Ab initio derivation of model energy density functionals
International Nuclear Information System (INIS)
Dobaczewski, Jacek
2016-01-01
I propose a simple and manageable method that allows for deriving coupling constants of model energy density functionals (EDFs) directly from ab initio calculations performed for finite fermion systems. A proof-of-principle application allows for linking properties of finite nuclei, determined by using the nuclear nonlocal Gogny functional, to the coupling constants of the quasilocal Skyrme functional. The method does not rely on properties of infinite fermion systems but on the ab initio calculations in finite systems. It also allows for quantifying merits of different model EDFs in describing the ab initio results. (letter)
Ab initio pseudopotential theory
International Nuclear Information System (INIS)
Yin, M.T.; Cohen, M.L.
1982-01-01
The ab initio norm-conserving pseudopotential is generated from a reference atomic configuration in which the pseudoatomic eigenvalues and wave functions outside the core region agree with the corresponding ab initio all-electron results within the density-functional formalism. This paper explains why such pseudopotentials accurately reproduce the all-electron results in both atoms and in multiatomic systems. In particular, a theorem is derived to demonstrate the energy- and perturbation-independent properties of ab initio pseudopotentials
Ab Initio Predictions of Structures and Densities of Energetic Solids
National Research Council Canada - National Science Library
Rice, Betsy M; Sorescu, Dan C
2004-01-01
We have applied a powerful simulation methodology known as ab initio crystal prediction to assess the ability of a generalized model of CHNO intermolecular interactions to predict accurately crystal...
The ab-initio density matrix renormalization group in practice.
Olivares-Amaya, Roberto; Hu, Weifeng; Nakatani, Naoki; Sharma, Sandeep; Yang, Jun; Chan, Garnet Kin-Lic
2015-01-21
The ab-initio density matrix renormalization group (DMRG) is a tool that can be applied to a wide variety of interesting problems in quantum chemistry. Here, we examine the density matrix renormalization group from the vantage point of the quantum chemistry user. What kinds of problems is the DMRG well-suited to? What are the largest systems that can be treated at practical cost? What sort of accuracies can be obtained, and how do we reason about the computational difficulty in different molecules? By examining a diverse benchmark set of molecules: π-electron systems, benchmark main-group and transition metal dimers, and the Mn-oxo-salen and Fe-porphine organometallic compounds, we provide some answers to these questions, and show how the density matrix renormalization group is used in practice.
The ab-initio density matrix renormalization group in practice
Energy Technology Data Exchange (ETDEWEB)
Olivares-Amaya, Roberto; Hu, Weifeng; Sharma, Sandeep; Yang, Jun; Chan, Garnet Kin-Lic [Department of Chemistry, Princeton University, Princeton, New Jersey 08544 (United States); Nakatani, Naoki [Department of Chemistry, Princeton University, Princeton, New Jersey 08544 (United States); Catalysis Research Center, Hokkaido University, Kita 21 Nishi 10, Sapporo, Hokkaido 001-0021 (Japan)
2015-01-21
The ab-initio density matrix renormalization group (DMRG) is a tool that can be applied to a wide variety of interesting problems in quantum chemistry. Here, we examine the density matrix renormalization group from the vantage point of the quantum chemistry user. What kinds of problems is the DMRG well-suited to? What are the largest systems that can be treated at practical cost? What sort of accuracies can be obtained, and how do we reason about the computational difficulty in different molecules? By examining a diverse benchmark set of molecules: π-electron systems, benchmark main-group and transition metal dimers, and the Mn-oxo-salen and Fe-porphine organometallic compounds, we provide some answers to these questions, and show how the density matrix renormalization group is used in practice.
Chan, Garnet Kin-Lic; Keselman, Anna; Nakatani, Naoki; Li, Zhendong; White, Steven R.
2016-07-01
Current descriptions of the ab initio density matrix renormalization group (DMRG) algorithm use two superficially different languages: an older language of the renormalization group and renormalized operators, and a more recent language of matrix product states and matrix product operators. The same algorithm can appear dramatically different when written in the two different vocabularies. In this work, we carefully describe the translation between the two languages in several contexts. First, we describe how to efficiently implement the ab initio DMRG sweep using a matrix product operator based code, and the equivalence to the original renormalized operator implementation. Next we describe how to implement the general matrix product operator/matrix product state algebra within a pure renormalized operator-based DMRG code. Finally, we discuss two improvements of the ab initio DMRG sweep algorithm motivated by matrix product operator language: Hamiltonian compression, and a sum over operators representation that allows for perfect computational parallelism. The connections and correspondences described here serve to link the future developments with the past and are important in the efficient implementation of continuing advances in ab initio DMRG and related algorithms.
Song, Lingchun; Han, Jaebeom; Lin, Yen-lin; Xie, Wangshen; Gao, Jiali
2009-10-29
The explicit polarization (X-Pol) method has been examined using ab initio molecular orbital theory and density functional theory. The X-Pol potential was designed to provide a novel theoretical framework for developing next-generation force fields for biomolecular simulations. Importantly, the X-Pol potential is a general method, which can be employed with any level of electronic structure theory. The present study illustrates the implementation of the X-Pol method using ab initio Hartree-Fock theory and hybrid density functional theory. The computational results are illustrated by considering a set of bimolecular complexes of small organic molecules and ions with water. The computed interaction energies and hydrogen bond geometries are in good accord with CCSD(T) calculations and B3LYP/aug-cc-pVDZ optimizations.
DEFF Research Database (Denmark)
Abild-Pedersen, Frank; Nørskov, Jens Kehlet; Rostrup-Nielsen, Jens
2006-01-01
Mechanisms and energetics of graphene growth catalyzed by nickel nanoclusters were studied using ab initio density functional theory calculations. It is demonstrated that nickel step-edge sites act as the preferential growth centers for graphene layers on the nickel surface. Carbon is transported......, and it is argued how these processes may lead to different nanofiber structures. The proposed growth model is found to be in good agreement with previous findings....
Indian Academy of Sciences (India)
mechanisms of two molecular crystals: An ab initio molecular dynamics ... for Computation in Molecular and Materials Science and Department of Chemistry, School of ..... NSAF Foundation of National Natural Science Foun- ... Matter 14 2717.
Using ab initio 'data' to accurately determine the fourth density virial coefficient of helium
International Nuclear Information System (INIS)
Moldover, Michael R.; McLinden, Mark O.
2010-01-01
We combine accurate ab initio calculations of the second and third density virial coefficients, B(T) and C(T), of 4 He with measurements of its (p-ρ-T) behavior to determine the fourth density virial coefficient D(T). The measurements were made with a two-sinker, magnetic-suspension densimeter at pressures up to 38 MPa. The measurements on isotherms from T = 223 K to T = 323 K were previously published; new measurements from T = 323 K to T = 500 K are presented here. On each isotherm, a regression of the virial expansion was constrained to the ab initio values of B(T) and C(T); the regression determined D(T) as well as two apparatus-dependent parameters that compensated for systematic errors in the measurements. The percentage uncertainties of D(T) ranged from 2.6% at T = 223 K to 9.5% at T = 400 K to 24.7% at T = 500 K, where these uncertainties are expanded uncertainties with coverage factor of k = 2 corresponding to a 95% confidence interval. These uncertainties are 1/6th of the uncertainty obtained without the ab initio values of B(T) and C(T). The apparatus-dependent parameters can be used to calibrate the densimeter, and this will reduce the uncertainty of other measurements made with this two-sinker densimeter. The new values of D(T) will find applications in accurate gas metrology, such as a primary pressure standard based on the refractive index of helium.
Faas, S.; Snijders, Jaap; van Lenthe, J.H.; HernandezLaguna, A; Maruani, J; McWeeny, R; Wilson, S
2000-01-01
In this paper we present the first application of the ZORA (Zeroth Order Regular Approximation of the Dirac Fock equation) formalism in Ab Initio electronic structure calculations. The ZORA method, which has been tested previously in the context of Density Functional Theory, has been implemented in
International Nuclear Information System (INIS)
Moradian, Rostam; Behzad, Somayeh; Chegel, Raad
2009-01-01
We present the results of ab initio density functional theory calculations on the energetic, and geometric and electronic structure of Li-intercalated (6,6) silicon carbide nanotube (SiCNT) bundles. Our results show that intercalation of lithium leads to the significant changes in the geometrical structure. The most prominent effect of Li intercalation on the electronic band structure is a shift of the Fermi energy which occurs as a result of charge transfer from lithium to the SiCNTs. All the Li-intercalated (6,6) SiCNT bundles are predicted to be metallic representing a substantial change in electronic properties relative to the undoped bundle, which is a wide band gap semiconductor. Both inside of the nanotube and the interstitial space are susceptible for intercalation. The present calculations suggest that the SiCNT bundle is a promising candidate for the anode material in battery applications.
Moradian, Rostam; Behzad, Somayeh; Chegel, Raad
2008-10-01
By using ab initio density functional theory the structural and electronic properties of isolated and bundled (8,0) and (6,6) silicon carbide nanotubes (SiCNTs) are investigated. Our results show that for such small diameter nanotubes the inter-tube interaction causes a very small radial deformation, while band splitting and reduction of the semiconducting energy band gap are significant. We compared the equilibrium interaction energy and inter-tube separation distance of (8,0) SiCNT bundle with (10,0) carbon nanotube (CNT) bundle where they have the same radius. We found that there is a larger inter-tube separation and weaker inter-tube interaction in the (8,0) SiCNT bundle with respect to (10,0) CNT bundle, although they have the same radius.
Moradian, Rostam; Behzad, Somayeh; Chegel, Raad
2009-06-01
We present the results of ab initio density functional theory calculations on the energetic, and geometric and electronic structure of Li-intercalated ( 6,6) silicon carbide nanotube (SiCNT) bundles. Our results show that intercalation of lithium leads to the significant changes in the geometrical structure. The most prominent effect of Li intercalation on the electronic band structure is a shift of the Fermi energy which occurs as a result of charge transfer from lithium to the SiCNTs. All the Li-intercalated ( 6,6) SiCNT bundles are predicted to be metallic representing a substantial change in electronic properties relative to the undoped bundle, which is a wide band gap semiconductor. Both inside of the nanotube and the interstitial space are susceptible for intercalation. The present calculations suggest that the SiCNT bundle is a promising candidate for the anode material in battery applications.
International Nuclear Information System (INIS)
Moradian, Rostam; Behzad, Somayeh; Chegel, Raad
2008-01-01
By using ab initio density functional theory the structural and electronic properties of isolated and bundled (8,0) and (6,6) silicon carbide nanotubes (SiCNTs) are investigated. Our results show that for such small diameter nanotubes the inter-tube interaction causes a very small radial deformation, while band splitting and reduction of the semiconducting energy band gap are significant. We compared the equilibrium interaction energy and inter-tube separation distance of (8,0) SiCNT bundle with (10,0) carbon nanotube (CNT) bundle where they have the same radius. We found that there is a larger inter-tube separation and weaker inter-tube interaction in the (8,0) SiCNT bundle with respect to (10,0) CNT bundle, although they have the same radius
Energy Technology Data Exchange (ETDEWEB)
Moradian, Rostam [Physics Department, Faculty of Science, Razi University, Kermanshah (Iran, Islamic Republic of); Nano Science and Technology Research Center, Razi University, Kermanshah (Iran, Islamic Republic of); Computational Physical Science Research Laboratory, Department of Nano Science, Institute for Studies in Theoretical Physics and Mathematics (IPM), PO Box 19395-5531, Tehran (Iran, Islamic Republic of)], E-mail: moradian.rostam@gmail.com; Behzad, Somayeh; Chegel, Raad [Physics Department, Faculty of Science, Razi University, Kermanshah (Iran, Islamic Republic of)
2009-06-15
We present the results of ab initio density functional theory calculations on the energetic, and geometric and electronic structure of Li-intercalated (6,6) silicon carbide nanotube (SiCNT) bundles. Our results show that intercalation of lithium leads to the significant changes in the geometrical structure. The most prominent effect of Li intercalation on the electronic band structure is a shift of the Fermi energy which occurs as a result of charge transfer from lithium to the SiCNTs. All the Li-intercalated (6,6) SiCNT bundles are predicted to be metallic representing a substantial change in electronic properties relative to the undoped bundle, which is a wide band gap semiconductor. Both inside of the nanotube and the interstitial space are susceptible for intercalation. The present calculations suggest that the SiCNT bundle is a promising candidate for the anode material in battery applications.
Gennari, Michael; Vorabbi, Matteo; Calci, Angelo; Navrátil, Petr
2018-03-01
Background: The nuclear optical potential is a successful tool for the study of nucleon-nucleus elastic scattering and its use has been further extended to inelastic scattering and other nuclear reactions. The nuclear density of the target nucleus is a fundamental ingredient in the construction of the optical potential and thus plays an important role in the description of the scattering process. Purpose: In this paper we derive a microscopic optical potential for intermediate energies using ab initio translationally invariant nonlocal one-body nuclear densities computed within the no-core shell model (NCSM) approach utilizing two- and three-nucleon chiral interactions as the only input. Methods: The optical potential is derived at first order within the spectator expansion of the nonrelativistic multiple scattering theory by adopting the impulse approximation. Nonlocal nuclear densities are derived from the NCSM one-body densities calculated in the second quantization. The translational invariance is generated by exactly removing the spurious center-of-mass (COM) component from the NCSM eigenstates. Results: The ground-state local and nonlocal densities of He 4 ,6 ,8 , 12C, and 16O are calculated and applied to optical potential construction. The differential cross sections and the analyzing powers for the elastic proton scattering off these nuclei are then calculated for different values of the incident proton energy. The impact of nonlocality and the COM removal is discussed. Conclusions: The use of nonlocal densities has a substantial impact on the differential cross sections and improves agreement with experiment in comparison to results generated with the local densities especially for light nuclei. For the halo nuclei 6He and 8He, the results for the differential cross section are in a reasonable agreement with the data although a more sophisticated model for the optical potential is required to properly describe the analyzing powers.
Hafner, Jürgen
2010-09-29
During the last 20 years computer simulations based on a quantum-mechanical description of the interactions between electrons and atomic nuclei have developed an increasingly important impact on materials science, not only in promoting a deeper understanding of the fundamental physical phenomena, but also enabling the computer-assisted design of materials for future technologies. The backbone of atomic-scale computational materials science is density-functional theory (DFT) which allows us to cast the intractable complexity of electron-electron interactions into the form of an effective single-particle equation determined by the exchange-correlation functional. Progress in DFT-based calculations of the properties of materials and of simulations of processes in materials depends on: (1) the development of improved exchange-correlation functionals and advanced post-DFT methods and their implementation in highly efficient computer codes, (2) the development of methods allowing us to bridge the gaps in the temperature, pressure, time and length scales between the ab initio calculations and real-world experiments and (3) the extension of the functionality of these codes, permitting us to treat additional properties and new processes. In this paper we discuss the current status of techniques for performing quantum-based simulations on materials and present some illustrative examples of applications to complex quasiperiodic alloys, cluster-support interactions in microporous acid catalysts and magnetic nanostructures.
Nag, Abhinav; Kumari, Anuja; Kumar, Jagdish
2018-05-01
We have investigated structural, electronic and transport properties of the alkali metals using ab-initio density functional theory. The electron energy dispersions are found parabolic free electron like which is expected for alkali metals. The lattice constants for all the studied metals are also in good agreement within 98% with experiments. We have further computed their transport properties using semi-classical Boltzmann transport equations with special focus on electrical and thermal conductivity. Our objective was to obtain Wiedemann-Franz law and hence Lorenz number. The motivation to do these calculations is to see that how the incorporation of different interactions such as electron-lattice, electron-electron interaction affect the Wiedeman-Franz law. By solving Boltzmann transport equations, we have obtained electrical conductivity (σ/τ) and thermal conductivity (κ0 /τ) at different temperatures and then calculated Lorenz number using L = κ0 /(σT). The obtained value of Lorenz number has been found to match with value derived for free electron Fermi gas 2.44× 10-8 WΩK-2. Our results prove that the Wiedemann-Franz law as derived for free electron gas does not change much for alkali metals, even when one incorporates interaction of electrons with atomic nuclei and other electrons. However, at lower temperatures, the Lorenz number, was found to be deviating from its theoretical value.
Moradian, Rostam; Behzad, Somayeh; Chegel, Raad
2009-12-01
By using ab initio density functional theory, the structural and electronic properties of (n,n)@(11,11) double-walled silicon carbide nanotubes (SiCNTs) are investigated. Our calculations reveal the existence of an energetically favorable double-walled nanotube whose interwall distance is about 4.3 Å. Interwall spacing and curvature difference are found to be essential for the electronic states around the Fermi level.
International Nuclear Information System (INIS)
Ng, T Y; Yeak, S H; Liew, K M
2008-01-01
A multiscale technique is developed that couples empirical molecular dynamics (MD) and ab initio density functional theory (DFT). An overlap handshaking region between the empirical MD and ab initio DFT regions is formulated and the interaction forces between the carbon atoms are calculated based on the second-generation reactive empirical bond order potential, the long-range Lennard-Jones potential as well as the quantum-mechanical DFT derived forces. A density of point algorithm is also developed to track all interatomic distances in the system, and to activate and establish the DFT and handshaking regions. Through parallel computing, this multiscale method is used here to study the dynamic behavior of single-walled carbon nanotubes (SWCNTs) under asymmetrical axial compression. The detection of sideways buckling due to the asymmetrical axial compression is reported and discussed. It is noted from this study on SWCNTs that the MD results may be stiffer compared to those with electron density considerations, i.e. first-principle ab initio methods
Energy Technology Data Exchange (ETDEWEB)
Borges, P. D., E-mail: pdborges@gmail.com, E-mail: lscolfaro@txstate.edu; Scolfaro, L., E-mail: pdborges@gmail.com, E-mail: lscolfaro@txstate.edu [Department of Physics, Texas State University, San Marcos, Texas 78666 (United States)
2014-12-14
The thermoelectric properties of indium nitride in the most stable wurtzite phase (w-InN) as a function of electron and hole concentrations and temperature were studied by solving the semiclassical Boltzmann transport equations in conjunction with ab initio electronic structure calculations, within Density Functional Theory. Based on maximally localized Wannier function basis set and the ab initio band energies, results for the Seebeck coefficient are presented and compared with available experimental data for n-type as well as p-type systems. Also, theoretical results for electric conductivity and power factor are presented. Most cases showed good agreement between the calculated properties and experimental data for w-InN unintentionally and p-type doped with magnesium. Our predictions for temperature and concentration dependences of electrical conductivity and power factor revealed a promising use of InN for intermediate and high temperature thermoelectric applications. The rigid band approach and constant scattering time approximation were utilized in the calculations.
Ab initio joint density-functional theory of solvated electrodes, with model and explicit solvation
Arias, Tomas
2015-03-01
First-principles guided design of improved electrochemical systems has the potential for great societal impact by making non-fossil-fuel systems economically viable. Potential applications include improvements in fuel-cells, solar-fuel systems (``artificial photosynthesis''), supercapacitors and batteries. Economical fuel-cell systems would enable zero-carbon footprint transportation, solar-fuel systems would directly convert sunlight and water into hydrogen fuel for such fuel-cell vehicles, supercapacitors would enable nearly full recovery of energy lost during vehicle braking thus extending electric vehicle range and acceptance, and economical high-capacity batteries would be central to mitigating the indeterminacy of renewable resources such as wind and solar. Central to the operation of all of the above electrochemical systems is the electrode-electrolyte interface, whose underlying physics is quite rich, yet remains remarkably poorly understood. The essential underlying technical challenge to the first principles studies which could explore this physics is the need to properly represent simultaneously both the interaction between electron-transfer events at the electrode, which demand a quantum mechanical description, and multiscale phenomena in the liquid environment such as the electrochemical double layer (ECDL) and its associated shielding, which demand a statistical description. A direct ab initio approach to this challenge would, in principle, require statistical sampling and thousands of repetitions of already computationally demanding quantum mechanical calculations. This talk will begin with a brief review of a recent advance, joint density-functional theory (JDFT), which allows for a fully rigorous and, in principle, exact representation of the thermodynamic equilibrium between a system described at the quantum-mechanical level and a liquid environment, but without the need for costly sampling. We then shall demonstrate how this approach applies in
Thiessen, P. A.; Treder, H.-J.
Der gegenwärtige Stand der physikalischen Erkenntnis, in Sonderheit die Atomistik und die Quantentheorie, ermöglicht (in wohldefinierten Energie-Bereichen) eine ab initio-Berechnung aller physikalischen und chemischen Prozesse und Strukturen. Die Schrödinger-Gleichung erlaubt zusammen mit den Prinzipien der Quantenstatistik (Pauli-Prinzip) aus dem Planckschen Wirkungsquantum h und den atomischen Konstanten die Berechnung aller Energieumsätze, Zeitabläufe etc., die insbesondere die chemische Physik bestimmen. Die Rechenresultate gelten auch quantitativ bis auf die unvermeidliche Stochastik.Die ab initio-Berechnungen korrespondieren einerseits und sind andererseits komplementär zu den auf den Methoden der theoretischen Chemie und der klassischen Thermodynamik beruhenden Ergebnissen ex eventu. Die theoretische Behandlung ab initio führt zu mathematischen Experimenten, die die Laboratoriums-Experimente ergänzen oder auch substituieren.Translated AbstractAb initio vel ex eventuThe present state of physical knowledge, in peculiar atomistic and quantum theory, makes an ab initio calculation of all physical and chemical processes and structures possible (in well defined reaches of energy). The Schrödinger equation together with the principles of quantum statistics (Pauli principle) permits from the Planck and atomistic constants to calculate all exchanges of energy, courses of time, etc. which govern chemical physics. The calculated results are valid even quantitatively apart from the unavoidable stochastics.These ab initio calculations on the one hand correspond and are on the other complimentary to results ex eventu based on the methods of theoretical chemistry and classical thermodynamics. Theoretical treatment ab initio leads to mathematical experiments which add to or even substitute experiments in the laboratory.
DEFF Research Database (Denmark)
Møgelhøj, Andreas; Kelkkanen, Kari André; Wikfeldt, K Thor
2011-01-01
The structure of liquid water at ambient conditions is studied in ab initio molecular dynamics simulations in the NVE ensemble using van der Waals (vdW) density-functional theory, i.e., using the new exchange-correlation functionals optPBE-vdW and vdW-DF2, where the latter has softer nonlocal...... protocol could cause the deviation. An O-O PCF consisting of a linear combination of 70% from vdW-DF2 and 30% from low-density liquid water, as extrapolated from experiments, reproduces near-quantitatively the experimental O-O PCF for ambient water. This suggests the possibility that the new functionals...... shows some resemblance with experiment for high-density water ( Soper , A. K. and Ricci , M. A. Phys. Rev. Lett. 2000 , 84 , 2881 ), but not directly with experiment for ambient water. Considering the accuracy of the new functionals for interaction energies, we investigate whether the simulation...
Ab Initio molecular dynamics with excited electrons
Alavi, A.; Kohanoff, J.; Parrinello, M.; Frenkel, D.
1994-01-01
A method to do ab initio molecular dynamics suitable for metallic and electronically hot systems is described. It is based on a density functional which is costationary with the finite-temperature functional of Mermin, with state being included with possibly fractional occupation numbers.
Ab initio translationally invariant nonlocal one-body densities from no-core shell-model theory
Burrows, M.; Elster, Ch.; Popa, G.; Launey, K. D.; Nogga, A.; Maris, P.
2018-02-01
Background: It is well known that effective nuclear interactions are in general nonlocal. Thus if nuclear densities obtained from ab initio no-core shell-model (NCSM) calculations are to be used in reaction calculations, translationally invariant nonlocal densities must be available. Purpose: Though it is standard to extract translationally invariant one-body local densities from NCSM calculations to calculate local nuclear observables like radii and transition amplitudes, the corresponding nonlocal one-body densities have not been considered so far. A major reason for this is that the procedure for removing the center-of-mass component from NCSM wave functions up to now has only been developed for local densities. Results: A formulation for removing center-of-mass contributions from nonlocal one-body densities obtained from NCSM and symmetry-adapted NCSM (SA-NCSM) calculations is derived, and applied to the ground state densities of 4He, 6Li, 12C, and 16O. The nonlocality is studied as a function of angular momentum components in momentum as well as coordinate space. Conclusions: We find that the nonlocality for the ground state densities of the nuclei under consideration increases as a function of the angular momentum. The relative magnitude of those contributions decreases with increasing angular momentum. In general, the nonlocal structure of the one-body density matrices we studied is given by the shell structure of the nucleus, and cannot be described with simple functional forms.
Ab initio potential for solids
DEFF Research Database (Denmark)
Chetty, N.; Stokbro, Kurt; Jacobsen, Karsten Wedel
1992-01-01
. At the most approximate level, the theory is equivalent to the usual effective-medium theory. At all levels of approximation, every term in the total-energy expression is calculated ab initio, that is, without any fitting to experiment or to other calculations. Every step in the approximation procedure can...
Waldrop, Jonathan M; Song, Bo; Patkowski, Konrad; Wang, Xiaopo
2015-05-28
A new highly accurate potential energy curve for the krypton dimer was constructed using coupled-cluster calculations up to the singles, doubles, triples, and perturbative quadruples level, including corrections for core-core and core-valence correlation and for relativistic effects. The ab initio data points were fitted to an analytic potential which was used to compute the most important transport properties of the krypton gas. The viscosity, thermal conductivity, self-diffusion coefficient, and thermal diffusion factor were calculated by the kinetic theory at low density and temperatures from 116 to 5000 K. The comparisons with literature experimental data as well as with values from other pair potentials indicate that our new potential is superior to all previous ones. The transport property values computed in this work are recommended as standard values over the complete temperature range.
Energy Technology Data Exchange (ETDEWEB)
Moradian, Rostam; Behzad, Somayeh; Chegel, Raad [Physics Department, Faculty of Science, Razi University, Kermanshah (Iran, Islamic Republic of)], E-mail: moradian.rostam@gmail.com
2008-11-19
By using ab initio density functional theory, the structural characterizations and electronic properties of two large-diameter (13, 13) and (14, 14) armchair silicon carbide nanotube (SiCNT) bundles are investigated. Full structural optimizations show that the cross sections of these large-diameter SiCNTs in the bundles have a nearly hexagonal shape. The effects of inter-tube coupling on the electronic dispersions of large-diameter SiCNT bundles are demonstrated. By comparing the band structures of the triangular lattices of (14, 14) SiCNTs with nearly hexagonal and circular cross sections we found that the polygonization of the tubes in the bundle leads to a further dispersion of the occupied bands and an increase in the bandgap by 0.18 eV.
Moradian, Rostam; Behzad, Somayeh; Azadi, Sam
2008-09-01
By using ab initio density functional theory we investigated the structural and electronic properties of semiconducting (7, 0), (8, 0) and (10, 0) carbon nanotube bundles. The energetic and electronic evolutions of nanotubes in the bundling process are also studied. The effects of inter-tube coupling on the electronic dispersions of semiconducting carbon nanotube bundles are demonstrated. Our results show that the inter-tube coupling decreases the energy gap in semiconducting nanotubes. We found that bundles of (7, 0) and (8, 0) carbon nanotubes have metallic feature, while (10, 0) bundle is a semiconductor with an energy gap of 0.22 eV. To clarify our results the band structures of isolated and bundled nanotubes are compared.
International Nuclear Information System (INIS)
Moradian, Rostam; Behzad, Somayeh; Chegel, Raad
2008-01-01
By using ab initio density functional theory, the structural characterizations and electronic properties of two large-diameter (13, 13) and (14, 14) armchair silicon carbide nanotube (SiCNT) bundles are investigated. Full structural optimizations show that the cross sections of these large-diameter SiCNTs in the bundles have a nearly hexagonal shape. The effects of inter-tube coupling on the electronic dispersions of large-diameter SiCNT bundles are demonstrated. By comparing the band structures of the triangular lattices of (14, 14) SiCNTs with nearly hexagonal and circular cross sections we found that the polygonization of the tubes in the bundle leads to a further dispersion of the occupied bands and an increase in the bandgap by 0.18 eV.
Moradian, Rostam; Behzad, Somayeh; Chegel, Raad
2008-11-01
By using ab initio density functional theory, the structural characterizations and electronic properties of two large-diameter (13, 13) and (14, 14) armchair silicon carbide nanotube (SiCNT) bundles are investigated. Full structural optimizations show that the cross sections of these large-diameter SiCNTs in the bundles have a nearly hexagonal shape. The effects of inter-tube coupling on the electronic dispersions of large-diameter SiCNT bundles are demonstrated. By comparing the band structures of the triangular lattices of (14, 14) SiCNTs with nearly hexagonal and circular cross sections we found that the polygonization of the tubes in the bundle leads to a further dispersion of the occupied bands and an increase in the bandgap by 0.18 eV.
International Nuclear Information System (INIS)
Skylaris, Chris-Kriton; Igglessi-Markopoulou, Olga; Detsi, Anastasia; Markopoulos, John
2003-01-01
We propose all the accessible paths of interconversion between the tautomers of 3-acetyl tetronic and 3-acetyl tetramic acids by performing calculations with the density functional B3LYP method and the ab initio MP2 method. Our findings clarify at the atomic level the mechanisms of the equilibria between these tautomers, a topic so far only partially understood on the basis of studies by nuclear magnetic resonance (NMR) spectroscopy. We show that thermal effects via relative Gibbs free energies ΔG must be taken into account in order to reach good quantitative agreement with the available experimental information on the ratios of the most stable tautomers. The calculated 1 H and 13 C chemical shifts are in agreement with the experimental values from NMR spectroscopy
Energy Technology Data Exchange (ETDEWEB)
Ribeiro, M., E-mail: ribeiro.jr@oorbit.com.br [Office of Operational Research for Business Intelligence and Technology, Principal Office, Buffalo, Wyoming 82834 (United States)
2015-06-21
Ab initio calculations of hydrogen-passivated Si nanowires were performed using density functional theory within LDA-1/2, to account for the excited states properties. A range of diameters was calculated to draw conclusions about the ability of the method to correctly describe the main trends of bandgap, quantum confinement, and self-energy corrections versus the diameter of the nanowire. Bandgaps are predicted with excellent accuracy if compared with other theoretical results like GW, and with the experiment as well, but with a low computational cost.
International Nuclear Information System (INIS)
Ribeiro, M.
2015-01-01
Ab initio calculations of hydrogen-passivated Si nanowires were performed using density functional theory within LDA-1/2, to account for the excited states properties. A range of diameters was calculated to draw conclusions about the ability of the method to correctly describe the main trends of bandgap, quantum confinement, and self-energy corrections versus the diameter of the nanowire. Bandgaps are predicted with excellent accuracy if compared with other theoretical results like GW, and with the experiment as well, but with a low computational cost
International Nuclear Information System (INIS)
Jursic, B.S.
1996-01-01
Up to four ionization potentials of elements from the second-row of the periodic table were computed using the ab initio (HF, MP2, MP3, MP4, QCISD, GI, G2, and G2MP2) and DFT (B3LY, B3P86, B3PW91, XALPHA, HFS, HFB, BLYP, BP86, BPW91, BVWN, XAPLY, XAP86, XAPW91, XAVWN, SLYR SP86, SPW91 and SVWN) methods. In all of the calculations, the large 6-311++G(3df,3pd) gaussian type of basis set was used. The computed values were compared with the experimental results and suitability of the ab initio and DFF methods were discussed, in regard to reproducing the experimental data. From the computed ionization potentials of the second-row elements, it can be concluded that the HF ab initio computation is not capable of reproducing the experimental results. The computed ionization potentials are too low. However, by using the ab initio methods that include electron correlation, the computed IPs are becoming much closer to the experimental values. In all cases, with the exception of the first ionization potential for oxygen, the G2 computation result produces ionization potentials that are indistinguishable from the experimental results
Energy Technology Data Exchange (ETDEWEB)
Osmani, O; Duvenbeck, A; Akcoeltekin, E; Meyer, R; Schleberger, M [Department of Physics, University of Duisburg-Essen, D-47048 Duisburg (Germany); Lebius, H [CIMAP, blvd Henri Becquerel, 14070 Caen (France)], E-mail: marika.schleberger@uni-due.de
2008-08-06
In recent experiments the irradiation of insulators of perovskite type with swift (E{approx}100 MeV) heavy ions under glancing incidence has been shown to provide a unique means to generate periodically arranged nanodots at the surface. The physical origin of these patterns has been suggested as stemming from a highly anisotropic electron density distribution within the bulk. In order to show the relevance of the electron density distribution of the target we present a model calculation for the system Xe{sup 23+} {yields} SrTiO{sub 3} that is known to produce the aforementioned surface modifications. On the basis of the Lindhard model of electronic stopping, we employ highly-resolved ab initio electron density data to describe the conversion of kinetic energy into excitation energy along the ion track. The primary particle dynamics are obtained via integration of the Newtonian equations of motion that are governed by a space- and time-dependent frictional force originating from Lindhard stopping. The analysis of the local electronic stopping power along the ion track reveals a pronounced periodic structure. The periodicity length varies strongly with the particular choice of the polar angle of incidence and is directly correlated to the experimentally observed formation of periodic nanodots at insulator surfaces.
International Nuclear Information System (INIS)
Veals, Jeffrey D.; Thompson, Donald L.
2014-01-01
Density functional theory and ab initio methods are employed to investigate decomposition pathways of 1,3,3-trinitroazetidine initiated by unimolecular loss of NO 2 or HONO. Geometry optimizations are performed using M06/cc-pVTZ and coupled-cluster (CC) theory with single, double, and perturbative triple excitations, CCSD(T), is used to calculate accurate single-point energies for those geometries. The CCSD(T)/cc-pVTZ energies for NO 2 elimination by N–N and C–N bond fission are, including zero-point energy (ZPE) corrections, 43.21 kcal/mol and 50.46 kcal/mol, respectively. The decomposition initiated by trans-HONO elimination can occur by a concerted H-atom and nitramine NO 2 group elimination or by a concerted H-atom and nitroalkyl NO 2 group elimination via barriers (at the CCSD(T)/cc-pVTZ level with ZPE corrections) of 47.00 kcal/mol and 48.27 kcal/mol, respectively. Thus, at the CCSD(T)/cc-pVTZ level, the ordering of these four decomposition steps from energetically most favored to least favored is: NO 2 elimination by N–N bond fission, HONO elimination involving the nitramine NO 2 group, HONO elimination involving a nitroalkyl NO 2 group, and finally NO 2 elimination by C–N bond fission
Energy Technology Data Exchange (ETDEWEB)
Veals, Jeffrey D.; Thompson, Donald L. [Department of Chemistry, University of Missouri-Columbia, Columbia, Missouri 65211 (United States)
2014-04-21
Density functional theory and ab initio methods are employed to investigate decomposition pathways of 1,3,3-trinitroazetidine initiated by unimolecular loss of NO{sub 2} or HONO. Geometry optimizations are performed using M06/cc-pVTZ and coupled-cluster (CC) theory with single, double, and perturbative triple excitations, CCSD(T), is used to calculate accurate single-point energies for those geometries. The CCSD(T)/cc-pVTZ energies for NO{sub 2} elimination by N–N and C–N bond fission are, including zero-point energy (ZPE) corrections, 43.21 kcal/mol and 50.46 kcal/mol, respectively. The decomposition initiated by trans-HONO elimination can occur by a concerted H-atom and nitramine NO{sub 2} group elimination or by a concerted H-atom and nitroalkyl NO{sub 2} group elimination via barriers (at the CCSD(T)/cc-pVTZ level with ZPE corrections) of 47.00 kcal/mol and 48.27 kcal/mol, respectively. Thus, at the CCSD(T)/cc-pVTZ level, the ordering of these four decomposition steps from energetically most favored to least favored is: NO{sub 2} elimination by N–N bond fission, HONO elimination involving the nitramine NO{sub 2} group, HONO elimination involving a nitroalkyl NO{sub 2} group, and finally NO{sub 2} elimination by C–N bond fission.
Veals, Jeffrey D.; Thompson, Donald L.
2014-04-01
Density functional theory and ab initio methods are employed to investigate decomposition pathways of 1,3,3-trinitroazetidine initiated by unimolecular loss of NO2 or HONO. Geometry optimizations are performed using M06/cc-pVTZ and coupled-cluster (CC) theory with single, double, and perturbative triple excitations, CCSD(T), is used to calculate accurate single-point energies for those geometries. The CCSD(T)/cc-pVTZ energies for NO2 elimination by N-N and C-N bond fission are, including zero-point energy (ZPE) corrections, 43.21 kcal/mol and 50.46 kcal/mol, respectively. The decomposition initiated by trans-HONO elimination can occur by a concerted H-atom and nitramine NO2 group elimination or by a concerted H-atom and nitroalkyl NO2 group elimination via barriers (at the CCSD(T)/cc-pVTZ level with ZPE corrections) of 47.00 kcal/mol and 48.27 kcal/mol, respectively. Thus, at the CCSD(T)/cc-pVTZ level, the ordering of these four decomposition steps from energetically most favored to least favored is: NO2 elimination by N-N bond fission, HONO elimination involving the nitramine NO2 group, HONO elimination involving a nitroalkyl NO2 group, and finally NO2 elimination by C-N bond fission.
International Nuclear Information System (INIS)
Cinakli, S.; Sert, Y.; Boeyuekata, M.; Ucun, F.
2010-01-01
The vibrational spectra of benzaldehyde and its derivatives have been studied earlier. The substitution of a functional group changes the spectra markedly. Recent spectroscopic studies of the benzaldehyde and their derivatives have been motivated because the vibrational spectra are very useful for understanding of specific biological process and in the analysis of relatively complex systems. The optimized molecular structure, vibrational frequencies and corresponding vibrational assignments, the total energy calculations, relative energies, the mean vibrational deviations of the two planar O-cis and O-trans roomers of 5-Hydroxy 2-nitrobenzaldehydes have been calculated using ab initio Hartree Fock (HF) and Density Functional Theory (B3LYP) with 6-311++G(d,p) basis set. All computations have been performed on personal computer using the Gaussian 03 program package. The calculations were adapted to Cs symmetries of all the molecules. The O-trans rotomers with lower energy of all the molecules have been found as preferential rotomers in the ground state.
Accuracy of ab initio electron correlation and electron densities in vanadium dioxide
Kylänpää, Ilkka; Balachandran, Janakiraman; Ganesh, Panchapakesan; Heinonen, Olle; Kent, Paul R. C.; Krogel, Jaron T.
2017-11-01
Diffusion quantum Monte Carlo results are used as a reference to analyze properties related to phase stability and magnetism in vanadium dioxide computed with various formulations of density functional theory. We introduce metrics related to energetics, electron densities and spin densities that give us insight on both local and global variations in the antiferromagnetic M1 and R phases. Importantly, these metrics can address contributions arising from the challenging description of the 3 d orbital physics in this material. We observe that the best description of energetics between the structural phases does not correspond to the best accuracy in the charge density, which is consistent with observations made recently by Medvedev et al. [Science 355, 371 (2017), 10.1126/science.aag0410] in the context of isolated atoms. However, we do find evidence that an accurate spin density connects to correct energetic ordering of different magnetic states in VO2, although local, semilocal, and meta-GGA functionals tend to erroneously favor demagnetization of the vanadium sites. The recently developed SCAN functional stands out as remaining nearly balanced in terms of magnetization across the M1-R transition and correctly predicting the ground state crystal structure. In addition to ranking current density functionals, our reference energies and densities serve as important benchmarks for future functional development. With our reference data, the accuracy of both the energy and the electron density can be monitored simultaneously, which is useful for functional development. So far, this kind of detailed high accuracy reference data for correlated materials has been absent from the literature.
Energy Technology Data Exchange (ETDEWEB)
Roemelt, Michael, E-mail: michael.roemelt@theochem.rub.de [Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, D-44780 Bochum, Germany and Max-Planck Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr (Germany)
2015-07-28
Spin Orbit Coupling (SOC) is introduced to molecular ab initio density matrix renormalization group (DMRG) calculations. In the presented scheme, one first approximates the electronic ground state and a number of excited states of the Born-Oppenheimer (BO) Hamiltonian with the aid of the DMRG algorithm. Owing to the spin-adaptation of the algorithm, the total spin S is a good quantum number for these states. After the non-relativistic DMRG calculation is finished, all magnetic sublevels of the calculated states are constructed explicitly, and the SOC operator is expanded in the resulting basis. To this end, spin orbit coupled energies and wavefunctions are obtained as eigenvalues and eigenfunctions of the full Hamiltonian matrix which is composed of the SOC operator matrix and the BO Hamiltonian matrix. This treatment corresponds to a quasi-degenerate perturbation theory approach and can be regarded as the molecular equivalent to atomic Russell-Saunders coupling. For the evaluation of SOC matrix elements, the full Breit-Pauli SOC Hamiltonian is approximated by the widely used spin-orbit mean field operator. This operator allows for an efficient use of the second quantized triplet replacement operators that are readily generated during the non-relativistic DMRG algorithm, together with the Wigner-Eckart theorem. With a set of spin-orbit coupled wavefunctions at hand, the molecular g-tensors are calculated following the scheme proposed by Gerloch and McMeeking. It interprets the effective molecular g-values as the slope of the energy difference between the lowest Kramers pair with respect to the strength of the applied magnetic field. Test calculations on a chemically relevant Mo complex demonstrate the capabilities of the presented method.
Collective rotation from ab initio theory
International Nuclear Information System (INIS)
Caprio, M.A.; Maris, P.; Vary, J.P.; Smith, R.
2015-01-01
Through ab initio approaches in nuclear theory, we may now seek to quantitatively understand the wealth of nuclear collective phenomena starting from the underlying internucleon interactions. No-core configuration interaction (NCCI) calculations for p-shell nuclei give rise to rotational bands, as evidenced by rotational patterns for excitation energies, electromagnetic moments and electromagnetic transitions. In this review, NCCI calculations of 7–9 Be are used to illustrate and explore ab initio rotational structure, and the resulting predictions for rotational band properties are compared with experiment. We highlight the robustness of ab initio rotational predictions across different choices for the internucleon interaction. (author)
International Nuclear Information System (INIS)
Delta, E.; Ucun, F.; Saglam, A.
2010-01-01
The ground state hydrogen conformations of 1,2-dihydroxyanthraquinone (alizarin) molecule have been investigated using ab initio Hartree-Fock (HF) and density functional theory (B3LYP) methods with 6-31G(d,p) basis set. The calculations indicate that the compound in the ground state exist with the doubly bonded O atom linked intra molecularly by the two hydrogen bonds. The vibrational analyses of the ground state conformation of the compound were also made and its optimized geometry parameters were given.
Energy Technology Data Exchange (ETDEWEB)
Ismayilova, N. A., E-mail: ismayilova-narmin-84@mail.ru; Orudjev, H. S.; Jabarov, S. H. [Azerbaijan National Academy of Sciences, Institute of Physics (Azerbaijan)
2017-04-15
The results of ab initio calculations of the electron spectrum of TlFeS{sub 2} and TlFeSe{sub 2} crystals in the antiferromagnetic phase are reported. Calculations are carried out in the context of the density functional theory. The origin of the bands of s, p, and d electron states of Tl, Fe, S, and Se atoms is studied. It is established that, in the antiferromagnetic phase, the crystals possess semiconductor properties. The band gaps are found to be 0.05 and 0.34 eV for TlFeS{sub 2} and TlFeSe{sub 2} crystals, respectively.
Narula, Chaitanya K; Allard, Lawrence F; Wu, Zili
2017-07-24
The ab initio density functional theoretical studies show that energetics favor CO oxidation on single Pd atoms supported on θ-alumina. The diffuse reflectance infra-red spectroscopy (DRIFTS) results show that carbonates are formed as intermediates when single supported Pd atoms are exposed to a gaseous mixture of CO + O 2 . The rapid agglomeration of Pd atoms under CO oxidation conditions even at 6 °C leads to the presence of Pd particles along with single atoms during CO oxidation experiments. Thus, the observed CO oxidation has contributions from both single Pd atoms and Pd particles.
Georgieva, Miglena K.
2004-03-01
The structure of diazonium dicyanomethylide (diazodicyanomethane) +N 2-C(CN) 2-↔N 2C(CN) 2 has been studied on the basis of ab initio HF, MP2 and DFT BLYP force field calculations, as well as of literature IR spectra and X-ray diffraction structural data. The results have been compared with those obtained for a series of chemical relatives of the title compound, i.e. molecules, push-pull molecules, anions and zwitterions, containing α-dicyano or diazo fragments, and especially substituted ammonium dicyanomethylides and diazomethane +N 2-CH 2-↔N 2CH 2. It has been found on the basis of spectral, bond length, bond order and electric charge analyses that the diazonium (or carbanionic, left) canonical form is much more important for the title zwitterion, than the corresponding one for diazomethane. So, the title compound can be named (and considered as) both diazonium dicyanomethylide and dicyanodiazomethane.
Ab initio lattice dynamics of metal surfaces
International Nuclear Information System (INIS)
Heid, R.; Bohnen, K.-P.
2003-01-01
Dynamical properties of atoms on surfaces depend sensitively on their bonding environment and thus provide valuable insight into the local geometry and chemical binding at the boundary of a solid. Density-functional theory provides a unified approach to the calculation of structural and dynamical properties from first principles. Its high accuracy and predictive power for lattice dynamical properties of semiconductor surfaces has been demonstrated in a previous article by Fritsch and Schroeder (Phys. Rep. 309 (1999) 209). In this report, we review the state-of-the-art of these ab initio approaches to surface dynamical properties of metal surfaces. We give a brief introduction to the conceptual framework with focus on recent advances in computational procedures for the ab initio linear-response approach, which have been a prerequisite for an efficient treatment of surface dynamics of noble and transition metals. The discussed applications to clean and adsorbate-covered surfaces demonstrate the high accuracy and reliability of this approach in predicting detailed microscopic properties of the phonon dynamics for a wide range of metallic surfaces
Young Modulus of Crystalline Polyethylene from ab Initio Molecular Dynamics
Hageman, J.C.L.; Meier, Robert J.; Heinemann, M.; Groot, R.A. de
1997-01-01
The Young modulus for crystalline polyethylene is calculated using ab initio molecular dynamics based on density functional theory in the local density approximation (DFT-LDA). This modulus, which can be seen as the ultimate value for the Young modulus of polyethylene fibers, is found to be 334 GPa.
Zhang, Yi-Quan; Luo, Cheng-Lin; Zhang, Qiang
2014-05-05
The origin of the magnetic anisotropy energy barriers in a series of bpym(-) (bpym = 2,2'-bipyrimidine) radical-bridged dilanthanide complexes [(Cp*2Ln)2(μ-bpym)](+) [Cp* = pentamethylcyclopentadienyl; Ln = Gd(III) (1), Tb(III) (2), Dy(III) (3), Ho(III) (4), Er(III) (5)] has been explored using density functional theory (DFT) and ab initio methods. DFT calculations show that the exchange coupling between the two lanthanide ions for each complex is very weak, but the antiferromagnetic Ln-bpym(-) couplings are strong. Ab initio calculations show that the effective energy barrier of 2 or 3 mainly comes from the contribution of a single Tb(III) or Dy(III) fragment, which is only about one third of a single Ln energy barrier. For 4 or 5, however, both of the two Ho(III) or Er(III) fragments contribute to the total energy barrier. Thus, it is insufficient to only increase the magnetic anisotropy energy barrier of a single Ln ion, while enhancing the Ln-bpym(-) couplings is also very important. Copyright © 2014 Wiley Periodicals, Inc.
Ab initio model of porous periclase
International Nuclear Information System (INIS)
Drummond, Neil D.; Swift, Damian C.; Ackland, Graeme J.
2004-01-01
A two-phase equilibrium equation of state (EOS) for periclase (MgO) was constructed using ab initio quantum mechanics, including a rigorous calculation of quasiharmonic phonon modes. Much of the shock wave data reported for periclase is on porous material. We compared the theoretical EOS with porous data using a simple 'snowplough' treatment and also a model using finite equilibration rates suitable for continuum mechanics simulations. (This model has been applied previously to various heterogeneous explosives as well as other porous materials.) The results were consistent and matched the data well at pressures above the regime affected by strength - and ramp-wave formation - during compaction. Ab initio predictions of the response of porous material have been cited recently as a novel and advanced capability; we feel that this is a fairly routine extension to established ab initio techniques
Yu, Yang; Li, Chen; Yin, Bing; Li, Jian-Li; Huang, Yuan-He; Wen, Zhen-Yi; Jiang, Zhen-Yi
2013-08-07
The structures, relative stabilities, vertical electron detachment energies, and magnetic properties of a series of trinuclear clusters are explored via combined broken-symmetry density functional theory and ab initio study. Several exchange-correlation functionals are utilized to investigate the effects of different halogen elements and central atoms on the properties of the clusters. These clusters are shown to possess stronger superhalogen properties than previously reported dinuclear superhalogens. The calculated exchange coupling constants indicate the antiferromagnetic coupling between the transition metal ions. Spin density analysis demonstrates the importance of spin delocalization in determining the strengths of various couplings. Spin frustration is shown to occur in some of the trinuclear superhalogens. The coexistence of strong superhalogen properties and spin frustration implies the possibility of trinuclear superhalogens working as the building block of new materials of novel magnetic properties.
Use of ab initio quantum chemical methods in battery technology
Energy Technology Data Exchange (ETDEWEB)
Deiss, E [Paul Scherrer Inst. (PSI), Villigen (Switzerland)
1997-06-01
Ab initio quantum chemistry can nowadays predict physical and chemical properties of molecules and solids. An attempt should be made to use this tool more widely for predicting technologically favourable materials. To demonstrate the use of ab initio quantum chemistry in battery technology, the theoretical energy density (energy per volume of active electrode material) and specific energy (energy per mass of active electrode material) of a rechargeable lithium-ion battery consisting of a graphite electrode and a nickel oxide electrode has been calculated with this method. (author) 1 fig., 1 tab., 7 refs.
