This review presents a concept, which assumes that thermal decomposition processes play a major role in defining the sensitivity of organic energetic materials to detonation initiation. As a science and engineering community we are still far away from having a comprehensive molecular detonation initiation theory in a widely agreed upon form. However, recent advances in experimental and theoretical methods allow for a constructive and rigorous approach to design and test the theory or at least some of its fundamental building blocks. In this review, we analyzed a set of select experimental and theoretical articles, which were augmented by our own first principles modeling and simulations, to reveal new trends in energetic materials and to refine known existing correlations between their structures, properties, and functions. Our consideration is intentionally limited to the processes of thermally stimulated chemical reactions at the earliest stage of decomposition of molecules and materials containing defects. PMID:26907231

  13. Molecular Theory of Detonation Initiation: Insight from First Principles Modeling of the Decomposition Mechanisms of Organic Nitro Energetic Materials

    DOE PAGESBeta

    Tsyshevsky, Roman; Sharia, Onise; Kuklja, Maija

    2016-02-19

    Our review presents a concept, which assumes that thermal decomposition processes play a major role in defining the sensitivity of organic energetic materials to detonation initiation. As a science and engineering community we are still far away from having a comprehensive molecular detonation initiation theory in a widely agreed upon form. However, recent advances in experimental and theoretical methods allow for a constructive and rigorous approach to design and test the theory or at least some of its fundamental building blocks. In this review, we analyzed a set of select experimental and theoretical articles, which were augmented by our ownmore » first principles modeling and simulations, to reveal new trends in energetic materials and to refine known existing correlations between their structures, properties, and functions. Lastly, our consideration is intentionally limited to the processes of thermally stimulated chemical reactions at the earliest stage of decomposition of molecules and materials containing defects.« less

  14. Thermoelectric properties of the unfilled skutterudite FeSb3 from first-principles and Seebeck local probes

    SciTech Connect

    Lemal, Sébastien; Nguyen, Ngoc; De Boor, Johannes; Ghosez, Philippe; Varignon, Julien; Klobes, B.; Hermann, Raphael P; Verstraete, Matthieu

    2015-01-01

    Using a combination of first-principles calculations and experimental transport measurements, we study the electronic and magnetic structure of the unfilled skutterudite FeSb3. We employ the hybrid functional approach for exchange-correlation. The ground state is determined to be anti-ferromagnetic with an atomic magnetic moment of 1.6 B/Fe. The N eel temperature TN is estimated at 6 K, in agreement with experiments which found a paramagnetic state down to 10 K. The ground state is semiconducting, with a small electronic gap of 33 meV, also consistent with previous experiments on films. Charge carrier concentrations are estimated from Hall resistance measurements. The Seebeck coefficient is measured and mapped using a scanning probe at room temperature that yields an average value of 38.6 VK 1, slightly lower than the theoretical result. The theoretical conductivity is analyzed as a function of temperature and concentration of charge carriers.

  15. Nonlinear Socio-Ecological Dynamics and First Principles ofCollective Choice Behavior of ``Homo Socialis"

    NASA Astrophysics Data System (ADS)

    Sonis, M.

    Socio-ecological dynamics emerged from the field of Mathematical SocialSciences and opened up avenues for re-examination of classical problems of collective behavior in Social and Spatial sciences. The ``engine" of this collective behavior is the subjective mental evaluation of level of utilities in the future, presenting sets of composite socio-economic-temporal-locational advantages. These dynamics present new laws of collective multi-population behavior which are the meso-level counterparts of the utility optimization individual behavior. The central core of the socio-ecological choice dynamics includes the following first principle of the collective choice behavior of ``Homo Socialis" based on the existence of ``collective consciousness": the choice behavior of ``Homo Socialis" is a collective meso-level choice behavior such that the relative changes in choice frequencies depend on the distribution of innovation alternatives between adopters of innovations. The mathematical basis of the Socio-Ecological Dynamics includes two complementary analytical approaches both based on the use of computer modeling as a theoretical and simulation tool. First approach is the ``continuous approach" --- the systems of ordinary and partial differential equations reflecting the continuous time Volterra ecological formalism in a form of antagonistic and/or cooperative collective hyper-games between different sub-sets of choice alternatives. Second approach is the ``discrete approach" --- systems of difference equations presenting a new branch of the non-linear discrete dynamics --- the Discrete Relative m-population/n-innovations Socio-Spatial Dynamics (Dendrinos and Sonis, 1990). The generalization of the Volterra formalism leads further to the meso-level variational principle of collective choice behavior determining the balance between the resulting cumulative social spatio-temporal interactions among the population of adopters susceptible to the choice alternatives and the

  16. First-principles prediction of superconductivity in LiBSi1-xAlx

    NASA Astrophysics Data System (ADS)

    Miao, Rende; Yang, Jun; Bai, Zhong; Can, Dan; Zhang, Xi; Jiang, Min; Liu, Cuicui; Wu, Fangping; Ma, Shuyun

    2015-02-01

    Electronic structure, lattice dynamics and superconducting properties for theoretically devised superconductor LiBSi1-x Alx are obtained by first-principles calculations. We assume that Lithium Boron Silicon (LiBSi) has the same crystal structure as that of Lithium borocarbide (LiBC). The pristine LiBSi is predicted to be a zero-gap semiconductor. Hole doping of LiBSi through partial substitution of Si by SiAl atoms can produce a semiconductor-metal transition and develop superconductivity. To assess the thermodynamic stability of LiBSi1-xAlx, the formation energies are calculated using the supercell method. For LiBSi0.75 Al0.25 and LiBSi0.875Al0.125, the obtained formation energies are -5.9 and -6.1 eV, respectively, indicating that LiBSi1-xAlx is energetically favorable at least in the range of 0 ≤ x ≤ 0.25. Phonon spectra and superconducting properties are obtained within the virtual-crystal approximation (VCA) treatment. The results show that LiBSi1-xAlx is dynamically stable approximately in the range of 0 ≤ x ≤ 0.35. For LiBSi0.8Al0.2, the obtained electron-phonon coupling constant λ is 0.86 and superconducting transition temperature TC is predicted to be in the range of 11-13 K (0.14 ≥ μ* ≥ 0.1).

  17. Phase diagrams for clathrate hydrates of methane, ethane, and propane from first-principles thermodynamics.

    PubMed

    Cao, Xiaoxiao; Huang, Yingying; Li, Wenbo; Zheng, Zhaoyang; Jiang, Xue; Su, Yan; Zhao, Jijun; Liu, Changling

    2016-01-28

    Natural gas hydrates are inclusion compounds composed of major light hydrocarbon gaseous molecules (CH4, C2H6, and C3H8) and a water clathrate framework. Understanding the phase stability and formation conditions of natural gas hydrates is crucial for their future exploitation and applications and requires an accurate description of intermolecular interactions. Previous ab initio calculations on gas hydrates were mainly limited by the cluster models, whereas the phase diagram and equilibrium conditions of hydrate formation were usually investigated using the thermodynamic models or empirical molecular simulations. For the first time, we construct the chemical potential phase diagrams of type II clathrate hydrates encapsulated with methane/ethane/propane guest molecules using first-principles thermodynamics. We find that the partially occupied structures (136H2O·1CH4, 136H2O·16CH4, 136H2O·20CH4, 136H2O·1C2H6, and 136H2O·1C3H8) and fully occupied structures (136H2O·24CH4, 136H2O·8C2H6, and 136H2O·8C3H8) are thermodynamically favorable under given pressure-temperature (p-T) conditions. The theoretically predicted equilibrium pressures for pure CH4, C2H6 and C3H8 hydrates at the phase transition point are consistent with the experimental data. These results provide valuable guidance for establishing the relationship between the accurate description of intermolecular noncovalent interactions and the p-T equilibrium conditions of clathrate hydrates and other molecular crystals. PMID:26745181

  18. First-Principles Study of Lattice Dynamics, Structural Phase Transition, and Thermodynamic Properties of Barium Titanate

    NASA Astrophysics Data System (ADS)

    Zhang, Huai-Yong; Zeng, Zhao-Yi; Zhao, Ying-Qin; Lu, Qing; Cheng, Yan

    2016-08-01

    Lattice dynamics, structural phase transition, and the thermodynamic properties of barium titanate (BaTiO3) are investigated by using first-principles calculations within the density functional theory (DFT). It is found that the GGA-WC exchange-correlation functional can produce better results. The imaginary frequencies that indicate structural instability are observed for the cubic, tetragonal, and orthorhombic phases of BaTiO3 and no imaginary frequencies emerge in the rhombohedral phase. By examining the partial phonon density of states (PDOSs), we find that the main contribution to the imaginary frequencies is the distortions of the perovskite cage (Ti-O). On the basis of the site-symmetry consideration and group theory, we give the comparative phonon symmetry analysis in four phases, which is useful to analyze the role of different atomic displacements in the vibrational modes of different symmetry. The calculated optical phonon frequencies at Γ point for the four phases are in good agreement with other theoretical and experimental data. The pressure-induced phase transition of BaTiO3 among four phases and the thermodynamic properties of BaTiO3 in rhombohedral phase have been investigated within the quasi-harmonic approximation (QHA). The sequence of the pressure-induced phase transition is rhombohedral→orthorhombic→tetragonal→cubic, and the corresponding transition pressure is 5.17, 5.92, 6.65 GPa, respectively. At zero pressure, the thermal expansion coefficient αV, heat capacity CV, Grüneisen parameter γ, and bulk modulus B of the rhombohedral phase BaTiO3 are estimated from 0 K to 200 K.

  19. Structure and mechanical properties of tantalum mononitride under high pressure: A first-principles study

    PubMed Central

    Chang, Jing; Zhao, Guo-Ping; Zhou, Xiao-Lin; Liu, Ke; Lu, Lai-Yu

    2012-01-01

    The structure and mechanical properties of tantalum mononitride (TaN) are investigated at high pressure from first-principles using the plane wave pseudopotential method within the local density approximation. Three stable phases were considered, i.e., two hexagonal phases (ε and θ) and a cubic δ phase. The obtained equilibrium structure parameters and ground state mechanical properties are in excellent agreement with the experimental and other theoretical results. A full elastic tensor and crystal anisotropy of the ultra-incompressible TaN in three stable phases are determined in the wide pressure range. Results indicated that the elastic properties of TaN in three phases are strongly pressure dependent. And the hexagonal θ-TaN is the most ultraincompressible among the consider phases, which suggests that the θ phase of TaN is a potential candidate structure to be one of the ultraincompressible and hard materials. By the elastic stability criteria, it is predicted that θ-TaN is not stable above 53.9 GPa. In addition, the calculated B/G ratio indicated that the ε and δ phases possess brittle nature in the range of pressure from 0 to 100 GPa. While θ phase is brittleness at low pressure (below 8.2 GPa) and is strongly prone to ductility at high pressure (above 8.2 GPa). The calculated elastic anisotropic factors for three phases of TaN suggest that they are elastically highly anisotropic and strongly dependent on the propagation direction. PMID:23185097

  20. Prediction of new high pressure structural sequence in thorium carbide: A first principles study

    SciTech Connect

    Sahoo, B. D. Joshi, K. D.; Gupta, Satish C.

