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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. Surface states and positron annihilation spectroscopy: results and prospects from a first-principles approach

    NASA Astrophysics Data System (ADS)

    Callewaert, V.; Saniz, R.; Barbiellini, B.; Partoens, B.

    2017-01-01

    The trapping of positrons at the surface of a material can be exploited to study quite selectively the surface properties of the latter by means of positron annihilation spectroscopy techniques. To support these, it is desirable to be able to theoretically predict the existence of such positronic surface states and to describe their annihilation characteristics with core or valence surface electrons in a reliable way. Here, we build on the well-developed first-principles techniques for the study of positrons in bulk solids as well as on previous models for surfaces, and investigate two schemes that can improve the theoretical description of the interaction of positrons with surfaces. One is based on supplementing the local-density correlation potential with the corrugated image potential at the surface, and the other is based on the weighted-density approximation to correlation. We discuss our results for topological insulators, graphene layers, and quantum dots, with emphasis on the information that can be directly related to experiment. We also discuss some open theoretical problems that should be addressed by future research.

  3. Vanadium doping of LiMnPO4: Vibrational spectroscopy and first-principle studies

    NASA Astrophysics Data System (ADS)

    Kellerman, D.; Medvedeva, N.; Mukhina, N.; Semenova, A.; Baklanova, I.; Perelyaeva, L.; Gorshkov, V.

    2014-01-01

    The samples of pure and 10% vanadium-doped LiMnPO4 have been synthesized by the solid-state reaction technique. The results of Raman and infrared absorption spectroscopy show that the vanadium atoms replace phosphorus giving rise to LiMn(PO4)1-x(VO4)x solid solutions. This conclusion is confirmed by the first-principle studies.

  4. 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.

  5. Structure of YSi2 nanowires from scanning tunneling spectroscopy and first principles

    PubMed Central

    Iancu, V.; Kent, P. R. C.; Zeng, C. G.; Weitering, H. H.

    2009-01-01

    Exceptionally long and uniform YSi2 nanowires are formed via self-assembly on Si(001). The in-plane width of the thinnest wires is known to be quantized in odd multiples of the silicon lattice constant. Here, we identify a class of nanowires that violates the “odd multiple” rule. The structure of the thinnest wire in this category is determined by comparing scanning tunneling spectroscopy measurements with the calculated surface density of states of candidate models by means of the Pendry R-factor analysis. The relative stability of the odd and even wire systems is analyzed via first-principles calculations. PMID:19859579

  6. 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.

  7. A theoretical study of blue phosphorene nanoribbons based on first-principles calculations

    SciTech Connect

    Xie, Jiafeng; Si, M. S. Yang, D. Z.; Zhang, Z. Y.; Xue, D. S.

    2014-08-21

    Based on first-principles calculations, we present a quantum confinement mechanism for the band gaps of blue phosphorene nanoribbons (BPNRs) as a function of their widths. The BPNRs considered have either armchair or zigzag shaped edges on both sides with hydrogen saturation. Both the two types of nanoribbons are shown to be indirect semiconductors. An enhanced energy gap of around 1 eV can be realized when the ribbon's width decreases to ∼10 Å. The underlying physics is ascribed to the quantum confinement effect. More importantly, the parameters to describe quantum confinement are obtained by fitting the calculated band gaps with respect to their widths. The results show that the quantum confinement in armchair nanoribbons is stronger than that in zigzag ones. This study provides an efficient approach to tune the band gap in BPNRs.

  8. Structural Polymorphism in "Kesterite" Cu2ZnSnS4: Raman Spectroscopy and First-Principles Calculations Analysis.

    PubMed

    Dimitrievska, Mirjana; Boero, Federica; Litvinchuk, Alexander P; Delsante, Simona; Borzone, Gabriella; Perez-Rodriguez, Alejandro; Izquierdo-Roca, Victor

    2017-03-20

    This work presents a comprehensive analysis of the structural and vibrational properties of the kesterite Cu2ZnSnS4 (CZTS, I4̅ space group) as well as its polymorphs with the space groups P4̅2c and P4̅2m, from both experimental and theoretical point of views. Multiwavelength Raman scattering measurements performed on bulk CZTS polycrystalline samples were utilized to experimentally determine properties of the most intense Raman modes expected in these crystalline structures according to group theory analysis. The experimental results compare well with the vibrational frequencies that have been computed by first-principles calculations based on density functional theory. Vibrational patterns of the most intense fully symmetric modes corresponding to the P4̅2c structure were compared with the corresponding modes in the I4̅ CZTS structure. The results point to the need to look beyond the standard phases (kesterite and stannite) of CZTS while exploring and explaining the electronic and vibrational properties of these materials, as well as the possibility of using Raman spectroscopy as an effective technique for detecting the presence of different crystallographic modifications within the same material.

  9. Theoretical development and first-principles analysis of strongly correlated systems

    NASA Astrophysics Data System (ADS)

    Liu, Chen

    A variety of quantum many-body methods have been developed for studying the strongly correlated electron systems. We have also proposed a computationally efficient and accurate approach, named the correlation matrix renormalization (CMR) method to address the challenges. The theoretic development and benchmark tests of the CMR method are included in this thesis. Meanwhile, ground state total energy is the most important property of electronic calculations. We also investigated an alternative approach to calculate the total energy, and extended this method for magnetic anisotropy energy of ferromagnetic materials. In addition, another theoretical tool, dynamical mean-field theory on top of the density functional theory, has also been used in electronic structure calculations for an Iridium oxide to study the phase transition, which results from an interplay of the d electrons' internal degrees of freedom.

  10. Quantum Interference Effects in Resonant Raman Spectroscopy of Single- and Triple-Layer MoTe2 from First-Principles.

    PubMed

    Miranda, Henrique P C; Reichardt, Sven; Froehlicher, Guillaume; Molina-Sánchez, Alejandro; Berciaud, Stéphane; Wirtz, Ludger

    2017-03-02

    We present a combined experimental and theoretical study of resonant Raman spectroscopy in single- and triple-layer MoTe2. Raman intensities are computed entirely from first-principles by calculating finite differences of the dielectric susceptibility. In our analysis, we investigate the role of quantum interference effects and the electron-phonon coupling. With this method, we explain the experimentally observed intensity inversion of the A1(') vibrational modes in triple-layer MoTe2 with increasing laser photon energy. Finally, we show that a quantitative comparison with experimental data requires the proper inclusion of excitonic effects.

  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. Extended x-ray absorption fine structure spectroscopy and first-principles study of SnWO4

    NASA Astrophysics Data System (ADS)

    Kuzmin, A.; Anspoks, A.; Kalinko, A.; Timoshenko, J.; Kalendarev, R.

    2014-04-01

    The local atomic structure in α- and β-SnWO4 was studied by synchrotron radiation W L3-edge x-ray absorption spectroscopy at 10 and 300 K. Strongly distorted WO6 octahedra were found in α-SnWO4, whereas nearly regular WO4 tetrahedra were observed in β-SnWO4, confirming previous results. The structural results obtained were supported by the first-principles calculations, suggesting that the second-order Jahn-Teller effect is responsible for octahedral distortion.

  13. 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

  14. First-Principles Simulations of Inelastic Electron Tunneling Spectroscopy of Molecular Electronic Devices

    NASA Astrophysics Data System (ADS)

    Jiang, Jun; Kula, Mathias; Lu, Wei; Luo, Yi

    2005-08-01

    A generalized Green's function theory is developed to simulate the inelastic electron tunneling spectroscopy (IETS) of molecular junctions. It has been applied to a realistic molecular junction with an octanedithiolate embedded between two gold contacts in combination with the hybrid density functional theory calculations. The calculated spectra are in excellent agreement with recent experimental results. Strong temperature dependence of the experimental IETS spectra is also reproduced. It is shown that the IETS is extremely sensitive to the intra-molecular conformation and to the molecule-metal contact geometry.

  15. Vibration eigenmodes of the Au-(5 ×2 ) /Si(111) surface studied by Raman spectroscopy and first-principles calculations

    NASA Astrophysics Data System (ADS)

    Liebhaber, M.; Halbig, B.; Bass, U.; Geurts, J.; Neufeld, S.; Sanna, S.; Schmidt, W. G.; Speiser, E.; Räthel, J.; Chandola, S.; Esser, N.

    2016-12-01

    Ordered submonolayers of adsorbate atoms on semiconductor surfaces constitute a playground for electronic correlation effects, which are tightly connected to the local atomic arrangement and the corresponding vibration eigenmodes. We report on a study of the vibration eigenmodes of Au-covered Si(111) surfaces with (5 ×2 ) reconstruction using polarized Raman spectroscopy and first-principles calculations. Upon Au coverage, the vibration eigenmodes of the clean reconstructed Si(111)-(7 ×7 ) surface are quenched and replaced by new eigenmodes, determined by the Au-(5 ×2 ) reconstruction. Several polarization-dependent surface eigenmodes emerge in the spectral range from 25 to 120 cm-1 , with the strongest ones at 29, 51, and 106 cm-1. In our first-principles calculations we have determined the vibration frequencies, the corresponding elongation patterns, and the Raman intensities for two different structure models currently discussed in the literature. The best agreement with the experimental results is achieved for a model with 0.7 monolayer coverage and seven Au atoms per unit cell, proposed by S. G. Kwon and M. H. Kang [Phys. Rev. Lett. 113, 086101 (2014), 10.1103/PhysRevLett.113.086101].

  16. Probing deactivation pathways of DNA nucleobases by two-dimensional electronic spectroscopy: first principles simulations.

    PubMed

    Nenov, Artur; Segarra-Martí, Javier; Giussani, Angelo; Conti, Irene; Rivalta, Ivan; Dumont, Elise; Jaiswal, Vishal K; Altavilla, Salvatore Flavio; Mukamel, Shaul; Garavelli, Marco

    2015-01-01

    The SOS//QM/MM [Rivalta et al., Int. J. Quant. Chem., 2014, 114, 85] method consists of an arsenal of computational tools allowing accurate simulation of one-dimensional (1D) and bi-dimensional (2D) electronic spectra of monomeric and dimeric systems with unprecedented details and accuracy. Prominent features like doubly excited local and excimer states, accessible in multi-photon processes, as well as charge-transfer states arise naturally through the fully quantum-mechanical description of the aggregates. In this contribution the SOS//QM/MM approach is extended to simulate time-resolved 2D spectra that can be used to characterize ultrafast excited state relaxation dynamics with atomistic details. We demonstrate how critical structures on the excited state potential energy surface, obtained through state-of-the-art quantum chemical computations, can be used as snapshots of the excited state relaxation dynamics to generate spectral fingerprints for different de-excitation channels. The approach is based on high-level multi-configurational wavefunction methods combined with non-linear response theory and incorporates the effects of the solvent/environment through hybrid quantum mechanics/molecular mechanics (QM/MM) techniques. Specifically, the protocol makes use of the second-order Perturbation Theory (CASPT2) on top of Complete Active Space Self Consistent Field (CASSCF) strategy to compute the high-lying excited states that can be accessed in different 2D experimental setups. As an example, the photophysics of the stacked adenine-adenine dimer in a double-stranded DNA is modeled through 2D near-ultraviolet (NUV) spectroscopy.

  17. Structural analysis of char by Raman spectroscopy: Improving band assignments through computational calculations from first principles

    SciTech Connect

    Smith, Matthew W.; Dallmeyer, Ian; Johnson, Timothy J.; Brauer, Carolyn S.; McEwen, Jean-Sabin; Espinal, Juan F.; Garcia-Perez, Manuel

    2016-04-01

    Raman spectroscopy is a powerful tool for the characterization of many carbon 27 species. The complex heterogeneous nature of chars and activated carbons has confounded 28 complete analysis due to the additional shoulders observed on the D-band and high intensity 29 valley between the D and G-bands. In this paper the effects of various vacancy and substitution 30 defects have been systematically analyzed via molecular modeling using density functional 31 theory (DFT) and how this is manifested in the calculated gas-phase Raman spectra. The 32 accuracy of these calculations was validated by comparison with (solid-phase) experimental 33 spectra, with a small correction factor being applied to improve the accuracy of frequency 34 predictions. The spectroscopic effects on the char species are best understood in terms of a 35 reduced symmetry as compared to a “parent” coronene molecule. Based upon the simulation 36 results, the shoulder observed in chars near 1200 cm-1 has been assigned to the totally symmetric 37 A1g vibrations of various small polyaromatic hydrocarbons (PAH) as well as those containing 38 rings of seven or more carbons. Intensity between 1400 cm-1 and 1450 cm-1 is assigned to A1g 39 type vibrations present in small PAHs and especially those containing cyclopentane rings. 40 Finally, band intensity between 1500 cm-1 and 1550 cm-1 is ascribed to predominately E2g 41 vibrational modes in strained PAH systems. A total of ten potential bands have been assigned 42 between 1000 cm-1 and 1800 cm-1. These fitting parameters have been used to deconvolute a 43 thermoseries of cellulose chars produced by pyrolysis at 300-700 °C. The results of the 44 deconvolution show consistent growth of PAH clusters with temperature, development of non-45 benzyl rings as temperature increases and loss of oxygenated features between 400 °C and 46 600 °C

  18. Tracking conformational dynamics of polypeptides by nonlinear electronic spectroscopy of aromatic residues: a first-principles simulation study.

    PubMed

    Nenov, Artur; Beccara, Silvio; Rivalta, Ivan; Cerullo, Giulio; Mukamel, Shaul; Garavelli, Marco

    2014-10-20

    The ability of nonlinear electronic spectroscopy to track folding/unfolding processes of proteins in solution by monitoring aromatic interactions is investigated by first-principles 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, which connects the initial folded configuration with stacked aromatic side chains and the final unfolded state with distant noninteracting aromatic residues. The π-stacking and excitonic coupling effects are included through ab initio simulations based on multiconfigurational methods within a hybrid quantum mechanics/molecular mechanics scheme. It is shown that linear absorption spectroscopy in the ultraviolet (UV) region 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 region, the excited-state absorptions (ESAs) that involve charge-transfer states. 2D UV spectroscopy offers the highest sensitivity to the unfolding process, by providing the disentanglement of ESA signals belonging to different aromatic chromophores and high correlation between the conformational dynamics and the quartic splitting.

  19. Two-dimensional near-ultraviolet spectroscopy of aromatic residues in amyloid fibrils: a first principles study.

    PubMed

    Jiang, Jun; Mukamel, Shaul

    2011-02-14

    We report a first principles study of two dimensional electronic spectroscopy of aromatic side chain transitions in the 32-residue β-amyloid (Aβ(9-40)) fibrils in the near ultraviolet (250-300 nm). An efficient exciton Hamiltonian with electrostatic fluctuations (EHEF) algorithm is used to compute the electronic excitations in the presence of environmental fluctuations. The through-space inter- and intra-molecular interactions are calculated with high level quantum mechanics (QM) approaches, and interfaced with molecular mechanics (MM) simulations. Distinct two dimensional near ultraviolet (2DNUV) spectroscopic signatures are identified for different aromatic transitions, and the couplings between them. 2DNUV signals associated with the transition couplings are shown to be very sensitive to the change of residue-residue interactions induced by residue mutations. Our simulations suggest that 2DNUV spectra could provide a useful local probe for the structure and kinetics of fibrils.

  20. 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.

  1. 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.

  2. 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.

  3. First-principles study of He effects in a bcc Fe grain boundary: site preference, segregation and theoretical tensile strength.

    PubMed

    Zhang, Lei; Shu, Xiaolin; Jin, Shuo; Zhang, Ying; Lu, Guang-Hong

    2010-09-22

    We perform a first-principles calculation to investigate the effects of He in an Fe Σ5(310)/[001] grain boundary (GB) with the SIESTA code, for which the reliability of the pseudopotential and the basis set are systematically tested. We calculate the formation and segregation energies for different substitutional and interstitial cases in order to determine the site preference and the segregation properties of He in the Fe GB. It is demonstrated that the He segregation either breaks (substitution) or weakens (interstitial) the surrounding interfacial Fe-Fe bonds, leading to the GB tensile strength reduction.

  4. sp2/sp3 hybridization ratio in amorphous carbon from C 1s core-level shifts: X-ray photoelectron spectroscopy and first-principles calculation

    NASA Astrophysics Data System (ADS)

    Haerle, Rainer; Riedo, Elisa; Pasquarello, Alfredo; Baldereschi, Alfonso

    2002-01-01

    Using a combined experimental and theoretical approach, we address C 1s core-level shifts in amorphous carbon. Experimental results are obtained by x-ray photoelectron spectroscopy (XPS) and electron-energy-loss spectroscopy (EELS) on thin-film samples of different atomic density, obtained by a pulsed-laser deposition growth process. The XPS spectra are deconvoluted into two contributions, which are attributed to sp2- and sp3-hybridized atoms, respectively, separated by 0.9 eV, independent of atomic density. The sp3 hybridization content extracted from XPS is consistent with the atomic density derived from the plasmon energy in the EELS spectrum. In our theoretical study, we generate several periodic model structures of amorphous carbon of different densities applying two schemes of increasing accuracy in sequence. We first use a molecular-dynamics approach, based on an environmental-dependent tight-binding Hamiltonian to quench the systems from the liquid phase. The final model structures are then obtained by further atomic relaxation using a first-principles pseudopotential plane-wave approach within density-functional theory. Within the latter framework, we also calculate carbon 1s core-level shifts for our disordered model structures. We find that the shifts associated to threefold- and fourfold- coordinated carbon atoms give rise to two distinct peaks separated by about 1.0 eV, independent of density, in close agreement with experimental observations. This provides strong support for decomposing the XPS spectra into two peaks resulting from sp2- and sp3-hybridized atoms. Core-hole relaxations effects account for about 30% of the calculated shifts.

  5. Valence Band Density of States of Cu3Si Studied by Soft X-Ray Emission Spectroscopy and a First-Principle Molecular Orbital Calculation

    NASA Astrophysics Data System (ADS)

    An, Zhenlian; Kamezawa, Chihiro; Hirai, Masaaki; Kusaka, Masahiko; Iwami, Motohiro

    2002-12-01

    A systematic study of the valence band structure of Cu3Si has been performed by soft X-ray emission spectroscopy and a first-principle molecular orbital calculation using the discrete-variational (DV)-Xα cluster model. The existence of Cu 4s, 4p states in the valence band and their important contributions to the valence band as that of Cu 3d are indicated together with previously reported ones. The high-binding energy peak in the Si L2,3 emission spectrum is considered to originate mainly from the Si-Si 3s bonding state but also have a certain contribution of Si 3s bonding state with Cu 4s, 4p. On the other hand, the low-binding energy peaks in the Si L2,3 emission band are attributed to both the antibonding states of Si 3s and the bonding states of Si 3d with Cu 4s, 4p and Cu 3d. The bonding states of Si 3s with Cu 4s, 4p and Cu 3d are expected to exist in the lower part of the valence band for η\\prime-Cu3Si on the basis of the theoretical calculations. As for Si p states, the high-binding energy peak and the low-binding energy peak in the Si Kβ emission spectrum should be attributed to the Si 3p bonding state and antibonding state with Cu 3d and Cu 4s, 4p, respectively, according to the theoretical calculations. A comparison is made between experimental spectra and theoretical density of states.

  6. Lithium-assisted plastic deformation of silicon electrodes in lithium-ion batteries: a first-principles theoretical study.

    PubMed

    Zhao, Kejie; Wang, Wei L; Gregoire, John; Pharr, Matt; Suo, Zhigang; Vlassak, Joost J; Kaxiras, Efthimios

    2011-07-13

    Silicon can host a large amount of lithium, making it a promising electrode for high-capacity lithium-ion batteries. Recent experiments indicate that silicon experiences large plastic deformation upon Li absorption, which can significantly decrease the stresses induced by lithiation and thus mitigate fracture failure of electrodes. These issues become especially relevant in nanostructured electrodes with confined geometries. On the basis of first-principles calculations, we present a study of the microscopic deformation mechanism of lithiated silicon at relatively low Li concentration, which captures the onset of plasticity induced by lithiation. We find that lithium insertion leads to breaking of Si-Si bonds and formation of weaker bonds between neighboring Si and Li atoms, which results in a decrease in Young's modulus, a reduction in strength, and a brittle-to-ductile transition with increasing Li concentration. The microscopic mechanism of large plastic deformation is attributed to continuous lithium-assisted breaking and re-forming of Si-Si bonds and the creation of nanopores.

  7. 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

  8. Electron-phonon interactions from first principles

    NASA Astrophysics Data System (ADS)

    Giustino, Feliciano

    2017-01-01

    This article reviews the theory of electron-phonon interactions in solids from the point of view of ab initio calculations. While the electron-phonon interaction has been studied for almost a century, predictive nonempirical calculations have become feasible only during the past two decades. Today it is possible to calculate from first principles many materials properties related to the electron-phonon interaction, including the critical temperature of conventional superconductors, the carrier mobility in semiconductors, the temperature dependence of optical spectra in direct and indirect-gap semiconductors, the relaxation rates of photoexcited carriers, the electron mass renormalization in angle-resolved photoelectron spectra, and the nonadiabatic corrections to phonon dispersion relations. In this article a review of the theoretical and computational framework underlying modern electron-phonon calculations from first principles as well as landmark investigations of the electron-phonon interaction in real materials is given. The first part of the article summarizes the elementary theory of electron-phonon interactions and their calculations based on density-functional theory. The second part discusses a general field-theoretic formulation of the electron-phonon problem and establishes the connection with practical first-principles calculations. The third part reviews a number of recent investigations of electron-phonon interactions in the areas of vibrational spectroscopy, photoelectron spectroscopy, optical spectroscopy, transport, and superconductivity.

  9. The structure of Mn-doped tris(8-hydroxyquinoline)gallium by extended x-ray absorption fine structure spectroscopy and first principles calculations

    NASA Astrophysics Data System (ADS)

    Fang, Shaojie; Pang, Zhiyong; Du, Yonghua; Zheng, Lirong; Zhang, Xijian; Wang, Fenggong; Yuan, Huimin; Han, Shenghao

    2012-12-01

    Metal-Mqx (M = Al, Ga, Zn, Be, and Ca, x = 2 or 3) complexes play a key role in organic spintronics and organic optoelectronics. However, the accurate structure determination of these complexes has been a challenge for a long time. Here, we report the structure of Mn-Gaq3 investigated by using first-principle density functional theory (DFT) calculations and extended X-ray absorption fine structure (EXAFS) spectroscopy. First, the structures of Mn-Gaq3 were predicted by first-principle DFT calculations. Then, all reasonable structures achieved from the calculations were used to fit the EXAFS spectra. By this method, the structure of Mn-Gaq3 is well obtained. We believe this method is also applicable to other metal-Mqx films.

  10. A theoretical study of perovskite CsXCl3 (X=Pb, Cd) within first principles calculations

    NASA Astrophysics Data System (ADS)

    Ilyas, Bahaa M.; Elias, Badal H.

    2017-04-01

    The structural, elastic, electronic, optical acoustic and thermodynamic properties of the cubic perovskite CsPbCl3 and CsCdCl3 unit cell, were studied using an ultra-soft pseudopotential plane wave, the Trouiller-Martins-Functional was utilized to perform these calculations. The study was implemented within both the Local Density Approximation (LDA) and the Generalized Gradient Approximation (GGA). the Generalized Gradient Approximation (GGA) scheme proposed by van Leeuwen-Baerends which is the same as the Perdew-Wang 92 functional have been carried out to preform our calculations. As for the Local Density Approximation (LDA) the Teter-Pade parametrization (4/93) was implemented which is the same as Perdew-Wang that in its turn reproduces the Ceperley-Alder-Functional. The computed GGA/LDA-lattice parameter for both CsCdCl3 and CsPbCl3 is in an exquisite agreement with the experimental and theoretical results. The energy band structure shows that CsCdCl3 is Γ-R indirect band gap insulator, while CsPbCl3 is an insulator with a direct band gap Γ-Γ separating the valence bands from the conduction bands, which shows metallic nature after pressure 30 GPa. A hybridization exists between Pb-p states and Cl-p states for CsPbCl3, and Cd-p states and Cs-p states for the CsCdCl3 in the valence bonding region. Optimization of both cell shape (geometry) volume were investigated as pressure of 0-20 GPa and 0-40 GPa for the CsCdCl3 and CsPbCl3 respectively. The Pressure dependence of cubic perovskite elastic constants, Young modulus, bulk and shear moduli, Lame's constants, elastic anisotropy factor, elastic wave velocities, phonon dispersion, Debye temperature and the density of states of CsXCl3 (X=Pb, Cd) were theoretically calculated and compared with the other available theoretical results. The above elastic constants reveal the fact that both compounds are stable and show nature of ductility. For the optical properties, both the static refractive index and dielectric

  11. 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.

  12. 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.

  13. Iodate in calcite and vaterite: Insights from synchrotron X-ray absorption spectroscopy and first-principles calculations

    NASA Astrophysics Data System (ADS)

    Podder, J.; Lin, J.; Sun, W.; Botis, S. M.; Tse, J.; Chen, N.; Hu, Y.; Li, D.; Seaman, J.; Pan, Y.

    2017-02-01

    Calcium carbonates such as calcite are the dominant hosts of inorganic iodine in nature and are potentially important for the retention and removal of radioactive iodine isotopes (129I and 131I) in contaminated water. However, little is known about the structural environment of iodine in carbonates. In this study, iodate (IO3-) doped calcite and vaterite have been synthesized using the gel-diffusion method at three NaIO3 concentrations (0.002; 0.004; 0.008 M) and a pH value of 9.0, under ambient temperature and pressure. Inductively coupled plasma mass spectrometry (ICP-MS) analyses show that iodine is preferentially incorporated into calcite over vaterite. Synchrotron iodine K-edge X-ray absorption near-edge structure (XANES) spectra confirm that IO3- is the dominant iodine species in synthetic calcite and vaterite. Analyses of iodine K-edge extended X-ray absorption fine structure (EXAFS) data, complemented by periodic first-principles calculations at the density functional theory (DFT) levels, demonstrate that the I5+ ion of the IO3- group in calcite and vaterite is bonded by three and two additional O atoms (i.e., coordination numbers = 6 and 5), respectively, and is incorporated via the charged coupled substitution I5+ + Na+ ↔ C4+ + Ca2+, with the Na+ cation at a nearest Ca2+ site being the most energetically favorable configuration.

  14. Accurate ab initio tight-binding Hamiltonians: Effective tools for electronic transport and optical spectroscopy from first principles

    NASA Astrophysics Data System (ADS)

    D'Amico, Pino; Agapito, Luis; Catellani, Alessandra; Ruini, Alice; Curtarolo, Stefano; Fornari, Marco; Nardelli, Marco Buongiorno; Calzolari, Arrigo

    2016-10-01

    The calculations of electronic transport coefficients and optical properties require a very dense interpolation of the electronic band structure in reciprocal space that is computationally expensive and may have issues with band crossing and degeneracies. Capitalizing on a recently developed pseudoatomic orbital projection technique, we exploit the exact tight-binding representation of the first-principles electronic structure for the purposes of (i) providing an efficient strategy to explore the full band structure En(k ) , (ii) computing the momentum operator differentiating directly the Hamiltonian, and (iii) calculating the imaginary part of the dielectric function. This enables us to determine the Boltzmann transport coefficients and the optical properties within the independent particle approximation. In addition, the local nature of the tight-binding representation facilitates the calculation of the ballistic transport within the Landauer theory for systems with hundreds of atoms. In order to validate our approach we study the multivalley band structure of CoSb3 and a large core-shell nanowire using the ACBN0 functional. In CoSb3 we point the many band minima contributing to the electronic transport that enhance the thermoelectric properties; for the core-shell nanowire we identify possible mechanisms for photo-current generation and justify the presence of protected transport channels in the wire.

  15. 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.

  16. 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.

  17. 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.

  18. Raman spectroscopy study and first-principles calculations of the interaction between nucleic acid bases and carbon nanotubes.

    PubMed

    Stepanian, Stepan G; Karachevtsev, Maksym V; Glamazda, Alexander Yu; Karachevtsev, Victor A; Adamowicz, L

    2009-04-16

    In this work, we have used Raman spectroscopy and quantum chemical methods (MP2 and DFT) to study the interactions between nucleic acid bases (NABs) and single-walled carbon nanotubes (SWCNT). We found that the appearance of the interaction between the nanotubes and the NABs is accompanied by a spectral shift of the high-frequency component of the SWCNT G band in the Raman spectrum to a lower frequency region. The value of this shift varies from 0.7 to 1.3 cm(-1) for the metallic nanotubes and from 2.1 to 3.2 cm(-1) for the semiconducting nanotubes. Calculations of the interaction energies between the NABs and a fragment of the zigzag(10,0) carbon nanotube performed at the MP2/6-31++G(d,p)[NABs atoms]|6-31G(d)[nanotube atoms] level of theory while accounting for the basis set superposition error during geometry optimization allowed us to order the NABs according to the increasing interaction energy value. The order is: guanine (-67.1 kJ mol(-1)) > adenine (-59.0 kJ mol(-1)) > cytosine (-50.3 kJ mol(-1)) approximately = thymine (-50.2 kJ mol(-1)) > uracil (-44.2 kJ mol(-1)). The MP2 equilibrium structures and the interaction energies were used as reference points in the evaluation of the ability of various functionals in the DFT method to predict those structures and energies. We showed that the M05, MPWB1K, and MPW1B95 density functionals are capable of correctly predicting the SWCNT-NAB geometries but not the interaction energies, while the M05-2X functional is capable of correctly predicting both the geometries and the interaction energies.

  19. First principles theoretical investigations of low Young's modulus beta Ti-Nb and Ti-Nb-Zr alloys compositions for biomedical applications.

    PubMed

    Karre, Rajamallu; Niranjan, Manish K; Dey, Suhash R

    2015-05-01

    High alloyed β-phase stabilized titanium alloys are known to provide comparable Young's modulus as that to the human bones (~30 GPa) but is marred by its high density. In the present study the low titanium alloyed compositions of binary Ti-Nb and ternary Ti-Nb-Zr alloy systems, having stable β-phase with low Young's modulus are identified using first principles density functional framework. The theoretical results suggest that the addition of Nb in Ti and Zr in Ti-Nb increases the stability of the β-phase. The β-phase in binary Ti-Nb alloys is found to be fully stabilized from 22 at.% of Nb onwards. The calculated Young's moduli of binary β-Ti-Nb alloy system are found to be lower than that of pure titanium (116 GPa). For Ti-25(at.%)Nb composition the calculated Young's modulus comes out to be ~80 GPa. In ternary Ti-Nb-Zr alloy system, the Young's modulus of Ti-25(at.%)Nb-6.25(at.%)Zr composition is calculated to be ~50 GPa. Furthermore, the directional Young's moduli of these two selected binary (Ti-25(at.%)Nb) and ternary alloy (Ti-25(at.%)Nb-6.25(at.%)Zr) compositions are found to be nearly isotropic in all crystallographic directions.

  20. 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.

  1. Exploring the time-scale of photo-initiated interfacial electron transfer through first-principles interpretation of ultrafast X-ray spectroscopy (Presentation Recording)

    NASA Astrophysics Data System (ADS)

    Prendergast, David; Pemmaraju, Sri Chaitanya Das

    2015-09-01

    With the advent of X-ray free electron lasers and table-top high-harmonic-generation X-ray sources, we can now explore changes in electronic structure on ultrafast time scales -- at or less than 1ps. Transient X-ray spectroscopy of this kind provides a direct probe of relevant electronic levels related to photoinitiated processes and associated interfacial electron transfer as the initial step in solar energy conversion. However, the interpretation of such spectra is typically fraught with difficulty, especially since we rarely have access to spectral standards for nonequilibrium states. To this end, direct first-principles simulations of X-ray absorption spectra can provide the necessary connection between measurements and reliable models of the atomic and electronic structure. We present examples of modeling excited states of materials interfaces relevant to solar harvesting and their corresponding X-ray spectra in either photoemission or absorption modalities. In this way, we can establish particular electron transfer mechanisms to reveal detailed working principles of materials systems in solar applications and provide insight for improved efficiency.

  2. Origin of robust nanoscale ferromagnetism in Fe-doped Ge revealed by angle-resolved photoemission spectroscopy and first-principles calculation

    NASA Astrophysics Data System (ADS)

    Sakamoto, S.; Wakabayashi, Y. K.; Takeda, Y.; Fujimori, S.-i.; Suzuki, H.; Ban, Y.; Yamagami, H.; Tanaka, M.; Ohya, S.; Fujimori, A.

    2017-02-01

    Ge1 -xFex (Ge:Fe) shows ferromagnetic behavior up to a relatively high temperature of 210 K and hence is a promising material for spintronic applications compatible with Si technology. Unlike the prototypical system (Ga,Mn)As where itinerant holes induce long-range ferromagnetic order of the Mn spins, however, its ferromagnetism evolves from robust nanoscale ferromagnetic domains formed in Fe-rich regions. We have studied its underlying electronic structure by soft x-ray angle-resolved photoemission spectroscopy measurements and first-principles supercell calculation. We observed finite Fe 3 d components in the states at the Fermi level (EF) in a wide region of momentum space, and the EF was located ˜0.35 eV above the valence-band maximum of the host Ge. Our calculation indicates that the EF is also within the deep acceptor-level impurity band induced by the strong p -d (t2) hybridization. We conclude that the additional minority-spin d (e ) electron characteristic of the Fe2 + state is responsible for the short-range ferromagnetic coupling between Fe atoms, making the magnetism markedly different from that of (Ga,Mn)As.

  3. Enlightening the ultrahigh electrical conductivities of doped double-wall carbon nanotube fibers by Raman spectroscopy and first-principles calculations.

    PubMed

    Tristant, Damien; Zubair, Ahmed; Puech, Pascal; Neumayer, Frédéric; Moyano, Sébastien; Headrick, Robert J; Tsentalovich, Dmitri E; Young, Colin C; Gerber, Iann C; Pasquali, Matteo; Kono, Junichiro; Leotin, Jean

    2016-12-01

    Highly aligned, packed, and doped carbon nanotube (CNT) fibers with electrical conductivities approaching that of copper have recently become available. These fibers are promising for high-power electrical applications that require light-weight, high current-carrying capacity cables. However, a microscopic understanding of how doping affects the electrical conductance of such CNT fibers in a quantitative manner has been lacking. Here, we performed Raman spectroscopy measurements combined with first-principles calculations to determine the position of the average Fermi energy and to obtain the temperature of chlorosulfonic-acid-doped double-wall CNT fibers under high current. Due to the unique way in which double-wall CNT Raman spectra depend on doping, it is possible to use Raman data to determine the doping level quantitatively. The correspondence between the Fermi level shift and the carbon charge transfer is derived from a tight-binding model and validated by several calculations. For the doped fiber, we were able to associate an average Fermi energy shift of ∼-0.7 eV with a conductance increase by a factor of ∼5. Furthermore, since current induces heating, local temperature determination is possible. Through the Stokes-to-anti-Stokes intensity ratio of the G-band peaks, we estimated a temperature rise at the fiber surface of ∼135 K at a current density of 2.27 × 10(8) A m(-2) identical to that from the G-band shift, suggesting that thermalization between CNTs is well achieved.

  4. First principles theoretical study of the hole-assisted conversion of CO to CO2 on the anatase TiO2(101) surface

    NASA Astrophysics Data System (ADS)

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

    2011-03-01

    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 CO2 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 CO2, 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.

  5. Speciation in Aqueous MgSO4 Fluid at High Pressures and Temperatures Studied by First-Principles Modeling and Raman Spectroscopy

    NASA Astrophysics Data System (ADS)

    Jahn, S.; Schmidt, C.

    2008-12-01

    Aqueous fluids play an essential role in mass and energy transfer in the lithosphere. Their presence has also a large effect on physical properties of rocks, e.g. the electrical conductivity. Many chemical and physical properties of aqueous fluids strongly depend on the speciation, but very little is known about this fundamental parameter at high pressures and temperatures, e.g. at subduction zone conditions. Here we use a combined approach of first-principles molecular dynamics simulation and Raman spectroscopy to study the molecular structure of aqueous 2~mol/kg MgSO4 fluids up to pressures of 3~GPa and temperatures of 750~°C. MgSO4-H2O is selected as a model system for sulfate bearing subduction zone fluids. The simulations are performed using Car-Parrinello dynamics, a system size of 120 water and four MgSO4 molecules with production runs of at least 10~ps at each P and T. Raman spectra were obtained in situ using a Bassett-type hydrothermal diamond anvil cell with external heating. Both simulation and spectroscopic data show a dynamic co-existence of various associated molecular species as well as dissociated Mg2+ and SO42- in the single phase fluid. Fitting the Raman signal in the frequency range of the ν1-SO42- stretching mode yields the P-T dependence of the relative proportions of different peaks. The latter can be assigned to species based on literature data and related to the species found in the simulation. The dominant associated species found in the P-T range of interest here are Mg-SO4 ion pairs with one (monodentate) and two (bidentate) binding sites. At the highest P and T, an additional peak is identified. At low pressures and high temperature (T>230~°C), kieserite, MgSO4·H2O, nucleated in the experiment. At the same conditions the simulations show a clustering of Mg, which is interpreted as a precursor of precipitation. In conclusion, the speciation of aqueous MgSO4 fluid shows a complex behavior at high P and T that cannot be extrapolated

  6. 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.

  7. 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

    2015-09-07

    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.

  8. Reversal of the lattice structure in SrCoO(x) epitaxial thin films studied by real-time optical spectroscopy and first-principles calculations.

    PubMed

    Choi, Woo Seok; Jeen, Hyoungjeen; Lee, Jun Hee; Seo, S S Ambrose; Cooper, Valentino R; Rabe, Karin M; Lee, Ho Nyung

    2013-08-30

    Using real-time spectroscopic ellipsometry, we directly observed a reversible lattice and electronic structure evolution in SrCoO(x) (x=2.5-3) epitaxial thin films. Drastically different electronic ground states, which are extremely susceptible to the oxygen content x, are found in the two topotactic phases: i.e., the brownmillerite SrCoO2.5 and the perovskite SrCoO3. First-principles calculations confirmed substantial differences in the electronic structure, including a metal-insulator transition, which originate from the modification in the Co valence states and crystallographic structures. More interestingly, the two phases can be reversibly controlled by changing the ambient pressure at greatly reduced temperatures. Our finding provides an important pathway to understanding the novel oxygen-content-dependent phase transition uniquely found in multivalent transition metal oxides.

