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.
A first-principles theoretical approach to heterogeneous nanocatalysis.
Negreiros, Fabio R; Aprà, Edoardo; Barcaro, Giovanni; Sementa, Luca; Vajda, Stefan; Fortunelli, Alessandro
2012-02-21
A theoretical approach to heterogeneous catalysis by sub-nanometre supported metal clusters and alloys is presented and discussed. Its goal is to perform a computational sampling of the reaction paths in nanocatalysis via a global search in the phase space of structures and stoichiometry combined with filtering which takes into account the given experimental conditions (catalytically relevant temperature and reactant pressure), and corresponds to an incremental exploration of the disconnectivity diagram of the system. The approach is implemented and applied to the study of propylene partial oxidation by Ag(3) supported on MgO(100). First-principles density-functional theory calculations coupled with a Reactive Global Optimization algorithm are performed, finding that: (1) the presence of an oxide support drastically changes the potential energy landscape of the system with respect to the gas phase, favoring configurations which interact positively with the electrostatic field generated by the surface; (2) the reaction energy barriers for the various mechanisms are crucial in the competition between thermodynamically and kinetically favored reaction products; (3) a topological database of structures and saddle points is produced which has general validity and can serve for future studies or for deriving general trends; (4) the MgO(100) surface captures some major features of the effect of an oxide support and appears to be a good model of a simple oxide substrate; (5) strong cooperative effects are found in the co-adsorption of O(2) and other ligands on small metal clusters. The proposed approach appears as a viable route to advance the role of predictive computational science in the field of heterogeneous nanocatalysis. PMID:22057595
NASA Astrophysics Data System (ADS)
Pemmaraju, Sri Chaitanya Das; Prendergast, David
2014-03-01
We present two case studies of first-principles theoretical methods applied in conjunction with experimental core-level spectroscopy measurements to investigate the electronic structure and dynamical processes in molecular and interfacial systems relevant to photoelectrochemical (PEC) technologies. In the first, we study the core-level and valence spectroscopies of two zinc(II)-porphyrin based Donor-pi-Acceptor (D-p-A) dyes using the occupancy-constrained excited electron and core-hole (XCH) approach and time-dependent density functional theory (TDDFT) simulations. In the second, we use constrained DFT and TDDFT to interpret measured transient core-level shifts in time-resolved femtosecond x-ray photoelectron spectroscopy, investigating the dynamics of the electron injection process from a N3 dye molecule chemisorbed onto a ZnO substrate. These studies illustrate the utility of first-principles methods in guiding the design of better PEC materials. This work was performed at the Molecular Foundry, LBNL, supported by the Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.
NASA Astrophysics Data System (ADS)
Nguyen, Ngoc Linh; Borghi, Giovanni; Ferretti, Andrea; Marzari, Nicola
The determination of spectral properties of the DNA and RNA nucleobases from first principles can provide theoretical interpretation for experimental data, but requires complex electronic-structure formulations that fall outside the domain of applicability of common approaches such as density-functional theory. In this work, we show that Koopmans-compliant functionals, constructed to enforce piecewise linearity in energy functionals with respect to fractional occupation-i.e., with respect to charged excitations-can predict not only frontier ionization potentials and electron affinities of the nucleobases with accuracy comparable or superior with that of many-body perturbation theory and high-accuracy quantum chemistry methods, but also the molecular photoemission spectra are shown to be in excellent agreement with experimental ultraviolet photoemsision spectroscopy data. The results highlight the role of Koopmans-compliant functionals as accurate and inexpensive quasiparticle approximations to the spectral potential, which transform DFT into a novel dynamical formalism where electronic properties, and not only total energies, can be correctly accounted for.
Roy, Tapta Kanchan; Kopysov, Vladimir; Nagornova, Natalia S; Rizzo, Thomas R; Boyarkin, Oleg V; Gerber, R Benny
2015-05-18
Calculated structures of the two most stable conformers of a protonated decapeptide gramicidin S in the gas phase have been validated by comparing the vibrational spectra, calculated from first- principles and measured in a wide spectral range using infrared (IR)-UV double resonance cold ion spectroscopy. All the 522 vibrational modes of each conformer were calculated quantum mechanically and compared with the experiment without any recourse to an empirical scaling. The study demonstrates that first-principles calculations, when accounting for vibrational anharmonicity, can reproduce high-resolution experimental spectra well enough for validating structures of molecules as large as of 200 atoms. The validated accurate structures of the peptide may serve as templates for in silico drug design and absolute calibration of ion mobility measurements. PMID:25721337
Ashbrook, Sharon E; McKay, David
2016-06-01
Recent advances in the application of first-principles calculations of NMR parameters to periodic systems have resulted in widespread interest in their use to support experimental measurement. Such calculations often play an important role in the emerging field of "NMR crystallography", where NMR spectroscopy is combined with techniques such as diffraction, to aid structure determination. Here, we discuss the current state-of-the-art for combining experiment and calculation in NMR spectroscopy, considering the basic theory behind the computational approaches and their practical application. We consider the issues associated with geometry optimisation and how the effects of temperature may be included in the calculation. The automated prediction of structural candidates and the treatment of disordered and dynamic solids are discussed. Finally, we consider the areas where further development is needed in this field and its potential future impact. PMID:27117884
Kadantsev, Eugene S; Ziegler, Tom
2010-12-01
The hyperfine A-tensor and Zeeman g-tensor parameterize the interaction of an 'effective' electron spin with the magnetic field due to the nuclear spin and the homogeneous external magnetic field, respectively. The A- and g-tensors are the quantities of primary interest in electron paramagnetic resonance (EPR) spectroscopy. In this paper, we review our work [E.S. Kadantsev, T. Ziegler, J. Phys. Chem. A 2008, 112, 4521; E. S. Kadantsev, T. Ziegler, J. Phys. Chem. A 2009, 113, 1327] on the calculation of these EPR parameters under periodic boundary conditions (PBC) from first-principles. Our methodology is based on the Kohn-Sham DFT (KS DFT), explicit usage of Bloch basis set made up of numerical and Slater-type atomic orbitals (NAOs/STOs), and is implemented in the 'full potential' program BAND. Our implementation does not rely on the frozen core approximation. The NAOs/STOs basis is well suited for the accurate representation of the electron density near the nuclei, a prerequisite for the calculation of highly accurate hyperfine parameters. In the case of g-tensor, our implementation is based on the method of Van Lenthe et al. [E. van Lenthe, P. E. S. Wormer, A. van der Avoird, J. Chem. Phys. 1997, 107, 2488] in which the spin-orbital coupling is taken into account variationally. We demonstrate the viability of our scheme by calculating EPR parameters of paramagnetic defects in solids. We consider the A-tensor of 'normal' and 'anomalous' muonium defect in IIIA-VA semiconductors as well as the S2 anion radical in KCl host crystal lattice. PMID:20821407
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.
First-Principles Theoretical Investigation of Neutral Vacancy-Associated Muonium Center in Silicon
NASA Astrophysics Data System (ADS)
Li, Hong; Nandini Usha Roy, Alok; Sahoo, N.; Das, T. P.; Scheuermann, R.; Nagamine, K.
2000-03-01
First-principles Hartree-Fock Cluster investigation has been carried out on the vacancy associated center MuV in silicon (B. Beck Nielsen et al, Phys. Rev. Lett. \\underline79, 1507 (1997)) and V_H, its H counterpart (M. Schefzik et al, Sol. St. Comm. \\underline107, 395 (1998)), using the cluster Si_4H_12Mu involving muonium and the four silicon neighbors nearest to the vacancy. Lattice relaxation effects are included. Our results explain the observed non-axial symmetry through Jahn-Teller distortion and provide reasonable quantitative agreement with experimental hyperfine data. The influence of using larger clusters and vibrational motion of the muon is being studied and results will be reported.
Theoretical studies of aluminum and aluminide alloys using CALPHAD and first-principles approach
NASA Astrophysics Data System (ADS)
Jiang, Chao
Heat-treatable aluminum alloys have been widely used in the automobile and aerospace industries as structural materials due to their light weight and high strength. To study the age-hardening process in heat-treatable aluminum alloys, the Gibbs energies of the strengthening metastable phases, e.g. theta ' and theta″, are critical. However, those data are not included in the existing thermodynamic databases for aluminum alloys due to the semi-empirical nature of the CALPHAD approach. In the present study, the thermodynamics of the Al-Cu system, the pivotal age-hardening system, is remodeled using a combined CALPHAD and first-principles approach. The formation enthalpies and vibrational formation entropies of the stable and metastable phases in the Al-Cu system are provided by first-principles calculations. Special Quasirandom Structures (SQS's) are applied to model the substitutionally random fee and bee alloys. SQS's for binary bee alloys are developed and tested in the present study. Finally, a self-consistent thermodynamic description of the Al-Cu system including the two metastable theta″ and theta' phases is obtained. During welding of heat-treatable aluminum alloys, a detrimental phenomenon called constitutional liquation, i.e. the local eutectic melting of second-phase particles in a matrix at temperatures above the eutectic temperature but below the solidus of the alloy, may occur in the heat-affected zone (HAZ). In the present study, diffusion code DICTRA coupled with realistic thermodynamic and kinetic databases is used to simulate the constitutional liquation in the model Al-Cu system. The simulated results are in quantitative agreement with experiments. The critical heating rate to avoid constitutional liquation is also determined through computer simulations. Besides the heat-treatable aluminum alloys, intermetallic compounds based on transition metal aluminides, e.g. NiAl and FeAl, are also promising candidates for the next-generation of high
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.
Nguyen, Ngoc Linh; Borghi, Giovanni; Ferretti, Andrea; Marzari, Nicola
2016-08-01
The need to interpret ultraviolet photoemission data strongly motivates the refinement of first-principles techniques that are able to accurately predict spectral properties. In this work, we employ Koopmans-compliant functionals, constructed to enforce piecewise linearity in approximate density functionals, to calculate the structural and electronic properties of DNA and RNA nucleobases. Our results show that not only ionization potentials and electron affinities are accurately predicted with mean absolute errors of <0.1 eV, but also that calculated photoemission spectra are in excellent agreement with experimental ultraviolet photoemission spectra. In particular, the role and contribution of different tautomers to the photoemission spectra are highlighted and discussed in detail. The structural properties of nucleobases are also investigated, showing an improved description with respect to local and semilocal density-functional theory. Methodologically, our results further consolidate the role of Koopmans-compliant functionals in providing, through orbital-density-dependent potentials, accurate electronic and spectral properties. PMID:27267665
First-principles study of phonon effects in x-ray absorption near-edge structure spectroscopy
NASA Astrophysics Data System (ADS)
Nemausat, R.; Brouder, Ch; Gervais, Ch; Cabaret, D.
2016-05-01
Usually first-principles x-ray absorption near-edge structure (XANES) calculations are performed in the Born-Oppenheimer approximation assuming a static lattice, whereas the nuclear motion undoubtedly impacts XANES spectra notably at the K pre-edge of light elements in oxides. Here, an efficient method based on density-functional theory to account for quantum thermal fluctuations of nuclei is developed and is successfully applied to the K edge of corundum for temperatures up to 930 K. The zero-point motion influence is estimated. Comparison is made with previous theoretical approaches also developed to account for vibrations in XANES.
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
NASA Astrophysics Data System (ADS)
Sharifzadeh, Sahar; Biller, Ariel; Kronik, Leeor; Neaton, Jeffrey B.
2012-03-01
The broad use of organic semiconductors for optoelectronic applications relies on quantitative understanding and control of their spectroscopic properties. Of paramount importance are the transport gap—the difference between ionization potential and electron affinity—and the exciton binding energy—inferred from the difference between the transport and optical absorption gaps. Transport gaps are commonly established via photoemission and inverse photoemission spectroscopy (PES/IPES). However, PES and IPES are surface-sensitive, average over a dynamic lattice, and are subject to extrinsic effects, leading to significant uncertainty in gaps. Here, we use density functional theory and many-body perturbation theory to calculate the spectroscopic properties of two prototypical organic semiconductors, pentacene, and 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA), quantitatively comparing with measured PES, IPES, and optical absorption spectra. For bulk pentacene and PTCDA, the computed transport gaps are 2.4 and 3.0 eV, and optical gaps are 1.7 and 2.1 eV, respectively. Computed bulk quasiparticle spectra are in excellent agreement with surface-sensitive photoemission measurements over several eV only if the measured gap is reduced by 0.6 eV for pentacene and 0.6-0.9 eV for PTCDA. We attribute this redshift to several physical effects, including incomplete charge screening at the surface, static and dynamical disorder, and experimental resolution. Optical gaps are in excellent agreement with experiment with solid-state exciton binding energies of ˜0.5 eV for both systems; for pentacene the exciton is delocalized over several molecules and exhibits significant charge transfer character. Our parameter-free calculations provide new interpretation of spectroscopic properties of organic semiconductors critical to optoelectronics.
Beccara, Silvio a; Rivalta, Ivan; Cerullo, Giulio
2014-01-01
The ability of non-linear electronic spectroscopy to track folding/unfolding processes of proteins in solution by monitoring aromatic interactions is investigated by first-principle simulations of two-dimensional (2D) electronic spectra of a model peptide. A dominant reaction pathway approach is employed to determine the unfolding pathway of a tetrapeptide, connecting the initial folded configuration with stacked aromatic side chains and the final unfolded state with distant non-interacting aromatic residues. π-stacking and excitonic coupling effects are included via ab-initio simulations based on multiconfigurational methods within a hybrid QM/MM scheme. We show that linear absorption spectroscopy in the ultraviolet (UV) is unable to resolve the unstacking dynamics characterized by the three-step process: T-shaped→twisted offset stacking→unstacking. Conversely, pump-probe spectroscopy can be used to resolve aromatic interactions by probing in the visible (Vis) the excited state absorptions (ESA) that involve charge transfer (CT) states. 2DUV spectroscopy offers the highest sensitivity to the unfolding process, providing the disentanglement of ESA signals belonging to different aromatic chromophores and high correlation between the conformational dynamics and the quartic splitting. PMID:25145908
Zhang, Lei; Ju, Ming-Gang; Liang, WanZhen
2016-08-17
With efficiencies exceeding 20% and low production costs, lead halide perovskite solar cells (PSCs) have become potential candidates for future commercial applications. However, there are serious concerns about their long-term stability and environmental friendliness, heavily related to their commercial viability. Herein, we present a theoretical investigation based on the ab initio molecular dynamics (AIMD) simulations and the first-principles density functional theory (DFT) calculations to investigate the effects of sunlight and moisture on the structures and properties of MAPbI3 perovskites. AIMD simulations have been performed to simulate the impact of a few water molecules on the structures of MAPbI3 surfaces terminated in three different ways. The evolution of geometric and electronic structures as well as the absorption spectra has been shown. It is found that the PbI2-terminated surface is the most stable while both the MAI-terminated and PbI2-defective surfaces undergo structural reconstruction, leading to the formation of hydrated compounds in a humid environment. The moisture-induced weakening of photoabsorption is closely related to the formation of hydrated species, and the hydrated crystals MAPbI3·H2O and MA4PbI6·2H2O scarcely absorb the visible light. The electronic excitation in the bare and water-absorbed MAPbI3 nanoparticles tends to weaken Pb-I bonds, especially those around water molecules, and the maximal decrease of photoexcitation-induced bond order can reach up to 20% in the excited state in which the water molecules are involved in the electronic excitation, indicating the accelerated decomposition of perovskites in the presence of sunlight and moisture. This work is valuable for understanding the mechanism of chemical or photochemical instability of MAPbI3 perovskites in the presence of moisture. PMID:27499005
Nenov, Artur; Mukamel, Shaul; Garavelli, Marco; Rivalta, Ivan
2015-08-11
First-principles simulations of two-dimensional electronic spectroscopy in the ultraviolet region (2DUV) require computationally demanding multiconfigurational approaches that can resolve doubly excited and charge transfer states, the spectroscopic fingerprints of coupled UV-active chromophores. Here, we propose an efficient approach to reduce the computational cost of accurate simulations of 2DUV spectra of benzene, phenol, and their dimer (i.e., the minimal models for studying electronic coupling of UV-chromophores in proteins). We first establish the multiconfigurational recipe with the highest accuracy by comparison with experimental data, providing reference gas-phase transition energies and dipole moments that can be used to construct exciton Hamiltonians involving high-lying excited states. We show that by reducing the active spaces and the number of configuration state functions within restricted active space schemes, the computational cost can be significantly decreased without loss of accuracy in predicting 2DUV spectra. The proposed recipe has been successfully tested on a realistic model proteic system in water. Accounting for line broadening due to thermal and solvent-induced fluctuations allows for direct comparison with experiments. PMID:26574458
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.
Pallister, Peter J; Moudrakovski, Igor L; Ripmeester, John A
2009-12-28
Due to sensitivity problems, (25)Mg remains a largely under-explored nucleus in solid state NMR spectroscopy. In this work at an ultrahigh magnetic field of 21.1 T, we have studied at natural abundance the (25)Mg solid state (SS) NMR spectra for a number of previously unreported magnesium compounds with known crystal structures. Some previously reported compounds have been revisited to clarify the spectra that were obtained at lower fields and were either not sufficiently resolved, or misinterpreted. First principles calculations of the (25)Mg SS NMR parameters have been carried out using plane wave basis sets and periodic boundary conditions (CASTEP) and the results are compared with experimental data. The calculations produce the (25)Mg absolute shielding scale and give us insight into the relationship between the NMR and structural parameters. At 21.1 T the effects of the quadrupolar interactions are reduced significantly and the sensitivity and accuracy in determining chemicals shifts and quadrupole coupling parameters improve dramatically. Although T(1) measurements were not performed explicitly, these proved to be longer than assumed in much of the previously reported work. We demonstrate that the chemical shift range of magnesium in diamagnetic compounds may approach 200 ppm. Most commonly, however, the observed shifts are between -15 and +25 ppm. Quadrupolar effects dominate the (25)Mg spectra of magnesium cations in non-cubic environments. The chemical shift anisotropy appears to be rather small and only in a few cases could the contribution of the CSA be detected reliably. A good correspondence between the calculated shielding constants and experimental chemical shifts was obtained, demonstrating the good potential of computational methods in spectroscopic assignments of solid state (25)Mg NMR spectroscopy. PMID:20024420
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
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.
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.
NASA Astrophysics Data System (ADS)
Migaou, Amani; Sarpi, Brice; Guiltat, Mathilde; Payen, Kevin; Daineche, Rachid; Landa, Georges; Vizzini, Sébastien; Hémeryck, Anne
2016-05-01
First principles calculations, scanning tunneling microscopy, and Auger spectroscopy experiments of the adsorption of Mg on Ag(111) substrate are conducted. This detailed study reveals that an atomic scale controlled deposition of a metallic Mg monolayer perfectly wets the silver substrate without any alloy formation at the interface at room temperature. A liquid-like behavior of the Mg species on the Ag substrate is highlighted as no dot formation is observed when coverage increases. Finally a layer-by-layer growth mode of Mg on Ag(111) can be predicted, thanks to density functional theory calculations as observed experimentally.
Migaou, Amani; Sarpi, Brice; Guiltat, Mathilde; Payen, Kevin; Daineche, Rachid; Landa, Georges; Vizzini, Sébastien; Hémeryck, Anne
2016-05-21
First principles calculations, scanning tunneling microscopy, and Auger spectroscopy experiments of the adsorption of Mg on Ag(111) substrate are conducted. This detailed study reveals that an atomic scale controlled deposition of a metallic Mg monolayer perfectly wets the silver substrate without any alloy formation at the interface at room temperature. A liquid-like behavior of the Mg species on the Ag substrate is highlighted as no dot formation is observed when coverage increases. Finally a layer-by-layer growth mode of Mg on Ag(111) can be predicted, thanks to density functional theory calculations as observed experimentally. PMID:27208966
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.
NASA Astrophysics Data System (ADS)
Reeves, Kyle G.; Kanai, Yosuke
2014-07-01
Oxidation state is a powerful concept that is widely used in chemistry and materials physics, although the concept itself is arguably ill-defined quantum mechanically. In this work, we present impartial comparison of four, well-recognized theoretical approaches based on Lowdin atomic orbital projection, Bader decomposition, maximally localized Wannier function, and occupation matrix diagonalization, for assessing how well transition metal oxidation states can be characterized. Here, we study a representative molecular complex, tris(bipyridine)ruthenium. We also consider the influence of water solvation through first-principles molecular dynamics as well as the improved electronic structure description for strongly correlated d-electrons by including Hubbard correction in density functional theory calculations.