    2015-05-14

    In the present work, we report the detailed electronic band structure calculations on thorium monocarbide. The comparison of enthalpies, derived for various phases using evolutionary structure search method in conjunction with first principles total energy calculations at several hydrostatic compressions, yielded a high pressure structural sequence of NaCl type (B1) → Pnma → Cmcm → CsCl type (B2) at hydrostatic pressures of ∼19 GPa, 36 GPa, and 200 GPa, respectively. However, the two high pressure experimental studies by Gerward et al. [J. Appl. Crystallogr. 19, 308 (1986); J. Less-Common Met. 161, L11 (1990)] one up to 36 GPa and other up to 50 GPa, on substoichiometric thorium carbide samples with carbon deficiency of ∼20%, do not report any structural transition. The discrepancy between theory and experiment could be due to the non-stoichiometry of thorium carbide samples used in the experiment. Further, in order to substantiate the results of our static lattice calculations, we have determined the phonon dispersion relations for these structures from lattice dynamic calculations. The theoretically calculated phonon spectrum reveal that the B1 phase fails dynamically at ∼33.8 GPa whereas the Pnma phase appears as dynamically stable structure around the B1 to Pnma transition pressure. Similarly, the Cmcm structure also displays dynamic stability in the regime of its structural stability. The B2 phase becomes dynamically stable much below the Cmcm to B2 transition pressure. Additionally, we have derived various thermophysical properties such as zero pressure equilibrium volume, bulk modulus, its pressure derivative, Debye temperature, thermal expansion coefficient and Gruneisen parameter at 300 K and compared these with available experimental data. Further, the behavior of zero pressure bulk modulus, heat capacity and Helmholtz free energy has been examined as a function temperature and compared with the experimental data of Danan [J

  1. Liquid Iron Alloys with Hydrogen at Outer Core Conditions by First Principles

    NASA Astrophysics Data System (ADS)

    Umemoto, K.; Hirose, K.

    2015-12-01

    Since the density of the outer core deduced from seismic data is about 10% lower than that of pure iron at core pressures and temperatures (P-T), it is widely believed that the outer core includes one or more light elements. Although intensive experimental and theoretical studies have been performed so far, the light element in the core has not yet been identified. Comparison of the density and sound velocity of liquid iron alloys with observations, such as the PREM, is a promising way to determine the species and quantity of light alloying component(s) in the outer core. Here we report the results of a first-principles molecular dynamics study on liquid iron alloyed with hydrogen, one of candidates of the light elements. Hydrogen had been much less studied than other candidates. However, hydrogen has been known to reduce the melting temperature of Fe-H solid [1]. Furthermore, very recently, Nomura et al. argued that the outer core may include 24 at.% H in order to be molten under relatively low temperature (< 3600 K) [2]. Since then hydrogen has attracted strong interests. We clarify the effects of hydrogen on density and sound velocity of liquid iron alloys under outer core P-T conditions. It is shown that ~1 wt% hydrogen can reproduce PREM density and sound velocity simultaneously very well. In addition, we show the presence of hydrogen rather reduces Gruneisen parameters. It indicates that, if hydrogen exists in the outer core, temperature profile of the outer core could be changed considerably from one estimated so far. [1] Sakamaki, K., E. Takahashi, Y. Nakajima, Y. Nishihara, K. Funakoshi, T. Suzuki, and Y. Fukai, Phys. Earth Planet. Inter., 174, 192-201 (2009). [2] Nomura, R., K. Hirose, K. Uesugi, Y. Ohishi, A. Tsuchiyama, A. Miyake, and Y. Ueno, Science 31, 522-525 (2014).

  2. 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.

  3. The study of Al-L23 ELNES with resolution-enhancement software and first-principles calculation.

    PubMed

    Kimoto, Koji; Ishizuka, Kazuo; Mizoguchi, Teruyasu; Tanaka, Isao; Matsui, Yoshio

    2003-01-01

    Resolution-enhancement software and first-principles calculation for electron energy-loss spectroscopy (EELS) were applied for the study of aluminium (Al) coordination in alumina. Al-L23 energy-loss near-edge structures (ELNES) of alpha- and gamma-aluminas were observed using a field-emission transmission electron microscope and advanced software for EELS. The inherent energy resolution of a cold field-emission gun (FEG) of approximately 0.3 eV was realized using drift-correction software. The energy spread of the cold FEG was deconvoluted by means of maximum-entropy or Richardson-Lucy algorithms and the energy resolution of the deconvoluted spectrum became comparable with that obtained using a monochromator, whose energy resolution was < 0.2 eV. Fine structures in Al L23-edge were observed, such as 0.5 eV splitting between L3 and L2 peaks in alpha-alumina (i.e. spin-orbit splitting). The difference in Al coordination was clearly observed in Al-L23 ELNES and the major structures near the threshold were assigned using first-principles calculations. PMID:12892219

  4. First-principles molecular dynamics simulation of the Ca2UO2(CO3)3 complex in water.

    PubMed

    Priest, Chad; Tian, Ziqi; Jiang, De-En

    2016-06-14

    Recent experiments have shown that the neutral Ca2UO2(CO3)3 complex is the dominant species of uranium in many uranyl-containing streams. However, the structure and solvation of such a species in water has not been investigated from first principles. Herein we present a first principles molecular dynamics perspective of the Ca2UO2(CO3)3 complex in water based on density functional theory and Born-Oppenheimer approximation. We find that the Ca2UO2(CO3)3 complex is very stable in our simulation timeframe for three different concentrations considered and that the key distances from our simulation are in good agreement with the experimental data from extended X-ray absorption fine structure (EXAFS) spectroscopy. More important, we find that the two Ca ions bind differently in the complex, as a result of the hydrogen-bonding network around the whole complex. This finding invites confirmation from time-resolved EXAFS and has implications in understanding the dissociative equilibrium of the Ca2UO2(CO3)3 complex in water. PMID:26901265

  5. 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.

  6. A theoretical study of the sum frequency vibrational spectroscopy of the carbon tetrachloride/water interface

    NASA Astrophysics Data System (ADS)

    Green, Anthony J.; Perry, Angela; Moore, Preston B.; Space, Brian

    2012-03-01

    Theoretical approximations to the sum frequency vibrational spectroscopy (SFVS) of the carbon tetrachloride/water interface are constructed using the quantum-corrected time correlation functions (TCF) to aid in interpretation of experimental data and to predict novel vibrational modes. Instantaneous normal mode (INM) methods are used to characterize the observed modes leading to the TCF signal, thus providing molecular resolution of the vibrational lineshapes. Detailed comparisons of the theoretical signals are made with those obtained experimentally and show excellent agreement for the spectral peaks in the O-H stretching region of water. An intermolecular mode, unique to the interface, at 848 cm-1 is also identifiable, similar to the one seen for the water/vapor interface. INM analysis reveals the resonance is due to a wagging mode (hindered rotation) that was previously identified (Perry et al 2005 J. Chem. Phys. 123 144705) as localized on a single water molecule with both hydrogens displaced normal to the interface—generally it is found that the symmetry breaking at the interface leads to hindered translations and rotations at hydrophilic/hydrophobic interfaces that assume finite vibrational frequencies due to anchoring at the aqueous interface. Additionally, examination of the real and imaginary parts of the theoretical SFVS spectra reveal the spectroscopic species attributed the resonances and possible subspecies in the O-H region; these results are consistent with extant experimental data and associated analysis.

  7. Experimental and theoretical investigation on the vibrational spectroscopy of L-theanine

    NASA Astrophysics Data System (ADS)

    Chen, Yongjian; Xi, Gangqin; Chen, Rong; Li, Yongzeng; Feng, Shangyuan; Lei, Jinping; Lin, Hongxing

    2011-12-01

    In this work, experimental and theoretical investigations on vibrational spectroscopy of L-theanine were presented. FT-IR and Raman spectra of L-theanine powder sample were recorded and corresponding theoretical calculations were performed based on Density Functional Theory (DFT) at B3LYP level using 6-31++G(d,p) and 6-311++G(d,p) basis sets combined with the Polarized Continuum Model (PCM) with water as the solvent. The experimental vibrational bands were assigned based on the basis of calculations while the predicted geometric parameters were compared with those obtained in experiment, most of the bands measured were well reproduced in the calculations while the discrepancies are significant for the bands mainly related to the vibrations of protonated amino group ( NH3+) and ionized carboxyl group (COO -), which are affected by the intramolecular hydrogen bond interaction. Good agreements between the theoretical and experimental results confirm the feasibility of the DFT method combined with PCM in the study of the molecular structure and vibrational spectra of L-theanine.

  8. Dispersion-corrected first-principles calculation of terahertz vibration, and evidence for weak hydrogen bond formation

    NASA Astrophysics Data System (ADS)

    Takahashi, Masae; Ishikawa, Yoichi; Ito, Hiromasa

    2013-03-01

    A weak hydrogen bond (WHB) such as CH-O is very important for the structure, function, and dynamics in a chemical and biological system WHB stretching vibration is in a terahertz (THz) frequency region Very recently, the reasonable performance of dispersion-corrected first-principles to WHB has been proven. In this lecture, we report dispersion-corrected first-principles calculation of the vibrational absorption of some organic crystals, and low-temperature THz spectral measurement, in order to clarify WHB stretching vibration. The THz frequency calculation of a WHB crystal has extremely improved by dispersion correction. Moreover, the discrepancy in frequency between an experiment and calculation and is 10 1/cm or less. Dispersion correction is especially effective for intermolecular mode. The very sharp peak appearing at 4 K is assigned to the intermolecular translational mode that corresponds to WHB stretching vibration. It is difficult to detect and control the WHB formation in a crystal because the binding energy is very small. With the help of the latest intense development of experimental and theoretical technique and its careful use, we reveal solid-state WHB stretching vibration as evidence for the WHB formation that differs in respective WHB networks The research was supported by the Ministry of Education, Culture, Sports, Science and Technology of Japan (Grant No. 22550003).