  9. 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.

  10. A valence state evaluation of a positive electrode material in an Li-ion battery with first-principles K- and L-edge XANES spectral simulations and resonance photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Kubobuchi, Kei; Mogi, Masato; Matsumoto, Masashi; Baba, Teruhisa; Yogi, Chihiro; Sato, Chikai; Yamamoto, Tomoyuki; Mizoguchi, Teruyasu; Imai, Hideto

    2016-10-01

    X-ray absorption near edge structure (XANES) analysis is an element-specific method for proving electronic state mostly in the field of applied physics, such as battery and catalysis reactions, where the valence change plays an important role. In particular, many results have been reported for the analysis of positive electrode materials of Li-ion batteries, where multiple transition materials contribute to the reactions. However, XANES analysis has been limited to identifying the valence state simply in comparison with reference materials. When the shape of XANES spectra shows complicated changes, we were not able to identify the valence states or estimate the valence quantitatively, resulting in insufficient reaction analysis. To overcome such issues, we propose a valence state evaluation method using K- and L-edge XANES analysis with first-principles simulations. By using this method, we demonstrated that the complicated reaction mechanism of Li(Ni1/3Co1/3Mn1/3)O2 can be successfully analyzed for distinguishing each contribution of Ni, Co, Mn, and O to the redox reactions during charge operation. In addition to the XANES analysis, we applied resonant photoelectron spectroscopy (RPES) and diffraction anomalous fine structure spectroscopy (DAFS) with first-principles calculations to the reaction analysis of Co and Mn, which shows no or very little contribution to the redox. The combination of RPES and first-principles calculations successfully enables us to confirm the contribution of Co at high potential regions by electively observing Co 3d orbitals. Through the DAFS analysis, we deeply analyzed the spectral features of Mn K-edges and concluded that the observed spectral shape change for Mn does not originate from the valence change but from the change in distribution of wave functions around Mn upon Li extraction.

  11. Optical phonons in the wurtzstannite Cu2ZnGeS4 semiconductor: Polarized Raman spectroscopy and first-principle calculations

    NASA Astrophysics Data System (ADS)

    Guc, M.; Litvinchuk, A. P.; Levcenko, S.; Izquierdo-Roca, V.; Fontané, X.; Valakh, M. Ya.; Arushanov, E.; Pérez-Rodríguez, A.

    2014-05-01

    The vibrational properties of the wurtzstannite Cu2ZnGeS4 are studied experimentally by polarized Raman scattering in off-resonant and resonant conditions and theoretically by ab initio lattice dynamics calculations. Twenty-nine modes from 45 Raman active theoretically predicted have been experimentally detected and identified, including polar A1(TO),A1(LO), and B1(TO+LO)/B2(TO+LO) and nonpolar A2 symmetry phonon modes from measurements on (2 1 0) and (0 0 1) crystallographic planes of Cu2ZnGeS4 single crystals. The lattice dynamics calculations provide a full picture of the zone center phonon spectrum and allow the assignment of experimentally observed lines to first- and second-order lattice vibrations. Using resonance Raman conditions, a strong enhancement of the A1(LO) modes with the highest longitudinal-transversal spiting is observed.

  12. Local variation in Bi crystal sites of epitaxial GaAsBi studied by photoelectron spectroscopy and first-principles calculations

    NASA Astrophysics Data System (ADS)

    Laukkanen, P.; Punkkinen, M. P. J.; Lahti, A.; Puustinen, J.; Tuominen, M.; Hilska, J.; Mäkelä, J.; Dahl, J.; Yasir, M.; Kuzmin, M.; Osiecki, J. R.; Schulte, K.; Guina, M.; Kokko, K.

    2017-02-01

    Epitaxial Bi-containing III-V crystals (III-V1-xBix) have attracted increasing interest due to their potential in infrared applications. Atomic-scale characterization and engineering of bulk-like III-V1-xBix properties (e.g., Bi incorporation and defect formation) are challenging but relevant to develop applications. Toward that target, we report here that the traditional surface-science measurement of photoelectron spectroscopy (PES) is a potential, non-destructive method to be combined in the studies of bulk-like properties, when surface effects are properly removed. We have investigated epitaxial GaAs1-xBix films, capped by epitaxial AlAs layers, with high-resolution photoelectron spectroscopy. The Bi5d core-level spectra of GaAs1-xBix together with ab-initio calculations give direct evidence of variation of Bi bonding environment in the lattice sites. The result agrees with photoluminescence (PL) measurement which shows that the studied GaAs1-xBix films include local areas with higher Bi content, which contribute to PL but do not readily appear in x-ray diffraction (XRD). The measured and calculated Bi core-level shifts show also that Ga vacancies and Bi clusters are dominant defects.

  13. Behavior of heptavalent technetium in sulfuric acid under α-irradiation: structural determination of technetium sulfate complexes by X-ray absorption spectroscopy and first principles calculations.

    PubMed

    Denden, I; Poineau, F; Schlegel, M L; Roques, J; Solari, P Lorenzo; Blain, G; Czerwinski, K R; Essehli, R; Barbet, J; Fattahi, M

    2014-03-06

    The effect of α-radiolysis on the behavior of heptavalent technetium has been investigated in 13 and 18 M H2SO4. Irradiation experiments were performed using α-particles ((4)He(2+), E = 68 MeV) generated by the ARRONAX cyclotron. UV-visible and X-ray absorption fine structure spectroscopic studies indicate that Tc(VII) is reduced to Tc(V) under α-irradiation. Extended X-ray absorption fine structure (EXAFS) spectroscopy measurements are consistent with the presence of mononuclear technetium sulfate complexes. Experimental results and density functional calculations show the formation of [TcO(HSO4)3(H2O)(OH)](-) and/or [TcO(HSO4)3(H2O)2] and [Tc(HSO4)3(SO4)(H2O)] and/or [Tc(HSO4)3(SO4)(OH)](-) for 13 and 18 M H2SO4, respectively.

  14. 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

  15. Electronic structure of metastable bcc Cu-Cr alloy thin films: Comparison of electron energy-loss spectroscopy and first-principles calculations.

    PubMed

    Liebscher, C H; Freysoldt, C; Dennenwaldt, T; Harzer, T P; Dehm, G

    2016-07-12

    Metastable Cu-Cr alloy thin films with nominal thickness of 300nm and composition of Cu67Cr33 (at%) are obtained by co-evaporation using molecular beam epitaxy. The microstructure, chemical phase separation and electronic structure are investigated by transmission electron microscopy (TEM). The thin film adopts the body-centered cubic crystal structure and consists of columnar grains with ~50nm diameter. Aberration-corrected scanning TEM in combination with energy dispersive X-ray spectroscopy confirms compositional fluctuations within the grains. Cu- and Cr-rich domains with composition of Cu85Cr15 (at%) and Cu42Cr58 (at%) and domain size of 1-5nm are observed. The alignment of the interface between the Cu- and Cr-rich domains shows a preference for {110}-type habit plane. The electronic structure of the Cu-Cr thin films is investigated by electron energy loss spectroscopy (EELS) and is contrasted to an fcc-Cu reference sample. The experimental EEL spectra are compared to spectra computed by density functional theory. The main differences between bcc-and fcc-Cu are related to differences in van Hove singularities in the electron density of states. In Cu-Cr solid solutions with bcc crystal structure a single peak after the L3-edge, corresponding to a van Hove singularity at the N-point of the first Brillouin zone is observed. Spectra computed for pure bcc-Cu and random Cu-Cr solid solutions with 10at% Cr confirm the experimental observations. The calculated spectrum for a perfect Cu50Cr50 (at%) random structure shows a shift in the van Hove singularity towards higher energy by developing a Cu-Cr d-band that lies between the delocalized d-bands of Cu and Cr.

  16. Structure-dependent vibrational dynamics of Mg(BH 4 ) 2 polymorphs probed with neutron vibrational spectroscopy and first-principles calculations

    DOE PAGES

    Dimitrievska, Mirjana; White, James L.; Zhou, Wei; ...

    2016-08-19

    We investigated the structure-dependent vibrational properties of different Mg(BH4)2 polymorphs (α, β, γ, and δ phases) with a combination of neutron vibrational spectroscopy (NVS) measurements and density functional theory (DFT) calculations, with emphasis placed on the effects of the local structure and orientation of the BH4- anions. DFT simulations closely match the neutron vibrational spectra. The main bands in the low-energy region (20–80 meV) are associated with the BH4- librational modes. The features in the intermediate energy region (80–120 meV) are attributed to overtones and combination bands arising from the lower-energy modes. The features in the high-energy region (120–200 meV)more » correspond to the BH4- symmetric and asymmetric bending vibrations, of which four peaks located at 140, 142, 160, and 172 meV are especially intense. There are noticeable intensity distribution variations in the vibrational bands for different polymorphs. We can explain these differences using the spatial distribution of BH4- anions within various structures. An example of the possible identification of products after the hydrogenation of MgB2, using NVS measurements, is presented. Our results provide fundamental insights of benefit to researchers currently studying these promising hydrogen-storage materials.« less

  17. Structure-dependent vibrational dynamics of Mg(BH 4 ) 2 polymorphs probed with neutron vibrational spectroscopy and first-principles calculations

    SciTech Connect

    Dimitrievska, Mirjana; White, James L.; Zhou, Wei; Stavila, Vitalie; Klebanoff, Leonard E.; Udovic, Terrence J.

    2016-01-01

    The structure-dependent vibrational properties of different Mg(BH4)2 polymorphs (..alpha.., ..beta.., ..gamma.., and ..delta.. phases) were investigated with a combination of neutron vibrational spectroscopy (NVS) measurements and density functional theory (DFT) calculations, with emphasis placed on the effects of the local structure and orientation of the BH4- anions. DFT simulations closely match the neutron vibrational spectra. The main bands in the low-energy region (20-80 meV) are associated with the BH4- librational modes. The features in the intermediate energy region (80-120 meV) are attributed to overtones and combination bands arising from the lower-energy modes. The features in the high-energy region (120-200 meV) correspond to the BH4- symmetric and asymmetric bending vibrations, of which four peaks located at 140, 142, 160, and 172 meV are especially intense. There are noticeable intensity distribution variations in the vibrational bands for different polymorphs. This is explained by the differences in the spatial distribution of BH4- anions within various structures. An example of the possible identification of products after the hydrogenation of MgB2, using NVS measurements, is presented. These results provide fundamental insights of benefit to researchers currently studying these promising hydrogen-storage materials.

  18. Structure-dependent vibrational dynamics of Mg(BH 4 ) 2 polymorphs probed with neutron vibrational spectroscopy and first-principles calculations

    SciTech Connect

    Dimitrievska, Mirjana; White, James L.; Zhou, Wei; Stavila, Vitalie; Klebanoff, Leonard E.; Udovic, Terrence J.

    2016-08-19

    We investigated the structure-dependent vibrational properties of different Mg(BH4)2 polymorphs (α, β, γ, and δ phases) with a combination of neutron vibrational spectroscopy (NVS) measurements and density functional theory (DFT) calculations, with emphasis placed on the effects of the local structure and orientation of the BH4- anions. DFT simulations closely match the neutron vibrational spectra. The main bands in the low-energy region (20–80 meV) are associated with the BH4- librational modes. The features in the intermediate energy region (80–120 meV) are attributed to overtones and combination bands arising from the lower-energy modes. The features in the high-energy region (120–200 meV) correspond to the BH4- symmetric and asymmetric bending vibrations, of which four peaks located at 140, 142, 160, and 172 meV are especially intense. There are noticeable intensity distribution variations in the vibrational bands for different polymorphs. We can explain these differences using the spatial distribution of BH4- anions within various structures. An example of the possible identification of products after the hydrogenation of MgB2, using NVS measurements, is presented. Our results provide fundamental insights of benefit to researchers currently studying these promising hydrogen-storage materials.

  19. Origin of magnetoelectric effect in Co4Nb2O9 and Co4Ta2O9 : The lessons learned from the comparison of first-principles-based theoretical models and experimental data

    NASA Astrophysics Data System (ADS)

    Solovyev, I. V.; Kolodiazhnyi, T. V.

    2016-09-01

    We report results of joint experimental and theoretical studies on magnetoelectric (ME) compounds Co4Nb2O9 and Co4Ta2O9 . On the experimental side, we present results of the magnetization and dielectric permittivity measurements in the magnetic field. On the theoretical side, we construct the low-energy Hubbard-type model for the magnetically active Co 3 d bands in the Wannier basis, using the input of the first-principles electronic structure calculations, solve this model in the mean-field Hartree-Fock approximation, and evaluate the electric polarization in terms of the Berry phase theory. Both experimental and theoretical results suggest that Co4Ta2O9 is magnetically softer than Co4Nb2O9 . Therefore, it is reasonable to expect that the antiferromagnetic structure of Co4Ta2O9 can be easier deformed by the external magnetic field, yielding larger polarization. This trend is indeed reproduced by our theoretical calculations, but does not seem to be consistent with the experimental behavior of the polarization and dielectric permittivity. Thus, we suggest that there should be a hidden mechanism controlling the ME coupling in these compounds, probably related to the magnetic striction or a spontaneous change of the magnetic structure, which breaks the inversion symmetry. Furthermore, we argue that unlike in other ME systems (e.g., Cr2O3 ), in Co4Nb2O9 and Co4Ta2O9 there are two crystallographic sublattices, which contribute to the ME effect. These contributions are found to be of the opposite sign and tend to compensate each other. The latter mechanism can be also used to control and reverse the electric polarization in these compounds.

  20. Graphene quantum dots with visible light absorption of the carbon core: insights from single-particle spectroscopy and first principles based theory

    NASA Astrophysics Data System (ADS)

    Ghosh, Siddharth; Awasthi, Manohar; Ghosh, Moumita; Seibt, Michael; Niehaus, Thomas A.

    2016-12-01

    Luminescent carbon nanodots (CND) are a recent addition to the family of carbon nanostructures. Interestingly, a large group of CNDs are fluorescent in the visible spectrum and possess single dipole emitters with potential applications in super-resolution microscopy, quantum information science, and optoelectronics. There is a large diversity of CND’s size as well as a strong variability of edge topology and functional groups in real samples. This hampers a direct comparison of experimental and theoretical findings that is necessary to understand the unusual photophysics of these systems. Here, we derive atomistic models of finite sized (<2.5 nm) CNDs from high resolution transmission electron microscopy (HRTEM) which are studied using approximate time-dependent density functional theory. The atomistic models are found to be primarily two-dimensional (2D) and can hence be categorised as graphene quantum dots (GQD). The GQD model structures that are presented here show excitation energies in the visible spectrum matching previous single GQD level photoluminescence studies. We also present the effect of edge hydroxyl and carboxyl functional groups on the absorption spectrum. Overall, the study reveals the atomistic origin of CNDs photoluminescence in the visible range.

  1. 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.

  2. TS-1 from First Principles

    NASA Astrophysics Data System (ADS)

    Gamba, Aldo; Tabacchi, Gloria; Fois, Ettore

    2009-09-01

    First principles studies on periodic TS-1 models at Ti content corresponding to 1.35% and 2.7% in weight of TiO2 are presented. The problem of Ti preferential siting is addressed by using realistic models corresponding to the TS-1 unit cell [TiSi95O192] and adopting for the first time a periodic DFT approach, thus providing an energy scale for Ti in the different crystallographic sites in nondefective TS-1. The structure with Ti in site T3 is the most stable, followed by T4 (+0.3 kcal/mol); the less stable structure, corresponding to Ti in T1, is 5.6 kcal/mol higher in energy. The work has been extended to investigate models with two Ti's per unit cell [Ti2Si94O192] (2.7%). The possible existence of Ti-O-Ti bridges, formed by two corner-sharing TiO4 tetrahedra, is discussed. By using cluster models cut from the optimized periodic DFT structures, both vibrational (DFT) and electronic excitation spectra (TDDFT) have been calculated and favorably compared with the experimental data available on TS-1. Interesting features emerged from excitation spectra: (i) Isolated tetrahedral Ti sites show a Beer-Lambert behavior, with absorption intensity proportional to concentration. Such a behavior is gradually lost when two Ti's occupy sites close to each other. (ii) The UV-vis absorption in the 200-250 nm region can be associated with transitions from occupied states delocalized on the framework oxygens to empty d states localized on Ti. Such extended-states-to-local-states transitions may help the interpretation of the photovoltaic activity recently detected in Ti zeolites.

  3. 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

  4. 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

  5. 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

  6. 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

  7. 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

  8. 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.

  9. 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

  10. 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

  11. Electronic absorption spectra from first principles

    NASA Astrophysics Data System (ADS)

    Hazra, Anirban

    Methods for simulating electronic absorption spectra of molecules from first principles (i.e., without any experimental input, using quantum mechanics) are developed and compared. The electronic excitation and photoelectron spectra of ethylene are simulated, using the EOM-CCSD method for the electronic structure calculations. The different approaches for simulating spectra are broadly of two types---Frank-Condon (FC) approaches and vibronic coupling approaches. For treating the vibrational motion, the former use the Born-Oppenheimer or single surface approximation while the latter do not. Moreover, in our FC approaches the vibrational Hamiltonian is additively separable along normal mode coordinates, while in vibronic approaches a model Hamiltonian (obtained from ab initio electronic structure theory) provides an intricate coupling between both normal modes and electronic states. A method called vertical FC is proposed, where in accord with the short-time picture of molecular spectroscopy, the approximate excited-state potential energy surface that is used to calculate the electronic spectrum is taken to reproduce the ab initio potential at the ground-state equilibrium geometry. The potential energy surface along normal modes may be treated either in the harmonic approximation or using the full one-dimensional potential. Systems with highly anharmonic potential surfaces can be treated and expensive geometry optimizations are not required, unlike the traditional FC approach. The ultraviolet spectrum of ethylene between 6.2 and 8.7 eV is simulated using vertical FC. While FC approaches for simulation are computationally very efficient, they are not accurate when the underlying approximations are unreasonable. Then, vibronic coupling model Hamiltonians are necessary. Since these Hamiltonians have an analytic form, they are used to map the potential energy surfaces and understand their topology. Spectra are obtained by numerical diagonalization of the Hamiltonians. The

  12. 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.

  13. Rediscovering First Principles through Online Learning.

    ERIC Educational Resources Information Center

    Kidney, Gary W.; Puckett, Edmond G.

    2003-01-01

    Describes an evaluation of Web-based instruction at the University of Houston-Clear Lake (Texas) that showed that the design team had been distracted from many first principles of instructional design by the creative chaos on the Web and discusses how self-reflection and role definitions allowed the team to overcome these disappointments and…

  14. 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.

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

    PubMed

    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.

  16. 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.

  17. First-principles study of transition metal carbides

    NASA Astrophysics Data System (ADS)

    Connétable, Damien

    2016-12-01

    This study investigates the physical properties of transition metal carbides compounds associated with the Nb-C, Ti-C, Mo-C and W-C alloys systems using first-principles calculations. The ground-state properties (lattice parameters, cohesive energies and magnetism) were analyzed and compared to the experimental and theoretical literature. The simulations are in excellent agreement with experimental findings concerning atomic positions and structures. Elastic properties, computed using a finite-differences approach, are then discussed in detail. To complete the work, their lattice dynamics properties (phonon spectra) were investigated. These results serve to establish that some structures, which are mechanically stable, are dynamically unstable.

  18. Thermoelastic properties of random alloys from first-principles theory

    NASA Astrophysics Data System (ADS)

    Huang, L.; Vitos, L.; Kwon, S. K.; Johansson, B.; Ahuja, R.

    2006-03-01

    We present a first-principles description of the temperature-dependent elastic constants in random alloys. The substitutional disorder is treated using the coherent potential approximation implemented within the frameworks of exact muffin-tin orbitals theory. The temperature effects are approximated as the sum of electronic and thermal expansion contributions. Calculations on pure Nb demonstrate that this approach correctly accounts for the main temperature dependence of cubic elastic constants. When extended to Nb-Zr solid solution, the theoretical results show good agreement with experiments at temperatures ≲300K .

  19. Highly Sensitive and Selective Uranium Detection in Natural Water Systems Using a Luminescent Mesoporous Metal-Organic Framework Equipped with Abundant Lewis Basic Sites: A Combined Batch, X-ray Absorption Spectroscopy, and First Principles Simulation Investigation.

    PubMed

    Liu, Wei; Dai, Xing; Bai, Zhuanling; Wang, Yanlong; Yang, Zaixing; Zhang, Linjuan; Xu, Lin; Chen, Lanhua; Li, Yuxiang; Gui, Daxiang; Diwu, Juan; Wang, Jianqiang; Zhou, Ruhong; Chai, Zhifang; Wang, Shuao

    2017-04-04

    Uranium is not only a strategic resource for the nuclear industry but also a global contaminant with high toxicity. Although several strategies have been established for detecting uranyl ions in water, searching for new uranium sensor material with great sensitivity, selectivity, and stability remains a challenge. We introduce here a hydrolytically stable mesoporous terbium(III)-based MOF material compound 1, whose channels are as large as 27 Å × 23 Å and are equipped with abundant exposed Lewis basic sites, the luminescence intensity of which can be efficiently and selectively quenched by uranyl ions. The detection limit in deionized water reaches 0.9 μg/L, far below the maximum contamination standard of 30 μg/L in drinking water defined by the United States Environmental Protection Agency, making compound 1 currently the only MOF material that can achieve this goal. More importantly, this material exhibits great capability in detecting uranyl ions in natural water systems such as lake water and seawater with pH being adjusted to 4, where huge excesses of competing ions are present. The uranyl detection limits in Dushu Lake water and in seawater were calculated to be 14.0 and 3.5 μg/L, respectively. This great detection capability originates from the selective binding of uranyl ions onto the Lewis basic sites of the MOF material, as demonstrated by synchrotron radiation extended X-ray adsorption fine structure, X-ray adsorption near edge structure, and first principles calculations, further leading to an effective energy transfer between the uranyl ions and the MOF skeleton.

  20. 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.

  1. 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

  2. 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.

  3. Primordial Black Holes from First Principles (Overview)

    NASA Astrophysics Data System (ADS)

    Lam, Casey; Bloomfield, Jolyon; Moss, Zander; Russell, Megan; Face, Stephen; Guth, Alan

    2017-01-01

    Given a power spectrum from inflation, our goal is to calculate, from first principles, the number density and mass spectrum of primordial black holes that form in the early universe. Previously, these have been calculated using the Press- Schechter formalism and some demonstrably dubious rules of thumb regarding predictions of black hole collapse. Instead, we use Monte Carlo integration methods to sample field configurations from a power spectrum combined with numerical relativity simulations to obtain a more accurate picture of primordial black hole formation. We demonstrate how this can be applied for both Gaussian perturbations and the more interesting (for primordial black holes) theory of hybrid inflation. One of the tools that we employ is a variant of the BBKS formalism for computing the statistics of density peaks in the early universe. We discuss the issue of overcounting due to subpeaks that can arise from this approach (the ``cloud-in-cloud'' problem). MIT UROP Office- Paul E. Gray (1954) Endowed Fund.

  4. First-principles determination of magnetic properties

    NASA Astrophysics Data System (ADS)

    Wu, Ruqian; Yang, Zongxian; Hong, Jisang

    2003-02-01

    First-principles density functional theory calculations have achieved great success in the exciting field of low-dimension magnetism, in explaining new phenomena observed in experiments as well as in predicting novel properties and materials. As known, spin-orbit coupling (SOC) plays an extremely important role in various magnetic properties such as magnetic anisotropy, magnetostriction, magneto-optical effects and spin-dynamics. Using the full potential linearized augmented plane wave approach, we have carried out extensive investigations for the effects of SOC in various materials. Results of selected examples, such as structure and magnetic properties of Ni/Cu(001), magnetism and magnetic anisotropy in magnetic Co/Cu(001) thin films, wires and clusters, magnetostriction in FeGa alloys and magneto-optical effects in Fe/Cr superlattices, are discussed.

  5. First principles approach to ionicity of fragments

    NASA Astrophysics Data System (ADS)

    Pilania, Ghanshyam; Liu, Xiang-Yang; Valone, Steven M.

    2015-02-01

    We develop a first principles approach towards the ionicity of fragments. In contrast to the bond ionicity, the fragment ionicity refers to an electronic property of the constituents of a larger system, which may vary from a single atom to a functional group or a unit cell to a crystal. The fragment ionicity is quantitatively defined in terms of the coefficients of contributing charge states in a superposition of valence configurations of the system. Utilizing the constrained density functional theory-based computations, a practical method to compute the fragment ionicity from valence electron charge densities, suitably decomposed according to the Fragment Hamiltonian (FH) model prescription for those electron densities, is presented for the first time. The adopted approach is illustrated using BeO, MgO and CaO diatomic molecules as simple examples. The results are compared and discussed with respect to the bond ionicity scales of Phillips and Pauling.

  6. Anisotropic Spin Hall Effect from First Principles

    NASA Astrophysics Data System (ADS)

    Freimuth, Frank; Blügel, Stefan; Mokrousov, Yuriy

    2011-03-01

    We present first principles calculations of the intrinsic non-dissipative spin Hall conductivity (SHC) for 3 d , 4 d and 5 d transition metals focusing in particular on the anisotropy of the SHC in nonmagnetic hcp metals and in antiferromagnetic Cr. For the metals of this study we generally find large anisotropies. We derive the general relation between the SHC vector and the direction of spin-polarization and discuss its consequences for hcp metals. Especially, it is predicted that for systems where the SHC changes sign due to the anisotropy the spin Hall effect may be tuned such that the spin polarization is parallel either to the electric field or to the spin current. Additionally, we describe our computational method [2,3] emphasizing the Wannier interpolation technique and the definition of the conserved spin current. This work is supported by the DFG Project MO 1731/3-1 and HGF-YIG grant VH-NG-513.

  7. Current status of single-molecule spectroscopy: Theoretical aspects

    NASA Astrophysics Data System (ADS)

    Jung, YounJoon; Barkai, Eli; Silbey, Robert J.

    2002-12-01

    We survey the current status of single-molecule spectroscopy in the view point of theoretical aspects. After an explanation of basic concepts in single-molecule spectroscopy, we focus on the following topics: (1) line shape phenomena in disordered media, (2) photon counting statistics for time-dependent fluctuations in single-molecule spectroscopy, (3) fluorescence intensity fluctuations for nonergodic systems, (4) time-resolved single-molecule fluorescence for conformational dynamics of single biomolecules, (5) single-molecule reaction dynamics at room temperature, and (6) quantum jump method of single quantum system. We conclude this paper with some open questions and perspectives of single-molecule spectroscopy.

  8. 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

  9. 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.

  10. First Principles Theoretical Studies of Ferroelectric Lattice Instabilities.

    DTIC Science & Technology

    2008-02-22

    systems that have yet to be synthesized. We also have performed work on the oxide-based systems based on the potential-induced-breathing ( PIB ) model which...with Dr. Boyer at the Naval Research Laboratory, extensions and applications of the PIB (potential induced breathing) model, which represented an...notably, ferroelectric perovskites. Unfortunately, this had only been carried to the point of determining the effect of PIB on rotational (nonpolar

  11. 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.

  12. 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).

  13. Dipole strength from first principles calculations

    NASA Astrophysics Data System (ADS)

    Miorelli, Mirko; Bacca, Sonia; Barnea, Nir; Hagen, Gaute; Jansen, Gustav R.; Papenbrock, Thomas; Orlandini, Giuseppina

    2016-09-01

    The electric dipole polarizability quantifies the low-energy behavior of the dipole strength. It is related to the proton and neutron distributions of the nucleus, and thereby can be used to constrain the neutron equation of state and the physics of neutron stars. Only recently however, new developments in ab initio methods finally allowed first principles studies of the dipole strength in medium-mass nuclei. Using the Lorentz integral transform coupled cluster method with the newly developed chiral interaction NNLOsat we study the low energy behavior of the dipole strength in 4He, 16O and 22O. For the exotic 22O we observe large contributions to the dipole strength at very low energy, indicating the presence of a pygmy dipole resonance, in agreement with what experimentally found by Leistenschneider et al.. We then study correlations between the electric dipole polarizability and the charge radius in 16O and 40Ca using a variety of realistic Hamiltonians, showing the importance of three-nucleon forces. We aknowledge NRC and NSERC.

  14. High Pressure Hydrogen from First Principles

    NASA Astrophysics Data System (ADS)

    Morales, M. A.

    2014-12-01

    Typical approximations employed in first-principles simulations of high-pressure hydrogen involve the neglect of nuclear quantum effects (NQE) and the approximate treatment of electronic exchange and correlation, typically through a density functional theory (DFT) formulation. In this talk I'll present a detailed analysis of the influence of these approximations on the phase diagram of high-pressure hydrogen, with the goal of identifying the predictive capabilities of current methods and, at the same time, making accurate predictions in this important regime. We use a path integral formulation combined with density functional theory, which allows us to incorporate NQEs in a direct and controllable way. In addition, we use state-of-the-art quantum Monte Carlo calculations to benchmark the accuracy of more approximate mean-field electronic structure calculations based on DFT, and we use GW and hybrid DFT to calculate the optical properties of the solid and liquid phases near metallization. We present accurate predictions of the metal-insulator transition on the solid, including structural and optical properties of the molecular phase. This work was supported by the U.S. Department of Energy at the Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344 and by LDRD Grant No. 13-LW-004.

  15. 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.

  16. 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.

  17. 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.

  18. 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

    2016-09-01

    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.

  19. 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

    2012-09-05

    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.

  20. Point defects in thorium nitride: A first-principles study

    NASA Astrophysics Data System (ADS)

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

    2016-11-01

    Thorium and its compounds (carbides and nitrides) are being investigated as possible materials to be used as nuclear fuels for Generation-IV reactors. As a first step in the research of these materials under irradiation, we study the formation energies and stability of point defects in thorium nitride by means of first-principles calculations within the framework of density functional theory. We focus on vacancies, interstitials, Frenkel pairs and Schottky defects. We found that N and Th vacancies have almost the same formation energy and that the most energetically favorable defects of all studied in this work are N interstitials. These kind of results for ThN, to the best authors' knowledge, have not been obtained previously, neither experimentally, nor theoretically.

  1. Stability of hydrogenated graphene: a first-principles study

    DOE PAGES

    Yi, Ding; Yang, Liu; Xie, Shijie; ...

    2015-02-10

    In order to explain the disagreement between present theoretical and experimental investigations on the stability of hydrogenated graphene, we have systematically studied hydrogenated graphene with different configurations from the consideration of single-side and double-side adsorption using first-principles calculations. Both binding energy and formation energy are calculated to characterize the stability of the system. It is found that single-side hydrogenated graphene is always unstable. However, for double-side hydrogenation, some configurations are stable due to the increased carbon–carbon sp3 hybridization compared to single-side hydrogenation. Furthermore, it is found that the system is energetically favorable when an equal number of hydrogen atoms aremore » adsorbed on each side of the graphene.« less

  2. First-principles study of optical excitations in alphaquartz

    SciTech Connect

    Chang, Eric K.; Rohlfing, Michael; Louie, Steven G.

    1999-06-15

    The properties of silicon dioxide have been studied extensively over the years. However, there still remain major unanswered questions regarding the nature of the optical spectrum and the role of excitonic effects in this technologically important material. In this work, we present an ab initio study of the optical absorption spectrum of alpha-quartz, using a newly developed first-principles method which includes self-energy and electron-hole interaction effects. The quasiparticle band structure is computed within the GW approximation to obtain a quantitative description of the single-particle excitations. The Bethe-Salpeter equation for the electron-hole excitations is solved to obtain the optical spectrum and to understand the spatial extent and physical properties of the excitons. The theoretical absorption spectrum is found to be in excellent agreement with the measured spectrum. We show that excitonic effects are crucial in the frequency range up to 5 eV above the absorption threshold.

  3. Stability of hydrogenated graphene: a first-principles study

    SciTech Connect

    Yi, Ding; Yang, Liu; Xie, Shijie; Saxena, Avadh

    2015-02-10

    In order to explain the disagreement between present theoretical and experimental investigations on the stability of hydrogenated graphene, we have systematically studied hydrogenated graphene with different configurations from the consideration of single-side and double-side adsorption using first-principles calculations. Both binding energy and formation energy are calculated to characterize the stability of the system. It is found that single-side hydrogenated graphene is always unstable. However, for double-side hydrogenation, some configurations are stable due to the increased carbon–carbon sp3 hybridization compared to single-side hydrogenation. Furthermore, it is found that the system is energetically favorable when an equal number of hydrogen atoms are adsorbed on each side of the graphene.

  4. 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.

  5. 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

  6. 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.

  7. First-Principles Thermodynamics of Energetic Materials

    DTIC Science & Technology

    2012-01-01

    experiment falls short of providing these properties over a wide range of pressures and temperatures , and is hindered by inaccuracies from shear...introduced by the compressive media used in diamond anvil cells [2]. As such, theoretical avenues for the acquisition of key input parameters for large...CTEs over a wide range of pressures and temperatures . In fact, as seen in Figure 2 (top and middle), fairly good agreement can be seen in the

  8. The Electron-Phonon Interaction from First Principles

    NASA Astrophysics Data System (ADS)

    Noffsinger, Jesse Dean

    2011-12-01

    In this thesis the ground state electronic properties, lattice dynamics, electron-phonon coupling and superconductivity of a variety materials are investigated from first principles. The first chapter provides an introduction to the material and concepts of this thesis as well as motivation for the work done herein. Additionally, an overview is given on the theoretical background governing the calculations of this work. This includes overviews of the topics of density functional theory, the pseudopotential approximation, density functional perturbation theory, and applications of these approaches to the calculations of superconductivity. In the second chapter the mechanics of actually performing calculations within the methodology of chapter one are explained. This is accomplished through a detailed description of the computer software EPW. This software has been developed to allow computationally efficient approaches for calculating the electron-phonon interaction. A description of the software package, the particular quantities which it calculates and example calculations are given. The following two chapters present the results of calculations regarding electron-phonon coupling and superconductivity in bulk carbon compounds. The occurrence or absence of superconductivity is found to be related in these compounds to Fermi surface nesting and carrier concentrations. In chapter five we investigate the role of the fluorine dopant in the recently discovered (1111) Fe-pnictide superconductors. Contrary to the results of the literature published shortly after the discovery of these compounds, the presence of the dopant is found to actually result in a net decrease in the electron concentration on the Fe-plane within the local density approximation to density functional theory. In the two chapters which follow, we investigate the limits of two dimensional superconductivity in the recent experiments on ultra-thin Pb samples. Chapter six details calculations on

  9. First Principles Atomistic Model for Carbon-Doped Boron Suboxide

    DTIC Science & Technology

    2014-09-01

    First Principles Atomistic Model for Carbon-Doped Boron Suboxide by Amol B Rahane, Jennifer S Dunn, and Vijay Kumar ARL-TR-7106...2014 First Principles Atomistic Model for Carbon-Doped Boron Suboxide Amol B Rahane Dr Vijay Kumar Foundation 1969 Sector 4 Gurgaon...Final 3. DATES COVERED (From - To) October 2013–July 2014 4. TITLE AND SUBTITLE First Principles Atomistic Model for Carbon-Doped Boron Suboxide

  10. 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.

  11. First principles study of hydroxyapatite surface

    NASA Astrophysics Data System (ADS)

    Slepko, Alexander; Demkov, Alexander A.

    2013-07-01

    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), 10.1088/0953-8984/23/6/065302].

  12. 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)].

  13. 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.

  14. 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.

  15. Designing Interactive Learning Environments: An Approach from First Principles

    ERIC Educational Resources Information Center

    Scott, Bernard; Cong, Chunyu

    2007-01-01

    Purpose: Today's technology supports the design of more and more sophisticated interactive learning environments. This paper aims to argue that such design should develop from first principles. Design/methodology/approach: In the paper by first principles is meant: learning theory and principles of course design. These principles are briefly…

  16. Theoretical Study of the Vibrational Spectroscopy of the Ethyl Radical

    NASA Astrophysics Data System (ADS)

    Tabor, Daniel P.; Sibert, Edwin. L. Sibert, Iii

    2013-06-01

    The rich spectroscopy of the ethyl radical has attracted the attention of several experimental and theoretical investigations. The purpose of these studies was to elucidate the signatures of hyperconjugation, torsion, inversion, and Fermi coupling in the molecular spectra. Due to the number of degrees of freedom in the system, previous theoretical studies have implemented reduced-dimensional models. Our ultimate goal is a full-dimensional theoretical treatment of the vibrations using both Van Vleck and variational approaches. The methods will be combined with the potential that we have calculated using the CCSD(T) method on the cc-pVTZ basis set. In this talk we will discuss our initial work, which builds up from these reduced-dimensional models. Our calculations use coordinates that exploit the system's G_{12} PI symmetry in a simple fashion. By systematically adding more degrees of freedom to our model, we can determine the effects of specific couplings on the spectroscopy. T. Häber, A. C. Blair, D. J. Nesbitt and M. D. Schuder J. Chem. Phys. {124}, 054316, (2006). G .E. Douberly, unpublished. R. S. Bhatta, A. Gao and D. S. Perry J. Mol. Struct.: THEOCHEM {941}, 22, (2010).