Belmonte, Donato; Gatti, Carlo; Ottonello, Giulio; Richet, Pascal; Vetuschi Zuccolini, Marino
2016-11-10
Thermodynamic and thermophysical properties of Na 2 SiO 3 in the Cmc2 1 structural state are computed ab initio using the hybrid B3LYP density functional method. The static properties at the athermal limit are first evaluated through a symmetry-preserving relaxation procedure. The thermodynamic properties that depend on vibrational frequencies, viz., heat capacities, thermal expansion, thermal derivative of the bulk modulus, thermal correction to internal energy, enthalpy, and Gibbs free energy, are then computed in the framework of quasi-harmonic approximation. Acoustic branches are computed by solving the Christoffel determinant and are assumed to follow sine wave dispersion when traveling within the Brillouin zone. The procedure generates several thermo-physical properties of interest in materials science and geophysics (transverse and longitudinal wave velocities, shear modulus, Young modulus, Poisson ratio) all consistent with experimentally determined properties. A representative cluster is then abstracted from the cell and a detailed electron localization/delocalization analysis is performed on it, in the ground state geometry, and on deformed states imposed by two peculiar mixed asymmetric stretching/bending modes affecting the silicate chain that, according to literature data, have anomalous mode Grüneisen parameters. A Bader analysis reveals an intriguing feature associated with these deformations: an increase in the covalence of the Si-O bond that strengthens the linkage opposing the weakening induced by thermal stress. Finally, on the same cluster, the Ramsey contributions to the J NM coupling are evaluated by the gauge-independent atomic orbital method. The calculated isotropic chemical shifts of both 23 Na and 29 Si are again in substantial agreement with observations.
Ab initio electronic stopping power in materials
International Nuclear Information System (INIS)
Shukri, Abdullah-Atef
2015-01-01
The average energy loss of an ion per unit path length when it is moving through the matter is named the stopping power. The knowledge of the stopping power is essential for a variety of contemporary applications which depend on the transport of ions in matter, especially ion beam analysis techniques and ion implantation. Most noticeably, the use of proton or heavier ion beams in radiotherapy requires the knowledge of the stopping power. Whereas experimental data are readily available for elemental solids, the data are much more scarce for compounds. The linear response dielectric formalism has been widely used in the past to study the electronic stopping power. In particular, the famous pioneering calculations due to Lindhard evaluate the electronic stopping power of a free electron gas. In this thesis, we develop a fully ab initio scheme based on linear response time-dependent density functional theory to predict the impact parameter averaged quantity named the random electronic stopping power (RESP) of materials without any empirical fitting. The purpose is to be capable of predicting the outcome of experiments without any knowledge of target material besides its crystallographic structure. Our developments have been done within the open source ab initio code named ABINIT, where two approximations are now available: the Random-Phase Approximation (RPA) and the Adiabatic Local Density Approximation (ALDA). Furthermore, a new method named 'extrapolation scheme' have been introduced to overcome the stringent convergence issues we have encountered. These convergence issues have prevented the previous studies in literature from offering a direct comparison to experiment. First of all, we demonstrate the importance of describing the realistic ab initio electronic structure by comparing with the historical Lindhard stopping power evaluation. Whereas the Lindhard stopping power provides a first order description that captures the general features of the
Ab initio valence calculations in chemistry
Cook, D B
1974-01-01
Ab Initio Valence Calculations in Chemistry describes the theory and practice of ab initio valence calculations in chemistry and applies the ideas to a specific example, linear BeH2. Topics covered include the Schrödinger equation and the orbital approximation to atomic orbitals; molecular orbital and valence bond methods; practical molecular wave functions; and molecular integrals. Open shell systems, molecular symmetry, and localized descriptions of electronic structure are also discussed. This book is comprised of 13 chapters and begins by introducing the reader to the use of the Schrödinge
Early stage precipitation in aluminum alloys : An ab initio study
Zhang, X.
2017-01-01
Multiscale computational materials science has reached a stage where many complicated phenomena or properties that are of great importance to manufacturing can be predicted or explained. The word “ab initio study” becomes commonplace as the development of density functional theory has enabled the
Ab initio molecular dynamics simulation of laser melting of silicon
Silvestrelli, P.-L.; Alavi, A.; Parrinello, M.; Frenkel, D.
1996-01-01
The method of ab initio molecular dynamics, based on finite temperature density functional theory, is used to simulate laser heating of crystal silicon. We have found that a high concentration of excited electrons dramatically weakens the covalent bond. As a result, the system undergoes a melting
Ab initio study of alanine polypeptide chain twisting
DEFF Research Database (Denmark)
Solov'yov, Ilia; Yakubovich, Alexander V.; Solov'yov, Andrey V.
2006-01-01
chains. These particular degrees of freedom are essential for the characterization of the proteins folding process. Calculations have been carried out within the ab initio theoretical framework based on the density functional theory and accounting for all the electrons in the system. We have determined...
Ab initio calculations and modelling of atomic cluster structure
DEFF Research Database (Denmark)
Solov'yov, Ilia; Lyalin, Andrey G.; Solov'yov, Andrey V.
2004-01-01
The optimized structure and electronic properties of small sodium and magnesium clusters have been investigated using it ab initio theoretical methods based on density-functional theory and post-Hartree-Fock many-body perturbation theory accounting for all electrons in the system. A new theoretical...
Indian Academy of Sciences (India)
The photophysical behaviour of N-(2-hydroxy benzylidene) aniline or most commonly known as salicylideneaniline (SA) has been investigated using the ab initio and DFT levels of theory. The quantum chemical calculations show that the optimized non planar enol (1) form of the SA molecule is the most stable conformer ...
Ucun, Fatih; Sağlam, Adnan; Güçlü, Vesile
2007-06-01
The molecular structures, vibrational frequencies and corresponding vibrational assignments of xanthine and its methyl derivatives (caffeine and theobromine) have been calculated using ab initio Hartree-Fock (HF) and density functional theory (B3LYP) methods with 6-31G(d, p) basis set level. The calculations were utilized to the CS symmetries of the molecules. The obtained vibrational frequencies and optimised geometric parameters (bond lengths and bond angles) were seen to be well agreement with the experimental data. The used scale factors which have been obtained the ratio of the frequency values of the strongest peaks in the calculated and experimental spectra seem to cause the gained vibrations well corresponding to the experimental ones. Theoretical infrared intensities and Raman activities are also reported.
International Nuclear Information System (INIS)
Hostert, C; Music, D; Schneider, J M; Bednarcik, J; Keckes, J; Kapaklis, V; Hjörvarsson, B
2011-01-01
Density, elastic modulus and the pair distribution function of Co-Fe-Ta-B metallic glasses were obtained by ab initio molecular dynamics simulations and measured for sputtered thin films using x-ray reflectivity, nanoindentation and x-ray diffraction using high energy photons. The computationally obtained density of 8.19 g cm -3 for Co 43 Fe 20 Ta 5.5 B 31.5 and 8.42 g cm -3 for Co 45.5 Fe 24 Ta 6 B 24.5 , as well as the Young’s moduli of 273 and 251 GPa, respectively, are consistent with our experiments and literature data. These data, together with the good agreement between the theoretical and the experimental pair distribution functions, indicate that the model established here is useful to describe the density, elasticity and short range order of Co-Fe-Ta-B metallic glass thin films. Irrespective of the investigated variation in chemical composition, (Co, Fe)-B cluster formation and Co-Fe interactions are identified by density-of-states analysis. Strong bonds within the structural units and between the metallic species may give rise to the comparatively large stiffness. (paper)
Towards hydrogen metallization: an Ab initio approach
International Nuclear Information System (INIS)
Bernard, St.
1998-01-01
The quest for metallic hydrogen is a major goal for both theoretical and experimental condensed matter physics. Hydrogen and deuterium have been compressed up to 200 GPa in diamond anvil cells, without any clear evidence for a metallic behaviour. Loubeyere has recently suggested that hydrogen could metallize, at pressures within experimental range, in a new Van der Waals compound: Ar(H 2 ) 2 which is characterized at ambient pressure by an open and anisotropic sublattice of hydrogen molecules, stabilized by an argon skeleton. This thesis deals with a detailed ab initio investigation, by Car-Parrinello molecular dynamics methods, of the evolution under pressure of this compound. In a last chapter, we go to much higher pressures and temperatures, in order to compare orbital and orbital free ab initio methods for the dense hydrogen plasma. (author)
Directory of Open Access Journals (Sweden)
Peng Xu
2018-04-01
Full Text Available The understanding of the excited-state properties of electron donors, acceptors and their interfaces in organic optoelectronic devices is a fundamental issue for their performance optimization. In order to obtain a balanced description of the different excitation types for electron-donor-acceptor systems, including the singlet charge transfer (CT, local excitations, and triplet excited states, several ab initio and density functional theory (DFT methods for excited-state calculations were evaluated based upon the selected model system of benzene-tetracyanoethylene (B-TCNE complexes. On the basis of benchmark calculations of the equation-of-motion coupled-cluster with single and double excitations method, the arithmetic mean of the absolute errors and standard errors of the electronic excitation energies for the different computational methods suggest that the M11 functional in DFT is superior to the other tested DFT functionals, and time-dependent DFT (TDDFT with the Tamm–Dancoff approximation improves the accuracy of the calculated excitation energies relative to that of the full TDDFT. The performance of the M11 functional underlines the importance of kinetic energy density, spin-density gradient, and range separation in the development of novel DFT functionals. According to the TDDFT results, the performances of the different TDDFT methods on the CT properties of the B-TCNE complexes were also analyzed.
Single-ion 4f element magnetism: an ab-initio look at Ln(COT)2(-).
Gendron, Frédéric; Pritchard, Benjamin; Bolvin, Hélène; Autschbach, Jochen
2015-12-14
The electron densities associated with the Ln 4f shell, and spin and orbital magnetizations ('magnetic moment densities'), are investigated for the Ln(COT)2(-) series. The densities are obtained from ab-initio calculations including spin-orbit coupling. For Ln = Ce, Pr the magnetizations are also derived from crystal field models and shown to agree with the ab-initio results. Analysis of magnetizations from ab-initio calculations may be useful in assisting research on single molecule magnets.
Highly scalable Ab initio genomic motif identification
Marchand, Benoit; Bajic, Vladimir B.; Kaushik, Dinesh
2011-01-01
We present results of scaling an ab initio motif family identification system, Dragon Motif Finder (DMF), to 65,536 processor cores of IBM Blue Gene/P. DMF seeks groups of mutually similar polynucleotide patterns within a set of genomic sequences and builds various motif families from them. Such information is of relevance to many problems in life sciences. Prior attempts to scale such ab initio motif-finding algorithms achieved limited success. We solve the scalability issues using a combination of mixed-mode MPI-OpenMP parallel programming, master-slave work assignment, multi-level workload distribution, multi-level MPI collectives, and serial optimizations. While the scalability of our algorithm was excellent (94% parallel efficiency on 65,536 cores relative to 256 cores on a modest-size problem), the final speedup with respect to the original serial code exceeded 250,000 when serial optimizations are included. This enabled us to carry out many large-scale ab initio motiffinding simulations in a few hours while the original serial code would have needed decades of execution time. Copyright 2011 ACM.
Ab initio study of hot electrons in GaAs
Bernardi, Marco; Vigil-Fowler, Derek; Ong, Chin Shen; Neaton, Jeffrey B.; Louie, Steven G.
2015-01-01
Hot carrier dynamics critically impacts the performance of electronic, optoelectronic, photovoltaic, and plasmonic devices. Hot carriers lose energy over nanometer lengths and picosecond timescales and thus are challenging to study experimentally, whereas calculations of hot carrier dynamics are cumbersome and dominated by empirical approaches. In this work, we present ab initio calculations of hot electrons in gallium arsenide (GaAs) using density functional theory and many-body perturbation...
Ab Initio Calculations of Oxosulfatovanadates
DEFF Research Database (Denmark)
Frøberg, Torben; Johansen, Helge
1996-01-01
Restricted Hartree-Fock and multi-configurational self-consistent-field calculations together with secondorder perturbation theory have been used to study the geometry, the electron density, and the electronicspectrum of (VO2SO4)-. A bidentate sulphate attachment to vanadium was found to be stabl...
International Nuclear Information System (INIS)
Sheng, S.H.; Zhang, R.F.; Veprek, S.
2011-01-01
Using ab initio density functional theory, the equilibrium properties, such as the total energy, the molar volume, the bulk modulus and its first derivative, as well as the formation enthalpy of monoclinic ZrO 2 and hexagonal α-Al 2 O 3 phases, were calculated and compared with the published theoretical and experimental data. Based on the good agreement of these data, we calculated the lattice instabilities of hypothetical binary hexagonal Zr 2 O 3 and monoclinic AlO 2 , and the interaction parameters of ternary Zr 1-x Al x O y solid solutions. The binodal and spinodal diagrams were then constructed to predict the possibility of the formation of oxide-based nanocomposites which may display hardness enhancement above that of the solid solutions. It is shown that exponential dependence of the interaction parameter on temperature yields the most reliable results. The system should undergo spinodal phase segregation within the composition range that is relevant for the formation of hard or superhard nanocomposites with high thermal and oxidation stability, which are important for their applications.
Augmented wave ab initio EFG calculations: some methodological warnings
International Nuclear Information System (INIS)
Errico, Leonardo A.; Renteria, Mario; Petrilli, Helena M.
2007-01-01
We discuss some accuracy aspects inherent to ab initio electronic structure calculations in the understanding of nuclear quadrupole interactions. We use the projector augmented wave method to study the electric-field gradient (EFG) at both Sn and O sites in the prototype cases SnO and SnO 2 . The term ab initio is used in the standard context of the also called first principles methods in the framework of the Density Functional Theory. As the main contributions of EFG calculations to problems in condensed matter physics are related to structural characterizations on the atomic scale, we discuss the 'state of the art' on theoretical EFG calculations and make a brief critical review on the subject, calling attention to some fundamental theoretical aspects
Augmented wave ab initio EFG calculations: some methodological warnings
Energy Technology Data Exchange (ETDEWEB)
Errico, Leonardo A. [Departamento de Fisica-IFLP (CONICET), Facultad de Ciencias Exactas, Universidad Nacional de La Plata, CC67 (1900) La Plata (Argentina); Renteria, Mario [Departamento de Fisica-IFLP (CONICET), Facultad de Ciencias Exactas, Universidad Nacional de La Plata, CC67 (1900) La Plata (Argentina); Petrilli, Helena M. [Instituto de Fisica-DFMT, Universidade de Sao Paulo, C.P. 66318, 05315-970 Sao Paulo, SP (Brazil)]. E-mail: hmpetril@macbeth.if.usp.br
2007-02-01
We discuss some accuracy aspects inherent to ab initio electronic structure calculations in the understanding of nuclear quadrupole interactions. We use the projector augmented wave method to study the electric-field gradient (EFG) at both Sn and O sites in the prototype cases SnO and SnO{sub 2}. The term ab initio is used in the standard context of the also called first principles methods in the framework of the Density Functional Theory. As the main contributions of EFG calculations to problems in condensed matter physics are related to structural characterizations on the atomic scale, we discuss the 'state of the art' on theoretical EFG calculations and make a brief critical review on the subject, calling attention to some fundamental theoretical aspects.
Energy Technology Data Exchange (ETDEWEB)
Bernard, S.; Jollet, F.; Jomard, G.; Siberchicot, B.; Torrent, M.; Zerah, G.; Amadon, B.; Bouchet, J.; Richard, N.; Robert, G. [CEA Bruyeres-le-Chatel, 91 (France)
2005-07-01
The determination of equations of states of heavy metals through ab initio calculation, i.e. without any adjustable parameter, allows to access to pressure and temperature thermodynamic conditions sometimes inaccessible to experiment. To perform such calculations, density functional theory (DFT) is a good starting point: when electronic densities are homogeneous enough, the local density approximation (LDA) remarkably accounts for thermodynamic properties of heavy metals, such as tantalum, or the light actinides, as well for static properties - equilibrium volume, elastic constants - as for dynamical quantities like phonon spectra. For heavier elements, like neptunium or plutonium, relativistic effects and strong electronic interactions must be taken into account, which requires more sophisticated theoretical approaches. (authors)
Ab Initio Calculations of Transport in Titanium and Aluminum Mixtures
Walker, Nicholas; Novak, Brian; Tam, Ka Ming; Moldovan, Dorel; Jarrell, Mark
In classical molecular dynamics simulations, the self-diffusion and shear viscosity of titanium about the melting point have fallen within the ranges provided by experimental data. However, the experimental data is difficult to collect and has been rather scattered, making it of limited value for the validation of these calculations. By using ab initio molecular dynamics simulations within the density functional theory framework, the classical molecular dynamics data can be validated. The dynamical data from the ab initio molecular dynamics can also be used to calculate new potentials for use in classical molecular dynamics, allowing for more accurate classical dynamics simulations for the liquid phase. For metallic materials such as titanium and aluminum alloys, these calculations are very valuable due to an increasing demand for the knowledge of their thermophysical properties that drive the development of new materials. For example, alongside knowledge of the surface tension, viscosity is an important input for modeling the additive manufacturing process at the continuum level. We are developing calculations of the viscosity along with the self-diffusion for aluminum, titanium, and titanium-aluminum alloys with ab initio molecular dynamics. Supported by the National Science Foundation through cooperative agreement OIA-1541079 and the Louisiana Board of Regents.
Ab Initio Calculation of Hyperfine Interaction Parameters: Recent Evolutions, Recent Examples
International Nuclear Information System (INIS)
Cottenier, Stefaan; Vanhoof, Veerle; Torumba, Doru; Bellini, Valerio; Cakmak, Mehmet; Rots, Michel
2004-01-01
For some years already, ab initio calculations based on Density Functional Theory (DFT) belong to the toolbox of the field of hyperfine interaction studies. In this paper, the standard ab initio approach is schematically sketched. New features, methods and possibilities that broke through during the past few years are listed, and their relation to the standard approach is explained. All this is illustrated by some highlights of recent ab initio work done by the Nuclear Condensed Matter Group at the K.U.Leuven.
Ab initio computation of the transition temperature of the charge density wave transition in TiS e2
Duong, Dinh Loc; Burghard, Marko; Schön, J. Christian
2015-12-01
We present a density functional perturbation theory approach to estimate the transition temperature of the charge density wave transition of TiS e2 . The softening of the phonon mode at the L point where in TiS e2 a giant Kohn anomaly occurs, and the energy difference between the normal and distorted phase are analyzed. Both features are studied as functions of the electronic temperature, which corresponds to the Fermi-Dirac distribution smearing value in the calculation. The transition temperature is found to be 500 and 600 K by phonon and energy analysis, respectively, in reasonable agreement with the experimental value of 200 K.
Directory of Open Access Journals (Sweden)
Loay A. Elalfy
2013-01-01
Full Text Available Density functional theory calculations using B3LYP/3-21G level of theory have been implemented on 6 carbon nanotubes (CNTs structures (3 zigzag and 3 armchair CNTs to study the energetics of the reverse osmosis during water desalination process. Calculations of the band gap, interaction energy, highest occupied molecular orbital, lowest unoccupied molecular orbital, electronegativity, hardness, and pressure of the system are discussed. The calculations showed that the water molecule that exists inside the CNT is about 2-3 Å away from its wall. The calculations have proven that the zigzag CNTs are more efficient for reverse osmosis water desalination process than armchair CNTs as the reverse osmosis process requires pressure of approximately 200 MPa for armchair CNTs, which is consistent with the values used in molecular dynamics simulations, while that needed when using zigzag CNTs was in the order of 60 MPa.
Ab Initio Molecular Dynamics Simulations of Furfural at the Liquid-Solid Interface
Sanwu Wang; Hongli Dang; Wenhua Xue; Darwin Shields; Xin Liu; Friederike C. Jentoft; Daniel E. Resasco
2013-01-01
The bonding configuration and the heat of adsorption of a furfural molecule on the Pd(111) surface were determined by ab initio density-functional-theory calculations. The dynamics of pure liquid water, the liquid-solid interface formed by liquid water and the Pd(111) surface, as well as furfural at the water-Pd interface, were investigated by ab initio molecular dynamics simulations at finite temperatures. Calculations and simulations suggest that the bonding configurati...
Adsorption of carbon monoxide on Ag(I)-ZSM-5 zeolite: An ab initio density functional theory study
Energy Technology Data Exchange (ETDEWEB)
Qiu Zhenzhen [College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029 (China); Department of Chemical Engineering, Tsinghua University, Beijing 100084 (China); Yu Yangxin, E-mail: yangxyu@mail.tsinghua.edu.cn [Department of Chemical Engineering, Tsinghua University, Beijing 100084 (China); Mi Jianguo [College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029 (China)
2012-10-01
Highlights: Black-Right-Pointing-Pointer Significant difference in adsorption energy is found for CO adsorbed on different Ag{sup +}-exchange sites. Black-Right-Pointing-Pointer Energetically stable sites in Ag-ZSM-5 are found. Black-Right-Pointing-Pointer Introduction of the two Al atoms to the site of Ag-ZSM-5 results in a reduction of CO adsorption energy. Black-Right-Pointing-Pointer Comparison of CO adsorption energy on the corresponding charge-exchange sites of Ag-ZSM-5 and Cu-ZSM-5 is made. - Abstract: Adsorption of carbon monoxide on different Ag{sup +}-exchange sites of Ag-ZSM-5 zeolite has been investigated using density functional theory. The coordination and local geometry of the Ag{sup +} ion in Ag-ZSM-5 as well as adsorption structures and energies of CO adsorbed on these sites are explored extensively. The structure of Ag{sup +}-exchange sites, location of the Al atom on the T site, and number of the Al atoms contained in the sites are considered in the theoretical calculations. The calculated results show that the Ag-O coordination number of two is strongly preferred before and after CO adsorption. The Ag-O bond lengths are in a broad range of 2.2-2.9 Angstrom-Sign , and the Ag-C bond lengths for CO adsorbed on Ag-ZSM-5 zeolite are calculated to be 2.0-2.2 Angstrom-Sign . Both Ag-O and Ag-C bond lengths for CO-Ag-ZSM-5 complex are longer than those for CO-Cu-ZSM-5 complex. The calculated adsorption energy of CO adsorbed on the I2 sites is between 28.5 and 29.6 kcal/mol, and that on the Z5, Z6, M5 and M6 sites containing one Al atom on the T position is between 11.3 and 18.9 kcal/mol whereas the calculated adsorption energy of CO adsorbed on the M7 site containing one Al atom is 19.9 kcal/mol. The introduction of the two Al atoms to the Ag{sup +}-exchange site results in a reduction of CO adsorption energy. In general, the adsorption energy of CO on Ag-ZSM-5 is lower than that on Cu-ZSM-5. The predicted coordination of the Ag{sup +} ion, bond lengths
Ab initio molecular dynamics in a finite homogeneous electric field.
Umari, P; Pasquarello, Alfredo
2002-10-07
We treat homogeneous electric fields within density functional calculations with periodic boundary conditions. A nonlocal energy functional depending on the applied field is used within an ab initio molecular dynamics scheme. The reliability of the method is demonstrated in the case of bulk MgO for the Born effective charges, and the high- and low-frequency dielectric constants. We evaluate the static dielectric constant by performing a damped molecular dynamics in an electric field and avoiding the calculation of the dynamical matrix. Application of this method to vitreous silica shows good agreement with experiment and illustrates its potential for systems of large size.
Zhang, Yi-Quan; Luo, Cheng-Lin; Wu, Xin-Bao; Wang, Bing-Wu; Gao, Song
2014-04-07
Until now, the expressions of the anisotropic energy barriers Δξ and ΔA, using the uniaxial magnetic anisotropy D, the intrachain coupling strength J, and the high-spin ground state S for single-chain magnets (SCMs) in the intermediate region between the Ising and the Heisenberg limits, were unknown. To explore this relationship, we used density functional theory and ab initio methods to obtain expressions of Δξ and ΔA in terms of D, J, and S of six R4Fe(II)-Re(IV)Cl4(CN)2 (R = diethylformamide (1), dibutylformamide (2), dimethylformamide (3), dimethylbutyramide (4), dimethylpropionamide (5), and diethylacetamide (6)) SCMs in the intermediate region. The ΔA value for compounds 1-3 was very similar to the magnetic anisotropic energy of a single Fe(II), while the value of Δξ was predicted using the exchange interaction of Fe(II) with the neighboring Re(IV), which could be expressed as 2JSReSFe. Similar to compounds 1-3, the anisotropy energy barrier ΔA of compounds 4 and 5 was also equal to (Di - Ei)SFe(2), but the correlation energy Δξ was closely equal to 2JSReSFe(cos 98.4 - cos 180) due to the reversal of the spins on the opposite Fe(II). For compound 6, one unit cell of Re(IV)Fe(II) was regarded as a domain wall since it had two different Re(IV)-Fe(II) couplings. Thus, the Δξ of compound 6 was expressed as 4J″SRe1Fe1SRe2Fe2, where J″ was the coupling constant of the neighboring unit cells of Re1Fe1 and Re2Fe2, and ΔA was equal to the anisotropic energy barrier of one domain wall given by DRe1Fe1(S(2)Re1Fe1 - 1/4).
Realization of prediction of materials properties by ab initio ...
Indian Academy of Sciences (India)
Unknown
alization of the results of ab initio molecular dynamics simulation on atom insertion process to C60 and to carbon nanotube ... micro-clusters to estimate absolute highest occupied mo- .... To analyse the observed properties theoretically,.
Ab Initio Atomistic Thermodynamics for Surfaces: A Primer
National Research Council Canada - National Science Library
Rogal, Jutta; Reuter, Karsten
2006-01-01
.... These techniques are referred to as first-principles (or in latin: ab initio) to indicate that they do not rely on empirical or fitted parameters, which then makes them applicable for a wide range of realistic conditions...
Phonocatalysis. An ab initio simulation experiment
Directory of Open Access Journals (Sweden)
Kwangnam Kim
2016-06-01
Full Text Available Using simulations, we postulate and show that heterocatalysis on large-bandgap semiconductors can be controlled by substrate phonons, i.e., phonocatalysis. With ab initio calculations, including molecular dynamic simulations, the chemisorbed dissociation of XeF6 on h-BN surface leads to formation of XeF4 and two surface F/h-BN bonds. The reaction pathway and energies are evaluated, and the sorption and reaction emitted/absorbed phonons are identified through spectral analysis of the surface atomic motion. Due to large bandgap, the atomic vibration (phonon energy transfer channels dominate and among them is the match between the F/h-BN covalent bond stretching and the optical phonons. We show that the chemisorbed dissociation (the pathway activation ascent requires absorption of large-energy optical phonons. Then using progressively heavier isotopes of B and N atoms, we show that limiting these high-energy optical phonons inhibits the chemisorbed dissociation, i.e., controllable phonocatalysis.
Ab initio thermodynamic model for magnesium carbonates and hydrates.
Chaka, Anne M; Felmy, Andrew R
2014-09-04
An ab initio thermodynamic framework for predicting properties of hydrated magnesium carbonate minerals has been developed using density-functional theory linked to macroscopic thermodynamics through the experimental chemical potentials for MgO, water, and CO2. Including semiempirical dispersion via the Grimme method and small corrections to the generalized gradient approximation of Perdew, Burke, and Ernzerhof for the heat of formation yields a model with quantitative agreement for the benchmark minerals brucite, magnesite, nesquehonite, and hydromagnesite. The model shows how small differences in experimental conditions determine whether nesquehonite, hydromagnesite, or magnesite is the result of laboratory synthesis from carbonation of brucite, and what transformations are expected to occur on geological time scales. Because of the reliance on parameter-free first-principles methods, the model is reliably extensible to experimental conditions not readily accessible to experiment and to any mineral composition for which the structure is known or can be hypothesized, including structures containing defects, substitutions, or transitional structures during solid state transformations induced by temperature changes or processes such as water, CO2, or O2 diffusion. Demonstrated applications of the ab initio thermodynamic framework include an independent means to evaluate differences in thermodynamic data for lansfordite, predicting the properties of Mg analogues of Ca-based hydrated carbonates monohydrocalcite and ikaite, which have not been observed in nature, and an estimation of the thermodynamics of barringtonite from the stoichiometry and a single experimental observation.
Devi, Assa Aravindh Sasikala
2014-01-01
Investigations on freestanding binary and ternary clusters of Fe (x) Co (y) Ir (z) (x + y + z = 5, 6) are carried out using ab initio density functional theory techniques. The geometry, chemical order, binding energy, magnetic moment and electronic
A hydronitrogen solid: high pressure ab initio evolutionary structure searches
International Nuclear Information System (INIS)
Hu Anguang; Zhang Fan
2011-01-01
High pressure ab initio evolutionary structure searches resulted in a hydronitrogen solid with a composition of (NH) 4 . The structure searches also provided two molecular isomers, ammonium azide (AA) and trans-tetrazene (TTZ) which were previously discovered experimentally and can be taken as molecular precursors for high pressure synthesis of the hydronitrogen solid. The computed pressure versus enthalpy diagram showed that the transformation pressure to the hydronitrogen solid is 36 GPa from AA and 75 GPa from TTZ. Its metastability was analyzed by the phonon dispersion spectrum and room-temperature vibrational density of state together with the transformation energy barrier back to molecular phases at 298 K. The predicted energy barrier of 0.21 eV/atom means that the proposed hydronitrogen solid should be very stable at ambient conditions. (fast track communication)
High-throughput ab-initio dilute solute diffusion database.
Wu, Henry; Mayeshiba, Tam; Morgan, Dane
2016-07-19
We demonstrate automated generation of diffusion databases from high-throughput density functional theory (DFT) calculations. A total of more than 230 dilute solute diffusion systems in Mg, Al, Cu, Ni, Pd, and Pt host lattices have been determined using multi-frequency diffusion models. We apply a correction method for solute diffusion in alloys using experimental and simulated values of host self-diffusivity. We find good agreement with experimental solute diffusion data, obtaining a weighted activation barrier RMS error of 0.176 eV when excluding magnetic solutes in non-magnetic alloys. The compiled database is the largest collection of consistently calculated ab-initio solute diffusion data in the world.
Westphal, Eduard; Pliego, Josefredo R
2007-10-11
The reaction pathways for the interaction of the nitrite ion with ethyl chloride and ethyl bromide in DMSO solution were investigated at the ab initio level of theory, and the solvent effect was included through the polarizable continuum model. The performance of BLYP, GLYP, XLYP, OLYP, PBE0, B3PW91, B3LYP, and X3LYP density functionals has been tested. For the ethyl bromide case, our best ab initio calculations at the CCSD(T)/aug-cc-pVTZ level predicts product ratio of 73% and 27% for nitroethane and ethyl nitrite, respectively, which can be compared with the experimental values of 67% and 33%. This translates to an error in the relative DeltaG* of only 0.17 kcal mol(-1). No functional is accurate (deviation X3LYP functional presents the best performance with deviation 0.82 kcal mol(-1). The present problem should be included in the test set used for the evaluation of new functionals.
Precise Ab-initio prediction of terahertz vibrational modes in crystalline systems
DEFF Research Database (Denmark)
Jepsen, Peter Uhd; Clark, Stewart J.
2007-01-01
We use a combination of experimental THz time-domain spectroscopy and ab-initio density functional perturbative theory to accurately predict the terahertz vibrational spectrum of molecules in the crystalline phase. Our calculations show that distinct vibrational modes found in solid-state materials...
de Lara-Castells, María Pilar; Aguirre, Néstor F.; Stoll, Hermann; Mitrushchenkov, Alexander O.; Mateo, David; Pi, Martí
2015-04-01
An ab-initio-based methodological scheme for He-surface interactions and zero-temperature time-dependent density functional theory for superfluid 4He droplets motion are combined to follow the short-time collision dynamics of the Au@4He300 system with the TiO2(110) surface. This composite approach demonstrates the 4He droplet-assisted sticking of the metal species to the surface at low landing energy (below 0.15 eV/atom), thus providing the first theoretical evidence of the experimentally observed 4He droplet-mediated soft-landing deposition of metal nanoparticles on solid surfaces [Mozhayskiy et al., J. Chem. Phys. 127, 094701 (2007) and Loginov et al., J. Phys. Chem. A 115, 7199 (2011)].
Energy Technology Data Exchange (ETDEWEB)
Lara-Castells, María Pilar de, E-mail: Pilar.deLara.Castells@csic.es; Aguirre, Néstor F. [Instituto de Física Fundamental (C.S.I.C.), Serrano 123, E-28006 Madrid (Spain); Stoll, Hermann [Institut für Theoretische Chemie, Universität Stuttgart, D-70550 Stuttgart (Germany); Mitrushchenkov, Alexander O. [Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallée (France); Mateo, David; Pi, Martí [Department ECM, Facultat de Física, and IN" 2UB, Universitat de Barcelona, Diagonal 645, E-08028 Barcelona (Spain)
2015-04-07
An ab-initio-based methodological scheme for He-surface interactions and zero-temperature time-dependent density functional theory for superfluid {sup 4}He droplets motion are combined to follow the short-time collision dynamics of the Au@{sup 4}He{sub 300} system with the TiO{sub 2}(110) surface. This composite approach demonstrates the {sup 4}He droplet-assisted sticking of the metal species to the surface at low landing energy (below 0.15 eV/atom), thus providing the first theoretical evidence of the experimentally observed {sup 4}He droplet-mediated soft-landing deposition of metal nanoparticles on solid surfaces [Mozhayskiy et al., J. Chem. Phys. 127, 094701 (2007) and Loginov et al., J. Phys. Chem. A 115, 7199 (2011)].
AB INITIO calculations of magneto-optical effects
Czech Academy of Sciences Publication Activity Database
Kuneš, Jan; Oppeneer, P. M.
2002-01-01
Roč. 2, - (2002), s. 141-146 ISSN 1346-7948 R&D Projects: GA AV ČR IAA1010214 Institutional research plan: CEZ:AV0Z1010914 Keywords : electronic structure * ab initio calculation * polar magneto-optical Kerr effect * transitiom metal * uranium intermetallics * CrO 2 Subject RIV: BM - Solid Matter Physics ; Magnetism
Multiple time step integrators in ab initio molecular dynamics
International Nuclear Information System (INIS)
Luehr, Nathan; Martínez, Todd J.; Markland, Thomas E.
2014-01-01
Multiple time-scale algorithms exploit the natural separation of time-scales in chemical systems to greatly accelerate the efficiency of molecular dynamics simulations. Although the utility of these methods in systems where the interactions are described by empirical potentials is now well established, their application to ab initio molecular dynamics calculations has been limited by difficulties associated with splitting the ab initio potential into fast and slowly varying components. Here we present two schemes that enable efficient time-scale separation in ab initio calculations: one based on fragment decomposition and the other on range separation of the Coulomb operator in the electronic Hamiltonian. We demonstrate for both water clusters and a solvated hydroxide ion that multiple time-scale molecular dynamics allows for outer time steps of 2.5 fs, which are as large as those obtained when such schemes are applied to empirical potentials, while still allowing for bonds to be broken and reformed throughout the dynamics. This permits computational speedups of up to 4.4x, compared to standard Born-Oppenheimer ab initio molecular dynamics with a 0.5 fs time step, while maintaining the same energy conservation and accuracy
Cyanogen Azide. Ionization Potentials and Ab Initio SCF MO Calculation
DEFF Research Database (Denmark)
Bak, Börge; Jansen, Peter; Stafast, Herbert
1975-01-01
The Ne(I) and He(I) photoelectron(PE) spectra of cyanogen azide, NCN3, have been recorded at high resolution. Their interpretation is achieved by comparison with the PE spectrum of HN3 and an ab initio LCGO SCF MO calculation. Deviations from Koopmans' theorem of quite different magnitudes...
Ab initio simulation of dislocation cores in metals
International Nuclear Information System (INIS)
Ventelon, L.
2008-01-01
In the framework of the multi scale simulation of metals and alloys plasticity, the aim of this study is to develop a methodology of ab initio dislocations study and to apply it to the [111] screw dislocation in the bc iron. (A.L.B.)
Ab initio electronic properties of dual phosphorus monolayers in silicon
DEFF Research Database (Denmark)
Drumm, Daniel W.; Per, Manolo C.; Budi, Akin
2014-01-01
In the midst of the epitaxial circuitry revolution in silicon technology, we look ahead to the next paradigm shift: effective use of the third dimension - in particular, its combination with epitaxial technology. We perform ab initio calculations of atomically thin epitaxial bilayers in silicon...
Quantifying transition voltage spectroscopy of molecular junctions: Ab initio calculations
DEFF Research Database (Denmark)
Chen, Jingzhe; Markussen, Troels; Thygesen, Kristian Sommer
2010-01-01
Transition voltage spectroscopy (TVS) has recently been introduced as a spectroscopic tool for molecular junctions where it offers the possibility to probe molecular level energies at relatively low bias voltages. In this work we perform extensive ab initio calculations of the nonlinear current...
Ab initio study of phase equilibria in TiCx
DEFF Research Database (Denmark)
Korzhavyi, P.A.; Pourovskii, L.V.; Hugosson, H.W.
2002-01-01
The phase diagram for the vacancy-ordered structures in the substoichiometric TiCx (x = 0.5-1.0) has been established from Monte Carlo simulations with the long-range pair and multisite effective interactions obtained from ab initio calculations. Three ordered superstructures of vacancies (Ti2C, Ti...
Ab initio and kinetic modeling studies of formic acid oxidation
DEFF Research Database (Denmark)
Marshall, Paul; Glarborg, Peter
2015-01-01
A detailed chemical kinetic model for oxidation of formic acid (HOCHO) in flames has been developed, based on theoretical work and data from literature. Ab initio calculations were used to obtain rate coefficients for reactions of HOCHO with H, O, and HO2. Modeling predictions with the mechanism...
Bicanonical ab Initio Molecular Dynamics for Open Systems.
Frenzel, Johannes; Meyer, Bernd; Marx, Dominik
2017-08-08
Performing ab initio molecular dynamics simulations of open systems, where the chemical potential rather than the number of both nuclei and electrons is fixed, still is a challenge. Here, drawing on bicanonical sampling ideas introduced two decades ago by Swope and Andersen [ J. Chem. Phys. 1995 , 102 , 2851 - 2863 ] to calculate chemical potentials of liquids and solids, an ab initio simulation technique is devised, which introduces a fictitious dynamics of two superimposed but otherwise independent periodic systems including full electronic structure, such that either the chemical potential or the average fractional particle number of a specific chemical species can be kept constant. As proof of concept, we demonstrate that solvation free energies can be computed from these bicanonical ab initio simulations upon directly superimposing pure bulk water and the respective aqueous solution being the two limiting systems. The method is useful in many circumstances, for instance for studying heterogeneous catalytic processes taking place on surfaces where the chemical potential of reactants rather than their number is controlled and opens a pathway toward ab initio simulations at constant electrochemical potential.
Ab initio calculations of mechanical properties: Methods and applications
Czech Academy of Sciences Publication Activity Database
Pokluda, J.; Černý, Miroslav; Šob, Mojmír; Umeno, Y.
2015-01-01
Roč. 73, AUG (2015), s. 127-158 ISSN 0079-6425 R&D Projects: GA ČR(CZ) GAP108/12/0311 Institutional support: RVO:68081723 Keywords : Ab initio methods * Elastic moduli * Intrinsic hardness * Stability analysis * Theoretical strength * Intrinsic brittleness/ductility Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 31.083, year: 2015
The Properties of Some Simple Covalent Hydrides: An Ab Initio ...
African Journals Online (AJOL)
Some properties of the monomeric binary hydrides of the elements of the first two rows of the periodic table have been determined using ab initio molecular orbital theory. The properties in question are the energetic, structural, electronic, topological and vibrational characteristics. In general, a gradual convergence towards ...
Hydrogen Bond Dynamics in Aqueous Solutions: Ab initio Molecular ...
Indian Academy of Sciences (India)
Rate equation for the decay of CHB(t) · Definition of Hydrogen Bonds · Results of Molecular Dynamics · Dynamics of anion-water and water-water hydrogen bonds · Structural relaxation of anion-water & water-water H-bonds · Ab initio Molecular Dynamics : · Slide 14 · Dynamics of hydrogen bonds : CPMD results · Slide 16.
Ab initio transport across bismuth selenide surface barriers
Narayan, Awadhesh; Rungger, Ivan; Droghetti, Andrea; Sanvito, Stefano
2014-01-01
© 2014 American Physical Society. We investigate the effect of potential barriers in the form of step edges on the scattering properties of Bi2Se3(111) topological surface states by means of large-scale ab initio transport simulations. Our results
Perspective: Ab initio force field methods derived from quantum mechanics
Xu, Peng; Guidez, Emilie B.; Bertoni, Colleen; Gordon, Mark S.
2018-03-01
It is often desirable to accurately and efficiently model the behavior of large molecular systems in the condensed phase (thousands to tens of thousands of atoms) over long time scales (from nanoseconds to milliseconds). In these cases, ab initio methods are difficult due to the increasing computational cost with the number of electrons. A more computationally attractive alternative is to perform the simulations at the atomic level using a parameterized function to model the electronic energy. Many empirical force fields have been developed for this purpose. However, the functions that are used to model interatomic and intermolecular interactions contain many fitted parameters obtained from selected model systems, and such classical force fields cannot properly simulate important electronic effects. Furthermore, while such force fields are computationally affordable, they are not reliable when applied to systems that differ significantly from those used in their parameterization. They also cannot provide the information necessary to analyze the interactions that occur in the system, making the systematic improvement of the functional forms that are used difficult. Ab initio force field methods aim to combine the merits of both types of methods. The ideal ab initio force fields are built on first principles and require no fitted parameters. Ab initio force field methods surveyed in this perspective are based on fragmentation approaches and intermolecular perturbation theory. This perspective summarizes their theoretical foundation, key components in their formulation, and discusses key aspects of these methods such as accuracy and formal computational cost. The ab initio force fields considered here were developed for different targets, and this perspective also aims to provide a balanced presentation of their strengths and shortcomings. Finally, this perspective suggests some future directions for this actively developing area.
Unraveling the structure of the h-BN/Rh(111) nanomesh with ab initio calculations
International Nuclear Information System (INIS)
Laskowski, R; Blaha, P
2008-01-01
The properties of a single layer of h-BN on top of a Rh(111) surface are discussed in terms of an ab initio generated force field approach as well as by direct ab initio density-functional theory (DFT) calculations. A single-layer model for the h-BN/Rh(111) nanomesh, in contrast to a previously considered (incomplete) double-layer model of h-BN, can explain the experimental data. The main focus of this work is to compare a force field approach described earlier in (Laskowski et al 2007 Phys. Rev. Lett. 98 106802) with direct ab initio calculations. The calculated geometry of the h-BN layer is very similar to the structure predicted by the force field approach. The ab initio calculated density of states projected on N-p x,y of BN corresponding to 'low' and 'high' regions with respect to the Rh surface shows a 1 eV splitting and thus explains the observed σ-band splitting. Moreover, we find good agreement between calculated and experimental scanning tunneling microscope (STM) images of this system
International Nuclear Information System (INIS)
Sakane, Shinichi; Yezdimer, Eric M.; Liu, Wenbin; Barriocanal, Jose A.; Doren, Douglas J.; Wood, Robert H.
2000-01-01
The ab initio/classical free energy perturbation (ABC-FEP) method proposed previously by Wood et al. [J. Chem. Phys. 110, 1329 (1999)] uses classical simulations to calculate solvation free energies within an empirical potential model, then applies free energy perturbation theory to determine the effect of changing the empirical solute-solvent interactions to corresponding interactions calculated from ab initio methods. This approach allows accurate calculation of solvation free energies using an atomistic description of the solvent and solute, with interactions calculated from first principles. Results can be obtained at a feasible computational cost without making use of approximations such as a continuum solvent or an empirical cavity formation energy. As such, the method can be used far from ambient conditions, where the empirical parameters needed for approximate theories of solvation may not be available. The sources of error in the ABC-FEP method are the approximations in the ab initio method, the finite sample of configurations, and the classical solvent model. This article explores the accuracy of various approximations used in the ABC-FEP method by comparing to the experimentally well-known free energy of hydration of water at two state points (ambient conditions, and 973.15 K and 600 kg/m3). The TIP4P-FQ model [J. Chem. Phys. 101, 6141 (1994)] is found to be a reliable solvent model for use with this method, even at supercritical conditions. Results depend strongly on the ab initio method used: a gradient-corrected density functional theory is not adequate, but a localized MP2 method yields excellent agreement with experiment. Computational costs are reduced by using a cluster approximation, in which ab initio pair interaction energies are calculated between the solute and up to 60 solvent molecules, while multi-body interactions are calculated with only a small cluster (5 to 12 solvent molecules). Sampling errors for the ab initio contribution to
International Nuclear Information System (INIS)
Nakayama, Akira; Taketsugu, Tetsuya; Shiga, Motoyuki
2009-01-01
Efficiency of the ab initio hybrid Monte Carlo and ab initio path integral hybrid Monte Carlo methods is enhanced by employing an auxiliary potential energy surface that is used to update the system configuration via molecular dynamics scheme. As a simple illustration of this method, a dual-level approach is introduced where potential energy gradients are evaluated by computationally less expensive ab initio electronic structure methods. (author)
Physical properties of molybdenum monoboride: Ab-initio study
Rajpoot, Priyanka; Rastogi, Anugya; Verma, U. P.
2018-02-01
The Ab initio investigations on structural, electronic, optical and thermal properties of MoB have been reported using full potential linearised-augmented plane wave method within the framework of density functional theory. The exchange and correlation potentials were calculated using the Perdew-Burke-Ernzerhof-Sol generalised gradient approximation. The calculated equilibrium lattice constants and cell volume are in excellent agreement with the experimental results as compared to the available theoretical data. Electronic band structure shows that MoB is metallic in nature. From the partial densities of states of MoB it has been found that major contribution on the Fermi level is due to Mo-4d states. Among the reported optical parameters the large value of reflectivity at low energy shows that MoB can be used as a coating material in IR region. Maximum absorption in extreme UV region shows that it can be used in production of electricity through solar power in space vehicles. Various thermal properties have been calculated in a wide temperature range at high pressures. Change in thermal expansion coefficient with respect to temperature shows that anharmonic effect in MoB is very weak at high temperature. The optical and thermal properties of MoB are presented for the first time in this work.
Ab initio study of point defects in magnesium oxide
International Nuclear Information System (INIS)
Gilbert, C. A.; Kenny, S. D.; Smith, R.; Sanville, E.
2007-01-01
Energetics of a variety of point defects in MgO have been considered from an ab initio perspective using density functional theory. The considered defects are isolated Schottky and Frenkel defects and interstitial pairs, along with a number of Schottky defects and di-interstitials. Comparisons were made between the density functional theory results and results obtained from empirical potential simulations and these generally showed good agreement. Both methodologies predicted the first nearest neighbor Schottky defects to be the most energetically favorable of the considered Schottky defects and that the first, second, and fifth nearest neighbor di-interstitials were of similar energy and were favored over the other di-interstitial configurations. Relaxed structures of the defects were analyzed, which showed that empirical potential simulations were accurately predicting the displacements of atoms surrounding di-interstitials, but were overestimating O atom displacement for Schottky defects. Transition barriers were computed for the defects using the nudged elastic band method. Vacancies and Schottky defects were found to have relatively high energy barriers, the majority of which were over 2 eV, in agreement with conclusions reached using empirical potentials. The lowest barriers for di-interstitial transitions were found to be for migration into a first nearest neighbor configuration. Charges were calculated using a Bader analysis and this found negligible charge transfer during the defect transitions and only small changes in the charges on atoms surrounding defects, indicating why fixed charge models work as well as they do
An ab-initio study of mechanical, dynamical and electronic properties of MgEu intermetallic
Kumar, S. Ramesh; Jaiganesh, G.; Jayalakshmi, V.
2018-04-01
The theoretical investigation on the mechanical, dynamical and electronic properties of MgEu in CsCl-type structure has been carried out through the ab-initio calculations within the framework of the density functional theory and the density functional perturbation theory. For the purpose, Vienna Ab initio Simulation Package and Phonopy packages were used. Our calculated ground-state properties of MgEu are in good agreement with other available results. Our computed elastic constants and phonon spectrum results suggest that MgEu is mechanically and dynamically stable up to 5 GPa. The thermodynamic quantities as a function of temperatures are also reported and discussed. The band structure, density of states and charge density also calculated to understand the electronic properties of MgEu.
Ab Initio Calculations for the BaTiO3 (001) Surface Structure
Institute of Scientific and Technical Information of China (English)
XUE Xu-Yan; WANG Chun-Lei; ZHONG Wei-Lie
2004-01-01
@@ The ab initio method within the local density approximation is applied to calculate cubic BaTiO3 (001) surface relaxation and rumpling for two different terminations (BaO and TiO2). Our calculations demonstrate that cubic perovskite BaTiO3 crystals possess surface polarization, accompanied by the presence of the relevant electric field.We analyse their electronic structures (band structure, density of states and the electronic density redistribution with emphasis on the covalency effects). The results are also compared with that of the previous ab initio calculations. Considerable increases of Ti-O chemical bond covalency nearby the surface have been observed.The band gap reduces especially for the TiO2 termination.
Ab initio molecular crystal structures, spectra, and phase diagrams.
Hirata, So; Gilliard, Kandis; He, Xiao; Li, Jinjin; Sode, Olaseni
2014-09-16
Conspectus Molecular crystals are chemists' solids in the sense that their structures and properties can be understood in terms of those of the constituent molecules merely perturbed by a crystalline environment. They form a large and important class of solids including ices of atmospheric species, drugs, explosives, and even some organic optoelectronic materials and supramolecular assemblies. Recently, surprisingly simple yet extremely efficient, versatile, easily implemented, and systematically accurate electronic structure methods for molecular crystals have been developed. The methods, collectively referred to as the embedded-fragment scheme, divide a crystal into monomers and overlapping dimers and apply modern molecular electronic structure methods and software to these fragments of the crystal that are embedded in a self-consistently determined crystalline electrostatic field. They enable facile applications of accurate but otherwise prohibitively expensive ab initio molecular orbital theories such as Møller-Plesset perturbation and coupled-cluster theories to a broad range of properties of solids such as internal energies, enthalpies, structures, equation of state, phonon dispersion curves and density of states, infrared and Raman spectra (including band intensities and sometimes anharmonic effects), inelastic neutron scattering spectra, heat capacities, Gibbs energies, and phase diagrams, while accounting for many-body electrostatic (namely, induction or polarization) effects as well as two-body exchange and dispersion interactions from first principles. They can fundamentally alter the role of computing in the studies of molecular crystals in the same way ab initio molecular orbital theories have transformed research practices in gas-phase physical chemistry and synthetic chemistry in the last half century. In this Account, after a brief summary of formalisms and algorithms, we discuss applications of these methods performed in our group as compelling
Thermal, spectroscopic, and ab initio structural characterization of carprofen polymorphs.