  9. Putting DFT to the test: a first-principles study of electronic, magnetic, and optical properties of Co3O4.

    PubMed

    Singh, Vijay; Kosa, Monica; Majhi, Koushik; Major, Dan Thomas

    2015-01-13

    First-principles density functional theory (DFT) and a many-body Green's function method have been employed to elucidate the electronic, magnetic, and photonic properties of a spinel compound, Co3O4. Co3O4 is an antiferromagnetic semiconductor composed of cobalt ions in the Co(2+) and Co(3+) oxidation states. Co3O4 is believed to be a strongly correlated material, where the on-site Coulomb interaction (U) on Co d orbitals is presumably important, although this view has recently been contested. The suggested optical band gap for this material ranges from 0.8 to 2.0 eV, depending on the type of experiments and theoretical treatment. Thus, the correlated nature of the Co d orbitals in Co3O4 and the extent of the band gap are still under debate, raising questions regarding the ability of DFT to correctly treat the electronic structure in this material. To resolve the above controversies, we have employed a range of theoretical methods, including pure DFT, DFT+U, and a range-separated exchange-correlation functional (HSE06) as well as many-body Green's function theory (i.e., the GW method). We compare the electronic structure and band gap of Co3O4 with available photoemission spectroscopy and optical band gap data and confirm a direct band gap of ca. 0.8 eV. Furthermore, we have also studied the optical properties of Co3O4 by calculating the imaginary part of the dielectric function (Im(ε)), facilitating direct comparison with the measured optical absorption spectra. Finally, we have calculated the nearest-neighbor interaction (J1) between Co(2+) ions to understand the complex magnetic structure of Co3O4. PMID:26574204

  10. First-Principles Molecular Dynamics Studies of Organometallic Complexes and Homogeneous Catalytic Processes.

    PubMed

    Vidossich, Pietro; Lledós, Agustí; Ujaque, Gregori

    2016-06-21

    Computational chemistry is a valuable aid to complement experimental studies of organometallic systems and their reactivity. It allows probing mechanistic hypotheses and investigating molecular structures, shedding light on the behavior and properties of molecular assemblies at the atomic scale. When approaching a chemical problem, the computational chemist has to decide on the theoretical approach needed to describe electron/nuclear interactions and the composition of the model used to approximate the actual system. Both factors determine the reliability of the modeling study. The community dedicated much effort to developing and improving the performance and accuracy of theoretical approaches for electronic structure calculations, on which the description of (inter)atomic interactions rely. Here, the importance of the model system used in computational studies is highlighted through examples from our recent research focused on organometallic systems and homogeneous catalytic processes. We show how the inclusion of explicit solvent allows the characterization of molecular events that would otherwise not be accessible in reduced model systems (clusters). These include the stabilization of nascent charged fragments via microscopic solvation (notably, hydrogen bonding), transfer of charge (protons) between distant fragments mediated by solvent molecules, and solvent coordination to unsaturated metal centers. Furthermore, when weak interactions are involved, we show how conformational and solvation properties of organometallic complexes are also affected by the explicit inclusion of solvent molecules. Such extended model systems may be treated under periodic boundary conditions, thus removing the cluster/continuum (or vacuum) boundary, and require a statistical mechanics simulation technique to sample the accessible configurational space. First-principles molecular dynamics, in which atomic forces are computed from electronic structure calculations (namely, density

  11. First Principles Investigations of Technologically and Environmentally Important Nano-structured Materials and Devices

    NASA Astrophysics Data System (ADS)

    Paul, Sujata

    In the course of my PhD I have worked on a broad range of problems using simulations from first principles: from catalysis and chemical reactions at surfaces and on nanostructures, characterization of carbon-based systems and devices, and surface and interface physics. My research activities focused on the application of ab-initio electronic structure techniques to the theoretical study of important aspects of the physics and chemistry of materials for energy and environmental applications and nano-electronic devices. A common theme of my research is the computational study of chemical reactions of environmentally important molecules (CO, CO2) using high performance simulations. In particular, my principal aim was to design novel nano-structured functional catalytic surfaces and interfaces for environmentally relevant remediation and recycling reactions, with particular attention to the management of carbon dioxide. We have studied the carbon-mediated partial sequestration and selective oxidation of carbon monoxide (CO), both in the presence and absence of hydrogen, on graphitic edges. Using first-principles calculations we have studied several reactions of CO with carbon nanostructures, where the active sites can be regenerated by the deposition of carbon decomposed from the reactant (CO) to make the reactions self-sustained. Using statistical mechanics, we have also studied the conditions under which the conversion of CO to graphene and carbon dioxide is thermodynamically favorable, both in the presence and in the absence of hydrogen. These results are a first step toward the development of processes for the carbon-mediated partial sequestration and selective oxidation of CO in a hydrogen atmosphere. We have elucidated the atomic scale mechanisms of activation and reduction of carbon dioxide on specifically designed catalytic surfaces via the rational manipulation of the surface properties that can be achieved by combining transition metal thin films on oxide

  12. Theoretical Simulations and Ultrafast Pump-probe Spectroscopy Experiments in Pigment-protein Photosynthetic Complexes

    SciTech Connect

    Buck, D.R.

    2000-09-12

    Theoretical simulations and ultrafast pump-probe laser spectroscopy experiments were used to study photosynthetic pigment-protein complexes and antennae found in green sulfur bacteria such as Prosthecochloris aestuarii, Chloroflexus aurantiacus, and Chlorobium tepidum. The work focused on understanding structure-function relationships in energy transfer processes in these complexes through experiments and trying to model that data as we tested our theoretical assumptions with calculations. Theoretical exciton calculations on tubular pigment aggregates yield electronic absorption spectra that are superimpositions of linear J-aggregate spectra. The electronic spectroscopy of BChl c/d/e antennae in light harvesting chlorosomes from Chloroflexus aurantiacus differs considerably from J-aggregate spectra. Strong symmetry breaking is needed if we hope to simulate the absorption spectra of the BChl c antenna. The theory for simulating absorption difference spectra in strongly coupled photosynthetic antenna is described, first for a relatively simple heterodimer, then for the general N-pigment system. The theory is applied to the Fenna-Matthews-Olson (FMO) BChl a protein trimers from Prosthecochloris aestuarii and then compared with experimental low-temperature absorption difference spectra of FMO trimers from Chlorobium tepidum. Circular dichroism spectra of the FMO trimer are unusually sensitive to diagonal energy disorder. Substantial differences occur between CD spectra in exciton simulations performed with and without realistic inhomogeneous distribution functions for the input pigment diagonal energies. Anisotropic absorption difference spectroscopy measurements are less consistent with 21-pigment trimer simulations than 7-pigment monomer simulations which assume that the laser-prepared states are localized within a subunit of the trimer. Experimental anisotropies from real samples likely arise from statistical averaging over states with diagonal energies shifted by

  13. Temperature-dependence of structural and mechanical properties of TiB{sub 2}: A first principle investigation

    SciTech Connect

    Xiang, Huimin; Feng, Zhihai; Li, Zhongping; Zhou, Yanchun E-mail: yczhou714@gmail.com

    2015-06-14

    High temperature mechanical and thermodynamic properties of TiB{sub 2} are important to its applications as ultrahigh temperature ceramic, which were not well understood. In this study, the thermodynamic and mechanical properties of TiB{sub 2} were investigated by the combination of first principle and phonon dispersion calculations. The thermal expansion of TiB{sub 2} was anisotropic, α{sub c}/α{sub a} is nearly constant (1.46) from 300 K to 1500 K, theoretically. The origination of this anisotropy is the anisotropic compressibility. The heat capacity at constant pressure was estimated from the theoretical entropy and fitted the experimental result quite well when higher-order anharmonic effects were considered. Theoretical isentropic elastic constants and mechanical properties were calculated and their temperature dependence agreed with the existed experiments. From room temperature to 1500 K, the theoretical slope is −0.0211 GPa·K{sup −1}, −0.0155 GPa·K{sup −1}, and −0.0384 GPa·K{sup −1} for B, G, and E, respectively. Our theoretical results highlight the suitability of this method in predicting temperature dependent properties of ultrahigh temperature ceramics and show ability in selecting and designing of novel ultrahigh temperature ceramics.

  14. 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

  15. 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

  16. FT-Raman, surface-enhanced Raman spectroscopy and theoretical investigations of diclofenac sodium

    NASA Astrophysics Data System (ADS)

    Iliescu, T.; Baia, M.; Kiefer, W.

    2004-03-01

    Raman and surface-enhanced Raman (SER) spectroscopies have been applied to the vibrational characterization of diclofenac sodium (DCF-Na). Theoretical calculations (DFT and ab initio) of two DCF-Na conformers have been performed to find the optimized structure and computed vibrational wavenumbers of the most stable one. SER spectra in silver colloid at different pH values have been also recorded and analyzed. Good SER spectra have been obtained in acidic and neutral environments, proving the chemisorption of the DCF-Na molecule on the silver surface. In the investigated pH range the carboxylate anion has been bonded to the silver surface through the lone pair oxygen electrons. The phenyl rings' orientation with respect to the silver surface changed on passing from acidic to neutral pH from a tilted close to flat to a more perpendicular one.

  17. Compensating for Electrode Polarization in Dielectric Spectroscopy Studies of Colloidal Suspensions: Theoretical Assessment of Existing Methods.

    PubMed

    Chassagne, Claire; Dubois, Emmanuelle; Jiménez, María L; van der Ploeg, J P M; van Turnhout, Jan

    2016-01-01

    Dielectric spectroscopy can be used to determine the dipole moment of colloidal particles from which important interfacial electrokinetic properties, for instance their zeta potential, can be deduced. Unfortunately, dielectric spectroscopy measurements are hampered by electrode polarization (EP). In this article, we review several procedures to compensate for this effect. First EP in electrolyte solutions is described: the complex conductivity is derived as function of frequency, for two cell geometries (planar and cylindrical) with blocking electrodes. The corresponding equivalent circuit for the electrolyte solution is given for each geometry. This equivalent circuit model is extended to suspensions. The complex conductivity of a suspension, in the presence of EP, is then calculated from the impedance. Different methods for compensating for EP are critically assessed, with the help of the theoretical findings. Their limit of validity is given in terms of characteristic frequencies. We can identify with one of these frequencies the frequency range within which data uncorrected for EP may be used to assess the dipole moment of colloidal particles. In order to extract this dipole moment from the measured data, two methods are reviewed: one is based on the use of existing models for the complex conductivity of suspensions, the other is the logarithmic derivative method. An extension to multiple relaxations of the logarithmic derivative method is proposed. PMID:27486575

  18. Compensating for Electrode Polarization in Dielectric Spectroscopy Studies of Colloidal Suspensions: Theoretical Assessment of Existing Methods

    PubMed Central

    Chassagne, Claire; Dubois, Emmanuelle; Jiménez, María L.; van der Ploeg, J. P. M; van Turnhout, Jan

    2016-01-01

    Dielectric spectroscopy can be used to determine the dipole moment of colloidal particles from which important interfacial electrokinetic properties, for instance their zeta potential, can be deduced. Unfortunately, dielectric spectroscopy measurements are hampered by electrode polarization (EP). In this article, we review several procedures to compensate for this effect. First EP in electrolyte solutions is described: the complex conductivity is derived as function of frequency, for two cell geometries (planar and cylindrical) with blocking electrodes. The corresponding equivalent circuit for the electrolyte solution is given for each geometry. This equivalent circuit model is extended to suspensions. The complex conductivity of a suspension, in the presence of EP, is then calculated from the impedance. Different methods for compensating for EP are critically assessed, with the help of the theoretical findings. Their limit of validity is given in terms of characteristic frequencies. We can identify with one of these frequencies the frequency range within which data uncorrected for EP may be used to assess the dipole moment of colloidal particles. In order to extract this dipole moment from the measured data, two methods are reviewed: one is based on the use of existing models for the complex conductivity of suspensions, the other is the logarithmic derivative method. An extension to multiple relaxations of the logarithmic derivative method is proposed. PMID:27486575

  19. Cesium stability in a typical mica structure in dry and wet environments from first-principles

    NASA Astrophysics Data System (ADS)

    Suehara, Shigeru; Yamada, Hirohisa

    2013-05-01

    Cesium ion stability in a typical mica structure in various environments of solid salts (XCl; X = Cs, K, and Na), metals (X) and saltwaters (XCl aqueous liquids) was investigated using first-principles density-functional theory (DFT) with the Perdew-Burke-Ernzerhof (PBE) functional as well as a van der Waals (vdW) corrected functional (vdW-DFC09x). We specifically examined interlayer ion-exchange in bulk phlogopite-type mica, which is expected to produce a well-defined benchmark in a thermodynamic equilibrium state. In general, theoretical models have well reproduced the experimental and theoretical data found in the literature from the viewpoints of structure, heat capacity, and entropy. The vdW-DFC09x lattice parameters of the mica appear to be better reproducible than the PBE parameters are. However, the vdW correction calculations of the thermodynamic properties with the harmonic approximation using the phonon frequencies showed poor results in some cases, whereas the PBE calculations yielded robust and reasonable results in terms of structure and thermodynamic properties. The isotope effect of the 137Cs atom appears to be confined in thermodynamic properties such as entropy, heat capacity, and ion-exchange energy, although the theoretical infrared spectra showed a small redshift ca. 1 cm-1 in the far-infrared region of 50-75 cm-1. The calculated RDF and the coordination number for X-O (i.e., X-H2O) for the saltwater model indicated that the Cs, K, and Na ions with respective hydrated radii of 0.323, 0.284, and 0.238 nm were surrounded, respectively, by 6.5, 4.5, and 4.0 of H2O molecules in a water solution. Ion-exchange energy values based on free-energy calculations around ambient temperatures derived using the PBE functional and a harmonic approximation suggest that the cesium ion in mica interlayer phlogopite is stable in an environment consisting of KCl, NaCl, K, and Na solids, and in NaCl saltwater as well. However, it can be exchanged competitively by

  20. Accurate First-Principles Spectra Predictions for Planetological and Astrophysical Applications at Various T-Conditions

    NASA Astrophysics Data System (ADS)

    Rey, M.; Nikitin, A. V.; Tyuterev, V.