Sarkar, Tanmay; Kumar, Parveen; Bharadwaj, Mridula Dixit; Waghmare, Umesh
2016-04-14
A double layer δ-NH4V4O10, due to its high energy storage capacity and excellent rate capability, is a very promising cathode material for Li-ion and Na-ion batteries for large-scale renewable energy storage in transportation and smart grids. While it possesses better stability, and higher ionic and electronic conductivity than the most widely explored V2O5, the mechanisms of its cyclability are yet to be understood. Here, we present a theoretical cyclic voltammetry as a tool based on first-principles calculations, and uncover structural transformations that occur during Li(+)/Na(+) insertion (x) into (Lix/Nax)NH4V4O10. Structural distortions associated with single-phase and multi-phase structural changes during the insertion of Li(+)/Na(+), identified through the analysis of voltage profile and theoretical cyclic voltammetry are in agreement with the reported experimental electrochemical measurements on δ-NH4V4O10. We obtain an insight into its electronic structure with a lower band gap that is responsible for the high rate capability of (Lix/Nax) δ-NH4V4O10. The scheme of theoretical cyclic voltammetry presented here will be useful for addressing issues of cyclability and energy rate in other electrode materials. PMID:26996324
Manceau, Alain; Lemouchi, Cyprien; Rovezzi, Mauro; Lanson, Martine; Glatzel, Pieter; Nagy, Kathryn L; Gautier-Luneau, Isabelle; Joly, Yves; Enescu, Mironel
2015-12-21
We present results obtained from high energy-resolution L3-edge XANES spectroscopy and first-principles calculations for the structure, bonding, and stability of mercury(II) complexes with thiolate and thioether ligands in crystalline compounds, aqueous solution, and macromolecular natural organic matter (NOM). Core-to-valence XANES features that vary in intensity differentiate with unprecedented sensitivity the number and identity of Hg ligands and the geometry of the ligand environment. Post-Hartree-Fock XANES calculations, coupled with natural population analysis, performed on MP2-optimized Hg[(SR)2···(RSR)n] complexes show that the shape, position, and number of electronic transitions observed at high energy-resolution are directly correlated to the Hg and S (l,m)-projected empty densities of states and occupations of the hybridized Hg 6s and 5d valence orbitals. Linear two-coordination, the most common coordination geometry in mercury chemistry, yields a sharp 2p to 6s + 5d electronic transition. This transition varies in intensity for Hg bonded to thiol groups in macromolecular NOM. The intensity variation is explained by contributions from next-nearest, low-charge, thioether-type RSR ligands at 3.0-3.3 Å from Hg. Thus, Hg in NOM has two strong bonds to thiol S and k additional weak Hg···S contacts, or 2 + k coordination. The calculated stabilization energy is -5 kcal/mol per RSR ligand. Detection of distant ligands beyond the first coordination shell requires precise measurement of, and comparison to, spectra of reference compounds as well as accurate calculation of spectra for representative molecular models. The combined experimental and theoretical approaches described here for Hg can be applied to other closed-shell atoms, such as Ag(I) and Au(I). To facilitate further calculation of XANES spectra, experimental data, a new crystallographic structure of a key mercury thioether complex, Cartesian coordinates of the computed models, and examples of
NASA Astrophysics Data System (ADS)
Zhao, Li-Juan; Tian, Wen-Juan; Ou, Ting; Xu, Hong-Guang; Feng, Gang; Xu, Xi-Ling; Zhai, Hua-Jin; Li, Si-Dian; Zheng, Wei-Jun
2016-03-01
We present a combined photoelectron spectroscopy and first-principles theory study on the structural and electronic properties and chemical bonding of B3O3-/0 and B3O3H-/0 clusters. The concerted experimental and theoretical data show that the global-minimum structures of B3O3 and B3O3H neutrals are very different from those of their anionic counterparts. The B3O3- anion is characterized to possess a V-shaped OB-B-BO chain with overall C2v symmetry (1A), in which the central B atom interacts with two equivalent boronyl (B≡O) terminals via B-B single bonds as well as with one O atom via a B=O double bond. The B3O3H- anion has a Cs (2A) structure, containing an asymmetric OB-B-OBO zig-zag chain and a terminal H atom interacting with the central B atom. In contrast, the C2v (1a) global minimum of B3O3 neutral contains a rhombic B2O2 ring with one B atom bonded to a BO terminal and that of neutral B3O3H (2a) is also of C2v symmetry, which is readily constructed from C2v (1a) by attaching a H atom to the opposite side of the BO group. The H atom in B3O3H-/0 (2A and 2a) prefers to interact terminally with a B atom, rather than with O. Chemical bonding analyses reveal a three-center four-electron (3c-4e) π hyperbond in the B3O3H- (2A) cluster and a four-center four-electron (4c-4e) π bond (that is, the so-called o-bond) in B3O3 (1a) and B3O3H (2a) neutral clusters.
Zhao, Li-Juan; Tian, Wen-Juan; Ou, Ting; Xu, Hong-Guang; Feng, Gang; Xu, Xi-Ling; Zhai, Hua-Jin; Li, Si-Dian; Zheng, Wei-Jun
2016-03-28
We present a combined photoelectron spectroscopy and first-principles theory study on the structural and electronic properties and chemical bonding of B3O3 (-/0) and B3O3H(-/0) clusters. The concerted experimental and theoretical data show that the global-minimum structures of B3O3 and B3O3H neutrals are very different from those of their anionic counterparts. The B3O3 (-) anion is characterized to possess a V-shaped OB-B-BO chain with overall C2 v symmetry (1A), in which the central B atom interacts with two equivalent boronyl (B≡O) terminals via B-B single bonds as well as with one O atom via a B=O double bond. The B3O3H(-) anion has a Cs (2A) structure, containing an asymmetric OB-B-OBO zig-zag chain and a terminal H atom interacting with the central B atom. In contrast, the C2 v (1a) global minimum of B3O3 neutral contains a rhombic B2O2 ring with one B atom bonded to a BO terminal and that of neutral B3O3H (2a) is also of C2 v symmetry, which is readily constructed from C2 v (1a) by attaching a H atom to the opposite side of the BO group. The H atom in B3O3H(-/0) (2A and 2a) prefers to interact terminally with a B atom, rather than with O. Chemical bonding analyses reveal a three-center four-electron (3c-4e) π hyperbond in the B3O3H(-) (2A) cluster and a four-center four-electron (4c-4e) π bond (that is, the so-called o-bond) in B3O3 (1a) and B3O3H (2a) neutral clusters. PMID:27036442
Soft modes and anharmonicity in H3[Co (CN )6] : Raman spectroscopy and first-principles calculations
NASA Astrophysics Data System (ADS)
Mishra, K. K.; Chandra, Sharat; Salke, Nilesh P.; Achary, S. N.; Tyagi, A. K.; Rao, Rekha
2015-10-01
In situ high-pressure Raman spectroscopy and ab initio calculations are carried out to investigate the phase stability and the thermal expansion behavior of H3[Co (CN )6] . Raman studies at high pressures in a diamond anvil cell identify soft phonons and phase instability at 2.3 GPa. Evidence of pressure-induced amorphization is found at 11 GPa. The phonon frequencies and eigenvectors obtained from ab initio calculation are used to complement the observed phonon spectra and for assignment of Raman modes. The computed eigenvector displacement patterns indicate that the soft modes correspond to the CN-librational vibrations (Eg mode) of the Co-CN-H-NC-Co linkages and their Grüneisen parameters are found to be negative, in agreement with our measured values. The thermal expansion coefficient (15.6 ×10-6K-1 ) calculated using our computed mode Grüneisen parameters is found to be in good agreement with the reported value (20 ×10-6K-1 ). Temperature-dependent phonon spectra down to 77 K are used to obtain the anharmonicities of different modes.
NASA Astrophysics Data System (ADS)
Hirayama, Naomi; Iida, Tsutomu; Funashima, Hiroki; Morioka, Shunsuke; Sakamoto, Mariko; Nishio, Keishi; Kogo, Yasuo; Takanashi, Yoshifumi; Hamada, Noriaki
2015-07-01
We theoretically investigate the impurity doping effects on the structural parameters such as lattice constant, atomic positions, and site preferences of impurity dopants for Al-doped magnesium silicide (Mg2Si) crystal using the first-principles calculation methods. We present comparison between several codes: ABCAP, Quantum Espresso, and Machikaneyama2002 (Akai KKR), which are based on the full-potential linearized augmented plane-wave method, the pseudopotential method, and KKR/GGA Green’s function method, respectively. As a result, any codes used in the present study exhibit qualitative consistency both in the dependence of the lattice constants on the doping concentration and the energetic preference of the Al atom for the following sites; substitutional Si and Mg sites, and interstitial 4b site; in particular, ABCAP, which is based on the all-electron full-potential method, and Quantum Espresso, which is a code of the pseudopotential method, produce closely-resemble calculation results. We also discuss the effects of local atomic displacement owing to the presence of impurities to the structural parameters of a bulk. Using the analytical method considering the local atomic displacement, moreover, we evaluate the formation energy of Na- and B-doped systems as examples of p-type doping in order to examine the possilbility of realizing p-type Mg2Si.
Anharmonic Theoretical Vibrational Spectroscopy of Polypeptides.
Panek, Paweł T; Jacob, Christoph R
2016-08-18
Because of the size of polypeptides and proteins, the quantum-chemical prediction of their vibrational spectra presents an exceptionally challenging task. Here, we address one of these challenges, namely, the inclusion of anharmonicities. By performing the expansion of the potential energy surface in localized-mode coordinates instead of the normal-mode coordinates, it becomes possible to calculate anharmonic vibrational spectra of polypeptides efficiently and reliably. We apply this approach to calculate the infrared, Raman, and Raman optical activity spectra of helical alanine polypeptides consisting of up to 20 amino acids. We find that while anharmonicities do not alter the band shapes, simple scaling procedures cannot account for the different shifts found for the individual bands. This closes an important gap in theoretical vibrational spectroscopy by making it possible to quantify the anharmonic contributions and opens the door to a first-principles calculation of multidimensional vibrational spectra. PMID:27472016
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.
NASA Astrophysics Data System (ADS)
Gambuzzi, Elisa; Pedone, Alfonso; Menziani, Maria Cristina; Angeli, Frédéric; Caurant, Daniel; Charpentier, Thibault
2014-01-01
Silicon and aluminium chemical environments in silicate and aluminosilicate glasses with compositions 60SiO2·20Na2O·20CaO (CSN), 60SiO2·20Al2O3·20CaO (CAS), 78SiO2·11Al2O3·11Na2O (NAS) and 60SiO2·10Al2O3·10Na2O·20CaO (CASN) have been investigated by 27Al and 29Si solid state magic angle spinning (MAS) and multiple quantum MAS (MQMAS) nuclear magnetic resonance (NMR) experiments. To interpret the NMR data, first-principles calculations using density functional theory were performed on structural models of these glasses. These models were generated by Shell-model molecular dynamics (MD) simulations. The theoretical NMR parameters and spectra were computed using the gauge including projected augmented wave (GIPAW) method and spin-effective Hamiltonians, respectively. This synergetic computational-experimental approach offers a clear structural characterization of these glasses, particularly in terms of network polymerization, chemical disorder (i.e. Si and Al distribution in second coordination sphere) and modifier cation distributions. The relationships between the local structural environments and the 29Si and 27Al NMR parameters are highlighted, and show that: (i) the isotropic chemical shift of both 29Si and 27Al increases of about +5 ppm for each Al added in the second sphere and (ii) both the 27Al and 29Si isotropic chemical shifts linearly decrease with the reduction of the average Si/Al-O-T bond angle. Conversely, 27Al and 29Si NMR parameters are much less sensitive to the connectivity with triple bridging oxygen atoms, precluding their indirect detection from 27Al and 29Si NMR.
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.
Theoretical methods for ultrafast spectroscopy.
Marquardt, Roberto
2013-05-10
Time-resolved spectroscopy in the femtosecond and attosecond time domain is a tool to unravel the dynamics of nuclear and electronic motion in molecular systems. Theoretical insight into the underlying physical processes is ideally gained by solving the time-dependent Schrödinger equation. In this work, methods currently used to solve this equation are reviewed in a compact presentation. These methods involve numerical representations of wavefunctions and operators, the calculation of time evolution operators, the setting up of the Hamiltonian operators and the types of coordinates to be used hereto. The advantages and disadvantages of some methods are discussed. PMID:23606322
Loganathan, B; Chandraboss, V L; Senthilvelan, S; Karthikeyan, B
2015-09-01
The Rh shell of the Au/Pt/Rh trimetallic nanoparticles induces a wide variety of interesting surface reactions by allowing the adsorption of amino acids like L-cysteine (L-Cys). We present a snapshot of theoretical and experimental investigation of L-Cys adsorption on the surface of noble trimetallic Au/Pt@Rh colloidal nanocomposites. Density functional theoretical (DFT) investigations of L-Cys interaction with the Rhodium (Rh) shell of a trimetallic Au/Pt@Rh cluster in terms of geometry, binding energy (E(B)), binding site, energy gap (E(g)), electronic and spectral properties have been performed. L-Cys establishes a strong interaction with the Rh shell. It binds to Rh by the S1-site, which makes a stable L-Cys-Rh surface complex. DFT can be taken as a valuable tool to assign the vibrational spectra of the adsorption of L-Cys on trimetallic Au/Pt@Rh colloidal nanocomposites and mono-metallic Rh nanoparticles. Surface-enhanced infrared spectroscopy (SEIRS) with L-Cys on a Rh6 cluster surface has been simulated for the first time. Experimental information on the L-Cys-Rh surface complex is included to examine the interaction. The experimental spectral observations are in good agreement with the simulated DFT results. Characterization of the synthesized trimetallic Au/Pt@Rh colloidal nanocomposites has been done by high-resolution transmission electron microscopy (HR-TEM) with selected area electron diffraction (SAED) pattern, energy dispersive X-ray (EDX) spectroscopy, dynamic light scattering (DLS) measurements, zeta potential, zeta deviation analysis and UV-visible (UV-Vis) spectroscopic studies. PMID:25650352
NASA Astrophysics Data System (ADS)
Schweflinghaus, Benedikt; dos Santos Dias, Manuel; Lounis, Samir
2016-01-01
Spin excitations in atomic-scale nanostructures have been investigated with inelastic scanning tunneling spectroscopy, sometimes with conflicting results. In this work, we present a theoretical viewpoint on a recent experimental controversy regarding the spin excitations of Co adatoms on Pt(111). While one group [Balashov et al., Phys. Rev. Lett. 102, 257203 (2009), 10.1103/PhysRevLett.102.257203] claims to have detected them, another group reported their observation only after the hydrogenation of the Co adatom [Dubout et al., Phys. Rev. Lett. 114, 106807 (2015), 10.1103/PhysRevLett.114.106807]. Utilizing time-dependent density functional theory in combination with many-body perturbation theory, we demonstrate that, although inelastic spin excitations are possible for Cr, Mn, Fe, and Co adatoms, their efficiency differs. While the excitation signature is less pronounced for Mn and Co adatoms, it is larger for Cr and Fe adatoms. We find that the tunneling matrix elements or the tunneling cross-section related to the nature and symmetry of the relevant electronic states are more favorable for triggering the spin excitations in Fe than in Co. An enhancement of the tunneling and of the inelastic spectra is possible by attaching hydrogen to the adatom at the appropriate position.
Dai, Xing; Gao, Yang; Xin, Minsi; Wang, Zhigang; Zhou, Ruhong
2014-12-28
As a representative lanthanide endohedral metallofullerene, Gd@C{sub 82} has attracted a widespread attention among theorists and experimentalists ever since its first synthesis. Through comprehensive comparisons and discussions, as well as references to the latest high precision experiments, we evaluated the performance of different computational methods. Our results showed that the appropriate choice of the exchange-correlation functionals is the decisive factor to accurately predict both geometric and electronic structures for Gd@C{sub 82}. The electronic structure of the ground state and energy gap between the septet ground state and the nonet low-lying state obtained from pure density functional methods, such as PBE and PW91, are in good agreement with current experiment. Unlike pure functionals, the popularly used hybrid functionals in previous studies, such as B3LYP, could infer the qualitative correct ground state only when small basis set for C atoms is employed. Furthermore, we also highlighted that other geometric structures of Gd@C{sub 82} with the Gd staying at different positions are either not stable or with higher energies. This work should provide some useful references for various theoretical methodologies in further density functional studies on Gd@C{sub 82} and its derivatives in the future.
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.
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
Valla, Maxence; Rossini, Aaron J; Caillot, Maxime; Chizallet, Céline; Raybaud, Pascal; Digne, Mathieu; Chaumonnot, Alexandra; Lesage, Anne; Emsley, Lyndon; van Bokhoven, Jeroen A; Copéret, Christophe
2015-08-26
Despite the widespread use of amorphous aluminosilicates (ASA) in various industrial catalysts, the nature of the interface between silica and alumina and the atomic structure of the catalytically active sites are still subject to debate. Here, by the use of dynamic nuclear polarization surface enhanced NMR spectroscopy (DNP SENS) and density functional theory (DFT) calculations, we show that on silica and alumina surfaces, molecular aluminum and silicon precursors are, respectively, preferentially grafted on sites that enable the formation of Al(IV) and Si(IV) interfacial sites. We also link the genesis of Brønsted acidity to the surface coverage of aluminum and silicon on silica and alumina, respectively. PMID:26244620
Drużbicki, Kacper; Mikuli, Edward; Pałka, Norbert; Zalewski, Sławomir; Ossowska-Chruściel, Mirosława D
2015-01-29
The polymorphism of resorcinol has been complementary studied by combining Raman, time-domain terahertz, and inelastic neutron scattering spectroscopy with modern solid-state density functional theory (DFT) calculations. The spectral differences, emerging from the temperature-induced structural phase transition, have been successfully interpreted with an emphasis on the low-wavenumber range. The given interpretation is based on the plane-wave DFT computations, providing an excellent overall reproduction of both wavenumbers and intensities and revealing the source of the observed spectral differences. The performance of the generalized gradient approximation (GGA) functionals in prediction of the structural parameters and the vibrational spectra of the normal-pressure polymorphs of resorcinol has been extensively examined. The results show that the standard Perdew, Burke, and Ernzerhof (PBE) approach along with its "hard" revised form tends to be superior if compared to the "soft" GGA approximation. PMID:25564699
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.
Culturing conceptions: From first principles
NASA Astrophysics Data System (ADS)
Roth, Wolff-Michael; Lee, Yew Jin; Hwang, Sungwon
2008-07-01
Over the past three decades, science educators have accumulated a vast amount of information on conceptions--variously defined as beliefs, ontologies, cognitive structures, mental models, or frameworks--that generally (at least initially) have been derived from interviews about certain topics. During the same time period, cultural studies has emerged as a field in which everyday social practices are interrogated with the objective to understand culture in all its complexity. Science educators have however yet to ask themselves what it would mean to consider the possession of conceptions as well as conceptual change from the perspective of cultural studies. The purpose of this article is thus to articulate in and through the analysis of an interview about natural phenomenon the first principles of such a cultural approach to scientific conceptions. Our bottom-up approach in fact leads us to develop the kind of analyses and theories that have become widespread in cultural studies. This promises to generate less presupposing and more parsimonious explanations of this core issue within science education than if conceptions are supposed to be structures inhabiting the human mind.
Chamber Clearing First Principles Modeling
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
Kerber, Rachel Nathaniel; Kermagoret, Anthony; Callens, Emmanuel; Florian, Pierre; Massiot, Dominique; Lesage, Anne; Copéret, Christophe; Delbecq, Françoise; Rozanska, Xavier; Sautet, Philippe
2012-04-18
The determination of the nature and structure of surface sites after chemical modification of large surface area oxides such as silica is a key point for many applications and challenging from a spectroscopic point of view. This has been, for instance, a long-standing problem for silica reacted with alkylaluminum compounds, a system typically studied as a model for a supported methylaluminoxane and aluminum cocatalyst. While (27)Al solid-state NMR spectroscopy would be a method of choice, it has been difficult to apply this technique because of large quadrupolar broadenings. Here, from a combined use of the highest stable field NMR instruments (17.6, 20.0, and 23.5 T) and ultrafast magic angle spinning (>60 kHz), high-quality spectra were obtained, allowing isotropic chemical shifts, quadrupolar couplings, and asymmetric parameters to be extracted. Combined with first-principles calculations, these NMR signatures were then assigned to actual structures of surface aluminum sites. For silica (here SBA-15) reacted with triethylaluminum, the surface sites are in fact mainly dinuclear Al species, grafted on the silica surface via either two terminal or two bridging siloxy ligands. Tetrahedral sites, resulting from the incorporation of Al inside the silica matrix, are also seen as minor species. No evidence for putative tri-coordinated Al atoms has been found. PMID:22440230
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
Theoretical aspects of light meson spectroscopy
Barnes, T. |
1995-12-31
In this pedagogical review the authors discuss the theoretical understanding of light hadron spectroscopy in terms of QCD and the quark model. They begin with a summary of the known and surmised properties of QCD and confinement. Following this they review the nonrelativistic quark potential model for q{anti q} mesons and discuss the quarkonium spectrum and methods for identifying q{anti q} states. Finally, they review theoretical expectations for non-q{anti q} states (glueballs, hybrids and multiquark systems) and the status of experimental candidates for these states.
NASA Astrophysics Data System (ADS)
Chang, Yunhee; Kim, Howon; Lee, Eui-Sup; Jang, Won-Jun; Kim, Yong-Hyun; Kahng, Se-Jong
2015-03-01
To microscopically understand the mechanisms of electron-induced NO dissociations, we performed first-principles density-functional theory (DFT) calculations for NO-CoTPP on Au(111). We explain the scanning tunneling microscopy (STM) results that the dissociations of NO were induced by both positive and negative voltage pulses with threshold voltages, +0.68 V and 0.74 V, respectively, at 0.1 nA tunneling current, showing power law relations between tunneling current and dissociation yield. To evaluate first-principles thermodynamics of the NO dissociation, we considered not only adsorption-desorption energetics, zero-point energy, and vibrational free energy at experiment temperature from first-principles, but also the chemical potential of NO gas at the cryogenic ultra-high vacuum condition. Using first-principles thermodynamics for the NO dissociation, we argue that the dissociations are induced with inelastic electron tunneling through molecular orbital resonances.
Methods for First-Principles Alloy Thermodynamics
NASA Astrophysics Data System (ADS)
van de Walle, Axel
2013-11-01
Traditional first-principles calculations excel at providing formation energies at absolute zero, but obtaining thermodynamic information at nonzero temperatures requires suitable sampling of all the excited states visited in thermodynamic equilibrium, which would be computationally prohibitive via brute-force quantum mechanical calculations alone. In the context of solid-state alloys, this issue can be addressed via the coarse-graining concept and the cluster expansion formalism. This process generates simple, effective Hamiltonians that accurately reproduce quantum mechanical calculation results and that can be used to efficiently sample configurational, vibrational, and electronic excitations and enable the prediction of thermodynamic properties at nonzero temperatures. Vibrational and electronic degrees of freedom are formally eliminated from the problem by writing the system's partition function in a nested form in which the inner sums can be readily evaluated to yield an effective Hamiltonian. The remaining outermost sum corresponds to atomic configurations and can be handled via Monte Carlo sampling driven by the resulting effective Hamiltonian, thereby delivering thermodynamic properties at nonzero temperatures. This article describes these techniques and their implementation in the alloy theoretic automated toolkit, an open-source software package. The methods are illustrated by applications to various alloy systems.
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
Intrinsic ferroelectric switching from first principles.
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
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
First-principles and angle-resolved photoemission study of lithium doped metallic black phosphorous
NASA Astrophysics Data System (ADS)
Sanna, A.; Fedorov, A. V.; Verbitskiy, N. I.; Fink, J.; Krellner, C.; Petaccia, L.; Chikina, A.; Usachov, D. Yu; Grüneis, A.; Profeta, G.
2016-06-01
First principles calculations demonstrate the metallization of phosphorene by means of Li doping filling the unoccupied antibonding p z states. The electron–phonon coupling in the metallic phase is strong enough to eventually lead to a superconducting phase at T c = 17 K for LiP8 stoichiometry. Using angle-resolved photoemission spectroscopy we confirm that the surface of black phosphorus can be chemically functionalized using Li atoms which donate their 2s electron to the conduction band. The combined theoretical and experimental study demonstrates the semiconductor-metal transition indicating a feasible way to induce a superconducting phase in phosphorene and few-layer black phosphorus.
Transversity from First Principles in QCD
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.
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
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
Description of charge conjugation from first principles
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.