Bruni, Giovanna; Gozzo, Fabia; Capsoni, Doretta; Bini, Marcella; Macchi, Piero; Simoncic, Petra; Berbenni, Vittorio; Milanese, Chiara; Girella, Alessandro; Ferrari, Stefania; Marini, Amedeo
2011-06-01
Commercial and recrystallized polycrystalline samples of carprofen, a nonsteroidal anti-inflammatory drug, were studied by thermal, spectroscopic, and structural techniques. Our investigations demonstrated that recrystallized sample, stable at room temperature (RT), is a single polymorphic form of carprofen (polymorph I) that undergoes an isostructural polymorphic transformation by heating (polymorph II). Polymorph II remains then metastable at ambient conditions. Commercial sample is instead a mixture of polymorphs I and II. The thermodynamic relationships between the two polymorphs were determined through the construction of an energy/temperature diagram. The ab initio structural determination performed on synchrotron X-Ray powder diffraction patterns recorded at RT on both polymorphs allowed us to elucidate, for the first time, their crystal structure. Both crystallize in the monoclinic space group type P2(1) /c, and the unit cell similarity index and the volumetric isostructurality index indicate that the temperature-induced polymorphic transformation I → II is isostructural. Polymorphs I and II are conformational polymorphs, sharing a very similar hydrogen bond network, but with different conformation of the propanoic skeleton, which produces two different packing. The small conformational change agrees with the low value of transition enthalpy obtained by differential scanning calorimetry measurements and the small internal energy computed with density functional methods. Copyright © 2011 Wiley-Liss, Inc.
Ab-initio calculations for dilute magnetic semiconductors
Energy Technology Data Exchange (ETDEWEB)
Belhadji, Brahim
2008-03-03
This thesis focusses on ab-initio calculations for the electronic structure and the magnetic properties of dilute magnetic semiconductors (DMS). In particular we aim at the understanding of the complex exchange interactions in these systems. Our calculations are based on density functional theory, being ideally suited for a description of the material specific properties of the considered DMS. Moreover we use the KKR Green function method in connection with the coherent potential approximation (CPA), which allows to include the random substitutional disorder in a mean field-like approximation for the electronic structure. Finally we calculate the exchange coupling constants J{sub ij} between two impurities in a CPA medium by using the Lichtenstein formula and from this calculate the Curie temperature by a numerically exact Monte Carlo method. Based on this analysis we found and investigated four different exchange mechanisms being of importance in DMS systems: Double exchange, p-d exchange, antiferromagnetic superexchanges, and ferromagnetic superexchange. A second topic we have investigated in this thesis is the pressure dependence of the exchange interactions and the Curie temperatures in (Ga,Mn)As and (In,Mn)As, using the LDA and the LDA+U approximations. Exact calculations of T{sub C} by Monte Carlo simulations show a somehow different behavior. (orig.)
Ab initio transport across bismuth selenide surface barriers
Narayan, Awadhesh
2014-11-24
© 2014 American Physical Society. We investigate the effect of potential barriers in the form of step edges on the scattering properties of Bi2Se3(111) topological surface states by means of large-scale ab initio transport simulations. Our results demonstrate the suppression of perfect backscattering, while all other scattering processes, which do not entail a complete spin and momentum reversal, are allowed. Furthermore, we find that the spin of the surface state develops an out-of-plane component as it traverses the barrier. Our calculations reveal the existence of quasibound states in the vicinity of the surface barriers, which appear in the form of an enhanced density of states in the energy window corresponding to the topological state. For double barriers we demonstrate the formation of quantum well states. To complement our first-principles results we construct a two-dimensional low-energy effective model and illustrate its shortcomings. Our findings are discussed in the context of a number of recent experimental works.
Double-walled silicon nanotubes: an ab initio investigation
Lima, Matheus P.
2018-02-01
The synthesis of silicon nanotubes realized in the last decade demonstrates multi-walled tubular structures consisting of Si atoms in {{sp}}2 and the {{sp}}3 hybridizations. However, most of the theoretical models were elaborated taking as the starting point {{sp}}2 structures analogous to carbon nanotubes. These structures are unfavorable due to the natural tendency of the Si atoms to undergo {{sp}}3. In this work, through ab initio simulations based on density functional theory, we investigated double-walled silicon nanotubes proposing layered tubes possessing most of the Si atoms in an {{sp}}3 hybridization, and with few {{sp}}2 atoms localized at the outer wall. The lowest-energy structures have metallic behavior. Furthermore, the possibility to tune the band structure with the application of a strain was demonstrated, inducing a metal-semiconductor transition. Thus, the behavior of silicon nanotubes differs significantly from carbon nanotubes, and the main source of the differences is the distortions in the lattice associated with the tendency of Si to make four chemical bonds.
Ab initio modelling of methane hydrate thermophysical properties.
Jendi, Z M; Servio, P; Rey, A D
2016-04-21
The key thermophysical properties of methane hydrate were determined using ab initio modelling. Using density functional theory, the second-order elastic constants, heat capacity, compressibility, and thermal expansion coefficient were calculated. A wide and relevant range of pressure-temperature conditions were considered, and the structures were assessed for stability using the mean square displacement and radial distribution functions. Methane hydrate was found to be elastically isotropic with a linear dependence of the bulk modulus on pressure. Equally significant, multi-body interactions were found to be important in hydrates, and water-water interactions appear to strongly influence compressibility like in ice Ih. While the heat capacity of hydrate was found to be higher than that of ice, the thermal expansion coefficient was significantly lower, most likely due to the lower rigidity of hydrates. The mean square displacement gave important insight into stability, heat capacity, and elastic moduli, and the radial distribution functions further confirmed stability. The presented results provide a much needed atomistic thermoelastic characterization of methane hydrates and are essential input for the large-scale applications of hydrate detection and production.
Computational methods for ab initio detection of microRNAs
Directory of Open Access Journals (Sweden)
Malik eYousef
2012-10-01
Full Text Available MicroRNAs are small RNA sequences of 18-24 nucleotides in length, which serve as templates to drive post transcriptional gene silencing. The canonical microRNA pathway starts with transcription from DNA and is followed by processing via the Microprocessor complex, yielding a hairpin structure. Which is then exported into the cytosol where it is processed by Dicer and then incorporated into the RNA induced silencing complex. All of these biogenesis steps add to the overall specificity of miRNA production and effect. Unfortunately, their modes of action are just beginning to be elucidated and therefore computational prediction algorithms cannot model the process but are usually forced to employ machine learning approaches. This work focuses on ab initio prediction methods throughout; and therefore homology-based miRNA detection methods are not discussed. Current ab initio prediction algorithms, their ties to data mining, and their prediction accuracy are detailed.
Ab Initio Calculations Of Light-Ion Reactions
International Nuclear Information System (INIS)
Navratil, P.; Quaglioni, S.; Roth, R.; Horiuchi, W.
2012-01-01
The exact treatment of nuclei starting from the constituent nucleons and the fundamental interactions among them has been a long-standing goal in nuclear physics. In addition to the complex nature of nuclear forces, one faces the quantum-mechanical many-nucleon problem governed by an interplay between bound and continuum states. In recent years, significant progress has been made in ab initio nuclear structure and reaction calculations based on input from QCD employing Hamiltonians constructed within chiral effective field theory. In this contribution, we present one of such promising techniques capable of describing simultaneously both bound and scattering states in light nuclei. By combining the resonating-group method (RGM) with the ab initio no-core shell model (NCSM), we complement a microscopic cluster approach with the use of realistic interactions and a microscopic and consistent description of the clusters. We discuss applications to light nuclei scattering, radiative capture and fusion reactions.
GAUSSIAN 76: an ab initio molecular orbital program
International Nuclear Information System (INIS)
Binkley, J.S.; Whiteside, R.; Hariharan, P.C.; Seeger, R.; Hehre, W.J.; Lathan, W.A.; Newton, M.D.; Ditchfield, R.; Pople, J.A.
Gaussian 76 is a general-purpose computer program for ab initio Hartree-Fock molecular orbital calculations. It can handle basis sets involving s, p and d-type gaussian functions. Certain standard sets (STO-3G, 4-31G, 6-31G*, etc.) are stored internally for easy use. Closed shell (RHF) or unrestricted open shell (UHF) wave functions can be obtained. Facilities are provided for geometry optimization to potential minima and for limited potential surface scans
Ab Initio Nuclear Structure and Reaction Calculations for Rare Isotopes
Energy Technology Data Exchange (ETDEWEB)
Draayer, Jerry P. [Louisiana State Univ., Baton Rouge, LA (United States)
2014-09-28
We have developed a novel ab initio symmetry-adapted no-core shell model (SA-NCSM), which has opened the intermediate-mass region for ab initio investigations, thereby providing an opportunity for first-principle symmetry-guided applications to nuclear structure and reactions for nuclear isotopes from the lightest p-shell systems to intermediate-mass nuclei. This includes short-lived proton-rich nuclei on the path of X-ray burst nucleosynthesis and rare neutron-rich isotopes to be produced by the Facility for Rare Isotope Beams (FRIB). We have provided ab initio descriptions of high accuracy for low-lying (including collectivity-driven) states of isotopes of Li, He, Be, C, O, Ne, Mg, Al, and Si, and studied related strong- and weak-interaction driven reactions that are important, in astrophysics, for further understanding stellar evolution, X-ray bursts and triggering of s, p, and rp processes, and in applied physics, for electron and neutrino-nucleus scattering experiments as well as for fusion ignition at the National Ignition Facility (NIF).
Ab initio nuclear structure - the large sparse matrix eigenvalue problem
Energy Technology Data Exchange (ETDEWEB)
Vary, James P; Maris, Pieter [Department of Physics, Iowa State University, Ames, IA, 50011 (United States); Ng, Esmond; Yang, Chao [Computational Research Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Sosonkina, Masha, E-mail: jvary@iastate.ed [Scalable Computing Laboratory, Ames Laboratory, Iowa State University, Ames, IA, 50011 (United States)
2009-07-01
The structure and reactions of light nuclei represent fundamental and formidable challenges for microscopic theory based on realistic strong interaction potentials. Several ab initio methods have now emerged that provide nearly exact solutions for some nuclear properties. The ab initio no core shell model (NCSM) and the no core full configuration (NCFC) method, frame this quantum many-particle problem as a large sparse matrix eigenvalue problem where one evaluates the Hamiltonian matrix in a basis space consisting of many-fermion Slater determinants and then solves for a set of the lowest eigenvalues and their associated eigenvectors. The resulting eigenvectors are employed to evaluate a set of experimental quantities to test the underlying potential. For fundamental problems of interest, the matrix dimension often exceeds 10{sup 10} and the number of nonzero matrix elements may saturate available storage on present-day leadership class facilities. We survey recent results and advances in solving this large sparse matrix eigenvalue problem. We also outline the challenges that lie ahead for achieving further breakthroughs in fundamental nuclear theory using these ab initio approaches.
Ab initio nuclear structure - the large sparse matrix eigenvalue problem
International Nuclear Information System (INIS)
Vary, James P; Maris, Pieter; Ng, Esmond; Yang, Chao; Sosonkina, Masha
2009-01-01
The structure and reactions of light nuclei represent fundamental and formidable challenges for microscopic theory based on realistic strong interaction potentials. Several ab initio methods have now emerged that provide nearly exact solutions for some nuclear properties. The ab initio no core shell model (NCSM) and the no core full configuration (NCFC) method, frame this quantum many-particle problem as a large sparse matrix eigenvalue problem where one evaluates the Hamiltonian matrix in a basis space consisting of many-fermion Slater determinants and then solves for a set of the lowest eigenvalues and their associated eigenvectors. The resulting eigenvectors are employed to evaluate a set of experimental quantities to test the underlying potential. For fundamental problems of interest, the matrix dimension often exceeds 10 10 and the number of nonzero matrix elements may saturate available storage on present-day leadership class facilities. We survey recent results and advances in solving this large sparse matrix eigenvalue problem. We also outline the challenges that lie ahead for achieving further breakthroughs in fundamental nuclear theory using these ab initio approaches.
Ab Initio Nuclear Structure and Reaction Calculations for Rare Isotopes
International Nuclear Information System (INIS)
Draayer, Jerry P.
2014-01-01
We have developed a novel ab initio symmetry-adapted no-core shell model (SA-NCSM), which has opened the intermediate-mass region for ab initio investigations, thereby providing an opportunity for first-principle symmetry-guided applications to nuclear structure and reactions for nuclear isotopes from the lightest p-shell systems to intermediate-mass nuclei. This includes short-lived proton-rich nuclei on the path of X-ray burst nucleosynthesis and rare neutron-rich isotopes to be produced by the Facility for Rare Isotope Beams (FRIB). We have provided ab initio descriptions of high accuracy for low-lying (including collectivity-driven) states of isotopes of Li, He, Be, C, O, Ne, Mg, Al, and Si, and studied related strong- and weak-interaction driven reactions that are important, in astrophysics, for further understanding stellar evolution, X-ray bursts and triggering of s, p, and rp processes, and in applied physics, for electron and neutrino-nucleus scattering experiments as well as for fusion ignition at the National Ignition Facility (NIF).
Ab initio multiple cloning algorithm for quantum nonadiabatic molecular dynamics
Energy Technology Data Exchange (ETDEWEB)
Makhov, Dmitry V.; Shalashilin, Dmitrii V. [Department of Chemistry, University of Leeds, Leeds LS2 9JT (United Kingdom); Glover, William J.; Martinez, Todd J. [Department of Chemistry and The PULSE Institute, Stanford University, Stanford, California 94305, USA and SLAC National Accelerator Laboratory, Menlo Park, California 94025 (United States)
2014-08-07
We present a new algorithm for ab initio quantum nonadiabatic molecular dynamics that combines the best features of ab initio Multiple Spawning (AIMS) and Multiconfigurational Ehrenfest (MCE) methods. In this new method, ab initio multiple cloning (AIMC), the individual trajectory basis functions (TBFs) follow Ehrenfest equations of motion (as in MCE). However, the basis set is expanded (as in AIMS) when these TBFs become sufficiently mixed, preventing prolonged evolution on an averaged potential energy surface. We refer to the expansion of the basis set as “cloning,” in analogy to the “spawning” procedure in AIMS. This synthesis of AIMS and MCE allows us to leverage the benefits of mean-field evolution during periods of strong nonadiabatic coupling while simultaneously avoiding mean-field artifacts in Ehrenfest dynamics. We explore the use of time-displaced basis sets, “trains,” as a means of expanding the basis set for little cost. We also introduce a new bra-ket averaged Taylor expansion (BAT) to approximate the necessary potential energy and nonadiabatic coupling matrix elements. The BAT approximation avoids the necessity of computing electronic structure information at intermediate points between TBFs, as is usually done in saddle-point approximations used in AIMS. The efficiency of AIMC is demonstrated on the nonradiative decay of the first excited state of ethylene. The AIMC method has been implemented within the AIMS-MOLPRO package, which was extended to include Ehrenfest basis functions.
Energy Technology Data Exchange (ETDEWEB)
Bernard, St
1999-12-31
The quest for metallic hydrogen is a major goal for both theoretical and experimental condensed matter physics. Hydrogen and deuterium have been compressed up to 200 GPa in diamond anvil cells, without any clear evidence for a metallic behaviour. Loubeyere has recently suggested that hydrogen could metallize, at pressures within experimental range, in a new Van der Waals compound: Ar(H{sub 2}){sub 2} which is characterized at ambient pressure by an open and anisotropic sublattice of hydrogen molecules, stabilized by an argon skeleton. This thesis deals with a detailed ab initio investigation, by Car-Parrinello molecular dynamics methods, of the evolution under pressure of this compound. In a last chapter, we go to much higher pressures and temperatures, in order to compare orbital and orbital free ab initio methods for the dense hydrogen plasma. (author) 109 refs.
Energy Technology Data Exchange (ETDEWEB)
Bernard, St
1998-12-31
The quest for metallic hydrogen is a major goal for both theoretical and experimental condensed matter physics. Hydrogen and deuterium have been compressed up to 200 GPa in diamond anvil cells, without any clear evidence for a metallic behaviour. Loubeyere has recently suggested that hydrogen could metallize, at pressures within experimental range, in a new Van der Waals compound: Ar(H{sub 2}){sub 2} which is characterized at ambient pressure by an open and anisotropic sublattice of hydrogen molecules, stabilized by an argon skeleton. This thesis deals with a detailed ab initio investigation, by Car-Parrinello molecular dynamics methods, of the evolution under pressure of this compound. In a last chapter, we go to much higher pressures and temperatures, in order to compare orbital and orbital free ab initio methods for the dense hydrogen plasma. (author) 109 refs.
Electronic properties of liquid Hg-In alloys : Ab-initio molecular dynamics study
International Nuclear Information System (INIS)
Sharma, Nalini; Ahluwalia, P. K.; Thakur, Anil
2016-01-01
Ab-initio molecular dynamics simulations are performed to study the structural properties of liquid Hg-In alloys. The interatomic interactions are described by ab-initio pseudopotentials given by Troullier and Martins. Three liquid Hg-In alloys (Hg_1_0In_9_0, Hg_3_0In_7_0_,_. Hg_5_0In_5_0, Hg_7_0In_3_0, and Hg_9_0Pb_1_0) at 299 K are considered. The calculated results for liquid Hg (l-Hg) and lead (l-In) are also drawn. Along with the calculated results of considered five liquid alloys of Hg-In alloy. The results obtained from electronic properties namely total density of state and partial density of states help to find the local arrangement of Hg and In atoms and the presence of liquid state in the considered five alloys.
Ab initio theory of the N2V defect in diamond for quantum memory implementation
Udvarhelyi, Péter; Thiering, Gergő; Londero, Elisa; Gali, Adam
2017-10-01
The N2V defect in diamond is characterized by means of ab initio methods relying on density functional theory calculated parameters of a Hubbard model Hamiltonian. It is shown that this approach appropriately describes the energy levels of correlated excited states induced by this defect. By determining its critical magneto-optical parameters, we propose to realize a long-living quantum memory by N2V defect, i.e., H 3 color center in diamond.
Study of carvedilol by combined Raman spectroscopy and ab initio MO calculations
Marques, M. P. M.; Oliveira, P. J.; Moreno, A. J. M.; Carvalho, L. A. E. Batista de
2002-01-01
The novel cardioprotective drug carvedilol was studied by both Raman spectroscopy and ab initio molecular orbital methods (using the density functional theory approach). The spectra, acquired both for the solid samples and DMSO solutions as a function of pH, were assigned in view of the calculated wavenumbers and intensities, and also based on the experimental data obtained for individual compounds which comprise the molecule, namely carbazole and 1,2-dimethoxybenzene. The pH dependence of th...
Ab initio lattice dynamics of complex structures
DEFF Research Database (Denmark)
Voss, Johannes
2008-01-01
In this thesis, density functional theory is applied in a study of thermodynamic properties of so-called complex metal hydrides, which are promising materials for hydrogen storage applications. Since the unit cells of these crystals can be relatively large with many symmetrically inequivalent ato...
Srivastava, Anubha; Tandon, Poonam; Jain, Sudha; Asthana, B P
2011-12-15
(+)-Bicuculline (hereinafter referred to as bicuculline), a phthalide isoquinoline alkaloid is of current interest as an antagonist of gamma-aminobutyric acid (GABA). Its inhibitor properties have been studied through molecular electrostatic potential (MEP) mapping of this molecule and GABA receptor. The hot site on the potential surface of bicuculline, which is also isosteric with GABA receptor, has been used to interpret the inhibitor property. A systematic quantum chemical study of the possible conformations, their relative stabilities, FT-Raman, FT-IR and UV-vis spectroscopic analysis of bicuculline has been reported. The optimized geometries, wavenumber and intensity of the vibrational bands of all the conformers of bicuculline have been calculated using ab initio Hartree-Fock (HF) and density functional theory (DFT) employing B3LYP functional and 6-311G(d,p) basis set. Mulliken atomic charges, HOMO-LUMO gap ΔE, ionization potential, dipole moments and total energy have also been obtained for the optimized geometries of both the molecules. TD-DFT method is used to calculate the electronic absorption parameters in gas phase as well as in solvent environment using integral equation formalism-polarizable continuum model (IEF-PCM) employing 6-31G basis set and the results thus obtained are compared with the UV absorption spectra. The combination of experimental and calculated results provides an insight into the structural and vibrational spectroscopic properties of bicuculline. Copyright © 2011 Elsevier B.V. All rights reserved.
Boda, Anil; Ali, Sk Musharaf; Rao, Hanmanth; Ghosh, Sandip K
2012-08-01
The structures, energetic and thermodynamic parameters of model crown ethers with different donor, cavity and electron donating/ withdrawing functional group have been determined with ab initio MP2 and density functional theory in gas and solvent phase. The calculated values of binding energy/ enthalpy for lithium ion complexation are marginally higher for hard donor based aza and oxa crown compared to soft donor based thia and phospha crown. The calculated values of binding enthalpy for lithium metal ion with 12C4 at MP2 level of theory is in good agreement with the available experimental result. The binding energy is altered due to the inductive effect imparted by the electron donating/ withdrawing group in crown ether, which is well correlated with the values of electron transfer. The role of entropy for extraction of hydrated lithium metal ion by different donor and functional group based ligand has been demonstrated. The HOMO-LUMO gap is decreased and dipole moment of the ligand is increased from gas phase to organic phase because of the dielectric constant of the solvent. The gas phase binding energy is reduced in solvent phase as the solvent molecules weaken the metal-ligand binding. The theoretical values of extraction energy for LiCl salt from aqueous solution in different organic solvent is validated by the experimental trend. The study presented here should contribute to the design of model host ligand and screening of solvent for metal ion recognition and thus can contribute in planning the experiments.
Moon, Jiwon; Kim, Joonghan
2016-09-29
Density functional theory (DFT) and ab initio calculations, including spin-orbit coupling (SOC), were performed to investigate the spin-orbit (SO) effect on the molecular properties of tellurium halides, TeXn (X = F, Cl, Br, and I; n = 1, 2, and 4). SOC elongates the Te-X bond and slightly reduces the vibrational frequencies. Consideration of SOC leads to better agreement with experimental values. Møller-Plesset second-order perturbation theory (MP2) seriously underestimates the Te-X bond lengths. In contrast, B3LYP significantly overestimates them. SO-PBE0 and multireference configuration interactions with the Davidson correction (MRCI+Q), which include SOC via a state-interaction approach, give the Te-I bond length of TeI2 that matches the experimental value. On the basis of the calculated thermochemical energy and optimized molecular structure, TeI4 is unlikely to be stable. The use of PBE0 including SOC is strongly recommended for predicting the molecular properties of Te-containing compounds.
An ab initio study of plutonium oxides surfaces
International Nuclear Information System (INIS)
Jomard, G.; Bottin, F.; Amadon, B.
2007-01-01
By means of first-principles calculations, we have studied the atomic structure as well as the thermodynamic stability of various plutonium dioxide surfaces in function of their environment (in terms of oxygen partial pressure and temperature). All these simulations have been performed with the ABINIT code. It is well known that DFT fails to describe correctly plutonium-based materials since 5f electrons in such systems are strongly correlated. In order to go beyond DFT, we have treated PuO 2 and β-Pu 2 O 3 in a DFT+U framework. We show that the couple of parameters (U,J) that works well for pure Pu is also well designed for describing ground state (GS) properties of these two oxides. The major improvement with respect with DFT is that we are able to predict an insulating GS in agreement with experiments. The presence of a gap in the DOS (Density of States) of plutonium oxides should play a significant role in the predicted surface reactivity. However, performing DFT+U calculations on surfaces of plutonium oxide from scratch was too ambitious. That is why we decided, as a first step, to study the stability of the (100), (110) and (111) surfaces of PuO 2 in a DFT-GGA framework. For each of these orientations, we considered various terminations. These ab initio results have been introduced in a thermodynamic model which allows us to predict the relative stability of the different terminations as a function of temperature and oxygen partial pressure (p O 2 ). We conclude that at room temperature and for p O 2 ∼10 atm., the polar O 2 -(100) termination is favoured. The stabilization of such a polar stoichiometric surface is surprising and should be confirmed by DFT+U calculations before any final conclusion. (authors)
Ab initio simulation of amorphous silicon
International Nuclear Information System (INIS)
Cooper, N.C.; McKenzie, D.R.; Goringe, C.M.
1999-01-01
Full text: A first-principles Car-Parrinello molecular dynamics simulation of amorphous silicon is presented. Density Functional Theory is used to describe the forces between the atoms in a 64 atom supercell which is periodically repeated throughout space in order to generate an infinite network of atoms (a good approximation to a real solid). A quench from the liquid phase is used to achieve a quenched amorphous structure, which is subjected to an annealing cycle to improve its stability. The final, annealed network is in better agreement with experiment than any previous simulation of amorphous silicon. Significantly, the predicted average first-coordination numbers of 3.56 and 3.84 for the quenched and annealed structures from this simulation agree very closely with the experimental values of 3.55 and 3.90 respectively, whereas all previous simulations yielded first coordination numbers greater than 4. This improved agreement in coordination numbers is important because it supports the experimental finding that dangling bonds (which are associated with under-coordinated atoms) are more prevalent than floating bonds (the strained, longer bond of a five coordinate atom) in pure amorphous silicon. Finally, the effect of adding hydrogen to amorphous silicon was investigated by specifically placing hydrogen atoms at the likely defect sites. After a structural relaxation to optimise the positions of these hydrogen atoms, the localised electronic states associated with these defects are absent. Thus hydrogen is responsible for removing these defect states (which are able to trap carriers) from the edge of the band gap of the amorphous silicon. These results confirm the widely held ideas about the effect of hydrogen in producing remarkable improvements in the electronic properties of amorphous silicon
Ab initio molecular dynamics simulation of liquid water by quantum Monte Carlo
International Nuclear Information System (INIS)
Zen, Andrea; Luo, Ye; Mazzola, Guglielmo; Sorella, Sandro; Guidoni, Leonardo
2015-01-01
Although liquid water is ubiquitous in chemical reactions at roots of life and climate on the earth, the prediction of its properties by high-level ab initio molecular dynamics simulations still represents a formidable task for quantum chemistry. In this article, we present a room temperature simulation of liquid water based on the potential energy surface obtained by a many-body wave function through quantum Monte Carlo (QMC) methods. The simulated properties are in good agreement with recent neutron scattering and X-ray experiments, particularly concerning the position of the oxygen-oxygen peak in the radial distribution function, at variance of previous density functional theory attempts. Given the excellent performances of QMC on large scale supercomputers, this work opens new perspectives for predictive and reliable ab initio simulations of complex chemical systems
Ab Initio Studies of Metal Hexaboride Materials
Schmidt, Kevin M.
Metal hexaborides are refractory ceramics with several qualities relevant to materials design, such as low work functions, high hardness, low thermal expansion coefficients, and high melting points, among many other properties of interest for industrial applications. Thermal and mechanical stability is a common feature provided by the covalently-bonded network boron atoms, and electronic properties can vary significantly with the resident metal. While these materials are currently employed as electron emitters and abrasives, promising uses of these materials also include catalytic applications for chemical dissociation reactions of various molecules such as hydrogen, water and carbon monoxide, for example. However, these extensions require a thorough understanding of particular mechanical and electronic properties. This dissertation is a collection of studies focused on understanding the behavior of metal hexaboride materials using computational modeling methods to investigate materials properties of these from both classical and quantum mechanical points of view. Classical modeling is performed using molecular dynamics methods with interatomic potentials obtained from density functional theory (DFT) calculations. Atomic mean-square displacements from the quasi-harmonic approximation and lattice energetic data are produced with DFT for developing the potentials. A generalized method was also developed for the inversion of cohesive energy curves of crystalline materials; pairwise interatomic potentials are extracted using detailed geometrical descriptions of the atomic interactions and a list of atomic displacements and degeneracies. The surface structure of metal hexaborides is studied with DFT using several model geometries to describe the terminal cation layouts, and these provide a basis for further studies on metal hexaboride interactions with hydrogen. The surface electronic structure calculations show that segregated regions of metal and boron
Allen, B. Danette; Alexandrov, Natalia
2016-01-01
Incremental approaches to air transportation system development inherit current architectural constraints, which, in turn, place hard bounds on system capacity, efficiency of performance, and complexity. To enable airspace operations of the future, a clean-slate (ab initio) airspace design(s) must be considered. This ab initio National Airspace System (NAS) must be capable of accommodating increased traffic density, a broader diversity of aircraft, and on-demand mobility. System and subsystem designs should scale to accommodate the inevitable demand for airspace services that include large numbers of autonomous Unmanned Aerial Vehicles and a paradigm shift in general aviation (e.g., personal air vehicles) in addition to more traditional aerial vehicles such as commercial jetliners and weather balloons. The complex and adaptive nature of ab initio designs for the future NAS requires new approaches to validation, adding a significant physical experimentation component to analytical and simulation tools. In addition to software modeling and simulation, the ability to exercise system solutions in a flight environment will be an essential aspect of validation. The NASA Langley Research Center (LaRC) Autonomy Incubator seeks to develop a flight simulation infrastructure for ab initio modeling and simulation that assumes no specific NAS architecture and models vehicle-to-vehicle behavior to examine interactions and emergent behaviors among hundreds of intelligent aerial agents exhibiting collaborative, cooperative, coordinative, selfish, and malicious behaviors. The air transportation system of the future will be a complex adaptive system (CAS) characterized by complex and sometimes unpredictable (or unpredicted) behaviors that result from temporal and spatial interactions among large numbers of participants. A CAS not only evolves with a changing environment and adapts to it, it is closely coupled to all systems that constitute the environment. Thus, the ecosystem that
Cooperative effects in spherical spasers: Ab initio analytical model
Bordo, V. G.
2017-06-01
A fully analytical semiclassical theory of cooperative optical processes which occur in an ensemble of molecules embedded in a spherical core-shell nanoparticle is developed from first principles. Both the plasmonic Dicke effect and spaser generation are investigated for the designs in which a shell/core contains an arbitrarily large number of active molecules in the vicinity of a metallic core/shell. An essential aspect of the theory is an ab initio account of the feedback from the core/shell boundaries which significantly modifies the molecular dynamics. The theory provides rigorous, albeit simple and physically transparent, criteria for both plasmonic superradiance and surface plasmon generation.
Tailoring magnetoresistance at the atomic level: An ab initio study
Tao, Kun
2012-01-05
The possibility of manipulating the tunneling magnetoresistance (TMR) of antiferromagnetic nanostructures is predicted in the framework of ab initio calculations. By the example of a junction composed of an antiferromagnetic dimer and a spin-polarized scanning tunneling microscopy tip we show that the TMR can be tuned and even reversed in sign by lateral and vertical movements of the tip. Moreover, our finite-bias calculations demonstrate that the magnitude and the sign of the TMR can also be tuned by an external voltage. © 2012 American Physical Society.
Tailoring magnetoresistance at the atomic level: An ab initio study
Tao, Kun; Stepanyuk, V. S.; Rungger, I.; Sanvito, S.
2012-01-01
The possibility of manipulating the tunneling magnetoresistance (TMR) of antiferromagnetic nanostructures is predicted in the framework of ab initio calculations. By the example of a junction composed of an antiferromagnetic dimer and a spin-polarized scanning tunneling microscopy tip we show that the TMR can be tuned and even reversed in sign by lateral and vertical movements of the tip. Moreover, our finite-bias calculations demonstrate that the magnitude and the sign of the TMR can also be tuned by an external voltage. © 2012 American Physical Society.
Ab initio calculations on hydrogen storage in porous carbons
International Nuclear Information System (INIS)
Maresca, O.; Marinelli, F.; Pellenq, R.J.M.; Duclaux, L.; Azais, Ph.; Conard, J.
2005-01-01
We have investigated through ab initio computations the possible ways to achieve efficient hydrogen storage on carbons. Firstly, we have considered how the curvature of a carbon surface could affect the chemisorption of atomic H 0 Secondly, we show that electron donor elements such as Li and K, used as dopants for the carbon substrate, strongly enhance the physi-sorption energy of H 2 , allowing in principle its storage in this type of material at room temperature under mild conditions of pressure. (authors)
Routine calculation of ab initio melting curves: application to aluminum
Robert, Grégory; Legrand, Philippe; Arnault, Philippe; Desbiens, Nicolas; Clérouin, Jean
2014-01-01
We present a simple, fast, and reliable method to compute the melting curves of materials with ab initio molecular dynamics. It is based on the two-phase thermodynamic model of [Lin et al., J. Chem. Phys. 119, 11792 (2003)] and its improved version given by [Desjarlais, Phys. Rev. E, 88, 062145 (2013)]. In this model, the velocity autocorrelation function is utilized to calculate the contribution of the nuclei motion to the entropy of the solid and liquid phases. It is then possible to find t...
TiAl doping by vanadium: ab initio study
International Nuclear Information System (INIS)
Smirnova, E.A.; Isaev, Eh.I.; Vekilov, Yu.Kh.
2004-01-01
Tetragonality degree in TiAl and vanadium doping effect on it were studied using the methods of calculation based on approximation of coherent potential and ab initio pseudopotentials. It is shown that vanadium substitution for Ti sublattice atoms entails increase in tetragonality degree but with substitution of the atoms in aluminium sublattice the tetragonality of the TiAl:V alloy decreases and at the content of vanadium about 8 at. % the lattice becomes actually cubical. In its turn, it may result in increase in TiAl ductility, the alloy being brittle at low temperatures [ru
Ab initio calculation of tensile strength in iron
Czech Academy of Sciences Publication Activity Database
Friák, Martin; Šob, Mojmír; Vitek, V.
2003-01-01
Roč. 83, 31-34 (2003), s. 3529-3537 ISSN 1478-6435. [Multiscale Materials Modelling: Working Theory for Industry /1./. London, 17.06.2002-20.06.2002] R&D Projects: GA AV ČR IAA1041302; GA ČR GA202/03/1351; GA MŠk OC 523.90 Institutional research plan: CEZ:AV0Z2041904 Keywords : ab initio calculations * electronic structure * theoretical tensile strength Subject RIV: BM - Solid Matter Physics ; Magnetism
An ab initio study of plutonium oxides surfaces; Etude ab initio des surfaces d'oxydes de Pu
Energy Technology Data Exchange (ETDEWEB)
Jomard, G.; Bottin, F.; Amadon, B
2007-07-01
By means of first-principles calculations, we have studied the atomic structure as well as the thermodynamic stability of various plutonium dioxide surfaces in function of their environment (in terms of oxygen partial pressure and temperature). All these simulations have been performed with the ABINIT code. It is well known that DFT fails to describe correctly plutonium-based materials since 5f electrons in such systems are strongly correlated. In order to go beyond DFT, we have treated PuO{sub 2} and {beta}-Pu{sub 2}O{sub 3} in a DFT+U framework. We show that the couple of parameters (U,J) that works well for pure Pu is also well designed for describing ground state (GS) properties of these two oxides. The major improvement with respect with DFT is that we are able to predict an insulating GS in agreement with experiments. The presence of a gap in the DOS (Density of States) of plutonium oxides should play a significant role in the predicted surface reactivity. However, performing DFT+U calculations on surfaces of plutonium oxide from scratch was too ambitious. That is why we decided, as a first step, to study the stability of the (100), (110) and (111) surfaces of PuO{sub 2} in a DFT-GGA framework. For each of these orientations, we considered various terminations. These ab initio results have been introduced in a thermodynamic model which allows us to predict the relative stability of the different terminations as a function of temperature and oxygen partial pressure (p{sub O{sub 2}}). We conclude that at room temperature and for p{sub O{sub 2}}{approx}10 atm., the polar O{sub 2}-(100) termination is favoured. The stabilization of such a polar stoichiometric surface is surprising and should be confirmed by DFT+U calculations before any final conclusion. (authors)
DEFF Research Database (Denmark)
Berg, Rolf W.; Riisager, Anders; Nguyen van Buu, Olivier
2010-01-01
The salt 1,1,3,3-tetramethylguanidinium bromide, [((CH3)2N)2C=NH2]+Br- or [tmgH]Br, was found to melt at 135(5) °C, forming what may be referred to as a moderate temperature ionic liquid. The chemistry was studied and compared with the corresponding chloride compound. We present X-ray diffraction...... and Raman evidence to show that also the bromide salt contains dimeric ion pair “molecules” in the crystalline state and probably also in the liquid state. The structure of [tmgH]Br determined at 120(2) K was found to be monoclinic, space group P21/n, with a = 7.2072(14), b = 13.335(3), c = 9.378(2) Å, beta......, for example, a characteristic strong band at 2229 cm-1. This band was interpreted by some of us to show that the [tmgH]Cl gas phase should consist of monomeric ion pair “molecules” held together by a single N-H+ · · · Cl- hydrogen bond, the stretching vibration of which should be causing the band, based on ab...
DEFF Research Database (Denmark)
Vitos, Levente; Kollár, J.; Skriver, Hans Lomholt
1997-01-01
We have used a full charge-density technique based on the linear muffin-tin orbitals method in first-principles calculations of the atomic volumes of the light actinides including Fr, Ra, and Ac in their low-temperature crystallographic phases. The good agreement between the theoretical and exper......We have used a full charge-density technique based on the linear muffin-tin orbitals method in first-principles calculations of the atomic volumes of the light actinides including Fr, Ra, and Ac in their low-temperature crystallographic phases. The good agreement between the theoretical...... and experimental values along the series support the picture of itinerant 5f electronic states in Th to Pu. The increased deviation between theory and experiment found in Np and Pu may be an indication of correlation effects not included in the local density approximation....
Ab Initio Predictions of Hexagonal Zr(B,C,N) Polymorphs for Coherent Interface Design
Energy Technology Data Exchange (ETDEWEB)
Hu, Chongze [Univ. of Minnesota-Twin Cities, Minneapolis, MN (United States); Huang, Jingsong [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Sumpter, Bobby G. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Meletis, Efstathios [Univ. of Texas at Arlington, Arlington, TX (United States); Dumitrica, Traian [Univ. of Minnesota-Twin Cities, Minneapolis, MN (United States)
2017-10-27
Density functional theory calculations are used to explore hexagonal (HX) NiAs-like polymorphs of Zr(B,C,N) and compare with corresponding Zr(B,C,N) Hagg-like face-centered cubic rocksalt (B1) phases. While all predicted compounds are mechanically stable according to the Born-Huang criteria, only HX Zr(C,N) are found dynamically stable from ab initio molecular dynamics simulations and lattice dynamics calculations. HX ZrN emerges as a candidate structure with ground state energy, elastic constants, and extrinsic mechanical parameters comparable with those of B1 ZrN. Ab initio band structure and semi-classical Boltzmann transport calculations predict a metallic character and a monotonic increase in electrical conductivity with the number of valence electrons. Electronic structure calculations indicate that the HX phases gain their stability and mechanical attributes by Zr d- non-metal p hybridization and by broadening of Zr d bands. Furthermore, it is shown that the HX ZrN phase provides a low-energy coherent interface model for connecting B1 ZrN domains, with significant energetic advantage over an atomistic interface model derived from high resolution transmission electron microscopy images. The ab initio characterizations provided herein should aid the experimental identification of non-Hagg-like hard phases. Furthermore, the results can also enrich the variety of crystalline phases potentially available for designing coherent interfaces in superhard nanostructured materials and in materials with multilayer characteristics.
Ab initio theory and calculations of X-ray spectra
International Nuclear Information System (INIS)
Rehr, J.J.; Kas, J.J.; Prange, M.P.; Sorini, A.P.; Takimoto, Y.; Vila, F.
2009-01-01
There has been dramatic progress in recent years both in the calculation and interpretation of various x-ray spectroscopies. However, current theoretical calculations often use a number of simplified models to account for many-body effects, in lieu of first principles calculations. In an effort to overcome these limitations we describe in this article a number of recent advances in theory and in theoretical codes which offer the prospect of parameter free calculations that include the dominant many-body effects. These advances are based on ab initio calculations of the dielectric and vibrational response of a system. Calculations of the dielectric function over a broad spectrum yield system dependent self-energies and mean-free paths, as well as intrinsic losses due to multielectron excitations. Calculations of the dynamical matrix yield vibrational damping in terms of multiple-scattering Debye-Waller factors. Our ab initio methods for determining these many-body effects have led to new, improved, and broadly applicable x-ray and electron spectroscopy codes. (authors)
(4)He Thermophysical Properties: New Ab Initio Calculations.
Hurly, John J; Mehl, James B
2007-01-01
Since 2000, atomic physicists have reduced the uncertainty of the helium-helium "ab initio" potential; for example, from approximately 0.6 % to 0.1 % at 4 bohr, and from 0.8 % to 0.1 % at 5.6 bohr. These results led us to: (1) construct a new inter-atomic potential ϕ 07, (2) recalculate values of the second virial coefficient, the viscosity, and the thermal conductivity of (4)He from 1 K to 10,000 K, and (3), analyze the uncertainties of the thermophysical properties that propagate from the uncertainty of ϕ 07 and from the Born-Oppenheimer approximation of the electron-nucleon quantum mechanical system. We correct minor errors in a previous publication [J. J. Hurly and M. R. Moldover, J. Res. Nat. Inst. Standards Technol. 105, 667 (2000)] and compare our results with selected data published after 2000. The ab initio results tabulated here can serve as standards for the measurement of thermophysical properties.
Chen, Chung-De; Huang, Yen-Chieh; Chiang, Hsin-Lin; Hsieh, Yin-Cheng; Guan, Hong-Hsiang; Chuankhayan, Phimonphan; Chen, Chun-Jung
2014-09-01
Optimization of the initial phasing has been a decisive factor in the success of the subsequent electron-density modification, model building and structure determination of biological macromolecules using the single-wavelength anomalous dispersion (SAD) method. Two possible phase solutions (φ1 and φ2) generated from two symmetric phase triangles in the Harker construction for the SAD method cause the well known phase ambiguity. A novel direct phase-selection method utilizing the θ(DS) list as a criterion to select optimized phases φ(am) from φ1 or φ2 of a subset of reflections with a high percentage of correct phases to replace the corresponding initial SAD phases φ(SAD) has been developed. Based on this work, reflections with an angle θ(DS) in the range 35-145° are selected for an optimized improvement, where θ(DS) is the angle between the initial phase φ(SAD) and a preliminary density-modification (DM) phase φ(DM)(NHL). The results show that utilizing the additional direct phase-selection step prior to simple solvent flattening without phase combination using existing DM programs, such as RESOLVE or DM from CCP4, significantly improves the final phases in terms of increased correlation coefficients of electron-density maps and diminished mean phase errors. With the improved phases and density maps from the direct phase-selection method, the completeness of residues of protein molecules built with main chains and side chains is enhanced for efficient structure determination.
International Nuclear Information System (INIS)
Chen, Chung-De; Huang, Yen-Chieh; Chiang, Hsin-Lin; Hsieh, Yin-Cheng; Guan, Hong-Hsiang; Chuankhayan, Phimonphan; Chen, Chun-Jung
2014-01-01
A novel direct phase-selection method to select optimized phases from the ambiguous phases of a subset of reflections to replace the corresponding initial SAD phases has been developed. With the improved phases, the completeness of built residues of protein molecules is enhanced for efficient structure determination. Optimization of the initial phasing has been a decisive factor in the success of the subsequent electron-density modification, model building and structure determination of biological macromolecules using the single-wavelength anomalous dispersion (SAD) method. Two possible phase solutions (ϕ 1 and ϕ 2 ) generated from two symmetric phase triangles in the Harker construction for the SAD method cause the well known phase ambiguity. A novel direct phase-selection method utilizing the θ DS list as a criterion to select optimized phases ϕ am from ϕ 1 or ϕ 2 of a subset of reflections with a high percentage of correct phases to replace the corresponding initial SAD phases ϕ SAD has been developed. Based on this work, reflections with an angle θ DS in the range 35–145° are selected for an optimized improvement, where θ DS is the angle between the initial phase ϕ SAD and a preliminary density-modification (DM) phase ϕ DM NHL . The results show that utilizing the additional direct phase-selection step prior to simple solvent flattening without phase combination using existing DM programs, such as RESOLVE or DM from CCP4, significantly improves the final phases in terms of increased correlation coefficients of electron-density maps and diminished mean phase errors. With the improved phases and density maps from the direct phase-selection method, the completeness of residues of protein molecules built with main chains and side chains is enhanced for efficient structure determination
Ab initio phonon dispersions of face centered cubic Pb: effects of spin-orbit coupling
International Nuclear Information System (INIS)
Dal Corso, Andrea
2008-01-01
I present the ab initio phonon dispersions of face centered cubic Pb calculated within the framework of density functional perturbation theory, with plane waves and a fully relativistic ultrasoft pseudopotential which includes spin-orbit coupling effects. I find that, within the local density approximation, the theory gives phonon frequencies close to the experimental inelastic neutron scattering data. Many of the anomalies present in these dispersions are well reproduced by the fully relativistic pseudopotential theory and can be shown to appear only for small values of the smearing parameter that controls the sharpness of the Fermi surface.
Giovannetti, G.; Brocks, G.; van den Brink, J.
2008-01-01
We investigate the effect that potassium intercalation has on the electronic structure of copper phthalocyanine (CuPc) molecular crystals by means of ab initio density functional calculations. Pristine CuPc (in its alpha and beta structures) is found to be an insulator containing local magnetic
Ab Initio Description of Disordered Sr1−xKxFe2As2 Using the Coherent Potential Approximation
Pulikkotil, J. J.; Schwingenschlö gl, Udo
2010-01-01
The electronic structure of disordered Sr1−xKxFe2As2 is studied by ab initio density functional theory. As no superstructure and/or atomic short range ordering is reported for Sr1−xKxFe2As2, the coherent potential approximation can be used
Silvestrelli, P.-L.; Alavi, A.; Parrinello, M.; Frenkel, D.
1997-01-01
The method of ab initio molecular dynamics, based on finite-temperature density-functional theory, is used to simulate laser heating of crystalline silicon. We found that a high concentration of excited electrons dramatically weakens the covalent bonding. As a result the system undergoes a melting
Ziaei, Vafa; Bredow, Thomas
2017-11-01
We study qualitatively ultra-fast proton transfer (PT) in the first singlet (S1) state of liquid water (absorption onset) through excited-state dynamics by means of time-dependent density functional theory and ab initio Born-Oppenheimer molecular dynamics. We find that after the initial excitation, a PT occurs in S1 in form of a rapid jump to a neighboring water molecule, on which the proton either may rest for a relatively long period of time (as a consequence of possible defect in the hydrogen bond network) followed by back and forth hops to its neighboring water molecule or from which it further moves to the next water molecule accompanied by back and forth movements. In this way, the proton may become delocalized over a long water wire branch, followed again by back and forth jumps or short localization on a water molecule for some femtoseconds. As a result, the mechanism of PT in S1 is in most cases highly non-Grotthuss-like, delayed and discrete. Furthermore, upon PT an excess charge is ejected to the solvent trap, the so-called solvated electron. The spatial extent of the ejected solvated electron is mainly localized within one solvent shell with overlappings on the nearest neighbor water molecules and delocalizing (diffuse) tails extending beyond the first solvent sphere. During the entire ultra-short excited-state dynamics the remaining OH radical from the initially excited water molecule exhibits an extremely low mobility and is non-reactive. Supplementary material in the form of one pdf file available from the Journal web page at http://https://doi.org/10.1140/epjb/e2017-80329-7.
Ab initio and Gordon--Kim intermolecular potentials for two nitrogen molecules
International Nuclear Information System (INIS)
Ree, F.H.; Winter, N.W.
1980-01-01
Both ab initio MO--LCAO--SCF and the electron-gas (or Gordon--Kim) methods have been used to compute the intermolecular potential (Phi) of N 2 molecules for seven different N 2 --N 2 orientations. The ab initio calculations were carried out using a [4s3p] contracted Gaussian basis set with and without 3d polarization functions. The larger basis set provides adequate results for Phi>0.002 hartree or intermolecular separations less than 6.5--7 bohr. We use a convenient analytic expression to represent the ab initio data in terms of the intermolecular distance and three angles defining the orientations of the two N 2 molecules. The Gordon--Kim method with Rae's self-exchange correction yields Phi, which agrees reasonably well over a large repulsive range. However, a detailed comparison of the electron kinetic energy contributions shows a large difference between the ab initio and the Gordon--Kim calculations. Using the ab initio data we derive an atom--atom potential of the two N 2 molecules. Although this expression does not accurately fit the data at some orientations, its spherical average agrees with the corresponding average of the ab initio Phi remarkably well. The spherically averaged ab initio Phi is also compared with the corresponding quantities derived from experimental considerations. The approach of the ab initio Phi to the classical quadrupole--quadrupole interaction at large intermolecular separation is also discussed
Modeling Disordered Materials with a High Throughput ab-initio Approach
2015-11-13
Modeling Disordered Materials with a High Throughput ab - initio Approach Kesong Yang,1 Corey Oses,2 and Stefano Curtarolo3, 4 1Department of...J. Furthmüller, Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set, Phys. Rev. B 54, 11169–11186 (1996
Embedded atom approach for gold–silicon system from ab initio
Indian Academy of Sciences (India)
In the present paper, an empirical embedded atom method (EAM) potential for gold–silicon (Au–Si) is developed by fitting to ab initio force (the 'force matching' method) and experimental data. The force database is generated within ab initio molecular dynamics (AIMD). The database includes liquid phase at various ...
Summation of Parquet diagrams as an ab initio method in nuclear structure calculations
International Nuclear Information System (INIS)
Bergli, Elise; Hjorth-Jensen, Morten
2011-01-01
Research highlights: → We present a Green's function based approach for doing ab initio nuclear structure calculations. → In particular the sum the subset of so-called Parquet diagrams. → Applying the theory to a simple but realistic model, results in good agreement with other ab initio methods. → This opens up for ab initio calculations for medium-heavy nuclei. - Abstract: In this work we discuss the summation of the Parquet class of diagrams within Green's function theory as a possible framework for ab initio nuclear structure calculations. The theory is presented and some numerical details are discussed, in particular the approximations employed. We apply the Parquet method to a simple model, and compare our results with those from an exact solution. The main conclusion is that even at the level of approximation presented here, the results shows good agreement with other comparable ab initio approaches.
K, Rajamallu; Niranjan, Manish K.; Ameyama, Kei; Dey, Suhash R.