    2014-06-01

    Knowledge of near infrared intensities of rovibrational transitions of polyatomic molecules is essential for the modeling of various planetary atmospheres, brown dwarfs and for other astrophysical applications 1,2,3. For example, to analyze exoplanets, atmospheric models have been developed, thus making the need to provide accurate spectroscopic data. Consequently, the spectral characterization of such planetary objects relies on the necessity of having adequate and reliable molecular data in extreme conditions (temperature, optical path length, pressure). On the other hand, in the modeling of astrophysical opacities, millions of lines are generally involved and the line-by-line extraction is clearly not feasible in laboratory measurements. It is thus suggested that this large amount of data could be interpreted only by reliable theoretical predictions. There exists essentially two theoretical approaches for the computation and prediction of spectra. The first one is based on empirically-fitted effective spectroscopic models. Another way for computing energies, line positions and intensities is based on global variational calculations using ab initio surfaces. They do not yet reach the spectroscopic accuracy stricto sensu but implicitly account for all intramolecular interactions including resonance couplings in a wide spectral range. The final aim of this work is to provide reliable predictions which could be quantitatively accurate with respect to the precision of available observations and as complete as possible. All this thus requires extensive first-principles quantum mechanical calculations essentially based on three necessary ingredients which are (i) accurate intramolecular potential energy surface and dipole moment surface components well-defined in a large range of vibrational displacements and (ii) efficient computational methods combined with suitable choices of coordinates to account for molecular symmetry properties and to achieve a good numerical

  1. Predicting Raman Spectra of Aqueous Silica and Alumina Species in Solution From First Principles

    NASA Astrophysics Data System (ADS)

    Hunt, J. D.; Schauble, E. A.; Manning, C. E.

    2006-12-01

    Dissolved silica and alumina play an important role in lithospheric fluid chemistry. Silica concentrations in aqueous fluids vary over the range of crustal temperatures and pressures enough to allow for significant mass transport of silica via fluid-rock interaction. The polymerization of silica, and the possible incorporation of alumina into the polymer structure, could afford crystal-like or melt-like sites to otherwise insoluble elements such as titanium, leading to enhanced mobility. Raman spectroscopy in a hydrothermal diamond anvil cell (HDAC) has been used to study silica polymerization at elevated pressure and temperature [Ref. 1, 2], but Raman spectra of expected solutes are not fully understood. We calculated Raman spectra of H4SiO4 monomers, H6Si2O7 dimers, and H6SiAlO_7^- dimers, from first principles using hybrid density functional theory (B3LYP). These spectra take into account the variation in bridging angle (Si-O-Si and Si-O-Al angles) that the dimers will have at a given temperature by calculating a potential energy surface of the dimer as the bridging angle varies, and using a Boltzmann distribution at that temperature to determine relative populations at each geometry. Solution effects can be incorporated by using a polarizable continuum model (PCM), and a potential energy surface has been constructed for the silica dimer using a PCM. The bridging angle variation explains the broadness of the 630 cm^-^1 silica dimer peak observed in HDAC experiments [Ref. 1, 2] at high temperatures. The silica-alumina dimer bridging angle is shown to be stiffer than the silica dimer bridging angle, which results in a much narrower main peak. The synthetic spectrum obtained for the silica-alumina dimer suggests that there may be a higher ratio of complexed alumina to free alumina in solution at highly basic pH than previously estimated [Ref. 3]. References: 1. Zotov, N. and H. Keppler, Chemical Geology, 2002. 184: p. 71-82. 2. Zotov, N. and H. Keppler, American

  2. A combined first principles and Mohr-Coulomb criterion for the determination of the nanohardness of amorphous silicon

    NASA Astrophysics Data System (ADS)

    Tabatabaei, Maryam; Shodja, Hossein M.

    2015-12-01

    Although, the evaluation of the nanohardness of amorphous silicon (a-Si) has been the subject of a few experimental works but, to date, it has not been addressed theoretically yet. In this work, first principles Kohn-Sham density functional theory (DFT)-based molecular dynamics (MD) in combination with Mohr-Coulomb criterion is employed to calculate the ideal shear strength of the damped MD annealed a-Si sample containing dangling and floating bonds which are pertinent to the threefold- and fivefold-coordinated defects, respectively, as well as distorted tetrahedral bonds. The stress state beneath the nanoindenter is triaxial, and is accounted for properly. The calculated values of nanohardness are in reasonable agreement with those values measured experimentally. Consideration of the electronic charge distribution under the state of triaxial tension test reveals that the yield phenomenon in a-Si is accompanied by the transformation of a threefold-coordinated Si atom to a fourfold-coordinated.

  3. Electronic and optical properties of RESn{sub 3} (RE=Pr & Nd) intermetallics: A first principles study

    SciTech Connect

    Pagare, G.; Abraham, Jisha A.; Sanyal, S. P.

    2015-06-24

    A theoretical study of structural, electronic and optical properties of RESn{sub 3} (RE = Pr & Nd) intermetallics have been investigated systematically using first principles density functional theory. The calculations are carried out within the PBE-GGA and LSDA for the exchange correlation potential. The ground state properties such as lattice parameter (a{sub 0}), bulk modulus (B) and its pressure derivative (B′) are calculated and the calculated lattice parameters show well agreement with the experimental results. We first time predict elastic constants for these compounds. From energy dispersion curves, it is found that these compounds are metallic in nature. The linear optical response of these compounds are also studied and the higher value of static dielectric constant shows the possibility to use them as good dielectric materials.

  4. Unraveling Thermal and Dynamical Properties of the Cubic BaVO_3 Perovskite from First-Principles Calculation

    NASA Astrophysics Data System (ADS)

    Mebrouki, M.; Ouahrani, T.; Çiftci, Y. Öztekin

    2016-07-01

    Using a toolkit of theoretical techniques comprising ab initio density functional theory calculations and quasiharmonic approximation, we investigate temperature dependence of dynamical properties of BaVO_3 perovskite. This interest is triggered by the fact that, recently, it was possible to synthesize a BaVO_3 perovskite, in a cubic phase, at high pressure and temperature. First-principle calculations are achieved thanks to recent development in numerical facilities, especially phonon dispersion curves which are then fully obtained. Elastic constants of the compound are dependent on temperature due to the inevitable anharmonic effects in solids. We show that at low temperature, the full account of the thermal effects incorporating the phonon densities and Sommerfeld model is more appropriate to calculate the thermal properties of a metal.

  5. Electro-oxidation of water on hematite: Effects of surface termination and oxygen vacancies investigated by first-principles

    NASA Astrophysics Data System (ADS)

    Hellman, Anders; Iandolo, Beniamino; Wickman, Björn; Grönbeck, Henrik; Baltrusaitis, Jonas

    2015-10-01

    The oxygen evolution reaction on hydroxyl- and oxygen-terminated hematite was investigated using first-principle calculations within a theoretical electrochemical framework. Both pristine hematite and hematite containing oxygen vacancies were considered. The onset potential was determined to be 1.79 V and 2.09 V vs. the reversible hydrogen electrode (RHE) for the pristine hydroxyl- and oxygen-terminated hematite, respectively. The presence of oxygen vacancies in the hematite surface resulted in pronounced shifts of the onset potential to 3.09 V and 1.83 V, respectively. Electrochemical oxidation measurements conducted on thin-film hematite anodes, resulted in a measured onset potential of 1.66 V vs. RHE. Furthermore, the threshold potential between the hydroxyl- and oxygen-terminated hematite was determined as a function of pH. The results indicate that electrochemical water oxidation on hematite occurs on the oxygen-terminated hematite, containing oxygen vacancies.

  6. First-principles prediction of solar radiation shielding performance for transparent windows of GdB6

    NASA Astrophysics Data System (ADS)

    Xiao, Lihua; Su, Yuchang; Ran, Jingyu; Liu, Yike; Qiu, Wei; Wu, Jianming; Lu, Fanghai; Shao, Fang; Tang, Dongsheng; Peng, Ping

    2016-04-01

    The structural, electronic, magnetic, and optical properties of GdB6 are studied using the first-principles calculations. Calculated values for magnetic and optical properties and lattice constant are found to be consistent with previously reported experimental results. The calculated results show that GdB6 is a perfect near-infrared absorption/reflectance material that could serve as a solar radiation shielding material for windows with high visible light transmittance, similar to LaB6, which is assigned to its plasma oscillation and a collective oscillation (volume plasmon) of carrier electrons. It was found that the magnetic 4f electrons of Gd are not relevant to the important optical properties of GdB6. These theoretical studies serve as a reference for future studies.

  7. First-principles study of SO2 molecule adsorption on the pristine and Mn-doped boron nitride nanotubes

    NASA Astrophysics Data System (ADS)

    Deng, Zun-Yi; Zhang, Jian-Min; Xu, Ke-Wei

    2015-08-01

    To exploit the potential application of nitride nanotube (BNNT), the adsorption of sulfur dioxide (SO2) on pristine and Mn-doped BNNT was theoretically studied using first-principles approach based on density functional theory (DFT). The most stable adsorption geometry, adsorption energy, magnetic moment, charge transfer and density of states of these systems are discussed. SO2 molecule is weakly adsorbed on the pristine BNNT. The Mn-doped BNNT show high reactivity toward SO2 regardless of the MnB site or MnN site adsorption. The larger formation energies and analysis of density of states show the SO2 molecules are chemically bonded to Mn-doped BNNT and the covalent interaction between the SO2 molecule and Mn atom can be formed. Therefore, the Mn-doped BNNT can be used as SO2 gas sensor manufacturing raw materials, and it may be a potential material for nanodevice applications.

  8. First principles DFT investigation of yttrium-decorated boron-nitride nanotube: Electronic structure and hydrogen storage

    NASA Astrophysics Data System (ADS)

    Jain, Richa Naja; Chakraborty, Brahmananda; Ramaniah, Lavanya M.