  17. Transport in Molecular Devices from First Principles

    NASA Astrophysics Data System (ADS)

    di Ventra, Massimiliano

    2000-03-01

    The simulation of transport properties of Si-based devices has relied on the Boltzmann's equation within a semiclassical framework. When the device dimensions are those of single molecules, however, quantum mechanical simulations are necessary. In particular, it is of fundamental importance to address the following questions: i) are the transport properties of molecular devices dependent only on the molecules electronic structure? ii) Do the contacts play any role? And if so, can we tailor ``better'' contacts? iii) How atoms rearrange when current flows into the device? Can we predict the largest bias at which the device fails to operate? In order to answer all these questions we developed a fully ab initio approach that combines the solution of the Lippman-Schwinger equation[1] with a Hellmann-Feynman-like theorem that applies to steady-state current conditions to calculate forces on atoms.[2] We applied the approach to the study of the transport properties of the benzene-1,4-dithiolate molecule between gold electrodes for which experimental data are available.[3] The theoretical I-V curve has the same overall shape as the experimental curve -- reflecting the electronic structure of the molecule in the presence of the electric field -- but the absolute value of the current is very sensitive to contact chemistry and geometry.[4] In particular the presence of a single gold atom between the molecule and the electrode surface reduces the conductance by more than an order of magnitude. Replacement of the single gold atom by an aluminum atom, whose p orbitals couple more effectively to the molecule's orbitals, increases the conductance by about an order of magnitude. We have also studied the polarization effects induced by a third terminal (gate) on the I-V characteristics of the above device. In particular, we have found that current gain due to the gate bias can be achieved at reasonable gate fields. Finally, we have found that the molecule twists around the axis

  18. First principles study of O defects in CdSe

    NASA Astrophysics Data System (ADS)

    T-Thienprasert, J.; Limpijumnong, S.; Du, M.-H.; Singh, D. J.

    2012-08-01

    Recently, the vibrational signatures related to oxygen defects in oxygen-doped CdSe were measured using ultrahigh resolution Fourier transform infrared (FTIR) spectroscopy by Chen et al.(2008) [1]. They observed two absorption bands centered at ∼1991.77 and 2001.3 cm-1, which they attributed to the LVMs of OCd, in the samples grown with the addition of CdO and excess Se. For the samples claimed to be grown with even more excess Se, three high-frequency modes (1094.11, 1107.45, and 1126.33) were observed and assigned to the LVMs of OSe-VCd complex. In this work, we explicitly calculated the vibrational signatures of OCd and OSe-VCd complex defects based on first principles approach. The calculated vibrational frequencies of OCd and OSe-VCd complex are inconsistent with the frequencies observed by Chen et al., indicating that their observed frequencies are from other defects. Potential defects that could explain the experimentally observed modes are suggested.

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

    SciTech Connect

    Lee, Yongbin

    2004-01-01

    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 AlMgB14.

  20. 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.

  1. 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.

  2. 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.

  3. First Principles Structure Calculations Using the General Potential Lapw Method

    NASA Astrophysics Data System (ADS)

    Wei, Su-Huai

    We have developed a completely general first principles self-consistent full-potential linearized-augmented-plane -wave (LAPW) method program within the density functional formalism to calculate electronic band structure, total energy, pressure and other quantities. No symmetry assumptions are used for the crystal structure. Shape unrestricted charge densities and potentials are calculated inside muffin -tin (MT) spheres as well as in the interstitial regions. All contributions to the Hamiltonian matrix elements are completely taken into account. The core states are treated fully relativistically using the spherical part of the potential only. Scalar relativistic effects are included for the band-states, and spin-orbit coupling is included using a second variation procedure. Both core states and valence states are treated self-consistently, the frozen core approximation is not required. The fast Fourier transformation method is used wherever it is applicable, and this greatly improves the efficiency. This state-of-the-art program has been tested extensively to check the accuracy and convergence properties by comparing calculated electronic band structures, ground state properties, equations of state and cohesive energies for bulk W and GaAs with other theoretical calculations and experimental results. It has been successfully applied to calculate and predict structural and metal-insulator phase transitions for close-packed crystal BaSe and BaTe and the geometric structure of the d-band metal W(001) surface. The results are in generally good agreement with experiment.

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

    PubMed

    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.

  5. First-principles structural design of superhard materials.

    PubMed

    Zhang, Xinxin; Wang, Yanchao; Lv, Jian; Zhu, Chunye; Li, Qian; Zhang, Miao; Li, Quan; Ma, Yanming

    2013-03-21

    We reported a developed methodology to design superhard materials for given chemical systems under external conditions (here, pressure). The new approach is based on the CALYPSO algorithm and requires only the chemical compositions to predict the hardness vs. energy map, from which the energetically preferable superhard structures are readily accessible. In contrast to the traditional ground state structure prediction method where the total energy was solely used as the fitness function, here we adopted hardness as the fitness function in combination with the first-principles calculation to construct the hardness vs. energy map by seeking a proper balance between hardness and energy for a better mechanical description of given chemical systems. To allow a universal calculation on the hardness for the predicted structure, we have improved the earlier hardness model based on bond strength by applying the Laplacian matrix to account for the highly anisotropic and molecular systems. We benchmarked our approach in typical superhard systems, such as elemental carbon, binary B-N, and ternary B-C-N compounds. Nearly all the experimentally known and most of the earlier theoretical superhard structures have been successfully reproduced. The results suggested that our approach is reliable and can be widely applied into design of new superhard materials.

  6. 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.

  7. Theoretical model of blood flow measurement by diffuse correlation spectroscopy

    NASA Astrophysics Data System (ADS)

    Sakadžić, Sava; Boas, David A.; Carp, Stefan

    2017-02-01

    Diffuse correlation spectroscopy (DCS) is a noninvasive method to quantify tissue perfusion from measurements of the intensity temporal autocorrelation function of diffusely scattered light. However, DCS autocorrelation function measurements in tissue better match theoretical predictions based on the diffusive motion of the scatterers than those based on a model where the advective nature of blood flow dominates the stochastic properties of the scattered light. We have recently shown using Monte Carlo (MC) simulations and assuming a simplistic vascular geometry and laminar flow profile that the diffusive nature of the DCS autocorrelation function decay is likely a result of the shear-induced diffusion of the red blood cells. Here, we provide theoretical derivations supporting and generalizing the previous MC results. Based on the theory of diffusing-wave spectroscopy, we derive an expression for the autocorrelation function along the photon path through a vessel that takes into account both diffusive and advective scatterer motion, and we provide the solution for the DCS autocorrelation function in a semi-infinite geometry. We also derive the correlation diffusion and correlation transfer equation, which can be applied for an arbitrary sample geometry. Further, we propose a method to take into account realistic vascular morphology and flow profile.

  8. 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.

  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. Prediction on technetium triboride from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Miao, Xiaojia; Xing, Wandong; Meng, Fanyan; Yu, Rong

    2017-02-01

    Taking the Tc-B binary system as an example, here we report the first-principles prediction on new phases of technetium borides, TcB3, which has an unprecedented stoichiometry. Crystal structures, phase stability, electronic properties and mechanical properties of TcB3 have been investigated using first-principles calculations. The hexagonal P 6 bar m 2 structure (No.187) TcB3 with a high value of hardness (29 GPa) is energetically stable against decomposition into other compounds under pressures above 4 GPa, indicating that TcB3 can be synthesized above this pressure.

  11. X-ray magnetic circular dichroism in Co2FeGa: First-principles calculations

    NASA Astrophysics Data System (ADS)

    Kukusta, D. A.; Antonov, V. N.; Yaresko, A. N.

    2011-08-01

    The electronic structure and x-ray magnetic circular dichroism (XMCD) spectra of the Heusler alloy Co2FeGa were investigated theoretically from first principles, using the fully relativistic Dirac linear MT-orbital (LMTO) band structure method. Densities of valence states, orbital and spin magnetic moments are analyzed and discussed. The origin of the XMCD spectra in the Co2FeGa compound is examined. The calculated results are compared with available experimental data.

  12. Fermions in d = 1 + 2 dimensions from first principles

    SciTech Connect

    Carrillo-Ruiz, Ma. Georgina; Napsuciale, Mauro

    2006-09-25

    In this work we construct states describing planar electrons ('spin' (1/2) particles with well defined parity) in d = 1 + 2 from first principles and show that they satisfy Dirac equation, which turns out to be the covariant form of the eigenvalue equation for spatial inversion (parity) just like in d = 1 + 3.

  13. 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.

  14. 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.

  15. 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

  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. 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.

  18. 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.

  19. 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.

  20. First-principles modeling of electrostatically doped perovskite systems.

    PubMed

    Stengel, Massimiliano

    2011-04-01

    Macroscopically, confined electron gases at polar oxide interfaces are rationalized within the simple "polar catastrophe" model. At the microscopic level, however, many other effects such as electric fields, structural distortions and quantum-mechanical interactions enter into play. Here, we show how to bridge the gap between these two length scales, by combining the accuracy of first-principles methods with the conceptual simplicity of model Hamiltonian approaches. To demonstrate our strategy, we address the equilibrium distribution of the compensating free carriers at polar LaAlO(3)/SrTiO(3) interfaces. Remarkably, a model including only calculated bulk properties of SrTiO(3) and no adjustable parameters accurately reproduces our full first-principles results. Our strategy provides a unified description of charge compensation mechanisms in SrTiO(3)-based systems.

  1. First-principles quantum chemistry in the life sciences.

    PubMed

    van Mourik, Tanja

    2004-12-15

    The area of computational quantum chemistry, which applies the principles of quantum mechanics to molecular and condensed systems, has developed drastically over the last decades, due to both increased computer power and the efficient implementation of quantum chemical methods in readily available computer programs. Because of this, accurate computational techniques can now be applied to much larger systems than before, bringing the area of biochemistry within the scope of electronic-structure quantum chemical methods. The rapid pace of progress of quantum chemistry makes it a very exciting research field; calculations that are too computationally expensive today may be feasible in a few months' time! This article reviews the current application of 'first-principles' quantum chemistry in biochemical and life sciences research, and discusses its future potential. The current capability of first-principles quantum chemistry is illustrated in a brief examination of computational studies on neurotransmitters, helical peptides, and DNA complexes.

  2. Predictions of the Properties of Water from First Principles

    NASA Astrophysics Data System (ADS)

    Bukowski, Robert; Szalewicz, Krzysztof; Groenenboom, Gerrit C.; van der Avoird, Ad

    2007-03-01

    A force field for water has been developed entirely from first principles, without any fitting to experimental data. It contains both pairwise and many-body interactions. This force field predicts the properties of the water dimer and of liquid water in excellent agreement with experiments, a previously elusive objective. Precise knowledge of the intermolecular interactions in water will facilitate a better understanding of this ubiquitous substance.

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

    DOE PAGES

    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

  4. 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.

  5. Angle-resolved photoemission and first-principles studies of topological thin films

    NASA Astrophysics Data System (ADS)

    Bian, Guang

    Topological insulators are electronic materials that have a bulk band gap like an ordinary insulator but have protected conducting states on their edge or surface. The exotic electronic properties of topological materials are of great interest for spin-related electronics and quantum computation. In this thesis research, the combination of angleresolved photoemission spectroscopy (ARPES) and first principles calculation is used to examine the electronic properties of topological thin films and 2D electronic systems with large spin-orbit splitting. The topological thin films are prepared in situ by molecular beam epitaxy (MBE) method and characterized by experimental tools such as reflection high-energy electron diffraction (RHEED) and low energy electron diffraction (LEED). The systems investigated in this thesis include topological Sb, Bi2Te3, Be2Se 3 thin films, Bi films, and Bi/Ag surface alloy. Topological Sb films have been successfully fabricated on Si(111) substrates. By examining the connection pattern between surface states and the quantum well bulk states, our photoemission spectra show clearly the topological order of the Sb films. When topological films become ultrathin, the quantum tunneling effect breaks the degeneracy at the Dirac point of the topological surface bands, resulting in a gap. Our ARPES mapping of the surface band structure of a 4-BL Sb film reveals no energy gap at the Dirac point. This lack of tunneling gap can be explained by a strong interfacial bonding between the film and the substrate. The topological order of topological materials is a robust quantity, but the topological surface states themselves can be highly sensitive to the boundary conditions. Specifically, the surface states of Bi2Se3 and Bi2Te3 form a single Dirac cone at the zone center. Our first-principles calculations based on a slab geometry show that, upon hydrogen termination of either face of the slab, the Dirac cone associated with this face is replaced by three

  6. 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.

  7. Value of first principles and phenomenological modeling in mineral processing

    SciTech Connect

    Concha, F.

    1995-12-31

    There is confusion in naming the several models developed in Mineral Processing. The authors often hear of empirical, first principle, mechanistic and phenomenological models. The objective of this paper is to clarify and distinguish between these models, based on a philosophical and linguistic analysis. A state of the art review for mathematical modeling in Mineral Processing is also made. The advantage of considering Mineral Processing as a series of unit operations was recognized by Gaudin a long time ago. He divided the area into four unit operations: (1) comminution, (2) classification, (3) concentration and (4) dewatering.

  8. Transition metal doped arsenene: A first-principles study

    NASA Astrophysics Data System (ADS)

    Sun, Minglei; Wang, Sake; Du, Yanhui; Yu, Jin; Tang, Wencheng

    2016-12-01

    Using first-principles calculations, we investigate the structural, electronic, and magnetic properties of 3d transition metal (TM) atoms substitutional doping of an arsenene monolayer. Based on the binding energy, the TM-substituted arsenene systems were found to be robust. Magnetic states were obtained for Ti, V, Cr, Mn and Fe doping. More importantly, a half-metallic state resulted from Ti and Mn doping, while the spin-polarized semiconducting state occurred with V, Cr and Fe doping. Our studies demonstrated the potential applications of TM-substituted arsenene for spintronics and magnetic storage devices.

  9. First-principles study of Frenkel pair recombination in tungsten

    NASA Astrophysics Data System (ADS)

    Qin, Shi-Yao; Jin, Shuo; Li, Yu-Hao; Zhou, Hong-Bo; Zhang, Ying; Lu, Guang-Hong

    2017-02-01

    The recombination of one Frenkel pair in tungsten has been investigated through first-principles simulation. Two different recombination types have been identified: instantaneous and thermally activated. The small recombination barriers for thermally activated recombination cases indicate that recombination can occur easily with a slightly increased temperature. For both of the two recombination types, recombination occurs through the self-interstitial atom moving towards the vacancy. The recombination process can be direct or through replacement sequences, depending on the vertical distance between the vacancy and the <1 1 1> line of self-interstitial atom pair.

  10. 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.

  11. 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.

  12. Hardness of covalent and ionic crystals: first-principle calculations.

    PubMed

    Simůnek, Antonín; Vackár, Jirí

    2006-03-03

    A new concept, the strength of bond, and a new form expressing the hardness of covalent and ionic crystals are presented. Hardness is expressed by means of quantities inherently coupled to the atomistic structure of matter, and, therefore, hardness can be determined by first-principles calculations. Good agreement between theory and experiment is observed in the range of 2 orders of magnitude. It is shown that a lower coordination number of atoms results in higher hardness, contrary to common opinion presented in general literature.

  13. First-Principles Calculation of forces and phonons in solid

    NASA Astrophysics Data System (ADS)

    Ning, Zhenhua; Shelton, William

    We have developed a multiple scattering theory approach to calculate Hellmann-Feynman forces and phonons via the calculation of the force constant and dynamical matrix. To demonstrate the accuracy and validity of our approach we compare with the ELK code, which is a full potential Linear Augmented Plane Wave (FLAPW) based method. As we will show our forces and phonon dispersion curves are in good agreement with the FLAPW code. This work lays the foundation for developing a first principles approach for calculation of phonons in substitutionally disordered materials.

  14. 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.

  15. Error propagation in first-principles kinetic Monte Carlo simulation

    NASA Astrophysics Data System (ADS)

    Döpking, Sandra; Matera, Sebastian

    2017-04-01

    First-principles kinetic Monte Carlo models allow for the modeling of catalytic surfaces with predictive quality. This comes at the price of non-negligible errors induced by the underlying approximate density functional calculation. On the example of CO oxidation on RuO2(110), we demonstrate a novel, efficient approach to global sensitivity analysis, with which we address the error propagation in these multiscale models. We find, that we can still derive the most important atomistic factors for reactivity, albeit the errors in the simulation results are sizable. The presented approach might also be applied in the hierarchical model construction or computational catalyst screening.

  16. First-principles study of blue silicate phosphors.

    PubMed

    Ishida, M; Imanari, Y; Isobe, T; Kuze, S; Ezuhara, T; Umeda, T; Ohno, K; Miyazaki, S

    2010-09-29

    First-principles calculations were performed to investigate the optical property of blue silicate phosphor, CMS:Eu. The optical absorption property is discussed based on electronic band structure and density of states. Our calculation results indicate that hybridization of the wavefunction plays an important role for nonradiative migration of electrons and holes. The calculated optical absorption spectrum could reproduce the optical features of the experimental excitation spectrum. It is also demonstrated that a practical approach using computational materials screening is effective in phosphor materials development.

  17. Investigation of segregation of silver at copper grain boundaries by first principles and empirical potential calculations

    NASA Astrophysics Data System (ADS)

    Kiyohara, Shin; Mizoguchi, Teruyasu

    2016-08-01

    Segregation of silver at copper grain boundaries was investigated using theoretical calculations. Empirical potentials for copper-silver alloys were generated to systematically investigate the segregation. The segregation energies of the [001]-axis symmetric tilt Σ5 (210) and Σ25 (430) grain boundaries were calculated, and the most stable segregation sites for silver at these copper grain boundaries were determined. The generated empirical potential was validated by comparing it with that obtained from the first principles calculation. The segregation of silver at copper grain boundaries strongly depends on the open space at the segregation site.

  18. Arsenene as a promising candidate for NO and NO2 sensor: A first-principles study

    NASA Astrophysics Data System (ADS)

    Liu, Can; Liu, Chun-Sheng; Yan, Xiaohong

    2017-03-01

    Based on first-principles calculations, we have studied the adsorption of CO, CO2, N2, NH3, NO and NO2 molecules on the pristine arsenene monolayer. These gas molecules are held by an interaction that is intermediate between the physisorbed and chemisorbed states. Furthermore, the adsorption of NO and NO2 can produce a noticeable modifications of the density of states near the Fermi level. Interestingly, only the adsorption of NO and NO2 can lead to a magnetic moment of 1 μB. Therefore, our results can provide a theoretical basis for the potential applications of arsenene monolayer in gas sensing with electrical and magnetic methods.

  19. Formation and Annealing Behaviors of Qubit Centers in 4H-SiC from First Principles

    NASA Astrophysics Data System (ADS)

    Zhao, Mingwen; Wang, Xiaopeng; Bu, Hongxia; Zhang, Hongyu; He, Xiujie; Wang, Aizhu; Mingwen Zhao's Lab in Shandong University Team

    Inspired by finding that the nitrogen-vacancy center in diamond is a qubit candidate, similar defects in silicon carbide 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.

  20. First-principles investigations for the catalytic dissociation and oxidation of methane on the Cu surfaces

    NASA Astrophysics Data System (ADS)

    Li, Ying; Mahadevan, Jagan; Wang, Sanwu

    2010-03-01

    The catalytic reactions of dissociation and oxidation of methane on the copper surfaces play a key role in, for example, the development of high-performance solid oxide fuel cells. We used first-principles quantum theory and large-scale parallel calculations to investigate the atomic-scale mechanism of the catalytic chemical reactions. We report the calculated results, which provide fundamental information and understanding about the atomic-scale dynamics and electronic structures pertinent to the reactions and specifically the catalytic role of the Cu(100) and Cu(111) surfaces. We also report comparison of our results with available experimental data and previous theoretical investigations.

  1. Efficient first-principles simulation of noncontact atomic force microscopy for structural analysis.

    PubMed

    Chan, T-L; Wang, C Z; Ho, K M; Chelikowsky, James R

    2009-05-01

    We propose an efficient scheme to simulate noncontact atomic force microscopy images by using first-principles self-consistent potential from the sample as input without explicit modeling of the atomic force microscopy tip. Our method is applied to various types of semiconductor surfaces including Si(111)-(7x7), TiO2(110)-(1x1), Ag/Si(111)-(sqrt[3]xsqrt[3])R30 degrees, and Ge/Si(105)-(1x2) surfaces. We obtain good agreement with experimental results and previous theoretical studies, and our method can aid in identifying different structural models for surface reconstruction.

  2. First-Principles Simulations of Armchair-Edge Graphene Nanostrips.

    NASA Astrophysics Data System (ADS)

    Li, Junwen; Mintmire, John W.; Gunlycke, Daniel; White, Carter T.

    2007-03-01

    We have carried out a series of first-principles, local-density functional band structure calculations of finite-width graphene nanostrips with armchair edges. A simple nearest-neighbor tight-binding model predicts that the band structures of these materials should be directly related to those of zigzag single wall carbon nanotubes, with two-thirds of the structures being small gap semiconductors and one-third of the structures being zero gap systems. The band gap in the semiconducting strips would be expected to decrease monotonically with increasing strip width. In our first-principles results, we find that in addition to the zero gap systems becoming finite gap quasimetallic systems because of symmetry breaking (as in the single-walled nanotubes), we also find that the semiconducting strips split into two families with band gaps that deviate from the simple nearest-neighbor tight binding model. Within the framework of our computational results, we compare the band structures of graphene, single-walled nanotubes, graphene nanostrips, and other carbon nanostructures. This work was supported by the US Office of Naval Research and the DoD HPCMO CHSSI program, both directly and through the US Naval Research Laboratory.

  3. First principles calculations of La2CuO4

    NASA Astrophysics Data System (ADS)

    Plamada, Andrei; Kozhevnikov, Anton; Haehner, Urs; Jiang, Mi; Staar, Peter; Maier, Thomas; Schulthess, Thomas

    We use the DFT+DCA method for a high-end study of the electronic structure properties of La2CuO4. The parameters of a tight-binding model are created using the first-principles electronic structure calculations. The all-electron full-potential linearised augmented plane-wave method is used to solve the non-interacting band problem. Then the set of physically relevant Wannier functions is chosen as a basis for the underlying Hubbard model. The Wannier functions and the corresponding non-interacting Hamiltonian Hnm0 (k) are created using the well-established downfolding approach. The screened Coulomb interaction parameters Unm of the model are computed using the constrained random-phase approximation technique. The double counting term is assumed to be a constant multiplied by the identity operator in the correlated subspace and it is determined based on first-principles considerations. The resulting ab-initio parameterisation of the Hubbard model is solved within dynamical cluster approximation (DCA).

  4. First-principles calculations for initial electronic excitation in dielectrics induced by intense femtosecond laser pulses

    NASA Astrophysics Data System (ADS)

    Sato, Shunsuke A.; Yabana, Kazuhiro

    2016-12-01

    Laser-induced damage of SiO2 (α-quartz) is investigated by first-principles calculations. The calculations are based on a coupled theoretical framework of the time-dependent density functional theory and Maxwell equation to describe strongly-nonlinear laser-solid interactions. We simulate irradiation of the bulk SiO2 with femtosecond laser pulses and compute energy deposition from the laser pulse to electrons as a function of the distance from the surface. We further analyze profiles of laser-induced craters, comparing the transferred energy with the cohesive energy of SiO2. The theoretical crater profile well reproduces the experimental features for a relatively weak laser pulse. In contrast, the theoretical result fails to reproduce the measured profiles for a strong laser pulse. This fact indicates a significance of the subsequent atomic motions that take place after the energy transfer ends for the formation of the crater under the strong laser irradiation.

  5. 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

  6. First principles nuclear magnetic resonance signatures of graphene oxide.

    PubMed

    Lu, Ning; Huang, Ying; Li, Hai-bei; Li, Zhenyu; Yang, Jinlong

    2010-07-21

    Nuclear magnetic resonance (NMR) has been widely used in graphene oxide (GO) structure studies. However, the detailed relationship between its spectroscopic features and the GO structural configuration remains elusive. Based on first principles (13)C chemical shift calculations using the gauge including projector augmented waves method, we provide a reliable spectrum-structure connection. The (13)C chemical shift in GO is found to be very sensitive to the atomic environment, even for the same type of oxidation groups. Factors determining the chemical shifts of epoxy and hydroxy groups have been discussed. GO structures previously reported in the literature have been checked from the NMR point of view. The energetically favorable hydroxy chain structure is not expected to be widely existed in real GO samples according to our NMR simulations. The epoxy pair species we proposed previously is also supported by chemical shift calculations.

  7. First principles nuclear magnetic resonance signatures of graphene oxide

    NASA Astrophysics Data System (ADS)

    Lu, Ning; Huang, Ying; Li, Hai-bei; Li, Zhenyu; Yang, Jinlong

    2010-07-01

    Nuclear magnetic resonance (NMR) has been widely used in graphene oxide (GO) structure studies. However, the detailed relationship between its spectroscopic features and the GO structural configuration remains elusive. Based on first principles C13 chemical shift calculations using the gauge including projector augmented waves method, we provide a reliable spectrum-structure connection. The C13 chemical shift in GO is found to be very sensitive to the atomic environment, even for the same type of oxidation groups. Factors determining the chemical shifts of epoxy and hydroxy groups have been discussed. GO structures previously reported in the literature have been checked from the NMR point of view. The energetically favorable hydroxy chain structure is not expected to be widely existed in real GO samples according to our NMR simulations. The epoxy pair species we proposed previously is also supported by chemical shift calculations.

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

    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.

  9. 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.

  10. First principle study of manganese doped cadmium sulphide sheet

    SciTech Connect

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

    2014-04-24

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

  11. 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.

  12. 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.

  13. 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).

  14. 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.

  15. First-principles studies of native defects in olivine phosphates

    NASA Astrophysics Data System (ADS)

    Hoang, Khang; Johannes, Michelle

    2011-03-01

    Olivine phosphates Li M PO4 (M = Mn, Fe, Co, Ni) are promising candidates for rechargeable Li-ion battery electrodes because of their energy storage capacity and electrochemical and thermal stability. It is known that native defects have strong effects on the performance of olivine phosphates. Yet, the formation and migration of these defects are not fully understood, and we expect that once such understanding has been established, one can envisage a solution for improving the materials' performance. In this talk, we present our first-principles density-functional theory studies of native point defects and defect complexes in Li M PO4 , and discuss the implications of these defects on the performance of the materials. Our results also provide guidelines for obtaining different native defects in experiments.

  16. 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.

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

    DOE PAGES

    Lovato, A.; Gandolfi, S.; Carlson, J.; ...

    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

  18. Vibrational and thermophysical properties of PETN from first principles

    NASA Astrophysics Data System (ADS)

    Gonzalez, Joseph M.; Landerville, Aaron C.; Oleynik, Ivan I.

    2017-01-01

    Thermophysical properties are urgently sought as input for meso- and continuum-scale modeling of energetic materials (EMs). However, experimental data are often limited as they cover a narrow region of 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 PVT equation of state, heat capacities, and coefficients of thermal expansion for pentaerythritol tetranitrate (PETN) using first-principles density functional theory, which includes proper description of van der Waals interactions, zero-point energy and thermal contributions to free energy calculated using the quasi-harmonic approximation. Further, we investigate the evolution of the vibration spectrum of PETN as a function of pressure.

  19. 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.

  20. Thermoelectric properties of titanium dioxide polymorphs from first principles

    NASA Astrophysics Data System (ADS)

    Bayerl, Dylan; Kioupakis, Emmanouil

    2014-03-01

    Titanium oxides are promising materials for high-temperature thermoelectrics because of their high Seebeck coefficients, thermal stability, and natural abundance. We use first-principles calculations to investigate the thermoelectric transport properties of several titanium dioxide polymorphs. Our methodology is based on density functional and many-body perturbation theory within the GW approximation. The maximally localized Wannier function method is employed to interpolate the GW bands in the Brillouin zone. We use the Boltzmann transport formalism within the constant relaxation time approximation to determine the temperature and carrier-density dependence of the Seebeck coefficient, electron mobility, and electron thermal conductivity from the calculated electronic band structures. We demonstrate agreement with experimentally measured transport parameters and enhanced power factor at high temperature in certain heavily doped phases. This research was supported as part of CSTEC, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science. Computational resources were provided by the DOE NERSC facility.

  1. First-principles study of high explosive decomposition energetics

    SciTech Connect

    Wu, C J

    1998-08-21

    The mechanism of the gas phase unimolecular decomposition of hexahydro-1,3,5,- trinitro- 1,3,5,-triazine (RDX) has been investigated using first principles gradient corrected density functional theory. Our results show that the dominant reaction channel is the N-NO* bond rupture, which has a barrier of 34.2 kcal/mol at the B- PW9 l/cc-pVDZ level and is 18.3 kcal/mol lower than that of the concerted ring fission to three methylenenitramine molecules. In addition, we have carried out a systematic study of homolytic bond dissociation energies of 14 other high explosives at the B-PW91/D95V level. We find that the correlation between the weakest bond strength and high explosive sensitivity is strong

  2. First-principles study on superconductivity of solid oxygen

    NASA Astrophysics Data System (ADS)

    Ishikawa, Takahiro; Mukai, Kenta; Shimizu, Katsuya

    2012-12-01

    The superconductivity of solid oxygen in ζ phase was investigated by first-principles calculations based on the density functional theory. Using a monoclinic C2/m structure, we calculated the superconducting transition temperature by the Allen-Dynes formula and obtained 2.4 K at 100 GPa for the effective screened Coulomb repulsion constant μ* of 0.13. The transition temperature slowly decreases with increasing pressure and becomes 1.3 K at 200 GPa. The phonon analysis shows that the electron-phonon coupling is dominantly enhanced by the intermolecular vibrations of O2 rather than the intramolecular ones. The phonon modes showing the strong electron-phonon coupling were found to be concentrated in the phonon frequency range of 100-150 cm-1 at around the M-point in the Brillouin zone.

  3. 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.

  4. Photoelectron Spectra of Aqueous Solutions from First Principles

    SciTech Connect

    Gaiduk, Alex P.; Govoni, Marco; Seidel, Robert; Skone, Jonathan H.; Winter, Bernd; Galli, Giulia

    2016-06-08

    We present a combined computational and experimental study of the photoelectron spectrum of a simple aqueous solution of NaCl. Measurements were conducted on microjets, and first-principles calculations were performed using hybrid functionals and many-body perturbation theory at the G0W0 level, starting with wave functions computed in ab initio molecular dynamics simulations. We show excellent agreement between theory and experiments for the positions of both the solute and solvent excitation energies on an absolute energy scale and for peak intensities. The best comparison was obtained using wave functions obtained with dielectric-dependent self-consistent and range-separated hybrid functionals. Our computational protocol opens the way to accurate, predictive calculations of the electronic properties of electrolytes, of interest to a variety of energy problems.

  5. First-principles calculations of PuO(2+/-x).

    PubMed

    Petit, L; Svane, A; Szotek, Z; Temmerman, W M

    2003-07-25

    The electronic structure of PuO(2+/-x) was studied using first-principles quantum mechanics, realized with the self-interaction corrected local spin density method. In the stoichiometric PuO2 compound, Pu occurs in the Pu(IV) oxidation state, corresponding to a localized f4 shell. If oxygen is introduced onto the octahedral interstitial site, the nearby Pu atoms turn into Pu(V) (f3) by transferring electrons to the oxygen. Oxygen vacancies cause Pu(III) (f5) to form by taking up electrons released by oxygen. At T = 0, the PuO2 compound is stable with respect to free oxygen, but the delicate energy balance suggests the possible deterioration of the material during long-term storage.

  6. Accurate first principles model potentials for intermolecular interactions.

    PubMed

    Gordon, Mark S; Smith, Quentin A; Xu, Peng; Slipchenko, Lyudmila V

    2013-01-01

    The general effective fragment potential (EFP) method provides model potentials for any molecule that is derived from first principles, with no empirically fitted parameters. The EFP method has been interfaced with most currently used ab initio single-reference and multireference quantum mechanics (QM) methods, ranging from Hartree-Fock and coupled cluster theory to multireference perturbation theory. The most recent innovations in the EFP model have been to make the computationally expensive charge transfer term much more efficient and to interface the general EFP dispersion and exchange repulsion interactions with QM methods. Following a summary of the method and its implementation in generally available computer programs, these most recent new developments are discussed.

  7. First principle study of manganese doped cadmium sulphide sheet

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

    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 μB 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.

  8. Elastic and piezoresistive properties of nickel carbides from first principles

    NASA Astrophysics Data System (ADS)

    Kelling, Jeffrey; Zahn, Peter; Schuster, Jörg; Gemming, Sibylle

    2017-01-01

    The nickel-carbon system has received increased attention over the past years due to the relevance of nickel as a catalyst for carbon nanotube and graphene growth, where nickel carbide intermediates may be involved or carbide interface layers form in the end. Nickel-carbon composite thin films comprising Ni3C are especially interesting in mechanical sensing applications. Due to the metastability of nickel carbides, formation conditions and the coupling between mechanical and electrical properties are not yet well understood. Using first-principles electronic structure methods, we calculated the elastic properties of Ni3C ,Ni2C , and NiC , as well as changes in electronic properties under mechanical strain. We observe that the electronic density of states around the Fermi level does not change under the considered strains of up to 1%, which correspond to stresses up to 3 GPa . Relative changes in conductivity of Ni3C range up to maximum values of about 10%.

  9. First-principles study of fluorination of L-Alanine

    NASA Astrophysics Data System (ADS)

    Sreepad, H. R.; Ravi, H. R.; Ahmed, Khaleel; Dayananda, H. M.; Umakanth, K.; Manohara, B. M.

    2013-02-01

    First-principles calculations based on Density Functional Theory have been done on effect of fluorination of an important amino acid - L-Alanine. Its structure has been simulated. The unit cell is orthorhombic with lattice parameters a=5.90Å, b=13.85Å and c=5.75Å with volume 470 (Å)3. Bond lengths and bond angles have been estimated. Electronic Density of States calculations show that the material has a band gap of 4.47eV. Electronic band structure indicates that the material can be effectively used for NLO applications. The electronic contribution to the dielectric constant has been calculated and its average value comes out to be 2.165.

  10. Liquid-state paramagnetic relaxation from first principles

    NASA Astrophysics Data System (ADS)

    Rantaharju, Jyrki; Vaara, Juha

    2016-10-01

    We simulate nuclear and electron spin relaxation rates in a paramagnetic system from first principles. Sampling a molecular dynamics trajectory with quantum-chemical calculations produces a time series of the instantaneous parameters of the relevant spin Hamiltonian. The Hamiltonians are, in turn, used to numerically solve the Liouville-von Neumann equation for the time evolution of the spin density matrix. We demonstrate the approach by studying the aqueous solution of the Ni2 + ion. Taking advantage of Kubo's theory, the spin-lattice (T1) and spin-spin (T2) relaxation rates are extracted from the simulations of the time dependence of the longitudinal and transverse magnetization, respectively. Good agreement with the available experimental data is obtained by the method.

  11. 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

  12. 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.

  13. First principles electrochemistry: Electrons and protons reacting as independent ions

    NASA Astrophysics Data System (ADS)

    Llano, Jorge; Eriksson, Leif A.

    2002-12-01

    We here present a first principles approach to calculate standard Gibbs energies and the corresponding observables (standard electrode potentials in the hydrogen scale ESHE0 and pKa values) of stoichiometric reactions involving electrons and/or protons as independent species in solution, from absolute electrochemical potentials defined according to quantum and statistical mechanics. In order to pass from the conventional electrodic and thermodynamic descriptions of electrochemistry to the first principles approach based on estimating absolute electrochemical potentials, we revisit the problem of the absolute and relative electrochemical scales from the macroscopic and microscopic viewpoints. A microscopic definition of the absolute electrochemical potential is presented in order to enable an identical thermodynamic treatment of any species in a given phase, i.e., electrons, protons, atoms, molecules, atomic and molecular ions, and electronically excited species. We show that absolute standard chemical potentials in the mole fraction scale can be easily computed with wave function and density functional theories in conjunction with self-consistent reaction field models. Based on Boltzmann and Fermi-Dirac statistics and experimental solvation data, we estimate an internally compatible set of absolute standard chemical and electrochemical potentials of protons and solvated electrons in the molality and molarity scales in aqueous solution at 298 K and 1 atm, within an absolute error of ±0.5 kcal/mol. This scheme enables a consistent and simultaneous description of the Gibbs energy changes and the observables (ESHE0 and pKa 's) of electron, proton, and proton-coupled electron transfer reactions in aqueous solution at 298 K and 1 atm.

  14. Emergent symmetries in atomic nuclei from first principles

    NASA Astrophysics Data System (ADS)

    Launey, K. D.; Dreyfuss, A. C.; Baker, R. B.; Draayer, J. P.; Dytrych, T.

    2015-04-01

    An innovative symmetry-guided approach and its applications to light and intermediate-mass nuclei is discussed. This approach, with Sp(3, R) the underpinning group, is based on our recent remarkable finding, namely, we have identified the symplectic Sp(3,R) as an approximate symmetry for low-energy nuclear dynamics. This study presents the results of two complementary studies, one that utilizes realistic nucleon-nucleon interactions and unveils symmetries inherent to nuclear dynamics from first principles (or ab initio), and another study, which selects important components of the nuclear interaction to explain the primary physics responsible for emergent phenomena, such as enhanced collectivity and alpha clusters. In particular, within this symmetry-guided framework, ab initio applications of the theory to light nuclei reveal the emergence of a simple orderly pattern from first principles. This provides a strategy for determining the nature of bound states of nuclei in terms of a relatively small fraction of the complete shell-model space, which, in turn, can be used to explore ultra-large model spaces for a description of alpha-cluster and highly deformed structures together with associated rotations. We find that by using only a fraction of the model space extended far beyond current no-core shell-model limits and a long-range interaction that respects the symmetries in play, the outcome reproduces characteristic features of the low-lying 0+ states in 12C (including the elusive Hoyle state of importance to astrophysics) and agrees with ab initio results in smaller spaces. For these states, we offer a novel perspective emerging out of no-core shell-model considerations, including a discussion of associated nuclear deformation, matter radii, and density distribution. The framework we find is also extensible beyond 12C, namely, to the low-lying 0+ states of 8Be as well as the ground-state rotational band of Ne, Mg, and Si isotopes.