Interface Structure Prediction from First-Principles
Zhao, Xin; Shu, Qiang; Nguyen, Manh Cuong; Wang, Yangang; Ji, Min; Xiang, Hongjun; Ho, Kai-Ming; Gong, Xingao; Wang, Cai-Zhuang
2014-05-08
Information about the atomic structures at solid–solid interfaces is crucial for understanding and predicting the performance of materials. Due to the complexity of the interfaces, it is very challenging to resolve their atomic structures using either experimental techniques or computer simulations. In this paper, we present an efficient first-principles computational method for interface structure prediction based on an adaptive genetic algorithm. This approach significantly reduces the computational cost, while retaining the accuracy of first-principles prediction. The method is applied to the investigation of both stoichiometric and nonstoichiometric SrTiO3 Σ3(112)[1¯10] grain boundaries with unit cell containing up to 200 atoms. Several novel low-energy structures are discovered, which provide fresh insights into the structure and stability of the grain boundaries.
First-principles transversal DNA conductance deconstructed
Zhang, Xiaoguang; Krstic, Predrag; Zikic, Radomir; Wells, Jack C; Fuentes-Cabrera, Miguel A
2006-01-01
First-principles calculation of the transverse conductance across DNA fragments placed between gold nanoelectrodes, reveals that such conductance describes electron tunneling that depends critically on geometrical rather than electronic-structure properties. By factoring the first-principles result into two simple and approximately independent tunneling factors, we show that the conductances of the A, C, G, and T fragments differ only because of their sizes: the larger is the DNA base, the smaller is the distance that separates the electrode from the corresponding molecule, and the larger is its conductance. Because the geometrical factors are difficult to control in an experiment, the DC-current measurements across DNA may not be a convenient approach to DNA sequencing.
First principles determination of dislocation properties.
Hamilton, John C.
2003-12-01
This report details the work accomplished on first principles determination of dislocation properties. It contains an introduction and three chapters detailing three major accomplishments. First, we have used first principle calculations to determine the shear strength of an aluminum twin boundary. We find it to be remarkably small ({approx}17 mJ/m{sup 2}). This unexpected result is explained and will likely pertain for many other grain boundaries. Second, we have proven that the conventional explanation for finite grain boundary facets is wrong for a particular aluminum grain boundary. Instead of finite facets being stabilized by grain boundary stress, we find them to originate from kinetic effects. Finally we report on a new application of the Frenkel-Kontorova model to understand reconstructions of (100) type surfaces. In addition to the commonly accepted formation of rectangular dislocation arrays, we find numerous other possible solutions to the model including hexagonal reconstructions and a clock-rotated structure.
First principle thousand atom quantum dot calculations
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.
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.
First principles calculations for lithiated manganese oxides.
Prasad, R.
1998-12-23
First principles calculations within the local-spin-density-functional theory (LSDFF) framework are presented of densities of electronic states for MnO, LiMnO{sub 2} in the monoclinic and orthorhombic structures, cubic LiMn{sub 2}O{sub 4} spinel and {lambda}-MnO{sub 2} (delithiated spinel), all in antiferromagnetic spin configurations. The changes in energy spectra as the Mn oxidation state varies between 2+ and 4+ are illustrated. Preliminary calculations for Co-doped LiMnO{sub 2} are presented, and the destabilization of a monoclinic relative to a rhombohedral structure is discussed.
First principles semiclassical calculations of vibrational eigenfunctions.
Ceotto, Michele; Valleau, Stéphanie; Tantardini, Gian Franco; Aspuru-Guzik, Alán
2011-06-21
Vibrational eigenfunctions are calculated on-the-fly using semiclassical methods in conjunction with ab initio density functional theory classical trajectories. Various semiclassical approximations based on the time-dependent representation of the eigenfunctions are tested on an analytical potential describing the chemisorption of CO on Cu(100). Then, first principles semiclassical vibrational eigenfunctions are calculated for the CO(2) molecule and its accuracy evaluated. The multiple coherent states initial value representations semiclassical method recently developed by us has shown with only six ab initio trajectories to evaluate eigenvalues and eigenfunctions at the accuracy level of thousands trajectory semiclassical initial value representation simulations. PMID:21837839
Liu, Hsiang-Lin; Hsueh, Hung-Chung; Lin, I-Nan; Yang, Ming-Ti; Lee, Wei-Chung; Chen, Yi-Chun; Chia, Chia-Ta; Cheng, Hsiu-Fung
2011-06-01
La(Mg(0.5)Ti(0.5))O(3) (LMT) ceramics were prepared by either the solid-state reaction (LMT)(SS) or the citric-acid chemical method (LMT)(CA). A combination of Raman scattering, infrared reflectivity, and first-principles calculations was carried out to elucidate the correlation between lattice dynamics and the dielectric properties of these materials. Twelve Raman-active phonons are observed in both samples, displaying similar frequency positions. Interestingly, the A(g) phonon (g(11) mode) of (LMT)(SS) at about 717 cm(-1) involving the oxygen octahedron breathing vibrations demonstrates a narrower linewidth, suggesting its better crystallinity. Furthermore, an infrared-active u(2) phonon band due to the vibrations of O(I) and O(II) layers, which possesses the largest oscillator strength, exhibits stronger intensity for (LMT)(SS), as compared with those for (LMT)(CA). Additionally, the Q × f values (the product of dielectric Q values and measurement frequency) of (LMT)(SS) estimated from either microwave cavity or infrared spectroscopic measurements are larger than those of (LMT)(CA). These results indicate that the better coherence of lattice vibrations in (LMT)(SS) leads to its higher Q × f value, providing evidence for a strong connection between optical spectroscopic behavior and microwave dielectric characteristics in these materials. PMID:21576769
NASA Astrophysics Data System (ADS)
Kim, Yong-Hyun; Zhang, S. B.
2006-03-01
Despite being one of the most important macroscopic measures and a long history even before the quantum mechanics, the concept of pH has rarely been mentioned in microscopic theories, nor being incorporated computationally into first-principles theory of aqueous solutions. Here, we formulate a theory for the pH dependence of solution formation energy by introducing the proton chemical potential as the microscopic counterpart of pH in atomistic solution models. Within the theory, the general acid-base chemistry can be cast in a simple pictorial representation. We adopt density-functional molecular dynamics to demonstrate the usefulness of the method by studying a number of solution systems including water, small solute molecules such as NH3 and HCOOH, and more complex amino acids with several functional groups. For pure water, we calculated the auto- ionization constant to be 13.2 with a 95 % accuracy. For other solutes, the calculated dissociation constants, i.e., the so- called pKa, are also in reasonable agreement with experiments. Our first-principles pH theory can be readily applied to broad solution chemistry problems such as redox reactions.
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
Numerical inductance calculations based on first principles.
Shatz, Lisa F; Christensen, Craig W
2014-01-01
A method of calculating inductances based on first principles is presented, which has the advantage over the more popular simulators in that fundamental formulas are explicitly used so that a deeper understanding of the inductance calculation is obtained with no need for explicit discretization of the inductor. It also has the advantage over the traditional method of formulas or table lookups in that it can be used for a wider range of configurations. It relies on the use of fast computers with a sophisticated mathematical computing language such as Mathematica to perform the required integration numerically so that the researcher can focus on the physics of the inductance calculation and not on the numerical integration. PMID:25402467
Phonon-phonon interactions: First principles theory
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.
First-principles simulations of thiophene oligomers
NASA Astrophysics Data System (ADS)
Scherlis, Damian; Marzari, Nicola
2003-03-01
Conducting polymers, extensively investigated for their use in electronic and nanotechnology applications, have recently gained prominence for their possible use as molecular actuators in mechanical and bioengineering devices. We have focused our efforts on thiophene-based compounds, a class of materials that can be designed for high stress generation and large linear displacement (actuation strain), ideally outperforming mammalian muscle. Key features for the development of these materials are the microscopic binding properties of thiophene and thiophene oligomers stacks, where applied electric fields lead to oxidation and enhanced pi-pi bonding. We have completed the structural studies of neutral and charged oligothiophene dimers, in the search for efficient dimerization mechanisms. A comparison between different density-functional and quantum-chemistry approaches is critically presented, as are solvation effects, described in this work with a combination of first-principles molecular dynamics and a QM/MM approach for the solvating medium.
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.
Theoretical Sum Frequency Generation Spectroscopy of Peptides.
Carr, Joshua K; Wang, Lu; Roy, Santanu; Skinner, James L
2015-07-23
Vibrational sum frequency generation (SFG) has become a very promising technique for the study of proteins at interfaces, and it has been applied to important systems such as anti-microbial peptides, ion channel proteins, and human islet amyloid polypeptide. Moreover, so-called "chiral" SFG techniques, which rely on polarization combinations that generate strong signals primarily for chiral molecules, have proven to be particularly discriminatory of protein secondary structure. In this work, we present a theoretical strategy for calculating protein amide I SFG spectra by combining line-shape theory with molecular dynamics simulations. We then apply this method to three model peptides, demonstrating the existence of a significant chiral SFG signal for peptides with chiral centers, and providing a framework for interpreting the results on the basis of the dependence of the SFG signal on the peptide orientation. We also examine the importance of dynamical and coupling effects. Finally, we suggest a simple method for determining a chromophore's orientation relative to the surface using ratios of experimental heterodyne-detected signals with different polarizations, and test this method using theoretical spectra. PMID:25203677
Theoretical Sum Frequency Generation Spectroscopy of Peptides
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
Transition Metal Nitrides: A First Principles Study
NASA Astrophysics Data System (ADS)
Pathak, Ashish; Singh, A. K.
2016-04-01
The present work describes the structural stability and electronic and mechanical properties of transition metal nitrides (TmNs: B1 cubic structure (cF8, Fm ‾ overline 3 m)) using first principles density functional theory (DFT) within generalized gradient approximation (GGA). The lattice constant of TmNs increases with increasing the atomic radii of the transition metals. Stability of the TmNs decreases from IVB to VIB groups due to increase in formation energy/atom. The bonding characteristics of these nitrides have been explained based on electronic density of states and charge density. All the TmNs satisfy Born stability criteria in terms of elastic constants except CrN and MoN that do not exist in equilibrium binary phase diagrams. The groups IVB and V-VIB nitrides are associated with brittle and ductile behaviour based on G/B ratios, respectively. The estimated melting temperatures of these nitrides exhibit reasonably good agreement with calculated with B than those of the C11 for all nitrides.
Safeguards First Principle Initiative (SFPI) Cost Model
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.
First principle study of sodium decorated graphyne
NASA Astrophysics Data System (ADS)
Sarkar, Utpal; Bhattacharya, Barnali; Seriani, Nicola
2015-11-01
We present first-principles calculations of the electronic properties of Na-decorated graphyne. This structure of the graphyne family is a direct band gap semiconductor with a band gap of 0.44 eV in absence of sodium, but Na-decorated graphyne compounds are metallic, and can then be employed as carbon-based conductors. Metallization is due to charge donation from sodium to carbon. Pristine graphyne is more stable than Na-decorated graphyne, therefore is seems probable that, if this material should be employed as electrode in Na-ion batteries, it would lead to the formation of metallic sodium rather than well dispersed sodium ions. On the other side, this property might be useful if graphyne is employed in water desalination. Finally, the abrupt change from a semiconducting to a metallic state in presence of a small amount of sodium might be exploited in electronics, e.g. for the production of smooth metal-semiconductor interfaces through spatially selective deposition of sodium.
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.
THERMODYNAMIC MODELING AND FIRST-PRINCIPLES CALCULATIONS
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.
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).
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.
First Principles Dynamics of Photoexcited DNA and RNA Bases
Hudock, Hanneli R.; Levine, Benjamin G.; Thompson, Alexis L.; Martinez, Todd J.
2007-12-26
The reaction dynamics of excited electronic states in nucleic acid bases is a key process in DNA photodamage. Recent ultrafast spectroscopy experiments have shown multi-component decays of excited uracil and thymine, tentatively assigned to nonadiabatic transitions involving multiple electronic states. Using both quantum chemistry and first principles quantum molecular dynamics methods we show that a true minimum on the bright S{sub 2} electronic state is responsible for the first step which occurs on a femtosecond timescale. Thus the observed femtosecond decay does not correspond to surface crossing as previously thought. We suggest that subsequent barrier crossing to the minimal energy S{sub 2}/S{sub 1} conical intersection is responsible for the picosecond decay.
First-principles study of hydrogen in perfect tungsten crystal
NASA Astrophysics Data System (ADS)
Xu, Jingcheng; Zhao, Jijun
2009-09-01
Tungsten-based materials are used as the first wall materials in ITER. Hydrogen impurities were introduced via bombarding with the reaction plasma, which are important for the behavior and stability of the tungsten wall. Using the first-principles density functional theory and planewave pseudopotential technique, we have simulated the behaviors of hydrogen atoms inside the perfect tungsten bcc lattice. The binding energies for different interstitial sites were compared to determine the optimal trapping site for the hydrogen atom inside the tungsten lattice. The diffusion barriers for hydrogen atom between nearby trapping sites and the interaction between two interstitial hydrogen atoms were also calculated. The implication of our theoretical results on the hydrogen diffusion and accumulation behavior was discussed.
Modeling of Co overlayers on Pd (111) from first principles
NASA Astrophysics Data System (ADS)
Uba, S.; Uba, L.; Antonov, V. N.
2007-04-01
The electronic, magnetic and magneto-optical properties of Co overlayers on Pd (1 1 1) substrate have been investigated by ab initio band structure calculations within the spin-polarized relativistic linear muffin-thin orbitals (LMTO) method and supercell approach. The role of the Co-Pd interface structure, the number of the Co atomic layers ( n Co ), as well as the spin-orbit interaction and induced Pd spin polarization, in formation of magneto-optical response of the structures for [ n CoCo/Pd (1 1 1)] system is shown. The sign reversal of the polar Kerr rotation obtained theoretically with decreasing thickness of Co overlayers agrees well with experiment. We will demonstrate the effectiveness of the extended numeric modeling of magneto-optical properties from first principles.
Adsorption of methylchloride on Si(100) from first principles
NASA Astrophysics Data System (ADS)
Romero, Aldo H.; Sbraccia, Carlo; Silvestrelli, Pier Luigi; Ancilotto, Francesco
2003-07-01
The chemisorption of methylchloride (CH3Cl) on Si(100) is studied from first principles. We find that, among a number of possible adsorption configurations, the lowest-energy structure is one in which the methylchloride molecule is dissociated into CH3 and Cl fragments which are bound to the two Si atoms of the same surface dimer. Our calculations show that dissociative chemisorption of methylchloride on Si(100) may proceed along different reaction paths characterized by different energy barriers that the system must overcome: some dissociation processes are mediated by a molecular precursor state and, at least in one case, we find that the dissociation process is nonactivated, in agreement with recent experimental findings. We have also generated, for many possible adsorption structures, theoretical scanning tunneling microscopy images which could facilitate the interpretation of experimental measurements.
First-principles study of 2D electride : Gadolinium carbide
NASA Astrophysics Data System (ADS)
Nandadasa, Chandani; Kim, Seong-Gon; Kim, Sungho; Kim, Sung Wng
Electrides are an exclusive class of ionic compounds in which some electrons are occupying crystal voids instead of attaching to specific atoms or bonds. Using first-principles density functional theory calculations, we study structural, electronic and magnetic properties of Gd2C. The theoretically predicted structure of Gd2C is in good agreement with the available experimental data. Energy band diagram of Gd2C shows that they are crossing the Fermi level. Projected electronic density of states plots indicate that the interstitial sites are the main contributor to the density of states at the Fermi level. Charge of individual atoms including interstitial site are obtained using Bader analysis. Magnetic properties of Gd2C is determined from magnetization density plots. Work functions of Gd2C are determined for (001) and (100) surfaces with the technique of macroscopic average of electrostatic potential with the Fermi energy of bulk.
Optimized Materials From First Principles Simulations: Are We There Yet?
Galli, G; Gygi, F
2005-07-26
In the past thirty years, the use of scientific computing has become pervasive in all disciplines: collection and interpretation of most experimental data is carried out using computers, and physical models in computable form, with various degrees of complexity and sophistication, are utilized in all fields of science. However, full prediction of physical and chemical phenomena based on the basic laws of Nature, using computer simulations, is a revolution still in the making, and it involves some formidable theoretical and computational challenges. We illustrate the progress and successes obtained in recent years in predicting fundamental properties of materials in condensed phases and at the nanoscale, using ab-initio, quantum simulations. We also discuss open issues related to the validation of the approximate, first principles theories used in large scale simulations, and the resulting complex interplay between computation and experiment. Finally, we describe some applications, with focus on nanostructures and liquids, both at ambient and under extreme conditions.
First principles modeling of grain boundaries in CdTe
NASA Astrophysics Data System (ADS)
Chan, Maria K. Y.; Sen, Fatih; Buurma, Christopher; Paulauskas, Tadas; Sun, Ce; Kim, Moon; Klie, Robert
The role of extended defects is of significant interest for semiconductors, especially photovoltaics since energy conversion efficiencies are often affected by such defects. In particular, grain boundaries in CdTe photovoltaics are enigmatic since the achievable efficiencies of CdTe photovoltaics are higher in polycrystalline devices as compared to single crystalline devices. Yet, despite recent advances, the efficiency of poly-CdTe devices are still substantially below the theoretical maximum. We carry out an atomistic-level study using Scanning Transmission Electron Microscopy (STEM), together with first principles density functional theory (DFT) modeling, in order to understand the properties of specific bicrystals, i.e. artificial grain boundaries, constructed using wafer bonding. We discuss examples of bicrystals, including some involving large scale DFT calculations, and trends in defect and electronic properties. This work was funded by DOE SunShot BRIDGE program.
First-principles study of silicon nitride nanotubes
NASA Astrophysics Data System (ADS)
Gao, Guohua; Kang, Hong Seok
2008-10-01
We have made a first-principles calculation of the topological, geometric, and electronic structures of nitrogen-doped armchair and zigzag silicon carbide nanotubes, where we have assumed that all carbon atoms have been substituted by nitrogen atoms. The doping was found to be substantially easier than for analogous carbon nanotubes. In addition, the doping process is cooperative, leading us to theoretically predict the stable existence of silicon nitride nanotubes (SiNNTs). For (n,n) SiNNTs, all kinds of chiral indices n are possible. These armchair tubes are semiconductors with much smaller band gaps than those of corresponding silicon carbide nanotubes, and the gap decreases with the tube diameter. For (n,0) chirality, only even-numbered chiral indices (n=2l) are possible. These nanotubes are also semiconductors with band gaps larger than those of armchair SiNNTs of similar diameters.
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.
Hadron Phenomenology from First-Principle QCD Studies
NASA Astrophysics Data System (ADS)
Papavassiliou, Joannis
2016-03-01
The form of the kernel that controls the dynamics of the Bethe-Salpeter equations is essential for obtaining quantitatively accurate predictions for the observable properties of hadrons. In the present work we briefly review the basic physical concepts and field-theoretic techniques employed in a first-principle derivation of a universal (process-independent) component of this kernel. This "top-down" approach combines nonperturbative ingredients obtained from lattice simulations and Dyson-Schwinger equations, and furnishes a renormalization-group invariant quark-gluon interaction strength, which is in excellent agreement with the corresponding quantity obtained from a systematic "bottom-up" treatment, where bound-state data are fitted within a well-defined truncation scheme.
Hadron Phenomenology from First-Principle QCD Studies
NASA Astrophysics Data System (ADS)
Papavassiliou, Joannis
2016-06-01
The form of the kernel that controls the dynamics of the Bethe-Salpeter equations is essential for obtaining quantitatively accurate predictions for the observable properties of hadrons. In the present work we briefly review the basic physical concepts and field-theoretic techniques employed in a first-principle derivation of a universal (process-independent) component of this kernel. This "top-down" approach combines nonperturbative ingredients obtained from lattice simulations and Dyson-Schwinger equations, and furnishes a renormalization-group invariant quark-gluon interaction strength, which is in excellent agreement with the corresponding quantity obtained from a systematic "bottom-up" treatment, where bound-state data are fitted within a well-defined truncation scheme.
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
NASA Astrophysics Data System (ADS)
Darriba, G. N.; Errico, L. A.; Eversheim, P. D.; Fabricius, G.; Rentería, M.
2009-03-01
The, time-differential γ-γ perturbed-angular-correlation (TDPAC) technique using ion-implanted H181f(→T181a) tracers was applied to study the hyperfine interactions of T181a impurities in the rutile structure of TiO2 single crystals. The experiments were performed in air in the temperature range of 300-1273 K, allowing the electric-field-gradient (EFG) tensor characterization (in magnitude, asymmetry, and orientation) at T181a probe atoms located in defect-free cation sites of the structure. The measured EFG is parallel to the [001] crystal axis, as occurs at Ti sites, but normal to the EFG orientation observed at C111d impurities in TiO2 single crystals [L. A. Errico , Phys. Rev. Lett. 89, 055503 (2002)]. In addition, ab initio calculations were performed using the full-potential augmented plane wave plus local orbital method that allow us to treat the electronic structure of the doped system and the atomic relaxations induced by the Ta impurity in a fully self-consistent way. We considered different dilutions of the doped system (using the supercell approach) and studied the electronic properties and structural atomic relaxation dependence on the charge state of the impurity. The accuracy of the calculations and the excellent agreement of the predicted magnitude, asymmetry, and orientation of the EFG tensor with the experimental results enable us to infer the EFG sign, not accessible with conventional TDPAC experiments. The comparison of the measured EFG at Ta sites with experimental and ab initio theoretical results reported in the literature at Cd, Ta, and Ti sites in TiO2 allowed us to obtain a deeper insight on the role played by metal impurities in oxide semiconductors.