    2015-06-01

    The electronic structure and hydrogen storage capability of Yttrium-doped BNNTs has been theoretically investigated using first principles density functional theory (DFT). Yttrium atom prefers the hollow site in the center of the hexagonal ring with a binding energy of 0.8048eV. Decorating by Y makes the system half-metallic and magnetic with a magnetic moment of 1.0µB. Y decorated Boron-Nitride (8,0) nanotube can adsorb up to five hydrogen molecules whose average binding energy is computed as 0.5044eV. All the hydrogen molecules are adsorbed with an average desorption temperature of 644.708 K. Taking that the Y atoms can be placed only in alternate hexagons, the implied wt% comes out to be 5.31%, a relatively acceptable value for hydrogen storage materials. Thus, this system can serve as potential hydrogen storage medium.

  9. Corrosion related properties of iron (100) surface in liquid lead and bismuth environments: A first-principles study

    NASA Astrophysics Data System (ADS)

    Song, Chi; Li, Dong-Dong; Xu, Yi-Chun; Pan, Bi-Cai; Liu, Chang-Song; Wang, Zhi-Guang

    2014-05-01

    The corrosion of steels in liquid metal lead (Pb) and bismuth (Bi) is a critical challenge in the development of accelerator driven systems (ADS). Using a first-principles method with a slab model, we theoretically investigate the interaction between the Pb (Bi) atom and the iron (Fe) (100) surface to assess the fundamental corrosion properties. Our investigation demonstrates that both Pb and Bi atoms favorably adsorb on the (100) surface. Such an adsorption decreases the energy required for the dissociation of an Fe atom from the surface, enhancing the dissolution tendency significantly. The segregation of six common alloying elements (Cr, Al, Mn, Ni, Nb, and Si) to the surface and their impacts on the corrosion properties are also considered. The present results reveal that Si seems to have a relatively good performance to stabilize the surface and alleviate the dissolving trend caused by Pb and Bi.

  10. Anisotropic elastic and vibrational properties of Ru2B3 and Os2B3: a first-principles investigation

    NASA Astrophysics Data System (ADS)

    Ozisik, Haci; Deligoz, Engin; Surucu, Gokhan; Bogaz Ozisik, Havva

    2016-07-01

    The structural, mechanical and lattice dynamical properties of Ru2B3 and Os2B3 have been investigated by using a first-principles method based on the density functional theory within the generalized gradient approximation. The single crystal elastic constants are numerically estimated using strain–stress approach. The polycrystalline aggregate elastic parameters are calculated from the single elastic constants via the Voigt–Reuss–Hill approximations. Subsequently, the ductility and brittleness are characterized with the estimation from Pugh’s rule (B/G) and Cauchy pressure. Additionally, the Debye temperature is calculated from the average elastic wave velocity obtained from bulk and shear moduli. The calculated parameters are consistent with the previous experimental and theoretical data. These borides are both mechanically and dynamically stable in the considered structure.

  11. Alloying effects on structural and thermal behavior of Ti1-xZrxC: A first principles study

    NASA Astrophysics Data System (ADS)

    Chauhan, Mamta; Gupta, Dinesh C.

    2016-05-01

    The formation energy, equilibrium lattice parameter, bulk modulus, Debye temperature and heat capacity at constant volume have been calculated for TiC, ZrC, and their intermediate alloys (Ti1-xZrxC, x = 0,0.25.0.5,0.75,1) using first principles approach. The calculated values of lattice parameter and bulk modulus agree well with the available experimental and earlier theoretical reports. The variation of lattice parameter and bulk modulus with the change in concentration of Zr atom in Ti1-xZrxC has also been reported. The heat capacities of TiC, ZrC, and their intermediate alloys have been calculated by considering both vibrational and electronic contributions.

  12. Structural, energetic and thermodynamic analyses of Ca(BH4)2·2NH3 from first principles calculations

    NASA Astrophysics Data System (ADS)

    Yuan, Peng-Fei; Wang, Fei; Sun, Qiang; Jia, Yu; Guo, Zheng-Xiao

    2012-01-01

    Ca(BH4)2·2NH3 is a relatively new compound with potential application in hydrogen storage. Here the fundamental properties of the compound, such as electronic structure, energetic and thermodynamic properties, were comprehensively studied using first-principles calculations. Results from electronic density of states (DOS) and electron localization function (ELF) indicate the covalent bond nature of the N-H bond and the B-H bond. Charge density analyses show weak ionic interactions between the Ca atom and the NH3 complexes or the (BH4)- complexes. The calculated vibration frequencies of B-H and N-H are in good agreement with other theoretical and experimental results. Furthermore, we calculated the reaction enthalpy and reaction Gibbs free energy at a range of temperature 0-700 K. Our results are in good agreement with experimental results in literature. Possible reaction mechanism of the decomposition reaction is proposed.

  13. Strong enhancement of piezoelectric constants in ScxAl1-xN: First-principles calculations

    NASA Astrophysics Data System (ADS)

    Momida, Hiroyoshi; Teshigahara, Akihiko; Oguchi, Tamio

    2016-06-01

    We theoretically investigate the piezoelectricity of ScxAl1-xN in the entire range of x by first-principles calculations. We find that the piezoelectric constants of wurtzite-type ScxAl1-xN significantly enhance as x increases from 0 to 0.75. However, the energy stability analyses between structure phases show that the cubic-type phases become more stable than the wurtzite-type phases at x of approximately 0.5 and higher, interfering with the ability of wurtzite-type ScxAl1-xN to realize the maximum piezoelectricity. Moreover, our study on element combination dependences on piezoelectricity in A0.5B0.5N (A = Sc, Y, La and B = Al, Ga, In) indicates that Sc, Y, and La have the strongest effect on the enhancement of piezoelectric constants in AlN, GaN, and InN, respectively.

  14. First-principles study on the effect of alloying elements on the elastic deformation response in β-titanium alloys

    SciTech Connect

    Gouda, Mohammed K. Gepreel, Mohamed A. H.; Nakamura, Koichi

    2015-06-07

    Theoretical deformation response of hypothetical β-titanium alloys was investigated using first-principles calculation technique under periodic boundary conditions. Simulation was carried out on hypothetical 54-atom supercell of Ti–X (X = Cr, Mn, Fe, Zr, Nb, Mo, Al, and Sn) binary alloys. The results showed that the strength of Ti increases by alloying, except for Cr. The most effective alloying elements are Nb, Zr, and Mo in the current simulation. The mechanism of bond breaking was revealed by studying the local structure around the alloying element atom with respect to volume change. Moreover, the effect of alloying elements on bulk modulus and admissible strain was investigated. It was found that Zr, Nb, and Mo have a significant effect to enhance the admissible strain of Ti without change in bulk modulus.

  15. First principles DFT investigation of yttrium-decorated boron-nitride nanotube: Electronic structure and hydrogen storage

    SciTech Connect

    Jain, Richa Naja; Chakraborty, Brahmananda; Ramaniah, Lavanya M.

    2015-06-24

    The electronic structure and hydrogen storage capability of Yttrium-doped BNNTs has been theoretically investigated using first principles density functional theory (DFT). Yttrium atom prefers the hollow site in the center of the hexagonal ring with a binding energy of 0.8048eV. Decorating by Y makes the system half-metallic and magnetic with a magnetic moment of 1.0µ{sub B}. Y decorated Boron-Nitride (8,0) nanotube can adsorb up to five hydrogen molecules whose average binding energy is computed as 0.5044eV. All the hydrogen molecules are adsorbed with an average desorption temperature of 644.708 K. Taking that the Y atoms can be placed only in alternate hexagons, the implied wt% comes out to be 5.31%, a relatively acceptable value for hydrogen storage materials. Thus, this system can serve as potential hydrogen storage medium.

  16. Red Shifted Absorbance of A-site Substituted Bismuth Titanate Pyrochlore: Characterization and Stability Analysis from First Principles

    NASA Astrophysics Data System (ADS)

    Mayfield, Cedric; Huda, Muhammad

    2015-03-01

    Transition metal inclusion has enhanced photocatalytic activity of bismuth titanate (Bi2Ti2O7) up to an impurity threshold concentration. Beyond the threshold, spectral absorbance is continually red shifted but increased photocurrent is not reciprocated. We investigated, from first principles, the origin of decreased photocurrent in modified Bi2Ti2O7 (BTO) by calculating the electronic structures of a representative set of doping configurations and by performing a phase stability analysis of the doping. We report our theoretical/computational strategy of analyzing free energy space and show an explicit dependence of pure phase synthesis on changes in free energy. Also, we present a probability distribution of the doping configurations based on formation enthalpy to better understand the nature of doping in BTO. We found that transition metal substitutions are favorable at the A-sites due to unchanging coordination with O ions. This work is supported by National Science Foundation, Award No. 1133672.

  17. First-principles calculation of the linear and nonlinear optical properties of LiTaO3

    NASA Astrophysics Data System (ADS)

    Cabuk, Suleyman; Simsek, Sevket

    2010-05-01

    The linear and nonlinear optical (NLO) properties of the paraelectric and ferroelectric (FE) phases of lithium tantalate crystals were calculated using a first-principles approach based on density functional theory with the generalized gradient approximation. We present our results for the structural parameters, the imaginary and real parts of the frequency-dependent linear optical response, optical functions such as the spectral reflectivity, the absorption coefficient and the electron energy-loss spectrum. A simple scissors operator is applied to adjust the energy gap from calculations to match the experimental value. In the FE phase, we also study the NLO susceptibilities and calculate the NLO susceptibility tensor. LiTaO3 displays a good NLO effect. The results are compared with the theoretical calculations and available experimental data.

  18. First-principles study on the effect of alloying elements on the elastic deformation response in β-titanium alloys

    NASA Astrophysics Data System (ADS)

    Gouda, Mohammed K.; Nakamura, Koichi; A. H. Gepreel, Mohamed

    2015-06-01

    Theoretical deformation response of hypothetical β-titanium alloys was investigated using first-principles calculation technique under periodic boundary conditions. Simulation was carried out on hypothetical 54-atom supercell of Ti-X (X = Cr, Mn, Fe, Zr, Nb, Mo, Al, and Sn) binary alloys. The results showed that the strength of Ti increases by alloying, except for Cr. The most effective alloying elements are Nb, Zr, and Mo in the current simulation. The mechanism of bond breaking was revealed by studying the local structure around the alloying element atom with respect to volume change. Moreover, the effect of alloying elements on bulk modulus and admissible strain was investigated. It was found that Zr, Nb, and Mo have a significant effect to enhance the admissible strain of Ti without change in bulk modulus.

  19. First-principles investigation of quantum mechanical effects on the diffusion of hydrogen in iron and nickel

    NASA Astrophysics Data System (ADS)

    Di Stefano, Davide; Mrovec, Matous; Elsässer, Christian

    2015-12-01

    The diffusion coefficients of interstitial hydrogen in bulk Fe and Ni crystals have been calculated over a wide range of temperatures employing first-principles methods based on density functional theory. Quantum mechanical effects have been included by means of the semiclassical transition state theory and the small-polaron model of Flynn and Stoneham. Our results show that to include such effects is crucial for a quantitative simulation of H diffusion in bcc Fe even at room temperature, while in the case of fcc Ni this is less important. The comparison with other theoretical approaches as well as with experimental studies emphasizes the main advantages of the present approach: it is quantitatively accurate and computationally efficient.

  20. On the dynamical stability of ferromagnetic Ru and Os in the bct structure: a first-principles study

    NASA Astrophysics Data System (ADS)

    Cifuentes-Quintal, M. E.; de Coss, R.