2017-12-01
Alloying effects of Zr and Sn on β phase stability and elastic properties in Ti-Nb alloys are investigated within the framework of first-principles density functional theory. Our results suggest that the stability of β phase can be significantly enhanced by the addition of Zr and Sn in Ti-Nb alloys. The computed results indicate that Zr and Sn behave as strong β stabilizers in the Ti-Nb system. The elastic properties are found to be altered considerably by the addition of ternary alloying elements (Zr and Sn). The computed elastic moduli of Ti18.75 at%Nb6.25 at%Zr and Ti25 at%NbxZr compositions are found to be lower than that for Ti18.75 at%Nb6.25 at%Sn and Ti25 at%NbxSn system. The lowest value of ˜54 GPa is obtained for Ti25 at%Nb6.25 at%Zr composition. Furthermore, the directional Young’s modulus is found to be in the order of E 100 system.
Thakur, Anil; Kashyap, Rajinder
2018-05-01
Single nanowire electrode devices have their application in variety of fields which vary from information technology to solar energy. Silver nanowires, made in an aqueous chemical reduction process, can be reacted with gold salt to create bimetallic nanowires. Silver nanowire can be used as electrodes in batteries and have many other applications. In this paper we investigated structural and electronic transport properties of Ag nanowire using density functional theory (DFT) with SIESTA code. Electronic transport properties of Ag nanowire have been studied theoretically. First of all an optimized geometry for Ag nanowire is obtained using DFT calculations, and then the transport relations are obtained using NEGF approach. SIESTA and TranSIESTA simulation codes are used in the calculations respectively. The electrodes are chosen to be the same as the central region where transport is studied, eliminating current quantization effects due to contacts and focusing the electronic transport study to the intrinsic structure of the material. By varying chemical potential in the electrode regions, an I-V curve is traced which is in agreement with the predicted behavior. Bulk properties of Ag are in agreement with experimental values which make the study of electronic and transport properties in silver nanowires interesting because they are promising materials as bridging pieces in nanoelectronics. Transmission coefficient and V-I characteristic of Ag nano wire reveals that silver nanowire can be used as an electrode device.
Palmer, Michael H.; Vrønning Hoffmann, Søren; Jones, Nykola C.; Coreno, Marcello; de Simone, Monica; Grazioli, Cesare
2018-06-01
The vacuum ultraviolet (VUV) spectrum for CH2F2 from a new synchrotron study has been combined with earlier data and subjected to detailed scrutiny. The onset of absorption, band I and also band IV, is resolved into broad vibrational peaks, which contrast with the continuous absorption previously claimed. A new theoretical analysis, using a combination of time dependent density functional theory (TDDFT) calculations and complete active space self-consistent field, leads to a major new interpretation. Adiabatic excitation energies (AEEs) and vertical excitation energies, evaluated by these methods, are used to interpret the spectra in unprecedented detail using theoretical vibronic analysis. This includes both Franck-Condon (FC) and Herzberg-Teller (HT) effects on cold and hot bands. These results lead to the re-assignment of several known excited states and the identification of new ones. The lowest calculated AEE sequence for singlet states is 11B1 ˜ 11A2 expected; the onset of the 15.5 eV band shows a set of vibrational peaks, but the vibration frequency does not correspond to any of the photoelectron spectral (PES) structure and is clearly valence in nature. The routine use of PES footprints to detect Rydberg states in VUV spectra is shown to be inadequate. The combined effects of FC and HT in the VUV spectral bands lead to additional vibrations when compared with the PES.
Ab initio study of isomerism in molecular ions Li2AB+ with 10 valence electrons
International Nuclear Information System (INIS)
Charkin, O.P.; Mak-Ki, M.L.; Shlojer, P.R.
1997-01-01
Ab initio calculations of surfaces of Li 2 AB + molecular ion potential energy with biatomic anions AB - with 10 valence electrons have been made in the framework of approximations MP2/6-31G 1 /HF/6-31G*+ZPE(HF/6-31G*) and MP4SDTQ/631G*//MP2/6-31G*+ZPE(MP2/6-31G*). Influence of electron correlation on the accuracy of calculations of their structural and vibrational characteristics is studied. The following most favourable structures have been found: linear for Li 2 BO + , Li 2 CN + , and bent one for Li 2 BS + , with cations coordinated at different anion atoms; onium one for AlOLi 2 + , AlSLi 2 + , SiNLi 2 + and SiPLi 2 + with both cations at electronegative atom of anion
Simple calculation of ab initio melting curves: Application to aluminum.
Robert, Grégory; Legrand, Philippe; Arnault, Philippe; Desbiens, Nicolas; Clérouin, Jean
2015-03-01
We present a simple, fast, and promising method to compute the melting curves of materials with ab initio molecular dynamics. It is based on the two-phase thermodynamic model of Lin et al [J. Chem. Phys. 119, 11792 (2003)] and its improved version given by Desjarlais [Phys. Rev. E 88, 062145 (2013)]. In this model, the velocity autocorrelation function is utilized to calculate the contribution of the nuclei motion to the entropy of the solid and liquid phases. It is then possible to find the thermodynamic conditions of equal Gibbs free energy between these phases, defining the melting curve. The first benchmark on the face-centered cubic melting curve of aluminum from 0 to 300 GPa demonstrates how to obtain an accuracy of 5%-10%, comparable to the most sophisticated methods, for a much lower computational cost.
Ab initio study of II-(VI){sub 2} dichalcogenides
Energy Technology Data Exchange (ETDEWEB)
Olsson, P; Vidal, J; Lincot, D, E-mail: polsson@kth.se [Institut de R and D sur l' energie photovoltaique (IRDEP), UMR 7174-EDF-CNRS-ENSCP, 6 quai Watier, 78401 Chatou Cedex (France)
2011-10-12
The structural stabilities of the (Zn,Cd)(S,Se,Te){sub 2} dichalcogenides have been determined ab initio. These compounds are shown to be stable in the pyrite phase, in agreement with available experiments. Structural parameters for the ZnTe{sub 2} pyrite semiconductor compound proposed here are presented. The opto-electronic properties of these dichalcogenide compounds have been calculated using quasiparticle GW theory. Bandgaps, band structures and effective masses are proposed as well as absorption coefficients and refraction indices. The compounds are all indirect semiconductors with very flat conduction band dispersion and high absorption coefficients. The work functions and surface properties are predicted. The Te and Se based compounds could be of interest as absorber materials in photovoltaic applications. (paper)
Quantitative verification of ab initio self-consistent laser theory.
Ge, Li; Tandy, Robert J; Stone, A D; Türeci, Hakan E
2008-10-13
We generalize and test the recent "ab initio" self-consistent (AISC) time-independent semiclassical laser theory. This self-consistent formalism generates all the stationary lasing properties in the multimode regime (frequencies, thresholds, internal and external fields, output power and emission pattern) from simple inputs: the dielectric function of the passive cavity, the atomic transition frequency, and the transverse relaxation time of the lasing transition.We find that the theory gives excellent quantitative agreement with full time-dependent simulations of the Maxwell-Bloch equations after it has been generalized to drop the slowly-varying envelope approximation. The theory is infinite order in the non-linear hole-burning interaction; the widely used third order approximation is shown to fail badly.
Ab initio elastic properties and tensile strength of crystalline hydroxyapatite.
Ching, W Y; Rulis, Paul; Misra, A
2009-10-01
We report elastic constant calculation and a "theoretical" tensile experiment on stoichiometric hydroxyapatite (HAP) crystal using an ab initio technique. These results compare favorably with a variety of measured data. Theoretical tensile experiments are performed on the orthorhombic cell of HAP for both uniaxial and biaxial loading. The results show considerable anisotropy in the stress-strain behavior. It is shown that the failure behavior of the perfect HAP crystal is brittle for tension along the z-axis with a maximum stress of 9.6 GPa at 10% strain. Biaxial failure envelopes from six "theoretical" loading tests show a highly anisotropic pattern. Structural analysis of the crystal under various stages of tensile strain reveals that the deformation behavior manifests itself mainly in the rotation of the PO(4) tetrahedron with concomitant movements of both the columnar and axial Ca ions. These results are discussed in the context of mechanical properties of bioceramic composites relevant to mineralized tissues.
Ab initio methods for electron-molecule collisions
International Nuclear Information System (INIS)
Collins, L.A.; Schneider, B.I.
1987-01-01
This review concentrates on the recent advances in treating the electronic aspect of the electron-molecule interaction and leaves to other articles the description of the rotational and vibrational motions. Those methods which give the most complete treatment of the direct, exchange, and correlation effects are focused on. Such full treatments are generally necessary at energies below a few Rydbergs (≅ 60 eV). This choice unfortunately necessitates omission of those active and vital areas devoted to the development of model potentials and approximate scattering formulations. The ab initio and model approaches complement each other and are both extremely important to the full explication of the electron-scattering process. Due to the rapid developments of recent years, the approaches that provide the fullest treatment are concentrated on. 81 refs
Ab initio Eliashberg Theory: Making Genuine Predictions of Superconducting Features
Sanna, Antonio; Flores-Livas, José A.; Davydov, Arkadiy; Profeta, Gianni; Dewhurst, Kay; Sharma, Sangeeta; Gross, E. K. U.
2018-04-01
We present an application of Eliashberg theory of superconductivity to study a set of novel superconducting systems with a wide range of structural and chemical properties. The set includes three intercalated group-IV honeycomb layered structures, SH3 at 200 GPa (the superconductor with the highest measured critical temperature), the similar system SeH3 at 150 GPa, and a lithium doped mono-layer of black phosphorus. The theoretical approach we adopt is a recently developed, fully ab initio Eliashberg approach that takes into account the Coulomb interaction in a full energy-resolved fashion avoiding any free parameters like μ*. This method provides reasonable estimations of superconducting properties, including TC and the excitation spectra of superconductors.
Ab Initio Symmetry-Adapted No-Core Shell Model
International Nuclear Information System (INIS)
Draayer, J P; Dytrych, T; Launey, K D
2011-01-01
A multi-shell extension of the Elliott SU(3) model, the SU(3) symmetry-adapted version of the no-core shell model (SA-NCSM), is described. The significance of this SA-NCSM emerges from the physical relevance of its SU(3)-coupled basis, which – while it naturally manages center-of-mass spuriosity – provides a microscopic description of nuclei in terms of mixed shape configurations. Since typically configurations of maximum spatial deformation dominate, only a small part of the model space suffices to reproduce the low-energy nuclear dynamics and hence, offers an effective symmetry-guided framework for winnowing of model space. This is based on our recent findings of low-spin and high-deformation dominance in realistic NCSM results and, in turn, holds promise to significantly enhance the reach of ab initio shell models.
Ab Initio Analysis of Auger-Assisted Electron Transfer.
Hyeon-Deuk, Kim; Kim, Joonghan; Prezhdo, Oleg V
2015-01-15
Quantum confinement in nanoscale materials allows Auger-type electron-hole energy exchange. We show by direct time-domain atomistic simulation and analytic theory that Auger processes give rise to a new mechanism of charge transfer (CT) on the nanoscale. Auger-assisted CT eliminates the renown Marcus inverted regime, rationalizing recent experiments on CT from quantum dots to molecular adsorbates. The ab initio simulation reveals a complex interplay of the electron-hole and charge-phonon channels of energy exchange, demonstrating a variety of CT scenarios. The developed Marcus rate theory for Auger-assisted CT describes, without adjustable parameters, the experimental plateau of the CT rate in the region of large donor-acceptor energy gap. The analytic theory and atomistic insights apply broadly to charge and energy transfer in nanoscale systems.
H3+: Ab initio calculation of the vibration spectrum
International Nuclear Information System (INIS)
Carney, G.D.; Porter, R.N.
1976-01-01
The vibration spectrum of H 3 + is calculated from the representation of a previously reported [J. Chem Phys. 60, 4251 (1974)] ab initio potential-energy surface in a fifth degree Simons--Parr--Finlan (SPF) expansion. Morse- and harmonic-oscillator basis functions are used to describe the motions of the three oscillators and the Harris--Engerholm--Gwinn quadrature technique is used to obtain matrix elements of the Hamiltonian in the basis of vibrational configurations. Our variational method is thus analogous to configuration--interaction calculations for electronic states. The ground state is found to have a zero-point energy of 4345 cm -1 and a vibrationally averaged geometry of R 1 =R 2 =0.91396 A, theta=60.0012degree, where theta is the angle between the two equivalent bonds. The transition frequencies for the E and A 1 fundamentals are nu-bar/sub E/=2516 cm -1 and nu-bar/sub A/=3185 cm -1 and those for the corresponding first overtones of the bending mode are 2nu-bar/sub E/=5004 +- 4 cm -1 and 2nu-bar/sub A/=4799 cm -1 . The first overtone of the breathing mode is 6264 cm -1 . The first-excited A 1 vibration state is metastable with a dipole--radiation lifetime of 3 sec. Transition frequencies, Einstein coefficients, and lifetimes are reported for a total of 21 transitions. Analysis of results for Dunham number and normal-coordinate expansions in comparison with those for SPF expansion show the latter to be superior for ab initio vibrational calculations. A scheme for possible direct measurement of the fundamental A 1 and E vibrational bands is suggested
Energy Technology Data Exchange (ETDEWEB)
Allali, D. [Laboratory for Developing New Materials and their Characterization, University of Setif 1, 19000 Setif (Algeria); Bouhemadou, A., E-mail: a_bouhemadou@yahoo.fr [Laboratory for Developing New Materials and their Characterization, University of Setif 1, 19000 Setif (Algeria); Safi, E. Muhammad Abud Al [Department of Physics and Astronomy, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451 (Saudi Arabia); Bin-Omran, S. [Department of Physics and Astronomy, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451 (Saudi Arabia); Department of Physics, Faculty of Science and Humanitarian Studies, Salman Bin Abdalaziz University, Alkharj 11942 (Saudi Arabia); Chegaar, M. [Department of Physics, Faculty of Science, University of Setif 1, 19000 Setif (Algeria); Khenata, R. [Laboratoire de Physique Quantique et de Modélisation Mathématique (LPQ3M), Département de Technologie, Université de Mascara, 29000 Mascara (Algeria); Reshak, A.H. [New Technologies-Research Center, University of West Bohemia, Univerzitni 8, 306 14 Pilson (Czech Republic); Center of Excellence Geopolymer and Green Technology, School of Material Engineering, University Malaysia Perlis, 01007 Kangar, Perlis (Malaysia)
2014-06-15
We report ab initio density functional theory calculations of the structural, electronic and optical properties of the spinel oxides SiMg{sub 2}O{sub 4}, SiZng{sub 2}O{sub 4}, and SiCd{sub 2}O{sub 4} using the full-potential linearized augmented plane-wave method. The structural parameters calculated using both the local density and generalized gradient approximations to the exchange-correlation potential are consistent with the literature data. To calculate the electronic properties, the exchange-correlation potential is treated with various functionals, and we find that the newly developed Tran–Blaha-modified Becke–Johnson functional significantly improves the band gap. We predict a direct band gap in all of the considered SiB{sub 2}O{sub 4} compounds, and the band gaps continuously decrease as the atomic size of the B element increases. The decrease in the fundamental direct band gap (Γ–Γ) from SiMg{sub 2}O{sub 4} to SiZn{sub 2}O{sub 4} to SiCd{sub 2}O{sub 4} can be attributed to p–d mixing in the upper valence bands of SiZn{sub 2}O{sub 4} and SiCd{sub 2}O{sub 4}. The lowest conduction band is well dispersive, similar to that found for transparent conducting oxides such as ZnO. This band is mainly defined by the s and p electrons of the Si and B (B=Mg, Zn, Cd) atoms. The topmost valence band is considerably less dispersive and is defined by O-2p and B–d electrons. The charge-carrier effective masses are evaluated at the topmost valence band and at the bottommost conduction band that were calculated. The frequency-dependent complex dielectric function, absorption coefficient, refractive index, extinction coefficient, reflectivity and electron energy loss function were estimated. We find that the value of the zero-frequency limit of the dielectric function ε(0) increases as the band gap decreases. The origins of the peaks and structures in the optical spectra are determined in terms of the calculated energy band structures.
International Nuclear Information System (INIS)
Holst, Bastian; French, Martin; Redmer, Ronald
2011-01-01
Using Kubo's linear response theory, we derive expressions for the frequency-dependent electrical conductivity (Kubo-Greenwood formula), thermopower, and thermal conductivity in a strongly correlated electron system. These are evaluated within ab initio molecular dynamics simulations in order to study the thermoelectric transport coefficients in dense liquid hydrogen, especially near the nonmetal-to-metal transition region. We also observe significant deviations from the widely used Wiedemann-Franz law, which is strictly valid only for degenerate systems, and give an estimate for its valid scope of application toward lower densities.
Electronic structure and magnetism of titanium substituted Cd3P2: An ab-initio study
Jaiganesh, G.; Jaya, S. Mathi
2018-05-01
Using the ab-initio computations that are based on the density functional theory, we have investigated the magnetism and electronic properties of one and two Ti atom substituted Cd3P2 compound. The magnetic stability of the substituted compounds was obtained by analyzing the minimum total energies in nonmagnetic, ferromagnetic and antiferromagnetic phases. Our results indicated the formation of magnetic order in one and two Ti atom substituted Cd3P2 as well as metallic characteristics in these systems. A significant value of the magnetic moment of Ti atom is observed from our calculations. We further find that the neighboring Cd and P atoms too acquire a small magnetic moment.
Ab initio study of spin-dependent transport in carbon nanotubes with iron and vanadium adatoms
DEFF Research Database (Denmark)
Fürst, Joachim Alexander; Brandbyge, Mads; Jauho, Antti-Pekka
2008-01-01
(majority or minority) being scattered depends on the adsorbate and is explained in terms of d-state filling. We contrast the single-walled carbon nanotube results to the simpler case of the adsorbate on a flat graphene sheet with periodic boundary conditions and corresponding width in the zigzag direction......We present an ab initio study of spin-dependent transport in armchair carbon nanotubes with transition metal adsorbates: iron or vanadium. The method based on density functional theory and nonequilibrium Green's functions is used to compute the electronic structure and zero-bias conductance...
Spin-orbit interaction effects in zincblende semiconductors: Ab initio pseudopotential calculations
International Nuclear Information System (INIS)
Li, Ming-Fu; Surh, M.P.; Louie, S.G.
1988-06-01
Ab initio band structure calculations have been performed for the spin-orbit interaction effects at the top of the valence bands for GaAs and InSb. Relativistic, norm-conserving pseudopotentials are used with no correction made for the gaps from the local density approximation. The spin-orbit splitting at Γ and linear terms in the /rvec char/k dependence of the splitting are found to be in excellent agreement with existing experiments and previous theoretical results. The effective mass and the cubic splitting terms are also examined. 6 refs., 1 fig., 2 tabs
Ab initio study of the EFG at the N sites in imidazole
Energy Technology Data Exchange (ETDEWEB)
Brown Goncalves, Marcos, E-mail: browngon@if.usp.br [Universidade de Sao Paulo, Instituto de Fisica (Brazil); Di Felice, R. [National Center on Nanostructures and Biosystems at Surfaces (S3) of INFM-CNR (Italy); Poleshchuk, O. Kh. [Tomsk State Pedagogical University (Russian Federation); Petrilli, H. M. [Universidade de Sao Paulo, Instituto de Fisica (Brazil)
2008-01-15
We study the nuclear quadrupole interaction at the nitrogen sites in the molecular and crystalline phases of the imidazole compound. We use PAW which is a state-of-the-art method to calculate the electronic structure and electric field gradient at the nucleus in the framework of the density functional theory. The quadrupole frequencies at both imino and amino N sites are in excellent agreement with measurements. This is the first time that the electric field gradient at crystalline imidazole is correctly treated by an ab initio theoretical approach.
Sumner, Isaiah; Iyengar, Srinivasan S
2007-10-18
We have introduced a computational methodology to study vibrational spectroscopy in clusters inclusive of critical nuclear quantum effects. This approach is based on the recently developed quantum wavepacket ab initio molecular dynamics method that combines quantum wavepacket dynamics with ab initio molecular dynamics. The computational efficiency of the dynamical procedure is drastically improved (by several orders of magnitude) through the utilization of wavelet-based techniques combined with the previously introduced time-dependent deterministic sampling procedure measure to achieve stable, picosecond length, quantum-classical dynamics of electrons and nuclei in clusters. The dynamical information is employed to construct a novel cumulative flux/velocity correlation function, where the wavepacket flux from the quantized particle is combined with classical nuclear velocities to obtain the vibrational density of states. The approach is demonstrated by computing the vibrational density of states of [Cl-H-Cl]-, inclusive of critical quantum nuclear effects, and our results are in good agreement with experiment. A general hierarchical procedure is also provided, based on electronic structure harmonic frequencies, classical ab initio molecular dynamics, computation of nuclear quantum-mechanical eigenstates, and employing quantum wavepacket ab initio dynamics to understand vibrational spectroscopy in hydrogen-bonded clusters that display large degrees of anharmonicities.
4He Thermophysical Properties: New Ab Initio Calculations
Hurly, John J.; Mehl, James B.
2007-01-01
Since 2000, atomic physicists have reduced the uncertainty of the helium-helium “ab initio” potential; for example, from approximately 0.6 % to 0.1 % at 4 bohr, and from 0.8 % to 0.1 % at 5.6 bohr. These results led us to: (1) construct a new inter-atomic potential ϕ07, (2) recalculate values of the second virial coefficient, the viscosity, and the thermal conductivity of 4He from 1 K to 10,000 K, and (3), analyze the uncertainties of the thermophysical properties that propagate from the uncertainty of ϕ07 and from the Born-Oppenheimer approximation of the electron-nucleon quantum mechanical system. We correct minor errors in a previous publication [J. J. Hurly and M. R. Moldover, J. Res. Nat. Inst. Standards Technol. 105, 667 (2000)] and compare our results with selected data published after 2000. The ab initio results tabulated here can serve as standards for the measurement of thermophysical properties. PMID:27110456
Efficient approach to compute melting properties fully from ab initio with application to Cu
Zhu, Li-Fang; Grabowski, Blazej; Neugebauer, Jörg
2017-12-01
Applying thermodynamic integration within an ab initio-based free-energy approach is a state-of-the-art method to calculate melting points of materials. However, the high computational cost and the reliance on a good reference system for calculating the liquid free energy have so far hindered a general application. To overcome these challenges, we propose the two-optimized references thermodynamic integration using Langevin dynamics (TOR-TILD) method in this work by extending the two-stage upsampled thermodynamic integration using Langevin dynamics (TU-TILD) method, which has been originally developed to obtain anharmonic free energies of solids, to the calculation of liquid free energies. The core idea of TOR-TILD is to fit two empirical potentials to the energies from density functional theory based molecular dynamics runs for the solid and the liquid phase and to use these potentials as reference systems for thermodynamic integration. Because the empirical potentials closely reproduce the ab initio system in the relevant part of the phase space the convergence of the thermodynamic integration is very rapid. Therefore, the proposed approach improves significantly the computational efficiency while preserving the required accuracy. As a test case, we apply TOR-TILD to fcc Cu computing not only the melting point but various other melting properties, such as the entropy and enthalpy of fusion and the volume change upon melting. The generalized gradient approximation (GGA) with the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional and the local-density approximation (LDA) are used. Using both functionals gives a reliable ab initio confidence interval for the melting point, the enthalpy of fusion, and entropy of fusion.
Experimental and ab initio investigations on textured Li–Mn–O spinel thin film cathodes
Energy Technology Data Exchange (ETDEWEB)
Fischer, J., E-mail: Julian.Fischer@kit.edu [Karlsruhe Institute of Technology (KIT), Institute for Applied Materials (IAM), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Music, D. [RWTH Aachen University, Materials Chemistry, Kopernikusstrasse 10, 52074 Aachen (Germany); Bergfeldt, T.; Ziebert, C.; Ulrich, S.; Seifert, H.J. [Karlsruhe Institute of Technology (KIT), Institute for Applied Materials (IAM), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany)
2014-12-01
This paper describes the tailored preparation of nearly identical lithium–manganese–oxide thin film cathodes with different global grain orientations. The thin films were synthesized by rf magnetron sputtering from a LiMn{sub 2}O{sub 4}-target in a pure argon plasma. Under appropriate processing conditions, thin films with a cubic spinel structure and a nearly similar density and surface topography but different grain orientation, i.e. (111)- and (440)-textured films, were achieved. The chemical composition was determined by inductively coupled plasma optical emission spectroscopy and carrier gas hot extraction. The constitution- and microstructure were evaluated by X-ray diffraction and Raman spectroscopy. The surface morphology and roughness were investigated by scanning electron and atomic force microscopy. The differently textured films represent an ideal model system for studying potential effects of grain orientation on the lithium ion diffusion and electrochemical behavior in LiMn{sub 2}O{sub 4}-based thin films. They are nearly identical in their chemical composition, atomic bonding behavior, surface-roughness, morphology and thickness. Our initial ab initio molecular dynamics data indicate that Li ion transport is faster in (111)-textured structure than in (440)-textured one. - Highlights: • Thin film model system of differently textured cubic Li–Mn–O spinels. • Investigation of the Li–Mn–O thin film mass density by X-ray reflectivity. • Ab initio molecular dynamics simulation on Li ion diffusion in LiMn{sub 2}O{sub 4}.
Ab initio investigation of superconductivity in orthorhombic MgPtSi
Energy Technology Data Exchange (ETDEWEB)
Tütüncü, H.M., E-mail: tutuncu@sakarya.edu.tr [Sakarya Üniversitesi, Fen-Edebiyat Fakültesi, Fizik Bölümü, 54187, Adapazarı (Turkey); Sakarya Üniversitesi, BIMAYAM Biyomedikal, Manyetik ve Yarıiletken Malzemeler Araştırma Merkezi, 54187, Adapazarı (Turkey); Ertuǧrul Karaca [Sakarya Üniversitesi, Fen-Edebiyat Fakültesi, Fizik Bölümü, 54187, Adapazarı (Turkey); Srivastava, G.P. [School of Physics, University of Exeter, Stocker Road, Exeter EX4 4QL (United Kingdom)
2016-07-15
We have performed an ab initio study of electronic, vibrational and superconducting properties of the orthorhombic MgPtSi by employing the density functional theory, a linear-response formalism, and the plane-wave pseudopotential method. Our electronic results suggest that the density of states at the Fermi level is primarily contributed by Pt 5d and Si 3p states with much smaller contribution from Mg electronic states. Phonon anomalies have been found for all three acoustic branches. Due to these phonon anomalies, the acoustic branches make large contributions to the average electron-phonon coupling parameter. From the Eliashberg spectral function, the value of average electron-phonon coupling parameter is found to 0.707. Using this value, the superconducting critical temperature is obtained to be 2.4 K, in excellent accordance with its experimental value of 2.5 K. - Highlights: • The electronic structure of MgPtSi is studied using ab initio pseudopotential method. • Phonons and electron–phonon interaction in MgPtSi are studied using a linear response theory. • The acoustic phonon modes couple more strongly with electrons. • The value of λ is found to be 0.707 which shows that MgPtSi is a conventional honon-mediated superconductor. • The calculated T{sub c} of 2.4 K is in excellent accordance with its experimental value of 2.5 K.
Ab initio study of hydrogen adsorption on benzenoid linkers in metal-organic framework materials
International Nuclear Information System (INIS)
Gao Yi; Zeng, X C
2007-01-01
We have computed the energies of adsorption of molecular hydrogen on a number of molecular linkers in metal-organic framework solid materials using density functional theory (DFT) and ab initio molecular orbital methods. We find that the hybrid B3LYP (Becke three-parameter Lee-Yang-Parr) DFT method gives a qualitatively incorrect prediction of the hydrogen binding with benzenoid molecular linkers. Both local-density approximation (LDA) and generalized gradient approximation (GGA) DFT methods are inaccurate in predicting the values of hydrogen binding energies, but can give a qualitatively correct prediction of the hydrogen binding. When compared to the more accurate binding-energy results based on the ab initio Moeller-Plesset second-order perturbation (MP2) method, the LDA results may be viewed as an upper limit while the GGA results may be viewed as a lower limit. Since the MP2 calculation is impractical for realistic metal-organic framework systems, the combined LDA and GGA calculations provide a cost-effective way to assess the hydrogen binding capability of these systems
Ab Initio periodic Hartree-Fock study of group IA cations in ANA-type zeolites
International Nuclear Information System (INIS)
Anchell, J.L.; White, J.C.; Thompson, M.R.; Hess, A.C.
1994-01-01
This study investigates the electronic structure of Group IA cations intercalated into zeolites with the analcime (ANA) framework using ab initio periodic Hartree-Fock theory. The purpose of the study is to gain a better understanding of the role played by electron-donating species in zeolites in general, with specific applications to materials that have been suggested as storage matrices for radioactive materials. The effect of the intercalated species (Na, K, Rb, and Cs) on the electronic structure of the zeolite is presented on the basis of an analysis of the total and projected density of states, Mulliken charges, and charge density differences. The results of those analyses indicate that, relative to a charge neutral atomic state, the Group IA species donate an electron to the zeolite lattice and interact most strongly with the s and p atomic states of oxygen as the species are moved through the lattice. In addition, estimates of the self-diffusion constants of Na, K, Rb, and Cs based upon a one-dimensional diffusion model parameterized from the ab initio total energy data will be presented. 24 refs., 8 figs., 4 tabs
Experimental and ab initio investigations on textured Li–Mn–O spinel thin film cathodes
International Nuclear Information System (INIS)
Fischer, J.; Music, D.; Bergfeldt, T.; Ziebert, C.; Ulrich, S.; Seifert, H.J.
2014-01-01
This paper describes the tailored preparation of nearly identical lithium–manganese–oxide thin film cathodes with different global grain orientations. The thin films were synthesized by rf magnetron sputtering from a LiMn 2 O 4 -target in a pure argon plasma. Under appropriate processing conditions, thin films with a cubic spinel structure and a nearly similar density and surface topography but different grain orientation, i.e. (111)- and (440)-textured films, were achieved. The chemical composition was determined by inductively coupled plasma optical emission spectroscopy and carrier gas hot extraction. The constitution- and microstructure were evaluated by X-ray diffraction and Raman spectroscopy. The surface morphology and roughness were investigated by scanning electron and atomic force microscopy. The differently textured films represent an ideal model system for studying potential effects of grain orientation on the lithium ion diffusion and electrochemical behavior in LiMn 2 O 4 -based thin films. They are nearly identical in their chemical composition, atomic bonding behavior, surface-roughness, morphology and thickness. Our initial ab initio molecular dynamics data indicate that Li ion transport is faster in (111)-textured structure than in (440)-textured one. - Highlights: • Thin film model system of differently textured cubic Li–Mn–O spinels. • Investigation of the Li–Mn–O thin film mass density by X-ray reflectivity. • Ab initio molecular dynamics simulation on Li ion diffusion in LiMn 2 O 4
Many-body perturbation theory for ab initio nuclear structure
International Nuclear Information System (INIS)
Tichai, Alexander
2017-01-01
The solution of the quantum many-body problem for medium-mass nuclei using realistic nuclear interactions poses a superbe challenge for nuclear structure research. Because an exact solution can only be provided for the lightest nuclei, one has to rely on approximate solutions when proceeding to heavier systems. Over the past years, tremendous progress has been made in the development and application of systematically improvable expansion methods and an accurate description of nuclear observables has become viable up to mass number A ∼ 100. While closed-shell systems are consistently described via a plethora of different many-body methods, the extension to genuine open-shell systems still remains a major challenge and up to now there is no ab initio many-body method which applies equally well to systems with even and odd mass numbers. The goal of this thesis is the development and implementation of innovative perturbative approaches with genuine open-shell capabilities. This requires the extension of well-known single-reference approaches to more general vacua. In this work we choose two complementary routes for the usage of generalized reference states. First, we derive a new ab initio approach based on multi-configurational reference states that are conveniently derived from a prior no-core shell model calculation. Perturbative corrections are derived via second-order many-body perturbation theory, thus, merging configuration interaction and many-body perturbation theory. The generality of this ansatz enables for a treatment of medium-mass systems with arbitrary mass number, as well as the extension to low-lying excited states such that ground and excited states are treated on an equal footing. In a complementary approach, we use reference states that break a symmetry of the underlying Hamiltonian. In the simplest case this corresponds to the expansion around a particle-number-broken Hartree-Fock-Bogolyubov vacuum which is obtained from a mean-field calculation
Messina, Luca; Castin, Nicolas; Domain, Christophe; Olsson, Pär
2017-02-01
The quality of kinetic Monte Carlo (KMC) simulations of microstructure evolution in alloys relies on the parametrization of point-defect migration rates, which are complex functions of the local chemical composition and can be calculated accurately with ab initio methods. However, constructing reliable models that ensure the best possible transfer of physical information from ab initio to KMC is a challenging task. This work presents an innovative approach, where the transition rates are predicted by artificial neural networks trained on a database of 2000 migration barriers, obtained with density functional theory (DFT) in place of interatomic potentials. The method is tested on copper precipitation in thermally aged iron alloys, by means of a hybrid atomistic-object KMC model. For the object part of the model, the stability and mobility properties of copper-vacancy clusters are analyzed by means of independent atomistic KMC simulations, driven by the same neural networks. The cluster diffusion coefficients and mean free paths are found to increase with size, confirming the dominant role of coarsening of medium- and large-sized clusters in the precipitation kinetics. The evolution under thermal aging is in better agreement with experiments with respect to a previous interatomic-potential model, especially concerning the experiment time scales. However, the model underestimates the solubility of copper in iron due to the excessively high solution energy predicted by the chosen DFT method. Nevertheless, this work proves the capability of neural networks to transfer complex ab initio physical properties to higher-scale models, and facilitates the extension to systems with increasing chemical complexity, setting the ground for reliable microstructure evolution simulations in a wide range of alloys and applications.
Ab initio theories of electric transport in solid systems with reduced dimensions
International Nuclear Information System (INIS)
Weinberger, Peter
2003-01-01
Ab initio theories of electric transport in solid systems with reduced dimensions, i.e., systems that at best are characterized by two-dimensional translational invariance, are reviewed in terms of a fully relativistic description of the Kubo-Greenwood equation. As the use of this equation requires concepts such as collinearity and non-collinearity in order to properly define resistivities or resistances corresponding to particular magnetic configurations, respective consequences of the (local) density functional theory are recalled in quite a detailed manner. Furthermore, since theoretical descriptions of solid systems with reduced dimensions require quantum mechanical methods different from bulk systems (three-dimensional periodicity), the so-called Screened Korringa-Kohn-Rostoker (SKKR-) method for layered systems is introduced together with a matching coherent potential approximation (inhomogeneous CPA). The applications shown are mainly meant to illustrate various aspects of electric transport in solid systems with reduced dimensions and comprise not only current-in-plane (CIP) experiments, but also current perpendicular to the planes of atoms geometries, consequences of tunneling, and finite nanostructures at or on metallic substrates. In order to give a more complete view of available ab initio methods also a non-relativistic approach based on the Tight Binding Linear Combination of muffin tin orbitals (TB-LMTO-) method and the so-called Kubo-Landauer equation in terms of transmission and reflection matrices is presented. A compilation of references with respect to ab-initio type approaches not explicitly discussed in here finally concludes the discussion of electric properties in solid systems with reduced dimensions
You, Y.; Yan, M. F.
2013-05-01
C and N atoms are the most frequent foreign interstitial atoms (FIAs), and often incorporated into the surface layers of steels to enhance their properties by thermochemical treatments. Al, Si, Ti, V, Cr, Mn, Co, Ni, Cu, Nb and Mo are the most common alloying elements in steels, also can be called foreign substitutional atoms (FSAs). The FIA and FSA interactions play an important role in the diffusion of C and N atoms, and the microstructures and mechanical properties of surface modified layers. Ab initio calculations based on the density functional theory are carried out to investigate FIA interactions with FSA in ferromagnetic bcc iron. The FIA-FSA interactions are analyzed systematically from five aspects, including interaction energies, density of states (DOS), bond populations, electron density difference maps and local magnetic moments.
DEFF Research Database (Denmark)
Wolf, T. J. A.; Kuhlman, Thomas Scheby; Schalk, O.
2014-01-01
Time-resolved photoelectron spectroscopy and ab initio multiple spawning were applied to the ultrafast non-adiabatic dynamics of hexamethylcyclopentadiene. The high level of agreement between experiment and theory associates wavepacket motion with a distinct degree of freedom.......Time-resolved photoelectron spectroscopy and ab initio multiple spawning were applied to the ultrafast non-adiabatic dynamics of hexamethylcyclopentadiene. The high level of agreement between experiment and theory associates wavepacket motion with a distinct degree of freedom....
International Nuclear Information System (INIS)
Garrett, W.R.
1979-01-01
Through the use of a molecular pseudopotential method, we determine the a approximate magnitudes of errors that result when electron affinity determinations of polar negative ions are made through ab initio calculations in which the use of a given basis set yields inappropriate values for permanent and induced dipole moments of the neutral molecule. These results should prove useful in assessing the adequacy of basis sets in ab initio calculations of molecular electron affinities for simple linear polar molecules
Feasible and realiable ab initio atomistic modeling for nuclear waste management
Energy Technology Data Exchange (ETDEWEB)
Beridze, George
2016-07-01
The studies in this PhD dissertation focus on finding a computationally feasible ab initio methodology which would make the reliable first principle atomistic modeling of nuclear materials possible. Here we tested the performance of the different DFT functionals and the DFT-based methods that explicitly account for the electronic correlations, such as the DFT+U approach, for prediction of structural and thermochemical properties of lanthanide- and actinide-bearing materials. In the previous studies, the value of the Hubbard U parameter, required by the DFT+U method, was often guessed or empirically derived. We applied and extensively tested the recently developed ab initio methods such as the constrained local density approximation (cLDA) and the constrained random phase approximation (cRPA), to compute the Hubbard U parameter values from first principles, thus making the DFT+U method a real it ab initio parameter free approach. Our successful benchmarking studies of the parameter-free DFT+U method, for prediction of the structures and the reaction enthalpies of actinide- and lanthanide-bearing molecular compounds and solids indicate, that the linear response method (cLDA) provides a very good, and consistent with the cRPA prediction, estimate of the Hubbard U parameter. In particular, we found that the Hubbard U parameter value, which describes the strength of the on-site Coulomb repulsion between f-electrons, depends strongly on the oxidation state of the f-element, its local bonding environment and crystalline structure of the materials, which has never been considered in such detail before. We have shown, that the applied computational approach substantially, if not dramatically, reduces the error of the predicted reaction enthalpies making the accuracy of the prediction comparable with the uncertainty of the computational unfeasible, higher order methods of quantum chemistry, and experiments. The derived methodology resulted in various, already published
Feasible and realiable ab initio atomistic modeling for nuclear waste management
International Nuclear Information System (INIS)
Beridze, George
2016-01-01
The studies in this PhD dissertation focus on finding a computationally feasible ab initio methodology which would make the reliable first principle atomistic modeling of nuclear materials possible. Here we tested the performance of the different DFT functionals and the DFT-based methods that explicitly account for the electronic correlations, such as the DFT+U approach, for prediction of structural and thermochemical properties of lanthanide- and actinide-bearing materials. In the previous studies, the value of the Hubbard U parameter, required by the DFT+U method, was often guessed or empirically derived. We applied and extensively tested the recently developed ab initio methods such as the constrained local density approximation (cLDA) and the constrained random phase approximation (cRPA), to compute the Hubbard U parameter values from first principles, thus making the DFT+U method a real it ab initio parameter free approach. Our successful benchmarking studies of the parameter-free DFT+U method, for prediction of the structures and the reaction enthalpies of actinide- and lanthanide-bearing molecular compounds and solids indicate, that the linear response method (cLDA) provides a very good, and consistent with the cRPA prediction, estimate of the Hubbard U parameter. In particular, we found that the Hubbard U parameter value, which describes the strength of the on-site Coulomb repulsion between f-electrons, depends strongly on the oxidation state of the f-element, its local bonding environment and crystalline structure of the materials, which has never been considered in such detail before. We have shown, that the applied computational approach substantially, if not dramatically, reduces the error of the predicted reaction enthalpies making the accuracy of the prediction comparable with the uncertainty of the computational unfeasible, higher order methods of quantum chemistry, and experiments. The derived methodology resulted in various, already published
Zirconium - ab initio modelling of point defects diffusion
International Nuclear Information System (INIS)
Gasca, Petrica
2010-01-01
Zirconium is the main element of the cladding found in pressurized water reactors, under an alloy form. Under irradiation, the cladding elongate significantly, phenomena attributed to the vacancy dislocation loops growth in the basal planes of the hexagonal compact structure. The understanding of the atomic scale mechanisms originating this process motivated this work. Using the ab initio atomic modeling technique we studied the structure and mobility of point defects in Zirconium. This led us to find four interstitial point defects with formation energies in an interval of 0.11 eV. The migration paths study allowed the discovery of activation energies, used as entry parameters for a kinetic Monte Carlo code. This code was developed for calculating the diffusion coefficient of the interstitial point defect. Our results suggest a migration parallel to the basal plane twice as fast as one parallel to the c direction, with an activation energy of 0.08 eV, independent of the direction. The vacancy diffusion coefficient, estimated with a two-jump model, is also anisotropic, with a faster process in the basal planes than perpendicular to them. Hydrogen influence on the vacancy dislocation loops nucleation was also studied, due to recent experimental observations of cladding growth acceleration in the presence of this element [fr
Ab Initio Liquid Water Dynamics in Aqueous TMAO Solution.
Usui, Kota; Hunger, Johannes; Sulpizi, Marialore; Ohto, Tatsuhiko; Bonn, Mischa; Nagata, Yuki
2015-08-20
Ab initio molecular dynamics (AIMD) simulations in trimethylamine N-oxide (TMAO)-D2O solution are employed to elucidate the effects of TMAO on the reorientational dynamics of D2O molecules. By decomposing the O-D groups of the D2O molecules into specific subensembles, we reveal that water reorientational dynamics are retarded considerably in the vicinity of the hydrophilic TMAO oxygen (O(TMAO)) atom, due to the O-D···O(TMAO) hydrogen-bond. We find that this reorientational motion is governed by two distinct mechanisms: The O-D group rotates (1) after breaking the O-D···O(TMAO) hydrogen-bond, or (2) together with the TMAO molecule while keeping this hydrogen-bond intact. While the orientational slow-down is prominent in the AIMD simulation, simulations based on force field models exhibit much faster dynamics. The simulated angle-resolved radial distribution functions illustrate that the O-D···O(TMAO) hydrogen-bond has a strong directionality through the sp(3) orbital configuration in the AIMD simulation, and this directionality is not properly accounted for in the force field simulation. These results imply that care must be taken when modeling negatively charged oxygen atoms as single point charges; force field models may not adequately describe the hydration configuration and dynamics.
Ab initio modeling of the motional Stark effect on MAST
International Nuclear Information System (INIS)
De Bock, M. F. M.; Conway, N. J.; Walsh, M. J.; Carolan, P. G.; Hawkes, N. C.
2008-01-01
A multichord motional Stark effect (MSE) system has recently been built on the MAST tokamak. In MAST the π and σ lines of the MSE spectrum overlap due to the low magnetic field typical for present day spherical tokamaks. Also, the field curvature results in a large change in the pitch angle over the observation volume. The measured polarization angle does not relate to one local pitch angle but to an integration over all pitch angles in the observation volume. The velocity distribution of the neutral beam further complicates the measurement. To take into account volume effects and velocity distribution, an ab initio code was written that simulates the MSE spectrum on MAST. The code is modular and can easily be adjusted for other tokamaks. The code returns the intensity, polarized fraction, and polarization angle as a function of wavelength. Results of the code are presented, showing the effect on depolarization and wavelength dependence of the polarization angle. The code is used to optimize the design and calibration of the MSE diagnostic.
Ab initio modelling of transition metals in diamond
International Nuclear Information System (INIS)
Watkins, M; Mainwood, A
2003-01-01
Transition metals (TM) from the first transition series are commonly used as solvent catalysts in the synthesis of diamond by high pressure, high temperature processes. Ab initio calculations on these metals, in finite clusters of tetrahedrally coordinated carbon, enable us to investigate trends in their stability and properties. By carrying out systematic studies of interstitial, substitutional and semi-vacancy TM defects, we show that the electronic structure of the TMs is complicated by the presence of 'dangling bonds' when the TM disrupts the crystal lattice: interstitial defects conform to the Ludwig-Woodbury (LW) model, whilst substitutional and semi-vacancy defects move from approximating the LW model early in the transition series to approaching the vacancy model for the heavier metals. Multi-configurational self-consistent field methods allow genuine many-electron states to be modelled; for neutral interstitial, and all substitutional TMs, the crystal fields are found to exceed the exchange energies in strength. Consequently, low spin states are found for these defects. We find substitutional defects to be the most stable, but that semi-vacancy TMs are very similar in energy to the substitutional defects late in the transition series; interstitial defects are only metastable in diamond. Given appropriate charge compensators neutral and positively charged interstitial TM defects were stable, while negatively charged species appeared to be strongly disfavoured
Predicting lattice thermal conductivity with help from ab initio methods
Broido, David
2015-03-01
The lattice thermal conductivity is a fundamental transport parameter that determines the utility a material for specific thermal management applications. Materials with low thermal conductivity find applicability in thermoelectric cooling and energy harvesting. High thermal conductivity materials are urgently needed to help address the ever-growing heat dissipation problem in microelectronic devices. Predictive computational approaches can provide critical guidance in the search and development of new materials for such applications. Ab initio methods for calculating lattice thermal conductivity have demonstrated predictive capability, but while they are becoming increasingly efficient, they are still computationally expensive particularly for complex crystals with large unit cells . In this talk, I will review our work on first principles phonon transport for which the intrinsic lattice thermal conductivity is limited only by phonon-phonon scattering arising from anharmonicity. I will examine use of the phase space for anharmonic phonon scattering and the Grüneisen parameters as measures of the thermal conductivities for a range of materials and compare these to the widely used guidelines stemming from the theory of Liebfried and Schölmann. This research was supported primarily by the NSF under Grant CBET-1402949, and by the S3TEC, an Energy Frontier Research Center funded by the US DOE, office of Basic Energy Sciences under Award No. DE-SC0001299.
Development of materials science by Ab initio powder diffraction analysis
International Nuclear Information System (INIS)
Fujii, Kotaro
2015-01-01
Crystal structure is most important information to understand properties and behavior of target materials. Technique to analyze unknown crystal structures from powder diffraction data (ab initio powder diffraction analysis) enables us to reveal crystal structures of target materials even we cannot obtain a single crystal. In the present article, three examples are introduced to show the power of this technique in the field of materials sciences. The first example is dehydration/hydration of the pharmaceutically relevant material erythrocycin A. In this example, crystal structures of two anhydrous phases were determined from synchrotron X-ray powder diffraction data and their different dehydration/hydration properties were understood from the crystal structures. In the second example, a crystal structure of a three dimensional metal-organic-framework prepared by a mechanochemical reaction was determined from laboratory X-ray powder diffraction data and the reaction scheme has been revealed. In the third example, a crystal structure of a novel oxide-ion conductor of a new structure family was determined from synchrotron X-ray and neutron powder diffraction data which gave an important information to understand the mechanism of the oxide-ion conduction. (author)
Ab initio study of MgH2 formation
International Nuclear Information System (INIS)
Novakovic, Nikola; Matovic, Ljiljana; Novakovic, Jasmina Grbovic; Manasijevic, Miodrag; Ivanovic, Nenad
2009-01-01
Even if there is considerable literature dealing with structure and properties of MgH 2 compound there are still some uncertain details about nature of bonding governing its formation and decomposition. In order to better understand the processes essential for absorption and desorption of MgH 2 , ab initio DFT based calculations of rutile MgH 2 compound, elemental hcp-Mg, and three different hypothetical hcp-Mg-derived hydrides are performed. Our findings show that all structures are unstable, and that MgH (Wurtzite) is a closest possible candidate for intermediate phase between the hcp-Mg and MgH 2 at 1:1 stoichiometry. An alternative hydration pathway is suggested, including promotion of hcp-Mg to bcc-Mg and consecutive transformation to rutile MgH 2 by means of hydrogen incorporation into Mg matrix. Rutile MgH 2 calculations with various hydrogen vacancies concentration are performed. Calculation shows that at high hydrogen concentration close to 1:2, stable substoichiometric hydride is possible. Calculation also shows that high vacancy (low hydrogen) concentration favors bcc-Mg 2 H over rutile Mg 2 H structure.
Domain Wall Formation in Ferromagnetic Layers: An Ab Initio Study
Herper, Heike C.
Domain walls are an inherent feature of ferromagnetic (FM) films consisting of layers with different magnetic orientations. Since FM films are used in electrical devices the question of the influence of domain walls on, e.g., the magnetoresistance has attracted much interest. Besides discussing the resistance contribution of domain walls, it is appropriate to study different types of domain walls and their energy of formation. The behaviour of domain walls is usually discussed within model calculations. In the present paper it is done within an ab initio Green's function technique for layered systems, i.e., the fully relativistic, spin-polarized screened Korringa-Kohn Rostoker method. Results are presented for fcc Co layers covered by two semi-infinite fcc Pt(001) bulk systems or by bulk fcc Co(001), respectively. The resistance, which is caused by the different types of domain walls is discussed within a Kubo-Greenwood approach considering Co(001)/Co24/Co(001) as an example.