  15. Fundamental limits on transparency: first-principles calculations of absorption

    NASA Astrophysics Data System (ADS)

    Peelaers, Hartwin

    2013-03-01

    Transparent conducting oxides (TCOs) are a technologically important class of materials with applications ranging from solar cells, displays, smart windows, and touch screens to light-emitting diodes. TCOs combine high conductivity, provided by a high concentration of electrons in the conduction band, with transparency in the visible region of the spectrum. The requirement of transparency is usually tied to the band gap being sufficiently large to prevent absorption of visible photons. This is a necessary but not sufficient condition: indeed, the high concentration of free carriers can also lead to optical absorption by excitation of electrons to higher conduction-band states. A fundamental understanding of the factors that limit transparency in TCOs is essential for further progress in materials and applications. The Drude theory is widely used, but it is phenomenological in nature and tends to work poorly at shorter wavelengths, where band-structure effects are important. First-principles calculations have been performed, but were limited to direct transitions; as we show in the present work, indirect transitions assisted by phonons or defects actually dominate. Our calculations are the first to address indirect free-carrier absorption in a TCO completely from first principles. We present results for SnO2, but the methodology is general and is also being applied to ZnO and In2O3. The calculations provide not just quantitative results but also deeper insights in the mechanisms that govern absorption processes in different wavelength regimes, which is essential for engineering improved materials to be used in more efficient devices. For SnO2, we find that absorption is modest in the visible, and much stronger in the ultraviolet and infrared. Work performed in collaboration with E. Kioupakis and C.G. Van de Walle, and supported by DOE, NSF, and BAEF.

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

    NASA Astrophysics Data System (ADS)

    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

    2014-01-01

    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.

  17. 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.

  18. Ti:sapphire - A theoretical assessment for its spectroscopy

    NASA Astrophysics Data System (ADS)

    Da Silva, A.; Boschetto, D.; Rax, J. M.; Chériaux, G.

    2017-03-01

    This article tries to theoretically compute the stimulated emission cross-sections when we know the oscillator strength of a broad material class (dielectric crystals hosting metal-transition impurity atoms). We apply the present approach to Ti:sapphire and check it by computing some emission cross-section curves for both π and σ polarizations. We also set a relationship between oscillator strength and radiative lifetime. Such an approach will allow future parametric studies for Ti:sapphire spectroscopic properties.

  19. Massively parallel first-principles simulation of electron dynamics in materials

    DOE PAGES

    Draeger, Erik W.; Andrade, Xavier; Gunnels, John A.; ...

    2017-03-04

    Here we present a highly scalable, parallel implementation of first-principles electron dynamics coupled with molecular dynamics (MD). By using optimized kernels, network topology aware communication, and by fully distributing all terms in the time-dependent Kohn–Sham equation, we demonstrate unprecedented time to solution for disordered aluminum systems of 2000 atoms (22,000 electrons) and 5400 atoms (59,400 electrons), with wall clock time as low as 7.5 s per MD time step. Despite a significant amount of non-local communication required in every iteration, we achieved excellent strong scaling and sustained performance on the Sequoia Blue Gene/Q supercomputer at LLNL. We obtained up tomore » 59% of the theoretical sustained peak performance on 16,384 nodes and performance of 8.75 Petaflop/s (43% of theoretical peak) on the full 98,304 node machine (1,572,864 cores). Lastly, scalable explicit electron dynamics allows for the study of phenomena beyond the reach of standard first-principles MD, in particular, materials subject to strong or rapid perturbations, such as pulsed electromagnetic radiation, particle irradiation, or strong electric currents.« less

  20. 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).

  1. Lattice dynamics and thermal conductivity of cesium chloride via first-principles investigation

    NASA Astrophysics Data System (ADS)

    He, Cui; Hu, Cui-E.; Zhang, Tian; Qi, Yuan-Yuan; Chen, Xiang-Rong

    2017-03-01

    The lattice thermal conductivity of CsCl crystal is theoretically investigated from a first-principles theoretical approach based on an iterative solution of the Boltzmann transport equation. Real-space finite-difference supercell approach is employed to generate the harmonic and anharmonic interatomic force constants. Phonon frequencies, velocities, and specific heat capacity as well as anharmonic properties are then obtained and applied to calculate the bulk thermal conductivity of CsCl crystal at the temperatures ranging from 20 K to 700 K. The calculated lattice thermal conductivity 1.14 W/mK of CsCl at room temperature agrees well with the experimental value, demonstrating that this parameter-free approach can provide a good description for the thermal transport of this material. The RTA and iterative solution of BTE are both presented. Our results show that both methods can obtain the thermal conductivity successfully.

  2. Revising Intramolecular Photoinduced Electron Transfer (PET) from First-Principles.

    PubMed

    Escudero, Daniel

    2016-09-20

    Photoinduced electron transfer (PET) plays relevant roles in many areas of chemistry, including charge separation processes in photovoltaics, natural and artificial photosynthesis, and photoluminescence sensors and switches. As in many other photochemical scenarios, the structural and energetic factors play relevant roles in determining the rates and efficiencies of PET and its competitive photodeactivation processes. Particularly, in the field of fluorescent sensors and switches, intramolecular PET is believed (in many cases without compelling experimental proof) to be responsible of the quench of fluorescence. There is an increasing experimental interest in fluorophore's molecular design and on achieving optimal excitation/emission spectra, excitation coefficients, and fluorescence quantum yields (importantly for bioimaging purposes), but less efforts are devoted to fundamental mechanistic studies. In this Account, I revise the origins of the fluorescence quenching in some of these systems with state-of-the-art quantum chemical tools. These studies go beyond the common strategy of analyzing frontier orbital energy diagrams and performing PET thermodynamics calculations. Instead, the potential energy surfaces (PESs) of the lowest-lying excited states are explored with time-dependent density functional theory (TD-DFT) and complete active space self-consistent field (CASSCF) calculations and the radiative and nonradiative decay rates from the involved excited states are computed from first-principles using a thermal vibration correlation function formalism. With such a strategy, this work reveals the real origins of the fluorescence quenching, herein entitled as dark-state quenching. Dark states (those that do not absorb or emit light) are often elusive to experiments and thus, computational investigations can provide novel insights into the actual photodeactivation mechanisms. The success of the dark-state quenching mechanism is demonstrated for a wide variety of

  3. 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

  4. Subsystem-based theoretical spectroscopy of biomolecules and biomolecular assemblies.

    PubMed

    Neugebauer, Johannes

    2009-12-21

    The absorption properties of chromophores in biomolecular systems are subject to several fine-tuning mechanisms. Specific interactions with the surrounding protein environment often lead to significant changes in the excitation energies, but bulk dielectric effects can also play an important role. Moreover, strong excitonic interactions can occur in systems with several chromophores at close distances. For interpretation purposes, it is often desirable to distinguish different types of environmental effects, such as geometrical, electrostatic, polarization, and response (or differential polarization) effects. Methods that can be applied for theoretical analyses of such effects are reviewed herein, ranging from continuum and point-charge models to explicit quantum chemical subsystem methods for environmental effects. Connections to physical model theories are also outlined. Prototypical applications to optical spectra and excited states of fluorescent proteins, biomolecular photoreceptors, and photosynthetic protein complexes are discussed.

  5. 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

  6. Auger recombination in scintillator materials from first principles

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

    Scintillators convert high energy radiation into lower energy photons which are easier to detect and analyze. One of the uses of these devices is identifying radioactive materials being transported across national borders. However, scintillating materials have a non-proportional light yield in response to incident radiation, which makes this task difficult. One possible cause of the non-proportional light yield is non-radiative Auger recombination. Auger recombination can occur in two ways - direct and phonon-assisted. We have studied both types of Auger recombination from first principles in the common scintillating material sodium iodide. Our results indicate that the phonon-assisted process, assisted primarily by short-range optical phonons, dominates the direct process. The corresponding Auger coefficients are 5 . 6 +/- 0 . 3 ×10-32cm6s-1 for the phonon-assisted process versus 1 . 17 +/- 0 . 01 ×10-33cm6s-1 for the direct process. At higher electronic temperatures the direct Auger recombination rate increases but remains lower than the phonon-assisted rate. This research was supported by the National Science Foundation CAREER award through Grant No. DMR-1254314 and NA-22. Computational Resources provide by LLNL and DOE NERSC Facility.

  7. "Postural first" principle when balance is challenged in elderly people.

    PubMed

    Lion, Alexis; Spada, Rosario S; Bosser, Gilles; Gauchard, Gérome C; Anello, Guido; Bosco, Paolo; Calabrese, Santa; Iero, Antonella; Stella, Giuseppe; Elia, Maurizio; Perrin, Philippe P

    2014-08-01

    Human cognitive processing limits can lead to difficulties in performing two tasks simultaneously. This study aimed to evaluate the effect of cognitive load on both simple and complex postural tasks. Postural control was evaluated in 128 noninstitutionalized elderly people (mean age = 73.6 ± 5.6 years) using a force platform on a firm support in control condition (CC) and mental counting condition (MCC) with eyes open (EO) and eyes closed (EC). Then, the same tests were performed on a foam support. Sway path traveled and area covered by the center of foot pressure were recorded, low values indicating efficient balance. On firm support, sway path was higher in MCC than in CC both in EO and EC conditions (p < 0.001). On foam support, sway path was higher in CC than in MCC in EC condition (p < 0.001), area being higher in CC than in MCC both in EO (p < 0.05) and EC (p < 0.001) conditions. The results indicate that cognitive load alters balance control in a simple postural task (i.e. on firm support), which is highlighted by an increase of energetic expenditure (i.e. increase of the sway path covered) to balance. Awareness may not be increased and the attentional demand may be shared between balance and mental task. Conversely, cognitive load does not perturb the realization of a new complex postural task. This result showed that postural control is prioritized ("postural first" principle) when seriously challenged.

  8. Coarse graining approach to First principles modeling of structural materials

    SciTech Connect

    Odbadrakh, Khorgolkhuu; Nicholson, Don M; Rusanu, Aurelian; Samolyuk, German D; Wang, Yang; Stoller, Roger E; Zhang, X.-G.; Stocks, George Malcolm

    2013-01-01

    Classical Molecular Dynamic (MD) simulations characterizing extended defects typically require millions of atoms. First principles calculations employed to understand these defect systems at an electronic level cannot, and should not deal with such large numbers of atoms. We present an e cient coarse graining (CG) approach to calculate local electronic properties of large MD-generated structures from the rst principles. We used the Locally Self-consistent Multiple Scattering (LSMS) method for two types of iron defect structures 1) screw-dislocation dipoles and 2) radiation cascades. The multiple scattering equations are solved at fewer sites using the CG. The atomic positions were determined by MD with an embedded atom force eld. The local moments in the neighborhood of the defect cores are calculated with rst-principles based on full local structure information, while atoms in the rest of the system are modeled by representative atoms with approximated properties. This CG approach reduces computational costs signi cantly and makes large-scale structures amenable to rst principles study. Work is sponsored by the USDoE, O ce of Basic Energy Sciences, Center for Defect Physics, an Energy Frontier Research Center. This research used resources of the Oak Ridge Leadership Computing Facility at the ORNL, which is supported by the O ce of Science of the USDoE under Contract No. DE-AC05-00OR22725.

  9. 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.

  10. Stress dependent defect energetics in Tungsten from first-principles

    NASA Astrophysics Data System (ADS)

    Hossain, Md.; Marian, Jaime

    2013-03-01

    Tungsten (W) is an important material for high temperature applications due to its refractory nature. However, like all transition metals from the VI-A group, W suffers from low-temperature brittleness and lack of ductility, which poses serious questions for its use as a structural material. Tungsten's mechanical properties can be enhanced by alloying with elements with d-electrons, such as Re, which has resulted in successful commercial alloys. In this work, we obtain the formation and migration energetics of Re solute atoms in terms of their interaction with vacancies and dislocations. To explore the influence of external stresses on Re transport properties, we examine the role of hydrostatic and shear deformation on the vacancy formation energy (VFE) and migration energy barrier (Em) in BCC W from first-principles calculations by developing a pseudopotential with 6s2, 6p0, 5d4, and 5f0 electronic states for the valence electrons. We find that under hydrostatic deformation, increase or decrease of vacancy formation energy depends on the type of deformation - tensile or compressive, while for shear deformation it decreases irrespective of the magnitude of applied deformation. On the other hand, migration energy barrier always decreases under hydrostatic deformation, but shows path-length dependent behavior under shear deformation. This talk will discuss the underlying principles and possible routes for enhancing mechanical strength from a physics perspective.

  11. High-Pressure Hydrogen from First-Principles

    NASA Astrophysics Data System (ADS)

    Morales, Miguel A.

    2014-03-01

    The main approximations typically employed in first-principles simulations of high-pressure hydrogen are the neglect of nuclear quantum effects (NQE) and the approximate treatment of electronic exchange and correlation, typically through a density functional theory (DFT) formulation. In this talk I'll present a detailed analysis of the influence of these approximations on the phase diagram of high-pressure hydrogen, with the goal of identifying the predictive capabilities of current methods and, at the same time, making accurate predictions in this important regime. We use a path integral formulation combined with density functional theory, which allows us to incorporate NQEs in a direct and controllable way. In addition, we use state-of-the-art quantum Monte Carlo calculations to benchmark the accuracy of more approximate mean-field electronic structure calculations based on DFT, and we use GW and hybrid DFT to calculate the optical properties of the solid and liquid phases near metallization. We present accurate predictions of the metal-insulator transition on the solid, including structural and optical properties of the molecular phase. MAM was supported by the U.S. Department of Energy at the Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344 and by LDRD Grant No. 13-LW-004.

  12. 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.

  13. Mechanical responses of borophene sheets: a first-principles study.

    PubMed

    Mortazavi, Bohayra; Rahaman, Obaidur; Dianat, Arezoo; Rabczuk, Timon

    2016-10-05

    Recent experimental advances for the fabrication of various borophene sheets introduced new structures with a wide range of applications. Borophene is the boron atom analogue of graphene. Borophene exhibits various structural polymorphs all of which are metallic. In this work, we employed first-principles density functional theory calculations to investigate the mechanical properties of five different single-layer borophene sheets. In particular, we analyzed the effect of the loading direction and point vacancy on the mechanical response of borophene. Moreover, we compared the thermal stabilities of the considered borophene systems. Based on the results of our modelling, borophene films depending on the atomic configurations and the loading direction can yield a remarkable elastic modulus in the range of 163-382 GPa nm and a high ultimate tensile strength from 13.5 GPa nm to around 22.8 GPa nm at the corresponding strain from 0.1 to 0.21. Our study reveals the remarkable mechanical characteristics of borophene films.

  14. First principles calculation of the activity of cytochrome P450

    NASA Astrophysics Data System (ADS)

    Segall, M. D.; Payne, M. C.; Ellis, S. W.; Tucker, G. T.; Boyes, R. N.

    1998-04-01

    The cytochrome P450 superfamily of enzymes is of enormous interest in the biological sciences due to the wide range of endogenous and xenobiotic compounds which it metabolises, including many drugs. We describe the use of first principles quantum mechanical modeling techniques, based on density functional theory, to determine the outcome of interactions between an enzyme and a number of compounds. Specifically, we calculate the spin state of an Fe3+ ion present in a haem moiety at the active site of these enzymes. The spin state of this ion indicates if the catalytic reaction will proceed. The computational results obtained compare favorably with experimental data. Only the principle components of the active site of the enzyme are included in the computational models, demonstrating that only a small fragment of the protein needs to be included in the models in order to accurately reproduce this aspect of the enzymes' function. These results open the way for further investigation of this superfamily of enzymes using the methods detailed in this paper.

  15. 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.

  16. 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.

  17. First-principles study on surface stability of tantalum carbides

    NASA Astrophysics Data System (ADS)

    Yan, Wen-Li; Sygnatowicz, Michael; Lu, Guang-Hong; Liu, Feng; Shetty, Dinesh K.

    2016-02-01

    Using first-principles method, surface energies of crystal planes of different tantalum carbide phases have been calculated. Quantum size effects are shown to possibly play a considerable role in determining accurate surface energies of these metallic films, which have been neglected in previous works. The γ-TaC phase has a more stable (0 0 1) surface than the close-packed (1 1 1) surface. In the α-Ta2C phase, (0 0 1) surface with only Ta termination is more stable than that of mixed Ta-C termination because the metallic bonds between Ta atoms are weaker than the Ta-C covalent bonds. The same is true for the ζ-Ta4C3 phase. The introduction of structural vacancies in the ζ-Ta4C3 -x phase creates more direct Ta metallic bonds, making the Ta-terminated surfaces even more stable. This is consistent with the experimental observations of cleavage of the basal planes, lamellae bridging of cracks, and the high fracture toughness of ζ-Ta4C3 -x.

  18. Electron-hole excitations and optical spectra from first principles

    SciTech Connect

    Rohlfing, Michael; Louie, Steven G.

    2000-08-15

    We present a recently developed approach to calculate electron-hole excitations and the optical spectra of condensed matter from first principles. The key concept is to describe the excitations of the electronic system by the corresponding one- and two-particle Green's function. The method combines three computational techniques. First, the electronic ground state is treated within density-functional theory. Second, the single-particle spectrum of the electrons and holes is obtained within the GW approximation to the electron self-energy operator. Finally, the electron-hole interaction is calculated and a Bethe-Salpeter equation is solved, yielding the coupled electron-hole excitations. The resulting solutions allow the calculation of the entire optical spectrum. This holds both for bound excitonic states below the band gap, as well as for the resonant spectrum above the band gap. We discuss a number of technical developments needed for the application of the method to real systems. To illustrate the approach, we discuss the excitations and optical spectra of spatially isolated systems (atoms, molecules, and semiconductor clusters) and of extended, periodic crystals (semiconductors and insulators). (c) 2000 The American Physical Society.

  19. 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.

  20. 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.

  1. First-principles reinvestigation of bulk WO3

    NASA Astrophysics Data System (ADS)

    Hamdi, Hanen; Salje, Ekhard K. H.; Ghosez, Philippe; Bousquet, Eric

    2016-12-01

    Using first-principles calculations, we analyze the structural properties of tungsten trioxide WO3. Our calculations rely on density functional theory and the use of the B1-WC hybrid functional, which provides very good agreement with experimental data. We show that the hypothetical high-symmetry cubic reference structure combines several ferroelectric and antiferrodistortive (antipolar cation motions, rotations, and tilts of oxygen octahedra) structural instabilities. Although the ferroelectric instability is the largest, the instability related to antipolar W motions combines with those associated to oxygen rotations and tilts to produce the biggest energy reduction, yielding a P 21/c ground state. This nonpolar P 21/c phase is only different from the experimentally reported P c ground state by the absence of a very tiny additional ferroelectric distortion. The calculations performed on a stoichiometric compound so suggest that the low-temperature phase of WO3 is not intrinsically ferroelectric and that the experimentally observed ferroelectric character might arise from extrinsic defects such as oxygen vacancies. Independently, we also identify never observed R 3 m and R 3 c ferroelectric metastable phases with large polarizations and low energies close to the P 21/c ground state, which makes WO3 a potential antiferroelectric material. The relative stability of various phases is discussed in terms of the anharmonic couplings between different structural distortions, highlighting a very complex interplay.

  2. Thermalisation of a quantum system from first principles

    NASA Astrophysics Data System (ADS)

    Ithier, Gregoire; Benaych-Georges, Florent

    2015-03-01

    How does a quantum system reach thermodynamical equilibrium? Answering such a question from first principles is, perhaps surprisingly, still an open issue (Popescu Nat. Phys. 2006, Goldstein PRL 2006, Genway PRL 2013). We present here a new model comprising an arbitrary quantum system interacting with a large arbitrary quantum environment, both initially prepared in a quantum pure state. We then demonstrate that thermalisation is an emergent property of the unitary evolution under a Schrödinger equation of this large composite system. The key conceptual tool of our method is the phenomenon of ``measure concentration'' appearing with functions defined on large dimension Hilbert spaces, a phenomenon which cancels out any effect of the microscopic structure of interaction Hamiltonians. Using our model, we first characterize the transient evolution or decoherence of the system and show its universal character. We then focus on the stationary regime and recover the canonical state well known from statistical thermodynamics. This finding leads us to propose an alternative and more general definition of the canonical partition function, that includes, among other things, the possibility of describing partial thermalisation.

  3. 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.

  4. First-principles studies of atomic dynamics in tetrahedrite thermoelectrics

    NASA Astrophysics Data System (ADS)

    Li, Junchao; Zhu, Mengze; Abernathy, Douglas L.; Ke, Xianglin; Morelli, Donald T.; Lai, Wei

    2016-10-01

    Cu12Sb4S13-based tetrahedrites are high-performance thermoelectrics that contain earth-abundant and environmentally friendly elements. At present, the mechanistic understanding of their low lattice thermal conductivity (<1 W m-1 K-1 at 300 K) remains limited. This work applies first-principles molecular dynamics simulations, along with inelastic neutron scattering (INS) experiments, to study the incoherent and coherent atomic dynamics in Cu10.5NiZn0.5Sb4S13, in order to deepen our insight into mechanisms of anomalous dynamic behavior and low lattice thermal conductivity in tetrahedrites. Our study of incoherent dynamics reveals the anomalous "phonon softening upon cooling" behavior commonly observed in inelastic neutron scattering data. By examining the dynamic Cu-Sb distances inside the Sb[CuS3]Sb cage, we ascribe softening to the decreased anharmonic "rattling" of Cu in the cage. On the other hand, our study of coherent dynamics reveals that acoustic modes are confined in a small region of dynamic scattering space, which we hypothesize leads to a minimum phonon mean free path. By assuming a Debye model, we obtain a lattice minimum thermal conductivity value consistent with experiments. We believe this study furthers our understanding of the atomic dynamics of tetrahedrite thermoelectrics and will more generally help shed light on the origin of intrinsically low lattice thermal conductivity in these and other structurally similar materials.

  5. Four superhard carbon allotropes: a first-principles study.

    PubMed

    He, Chaoyu; Sun, Lizhong; Zhang, Chunxiao; Peng, Xiangyang; Zhang, Kaiwang; Zhong, Jianxin

    2012-06-21

    Using a generalized genetic algorithm, we propose four new sp(3) carbon allotropes with 5-6-7 (5-6-7-type Z-ACA and Z-CACB) or 4-6-8 (4-6-8-type Z4-A(3)B(1) and A4-A(2)B(2)) carbon rings. Their stability, mechanical and electronic properties are systematically studied using a first-principles method. We find that the four new carbon allotropes show amazing stability in comparison with the carbon phases proposed recently. Both 5-6-7-type Z-ACA and Z-CACB are direct band-gap semiconductors with band gaps of 2.261 eV and 4.196 eV, respectively. However, the 4-6-8-type Z4-A(3)B(1) and A4-A(2)B(2) are indirect band-gap semiconductors with band gaps of 3.105 eV and 3.271 eV, respectively. Their mechanical properties reveal that all the four carbon allotropes proposed in present work are superhard materials, which are comparable to diamond.

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

    SciTech Connect

    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 (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. 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.

  7. 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.

  8. Lattice thermal conductivity of borophene from first principle calculation

    PubMed Central

    Xiao, Huaping; Cao, Wei; Ouyang, Tao; Guo, Sumei; He, Chaoyu; Zhong, Jianxin

    2017-01-01

    The phonon transport property is a foundation of understanding a material and predicting the potential application in mirco/nano devices. In this paper, the thermal transport property of borophene is investigated by combining first-principle calculations and phonon Boltzmann transport equation. At room temperature, the lattice thermal conductivity of borophene is found to be about 14.34 W/mK (error is about 3%), which is much smaller than that of graphene (about 3500 W/mK). The contributions from different phonon modes are qualified, and some phonon modes with high frequency abnormally play critical role on the thermal transport of borophene. This is quite different from the traditional understanding that thermal transport is usually largely contributed by the low frequency acoustic phonon modes for most of suspended 2D materials. Detailed analysis further reveals that the scattering between the out-of-plane flexural acoustic mode (FA) and other modes likes FA + FA/TA/LA/OP ↔ TA/LA/OP is the predominant phonon process channel. Finally the vibrational characteristic of some typical phonon modes and mean free path distribution of different phonon modes are also presented in this work. Our results shed light on the fundamental phonon transport properties of borophene, and foreshow the potential application for thermal management community. PMID:28374853

  9. First-principles investigation of antiphase boundaries in perovskites

    NASA Astrophysics Data System (ADS)

    Naumov, Ivan; Rabe, Karin

    2002-03-01

    The lowering of the dielectric constant of Ba_xSr_1-xTiO3 (BST) films compared to bulk can be attributed, at least in part, to the effects of defects associated with film growth. In BST films grown on MgO substrates, such defects include antiphase boundaries (APBs), which have been clearly observed using electron microscopy. In this work, using a first-principles pseudopotential approach based on variational density functional pertubation theory, we have investigated the structure, lattice dynamics and dielectric properties of two relevant APBs in SrTiO3 (Sr-rich and Ti-rich) using ordered supercells. Comparison with bulk SrTiO3 shows that the Born effective charges and electronic dielectric tensor decrease and the characteristic low-frequency polar mode increases in frequency, leading to a significant lowering of the lattice contribution to the dielectric response. We suggest that this change can be understood as the result of the disruption of the Ti-O chains normal to the APB, and thus that this mechanism is also relevant to the solid solution. This work is supported by U. Maryland/Rutgers NSF-MRSEC DMR-00-80008.

  10. First-principles calculations of mobilities in MOSFETs

    NASA Astrophysics Data System (ADS)

    Hadjisavvas, George; Tsetseris, Leonidas; Evans, Matthew; Pantelides, Sokrates

    2007-03-01

    Nano-scale MOSFETs demonstrate interesting electron transport behavior. Straining the silicon lattice results in significant increases in carrier mobility up to 100%. Transport properties are known to depend also on the presence of interface traps. Due to their significance, a large number of studies have obtained mobilities, but in an empirical and semi-classical fashion, whereas, in nano-devices quantum mechanical effects and atomic-scale structural details are the key factors of mobility calculations. Here we use a recently developed method[1] for first-principles calculations of mobilites within DFT to probe the effect of strain and interface point defects (e.g., dangling bonds) on mobilities in double gate ultra-thin SOI (UTSOI) MOSFETs. The transport properties are described in a fully self-consistent quantum mechanical fashion and mobilities are calculated within the Born approximation. The results show that biaxial tensile strain is shown to significantly increase carrier mobility in UTSOI devices by suppressing the effective scattering from atomic-scale interface inhomogeneities; the effect of dangling bonds on mobility in a UTSOI channel is weaker than in conventional MOSFETs because the carrier density peaks at the center of the channel. This work was supported in part by NSF Grant ECS-0524655 and by AFOSR Grant 4224224232. [1] M.H. Evans et al., Phys. Rev. Lett. 95, 106802 (2005).

  11. NMR quadruopole spectra of PZT from first-principles

    NASA Astrophysics Data System (ADS)

    Mao, Dandan; Walter, Eric J.; Krakauer, Henry

    2006-03-01

    High performance piezoelectric materials are disordered alloys, so it can be difficult to determine the local atomic geometry. Recently, high field NMR measurements have shown great promise as a microscopic probe of ABO3 perovskite-based alloys by their ability to resolve line-splittings due to nuclear quadrupolar coupling with the electric field gradient (EFG) at the nucleus. We report first-principles LDA calculations of the EFG's in monoclinic and tetragonal Pb(Zr0.5Ti0.5)O3 systems using the linear augmented planewave (LAPW) method, and we compute NMR static powder spectra for ^91Zr, ^47Ti, and ^17O atoms as a function of applied strain. With decreasing c/a ratio PZT converts from tetragonal to monoclinic symmetry. We observe that the calculated NMR spectra show dramatic deviations with decreasing c/a from that in tetragonal P4mm well before the electric polarization begins to rotate away from the [001] direction. This indicates that NMR measurements can be a very accurate probe of local structural changes in perovskite piezoelectrics. G. L. Hoatson, D. H. Zhou, F. Fayon, D. Massiot, and R. L. Vold, Phys. Rev. B, 66, 224103 (2002).

  12. Solubility of nonelectrolytes: a first-principles computational approach.

    PubMed

    Jackson, Nicholas E; Chen, Lin X; Ratner, Mark A

    2014-05-15

    Using a combination of classical molecular dynamics and symmetry adapted intermolecular perturbation theory, we develop a high-accuracy computational method for examining the solubility energetics of nonelectrolytes. This approach is used to accurately compute the cohesive energy density and Hildebrand solubility parameters of 26 molecular liquids. The energy decomposition of symmetry adapted perturbation theory is then utilized to develop multicomponent Hansen-like solubility parameters. These parameters are shown to reproduce the solvent categorizations (nonpolar, polar aprotic, or polar protic) of all molecular liquids studied while lending quantitative rigor to these qualitative categorizations via the introduction of simple, easily computable parameters. Notably, we find that by monitoring the first-order exchange energy contribution to the total interaction energy, one can rigorously determine the hydrogen bonding character of a molecular liquid. Finally, this method is applied to compute explicitly the Flory interaction parameter and the free energy of mixing for two different small molecule mixtures, reproducing the known miscibilities. This methodology represents an important step toward the prediction of molecular solubility from first principles.

  13. A First-principles Molecular Dynamics Investigation of Superionic Conductivity

    NASA Astrophysics Data System (ADS)

    Wood, Brandon; Marzari, Nicola

    2007-03-01

    Superionic materials---solids with liquid-like transport properties---have found widespread use in a variety of applications in fuel cells, switches, sensors, and batteries. However, reasons for fast-ion conduction in such materials, as well as the specific atomistic mechanisms involved, remain ill understood. Our work uses first-principles molecular dynamics to illuminate the mechanisms, pathways, and motivations for superionic conductivity in two materials representing different classes of ion conductors: α-AgI, an archetypal Type-I superionic; and CsHSO4, an anhydrous solid-state electrolyte candidate for hydrogen fuel cells. For α-AgI, we trace common pathways for silver ion conduction and discuss how a chemical signature in the electronic structure relates to enhanced silver ion mobility. We also characterize the dynamical lattice structure in the superionic phase and present the likely motivations for its existence. For CsHSO4, we isolate the dominant atomistic mechanisms involved in superprotonic conduction and discuss the effect of correlated diffusive events in enhancing proton transport. We also offer a detailed description of the dynamics of the hydrogen bond network topology in the course of proton diffusion and discuss the relevance of atomistic processes with competing timescales in facilitating proton transport.

  14. 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.

  15. Electronic and structural reconstruction in titanate heterostructures from first principles

    NASA Astrophysics Data System (ADS)

    Mulder, Andrew T.; Fennie, Craig J.

    2014-03-01

    Recent advances in transition metal oxide heterostructures have opened new routes to create materials with novel functionalities and properties. One direction has been to combine a Mott insulating perovskite with an electronic d1 configuration, such as LaTiO3, with a band insulating d0 perovskite, such as SrTiO3. An exciting recent development is the demonstration of interfacial conductivity in GdTiO3/SrTiO3 heterostructures that display a complex structural motif of octahedral rotations and ferromagnetic properties similar to bulk GdTiO3. In this talk we present our first principles investigation of the interplay of structural, electronic, magnetic, and orbital degrees of freedom for a wide range of d1/d0 titanate heterostructures. We find evidence for both rotation driven ferroelectricity and a symmetry breaking electronic reconstruction with a concomitant structural distortion at the interface. We argue that these materials represent an ideal platform to realize novel functionalities such as the electric field control of electronic and magnetic properties.

  16. Predicting catalysis: understanding ammonia synthesis from first-principles calculations.

    PubMed

    Hellman, A; Baerends, E J; Biczysko, M; Bligaard, T; Christensen, C H; Clary, D C; Dahl, S; van Harrevelt, R; Honkala, K; Jonsson, H; Kroes, G J; Luppi, M; Manthe, U; Nørskov, J K; Olsen, R A; Rossmeisl, J; Skúlason, E; Tautermann, C S; Varandas, A J C; Vincent, J K

    2006-09-14

    Here, we give a full account of a large collaborative effort toward an atomic-scale understanding of modern industrial ammonia production over ruthenium catalysts. We show that overall rates of ammonia production can be determined by applying various levels of theory (including transition state theory with or without tunneling corrections, and quantum dynamics) to a range of relevant elementary reaction steps, such as N(2) dissociation, H(2) dissociation, and hydrogenation of the intermediate reactants. A complete kinetic model based on the most relevant elementary steps can be established for any given point along an industrial reactor, and the kinetic results can be integrated over the catalyst bed to determine the industrial reactor yield. We find that, given the present uncertainties, the rate of ammonia production is well-determined directly from our atomic-scale calculations. Furthermore, our studies provide new insight into several related fields, for instance, gas-phase and electrochemical ammonia synthesis. The success of predicting the outcome of a catalytic reaction from first-principles calculations supports our point of view that, in the future, theory will be a fully integrated tool in the search for the next generation of catalysts.

  17. First-principle studies on the Li-Te system

    NASA Astrophysics Data System (ADS)

    Wang, Youchun; Tian, Fubo; Li, Da; Duan, Defang; Liu, Yunxian; Liu, Bingbing; Zhou, Qiang; Cui, Tian

    2017-01-01

    First-principle evolutionary calculation was performed to search for all probable stable lithium tellurium compounds. In addition to the well-known structures of Fm-3m Li2Te and Pnma Li2Te, several novel structures, including those of P4/nmm Li2Te, Imma Li8Te2, and C2/m Li9Te2, were determined under high pressure. The transformation sequence of Li2Te induced by pressure was presented as follows. The phase transition occurred at 7.5 GPa while transforming from Fm-3m phase to Pnma structure, then transformed to P4/nmm phase at 14 GPa. P4/nmm Li2Te can remain stable at least up to 140 GPa. Li8Te2 and Li9Te2 were stable at 8-120 GPa and 80-120 GPa, respectively. Interestingly, Li8Te2 and Li9Te2 were predicted to be metallic under high pressure, Li2Te would metalize on compression. P4/nmm Li2Te is likely a super ionic conductor due to the special characteristic. Metallic P4/nmm Li2Te may be a candidate mixed conductor material under extreme pressure. Charge transfer was studied using Bader charge analysis. Charge transferred from Li to Te, and the relative debilitated ionicity between Li and Te atoms existed at high pressure.

  18. Electronic stopping of slow H and He atoms in gold from first principles

    NASA Astrophysics Data System (ADS)

    Ahsan Zeb, M.; Kohanoff, Jorge; Sanchez-Portal, Daniel; Arnau, Andres; Juaristi, J. I.; Artacho, Emilio

    2012-02-01

    In spite of a long history, the quantitative understanding of non-adiabatic processes in condensed matter and our ability to perform predictive theoretical simulations of processes coupling many adiabatic energy surfaces is very much behind what accomplished for adiabatic situations, for which first-principles calculations provide predictions of varied properties within a few percent accuracy. We will present here high-accuracy results for the electronic stopping power of H and He moving through gold, using time-evolving density-functional theory, thereby conveying usual first-principles accuracies to strongly coupled, continuum non-adiabatic processes in condensed matter. The two key unexplained features of what observed experimentally have been reproduced and understood: (i) The non-linear behavior of stopping power versus velocity is a gradual crossover as excitations tail into the d-electron spectrum; and (ii) the higher stopping for He than for H at low velocities is explained by the substantial involvement of the d electrons in the screening of the projectile even at the lowest velocities where the energy loss is generated by s-like electron-hole pair formation only.

  19. Anisotropic intrinsic lattice thermal conductivity of borophane from first-principles calculations.

    PubMed

    Liu, Gang; Wang, Haifeng; Gao, Yan; Zhou, Jian; Wang, Hui

    2017-01-25

    Borophene (boron sheet) as a new type of two-dimensional (2D) material was grown successfully recently. Unfortunately, the structural stability of freestanding borophene is still an open issue. Theoretical research has found that full hydrogenation can remove such instability, and the product is called borophane. In this paper, using first-principles calculations we investigate the lattice dynamics and thermal transport properties of borophane. The intrinsic lattice thermal conductivity and the relaxation time of borophane are investigated by solving the phonon Boltzmann transport equation (BTE) based on first-principles calculations. We find that the intrinsic lattice thermal conductivity of borophane is anisotropic, as the higher value (along the zigzag direction) is about two times of the lower one (along the armchair direction). The contributions of phonon branches to the lattice thermal conductivities along different directions are evaluated. It is found that both the anisotropy of thermal conductivity and the different phonon branches which dominate the thermal transport along different directions are decided by the group velocity and the relaxation time of phonons with very low frequency. In addition, the size dependence of thermal conductivity is investigated using cumulative thermal conductivity. The underlying physical mechanisms of these unique properties are also discussed in this paper.

  20. 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.

  1. Infrared spectroscopy and theoretical studies of group IV molecules

    NASA Astrophysics Data System (ADS)

    Gonzalez, Eric

    This research involved the formation of novel molecules, and the first observation of infrared active modes and infrared active combination bands of already discovered molecules. The molecules were produced by the laser evaporation of germanium, germanium-carbon, and carbons rod previously sintered in a new built vacuum furnace. The infrared spectra were taken using Bomem FTIR spectrometer with an interface infrared optics toward the formation chamber. These molecules were theoretically simulated using commercial quantum chemistry suites of programs and homemade codes. The linear GeC5Ge germanium-carbon chain has been detected for the first time through the dual laser evaporation of graphite and germanium, the nu4(sigmau) vibrational fundamental was observed at 2158.0 cm-1. Two new vibrational fundamentals of linear GeC3Ge, nu 4(sigma4 = 735.3 cm-1 and nu6(sigma u) = 580.1 cm-1, have been observed. This is apparently the first observation of germanium isotopic shifts in vibrational spectra. Linear GeC3 has been formed by the dual laser ablation of germanium and carbon rods and by single laser ablation of a sintered germanium-carbon rod, and trapped in Ar matrices. Two vibrational fundamentals of linear GeC 3 nu1(sigma) = 1903.9 cm-1 and nu 2(sigma) = 1279.6 cm-1, have been observed. In the present work there is no spectroscopic evidence of cyclic structures for GeC 3 with either the transannular Ge-C or C-C bond although at the coupled cluster level of theory they are both predicted to be ˜7-9 kcal/mol lower in energy than the linear isomer. This result suggests a need for further theoretical studies of GeC3 to see if the cyclic isomers are indeed more stable than the linear. New combination bands of carbon chains have been observed, (nu 1+nu4) = 3388.8 cm-1 of linear C5 and (nu2+nu7) = 3471.8 cm-1 of linear C9. Since the asymmetric stretching1 modes involved in these absorptions have been measured previously it has been possible to assign the infrared inactive

  2. Thermodynamic stability and properties of boron subnitrides from first principles

    NASA Astrophysics Data System (ADS)

    Ektarawong, A.; Simak, S. I.; Alling, B.