    2015-08-01

    Recent theoretical studies have predicted magnetic states for Ru and Os in the body-centred tetragonal structure (bct) with ?. In this study, we present first principles calculations of the phonon dispersion for ferromagnetic Ru- and Os-bct along the epitaxial and uniaxial Bain paths, to evaluate their dynamical stability. The phonon dispersions were computed using the density functional perturbation theory, including the gradient corrections to the exchange-correlation functional within the plane-waves ultrasoft-pseudopotential approximation. The phonon dispersion for the local minimum in the Bain path with ? as well as the uniaxial and epitaxial strained structures are analysed. We find imaginary frequencies along different directions of the Brillouin zone, which indicates that both systems are dynamically unstable. Consequently, ferromagnetic Ru and Os in the bct with ? are not truly metastable phases.

  1. Pressure effects on the elastic and lattice dynamics properties of AlP from first-principles calculations

    SciTech Connect

    Lakel, S.; Okbi, F.; Ibrir, M.; Almi, K.

    2015-03-30

    We have performed first-principles calculations to investigate the behavior under hydrostatic pressure of the structural, elastic and lattice dynamics properties of aluminum phosphide crystal (AlP), in both zinc-blende (B3) and nickel arsenide (B8) phases. Our calculated structural and electronic properties are in good agreement with previous theoretical and experimental results. The elastic constants, bulk modulus (B), shear modulus (G), and Young's modulus (E), Born effective charge and static dielectric constant ε{sub 0}, were calculated with the generalized gradient approximations and the density functional perturbation theory (DFPT). Our results in the pressure behavior of the elastic and dielectric properties of both phases are compared and contrasted with the common III–V materials. The Born effective charge ZB decreases linearly with pressure increasing, while the static dielectric constant decreases quadratically with the increase of pressure.

  2. High-level theoretical rovibrational spectroscopy beyond fc-CCSD(T): The C3 molecule

    NASA Astrophysics Data System (ADS)

    Schröder, Benjamin; Sebald, Peter

    2016-01-01

    An accurate local (near-equilibrium) potential energy surface (PES) is reported for the C3 molecule in its electronic ground state ( X ˜ 1 Σg + ). Special care has been taken in the convergence of the potential relative to high-order correlation effects, core-valence correlation, basis set size, and scalar relativity. Based on the aforementioned PES, several rovibrational states of all 12C and 13C substituted isotopologues have been investigated, and spectroscopic parameters based on term energies up to J = 30 have been calculated. Available experimental vibrational term energies are reproduced to better than 1 cm-1 and rotational constants show relative errors of not more than 0.01%. The equilibrium bond length has been determined in a mixed experimental/theoretical approach to be 1.294 07(10) Å in excellent agreement with the ab initio composite value of 1.293 97 Å. Theoretical band intensities based on a newly developed electric dipole moment function also suggest that the infrared active (1, 11, 0)←(0, 00, 0) combination band might be observable by high-resolution spectroscopy.

  3. High-level theoretical rovibrational spectroscopy beyond fc-CCSD(T): The C3 molecule.

    PubMed

    Schröder, Benjamin; Sebald, Peter

    2016-01-28

    An accurate local (near-equilibrium) potential energy surface (PES) is reported for the C3 molecule in its electronic ground state (X̃(1)Σg (+)). Special care has been taken in the convergence of the potential relative to high-order correlation effects, core-valence correlation, basis set size, and scalar relativity. Based on the aforementioned PES, several rovibrational states of all (12)C and (13)C substituted isotopologues have been investigated, and spectroscopic parameters based on term energies up to J = 30 have been calculated. Available experimental vibrational term energies are reproduced to better than 1 cm(-1) and rotational constants show relative errors of not more than 0.01%. The equilibrium bond length has been determined in a mixed experimental/theoretical approach to be 1.294 07(10) Å in excellent agreement with the ab initio composite value of 1.293 97 Å. Theoretical band intensities based on a newly developed electric dipole moment function also suggest that the infrared active (1, 1(1), 0)←(0, 0(0), 0) combination band might be observable by high-resolution spectroscopy. PMID:26827217

  4. 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.

  5. 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).

  6. Nonlinear elastic response of strong solids: First-principles calculations of the third-order elastic constants of diamond

    NASA Astrophysics Data System (ADS)

    Hmiel, A.; Winey, J. M.; Gupta, Y. M.; Desjarlais, M. P.

    2016-05-01

    Accurate theoretical calculations of the nonlinear elastic response of strong solids (e.g., diamond) constitute a fundamental and important scientific need for understanding the response of such materials and for exploring the potential synthesis and design of novel solids. However, without corresponding experimental data, it is difficult to select between predictions from different theoretical methods. Recently the complete set of third-order elastic constants (TOECs) for diamond was determined experimentally, and the validity of various theoretical approaches to calculate the same may now be assessed. We report on the use of density functional theory (DFT) methods to calculate the six third-order elastic constants of diamond. Two different approaches based on homogeneous deformations were used: (1) an energy-strain fitting approach using a prescribed set of deformations, and (2) a longitudinal stress-strain fitting approach using uniaxial compressive strains along the [100], [110], and [111] directions, together with calculated pressure derivatives of the second-order elastic constants. The latter approach provides a direct comparison to the experimental results. The TOECs calculated using the energy-strain approach differ significantly from the measured TOECs. In contrast, calculations using the longitudinal stress-uniaxial strain approach show good agreement with the measured TOECs and match the experimental values significantly better than the TOECs reported in previous theoretical studies. Our results on diamond have demonstrated that, with proper analysis procedures, first-principles calculations can indeed be used to accurately calculate the TOECs of strong solids.

  7. First Principles Evaluation of Nickel Oxide and Other Materials for Solar Energy Conversion

    NASA Astrophysics Data System (ADS)

    Alidoust, Nima

    Global climate change and pollution caused by fossil fuels necessitate the search for inexpensive, clean, renewable energy sources. Photocatalytic and photovoltaic solar energy conversion to fuels and electricity, respectively, are among the possible solutions to this challenge. Engineering devices that can efficiently achieve these tasks requires fundamental understanding of the materials involved, identification of ways to improve these materials, and discovery of new materials that could help achieve higher efficiencies and lower costs. The work presented in this dissertation contributes to these fronts via first-principles quantum mechanical calculations. In particular, we extensively study nickel oxide (NiO), an inexpensive semiconductor, with the desired potentially carrier-lifetime-extending charge-transfer property. We identify and devise various theoretical models that accurately describe NiO's electronic structure. We use these models to show that alloying NiO with Li2O could decrease NiO's band gap from ˜4 eV to ˜2 eV, making it an appropriate light absorber for use in various solar energy conversion devices. We study hole transport in NiO and NiO alloys. We show that hole conductivity in NiO can be enhanced by forming homogeneous LixNi1-xO alloys with high enough Li concentration, making LixNi1-x O alloys suitable for use as p-type hole conductors. We further find that hole transport in NiO is confined to two dimensions. We predict that forming MgxNi1-xO and ZnxNi 1-xO (which we find to be transparent to visible light) disrupts this confinement and leads to three-dimensional hole transport, thereby increasing conductivity. This makes MgxNi1-xO and ZnxNi 1-xO alloys suitable for use as transparent conducting oxides. We introduce CoO and Co0.25Ni0.75O alloy as new intermediate band semiconductors (IBSCs), capable of absorbing light across multiple band gaps and enhancing light absorption in IBSC-based solar cells. Finally, we investigate the spatial

  8. Large magnetocrystalline anisotropy in bilayer transition metal phases from first-principles full-potential calculations

    NASA Astrophysics Data System (ADS)

    Ravindran, P.; Kjekshus, A.; Fjellvåg, H.; James, P.; Nordström, L.; Johansson, B.; Eriksson, O.

    2001-04-01

    The computational framework of this study is based on the local-spin-density approximation with first-principles full-potential linear muffin-tin orbital calculations including orbital polarization (OP) correction. We have studied the magnetic anisotropy for a series of bilayer CuAu(I)-type materials such as FeX, MnX (X=Ni,Pd,Pt), CoPt, NiPt, MnHg, and MnRh in a ferromagnetic state using experimental structural parameters to understand the microscopic origin of magnetic-anisotropy energy (MAE) in magnetic multilayers. Except for MnRh and MnHg, all these phases show perpendicular magnetization. We have analyzed our results in terms of angular momentum-, spin- and site-projected density of states, magnetic-angular-momentum-projected density of states, orbital-moment density of states, and total density of states. The orbital-moment number of states and the orbital-moment anisotropy for FeX (X=Ni,Pd,Pt) are calculated as a function of band filling to study its effect on MAE. The total and site-projected spin and orbital moments for all these systems are calculated with and without OP when the magnetization is along or perpendicular to the plane. The results are compared with available experimental as well as theoretical results. Our calculations show that OP always enhances the orbital moment in these phases and brings them closer to experimental values. The changes in MAE are analyzed in terms of exchange splitting, spin-orbit splitting, and tetragonal distortion/crystal-field splitting. The calculated MAE is found to be in good agreement with experimental values when the OP correction is included. Some of the materials considered here show large magnetic anisotropy of the order of meV. In particular we found that MnPt will have a very large MAE if it could be stabilized in a ferromagnetic configuration. Our analysis indicates that apart from large spin-orbit interaction and exchange interaction from at least one of the constituents, a large crystal-field splitting

  9. [First-principles study of vibrational Raman spectra of amorphous carbon].

    PubMed

    Niu, Li; Zhu, Jia-qi; Gao, Wei; Du, Shan-yi

    2009-09-01

    The vibrational density of states and nonresonant reduced Raman spectra of amorphous carbon at densities of 2.6, 2.9 and 3.2 g x cm(-3) were calculated by the use of a first-principles plane-wave pesudopotential method. Three structural models were generated by liquid-quench method using Car-Parinello molecular dynamics, their vibrational frequencies and eigenmodes were determined using the linear response approach, and Raman coupling tensors were calculated using the finite electric field method. The calculated results show that the sp3 fraction increases from 50% to 84.4%, the sp2 configuration changes from mainly rings to short chains, the position of the G peak moves to higher frequencies, the intensity ratio of D and G peaks decreases, the position of the T peak moves to lower frequencies and the intensity ratio of T and G peaks increases as density increases from 2.6 to 3.2 g x cm(-3). The authors' calculated Raman spectra show an overall good agreement with experimental spectra. The analysis in terms of atomic vibrations confirms that the G and D peaks both come from sp2 C contribution, G peak is due to the stretching vibration of any pair of sp2 atoms and the T peak is due to the C-C sp3 vibration. The authors' analysis also confirms that the dispersion of G and T peaks is due to bond-length changes. The bond length of chains (olefins) is shorter than that of rings, so their vibrational frequency is higher and the G-peak position moves to higher frequencies with increasing the sp3 fraction. The number of sp3-sp2 type bonds decreases as the sp3 fraction increases. These bonds are shorter than pure sp3-sp3 bonds, hence the T-peak position moves to lower frequencies. The research results provide a theoretic basis for analyzing experimental Raman spectra of amorphous carbon. PMID:19950647

  10. Unraveling The Origin of Enhanced Field Emission from Irradiated FeCo-SiO2 Nanocomposites: A Combined Experimental and First-Principles Based Study.