Accurate ab initio vibrational energies of methyl chloride
International Nuclear Information System (INIS)
Owens, Alec; Yurchenko, Sergei N.; Yachmenev, Andrey; Tennyson, Jonathan; Thiel, Walter
2015-01-01
Two new nine-dimensional potential energy surfaces (PESs) have been generated using high-level ab initio theory for the two main isotopologues of methyl chloride, CH 3 35 Cl and CH 3 37 Cl. The respective PESs, CBS-35 HL , and CBS-37 HL , are based on explicitly correlated coupled cluster calculations with extrapolation to the complete basis set (CBS) limit, and incorporate a range of higher-level (HL) additive energy corrections to account for core-valence electron correlation, higher-order coupled cluster terms, scalar relativistic effects, and diagonal Born-Oppenheimer corrections. Variational calculations of the vibrational energy levels were performed using the computer program TROVE, whose functionality has been extended to handle molecules of the form XY 3 Z. Fully converged energies were obtained by means of a complete vibrational basis set extrapolation. The CBS-35 HL and CBS-37 HL PESs reproduce the fundamental term values with root-mean-square errors of 0.75 and 1.00 cm −1 , respectively. An analysis of the combined effect of the HL corrections and CBS extrapolation on the vibrational wavenumbers indicates that both are needed to compute accurate theoretical results for methyl chloride. We believe that it would be extremely challenging to go beyond the accuracy currently achieved for CH 3 Cl without empirical refinement of the respective PESs
Accurate ab initio vibrational energies of methyl chloride
Energy Technology Data Exchange (ETDEWEB)
Owens, Alec, E-mail: owens@mpi-muelheim.mpg.de [Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr (Germany); Department of Physics and Astronomy, University College London, Gower Street, WC1E 6BT London (United Kingdom); Yurchenko, Sergei N.; Yachmenev, Andrey; Tennyson, Jonathan [Department of Physics and Astronomy, University College London, Gower Street, WC1E 6BT London (United Kingdom); Thiel, Walter [Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr (Germany)
2015-06-28
Two new nine-dimensional potential energy surfaces (PESs) have been generated using high-level ab initio theory for the two main isotopologues of methyl chloride, CH{sub 3}{sup 35}Cl and CH{sub 3}{sup 37}Cl. The respective PESs, CBS-35{sup HL}, and CBS-37{sup HL}, are based on explicitly correlated coupled cluster calculations with extrapolation to the complete basis set (CBS) limit, and incorporate a range of higher-level (HL) additive energy corrections to account for core-valence electron correlation, higher-order coupled cluster terms, scalar relativistic effects, and diagonal Born-Oppenheimer corrections. Variational calculations of the vibrational energy levels were performed using the computer program TROVE, whose functionality has been extended to handle molecules of the form XY {sub 3}Z. Fully converged energies were obtained by means of a complete vibrational basis set extrapolation. The CBS-35{sup HL} and CBS-37{sup HL} PESs reproduce the fundamental term values with root-mean-square errors of 0.75 and 1.00 cm{sup −1}, respectively. An analysis of the combined effect of the HL corrections and CBS extrapolation on the vibrational wavenumbers indicates that both are needed to compute accurate theoretical results for methyl chloride. We believe that it would be extremely challenging to go beyond the accuracy currently achieved for CH{sub 3}Cl without empirical refinement of the respective PESs.
Directory of Open Access Journals (Sweden)
Hirokazu Takaki
2014-01-01
Full Text Available We present an efficient computation technique for ab-initio electron transport calculations based on density functional theory and the nonequilibrium Green’s function formalism for application to heterostructures with two-dimensional (2D interfaces. The computational load for constructing the Green’s functions, which depends not only on the energy but also on the 2D Bloch wave vector along the interfaces and is thus catastrophically heavy, is circumvented by parallel computational techniques with the message passing interface, which divides the calculations of the Green’s functions with respect to energy and wave vectors. To demonstrate the computational efficiency of the present code, we perform ab-initio electron transport calculations of Al(100-Si(100-Al(100 heterostructures, one of the most typical metal-semiconductor-metal systems, and show their transmission spectra, density of states (DOSs, and dependence on the thickness of the Si layers.
International Nuclear Information System (INIS)
Palacios, P.; Aguilera, I.; Wahnon, P.
2008-01-01
In this work, we present frozen phonon and linear response ab-initio research into the vibrational properties of the CuGaS 2 chalcopyrite and transition metal substituted (CuGaS 2 )M alloys. These systems are potential candidates for developing a novel solar-cell material with enhanced optoelectronic properties based in the implementation of the intermediate-band concept. We have previously carried out ab-initio calculations of the electronic properties of these kinds of chalcopyrite metal alloys showing a narrow transition metal band isolated in the semiconductor band gap. The substitutes used in the present work are the 3d metal elements, Titanium and Chromium. For the theoretical calculations we use standard density functional theory at local density and generalized gradient approximation levels. We found that the optical phonon branches of the transition metal chalcopyrite, are very sensitive to the specific bonding geometry and small changes in the transition metal environment
Ab initio molecular dynamics of the reaction of quercetin with superoxide radical
International Nuclear Information System (INIS)
Lespade, Laure
2016-01-01
Highlights: • Ab initio molecular dynamics is performed to describe the reaction of quercetin and superoxide. • The reaction occurs near the sites 4′ and 7 when the system contains sufficiently water molecules. • The difference of reactivity of superoxide compared to commonly used radicals as DPPH · or ABTS ·+ is explained. - Abstract: Superoxide plays an important role in biology but in unregulated concentrations it is implicated in a lot of diseases such as cancer or atherosclerosis. Antioxidants like flavonoids are abundant in plant and are good scavengers of superoxide radical. The modeling of superoxide scavenging by flavonoids from the diet still remains a challenge. In this study, ab initio molecular dynamics of the reaction of the flavonoid quercetin toward superoxide radical has been carried out using Car–Parrinello density functional theory. The study has proven different reactant solvation by modifying the number of water molecules surrounding superoxide. The reaction consists in the gift of a hydrogen atom of one of the hydroxyl groups of quercetin to the radical. When it occurs, it is relatively fast, lower than 100 fs. Calculations show that it depends largely on the environment of the hydroxyl group giving its hydrogen atom, the geometry of the first water layer and the presence of a certain number of water molecules in the second layer, indicating a great influence of the solvent on the reactivity.
Ab initio determination of the nuclear quadrupole moments of 114In, 115In, and 117In
International Nuclear Information System (INIS)
Errico, Leonardo A.; Renteria, Mario
2006-01-01
We present here ab initio determinations of the nuclear-quadrupole moment Q of hyperfine-probe-nuclear states of three different In isotopes: the 5 + 192 keV excited state of 114 In (probe for nuclear quadrupole alignment spectroscopy), the 9/2 + ground state of 115 In (nuclear magnetic and nuclear quadrupole resonance probe), and the 3/2 + 659 keV excited state of 117 In (perturbed angular correlations probe). These nuclear-quadrupole moments were determined by comparing experimental nuclear-quadrupole frequencies to the electric field gradient tensor calculated with high accuracy at In sites in metallic indium within the density functional theory. These ab initio calculations were performed with the full-potential linearized augmented plane wave method. The results obtained for the quadrupole moments of 114 In [Q( 114 In)=-0.14(1) b] are in clear discrepancy with those reported in the literature [Q( 114 In)=+0.16(6) b and +0.739(12) b]. For 115 In and 117 In our results are in excellent agreement with the literature and in the last case Q( 117 In) is determined with more precision. In the case of Q( 117 In), its sign cannot be determined because standard γ-γ perturbed angular correlations experiments are not sensitive to the sign of the nuclear-quadrupole frequency
Ab initio modeling of plasticity in HCP metals: pure zirconium and titanium and effect of oxygen
International Nuclear Information System (INIS)
Chaari, Nermine
2015-01-01
We performed atomistic simulations to determine screw dislocations properties in pure zirconium and titanium and to explain the hardening effect attributed to oxygen alloying in both hexagonal close-packed transition metals. We used two energetic models: ab initio calculations based on the density functional theory and calculations with an empirical potential. The complete energetic profile of the screw dislocation when gliding in the different slip planes is obtained in pure Zr. Our calculations reveal the existence of a metastable configuration of the screw dislocation partially spread in the first order pyramidal plane. This configuration is responsible for the cross slip of screw dislocations from prismatic planes, the easiest glide planes, to pyramidal or basal planes. This energy profile is affected by oxygen addition. Ab initio calculations reveal two main effects: oxygen enhances pyramidal cross slip by modifying the dislocation core structure, and pins the dislocation in its metastable sessile configuration. The same modeling approach is applied to titanium. In pure Ti, the same configurations of the screw dislocation in Zr are obtained, but with different energy levels. This leads to a different gliding mechanism. The same way as in Zr, oxygen enhances pyramidal glide in Ti by modifying the dislocation core structure. Besides, oxygen atom lowers the energy of the metastable configuration but not enough to pin the dislocation in this sessile configuration. (author) [fr
Ab initio molecular dynamics of the reaction of quercetin with superoxide radical
Energy Technology Data Exchange (ETDEWEB)
Lespade, Laure, E-mail: l.lespade@ism.u-bordeaux1.fr
2016-08-22
Highlights: • Ab initio molecular dynamics is performed to describe the reaction of quercetin and superoxide. • The reaction occurs near the sites 4′ and 7 when the system contains sufficiently water molecules. • The difference of reactivity of superoxide compared to commonly used radicals as DPPH{sup ·} or ABTS{sup ·+} is explained. - Abstract: Superoxide plays an important role in biology but in unregulated concentrations it is implicated in a lot of diseases such as cancer or atherosclerosis. Antioxidants like flavonoids are abundant in plant and are good scavengers of superoxide radical. The modeling of superoxide scavenging by flavonoids from the diet still remains a challenge. In this study, ab initio molecular dynamics of the reaction of the flavonoid quercetin toward superoxide radical has been carried out using Car–Parrinello density functional theory. The study has proven different reactant solvation by modifying the number of water molecules surrounding superoxide. The reaction consists in the gift of a hydrogen atom of one of the hydroxyl groups of quercetin to the radical. When it occurs, it is relatively fast, lower than 100 fs. Calculations show that it depends largely on the environment of the hydroxyl group giving its hydrogen atom, the geometry of the first water layer and the presence of a certain number of water molecules in the second layer, indicating a great influence of the solvent on the reactivity.
Gorai, S.; Ghosh, P. S.; Bhattacharya, C.; Arya, A.
2018-04-01
The pressure evolution of phase stability, structural and mechanical properties of Fe3C in ferro-magnetic (FM) and high pressure non magnetic (NM) phase is investigated from first principle calculations. The 2nd order FM to NM phase transition of Fe3C is identified around 60 GPa. Pressure (or density) variation of sound velocities from our ab-initio calculated single crystal elastic constants are determined to predict these parameters at Earth's outer core pressure.
International Nuclear Information System (INIS)
Timoshkin, A.Yu.; Suvorov, A.V.; Shefer, G.F.
1999-01-01
By the ab initio and density functional methods the structural characteristics and vibrational spectra of gallium iodide donor-acceptor complexes with pyridine have been calculated. The standard thermodynamic characteristics of GaI 3 Py complex dissociation in gaseous phase have been calculated, as well. Short I-H intramolecular distances suggest that hydrogen iodide elimination with Ga-N chemical bond retention is the first stage of the complex pyrolysis [ru
Quantifying Ab Initio Equation of State Errors for Hydrogen-Helium Mixtures
Clay, Raymond; Morales, Miguel
2017-06-01
In order to produce predictive models of Jovian planets, an accurate equation of state for hydrogen-helium mixtures is needed over pressure and temperature ranges spanning multiple orders of magnitude. While extensive theoretical work has been done in this area, previous controversies regarding the equation of state of pure hydrogen have demonstrated exceptional sensitivity to approximations commonly employed in ab initio calculations. To this end, we present the results of our quantum Monte Carlo based benchmarking studies for several major classes of density functionals. Additionally, we expand upon our published results by considering the impact that ionic finite size effects and density functional errors translate to errors in the equation of state. Sandia National Laboratories is a multi-mission 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.
Ab initio approach to the ion stopping power at the plasma-solid interface
Bonitz, Michael; Schlünzen, Niclas; Wulff, Lasse; Joost, Jan-Philip; Balzer, Karsten
2016-10-01
The energy loss of ions in solids is of key relevance for many applications of plasmas, ranging from plasma technology to fusion. Standard approaches are based on density functional theory or SRIM simulations, however, the applicability range and accuracy of these results are difficult to assess, in particular, for low energies. Here we present an independent approach that is based on ab initio nonequilibrium Green functions theory, e.g. that allows to incorporate electronic correlations effects of the solid. We present the first application of this method to low-temperature plasmas, concentrating on proton and alpha-particle stopping in a graphene layer. In addition to the stopping power we present time-dependent results for the local electron density, the spectral function and the photoemission spectrum that is directly accessible in optical, UV or x-ray diagnostics. http://www.itap.uni-kiel.de/theo-physik/bonitz/.
Carbon diffusion in molten uranium: an ab initio molecular dynamics study
Garrett, Kerry E.; Abrecht, David G.; Kessler, Sean H.; Henson, Neil J.; Devanathan, Ram; Schwantes, Jon M.; Reilly, Dallas D.
2018-04-01
In this work we used ab initio molecular dynamics within the framework of density functional theory and the projector-augmented wave method to study carbon diffusion in liquid uranium at temperatures above 1600 K. The electronic interactions of carbon and uranium were described using the local density approximation (LDA). The self-diffusion of uranium based on this approach is compared with literature computational and experimental results for liquid uranium. The temperature dependence of carbon and uranium diffusion in the melt was evaluated by fitting the resulting diffusion coefficients to an Arrhenius relationship. We found that the LDA calculated activation energy for carbon was nearly twice that of uranium: 0.55 ± 0.03 eV for carbon compared to 0.32 ± 0.04 eV for uranium. Structural analysis of the liquid uranium-carbon system is also discussed.
Ab initio research of stopping power for energetic ions in solids
Energy Technology Data Exchange (ETDEWEB)
He, Bin, E-mail: hebin-rc@163.com; Meng, Xu-Jun; Wang, Jian-Guo
2017-03-01
A new physical scenario is suggested to estimate the stopping power of energetic α particles in solid-density Be, Na, and Al at room temperature in an ab initio way based on the average atom model. In the scenario the stopping power is caused by the transition of free electrons to higher energy states and the ionization of bound electrons of the atom. Our results are found generally in good agreement with the recommended data in Al, Be and Na as well as the experimental data in Al. A comparison of energy loss with the recent experiment of protons in Be indicates that the scenario is more reasonable than the local density approximation in this case.
Magnetic properties of vanadium doped CdTe: Ab initio calculations
Energy Technology Data Exchange (ETDEWEB)
Goumrhar, F. [Laboratory of Physics of High Energy, Modeling & Simulations (LPHE-MS), Faculty of Sciences, Mohammed V University of Rabat, Av. Ibn Batouta, B.P. 1014 Rabat (Morocco); Bahmad, L., E-mail: bahmad@fsr.ac.ma [Laboratory of Magnetism and High Energy Physics (LMPHE-URAC12), Faculty of Sciences, Mohammed V University of Rabat, Av. Ibn Batouta, B.P. 1014 Rabat (Morocco); Mounkachi, O. [Material and Nanomaterial Center, MAScIR Fondation, Rabat (Morocco); Benyoussef, A. [Laboratory of Magnetism and High Energy Physics (LMPHE-URAC12), Faculty of Sciences, Mohammed V University of Rabat, Av. Ibn Batouta, B.P. 1014 Rabat (Morocco); Material and Nanomaterial Center, MAScIR Fondation, Rabat (Morocco); Hassan II Academy of Sciences and Technology, Rabat (Morocco)
2017-04-15
In this paper, we are applying the ab initio calculations to study the magnetic properties of vanadium doped CdTe. This study is based on the Korringa–Kohn–Rostoker method (KKR) combined with the coherent potential approximation (CPA), within the local density approximation (LDA). This method is called KKR-CPA-LDA. We have calculated and plotted the density of states (DOS) in the energy diagram for different concentrations of dopants. We have also investigated the magnetic and half-metallic properties of this compound and shown the mechanism of exchange interaction. Moreover, we have estimated the Curie temperature T{sub c} for different concentrations. Finally, we have shown how the crystal field and the exchange splittings vary as a function of the concentrations.
AN AB INITIO MODEL FOR COSMIC-RAY MODULATION
Energy Technology Data Exchange (ETDEWEB)
Engelbrecht, N. E.; Burger, R. A. [Center for Space Research, North-West University, Potchefstroom 2520 (South Africa)
2013-07-20
A proper understanding of the effects of turbulence on the diffusion and drift of cosmic rays (CRs) is of vital importance for a better understanding of CR modulation in the heliosphere. This study presents an ab initio model for CR modulation, incorporating for the first time the results yielded by a two-component turbulence transport model. This model is solved for solar minimum heliospheric conditions, utilizing boundary values chosen so that model results are in reasonable agreement with spacecraft observations of turbulence quantities in the solar ecliptic plane and along the out-of-ecliptic trajectory of the Ulysses spacecraft. These results are employed as inputs for modeled slab and two-dimensional (2D) turbulence energy spectra. The modeled 2D spectrum is chosen based on physical considerations, with a drop-off at the very lowest wavenumbers. There currently exist no models or observations for the wavenumber where this drop-off occurs, and it is considered to be the only free parameter in this study. The modeled spectra are used as inputs for parallel mean free path expressions based on those derived from quasi-linear theory and perpendicular mean free paths from extended nonlinear guiding center theory. Furthermore, the effects of turbulence on CR drifts are modeled in a self-consistent way, also employing a recently developed model for wavy current sheet drift. The resulting diffusion and drift coefficients are applied to the study of galactic CR protons and antiprotons using a 3D, steady-state CR modulation code, and sample solutions in fair to good agreement with multiple spacecraft observations are presented.
Cosmic-ray modulation: an ab initio approach
Energy Technology Data Exchange (ETDEWEB)
Engelbrecht, N.E.; Burger, R.A., E-mail: 12580996@nwu.ac.za [Center for Space Research, North-West University, Potchefstroom (South Africa)
2014-07-01
A better understanding of cosmic-ray modulation in the heliosphere can only be gained through a proper understanding of the effects of turbulence on the diffusion and drift of cosmic rays. We present an ab initio model for cosmic-ray modulation, incorporating for the first time the results yielded by a two-component turbulence transport model. This model is solved for periods of minimum solar activity, utilizing boundary values chosen so that model results are in fair to good agreement with spacecraft observations of turbulence quantities, not only in the solar ecliptic plane but also along the out-of-ecliptic trajectory of the Ulysses spacecraft. These results are employed as inputs for modelled slab and 2D turbulence energy spectra. The latter spectrum is chosen based on physical considerations, with a drop-off at the very lowest wavenumbers commencing at the 2D outerscale. There currently exist no models or observations for this quantity, and it is the only free parameter in this study. The modelled turbulence spectra are used as inputs for parallel mean free path expressions based on those derived from quasi-linear theory and perpendicular mean free paths from extended nonlinear guiding center theory. Furthermore, the effects of turbulence on cosmic-ray drifts are modelled in a self-consistent way, employing a recently developed model for drift along the wavy current sheet. The resulting diffusion coefficients and drift expressions are applied to the study of galactic cosmic-ray protons and antiprotons using a three dimensional, steady-state cosmic-ray modulation code, and sample solutions in fair agreement with multiple spacecraft observations are presented. (author)
Cosmic-ray modulation: an ab initio approach
International Nuclear Information System (INIS)
Engelbrecht, N.E.; Burger, R.A.
2014-01-01
A better understanding of cosmic-ray modulation in the heliosphere can only be gained through a proper understanding of the effects of turbulence on the diffusion and drift of cosmic rays. We present an ab initio model for cosmic-ray modulation, incorporating for the first time the results yielded by a two-component turbulence transport model. This model is solved for periods of minimum solar activity, utilizing boundary values chosen so that model results are in fair to good agreement with spacecraft observations of turbulence quantities, not only in the solar ecliptic plane but also along the out-of-ecliptic trajectory of the Ulysses spacecraft. These results are employed as inputs for modelled slab and 2D turbulence energy spectra. The latter spectrum is chosen based on physical considerations, with a drop-off at the very lowest wavenumbers commencing at the 2D outerscale. There currently exist no models or observations for this quantity, and it is the only free parameter in this study. The modelled turbulence spectra are used as inputs for parallel mean free path expressions based on those derived from quasi-linear theory and perpendicular mean free paths from extended nonlinear guiding center theory. Furthermore, the effects of turbulence on cosmic-ray drifts are modelled in a self-consistent way, employing a recently developed model for drift along the wavy current sheet. The resulting diffusion coefficients and drift expressions are applied to the study of galactic cosmic-ray protons and antiprotons using a three dimensional, steady-state cosmic-ray modulation code, and sample solutions in fair agreement with multiple spacecraft observations are presented. (author)
Lithium Insertion In Silicon Nanowires: An ab Initio Study
Zhang, Qianfan
2010-09-08
The ultrahigh specific lithium ion storage capacity of Si nanowires (SiNWs) has been demonstrated recently and has opened up exciting opportunities for energy storage. However, a systematic theoretical study on lithium insertion in SiNWs remains a challenge, and as a result, understanding of the fundamental interaction and microscopic dynamics during lithium insertion is still lacking. This paper focuses on the study of single Li atom insertion into SiNWs with different sizes and axis orientations by using full ab initio calculations. We show that the binding energy of interstitial Li increases as the SiNW diameter grows. The binding energies at different insertion sites, which can be classified as surface, intermediate, and core sites, are quite different. We find that surface sites are energetically the most favorable insertion positions and that intermediate sites are the most unfavorable insertion positions. Compared with the other growth directions, the [110] SiNWs with different diameters always present the highest binding energies on various insertion locations, which indicates that [110] SiNWs are more favorable by Li doping. Furthermore, we study Li diffusion inside SiNWs. The results show that the Li surface diffusion has a much higher chance to occur than the surface to core diffusion, which is consistent with the experimental observation that the Li insertion in SiNWs is layer by layer from surface to inner region. After overcoming a large barrier crossing surface-to-intermediate region, the diffusion toward center has a higher possibility to occur than the inverse process. © 2010 American Chemical Society.
Ab-initio atomic level stress and role of d-orbitals in CuZr, CuZn and CuY
Ojha, Madhusudan; Nicholson, Don M.; Egami, Takeshi
2015-03-01
Atomic level stress offers a new tool to characterize materials within the local approximation to density functional theory (DFT). Ab-initio atomic level stresses in B2 structures of CuZr, CuZn and CuY are calculated and results are explained on the basis of d-orbital contributions to Density of States (DOS). The overlap of d-orbital DOS plays an important role in the relative magnitude of atomic level stresses in these structures. The trends in atomic level stresses that we observed in these simple B2 structures are also seen in complex structures such as liquids, glasses and solid solutions. The stresses are however modified by the different coordination and relaxed separation distances in these complex structures. We used the Locally Self-Consistent Multiple Scattering (LSMS) code and Vienna Ab-initio Simulation Package (VASP) for ab-initio calculations.
Ab initio thermodynamics for the growth of ultra-thin Cu film on a perfect Mg O(001) surface
Energy Technology Data Exchange (ETDEWEB)
Zhukovskii, Yuri F. [Institute for Solid State Physics, University of Latvia, Kengaraga str. 8, Riga LV-1063 (Latvia)]. E-mail: quantzh@latnet.lv; Fuks, David [Materials Engineering Department, Ben-Gurion University of the Negev, POB 653, Beer-Sheva IL-84105 (Israel); Kotomin, Eugene A. [Institute for Solid State Physics, University of Latvia, Kengaraga str. 8, Riga LV-1063 (Latvia); Dorfman, Simon [Department of Physics, Israel Institute of Technology-Technion, Haifa IL-32000 (Israel)
2005-12-15
Controlled growth of thin metallic films on oxide substrates is important for numerous micro-and nano electronic applications. Our ab initio study is devoted to the periodic slab simulations for a series of ordered 2a Cu superlattices on the regular Mg O(001) substrate. Submonolayer and monolayer substrate Cu coverages were calculated using the Daft-Gaga method, as implemented into the Crystal-98 code. The results of ab initio calculations have been combined with thermodynamic theory which allows US to predict the growth mode of ultra-thin metal films (spinodal decomposition vs. nucleation-and-growth regime) as a function of the metal coverage and the temperature, and to estimate the metal density in clusters. We show that 3a cluster formation becomes predominant already at low Cu coverages, in agreement with the experiment.
Ab initio thermodynamics for the growth of ultra-thin Cu film on a perfect Mg O(001) surface
International Nuclear Information System (INIS)
Zhukovskii, Yuri F.; Fuks, David; Kotomin, Eugene A.; Dorfman, Simon
2005-01-01
Controlled growth of thin metallic films on oxide substrates is important for numerous micro-and nano electronic applications. Our ab initio study is devoted to the periodic slab simulations for a series of ordered 2a Cu superlattices on the regular Mg O(001) substrate. Submonolayer and monolayer substrate Cu coverages were calculated using the Daft-Gaga method, as implemented into the Crystal-98 code. The results of ab initio calculations have been combined with thermodynamic theory which allows US to predict the growth mode of ultra-thin metal films (spinodal decomposition vs. nucleation-and-growth regime) as a function of the metal coverage and the temperature, and to estimate the metal density in clusters. We show that 3a cluster formation becomes predominant already at low Cu coverages, in agreement with the experiment
Byrne, Aaron; English, Niall J.; Schwingenschlö gl, Udo; Coker, David F.
2015-01-01
Ab initio, density functional theory (DFT)-based molecular dynamics (MD) has been carried out to investigate the effect of explicit solvation on the dynamical and structural properties of a [bmim][NTf2] room-temperature ionic liquid (RTIL
A Force Balanced Fragmentation Method for ab Initio Molecular Dynamic Simulation of Protein
Directory of Open Access Journals (Sweden)
Mingyuan Xu
2018-05-01
Full Text Available A force balanced generalized molecular fractionation with conjugate caps (FB-GMFCC method is proposed for ab initio molecular dynamic simulation of proteins. In this approach, the energy of the protein is computed by a linear combination of the QM energies of individual residues and molecular fragments that account for the two-body interaction of hydrogen bond between backbone peptides. The atomic forces on the caped H atoms were corrected to conserve the total force of the protein. Using this approach, ab initio molecular dynamic simulation of an Ace-(ALA9-NME linear peptide showed the conservation of the total energy of the system throughout the simulation. Further a more robust 110 ps ab initio molecular dynamic simulation was performed for a protein with 56 residues and 862 atoms in explicit water. Compared with the classical force field, the ab initio molecular dynamic simulations gave better description of the geometry of peptide bonds. Although further development is still needed, the current approach is highly efficient, trivially parallel, and can be applied to ab initio molecular dynamic simulation study of large proteins.
Progress towards an ab initio real-time treatment of warm dense matter
Baczewski, Andrew; Cangi, Attila; Hansen, Stephanie; Jensen, Daniel
2017-10-01
Time-dependent density functional theory (TDDFT) provides an accurate description of equilibrium properties of warm dense matter, such as the dynamic structure factor (Baczewski et al., Phys. Rev. Lett., 116(11), 2016). While non-equilibrium properties, such as stopping power, have also been demonstrated to be within the grasp of TDDFT, the ultrafast isochoric heating of condensed matter into the warm dense state, enabled by recent advances in XFELs, remains beyond its capabilities. In this talk, we will describe the successes of and continuing challenges for TDDFT for warm dense matter, and present progress towards a more complete ab initio treatment of isochoric x-ray heating. Sandia National Laboratories is a multi-mission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International, Inc., for the DOE's National Nuclear Security Administration under contract DE-NA0003525.
Ab initio modeling of Al adsorption on CaF2 surfaces
International Nuclear Information System (INIS)
Barzilai, S.; Argaman, N.; Froumin, N.; Fuks, D.; Frage, N.
2008-01-01
Ab initio simulations of the adsorption of Al atoms on CaF 2 (0 0 1) and (1 1 1) surfaces have been performed for supercells with 7 different atomic configurations, using density functional theory. For (1 1 1) surfaces, a repulsive interaction was observed for most configurations, while a weak attraction was obtained when the Al atom was placed above F atoms. For the Ca-terminated (0 0 1) surface, the adsorption energy was about 5 times larger, whereas for the F-terminated (0 0 1) surface it was about 20 times greater. The comparative analysis indicates that the (0 0 1) surfaces are reactive and have a strong Al adatom bonding (chemisorption), especially for the F-terminated substrate. On the contrary, the (1 1 1) plane may be considered as non-reactive (physisorption), having a weak bonding of the Al adatom above the F site
Ab initio theory for current-induced molecular switching: Melamine on Cu(001)
Ohto, Tatsuhiko
2013-05-28
Melamine on Cu(001) is mechanically unstable under the current of a scanning tunneling microscope tip and can switch among configurations. However, these are not equally accessible, and the switching critical current depends on the bias polarity. In order to explain such rich phenomenology, we have developed a scheme to evaluate the evolution of the reaction paths and activation barriers as a function of bias, which is rooted in the nonequilibrium Green\\'s function method implemented within density functional theory. This, combined with the calculation of the inelastic electron tunneling spectroscopy signal, allows us to identify the vibrational modes promoting the observed molecular conformational changes. Finally, once our ab initio results are used within a resonance model, we are able to explain the details of the switching behavior, such as its dependence on the bias polarity, and the noninteger power relation between the reaction rate constants and both the bias voltage and the electric current. © 2013 American Physical Society.
International Nuclear Information System (INIS)
Fink, R.F.; Pfister, J.; Schneider, A.; Zhao, H.; Engels, B.
2008-01-01
We present new, generally applicable protocols for the computation of the coupling parameter, J, of excitation energy transfer with quantum chemical ab initio methods. The protocols allow to select the degree of approximation and computational demand such that they are applicable for realistic systems and still allow to control the quality of the approach. We demonstrate the capabilities of the different protocols using the CO dimer as a first example. Correlation effects are found to scale J by a factor of about 0.7 which is in good agreement to earlier results obtained for the ethene dimer. The various levels of the protocol allow to assess the influence of ionic configurations and the polarisation within the dimer. Further, the interplay between the Foerster and Dexter contribution to J is investigated. The computations also show error compensation within approximations that are widely used for extended systems as in particular the transition density cube method
Trends in magnetism of free Rh clusters via relativistic ab-initio calculations.
Šipr, O; Ebert, H; Minár, J
2015-02-11
A fully relativistic ab-initio study on free Rh clusters of 13-135 atoms is performed to identify general trends concerning their magnetism and to check whether concepts which proved to be useful in interpreting magnetism of 3d metals are applicable to magnetism of 4d systems. We found that there is no systematic relation between local magnetic moments and coordination numbers. On the other hand, the Stoner model appears well-suited both as a criterion for the onset of magnetism and as a guide for the dependence of local magnetic moments on the site-resolved density of states at the Fermi level. Large orbital magnetic moments antiparallel to spin magnetic moments were found for some sites. The intra-atomic magnetic dipole Tz term can be quite large at certain sites but as a whole it is unlikely to affect the interpretation of x-ray magnetic circular dichroism experiments based on the sum rules.
Ab initio study of structural and mechanical property of solid molecular hydrogens
Ye, Yingting; Yang, Li; Yang, Tianle; Nie, Jinlan; Peng, Shuming; Long, Xinggui; Zu, Xiaotao; Du, Jincheng
2015-06-01
Ab initio calculations based on density functional theory (DFT) were performed to investigate the structural and the elastic properties of solid molecular hydrogens (H2). The influence of molecular axes of H2 on structural relative stabilities of hexagonal close-packed (hcp) and face-centered cubic (fcc) structured hydrogen molecular crystals were systematically investigated. Our results indicate that for hcp structures, disordered hydrogen molecule structure is more stable, while for fcc structures, Pa3 hydrogen molecular crystal is most stable. The cohesive energy of fcc H2 crystal was found to be lower than hcp. The mechanical properties of fcc and hcp hydrogen molecular crystals were obtained, with results consistent with previous theoretical calculations. In addition, the effects of zero point energy (ZPE) and van der Waals (vdW) correction on the cohesive energy and the stability of hydrogen molecular crystals were systematically studied and discussed.
International Nuclear Information System (INIS)
Bernholc, J.
1998-01-01
The field of computational materials physics has grown very quickly in the past decade, and it is now possible to simulate properties of complex materials completely from first principles. The presentation has mostly focused on first-principles dynamic simulations. Such simulations have been pioneered by Car and Parrinello, who introduced a method for performing realistic simulations within the context of density functional theory. The Car-Parrinello method and related plane wave approaches are reviewed in depth. The Car-Parrinello method was reviewed and illustrated with several applications: the dynamics of the C 60 solid, diffusion across Si steps, and computing free energy differences. Alternative ab initio simulation schemes, which use preconditioned conjugate gradient techniques for energy minimization and dynamics were also discussed
Ab initio determination of effective electron-phonon coupling factor in copper
Ji, Pengfei; Zhang, Yuwen
2016-04-01
The electron temperature Te dependent electron density of states g (ε), Fermi-Dirac distribution f (ε), and electron-phonon spectral function α2 F (Ω) are computed as prerequisites before achieving effective electron-phonon coupling factor Ge-ph. The obtained Ge-ph is implemented into a molecular dynamics (MD) and two-temperature model (TTM) coupled simulation of femtosecond laser heating. By monitoring temperature evolutions of electron and lattice subsystems, the result utilizing Ge-ph from ab initio calculation shows a faster decrease of Te and increase of Tl than those using Ge-ph from phenomenological treatment. The approach of calculating Ge-ph and its implementation into MD-TTM simulation is applicable to other metals.
Ab initio theory for current-induced molecular switching: Melamine on Cu(001)
Ohto, Tatsuhiko; Rungger, Ivan; Yamashita, Koichi; Nakamura, Hisao; Sanvito, Stefano
2013-01-01
Melamine on Cu(001) is mechanically unstable under the current of a scanning tunneling microscope tip and can switch among configurations. However, these are not equally accessible, and the switching critical current depends on the bias polarity. In order to explain such rich phenomenology, we have developed a scheme to evaluate the evolution of the reaction paths and activation barriers as a function of bias, which is rooted in the nonequilibrium Green's function method implemented within density functional theory. This, combined with the calculation of the inelastic electron tunneling spectroscopy signal, allows us to identify the vibrational modes promoting the observed molecular conformational changes. Finally, once our ab initio results are used within a resonance model, we are able to explain the details of the switching behavior, such as its dependence on the bias polarity, and the noninteger power relation between the reaction rate constants and both the bias voltage and the electric current. © 2013 American Physical Society.
Estudo ab-initio da a-alanina em meio aquoso
Directory of Open Access Journals (Sweden)
Sambrano Júlio Ricardo
1999-01-01
Full Text Available Ab initio Hartree-Fock (HF, Density Functional (B3LYP and electron correlation (MP2 methods have been used to caracterize the aqueous medium intramolecular hydrogen bond in a-alanine. The 6-31G* and 6-31++G** were taken from Gaussian94 library. We were concerned on the structure of three conformers of a-alanine, in their neutral form plus on the structure of the zwitterionic form (Z. The Z structure is a stationary point at the HF/6-31G* level but it is not when diffuse functions and electron correlation are included. This results shows that the Z form does not exist in the gas phase. The inclusion of solvent effects changed significantly the results obtained in gas phase, therefore this inclusion make the Z form a stationary point within all level of theory, and the relative energy depends dramatically on the level of calculation.
Ab initio thermodynamic properties of stoichiometric phases in the Ni-Al system
International Nuclear Information System (INIS)
Arroyave, R.; Shin, D.; Liu, Z.-K.
2005-01-01
In this work the thermodynamic properties of Al, Ni, NiAl and Ni 3 Al were obtained through ab initio methods. Through the use of density functional theory within the generalized gradient approximation and projector augmented-wave (PAW) pseudopotentials, the 0 K energetics of the structures were calculated. The supercell method was used to calculate the vibrational contributions to the free energy. The contribution of electronic degrees of freedom to the total free energy was also included in the calculations. The resulting free energy was used to calculate the enthalpies and entropies of the structures investigated. The comparison with experimental data is satisfactory, and the calculations compare well with recent results using linear response theory
An ab initio approach to free-energy reconstruction using logarithmic mean force dynamics
International Nuclear Information System (INIS)
Nakamura, Makoto; Obata, Masao; Morishita, Tetsuya; Oda, Tatsuki
2014-01-01
We present an ab initio approach for evaluating a free energy profile along a reaction coordinate by combining logarithmic mean force dynamics (LogMFD) and first-principles molecular dynamics. The mean force, which is the derivative of the free energy with respect to the reaction coordinate, is estimated using density functional theory (DFT) in the present approach, which is expected to provide an accurate free energy profile along the reaction coordinate. We apply this new method, first-principles LogMFD (FP-LogMFD), to a glycine dipeptide molecule and reconstruct one- and two-dimensional free energy profiles in the framework of DFT. The resultant free energy profile is compared with that obtained by the thermodynamic integration method and by the previous LogMFD calculation using an empirical force-field, showing that FP-LogMFD is a promising method to calculate free energy without empirical force-fields
Energy Technology Data Exchange (ETDEWEB)
Fink, R.F. [University of Wuerzburg, Institute of Organic Chemistry, Am Hubland, D-97074 Wuerzburg (Germany)], E-mail: reinhold.fink@rub.de; Pfister, J.; Schneider, A.; Zhao, H.; Engels, B. [University of Wuerzburg, Institute of Organic Chemistry, Am Hubland, D-97074 Wuerzburg (Germany)
2008-01-29
We present new, generally applicable protocols for the computation of the coupling parameter, J, of excitation energy transfer with quantum chemical ab initio methods. The protocols allow to select the degree of approximation and computational demand such that they are applicable for realistic systems and still allow to control the quality of the approach. We demonstrate the capabilities of the different protocols using the CO dimer as a first example. Correlation effects are found to scale J by a factor of about 0.7 which is in good agreement to earlier results obtained for the ethene dimer. The various levels of the protocol allow to assess the influence of ionic configurations and the polarisation within the dimer. Further, the interplay between the Foerster and Dexter contribution to J is investigated. The computations also show error compensation within approximations that are widely used for extended systems as in particular the transition density cube method.
Ab initio investigation of the switching behavior of the dithiole-benzene nano-molecular wire
International Nuclear Information System (INIS)
Darvish Ganji, M.; Rungger, I.
2008-01-01
We report a first-principle study of electrical transport and switching behavior in a single molecular conductor consisting of a dithiole-benzene sandwiched between two Au( 100) electrodes. Ab initio total energy calculations reveal dithiole-benzene molecules on a gold surface, contacted by a monoatomic gold scanning tunneling microscope tip to have two classes of low energy conformations with differing symmetries. Lateral motion of the tip or excitation of the molecule cause it 10 change from one conformation class to the other and to switch between a strongly and a weakly conducting state. Thus, surprisingly. despite their apparent simplicity, these Au-dithiole-benzene -Au nano wires are shown to be electrically bi-stable switches, the smallest two-terminal molecular switches to date. The projected density of states and transmission coefficients are analyzed, and it suggests that the variation of the coupling between the molecule and the electrodes with external bias leads to switching behavior
Ab initio calculation of molecular energies including parity violating interactions
International Nuclear Information System (INIS)
Bakasov, A.; Ha Taekyu; Quack, M.
1995-01-01
A new approach, RHF-CIS, based on the perturbation of the ground state RHF wave function by the CIS excitations, has been implemented for evaluation of energy of parity violating interaction in molecules, E pv . The earlier approach, RHF-SDE, was based on the perturbation of the RHF ground states by the single-determinant ''excitations'' (SDE). The results obtained show the dramatic difference between E pv values in the RHF-CIS framework and those in the RHF-SDE framework: the E pv values of the RHF-CIS formalism are more than one order of magnitude greater compared to the RHF-SDE formalism as well as the corresponding tensor components. The maximal total value obtained for hydrogen peroxide in the RHF-CIS framework is 3.661 X 10 -19 E H (DZ ** basis set) while the maximal E pv value for the RHF-SDE formalism is just 3.635 X 10 -20 E H (TZ basis set). It is remarkable that both in the RFH-CIS and in the RHF-SDE approaches the diagonal tensor components of E pv strictly follow the geometry of a molecule and are always different from zero at chiral conformations. The zeros of the total E pv at chiral geometries are now found to be the results of the interplay between the diagonal tensor components values. We have carried out exhaustive analysis of the RHF-SDE formalism and found that it is not sufficiently accurate for studies of E pv . To this end, we have completely reproduced the previous work, which has been done in the RHF-SDE frame-work, and developed it further, studying how the RHF-SDE results vary when changing size and quality of basis sets. This last resource does not save the RHF-SDE formalism for evaluations of E pv from the general failure. Packages of FORTRAN routines called ENWEAK/RHFSDE-93 and ENWEAK/RHFCIS-94 have been developed which run on top of an ab initio MO package. We used 6-31G and 6-31G**, DZ and DZ**, TZ and TZ**, and (10s, 6p,**) basis sets. We will discuss the importance of the present results for possible measurement of the parity
Ab-initio study on electronic properties of rocksalt SnAs
Babariya, Bindiya; Vaghela, M. V.; Gajjar, P. N.
2018-05-01
Within the frame work of Local Density Approximation of Exchange and Correlation, ab-initio method of density functional theory with Abinit code is used to compute electronic energy band structure, density of States and charge density of SnAs in rocksalt phase. Our result after optimization for lattice constant agrees with experimental value within 0.59% deviation. The computed electronic energy bands in high symmetry directions Γ→K→X→Γ→L→X→W→L→U shown metallic nature. The lowest band in the electronic band structure is showing band-gap approximately 1.70 eV from next higher band and no crossing between lowest two bands are seen. The density of states revels p-p orbit hybridization between Sn and As atoms. The spherical contour around Sn and As in the charge density plot represent partly ionic and partly covalent bonding. Fermi surface topology is the resultant effect of the single band crossing along L direction at Ef.
Many-body optimization using an ab initio monte carlo method.
Haubein, Ned C; McMillan, Scott A; Broadbelt, Linda J
2003-01-01
Advances in computing power have made it possible to study solvated molecules using ab initio quantum chemistry. Inclusion of discrete solvent molecules is required to determine geometric information about solute/solvent clusters. Monte Carlo methods are well suited to finding minima in many-body systems, and ab initio methods are applicable to the widest range of systems. A first principles Monte Carlo (FPMC) method was developed to find minima in many-body systems, and emphasis was placed on implementing moves that increase the likelihood of finding minimum energy structures. Partial optimization and molecular interchange moves aid in finding minima and overcome the incomplete sampling that is unavoidable when using ab initio methods. FPMC was validated by studying the boron trifluoride-water system, and then the method was used to examine the methyl carbenium ion in water to demonstrate its application to solvation problems.
Ab-initio calculations of superconducting properties of YBa2Cu3O7
International Nuclear Information System (INIS)
Zhao, G.L.; Bagayoko, D.
1999-01-01
The authors present ab-initio calculations for the electronic structure and superconducting properties of YBa 2 Cu 3 O 7 (YBCO). The electronic structure was calculated using a self-consistent ab-initio LCAO method. They solved the anisotropic Eliashberg gap equation numerically. The strong coupling of the high energy optical phonons around 60--73 meV, with the electrons at the Fermi surface, leads to a high Tc in YBCO. The calculated Tc is about 89 K for μ* = 0.1. The good agreement of the calculated results with experimental measurements and the ab-initio nature of the calculations support the scenario of an anisotropic s-wave superconductor for YBCO
Inelastic neutron scattering an ab-initio calculation of negative thermal expansion in Ag2O
International Nuclear Information System (INIS)
Gupta, M.K.; Mittal, R.; Rols, S.; Chaplot, S.L.
2012-01-01
The compound Ag 2 O undergoes large and isotropic negative thermal expansion over 0-500 K. We report temperature dependent inelastic neutron scattering measurements and ab-initio calculations of the phonon spectrum. The temperature dependence of the experimental phonon spectrum shows strong anharmonic nature of phonon modes of energy around 2.4 meV. The ab-initio calculations reveal that the maximum negative Grüneisen parameter, which is a measure of the relevant anharmonicity, occurs for the transverse phonon modes that involve bending motions of the Ag 4 O tetrahedra. The thermal expansion is evaluated from the ab-initio calculation of the pressure dependence of the phonon modes, and found in good agreement with available experimental data.
Ab initio calculations of 3H(d,n)4He fusion
International Nuclear Information System (INIS)
Navratil, Petr; Quaglioni, Sofia
2012-01-01
We build a new ab initio many-body approach capable of describing simultaneously both bound and scattering states in light nuclei, by combining the resonating-group method with the ab initio no-core shell model. In this way, we complement a microscopic-cluster technique with the use of realistic interactions, and a microscopic and consistent description of the nucleon clusters. We will present the first results of the d- 3 H and d- 3 He fusion calculation obtained within our ab initio approach. We will also discuss our d- 4 He, 3 H- 4 He and 3 H- 3 H scattering calculations and the outline of the extension of the formalism to include three-cluster final states with the goal to calculate the 3 H( 3 H,2n) 4 He cross section
Shear stiffness in nanolaminar Ti3SiC2 challenges ab initio calculations
International Nuclear Information System (INIS)
Kisi, E H; Zhang, J F; Kirstein, O; Riley, D P; Styles, M J; Paradowska, A M
2010-01-01
Nanolaminates such as the M n+1 AX n (MAX) phases are a material class with ab initio derived elasticity tensors published for over 250 compounds. We have for the first time experimentally determined the full elasticity tensor of the archetype MAX phase, Ti 3 SiC 2 , using polycrystalline samples and in situ neutron diffraction. The experimental elastic constants show extreme shear stiffness, with c 44 more than five times greater than expected for an isotropic material. Such shear stiffness is quite rare in hexagonal materials and strongly contradicts the predictions of all published MAX phase elastic constants derived from ab initio calculations. It is concluded that second order properties such as elastic moduli derived from ab initio calculations require careful experimental verification. The diffraction technique used currently provides the only method of verification for the elasticity tensor for the majority of new materials where single crystals are not available. (fast track communication)
International Nuclear Information System (INIS)
Thompson, K.; Martinez, T.J.
1999-01-01
We present a new approach to first-principles molecular dynamics that combines a general and flexible interpolation method with ab initio evaluation of the potential energy surface. This hybrid approach extends significantly the domain of applicability of ab initio molecular dynamics. Use of interpolation significantly reduces the computational effort associated with the dynamics over most of the time scale of interest, while regions where potential energy surfaces are difficult to interpolate, for example near conical intersections, are treated by direct solution of the electronic Schroedinger equation during the dynamics. We demonstrate the concept through application to the nonadiabatic dynamics of collisional electronic quenching of Li(2p). Full configuration interaction is used to describe the wave functions of the ground and excited electronic states. The hybrid approach agrees well with full ab initio multiple spawning dynamics, while being more than an order of magnitude faster. copyright 1999 American Institute of Physics
Energy Technology Data Exchange (ETDEWEB)
Keegan, Ronan M. [STFC Rutherford Appleton Laboratory, Didcot OX11 0FA (United Kingdom); Bibby, Jaclyn; Thomas, Jens [University of Liverpool, Liverpool L69 7ZB (United Kingdom); Xu, Dong [Sanford-Burnham Medical Research Institute, 10901 North Torrey Pines Road, La Jolla, CA 92037 (United States); Zhang, Yang [University of Michigan, Ann Arbor, MI 48109 (United States); Mayans, Olga [University of Liverpool, Liverpool L69 7ZB (United Kingdom); Winn, Martyn D. [Science and Technology Facilities Council Daresbury Laboratory, Warrington WA4 4AD (United Kingdom); Rigden, Daniel J., E-mail: drigden@liv.ac.uk [University of Liverpool, Liverpool L69 7ZB (United Kingdom); STFC Rutherford Appleton Laboratory, Didcot OX11 0FA (United Kingdom)
2015-02-01
Two ab initio modelling programs solve complementary sets of targets, enhancing the success of AMPLE with small proteins. AMPLE clusters and truncates ab initio protein structure predictions, producing search models for molecular replacement. Here, an interesting degree of complementarity is shown between targets solved using the different ab initio modelling programs QUARK and ROSETTA. Search models derived from either program collectively solve almost all of the all-helical targets in the test set. Initial solutions produced by Phaser after only 5 min perform surprisingly well, improving the prospects for in situ structure solution by AMPLE during synchrotron visits. Taken together, the results show the potential for AMPLE to run more quickly and successfully solve more targets than previously suspected.
Virtual synthesis of crystals using ab initio MD: Case study on LiFePO4
Mishra, S. B.; Nanda, B. R. K.
2017-05-01
Molecular dynamics simulation technique is fairly successful in studying the structural aspects and dynamics of fluids. Here we study the ability of ab initio molecular dynamics (ab initio MD) to carry out virtual experiments to synthesize new crystalline materials and to predict their structures. For this purpose the olivine phosphate LiFePO4 (LFPO) is used as an example. As transition metal oxides in general are stabilized with layered geometry, we carried out ab initio MD simulations over a hypothetical layered configuration consisting of alternate LiPO2 and FeO2 layers. With intermittent steps of electron minimization, the resulted equilibrium lattice consist of PO4 tetrahedra and distorted Fe-O complexes similar to the one observed in the experimental lattice.
Vlahos, Vasilios; Booske, John H.; Morgan, Dane
2010-02-01
Microwave, x-ray, and radio-frequency radiation sources require a cathode emitting electrons into vacuum. Thermionic B-type dispenser cathodes consist of BaxOz coatings on tungsten (W), where the surface coatings lower the W work function and enhance electron emission. The new and promising class of scandate cathodes modifies the B-type surface through inclusion of Sc, and their superior emissive properties are also believed to stem from the formation of a low work function surface alloy. In order to better understand these cathode systems, density-functional theory (DFT)-based ab initio modeling is used to explore the stability and work function of BaxScyOz on W(001) monolayer-type surface structures. It is demonstrated how surface depolarization effects can be calculated easily using ab initio calculations and fitted to an analytic depolarization equation. This approach enables the rapid extraction of the complete depolarization curve (work function versus coverage relation) from relatively few DFT calculations, useful for understanding and characterizing the emitting properties of novel cathode materials. It is generally believed that the B-type cathode has some concentration of Ba-O dimers on the W surface, although their structure is not known. Calculations suggest that tilted Ba-O dimers are the stable dimer surface configuration and can explain the observed work function reduction corresponding to various dimer coverages. Tilted Ba-O dimers represent a new surface coating structure not previously proposed for the activated B-type cathode. The thermodynamically stable phase of Ba and O on the W surface was identified to be the Ba0.25O configuration, possessing a significantly lower Φ value than any of the Ba-O dimer configurations investigated. The identification of a more stable Ba0.25O phase implies that if Ba-O dimers cover the surface of emitting B-type cathodes, then a nonequilibrium steady state must dominate the emitting surface. The identification of
Ab initio study of perovskite type oxide materials for solid oxide fuel cells
Lee, Yueh-Lin
2011-12-01
Perovskite type oxides form a family of materials of significant interest for cathodes and electrolytes of solid oxide fuel cells (SOFCs). These perovskites not only are active catalysts for surface oxygen reduction (OR) reactions but also allow incorporating the spilt oxygen monomers into their bulk, an unusual and poorly understood catalytic mechanism that couples surface and bulk properties. The OR mechanisms can be influenced strongly by defects in perovskite oxides, composition, and surface defect structures. This thesis work initiates a first step in developing a general strategy based on first-principles calculations for detailed control of oxygen vacancy content, transport rates of surface and bulk oxygen species, and surface/interfacial reaction kinetics. Ab initio density functional theory methods are used to model properties relevant for the OR reactions on SOFC cathodes. Three main research thrusts, which focus on bulk defect chemistry, surface defect structures and surface energetics, and surface catalytic properties, are carried to investigate different level of material chemistry for improved understanding of key physics/factors that govern SOFC cathode OR activity. In the study of bulk defect chemistry, an ab initio based defect model is developed for modeling defect chemistry of LaMnO 3 under SOFC conditions. The model suggests an important role for defect interactions, which are typically excluded in previous defect models. In the study of surface defect structures and surface energetics, it is shown that defect energies change dramatically (1˜2 eV lower) from bulk values near surfaces. Based on the existing bulk defect model with the calculated ab initio surface defect energetics, we predict the (001) MnO 2 surface oxygen vacancy concentration of (La0.9Sr0.1 )MnO3 is about 5˜6 order magnitude higher than that of the bulk under typical SOFC conditions. Finally, for surface catalytic properties, we show that area specific resistance, oxygen
International Nuclear Information System (INIS)
Masrour, R.; Jabar, A.; Hlil, E.K.; Hamedoun, M.; Benyoussef, A.; Hourmatallah, A.; Rezzouk, A.; Bouslykhane, K.; Benzakour, N.