    2017-02-01

    We use the first-principles approach to clarify the thermodynamic stability as a function of pressure and temperature of three different α -rhombohedral-boron-like boron subnitrides, with the compositions of B6N , B13N2 , and B38N6 , proposed in the literature. We find that, out of these subnitrides with the structural units of B12(N-N), B12(NBN), and [B12(N-N) ] 0.33[B12(NBN)] 0.67 , respectively, only B38N6 , represented by [B12(N-N) ] 0.33[B12(NBN)] 0.67 , is thermodynamically stable. Beyond a pressure of about 7.5 GPa depending on the temperature, also B38N6 becomes unstable, and decomposes into cubic boron nitride and α -tetragonal-boron-like boron subnitride B50N2 . The thermodynamic stability of boron subnitrides and relevant competing phases is determined by the Gibbs free energy, in which the contributions from the lattice vibrations and the configurational disorder are obtained within the quasiharmonic and the mean-field approximations, respectively. We calculate lattice parameters, elastic constants, phonon and electronic density of states, and demonstrate that [B12(N-N) ] 0.33[B12(NBN)] 0.67 is both mechanically and dynamically stable, and is an electrical semiconductor. The simulated x-ray powder-diffraction pattern as well as the calculated lattice parameters of [B12(N-N) ] 0.33[B12(NBN)] 0.67 are found to be in good agreement with those of the experimentally synthesized boron subnitrides reported in the literature, verifying that B38N6 is the stable composition of α -rhombohedral-boron-like boron subnitride.

  3. First-principles study of polyacetylene derivatives bearing nitroxide radicals

    NASA Astrophysics Data System (ADS)

    Bilgiç, Beyza; Kılıç, Çetin; Esat, Burak

    2011-09-01

    Electrodes made of organic polymers bearing redox-active radical pendant groups have attractive features for use in rechargeable batteries. Electronic structure and electrochemical properties of cathode- and anode-active organic polymers are investigated here by means of first-principles calculations performed in the framework of the density functional theory. We consider organic radical polymers (ORPs) that consist of trans-polyacetylene derivatives bearing a variety of nitroxide radicals. A number of neutral and charged supercells are utilized to compute the ionization potentials and electron affinities as well as the one-electron states of these ORPs. By revealing the polyacetylene-derived highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) as well as the radical-derived singly occupied molecular orbital (SOMO), the variation of the SOMO energy within the HOMO-LUMO gap is determined in the course of the oxidization or reduction of ORPs. Our results indicate that the ionization potential I and electron affinity A of polyacetylene would act as a lower or upper bound in the variation of the electrochemical potential of cathode- or anode-active ORPs in the course of battery discharge or charge owing to pinning of the radical-derived SOMO to the polyacetylene-derived HOMO or LUMO. Accordingly, it is anticipated that the electrochemical “window” [-I,-A] of the polymeric backbone of ORPs will impose certain limitations in accomplishing a high charge/discharge voltage range in a totally organic rechargeable battery with positive and negative electrodes made of cathode- and anode-active ORPs, respectively. On the other hand, our findings suggest that one could, in principle, take advantage of using two different (conducting) polymeric backbones in the anode and cathode with adjusted HOMO and LUMO offsets once the electron transfer is accomplished to take place through the conducting backbones.

  4. First principles investigation of copper and silver intercalated molybdenum disulfide

    NASA Astrophysics Data System (ADS)

    Guzman, D. M.; Onofrio, N.; Strachan, A.

    2017-02-01

    We characterize the energetics and atomic structures involved in the intercalation of copper and silver into the van der Waals gap of molybdenum disulfide as well as the resulting ionic and electronic transport properties using first-principles density functional theory. The intercalation energy of systems with formula (Cu,Ag)xMoS2 decreases with ion concentration and ranges from 1.2 to 0.8 eV for Cu; Ag exhibits a stronger concentration dependence from 2.2 eV for x = 0.014 to 0.75 eV for x = 1 (using the fcc metal as a reference). Partial atomic charge analysis indicates that approximately half an electron is transferred per metallic ion in the case of Cu at low concentrations and the ionicity decreases only slightly with concentration. In contrast, while Ag is only slightly less ionic than Cu for low concentrations, charge transfer reduces significantly to approximately 0.1 e for x = 1. This difference in ionicity between Cu and Ag correlates with their intercalation energies. Importantly, the predicted values indicate the possibility of electrochemical intercalation of both Cu and Ag into MoS2 and the calculated activation energies associated with ionic transport within the gaps, 0.32 eV for Cu and 0.38 eV for Ag, indicate these materials to be good ionic conductors. Analysis of the electronic structure shows that charge transfer leads to a shift of the Fermi energy into the conduction band resulting in a semiconductor-to-metal transition. Electron transport calculations based on non-equilibrium Green's function show that the low-bias conductance increases with metal concentration and is comparable in the horizontal and vertical transport directions. These properties make metal intercalated transition metal di-chalcogenides potential candidates for several applications including electrochemical metallization cells and contacts in electronics based on 2D materials.

  5. 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.

  6. First principles explanation of the positive Seebeck coefficient of lithium.

    PubMed

    Xu, Bin; Verstraete, Matthieu J

    2014-05-16

    Lithium is one of the simplest metals, with negative charge carriers and a close reproduction of free-electron dispersion. Experimentally, however, Li is one of a handful of elemental solids (along with Cu, Ag, and Au) where the sign of the Seebeck coefficient (S) is opposite to that of the carrier. This counterintuitive behavior still lacks a satisfactory interpretation. We calculate S fully from first principles, within the framework of Allen's formulation of Boltzmann transport theory. Here it is crucial to avoid the constant relaxation time approximation, which gives a sign for S which is necessarily that of the carriers. Our calculated S are in excellent agreement with experimental data, up to the melting point. In comparison with another alkali metal, Na, we demonstrate that within the simplest nontrivial model for the energy dependency of the electron lifetimes, the rapidly increasing density of states (DOS) across the Fermi energy is related to the sign of S in Li. The exceptional energy dependence of the DOS is beyond the free-electron model, as the dispersion is distorted by the Brillouin zone edge; this has a stronger effect in Li than other alkali metals. The electron lifetime dependency on energy is central, but the details of the electron-phonon interaction are found to be less important, contrary to what has been believed for several decades. Band engineering combined with the mechanism exposed here may open the door to new "ambipolar" thermoelectric materials, with a tunable sign for the thermopower even if either n- or p-type doping is impossible.

  7. First principle kinetic studies of zeolite-catalyzed methylation reactions.

    PubMed

    Van Speybroeck, Veronique; Van der Mynsbrugge, Jeroen; Vandichel, Matthias; Hemelsoet, Karen; Lesthaeghe, David; Ghysels, An; Marin, Guy B; Waroquier, Michel

    2011-02-02

    Methylations of ethene, propene, and butene by methanol over the acidic microporous H-ZSM-5 catalyst are studied by means of state of the art computational techniques, to derive Arrhenius plots and rate constants from first principles that can directly be compared with the experimental data. For these key elementary reactions in the methanol to hydrocarbons (MTH) process, direct kinetic data became available only recently [J. Catal.2005, 224, 115-123; J. Catal.2005, 234, 385-400]. At 350 °C, apparent activation energies of 103, 69, and 45 kJ/mol and rate constants of 2.6 × 10(-4), 4.5 × 10(-3), and 1.3 × 10(-2) mol/(g h mbar) for ethene, propene, and butene were derived, giving following relative ratios for methylation k(ethene)/k(propene)/k(butene) = 1:17:50. In this work, rate constants including pre-exponential factors are calculated which give very good agreement with the experimental data: apparent activation energies of 94, 62, and 37 kJ/mol for ethene, propene, and butene are found, and relative ratios of methylation k(ethene)/k(propene)/k(butene) = 1:23:763. The entropies of gas phase alkenes are underestimated in the harmonic oscillator approximation due to the occurrence of internal rotations. These low vibrational modes were substituted by manually constructed partition functions. Overall, the absolute reaction rates can be calculated with near chemical accuracy, and qualitative trends are very well reproduced. In addition, the proposed scheme is computationally very efficient and constitutes significant progress in kinetic modeling of reactions in heterogeneous catalysis.

  8. Liquid Water from First Principles: Validation of Different Sampling Approaches

    SciTech Connect

    Mundy, C J; Kuo, W; Siepmann, J; McGrath, M J; Vondevondele, J; Sprik, M; Hutter, J; Parrinello, M; Mohamed, F; Krack, M; Chen, B; Klein, M

    2004-05-20

    A series of first principles molecular dynamics and Monte Carlo simulations were carried out for liquid water to assess the validity and reproducibility of different sampling approaches. These simulations include Car-Parrinello molecular dynamics simulations using the program CPMD with different values of the fictitious electron mass in the microcanonical and canonical ensembles, Born-Oppenheimer molecular dynamics using the programs CPMD and CP2K in the microcanonical ensemble, and Metropolis Monte Carlo using CP2K in the canonical ensemble. With the exception of one simulation for 128 water molecules, all other simulations were carried out for systems consisting of 64 molecules. It is found that the structural and thermodynamic properties of these simulations are in excellent agreement with each other as long as adiabatic sampling is maintained in the Car-Parrinello molecular dynamics simulations either by choosing a sufficiently small fictitious mass in the microcanonical ensemble or by Nos{acute e}-Hoover thermostats in the canonical ensemble. Using the Becke-Lee-Yang-Parr exchange and correlation energy functionals and norm-conserving Troullier-Martins or Goedecker-Teter-Hutter pseudopotentials, simulations at a fixed density of 1.0 g/cm{sup 3} and a temperature close to 315 K yield a height of the first peak in the oxygen-oxygen radial distribution function of about 3.0, a classical constant-volume heat capacity of about 70 J K{sup -1} mol{sup -1}, and a self-diffusion constant of about 0.1 Angstroms{sup 2}/ps.

  9. 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.

  10. First Principles Design of Non-Centrosymmetric Metal Oxides

    NASA Astrophysics Data System (ADS)

    Young, Joshua Aaron

    The lack of an inversion center in a material's crystal structure can result in many useful material properties, such as ferroelectricity, piezoelectricity and non-linear optical behavior. Recently, the desire for low power, high efficiency electronic devices has spurred increased interest in these phenomena, especially ferroelectricity, as well as their coupling to other material properties. By studying and understanding the fundamental structure-property relationships present in non-centrosymmetric materials, it is possible to purposefully engineer new compounds with the desired "acentric" qualities through crystal engineering. The families of ABO3 perovskite and ABO2.5 perovskite-derived brownmillerite oxides are ideal for such studies due to their wide range of possible chemistries, as well as ground states that are highly tunable owing to strong electron-lattice coupling. Furthermore, control over the B-O-B bond angles through epitaxial strain or chemical substitution allows for the rapid development of new emergent properties. In this dissertation, I formulate the crystal-chemistry criteria necessary to design functional non-centrosymmetric oxides using first-principles density functional theory calculations. Recently, chemically ordered (AA')B2O 6 oxides have been shown to display a new form of rotation-induced ferroelectric polarizations. I now extend this property-design methodology to alternative compositions and crystal classes and show it is possible to induce a host of new phenomena. This dissertation will address: 1) the formulation of predictive models allowing for a priori design of polar oxides, 2) the optimization of properties exhibited by these materials through chemical substitution and cation ordering, and 3) the use of strain to control the stability of new phases. Completion of this work has led to a deeper understanding of how atomic structural features determine the physical properties of oxides, as well as the successful elucidation of

  11. 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

  12. First-principles investigation of hydrous post-perovskite

    DOE PAGES

    Townsend, Joshua P.; Tsuchiya, Jun; Bina, Craig R.; ...

    2015-04-11

    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, resultingmore » 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. Furthermore, 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.« less

  13. First-principles investigation of hydrous post-perovskite

    SciTech Connect

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

    2015-04-11

    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. Furthermore, 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.

  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.

  15. 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.

  16. A digitally reconstructed radiograph algorithm calculated from first principles

    PubMed Central

    Staub, David; Murphy, Martin J.

    2013-01-01

    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

  17. 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.

  18. X-ray magnetic dichroism in (Zn,Mn)O diluted magnetic semiconductors: First-principles calculations

    NASA Astrophysics Data System (ADS)

    Antonov, V. N.; Bekenov, L. V.; Mazur, D. V.; Germash, L. P.

    2012-06-01

    The electronic structure of (Zn,Mn)O diluted magnetic semiconductors was investigated theoretically from first principles by using the fully-relativistic Dirac linear muffin-tin orbital band structure method with the local spin-density approximation (LSDA) and the LSDA+ U approach. The X-ray magnetic circular dichroism (XMCD) spectra at the Mn, Zn, and O K and Mn L 2,3 edges were investigated theoretically from first principles. The origin of the XMCD spectra in these compounds was examined. The effect of oxygen vacancy atoms was found to be crucial for the X-ray magnetic dichroism at the Mn L 2,3 edges. The calculated results are compared with available experimental data.

  19. 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

    2016-02-08

    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.

  20. First-principles study of structural and thermodynamic properties of osmium

    NASA Astrophysics Data System (ADS)

    Liu, Ke; He, Duan-Wei; Zhou, Xiao-Lin; Chen, Hai-Hua

    2011-08-01

    We employ the first-principles plane wave pseudopotential density functional theory method to calculate the equilibrium lattice parameters of osmium and the thermodynamic properties of hcp structure osmium. The obtained lattice parameters are in good agreement with the experimental data investigated up to 58.2 GPa using radial X-ray diffraction (RXRD) together with lattice strain theory in a diamond-anvil cell and the available theoretical data of others. Through the quasi-harmonic Debye model, the dependencies of the normalized lattice parameters a/ a0 and c/ c0 on pressure P, the normalized primitive volume V/V0 on pressure P, the Debye temperature ΘD and the heat capacity CV on pressure P and temperature T, as well as the variation of the thermal expansion α with temperature and pressure are obtained successfully.

  1. First-principles study of the spin-orbit interaction in graphene induced by hydrogen adatoms

    NASA Astrophysics Data System (ADS)

    Gmitra, Martin; Kochan, Denis; Fabian, Jaroslav

    2013-03-01

    We have performed first principles calculations of the spin-orbit coupling effects in hydrogenated graphene structures, for varying hydrogen coverage densities, using the linearized augmented plane wave method as implemented in the FLEUR code. The covalent bonding between the hydrogen and carbon atoms leads to a local structural puckering of graphene sheets, giving rise to an overlap between the Dirac and sigma electrons and a giant enhancement (from roughly 0.01 to 1 meV) of the local spin-orbit interaction. The calculated effects on the band structure and the emerging spin patterns of the electronic states can be well explained by effective Hamiltonian models derived from group theoretical principles. This work is supported by the DFG SPP 1285, SFB 689, and GRK 1570

  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.

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

    SciTech Connect

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

    2016-03-20

    Here, 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 pressure 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.

  4. Li-Na ternary amidoborane for hydrogen storage: experimental and first-principles study.

    PubMed

    Li, Wen; Miao, Ling; Scheicher, Ralph H; Xiong, Zhitao; Wu, Guotao; Araújo, C Moysés; Blomqvist, Andreas; Ahuja, Rajeev; Feng, Yuanping; Chen, Ping

    2012-04-28

    Li-Na ternary amidoborane, Na[Li(NH(2)BH(3))(2)], was recently synthesized by reacting LiH and NaH with NH(3)BH(3). This mixed-cation amidoborane shows improved dehydrogenation performance compared to that of single-cation amidoboranes, i.e., LiNH(2)BH(3) and NaNH(2)BH(3). In this paper, we synthesized the Li-Na ternary amidoborane by blending and re-crystallizing equivalent LiNH(2)BH(3) and NaNH(2)BH(3) in tetrahydrofuran (THF), and employed first-principles calculations and the special quasirandom structure (SQS) method to theoretically explore the likelihood for the existence of Li(1-x)Na(x)(NH(2)BH(3)) for various Li/Na ratios. The thermodynamic, electronic and phononic properties were investigated to understand the possible dehydrogenation mechanisms of Na[Li(NH(2)BH(3))(2)].

  5. Establishing the limits of efficiency of perovskite solar cells from first principles modeling

    PubMed Central

    Grånäs, Oscar; Vinichenko, Dmitry; Kaxiras, Efthimios

    2016-01-01

    The recent surge in research on metal-halide-perovskite solar cells has led to a seven-fold increase of efficiency, from ~3% in early devices to over 22% in research prototypes. Oft-cited reasons for this increase are: (i) a carrier diffusion length reaching hundreds of microns; (ii) a low exciton binding energy; and (iii) a high optical absorption coefficient. These hybrid organic-inorganic materials span a large chemical space with the perovskite structure. Here, using first-principles calculations and thermodynamic modelling, we establish that, given the range of band-gaps of the metal-halide-perovskites, the theoretical maximum efficiency limit is in the range of ~25–27%. Our conclusions are based on the effect of level alignment between the perovskite absorber layer and carrier-transporting materials on the performance of the solar cell as a whole. Our results provide a useful framework for experimental searches toward more efficient devices. PMID:27824030

  6. First principles study of crystal Si-doped Ge2Sb2Te5

    NASA Astrophysics Data System (ADS)

    Yan, Beibei; Yang, Fei; Chen, Tian; Wang, Minglei; Chang, Hong; Ke, Daoming; Dai, Yuehua

    2017-02-01

    Ge2Sb2Te5 (GST) and Si-doped GST with hexagonal structure were investigated by means of First-principles calcucations. We performed many kinds of doping types and studied the electronic properties of Si-doped GST with various Si concentrations. The theoretical calculations show that the lowest formation energy appeared when Si atoms substitute the Sb atoms (SiSb). With the increasing of Si concentrations from 10% to 30%, the impurity states arise around the Fermi level and the band gap of the SiSb structure broadens. Meanwhile, the doping supercell has the most favorable structure when the doping concentration keeps in 20%. The Si-doped GST exhibits p-type metallic characteristics more distinctly owing to the Fermi level moves toward the valence band. The Te p, d-orbitals electrons have greater impact on electronic properties than that of Te s-orbitals.

  7. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

    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. Obtaining Mixed-Basis Ising-Like Expansions of Binary Alloys from First Principles

    NASA Astrophysics Data System (ADS)

    Hart, Gus L. W.; Sanati, Mahdi; Wang, Ligen; Zunger, Alex

    2002-03-01

    Many electronic and structural properties of A_1-xBx alloys can be predicted theoretically if one can find (and quickly compute) the ``configurational energy function''--that is, the energy for any given configuration of A and B atoms on the crystal lattice. Cluster expansion methods provide one such approach. We describe our mixed-basis cluster expansion (MBCE) based on first-principles total energy calculations for only a few ordered A_mBn compounds. Our MBCE can robustly predict a variety of material properties including ground states, phase diagrams, precipitate formation, etc. Specifically, we illustrate how systematic choice of interaction parameters, numerical parameters, and choice of input structures can significantly increase the accuracy and the predictive capability of the expansion. We illustrate how the fit of LDA data can be done essentially automatically. Examples include Cu-Au, Ni-Pt, and Sc_1-xBox_xS.

  10. Establishing the limits of efficiency of perovskite solar cells from first principles modeling.

    PubMed

    Grånäs, Oscar; Vinichenko, Dmitry; Kaxiras, Efthimios

    2016-11-08

    The recent surge in research on metal-halide-perovskite solar cells has led to a seven-fold increase of efficiency, from ~3% in early devices to over 22% in research prototypes. Oft-cited reasons for this increase are: (i) a carrier diffusion length reaching hundreds of microns; (ii) a low exciton binding energy; and (iii) a high optical absorption coefficient. These hybrid organic-inorganic materials span a large chemical space with the perovskite structure. Here, using first-principles calculations and thermodynamic modelling, we establish that, given the range of band-gaps of the metal-halide-perovskites, the theoretical maximum efficiency limit is in the range of ~25-27%. Our conclusions are based on the effect of level alignment between the perovskite absorber layer and carrier-transporting materials on the performance of the solar cell as a whole. Our results provide a useful framework for experimental searches toward more efficient devices.

  11. Establishing the limits of efficiency of perovskite solar cells from first principles modeling

    NASA Astrophysics Data System (ADS)

    Grånäs, Oscar; Vinichenko, Dmitry; Kaxiras, Efthimios

    2016-11-01

    The recent surge in research on metal-halide-perovskite solar cells has led to a seven-fold increase of efficiency, from ~3% in early devices to over 22% in research prototypes. Oft-cited reasons for this increase are: (i) a carrier diffusion length reaching hundreds of microns; (ii) a low exciton binding energy; and (iii) a high optical absorption coefficient. These hybrid organic-inorganic materials span a large chemical space with the perovskite structure. Here, using first-principles calculations and thermodynamic modelling, we establish that, given the range of band-gaps of the metal-halide-perovskites, the theoretical maximum efficiency limit is in the range of ~25–27%. Our conclusions are based on the effect of level alignment between the perovskite absorber layer and carrier-transporting materials on the performance of the solar cell as a whole. Our results provide a useful framework for experimental searches toward more efficient devices.

  12. 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.

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. First-principles calculations on thermodynamic properties of BaTiO3 rhombohedral phase.

    PubMed

    Bandura, Andrei V; Evarestov, Robert A

    2012-07-05

    The calculations based on the linear combination of atomic orbitals have been performed for the low-temperature phase of BaTiO(3) crystal. Structural and electronic properties, as well as phonon frequencies were obtained using hybrid PBE0 exchange-correlation functional. The calculated frequencies and total energies at different volumes have been used to determine the equation of state and thermal contribution to the Helmholtz free energy within the quasiharmonic approximation. For the first time, the bulk modulus, volume thermal expansion coefficient, heat capacity, and Grüneisen parameters in BaTiO(3) rhombohedral phase have been estimated at zero pressure and temperatures form 0 to 200 K, based on the results of first-principles calculations. Empirical equation has been proposed to reproduce the temperature dependence of the calculated quantities. The agreement between the theoretical and experimental thermodynamic properties was found to be satisfactory.

  18. Strain effect on electronic structures of graphene nanoribbons: A first-principles study.

    PubMed

    Sun, Lian; Li, Qunxiang; Ren, Hao; Su, Haibin; Shi, Q W; Yang, Jinlong

    2008-08-21

    We report a first-principles study on the electronic structures of deformed graphene nanoribbons (GNRs). Our theoretical results show that the electronic properties of zigzag GNRs are not sensitive to uniaxial strain, while the energy gap modification of armchair GNRs (AGNRs) as a function of uniaxial strain displays a nonmonotonic relationship with a zigzag pattern. The subband spacings and spatial distributions of the AGNRs can be tuned by applying an external strain. Scanning tunneling microscopy dI/dV maps can be used to characterize the nature of the strain states, compressive or tensile, of AGNRs. In addition, we find that the nearest neighbor hopping integrals between pi-orbitals of carbon atoms are responsible for energy gap modification under uniaxial strain based on our tight binding approximation simulations.

  19. 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.

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

    DOE PAGES

    Mast, Daniel S.; Kim, Eunja; Siska, Emily M.; ...

    2016-03-20

    Here, 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 pressure 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 anmore » 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.« less

  1. Temperature effect on lattice and electronic structures of WTe2 from first-principles study

    NASA Astrophysics Data System (ADS)

    Liu, Gang; Liu, Huimei; Zhou, Jian; Wan, Xiangang

    2017-01-01

    Tungsten ditelluride (WTe2) exhibits extremely large and unsaturated magnetoresistance (MR). Due to the large spatial extensions of Te-5p and W-5d orbitals, the electronic properties of WTe2 are sensitive to the lattice structures, which can probably affect the strongly temperature dependent MR found in the experiment. Based on first-principle calculations, we investigate the temperature effect on the lattice and electronic structures of WTe2. Our numerical results show that the thermal expansion coefficients of WTe2 are highly anisotropic and considerably large. However, the temperature (less than 300 K) has an ignorable effect on the Fermi surface of WTe2. Our theoretical results clarify that the thermal expansion is not the main reason for the temperature-induced rapid decrease of magnetoresistance.

  2. 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.

  3. 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.

  4. First-principles calculation for phonon and optoelectronic properties of CsSnI3

    NASA Astrophysics Data System (ADS)

    Bano, Amreen; Khare, Preeti; Gaur, N. K.

    2016-05-01

    The CsSnI3 crystal belongs to an interesting class of semiconducting perovskite which is currently used in thin-film field-effect transistor made of organics-inorganics hybrid compounds. 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 dielectric and optical properties of the inorganic part of this compounds. A theoretical study of phonon, dielectric and optical properties of metal-halide cubic perovskite, CsSnI3 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. The optical properties shows that this compound has applications in optoelectronic devices.

  5. 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.

  6. 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.

  7. Exotic Multigap Structure in UPt3 Unveiled by a First-Principles Analysis

    NASA Astrophysics Data System (ADS)

    Nomoto, Takuya; Ikeda, Hiroaki

    2016-11-01

    A heavy-fermion superconductor UPt3 is a unique spin-triplet superconductor with multiple superconducting phases. Here, we provide the first report on a first-principles analysis of the microscopic superconducting gap structure. We find that the promising gap structure is an unprecedented E2 u state, which is completely different from the previous phenomenological E2 u models. Our obtained E2 u state has in-plane twofold vertical line nodes on small Fermi surfaces and point nodes with linear dispersion on a large Fermi surface. These peculiar features cannot be explained in the conventional spin 1 /2 representation, but is described by the group-theoretical representation of the Cooper pairs in the total angular momentum j =5 /2 space. Our findings shed new light on the long-standing problems in the superconductivity of UPt3 .

  8. Domains and ferroelectric switching pathways in Ca3Ti2O7 from first principles

    NASA Astrophysics Data System (ADS)

    Nowadnick, Elizabeth A.; Fennie, Craig J.

    2016-09-01

    Hybrid improper ferroelectricity, where an electrical polarization can be induced via a trilinear coupling to two nonpolar structural distortions of different symmetries, recently was demonstrated experimentally in the n =2 Ruddlesden-Popper compound Ca3Ti2O7 . In this paper we use group theoretic methods and first-principles calculations to identify possible ferroelectric switching pathways in Ca3Ti2O7 . We identify low-energy paths that reverse the polarization direction by switching via an orthorhombic twin domain or via an antipolar structure. We also introduce a chemically intuitive set of local order parameters to give insight into how these paths are relevant to ferroelectric switching nucleated at domain walls. Our findings suggest that switching may proceed via more than one mechanism in this material.

  9. 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.

  10. Infrared absorption and Raman scattering spectra of water under pressure via first principles molecular dynamics.

    PubMed

    Ikeda, Takashi

    2014-07-28

    From both the polarized and depolarized Raman scattering spectra of supercritical water a peak located at around 1600 cm(-1), attributed normally to bending mode of water molecules, was experimentally observed to vanish, whereas the corresponding peak remains clearly visible in the measured infrared (IR) absorption spectrum. In this computational study a theoretical formulation for analyzing the IR and Raman spectra is developed via first principles molecular dynamics combined with the modern polarization theory. We demonstrate that the experimentally observed peculiar behavior of the IR and Raman spectra for water are well reproduced in our computational scheme. We discuss the origins of a feature observed at 1600 cm(-1) in Raman spectra of ambient water.

  11. Electronic and optical properties of RESn3 (RE=Pr & Nd) intermetallics: A first principles study

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

    A theoretical study of structural, electronic and optical properties of RESn3 (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 (a0), 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.

  12. First principles study of properties of the oxidized Cu(100) and Cu(110)

    NASA Astrophysics Data System (ADS)

    Olenga, Antoine

    Copper based catalysts are of importance to a number of industrial processes including the synthesis of methanol, the reduction and decomposition of nitrogen oxides, and treatment of waste water. In copper catalysis surface oxidation and oxidic overlayers are believed to play a crucial role. In this work using density functional theory (DFT) within the generalized gradient approximation (GGA) we have studied the stability and associated electronic properties of the oxidized Cu(100) and Cu(110) surfaces. Especially, we have focused on studies of changes in the interlayer spacing, electron work function, binding energy, and density of states with oxygen coverage. We have examined the cases of various oxygen coverages of the non-reconstructed, missing row reconstructed Cu(100), and added row reconstructed Cu (110) surfaces. The first-principles calculations in this work have been performed using DMOl3 code. The obtained theoretical results have been compared with available experimental data.

  13. 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

  14. 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

  15. 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

  16. Theoretical Studies of Laser-Induced Molecular Rate Processes: Topics in Line Broadening and Spectroscopy.

    DTIC Science & Technology

    1985-10-01

    GROUP SU. GRF. MOLECULAR RATE PROCESSES MOLECULAR DYNAMICS LASER-INDUCED LINE BROADENING THEORETICAL STUDIES SPECTROSCOPY 19. ABSI*ACT (Continue On...approaches half the band-gap energy. -q 14 This idea of using a laser to "charge" the surface region has fomed the basis of a semiclassical theory of charge

  17. Electron field emission in nanostructures: A first-principles study

    NASA Astrophysics Data System (ADS)

    Driscoll, Joseph Andrew

    The objective of this work was to study electron field emission from several nanostructures using a first-principles framework. The systems studied were carbon nanowires, graphene nanoribbons, and nanotubes of varying composition. These particular structures were chosen because they have recently been identified as showing novel physical phenomena, as well as having tremendous industrial applications. We examined the field emission under a variety of conditions, including laser illumination and the presence of adsorbates. The goal was to explore how these conditions affect the field emission performance. In addition to the calculations, this dissertation has presented computational developments by the author that allowed these demanding calculations to be performed. There are many possible choices for basis when performing an electronic structure calculation. Examples are plane waves, atomic orbitals, and real-space grids. The best choice of basis depends on the structure of the system being analyzed and the physical processes involved (e.g., laser illumination). For this reason, it was important to conduct rigorous tests of basis set performance, in terms of accuracy and computational efficiency. There are no existing benchmark calculations for field emission, but transport calculations for nanostructures are similar, and so provide a useful reference for evaluating the performance of various basis sets. Based on the results, for the purposes of studying a non-periodic nanostructure under field emission conditions, we decided to use a real-space grid basis which incorporates the Lagrange function approach. Once a basis was chosen, in this case a real-space grid, the issue of boundary conditions arose. The problem is that with a non-periodic system, field emitted electron density can experience non-physical reflections from the boundaries of the calculation volume, leading to inaccuracies. To prevent this issue, we used complex absorbing potentials (CAPs) to absorb

  18. Calculating branching ratio and spin-orbit coupling from first principles: A formalism and its application to iridates

    NASA Astrophysics Data System (ADS)

    Sim, Jae-Hoon; Yoon, Hongkee; Park, Sang Hyeon; Han, Myung Joon

    2016-09-01

    We present a simple technique to calculate spin-orbit coupling, , and branching ratio measured in x-ray absorption spectroscopy. Our method is for first-principles electronic structure calculation, and its implementation is straightforward for any of the standard formulations and codes. We applied this technique to several different large spin-orbit coupling iridates. The calculated and branching ratio of a prototype jeff=1 /2 Mott insulator, Sr2IrO4 , are in good agreement with recent experimental data over the wide range of Rh doping. Three different double-perovskite iridates (namely, Sr2MgIrO6 , Sr2ScIrO6 , and Sr2TiIrO6 ) are also well described. This technique can serve as a promising tool for studying large spin-orbit coupling materials from first principles and for understanding experiments.

  19. 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.

  20. Topological semimetals predicted from first-principles calculations.

    PubMed

    Weng, Hongming; Dai, Xi; Fang, Zhong

    2016-08-03

    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.

  1. First-principles models of equilibrium tellurium isotope fractionation

    NASA Astrophysics Data System (ADS)

    Haghnegahdar, M. A.; Schauble, E. A.; Fornadel, A. P.; Spry, P. G.

    2013-12-01

    In this study, equilibrium mass-dependent isotopic fractionation among representative Te-bearing species is estimated with first-principles thermodynamic calculations. Tellurium is a group 16 element (along with O, S, and Se) with eight stable isotopes ranging in mass from 120Te to 130Te, and six commonly-occurring oxidation states: -II, -I, 0, +II, +IV, and +VI. In its reduced form, Te(-II), tellurium has a unique crystal-chemical role as a bond partner for gold and silver in epithermal and orogenic gold deposits, which likely form when oxidized Te species (e.g., H2TeO3, TeO32-) or perhaps polytellurides (e.g., Te22-) interact with precious metals in hydrothermal solution. Te(IV) is the most common oxidation state at the Earth's surface, including surface outcrops of telluride ore deposits, where tellurite and tellurate minerals form by oxidation. In the ocean, dissolved tellurium tends to be scavenged by particulate matter. Te(VI) is more abundant than Te(IV) in the ocean water (1), even though it is thought to be less stable thermodynamically. This variety of valence states in natural systems and range of isotopic masses suggest that tellurium could exhibit geochemically useful isotope abundance variations. Tellurium isotope fractionations were determined for representative molecules and crystals of varying complexity and chemistry. Gas-phase calculations are combined with supermolecular cluster models of aqueous and solid species. These in turn are compared with plane-wave density functional theory calculations with periodic boundary conditions. In general, heavyTe/lightTe is predicted to be higher for more oxidized species, and lower for reduced species, with 130Te/125Te fractionations as large as 4‰ at 100οC between coexisting Te(IV) and Te(-II) or Te(0) compounds. This is a much larger fractionation than has been observed in naturally occurring redox pairs (i.e., Te (0) vs. Te(IV) species) so far, suggesting that disequilibrium processes may control

  2. Photoexcitation and Photochemical Stability of Organic Photovoltaic Materials from First Principles

    NASA Astrophysics Data System (ADS)

    Sai, Na; Leung, Kevin

    2013-03-01

    The development of high efficiency organic photovoltaics (OPV) has recently become enabled by the synthesis of new conjugated polymers with low band gap that allow light absorption over a broader range of the spectrum. Stability of these new polymers, a key requirement for commercialization, has not yet received sufficient attention. Here, we report first-principles theoretical modeling of photo-induced degradation of OPV polymers carried out using ab-initio density functional theory (DFT). We report photooxidation routes and reaction products for reactive species including superoxide oxygen anions and hydroxyl groups interacting with the standard workhorse OPV polymer, poly(3-hexyl-thiophene) (P3HT). We discuss theoretical issues and challenges affecting the modeling such reactions in OPV polymers. We also discuss the application of theoretical methods to low-band-gap polymers, and in particular, the effect of the chemical substitution on the photoexcitation properties of these new polymers. Sandia National Laboratories is a multiprogram laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Deparment of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000. This work is supported by the Energy Frontier Research Center funded by the U.S. DOE Office of Basic Energy Sciences under Award number DE-SC0001091.

  3. 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

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. First principles Investigations of the Conductance of Stretched Molecules

    NASA Astrophysics Data System (ADS)

    Speyer, Gil; Akis, Richard; Ferry, David K.; Li, Jun; Sankey, Otto F.

    2004-03-01

    A novel experimental setup developed at Arizona State University examines the molecular conductance across a variety of gap lengths by lowering a gold-plated AFM tip into a monolayer deposited on a gold substrate [1]. Theoretical investigations into these systems have revealed interesting trends in the conductance of these molecules as they are stretched. We investigate this system using a variety of theoretical models, such as DFT and Hartree-Fock calculations of the Hamiltonian (and a variety of basis sets), which is implemented into a Landauer formula based rapid transfer matrix method with charge self-consistency [2]. Here we solve a self-consistent potential, which obviates the need to parameterize the voltage. Conduction across the molecule occurs in multiple channels; gold states couple with varying strengths to the orbitals of the molecule. We will report the effects of strain across the molecule, and distortion of the molecule, on the conductive nature of the coupling. * Work supported by the Office of Naval Research [1] B. Xu and N. J. Tao, Science 301, 1221 (2003). [2] T. Usuki, M. Saito, M. Takatsu, R.A. Kiehl, and N. Yokoyama, Phys. Rev. B 52, 8244 (1995).

  9. Theoretical and experimental vibrational spectroscopy study on rotational isomer of 4-phenylbutylamine

    NASA Astrophysics Data System (ADS)

    Ünal, A.; Okur, M.

    2017-02-01

    The possible four stable rotational isomers of 4-phenylbutylamine (4PBA) molecule were experimentally and theoretically studied by vibrational spectroscopy. The FT-IR (4000-400 cm-1) and Raman (3700-60 cm-1) spectra of 4PBA were recorded at room temperature in liquid phase. The complete vibrational wavenumbers and corresponding vibrational assignments of 4PBA molecule were discussed assisted with B3LYP/6-311++G(d,p) level of theory along with scaled quantum mechanics force field (SQM-FF) method. Results from experimental and theoretical data the most stable form of 4PBA molecule was obtained.

  10. First principles study of halogens adsorption on intermetallic surfaces

    NASA Astrophysics Data System (ADS)

    Zhu, Quanxi; Wang, Shao-qing

    2016-02-01

    Halides are often present at electrochemical environment, they can directly influence the electrode potential or zero charge potential through the induced work-function change. In this work, we focused in particular on the halogen-induced work function change as a function of the coverage of fluorine, chlorine, bromine and iodine on Al2Au and Al2Pt (110) surfaces. Results show that the real relation between work function change and dipole moment change for halogens adsorption on intermetallic surfaces is just a common linear relationship rather than a directly proportion. Besides, the different slopes between fitted lines and the theoretical slope employed in pure metal surfaces demonstrating that the halogens adsorption on intermetallic surfaces are more complicated. We also present a weight parameter β to describe different factors effect on work function shift and finally qualify which factor dominates the shift direction.

  11. Pressure Dependent Electronic Properties of Organic Semiconductors from First Principles

    NASA Astrophysics Data System (ADS)

    Knuth, Franz; Carbogno, Christian; Blum, Volker; Scheffler, Matthias

    2015-03-01

    The electronic properties of organic semiconductors typically exhibit a significant dependence on the strain, stress, and pressure. In this contribution, we present the theoretical background, assessment of approximations, and results of electronic and transport properties in the framework of density-functional theory. Our implementation considers the analytical strain derivatives (stress tensor) including the contributions that stem from (a) van-der-Waals interactions and (b) the Fock-exchange in hybrid functionals. We validate our approach by investigating the geometric and electronic changes that occur in polyacetylene and anthracene under hydrostatic pressure. We show that the fraction of exact exchange included in the calculations is critical - and non-trivial to choose - for a correct description of these systems. Furthermore, we point out trends for the electrical conductivity under pressure and identify the dominant charge carriers and transport directions.