    PubMed

    Sarker, Debalaya; Bhattacharya, Saswata; Rodriguez, Raul D; Sheremet, Evgeniya; Kabiraj, D; Avasthi, D K; Zahn, Dietrich R T; Schmidt, H; Srivastava, P; Ghosh, S

    2016-02-01

    This work is driven by the vision of engineering planar field emitters with ferromagnetic metal-insulator nanocomposite thin films, using swift heavy ion (SHI) irradiation method. FeCo nanoparticles inside SiO2 matrix, when subjected to SHI get elongated. Using this, we demonstrate here a planar field emitter with maximum current density of 550 μA/cm(2) at an applied field of 15 V/μm. The film, irradiated with 5 × 10(13) ions/cm(2) fluence (5e13) of 120 MeV Au(9+) ions, shows very high electron emitting quantum efficiency in comparison to its unirradiated counterpart. Surface enhanced Raman spectroscopy analysis of unirradiated and 5e13 films further confirms that the field emission (FE) enhancement is not only due to surface protrusions but also depends on the properties of entire matrix. We find experimental evidence of enhanced valence band density of states (VB DOS) for 5e13 film from XPS, which is verified in the electronic structure of a model FeCo cluster from first-principles based calculations combining density functional theory (DFT) and molecular dynamics (MD) simulations. The MD temperature is selected from the lattice temperature profile inside nanoparticles as deduced from thermal spike model. Increasing the irradiation fluence beyond 5e13, results in reduced VB DOS and melting of surface protrusions, thus causing reduction of FE current density. We finally conclude from theoretical analysis that change in fluence alters the co-ordination chemistry followed by the charge distribution and spin alignment, which influence the VB DOS and concurrent FE as evident from our experiment. PMID:26812580

  11. On structural and lattice dynamic stability of LaF{sub 3} under high pressure: A first principle study

    SciTech Connect

    Sahoo, B. D. Joshi, K. D.; Gupta, Satish C.

    2015-06-24

    Structural and lattice dynamical stability of the LaF3 has been analyzed as a function of hydrostatic compression through first principle electronic band structure calculations. The comparison of enthalpies of various plausible structures calculated at various pressures suggests a phase transition from ambient condition tysonite structure (space group P-3c1) to a primitive orthorhombic structure (space group Pmmn) at a pressure of ∼19.5 GPa, in line with the experimental value of 16 GPa. Further, it is predicted that this phase will remain stable up to 100 GPa (the maximum pressure up to which calculations have been performed in the present work). The theoretically determined equation of state displays a good agreement with experimental data. Various physical quantities such as zero pressure equilibrium volume, bulk modulus, and pressure derivative of bulk modulus have been derived from the theoretically determined equation of state and compared with the available experimental data. Our lattice dynamic calculations correctly demonstrate that at zero pressure the tysonite structure is lattice dynamically stable whereas the Pmmn structure is unstable lattice dynamically. Further, at transition pressure the theoretically calculated phonon spectra clearly show that the Pmmn phase emerges as lattice dynamically stable phase whereas the tysonite structure becomes unstable dynamically, supporting our static lattice calculations.

  12. A First Principles Molecular Dynamics Study Of Calcium Ion In Water

    SciTech Connect

    Lightstone, F; Schwegler, E; Allesch, M; Gygi, F; Galli, G

    2005-01-28

    In this work we report on Car-Parrinello simulations of the divalent calcium ion in water, aimed at understanding the structure of the hydration shell and at comparing theoretical results with a series of recent experiments. Our paper shows some of the progress in the investigation of aqueous solutions brought about by the advent of ab initio molecular dynamics and highlights the importance of accessing subtle details of ion-water interactions from first-principles. Calcium plays a vital role in many biological systems, including signal transduction, blood clotting and cell division. In particular, calcium ions are known to interact strongly with proteins as they tend to bind well to both negatively charged (e.g. in aspartate and glutamate) and uncharged oxygens (e.g. in main-chain carbonyls). The ability of calcium to coordinate multiple ligands (from 6 to 8 oxygen atoms) with an asymmetric coordination shell enables it to cross-link different segments of a protein and induce large conformational changes. The great biochemical importance of the calcium ion has led to a number of studies to determine its hydration shell and its preferred coordination number in water. Experimental studies have used a variety of techniques, including XRD, EXAFS, and neutron diffraction to elucidate the coordination of Ca{sup 2+} in water. The range of coordination numbers (n{sub C}) inferred by X-ray diffraction studies varies from 6 to 8, and is consistent with that reported in EXAFS experiments (8 and 7.2). A wider range of values (6 to 10) was found in early neutron diffraction studies, depending on concentration, while a more recent measurement by Badyal, et al. reports a value close to 7. In addition to experimental measurements, many theoretical studies have been carried out to investigate the solvation of Ca{sup 2+} in water and have also reported a wide range of coordination numbers. Most of the classical molecular dynamics (MD) and QM/MM simulations report n{sub C} in the

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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

  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. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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

  12. Photoelectron Spectroscopy and Theoretical Studies of Anion-pi Interactions: Binding Strength and Anion Specificity

    SciTech Connect

    Zhang, Jian; Zhou, Bin; Sun, Zhenrong; Wang, Xue B.

    2015-01-01

    illustrates that size-selective photoelectron spectroscopy combined with theoretical calculations represent a powerful technique to probe intrinsic anion–π interactions and has potential to provide quantitative guest-host molecular binding strengths and unravel fundamental insights in specific anion recognitions.

  13. Photoelectron spectroscopy and theoretical studies of anion-π interactions: binding strength and anion specificity.

    PubMed

    Zhang, Jian; Zhou, Bin; Sun, Zhen-Rong; Wang, Xue-Bin

    2015-02-01

    spectroscopy combined with theoretical calculations represents a powerful technique to probe anion-π interactions and has potential to provide quantitative guest-host molecular binding strengths and unravel fundamental insights in specific anion recognitions. PMID:25515705

  14. First-principles method for electron-phonon coupling and electron mobility: Applications to two-dimensional materials

    NASA Astrophysics Data System (ADS)

    Gunst, Tue; Markussen, Troels; Stokbro, Kurt; Brandbyge, Mads

    2016-01-01

    We present density functional theory calculations of the phonon-limited mobility in n -type monolayer graphene, silicene, and MoS2. The material properties, including the electron-phonon interaction, are calculated from first principles. We provide a detailed description of the normalized full-band relaxation time approximation for the linearized Boltzmann transport equation (BTE) that includes inelastic scattering processes. The bulk electron-phonon coupling is evaluated by a supercell method. The method employed is fully numerical and does therefore not require a semianalytic treatment of part of the problem and, importantly, it keeps the anisotropy information stored in the coupling as well as the band structure. In addition, we perform calculations of the low-field mobility and its dependence on carrier density and temperature to obtain a better understanding of transport in graphene, silicene, and monolayer MoS2. Unlike graphene, the carriers in silicene show strong interaction with the out-of-plane modes. We find that graphene has more than an order of magnitude higher mobility compared to silicene in the limit where the silicene out-of-plane interaction is reduced to zero (by substrate interaction, clamping, or similar). If the out-of-plane interaction is not actively reduced, the mobility of silicene will essentially be zero. For MoS2, we obtain several orders of magnitude lower mobilities compared to graphene in agreement with other recent theoretical results. The simulations illustrate the predictive capabilities of the newly implemented BTE solver applied in simulation tools based on first-principles and localized basis sets.

  15. Theoretical vibrational sum-frequency generation spectroscopy of water near lipid and surfactant monolayer interfaces

    SciTech Connect

    Roy, S.; Gruenbaum, S. M.; Skinner, J. L.

    2014-11-14

    Understanding the structure of water near cell membranes is crucial for characterizing water-mediated events such as molecular transport. To obtain structural information of water near a membrane, it is useful to have a surface-selective technique that can probe only interfacial water molecules. One such technique is vibrational sum-frequency generation (VSFG) spectroscopy. As model systems for studying membrane headgroup/water interactions, in this paper we consider lipid and surfactant monolayers on water. We adopt a theoretical approach combining molecular dynamics simulations and phase-sensitive VSFG to investigate water structure near these interfaces. Our simulated spectra are in qualitative agreement with experiments and reveal orientational ordering of interfacial water molecules near cationic, anionic, and zwitterionic interfaces. OH bonds of water molecules point toward an anionic interface leading to a positive VSFG peak, whereas the water hydrogen atoms point away from a cationic interface leading to a negative VSFG peak. Coexistence of these two interfacial water species is observed near interfaces between water and mixtures of cationic and anionic lipids, as indicated by the presence of both negative and positive peaks in their VSFG spectra. In the case of a zwitterionic interface, OH orientation is toward the interface on the average, resulting in a positive VSFG peak.

  16. Theoretical and experimental evaluation of broadband decoupling techniques for in vivo nuclear magnetic resonance spectroscopy.

    PubMed

    de Graaf, Robin A

    2005-06-01

    A theoretical and experimental evaluation of existing broadband decoupling methods with respect to their utility for in vivo (1)H-(13)C NMR spectroscopy is presented. Simulations are based on a modified product operator formalism, while an experimental evaluation is performed on in vitro samples and human leg and rat brain in vivo. The performance of broadband decoupling methods was evaluated with respect to the required peak and average RF powers, decoupling bandwidth, decoupling side bands, heteronuclear scalar coupling constant, and sensitivity toward B(2) inhomogeneity. In human applications only the WALTZ and MLEV decoupling methods provide adequate decoupling performance at RF power levels that satisfy the FDA guidelines on local tissue heating. For very low RF power levels (B(2max) < 300 Hz) one should verify empirically whether the experiment will benefit from broadband decoupling. At higher RF power levels acceptable for animal studies additional decoupling techniques become available and provide superior performance. Since the average RF power of adiabatic RF pulses is almost always significantly lower than the peak RF power, it can be stated that for average RF powers suitable for animal studies it is always possible to design an adiabatic decoupling scheme that outperforms all other schemes. B(2) inhomogeneity degrades the decoupling performance of all methods, but the decoupling bandwidths for WALTZ-16 and especially adiabatic methods are still satisfactory for useful in vivo decoupling with a surface coil. PMID:15906279

  17. Protonation Preferentially Stabilizes Minor Tautomers of the Halouracils: IRMPD Action Spectroscopy and Theoretical Studies

    NASA Astrophysics Data System (ADS)

    Crampton, K. T.; Rathur, A. I.; Nei, Y.-w.; Berden, G.; Oomens, J.; Rodgers, M. T.

    2012-09-01

    Tautomerization induced by protonation of halouracils may increase their efficacy as anti-cancer drugs by altering their reactivity and hydrogen bonding characteristics, potentially inducing errors during DNA and RNA replication. The gas-phase structures of protonated complexes of five halouracils, including 5-fluorouracil, 5-chlorouracil, 5-bromouracil, 5-iodouracil, and 6-chlorouracil are examined via infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical electronic structure calculations. IRMPD action spectra were measured for each complex in the IR fingerprint region extending from ~1000 to 1900 cm-1 using the free electron laser (FELIX). Correlations are made between the measured IRMPD action spectra and the linear IR spectra for the stable low-energy tautomeric conformations computed at the B3LYP/6-311+G(2d,2p)//B3LYP/6-31G* level of theory. Absence of an intense band(s) in the IRMPD spectrum arising from the carbonyl stretch(es) that are expected to appear near 1825 cm-1 provides evidence that protonation induces tautomerization and preferentially stabilizes alternative, noncanonical tautomers of these halouracils where both keto functionalities are converted to hydroxyl groups upon binding of a proton. The weak, but measurable absorption, which does occur for these systems near 1835 cm-1 suggests that in addition to the ground-state conformer, very minor populations of excited, low-energy conformers that contain keto functionalities are also present in these experiments.