2017-01-01
Self-consistent ab initio calculations, based on Density Functional Theory (DFT) approach and using Full potential Linear Augmented Plane Wave (FLAPW) method, are performed to investigate both electronic and magnetic properties of the Mn 2 NiAl. Magnetic moment considered to lie along (001) axes are computed. Obtained data from ab initio calculations are used as input for Monte Carlo simulations to compute other magnetic parameters. Also, the magnetic properties of Mn 2 NiAl are studied using the Monte Carlo simulations. The variation of magnetization and magnetic susceptibility with the reduced temperature of Mn 2 NiAl are investigated. The transition temperature of this system is deduced for different values exchange interaction and crystal field. The thermal total magnetization has been obtained, and the magnetic hysteresis cycle is established. The total magnetic moment is superior to those obtained by the other method and is mainly determined by the antiparallel aligned Mn I , Mn II and Ni spin moments. The superparamagnetic phase is found at the neighborhood of transition temperature. - Highlights: • Ab initio calculations are used to study magnetic and electronic properties of Mn 2 NiX. • The transition temperature of Mn 2 NiX is established. • The magnetic hysteresis cycle of M n2 NiX (X = Al, Ga, In, Sn) is deduced. • The magnetic coercive field of Mn 2 NiX (X = Al, Ga, In, Sn) is given.
International Nuclear Information System (INIS)
Colgan, J.; Judge, E.J.; Kilcrease, D.P.; Barefield, J.E.
2014-01-01
We report on efforts to model the Fe emission spectrum generated from laser-induced breakdown spectroscopy (LIBS) measurements on samples of pure iron oxide (Fe 2 O 3 ). Our modeling efforts consist of several components. We begin with ab-initio atomic structure calculations performed by solving the Hartree–Fock equations for the neutral and singly ionized stages of Fe. Our energy levels are then adjusted to their experimentally known values. The atomic transition probabilities and atomic collision quantities are also computed in an ab-initio manner. We perform LTE or non-LTE calculations that generate level populations and, subsequently, an emission spectrum for the iron plasma for a range of electron temperatures and electron densities. Such calculations are then compared to the experimental spectrum. We regard our work as a preliminary modeling effort that ultimately strives towards the modeling of emission spectra from even more complex samples where less atomic data are available. - Highlights: • LIBS plasma of iron oxide • Ab-initio theoretical Modeling • Discussion of LTE versus non-LTE criteria and assessment • Boltzmann plots for Fe—determination of when LTE is a valid assumption • Emission spectra for Fe—comparison of theoretical modeling and measurement: good agreement obtained
International Nuclear Information System (INIS)
Music, Denis; Schneider, Jochen M
2008-01-01
We have studied the correlation between chemical composition, structure, chemical bonding and elastic properties of amorphous B 6 O based solids using ab initio molecular dynamics. These solids are of different chemical compositions, but the elasticity data appear to be a function of density. This is in agreement with previous experimental observations. As the density increases from 1.64 to 2.38 g cm -3 , the elastic modulus increases from 74 to 253 GPa. This may be understood by analyzing the cohesive energy and the chemical bonding of these compounds. The cohesive energy decreases from -7.051 to -7.584 eV/atom in the elastic modulus range studied. On the basis of the electron density distributions, Mulliken analysis and radial distribution functions, icosahedral bonding is the dominating bonding type. C and N promote cross-linking of icosahedra and thus increase the density, while H hinders the cross-linking by forming OH groups. The presence of icosahedral bonding is independent of the density
Ab initio study of He-He interactions in homogeneous electron gas
Energy Technology Data Exchange (ETDEWEB)
Wang, Jinlong; Niu, Liang-Liang; Zhang, Ying, E-mail: zhyi@buaa.edu.cn
2017-02-15
Highlights: • Helium atoms interact via the He induced Friedel oscillations of electron densities. • He-He global binding energy minimum of ∼−0.09 eV is reached at an optimal electron density of 0.04 e/Å{sup 3}, corresponding to an optimal He-He separation of ∼1.7 Å. • The present results can qualitatively interpret the well-known He self-trapping behavior in metals. - Abstract: We have investigated the immersion energy of a single He and the He-He interactions in homogeneous electron gas using ab initio calculations. It is found that He dislikes electrons and He-He interact via the He induced Friedel oscillations of electron densities. A critical electron density at which the global binding energy extremum shifts from the first minimum to the second one is identified. We also discover that the He-He global binding energy minimum of ∼−0.09 eV is reached at an optimal electron density of 0.04 e/Å{sup 3}, corresponding to an optimal He-He separation of ∼1.7 Å. Further, the He atoms are found to gain a trivial amount of 2s and 2p states from the free electrons, inducing a hybridization between the He s- and p-states. The present results can qualitatively interpret the well-known He self-trapping behavior in metals.
Ab Initio Calculations and Raman and SERS Spectral Analyses of Amphetamine Species
DEFF Research Database (Denmark)
Berg, Rolf W.; Nørbygaard, Thomas; White, Peter C.
2011-01-01
For the first time, the differences between the spectra of amphetamine and amphetamine-H+ and between different conformers are thoroughly studied by ab initio model calculations, and Raman and surface-enhanced Raman spectroscopy (SERS) spectra are measured for different species of amphetamine....... The spectra of amphetamine and amphetamine-H+ sampleswere obtained and assigned according to a comparison of the experimental spectra and the ab initio MO calculations, performed using the Gaussian 03W program (Gaussian, Inc., Pittsburgh, PA). The analyses were based on complete geometry minimization...
Atomic carbon chains as spin-transmitters: An ab initio transport study
DEFF Research Database (Denmark)
Fürst, Joachim Alexander; Brandbyge, Mads; Jauho, Antti-Pekka
2010-01-01
An atomic carbon chain joining two graphene flakes was recently realized in a ground-breaking experiment by Jin et al. (Phys. Rev. Lett., 102 (2009) 205501). We present ab initio results for the electron transport properties of such chains and demonstrate complete spin-polarization of the transmi......An atomic carbon chain joining two graphene flakes was recently realized in a ground-breaking experiment by Jin et al. (Phys. Rev. Lett., 102 (2009) 205501). We present ab initio results for the electron transport properties of such chains and demonstrate complete spin...
Studies of urea geometry by means of ab initio methods and computer simulations of liquids
Cirino, José Jair Vianna; Bertran, Celso Aparecido
2002-01-01
A study was carried out on the urea geometries using ab initio calculation and Monte Carlo computational simulation of liquids. The ab initio calculated results showed that urea has a non-planar conformation in the gas phase in which the hydrogen atoms are out of the plane formed by the heavy atoms. Free energies associated to the rotation of the amino groups of urea in water were obtained using the Monte Carlo method in which the thermodynamic perturbation theory is implemented. The magnitud...
Ab initio study of H + + H 2 collisions: Elastic/inelastic and charge transfer processes
Saieswari, A.; Kumar, Sanjay
2007-12-01
An ab initio full configuration interaction study has been undertaken to obtain the global potential energy surfaces for the ground and the first excited electronic state of the H + + H 2 system employing Dunning's cc-pVQZ basis set. Using the ab initio approach the corresponding quasi-diabatic potential energy surfaces and coupling potentials have been obtained. A time-independent quantum mechanical study has been also undertaken for both the inelastic and charge transfer processes at the experimental collision energy Ec.m. = 20.0 eV and the preliminary results show better agreement with the experimental data as compared to the earlier available theoretical studies.
Energy Technology Data Exchange (ETDEWEB)
Ganster, P
2004-10-15
A calcium aluminosilicate glass of molar composition 67 % SiO{sub 2} - 12 % Al{sub 2}O{sub 3} - 21 % CaO was modelled by classical and ab initio molecular dynamics. The size effect study in classical MD shows that the systems of 100 atoms are more ordered than the larger ones. These effects are mainly due to the 3-body terms in the empirical potentials. Nevertheless, these effects are small and the structures generated are in agreement with experimental data. In such kind of glass, we denote an aluminium avoidance and an excess of non bridging oxygens which can be compensated by tri coordinated oxygens. When the dynamics of systems of 100 and 200 atoms is followed by ab initio MD, some local arrangements occurs (bond length, angular distributions). Thus, more realistic vibrational properties are obtained in ab initio MD. The modelling of thin films shows that aluminium atoms extend to the most external part of the surface and they are all tri-coordinated. Calcium atoms are set in the sub layer part of the surface and they produce a depolymerization of the network. In classical MD, tri-coordinated aluminium atoms produce an important electric field above the surface. With non bridging oxygens, they constitute attractive sites for single water molecules. (author)
Study on the surface hydroxyl group on solid breeding materials by ab-initio calculations
Energy Technology Data Exchange (ETDEWEB)
Tanaka, Satoru; Taniguchi, Masaki [Tokyo Univ. (Japan). Faculty of Engineering
1996-10-01
The nature of -OH on the surface of Li{sub 2}O was analyzed with the ab-initio quantum chemical calculation technique. Calculation results showed that the stretching vibration of O-H is affected by the chemical species around the -OH. (author)
Understanding hydration of Zn(2+) in hydrothermal fluids with ab initio molecular dynamics
Liu, X.; Lu, X.; Wang, R.; Meijer, E.J.
2011-01-01
With ab initio molecular dynamics simulations, the free-energy profiles of hydrated Zn2+ are calculated for both gaseous and aqueous systems from ambient to supercritical conditions, and from the derived free-energy information, the speciation of hydrated Zn2+ has been revealed. It is shown that the
Sphinx: merging knowledge-based and ab initio approaches to improve protein loop prediction.
Marks, Claire; Nowak, Jaroslaw; Klostermann, Stefan; Georges, Guy; Dunbar, James; Shi, Jiye; Kelm, Sebastian; Deane, Charlotte M
2017-05-01
Loops are often vital for protein function, however, their irregular structures make them difficult to model accurately. Current loop modelling algorithms can mostly be divided into two categories: knowledge-based, where databases of fragments are searched to find suitable conformations and ab initio, where conformations are generated computationally. Existing knowledge-based methods only use fragments that are the same length as the target, even though loops of slightly different lengths may adopt similar conformations. Here, we present a novel method, Sphinx, which combines ab initio techniques with the potential extra structural information contained within loops of a different length to improve structure prediction. We show that Sphinx is able to generate high-accuracy predictions and decoy sets enriched with near-native loop conformations, performing better than the ab initio algorithm on which it is based. In addition, it is able to provide predictions for every target, unlike some knowledge-based methods. Sphinx can be used successfully for the difficult problem of antibody H3 prediction, outperforming RosettaAntibody, one of the leading H3-specific ab initio methods, both in accuracy and speed. Sphinx is available at http://opig.stats.ox.ac.uk/webapps/sphinx. deane@stats.ox.ac.uk. Supplementary data are available at Bioinformatics online. © The Author 2017. Published by Oxford University Press.
The Influence of Square Planar Platinum Complexes on DNA Bases Pairing. An ab initio DFT Study
Czech Academy of Sciences Publication Activity Database
Burda, J. V.; Šponer, Jiří; Leszczynski, J.
2001-01-01
Roč. 3, č. 19 (2001), s. 4404-4411 ISSN 1463-9076 R&D Projects: GA MŠk LN00A032 Institutional research plan: CEZ:AV0Z4040901 Keywords : DNA base pairing * platinated base pairs * ab initio DFT study Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.787, year: 2001
Ab initio Defect Energetics in LaBO3 Perovskite Solid Oxide Fuel Cell Materials
DEFF Research Database (Denmark)
Lee, Yueh-Lin; Morgan, Dane; Kleis, Jesper
2009-01-01
Perovskite materials of the form ABO3 are a promising family of compounds for use in solid oxide fuel cell (SOFC) cathodes. Study of the physics of these compounds under SOFC conditions with ab initio methods is particularly challenging due to high temperatures, exchange of oxygen with O2 gas...
Ab initio molecular dynamics simulation of hydrogen fluoride at several thermodynamic states
DEFF Research Database (Denmark)
Kreitmeir, M.; Bertagnolli, H.; Mortensen, Jens Jørgen
2003-01-01
Liquid hydrogen fluoride is a simple but interesting system for studies of the influence of hydrogen bonds on physical properties. We have performed ab initio molecular dynamics simulations of HF at several thermodynamic states, where we examine the microscopic structure of the liquid as well...
Ab initio Calculations of Charge Symmetry Breaking in the A=4 Hypernuclei
Czech Academy of Sciences Publication Activity Database
Gazda, Daniel; Gal, A.
2016-01-01
Roč. 116, č. 12 (2016), s. 122501 ISSN 0031-9007 R&D Projects: GA ČR(CZ) GA15-04301S Institutional support: RVO:61389005 Keywords : ab initio * shell model * four-body calculations Subject RIV: BE - Theoretical Physics Impact factor: 8.462, year: 2016
An Efficient Method for Electron-Atom Scattering Using Ab-initio Calculations
Energy Technology Data Exchange (ETDEWEB)
Xu, Yuan; Yang, Yonggang; Xiao, Liantuan; Jia, Suotang [Shanxi University, Taiyuan (China)
2017-02-15
We present an efficient method based on ab-initio calculations to investigate electron-atom scatterings. Those calculations profit from methods implemented in standard quantum chemistry programs. The new approach is applied to electron-helium scattering. The results are compared with experimental and other theoretical references to demonstrate the efficiency of our method.
Ab initio theory of charge-carrier conduction in ultrapure organic crystals
Hannewald, K.; Bobbert, P.A.
2004-01-01
We present an ab initio description of charge-carrier mobilities in organic molecular crystals of high purity. Our approach is based on Holstein's original concept of small-polaron bands but generalized with respect to the inclusion of nonlocal electron-phonon coupling. By means of an explicit
Limitations of Ab Initio Predictions of Peptide Binding to MHC Class II Molecules
DEFF Research Database (Denmark)
Zhang, Hao; Lund, Ole; Nielsen, Morten
2010-01-01
potentials derived from the analysis of known protein structures; energetic evaluation of different peptide snapshots in a molecular dynamics simulation; and direct analysis of contacts made in known 3D structures of peptide:MHC complexes. These methods are ab initio in that they require structural data...
The Pu–U–Am system: An ab initio informed CALPHAD thermodynamic study
International Nuclear Information System (INIS)
Perron, A.; Turchi, P.E.A.; Landa, A.; Söderlind, P.; Ravat, B.; Oudot, B.; Delaunay, F.
2015-01-01
Highlights: • The ab initio informed CALPHAD assessment of the Am–U system has been realized. • A strong tendency toward phase separation across the whole composition range is predicted. • The ab initio informed Pu–U–Am thermodynamic database has been developed. • The solubility of Am and U in the liquid phase is improved by adding Pu. • The δ-Pu (fcc) phase is strongly stabilized by Am, on the contrary to the bcc phase. - Abstract: Phase diagram and thermodynamic properties of the Am–U system, that are experimentally unknown, are calculated using the CALPHAD method with input from ab initio electronic-structure calculations for the fcc and bcc phases. A strong tendency toward phase separation across the whole composition range is predicted. In addition, ab initio informed Pu–U and Am–Pu thermodynamic assessments are combined to build a Pu–U–Am thermodynamic database. Regarding the Pu-rich corner of the ternary system, predictions indicate that Am acts as a powerful δ-Pu (fcc) stabilizer. In the U-rich corner, similar predictions are made but to a lesser extent. In both cases, the bcc phase is destabilized and the fcc phase is enhanced. Finally, results and methodology are discussed and compared with previous assessments and guidelines are provided for further experimental studies
All electron ab initio investigations of the electronic states of the FeC molecule
DEFF Research Database (Denmark)
Shim, Irene; Gingerich, Karl A.
1999-01-01
The low lying electronic states of the molecule FeC have been investigated by performing all electron ab initio multi-configuration self-consistent-field (CASSCF) and multi reference configuration interaction (MRCI) calculations. The relativistic corrections for the one electron Darwin contact term...
All Electron ab initio Investigations of the Electronic States of the MoN Molecule
DEFF Research Database (Denmark)
Shim, Irene; Gingerich, Karl A.
1999-01-01
The low lying electronic states of the molecule MoN have been investigated by performing all electron ab initio multi-configuration self-consistent-field (CASSCF) calculations. The relativistic corrections for the one electron Darwin contact term and the relativistic mass-velocity correction have...
Ab initio I-V characteristics of short C-20 chains
DEFF Research Database (Denmark)
Roland, C.; Larade, B.; Taylor, Jeremy Philip
2002-01-01
We have calculated the I-V characteristics of short chains of C-20 molecular cages between Al and Au leads with an ab initio formalism. The results indicate that a linear chain of such molecules acts primarily as metallic nanowires. The transmission, however, depends sensitively both...
DEFF Research Database (Denmark)
Andersen, Vinca Bonde; Berg, Rolf W.; Shim, Irene
2017-01-01
The iminodisulfonate, [N(SO3)2]3–, and phosphinodisulfonate, [P(SO3)2]3–, ions have been investigated by performing ab initio MP2/6-311+G**calculations. The nitrogen and phosphorus atoms as part of the ions are shown to be divalent with a negative charge and two lone pairs on the nitrogen...
Raman Spectroscopy and Ab-Initio Model Calculations on Ionic Liquids
DEFF Research Database (Denmark)
Berg, Rolf W.
2007-01-01
spectroscopy and ab-initio molecular orbital calculations. A discussion is given, based mainly on some recent FT-Raman spectroscopic results on the model ionic liquid system of 1-butyl-3-methylimidazolium ([C4mim][X]) salts. The rotational isomerism of the [C4mim]þ cation is described: the presence of anti...
All-electron ab initio investigations of the electronic states of the NiC molecule
DEFF Research Database (Denmark)
Shim, Irene; Gingerich, Karl. A.
1999-01-01
The low-lying electronic states of NiC are investigated by all-electron ab initio multi-configuration self-consistent-field (CASSCF) calculations including relativistic corrections. The electronic structure of NiC is interpreted as perturbed antiferromagnetic couplings of the localized angular...
Force fields for silicas and aluminophosphates based on ab initio calculations
Beest, van B.W.H.; Kramer, G.J.; Santen, van R.A.
1990-01-01
Authors address the problem of finding interat. force fields for silicas from ab initio calcns. on small clusters. The force field cannot be detd. from cluster data alone; incorporation of bulk-system information into the force field remains essential. Bearing this in mind, authors derive a force
DEFF Research Database (Denmark)
Wolf, T. J. A.; Kuhlman, Thomas Scheby; Schalk, O.
2014-01-01
comparing time-resolved photoelectron spectroscopy (TRPES) with ab initio multiple spawning (AIMS) simulations on the MS-MR-CASPT2 level of theory. We disentangle the relationship between two phenomena that dominate the immediate molecular response upon light absorption: a spectrally dependent delay...
Ab initio study of gas phase and water-assisted tautomerization of ...
Indian Academy of Sciences (India)
WINTEC
Water-assisted tautomerization in maleimide and formamide showed that difference in energy barrier reduces to 2⋅83 kcal/mol from 10⋅41 kcal/mol (in gas phase) at B3LYP level, which resulted that maleimide readily undergoes tautomerization in water molecule. Keywords. Ab Initio calculations; maleimide; formamide; ...
Czech Academy of Sciences Publication Activity Database
Sandlöbes, S.; Pei, Z.; Friák, Martin; Zhu, L.-F.; Wang, F.; Zaefferer, S.; Raabe, D.; Neugebauer, J.
2014-01-01
Roč. 70, MAY (2014), s. 92-104 ISSN 1359-6454 Grant - others:GA MŠk(CZ) LM2010005 Institutional support: RVO:68081723 Keywords : Magnesium * Rare-earth elements * Ductility * Modeling * Ab initio Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 4.465, year: 2014
Czech Academy of Sciences Publication Activity Database
Ma, D.; Friák, Martin; von Pezold, J.; Raabe, D.; Neugebauer, J.
2015-01-01
Roč. 85, FEB (2015), s. 53-66 ISSN 1359-6454 Institutional support: RVO:68081723 Keywords : Solid-solution strengthening * DFT * Peierls–Nabarro model * Ab initio * Al alloys Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 5.058, year: 2015
A fragment-based approach towards ab-initio treatment of polymeric ...
Indian Academy of Sciences (India)
Reshma S Pingale
2017-06-20
Jun 20, 2017 ... Keywords. π-Conjugated polymer; divide and conquer; ab-initio; fragmentation. PACS Nos 31.15.A−; 36.20. ... cut the parent system into a set of overlapping small fragments and .... some oligomers, we approached the problem by increas- ..... Financial support of DST, Govt. of India, New Delhi, in the form of ...
Ab initio molecular dynamics approach to a quantitative description of ion pairing in water
Czech Academy of Sciences Publication Activity Database
Pluhařová, Eva; Maršálek, Ondřej; Schmidt, B.; Jungwirth, Pavel
2013-01-01
Roč. 4, č. 23 (2013), s. 4177-4181 ISSN 1948-7185 R&D Projects: GA ČR GBP208/12/G016 Institutional support: RVO:61388963 Keywords : ion pairing * charge transfer * water * ab initio molecular dynamics Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 6.687, year: 2013
Sanz, Cristina; Lin, Hui-Ju; Lado, Beatriz; Stafford, Catherine A.; Bowden, Harriet W.
2016-01-01
The article summarizes results from two experimental studies (N = 23, N = 21) investigating the extent to which working memory capacity (WMC) intervenes in "ab initio" language development under two pedagogical conditions [± grammar lesson + input-based practice + explicit feedback]. The linguistic target is the use of morphosyntax to…
Czech Academy of Sciences Publication Activity Database
Dračínský, Martin; Möller, H. M.; Exner, T. E.
2013-01-01
Roč. 9, č. 8 (2013), s. 3806-3815 ISSN 1549-9618 R&D Projects: GA ČR GA13-24880S Institutional support: RVO:61388963 Keywords : ab initio molecular dynamics * NMR spectroscopy * DFT calculations * hydration Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.310, year: 2013
Ab initio calculation atomics ground state wave function for interactions Ion- Atom
International Nuclear Information System (INIS)
Shojaee, F.; Bolori zadeh, M. A.
2007-01-01
Ab initio calculation atomics ground state wave function for interactions Ion- Atom Atomic wave function expressed in a Slater - type basis obtained within Roothaan- Hartree - Fock for the ground state of the atoms He through B. The total energy is given for each atom.
Ab initio and work function and surface energy anisotropy of LaB6
Uijttewaal, M. A.; de Wijs, G. A.; de Groot, R. A.
2006-01-01
Lanthanum hexaboride is one of the cathode materials most used in high-power electronics technology, but the many experimental results do not provide a consistent picture of the surface properties. Therefore, we report the first ab initio calculations of the work functions and surface energies of
Mechanical properties of carbynes investigated by ab initio total-energy calculations
DEFF Research Database (Denmark)
Castelli, Ivano E.; Salvestrini, Paolo; Manini, Nicola
2012-01-01
As sp carbon chains (carbynes) are relatively rigid molecular objects, can we exploit them as construction elements in nanomechanics? To answer this question, we investigate their remarkable mechanical properties by ab initio total-energy simulations. In particular, we evaluate their linear...
Czech Academy of Sciences Publication Activity Database
Meliá, C.; Ferrer, S.; Řezáč, Jan; Parisel, O.; Reinaud, O.; Moliner, V.; de la Lande, A.
2013-01-01
Roč. 19, č. 51 (2013), s. 17328-17337 ISSN 0947-6539 Institutional support: RVO:61388963 Keywords : ab initio calculations * copper * electron transfer * enzymes * molecular dynamics * reaction mechanisms Subject RIV: CC - Organic Chemistry Impact factor: 5.696, year: 2013
Ab initio study of antiphase boundaries and stacking faults in L12 and DO22 compounds
DEFF Research Database (Denmark)
Rosengaard, N. M.; Skriver, Hans Lomholt
1994-01-01
We have performed ab initio calculations of the energies of antiphase boundaries as well as complex and superlattice intrinsic stacking faults in nine intermetallic compounds observed in the face-centered-cubic L1(2) and DO22 structures. The calculations were performed by means of a Green...
The Pu–U–Am system: An ab initio informed CALPHAD thermodynamic study
Energy Technology Data Exchange (ETDEWEB)
Perron, A., E-mail: perron1@llnl.gov [Lawrence Livermore National Laboratory, Livermore, CA 94550 (United States); Turchi, P.E.A.; Landa, A.; Söderlind, P. [Lawrence Livermore National Laboratory, Livermore, CA 94550 (United States); Ravat, B.; Oudot, B.; Delaunay, F. [CEA-Centre de Valduc, 21120 Is sur Tille (France)
2015-03-15
Highlights: • The ab initio informed CALPHAD assessment of the Am–U system has been realized. • A strong tendency toward phase separation across the whole composition range is predicted. • The ab initio informed Pu–U–Am thermodynamic database has been developed. • The solubility of Am and U in the liquid phase is improved by adding Pu. • The δ-Pu (fcc) phase is strongly stabilized by Am, on the contrary to the bcc phase. - Abstract: Phase diagram and thermodynamic properties of the Am–U system, that are experimentally unknown, are calculated using the CALPHAD method with input from ab initio electronic-structure calculations for the fcc and bcc phases. A strong tendency toward phase separation across the whole composition range is predicted. In addition, ab initio informed Pu–U and Am–Pu thermodynamic assessments are combined to build a Pu–U–Am thermodynamic database. Regarding the Pu-rich corner of the ternary system, predictions indicate that Am acts as a powerful δ-Pu (fcc) stabilizer. In the U-rich corner, similar predictions are made but to a lesser extent. In both cases, the bcc phase is destabilized and the fcc phase is enhanced. Finally, results and methodology are discussed and compared with previous assessments and guidelines are provided for further experimental studies.
Ab-initio calculations of electric field gradient in Ru compounds and ...
Indian Academy of Sciences (India)
S N Mishra
2017-07-11
Jul 11, 2017 ... with calculated electric field gradient (EFG) for a large number of Ru-based compounds. The ab-initio ... zz assumed to stem from geometric arrangement of ... tant nuclear probes for the measurements of quadrupole ... with the unit cell including the nucleus and no restriction is put on ..... The effect of on-site ...
Steel — ab Initio: Quantum Mechanics Guided Design of New Fe-Based Materials
Prahl, Ulrich; Bleck, Wolfgang; Saeed-Akbari, Alireza
This contribution reports the results of the collaborative research unit SFB 761 "Steel — ab initio", a cooperative project between RWTH Aachen University and the Max-Planck-Institute for Iron Research in Düsseldorf (MPIE) financed by the German Research Foundation (DFG). For the first time, it is exploited how ab initio approaches may lead to a detailed understanding and thus to a specific improvement of material development. The challenge lies in the combination of abstract natural science theories with rather engineering-like established concepts. Aiming at the technological target of the development of a new type of structural materials based on Fe-Mn-C alloys, the combination of ab initio and engineering methods is new, but could be followed quite successfully. Three major topics are treated in this research unit: a) development of a new method for material- and process-development based on ab initio calculations; b) design of a new class of structural materials with extraordinary property combinations; c) acceleration of development time and reduction of experimental efforts and complexity for material- and process-development. In the present work, an overview of the results of the first five years as well as an outlook for the upcoming three-year period is given.
Ab initio study of the bcc-hcp transformation in iron
Czech Academy of Sciences Publication Activity Database
Friák, Martin; Šob, Mojmír
2008-01-01
Roč. 77, č. 17 (2008), 174117/1-174117/7 ISSN 1098-0121 R&D Projects: GA MŠk OC 147; GA AV ČR IAA1041302 Institutional research plan: CEZ:AV0Z20410507 Keywords : ab initio calculations * phase transformations * iron Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.322, year: 2008
Ab initio theory of noble gas atoms in bcc transition metals.
Jiang, Chao; Zhang, Yongfeng; Gao, Yipeng; Gan, Jian
2018-06-18
Systematic ab initio calculations based on density functional theory have been performed to gain fundamental understanding of the interactions between noble gas atoms (He, Ne, Ar and Kr) and bcc transition metals in groups 5B (V, Nb and Ta), 6B (Cr, Mo and W) and 8B (Fe). Our charge density analysis indicates that the strong polarization of nearest-neighbor metal atoms by noble gas interstitials is the electronic origin of their high formation energies. Such polarization becomes more significant with an increasing gas atom size and interstitial charge density in the host bcc metal, which explains the similar trend followed by the unrelaxed formation energies of noble gas interstitials. Upon allowing for local relaxation, nearby metal atoms move farther away from gas interstitials in order to decrease polarization, albeit at the expense of increasing the elastic strain energy. Such atomic relaxation is found to play an important role in governing both the energetics and site preference of noble gas atoms in bcc metals. Our most notable finding is that the fully relaxed formation energies of noble gas interstitials are strongly correlated with the elastic shear modulus of the bcc metal, and the physical origin of this unexpected correlation has been elucidated by our theoretical analysis based on the effective-medium theory. The kinetic behavior of noble gas atoms and their interaction with pre-existing vacancies in bcc transition metals have also been discussed in this work.
Ab-initio Computation of the Electronic, transport, and Bulk Properties of Calcium Oxide.
Mbolle, Augustine; Banjara, Dipendra; Malozovsky, Yuriy; Franklin, Lashounda; Bagayoko, Diola
We report results from ab-initio, self-consistent, local Density approximation (LDA) calculations of electronic and related properties of calcium oxide (CaO) in the rock salt structure. We employed the Ceperley and Alder LDA potential and the linear combination of atomic orbitals (LCAO) formalism. Our calculations are non-relativistic. We implemented the LCAO formalism following the Bagayoko, Zhao, and Williams (BZW) method, as enhanced by Ekuma and Franklin (BZW-EF). The BZW-EF method involves a methodical search for the optimal basis set that yields the absolute minima of the occupied energies, as required by density functional theory (DFT). Our calculated, indirect band gap of 6.91eV, from towards the L point, is in excellent agreement with experimental value of 6.93-7.7eV, at room temperature (RT). We have also calculated the total (DOS) and partial (pDOS) densities of states as well as the bulk modulus. Our calculated bulk modulus is in excellent agreement with experiment. Work funded in part by the US Department of Energy (DOE), National Nuclear Security Administration (NNSA) (Award No.DE-NA0002630), the National Science Foundation (NSF) (Award No, 1503226), LaSPACE, and LONI-SUBR.
Ab initio pseudopotential studies of cubic BC2N under high pressure
International Nuclear Information System (INIS)
Pan Zicheng; Sun Hong; Chen Changfeng
2005-01-01
We present the results of a systematic study of the structural, electronic, and vibrational properties of various cubic BC 2 N phases under high pressure. Ab initio pseudopotential total-energy and phonon calculations have been carried out to examine the changes in the structural parameters, bonding behaviours, band structures, and dynamic instabilities caused by phonon softening in these phases. We find that an experimentally synthesized high-density phase of cubic BC 2 N exhibits outstanding stability in the structural and electronic properties up to very high pressures. On the other hand, another experimentally identified phase with lower density and lower symmetry undergoes a dramatic structural transformation with a volume and bond-length collapse and a concomitant semi-metal to semiconductor transition. A third phase is predicted to be favourable over the above-mentioned lower-density phase by the enthalpy calculations. However, the dynamic phonon calculations reveal that it develops imaginary phonon modes and, therefore, is unstable in the experimental pressure range. The calculations indicate that its synthesis may be achieved at reduced pressures. These results provide a comprehensive understanding for the high-pressure behaviour of the cubic BC 2 N phases and reveal their interesting properties that can be verified by experiments
Timko, Jeff; Kuyucak, Serdar
2012-11-28
Polarization is an important component of molecular interactions and is expected to play a particularly significant role in inhomogeneous environments such as pores and interfaces. Here we investigate the effects of polarization in the gramicidin A ion channel by performing quantum mechanics/molecular mechanics molecular dynamics (MD) simulations and comparing the results with those obtained from classical MD simulations with non-polarizable force fields. We consider the dipole moments of backbone carbonyl groups and channel water molecules as well as a number of structural quantities of interest. The ab initio results show that the dipole moments of the carbonyl groups and water molecules are highly sensitive to the hydrogen bonds (H-bonds) they participate in. In the absence of a K(+) ion, water molecules in the channel are quite mobile, making the H-bond network highly dynamic. A central K(+) ion acts as an anchor for the channel waters, stabilizing the H-bond network and thereby increasing their average dipole moments. In contrast, the K(+) ion has little effect on the dipole moments of the neighboring carbonyl groups. The weakness of the ion-peptide interactions helps to explain the near diffusion-rate conductance of K(+) ions through the channel. We also address the sampling issue in relatively short ab initio MD simulations. Results obtained from a continuous 20 ps ab initio MD simulation are compared with those generated by sampling ten windows from a much longer classical MD simulation and running each window for 2 ps with ab initio MD. Both methods yield similar results for a number of quantities of interest, indicating that fluctuations are fast enough to justify the short ab initio MD simulations.
International Nuclear Information System (INIS)
Yamacli, Serhan; Avci, Mutlu
2009-01-01
In this work, development of a voltage dependent resistance model for metallic carbon nanotubes is aimed. Firstly, the resistance of metallic carbon nanotube interconnects are obtained from ab initio simulations and then the voltage dependence of the resistance is modeled through regression. Self-consistent non-equilibrium Green's function formalism combined with density functional theory is used for calculating the voltage dependent resistance of metallic carbon nanotubes. It is shown that voltage dependent resistances of carbon nanotubes can be accurately modeled as a polynomial function which enables rapid integration of carbon nanotube interconnect models into electronic design automation tools.
Quantum-chemical ab initio and B3LYP investigation of tricyanides and triisocyanides of Al, Ga, In
International Nuclear Information System (INIS)
Timoshkin, A.Yu.; Shefer, G.F.
2000-01-01
Ab initio and density functional B3LYP methods are used to obtain structural parameters, standard entropies and vibrational spectra of cyanides and isocyanides of trivalent Al, Ga, In for the first time. It is pointed out that for In cyanide form is more stable. There is divergence in data obtained in the framework of self-consistent field and by B3LYP methods what indicates importance of estimation of energy of electronic correlation and in the same time comparison of basic sets DZP and LANL2DZP demonstrates insufficiency of basic sets with effective potentials of skeleton for description molecular tricyanides of elements of the 3a group [ru
Directory of Open Access Journals (Sweden)
G.M. Bhuiyan
2012-10-01
Full Text Available Several static and dynamic properties of liquid Cu, Ag and Au at thermodynamic states near their respective melting points, have been evaluated by means of the orbital free ab-initio molecular dynamics simulation method. The calculated static structure shows good agreement with the available X-ray and neutron diffraction data. As for the dynamic properties, the calculated dynamic structure factors point to the existence of collective density excitations along with a positive dispersion for l-Cu and l-Ag. Several transport coefficients have been obtained which show a reasonable agreement with the available experimental data.
Electronic Structure of Hydrogenated and Surface-Modified GaAs Nanocrystals: Ab Initio Calculations
Directory of Open Access Journals (Sweden)
Hamsa Naji Nasir
2012-01-01
Full Text Available Two methods are used to simulate electronic structure of gallium arsenide nanocrystals. The cluster full geometrical optimization procedure which is suitable for small nanocrystals and large unit cell that simulates specific parts of larger nanocrystals preferably core part as in the present work. Because of symmetry consideration, large unit cells can reach sizes that are beyond the capabilities of first method. The two methods use ab initio Hartree-Fock and density functional theory, respectively. The results show that both energy gap and lattice constant decrease in their value as the nanocrystals grow in size. The inclusion of surface part in the first method makes valence band width wider than in large unit cell method that simulates the core part only. This is attributed to the broken symmetry and surface passivating atoms that split surface degenerate states and adds new levels inside and around the valence band. Bond length and tetrahedral angle result from full geometrical optimization indicate good convergence to the ideal zincblende structure at the centre of hydrogenated nanocrystal. This convergence supports large unit cell methodology. Existence of oxygen atoms at nanocrystal surface melts down density of states and reduces energy gap.
Conformational study of glyoxal bis(amidinohydrazone) by ab initio methods
Mannfors, B.; Koskinen, J. T.; Pietilä, L.-O.
1997-08-01
We report the first ab initio molecular orbital study on the ground state of the endiamine tautomer of glyoxal bis(amidinohydrazone) (or glyoxal bis(guanylhydrazone), GBG) free base. The calculations were performed at the following levels of theory: Hartree-Fock, second-order Møller-Plesset perturbation theory and density functional theory (B-LYP and B3-LYP) as implemented in the Gaussian 94 software. The standard basis set 6-31G(d) was found to be sufficient. The default fine grid of Gaussian 94 was used in the density functional calculations. Molecular properties, such as optimized structures, total energies and the electrostatic potential derived (CHELPG) atomic charges, were studied as functions of C-C and N-N conformations. The lowest energy conformation was found to be all- trans, in agreement with the experimental solid-state structure. The second conformer with respect to rotation around the central C-C bond was found to be the cis conformer with an MP2//HF energy of 4.67 kcal mol -1. For rotation around the N-N bond the energy increased monotonically from the trans conformation to the cis conformation, the cis energy being very high, 22.01 kcal mol -1 (MP2//HF). The atomic charges were shown to be conformation dependent, and the bond charge increments and especially the conformational changes of the bond charge increments were found to be easily transferable between structurally related systems.
Djordjević, Tijana; Radović, Ivan; Despoja, Vito; Lyon, Keenan; Borka, Duško; Mišković, Zoran L
2018-01-01
We present an analytical modeling of the electron energy loss (EEL) spectroscopy data for free-standing graphene obtained by scanning transmission electron microscope. The probability density for energy loss of fast electrons traversing graphene under normal incidence is evaluated using an optical approximation based on the conductivity of graphene given in the local, i.e., frequency-dependent form derived by both a two-dimensional, two-fluid extended hydrodynamic (eHD) model and an ab initio method. We compare the results for the real and imaginary parts of the optical conductivity in graphene obtained by these two methods. The calculated probability density is directly compared with the EEL spectra from three independent experiments and we find very good agreement, especially in the case of the eHD model. Furthermore, we point out that the subtraction of the zero-loss peak from the experimental EEL spectra has a strong influence on the analytical model for the EEL spectroscopy data. Copyright © 2017 Elsevier B.V. All rights reserved.
Ab initio study of the EFG tensor at Cd impurities in Sc2O3 semiconductor
International Nuclear Information System (INIS)
Munoz, E.L.; Richard, D.; Errico, L.A.; Renteria, M.
2009-01-01
We present an ab initio study of diluted Cd impurities localized at both cation sites of the semiconductor Sc 2 O 3 . The electric-field-gradient (EFG) tensor at Cd impurities located at both cationic sites of the host structure was determined from the calculation of the electronic structure of the doped system. Calculations were performed with the full-potential augmented-plane wave plus local orbitals (APW+lo) method within the framework of the density functional theory. We studied the atomic structural relaxations and the perturbation of the electronic charge density induced by the impurities in the host system in a fully self-consistent way. We showed that the Cd impurity introduces an increase of 8% in the nearest oxygen neighbors bond-lengths, changing the EFG sign for probes located at the asymmetric cation site. The APW+lo predictions for the charged state of the Cd impurity were compared with EFG results existent in the literature, coming from time-differential γ-γ perturbed-angular-correlations experiments performed on 111 Cd-implanted Sc 2 O 3 powder samples. From the excellent agreement between theory and experiment, we can strongly suggest that the Cd acceptor impurities are ionized at room temperature. Finally, we showed that simple calculations like those performed within the point-charge model with antishielding factors do not correctly describe the problem of a Cd impurity in Sc 2 O 3 .
International Nuclear Information System (INIS)
Monteseguro, V.; Rodríguez-Hernández, P.; Muñoz, A.
2015-01-01
The structural, elastic, and vibrational properties of yttrium aluminum garnet Y 3 Al 5 O 12 are studied under high pressure by ab initio calculations in the framework of the density functional theory. The calculated ground state properties are in good agreement with the available experimental data. Pressure dependences of bond length and bulk moduli of the constituent polyhedra are reported. The evolution of the elastic constants and the major elastic properties, Young and shear modulus, Poisson's ratios, and Zener anisotropy ratio, are described. The mechanical stability is analyzed, on the light of “Born generalized stability criteria,” showing that the garnet is mechanically unstable above 116 GPa. Symmetries, frequencies, and pressure coefficients of the Raman-active modes are discussed on the basis of the calculated total and partial phonon density of states, which reflect the dynamical contribution of each atom. The relations between the phonon modes of Y 3 Al 5 O 12 and the internal and external molecular modes of the different polyhedra are discussed. Infrared-active modes, as well as the silent modes, and their pressure dependence are also investigated. No dynamical instabilities were found below 116 GPa
Characterization of Elastic Properties of Porous Graphene Using an Ab Initio Study
Directory of Open Access Journals (Sweden)
Reza Ansari
2016-12-01
Full Text Available Importance of covalent bonded two-dimensional monolayer nanostructures and also hydrocarbons is undeniably responsible for creation of new fascinating materials like polyphenylene polymer, a hydrocarbon super honeycomb network, so-called porous graphene. The mechanical properties of porous graphene such as its Young’s modulus, Poisson’s ratio and the bulk modulus as the determinative properties are calculated in this paper using ab initio calculations. To accomplish this aim, the density functional theory on the basis of generalized gradient approximation and the Perdew–Burke–Ernzerhof exchange correlation is employed. Density functional theory calculations are used to calculate strain energy of porous graphene with respect to applied strain. Selected numerical results are then presented to study the properties of porous graphene. Comparisons are made between the properties of porous graphene and those of other analogous nanostructures. The results demonstrated lower stiffness of porous graphene than those of graphene and graphyne, and higher stiffness than that of graphdyine and other graphyne families. Unlikely, Poisson’s ratio is observed to be more than that of graphene and also less than that of graphyne. It is further observed that the presence of porosity and also formation of C-H bond in the pore sites is responsible for these discrepancies. Porous graphene is found to behave as the isotropic material.
The role of metallic ions in nano-bio hybrid catalysts from ab initio first principles
Behera, Sushant; Deb, Pritam
We employ high-accuracy linear-scaling density functional theory calculations with a near-complete basis set and a minimal parameter implicit solvent model, within the self-consistent calculation, on silver ion assimilated on bacteriorhodopsin (bR) at specific binding sites. The geometry optimization indicates the formation of stable active sites at the interface of nano-bio hybrid and density of states reflects the metallic behavior of the active sites. Detailed kinetics of the catalytic reaction is revealed using ab initio electronic structure calculations. We observed that the metal ion incorporated active sites are more efficient in electrolytic splitting of water than pristine sites due to their less value of Gibbs free energy for hydrogen evolution reaction and strong synergistic effect. The volcano plot analysis and free energy diagram are considered to understan hydrogen evolution efficiency. Moreover, the essential role of metallic ion on catalytic efficiency is elucidated. DBT, Government of India, vide Grant No BT/357/NE/TBP/ 2012. DST, GoI for financial support under INSPIRE Fellowship(IF150325).
Ab Initio Modeling of Structure and Properties of Single and Mixed Alkali Silicate Glasses.
Baral, Khagendra; Li, Aize; Ching, Wai-Yim
2017-10-12
A density functional theory (DFT)-based ab initio molecular dynamics (AIMD) has been applied to simulate models of single and mixed alkali silicate glasses with two different molar concentrations of alkali oxides. The structural environments and spatial distributions of alkali ions in the 10 simulated models with 20% and 30% of Li, Na, K and equal proportions of Li-Na and Na-K are studied in detail for subtle variations among the models. Quantum mechanical calculations of electronic structures, interatomic bonding, and mechanical and optical properties are carried out for each of the models, and the results are compared with available experimental observation and other simulations. The calculated results are in good agreement with the experimental data. We have used the novel concept of using the total bond order density (TBOD), a quantum mechanical metric, to characterize internal cohesion in these glass models. The mixed alkali effect (MAE) is visible in the bulk mechanical properties but not obvious in other physical properties studied in this paper. We show that Li doping deviates from expected trend due to the much stronger Li-O bonding than those of Na and K doping. The approach used in this study is in contrast with current studies in alkali-doped silicate glasses based only on geometric characterizations.
Ab initio calculations of the electronic structure and bonding characteristics of LaB6
International Nuclear Information System (INIS)
Hossain, Faruque M.; Riley, Daniel P.; Murch, Graeme E.
2005-01-01
Lanthanum hexaboride (LaB 6 , NIST SRM-660a) is widely used as a standard reference material for calibrating the line position and line shape parameters of powder diffraction instruments. The accuracy of this calibration technique is highly dependent on how completely the reference material is characterized. Critical to x-ray diffraction, this understanding must include the valence of the La atomic position, which in turn will influence the x-ray form factor (f) and hence the diffracted intensities. The electronic structure and bonding properties of LaB 6 have been investigated using ab initio plane-wave pseudopotential total energy calculations. The electronic properties and atomic bonding characteristics were analyzed by estimating the energy band structure and the density of states around the Fermi energy level. The calculated energy band structure is consistent with previously reported experimental findings; de Haas-van Alphen and two-dimensional angular correlation of electron-positron annihilation radiation. In addition, the bond strengths and types of atomic bonds in the LaB 6 compound were estimated by analyzing the Mulliken charge density population. The calculated result revealed the coexistence of covalent, ionic, and metallic bonding in the LaB 6 system and partially explains its high efficiency as a thermionic emitter
2018-01-01
We introduce a simple scheme to efficiently compute photon exchange-correlation contributions due to the coupling to transversal photons as formulated in the newly developed quantum-electrodynamical density-functional theory (QEDFT).1−5 Our construction employs the optimized-effective potential (OEP) approach by means of the Sternheimer equation to avoid the explicit calculation of unoccupied states. We demonstrate the efficiency of the scheme by applying it to an exactly solvable GaAs quantum ring model system, a single azulene molecule, and chains of sodium dimers, all located in optical cavities and described in full real space. While the first example is a two-dimensional system and allows to benchmark the employed approximations, the latter two examples demonstrate that the correlated electron-photon interaction appreciably distorts the ground-state electronic structure of a real molecule. By using this scheme, we not only construct typical electronic observables, such as the electronic ground-state density, but also illustrate how photon observables, such as the photon number, and mixed electron-photon observables, for example, electron–photon correlation functions, become accessible in a density-functional theory (DFT) framework. This work constitutes the first three-dimensional ab initio calculation within the new QEDFT formalism and thus opens up a new computational route for the ab initio study of correlated electron–photon systems in quantum cavities. PMID:29594185
A Review of Solid-Solution Models of High-Entropy Alloys Based on Ab Initio Calculations
Directory of Open Access Journals (Sweden)
Fuyang Tian
2017-11-01
Full Text Available Similar to the importance of XRD in experiments, ab initio calculations, as a powerful tool, have been applied to predict the new potential materials and investigate the intrinsic properties of materials in theory. As a typical solid-solution material, the large degree of uncertainty of high-entropy alloys (HEAs results in the difficulty of ab initio calculations application to HEAs. The present review focuses on the available ab initio based solid-solution models (virtual lattice approximation, coherent potential approximation, special quasirandom structure, similar local atomic environment, maximum-entropy method, and hybrid Monte Carlo/molecular dynamics and their applications and limits in single phase HEAs.
Energy Technology Data Exchange (ETDEWEB)
Wagner, Jan-Martin
2004-10-14
In this dissertation, ab-initio investigations of the strain influence on vibrational properties of GaN and AlN as well as of short-period GaN/AlN superlattices are presented. Based on densityfunctional theory and density-functional perturbation theory, for differently strained structures complete phonon spectra and related properties are calculated using the local-density approximation and norm-conserving pseudopotentials. (orig.)