  12. Structure of Ni78 from First-Principles Computations

    DOE PAGES

    Hagen, Gaute; Univ. of Tennessee, Knoxville, TN; Jansen, Gustav R.; ...

    2016-10-17

    Doubly magic nuclei have a simple structure and are the cornerstones for entire regions of the nuclear chart. Theoretical insights into the supposedly doubly magic 78Ni and its neighbors are challenging because of the extreme neutron-to-proton ratio and the proximity of the continuum. In this study, we predict the Jπ = 2more » $$+\\atop{1}$$ state in 78Ni from a correlation with the Jπ = 2$$+\\atop{1}$$ state in 48Ca using chiral nucleon-nucleon and three-nucleon interactions. Our results confirm that 78Ni is doubly magic, and the predicted low-lying states of 79,80Ni open the way for shell-model studies of many more rare isotopes.« less

  13. First-principles study of anhydrite, polyhalite and carnallite

    NASA Astrophysics Data System (ADS)

    Weck, Philippe F.; Kim, Eunja; Jové-Colón, Carlos F.; Sassani, David C.

    2014-02-01

    We report density functional calculations of the structures and properties of anhydrite (CaSO4), polyhalite (K2SO4·MgSO4·2CaSO4·2H2O) and carnallite (KCl·MgCl2·6H2O). Densities of states are systematically investigated and phonon analysis using density functional perturbation theory is performed at constant equilibrium volume for anhydrite and polyhalite in order to derive their isochoric thermal properties. Thermal properties at constant atmospheric pressure are also calculated using the quasi-harmonic approximation. The computed molar entropy and isobaric heat capacity for anhydrite reproduce experimental data up to 800 K to within 3% and 10%, respectively, while further experimental work is needed to assess our theoretical predictions for polyhalite.

  14. Conformational equilibrium of phenylacetic acid and its halogenated analogues through theoretical studies, NMR and IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Levandowski, Mariana N.; Rozada, Thiago C.; Melo, Ulisses Z.; Basso, Ernani A.; Fiorin, Barbara C.

    2017-03-01

    This paper presents a study on the conformational preferences of phenylacetic acid (PA) and its halogenated analogues (FPA, CPA, BPA). To clarify the effects that rule these molecules' behaviour, theoretical calculations were used, for both the isolated phase and solution, combined with nuclear magnetic resonance (NMR) and infrared (IR) spectroscopy. Most conformations of phenylacetic acid and its halogenated derivatives are stabilized through the hyperconjugative effect, which rules the conformational preference. NMR analyses showed that even with the variation in medium polarity, there was no significant change in the conformation population. Infrared spectroscopy showed similar results for all compounds under study. In most spectra, two bands were found through the carbonyl deconvolution, which is in accordance with the theoretical data. It was possible to prove that variation in the nature of the substituent in the ortho position had no significant influence on the conformational equilibrium.

  15. Soft X-ray spectroscopy of transition metal compounds: a theoretical perspective

    NASA Astrophysics Data System (ADS)

    Bokarev, S. I.; Hilal, R.; Aziz, S. G.; Kühn, O.

    2016-12-01

    To date, X-ray spectroscopy has become a routine tool that can reveal highly local and element-specific information on the electronic structure of atoms in complex environments. Here, we report on the development of an efficient and versatile theoretical methodology for the treatment of soft X-ray spectra of transition metal compounds based on the multi-configurational self-consistent field electronic structure theory. A special focus is put on the L-edge photon-in/photon-out and photon-in/electron-out processes, i.e. X-ray absorption, resonant inelastic scattering, partial fluorescence yield, and photoelectron spectroscopy, all treated on the same theoretical footing. The investigated systems range from small prototypical coordination compounds and catalysts to aggregates of biomolecules.

  16. Pressure-dependent semiconductor to semimetal and Lifshitz transitions in 2H-MoTe2: Raman and first-principles studies

    NASA Astrophysics Data System (ADS)

    Bera, Achintya; Singh, Anjali; Muthu, D. V. S.; Waghmare, U. V.; Sood, A. K.

    2017-03-01

    High pressure Raman spectroscopy of bulk 2H-MoTe2 up to  ∼29 GPa is shown to reveal two phase transitions (at  ∼6 and 16.5 GPa), which are analyzed using first-principles density functional theoretical calculations. The transition at 6 GPa is marked by changes in the pressure coefficients of A 1g and E2g1 Raman mode frequencies as well as in their relative intensity. Our calculations show that this is an isostructural semiconductor to a semimetal transition. The transition at  ∼16.5 GPa is identified with the changes in linewidths of the Raman modes as well as in the pressure coefficients of their frequencies. Our theoretical analysis clearly shows that the structure remains the same up to 30 GPa. However, the topology of the Fermi-surface evolves as a function of pressure, and abrupt appearance of electron and hole pockets at P∼ 20 GPa marks a Lifshitz transition.

  17. First-Principles Study of Structural, Magnetic, Electronic and Elastic Properties of PuC2

    NASA Astrophysics Data System (ADS)

    Yang, Rong; Tang, Bin; Gao, Tao; Ao, Bing-Yun

    2016-10-01

    We perform first-principles calculations of crystal structure, magnetism, electronic structure, chemical bonding and elastic properties for PuC2 using the standard local spin-density approximation (LSDA)+U scheme. The use of the Hubbard term to describe the 5f electrons of plutonium is discussed according to the lattice parameters, magnetism and densities of states. Our calculated lattice constants and magnetism are in good agreement with the experimental data or other theoretical calculations. It is shown that the total densities of states at the Fermi energy level mainly come from the contribution of narrow f band. The Pu-C bonds of PuC2 have a mixture of covalent character and ionic character, while covalent character is stronger than ionic character. The C1-C2 bonding has strong covalent character because of sp2 hybridization between C atoms. Lastly, the elastic properties of PuC2 are studied. We hope that our results can provide a useful reference for further theoretical and experimental research on PuC2. Supported by the National Natural Science Foundation of China under Grant Nos. 21371160, 21401173, and the Science Challenge Program of China

  18. 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.

  19. 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

  20. Theoretical background of optical emission spectroscopy for analysis of atmospheric pressure plasmas

    NASA Astrophysics Data System (ADS)

    Belmonte, Thierry; Noël, Cédric; Gries, Thomas; Martin, Julien; Henrion, Gérard

    2015-12-01

    This review contains a theoretical background of optical emission spectroscopy and some selected examples of issues in the field of atmospheric plasmas. It includes elements like line broadening, emission of continua and molecules, radiation models, etc. Modernized expressions figuring the terms hidden in global constants where cgs units prevail are given together with restrictions of use. Easy-to-use formulas are provided to give access to essential plasma parameters.

  1. Adsorption of carbon on Pd clusters of nanometer size: a first-principles theoretical study.

    PubMed

    Neyman, Konstantin M; Inntam, Chan; Gordienko, Alexei B; Yudanov, Ilya V; Rösch, Notker

    2005-05-01

    Adsorbed atomic C species can be formed in the course of surface reactions and commonly decorate metal catalysts. We studied computationally C adsorption on Pd nanoclusters using an all-electron scalar relativistic density functional method. The metal particles under investigation, Pd(55), Pd(79), Pd(85), Pd(116), Pd(140), and Pd(146), were chosen as fragments of bulk Pd in the form of three-dimensional octahedral or cuboctahedral crystallites, exposing (111) and (100) facets as well as edge sites. These cluster models are shown to yield size-converged adsorption energies. We examined which surface sites of these clusters are preferentially occupied by adsorbed C. According to calculations, surface C atoms form strongly adsorbed carbide species (with adsorption energies of more than 600 kJ mol(-1)) bearing a significant negative charge. Surface sites allowing high, fourfold coordination of carbon are overall favored. To avoid effects of adsorbate-adsorbate interaction in the cluster models for carbon species in the vicinity of cluster edges, we reduced the local symmetry of selected adsorption complexes on the nanoclusters by lowering the global symmetry of the nanocluster models from point group O(h) to D(4h). On (111) facets, threefold hollow sites in the center are energetically preferred; adsorbed C is calculated to be slightly less stable when displaced to the facet borders.

  2. 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.)

  3. First-principle Simulations of Heavy Fermion Materials

    NASA Astrophysics Data System (ADS)

    Dong, Ruanchen

    Heavy fermion materials, one of the most challenging topics in condensed matter physics, pose a variety of interesting properties and have attracted extensive studies for decades. Although there has been great success in explaining many ground- state properties of solids, the well-known theoretical calculations based on density functional theory (DFT) in its popular local density approximation (LDA) fail to describe heavy fermion materials due to improper treatment of many-body correlation effects. Here with the implementations of dynamical mean-field theory (DMFT) and the Gutzwiller variational method, the computational simulation of the heavy fermion materials is explored further and better compared with experimental data. In this dissertation, first, the theoretical background of DMFT and LDA+G methods is described in detail. The rest is the application of these techniques and is basically divided into two parts. First, the continuous-time quantum Monte Carlo (CT-QMC) method combined with DMFT is used to calculate and compare both the periodic Anderson model (PAM) and the Kondo lattice model (KLM). Different parameter sets of both models are connected by the Schrieffer-Wolff transformation. For spin and orbital degeneracy N = 2 case, a special particle-hole symmetric case of PAM at half-filling which always fixes one electron per impurity site is compared with the results of the KLM. We find a good mapping between PAM and KLM in the limit of large on-site Hubbard interaction U for different properties like self-energy, quasiparticle residue and susceptibility. This allows us to extract quasiparticle mass renormalizations for the f-electrons directly from KLM. The method is further applied to higher degenerate cases and to the realistic heavy fermion system CeRhIn5 in which the estimate of the Sommerfeld coefficient is proven to be close to the experimental value. Second, a series of Cerium based heavy fermion materials is studied using a combination of local

  4. Effect of Pressure on Valence and Structural Properties of YbFe 2 Ge 2 Heavy Fermion Compound—A Combined Inelastic X-ray Spectroscopy, X-ray Diffraction, and Theoretical Investigation

    DOE PAGES

    Kumar, Ravhi S.; Svane, Axel; Vaitheeswaran, Ganapathy; ...

    2015-10-19

    We measured the crystal structure and the Yb valence of the YbFe2Ge2 heavy fermion compound 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. Moreover, 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. Finally, 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) atmore » ambient pressure to v = 2.93(3) at ~9 GPa, where at low temperature a pressure-induced quantum critical state was reported.« less

  5. 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

    2016-06-03

    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.

  6. 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

    2015-11-02

    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.

  7. Application of Merrill's First Principles of Instruction in a Museum Education Context

    ERIC Educational Resources Information Center

    Nelson, Kari Ross

    2015-01-01

    In an effort to support a solid grounding in educational theory within the field of museum education, three texts considered essential reading for museum educators were surveyed for correlations with Merrill's First Principles of Instruction, an influential work in the field of instructional design. Each of five First Principles were found to be…

  8. Electron-electron correlation in graphite: a combined angle-resolved photoemission and first-principles study.

    PubMed

    Grüneis, A; Attaccalite, C; Pichler, T; Zabolotnyy, V; Shiozawa, H; Molodtsov, S L; Inosov, D; Koitzsch, A; Knupfer, M; Schiessling, J; Follath, R; Weber, R; Rudolf, P; Wirtz, L; Rubio, A

    2008-01-25

    The full three-dimensional dispersion of the pi bands, Fermi velocities, and effective masses are measured with angle-resolved photoemission spectroscopy and compared to first-principles calculations. The band structure by density-functional theory underestimates the slope of the bands and the trigonal warping effect. Including electron-electron correlation on the level of the GW approximation, however, yields remarkable improvement in the vicinity of the Fermi level. This demonstrates the breakdown of the independent electron picture in semimetallic graphite and points toward a pronounced role of electron correlation for the interpretation of transport experiments and double-resonant Raman scattering for a wide range of carbon based materials.

  9. 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.

  10. Length dependence of electron transport through molecular wires--a first principles perspective.

    PubMed

    Khoo, Khoong Hong; Chen, Yifeng; Li, Suchun; Quek, Su Ying

    2015-01-07

    One-dimensional wires constitute a fundamental building block in nanoscale electronics. However, truly one-dimensional metallic wires do not exist due to Peierls distortion. Molecular wires come close to being stable one-dimensional wires, but are typically semiconductors, with charge transport occurring via tunneling or thermally-activated hopping. In this review, we discuss electron transport through molecular wires, from a theoretical, quantum mechanical perspective based on first principles. We focus specifically on the off-resonant tunneling regime, applicable to shorter molecular wires (<∼4-5 nm) where quantum mechanics dictates electron transport. Here, conductance decays exponentially with the wire length, with an exponential decay constant, beta, that is independent of temperature. Different levels of first principles theory are discussed, starting with the computational workhorse - density functional theory (DFT), and moving on to many-electron GW methods as well as GW-inspired DFT + Sigma calculations. These different levels of theory are applied in two major computational frameworks - complex band structure (CBS) calculations to estimate the tunneling decay constant, beta, and Landauer-Buttiker transport calculations that consider explicitly the effects of contact geometry, and compute the transmission spectra directly. In general, for the same level of theory, the Landauer-Buttiker calculations give more quantitative values of beta than the CBS calculations. However, the CBS calculations have a long history and are particularly useful for quick estimates of beta. Comparing different levels of theory, it is clear that GW and DFT + Sigma calculations give significantly improved agreement with experiment compared to DFT, especially for the conductance values. Quantitative agreement can also be obtained for the Seebeck coefficient - another independent probe of electron transport. This excellent agreement provides confirmative evidence of off

  11. 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

  12. High-pressure elastic properties of major materials of Earth's mantle from first principles

    NASA Astrophysics Data System (ADS)

    Karki, Bijaya B.; Stixrude, Lars; Wentzcovitch, Renata M.

    2001-11-01

    The elasticity of materials is important for our understanding of processes ranging from brittle failure, to flexure, to the propagation of elastic waves. Seismologically revealed structure of the Earth's mantle, including the radial (one-dimensional) profile, lateral heterogeneity, and anisotropy are determined largely by the elasticity of the materials that make up this region. Despite its importance to geophysics, our knowledge of the elasticity of potentially relevant mineral phases at conditions typical of the Earth's mantle is still limited: Measuring the elastic constants at elevated pressure-temperature conditions in the laboratory remains a major challenge. Over the past several years, another approach has been developed based on first-principles quantum mechanical theory. First-principles calculations provide the ideal complement to the laboratory approach because they require no input from experiment; that is, there are no free parameters in the theory. Such calculations have true predictive power and can supply critical information including that which is difficult to measure experimentally. A review of high-pressure theoretical studies of major mantle phases shows a wide diversity of elastic behavior among important tetrahedrally and octahedrally coordinated Mg and Ca silicates and Mg, Ca, Al, and Si oxides. This is particularly apparent in the acoustic anisotropy, which is essential for understanding the relationship between seismically observed anisotropy and mantle flow. The acoustic anisotropy of the phases studied varies from zero to more than 50% and is found to depend on pressure strongly, and in some cases nonmonotonically. For example, the anisotropy in MgO decreases with pressure up to 15 GPa before increasing upon further compression, reaching 50% at a pressure of 130 GPa. Compression also has a strong effect on the elasticity through pressure-induced phase transitions in several systems. For example, the transition from stishovite to CaCl2

  13. Influence of oxygen vacancies on the dielectric properties of hafnia: First-principles calculations

    NASA Astrophysics Data System (ADS)

    Cockayne, Eric

    2007-03-01

    First-principles calculations were used to study the effects of neutral and 2+ charged oxygen vacancies on the dielectric properties of crystalline HfO2 . In agreement with previous results, the neutral vacancy is more stable on four fold-coordinated site, while the charged vacancy is more stable on a three fold-coordinated site. For both vacancy positions, HfO2 remains insulating whether the vacancy is neutral or in the 2+ charge state. The dynamical matrix, Born effective charges, and electronic dielectric tensor were calculated for each structure. With one oxygen vacancy per 64 oxygen atoms, the static dielectric constant κs is increased by 1%-2% for neutral vacancies and suppressed by 1%-3% for 2+ charged vacancies, with the larger changes for three fold-coordinated vacancies. The exact result in the case of a charged vacancy depends on how the neutralizing charge necessary for macroscopic charge neutrality is modeled. The increase in κs for neutral oxygen vacancies arises from an enhancement of the electronic dielectric response due to a pair of electrons occupying an easily polarizable F -center defect state. The suppression in κs for charged oxygen vacancies is due to phonon hardening, which reduces the ionic response. No evidence is found for characteristic localized phonons induced by oxygen vacancies that could be detected by infrared or Raman spectroscopy.

  14. 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.

  15. Iron isotope fractionation between pyrite (FeS 2), hematite (Fe 2O 3) and siderite (FeCO 3): A first-principles density functional theory study

    NASA Astrophysics Data System (ADS)

    Blanchard, Marc; Poitrasson, Franck; Méheut, Merlin; Lazzeri, Michele; Mauri, Francesco; Balan, Etienne

    2009-11-01

    In addition to equilibrium isotopic fractionation factors experimentally derived, theoretical predictions are needed for interpreting isotopic compositions measured on natural samples because they allow exploring more easily a broader range of temperature and composition. For iron isotopes, only aqueous species were studied by first-principles methods and the combination of these data with those obtained by different methods for minerals leads to discrepancies between theoretical and experimental isotopic fractionation factors. In this paper, equilibrium iron isotope fractionation factors for the common minerals pyrite, hematite, and siderite were determined as a function of temperature, using first-principles methods based on the density functional theory (DFT). In these minerals belonging to the sulfide, oxide and carbonate class, iron is present under two different oxidation states and is involved in contrasted types of interatomic bonds. Equilibrium fractionation factors calculated between hematite and siderite compare well with the one estimated from experimental data (ln α57Fe/ 54Fe = 4.59 ± 0.30‰ and 5.46 ± 0.63‰ at 20 °C for theoretical and experimental data, respectively) while those for Fe(III) aq-hematite and Fe(II) aq-siderite are significantly higher that experimental values. This suggests that the absolute values of the reduced partition functions ( β-factors) of aqueous species are not accurate enough to be combined with those calculated for minerals. When compared to previous predictions derived from Mössbauer or INRXS data [Polyakov V. B., Clayton R. N., Horita J. and Mineev S. D. (2007) Equilibrium iron isotope fractionation factors of minerals: reevaluation from the data of nuclear inelastic resonant X-ray scattering and Mössbauer spectroscopy. Geochim. Cosmochim. Acta71, 3833-3846], our iron β-factors are in good agreement for siderite and hematite while a discrepancy is observed for pyrite. However, the detailed investigation of the

  16. First-principles study of electronic structures and stability of body-centered cubic Ti–Mo alloys by special quasirandom structures

    PubMed Central

    Sahara, Ryoji; Emura, Satoshi; Ii, Seiichiro; Ueda, Shigenori; Tsuchiya, Koichi

    2014-01-01

    The electronic structures and structural properties of body-centered cubic Ti–Mo alloys were studied by first-principles calculations. The special quasirandom structures (SQS) model was adopted to emulate the solid solution state of the alloys. The valence band electronic structures of Ti–Mo and Ti–Mo–Fe alloys were measured by hard x-ray photoelectron spectroscopy. The structural parameters and valence band photoelectron spectra were calculated using first-principles calculations. The results obtained with the SQS models showed better agreement with the experimental results than those obtained using the conventional ordered structure models. This indicates that the SQS model is effective for predicting the various properties of solid solution alloys by means of first-principles calculations. PMID:27877690

  17. First-principles study of electronic structures and stability of body-centered cubic Ti-Mo alloys by special quasirandom structures.

    PubMed

    Sahara, Ryoji; Emura, Satoshi; Ii, Seiichiro; Ueda, Shigenori; Tsuchiya, Koichi

    2014-06-01

    The electronic structures and structural properties of body-centered cubic Ti-Mo alloys were studied by first-principles calculations. The special quasirandom structures (SQS) model was adopted to emulate the solid solution state of the alloys. The valence band electronic structures of Ti-Mo and Ti-Mo-Fe alloys were measured by hard x-ray photoelectron spectroscopy. The structural parameters and valence band photoelectron spectra were calculated using first-principles calculations. The results obtained with the SQS models showed better agreement with the experimental results than those obtained using the conventional ordered structure models. This indicates that the SQS model is effective for predicting the various properties of solid solution alloys by means of first-principles calculations.

  18. 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.

  19. 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).

  20. Electronic structure and thermoelectric property of Co2YGe (Y=Mn, Fe) Heusler compounds: a first principle study

    NASA Astrophysics Data System (ADS)

    Joshi, Himanshu; Rai, D. P.; Sandeep; Thapa, R. K.

    2016-10-01

    The electronic and thermoelectric properties of Co2YGe (Y=Mn, Fe) Heusler compounds have been studied by first principle density functional theory and compared with the known experimental and theoretical results. Results of the density of states (DOS) and band structures shows the half-metallicity of the Heusler alloy Co2MnGe, whereas the Heusler alloy Co2FeGe fails to give half-metallicity when treated with GGA. The ZT value calculated for these materials is much below the benchmark value 1.

  1. Predicted Thermoelectric Properties of the Layered XBi4S7 (X = Mn, Fe) Based Materials: First Principles Calculations

    NASA Astrophysics Data System (ADS)

    Azam, Sikander; Khan, Saleem Ayaz; Goumri-Said, Souraya; Kanoun, Mohammed Benali

    2017-01-01

    We report a theoretical investigation of electronic structures, optical and thermoelectric properties of two ternary-layered chalcogenides, MnBi4S7 and FeBi4S7 , by combining the first principles density functional calculations and semi-local Boltzmann transport theory. The calculated electronic band structure have demonstrated that both compounds exhibit indirect band gaps. The optical transitions are explored via the dielectric function (real and imaginary parts) along with other related optical constants including refractive index, reflectivity, and energy loss spectrum. These chalcogenides have exhibited interesting thermoelectric properties such as Seebeck's coefficient, electrical and thermal conductivity, and power factor as function of temperatures.

  2. Insight into the origin of magnetism in Iron-doped cadmium sulfide thin films from first principles calculations

    NASA Astrophysics Data System (ADS)

    Kanoun, Mohammed Benali

    2017-03-01

    We report a theoretical study of electronic structures and magnetic properties of Fe-doped CdS (10-10) thin films using first principle calculations within the density functional theory. It is shown that Fe atoms occupying Cd sites prefer to reside on the surface and couple antiferromagnetically. However, our results show the existence of competition between ferromagnetic and antiferromagnetic coupling because of the smaller total energy difference. Moreover, our density of states shows the existence of a simultaneous hybridization between the Fe d and S p states near the Fermi level.

  3. 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.

  4. 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.

  5. First-principles calculation on dilute magnetic alloys in zinc blend crystal structure

    NASA Astrophysics Data System (ADS)

    Ullah, Hamid; Inayat, Kalsoom; Khan, S. A.; Mohammad, S.; Ali, A.; Alahmed, Z. A.; Reshak, A. H.

    2015-07-01

    Ab-initio calculations are performed to investigate the structural, electronic and magnetic properties of spin-polarized diluted magnetic alloys in zinc blende structure. The first-principles study is carried out on Mn doped III-V semiconductors. The calculated band structures, electronic properties and magnetic properties of Ga1-xMnxX (X=P, As) compounds reveal that Ga0.75Mn0.25P is half metallic turned to be metallic with increasing x to 0.5 and 0.75, whereas substitute P by As cause to maintain the half-metallicity nature in both of Ga0.75Mn0.25As and Ga0.5Mn0.5As and tune Ga0.25Mn0.75As to be metallic. Calculated total magnetic moments and the robustness of half-metallicity of Ga0.75Mn0.25P, Ga0.75Mn0.25As and Ga0.5Mn0.5As with respect to the variation in lattice parameters are also discussed. The predicted theoretical evidence shows that some Mn-doped III-V semiconductors can be effectively used in spintronic devices.

  6. First-principles investigation on elastic and thermodynamic properties of Pnnm-CN under high pressure

    NASA Astrophysics Data System (ADS)

    Ya-Ru, Zhao; Hai-Rong, Zhang; Gang-Tai, Zhang; Qun, Wei; Yu-Quan, Yuan

    2016-12-01

    The elastic anisotropy and thermodynamic properties of the recently synthesized Pnnm-CN have been investigated using first-principles calculations under high temperature and high pressure. The calculated equilibrium crystal parameters and normalized volume dependence of the resulting pressure agree with available experimental and theoretical results. Within the considered pressure range of 0-90 GPa, the dependences of the bulk modulus, Young's modulus, and shear modulus on the crystal orientation for Pnnm-CN have been systematically studied. The results show that the Pnnm-CN exhibits a well-pronounced elastic anisotropy. The incompressibility is largest along the c-axis. For tension or compression loading, the Pnnm-CN is stiffest along [001] and the most obedient along [100] direction. On the basis of the quasi-harmonic Debye model, we have explored the Debye temperature, heat capacity, thermal expansion coefficient, and Grüneisen parameters within the pressure range of 0-90 GPa and temperature range of 0-1600K.

  7. First principles computations to predict and understand H storage in metals and complex hydrides

    NASA Astrophysics Data System (ADS)

    Ceder, Gerbrand

    2004-03-01

    Hydrogen is expected to play an important role in the future distribution of energy. While hydrogen fuel cells have seen significant improvements, the problem of hydrogen storage remains. A key property of any potential H-storage material is its reaction enthalpy with hydrogen. This quantity can directly be calculated with standard first principles total energy methods. We find that hydriding behavior can be almost completely explained by electronic structure of the metal and the electron transfer reactions between the metal and hydrogen. These observations explain the observed trends in the hydride formation energy and gives a theoretical basis for the empirically established rule of reverse stability. We discuss the potential for making hydrides with higher energy density than MgH2. In complex hydrides, such as alanates we find that substitution of the alkali metal can be used to modify the overall affinity for hydrogen while substitution on the Al site modifies the ration between the two plateau pressures at which H is absorbed.

  8. Full first-principles simulations on 180^o ferroelectric stripe domains in realistic ferroelectric capacitors.

    NASA Astrophysics Data System (ADS)

    Junquera, Javier; Aguado-Puente, Pablo

    2007-03-01

    The field of ferroelectric thin films is at a momentous stage. Several experimental and theoretical works, both within a phenomenological approach or atomistic models, have been devoted to ascertain the ground state of ferroelectric thin-film capacitors. Using a full first-principles density-functional-theory approach, we have simulated 180^o ferroelectric stripe domains at 0 K in SrRuO3/BaTiO3/SrRuO3 and SrRuO3/PbTiO3/SrRuO3 realistic ferroelectric capacitors epitaxially grown on a SrTiO3 substrate. For a ferroelectic thin-film 2 unit cells thick, the lateral sizes of the domains ranged from 2 to 4 unit cells. The in-plane displacement of the atoms is essential to stabilize the domain structure. A exotic vortex structure, closed by the atoms of the first metallic layer, is found for the polarization. Ph. Ghosez and J. Junquera, http://xxx.lanl.gov/pdf/cond-mat/0605299, and references therein. J. M. Soler et al., J. Phys.: Condens. Matter 14 2745 (2002)

  9. Defective germanene as a high-efficiency helium separation membrane: a first-principles study.

    PubMed

    Zhu, Lei; Chang, Xiao; He, Daliang; Xue, Qingzhong; Li, Xiaofang; Jin, Yakang; Zheng, Haixia; Ling, Cuicui

    2017-03-01

    Development of low energy cost membranes for separating helium from natural gas is highly desired. Using van der Waals-corrected first-principles density functional theory (DFT) calculations, we theoretically investigate the helium separation performance of divacancy-defective germanene. The 555 777 divacancy-defective germanene presents a 0.53 eV energy barrier for helium, which is slightly larger than the energy threshold value of gas molecule penetration of a membrane (0.5 eV). Thus, the 555 777 divacancy-defective germanene is difficult for helium to permeate, except under high temperature or pressure. However, the 585 divacancy-defective germanene presents a surmountable energy barrier (0.27 eV) for helium, and it shows extremely high helium selectivities relative to other studied gas molecules. Especially, the He/Ne selectivity can be as high as 1 × 10(4) at room temperature. Together with the acceptable permeance for helium, the 585 divacancy-defective germanene can be used for helium separation with remarkably good performance.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

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

    PubMed

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

    2013-01-15

    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.

  15. 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.

  16. 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.

  17. 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.

  18. First-principles simulations on bonding pathways of chemical transformations under hydrostatic compression

    NASA Astrophysics Data System (ADS)

    Hu, Anguang; Zhang, Fan

    2012-02-01

    High pressure as a thermodynamic parameter provides a strong structural constraint to lead chemical transformations with selective ways. Thus, chemical transformations under pressure can create novel materials which may not be accessible by covalent synthesis. However, bonding evolution toward high pressure chemical transformations can be a complex process and may happen over widely different pressures. To understand bonding evolution pathways of high pressure chemical transformations, first-principles simulations were performed following hydrostatic compression enthalpy minimization paths to obtain experimentally and theoretically established phase transitions of carbon. The results showed that the chemical transformations from hydrostatic compression carbon to single-bonded phases were characterized by a sudden decrease in principal stress components, indicating the onset of chemical transformation. On this basis, a number of hydrostatic compression chemical transformations from molecular precursors to novel materials were predicted, such as hydrocarbon graphane, a hydrogenated carbon nitride sheet, and carbon nitrides. All predicted hydrostatic compression transformations are featured as a sudden change in principal stress components, representing chemical bonding destruction and formation reactions with a cell volume collapse.

  19. Infrared radiative properties of alumina up to the melting point: A first-principles study

    NASA Astrophysics Data System (ADS)

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

    2016-11-01

    The high thermal emission of alumina dominates the radiative heat transfer of rocket exhaust plume. Yet numerous experimental measurements on radiative properties of alumina at high temperatures vary considerably from each other and cannot provide physical insight into the underlying mechanism. In this work, the ab initio molecular dynamics (AIMD) method and ab initio parameterized Drude model are combined to predict the radiative properties of alumina for temperatures up to 2327 K (the melting point) in the spectral range 1-12 μm. Contributed by different microscopic processes, the optical absorption of alumina in the spectral range 1-4 and 4-12 μm is described by two distinct methods. In the spectral range 4-12 μm, the multi-phonon process mainly contributes to optical absorption and can be simulated by the AIMD method based on the linear response theory. While in the spectral range 1-4 μm, the optical absorption is mainly caused by intrinsic carriers and can be effectively described by the ab initio parameterized Drude model. The first-principles calculations can successfully predict the infrared radiative properties of alumina at high temperatures and well reproduce the literature experiments. Moreover, the theoretical simulations verify that alumina can retain its semiconducting character even in the liquid phase and there emerges sharp increase in the near-infrared optical absorption of alumina upon melting.

  20. 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.

  1. Prediction of superhard cubic boron-carbon nitride through first principles.

    PubMed

    Yuge, Koretaka

    2009-10-14

    Superhard cubic boron-carbon nitride (c-BNC) in terms of bulk modulus along a composition range of (BN)((1-x))(C(2))(x) (0≤x≤1) is systematically explored by Monte Carlo simulations and cluster expansion techniques based on first-principles calculation. Bulk moduli for the c-BNC ordered structures are reasonably expanded up to quadruplet clusters, indicating that dependence of the bulk modulus on atomic arrangements is not simply attributed to pairwise interactions. A negative correlation can be seen between bulk modulus and formation energies, which is consistent with previous theoretical works. Monte Carlo simulation reveals that all the ordered structures with the highest bulk modulus at each composition exhibit a strong preference of neighboring B-N and C-C atoms, which is consistent with the bond counting rule previously suggested. A composition dependence of these ordered structures can be observed. At a BN-rich composition of x = 0.25, C atoms form a nearest-neighbor network with a hexagonal cluster shape, while at equiatomic and diamond-rich compositions of x = 0.5 and 0.75, B and N atoms form nearest-neighbor networks with a planar shape. At x = 0.875, c-BNC ordered structure with neighboring B and N atoms forming a stereoscopic shape exhibit the highest bulk modulus of 459.3 GPa, which is ∼0.6% smaller than that of diamond.

  2. 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.

  3. Defective germanene as a high-efficiency helium separation membrane: a first-principles study

    NASA Astrophysics Data System (ADS)

    Zhu, Lei; Chang, Xiao; He, Daliang; Xue, Qingzhong; Li, Xiaofang; Jin, Yakang; Zheng, Haixia; Ling, Cuicui

    2017-03-01

    Development of low energy cost membranes for separating helium from natural gas is highly desired. Using van der Waals-corrected first-principles density functional theory (DFT) calculations, we theoretically investigate the helium separation performance of divacancy-defective germanene. The 555 777 divacancy-defective germanene presents a 0.53 eV energy barrier for helium, which is slightly larger than the energy threshold value of gas molecule penetration of a membrane (0.5 eV). Thus, the 555 777 divacancy-defective germanene is difficult for helium to permeate, except under high temperature or pressure. However, the 585 divacancy-defective germanene presents a surmountable energy barrier (0.27 eV) for helium, and it shows extremely high helium selectivities relative to other studied gas molecules. Especially, the He/Ne selectivity can be as high as 1 × 104 at room temperature. Together with the acceptable permeance for helium, the 585 divacancy-defective germanene can be used for helium separation with remarkably good performance.

  4. First-principles studies of hydrogen interaction with ultrathin Mg and Mg-based alloy films

    NASA Astrophysics Data System (ADS)

    Yoon, Mina; Weitering, Hanno H.; Zhang, Zhenyu

    2011-01-01

    The search for technologically and economically viable storage solutions for hydrogen fuel would benefit greatly from research strategies that involve systematic property tuning of potential storage materials via atomic-level modification. Here, we use first-principles density-functional theory to investigate theoretically the structural and electronic properties of ultrathin Mg films and Mg-based alloy films and their interaction with atomic hydrogen. Additional delocalized charges are distributed over the Mg films upon alloying them with 11.1% of Al or Na atoms. These extra charges contribute to enhance the hydrogen binding strength to the films. We calculated the chemical potential of hydrogen in Mg films for different dopant species and film thickness, and we included the vibrational degrees of freedom. By comparing the chemical potential with that of free hydrogen gas at finite temperature (T) and pressure (P), we construct a hydrogenation phase diagram and identify the conditions for hydrogen absorption or desorption. The formation enthalpies of metal hydrides are greatly increased in thin films, and in stark contrast to its bulk phase, the hydride state can only be stabilized at high P and T (where the chemical potential of free H2 is very high). Metal doping increases the thermodynamic stabilities of the hydride films and thus significantly helps to reduce the required pressure condition for hydrogen absorption from H2 gas. In particular, with Na alloying, hydrogen can be absorbed and/or desorbed at experimentally accessible T and P conditions.

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

    SciTech Connect

    Wang, Hui; LeBlanc, K. A.; Gao, Bo; Yao, Yansun

    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.

  6. First-principles investigation on elastic and thermodynamic properties of Pnnm-CN under high pressure

    PubMed Central

    Ya-Ru, Zhao; Hai-Rong, Zhang; Gang-Tai, Zhang; Qun, Wei; Yu-Quan, Yuan

    2016-01-01

    The elastic anisotropy and thermodynamic properties of the recently synthesized Pnnm-CN have been investigated using first-principles calculations under high temperature and high pressure. The calculated equilibrium crystal parameters and normalized volume dependence of the resulting pressure agree with available experimental and theoretical results. Within the considered pressure range of 0–90 GPa, the dependences of the bulk modulus, Young’s modulus, and shear modulus on the crystal orientation for Pnnm-CN have been systematically studied. The results show that the Pnnm-CN exhibits a well-pronounced elastic anisotropy. The incompressibility is largest along the c-axis. For tension or compression loading, the Pnnm-CN is stiffest along [001] and the most obedient along [100] direction. On the basis of the quasi-harmonic Debye model, we have explored the Debye temperature, heat capacity, thermal expansion coefficient, and Grüneisen parameters within the pressure range of 0–90 GPa and temperature range of 0–1600K. PMID:28090376

  7. The effects of hydrogenation and high pressure on α-tetragonal boron: a first principles study

    NASA Astrophysics Data System (ADS)

    Uemura, Naoki; Shirai, Koun

    It is well known that boron rich crystals are superhard materials. α-tetragonal (α-tet) boron is one of the metastable phase in elemental boron crystals under high temperature and high pressure. This phase has a possibility of including some hydrogen atoms due to the experimental process, but it has not yet been shown crystal structures and electronic properties of hydrogenated α-tet boron. Using first-principles calculations, we theoretically predicted stable structures and investigated the influences from hydrogenation of α-tet boron and high pressures. According to our calculations, non-bonding states of pure α-tet boron, which were mostly occupied by Pz like orbitals coming from interstitial boron atoms in α-tet boron, were completely vanished by doping some hydrogen atoms and the higher the pressure was, the lager energy gaps between the valence band maximum and the conduction band minimum on α-tet boron were. These results provide that the deformation potential depended on the pressure is positive, which is basically negative on semiconductors except for diamonds and is an index of the hardness under pressure on semiconductors.

  8. First-principles calculation on β-SiC(111)/α-WC(0001) interface

    SciTech Connect

    Jin, Na; Yang, Yanqing E-mail: jinna319@163.com; Li, Jian; Luo, Xian; Huang, Bin; Sun, Qing; Guo, Pengfei

    2014-06-14

    The α-WC(0001) surface and β-SiC(111)/α-WC(0001) interface were studied by first-principles calculation based on density functional theory. It is demonstrated that the α-WC(0001) surface models with more than nine atom-layers exhibit bulk-like interior, wherein the surface relaxations localized within the top three layers are well converged. Twenty-four specific geometry models of SiC/WC interface structures with different terminations and stacking sites were chosen. The calculated work of adhesion and interface energy suggest that the most stable interface structure has the C-C bonding across the interface, yielding the largest work of adhesion and the lowest interface energy. Moreover, the top-site stacking sequence is preferable for the C/C-terminated interface. The effects of the interface on the electronic structures of the C/C-terminated interfaces are mainly localized within the first and second layers of the interface. Calculations of the work of adhesion and interface energy provide theoretical evidence that the mechanical failure may initiate at the interface or in SiC but not in WC.