Buannic, Lucienne; Blanc, Frédéric; Middlemiss, Derek S; Grey, Clare P
2012-09-01
Hydrated BaSn(1-x)Y(x)O(3-x/2) is a protonic conductor that, unlike many other related perovskites, shows high conductivity even at high substitution levels. A joint multinuclear NMR spectroscopy and density functional theory (total energy and GIPAW NMR calculations) investigation of BaSn(1-x)Y(x)O(3-x/2) (0.10 ≤ x ≤ 0.50) was performed to investigate cation ordering and the location of the oxygen vacancies in the dry material. The DFT energetics show that Y doping on the Sn site is favored over doping on the Ba site. The (119)Sn chemical shifts are sensitive to the number of neighboring Sn and Y cations, an experimental observation that is supported by the GIPAW calculations and that allows clustering to be monitored: Y substitution on the Sn sublattice is close to random up to x = 0.20, while at higher substitution levels, Y-O-Y linkages are avoided, leading, at x = 0.50, to strict Y-O-Sn alternation of B-site cations. These results are confirmed by the absence of a "Y-O-Y" (17)O resonance and supported by the (17)O NMR shift calculations. Although resonances due to six-coordinate Y cations were observed by (89)Y NMR, the agreement between the experimental and calculated shifts was poor. Five-coordinate Sn and Y sites (i.e., sites next to the vacancy) were observed by (119)Sn and (89)Y NMR, respectively, these sites disappearing on hydration. More five-coordinated Sn than five-coordinated Y sites are seen, even at x = 0.50, which is ascribed to the presence of residual Sn-O-Sn defects in the cation-ordered material and their ability to accommodate O vacancies. High-temperature (119)Sn NMR reveals that the O ions are mobile above 400 °C, oxygen mobility being required to hydrate these materials. The high protonic mobility, even in the high Y-content materials, is ascribed to the Y-O-Sn cation ordering, which prevents proton trapping on the more basic Y-O-Y sites. PMID:22691062
NASA Astrophysics Data System (ADS)
Koch-Müller, Monika; Jahn, Sandro; Birkholz, Natalie; Ritter, Eglof; Schade, Ulrich
2016-05-01
The stability of the high-pressure CaCO3 calcite (cc)-related polymorphs was studied in experiments that were performed in conventional diamond anvil cells (DAC) at room temperature as a function of pressure up to 30 GPa as well as in internally heated diamond anvil cells (DAC-HT) at pressures and temperatures up to 20 GPa and 800 K. To probe structural changes, we used Raman and FTIR spectroscopy. For the latter, we applied conventional and synchrotron mid-infrared as well as synchrotron far-infrared radiation. Within the cc-III stability field (2.2-15 GPa at room temperature, e.g., Catalli and Williams in Phys Chem Miner 32(5-6):412-417, 2005), we observed in the Raman spectra consistently three different spectral patterns: Two patterns at pressures below and above 3.3 GPa were already described in Pippinger et al. (Phys Chem Miner 42(1):29-43, 2015) and assigned to the phase transition of cc-IIIb to cc-III at 3.3 GPa. In addition, we observed a clear change between 5 and 6 GPa that is independent of the starting material and the pressure path and time path of the experiments. This apparent change in the spectral pattern is only visible in the low-frequency range of the Raman spectra—not in the infrared spectra. Complementary electronic structure calculations confirm the existence of three distinct stability regions of cc-III-type phases at pressures up to about 15 GPa. By combining experimental and simulation data, we interpret the transition at 5-6 GPa as a re-appearance of the cc-IIIb phase. In all types of experiments, we confirmed the transition from cc-IIIb to cc-VI at about 15 GPa at room temperature. We found that temperature stabilizes cc-VI to lower pressure. The reaction cc-IIIb to cc-VI has a negative slope of -7.0 × 10-3 GPa K-1. Finally, we discuss the possibility of the dense cc-VI phase being more stable than aragonite at certain pressure and temperature conditions relevant to the Earth's mantle.
Two-dimensional electronic spectroscopy using incoherent light: theoretical analysis.
Turner, Daniel B; Howey, Dylan J; Sutor, Erika J; Hendrickson, Rebecca A; Gealy, M W; Ulness, Darin J
2013-07-25
Electronic energy transfer in photosynthesis occurs over a range of time scales and under a variety of intermolecular coupling conditions. Recent work has shown that electronic coupling between chromophores can lead to coherent oscillations in two-dimensional electronic spectroscopy measurements of pigment-protein complexes measured with femtosecond laser pulses. A persistent issue in the field is to reconcile the results of measurements performed using femtosecond laser pulses with physiological illumination conditions. Noisy-light spectroscopy can begin to address this question. In this work we present the theoretical analysis of incoherent two-dimensional electronic spectroscopy, I((4)) 2D ES. Simulations reveal diagonal peaks, cross peaks, and coherent oscillations similar to those observed in femtosecond two-dimensional electronic spectroscopy experiments. The results also expose fundamental differences between the femtosecond-pulse and noisy-light techniques; the differences lead to new challenges and new opportunities. PMID:23176195
Shell Model in a First Principles Approach
Navratil, P; Nogga, A; Lloyd, R; Vary, J P; Ormand, W E; Barrett, B R
2004-01-08
We develop and apply an ab-initio approach to nuclear structure. Starting with the NN interaction, that fits two-body scattering and bound state data, and adding a theoretical NNN potential, we evaluate nuclear properties in a no-core approach. For presently feasible no-core model spaces, we evaluate an effective Hamiltonian in a cluster approach which is guaranteed to provide exact answers for sufficiently large model spaces and/or sufficiently large clusters. A number of recent applications are surveyed including an initial application to exotic multiquark systems.
First principles study of hydroxyapatite surface.
Slepko, Alexander; Demkov, Alexander A
2013-07-28
The biomineral hydroxyapatite (HA) [Ca10(PO4)6(OH)2] is the main mineral constituent of mammal bone. We report a theoretical investigation of the HA surface. We identify the low energy surface orientations and stoichiometry under a variety of chemical environments. The surface most stable in the physiologically relevant OH-rich environment is the OH-terminated (1000) surface. We calculate the work function of HA and relate it to the surface composition. For the lowest energy OH-terminated surface we find the work function of 5.1 eV, in close agreement with the experimentally reported range of 4.7 eV-5.1 eV [V. S. Bystrov, E. Paramonova, Y. Dekhtyar, A. Katashev, A. Karlov, N. Polyaka, A. V. Bystrova, A. Patmalnieks, and A. L. Kholkin, J. Phys.: Condens. Matter 23, 065302 (2011)]. PMID:23902010
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.
First principles calculations for modern ceramic science and engineering
NASA Astrophysics Data System (ADS)
Tanaka, Isao; Oba, Fumiyasu
2008-02-01
The free energy of compounds can be theoretically obtained as a function of temperature, pressure and chemical potentials by a combination of a first principles method including phonon calculations and statistical approaches using cluster expansion and Monte Carlo simulations. The information is quite useful in ceramic science and engineering since experimental data are not abundantly available. As an example of phonon calculations, results for graphite in comparison to diamond are presented. The free energy difference among polymorphs of Ga2O3 is shown as a function of temperature as well. Theoretical calculations of x-ray absorption near edge structures (XANES) and electron energy loss near edge structures (ELNES) are also demonstrated. Proper inclusion of the core-hole effect is mandatory in the calculation. For 3d transition element L2,3 XANES/ELNES, a configuration interaction approach to take account of the correlation among the core-hole and the excited electron satisfactorily reproduces experimental spectra. As an example, results for Mn-doped ZnO are shown.
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.
A first-principle calculation of the XANES spectrum of Cu{sup 2+} in water
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.
NASA Astrophysics Data System (ADS)
Saavedra Arias, Jose Javier
We have studied the properties of spinel and layered cathode materials for Li ion rechargeable batteries. The analysis was done by first principle calculations, and experimental techniques to elucidate materials that can substitute the presently commercialized material, namely LiCoO 2. We have studied the influence of Ni substitution for Mn in spinel Li 2MnO4. To understand the effects of this substitution on the crystal structure and electronic properties, first principle DFT calculations were performed using VASP. The substitution was done systematically for up to 25% of Mn replacement by Ni in a super cell configuration. Furthermore, the influence of Ni substitution on lithium hoping pathways between the two stable Li positions was also studied by first principle calculations in LiMn 2-xNixO4. These calculations revealed that Ni substitution for Mn in LiMn2O4 indeed improved Li ion mobility. Thereafter, systematic experimental studies were performed on LiMn 2-xNixO4 (0
First principles molecular dynamics study of filled ice hydrogen hydrate.
Zhang, Jingyun; Kuo, Jer-Lai; Iitaka, Toshiaki
2012-08-28
We investigated structural changes, phase diagram, and vibrational properties of hydrogen hydrate in filled-ice phase C(2) by using first principles molecular dynamics simulation. It was found that the experimentally reported "cubic" structure is unstable at low temperature and/or high pressure: The "cubic" structure reflects the symmetry at high (room) temperature where the hydrogen bond network is disordered and the hydrogen molecules are orientationally disordered due to thermal rotation. In this sense, the "cubic" symmetry would definitely be lowered at low temperature where the hydrogen bond network and the hydrogen molecules are expected to be ordered. At room temperature and below 30 GPa, it is the thermal effects that play an essential role in stabilizing the structure in "cubic" symmetry. Above 60 GPa, the hydrogen bonds in the framework would be symmetrized and the hydrogen bond order-disorder transition would disappear. These results also suggest the phase behavior of other filled-ice hydrates. In the case of rare gas hydrate, there would be no guest molecules' rotation-nonrotation transition since the guest molecules keep their spherical symmetry at any temperature. On the contrary methane hydrate MH-III would show complex transitions due to the lower symmetry of the guest molecule. These results would encourage further experimental studies, especially nuclear magnetic resonance spectroscopy and neutron scattering, on the phases of filled-ice hydrates at high pressures and/or low temperatures. PMID:22938248
First principles molecular dynamics study of filled ice hydrogen hydrate
NASA Astrophysics Data System (ADS)
Zhang, Jingyun; Kuo, Jer-Lai; Iitaka, Toshiaki
2012-08-01
We investigated structural changes, phase diagram, and vibrational properties of hydrogen hydrate in filled-ice phase C2 by using first principles molecular dynamics simulation. It was found that the experimentally reported "cubic" structure is unstable at low temperature and/or high pressure: The "cubic" structure reflects the symmetry at high (room) temperature where the hydrogen bond network is disordered and the hydrogen molecules are orientationally disordered due to thermal rotation. In this sense, the "cubic" symmetry would definitely be lowered at low temperature where the hydrogen bond network and the hydrogen molecules are expected to be ordered. At room temperature and below 30 GPa, it is the thermal effects that play an essential role in stabilizing the structure in "cubic" symmetry. Above 60 GPa, the hydrogen bonds in the framework would be symmetrized and the hydrogen bond order-disorder transition would disappear. These results also suggest the phase behavior of other filled-ice hydrates. In the case of rare gas hydrate, there would be no guest molecules' rotation-nonrotation transition since the guest molecules keep their spherical symmetry at any temperature. On the contrary methane hydrate MH-III would show complex transitions due to the lower symmetry of the guest molecule. These results would encourage further experimental studies, especially nuclear magnetic resonance spectroscopy and neutron scattering, on the phases of filled-ice hydrates at high pressures and/or low temperatures.
First Principles Modelling of Oxygen Impurities in UN Nuclear Fuels
Kotomin, Eugene Alexej; Mastrikov, Yuri A.
2008-07-15
We report results of first principles VASP supercell calculations of O impurity in UN fuels placed either at an interstitial tetrahedral position or as a substitution for a host N ion. In the latter case O perfectly fits into N site producing no lattice distortion. Such the O substitutional impurity only slightly affects the formation energies of U and N vacancies nearby. In both interstitial and substitutional positions O atom attracts the additional electron density and transforms into the negatively charged ion. Oxygen incorporation into pre-existing N vacancy is energetically more favourable than into the interstitial position. The O impurities produce an additional peak at the low energy side of N contribution to the DOS calculated for uranium mononitride which could be used for the O identification by means of the UPS spectroscopy. We compare also the DOS calculated for UN and hypothetical isostructural UO. Both O solution and incorporation energies are negative, indicating that O penetration into UN fuel is the energetically favourable. The migration energy of the interstitial O ion is estimated as 2.8 eV.
First Principles Calculations for X-ray Resonant Spectra and Elastic Properties
Yongbin Lee
2006-05-01
In this thesis, we discuss applications of first principles methods to x-ray resonant spectra and elastic properties calculation. We start with brief reviews about theoretical background of first principles methods, such as density functional theory, local density approximation (LDA), LDA+U, and the linear augmented plane wave (LAPW) method to solve Kohn-Sham equations. After that we discuss x-ray resonant scattering (XRMS), x-ray magnetic circular dichroism (XMCD) and the branching problem in the heavy rare earths Ledges. In the last chapter we discuss the elastic properties of the second hardest material AlMgB{sub 14}.
First principles Tafel kinetics of methanol oxidation on Pt(111)
NASA Astrophysics Data System (ADS)
Fang, Ya-Hui; Liu, Zhi-Pan
2015-01-01
Electrocatalytic methanol oxidation is of fundamental importance in electrochemistry and also a key reaction in direct methanol fuel cell. To resolve the kinetics at the atomic level, this work investigates the potential-dependent reaction kinetics of methanol oxidation on Pt(111) using the first principles periodic continuum solvation model based on modified-Poisson-Boltzmann equation (CM-MPB), focusing on the initial dehydrogenation elementary steps. A theoretical model to predict Tafel kinetics (current vs potential) is established by considering that the rate-determining step of methanol oxidation (to CO) is the first Csbnd H bond breaking (CH3OH(aq) → CH2OH* + H*) according to the computed free energy profile. The first Csbnd H bond breaking reaction needs to overcome a large entropy loss during methanol approaching to the surface and replacing the adsorbed water molecules. While no apparent charge transfer is involved in this elementary step, the charge transfer coefficient of the reaction is calculated to be 0.36, an unconventional value for charge transfer reactions, and the Tafel slope is deduced to be 166 mV. The results show that the metal/adsorbate interaction and the solvation environment play important roles on influencing the Tafel kinetics. The knowledge learned from the potential-dependent kinetics of methanol oxidation can be applied in general for understanding the electrocatalytic reactions of organic molecules at the solid-liquid interface.
First principles based mean field model for oxygen reduction reaction.
Jinnouchi, Ryosuke; Kodama, Kensaku; Hatanaka, Tatsuya; Morimoto, Yu
2011-12-21
A first principles-based mean field model was developed for the oxygen reduction reaction (ORR) taking account of the coverage- and material-dependent reversible potentials of the elementary steps. This model was applied to the simulation of single crystal surfaces of Pt, Pt alloy and Pt core-shell catalysts under Ar and O(2) atmospheres. The results are consistent with those shown by past experimental and theoretical studies on surface coverages under Ar atmosphere, the shape of the current-voltage curve for the ORR on Pt(111) and the material-dependence of the ORR activity. This model suggests that the oxygen associative pathway including HO(2)(ads) formation is the main pathway on Pt(111), and that the rate determining step (RDS) is the removal step of O(ads) on Pt(111). This RDS is accelerated on several highly active Pt alloys and core-shell surfaces, and this acceleration decreases the reaction intermediate O(ads). The increase in the partial pressure of O(2)(g) increases the surface coverage with O(ads) and OH(ads), and this coverage increase reduces the apparent reaction order with respect to the partial pressure to less than unity. This model shows details on how the reaction pathway, RDS, surface coverages, Tafel slope, reaction order and material-dependent activity are interrelated. PMID:22064886
First principles molecular dynamics without self-consistent field optimization
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.
First principle investigation of isolated vacancy in (111) diamond surface
NASA Astrophysics Data System (ADS)
Hu, Wenhao; Flatté, Michael
As the simplest intrinsic defect, isolated vacancy has been studied intensively theoretically and experimentally in diamond's bulk phase. Nevertheless, its correspondence in surface phase still lacks people's attention. Nitrogen vacancy center has become the most ideal candidates for solid states computing due to its long coherence time at room temperature. Resembling NV center, the isolated vacancy on surface exhibits a similar ambient potential and the same 3-fold rotational symmetry due to the asymmetry of surface, which implies a similar character in them. In our work, the isolated vacancy in clean and hydrogen terminated (111) surface of diamond are investigated from first principle perspective. Full potential LAPW method implemented in WIEN2K is exploited under GGA approximation. To evaluated the surface effect, the defect depth from topmost layer to fifth subsurface are considered with different slab thickness. By checking the spin density distribution and electronic structure, the hydrogen vacancy in H-terminated surface exhibit a spin-1/2 center with a 0/-1 transition level located in the middle of band gap. The -1/-2 transition level of carbon vacancy in the subsurface approaches the 0/-1 transition level implying the potential stability of spin-1 center. The work was supported by an AFOSR MURI.
Predicted boron-carbide compounds: a first-principles study.
Wang, De Yu; Yan, Qian; Wang, Bing; Wang, Yuan Xu; Yang, Jueming; Yang, Gui
2014-06-14
By using developed particle swarm optimization algorithm on crystal structural prediction, we have explored the possible crystal structures of B-C system. Their structures, stability, elastic properties, electronic structure, and chemical bonding have been investigated by first-principles calculations with density functional theory. The results show that all the predicted structures are mechanically and dynamically stable. An analysis of calculated enthalpy with pressure indicates that increasing of boron content will increase the stability of boron carbides under low pressure. Moreover, the boron carbides with rich carbon content become more stable under high pressure. The negative formation energy of predicted B5C indicates its high stability. The density of states of B5C show that it is p-type semiconducting. The calculated theoretical Vickers hardnesses of B-C exceed 40 GPa except B4C, BC, and BC4, indicating they are potential superhard materials. An analysis of Debye temperature and electronic localization function provides further understanding chemical and physical properties of boron carbide. PMID:24929411
Predicted boron-carbide compounds: A first-principles study
NASA Astrophysics Data System (ADS)
Wang, De Yu; Yan, Qian; Wang, Bing; Wang, Yuan Xu; Yang, Jueming; Yang, Gui
2014-06-01
By using developed particle swarm optimization algorithm on crystal structural prediction, we have explored the possible crystal structures of B-C system. Their structures, stability, elastic properties, electronic structure, and chemical bonding have been investigated by first-principles calculations with density functional theory. The results show that all the predicted structures are mechanically and dynamically stable. An analysis of calculated enthalpy with pressure indicates that increasing of boron content will increase the stability of boron carbides under low pressure. Moreover, the boron carbides with rich carbon content become more stable under high pressure. The negative formation energy of predicted B5C indicates its high stability. The density of states of B5C show that it is p-type semiconducting. The calculated theoretical Vickers hardnesses of B-C exceed 40 GPa except B4C, BC, and BC4, indicating they are potential superhard materials. An analysis of Debye temperature and electronic localization function provides further understanding chemical and physical properties of boron carbide.
Predicted boron-carbide compounds: A first-principles study
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.
Semiconducting Graphene on Silicon from First-Principles Calculations.
Dang, Xuejie; Dong, Huilong; Wang, Lu; Zhao, Yanfei; Guo, Zhenyu; Hou, Tingjun; Li, Youyong; Lee, Shuit-Tong
2015-08-25
Graphene is a semimetal with zero band gap, which makes it impossible to turn electric conduction off below a certain limit. Transformation of graphene into a semiconductor has attracted wide attention. Owing to compatibility with Si technology, graphene adsorbed on a Si substrate is particularly attractive for future applications. However, to date there is little theoretical work on band gap engineering in graphene and its integration with Si technology. Employing first-principles calculations, we study the electronic properties of monolayer and bilayer graphene adsorbed on clean and hydrogen (H)-passivated Si (111)/Si (100) surfaces. Our calculation shows that the interaction between monolayer graphene and a H-passivated Si surface is weak, with the band gap remaining negligible. For bilayer graphene adsorbed onto a H-passivated Si surface, the band gap opens up to 108 meV owing to asymmetry introduction. In contrast, the interaction between graphene and a clean Si surface is strong, leading to formation of chemical bonds and a large band gap of 272 meV. Our results provide guidance for device designs based on integrating graphene with Si technology. PMID:26213346
First principles characterization of silicate sites in clay surfaces.
Alvim, Raphael S; Miranda, Caetano R
2015-02-21
Aluminosilicate clays like Montmorillonite (MMT) and Muscovite Mica (MT) have siloxane cavities on the basal plane. The hydroxyl groups localized in these cavities and van der Waals (vdW) forces contribute significantly to adsorption processes. However, the basal sites are found to be difficult to characterize experimentally. Here, (001) surfaces of MMT and MT clays were investigated using first-principles calculations to understand how these silicate surface sites are influenced by hydroxyl groups and the effective role of inner layer vdW interactions. Based on density-functional theory (DFT) within the generalized gradient approximation (GGA), different types of exchange-correlation functionals were tested to check the effect of vdW dispersion correction. Noncontact atomic force microscopy (nc-AFM), X-ray absorption spectroscopy (XAS) in the near-edge region and solid-state nuclear magnetic resonance (SS-NMR) spectroscopy were simulated. In both clays, the oxygen surface sites are directly affected by the intralayer interaction through hydroxyl groups. Our results indicated that the chemical environment of the hydroxyl groups is distinct in the MMT and MT structures. The vdW correction was essential for a better description of the surface oxygen sites and correctly describes the similarity between both clays. Particularly, the bulk apical oxygen sites in the MT structure are less influenced by vdW interaction. Compared to MMT, the silicon surface sites of MT are more sensitive to the intralayer changes in Si-Oapical-Al and with less effect of the hydroxyl groups. These results provide a clear understanding of influence of the siloxane cavity on the oxygen and silicon surface sites in aluminosilicates. PMID:25592132
First-Principles and Semi-Empirical Studies of Microclusters.
NASA Astrophysics Data System (ADS)
Chang, Audrey Young-Zee
The structural, electronic and magnetic properties of clusters have been a subject of intense investigation in recent years, due to many advancements in theoretical and experimental techniques. Since the bonding of atoms in clusters is often different from in bulk, clusters may assume different shapes and structures as the size varies. They therefore provide a model for understanding the transition and structural formation of bulk materials. In this dissertation, two different approaches for pursuing cluster study are carried out: one is based on a realistic but semi-empirical method, the other is more of a first-principles type of calculation. In the first part, the implementation and application of a dynamics simulated annealing scheme, introduced by Car and Parrinello, to a semi-empirical tight-binding model for studying the silicon clusters is presented. In searching for the ground state structures, Langevin molecular dynamics is employed to allow relaxation of the nuclei. For small silicon clusters, Si_{n} (n <= 10), a preference of close-packed structure with binding energies depending on the size are found. Relatively stable structures are observed for clusters of size 4, 6 and 7 which are in accordance with the experimentally found "magic number". In the second part, the study of transition-metal chromium clusters via a first-principles, all-electron, linear combination of Gaussian orbitals method is presented. Transition -metal elements are characterized by having contracted valence d-orbitals containing up to ten electrons, which make them a highly correlated system. The many-electron effects attributed to interactions among these electrons are manifested rather dramatically through the observed magnetic ordering. In this study, the magnetic and structural properties of chromium clusters, (Cr_{n} n <= 9), are investigated based on density functional theory. In bulk, the bcc chromium crystal has a weak antiferromagnetic coupling due to Fermi surfaces
Theoretical Modeling of Various Spectroscopies for Cuprates and Topological Insulators
NASA Astrophysics Data System (ADS)
Basak, Susmita
structure, strong electron correlations (for cuprates) and spin-orbit coupling (for TIs) are included realistically in material-specific detail. Turning to the cuprates, in order to obtain a realistic description of various spectroscopies, one must include not only the effects of the matrix elements and the complexity of the crystal structure, but also of strong electronic correlations beyond the local density approximation (LDA)-based conventional picture, so that the physics of kinks, pseudogaps and superconductivity can be taken into account properly. In this connection, a self-consistent, intermediate coupling scheme informed by material-specific, first-principles band structures has been developed, where electron correlation effects beyond the LDA are incorporated via appropriate self-energy corrections to the electron and hole one-particle Green's functions. Here the antiferromagnetic (AFM) order is used as the simplest model of a competing order. A number of salient features of the resulting electronic spectrum and its energy, momentum and doping dependencies are in accord with experimental observations in electron as well as hole doped cuprates. This scheme thus provides a reasonable basis for undertaking a comprehensive, beyond-LDA level of modeling of various spectroscopies. The specific topics considered here are: (i) Origin of high-energy kink or the waterfall effect found in ARPES; (ii) Identification of the three energy scales observed in RIXS spectra as the pseudogap, charge transfer gap, and Mott gap; (iii) Evolution of the electron momentum densities with holedoping as seen in Compton scattering experiments. For three dimensional topological insulators, the ARPES and scanning tunneling microscopy (STM) spectra has been analyzed using a tight-binding model as well as a k · p model. The spin-orbit coupling, which is essential to produce the characteristic features of the surface states of a TI, is included realistically in the above models. In our
Time-dependent first-principles approaches to PV materials
Miyamoto, Yoshiyuki
2013-12-10
Computational scheme for designing photovoltaic (PV) materials is presented. First-principles electron dynamics of photo-excitation and subsequent electron-hole splitting is performed based on the time-dependent density functional theory. Photo-induced enhancement of dipole moment was observed in a polar crystal and a donor-acceptor molecular pair. These experiences will pave a way to design PV material from first-principles simulations.