International Nuclear Information System (INIS)
Chen, Ji; Ren, Xinguo; Li, Xin-Zheng; Alfè, Dario; Wang, Enge
2014-01-01
The finite-temperature phase diagram of hydrogen in the region of phase IV and its neighborhood was studied using the ab initio molecular dynamics (MD) and the ab initio path-integral molecular dynamics (PIMD). The electronic structures were analyzed using the density-functional theory (DFT), the random-phase approximation, and the diffusion Monte Carlo (DMC) methods. Taking the state-of-the-art DMC results as benchmark, comparisons of the energy differences between structures generated from the MD and PIMD simulations, with molecular and dissociated hydrogens, respectively, in the weak molecular layers of phase IV, indicate that standard functionals in DFT tend to underestimate the dissociation barrier of the weak molecular layers in this mixed phase. Because of this underestimation, inclusion of the quantum nuclear effects (QNEs) in PIMD using electronic structures generated with these functionals leads to artificially dissociated hydrogen layers in phase IV and an error compensation between the neglect of QNEs and the deficiencies of these functionals in standard ab initio MD simulations exists. This analysis partly rationalizes why earlier ab initio MD simulations complement so well the experimental observations. The temperature and pressure dependencies for the stability of phase IV were also studied in the end and compared with earlier results
Energy Technology Data Exchange (ETDEWEB)
Masrour, R., E-mail: rachidmasrour@hotmail.com [Laboratory of Materials, Processes, Environment and Quality, Cady Ayyed University, National School of Applied Sciences, BP. 63, 46000 Safi (Morocco); LMPHE (URAC 12), Faculty of Science, Mohammed V-Agdal University, Rabat (Morocco); Hlil, E.K. [Institut Néel, CNRS et Université Joseph Fourier, BP 166, F-38042 Grenoble Cedex 9 (France); Hamedoun, M. [Institute of Nanomaterials and Nanotechnologies, MAScIR, Rabat (Morocco); Benyoussef, A. [LMPHE (URAC 12), Faculty of Science, Mohammed V-Agdal University, Rabat (Morocco); Institute of Nanomaterials and Nanotechnologies, MAScIR, Rabat (Morocco); Hassan II Academy of Science and Technology, Rabat (Morocco); Mounkachi, O.; El Moussaoui, H. [Institute of Nanomaterials and Nanotechnologies, MAScIR, Rabat (Morocco)
2014-06-01
Self-consistent ab initio calculations, based on DFT (Density Functional Theory) approach and using FLAPW (Full potential Linear Augmented Plane Wave) method, are performed to investigate both electronic and magnetic properties of the MnSe lattice. Polarized spin and spin–orbit coupling are included in calculations within the framework of the antiferromagnetic state between two adjacent Mn lattices. Magnetic moments considered to lie along (001) axes are computed. Obtained data from ab initio calculations are used as input for the high temperature series expansions (HTSEs) calculations to compute other magnetic parameters. The zero-field high temperature static susceptibility series of the spin −4.28 nearest-neighbor Ising model on face centered cubic (fcc) and lattices is thoroughly analyzed by means of a power series coherent anomaly method (CAM). The exchange interaction between the magnetic atoms and the Néel temperature are deduced using the mean filed and HTSEs theories. - Highlights: • Ab initio calculations are used to investigate both electronic and magnetic properties of the MnSe alloys. • Obtained data from ab initio calculations are used as input for the HTSEs. • The Néel temperature is obtained for MnSe alloys.
Hoy, Erik P; Mazziotti, David A
2015-08-14
Tensor factorization of the 2-electron integral matrix is a well-known technique for reducing the computational scaling of ab initio electronic structure methods toward that of Hartree-Fock and density functional theories. The simplest factorization that maintains the positive semidefinite character of the 2-electron integral matrix is the Cholesky factorization. In this paper, we introduce a family of positive semidefinite factorizations that generalize the Cholesky factorization. Using an implementation of the factorization within the parametric 2-RDM method [D. A. Mazziotti, Phys. Rev. Lett. 101, 253002 (2008)], we study several inorganic molecules, alkane chains, and potential energy curves and find that this generalized factorization retains the accuracy and size extensivity of the Cholesky factorization, even in the presence of multi-reference correlation. The generalized family of positive semidefinite factorizations has potential applications to low-scaling ab initio electronic structure methods that treat electron correlation with a computational cost approaching that of the Hartree-Fock method or density functional theory.
Energy Technology Data Exchange (ETDEWEB)
Hoy, Erik P.; Mazziotti, David A., E-mail: damazz@uchicago.edu [Department of Chemistry and The James Franck Institute, The University of Chicago, Chicago, Illinois 60637 (United States)
2015-08-14
Tensor factorization of the 2-electron integral matrix is a well-known technique for reducing the computational scaling of ab initio electronic structure methods toward that of Hartree-Fock and density functional theories. The simplest factorization that maintains the positive semidefinite character of the 2-electron integral matrix is the Cholesky factorization. In this paper, we introduce a family of positive semidefinite factorizations that generalize the Cholesky factorization. Using an implementation of the factorization within the parametric 2-RDM method [D. A. Mazziotti, Phys. Rev. Lett. 101, 253002 (2008)], we study several inorganic molecules, alkane chains, and potential energy curves and find that this generalized factorization retains the accuracy and size extensivity of the Cholesky factorization, even in the presence of multi-reference correlation. The generalized family of positive semidefinite factorizations has potential applications to low-scaling ab initio electronic structure methods that treat electron correlation with a computational cost approaching that of the Hartree-Fock method or density functional theory.
Optical absorption spectra and g factor of MgO: Mn2+explored by ab initio and semi empirical methods
Andreici Eftimie, E.-L.; Avram, C. N.; Brik, M. G.; Avram, N. M.
2018-02-01
In this paper we present a methodology for calculations of the optical absorption spectra, ligand field parameters and g factor for the Mn2+ (3d5) ions doped in MgO host crystal. The proposed technique combines two methods: the ab initio multireference (MR) and the semi empirical ligand field (LF) in the framework of the exchange charge model (ECM) respectively. Both methods of calculations are applied to the [MnO6]10-cluster embedded in an extended point charge field of host matrix ligands based on Gellé-Lepetit procedure. The first step of such investigations was the full optimization of the cubic structure of perfect MgO crystal, followed by the structural optimization of the doped of MgO:Mn2+ system, using periodic density functional theory (DFT). The ab initio MR wave functions approaches, such as complete active space self-consistent field (CASSCF), N-electron valence second order perturbation theory (NEVPT2) and spectroscopy oriented configuration interaction (SORCI), are used for the calculations. The scalar relativistic effects have also been taken into account through the second order Douglas-Kroll-Hess (DKH2) procedure. Ab initio ligand field theory (AILFT) allows to extract all LF parameters and spin-orbit coupling constant from such calculations. In addition, the ECM of ligand field theory (LFT) has been used for modelling theoptical absorption spectra. The perturbation theory (PT) was employed for the g factor calculation in the semi empirical LFT. The results of each of the aforementioned types of calculations are discussed and the comparisons between the results obtained and the experimental results show a reasonable agreement, which justifies this new methodology based on the simultaneous use of both methods. This study establishes fundamental principles for the further modelling of larger embedded cluster models of doped metal oxides.
Černý, Jiří; Schneider, Bohdan; Biedermannová, Lada
2017-07-14
Water molecules represent an integral part of proteins and a key determinant of protein structure, dynamics and function. WatAA is a newly developed, web-based atlas of amino-acid hydration in proteins. The atlas provides information about the ordered first hydration shell of the most populated amino-acid conformers in proteins. The data presented in the atlas are drawn from two sources: experimental data and ab initio quantum-mechanics calculations. The experimental part is based on a data-mining study of a large set of high-resolution protein crystal structures. The crystal-derived data include 3D maps of water distribution around amino-acids and probability of occurrence of each of the identified hydration sites. The quantum mechanics calculations validate and extend this primary description by optimizing the water position for each hydration site, by providing hydrogen atom positions and by quantifying the interaction energy that stabilizes the water molecule at the particular hydration site position. The calculations show that the majority of experimentally derived hydration sites are positioned near local energy minima for water, and the calculated interaction energies help to assess the preference of water for the individual hydration sites. We propose that the atlas can be used to validate water placement in electron density maps in crystallographic refinement, to locate water molecules mediating protein-ligand interactions in drug design, and to prepare and evaluate molecular dynamics simulations. WatAA: Atlas of Protein Hydration is freely available without login at .
Ab initio molecular dynamics: basic concepts, current trends and novel applications
International Nuclear Information System (INIS)
Tuckerman, Mark E
2002-01-01
The field of ab initio molecular dynamics (AIMD), in which finite temperature molecular dynamics (MD) trajectories are generated with forces obtained from accurate 'on the fly' electronic structure calculations, is a rapidly evolving and growing technology that allows chemical processes in condensed phases to be studied in an accurate and unbiased way. This article is intended to present the basics of the AIMD method as well as to provide a broad survey of the state of the art of the field and showcase some of its capabilities. Beginning with a derivation of the method from the Born-Oppenheimer approximation, issues including the density functional representation of electronic structure, basis sets, calculation of observables and the Car-Parrinello extended Lagrangian algorithm are discussed. A number of example applications, including liquid structure and dynamics and aqueous proton transport, are presented in order to highlight some of the current capabilities of the approach. Finally, advanced topics such as inclusion of nuclear quantum effects, excited states and scaling issues are addressed. (topical review)
International Nuclear Information System (INIS)
Rosenow, Phil; Tonner, Ralf
2016-01-01
The extent of hydrogen coverage of the Si(001) c(4 × 2) surface in the presence of hydrogen gas has been studied with dispersion corrected density functional theory. Electronic energy contributions are well described using a hybrid functional. The temperature dependence of the coverage in thermodynamic equilibrium was studied computing the phonon spectrum in a supercell approach. As an approximation to these demanding computations, an interpolated phonon approach was found to give comparable accuracy. The simpler ab initio thermodynamic approach is not accurate enough for the system studied, even if corrections by the Einstein model for surface vibrations are considered. The on-set of H 2 desorption from the fully hydrogenated surface is predicted to occur at temperatures around 750 K. Strong changes in hydrogen coverage are found between 1000 and 1200 K in good agreement with previous reflectance anisotropy spectroscopy experiments. These findings allow a rational choice for the surface state in the computational treatment of chemical reactions under typical metal organic vapor phase epitaxy conditions on Si(001).
Energy Technology Data Exchange (ETDEWEB)
Rosenow, Phil; Tonner, Ralf, E-mail: tonner@chemie.uni-marburg.de [Fachbereich Chemie and Wissenschaftliches Zentrum für Materialwissenschaften, Philipps-Universität Marburg, Hans-Meerwein-Straße, Marburg 35032 (Germany)
2016-05-28
The extent of hydrogen coverage of the Si(001) c(4 × 2) surface in the presence of hydrogen gas has been studied with dispersion corrected density functional theory. Electronic energy contributions are well described using a hybrid functional. The temperature dependence of the coverage in thermodynamic equilibrium was studied computing the phonon spectrum in a supercell approach. As an approximation to these demanding computations, an interpolated phonon approach was found to give comparable accuracy. The simpler ab initio thermodynamic approach is not accurate enough for the system studied, even if corrections by the Einstein model for surface vibrations are considered. The on-set of H{sub 2} desorption from the fully hydrogenated surface is predicted to occur at temperatures around 750 K. Strong changes in hydrogen coverage are found between 1000 and 1200 K in good agreement with previous reflectance anisotropy spectroscopy experiments. These findings allow a rational choice for the surface state in the computational treatment of chemical reactions under typical metal organic vapor phase epitaxy conditions on Si(001).
Rosenow, Phil; Tonner, Ralf
2016-05-01
The extent of hydrogen coverage of the Si(001) c(4 × 2) surface in the presence of hydrogen gas has been studied with dispersion corrected density functional theory. Electronic energy contributions are well described using a hybrid functional. The temperature dependence of the coverage in thermodynamic equilibrium was studied computing the phonon spectrum in a supercell approach. As an approximation to these demanding computations, an interpolated phonon approach was found to give comparable accuracy. The simpler ab initio thermodynamic approach is not accurate enough for the system studied, even if corrections by the Einstein model for surface vibrations are considered. The on-set of H2 desorption from the fully hydrogenated surface is predicted to occur at temperatures around 750 K. Strong changes in hydrogen coverage are found between 1000 and 1200 K in good agreement with previous reflectance anisotropy spectroscopy experiments. These findings allow a rational choice for the surface state in the computational treatment of chemical reactions under typical metal organic vapor phase epitaxy conditions on Si(001).
Perpendicular magnetic anisotropy in Mn2VIn (001) films: An ab initio study
Zipporah, Muthui; Robinson, Musembi; Julius, Mwabora; Arti, Kashyap
2018-05-01
First principles study of the magnetic anisotropy of Mn2VIn (001) films show perpendicular magnetic anisotropy (PMA), which increases as a function of the thickness of the film. Density functional theory (DFT) as implemented in the Vienna Ab initio simulation package (VASP) is employed here to perform a comprehensive theoretical investigation of the structural, electronic and magnetic properties of the Mn2VIn(001) films of varying thickness. Our calculations were performed on fully relaxed structures, with five to seventeen mono layers (ML). The degree of spin polarization is higher in the (001) Mn2VIn thin films as compared to the bulk in contrast to what is usually the case and as in Mn2VAl, which is isoelectronic to Mn2VIn as well as inCo2VIn (001) films studied for comparison. Tetragonal distortions are found in all the systems after relaxation. The distortion in the Mn2VIn system persists even for the 17ML thin film, resulting in PMA in the Mn2VIn system. This significant finding has potential to contribute to spin transfer torque (STT) and magnetic random access memory MRAM applications, as materials with PMA derived from volume magnetocrystalline anisotropy are being proposed as ideal magnetic electrodes.
SGO: A fast engine for ab initio atomic structure global optimization by differential evolution
Chen, Zhanghui; Jia, Weile; Jiang, Xiangwei; Li, Shu-Shen; Wang, Lin-Wang
2017-10-01
As the high throughout calculations and material genome approaches become more and more popular in material science, the search for optimal ways to predict atomic global minimum structure is a high research priority. This paper presents a fast method for global search of atomic structures at ab initio level. The structures global optimization (SGO) engine consists of a high-efficiency differential evolution algorithm, accelerated local relaxation methods and a plane-wave density functional theory code running on GPU machines. The purpose is to show what can be achieved by combining the superior algorithms at the different levels of the searching scheme. SGO can search the global-minimum configurations of crystals, two-dimensional materials and quantum clusters without prior symmetry restriction in a relatively short time (half or several hours for systems with less than 25 atoms), thus making such a task a routine calculation. Comparisons with other existing methods such as minima hopping and genetic algorithm are provided. One motivation of our study is to investigate the properties of magnetic systems in different phases. The SGO engine is capable of surveying the local minima surrounding the global minimum, which provides the information for the overall energy landscape of a given system. Using this capability we have found several new configurations for testing systems, explored their energy landscape, and demonstrated that the magnetic moment of metal clusters fluctuates strongly in different local minima.
Ab initio screening methodology applied to the search for new permanent magnetic materials
International Nuclear Information System (INIS)
Drebov, Nedko; Gumbsch, Peter; Elsässer, Christian; Martinez-Limia, Alberto; Kunz, Lothar; Gola, Adrien; Eckl, Thomas; Shigematsu, Takashi
2013-01-01
In this paper a computational high-throughput screening (HTS) approach to the search for alternative permanent magnetic materials is presented. Systems considered for a start are binary intermetallic compounds composed of rare-earth (RE) and transition metal (TM) elements. With the tight-binding-linear muffin-tin-orbital-atomic-sphere-approximation (TB-LMTO-ASA) method of density functional theory (DFT) a variety of RE–TM intermetallic phases is investigated and their magnetic properties are obtained at rather low computational costs. Next, interstitial elements such as boron, carbon and nitrogen in these phases are considered. For promising candidate phases with high and stable spontaneous ferromagnetic polarization, the calculated local magnetic moments and exchange coupling parameters, as obtained from TB-LMTO-ASA calculations, are then used for Monte Carlo simulations to identify candidates with sufficiently high Curie temperatures (T c ). Finally, magnetocrystalline anisotropy constants (K 1 ) of the most promising candidate phases are calculated with accurate, potential-shape-unrestricted DFT calculations using the Vienna ab initio simulation package. The computational HTS procedure is illustrated by results for a selection of hard-magnetic RE–TM phases like RETM 5 , RE 2 TM 17 and RE 2 TM 14 B. (paper)
Systematic ab initio study of half-Heusler materials for optoelectronic applications
Energy Technology Data Exchange (ETDEWEB)
Gruhn, Thomas; Felser, Claudia [Institute of Inorganic and Analytical Chemistry, Johannes Gutenberg University, Mainz (Germany)
2010-07-01
The development of new, optimized optoelectronic devices depends crucially on the availability of semiconductors with taylored electronic and structural properties. At the moment, the majority of applications is based on a rather small set of semiconducting materials, while many more semiconductors exist in the huge class of ternary compounds. Especially, the class of 8-electron half-Heusler materials comprises a large number semiconducters with various properties. With the help of ab initio density functional theory we have studied essentially all 8-electron half-Heusler compounds that are of technological relevance. For more than 650 compounds we have determined the optimum configuration by varying the lattice constant and permuting the elements over the sublattices. Within this exceptionally large data set we have studied the band structure and the lattice constants as a function of the electronegativities of the elements, the arrangement of the atoms, and the atomic radii. The results are used to select suitable materials for the buffer layer in thin-film solar cells with a Cu(In,Ga)Se{sub 2} (CIGS) absorber layer. Considering the bandgap and the geometrical matching with the CIGS film, we have obtained a set of 29 compounds that are promissing materials for cadmium-free CIGS buffer layer.
Ab initio study of the electron-phonon coupling at the Cr(001) surface
Peters, L.; Rudenko, A. N.; Katsnelson, M. I.
2018-04-01
It is experimentally well established that the Cr(001) surface exhibits a sharp resonance around the Fermi level. However, there is no consensus about its physical origin. It is proposed to be either due to a single particle dz2 surface state renormalized by electron-phonon coupling or the orbital Kondo effect involving the degenerate dx z/ dy z states. In this paper we examine the electron-phonon coupling of the Cr(001) surface by means of ab-initio calculations in the form of density functional perturbation theory. More precisely, the electron-phonon mass-enhancement factor of the surface layer is investigated for the 3d states. For the majority and minority spin dz2 surface states we find values of 0.19 and 0.16. We show that these calculated electron-phonon mass-enhancement factors are not in agreement with the experimental data even if we use realistic values for the temperature range and surface Debye frequency for the fit of the experimental data. More precisely, then experimentally an electron-phonon mass-enhancement factor of 0.70 ±0.10 is obtained, which is not in agreement with our calculated values of 0.19 and 0.16. Our findings suggest that the experimentally observed resonance at the Cr(001) surface is not due to electron-phonon effects but due to electron-electron correlation effects.
An ab initio study of the polytypism in InP
Dacal, Luis C. O.; Cantarero, A.
2016-09-01
The existence of polytypism in semiconductor nanostructures gives rise to the appearance of stacking faults which many times can be treated as quantum wells. In some cases, despite of a careful growth, the polytypism can be hardly avoided. In this work, we perform an ab initio study of zincblende stacking faults in a wurtzite InP system, using the supercell approach and taking the limit of low density of narrow stacking faults regions. Our results confirm the type II band alignment between the phases, producing a reliable qualitative description of the band gap evolution along the growth axis. These results show an spacial asymmetry in the zincblende quantum wells, that is expected due to the fact that the wurtzite stacking sequence (ABAB) is part of the zincblende one (ABCABC), but with an unexpected asymmetry between the valence and the conduction bands. We also present results for the complex dielectric function, clearly showing the influence of the stacking on the homostructure values and surprisingly proving that the correspondent bulk results can be used to reproduce the polytypism even in the limit we considered.
360⁰ -View of Quantum Theory and Ab Initio Simulation at Extreme Conditions: 2014 Sanibel Symposium
Energy Technology Data Exchange (ETDEWEB)
Cheng, Hai-Ping [Univ. of Florida, Gainesville, FL (United States)
2016-09-02
The Sanibel Symposium 2014 was held February 16-21, 2014, at the King and Prince, St. Simons Island, GA. It was successful in bringing condensed-matter physicists and quantum chemists together productively to drive the emergence of those specialties. The Symposium had a significant role in preparing a whole generation of quantum theorists. The 54th Sanibel meeting looked to the future in two ways. We had 360⁰-View sessions to honor the exceptional contributions of Rodney Bartlett (70), Bill Butler (70), Yngve Öhrn (80), Fritz Schaefer (70), and Malcolm Stocks (70). The work of these five has greatly impacted several generations of quantum chemists and condensed matter physicists. The “360⁰” is the sum of their ages. More significantly, it symbolizes a panoramic view of critical developments and accomplishments in theoretical and computational chemistry and physics oriented toward the future. Thus, two of the eight 360⁰-View sessions focused specifically on younger scientists. The 360⁰-View program was the major component of the 2014 Sanibel meeting. Another four sessions included a sub-symposium on ab initio Simulations at Extreme Conditions, with focus on getting past the barriers of present-day Born-Oppenheimer molecular dynamics by advances in finite-temperature density functional theory, orbital-free DFT, and new all-numerical approaches.
Synthesis, FTIR, FT-Raman, UV-visible, ab initio and DFT studies on benzohydrazide.
Arjunan, V; Rani, T; Mythili, C V; Mohan, S
2011-08-01
A systematic vibrational spectroscopic assignment and analysis of benzohydrazide (BH) has been carried out by using FTIR and FT-Raman spectral data. The vibrational analysis were aided by electronic structure calculations--ab initio (RHF) and hybrid density functional methods (B3LYP and B3PW91) performed with 6-31G(d,p) and 6-311++G(d,p) basis sets. Molecular equilibrium geometries, electronic energies, IR intensities, harmonic vibrational frequencies, depolarization ratios and Raman activities have been computed. Potential energy distribution (PED) and normal mode analysis have also been performed. The assignments proposed based on the experimental IR and Raman spectra have been reviewed and complete assignment of the observed spectra have been proposed. UV-visible spectrum of the compound was also recorded and the electronic properties, such as HOMO and LUMO energies and λ(max) were determined by time-dependent DFT (TD-DFT) method. The geometrical, thermodynamical parameters and absorption wavelengths were compared with the experimental data. The interactions of carbonyl and hydrazide groups on the benzene ring skeletal modes were investigated. Copyright © 2011 Elsevier B.V. All rights reserved.
LaPlante, Arthur J.; Stidham, Howard D.
2009-10-01
The mid and far infrared and the Raman spectrum of 1,2-dibromopropane is reported in solid, liquid and gas. Several bands reported by earlier workers are not present in the spectrum of the purified material. Ab initio calculations of optimized geometry, energy, dipole moment, molar volume, vibrational spectrum and normal coordinate calculation were performed using the density functional B3LYP/6-311++g(3df,2pd), and the results used to assist a complete assignment of the 81 fundamental modes of vibrations of the three conformers of 1,2-dibromopropane. Relative energies found conformer A the lowest with G and G' at 815.6 and 871.4 cm -1 higher. The temperature dependence of the Raman spectrum of the liquid was investigated in the CCC bending region and the relative energies determined. It was found that the G' and G conformers lie 236 ± 11 and 327 ±11 cm -1, respectively above the A conformer, leading to the room temperature composition of the liquid as A, 65 ± 1; G', 21 ± 1; G, 14 ± 1%. It is apparent that the calculated highest energy conformer G' is stabilized more than the G conformer in the liquid. The G' conformer has the lowest molar volume effectively changing the interaction distance between conformers in the liquid, and enhancing the effect of its dipole moment.
Hydrogen interaction with ferrite/cementite interface: ab initio calculations and thermodynamics
Mirzoev, A. A.; Verkhovykh, A. V.; Okishev, K. Yu.; Mirzaev, D. A.
2018-02-01
The paper presents the results of ab initio modelling of the interaction of hydrogen atoms with ferrite/cementite interfaces in steels and thermodynamic assessment of the ability of interfaces to trap hydrogen atoms. Modelling was performed using the density functional theory with generalised gradient approximation (GGA'96), as implemented in WIEN2k package. An Isaichev-type orientation relationship between the two phases was accepted, with a habit plane (101)c ∥ (112)α. The supercell contained 64 atoms (56 Fe and 8 C). The calculated formation energies of ferrite/cementite interface were 0.594 J/m2. The calculated trapping energy at cementite interstitial was 0.18 eV, and at the ferrite/cementite interface - 0.30 eV. Considering calculated zero-point energy, the trapping energies at cementite interstitial and ferrite/cementite interface become 0.26 eV and 0.39 eV, respectively. The values are close to other researchers' data. These results were used to construct a thermodynamic description of ferrite/cementite interface-hydrogen interaction. Absorption calculations using the obtained trapping energy values showed that even thin lamellar ferrite/cementite mixture with an interlamellar spacing smaller than 0.1 μm has noticeable hydrogen trapping ability at a temperature below 400 K.
Experimental and ab initio DFT calculated Raman Spectrum of Sudan I, a Red Dye
DEFF Research Database (Denmark)
Kunov-Kruse, Andreas Jonas; Kristensen, Steffen Buus; Liu, Chuan
2011-01-01
The red dye Sudan I was investigated by Raman spectroscopy using different excitation wavelengths (1064, 532 and 244 nm). A calculation of the Raman spectrum based on quantum mechanical ab initio density functional theory (DFT) was made using the RB3LYP method with the 3-21G and 6-311+G(d,p) basis...... of the Sudan I molecule was involved in the majority of the vibrations through N N and C–N stretching and various bending modes. Low-intensity bands in the lower wavenumber range (at about 721, 616, 463 and 218 cm−1) were selectively enhanced by the resonance Raman effect when using the 532 nm excitation line....... Comparison was made with other azo dyes in the literature on natural, abundant plant pigments. The results show that there is a possibility in foodstuff analysis to distinguish Sudan I from other dyes by using Raman spectroscopy with more than one laser wavelength for resonance enhancement of the different...
Ab-initio and atomistic study of the ferroelectric properties of Cu doped potassium niobate
Energy Technology Data Exchange (ETDEWEB)
Koerbel, Sabine; Elsaesser, Christian [Fraunhofer-Institut fuer Werkstoffmechanik IWM, Woehlerstrasse 11, 79108 Freiburg (Germany)
2011-07-01
KNbO{sub 3} is one end member of the solid solution (K,Na)NbO{sub 3} (KNN), which has promising ferroelectric properties to become a future lead-free substitute for lead zirconate titanate Pb(Zr,Ti)O{sub 3} (PZT) in piezoelectric actors and sensors. Both KNN and PZT exhibit a phase transition with composition and a morphotropic phase boundary, at which enhanced piezoelectric coefficients are obtained. The material properties of PZT and KNN are commonly optimized by doping. E.g., CuO can be added when fabricating KNN as a sintering aid. Ab initio density functional theory and atomistic simulation using a classical shell model potential have been combined to investigate low Cu concentrations in the KNbO{sub 3}-CuNbO{sub 3} system. The atomistic model predicts a morphotropic phase boundary at a few percent Cu, analogous to the one found in the LiNbO{sub 3}-KNbO{sub 3} system.
Mutual influence between triel bond and cation-π interactions: an ab initio study
Esrafili, Mehdi D.; Mousavian, Parisasadat
2017-12-01
Using ab initio calculations, the cooperative and solvent effects on cation-π and B...N interactions are studied in some model ternary complexes, where these interactions coexist. The nature of the interactions and the mechanism of cooperativity are investigated by means of quantum theory of atoms in molecules (QTAIM), noncovalent interaction (NCI) index and natural bond orbital analysis. The results indicate that all cation-π and B...N binding distances in the ternary complexes are shorter than those of corresponding binary systems. The QTAIM analysis reveals that ternary complexes have higher electron density at their bond critical points relative to the corresponding binary complexes. In addition, according to the QTAIM analysis, the formation of cation-π interaction increases covalency of B...N bonds. The NCI analysis indicates that the cooperative effects in the ternary complexes make a shift in the location of the spike associated with each interaction, which can be regarded as an evidence for the reinforcement of both cation-π and B...N interactions in these systems. Solvent effects on the cooperativity of cation-π and B...N interactions are also investigated.
Tunneling of electrons via rotor–stator molecular interfaces: Combined ab initio and model study
Energy Technology Data Exchange (ETDEWEB)
Petreska, Irina, E-mail: irina.petreska@pmf.ukim.mk [Institute of Physics, Faculty of Natural Sciences and Mathematics, Ss. Cyril and Methodius University, PO Box 162, 1000 Skopje, Former Yugolav Republic of Macedonia, The (Macedonia, The Former Yugoslav Republic of); Ohanesjan, Vladimir [Institute of Physics, Faculty of Natural Sciences and Mathematics, Ss. Cyril and Methodius University, PO Box 162, 1000 Skopje, Former Yugolav Republic of Macedonia, The (Macedonia, The Former Yugoslav Republic of); Pejov, Ljupčo [Institute of Chemistry, Department of Physical Chemistry, Ss. Cyril and Methodius University, Arhimedova 5, P.O. Box 162, 1000 Skopje, Former Yugolav Republic of Macedonia, The (Macedonia, The Former Yugoslav Republic of); Kocarev, Ljupčo [Macedonian Academy of Sciences and Arts, Krste Misirkov 2, PO Box 428, 1000 Skopje, Former Yugolav Republic of Macedonia, The (Macedonia, The Former Yugoslav Republic of); Faculty of Computer Science and Engineering, Ss. Cyril and Methodius University, Skopje, Former Yugolav Republic of Macedonia, The (Macedonia, The Former Yugoslav Republic of)
2016-07-01
Tunneling of electrons through rotor–stator anthracene aldehyde molecular interfaces is studied with a combined ab initio and model approach. Molecular electronic structure calculated from first principles is utilized to model different shapes of tunneling barriers. Together with a rectangular barrier, we also consider a sinusoidal shape that captures the effects of the molecular internal structure more realistically. Quasiclassical approach with the Simmons’ formula for current density is implemented. Special attention is paid on conformational dependence of the tunneling current. Our results confirm that the presence of the side aldehyde group enhances the interesting electronic properties of the pure anthracene molecule, making it a bistable system with geometry dependent transport properties. We also investigate the transition voltage and we show that conformation-dependent field emission could be observed in these molecular interfaces at realistically low voltages. The present study accompanies our previous work where we investigated the coherent transport via strongly coupled delocalized orbital by application of Non-equilibrium Green’s Function Formalism.
Ab initio random structure search for 13-atom clusters of fcc elements
International Nuclear Information System (INIS)
Chou, J P; Hsing, C R; Wei, C M; Cheng, C; Chang, C M
2013-01-01
The 13-atom metal clusters of fcc elements (Al, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au) were studied by density functional theory calculations. The global minima were searched for by the ab initio random structure searching method. In addition to some new lowest-energy structures for Pd 13 and Au 13 , we found that the effective coordination numbers of the lowest-energy clusters would increase with the ratio of the dimer-to-bulk bond length. This correlation, together with the electronic structures of the lowest-energy clusters, divides the 13-atom clusters of these fcc elements into two groups (except for Au 13 , which prefers a two-dimensional structure due to the relativistic effect). Compact-like clusters that are composed exclusively of triangular motifs are preferred for elements without d-electrons (Al) or with (nearly) filled d-band electrons (Ni, Pd, Cu, Ag). Non-compact clusters composed mainly of square motifs connected by some triangular motifs (Rh, Ir, Pt) are favored for elements with unfilled d-band electrons. (paper)
Effect of Au proximity on the LSMO surface: An ab initio study
International Nuclear Information System (INIS)
Petti, D.; Stroppa, A.; Picozzi, S.; Brivio, S.; Cantoni, M.; Bertacco, R.
2012-01-01
The effect of the proximity of Au on the electronic and magnetic properties of La 0.66 Sr 0.33 MnO 3 (LSMO) has been investigated by means of ab initio calculations within the density-functional theory. The calculations show an orbital reconstruction of the interfacial Mn, which is due more to the presence of a discontinuity rather than to a real chemical interaction with Au atoms. In fact, the same orbital reconstruction is found in the free LSMO surface. In both cases of Au/LSMO and LSMO surface, the Mn magnetic moments change very little with respect to the bulk case. In general, the calculations show a negligible influence of the Au atomic layer on LSMO at an ideal interface, with the LSMO surface magnetic and electronic properties essentially unchanged. - Highlights: ► Three structures considered: bulk LSMO, Au/LSMO and vacuum LSMO interfaces. ► At the two interfaces the formation of a discontinuity creates an orbital ordering. ► DFT calculations point toward an enhancement of the magnetization at the interface. ► Negligible chemical interaction with gold is seen for a 2D ideal interface. ► Crucial role of the 3D nature of Au on LSMO in depressing LSMO magnetic properties.
Ruggiero, Michael T; Zeitler, J Axel
2016-11-17
Anharmonicity has been shown to be an important piece of the fundamental framework that dictates numerous observable phenomena. In particular, anharmonicity is the driving force of vibrational relaxation processes, mechanisms that are integral to the proper function of numerous chemical processes. However, elucidating its origins has proven difficult due to experimental and theoretical challenges, specifically related to separating the anharmonic contributions from other unrelated effects. While no one technique is particularly suited for providing a complete picture of anharmonicity, by combining multiple complementary methods such a characterization can be made. In this study the role of individual atomic interactions on the anharmonic properties of crystalline purine, the building block of many DNA and RNA nucleobases, is studied by experimental terahertz time-domain spectroscopy and first-principles density functional theory (DFT) and ab initio molecular dynamics simulations (AIMD). In particular, the detailed vibrational information provided by the DFT calculations is used to interpret the atomic origins of anharmonic-related effects as determined by the AIMD calculations, which are in good agreement with the experimental data. The results highlight that anharmonicity is especially pronounced in the intermolecular interactions, particularly along the amine hydrogen bond coordinate, and yields valuable insight into what is similarly observed complex biosystems and crystalline solids.
Ab initio study of stability and migration of H and He in hcp-Sc
International Nuclear Information System (INIS)
Yang, L; Zu, X T; Peng, S M; Long, X G; Gao, F; Heinisch, H L; Kurtz, R J
2011-01-01
Ab initio calculations based on density functional theory have been performed to determine the relative stabilities and migration of H and He atoms in hcp-Sc. The results show that the formation energy of an interstitial H or He atom is smaller than that of a corresponding substitutional atom. The tetrahedral (T) interstitial position is more stable than an octahedral (O) position for both He and H interstitials. The nudged elastic band method has been used to study the migration of interstitial H and He atoms in hcp-Sc. It is found that the migration energy barriers for H interstitials in hcp-Sc are significantly different from those for He interstitials, but their migration mechanisms are similar. In addition, the formation energies of five different configurations of a H-H pair were determined, revealing that the most stable configuration consists of two H atoms located at the second-neighbor tetrahedral interstitial sites along the hexagonal direction. The formation and relative stabilities of some small He clusters have also been investigated.
Ab initio identification of the Li-rich phase in LiFePO4.
Zeng, Hua; Gu, Yue; Teng, Gaofeng; Liu, Yimeng; Zheng, Jiaxin; Pan, Feng
2018-06-27
A recent discovery of anionic redox activity in Li-rich layered compounds opens a new direction for the design of high-capacity cathode materials for lithium-ion batteries. Here using extensive ab initio calculations, the thermodynamic existence of the Li-rich phase in LiFePO4 to form Li1+xFe1-xPO4 with x not exceeding 12.5% has been proved. Anionic redox activity and structural stability during delithiation are further investigated. Interestingly, it is found that Li1+xFe1-xPO4 cannot be delithiated completely and thus cannot achieve extra capacity by anionic redox activity, because the local oxygen-ion redox will cause the fracture of the rigid framework formed by phosphate tetrahedral polyanions. Although an extra capacity cannot be realized, the excess Li-ions at Fe sites can enhance the Li-ion diffusivity along the adjacent [010] channel and contribute to the shift from 1D to 2D/3D diffusion. This study provides a fresh perspective on olivine-type LiFePO4 and offers some important clues on designing Li-rich cathode materials with high energy density.
Ab initio study of Cr interactions with point defects in bcc Fe
International Nuclear Information System (INIS)
Olsson, P.; Domain, Ch.; Wallenius, J.
2008-01-01
Full text of publication follows. Ferritic martensitic steels are candidate structural materials for fast neutron reactors, and in particular high-Cr reduced-activation steels. In Fe-Cr alloys, Cr plays a major role in the radiation-induced evolution of the mechanical properties. Using ab initio calculations based on density functional theory, the properties of Cr in α-Fe have been investigated. The intrinsic point defect formation energies were found to be larger in model bcc Cr as compared to those in ferromagnetic bcc Fe. The interactions of Cr with point defects (vacancy and self interstitials) have been characterised. Single Cr atoms interact weakly with vacancies but significantly with self-interstitial atoms. Mixed interstitials of any interstitial symmetry are bound. Configurations where two Cr atoms are in nearest neighbour position are generally unfavourable in bcc Fe except when they are a part of a interstitial complex. Mixed interstitials do not have as strong directional stability as pure Fe interstitials have. The effects on the results using the atom description scheme of either the ultrasoft pseudo-potential (USPP) or the projector augmented wave (PAW) formalisms are connected to the differences in local magnetic moments that the two methods predict. As expected for the Fe-Cr system, the results obtained using the PAW method are more reliable than the ones obtained with USPP. (authors)
Ab initio quasiparticle bandstructure of ABA and ABC-stacked graphene trilayers
Menezes, Marcos; Capaz, Rodrigo; Louie, Steven
2013-03-01
We obtain the quasiparticle band structure of ABA and ABC-stacked graphene trilayers through ab initio density functional theory (DFT) and many-body quasiparticle calculations within the GW approximation. To interpret our results, we fit the DFT and GW π bands to a low energy tight-binding model, which is found to reproduce very well the observed features near the K point. The values of the extracted hopping parameters are reported and compared with available theoretical and experimental data. For both stackings, the quasiparticle corrections lead to a renormalization of the Fermi velocity, an effect also observed in previous calculations on monolayer graphene. They also increase the separation between the higher energy bands, which is proportional to the nearest neighbor interlayer hopping parameter γ1. Both features are brought to closer agreement with experiment through the quasiparticle corrections. Finally, other effects, such as trigonal warping, electron-hole assymetry and energy gaps are discussed in terms of the associated parameters. This work was supported by the Brazilian funding agencies: CAPES, CNPq, FAPERJ and INCT-Nanomateriais de Carbono. It was also supported by NSF grant No. DMR10-1006184 and U.S. DOE under Contract No. DE-AC02-05CH11231.
Ab initio studies on [bmim][PF6]–CO2 mixture and CO2 clusters
Indian Academy of Sciences (India)
Wintec
Ionic liquids; supercritical carbon dioxide; ab initio; molecular dynamics. 1. Introduction .... Several experi- mental and simulation studies have been carried out to .... from an analysis of its electronic polarizability (α), which is a measure of the ...
Energy Technology Data Exchange (ETDEWEB)
Halasyamani, Shiv [Univ. of Houston, TX (United States); Fennie, Craig [Cornell Univ., Ithaca, NY (United States)
2016-11-03
We have focused on the synthesis, characterization, and ab initio theory on multi-functional mixed-metal fluorides. With funding from the DOE, we have successfully synthesized and characterized a variety of mixed metal fluoride materials.
Odell, Anders; Delin, Anna; Johansson, Bö rje; Ulman, Kanchan; Narasimhan, Shobhana; Rungger, Ivan; Sanvito, Stefano
2011-01-01
The influence of the electrode's Fermi surface on the transport properties of a photoswitching molecule is investigated with state-of-the-art ab initio transport methods. We report results for the conducting properties of the two forms
Ab initio assisted process modeling for Si-based nanoelectronic devices
International Nuclear Information System (INIS)
Windl, Wolfgang
2005-01-01
In this paper, we discuss concepts and examples of ab initio calculations assisting physics-based process simulation. We focus on how to determine diffusion and reaction constants, where modern methods such as the nudged elastic band method allow a systematic and reliable search for the minimum energy migration path and barrier. We show that once the saddle point is determined, the underlying harmonic transition state theory also allows to calculate the prefactors. The discussed examples include nitrogen diffusion, boron deactivation and boron interface segregation. Finally, some concepts are discussed for future device technologies such as molecular devices, where the currently prevalent multiscale approach (kinetic parameters used in higher level models like diffusion-reaction or kinetic Monte Carlo modeling) would not be sensible anymore. As an example, we described the ab initio temperature-accelerated dynamics modeling of contact formation in carbon nanotube devices
Nuclear quantum effects in ab initio dynamics: Theory and experiments for lithium imide
Ceriotti, Michele; Miceli, Giacomo; Pietropaolo, Antonino; Colognesi, Daniele; Nale, Angeloclaudio; Catti, Michele; Bernasconi, Marco; Parrinello, Michele
2010-11-01
Owing to their small mass, hydrogen atoms exhibit strong quantum behavior even at room temperature. Including these effects in first-principles calculations is challenging because of the huge computational effort required by conventional techniques. Here we present the first ab initio application of a recently developed stochastic scheme, which allows to approximate nuclear quantum effects inexpensively. The proton momentum distribution of lithium imide, a material of interest for hydrogen storage, was experimentally measured by inelastic neutron-scattering experiments and compared with the outcome of quantum thermostatted ab initio dynamics. We obtain favorable agreement between theory and experiments for this purely quantum-mechanical property, thereby demonstrating that it is possible to improve the modeling of complex hydrogen-containing materials without additional computational effort.
Computational prediction of muon stopping sites using ab initio random structure searching (AIRSS)
Liborio, Leandro; Sturniolo, Simone; Jochym, Dominik
2018-04-01
The stopping site of the muon in a muon-spin relaxation experiment is in general unknown. There are some techniques that can be used to guess the muon stopping site, but they often rely on approximations and are not generally applicable to all cases. In this work, we propose a purely theoretical method to predict muon stopping sites in crystalline materials from first principles. The method is based on a combination of ab initio calculations, random structure searching, and machine learning, and it has successfully predicted the MuT and MuBC stopping sites of muonium in Si, diamond, and Ge, as well as the muonium stopping site in LiF, without any recourse to experimental results. The method makes use of Soprano, a Python library developed to aid ab initio computational crystallography, that was publicly released and contains all the software tools necessary to reproduce our analysis.
Ab Initio Many-Body Calculations Of Nucleon-Nucleus Scattering
Energy Technology Data Exchange (ETDEWEB)
Quaglioni, S; Navratil, P
2008-12-17
We develop a new ab initio many-body approach capable of describing simultaneously both bound and scattering states in light nuclei, by combining the resonating-group method with the use of realistic interactions, and a microscopic and consistent description of the nucleon clusters. This approach preserves translational symmetry and Pauli principle. We outline technical details and present phase shift results for neutron scattering on {sup 3}H, {sup 4}He and {sup 10}Be and proton scattering on {sup 3,4}He, using realistic nucleon-nucleon (NN) potentials. Our A = 4 scattering results are compared to earlier ab initio calculations. We find that the CD-Bonn NN potential in particular provides an excellent description of nucleon-{sup 4}He S-wave phase shifts. We demonstrate that a proper treatment of the coupling to the n-{sup 10}Be continuum is successful in explaining the parity-inverted ground state in {sup 11}Be.
Large-scale ab initio configuration interaction calculations for light nuclei
International Nuclear Information System (INIS)
Maris, Pieter; Potter, Hugh; Vary, James P; Aktulga, H Metin; Ng, Esmond G; Yang Chao; Caprio, Mark A; Çatalyürek, Ümit V; Saule, Erik; Oryspayev, Dossay; Sosonkina, Masha; Zhou Zheng
2012-01-01
In ab-initio Configuration Interaction calculations, the nuclear wavefunction is expanded in Slater determinants of single-nucleon wavefunctions and the many-body Schrodinger equation becomes a large sparse matrix problem. The challenge is to reach numerical convergence to within quantified numerical uncertainties for physical observables using finite truncations of the infinite-dimensional basis space. We discuss strategies for constructing and solving the resulting large sparse matrix eigenvalue problems on current multicore computer architectures. Several of these strategies have been implemented in the code MFDn, a hybrid MPI/OpenMP Fortran code for ab-initio nuclear structure calculations that can scale to 100,000 cores and more. Finally, we will conclude with some recent results for 12 C including emerging collective phenomena such as rotational band structures using SRG evolved chiral N3LO interactions.
Geometry optimization of supersymmetrical molecules in quantum chemical ab-initio calculations
International Nuclear Information System (INIS)
Gruenbichler, H.
1985-01-01
One-dimensional geometry optimizations in ab-initio SCF-calculations are investigated. It is shown, that the well known standard algorithms are sometimes too expensive and can be replaced or accompanied by more recent algorithms. Two alternatives were realized in the molecule calculating program GAUSSIAN 80, basing on the Fibonacci algorithm and Kryachco potential adjustment. The algorithms were compared in terms of accuracy of results, CPU-time used and reliability of the method. The results are presented in various tables, showing the efficiency of the various methods. A survey of the usual model potentials is given and the compatibility with ab-initio data is evaluated. (Author, shortened and translated by A.N.)
Raman spectroscopy, ab-initio model calculations, and conformational, equilibria in ionic liquids
DEFF Research Database (Denmark)
Berg, Rolf W.
2009-01-01
spectroscopy and ab-initio molecular orbital calculations. A discussion is given, based mainly on some recent FT- Raman spectroscopic results on the model ionic liquid system of 1-butyl-3-methyl-imidazolium ([C4C1Im]+X-) salts. The rotational isomerism of the [C4C1Im]+ cation is described: the presence of anti.......3 Brief introduction to ab-initio model calculations .... 312 12.4 Case study on Raman spectroscopy and structure of imidazolium-based ionic liquids ..... 312 12.5 Raman spectra and structure of [C4C1Im]+ liquids ..... 315 12.6 Normal mode analysis and rotational isomerism of the [C4C1Im]+ cation...
International Nuclear Information System (INIS)
Matsushita, Y.; Murakawa, T.; Shimamura, K.; Oishi, M.; Ohyama, T.; Kurita, N.
2015-01-01
The catabolite activator protein (CAP) is one of the regulatory proteins controlling the transcription mechanism of gene. Biochemical experiments elucidated that the complex of CAP with cyclic AMP (cAMP) is indispensable for controlling the mechanism, while previous molecular simulations for the monomer of CAP+cAMP complex revealed the specific interactions between CAP and cAMP. However, the effect of cAMP-binding to CAP on the specific interactions between CAP and DNA is not elucidated at atomic and electronic levels. We here considered the ternary complex of CAP, cAMP and DNA in solvating water molecules and investigated the specific interactions between them at atomic and electronic levels using ab initio molecular simulations based on classical molecular dynamics and ab initio fragment molecular orbital methods. The results highlight the important amino acid residues of CAP for the interactions between CAP and cAMP and between CAP and DNA
Ab initio theoretical calculations of the electronic excitation energies of small water clusters.
Tachikawa, Hiroto; Yabushita, Akihiro; Kawasaki, Masahiro
2011-12-14
A direct ab initio molecular dynamics method has been applied to a water monomer and water clusters (H(2)O)(n) (n = 1-3) to elucidate the effects of zero-point energy (ZPE) vibration on the absorption spectra of water clusters. Static ab initio calculations without ZPE showed that the first electronic transitions of (H(2)O)(n), (1)B(1)←(1)A(1), are blue-shifted as a function of cluster size (n): 7.38 eV (n = 1), 7.58 eV (n = 2) and 8.01 eV (n = 3). The inclusion of the ZPE vibration strongly affects the excitation energies of a water dimer, and a long red-tail appears in the range of 6.42-6.90 eV due to the structural flexibility of a water dimer. The ultraviolet photodissociation of water clusters and water ice surfaces is relevant to these results.
Energy Technology Data Exchange (ETDEWEB)
Matsushita, Y., E-mail: kurita@cs.tut.ac.jp; Murakawa, T., E-mail: kurita@cs.tut.ac.jp; Shimamura, K., E-mail: kurita@cs.tut.ac.jp; Oishi, M., E-mail: kurita@cs.tut.ac.jp; Ohyama, T., E-mail: kurita@cs.tut.ac.jp; Kurita, N., E-mail: kurita@cs.tut.ac.jp [Department of Computer Science and Engineering, Toyohashi University of Technology, Tempaku-cho, Toyohashi, Aichi, 441-8580 (Japan)
2015-02-27
The catabolite activator protein (CAP) is one of the regulatory proteins controlling the transcription mechanism of gene. Biochemical experiments elucidated that the complex of CAP with cyclic AMP (cAMP) is indispensable for controlling the mechanism, while previous molecular simulations for the monomer of CAP+cAMP complex revealed the specific interactions between CAP and cAMP. However, the effect of cAMP-binding to CAP on the specific interactions between CAP and DNA is not elucidated at atomic and electronic levels. We here considered the ternary complex of CAP, cAMP and DNA in solvating water molecules and investigated the specific interactions between them at atomic and electronic levels using ab initio molecular simulations based on classical molecular dynamics and ab initio fragment molecular orbital methods. The results highlight the important amino acid residues of CAP for the interactions between CAP and cAMP and between CAP and DNA.
Atomic defects in monolayer WSe2 tunneling FETs studied by systematic ab initio calculations
Wu, Jixuan; Fan, Zhiqiang; Chen, Jiezhi; Jiang, Xiangwei
2018-05-01
Atomic defects in monolayer WSe2 tunneling FETs (TFETs) are studied through systematic ab initio calculations aiming at performance predictions and enhancements. The effects of various defect positions and different passivation atoms are characterized in WSe2 TFETs by rigorous ab initio quantum transport simulations. It is suggested that the Se vacancy (VSe) defect located in the gate-controlled channel region tends to increase the OFF current (I off), whereas it can be well suppressed by oxygen passivation. It is demonstrated that chlorine (Cl) passivation at the source-side tunneling region can largely suppress I off, leading to an impressively improved on–off ratio (I on/I off) compared with that without any defect. However, it is also observed that randomly positioned atomic defects tend to induce significant fluctuation of the TFET output. Further discussions are made with focus on the performance-variability trade-off for robust circuit design.
Bridging a gap between continuum-QCD and ab initio predictions of hadron observables
Energy Technology Data Exchange (ETDEWEB)
Binosi, Daniele [European Centre for Theoretical Studies in Nuclear Physics and Related Areas - ECT* and Fondazione Bruno Kessler, Villa Tambosi, Strada delle Tabarelle 286, I-38123 Villazzano (Italy); Chang, Lei [CSSM, School of Chemistry and Physics, University of Adelaide, Adelaide, SA 5005 (Australia); Papavassiliou, Joannis [Department of Theoretical Physics and IFIC, University of Valencia and CSIC, E-46100, Valencia (Spain); Roberts, Craig D., E-mail: cdroberts@anl.gov [Physics Division, Argonne National Laboratory, Argonne, IL 60439 (United States)
2015-03-06
Within contemporary hadron physics there are two common methods for determining the momentum-dependence of the interaction between quarks: the top-down approach, which works toward an ab initio computation of the interaction via direct analysis of the gauge-sector gap equations; and the bottom-up scheme, which aims to infer the interaction by fitting data within a well-defined truncation of those equations in the matter sector that are relevant to bound-state properties. We unite these two approaches by demonstrating that the renormalisation-group-invariant running-interaction predicted by contemporary analyses of QCD's gauge sector coincides with that required in order to describe ground-state hadron observables using a nonperturbative truncation of QCD's Dyson–Schwinger equations in the matter sector. This bridges a gap that had lain between nonperturbative continuum-QCD and the ab initio prediction of bound-state properties.