  9. First-principles study of the elastic properties of In-Tl random alloys

    NASA Astrophysics Data System (ADS)

    Li, Chun-Mei; Hu, Qing-Miao; Yang, Rui; Johansson, Börje; Vitos, Levente

    2010-09-01

    The composition-dependent lattice parameters and elastic constants of In1-xTlx(0first-principles exact muffin-tin orbitals method in combination with coherent-potential approximation. The calculated lattice parameters and elastic constants agree well with the available theoretical and experimental data. For pure In, the fcc phase is mechanically unstable as shown by its negative tetragonal shear modulus C' . With Tl addition, C' of the fcc phase increases whereas that of the fct phase decreases, indicating that the fcc phase becomes mechanically more stable and the fct phase becomes less stable. In addition, the structural energy difference between the fcc and fct phases decreases with x . Both of these effects account for the observed lowering of the fcc-fct martensitic transition temperature upon Tl addition to In. The density of states indicates that the stability of the fct phase relative to the fcc one at low temperatures is due to the particular electronic structure of In and In-Tl alloys.

  10. 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.

  11. First principles study of magneto-optical properties of Fe-doped ZnO

    NASA Astrophysics Data System (ADS)

    Shaoqiang, Guo; Qingyu, Hou; Zhenchao, Xu; Chunwang, Zhao

    2016-12-01

    Studies on optical band gaps and absorption spectra of Fe-doped ZnO have conflicting conclusions, such as contradictory redshifted and blueshifted spectra. To solve this contradiction, we constructed models of un-doped and Fe-doped ZnO using first-principles theory and optimized the geometry of the three models. Electronic structures and absorption spectra were also calculated using the GGA+U method. Higher doping content of Fe resulted in larger volume of doped system, and higher total energy resulted in lower stability. Higher formation energy also led to more difficult doping. Meanwhile, the band gaps broadened and the absorption spectra exhibited an evident blue shift. The calculations were in good agreement with the experimental results. Given the unipolar structure of ZnO, four possible magnetic coupling configurations for Zn14Fe2O16 were calculated to investigate the magnetic properties. Results suggest that Fe doping can improve ferromagnetism in the ZnO system and that ferromagnetic stabilization was mediated by p-d exchange interaction between Fe-3d and O-2p orbitals. Therefore, the doped system is expected to obtain high stability and high Curie temperature of diluted magnetic semiconductor material, which are useful as theoretical bases for the design and preparation of the Fe-doped ZnO system's magneto-optical properties.

  12. Submillimeter Absorption Spectroscopy in Semiconductor Manufacturing Plasmas and Comparison to Theoretical Models

    NASA Astrophysics Data System (ADS)

    Helal, Yaser H.; Neese, Christopher F.; De Lucia, Frank C.; Ewing, Paul R.; Agarwal, Ankur; Craver, Barry; Stout, Phillip J.; Armacost, Michael D.

    2015-06-01

    Plasmas used in the semiconductor manufacturing industry are of a similar nature to the environments often created for submillimeter spectroscopic study of astrophysical species. At the low operating pressures of these plasmas, submillimeter absorption spectroscopy is a method capable of measuring the abundances and temperatures of molecules, radicals, and ions without disturbing any of the properties of the plasma. These measurements provide details and insight into the interactions and reactions occurring within the plasma and their implications for semiconductor manufacturing processes. A continuous wave, 500 to 750 GHz, absorption spectrometer was designed and used to make measurements of species in semiconductor processing plasmas. Comparisons with expectations from theoretical plasma models provide a basis for validating and improving these models, which is a complex and difficult science itself. Furthermore, these comparisons are an evaluation for the use of submillimeter spectroscopy as a diagnostic tool in manufacturing processes.

  13. First-principles study of pressure-induced structural phase transitions in MnF2.

    PubMed

    López-Moreno, S; Romero, A H; Mejía-López, J; Muñoz, A

    2016-12-07

    In this work we report a complete structural and magnetic characterization of crystalline MnF2 under pressure obtained using first principle calculations. Density functional theory was used as the theoretical framework, within the generalized gradient approximation plus the Hubbard formalism (GGA+U) necessary to describe the strong correlations present in this material. The vibrational, the magnetic exchange couplings and the structural characterization of MnF2 in the rutile ground state structure and potential high pressure phases are reported. The quasiharmonic approximation has been used to obtain the free energy, which at the same time is used to evaluate the different structural transitions at 300 K. Based on previous theoretical and experimental studies on AF2 compounds, ten different structural candidates were considered for the high pressure regime, which led us to propose a path for the MnF2 structural transitions under pressure. As experimental pressure settings can lead to non-hydrostatic conditions, we consider hydrostatic and non-hydrostatic strains in our calculations. According to our results we found the following sequence for the pressure-driven structural phase transition in MnF2: rutile (P42/mnm) → α-PbO2-type (Pbcn) → dist. HP PdF2-type (Pbca) → dist. fluorite (I4/mmm) → cotunnite (Pnma). This structural path is correlated with other phase transitions reported on other metal rutile fluorides. In particular, we found that our proposed structural phase transition sequence offers an explanation of the different paths observed in the literature by taking into account the role of the hydrostatic conditions. In order to get a deep understanding of the modifications of MnF2 under pressure, we have analyzed the pressure evolution of the structural, vibrational, electronic, and magnetic properties for rutile and for each of the high pressure phases.

  14. 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.

  15. Structural and electronic phase transitions of ThS2 from first-principles calculations

    DOE PAGES

    Guo, Yongliang; Wang, Changying; Qiu, Wujie; ...

    2016-10-07

    Performed a systematic study using first-principles methods of the pressure-induced structural and electronic phase transitions in ThS2, which may play an important role in the next generation nuclear energy fuel technology.

  16. 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.

  17. 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.

  18. 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.

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

    DOE PAGES

    Sun, Shou -Tian; Jiang, Ling; Liu, J. W.; ...

    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

  20. 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

    2016-02-19

    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.

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

    SciTech Connect

    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 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. 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.

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

    DOE PAGES

    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

  3. 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.

  4. First-principles Study of the Electronic Structure and Optical Properties of MgH2

    NASA Astrophysics Data System (ADS)

    Alford, Ashley; Chou, Mei-Yin

    2003-03-01

    It has been noticed that magnesium might play an interesting role in recently discovered switchable-mirror systems. For example, the films of rare earth and magnesium alloys are found to be superior to the pure rare-earth samples in maximum transparency and mirror-state reflectivity [1]. Moreover, the magnesium-rich Ni-Mg alloy films turned out to be a switchable-mirror system without rare earths [2]. In both cases, pure transparent MgH2 is reversibly formed when these alloys take up hydrogen. In order to model the optical properties of these films, we need to know the electronic and optical properties of MgH2. In this work, we investigate its bonding characteristics, band structure, and dielectric properties with first-principles theoretical methods. The stability of the crystal and the bonding are studied using density functional theory and pseudopotential methods. The excited state properties (the quasiparticle spectra) are studied by many-body perturbation theory within the so-called GW approximation in which the electronic self-energy is approximated by the full Green's function (G) times the screened Coulomb interaction (W). We will report the results for both the rutile-structured alpha-MgH2 and the low-symmetry gamma-MgH2. [1] P. van der Sluis, M. Ouwerkerk, and P. A. Duine, Appl. Phys. Lett. 70, 3356 (1997). [2] T. J. Richardson, J. L. Slack, R. D. armitage, R. Kostecki, B. Farangis, and M. D. Rubin, Appl. Phys. Lett. 78, 3047 (2001).

  5. Thermoelectric properties of orthorhombic group IV-VI monolayers from the first-principles calculations

    NASA Astrophysics Data System (ADS)

    Guo, San-Dong; Wang, Yue-Hua

    2017-01-01

    Two-dimensional (2D) materials may have potential applications in thermoelectric devices. In this work, the thermoelectric properties of orthorhombic group IV-VI monolayers AB (A = Ge and Sn; B = S and Se) are systematically investigated by the first-principles calculations and semiclassical Boltzmann transport theory. The spin-orbit coupling (SOC) is considered for their electron part, which produces observable effects on the power factor, especially for n-type doping. According to the calculated ZT, the four monolayers exhibit diverse anisotropic thermoelectric properties although they have a similar hinge-like crystal structure. The GeS along zigzag and armchair directions shows the strongest anisotropy, while SnS and SnSe show mostly isotropic efficiency of thermoelectric conversion. This can be explained by the strength of anisotropy of their respective power factor and electronic and lattice thermal conductivities. The calculated results show that the ZT between n- and p-type doping has little difference for GeS, SnS, and SnSe. It is found that GeSe, SnS, and SnSe show better thermoelectric performance compared to GeS in n-type doping and that SnS and SnSe exhibit higher efficiency of thermoelectric conversion in p-type doping. Compared to other many 2D materials, orthorhombic group IV-VI monolayers AB (A = Ge and Sn; B = S and Se) may possess better thermoelectric performance due to lower lattice thermal conductivities. Our work would be beneficial to stimulate further theoretical and experimental works.

  6. 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

  7. A first-principles study of the SnO2 monolayer with hexagonal structure.

    PubMed

    Xiao, Wen-Zhi; Xiao, Gang; Wang, Ling-Ling

    2016-11-07

    We report the structural, electronic, magnetic, and elastic properties of a two-dimensional (2D) honeycomb stannic oxide (SnO2) monolayer based on comprehensive first-principles calculations. The free-standing and well-ordered 2D centered honeycomb SnO2 (T-SnO2) monolayer with D3d point-group symmetry has good dynamical stability, as well as thermal stability at 500 K. The T-SnO2 monolayer is a nonmagnetic wide-bandgap semiconductor with an indirect bandgap of 2.55/4.13 eV obtained by the generalized gradient approximation with the Perdew-Burke-Ernzerhof/Heyd-Scuseria-Ernzerhof hybrid functional, but it acquires a net magnetic moment upon creation of a Sn vacancy defect. The elastic constants obtained from the relaxed ion model show that the T-SnO2 monolayer is much softer than MoS2. The bandgap monotonically decreases with increasing strain from -8% to 15%. An indirect-to-direct bandgap transition occurs upon applying biaxial strain below -8%. Synthesis of the T-SnO2 monolayer is proposed. We identify the Zr(0001) surface as being suitable to grow and stabilize the T-SnO2 monolayer. The unique structure and electronic properties mean that the T-SnO2 monolayer has promising applications in nanoelectronics. We hope that the present study on the stable free-standing SnO2 monolayer will inspire researchers to further explore its importance both experimentally and theoretically.

  8. First-principles study of Ni-Al intermetallic compounds under various temperature and pressure

    NASA Astrophysics Data System (ADS)

    Wen, Zhiqin; Zhao, Yuhong; Hou, Hua; Tian, Jinzhong; Han, Peide

    2017-03-01

    The pressure dependence behaviors of structural and mechanical properties as well as the effect of temperature on thermodynamic properties of Ni-Al ordered intermetallic compounds (i. e. Ni3Al, Ni5Al3, NiAl, Ni2Al3 and NiAl3) are investigated in details by implementing first-principles calculations. The calculated lattice parameters, bulk modulus and its pressure derivative are well in agreement with available experimental and theoretical values at zero pressure. All the compounds are mechanically stable with pressure going up to 50 GPa, and the volume change resistance of nickel aluminum alloys can be improved by increasing pressure and Ni concentration. The shear deformation resistance, elastic stiffness and microhardness of nickel aluminum alloys can be strengthened by increasing the content of Ni5Al3 and Ni2Al3, and pressure can also enhance these properties of Ni5Al3, NiAl and Ni2Al3. The ductility of Ni3Al, Ni5Al3 and NiAl can be improved by increasing pressure, while brittle nature turns into ductile nature in 20-30 GPa and 10-20 GPa for Ni2Al3 and NiAl3, respectively. Furthermore, the elastic anisotropy of Ni3Al, Ni5Al3, Ni2Al3 and NiAl3 enhances with pressure, while NiAl shows few change with pressure increasing. In addition, Ni3Al is the most sensitive to pressure change among considered compounds. Finally, the Debye temperature, linear thermal expansion coefficient and heat capacity of these compounds are calculated using the quasi-harmonic Debye model in pressure ranging from 0 to 50 GPa and temperature ranging from 0 to 1200 K to elucidate the relationships between thermodynamic parameters and temperature under various pressure. The results are helpful insights into the study of nickel aluminum alloys.

  9. 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).

  10. 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.

  11. Review of high pressure phases of calcium by first-principles calculations

    NASA Astrophysics Data System (ADS)

    Ishikawa, T.; Nagara, H.; Suzuki, N.; Tsuchiya, J.; Tsuchiya, T.

    2010-03-01

    We review high pressure phases of calcium which have obtained by recent experimental and first-principles studies. In this study, we investigated the face-centered cubic (fcc) structure, the body-centered cubic (bcc) structure, the simple cubic (sc) structure, a tetragonal P43212 [Ishikawa T et al. 2008 Phys. Rev. B 77 020101(R)], an orthorhombic Cmca [Ishikawa T et al. 2008 Phys. Rev. B 77 020101(R)], an orthorhombic Cmcm [Teweldeberhan A M and Bonev S A 2008 Phys. Rev. B 78 140101(R)], an orthorhombic Pnma [Yao Y et al. 2008 Phys. Rev. B 78 054506] and a tetragonal I4/mcm(00) [Arapan S et al. 2008 Proc. Natl. Acad. Sci. USA 105 20627]. We compared the enthalpies among the structures up to 200 GPa and theoretically determined the phase diagram of calcium. The sequence of the structural transitions is fcc (0- 3.5 GPa) → bcc (3.5 - 35.7 GPa) → Cmcm (35.7- 52GPa) → P43212 (52-109 GPa) → Cmca (109-117.4GPa) → Pnma (117.4-134.6GPa) → I4/mcm(00) (134.6 GPa -). The sc phase is experimentally observed in the pressure range from 32 to 113 GPa but, in our calculation, there is no pressure region where the sc phase is the most stable. In addition, we found that the enthalpy of the hexagonal close-packed (hcp) structure is lower than that of I4/mcm(00) above 495 GPa.

  12. First-principles-based multiscale, multiparadigm molecular mechanics and dynamics methods for describing complex chemical processes.

    PubMed

    Jaramillo-Botero, Andres; Nielsen, Robert; Abrol, Ravi; Su, Julius; Pascal, Tod; Mueller, Jonathan; Goddard, William A

    2012-01-01

    We expect that systematic and seamless computational upscaling and downscaling for modeling, predicting, or optimizing material and system properties and behavior with atomistic resolution will eventually be sufficiently accurate and practical that it will transform the mode of development in the materials, chemical, catalysis, and Pharma industries. However, despite truly dramatic progress in methods, software, and hardware, this goal remains elusive, particularly for systems that exhibit inherently complex chemistry under normal or extreme conditions of temperature, pressure, radiation, and others. We describe here some of the significant progress towards solving these problems via a general multiscale, multiparadigm strategy based on first-principles quantum mechanics (QM), and the development of breakthrough methods for treating reaction processes, excited electronic states, and weak bonding effects on the conformational dynamics of large-scale molecular systems. These methods have resulted directly from filling in the physical and chemical gaps in existing theoretical and computational models, within the multiscale, multiparadigm strategy. To illustrate the procedure we demonstrate the application and transferability of such methods on an ample set of challenging problems that span multiple fields, system length- and timescales, and that lay beyond the realm of existing computational or, in some case, experimental approaches, including understanding the solvation effects on the reactivity of organic and organometallic structures, predicting transmembrane protein structures, understanding carbon nanotube nucleation and growth, understanding the effects of electronic excitations in materials subjected to extreme conditions of temperature and pressure, following the dynamics and energetics of long-term conformational evolution of DNA macromolecules, and predicting the long-term mechanisms involved in enhancing the mechanical response of polymer-based hydrogels.

  13. 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

  14. 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

  15. 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.

  16. 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.

  17. A theoretical analysis on the vibronic spectra with mass analyzed threshold ionization spectroscopy

    NASA Astrophysics Data System (ADS)

    Chao, Sheng D.; Peng, Hsin Y.

    2008-01-01

    We have theoretically studied the absorption vibronic spectra with the resonance two-photon (R2P) and non-resonance two-photon (NR2P) mass analyzed threshold ionization (MATI) spectroscopy. The theory uses the inverse Born-Oppenheimer approximation (IBOA) to establish a proper basis set. To analyze the MATI vibronic spectra, we have calculated the Franck-Condon factors involved in the vibronic transitions. Several experimental spectra are analyzed using this theory with emphasis on the importance of the resonance intermediate states. The long vibrational progression in a MATI spectrum can be partly attributed to the result of including the anharmonic correction in the calculated Franck-Condon factors. The experimentally observed isotope effect is also analyzed.

  18. Atomic ordering in Au-(42 to 50) at.% Pd: A diffuse scattering and first-principles investigation

    NASA Astrophysics Data System (ADS)

    Schönfeld, B.; Sax, C. R.; Ruban, A. V.

    2012-01-01

    Atomic ordering in Au-Pd alloys was studied by diffuse x-ray scattering and first-principles methods. Diffuse scattering was done of a single crystal of Au-48 at.% Pd that was aged at 703 K for 24 days. The weakly modulated short-range-order scattering exhibits diffuse maxima with an incommensurate wave vector, which can be related to a Fermi-surface nesting mechanism. From effective pair interaction parameters determined by the inverse Monte Carlo method, a one-dimensional long-period superstructure of the CH structure, LPS1, was found for AuPd. Concurrent electronic-structure calculations of the effective cluster interaction (ECI) parameters indicated the presence of another closely related superstructure, LPS2, at 0 K. At the same time, direct first-principles calculations of the total energies of the CH structure and further one-dimensional long-period superstructures predicted the stabilization of LPS4. Although the energy differences between these structures are small and a complex behavior of the effective interactions is expected due to the Fermi-surface nesting, experimental data and theoretical results both support the stabilization of a long-period superstructure of the CH structure for AuPd at 0 K. The ECI parameters determined by the screened generalized perturbation method also predicted a ground-state structure different from Au7Pd5, previously obtained from cluster expansion calculations. Its energetic preference was confirmed by direct total-energy calculations.

  19. 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).

  20. First-principles calculation of pKa for cocaine, nicotine, neurotransmitters, and anilines in aqueous solution.

    PubMed

    Lu, Haiting; Chen, Xi; Zhan, Chang-Guo

    2007-09-06

    The absolute pKa values of 24 representative amine compounds, including cocaine, nicotine, 10 neurotransmitters, and 12 anilines, in aqueous solution were calculated by performing first-principles electronic structure calculations that account for the solvent effects using four different solvation models, i.e., the surface and volume polarization for electrostatic interaction (SVPE) model, the standard polarizable continuum model (PCM), the integral equation formalism for the polarizable continuum model (IEFPCM), and the conductor-like screening solvation model (COSMO). Within the examined computational methods, the calculations using the SVPE model lead to the absolute pKa values with the smallest root-mean-square-deviation (rmsd) value (1.18). When the SVPE model was replaced by the PCM, IEFPCM, and COSMO, the rmsd value of the calculated absolute pKa values became 3.21, 2.72, and 3.08, respectively. All types of calculated pKa values linearly correlate with the experimental pKa values very well. With the empirical corrections using the linear correlation relationships, the theoretical pKa values are much closer to the corresponding experimental data and the rmsd values become 0.51-0.83. The smallest rmsd value (0.51) is also associated with the SVPE model. All of the results suggest that the first-principles electronic structure calculations using the SVPE model are a reliable approach to the pKa prediction for the amine compounds.

  1. Revisiting the zero-temperature phase diagram of stoichiometric SrCoO3 with first-principles methods.

    PubMed

    Rivero, Pablo; Cazorla, Claudio

    2016-11-09

    By using first-principles methods based on density functional theory we revisited the zero-temperature phase diagram of stoichiometric SrCoO3, a ferromagnetic metallic perovskite that undergoes significant structural, electronic, and magnetic changes as its content of oxygen is decreased. We considered both bulk and epitaxial thin film geometries. In the bulk case, we found that a tetragonal P4/mbm phase with moderate Jahn-Teller distortions and a c/a ratio of is consistently predicted to have a lower energy than the thus far assumed ground-state cubic Pm3[combining macron]m phase. In thin films, we found two phase transitions occurring at compressive and tensile epitaxial strains. However, in contrast to previous theoretical predictions, our results show that: (i) the phase transition induced by tensile strain is isostructural and involves only a change in magnetic spin order (that is, not a metallic to insulator transformation), and (ii) the phase transition induced by compressive strain comprises simultaneous structural, electronic and magnetic spin order changes, but the required epitaxial stress is so large (<-6%) that is unlikely to be observed in practice. Our findings call for a revision of the crystallographic data obtained in fully oxidised SrCoO3 samples at low temperatures, as well as of previous first-principles studies.

  2. First principle chemical kinetics in zeolites: the methanol-to-olefin process as a case study.

    PubMed

    Van Speybroeck, Veronique; De Wispelaere, Kristof; Van der Mynsbrugge, Jeroen; Vandichel, Matthias; Hemelsoet, Karen; Waroquier, Michel

    2014-11-07

    To optimally design next generation catalysts a thorough understanding of the chemical phenomena at the molecular scale is a prerequisite. Apart from qualitative knowledge on the reaction mechanism, it is also essential to be able to predict accurate rate constants. Molecular modeling has become a ubiquitous tool within the field of heterogeneous catalysis. Herein, we review current computational procedures to determine chemical kinetics from first principles, thus by using no experimental input and by modeling the catalyst and reacting species at the molecular level. Therefore, we use the methanol-to-olefin (MTO) process as a case study to illustrate the various theoretical concepts. This process is a showcase example where rational design of the catalyst was for a long time performed on the basis of trial and error, due to insufficient knowledge of the mechanism. For theoreticians the MTO process is particularly challenging as the catalyst has an inherent supramolecular nature, for which not only the Brønsted acidic site is important but also organic species, trapped in the zeolite pores, must be essentially present during active catalyst operation. All these aspects give rise to specific challenges for theoretical modeling. It is shown that present computational techniques have matured to a level where accurate enthalpy barriers and rate constants can be predicted for reactions occurring at a single active site. The comparison with experimental data such as apparent kinetic data for well-defined elementary reactions has become feasible as current computational techniques also allow predicting adsorption enthalpies with reasonable accuracy. Real catalysts are truly heterogeneous in a space- and time-like manner. Future theory developments should focus on extending our view towards phenomena occurring at longer length and time scales and integrating information from various scales towards a unified understanding of the catalyst. Within this respect molecular

  3. First principles modeling of the metal-electrolyte interface: A novel approach to the study of the electrochemical interface

    SciTech Connect

    Fernandez-Serra, Maria Victoria

    2016-09-12

    The research objective of this proposal is the computational modeling of the metal-electrolyte interface purely from first principles. The accurate calculation of the electrostatic potential at electrically biased metal-electrolyte interfaces is a current challenge for periodic “ab-initio” simulations. It is also an essential requisite for predicting the correspondence between the macroscopic voltage and the microscopic interfacial charge distribution in electrochemical fuel cells. This interfacial charge distribution is the result of the chemical bonding between solute and metal atoms, and therefore cannot be accurately calculated with the use of semi-empirical classical force fields. The project aims to study in detail the structure and dynamics of aqueous electrolytes at metallic interfaces taking into account the effect of the electrode potential. Another side of the project is to produce an accurate method to simulate the water/metal interface. While both experimental and theoretical surface scientists have made a lot of progress on the understanding and characterization of both atomistic structures and reactions at the solid/vacuum interface, the theoretical description of electrochemical interfaces is still lacking behind. A reason for this is that a complete and accurate first principles description of both the liquid and the metal interfaces is still computationally too expensive and complex, since their characteristics are governed by the explicit atomic and electronic structure built at the interface as a response to environmental conditions. This project will characterize in detail how different theoretical levels of modeling describer the metal/water interface. In particular the role of van der Waals interactions will be carefully analyzed and prescriptions to perform accurate simulations will be produced.

  4. Point defects in ZnO: an approach from first principles

    PubMed Central

    Oba, Fumiyasu; Choi, Minseok; Togo, Atsushi; Tanaka, Isao

    2011-01-01

    Recent first-principles studies of point defects in ZnO are reviewed with a focus on native defects. Key properties of defects, such as formation energies, donor and acceptor levels, optical transition energies, migration energies and atomic and electronic structure, have been evaluated using various approaches including the local density approximation (LDA) and generalized gradient approximation (GGA) to DFT, LDA+U/GGA+U, hybrid Hartree–Fock density functionals, sX and GW approximation. Results significantly depend on the approximation to exchange correlation, the simulation models for defects and the post-processes to correct shortcomings of the approximation and models. The choice of a proper approach is, therefore, crucial for reliable theoretical predictions. First-principles studies have provided an insight into the energetics and atomic and electronic structures of native point defects and impurities and defect-induced properties of ZnO. Native defects that are relevant to the n-type conductivity and the non-stoichiometry toward the O-deficient side in reduced ZnO have been debated. It is suggested that the O vacancy is responsible for the non-stoichiometry because of its low formation energy under O-poor chemical potential conditions. However, the O vacancy is a very deep donor and cannot be a major source of carrier electrons. The Zn interstitial and anti-site are shallow donors, but these defects are unlikely to form at a high concentration in n-type ZnO under thermal equilibrium. Therefore, the n-type conductivity is attributed to other sources such as residual impurities including H impurities with several atomic configurations, a metastable shallow donor state of the O vacancy, and defect complexes involving the Zn interstitial. Among the native acceptor-type defects, the Zn vacancy is dominant. It is a deep acceptor and cannot produce a high concentration of holes. The O interstitial and anti-site are high in formation energy and/or are electrically

  5. 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

  6. First-principles and classical molecular dynamics study of threshold displacement energy in beryllium

    NASA Astrophysics Data System (ADS)

    Vladimirov, P. V.; Borodin, V. A.

    2017-02-01

    Beryllium selected as a neutron multiplier material for the tritium breeding blanket of fusion reactor should withstand high doses of fast neutron irradiation. The damage produced by irradiation is usually evaluated assuming that the number of atomic displacements to the threshold displacement energy, Ed, which is considered as an intrinsic material parameter. In this work the value of Ed for hcp beryllium is estimated simultaneously from classical and first-principles molecular dynamics simulations. Quite similar quantitative pictures of defect production are observed in both simulation types, though the predicted displacement threshold values seem to be approximately two times higher in the first-principles approach. We expect that, after more detailed first-principles investigations, this approach can be used for scaling the damage prediction predictions by classical molecular dynamics, opening a way for more consistent calculations of displacement damage in materials.

  7. 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.

  8. Experimental and theoretical comparison of NIR spectroscopy measurements of cerebral hemoglobin changes.

    PubMed

    Firbank, M; Elwell, C E; Cooper, C E; Delpy, D T

    1998-11-01

    Two near-infrared spectroscopy (NIRS) methods are available for measuring changes (Delta) in total cerebral hemoglobin concentration (CHC): 1) a continuous measurement of the changes in total hemoglobin concentration (Delta[Hb]tot) and 2) the difference between two absolute measurements of CHC, each derived from a small, controlled change in inspired O2 fraction. This paper investigates the internal consistency of these two methods by using an experimental and theoretical comparison. NIRS was used to measure [Hb]tot in five newborn piglets before and after a change in arterial PCO2. Delta[Hb]tot demonstrated a low coefficient of variation of 2.8 +/- 2.8 (SD) % which allowed changes in CO2-cerebral blood volume reactivity to be clearly discriminated. However, a high coefficient of variation of 22.8 +/- 3.5% on the DeltaCHC measurements obscured any CO2 reactivity changes. A theoretical analysis demonstrates the effects of optical pathlength, background absorption, scatter, and blood vessel diameter on both methods. For more accurate monitoring of CHC, individual measurements of optical pathlength and more accurate pulse oximetry are required.

  9. First-principles calculations of momentum distributions of annihilating electron-positron pairs in defects in UO2

    NASA Astrophysics Data System (ADS)

    Wiktor, Julia; Jomard, Gérald; Torrent, Marc; Bertolus, Marjorie

    2017-01-01

    We performed first-principles calculations of the momentum distributions of annihilating electron-positron pairs in vacancies in uranium dioxide. Full atomic relaxation effects (due to both electronic and positronic forces) were taken into account and self-consistent two-component density functional theory schemes were used. We present one-dimensional momentum distributions (Doppler-broadened annihilation radiation line shapes) along with line-shape parameters S and W. We studied the effect of the charge state of the defect on the Doppler spectra. The effect of krypton incorporation in the vacancy was also considered and it was shown that it should be possible to observe the fission gas incorporation in defects in UO2 using positron annihilation spectroscopy. We suggest that the Doppler broadening measurements can be especially useful for studying impurities and dopants in UO2 and of mixed actinide oxides.

  10. 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.

  11. Growth mechanisms of ZnO(0001) investigated using the first-principles calculation

    SciTech Connect

    Fujiwara, Katsutoshi; Ishii, Akira; Abe, Tomoki; Ando, Koshi

    2012-09-15

    We investigated the dynamics of zinc (Zn) and oxygen (O) adsorbed atoms (adatoms) on a Zn-polar ZnO(0001) surface using the first-principles calculation. The results of the first-principles calculation revealed that a high-quality ZnO crystalline growth condition is induced by wurtzite structure packing under a Zn-rich growth condition using a Zn-polar ZnO(0001) surface. However, it was shown that an O adatom is not sufficient to promote surface atomic diffusion. For high-quality ZnO crystal, promoting surface diffusion of adatoms using high temperature is important.

  12. First-principles calculation of the Curie temperature Slater-Pauling curve.

    PubMed

    Takahashi, C; Ogura, M; Akai, H

    2007-09-12

    It is well known that the magnetizations as a function of the valence electron number per atom of 3d transition metal substitutional alloys form the so-called Slater-Pauling curve. Similarly, the Curie temperatures of these alloys also show systematic behaviour against the valence electron number. Though this fact has long been known, no attempt has been made so far to explain this behaviour from first principles. In this paper we calculate T(C) of 3d transition metal alloys in the framework of first-principles electronic structure calculation based on the local density approximation.

  13. 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

  14. 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

  15. 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

  16. First-principles study of H ordering in α-RHx ( R=Sc , Y, Ho, Er, Tm, and Lu)

    NASA Astrophysics Data System (ADS)

    Garcés, Jorge; González, Rafael; Vajda, Peter

    2009-02-01

    The effect of local atomic relaxations on the structural stability of the peculiar quasiunidimensional H-R-H pair ordering occurring at low-temperature in a series of hexagonal rare-earth-hydrogen solid solutions, α-RHx , ( R=Sc , Y, Ho, Er, Tm, and Lu) is studied by means of density-functional theory. We are proposing here a first-principles-based model, which, by considering the relaxation of the host metal cell, yields for the first time a suitable explanation for the observed chainlike short-range ordering through a coherent stress field along the chain, as well as for its limitation to the six metals in question—a phenomenon never completely understood theoretically.

  17. Cation disorder in MgX2O4 (X = Al, Ga, In) spinels from first principles

    NASA Astrophysics Data System (ADS)

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

    2012-07-01

    We have performed first-principles density functional theory calculations to investigate the possible physical origins of the discrepancies between the existing theoretical and experimental studies on cation distribution in MgX2O4 (X = Al, Ga, In) spinel oxides. We show that for MgGa2O4 and MgIn2O4, it is crucial to consider the effects of lattice vibrations to achieve agreement between theory and experiment. For MgAl2O4, we find that neglecting short-range order effects in thermodynamic modeling can lead to significant underestimation of the degree of inversion. Furthermore, we demonstrate that the common practice of representing disordered structures by randomly exchanging atoms within a small periodic supercell can incur large computational error due to either insufficient statistical sampling or finite supercell size effects.

  18. Highly frustrated quantum magnetism in the mineral azurite: multi-step approach from first-principles computations to experimental data

    NASA Astrophysics Data System (ADS)

    Jeschke, Harald O.; Opahle, Ingo; Valenti, Roser; Das, Hena; Saha-Dasgupta, Tanusri; Lang, Michael; Hu, Shijie; Wang, Xiaoqun; Peters, Robert; Honecker, Andreas

    2012-02-01

    The natural mineral azurite Cu3(CO3)2(OH)2 is a frustrated magnet displaying unusual and controversially discussed magnetic behavior. We perform a theoretical study based on density functional theory as well as state-of-the-art numerical many-body calculations [1]. We propose an effective generalized spin-1/2 diamond chain model which provides a consistent description of experiments: low-temperature magnetization, inelastic neutron scattering, nuclear magnetic resonance measurements, magnetic susceptibility as well as new specific heat measurements. With this study we demonstrate that the balanced combination of first principles with powerful many-body methods successfully describes the behavior of this frustrated material. [1] H. O. Jeschke et al., Phys. Rev. Lett. 106, 217201 (2011)

  19. 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.

  20. First-principles approach to investigate toroidal property of magnetoelectric multiferroic GaFeO{sub 3}

    SciTech Connect

    Nie, Yung-mau

    2016-01-14

    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 GaFeO{sub 3}. The nature of space-inversion and time-reversal violations of ferrotoroidics is reproduced in the simulated magnetic structure of GaFeO{sub 3}. For undoped GaFeO{sub 3}, a toroidal moment of −22.38 μ{sub B} 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. First-principle studies on the influence of anisotropic pressure on the physical properties of aluminum nitride

    NASA Astrophysics Data System (ADS)

    Wang, Zhifan; Zhao, Junwu; Gao, Yang; Zhang, Yanning

    2017-01-01

    In this work, we performed extensive first-principle studies to discuss the effect of uniaxial and biaxial mechanical pressure on the structural and physical properties of AlN piezoelectric material, including the longitudinal elastic constant (C 33), piezoelectric constant (e 33), static dielectric constant (ε 33), and mass density (ρ). In particular, we give the relationship between the paramters mentioned above and the longitudinal acoustic wave velocity (V) under anisotropic pressure. Our results show that the applied uniaxial or biaxial pressure in the basal plane has a more obvious influence on physical properties of AlN than the uniaxial pressure along hexagonal axis. The pressure-induced variations of C 33, e 33 and ρ significantly change the V value, whereas the effect of ε 33 on V is negligible. Our theoretical results provide useful information for the performance predictions of electro-acoustic mechanics sensors, such as FBAR mechanical sensors, based on the intrinsic properties of piezoelectric materials.

  7. Generating Tunable Magnetism in AlN Nanoribbons Using Anion/Cation Vacancies:a First-Principles Prediction

    NASA Astrophysics Data System (ADS)

    Chegeni, Mahdieh; Beiranvand, Razieh; Valedbagi, Shahoo

    2017-01-01

    Using first-principles approach, we theoretically study the effect of anion/cation vacancies on structural and electro-magnetic properties of zigzag AlN nanoribbons (ZAlNNRs). Calculations were performed using a full spin-polarized method within the density functional theory (DFT). Our findings shed light on how the edge states combined with vacancy engineering can affect electro-magnetic properties of ZAlNNRs. We found that depending on the nature and number of vacancies, ZAlNNRs can design as half-metal or semiconductor. Our results reveal a significant amount of spin magnetic moment for ZAlNNR with Al vacancies (VAl). These results may open new applications of AlN nano-materials in spintronics.

  8. Generating Tunable Magnetism in AlN Nanoribbons Using Anion/Cation Vacancies:a First-Principles Prediction

    NASA Astrophysics Data System (ADS)

    Chegeni, Mahdieh; Beiranvand, Razieh; Valedbagi, Shahoo

    2017-04-01

    Using first-principles approach, we theoretically study the effect of anion/cation vacancies on structural and electro-magnetic properties of zigzag AlN nanoribbons (ZAlNNRs). Calculations were performed using a full spin-polarized method within the density functional theory (DFT). Our findings shed light on how the edge states combined with vacancy engineering can affect electro-magnetic properties of ZAlNNRs. We found that depending on the nature and number of vacancies, ZAlNNRs can design as half-metal or semiconductor. Our results reveal a significant amount of spin magnetic moment for ZAlNNR with Al vacancies (VAl). These results may open new applications of AlN nano-materials in spintronics.

  9. 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.

  10. Application of THz Vibrational Spectroscopy to Molecular Characterization and the Theoretical Fundamentals: An Illustration Using Saccharide Molecules.

    PubMed

    Zhang, Feng; Wang, Houng-Wei; Tominaga, Keisuke; Hayashi, Michitoshi; Hasunuma, Tomohisa; Kondo, Akihiko

    2017-02-01

    This work illustrates several theoretical fundamentals for the application of THz vibrational spectroscopy to molecular characterization in the solid state using two different types of saccharide systems as examples. Four subjects have been specifically addressed: (1) the qualitative differences in the molecular vibrational signatures monitored by THz and mid-IR vibrational spectroscopy; (2) the selection rules for THz vibrational spectroscopy as applied to crystalline and amorphous systems; (3) a normal mode simulation, using α-l-xylose as an example; and (4) a rigorous mode analysis to quantify the percentage contributions of the intermolecular and intramolecular vibrations to the normal mode of interest.

  11. a Theoretical Study of CN Spectroscopy from the IR to the VUV

    NASA Astrophysics Data System (ADS)

    Schwenke, David W.

    2013-06-01

    We have carried out first principles calculations of the spectrum of CN. We have included Rydberg states, spin-orbit and non-adiabatic coupling between different electronic states, and an accurate treatment of the ro-vib-spin-electronic wavefunctions. Doublet, quartet and sextet spin states are included in our calculations. These wavefunctions are used with electric dipole and quadrapole and magnetic dipole transition moments to predict spectra. We consider both bound-bound, bound-free and free-bound transitions. When possible, comparisons are made with experimental results, both for energy levels and radiative lifetimes. Many previously uncharacterized bands are predicted.

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

    SciTech Connect

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

    2016-05-23

    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. Lastly, 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.

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

    SciTech Connect

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

    2016-05-23

    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. Lastly, 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.