NMR characterization of hydrocarbon adsorption on calcite surfaces: A first principles study
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.
NMR characterization of hydrocarbon adsorption on calcite surfaces: a first principles study.
Bevilaqua, Rochele C A; Rigo, Vagner A; Veríssimo-Alves, Marcos; Miranda, Caetano R
2014-11-28
The electronic and coordination environment of minerals surfaces, as calcite, are very difficult to characterize experimentally. This is mainly due to the fact that there are relatively few spectroscopic techniques able to detect Ca(2+). Since calcite is a major constituent of sedimentary rocks in oil reservoir, a more detailed characterization of the interaction between hydrocarbon molecules and mineral surfaces is highly desirable. Here we perform a first principles study on the adsorption of hydrocarbon molecules on calcite surface (CaCO3 (101¯4)). The simulations were based on Density Functional Theory with Solid State Nuclear Magnetic Resonance (SS-NMR) calculations. The Gauge-Including Projector Augmented Wave method was used to compute mainly SS-NMR parameters for (43)Ca, (13)C, and (17)O in calcite surface. It was possible to assign the peaks in the theoretical NMR spectra for all structures studied. Besides showing different chemical shifts for atoms located on different environments (bulk and surface) for calcite, the results also display changes on the chemical shift, mainly for Ca sites, when the hydrocarbon molecules are present. Even though the interaction of the benzene molecule with the calcite surface is weak, there is a clearly distinguishable displacement of the signal of the Ca sites over which the hydrocarbon molecule is located. A similar effect is also observed for hexane adsorption. Through NMR spectroscopy, we show that aromatic and alkane hydrocarbon molecules adsorbed on carbonate surfaces can be differentiated. PMID:25429955
NMR characterization of hydrocarbon adsorption on calcite surfaces: A first principles study
NASA Astrophysics Data System (ADS)
Bevilaqua, Rochele C. A.; Rigo, Vagner A.; Veríssimo-Alves, Marcos; Miranda, Caetano R.
2014-11-01
The electronic and coordination environment of minerals surfaces, as calcite, are very difficult to characterize experimentally. This is mainly due to the fact that there are relatively few spectroscopic techniques able to detect Ca2+. Since calcite is a major constituent of sedimentary rocks in oil reservoir, a more detailed characterization of the interaction between hydrocarbon molecules and mineral surfaces is highly desirable. Here we perform a first principles study on the adsorption of hydrocarbon molecules on calcite surface (CaCO3 ( {10bar 14} )). The simulations were based on Density Functional Theory with Solid State Nuclear Magnetic Resonance (SS-NMR) calculations. The Gauge-Including Projector Augmented Wave method was used to compute mainly SS-NMR parameters for 43Ca, 13C, and 17O in calcite surface. It was possible to assign the peaks in the theoretical NMR spectra for all structures studied. Besides showing different chemical shifts for atoms located on different environments (bulk and surface) for calcite, the results also display changes on the chemical shift, mainly for Ca sites, when the hydrocarbon molecules are present. Even though the interaction of the benzene molecule with the calcite surface is weak, there is a clearly distinguishable displacement of the signal of the Ca sites over which the hydrocarbon molecule is located. A similar effect is also observed for hexane adsorption. Through NMR spectroscopy, we show that aromatic and alkane hydrocarbon molecules adsorbed on carbonate surfaces can be differentiated.
NASA Astrophysics Data System (ADS)
Li, Guo; Yan, Qimin; Zhou, Lan; Newhouse, Paul; Gregoire, John; Neaton, Jeffrey
To identify material phases in experimental combinatorial libraries, we develop a theoretical model as a complementary approach to accelerate phase identification. In this approach, samples in a combinatorial library are simulated as mixtures in chemical equilibria. Each of these mixtures contains all the solid-state phases, which can possibly exist in the library. Using the total energies of these phases obtained in first-principle calculations, we calculate the Gibbs free energy changes in the corresponding chemical reactions, and subsequently evaluate the equilibrium concentrations of the phases in every sample according to the law of mass action. Furthermore, to test this approach, we simulate pseudobinary libraries MnxV1-xOy and CuxV1-xOy. Interestingly, we find that the composition-dependent phase concentrations calculated within our approach agree well with the experimental results measured with XRD spectroscopy. This work supported by DOE (the JCAP under Award Number DE-SC0004993 and the Molecular Foundry of LBNL), and computational resources provided by NERSC.
Atomistic models of hydrogenated amorphous silicon nitride from first principles
NASA Astrophysics Data System (ADS)
Jarolimek, K.; de Groot, R. A.; de Wijs, G. A.; Zeman, M.
2010-11-01
We present a theoretical study of hydrogenated amorphous silicon nitride (a-SiNx:H) , with equal concentrations of Si and N atoms (x=1) , for two considerably different densities (2.0 and 3.0g/cm3 ). Densities and hydrogen concentration were chosen according to experimental data. Using first-principles molecular-dynamics within density-functional theory the models were generated by cooling from the liquid. Where both models have a short-range order resembling that of crystalline Si3N4 because of their different densities and hydrogen concentrations they show marked differences at longer length scales. The low-density nitride forms a percolating network of voids with the internal surfaces passivated by hydrogen. Although some voids are still present for the high-density nitride, this material has a much denser and uniform space filling. The structure factors reveal some tendency for the nonstoichiometric high-density nitride to phase separate into nitrogen rich and poor areas. For our slowest cooling rate (0.023 K/fs) we obtain models with a modest number of defect states, where the low (high) density nitride favors undercoordinated (overcoordinated) defects. Analysis of the structural defects and electronic density of states shows that there is no direct one-to-one correspondence between the structural defects and states in the gap. There are several structural defects that do not contribute to in-gap states and there are in-gap states that do only have little to no contributions from (atoms in) structural defects. Finally an estimation of the size and cooling rate effects on the amorphous network is reported.
Materials Databases Infrastructure Constructed by First Principles Calculations: A Review
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.
Transport and first-principles study of novel thermoelectric materials
NASA Astrophysics Data System (ADS)
Chi, Hang
Thermoelectric materials can recover waste industrial heat and convert it to electricity as well as provide efficient local cooling of electronic devices. The efficiency of such environmentally responsible and exceptionally reliable solid state energy conversion is determined by the dimensionless figure-of-merit ZT = alpha2 sigmaT/kappa, where alpha is the Seebeck coefficient, sigma is the electrical conductivity, kappa is the thermal conductivity, and T is the absolute temperature. The goal of the thesis is to (i) illustrate the physics to achieve high ZT of advanced thermoelectric materials and (ii) explore fundamental structure and transport properties in novel condensed matter systems, via an approach combining comprehensive experimental techniques and state-of-the-art first-principles simulation methods. Thermo-galvanomagnetic transport coefficients are derived from Onsager's reciprocal relations and evaluated via solving Boltzmann transport equation using Fermi-Dirac statistics, under the relaxation time approximation. Such understanding provides insights on enhancing ZT through two physically intuitive and very effective routes: (i) improving power factor PF = alpha2sigma; and (ii) reducing thermal conductivity kappa, as demonstrated in the cases of Mg2Si1-xSnx solid solution and Ge/Te double substituted skutterudites CoSb3(1-x)Ge1.5x Te1.5x, respectively. Motivated by recent theoretical predictions of enhanced thermoelectric performance in highly mismatched alloys, ZnTe:N molecular beam epitaxy (MBE) films deposited on GaAs (100) substrates are carefully examined, which leads to a surprising discovery of significant phonon-drag thermopower (reaching 1-2 mV/K-1) at ~13 K. Further systematic study in Bi2Te3 MBE thin films grown on sapphire (0001) and/or BaF2 (111) substrates, reveal that the peak of phonon drag can be tuned by the choice of substrates with different Debye temperatures. Moreover, the detailed transport and structure studies of Bi2-xTl xTe3
Force field development from first principles for materials design
NASA Astrophysics Data System (ADS)
Chan, Maria; Kinaci, Alper; Narayanan, Badri; Sen, Fatih; Gray, Stephen; Davis, Michael; Sankaranaryanan, Subramanian
2015-03-01
The ability to perform accurate calculations efficiently is crucial for computational materials design. In this talk, we will discuss a stream-lined approach to force field development using first principles density functional theory training data and machine learning algorithms. We will also discuss the validation of this approach on precious metal nanoparticles.
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.
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.
Intrinsic buckling strength of graphene: First-principles density functional theory calculations
NASA Astrophysics Data System (ADS)
Kumar, Sandeep; Hembram, K. P. S. S.; Waghmare, Umesh V.
2010-09-01
How graphene, an atomically thin two-dimensional crystal, explores the third spatial dimension by buckling under compression is not yet understood. Knowledge of graphene’s buckling strength, the load at which it transforms from planar to buckled form, is a key to ensure mechanical stability of graphene-based nanoelectronic and nanocomposite devices. Here, we establish using first-principles theoretical analysis that graphene has an intrinsic rigidity against buckling, and it manifests in a weakly linear component in the dispersion of graphene’s flexural acoustic mode, which is believed to be quadratic. Contrary to the expectation from the elastic plate theory, we predict within continuum analysis that a graphene monolayer of macroscopic size buckles at a nonzero critical compressive strain at T=0K , and demonstrate it numerically from first principles. The origin of this rigidity is traced to the coupling between structural and electronic degrees of freedom arising from curvature-induced overlap between π orbitals in graphene.
First-Principles Atomic Force Microscopy Image Simulations with Density Embedding Theory.
Sakai, Yuki; Lee, Alex J; Chelikowsky, James R
2016-05-11
We present an efficient first-principles method for simulating noncontact atomic force microscopy (nc-AFM) images using a "frozen density" embedding theory. Frozen density embedding theory enables one to efficiently compute the tip-sample interaction by considering a sample as a frozen external field. This method reduces the extensive computational load of first-principles AFM simulations by avoiding consideration of the entire tip-sample system and focusing on the tip alone. We demonstrate that our simulation with frozen density embedding theory accurately reproduces full density functional theory simulations of freestanding hydrocarbon molecules while the computational time is significantly reduced. Our method also captures the electronic effect of a Cu(111) substrate on the AFM image of pentacene and reproduces the experimental AFM image of Cu2N on a Cu(100) surface. This approach is applicable for theoretical imaging applications on large molecules, two-dimensional materials, and materials surfaces. PMID:27050710
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.
Lack of support for adaptive superstructure NiPt7 : Experiment and first-principles calculations
NASA Astrophysics Data System (ADS)
Schönfeld, B.; Engelke, M.; Ruban, A. V.
2009-02-01
Order and effective interaction parameters on the Pt-rich side of solid Ni-Pt alloys have been investigated by experimental and first-principles theoretical techniques. Diffuse x-ray scattering was taken from single-crystalline Ni-87.8at.%Pt aged at 603 K to set up a state of thermal equilibrium. From the separated short-range order scattering, effective pair interaction parameters were determined. These experimentally deduced values do not produce the suggested NiPt7 superstructure at lower temperatures. Instead of that, phase separation into NiPt3 regions with L12 structure and a Pt-rich matrix is observed in Monte Carlo simulations and supported by x-ray scattering of Ni-75.2at.%Pt . First-principles calculations at 0 K also show that the suggested NiPt7 phase is unstable against decomposition into NiPt3 and Pt.
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.
Diagnosis: Reasoning from first principles and experiential knowledge
NASA Technical Reports Server (NTRS)
Williams, Linda J. F.; Lawler, Dennis G.
1987-01-01
Completeness, efficiency and autonomy are requirements for suture diagnostic reasoning systems. Methods for automating diagnostic reasoning systems include diagnosis from first principles (i.e., reasoning from a thorough description of structure and behavior) and diagnosis from experiential knowledge (i.e., reasoning from a set of examples obtained from experts). However, implementation of either as a single reasoning method fails to meet these requirements. The approach of combining reasoning from first principles and reasoning from experiential knowledge does address the requirements discussed above and can possibly ease some of the difficulties associated with knowledge acquisition by allowing developers to systematically enumerate a portion of the knowledge necessary to build the diagnosis program. The ability to enumerate knowledge systematically facilitates defining the program's scope, completeness, and competence and assists in bounding, controlling, and guiding the knowledge acquisition process.
Hybrid first-principles/neural networks model for column flotation
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.
First principles molecular dynamics of molten NaCl
NASA Astrophysics Data System (ADS)
Galamba, N.; Costa Cabral, B. J.
2007-03-01
First principles Hellmann-Feynman molecular dynamics (HFMD) results for molten NaCl at a single state point are reported. The effect of induction forces on the structure and dynamics of the system is studied by comparison of the partial radial distribution functions and the velocity and force autocorrelation functions with those calculated from classical MD based on rigid-ion and shell-model potentials. The first principles results reproduce the main structural features of the molten salt observed experimentally, whereas they are incorrectly described by both rigid-ion and shell-model potentials. Moreover, HFMD Green-Kubo self-diffusion coefficients are in closer agreement with experimental data than those predicted by classical MD. A comprehensive discussion of MD results for molten NaCl based on different ab initio parametrized polarizable interionic potentials is also given.
First-principles study of complex material systems
NASA Astrophysics Data System (ADS)
He, Lixin
This thesis covers several topics concerning the study of complex materials systems by first-principles methods. It contains four chapters. A brief, introductory motivation of this work will be given in Chapter 1. In Chapter 2, I will give a short overview of the first-principles methods, including density-functional theory (DFT), planewave pseudopotential methods, and the Berry-phase theory of polarization in crystallines insulators. I then discuss in detail the locality and exponential decay properties of Wannier functions and of related quantities such as the density matrix, and their application in linear-scaling algorithms. In Chapter 3, I investigate the interaction of oxygen vacancies and 180° domain walls in tetragonal PbTiO3 using first-principles methods. Our calculations indicate that the oxygen vacancies have a lower formation energy in the domain wall than in the bulk, thereby confirming the tendency of these defects to migrate to, and pin, the domain walls. The pinning energies are reported for each of the three possible orientations of the original Ti--O--Ti bonds, and attempts to model the results with simple continuum models are discussed. CaCu3Ti4O12 (CCTO) has attracted a lot of attention recently because it was found to have an enormous dielectric response over a very wide temperature range. In Chapter 4, I study the electronic and lattice structure, and the lattice dynamical properties, of this system. Our first-principles calculations together with experimental results point towards an extrinsic mechanism as the origin of the unusual dielectric response.
Understanding and Predicting Thiolated Gold Nanoclusters from First Principles
Jiang, Deen
2010-01-01
This is an exciting time for studying thiolated gold nanoclusters. Single crystal structures of Au{sub 102}(SR){sub 44} and Au{sub 25}(SR){sub 18}{sup -} (-SR being an organothiolate group) bring both surprises and excitement in this field. First principles density functional theory (DFT) simulations turn out to be an important tool to understand and predict thiolated gold nanoclusters. In this review, I summarize the progresses made by us and others in applying first principles DFT to thiolated gold nanoclusters, as inspired by the recent experiments. First, I will give some experimental background on synthesis of thiolated gold nanoclusters, followed by a description of the recent experimental breakthroughs. Then I will introduce the superatom complex concept as a way to understand the electronic structure of thiolated gold nanoclusters or smaller nanoparticles. Next, I will describe in detail how first principles DFT is used to understand the Au-thiolate interface, predict structures for Au{sub 38}(SR){sub 24}, screen good dopants for the Au{sub 25}(SR){sub 18}{sup -} cluster, design the smallest magic thiolated gold cluster, and demonstrate the need for the trimer protecting motif. I will conclude with a grand challenge: the real time monitoring of nucleation of thiolated gold nanoclusters.
Materials Databases Infrastructure Constructed by First Principles Calculations: A Review
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
Evolutionary approach for determining first-principles hamiltonians
NASA Astrophysics Data System (ADS)
Hart, Gus L. W.; Blum, Volker; Walorski, Michael J.; Zunger, Alex
2005-05-01
Modern condensed-matter theory from first principles is highly successful when applied to materials of given structure-type or restricted unit-cell size. But this approach is limited where large cells or searches over millions of structure types become necessary. To treat these with first-principles accuracy, one 'coarse-grains' the many-particle Schrödinger equation into 'model hamiltonians' whose variables are configurational order parameters (atomic positions, spin and so on), connected by a few 'interaction parameters' obtained from a microscopic theory. But to construct a truly quantitative model hamiltonian, one must know just which types of interaction parameters to use, from possibly 106-108 alternative selections. Here we show how genetic algorithms, mimicking biological evolution ('survival of the fittest'), can be used to distil reliable model hamiltonian parameters from a database of first-principles calculations. We demonstrate this for a classic dilemma in solid-state physics, structural inorganic chemistry and metallurgy: how to predict the stable crystal structure of a compound given only its composition. The selection of leading parameters based on a genetic algorithm is general and easily applied to construct any other type of complex model hamiltonian from direct quantum-mechanical results.
Evolutionary approach for determining first-principles hamiltonians.
Hart, Gus L W; Blum, Volker; Walorski, Michael J; Zunger, Alex
2005-05-01
Modern condensed-matter theory from first principles is highly successful when applied to materials of given structure-type or restricted unit-cell size. But this approach is limited where large cells or searches over millions of structure types become necessary. To treat these with first-principles accuracy, one 'coarse-grains' the many-particle Schrodinger equation into 'model hamiltonians' whose variables are configurational order parameters (atomic positions, spin and so on), connected by a few 'interaction parameters' obtained from a microscopic theory. But to construct a truly quantitative model hamiltonian, one must know just which types of interaction parameters to use, from possibly 10(6)-10(8) alternative selections. Here we show how genetic algorithms, mimicking biological evolution ('survival of the fittest'), can be used to distil reliable model hamiltonian parameters from a database of first-principles calculations. We demonstrate this for a classic dilemma in solid-state physics, structural inorganic chemistry and metallurgy: how to predict the stable crystal structure of a compound given only its composition. The selection of leading parameters based on a genetic algorithm is general and easily applied to construct any other type of complex model hamiltonian from direct quantum-mechanical results. PMID:15834412
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
NASA Astrophysics Data System (ADS)
Dal Corso, Andrea
2015-07-01
We present a first-principle investigation of the fully relativistic electronic surface states and resonances of clean Pt(111) and Ir(111) and compare them with those of Au(111). Our calculations are based on a recently introduced fully relativistic projector augmented-wave (PAW) approach that includes spin-orbit coupling and allows us to access both the relativistic energy splittings and the spin polarization of the surface states. The maps of the electronic structure of the two surfaces are critically discussed in comparison with previous calculations and with some of the available angle-resolved photoelectron spectroscopy data.
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.
Electromagnetic Response of 12C: A First-Principles Calculation
NASA Astrophysics Data System (ADS)
Lovato, A.; Gandolfi, S.; Carlson, J.; Pieper, Steven C.; Schiavilla, R.
2016-08-01
The longitudinal and transverse electromagnetic response functions of 12C are computed in a "first-principles" Green's function Monte Carlo calculation, based on realistic two- and three-nucleon interactions and associated one- and two-body currents. We find excellent agreement between theory and experiment and, in particular, no evidence for the quenching of the measured versus calculated longitudinal response. This is further corroborated by a reanalysis of the Coulomb sum rule, in which the contributions from the low-lying Jπ=2+, 02+ (Hoyle), and 4+ states in 12 are accounted for explicitly in evaluating the total inelastic strength.
Computation of Mössbauer isomer shifts from first principles
NASA Astrophysics Data System (ADS)
Zwanziger, J. W.
2009-05-01
Computation of the observables of a Mössbauer spectrum, primarily the isomer shift, from a first-principles approach is described. The framework used is density functional theory using the projector augmented wave formalism (DFT PAW), which enables efficient computation even of many-electron solids such as SnCl2. The proper PAW version of the isomer shift is derived and shown to be correct through comparison of computed shifts and experiment in a variety of compounds based on tin, germanium and zinc. The effects of pressure are considered as well as motional effects including the Lamb-Mössbauer factor and the second-order Doppler shift.
Ethanol adsorption on the Si (111) surface: First principles study
NASA Astrophysics Data System (ADS)
Gavrilenko, Alexander V.; Bonner, Carl E.; Gavrilenko, Vladimir I.
2012-03-01
Equilibrium atomic configurations and electron energy structure of ethanol adsorbed on the Si (111) surface are studied by the first principles density functional theory. Geometry optimization is performed by the total energy minimization method. Equilibrium atomic geometries of ethanol, both undissociated and dissociated, on the Si (111) surface are found and analysed. Reaction pathways and predicted transition states are discussed in comparison with available experimental data in terms of the feasibility of the reactions occurring. Analysis of atom and orbital resolved projected density of states indicates substantial modifications of the Si surface valence and conduction electron bands due to the adsorption of ethanol affecting the electronic properties of the surface.
Oxygen diffusion in hcp metals from first principles
NASA Astrophysics Data System (ADS)
Wu, Henry H.; Wisesa, Pandu; Trinkle, Dallas R.
2016-07-01
Oxygen interstitial site energies and migration barriers in 15 hexagonal close-packed (hcp) metals have been calculated with first-principles density functional theory. Multiple hcp systems show a preference for the hexahedral site over the tetrahedral site, as well as a stable crowdion site. More surprisingly, in more than half of the hcp systems, the oxygen does not choose the large octahedral interstitial as its ground state. We explain this result based on the effective valence of the metal from crystal-field splitting and the c /a ratio. Diffusion constants for oxygen in all 15 hcp systems are calculated from analytically derived diffusion equations and match available experimental data.