  18. Protonation preferentially stabilizes minor tautomers of the halouracils: IRMPD action spectroscopy and theoretical studies.

    PubMed

    Crampton, K T; Rathur, A I; Nei, Y-w; Berden, G; Oomens, J; Rodgers, M T

    2012-09-01

    Tautomerization induced by protonation of halouracils may increase their efficacy as anti-cancer drugs by altering their reactivity and hydrogen bonding characteristics, potentially inducing errors during DNA and RNA replication. The gas-phase structures of protonated complexes of five halouracils, including 5-fluorouracil, 5-chlorouracil, 5-bromouracil, 5-iodouracil, and 6-chlorouracil are examined via infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical electronic structure calculations. IRMPD action spectra were measured for each complex in the IR fingerprint region extending from ~1000 to 1900 cm(-1) using the free electron laser (FELIX). Correlations are made between the measured IRMPD action spectra and the linear IR spectra for the stable low-energy tautomeric conformations computed at the B3LYP/6-311+G(2d,2p)//B3LYP/6-31G* level of theory. Absence of an intense band(s) in the IRMPD spectrum arising from the carbonyl stretch(es) that are expected to appear near 1825 cm(-1) provides evidence that protonation induces tautomerization and preferentially stabilizes alternative, noncanonical tautomers of these halouracils where both keto functionalities are converted to hydroxyl groups upon binding of a proton. The weak, but measurable absorption, which does occur for these systems near 1835 cm(-1) suggests that in addition to the ground-state conformer, very minor populations of excited, low-energy conformers that contain keto functionalities are also present in these experiments. PMID:22821195

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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

  14. Conductivity and transparency of TiO2 from first principles

    NASA Astrophysics Data System (ADS)

    Schleife, André; Varley, Joel B.; Janotti, Anderson; Van de Walle, Chris G.

    2013-09-01

    Titanium dioxide is a versatile material with ubiquitous applications, many of which are critically linked to either light absorption or transparency in the visible spectral range in addition to electrical conductivity. Doping is a well-known way to influence those properties in order to bring them into a desired range. Working towards a comprehensive understanding of the electronic and optical properties of TiO2 (as well as of the link between them) we review and summarize electronicstructure results that we obtained using cutting-edge theoretical spectroscopy techniques. We focus on the formation of electron and hole polarons and we elucidate the influence of doping on the optical properties of TiO2. In addition, we present new results for the reflectivity of pure TiO2.

  15. Mass-Independent Fractionation of Oxygen Isotope in Earth Wind: First Principle Calculations for Photodissociation

    NASA Astrophysics Data System (ADS)

    Yamada, A.; Nanbu, S.; Kasai, Y.; Ozima, M.

    2009-12-01

    Mass-independently fractionated oxygen isotope were reported on metal particles extracted from Apollo lunar soils [1, 2], but these origins are still unknown. Since the substantial fraction of Earth-escaping O+ flux (Earth Wind, EW hereafter), comparable to the amount of the anomalous oxygen implanted on the metal particles, could reach the lunar surface [3], Ozima et al. [4] suggested that EW may be responsible to the anomalous oxygen. The purpose is to test this EW hypothesiss, we study oxygen isotopic ratios of O+ at the upper atmosphere. From quantum chemical calculations of photo-dissociation of O2, we show the results in mass-independent isotopic fractionation of oxygen, thereby in conformity with the EW hypothesis. First principles reaction dynamics simulations were performed to compute the photolysis rate for the B3Σu- ← X3Σg- electronic transition, for Schumann-Runge band. With the assumption of the Born-Oppenheimer approximation, we performed the wave-packet dynamics for the nuclei-motion in the potential energy curves determined by the first step calculation. Quantum chemical program package [5] was used for the first step calculation, and the quantum dynamics was carried out by our own program package. Assuming the quantum yield of the corresponding photolysis is unity, the photo-absorption cross section can be correlated with the photolysis rate. Therefore, following the time dependent approach, the autocorrelation function (A(t) = <φ(0)|φ(t)>) was numerically computed by the second step calculation. Finally, the theoretical spectrum as a function of wavelength of excitation light was estimated by the Fourier transform of the autocorrelation function A(t) [6]. Calculated absorption cross sections for C16O showed similar wavelength dependence with experiment [7], although the absolute magnitude was yet to be calibrated for a quantitative comparison. Assuming Boltzmann distribution at 1200 K, we estimated enrichment factors defined as σι(λ)/σ16

  16. High pressure behavior of phlogopite using neutron diffraction and first principle simulations

    NASA Astrophysics Data System (ADS)

    Chheda, T. D.; Mookherjee, M.; dos Santos, A. M.; Molaison, J.; Manthilake, G. M.; Chantel, J.; Mainprice, D.

    2013-12-01

    Hydrous phases play an important role in the deep water cycle by transporting water into the Earth's interior. Upon, reaching their thermodynamic stability, these hydrous phases decompose and release the water. A part of the water is cycled back to the arc, thus completing the deep water cycle, the remaining water is partitioned into dense hydrous phases and nominally anhydrous phases. Hence, in order to understand the role the hydrous phases in the deep water cycle, it is important to constrain the effect of pressure, temperature, and chemistry on the thermodynamic stability of the hydrous phases. In addition, it is important to constrain the elasticity of these hydrous phases to test whether they can explain the distinct geophysical observations such as lower bulk sound velocities and elastic anisotropy. Phlogopite is a potassium bearing mica that is stable in the hydrated crust and metasomatized mantle up to pressures of ~9 GPa, i.e., base of the upper mantle. We investigated the response of the crystal structure, lattice parameters and unit-cell volume of a natural phlogopite upon compression. We conducted in situ neutron diffraction studies at high-pressures using Paris-Edinburgh press at the Spallation Neutrons and Pressure Diffractometer (SNAP), Oak Ridge National Laboratory. All the experiments were conducted at room temperatures and pressures up to 10 GPa were explored. The equation of state parameters from our experiments could be explained by a finite strain formulation with V0= 487 Å3, K0 = 49 GPa, K' = 4.1. In addition, we have used first principle simulations based on density functional theory to calculate the equation of state and elasticity. The predicted equation of state is in good agreement with the experiments, with V0= 519 Å3, K0 = 45.8 GPa and K'= 6.9. The full elastic constant tensor shows significant anisotropy with the principal elastic constants at theoretical V0: C11= 181 GPa, C22= 185 GPa, C33= 62 GPa, the shear elastic constants- C44

  17. Thermoelectric properties of the unfilled skutterudite FeSb3 from first principles and Seebeck local probes

    DOE PAGESBeta

    Lemal, Sébastien; Nguyen, Ngoc; de Boor, Johannes; Ghosez, Philippe; Varignon, Julien; Klobes, Benedikt; Hermann, Raphaël P.; Verstraete, Matthieu J.

    2015-11-16

    In this paper, using a combination of first-principles calculations and experimental transport measurements, we study the electronic and magnetic structure of the unfilled skutterudite FeSb3. We employ the hybrid functional approach for exchange correlation. The ground state is determined to be antiferromagnetic with an atomic magnetic moment of 1.6μB/Fe. The Néel temperature TN is estimated at 6 K, in agreement with experiments which found a paramagnetic state down to 10 K. The ground state is semiconducting, with a small electronic gap of 33meV, also consistent with previous experiments on films. Charge carrier concentrations are estimated from Hall resistance measurements. Themore » Seebeck coefficient is measured and mapped using a scanning probe at room temperature that yields an average value of 38.6μVK-1, slightly lower than the theoretical result. Finally, the theoretical conductivity is analyzed as a function of temperature and concentration of charge carriers.« less

  18. Thermoelectric properties of the unfilled skutterudite FeSb3 from first principles and Seebeck local probes

    SciTech Connect

    Lemal, Sébastien; Nguyen, Ngoc; de Boor, Johannes; Ghosez, Philippe; Varignon, Julien; Klobes, Benedikt; Hermann, Raphaël P.; Verstraete, Matthieu J.

    2015-11-16

    In this paper, using a combination of first-principles calculations and experimental transport measurements, we study the electronic and magnetic structure of the unfilled skutterudite FeSb3. We employ the hybrid functional approach for exchange correlation. The ground state is determined to be antiferromagnetic with an atomic magnetic moment of 1.6μB/Fe. The Néel temperature TN is estimated at 6 K, in agreement with experiments which found a paramagnetic state down to 10 K. The ground state is semiconducting, with a small electronic gap of 33meV, also consistent with previous experiments on films. Charge carrier concentrations are estimated from Hall resistance measurements. The Seebeck coefficient is measured and mapped using a scanning probe at room temperature that yields an average value of 38.6μVK-1, slightly lower than the theoretical result. Finally, the theoretical conductivity is analyzed as a function of temperature and concentration of charge carriers.

  19. First-principles calculation of multiphoton absorption cross section of α-quartz under femtosecond laser irradiation

    NASA Astrophysics Data System (ADS)

    Yu, Dong; Jiang, Lan; Wang, Feng; Qu, Liangti; Lu, Yongfeng

    2016-05-01

    Time-dependent density functional theory-based first-principles calculations have been used to study the ionization process and electron excitation. The results show that the number of excited electrons follows the power law σ k I k at peak intensities of I < 5 × 1013 W/cm2, indicating that the multiphoton ionization plays a key role. The multiphoton absorption cross section of α-quartz σ k is further calculated to be 3.54 × 1011 cm-3 ps-1 (cm2/TW)6. Using the plasma model, the theoretical results of the damage threshold fluences are consistent with the experimental data, which validates the calculated value of multiphoton absorption cross section. By employing the calculated cross section value in the plasma model, the damage threshold fluences are theoretically estimated, being consistent with the experimental data, which validates the calculated value of multiphoton absorption cross section. The preliminary multiscale model shows great potential in the simulation of laser processing.

  20. A first principles study on CVD graphene growth on copper surfaces: C-C bonding reactions at graphene edges

    NASA Astrophysics Data System (ADS)

    Tajima, Nobuo; Kaneko, Tomoaki; Nara, Jun; Takahisa, Ohno

    2015-03-01

    Graphene has attracted considerable research interest owing to its potential application to future electronic devices. Large area and high quality graphene is needed for device applications. Chemical vapor deposition (CVD) using a copper surface with a hydrocarbon source is one of the practical methods to produce graphene. This method is appropriate for creating large area graphene with low cost, and the graphene growth control to obtain a high quality product is a remaining challenge. The carbon atom nucleation and cluster growth processes in the CVD reactions have been studied extensively as key steps that affect the graphene growth behavior. We have been studying the carbon atom reactions in these processes by theoretical approaches In the present study, we have focused on the later stage of CVD reaction, that is, carbon atom reactions at graphene edges by which carbon clusters grow in the Cu-CVD We have found that these reactions have energy barriers of ~1 eV. First principles simulation code PHASE http://www.ciss.iis.u-tokyo.ac.jp/riss/english/project/device/) was used in the theoretical calculations.