  14. New Methodology for First Principle Calculations of Electrical Levels for Radiation Induced Defects in Silicates

    DTIC Science & Technology

    2005-02-22

    GRANT NUMBER 4. TITLE AND SUBTITLE New Methodology For First Principle Calculations Of Electrical Levels For Radiation Induced Defects In Silicates ...materials, space materials, Silicon on Insulator ( SOI ) materials 16. SECURITY CLASSIFICATION OF: 19a. NAME OF RESPONSIBLE PERSON DONALD J SMITH

  15. Calculating Interaction Energies Using First Principle Theories: Consideration of Basis Set Superposition Error and Fragment Relaxation

    ERIC Educational Resources Information Center

    Bowen, J. Philip; Sorensen, Jennifer B.; Kirschner, Karl N.

    2007-01-01

    The analysis explains the basis set superposition error (BSSE) and fragment relaxation involved in calculating the interaction energies using various first principle theories. Interacting the correlated fragment and increasing the size of the basis set can help in decreasing the BSSE to a great extent.

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

    SciTech Connect

    Khokhlov, Alexei; Austin, Joanna; Bacon, C.

    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 deflagration-to-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 Laboratory, currently the fourth fastest super-computer in the world.

  17. First-principles Calculations of Twin-boundary and Stacking-fault Energies in Magnesium

    DTIC Science & Technology

    2010-01-01

    The interfacial energies of twin boundaries and stacking faults in metal magnesium have been calculated using first-principles supercell approach...Four types of twin boundaries and two types of stacking faults are investigated, namely, those due to the mirror reflection, the mirror glide and the

  18. First-principles calculations of shear moduli for Monte Carlo-simulated Coulomb solids

    NASA Technical Reports Server (NTRS)

    Ogata, Shuji; Ichimaru, Setsuo

    1990-01-01

    The paper presents a first-principles study of the shear modulus tensor for perfect and imperfect Coulomb solids. Allowance is made for the effects of thermal fluctuations for temperatures up to the melting conditions. The present theory treats the cases of the long-range Coulomb interaction, where volume fluctuations should be avoided in the Ewald sums.

  19. Course-Level Implementation of First Principles, Goal Orientations, and Cognitive Engagement: A Multilevel Mediation Model

    ERIC Educational Resources Information Center

    Lee, Sunghye; Koszalka, Tiffany A.

    2016-01-01

    The First Principles of Instruction (FPI) represent ideologies found in most instructional design theories and models. Few attempts, however, have been made to empirically test the relationship of these FPI to instructional outcomes. This study addresses whether the degree to which FPI are implemented in courses makes a difference to student…

  20. New high-pressure phase of Fe3S predicted from first-principles calculation

    NASA Astrophysics Data System (ADS)

    Ishikawa, T.; Tsuchiya, T.

    2010-12-01

    It has long been recognized that the Earth's outer core must contain a significant amount of light elements, candidates for which have included hydrogen, carbon, silicon, sulfur and oxygen. High-P,T experiments (Jephcoat and Olson, 1987; Mao et al., 1998; Fiquet et al., 2001;Uchida et al., 2001) extended this argument to the inner core on the basis of the equation of state analysis of the hexagonal-closed-pack (hcp) form of pure iron, which concluded that it still has 4-5% excess density compared to the inner core values, although significant extrapolations were usually applied. At present, one of the most popular light-element candidates is sulfur. Therefore, it is crucial to determine the melting behavior of the Fe-FeS binary under core conditions, before models of core formation can be developed. The Fe-FeS binary was known to form a eutectic at low pressures (Usselman, 1975). Sherman (1995), however, suggested the stabilization of an intermediate iron sulfide compound Fe3S with AuCu3 form theoretically, and then Fei et al. (1997) found in the high-P,T experiments that Fe3S2 forms over 14 GPa, and Fe3S and Fe2S further form over 21 GPa (Fei et al., 2000). Fe3S, which is the most iron-rich sulfide compound known to exist, has a tetragonal cell isostructural with the Fe3P structure (space group No.82, Z = 8) and no phase transition has so far been identified up to 80 GPa (Seagle et al., 2006) and even at over 200 GPa (Kuwayama private comm.). These are supportive of an ab initio investigation (Martin et al., 2004), which found that the Fe3P structure is the most stable among fcc, LaF3, YF3 and Fe3P postulations. In this study, we explored higher-pressure phases of Fe3S using first-principles calculations. Comparing enthalpies among candidate structures, we found a new structure which is more stable than the Fe3P structure at the inner core pressures. In our presentation, we will make a detailed report with respect to the new stable structure and discuss phase

  1. 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

  2. Theoretical analysis of anharmonic coupling and cascading Raman signals observed with femtosecond stimulated Raman spectroscopy.

    PubMed

    Mehlenbacher, Randy D; Lyons, Brendon; Wilson, Kristina C; Du, Yong; McCamant, David W

    2009-12-28

    We present a classical theoretical treatment of a two-dimensional Raman spectroscopy based on the initiation of vibrational coherence with an impulsive Raman pump and subsequent probing by two-pulse femtosecond stimulated Raman spectroscopy (FSRS). The classical model offers an intuitive picture of the molecular dynamics initiated by each laser pulse and the generation of the signal field traveling along the probe wave vector. Previous reports have assigned the observed FSRS signals to anharmonic coupling between the impulsively driven vibration and the higher-frequency vibration observed with FSRS. However, we show that the observed signals are not due to anharmonic coupling, which is shown to be a fifth-order coherent Raman process, but instead due to cascades of coherent Raman signals. Specifically, the observed vibrational sidebands are generated by parallel cascades in which a coherent anti-Stokes or Stokes Raman spectroscopy (i.e., CARS or CSRS) field generated by the coherent coupling of the impulsive pump and the Raman pump pulses participates in a third-order FSRS transition. Additional sequential cascades are discussed that will give rise to cascade artifacts at the fundamental FSRS frequencies. It is shown that the intended fifth-order FSRS signals, generated by an anharmonic coupling mechanism, will produce signals of approximately 10(-4) DeltaOD (change in the optical density). The cascading signals, however, will produce stimulated Raman signal of approximately 10(-2) DeltaOD, as has been observed experimentally. Experiments probing deuterochloroform find significant sidebands of the CCl(3) bend, which has an E type symmetry, shifted from the A(1) type C-D and C-Cl stretching modes, despite the fact that third-order anharmonic coupling between these modes is forbidden by symmetry. Experiments probing a 50:50 mixture of chloroform and d-chloroform find equivalent intensity signals of low-frequency CDCl(3) modes as sidebands shifted from both the C

  3. Fracture behavior of lithium single crystal in the framework of (semi-)empirical force field derived from first-principles

    NASA Astrophysics Data System (ADS)

    Groh, Sébastien; Alam, Masud

    2015-06-01

    An approach to derive, from first-principles data, accurate and reliable potentials in the modified embedded-atom method in view of modeling the mechanical behavior of metals is presented in this work and applied to the optimization of a potential representative of lithium (Li). Although the theoretical background of the modified embedded-atom method was considered in this work, the proposed method is general and it can be applied to any other functional form. The main feature of the method is to introduce several path transformations in the material database that are critical for plastic and failure behavior. As part of the potential validation, path transformations different from the ones used for the parameterization procedure are considered. Applied in the case of Li, the material database was enriched with the generalized stacking fault energy curve along the  <1 1 1>  -direction on the {1 1 0}-plane, and with the traction-separation behavior of a {1 0 0}-surface. The path transformations used to enrich the material database were initially derived from first-principles calculations. For validation, the generalized stacking fault energy curves along the  <1 1 1>  -direction on the {1 1 2}- and {1 2 3}-planes were considered for plasticity, while traction-separation behavior of {1 1 0} and {1 1 1}-planes were considered for failure behavior. As part of the validation procedure, the predictions made in the MEAM framework were validated by first-principles data. The final potential accurately reproduced basic equilibrium properties, elastic constants, surface energies in agreement with first-principles predictions, and transition energy between different crystal structures. Furthermore, generalized stacking fault energy curves along the  <1 1 1>  -direction on the {1 1 0}, {1 1 2}, and {1 2 3}-planes, and tensile cohesive stress, characteristic length of fracture, and work of separation of a

  4. 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.

  5. Comparative study of the absorption spectrum of Li 2CaSiO 4:Cr 4+: First-principles fully relativistic and crystal field calculations

    NASA Astrophysics Data System (ADS)

    Brik, M. G.; Ogasawara, K.

    2007-11-01

    Systematic analysis of the energy level scheme and ground state absorption of the Cr4+ ion in Li2CaSiO4 crystal was performed using the exchange charge model of the crystal field [B.Z. Malkin, in: A.A. Kaplyanskii, B.M. Macfarlane (Eds.), Spectroscopy of Solids Containing Rare-earth Ions, North-Holland, Amsterdam, 1987, pp. 33-50] and recently developed first-principles approach to the analysis of the absorption spectra of impurity ions in crystals based on the discrete variational multielectron (DVME) method [K. Ogasawara, T. Iwata, Y. Koyama, T. Ishii, I. Tanaka, H. Adachi, Phys. Rev. B 64 (2001) 115413]. Using the former method, the values of parameters of crystal field acting on the Cr4+ ion valence electrons were calculated using the Li2CaSiO4 crystal structure data. Energy levels of the Cr4+ ion obtained after diagonalizing the crystal field Hamiltonian are in good agreement with those obtained from the experimental spectra. The latter method is based on the numerical solution of the Dirac equation; therefore, all relativistic effects are automatically considered. As a result, energy level scheme of Cr4+ and its absorption spectra in both polarizations were calculated, assigned and compared with experimental data; energy of the lowest charge transfer transition was evaluated and compared with theoretical predictions for the CrO44- complex available in the literature. The main features of the experimental spectra shape are reproduced well by the calculations. By performing analysis of the molecular orbitals (MO) population, it was shown that the covalent effects play an important role in formation of the spectral properties of Cr4+ ion in the considered crystal.

  6. 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.

  7. 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.

  8. 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.

  9. [Study on the absorption spectrum properties of flexible black silicon doped with sulfur and fluorine based on first-principles].

    PubMed

    Wei, Wei; Zhu, Yong; Lin, Cheng; Tian, Li; Xu, Zu-Wen; Nong, Jin-Peng

    2014-04-01

    It is quite urgent to need a flexible photodetector in the ultraviolet-visible-near infrared region for building a miniaturization broadband spectrometer. In the present paper, one kind of flexible black silicon doped with sulfur and fluorine was proposed and the optical absorption spectrum was investigated in broadband region. Firstly, the electronic structure, band structure and the optical absorption properties of the flexible black silicon doped with sulfur and fluoride were calculated using the first-principles pseudo potential calculations based on density-functional theory. Then, the absorption spectrum model of the flexible black silicon was built based on both the first-principles and finite domain time difference method. The results show that the cut-off wavelength has a red shift as the band gap of doped material becomes narrower. The higher the doping concentration is, the higher the optical absorption coefficient is obtained. The absorption coefficient of flexible black silicon doped with 50% sulfur is 8.3 times higher than that of 1.5% sulfur doping sample at the wavelength of 1 500 nm while the ratio turns to be 3 times when doped with 50% and 1.5% fluoride. The black silicon with small-size surface microstructure has the highest absorptance in the near-infrared region at the same doping concentration of 50%. Finally, a sample of flexible black silicon was fabricated by the femtosecond laser auto scanning system. The test results indicate that the absorptance of the sample is higher than 95% both in the ultraviolet and visible region and is fluctuated from 70% to 80% in the near-infrared region. It shows that as a novel light-absorbing material in broadband region the flexible black silicon doped with Sulfur and Fluorine has an potential application in exploring miniaturization broadband spectroscopy.

  10. 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.

  11. Accuracy of color prediction of anthraquinone dyes in methanol solution estimated from first principle quantum chemistry computations.

    PubMed

    Cysewski, Piotr; Jeliński, Tomasz

    2013-10-01

    The electronic spectrum of four different anthraquinones (1,2-dihydroxyanthraquinone, 1-aminoanthraquinone, 2-aminoanthraquinone and 1-amino-2-methylanthraquinone) in methanol solution was measured and used as reference data for theoretical color prediction. The visible part of the spectrum was modeled according to TD-DFT framework with a broad range of DFT functionals. The convoluted theoretical spectra were validated against experimental data by a direct color comparison in terms of CIE XYZ and CIE Lab tristimulus model color. It was found, that the 6-31G** basis set provides the most accurate color prediction and there is no need to extend the basis set since it does not improve the prediction of color. Although different functionals were found to give the most accurate color prediction for different anthraquinones, it is possible to apply the same DFT approach for the whole set of analyzed dyes. Especially three functionals seem to be valuable, namely mPW1LYP, B1LYP and PBE0 due to very similar spectra predictions. The major source of discrepancies between theoretical and experimental spectra comes from L values, representing the lightness, and the a parameter, depicting the position on green→magenta axis. Fortunately, the agreement between computed and observed blue→yellow axis (parameter b) is very precise in the case of studied anthraquinone dyes in methanol solution. Despite discussed shortcomings, color prediction from first principle quantum chemistry computations can lead to quite satisfactory results, expressed in terms of color space parameters.

  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. Solution-based thermodynamic modeling of the Ni-Al-Mo system using first-principles calculations

    SciTech Connect

    Zhou, S H; Wang, Y; Chen, L -Q; Liu, Z -K; Napolitano, R E

    2014-09-01

    A solution-based thermodynamic description of the ternary Ni–Al–Mo system is developed here, incorporating first-principles calculations and reported modeling of the binary Ni–Al, Ni–Mo and Al–Mo systems. To search for the configurations with the lowest energies of the N phase, the Alloy Theoretic Automated Toolkit (ATAT) was employed and combined with VASP. The liquid, bcc and γ-fcc phases are modeled as random atomic solutions, and the γ'-Ni3Al phase is modeled by describing the ordering within the fcc structure using two sublattices, summarized as (Al,Mo,Ni)0.75(Al,Mo,Ni)0.25. Thus, γ-fcc and γ'-Ni3Al are modeled with a single Gibbs free energy function with appropriate treatment of the chemical ordering contribution. In addition, notable improvements are the following: first, the ternary effects of Mo and Al in the B2-NiAl and D0a-Ni3Mo phases, respectively, are considered; second, the N-NiAl8Mo3 phase is described as a solid solution using a three-sublattice model; third, the X-Ni14Al75Mo11 phase is treated as a stoichiometric compound. Model parameters are evaluated using first-principles calculations of zero-Kelvin formation enthalpies and reported experimental data. In comparison with the enthalpies of formation for the compounds ψ-AlMo, θ-Al8Mo3 and B2-NiAl, the first-principles results indicate that the N-NiAl8Mo3 phase, which is stable at high temperatures, decomposes into other phases at low temperature. Resulting phase equilibria are summarized in the form of isothermal sections and liquidus projections. To clearly identify the relationship between the γ-fcc and γ'-Ni3Al phases in the ternary Ni–Al–Mo system, the specific γ-fcc and γ'-Ni3Al phase fields are plotted in x(Al)–x(Mo)–T space for a temperature range 1200–1800 K.

  14. First-principles based calculation of phonon spectrain substitutionally disordered alloys

    NASA Astrophysics Data System (ADS)

    Ghosh, Subhradip

    2013-02-01

    A first-principles based solution to the longstanding problem of calculating the phonon spectra in substitutional disordered alloys where strong force-constant disorder plays a significantrole is provided by a combination of first-principles electronicstructure tools, physically reasonable models of force-constant in alloyenvironments, and the Itinerant Coherent-Potntial Approximation (ICPA) by Ghosh and co-workers (S. Ghosh et. al., Physical Review B 66, 214206 (2002)). Wehere present the salient features of such hybrid formalism and illustrate its capability by the computation of phonon spectrafor disordered alloys with large size mismatch of end point components. We demonstrate that the consideration of local environments insize-mismatched alloys is crucial in understanding the microscopicinterplay of forces between various pairs of chemical specie and a correctdepiction of these is important for computation of accurate phonondispersions in these systems.

  15. 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.

  16. Magnetically induced phonon splitting in ACr2O4 spinels from first principles

    DOE PAGES

    Wysocki, Aleksander L.; Birol, Turan

    2016-04-22

    We study the magnetically-induced phonon splitting in cubic ACr2O4 (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)] that includes only the nearest neighbor exchange. In conclusion, using this model with materialsmore » specific parameters calculated from first principles, we provide additional insights into the physics of spin-phonon coupling in this intriguing family of compounds.« less

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

    PubMed

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

    2015-12-08

    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 the study of the enzymatic reaction catalyzed by acetylcholinesterase. We carried out density functional theory calculations for a quantum-mechanical (QM) subsystem consisting of 612 atoms with an O(N) complexity finite-difference approach. The QM subsystem 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 show two energy barriers along the reaction coordinate for the enzyme-catalyzed acylation of acetylcholine. The second barrier (8.5 kcal/mol) is rate-limiting for the acylation reaction and in good agreement with experiment.

  18. First-principles investigation of mechanical properties of silicene, germanene and stanene

    NASA Astrophysics Data System (ADS)

    Mortazavi, Bohayra; Rahaman, Obaidur; Makaremi, Meysam; Dianat, Arezoo; Cuniberti, Gianaurelio; Rabczuk, Timon

    2017-03-01

    Two-dimensional allotropes of group-IV substrates including silicene, germanene and stanene have recently attracted considerable attention in nanodevice fabrication industry. These materials involving the buckled structure have been experimentally fabricated lately. In this study, first-principles density functional theory calculations were utilized to investigate the mechanical properties of single-layer and free-standing silicene, germanene and stanene. Uniaxial tensile and compressive simulations were carried out to probe and compare stress-strain properties; such as the Young's modulus, Poisson's ratio and ultimate strength. We evaluated the chirality effect on the mechanical response and bond structure of the 2D substrates. Our first-principles simulations suggest that in all studied samples application of uniaxial loading can alter the electronic nature of the buckled structures into the metallic character. Our investigation provides a general but also useful viewpoint with respect to the mechanical properties of silicene, germanene and stanene.

  19. Thermal conductivity of glassy GeTe4 by first-principles molecular dynamics.

    PubMed

    Bouzid, Assil; Zaoui, Hayat; Luca Palla, Pier; Ori, Guido; Boero, Mauro; Massobrio, Carlo; Cleri, Fabrizio; Lampin, Evelyne

    2017-03-29

    A transient thermal regime is achieved in glassy GeTe4 by first-principles molecular dynamics following the recently proposed "approach-to-equilibrium" methodology. The temporal and spatial evolution of the temperature do comply with the time-dependent solution of the heat equation. We demonstrate that the time scales required to create the hot and the cold parts of the system and observe the resulting approach to equilibrium are accessible to first-principles molecular dynamics. Such a strategy provides the thermal conductivity from the characteristic decay time. We rationalize in detail the impact on the thermal conductivity of the initial temperature difference, the equilibration duration, and the main simulation features.

  20. 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.

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

    DOE PAGES

    Fattebert, Jean-Luc; Lau, Edmond Y.; Bennion, Brian J.; ...

    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. 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.

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

    NASA Astrophysics Data System (ADS)

    Bennett, Joseph W.; Rabe, Karin M.

    2012-11-01

    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(Sb1/2Mn1/2)O3 as a candidate semiconducting ferroelectric; (2) polar derivatives of schafarzikite MSb2O4; and (3) ferroelectric semiconductors with formula M2P2(S,Se)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.

  4. 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.

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

    DOE PAGES

    Zhou, Fei; Nielson, Weston; Xia, Yi; ...

    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

  6. 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.

  7. First principles finite temperature magnetism of defects in Fe using Wang-Landau method

    NASA Astrophysics Data System (ADS)

    Rusanu, Aurelian; Nicholson, D. M.; Odbadrakh, Kh.; Brown, Gregory; Eisenbach, Markus

    2011-03-01

    Magnetic structure of materials with defects presents a strong dependence on local atomic arrangements. This dependence affects mechanical, magneto-caloric, and magnetization properties. Insights into thermodynamic and magnetic fluctuations at defects in Fe are obtained from first principle analysis by deploying the first principle local self consistent multiple scattering method(LSMS) and Wang-Landau statistical method. The computation of thermodynamic properties requires the sampling of a large number of configurations. To reduce the computational effort a Heisenberg model will be used to speed the configuration sampling procedures. The approach will be demonstrated for Fe systems and will address the magnetic structure of defects. This work was supported by the Center for Defect Physics, an Energy Frontier Research Center funded by the US DoE, Office of Science, Office of Basic Energy Sciences. Calculations performed at the National Center for Computational Sciences.

  8. 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.

  9. A comparative first-principles study of martensitic phase transformations in TiPd2 and TiPd

    SciTech Connect

    Krcmar, Maja; Morris, James R

    2014-01-01

    Martensitic phase transformations in TiPd2 and TiPd alloys are studied employing density-functional, first-principles calculations. We examine the transformation of tetragonal C11b TiPd2 to the low-temperature orthorhombic phase (C11b oI6), and the transformation of cubic B2 TiPd under orthorhombic (B2 B19) and subsequent monoclinic transformations (B19 B19 ) as the system is cooled. To evaluate the transition temperature for TiPd2 we employ a theoretical approach based on a phenomenological Landau theory of the structural phase transition and a mean-field approximation for the free energy, utilizing first-principles calculations to obtain the deformation energy as a function of strains and to deduce parameters for constructing the free energy. The predicted transition temperature for the TiPd2 C11b oI6 transition temperature is in good agreement with reported experimental results. To investigate the TiPd B2 B19 transformation, we employ both the Cauchy-Born rule and a soft-mode- based approach, and elucidate on the importance of coupling of lattice distortion and atomic displacements (i.e., shuffling) in the formation of the final structure. The estimated B2 B19 transition temperature for TiPd system agrees well with the experimental results. We also find that there exists a very small but finite (0.0005 eV/atom) energy barrier of B19 TiPd under monoclinic deformation for B19 B19 structural phase transformation.

  10. A comparative first-principles study of martensitic phase transformations in TiPd2 and TiPd intermetallics.

    PubMed

    Krcmar, M; Morris, James R

    2014-04-02

    Martensitic phase transformations in TiPd2 and TiPd alloys are studied employing density-functional, first-principles calculations. We examine the transformation of tetragonal C11b TiPd2 to the low-temperature orthorhombic phase (C11b → oI6), and the transformation of cubic B2 TiPd under orthorhombic (B2→B19) and subsequent monoclinic transformations (B19→B19') as the system is cooled. We employ a theoretical approach based on a phenomenological Landau theory of the structural phase transitions and a mean-field approximation for the free energy, utilizing first-principles calculations to obtain the deformation energy as a function of strains and to deduce parameters for constructing the free energy. The predicted transition temperature for the TiPd2 C11b → oI6 transition is in good agreement with reported experimental results. To investigate the TiPd B2→B19 transformation, we employ both the Cauchy-Born rule and a soft-mode-based approach, and elucidate the importance of the coupling between lattice distortion and atomic displacements (i.e. shuffling) in the formation of the final structure. The calculated B2→B19 transition temperature for TiPd alloy agrees well with the experimental results. We also find that there exists a very small but finite (0.0005 eV/atom) energy barrier of B19 TiPd under monoclinic deformation for B19→B19' structural phase transformation.

  11. First principles total energy study of NbCr{sub 2} + V Laves phase ternary system

    SciTech Connect

    Ormeci, A.; Chen, S.P.; Wills, J.M.; Albers, R.C.

    1999-04-01

    The C15 NbCr{sub 2} + V Laves phase ternary system is studied by using a first-principles, self-consistent, full-potential total energy method. Equilibrium lattice parameters, cohesive energies, density of states and formation energies of substitutional defects are calculated. Results of all these calculations show that in the C15 NbCr{sub 2} + V compounds, V atoms substitute Cr atoms only.

  12. Energetics of point and planar defects in aluminium from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Denteneer, P. J. H.; Soler, J. M.

    1991-06-01

    Formation energies of the vacancy and self-interstitial in Al, as well as energies of intrinsic, extrinsic, and twin-boundary stacking faults are calculated from first-principles. The electronic structure and forces on the atoms are calculated in the framework of the Augmented Plane Wave method using new algorithms proposed by Williams and Soler, enabling an ab initio approach to long-standing questions on defects in metals.

  13. 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.

  14. First-principles Electronic Structure Calculations for Scintillation Phosphor Nuclear Detector Materials

    NASA Astrophysics Data System (ADS)

    Canning, Andrew

    2013-03-01

    Inorganic scintillation phosphors (scintillators) are extensively employed as radiation detector materials in many fields of applied and fundamental research such as medical imaging, high energy physics, astrophysics, oil exploration and nuclear materials detection for homeland security and other applications. The ideal scintillator for gamma ray detection must have exceptional performance in terms of stopping power, luminosity, proportionality, speed, and cost. Recently, trivalent lanthanide dopants such as Ce and Eu have received greater attention for fast and bright scintillators as the optical 5d to 4f transition is relatively fast. However, crystal growth and production costs remain challenging for these new materials so there is still a need for new higher performing scintillators that meet the needs of the different application areas. First principles calculations can provide a useful insight into the chemical and electronic properties of such materials and hence can aid in the search for better new scintillators. In the past there has been little first-principles work done on scintillator materials in part because it means modeling f electrons in lanthanides as well as complex excited state and scattering processes. In this talk I will give an overview of the scintillation process and show how first-principles calculations can be applied to such systems to gain a better understanding of the physics involved. I will also present work on a high-throughput first principles approach to select new scintillator materials for fabrication as well as present more detailed calculations to study trapping process etc. that can limit their brightness. This work in collaboration with experimental groups has lead to the discovery of some new bright scintillators. Work supported by the U.S. Department of Homeland Security and carried out under U.S. Department of Energy Contract no. DE-AC02-05CH11231 at Lawrence Berkeley National Laboratory.

  15. First-principles investigation of anistropic hole mobilities in organic semiconductors.

    PubMed

    Wen, Shu-Hao; Li, An; Song, Junling; Deng, Wei-Qiao; Han, Ke-Li; Goddard, William A

    2009-07-02

    We report a simple first-principles-based simulation model (combining quantum mechanics with Marcus-Hush theory) that provides the quantitative structural relationships between angular resolution anisotropic hole mobility and molecular structures and packing. We validate that this model correctly predicts the anisotropic hole mobilities of ruberene, pentacene, tetracene, 5,11-dichlorotetracene (DCT), and hexathiapentacene (HTP), leading to results in good agreement with experiment.

  16. 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.

  17. (Un)folding of a high-temperature stable polyalanine helix from first principles

    NASA Astrophysics Data System (ADS)

    Blum, Volker; Rossi, Mariana; Tkatchenko, Alex; Scheffler, Matthias

    2010-03-01

    Peptides in vacuo offer a unique, well-defined testbed to match experiments directly against first-principles approaches that predict the intramolecular interactions that govern peptide and protein folding. In this respect, the polyalanine-based peptide Ac-Ala15-LysH^+ is particularly interesting, as it is experimentally known to form helices in vacuo, with stable secondary structure up to 750 K [1]. Room-temperature folding and unfolding timescales are usually not accessible by direct first-principles simulations, but this high T scale allows a rare direct first-principles view. We here use van der Waals corrected [2] density functional theory in the PBE generalized gradient approximation as implemented in the all-electron code FHI-aims [3] to show by Born-Oppenheimer ab initio molecular dynamics that Ac-Ala15-LysH^+ indeed unfolds rapidly (within a few ps) at T=800 K and 1000 K, but not at 500 K. We show that the structural stability of the α helix at 500 K is critically linked to a correct van der Waals treatment, and that the designed LysH^+ ionic termination is essential for the observed helical secondary structure. [1] M. Kohtani et al., JACS 126, 7420 (2004). [2] A. Tkatchenko, M. Scheffler, PRL 102, 073005 (2009). [3] V. Blum et al, Comp. Phys. Comm. 180, 2175 (2009).

  18. 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.

  19. Coarse graining approach to First principles modeling of radiation cascade in large Fe super-cells

    NASA Astrophysics Data System (ADS)

    Odbadrakh, Khorgolkhuu; Nicholson, Don; Rusanu, Aurelian; Wang, Yang; Stoller, Roger; Zhang, Xiaoguang; Stocks, George

    2012-02-01

    First principles techniques employed to understand systems at an atomistic level are not practical for large systems consisting of millions of atoms. We present an efficient coarse graining approach to bridge the first principles calculations of local electronic properties to classical Molecular Dynamics (MD) simulations of large structures. Local atomic magnetic moments in crystalline Fe are perturbed by radiation generated defects. The effects are most pronounced near the defect core and decay with distance. We develop a coarse grained 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. This work was supported by the Center for Defect Physics, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences.

  20. Difference Between Far-Infrared Photoconductivity Spectroscopy and Absorption Spectroscopy: Theoretical Evidence of the Electron Reservoir Mechanism

    NASA Astrophysics Data System (ADS)

    Toyoda, Tadashi; Fujita, Maho; Uchida, Tomohisa; Hiraiwa, Nobuyoshi; Fukuda, Taturo; Koizumi, Hideki; Zhang, Chao

    2013-08-01

    The intriguing difference between far-infrared photoconductivity spectroscopy and absorption spectroscopy in the measurement of the magnetoplasmon frequency in GaAs quantum wells reported by Holland et al. [Phys. Rev. Lett. 93, 186804 (2004)] remains unexplained to date. This Letter provides a consistent mechanism to solve this puzzle. The mechanism is based on the electron reservoir model for the integer quantum Hall effect in graphene [Phys. Lett. A 376, 616 (2012)]. We predict sharp kinks to appear in the magnetic induction dependence of the magnetoplasmon frequency at very low temperatures such as 14 mK in the same GaAs quantum well sample used by Holland et al..

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

    DOE PAGES

    Lemal, Sébastien; Nguyen, Ngoc; de Boor, Johannes; ...

    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

  2. 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.

  3. 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.

  4. 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.

  5. Zirconium metal-based MAX phases Zr2AC (A = Al, Si, P and S): A first-principles study

    NASA Astrophysics Data System (ADS)

    Nasir, M. T.; Hadi, M. A.; Naqib, S. H.; Parvin, F.; Islam, A. K. M. A.; Roknuzzaman, M.; Ali, M. S.

    2014-11-01

    We have investigated theoretical Vickers hardness, thermodynamic and optical properties of four zirconium metal-based MAX phases Zr2AC (A = Al, Si, P and S) for the first time in addition to revisiting the structural, elastic and electronic properties. First-principles calculations are employed based on density functional theory (DFT) by means of the plane-wave pseudopotential method. The theoretical Vickers hardness has been estimated via the calculation of Mulliken bond populations and electronic density of states. The thermodynamic properties such as the temperature and pressure dependent bulk modulus, Debye temperature, specific heats and volume thermal expansion coefficient of all the compounds are derived from the quasi-harmonic Debye model. Further, the optical properties, e.g., dielectric functions, indices of refraction, absorption, energy loss function, reflectivity and optical conductivity of the nanolaminates have been calculated. The results are compared with available experiments and their various implications are discussed in detail. We have also shed light on the effect of different properties of Zr2AC as the A-group atom moves from Al to S across the periodic table.

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

    DOE PAGES

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

    2016-05-23

    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 elasticmore » 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. Lastly, 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.« less

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

    DOE PAGES

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

    2016-05-23

    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 elasticmore » 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. Lastly, 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.« less

  8. Effect of Pressure on Valence and Structural Properties of YbFe 2 Ge 2 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

    We measured the crystal structure and the Yb valence of the YbFe2Ge2 heavy fermion compound 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. Moreover, 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. Finally, 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.

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

    NASA Astrophysics Data System (ADS)

    Mantina, Manjeera

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

  10. First-principles quantum transport method for disordered nanoelectronics: Disorder-averaged transmission, shot noise, and device-to-device variability

    NASA Astrophysics Data System (ADS)

    Yan, Jiawei; Wang, Shizhuo; Xia, Ke; Ke, Youqi

    2017-03-01

    Because disorders are inevitable in realistic nanodevices, the capability to quantitatively simulate the disorder effects on electron transport is indispensable for quantum transport theory. Here, we report a unified and effective first-principles quantum transport method for analyzing effects of chemical or substitutional disorder on transport properties of nanoelectronics, including averaged transmission coefficient, shot noise, and disorder-induced device-to-device variability. All our theoretical formulations and numerical implementations are worked out within the framework of the tight-binding linear muffin tin orbital method. In this method, we carry out the electronic structure calculation with the density functional theory, treat the nonequilibrium statistics by the nonequilbrium Green's function method, and include the effects of multiple impurity scattering with the generalized nonequilibrium vertex correction (NVC) method in coherent potential approximation (CPA). The generalized NVC equations are solved from first principles to obtain various disorder-averaged two-Green's-function correlators. This method provides a unified way to obtain different disorder-averaged transport properties of disordered nanoelectronics from first principles. To test our implementation, we apply the method to investigate the shot noise in the disordered copper conductor, and find all our results for different disorder concentrations approach a universal Fano factor 1 /3 . As the second test, we calculate the device-to-device variability in the spin-dependent transport through the disordered Cu/Co interface and find the conductance fluctuation is very large in the minority spin channel and negligible in the majority spin channel. Our results agree well with experimental measurements and other theories. In both applications, we show the generalized nonequilibrium vertex corrections play a determinant role in electron transport simulation. Our results demonstrate the

  11. Cyclic density functional theory: A route to the first principles simulation of bending in nanostructures

    NASA Astrophysics Data System (ADS)

    Banerjee, Amartya S.; Suryanarayana, Phanish

    2016-11-01

    We formulate and implement Cyclic Density Functional Theory (Cyclic DFT) - a self-consistent first principles simulation method for nanostructures with cyclic symmetries. Using arguments based on Group Representation Theory, we rigorously demonstrate that the Kohn-Sham eigenvalue problem for such systems can be reduced to a fundamental domain (or cyclic unit cell) augmented with cyclic-Bloch boundary conditions. Analogously, the equations of electrostatics appearing in Kohn-Sham theory can be reduced to the fundamental domain augmented with cyclic boundary conditions. By making use of this symmetry cell reduction, we show that the electronic ground-state energy and the Hellmann-Feynman forces on the atoms can be calculated using quantities defined over the fundamental domain. We develop a symmetry-adapted finite-difference discretization scheme to obtain a fully functional numerical realization of the proposed approach. We verify that our formulation and implementation of Cyclic DFT is both accurate and efficient through selected examples. The connection of cyclic symmetries with uniform bending deformations provides an elegant route to the ab-initio study of bending in nanostructures using Cyclic DFT. As a demonstration of this capability, we simulate the uniform bending of a silicene nanoribbon and obtain its energy-curvature relationship from first principles. A self-consistent ab-initio simulation of this nature is unprecedented and well outside the scope of any other systematic first principles method in existence. Our simulations reveal that the bending stiffness of the silicene nanoribbon is intermediate between that of graphene and molybdenum disulphide - a trend which can be ascribed to the variation in effective thickness of these materials. We describe several future avenues and applications of Cyclic DFT, including its extension to the study of non-uniform bending deformations and its possible use in the study of the nanoscale flexoelectric effect.

  12. Configurations of nuclei in Au-catalyzed Si nanowire growth: a first-principles study

    NASA Astrophysics Data System (ADS)

    Yao, Luchi; Zhou, Xiaohao; Chen, Xiaoshuang

    2016-10-01

    The configurations of nuclei in Au catalyzed Si nanowire growth were investigated through an ab-initio thermodynamic-combined approach. We discussed the relation between the configurations and formation energies of the lateral walls of the nucleus in nanowire growth numerically by the classical nucleation theory. The nucleation model was parameterized by the formation energies of surfaces, interfaces and steps calculated in first-principles methods. The configurations of the nuclei were determined by the Wulff theorem. Moreover, we found configurations of the nuclei are different in two different Si-Au contact structures. This study provides an important basis to understand the step-flow process in nanowire growth.

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

    NASA Astrophysics Data System (ADS)

    Kaneko, Tomoaki; Tajima, Nobuo; Ohno, Takahisa

    2016-06-01

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

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

    SciTech Connect

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

    2015-04-20

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

  15. First-principles calculations on the structural evolution of solid fullerene-like CP x

    NASA Astrophysics Data System (ADS)

    Gueorguiev, G. K.; Furlan, A.; Högberg, H.; Stafström, S.; Hultman, L.

    2006-08-01

    The formation and structural evolution of fullerene-like (FL) carbon phosphide (CP x) during synthetic growth were studied by first-principles calculations. Geometry optimizations and comparison between the cohesive energies suggest stability for solid FL-CP x compounds. In comparison with fullerene-like carbon nitride, higher curvature of the graphene sheets and higher density of cross-linkages between them is predicted and explained by the different electronic properties of P and N. Cage-like and onion-like structures, both containing tetragons, are found to be typical for fullerene-like CP x. Segregation of P is predicted at fractions exceeding ˜20 at.%.

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

    SciTech Connect

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

    2015-05-15

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

  17. Liquid-Liquid Phase Transformation in Silicon: Evidence from First-Principles Molecular Dynamics Simulations

    NASA Astrophysics Data System (ADS)

    Jakse, N.; Pasturel, A.

    2007-11-01

    We report results of first principles molecular dynamics simulations that confirm early speculations on the presence of liquid-liquid phase transition in undercooled silicon. However, we find that structural and electronic properties of both low-density liquid (LDL) and high-density liquid (HDL) phases are quite different from those obtained by empirical calculations, the difference being more pronounced for the HDL phase. The discrepancy between quantum and classical simulations is attributed to the inability of empirical potentials to describe changes in chemical bonds induced by density and temperature variations.

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

    NASA Astrophysics Data System (ADS)

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

    2012-05-01

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

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

    PubMed Central

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

    2015-01-01

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

  20. Circuit elements at optical frequencies from first principles: A synthesis of electronic structure and circuit theories

    NASA Astrophysics Data System (ADS)

    Ramprasad, R.; Tang, C.

    2006-08-01

    A first principles electronic structure based method is presented to determine the equivalent circuit representations of nanostructured physical systems at optical frequencies, via a mapping of the effective permittivity calculated for a lattice of physical nano-elements using density functional theory to that calculated for a lattice of impedances using circuit theory. Specifically, it is shown that silicon nanowires and carbon nanotubes can be represented as series combinations of inductance, capacitance and resistance. It is anticipated that the generality of this approach will allow for an alternate description of physical systems at optical frequencies, and in the realization of novel opto- and nanoelectronic devices, including negative refractive index materials.