Superconductivity of compressed solid argon from first principles
NASA Astrophysics Data System (ADS)
Ishikawa, Takahiro; Asano, Masamichi; Suzuki, Naoshi; Shimizu, Katsuya
2015-02-01
We present first-principles calculations on the superconductivity of solid argon under high pressure. Solid argon is found to take the double hexagonal close-packed structure in pressure range from 420 to 690 GPa, where an insulator-to-metal transition occurs at around 590 GPa. The crystal structure transforms into the hexagonal close-packed structure at 690 GPa and into the face-centered cubic structure at 2300 GPa. The superconducting critical temperature is gradually increased with the successive phase transitions and reaches the maximum value of 12 K at 2600 GPa due to the enhancement of the Fermi surface nesting.
First-Principles Study of Impurities in TlBr
Du, Mao-Hua
2012-01-01
TlBr is a promising semiconductor material for room-temperature radiation detection. Material purification has been the driver for the recent improvement in the TlBr detector performance, mainly reflected by the significant increase in the carrier mobility-lifetime product. This suggests that impurities have significant impact on the carrier transport in TlBr. In this paper, first-principles calculations are used to study the properties of a number of commonly observed impurities in TlBr. The impurity-induced gap states are presented and their effects on the carrier trapping are discussed.
First-Principles Studies of Li Nucleation on Graphene.
Liu, Mingjie; Kutana, Alex; Liu, Yuanyue; Yakobson, Boris I
2014-04-01
We study the Li clustering process on graphene and obtain the geometry, nucleation barrier, and electronic structure of the clusters using first-principles calculations. We estimate the concentration-dependent nucleation barrier for Li on graphene. While the nucleation occurs more readily with increasing Li concentration, possibly leading to the dendrite formation and failure of the Li-ion battery, the existence of the barrier delays nucleation and may allow Li storage on graphene. Our electronic structure and charge transfer analyses reveal how the fully ionized Li adatoms transform to metallic Li during the cluster growth on graphene. PMID:26274475
First-principles theory of multipolar order in neptunium dioxide
NASA Astrophysics Data System (ADS)
Suzuki, M.-T.; Magnani, N.; Oppeneer, P. M.
2010-12-01
We provide a first-principles, materials-specific theory of multipolar order and superexchange in NpO2 by means of a noncollinear local-density approximation +U (LDA+U) method. Our calculations offer a precise microscopic description of the triple- q antiferro ordered phase in the absence of any dipolar moment. We find that, while the most common nondipolar degrees of freedom (e.g., electric quadrupoles and magnetic octupoles) are active in the ordered phase, both the usually neglected higher-order multipoles (electric hexadecapoles and magnetic triakontadipoles) have at least an equally significant effect.
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.
Accurately Predicting Complex Reaction Kinetics from First Principles
NASA Astrophysics Data System (ADS)
Green, William
Many important systems contain a multitude of reactive chemical species, some of which react on a timescale faster than collisional thermalization, i.e. they never achieve a Boltzmann energy distribution. Usually it is impossible to fully elucidate the processes by experiments alone. Here we report recent progress toward predicting the time-evolving composition of these systems a priori: how unexpected reactions can be discovered on the computer, how reaction rates are computed from first principles, and how the many individual reactions are efficiently combined into a predictive simulation for the whole system. Some experimental tests of the a priori predictions are also presented.
Large impurity effects in rubrene crystals: First-principles calculations
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.
Rare-earth pnictides and chalcogenides from first-principles.
Petit, L; Szotek, Z; Lüders, M; Svane, A
2016-06-01
This review tries to establish what is the current understanding of the rare-earth monopnictides and monochalcogenides from first principles. The rock salt structure is assumed for all the compounds in the calculations and wherever possible the electronic structure/properties of these compounds, as obtained from different ab initio methods, are compared and their relation to the experimental evidence is discussed. The established findings are summarised in a set of conclusions and provide outlook for future study and possible design of new materials. PMID:27165563
Rare-earth pnictides and chalcogenides from first-principles
NASA Astrophysics Data System (ADS)
Petit, L.; Szotek, Z.; Lüders, M.; Svane, A.
2016-06-01
This review tries to establish what is the current understanding of the rare-earth monopnictides and monochalcogenides from first principles. The rock salt structure is assumed for all the compounds in the calculations and wherever possible the electronic structure/properties of these compounds, as obtained from different ab initio methods, are compared and their relation to the experimental evidence is discussed. The established findings are summarised in a set of conclusions and provide outlook for future study and possible design of new materials.
Collective modes in light nuclei from first principles.
Dytrych, T; Launey, K D; Draayer, J P; Maris, P; Vary, J P; Saule, E; Catalyurek, U; Sosonkina, M; Langr, D; Caprio, M A
2013-12-20
Results for ab initio no-core shell model calculations in a symmetry-adapted SU(3)-based coupling scheme demonstrate that collective modes in light nuclei emerge from first principles. The low-lying states of 6Li, 8Be, and 6He are shown to exhibit orderly patterns that favor spatial configurations with strong quadrupole deformation and complementary low intrinsic spin values, a picture that is consistent with the nuclear symplectic model. The results also suggest a pragmatic path forward to accommodate deformation-driven collective features in ab initio analyses when they dominate the nuclear landscape. PMID:24483740
First-Principles Study of LiPON Solid Electrolyte
NASA Astrophysics Data System (ADS)
Santosh, K. C.; Xiong, Ka; Cho, Kyeongjae
2011-03-01
There has been much interest in the thin-film solid electrolyte for solid state battery and ionics applications. LiPON is a representative material developed by Oak Ridge National Laboratory. In this work, we use first principles calculations based on the density functional theory to investigate the Li- ion migration mechanisms of LiPON family materials. We investigate atomic structures, electronic structures and defect formation energies of these materials. To determine the migration path of Li diffusion, the activation energies are calculated. This study helps us to understand fundamental mechanisms of Li-ion migration and to improve Li ion conductivity in the solid electrolytes.
First principles pseudopotential calculations on aluminum and aluminum alloys
Davenport, J.W.; Chetty, N.; Marr, R.B.; Narasimhan, S.; Pasciak, J.E.; Peierls, R.F.; Weinert, M.
1993-12-31
Recent advances in computational techniques have led to the possibility of performing first principles calculations of the energetics of alloy formation on systems involving several hundred atoms. This includes impurity concentrations in the 1% range as well as realistic models of disordered materials (including liquids), vacancies, and grain boundaries. The new techniques involve the use of soft, fully nonlocal pseudopotentials, iterative diagonalization, and parallel computing algorithms. This approach has been pioneered by Car and Parrinello. Here the authors give a review of recent results using parallel and serial algorithms on metallic systems including liquid aluminum and liquid sodium, and also new results on vacancies in aluminum and on aluminum-magnesium alloys.
Electromagnetic Response of ^{12}C: A First-Principles Calculation.
Lovato, A; Gandolfi, S; Carlson, J; Pieper, Steven C; Schiavilla, R
2016-08-19
The longitudinal and transverse electromagnetic response functions of ^{12}C are computed in a "first-principles" Green's function Monte Carlo calculation, based on realistic two- and three-nucleon interactions and associated one- and two-body currents. We find excellent agreement between theory and experiment and, in particular, no evidence for the quenching of the measured versus calculated longitudinal response. This is further corroborated by a reanalysis of the Coulomb sum rule, in which the contributions from the low-lying J^{π}=2^{+}, 0_{2}^{+} (Hoyle), and 4^{+} states in ^{12}C are accounted for explicitly in evaluating the total inelastic strength. PMID:27588850
First Principles Phase Diagram Calculaions with the Maps Package
NASA Astrophysics Data System (ADS)
Burton, B. P.
2003-12-01
The MAPS, MIT ab initio software package (http://cms.northwestern.edu/Group.html) was used to perform first principles phase diagram calculations (FPPD) for the mineral systems: CaCO3}-MgCO{3; CdCO3}-MgCO{3; CaCO3}-MgCO{3; and NaCl-KCl. General characteristics of FPPD calculations will be reviewed and details of specific calculations will be discussed. Particular attention will be given to: the prediction of new stable ordered phases; metastable ordered phases; and the role of vibrational entropy in phase stability.
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.
Optical properties of Yb-doped LaB6 from first-principles calculation
NASA Astrophysics Data System (ADS)
Chao, Luomeng; Bao, Lihong; Wei, Wei; Tegus, O.
2016-03-01
The optical properties of Yb-doped LaB6 have been investigated by first-principles calculations within the framework of density functional theory. The results show that the Yb 4f states at near Fermi surface affect their optical properties and the Yb-doping leads to a reduction of the plasmon energy of LaB6, i.e. a redshift of the position of transmission peak in the visible-near infrared region. This study offers a theoretical prediction for the design and application of Yb-doped LaB6 as an optoelectronic material.
NASA Astrophysics Data System (ADS)
Ren, Jun-Feng; Yuan, Xiao-Bo; Hu, Gui-Chao
2014-04-01
We theoretically investigate the electronic structure and spin polarization properties of Na-doped meridianal tris(8-hydroxyquinoline) aluminum (Alq3) by first principles calculations. It is found that the spin density is distributed mainly in the Alq3 part in the Alq3:Na complex. Electron charge transfer takes place from the Na atom to the Alq3 molecule, which induces asymmetric changing of the molecule bond lengths, thus the spin density distribution becomes asymmetric. Spin polarization of the complex originates from the preferable filling of the spin-split nitrogen and carbon p-orbitals because of the different bond length changes of the Alq3 molecule upon Na doping.
First-principles study of the electronic and molecular structure of protein nanotubes
NASA Astrophysics Data System (ADS)
Okamoto, Hajime; Takeda, Kyozaburo; Shiraishi, Kenji
2001-09-01
The electronic and molecular structures of protein nanotubes (PNT's) have been investigated theoretically by first-principles electronic structure calculations. The results have been discussed in comparison to those of the polypeptide open chains (POC's) and polypeptide closed rings (PCR's) in order to give a systematic understanding. Focusing on the intra-ring and inter-ring hydrogen bonds (HB's), we also investigate the PCR stacking mechanism. The present calculation reveals that PNT's are semiconductors and that an extra proton in the tube interior has the potential to be an electron acceptor.
Spin Crossover in Ferropericlase From First-Principles Molecular Dynamics Simulations
NASA Astrophysics Data System (ADS)
Holmstrom, E.; Stixrude, L. P.
2013-12-01
Ferropericlase is believed to be the second-most abundant mineral of the lower mantle of the Earth. It is experimentally known that with increasing pressure, the iron ions in the mineral begin to collapse from a high-spin to low-spin state. This spin crossover looks certain to have geophysical effects, and hence a good theoretical understanding of the phenomenon is necessary. Using first-principles molecular dynamics simulations in conjunction with thermodynamic integration, we construct a phase diagram of the spin crossover as a function of pressure and temperature. In addition, we predict that the mineral loses its electrically insulating character within the lower mantle.
First-principles investigation of high pressure Pbca phase of carbon mononitride
NASA Astrophysics Data System (ADS)
Wei, Qun; Zhang, Meiguang; Yan, Haiyan
2016-09-01
A theoretical investigations on the stability, mechanical and electronic properties of Pbca-CN was performed by using first principle calculations. According to our calculations, Pbca-CN exhibits a large elastic anisotropy. The further mechanical calculations demonstrated that Pbca-CN shows high elastic moduli. Young's modulus of Pbca-CN is found to reach a maximum along [001] direction and a minimum along [100] direction. The ideal tensile and shear strength at large strains of Pbca-CN are also examined. The ideal shear strength along the weakest (100)[010] slip system is about 20 GPa, which shows Pbca-CN is not an intrinsic superhard material.
First-principles studies of low tolerance factor perovskites
NASA Astrophysics Data System (ADS)
Kang, Sung Gu; Fennie, Craig J.
2014-03-01
Most perovskites form in the non-polar Pnma structure, however, materials found in the polar subgroup of this structure, e.g., space group Pna21, are rare. Here we study from first principles the structural and vibrational properties of twelve materials that span a wide range of tolerance factors (MgSnO3, ZnSnO3, MgTiO3, ZnTiO3, MgGeO3, ZnGeO3, CdSnO3, CaSnO3, CdTiO3, CaTiO3, CdGeO3, and CaGeO3) . We illustrate how low tolerance factor materials that have been artificially constrained to the Pnma structure do in fact display ferroelectric instabilities. Insight is gained by further studying the energetics for each material in the ilmenite, lithium niobate, and perovskite structures over a wide pressure range. Our first-principles results are shown to correlate with physical descriptors, such as tolerance factor, ionic radii, and electronegativity. The rationalized rules from our data analysis will guide to design the new ferroelectric/functional materials.
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
Thermoelastic properties of α -iron from first-principles
NASA Astrophysics Data System (ADS)
Dragoni, Daniele; Ceresoli, Davide; Marzari, Nicola
2015-03-01
We calculate the thermomechanical properties of α -iron, and in particular its isothermal and adiabatic elastic constants, using first-principles total-energy and lattice-dynamics calculations, minimizing the quasiharmonic vibrational free energy under finite strain deformations. Particular care is made in the fitting procedure for the static and temperature-dependent contributions to the free energy, in discussing error propagation for the two contributions separately, and in the verification and validation of pseudopotential and all-electron calculations. We find that the zero-temperature mechanical properties are sensitive to the details of the calculation strategy employed, and common semilocal exchange-correlation functionals provide only fair to good agreement with experimental elastic constants, while their temperature dependence is in excellent agreement with experiments in a wide range of temperature almost up to the Curie transition.
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.
First-principles study of interface doping in ferroelectric junctions
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
Helium diffusion in olivine based on first principles calculations
NASA Astrophysics Data System (ADS)
Wang, Kai; Brodholt, John; Lu, Xiancai
2015-05-01
As a key trace element involved in mantle evolution, the transport properties of helium in the mantle are important for understanding the thermal and chemical evolution of the Earth. However, the mobility of helium in the mantle is still unclear due to the scarcity of measured diffusion data from minerals under mantle conditions. In this study, we used first principles calculations based on density functional theory to calculate the absolute diffusion coefficients of the helium in olivine. Using the climbing images nudged elastic band method, we defined the diffusion pathways, the activation energies (Ea), and the prefactors. Our results demonstrate that the diffusion of helium has moderate anisotropy. The directionally dependent diffusion of helium in olivine can be written in Arrhenius form as follows.
Electromagnetic response of C12 : A first-principles calculation
Lovato, A.; Gandolfi, S.; Carlson, J.; Pieper, Steven C.; Schiavilla, R.
2016-08-15
Here, the longitudinal and transverse electromagnetic response functions ofmore » $$^{12}$$C are computed in a ``first-principles'' Green's function Monte Carlo calculation, based on realistic two- and three-nucleon interactions and associated one- and two-body currents. We find excellent agreement between theory and experiment and, in particular, no evidence for the quenching of measured versus calculated longitudinal response. This is further corroborated by a re-analysis of the Coulomb sum rule, in which the contributions from the low-lying $$J^\\pi\\,$$=$$\\, 2^+$$, $0^+$ (Hoyle), and $4^+$ states in $$^{12}$$C are accounted for explicitly in evaluating the total inelastic strength.« less
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).
Vibrational and Thermophysical Properties of PETN from First Principles
NASA Astrophysics Data System (ADS)
Gonzalez, Joseph; Landerville, Aaron; Oleynik, Ivan
2015-06-01
Thermophysical properties are urgently sought as input for meso- and continuum-scale modeling of energetic materials (EMs). However, empirical data in this regard are often limited to specific pressures and temperatures. Such modeling of EMs can be greatly improved by inclusion of thermophysical properties over a wide range of pressures and temperatures, provided such data could be reliably obtained from theory. We demonstrate such a capability by calculating the equation of state, heat capacities, coefficients of thermal expansion, and Gruneissen parameters for pentaerythritol tetranitrate (PETN) using first-principles density functional theory, which includes proper description of van der Waals interactions and zero-point and thermal free energy contributions to pressure, the latter being calculated using the quasi-harmonic approximation. Further, we investigate the evolution of the vibration spectrum of PETN as a function of pressure.
High pressure polyhydrides of molybdenum: A first-principles study
NASA Astrophysics Data System (ADS)
Feng, Xiaolei; Zhang, Jurong; Liu, Hanyu; Iitaka, Toshiaki; Yin, Ketao; Wang, Hui
2016-07-01
We present results from first-principles calculations on molybdenum polyhydrides under pressure. In addition to the experimental ε-phase of MoH, we find several novel structures of MoH2 and MoH3 at pressures below 100 GPa. A hexagonal structure of MoH2 becomes stable with respect to decomposition into MoH and H2 above 9 GPa, and transforms into an orthorhombic structure at 24 GPa, which remains stable up to 100 GPa. MoH3 is unstable relative to decomposition into MoH and H2 over the whole pressure range studied. Electronic structure calculations reveal that molybdenum polyhydrides are metallic under pressure.
Defects in AIN/GaN Superlattice: First Principle Calculations.
Rao, Xue; Wang, Ru-Zhi; Cao, Juexian; Yan, Hui
2016-01-01
In this paper we investigate the atomic configurations, electronic structure and formation energies of native point defects, (such as vacancies and self-interstitials), in an AIN/GaN superlattice (SL) constructed on a wurtzite structure along a [0001] growth direction. Comprehensive first-principle calculations based on the density functional theory (DFT) are used. Cation and anion vacancies in the neutral charge state are calculated. For the native defects, the results showed that the most favorable configurations are the cation vacancies at the interface of the SL, or the anion vacancies in the GaN wells. Considering the formation energies of different vacancies, the results show that the nitrogen vacancy has the lowest formation energy, indicating that they are significantly the most stable configuration, and thus should be expected to be the major defect in a AIN/GaN superlattice. PMID:27398499
Hydrogen storage in LiH: A first principle study
NASA Astrophysics Data System (ADS)
Banger, Suman; Nayak, Vikas; Verma, U. P.
2014-04-01
First principles calculations have been performed on the Lithium hydride (LiH) using the full potential linearized augmented plane wave (FP-LAPW) method within the framework of density functional theory. We have extended our calculations for LiH+2H and LiH+6H in NaCl structure. The structural stability of three compounds have been studied. It is found that LiH with 6 added Hydrogen atoms is most stable. The obtained results for LiH are in good agreement with reported experimental data. Electronic structures of three compounds are also studied. Out of three the energy band gap in LiH is ˜3.0 eV and LiH+2H and LiH+6H are metallic.
Two Dimensional Ice from First Principles: Structures and Phase Transitions.
Chen, Ji; Schusteritsch, Georg; Pickard, Chris J; Salzmann, Christoph G; Michaelides, Angelos
2016-01-15
Despite relevance to disparate areas such as cloud microphysics and tribology, major gaps in the understanding of the structures and phase transitions of low-dimensional water ice remain. Here, we report a first principles study of confined 2D ice as a function of pressure. We find that at ambient pressure hexagonal and pentagonal monolayer structures are the two lowest enthalpy phases identified. Upon mild compression, the pentagonal structure becomes the most stable and persists up to ∼2 GPa, at which point the square and rhombic phases are stable. The square phase agrees with recent experimental observations of square ice confined within graphene sheets. This work provides a fresh perspective on 2D confined ice, highlighting the sensitivity of the structures observed to both the confining pressure and the width. PMID:26824547
Auger recombination in sodium-iodide scintillators from first principles
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.
Electronic Stopping Power in LiF from First Principles
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.
Two Dimensional Ice from First Principles: Structures and Phase Transitions
NASA Astrophysics Data System (ADS)
Chen, Ji; Schusteritsch, Georg; Pickard, Chris J.; Salzmann, Christoph G.; Michaelides, Angelos
2016-01-01
Despite relevance to disparate areas such as cloud microphysics and tribology, major gaps in the understanding of the structures and phase transitions of low-dimensional water ice remain. Here, we report a first principles study of confined 2D ice as a function of pressure. We find that at ambient pressure hexagonal and pentagonal monolayer structures are the two lowest enthalpy phases identified. Upon mild compression, the pentagonal structure becomes the most stable and persists up to ˜2 GPa , at which point the square and rhombic phases are stable. The square phase agrees with recent experimental observations of square ice confined within graphene sheets. This work provides a fresh perspective on 2D confined ice, highlighting the sensitivity of the structures observed to both the confining pressure and the width.
2D ice from first principles: structures and phase transitions
NASA Astrophysics Data System (ADS)
Chen, Ji; Schusteritsch, Georg; Pickard, Chris J.; Salzmann, Christoph G.; Michaelides, Angelos
Despite relevance to disparate areas such as cloud microphysics and tribology, major gaps in the understanding of the structures and phase transitions of low-dimensional water ice remain. Here we report a first principles study of confined 2D ice as a function of pressure. We find that at ambient pressure hexagonal and pentagonal monolayer structures are the two lowest enthalpy phases identified. Upon mild compression the pentagonal structure becomes the most stable and persists up to ca. 2 GPa at which point square and rhombic phases are stable. The square phase agrees with recent experimental observations of square ice confined within graphene sheets. We also find a double layer AA stacked square ice phase, which clarifies the difference between experimental observations and earlier force field simulations. This work provides a fresh perspective on 2D confined ice, highlighting the sensitivity of the structures observed to both the confining pressure and width.
First-principles simulations of electrostatic interactions between dust grains
Itou, H. Amano, T.; Hoshino, M.
2014-12-15
We investigated the electrostatic interaction between two identical dust grains of an infinite mass immersed in homogeneous plasma by employing first-principles N-body simulations combined with the Ewald method. We specifically tested the possibility of an attractive force due to overlapping Debye spheres (ODSs), as was suggested by Resendes et al. [Phys. Lett. A 239, 181–186 (1998)]. Our simulation results demonstrate that the electrostatic interaction is repulsive and even stronger than the standard Yukawa potential. We showed that the measured electric field acting on the grain is highly consistent with a model electrostatic potential around a single isolated grain that takes into account a correction due to the orbital motion limited theory. Our result is qualitatively consistent with the counterargument suggested by Markes and Williams [Phys. Lett. A 278, 152–158 (2000)], indicating the absence of the ODS attractive force.
First principles modeling of panchromatic dyes for solar cells applications.
NASA Astrophysics Data System (ADS)
di Felice, Rosa; Calzolari, Arrigo; Dong, Rui; Buongiorno Nardelli, Marco
2013-03-01
The state-of-the-art dye in Grätzel solar cells, N719, exhibits a total solar-to-electric conversion efficiency of 11.2%. However, it severely lacks absorption in the red and the near infrared regions of the electromagnetic spectrum, which represent more than 70% of the solar radiation spectrum. Using calculations from first principles in the time-dependent domain, we have studied the electronic and optical response of a novel class of panchromatic sensitizers that can harvest solar energy efficiently across the visible and near infrared regions, which have been recently synthesized [A. El-Shafei, M. Hussain, A. Atiq, A. Islam, and L. Han, J. Mater. Chem. 22, 24048 (2012)]. Our calculations show that, by tuning the properties of antenna groups, one can achieve a substantial improvement of the optical properties.
First-Principles Dielectric Spectra of Silicon: THz through UV
NASA Astrophysics Data System (ADS)
Lawler, H. M.; Dalosto, S.; Levine, Z. H.; Shirley, E. L.; Rehr, J. J.
2007-03-01
We present an implementation of the GW-Bethe-Salpeter-equation approach to first-principles calculations of dielectric response based in part on input from the plane-wave, pseudopotential code ABINIT. This work, together with lattice dynamical calculations, aims to develop versatile codes capable of calculating dielectric spectra in insulators for the full spectral range from THz to the UV. Below the bandgap, lattice vibrations absorb light in the THz range. These spectra are generally composed of sharp infrared-active features (absent by symmetry in silicon); weak, temperature dependent continuum effects from IR-active-multiphonon state hybridization; and contributions to the macroscopic polarization directly from multiphonon states. Above the bandgap, density-functional band structures are taken as a starting point for the inclusion of many-body interactions within the GW-BSE approximation. Emphasis will be on treating the excitionic effects and non-zero-momentum application of the modern theory of polarization with ABINIT.
NMR shifts for polycyclic aromatic hydrocarbons from first-principles
Thonhauser, Timo; Ceresoli, Davide; Marzari, Nicola N.
2009-09-03
We present first-principles, density-functional theory calculations of the NMR chemical shifts for polycyclic aromatic hydrocarbons, starting with benzene and increasing sizes up to the one- and two-dimensional infinite limits of graphene ribbons and sheets. Our calculations are performed using a combination of the recently developed theory of orbital magnetization in solids, and a novel approach to NMR calculations where chemical shifts are obtained from the derivative of the orbital magnetization with respect to a microscopic, localized magnetic dipole. Using these methods we study on equal footing the 1H and 13C shifts in benzene, pyrene, coronene, in naphthalene, anthracene, naphthacene, and pentacene, and finally in graphene, graphite, and an infinite graphene ribbon. Our results show very good agreement with experiments and allow us to characterize the trends for the chemical shifts as a function of system size.
First principles electron transport simulations in the Kondo regime
NASA Astrophysics Data System (ADS)
Rungger, Ivan; Radonjic, Milos; Appelt, Wilhelm; Chioncel, Liviu; Droghetti, Andrea
When magnetic atoms, molecules or thin films are brought into contact with metals the electron-electron interaction leads to the appearance of the correlated Kondo state at low temperatures. In this talk we will present results for the electronic structure and conductance in the Kondo regime of recent STM and break junction experiments for stable radical molecules, which correspond to spin half molecular magnets. We will outline the methodological approach to evaluate the conductance of such systems from first principles, as implemented in the Smeagol electron transport code. The method combines the density functional theory (DFT) with Anderson impurity solvers within the continuum time quantum Monte Carlo (CTQMC) and numerical renormalization group (NRG) approaches.
First principle study of manganese doped cadmium sulphide sheet
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.
First principles pseudopotential calculations on aluminum and aluminum alloys
Davenport, J.W.; Chetty, N.; Marr, R.B.; Narasimhan, S.; Pasciak, J.E.; Peierls, R.F.; Weinert, M.; Rahman, T.S.
1994-12-31
Recent advances in computational techniques have led to the possibility of performing first principles calculations of the energetics of alloy formation on systems involving several hundred atoms. This includes impurity concentrations in the 1% range as well as realistic models of disordered materials (including liquids), vacancies, and grain boundaries. The new techniques involve the use of soft, fully nonlocal pseudopotentials, iterative diagonalization, and parallel computing algorithms. This approach has been pioneered by Car and Parrinello. Here the authors give a review of recent results using parallel and serial algorithms by their group on metallic systems including liquid aluminum and liquid sodium, and also new results on vacancies in aluminum and on aluminum-magnesium alloys.
First-principles semiclassical initial value representation molecular dynamics.
Ceotto, Michele; Atahan, Sule; Shim, Sangwoo; Tantardini, Gian Franco; Aspuru-Guzik, Alán
2009-05-28
In this work, we explore the use of the semiclassical initial value representation (SC-IVR) method with first-principles electronic structure approaches to carry out classical molecular dynamics. The proposed approach can extract the vibrational power spectrum of carbon dioxide from a single trajectory providing numerical results that agree with experiment and quantum calculations. The computational demands of the method are comparable to those of classical single-trajectory calculations, while describing uniquely quantum features such as the zero-point energy and Fermi resonances. The method can also be used to identify symmetry properties of given vibrational peaks and investigate vibrational couplings by selected classical trajectories. The accuracy of the method degrades for the reproduction of anharmonic shifts for high-energy vibrational levels. PMID:19440613
Carbon-rich icosahedral boron carbide designed from first principles
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.
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.
First-principles study of thermal properties of borophene.
Sun, Hongyi; Li, Qingfang; Wan, X G
2016-06-01
Very recently, a new single-element two-dimensional (2D) material borophene was successfully grown on a silver surface under pristine ultrahigh vacuum conditions which attracts tremendous interest. In this paper, the lattice thermal conductivity, phonon lifetimes, thermal expansion and temperature dependent elastic moduli of borophene are systematically studied by using first-principles. Our simulations show that borophene possesses unique thermal properties. Strong phonon-phonon scattering is found in borophene, which results in its unexpectedly low lattice thermal conductivity. Thermal expansion coefficients along both the armchair and zigzag directions of borophene show impressive negative values. More strikingly, the elastic moduli are sizably strengthened as temperature increases, and the negative in-plane Poisson's ratios are found along both the armchair and zigzag directions at around 120 K. The mechanisms of these unique thermal properties are also discussed in this paper. PMID:27188523
Thermodynamics of Magnetic Systems from First Principles: WL-LSMS
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.
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.
Structural instabilities in strontium titanate from first-principles calculations
NASA Astrophysics Data System (ADS)
Lasota, Christopher Andrew
For some time now, first-principles calculation methods have proven to be an effective tool for investigating the physics of condensed matter systems. The additional use of density functional theory (DFT) and the local density approximation (LDA) has permitted even complex materials to be studied on desktop workstations with remarkable success. The incorporation of linear response theory into these methods has extended their power, allowing investigation of important dynamical properties. Contained within the following pages are the results of a first-principles study of SrTiO3. This transition metal oxide is often grouped with ferroelectric materials, due to its similar composition and perovskite structure. Although it behaves as if it were to become ferroelectric, it fails to do so, even at the lowest temperatures. Using the LAPW method for bulk materials, the ground-state equilibrium properties for the cubic phase were found. Additional linear response calculations produced the phonon frequencies throughout the Brillouin zone. Imaginary values for these frequencies revealed two distinct regions of reciprocal space corresponding to structural instabilities of the ferroelectric (FE) and antiferrodistortive (AFD) types. A cell-doubling AFD transition to tetragonal structure is observed experimentally, so subsequent calculations were continued in this phase. Total energy calculations were performed for both FE and AFD distortions in this new phase, and it was found that the AFD instability is enhanced with decreasing lattice parameter, while the FE instability is diminished. Furthermore, these calculations suggest that this material is marginally stable against FE distortions, even at the 105 K volume.
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.
NASA Astrophysics Data System (ADS)
Fraxedas, J.; Lee, Y. J.; Jiménez, I.; Gago, R.; Nieminen, R. M.; Ordejón, P.; Canadell, E.
2003-11-01
We report a combined experimental and theoretical study of the unoccupied electronic states of the neutral molecular organic materials TTF (tetrathiafulvalene) and TCNQ (7,7,8,8-tetracyano-p-quinodimethane) and of the one-dimensional metallic charge transfer salt TTF-TCNQ. The experimental density of states (DOS) is obtained by x-ray absorption near edge spectroscopy (XANES) with synchrotron light and the predicted DOS by means of first-principles density functional theory calculations. Most of the experimentally derived element-specific XANES features can be associated to molecular orbitals of defined symmetry. Because of the planar geometry of the TTF and TCNQ molecules and the polarization of the synchrotron light, the energy dependent σ or π character of the orbitals can be inferred from angular dependent XANES measurements. The present work represents the state of the art analysis of the XANES spectra of this type of materials and points out the need for additional work in order to elucidate the governing selection rules in the excitation process.
Pascal, Tod A; Boesenberg, Ulrike; Kostecki, Robert; Richardson, Thomas J; Weng, Tsu-Chien; Sokaras, Dimosthenis; Nordlund, Dennis; McDermott, Eamon; Moewes, Alexander; Cabana, Jordi; Prendergast, David
2014-01-21
We elucidate the role of room-temperature-induced instantaneous structural distortions in the Li K-edge X-ray absorption spectra (XAS) of crystalline LiF, Li2SO4, Li2O, Li3N, and Li2CO3 using high resolution X-ray Raman spectroscopy (XRS) measurements and first-principles density functional theory calculations within the eXcited electron and Core Hole approach. Based on thermodynamic sampling via ab initio molecular dynamics simulations, we find calculated XAS in much better agreement with experiment than those computed using the rigid crystal structure alone. We show that local instantaneous distortion of the atomic lattice perturbs the symmetry of the Li 1s core-excited-state electronic structure, broadening spectral line-shapes and, in some cases, producing additional spectral features. The excellent agreement with high-resolution XRS measurements validates the accuracy of our first-principles approach to simulating XAS, and provides both accurate benchmarks for model compounds and a predictive theoretical capability for identification and characterization of multi-component systems, such as lithium-ion batteries, under working conditions. PMID:25669363
NASA Astrophysics Data System (ADS)
Akashi, Ryosuke
The recent discovery of high-temperature superconductivity in sulfur hydride under extreme pressure has broken the long-standing record of superconducting transition temperature (Tc) in the Hg-cuprate. According to the isotope effect measurement and theoretical calculations, the superconducting transition is mainly ascribed to the conventional phonon-mediated pairing interaction. It is, however, not enough for understanding the high-Tc superconductivity in the sulfur hydride. To elucidate various possible effects on Tc with accuracy, we have analyzed Tc with first-principles methods without any empirical parameters. First, for various pressures and theoretically proposed crystal structures, we calculated Tc with the density functional theory for superconductors (SCDFT) to examine which structure(s) can explain experimentally measured Tc data [Akashi et al., PRB 91, 224513 (2015)]. We next solved the Eliashberg equations without introducing the renormalized Coulomb parameter mu*, which is the Green-function-based counterpart of the SCDFT, and evaluated the effects of rapidly varying electron density of states, atomic zero-point motion, and phonon anharmonic corrections on Tc [Sano et al., in preparation]. In the talk, we review these results and discuss the dominant factors for the Tc and their relation to the experimental results. We also report some crystal structures that we recently found with first-principles calculations, which could have a key role for the pressure-induced transformation to the high-Tc phase.
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).
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
NASA Astrophysics Data System (ADS)
2009-12-01
First-principles methods based on density functional theory (DFT) have been the mainstay of theoretical studies of the properties of semiconductor and oxide materials. Despite the tremendous successes of the past few decades, significant challenges remain in adapting these methods for predictive simulations that are quantitatively useful in predicting device behavior. Recent advances in computational capabilities, and improved theoretical methods taking advantage of ever more powerful computer hardware, offer the possibility that computational modeling may finally fulfill the long-sought goal of truly predictive simulations for defect properties. The exciting prospect of using modelling as `virtual experiments' to obtain quantitatively accurate predictions of semiconductor behavior seems tantalizingly close, but challenges still remain, which is evident in the many divergent approaches adopted for the modelling and simulation of various aspects of defect behavior. This special issue consists of papers describing different approaches to the study of defects, and the challenges that remain from the perspective of leading scientists in the field. It includes contributions on the theoretical and computational issues of using density functional methods for defect calculations [Nieminen], treatments to account for finite computational cell effects in periodic defect supercell calculations using analytical constructions [Lany and Zunger], or cell-size extrapolation techniques [Castleton et al], or instead using embedded cluster calculations to model charge-trapping defects [Shluger et al]. This issue also includes a description of the computation of g-tensor and hyperfine splitting for defect centers [Valentin and Pacchione], computation of vibrational properties of impurities from dynamical DFT calculations [Estreicher et al], and the use of DFT supercell calculations to predict charge transition energy levels of intrinsic defects in GaAs [Schultz and von Lilienfeld
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.
First-principles calculations of gated adatoms on graphene
NASA Astrophysics Data System (ADS)
Chan, Kevin T.; Lee, Hoonkyung; Cohen, Marvin L.
2011-03-01
The two-dimensional surface of graphene is well-suited for adsorption of adatoms or molecules. The application of a gate voltage can be used to precisely control the electron concentration of the adsorbate-graphene system. Such control over electronic properties of adsorbates on graphene might have useful applications in areas such as catalysis and hydrogen storage. In this work, the gating of a variety of adatoms adsorbed on graphene is studied using first-principles calculations. We compute the projected density of states, local electrostatic potential, and charge density of the adatom-graphene system as a function of gate voltage. We demonstrate that adatoms on graphene can be ionized by gating, and that the ionization causes a sharp change in the electrostatic potential. Additional interesting features of our results are also discussed. This work was supported by NSF Grant No. DMR10-1006184 and DOE under Contract No. DE-AC02-05CH11231. Computational resources were provided by the IT Division at LBNL.
The Effects of Relativity on First-Principles Calculations
NASA Astrophysics Data System (ADS)
Semi, T.; Mattsson, A. E.; Wills, J. M.
2011-06-01
The construction of the equation of state for a given material is of central importance to its characterization. Hugoniots can be calculated using Density Functional Theory (DFT), and DFT points compared to available experimental results. By evaluating the accuracy in a relevant phase space, confidence is gained in the DFT method. This bolsters the dependability of DFT data in phase spaces in which experiment may be difficult or impossible to perform, and verifies its usefulness. The equation of state is comprised of the cold curve and thermal electronic and ionic terms. We discuss differences in the cold curve of Ce produced by first principles calculations using the Scalar Dirac equation with variational spin-orbit coupling treatment and that generated by the full relativistic formulation, both with the same DFT functionals. The relativistic effects of f-electrons in systems like Ce are expected to be of a magnitude substantial enough to be consequential to the description of these structures. ``Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.''
First-principles investigation of graphene-metal interfaces
NASA Astrophysics Data System (ADS)
Ross, Andrew; Adamska, Lyudmyla; Lin, You; Oleynik, Ivan
2011-03-01
Epitaxial growth of graphene on Ni(111) substrates is one promising method of large-scale, high-quality graphene wafer production, due to the small lattice mismatch between these two materials. We present results of first-principles density functional theory (DFT) investigation of thestructural, electronic, and magnetic properties of graphene/Ni(111) interfaces relevant to experimental studies of graphene growth on nickel substrates. DFT calculations were performed to identify the favored interface geometries and binding sites for different interface configurations. Additional adlayers of Ni and Cu were either adsorbed on top of the graphene/metal interface, or placed between the graphene and substrate to model processes of metal intercalation. It was also found that the interaction between graphene/Ni(111) and the top Cu adlayer is much weaker compared to that for Ni adlayer. The atomic, electronic, and magnetic properties of these interfaces, including induced magnetic moments in graphene/Ni(111) and Cu,Ni/graphene/Ni(111) systems are also discussed. This work was supported by NSF REU supplement to the award CCF-0726842.
Electronic structure and ionicity of actinide oxides from first principles
NASA Astrophysics Data System (ADS)
Petit, L.; Svane, A.; Szotek, Z.; Temmerman, W. M.; Stocks, G. M.
2010-01-01
The ground-state electronic structures of the actinide oxides AO , A2O3 , and AO2 ( A=U , Np, Pu, Am, Cm, Bk, and Cf) are determined from first-principles calculations, using the self-interaction corrected local spin-density approximation. Emphasis is put on the degree of f -electron localization, which for AO2 and A2O3 is found to follow the stoichiometry, namely, corresponding to A4+ ions in the dioxide and A3+ ions in the sesquioxides. In contrast, the A2+ ionic configuration is not favorable in the monoxides, which therefore become metallic. The energetics of the oxidation and reduction in the actinide dioxides is discussed, and it is found that the dioxide is the most stable oxide for the actinides from Np onward. Our study reveals a strong link between preferred oxidation number and degree of localization which is confirmed by comparing to the ground-state configurations of the corresponding lanthanide oxides. The ionic nature of the actinide oxides emerges from the fact that only those compounds will form where the calculated ground-state valency agrees with the nominal valency expected from a simple charge counting.
Incorporation of water in pyrope: a first principles study
NASA Astrophysics Data System (ADS)
Manga, V. R.; Mookherjee, M.; Muralidharan, K.
2014-12-01
Pyrope (Mg3Al2Si3O12) rich garnet is the most important secondary mineral phase with volume fractions ranging between 20 % in the shallow upper mantle to 40 % in the lower part of upper mantle. The volume fractions of garnet in subducted oceanic crusts are as high as 80 %. However, our understanding of the incorporation of water in garnet as proton defect is rather limited. Experimental studies conducted at pressures and temperatures relevant to the deep lower mantle have resulted in wide range of water contents ranging between 0 wt % to ~ 0.8 wt %. In a pyriolyte composition representative of the upper mantle, unlike olivine (Mg2SiO4), which remains largely iso-chemical upon compression, garnet undergoes solid solution with pyroxene (MgSiO3) and as a result there is a continuous evolution of the chemistry of garnet as a function of pressure. This complicates the analysis of proton defects using conventional thermodynamics expressing water solubility as a function of water fugacity, oxide activity, and activation volume. To circumvent this issue, we use first principles simulations to explore the relative energetics of the formation of protons in Mg, Al, and Si sites. Preliminary results at ambient conditions indicate positive enthalpy changes for the proton defects in all the sites, with silicon site being the most favorable. We intend to explore the effect of pressure and temperature on the defect formation energies. Acknowledgement- MM is supported by the US National Science Foundation grant (EAR-1250477).
First-principles design of organo-Sn polymeric dielectrics
NASA Astrophysics Data System (ADS)
Tran, Huan; Kumar, Arun; Wang, Chenchen; Baldwin, Aaron; Ma, Rui; Sotzing, Gregory; Ramprasad, Rampi
2014-03-01
Following on from recent computation-based suggestions that Sn-containing polymers may be promising dielectrics, one of them, poly (dimethyltin glutarate) (pDMTG), has been synthesized. The measured dielectric constant of pDMTG is ɛ ~= 7 . 4 , significantly higher than the current standard material used for high-energy-density applications, namely, polypropylene (ɛ ~= 2 . 2). By performing first-principles calculations at the level of density functional theory and using the minima-hopping method to predict the stable structures (given that just the composition is provided), we propose four structural models of pDMTG. Based on these models, various physical properties of pDMTG, e.g., dielectric constant, infrared spectra and refractive index, are determined to closely agree with experimental data. The calculated band gap of pDMTG is high (Eg ~= 6 . 1 eV), implying that pDMTG is a promising candidate for high-energy-density materials. The strategy that has lead to the synthesis and understanding of pDMTG shows that density functional theory is a powerful method to study and design new materials. Our work is supported by the Office of Naval Research through the Multidisciplinary University Research Initiative (MURI).
First-principles study of liquid and amorphous metals
NASA Astrophysics Data System (ADS)
Ganesh, Panchapakesan
Computer simulations using state of the art First-Principles ab-initio methods enable us to probe the structural features of novel materials like liquid metals and metallic glass forming alloys, both in their supercooled liquid state as well as in their quenched amorphous forms where available. The ab-initio nature of the calculations enable us to capture the chemical identity realistically at the atomistic level without any free parameters. The results show that even though elemental liquid metals like face-centered cubic (FCC) Cu and body-centered cubic (BCC) Fe (and W) have similar atomic structure at high temperature, which is also similar to jammed packing of hard-spheres, they differ quite appreciably even with slight supercooling. This difference enables us to further supercool Fe and W to a much greater degree than Cu. The origin of this difference between elemental metals with different crystalline ground states can be understood based on concepts of geometric frustration. Further, the role played by atoms of different sizes in controlling the geometric frustration in glass forming alloys has been investigated. Studies of Silicon in its supercooled regime have been made to investigate the existence of a possible structural transition. Attempts to clarify if the structural transition could be a thermodynamic phase transition have been made and changes in electronic properties accompanying this structural change have been studied.
First-Principle Characterization for Singlet Fission Couplings.
Yang, Chou-Hsun; Hsu, Chao-Ping
2015-05-21
The electronic coupling for singlet fission, an important parameter for determining the rate, has been found to be too small unless charge-transfer (CT) components were introduced in the diabatic states, mostly through perturbation or a model Hamiltonian. In the present work, the fragment spin difference (FSD) scheme was generalized to calculate the singlet fission coupling. The largest coupling strength obtained was 14.8 meV for two pentacenes in a crystal structure, or 33.7 meV for a transition-state structure, which yielded a singlet fission lifetime of 239 or 37 fs, generally consistent with experimental results (80 fs). Test results with other polyacene molecules are similar. We found that the charge on one fragment in the S1 diabatic state correlates well with FSD coupling, indicating the importance of the CT component. The FSD approach is a useful first-principle method for singlet fission coupling, without the need to include the CT component explicitly. PMID:26263271
Ions in solutions: Determining their polarizabilities from first-principles
NASA Astrophysics Data System (ADS)
Molina, John J.; Lectez, Sébastien; Tazi, Sami; Salanne, Mathieu; Dufrêche, Jean-François; Roques, Jérôme; Simoni, Eric; Madden, Paul A.; Turq, Pierre
2011-01-01
Dipole polarizabilities of a series of ions in aqueous solutions are computed from first-principles. The procedure is based on the study of the linear response of the maximally localized Wannier functions to an applied external field, within density functional theory. For most monoatomic cations (Li ^+, Na ^+, K ^+, Rb ^+, Mg ^{2+}, Ca ^{2+} and Sr ^{2+}) the computed polarizabilities are the same as in the gas phase. For Cs ^+ and a series of anions (F ^-, Cl ^-, Br ^- and I ^-), environmental effects are observed, which reduce the polarizabilities in aqueous solutions with respect to their gas phase values. The polarizabilities of H ^+_(aq), OH ^-_(aq) have also been determined along an ab initio molecular dynamics simulation. We observe that the polarizability of a molecule instantaneously switches upon proton transfer events. Finally, we also computed the polarizability tensor in the case of a strongly anisotropic molecular ion, UO _2^{2+}. The results of these calculations will be useful in building interaction potentials that include polarization effects.
First-principles study of hydrogen storage materials
NASA Astrophysics Data System (ADS)
Ma, Zhu
2008-10-01
In this thesis, we use first-principles calculations to study the structural, electronic, and thermal properties of several complex hydrides. We investigate structural and electronic properties of Na-Li alanates. Although Na alanate can reversibly store H with Ti catalyst, its weight capacity needs to be improved. This can be accomplished by partial replacement of Na with lighter elements. We explore the structures of possible Na-Li alloy alanates, and study their phase stability. We also study the structural and thermal properties of Li/Mg/Li-Mg Amides/Imides. Current experimental results give a disordered model about the structure of Li-Mg Imide, in which the positions of Li and Mg are not specified. In addition the model gives a controversial composition stoichiometry. We try to resolve this controversy by searching for low-energy ordered phases. In the last part, we study the structural, energetic, and electronic properties of the La-Mg-Pd-H system. This quaternary system is another example of hydrogenation-induced metal-nonmetal transition without major reconstruction of metal host structure, and it is also with partial reversible H capacity. Experiment gives partially disordered H occupancy on two Wyckoff positions. Our calculation explains the structural and bonding characteristics observed in experiment.
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.
First-principles prediction of disordering tendencies in complex oxides
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.
Dissolved carbon in extreme conditions characterized by first principles simulations
NASA Astrophysics Data System (ADS)
Pan, Ding; Galli, Giulia
One key component to understanding carbon transport in the Earth interior is the determination of the molecular species formed when carbon bearing materials are dissolved in water at extreme conditions. We used first principles molecular dynamics to investigate oxidized carbon in water at high pressure (P) and high temperature (T), up to the conditions of the Earth's upper mantle. Contrary to popular geochemistry models assuming that CO2 is the major carbon species present in water, we found that most of the dissolved carbon at 10 GPa and 1000 K is in the form of solvated CO32- and HCO3-anions. We also found that ion pairing between alkali metal cations and CO32- or HCO3-anions is greatly affected by P-T conditions, decreasing with pressure along an isotherm. Our study shows that it is crucial to take into account the specific molecular structure of water under extreme conditions and the changes in hydrogen bonding occurring at high P and T, in order to predict chemical reactions in dissolved carbon. Our findings also shed light on possible reduction mechanisms of CO2 when it is geologically stored, depending on the availability of water. The work is supported by the Sloan Foundation through the Deep Carbon Observatory.
Properties of nanoscale dielectrics from first principles computations
NASA Astrophysics Data System (ADS)
Shi, Ning
In recent years, dielectric materials of nanoscale dimensions have aroused considerable interest. We mention two examples. First, in the semiconductor industry, in order to keep pace with Moore's law scaling, the thickness of gate oxide dielectric material is reaching nanoscale dimensions. Second, the high energy density capacitor industry is currently considering dielectric composites with a polymer host matrix filled with inorganic dielectric nanoparticles or polarizable organic molecules. The driving force for the former application is high dielectric constants (or high-k), and those for the latter are high-k and/or high dielectric breakdown strengths. Thus, it is important to characterize the electronic and dielectric properties of materials in the nano-regime, where surface and interface effects naturally play a dominant role. The primary goal of this work is to determine the extent to which such surface/interface effects modify the dielectric constants, band edges, and dielectric breakdown strengths of systems with at least one of their dimensions in the nano-regime. Towards that end, we have developed new computational methodologies at the first principles (density functional) level of theory. These methods have then been applied to several relevant and critical nanoscale systems, including Si:SiO2 and Si:HfO2 heterojunctions, and polymeric composites containing Cu-phthalocyanine and SiO2 nanoparticles.
Electrostatic engineering of strained ferroelectric perovskites from first principles
NASA Astrophysics Data System (ADS)
Cazorla, Claudio; Stengel, Massimiliano
2015-12-01
Design of novel artificial materials based on ferroelectric perovskites relies on the basic principles of electrostatic coupling and in-plane lattice matching. These rules state that the out-of-plane component of the electric displacement field and the in-plane components of the strain are preserved across a layered superlattice, provided that certain growth conditions are respected. Intense research is currently directed at optimizing materials functionalities based on these guidelines, often with remarkable success. Such principles, however, are of limited practical use unless one disposes of reliable data on how a given material behaves under arbitrary electrical and mechanical boundary conditions. Here we demonstrate, by focusing on the prototypical ferroelectrics PbTiO3 and BiFeO3 as test cases, how such information can be calculated from first principles in a systematic and efficient way. In particular, we construct a series of two-dimensional maps that describe the behavior of either compound (e.g., concerning the ferroelectric polarization and antiferrodistortive instabilities) at any conceivable choice of the in-plane lattice parameter, a , and out-of-plane electric displacement, D . In addition to being of immediate practical applicability to superlattice design, our results bring new insight into the complex interplay of competing degrees of freedom in perovskite materials and reveal some notable instances where the behavior of these materials depart from what naively is expected.
Oxygen transport in ceria: a first-principles study
NASA Astrophysics Data System (ADS)
Sergei, Simak
2012-02-01
Ceria (CeO2) is an important material for environmentally benign applications, ranging from solid-oxide fuel cells (SOFC) to oxygen storage [1-2]. The key characteristic needed to be improved is the mobility of oxygen ions. Optimization of ionic transport in ceria has been the topic of many studies. In particular, it has been discovered how the ionic conductivity in ceria might be improved by choosing the proper kind and concentration of dopants [3]. In this presentation we will approach the problem from a different direction by adjusting structural parameters of ceria via the change of external conditions. A systematic first-principles study of the energy landscape and kinetics of reduced ceria as a function of external parameters reveals a physically transparent way to improve oxygen transport in ceria. [4pt] [1] N. Skorodumova, S. Simak, B. Lundqvist, I. Abrikosov, and B. Johansson, Physical Review Letters 89, 14 (2002). [0pt] [2] A. Trovarelli, in Catalysis by Ceria and related materials (Imperial College Press, London, 2002). [0pt] [3] D. A. Andersson, S. I. Simak, N. V. Skorodumova, I. A.Abrikosov, and B. Johansson, Proceedings of the National Academy of Sciences of the United States of America 103, 3518 (2006).
First-principles prediction of a native ferroelectric metal
NASA Astrophysics Data System (ADS)
Iniguez, Jorge; Filippetti, Alessio; Fiorentini, Vincenzo; Ricci, Francesco; Delugas, Pietro
The possibility that metals may support ferroelectricity is an intriguing open issue. Over the years, various compounds have been referred to as ferroelectric metals, including non-centrosymmetric metals as well as ferroelectrics whose polar distortion survives moderate metallicity induced by doping or proximity. Yet, we think none of these systems embodies a truly ferroelectric metal with native switchable polarization and native metallicity coexisting in a single phase. Here we report a first-principles prediction of such a material. We show that the layered perovskite Bi5Ti5O17 has a non-zero density of states at the Fermi level and metal-like conductivity, as well as a spontaneous polarization in zero field. Further, we predict that the polarization of Bi5Ti5O17 is switchable both in principle (the material complies with the sufficient symmetry requirements) and in practice (in spite of being a metal, Bi5Ti5O17 can sustain a sizable potential drop along the polar direction, as needed to revert its polarization by application of an electric bias). Our results also reveal striking behaviors - such as the self screening mechanism at work in thin Bi5Ti5O17 layers - emerging from the intimate interplay between polar distortions and free carriers in such an exotic material. Supported by MIUR-PRIN, Fondazione Banco di Sardegna, FNR Luxembourg, MINECO-Spain, CINECA-ISCRA and CESGA.
First-principles stability study of clathrate hydrates under pressure
NASA Astrophysics Data System (ADS)
Thonhauser, Timo; Li, Qi; Kolb, Brian
2010-03-01
We present a first-principles DFT study of the structural stability of clathrate hydrates under pressure. These materials form under high pressure and low temperature and consist of polyhedral water cages that form an ice-like framework of hydrogen bonds. Clathrate hydrates can be filled with guest molecules such as methane or molecular hydrogen, in which case these materials and their stability are of interest for energy-storage solutions. Since the interactions between the water molecules themselves---but also between the water molecules and the guest molecules---is at least partly determined by van der Waals forces, we utilize the recently developed self-consistent van der Waals density functional vdW-DF (T. Thonhauser, V.R. Cooper, S. Li, A. Puzder, P. Hyldgaard, and D.C. Langreth, Phys. Rev. B 76, 125112 (2007)). For our simulations we consider the empty host lattice, as well as the host lattice filled with methane and molecular hydrogen, for pressures up to 1 GPa. Our results show that the system undergoes phase transitions from structure I to structure II and finally to structure H, in good agreement with experiment.
First principles simulations of fluid water: The radial distribution functions
NASA Astrophysics Data System (ADS)
Ortega, José; Lewis, James P.; Sankey, Otto F.
1997-03-01
We apply a recently developed first principles but simplified molecular dynamics method to the simulation of water at different conditions. The computational simplicity of this method allows its application to systems containing a significant number of molecules, yet still taking explicitly into account the quantum electronic structure of the system. In the present work we simulate a system of 216 H2O molecules with periodic boundary conditions at two different densities (ρ=1.0 g/cm3 and ρ=0.72 g/cm3 and temperatures ranging from ˜300 K to ˜580 K. The effect of density and temperature on the structure of water is analyzed by means of the partial radial distribution functions gOO, gOH and gHH . We find an important reduction of the hydrogen-bond peak for water at the supercritical conditions ρ= 0.72 g/cm3, T=580 K, in good agreement with recent experimental results.
Safeguards First Principles Initiative at the Nevada Test Site
Geneva Johnson
2007-07-08
The Material Control and Accountability (MC&A) program at the Nevada Test Site (NTS) was selected as a test bed for the Safeguards First Principles Initiative (SFPI). The implementation of the SFPI is evaluated using the system effectiveness model and the program is managed under an approved MC&A Plan. The effectiveness model consists of an evaluation of the critical elements necessary to detect, deter, and/or prevent the theft or diversion of Special Nuclear Material (SNM). The modeled results indicate that the MC&A program established under this variance is still effective, without creating unacceptable risk. Extensive performance testing is conducted through the duration of the pilot to ensure the protection system is effective and no material is at an unacceptable risk. The pilot was conducted from January 1, 2007, through May 30, 2007. This paper will discuss the following activities in association with SFPI: 1. Development of Timeline 2. Crosswalk of DOE Order and SFPI 3. Peer Review 4. Deviation 5. MC&A Plan and Procedure changes 6. Changes implemented at NTS 7. Training 8. Performance Test
Transport Properties of Nanoscale Materials by First-principles Calculations
NASA Astrophysics Data System (ADS)
Mizuseki, Hiroshi; Belosludov, Rodion V.; Lee, S.-U.; Kawazoe, Yoshiyuki
2009-03-01
Molecular devices are potential candidates for the next step towards nanoelectronic technology. Our group has covered a wide range of nanoscale wires, which have potential application in molecular electronics using first-principles calculations and nonequilibrium Green's function formalism [1]. Our target materials are supramolecular enamel wires (covered wires) [2], connection between organic molecules and metal electrodes, self-assembled nanowires on silicon surface [3], porphyrin [4], phthalocyanine, metallocene [5], fused-ring thiophene molecules, length dependence of conductance in alkanedithiols and so on. Namely, we have investigated a relationship of the energy levels of delocalized frontier orbitals (HOMO and LUMO) and Fermi level of metal electrodes and estimate the electronic transport properties through atomic and molecular wires using Green's function approach. References [1] http://www-lab.imr.edu/˜mizuseki/nanowire.html [2] R. V. Belosludov, A. A. Farajian, H. Baba, H. Mizuseki, and Y. Kawazoe, Jpn. J. Appl. Phys., 44, 2823 (2005). [3] R. V. Belosludov, A. A. Farajian, H. Mizuseki, K. Miki, and Y. Kawazoe, Phys. Rev. B, 75, 113411 (2007). [4] S.-U. Lee, R. V. Belosludov, H. Mizuseki, and Y. Kawazoe, Small 4 (2008) 962. [5] S.-U Lee, R. V. Belosludov, H. Mizuseki, and Y. Kawazoe, J. Phys. Chem. C. 111 (2007) 15397.
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.
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.
First principles calculation of finite temperature magnetism in Ni
NASA Astrophysics Data System (ADS)
Eisenbach, Markus; Yin, Junqi; Nicholson, Don M.; Li, Ying Wai
2013-03-01
We harnesses the computational power of massively parallel computers to calculate finite temperature magnetic properties by combining classical Monte-Carlo calculations with our first principles multiple scattering electronic structure code (LSMS) for constrained magnetic states. Our previous calculations of Fe and Fe3 C [J. Appl. Phys. 109, 07E138 (2011)] only considered fluctuations in the local moment directions. Recent advances, both in the understanding of the Wang-Landau method used in our calculations [Phys. Rev. E 84, 065702(R) (2011)] and more powerful computing resources have enabled us to investigate Ni where the fluctuation in the magnitude of the local magnetic moments is of importance equal to their directional fluctuations. Here we will present our recent results for Ni that axpands our method to an even wider class of 3d element based ferromagnets. This research was sponsored by the Offices of Basic Energy Science (M.E. and D.M.N) and the Office of Advanced Computing Research (J.Y. and Y.W.L) of the US Department of Energy. This research used resources of the Oak Ridge Leadership Computing Facility at Oak Ridge National Laboratory, which is supported by the Office of Science of the Department of Energy under contract DE-AC05-00OR22725.
Designing substrates for silicene and germanene: First-principles calculations
NASA Astrophysics Data System (ADS)
Chen, M. X.; Zhong, Z.; Weinert, M.
2016-08-01
We propose a guideline for exploring substrates that stabilize the monolayer honeycomb structure of silicene and germanene while simultaneously preserving the Dirac states: in addition to having a strong binding energy to the monolayer, a suitable substrate should be a large-gap semiconductor with a proper work function such that the Dirac point lies in the gap and far from the substrate states when their bands align. We illustrate our idea by performing first-principles calculations for silicene and germanene on the Al-terminated (0001) surface of Al2O3 . The overlaid monolayers on Al-terminated Al2O3 (0001) retain the main structural profile of the low-buckled honeycomb structure via a binding energy comparable to the one between silicene and Ag(111). An unfolded band structure derived from the k -projection method reveals that a gapped Dirac cone is formed at the K point due to the structural distortion and the interaction with the substrate. The gaps of 0.4 and 0.3 eV, respectively, for the supported silicene and germanene suggest that they may have potential applications in nanoelectronics.
First-Principles Investigation of the Electronic Properties of Interfaces
NASA Astrophysics Data System (ADS)
Lucking, Michael C.
Modern technology depends on the interfaces between materials. Nanomaterials and 2D systems are also promising for future energy and electronics applications. The much larger surface to volume ration of these systems compared to their bulk counterparts makes the interface properties even more important. Understanding the properties of interfaces is vital for technological advancement. First-principles calculations utilizing Density Functional Theory (DFT) can be applied to interfaces and nanostructures to improve the understanding of these systems. I have used these methods to investigate several systems with energy and electronics applications. Several aspects of solar water splitting have been examined, leading to a method of calculating redox levels as well as alignments for amorphous materials. A derailed understanding of the hole transfer reaction on surfaces has also been developed, as well as an understanding of band edge engineering in the promising photocatalyst CoO. In the field if electronics, edge engineering possibilities have been discovered in MoS2, also leading to a general electron counting method that is widely applicable. The nature of the insulating state as well as a model for the transition to the superconducting state has been proposed in (Li,Fe)OHFeSe. The interface between STO and FeSe has also been investigated and the issues are discussed.
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.
Auger recombination in InN from first principles
NASA Astrophysics Data System (ADS)
McAllister, Andrew; Kioupakis, Emmanouil
Group-III Nitride materials are used in numerous electronic and optoelectronic devices including solid-state lighting, energy conversion, sensor technologies, and high-power electronics. Indium nitride in particular is interesting for fast electronics and optoelectronics in the infrared. Auger recombination is a non-radiative carrier recombination process that would limit the efficiency of these devices. The small band gap (0.7 eV) and the high intrinsic free-electron concentrations in InN possibly make Auger recombination particularly important in this material. We used first-principles computational methods to determine the Auger recombination rates in InN. Our results suggest that direct Auger recombination is dominant in this material and that phonon-assisted Auger processes are not as important as in wider-gap nitrides such as GaN. This research was supported by the National Science Foundation CAREER award through Grant No. DMR-1254314. Computational resources were provided by the DOE NERSC facility.
Thermal conductivity of silicene from first-principles
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.
First-principles pressure-temperature phase diagrams in metals
Moriarty, J.A.
1993-07-01
Using interatomic potentials derived from first-principles generalized pseudopotential theory, finite-temperature phase transitions in both simple and transition metals can be studied through a combination of analytic statistical methods and molecular-dynamics simulation. In the prototype simple metal-Mg, where volume and pair forces adequately describe the energetics, a complete and accurate phase diagram has thereby been obtained to 60 GPa. A rapidly temperature-dependent hcp-bcc phase line is predicted which ends in a triple point on the melting curve near 4 GPa. In central transition metals such as Mo or Fe, on the other hand, the energetics are complicated by d-state interactions which give rise to both many-body angular forces and enhanced electron-thermal contributions. We have made a detailed study of these phenomena and their impact on melting in the prototype case of Mo and a full melting curve to 2 Mbar has been obtained. In the case of Fe, we are examining the high-pressure phase diagram and the question of whether or not there exists a high-pressure, high-temperature solid bcc phase, as has been speculated. To date, we have shown that the bcc structure is both thermodynamically and mechanically unstable at high pressure and zero temperature, with a large and increasing bcc-hcp energy difference under compression.
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.
Theoretical ultra-fast spectroscopy in transition metal dichalcogenides
NASA Astrophysics Data System (ADS)
Molina-Sanchez, Alejandro; Sangalli, Davide; Marini, Andrea; Wirtz, Ludger
Semiconducting 2D-materials like the transition metal dichalcogenides (TMDs) MoS2, MoSe2, WS2, WSe2 are promising alternatives to graphene for designing novel opto-electronic devices. The strong spin-orbit interaction along with the breaking of inversion symmetry in single-layer TMDs allow using the valley-index as a new quantum number. The practical use of valley physics depends on the lifetimes of valley-polarized excitons which are affected by scattering at phonons, impurities and by carrier-carrier interactions. The carrier dynamics can be monitored using ultra-fast spectroscopies such as pump-probe experiments. The carrier dynamics is simulated using non-equilibrium Green's function theory in an ab-initio framework. We include carrier relaxation through electron-phonon interaction. We obtain the transient absorption spectra of single-layer TMD and compare our simulations with recent pump-probe experiments
Kumar, Ravhi S; Svane, A; Vaitheeswaran, G; Zhang, Y; Kanchana, V; Hofmann, M; Campbell, S J; Xiao, Yuming; Chow, P; Chen, Changfeng; Zhao, Yusheng; Cornelius, Andrew L
2013-01-08
The pressure-induced valence change of Yb in YbMn_{2}Ge_{2} has been studied by high pressure inelastic X-ray emission and absorption spectroscopy in the partial fluorescence yield mode up to 30 GPa. The crystal structure of YbMn_{2}Ge_{2} has been investigated by high pressure powder X-ray diffraction experiments up to 40 GPa. The experimental investigations have been complemented by first principles density functional theoretical calculations using the generalized gradient approximation with an evolutionary algorithm for structural determination. The Yb valence and magnetic structures have been calculated using the self-interaction corrected local spin density approximation. The X-ray emission results indicate a sharp increase of Yb valence from v = 2.42(2) to v = 2.75(3) around 1.35 GPa, and Yb reaches a near trivalent state (v = 2.95(3)) around 30 GPa. Further, a new monoclinic P1 type high pressure phase is found above 35 GPa; this structure is characterized by the Mn layer of the ambient (I4/mmm) structure transforming into a double layer. The theoretical calculations yield an effective valence of v = 2.48 at ambient pressure in agreement with experiment, although the pure trivalent state is attained theoretically at significantly higher pressures (above 40 GPa).
First-principles study on oxidation of Ge and its interface electronic structures
NASA Astrophysics Data System (ADS)
Ono, Tomoya; Saito, Shoichiro; Iwase, Shigeru
2016-08-01
We review a series of first-principles studies on the defect generation mechanism and electronic structures of the Ge/GeO2 interface. Several experimental and theoretical studies proved that Si atoms at the Si/SiO2 interface are emitted to release interface stress. In contrast, total-energy calculation reveals that Ge atoms at the Ge/GeO2 interface are hardly emitted, resulting in the low trap density. Even if defects are generated, those at the Ge/GeO2 interface are found to behave differently from those at the Si/SiO2 interface. The states attributed to the dangling bonds at the Ge/GeO2 interface lie below the valence-band maximum of Ge, while those at the Si/SiO2 interface generate the defect state within the band gap of Si. First-principles electron-transport calculation elucidates that this characteristic behavior of the defect states is relevant to the difference in the leakage current through the Si/SiO2 and Ge/GeO2 interfaces.
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.
The Role of the Cluster Variation Method in the First Principles Calculation of Phase Diagrams
NASA Astrophysics Data System (ADS)
Sanchez, J. M.; Becker, J. D.
The Cluster Variation Method (CVM) proposed by Professor Kikuchi to study cooperative phenomena in solids has played a major role in the development of phenomenological and first principles theories of phase equilibrium. The CVM provides an accurate and rigorous framework for the study of the configurational thermodynamics of alloys. As such, the method has been a powerful tool in the quest for insight into the main contributions to alloy phase stability and in the interpretation of complex and extensive experimental data. The early successes of the CVM have also been instrumental in the development of ab-initio methods for the reliable description of phase equilibrium and, in particular, of phase diagrams. These new developments have relied heavily on the CVM and on the theoretical ideas put forth over 40 years ago by Professor Kikuchi. Here, we review the use of the CVM in the first-principles computation of phase diagrams, and present results for the Zr-Nb system. The theory that emerges is one that incorporates the calculation of total energies in the local density approximation, configurational entropies using the CVM, and vibrational modes in the Debye-Grüneisen approximation.
Atta-Fynn, Raymond; Biswas, Parthapratim
2009-07-01
Localized basis ab initio molecular dynamics simulation within the density functional framework has been used to generate realistic configurations of amorphous silicon carbide (a-SiC). Our approach consists of constructing a set of smart initial configurations that conform to essential geometrical and structural aspects of the materials obtained from experimental data, which is subsequently driven via a first-principles force field to obtain the best solution in a reduced solution space. A combination of a priori information (primarily structural and topological) along with the ab initio optimization of the total energy makes it possible to model a large system size (1000 atoms) without compromising the quantum mechanical accuracy of the force field to describe the complex bonding chemistry of Si and C. The structural, electronic and vibrational properties of the models have been studied and compared to existing theoretical models and available data from experiments. We demonstrate that the approach is capable of producing large, realistic configurations of a-SiC from first-principles simulation that display its excellent structural and electronic properties. Our study reveals the presence of predominant short range order in the material originating from heteronuclear Si-C bonds with a coordination defect concentration as small as 5% and a chemical disorder parameter of about 8%. PMID:21828477
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