Ab initio study on the thermal properties of the fcc Al3Mg and Al3Sc alloys
International Nuclear Information System (INIS)
Li Donglin; Chen Ping; Yi Jianxiong; Tang Biyu; Peng Liming; Ding Wenjiang
2009-01-01
Ab initio density functional theory (DFT) and density function perturbation theory (DFPT) have been used to investigate the thermal properties of the fcc Al 3 Mg and Al 3 Sc alloys over a wide range of pressure and temperature, in comparison with fcc Al. Phonon dispersions were obtained at equilibrium and strained configurations by density functional perturbation theory. Using the quasiharmonic approximation for the free energy, several thermal quantities of interest, such as the thermal Grueneisen parameter, heat capacity, thermal expansion coefficient and entropy, were calculated as a function of temperature and pressure, and the variation features of these quantities were discussed in detail. This investigation provides useful information for design and applications of technologically relevant Al-based alloys.
International Nuclear Information System (INIS)
Souto, J; Alemany, M M G; Gallego, L J; González, L E; González, D J
2013-01-01
We report an ab initio molecular dynamics study of the static, dynamic and electronic properties of the liquid Bi x Li 1−x alloy, which is a complex binary system with a marked tendency to heterocoordination. The calculated total static structure factors are in good agreement with the available experimental data. The partial dynamic structure factors exhibit side peaks indicative of propagating density fluctuations, and for some concentrations we have found a density fluctuation mode with phase velocity greater than the hydrodynamic sound velocity. We have also evaluated other dynamical properties such as the diffusion coefficients, the shear viscosity and the adiabatic sound velocity. The electronic density of states show that the liquid Bi x Li 1−x alloy has a metallic character, although with strong deviations from the free-electron parabolic curve. The results reported improve the understanding of binary liquid alloys with both fast and slow propagating collective modes. (paper)
Raman spectroscopy, ab-initio model calculations, and conformational, equilibria in ionic liquids
Berg, Rolf W.
2009-01-01
A review of the recent developments in the study and understanding of room temperature ionic liquids are given. An intimate picture of how and why these liquids are not crystals at ambient conditions is attempted, based on evidence from crystallographical results combined with vibrational spectroscopy and ab-initio molecular orbital calculations. A discussion is given, based mainly on some recent FT- Raman spectroscopic results on the model ionic liquid system of 1-butyl-3-methyl-imidazolium ...
Raman Spectroscopy and Ab-Initio Model Calculations on Ionic Liquids:Invited Review
Berg, Rolf W.
2007-01-01
A review of the recent developments in the study and understanding of room temperature ionic liquids are given. An intimate picture of how and why these liquids are not crystals at ambient conditions is attempted, based on evidence from crystallographical results combined with vibrational spectroscopy and ab-initio molecular orbital calculations. A discussion is given, based mainly on some recent FT-Raman spectroscopic results on the model ionic liquid system of 1-butyl-3-methylimidazolium ([...
Ab Initio theory of the Gilbert damping in random ferromagnetic alloys
Czech Academy of Sciences Publication Activity Database
Drchal, Václav; Turek, I.; Kudrnovský, Josef
2017-01-01
Roč. 30, č. 6 (2017), s. 1669-1672 ISSN 1557-1939 R&D Projects: GA ČR GA15-13436S Institutional support: RVO:68378271 Keywords : Gilbert damping * ferromagnetic alloys * ab initio * nonlocal torques Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 1.180, year: 2016
Ab initio calculation of positron distribution, ACAR and lifetime in TTF-TCNQ
International Nuclear Information System (INIS)
Ishibashi, Shoji; Kohyama, Masanori
2000-01-01
We have performed ab initio calculations of positron distribution, ACAR and lifetime in the quasi-one-dimensional organic conductor TTF-TCNQ. The electronic structure is obtained within the LDA, while the positron state is calculated either with the LDA or with the GGA. Except the positron lifetime, differences between the LDA and GGA results are rather small. The obtained results are compared with our previous experiments and calculations.
Pair potentials for alumina from ab initio results on the Al2O3 molecule
International Nuclear Information System (INIS)
Akdeniz, Z.; Cicek, Z.; Tosi, M.P.
2000-08-01
We use results from an ab initio investigation by Chang et al. on energetically low-lying stationary points of the Al 2 O 3 molecule to determine interionic potentials for the Al-O, O-O and Al-Al pairs. Our results are discussed in the perspective of previous studies of the condensed phases of alumina, with special regard to the structure of its molten state. (author)
De Almeida, Wagner B.
2000-01-01
The determination of the molecular structure of molecules is of fundamental importance in chemistry. X-rays and electron diffraction methods constitute in important tools for the elucidation of the molecular structure of systems in the solid state and gas phase, respectively. The use of quantum mechanical molecular orbital ab initio methods offer an alternative for conformational analysis studies. Comparison between theoretical results and those obtained experimentally in the gas phase can ma...
Ab initio quantum-enhanced optical phase estimation using real-time feedback control
DEFF Research Database (Denmark)
Berni, Adriano; Gehring, Tobias; Nielsen, Bo Melholt
2015-01-01
of a quantum-enhanced and fully deterministic ab initio phase estimation protocol based on real-time feedback control. Using robust squeezed states of light combined with a real-time Bayesian adaptive estimation algorithm, we demonstrate deterministic phase estimation with a precision beyond the quantum shot...... noise limit. The demonstrated protocol opens up new opportunities for quantum microscopy, quantum metrology and quantum information processing....
Ab initio excited states calculations of Kr3+, probing semi-empirical modelling
Czech Academy of Sciences Publication Activity Database
Milko, Petr; Kalus, R.; Paidarová, Ivana; Hrušák, Jan; Gadéa, F. X.
-, 23 June (2009), s. 25 ISSN 1432-2234 R&D Projects: GA AV ČR IAA100400501 Institutional research plan: CEZ:AV0Z40400503 Keywords : cluster modelling * rare gas ions * ab initio potential energie * evaporation energies Subject RIV: CF - Physical ; Theoretical Chemistry http://www.springerlink.com/content/100493/?Content+Status=Accepted&sort=p_OnlineDate&sortorder=desc&v=condensed&o=20
Czech Academy of Sciences Publication Activity Database
Hemzalová, P.; Friák, Martin; Šob, Mojmír; Ma, D.; Udyansky, A.; Raabe, D.; Neugebauer, J.
2013-01-01
Roč. 88, č. 17 (2013), Art. no. 174103 ISSN 1098-0121 R&D Projects: GA ČR(CZ) GAP108/12/0311; GA ČR GD106/09/H035; GA AV ČR IAA100100920 Institutional support: RVO:68081723 Keywords : nitrides * ab initio * thermodynamics * elasticity Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.664, year: 2013
Ab initio study of Co and Ni under uniaxial and biaxial loading and in epitaxial overlayers
Czech Academy of Sciences Publication Activity Database
Zelený, Martin; Legut, Dominik; Šob, Mojmír
2008-01-01
Roč. 78, č. 22 (2008), 224105/1-224105/11 ISSN 1098-0121 R&D Projects: GA ČR GD106/05/H008; GA AV ČR IAA1041302; GA MŠk OC 147 Institutional research plan: CEZ:AV0Z20410507 Keywords : ab initio calculations * epitaxial overlayers * uniaxial and biaxial loading Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.322, year: 2008
The onset of ion solvation by ab initio calculations: Comparison of water and methanol
Czech Academy of Sciences Publication Activity Database
Pluhařová, Eva; Jungwirth, Pavel
2008-01-01
Roč. 73, 6/7 (2008), s. 733-744 ISSN 0010-0765 R&D Projects: GA MŠk LC512; GA ČR GA203/07/1006 Institutional research plan: CEZ:AV0Z40550506 Keywords : ions * water cluster * methanol * ab initio calculations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.784, year: 2008
DNA oligonucleotide-cis-platin Binding: Ab initio interpretation of the vibrational spectra
Czech Academy of Sciences Publication Activity Database
Andrushchenko, Valery; Wieser, H.; Bouř, Petr
2007-01-01
Roč. 111, č. 39 (2007), s. 9714-9723 ISSN 1089-5639 R&D Projects: GA AV ČR IAA400550702; GA ČR GA202/07/0732 Institutional research plan: CEZ:AV0Z40550506 Keywords : cis - platin * DNA * vibrational spektra * ab initio Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.918, year: 2007
Calibration of Sn-119 isomer shift using ab initio wave function methods
Kurian, Reshmi; Filatov, Michael
2009-01-01
The isomer shift for the 23.87 keV M1 resonant transition in the Sn-119 nucleus is calibrated with the help of ab initio calculations. The calibration constant alpha(Sn-119) obtained from Hartree-Fock (HF) calculations (alpha(HF)(Sn-119)=(0.081 +/- 0.002)a(0)(-3) mm/s) and from second-order
Advances and applications in the FIREBALL ab initio tight-binding molecular-dynamics formalism
Czech Academy of Sciences Publication Activity Database
Lewis, J.P.; Jelínek, Pavel; Ortega, J.; Demkov, A.A.; Trabada, D.G.; Haycock, B.; Wang, H.; Adams, G.; Tomfohr, J.K.; Abad, E.; Wang, Ho.; Drabold, D.A.
2011-01-01
Roč. 248, č. 9 (2011), 1989-2007 ISSN 0370-1972 R&D Projects: GA ČR GA202/09/0545; GA ČR GAP204/10/0952 Grant - others:AVČR(CZ) M100100904 Institutional research plan: CEZ:AV0Z10100521 Keywords : DFT * ab initio molecular-dynamics Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.316, year: 2011
Thermodynamically constrained correction to ab initio equations of state
International Nuclear Information System (INIS)
French, Martin; Mattsson, Thomas R.
2014-01-01
We show how equations of state generated by density functional theory methods can be augmented to match experimental data without distorting the correct behavior in the high- and low-density limits. The technique is thermodynamically consistent and relies on knowledge of the density and bulk modulus at a reference state and an estimation of the critical density of the liquid phase. We apply the method to four materials representing different classes of solids: carbon, molybdenum, lithium, and lithium fluoride. It is demonstrated that the corrected equations of state for both the liquid and solid phases show a significantly reduced dependence of the exchange-correlation functional used.
International Nuclear Information System (INIS)
Lucas, G.
2006-10-01
The behaviour of silicon carbide under irradiation has been studied using classical and ab initio simulations, focusing on the nano scale elementary processes. First, we have been interested in the calculation of threshold displacement energies, which are difficult to determine both experimentally and theoretically, and also the associated Frenkel pairs. In the framework of this thesis, we have carried out simulations in classical and ab initio molecular dynamics. For the classical approach, two types of potentials have been used: the Tersoff potential, which led to non satisfactory results, and a new one which has been developed during this thesis. This potential allows a better modelling of SiC under irradiation than most of the empirical potentials available for SiC. It is based on the EDIP potential, initially developed to describe defects in silicon, that we have generalized to SiC. For the ab initio approach, the feasibility of the calculations has been validated and average energies of 19 eV for the C and 38 eV for the Si sublattices have been determined, close to the values empirically used in the fusion community. The results obtained with the new potential EDIP are globally in agreement with those values. Finally, the elementary processes involved in the crystal recovery have been studied by calculating the stability of the created Frenkel pairs and determining possible recombination mechanisms with the nudged elastic band method. (author)
Legrain, Fleur; Carrete, Jesús; van Roekeghem, Ambroise; Madsen, Georg K H; Mingo, Natalio
2018-01-18
Machine learning (ML) is increasingly becoming a helpful tool in the search for novel functional compounds. Here we use classification via random forests to predict the stability of half-Heusler (HH) compounds, using only experimentally reported compounds as a training set. Cross-validation yields an excellent agreement between the fraction of compounds classified as stable and the actual fraction of truly stable compounds in the ICSD. The ML model is then employed to screen 71 178 different 1:1:1 compositions, yielding 481 likely stable candidates. The predicted stability of HH compounds from three previous high-throughput ab initio studies is critically analyzed from the perspective of the alternative ML approach. The incomplete consistency among the three separate ab initio studies and between them and the ML predictions suggests that additional factors beyond those considered by ab initio phase stability calculations might be determinant to the stability of the compounds. Such factors can include configurational entropies and quasiharmonic contributions.
Ab initio and empirical studies on the asymmetry of molecular current-voltage characteristics
International Nuclear Information System (INIS)
Hoft, R C; Armstrong, N; Ford, M J; Cortie, M B
2007-01-01
We perform theoretical calculations of the tunnelling current through various small organic molecules sandwiched between gold electrodes by using both a tunnel barrier model and an ab initio transport code. The height of the tunnelling barrier is taken to be the work function of gold as modified by the adsorbed molecule and calculated from an ab initio electronic structure code. The current-voltage characteristics of these molecules are compared. Asymmetry is introduced into the system in two ways: an asymmetric molecule and a gap between the molecule and the right electrode. The latter is a realistic situation in scanning probe experiments. The asymmetry is also realized in the tunnel barrier model by two distinct work functions on the left and right electrodes. Significant asymmetry is observed in the ab initio i(V) curves. The tunnel barrier i(V) curves show much less pronounced asymmetry. The relative sizes of the currents through the molecules are compared. In addition, the performance of the WKB approximation is compared to the results obtained from the exact Schroedinger solution to the tunnelling barrier problem
Dominant Modes in Light Nuclei - Ab Initio View of Emergent Symmetries
International Nuclear Information System (INIS)
Draayer, J P; Dytrych, T; Launey, K D; Dreyfuss, A C; Langr, D
2015-01-01
An innovative symmetry-guided concept is discussed with a focus on emergent symmetry patterns in complex nuclei. In particular, the ab initio symmetry-adapted no-core shell model (SA-NCSM), which capitalizes on exact as well as partial symmetries that underpin the structure of nuclei, provides remarkable insight into how simple symmetry patterns emerge in the many-body nuclear dynamics from first principles. This ab initio view is complemented by a fully microscopic no-core symplectic shell-model framework (NCSpM), which, in turn, informs key features of the primary physics responsible for the emergent phenomena of large deformation and alpha-cluster substructures in studies of the challenging Hoyle state in Carbon-12 and enhanced collectivity in intermediate-mass nuclei. Furthermore, by recognizing that deformed configurations often dominate the low-energy regime, the SA-NCSM provides a strategy for determining the nature of bound states of nuclei in terms of a relatively small subspace of the symmetry-reorganized complete model space, which opens new domains of nuclei for ab initio investigations, namely, the intermediate-mass region, including isotopes of Ne, Mg, and Si
Thermal transport in nanocrystalline Si and SiGe by ab initio based Monte Carlo simulation.
Yang, Lina; Minnich, Austin J
2017-03-14
Nanocrystalline thermoelectric materials based on Si have long been of interest because Si is earth-abundant, inexpensive, and non-toxic. However, a poor understanding of phonon grain boundary scattering and its effect on thermal conductivity has impeded efforts to improve the thermoelectric figure of merit. Here, we report an ab-initio based computational study of thermal transport in nanocrystalline Si-based materials using a variance-reduced Monte Carlo method with the full phonon dispersion and intrinsic lifetimes from first-principles as input. By fitting the transmission profile of grain boundaries, we obtain excellent agreement with experimental thermal conductivity of nanocrystalline Si [Wang et al. Nano Letters 11, 2206 (2011)]. Based on these calculations, we examine phonon transport in nanocrystalline SiGe alloys with ab-initio electron-phonon scattering rates. Our calculations show that low energy phonons still transport substantial amounts of heat in these materials, despite scattering by electron-phonon interactions, due to the high transmission of phonons at grain boundaries, and thus improvements in ZT are still possible by disrupting these modes. This work demonstrates the important insights into phonon transport that can be obtained using ab-initio based Monte Carlo simulations in complex nanostructured materials.
Proper construction of ab initio global potential surfaces with accurate long-range interactions
International Nuclear Information System (INIS)
Ho, Tak-San; Rabitz, Herschel
2000-01-01
An efficient procedure based on the reproducing kernel Hilbert space interpolation method is presented for constructing intermolecular potential energy surfaces (PES) using not only calculated ab initio data but also a priori information on long-range interactions. Explicitly, use of the reciprocal power reproducing kernel on the semiinfinite interval [0,∞) yields a set of exact linear relations between dispersion (multipolar) coefficients and PES data points at finite internuclear separations. Consequently, given a combined set of ab initio data and the values of dispersion (multipolar) coefficients, the potential interpolation problem subject to long-range interaction constraints can be solved to render globally smooth, asymptotically accurate ab initio potential energy surfaces. Very good results have been obtained for the one-dimensional He-He potential curve and the two-dimensional Ne-CO PES. The construction of the Ne-CO PES was facilitated by invoking a new reproducing kernel for the angular coordinate based on the optimally stable and shape-preserving Bernstein basis functions. (c) 2000 American Institute of Physics
Common lines modeling for reference free Ab-initio reconstruction in cryo-EM.
Greenberg, Ido; Shkolnisky, Yoel
2017-11-01
We consider the problem of estimating an unbiased and reference-free ab initio model for non-symmetric molecules from images generated by single-particle cryo-electron microscopy. The proposed algorithm finds the globally optimal assignment of orientations that simultaneously respects all common lines between all images. The contribution of each common line to the estimated orientations is weighted according to a statistical model for common lines' detection errors. The key property of the proposed algorithm is that it finds the global optimum for the orientations given the common lines. In particular, any local optima in the common lines energy landscape do not affect the proposed algorithm. As a result, it is applicable to thousands of images at once, very robust to noise, completely reference free, and not biased towards any initial model. A byproduct of the algorithm is a set of measures that allow to asses the reliability of the obtained ab initio model. We demonstrate the algorithm using class averages from two experimental data sets, resulting in ab initio models with resolutions of 20Å or better, even from class averages consisting of as few as three raw images per class. Copyright © 2017 Elsevier Inc. All rights reserved.
Modeling of nuclear glasses by classical and ab initio molecular dynamics
International Nuclear Information System (INIS)
Ganster, P.
2004-01-01
A calcium aluminosilicate glass of molar composition 67 % SiO 2 - 12 % Al 2 O 3 - 21 % CaO was modelled by classical and ab initio molecular dynamics. The size effect study in classical MD shows that the systems of 100 atoms are more ordered than the larger ones. These effects are mainly due to the 3-body terms in the empirical potentials. Nevertheless, these effects are small and the structures generated are in agreement with experimental data. In such kind of glass, we denote an aluminium avoidance and an excess of non bridging oxygens which can be compensated by tri-coordinated oxygens. When the dynamics of systems of 100 and 200 atoms is followed by ab initio MD, some local arrangements occurs (bond length, angular distributions). Thus, more realistic vibrational properties are obtained in ab initio MD. The modelling of thin films shows that aluminum atoms extend to the most external part of the surface and they are all tri-coordinated. Calcium atoms are set in the sub layer part of the surface and they produce a depolymerization of the network. In classical MD, tri-coordinated aluminium atoms produce an important electric field above the surface. With non bridging oxygens, they constitute attractive sites for single water molecules. (author) [fr
Modelling of nuclear glasses by classical and ab initio molecular dynamics
International Nuclear Information System (INIS)
Ganster, P.
2004-10-01
A calcium aluminosilicate glass of molar composition 67 % SiO 2 - 12 % Al 2 O 3 - 21 % CaO was modelled by classical and ab initio molecular dynamics. The size effect study in classical MD shows that the systems of 100 atoms are more ordered than the larger ones. These effects are mainly due to the 3-body terms in the empirical potentials. Nevertheless, these effects are small and the structures generated are in agreement with experimental data. In such kind of glass, we denote an aluminium avoidance and an excess of non bridging oxygens which can be compensated by tri coordinated oxygens. When the dynamics of systems of 100 and 200 atoms is followed by ab initio MD, some local arrangements occurs (bond length, angular distributions). Thus, more realistic vibrational properties are obtained in ab initio MD. The modelling of thin films shows that aluminium atoms extend to the most external part of the surface and they are all tri-coordinated. Calcium atoms are set in the sub layer part of the surface and they produce a depolymerization of the network. In classical MD, tri-coordinated aluminium atoms produce an important electric field above the surface. With non bridging oxygens, they constitute attractive sites for single water molecules. (author)
Iron -chromium alloys and free surfaces: from ab initio calculations to thermodynamic modeling
International Nuclear Information System (INIS)
Levesque, M.
2010-11-01
Ferritic steels possibly strengthened by oxide dispersion are candidates as structural materials for generation IV and fusion nuclear reactors. Their use is limited by incomplete knowledge of the iron-chromium phase diagram at low temperatures and of the phenomena inducing preferential segregation of one element at grain boundaries or at surfaces. In this context, this work contributes to the multi-scale study of the model iron-chromium alloy and their free surfaces by numerical simulations. This study begins with ab initio calculations of properties related to the mixture of atoms of iron and chromium. We highlight complex dependency of the magnetic moments of the chromium atoms on their local chemical environment. Surface properties are also proving sensitive to magnetism. This is the case of impurity segregation of chromium in iron and of their interactions near the surface. In a second step, we construct a simple energy model for high numerical efficiency. It is based on pair interactions on a rigid lattice to which are given local chemical environment and temperature dependencies. With this model, we reproduce the ab initio results at zero temperature and experimental results at high temperature. We also deduce the solubility limits at all intermediate temperatures with mean field approximations that we compare to Monte Carlo simulations. The last step of our work is to introduce free surfaces in our model. We then study the effect of ab initio calculated bulk and surface properties on surface segregation.Finally, we calculate segregation isotherms. We therefore propose an evolution model of surface composition of iron-chromium alloys as a function of bulk composition. which are given local chemical environment and temperature dependencies. With this model, we reproduce the ab initio results at zero temperature and experimental results at high temperature. We also deduce the solubility limits at all intermediate temperatures with mean field approximations that
Arroyo-Currás, Netzahualcóyotl; Rosas-García, Víctor M; Videa, Marcelo
2016-10-27
Flavonoids are natural products commonly found in the human diet that show antioxidant, anti-inflammatory and anti-hepatotoxic activities. These nutraceutical properties may relate to the electrochemical activity of flavonoids. To increase the understanding of structure-electrochemical activity relations and the inductive effects that OH substituents have on the redox potential of flavonoids, we carried out square-wave voltammetry experiments and ab initio calculations of eight flavonoids selected following a systematic variation in the number of hydroxyl substituents and their location on the flavan backbone: three flavonols, three anthocyanidins, one anthocyanin and the flavonoid backbone flavone. We compared the effect that the number of -OH groups in the ring B of flavan has on the oxidation potential of the flavonoids considered, finding linear correlations for both flavonols and anthocyanidins ( R 2 = 0.98 ). We analyzed the effects that position and number of -OH substituents have on electron density distributions via ab initio quantum chemical calculations. We present direct correlations between structural features and oxidation potentials that provide a deeper insight into the redox chemistry of these molecules.
International Nuclear Information System (INIS)
Izquierdo, J.; Vega, A.; Balbas, L. C.; Sanchez-Portal, Daniel; Junquera, Javier; Artacho, Emilio; Soler, Jose M.; Ordejon, Pablo
2000-01-01
We present a theoretical study of the electronic and magnetic properties of iron systems in different environments: pure iron systems [dimer, bcc bulk, (100) surface, and free-standing iron monolayer], and low-dimensional iron systems deposited on Ag (100) surface (monoatomic linear wires, iron monolayer, planar, and three-dimensional clusters). Electronic and magnetic properties have been calculated using a recently developed total-energy first-principles method based on density-functional theory with numerical atomic orbitals as a basis set for the description of valence electrons and nonlocal pseudopotentials for the atomic core. The Kohn-Sham equations are solved self-consistently within the generalized gradient approximation for the exchange-correlation potential. Tests on the pseudopotential, the basis set, grid spacing, and k sampling are carefully performed. This technique, which has been proved to be very efficient for large nonmagnetic systems, is applied in this paper to calculate electronic and magnetic properties of different iron nanostructures. The results compare well with previous ab initio all-electron calculations and with experimental data. The method predicts the correct trends in the magnetic moments of Fe systems for a great variety of environments and requires a smaller computational effort than other ab initio methods. (c) 2000 The American Physical Society
Energy Technology Data Exchange (ETDEWEB)
Izquierdo, J. [Departamento de Fisica Teorica, Universidad de Valladolid, E-47011 Valladolid, (Spain); Vega, A. [Departamento de Fisica Teorica, Universidad de Valladolid, E-47011 Valladolid, (Spain); Balbas, L. C. [Departamento de Fisica Teorica, Universidad de Valladolid, E-47011 Valladolid, (Spain); Sanchez-Portal, Daniel [Department of Physics and Materials Research Laboratory, University of Illinois, Urbana, Illinois 61801 (United States); Junquera, Javier [Departamento de Fisica de la Materia Condensada, C-III, and Institut Nicolas Cabrera, Universidad Autonoma de Madrid, 28049 Madrid, (Spain); Artacho, Emilio [Departamento de Fisica de la Materia Condensada, C-III, and Institut Nicolas Cabrera, Universidad Autonoma de Madrid, 28049 Madrid, (Spain); Soler, Jose M. [Department of Physics, Harvard University, Cambridge, Massachusetts 02138 (United States); Ordejon, Pablo [Institut de Ciencia de Materials de Barcelona (CSIC), Campus de la U.A.B., Bellaterra, E-08193 Barcelona, (Spain)
2000-05-15
We present a theoretical study of the electronic and magnetic properties of iron systems in different environments: pure iron systems [dimer, bcc bulk, (100) surface, and free-standing iron monolayer], and low-dimensional iron systems deposited on Ag (100) surface (monoatomic linear wires, iron monolayer, planar, and three-dimensional clusters). Electronic and magnetic properties have been calculated using a recently developed total-energy first-principles method based on density-functional theory with numerical atomic orbitals as a basis set for the description of valence electrons and nonlocal pseudopotentials for the atomic core. The Kohn-Sham equations are solved self-consistently within the generalized gradient approximation for the exchange-correlation potential. Tests on the pseudopotential, the basis set, grid spacing, and k sampling are carefully performed. This technique, which has been proved to be very efficient for large nonmagnetic systems, is applied in this paper to calculate electronic and magnetic properties of different iron nanostructures. The results compare well with previous ab initio all-electron calculations and with experimental data. The method predicts the correct trends in the magnetic moments of Fe systems for a great variety of environments and requires a smaller computational effort than other ab initio methods. (c) 2000 The American Physical Society.
Energy Technology Data Exchange (ETDEWEB)
Trevisanutto, Paolo E. [Graphene Research Centre and CA2DM, National University of Singapore, Singapore 117542, Singapore and Singapore Synchrotron Light Source, National University of Singapore, Singapore 117603 (Singapore); Vignale, Giovanni, E-mail: vignaleg@missouri.edu [Department of Physics and Astronomy, University of Missouri, Columbia, Missouri 65211 (United States)
2016-05-28
Ab initio electronic structure calculations of two-dimensional layered structures are typically performed using codes that were developed for three-dimensional structures, which are periodic in all three directions. The introduction of a periodicity in the third direction (perpendicular to the layer) is completely artificial and may lead in some cases to spurious results and to difficulties in treating the action of external fields. In this paper we develop a new approach, which is “native” to quasi-2D materials, making use of basis function that are periodic in the plane, but atomic-like in the perpendicular direction. We show how some of the basic tools of ab initio electronic structure theory — density functional theory, GW approximation and Bethe-Salpeter equation — are implemented in the new basis. We argue that the new approach will be preferable to the conventional one in treating the peculiarities of layered materials, including the long range of the unscreened Coulomb interaction in insulators, and the effects of strain, corrugations, and external fields.
Ab initio study of the adducts of carbon monoxide with alkaline cations
Ferrari, A. M.; Ugliengo, P.; Garrone, E.
1996-09-01
The interaction between CO (either via the C or the O end) and the alkaline cations (Li+, Na+, K+, Rb+, and Cs+) has been studied by means of six ab initio methods, featuring the classical Hartree-Fock, the second order Møller-Plesset treatment of electron correlation, one local density functional and two gradient-corrected methods as well as a quadratic configuration interaction inclusive of single and double substitutions with a noniterative triples contribution to the energy. Basis sets adopted for CO, Li+, Na+, and K+ and the corresponding adducts are of triple-ζ valence quality augmented with a double set of polarization functions (d on C and O; p on the cations). For Rb+ and Cs+, Hay-Wadt effective core potential basis sets have been adopted. Calculated features are the binding energy, the frequency and intensity of the CO stretch, the bending mode, the cation-carbon (or oxygen) stretch, and the equilibrium geometry. Gradient-corrected density functional methods yield results nearly as good as the most expensive correlated method based on configurations interaction. A number of correlations are established among the observables. The role of electrostatics in the interaction is analyzed both by studying the molecular electrostatic potential of CO and by replacing the cation with a proton in the same position. Binding through the C end is invariably preferred, though, with increasing size of the cation, binding through the O end become progressively less unfavored. Experimental data concerning alkaline-cation substituted zeolites are compared with computational results, and an overall agreement is observed.
International Nuclear Information System (INIS)
Mo, Shang-Di; Ching, W. Y.
2001-01-01
Ab initio calculation of the XANSE/ELNES spectra for α quartz and stishovite were carried out using a large-supercell approach that includes the electron - core - hole interaction. Excellent agreements with experimental spectra were obtained for Si - K, Si - L 2,3 , and O - K edges. The usual interpretation using orbital-resolved local density of states in the conduction band is unsatisfactory. [copyright] 2001 American Institute of Physics
Ab Initio Studies of Shock-Induced Chemical Reactions of Inter-Metallics
Zaharieva, Roussislava; Hanagud, Sathya
2009-06-01
Shock-induced and shock assisted chemical reactions of intermetallic mixtures are studied by many researchers, using both experimental and theoretical techniques. The theoretical studies are primarily at continuum scales. The model frameworks include mixture theories and meso-scale models of grains of porous mixtures. The reaction models vary from equilibrium thermodynamic model to several non-equilibrium thermodynamic models. The shock-effects are primarily studied using appropriate conservation equations and numerical techniques to integrate the equations. All these models require material constants from experiments and estimates of transition states. Thus, the objective of this paper is to present studies based on ab initio techniques. The ab inito studies, to date, use ab inito molecular dynamics. This paper presents a study that uses shock pressures, and associated temperatures as starting variables. Then intermetallic mixtures are modeled as slabs. The required shock stresses are created by straining the lattice. Then, ab initio binding energy calculations are used to examine the stability of the reactions. Binding energies are obtained for different strain components super imposed on uniform compression and finite temperatures. Then, vibrational frequencies and nudge elastic band techniques are used to study reactivity and transition states. Examples include Ni and Al.
Ab-initio theoretical predictions of structure properties of semiconductors
International Nuclear Information System (INIS)
Rodriguez, C.O.; Peltzer y Blanca, E.L.; Cappannini, O.M.
1983-01-01
In this paper, calculations of the total energies and related structural properties of Si, GaP and C are presented showing good agreement with experimental values. The total energy is calculated within the local-density functional formalism using first principles non-local pseudopotentials. (A.C.A.S.) [pt
Ultra strong polymer fibers : Ab initio calculations on polyethylene
Hageman, J.C.L.; Groot, R.A. de; Meier, Robert J.
1998-01-01
The Car-Parrinello technique is used to study the electronic structure of orthorhombic polyethylene as well as the elastic modulus. The theoretical band structure and density of states are in very good agreement with experiments. The best experimentally realized elastic modulus is better than 86% of
Statistical properties of the dense hydrogen plasma: An ab initio molecular dynamics investigation
International Nuclear Information System (INIS)
Kohanoff, J.; Hansen, J.P.
1995-12-01
The hydrogen plasma is studied in the very high density (atomic and metallic) regime by extensive ab initio Molecular Dynamics simulations. Protons are treated classically, and electrons in the Born-Oppenheimer framework, within the local density approximation (LDA). Densities and temperatures studied fall within the strong coupling regime of the protons. We address the question of the validity of linear screening, and we find it to yield a reasonably good description up to r s approx. 0.5, but already too crude for r s = 1 (with r s = (3/4πρ) 1/3 the ion sphere radius). Finite-size and Brillouin zone sampling effects in metallic systems are studied and shown to be very delicate also in the fluid (liquid metal) phase. We analyse the low-temperature phase diagram and the melting transition. A remarkably fast decrease of the melting temperature with decreasing density is found, up to a point when it becomes comparable to the Fermi temperature of the protons. The possible vicinity of a triple point bcc-hcp(fcc)- liquid is discussed in the region of r s approx. 1.1 and T approx. 100 - 200K. The fluid phase is studied in detail for several temperatures. Proton-electron correlations show a weak temperature dependence, and proton-proton correlations exhibit a well-defined first coordination shell, thus characterizing fluid H in this regime as an atomic liquid. Diffusion coefficients are compared to the values for the one-component plasma. Vibrational densities of states (VDOS) show a plasmon renormalization due to electron screening, and the presence of a plasmon-coupled single-particle mode up to very high temperatures. Collective modes are studied through dynamical structure factors. In close relationship with the VDOS, the simulations reveal the remarkable persistent of a weakly damped high-frequency ion acoustic mode, even under conditions of strong electron screening. The possibility of using this observation as a diagnostic for the plasma phase transition to the
Energy Technology Data Exchange (ETDEWEB)
Orlando, Roberto, E-mail: roberto.orlando@unito.it; Erba, Alessandro; Dovesi, Roberto [Dipartimento di Chimica, Università di Torino and NIS, Nanostructured Interfaces and Surfaces, Centre of Excellence, Via P. Giuria 7, 10125 Torino (Italy); De La Pierre, Marco [Dipartimento di Chimica, Università di Torino and NIS, Nanostructured Interfaces and Surfaces, Centre of Excellence, Via P. Giuria 7, 10125 Torino (Italy); Nanochemistry Research Institute, Department of Chemistry, Curtin University, GPO Box U1987, Perth, WA 6845 (Australia); Zicovich-Wilson, Claudio M. [Facultad de Ciencias, Universidad Autónoma del Estado de Morelos, Av. Universidad, 1001, Col. Chamilpa, 62209 Cuernavaca (Morelos) (Mexico)
2014-09-14
Use of symmetry can dramatically reduce the computational cost (running time and memory allocation) of self-consistent-field ab initio calculations for molecular and crystalline systems. Crucial for running time is symmetry exploitation in the evaluation of one- and two-electron integrals, diagonalization of the Fock matrix at selected points in reciprocal space, reconstruction of the density matrix. As regards memory allocation, full square matrices (overlap, Fock, and density) in the Atomic Orbital (AO) basis are avoided and a direct transformation from the packed AO to the symmetry adapted crystalline orbital basis is performed, so that the largest matrix to be handled has the size of the largest sub-block in the latter basis. Quantitative examples, referring to the implementation in the CRYSTAL code, are given for high symmetry families of compounds such as carbon fullerenes and nanotubes.
Ab Initio Description of Disordered Sr1−xKxFe2As2 Using the Coherent Potential Approximation
Pulikkotil, J. J.
2010-04-29
The electronic structure of disordered Sr1−xKxFe2As2 is studied by ab initio density functional theory. As no superstructure and/or atomic short range ordering is reported for Sr1−xKxFe2As2, the coherent potential approximation can be used to describe the effects of chemical disorder. We find clear deviations from the rigid band model characteristics. Nonmagnetic calculations show an enhancement of the density of states at the Fermi energy in the range 0.4≤x≤0.65, which coincides with the region where experiments observe an enhanced superconducting transition temperature, and antiferromagnetic calculations indicate a significant renormalization of states at Fermi energy. Analyzing the distribution of the Fe 3d states over the range 0≤x≤1 we propose an effective three band model.
An ab initio study of the structure and dynamics of bulk liquid Cd and its liquid-vapor interface
International Nuclear Information System (INIS)
Calderín, L; González, L E; González, D J
2013-01-01
Several static and dynamic properties of bulk liquid Cd at a thermodynamic state near its triple point have been calculated by means of ab initio molecular dynamics simulations. The calculated static structure shows a very good agreement with the available experimental data. The dynamical structure reveals collective density excitations with an associated dispersion relation which points to a small positive dispersion. Results are also reported for several transport coefficients. Additional simulations have also been performed at a slightly higher temperature in order to study the structure of the free liquid surface. The ionic density profile shows an oscillatory behavior with two different wavelengths, as the spacing between the outer and first inner layer is different from that between the other inner layers. The calculated reflectivity shows a marked maximum whose origin is related to the surface layering, along with a shoulder located at a much smaller wavevector transfer.
Plasmon Lifetime in K: A Case Study of Correlated Electrons in Solids Amenable to Ab Initio Theory
International Nuclear Information System (INIS)
Ku, W.; Eguiluz, A.G.
1999-01-01
We solve the puzzle posed by the anomalous dispersion of the plasmon linewidth in K via all-electron density-response calculations, performed within the framework of time-dependent density-functional theory. The key damping mechanism is shown to be decay into particle-hole pairs involving empty states of d symmetry. While the effect of many-particle correlations is small, the correlations built into the 'final-state' d bands play an important, and novel, role related to the phase-space complexity introduced by these flat bands. Our case study of plasmon lifetime in K illustrates the importance of ab initio paradigms for the study of excitations in correlated-electron systems. copyright 1999 The American Physical Society
Bano, Amreen; Gaur, N. K.
2018-05-01
Ab-initio calculations are carried out to study the electronic and chemical bonding properties of Intermetallic full Heusler compound Pd2HfIn which crystallizes in F-43m structure. All calculations are performed by using density functional theory (DFT) based code Quantum Espresso. Generalized gradient approximations (GGA) of Perdew- Burke- Ernzerhof (PBE) have been adopted for exchange-correlation potential. Calculated electronic band structure reveals the metallic character of the compound. From partial density of states (PDoS), we found the presence of relatively high intensity electronic states of 4d-Pd atom at Fermi level. We have found a pseudo-gap just abouve the Fermi level and N(E) at Fermi level is observed to be 0.8 states/eV, these finding indicates the existence of superconducting character in Pd2HfIn.
Energy Technology Data Exchange (ETDEWEB)
Taioli, Simone [Interdisciplinary Laboratory for Computational Science, FBK-Center for Materials and Microsystems and University of Trento, Trento (Italy); Department of Physics, University of Trento, Trento (Italy); Istituto Nazionale di Fisica Nucleare, Sezione di Perugia (Italy); Department of Chemistry, University of Bologna, Bologna (Italy); Garberoglio, Giovanni [Interdisciplinary Laboratory for Computational Science, FBK-Center for Materials and Microsystems and University of Trento, Trento (Italy); Simonucci, Stefano [Interdisciplinary Laboratory for Computational Science, FBK-Center for Materials and Microsystems and University of Trento, Trento (Italy); Istituto Nazionale di Fisica Nucleare, Sezione di Perugia (Italy); Department of Physics, University of Camerino, Camerino (Italy); Beccara, Silvio a [Interdisciplinary Laboratory for Computational Science, FBK-Center for Materials and Microsystems and University of Trento, Trento (Italy); Department of Physics, University of Trento, Trento (Italy); Aversa, Lucrezia [Institute of Materials for Electronics and Magnetism, IMEM-CNR, Trento (Italy); Nardi, Marco [Institute of Materials for Electronics and Magnetism, IMEM-CNR, Trento (Italy); Institut fuer Physik, Humboldt-Universitaet zu Berlin, Berlin (Germany); Verucchi, Roberto [Institute of Materials for Electronics and Magnetism, FBK-CNR, Trento (Italy); Iannotta, Salvatore [Institute of Materials for Electronics and Magnetism, IMEM-CNR, Parma (Italy); Dapor, Maurizio [Interdisciplinary Laboratory for Computational Science, FBK-Center for Materials and Microsystems and University of Trento, Trento (Italy); Department of Materials Engineering and Industrial Technologies, University of Trento, Trento (Italy); Istituto Nazionale di Fisica Nucleare, Sezione di Padova (Italy); and others
2013-01-28
In this work, we investigate the processes leading to the room-temperature growth of silicon carbide thin films by supersonic molecular beam epitaxy technique. We present experimental data showing that the collision of fullerene on a silicon surface induces strong chemical-physical perturbations and, for sufficient velocity, disruption of molecular bonds, and cage breaking with formation of nanostructures with different stoichiometric character. We show that in these out-of-equilibrium conditions, it is necessary to go beyond the standard implementations of density functional theory, as ab initio methods based on the Born-Oppenheimer approximation fail to capture the excited-state dynamics. In particular, we analyse the Si-C{sub 60} collision within the non-adiabatic nuclear dynamics framework, where stochastic hops occur between adiabatic surfaces calculated with time-dependent density functional theory. This theoretical description of the C{sub 60} impact on the Si surface is in good agreement with our experimental findings.
Taşal, Erol; Kumalar, Mustafa
2012-09-01
In this work, the experimental and theoretical spectra of 5-chloro-3-(2-(4-methylpiperazin-1-yl)-2-oxoethyl)benzo[d]thiazol-2(3H)-one molecule (abbreviated as 5CMOT) are studied. The molecular geometry and vibrational frequencies are calculated in the ground state of molecule using ab initio Hartree-Fock (HF) and Density Function Theory (DFT) methods with 6-311++G(d,p), 6-31G++(d,p), 6-31G(d,p), 6-31G(d) and 6-31G basis sets. Three staggered stable conformers were observed on the torsional potential energy surfaces. The complete assignments were performed on the basis of the total energy distribution (TED) of the vibrational modes calculated. The comparison of the theoretical and experimental geometries of the title compound indicated that the X-ray parameters fairly well agree with the theoretically obtained values for the most stable conformer. The theoretical results showed an excellent agreement with the experimental values. The calculated HOMO and LUMO energies show that the charge transfer occurs within the molecule. Copyright © 2012 Elsevier B.V. All rights reserved.
Ab initio charge analysis of pure and hydrogenated perovskites
DEFF Research Database (Denmark)
Bork, Nicolai Christian; Bonanos, Nikolaos; Rossmeisl, Jan
2011-01-01
We present a density functional theory based Bader analysis on the charge distribution in pure and hydrogenated SrTiO3. We find the hydrogen defect carries a +0.56e charge and the OH defect carrying a +0.50e charge compared to the host oxygen. Calculations on BaNbO3, CaTiO3, and SrZrO3 support th...
Ab initio Investigation of Helium in Vanadium Oxide Nanoclusters
Danielson, Thomas; Tea, Eric; Hin, Celine
Nanostructured ferritic alloys (NFAs) are strong candidate materials for the next generation of fission reactors and future fusion reactors. They are characterized by a large number density of oxide nanoclusters dispersed throughout a BCC iron matrix, where current oxide nanoclusters are primarily comprised of Y-Ti-O compounds. The oxide nanoclusters provide the alloy with high resistance to neutron irradiation, high yield strength and high creep strength at the elevated temperatures of a reactor environment. In addition, the oxide nanoclusters serve as trapping sites for transmutation product helium providing substantially increased resistance to catastrophic cracking and embrittlement. Although the mechanical properties and radiation resistance of the existing NFAs is promising, the problem of forming large scale reactor components continues to present a formidable challenge due to the high hardness and unpredictable fracture behavior of the alloys. An alternative alloy has been previously proposed and fabricated where vanadium is added in order to form vanadium oxide nanoclusters that serve as deflection sites for crack propagation. Although experiments have shown evidence that the fracture behavior of the alloys is improved, it is unknown whether or not the vanadium oxide nanoclusters are effective trapping sites for helium. We present results obtained using density functional theory investigating the thermodynamic stability of helium with the vanadium oxide matrix to make a comparison of trapping effectiveness to traditional Y-Ti-O compounds.
Ab-initio study of surface segregation in aluminum alloys
Energy Technology Data Exchange (ETDEWEB)
Qin, Yifa, E-mail: yfqin10s@imr.ac.cn; Wang, Shaoqing
2017-03-31
Highlights: • A thorough study of surface segregation energies of 41 elements in Al is performed. • Segregation energies vary periodically with the atomic numbers of impurities. • 41 elements are classified into 3 groups according to the signs of segregation energies. • The results are validated by the surface/total concentration ratio in Al alloys. - Abstract: We have calculated surface segregation energies of 41 impurities by means of density functional theory calculations. An interesting periodical variation tendency was found for surface segregation energies derived. For the majority of main group elements, segregation energies are negative which means solute elements enrichment at Al surface is energetically more favorable than uniformly dissolution. Half of transition elements possess positive segregation energies and the energies are sensitive to surface crystallographic orientations. A strong correlation is found between the segregation energies at the Al surface and the surface energ of solute elements.
Amino acids interacting with defected carbon nanotubes: ab initio calculations
Directory of Open Access Journals (Sweden)
M. Darvish Ganji
2016-09-01
Full Text Available The adsorption of a number of amino acids on a defected single-walled carbon nanotube (SWCNT is investigated by using the density-functional theory (DFT calculations. The adsorption energies and equilibrium distances are calculated for various configurations such as amino acid attaching to defect sites heptagon, pentagon and hexagon in defective tube and also for several molecular orientations with respect to the nanotube surface. The results showed that amino acids prefer to be physisorbed on the outer surface of the defected nanotube with different interaction strength following the hierarchy histidine > glycine > phenylalanine > cysteine. Comparing these findings with those obtained for perfect SWCNTs reveals that the adsorption energy of the amino acids increase for adsorption onto defected CNTs. The adsorption nature has also been evaluated by means of electronics structures analysis within the Mulliken population and DOS spectra for the interacting entities.
Ab initio theory of magnetic interactions at surfaces
International Nuclear Information System (INIS)
Sousa, C; Graaf, C de; Lopez, N; Harrison, N M; Illas, F
2004-01-01
The low to high spin energy transition of Ni adsorbed on regular and defective sites of MgO(100) and the relative strengths of bulk and surface magnetic coupling constants of first row transition metal oxides (MnO, FeO, CoO, NiO and CuO) are taken as examples to illustrate some deficiencies of density functional theory (DFT). For these ionic systems a cluster/periodic comparison within the same computational method (either DFT or Hartree-Fock) is used to establish that embedded cluster models provide an adequate representation. The cluster model approach is then used to obtain accurate values for the magnetic properties of interest by using explicitly correlated wavefunction methods which handle the electronic open shell rigorously as spin eigenfunctions
Ab initio theory of magnetic interactions at surfaces
Energy Technology Data Exchange (ETDEWEB)
Sousa, C [Departament de Quimica Fisica i Centre de Recerca en Quimica Teorica, Universitat de Barcelona i Parc Cientific de Barcelona, C/ MartI i Franques 1, E-08028 Barcelona (Spain); Graaf, C de [Departament de Quimica Fisica i Inorganica, Universitat Rovira i Virgili, P. Imperial Tarraco 1, E-43005 Tarragona (Spain); Lopez, N [Departament de Quimica Fisica i Centre de Recerca en Quimica Teorica, Universitat de Barcelona i Parc Cientific de Barcelona, C/ Marti i Franques 1, E-08028 Barcelona (Spain); Harrison, N M [Department of Chemistry, Imperial College of Science, Technology and Medicine, London SW7 2AY (United Kingdom); Illas, F [Departament de Quimica Fisica i Centre de Recerca en Quimica Teorica, Universitat de Barcelona i Parc Cientific de Barcelona, C/ Marti i Franques 1, E-08028 Barcelona (Spain)
2004-07-07
The low to high spin energy transition of Ni adsorbed on regular and defective sites of MgO(100) and the relative strengths of bulk and surface magnetic coupling constants of first row transition metal oxides (MnO, FeO, CoO, NiO and CuO) are taken as examples to illustrate some deficiencies of density functional theory (DFT). For these ionic systems a cluster/periodic comparison within the same computational method (either DFT or Hartree-Fock) is used to establish that embedded cluster models provide an adequate representation. The cluster model approach is then used to obtain accurate values for the magnetic properties of interest by using explicitly correlated wavefunction methods which handle the electronic open shell rigorously as spin eigenfunctions.
Thermodynamic properties of titanium from ab initio calculations
International Nuclear Information System (INIS)
Argaman, Uri; Makov, Guy; Eidelstein, Eitan; Levy, Ohad
2015-01-01
The lattice parameters, lattice stability and phonon dispersion curves of five proposed phases of Ti: α, β, γ, δ and ω are investigated within density functional theory (DFT). It is found that the sequence of high pressure phases at zero temperature is α→ω→γ→δ→β with the δ and β phases becoming degenerate at high pressure. However, the γ phase may be unstable as is reflected by the existence of imaginary values in the phonon spectra. The results of the DFT calculations are employed to estimate the entropy and free energies of the α and ω phases. It is found that converged phonon calculations lead to an entropy difference which is much smaller than previous estimates, and a much steeper α−ω phase transition line. (paper)
An Automated Ab Initio Framework for Identifying New Ferroelectrics
Smidt, Tess; Reyes-Lillo, Sebastian E.; Jain, Anubhav; Neaton, Jeffrey B.
Ferroelectric materials have a wide-range of technological applications including non-volatile RAM and optoelectronics. In this work, we present an automated first-principles search for ferroelectrics. We integrate density functional theory, crystal structure databases, symmetry tools, workflow software, and a custom analysis toolkit to build a library of known and proposed ferroelectrics. We screen thousands of candidates using symmetry relations between nonpolar and polar structure pairs. We use two search strategies 1) polar-nonpolar pairs with the same composition and 2) polar-nonpolar structure type pairs. Results are automatically parsed, stored in a database, and accessible via a web interface showing distortion animations and plots of polarization and total energy as a function of distortion. We benchmark our results against experimental data, present new ferroelectric candidates found through our search, and discuss future work on expanding this search methodology to other material classes such as anti-ferroelectrics and multiferroics.
Ab initio calculation of chromium oxide containing Ti dopant
International Nuclear Information System (INIS)
Maldonado, Frank; Novillo, Corina; Stashans, Arvids
2012-01-01
Highlights: ► Microstructure changes in chromium oxide due to the Ti doping. ► Discovery of magnetism in Ti-doped α-Cr 2 O 3 crystal. ► Explanation of the origin of n-type electrical conductivity. ► Detailed analysis of electronic properties and density of states. ► As to authors’ knowledge, Ti-doped crystal is studied for the first time by the DFT. - Abstract: First-principles computations based on the density functional theory within the generalised gradient approximation and introduced intra-atomic interaction term for strongly correlated electrons (DFT + U method) has been used in this work. Ti impurity doping in the α-Cr 2 O 3 crystal has been carried out considering single defect model within the periodic crystalline structure. Atomic displacements, Bader charges on atoms have been computed showing that Ti dopant converts the chemical bonding in its neighbourhood into more ionic one. The defect-local microstructure is such as there exist general tendency of atomic rearrangements away with respect to the Ti imperfection. It is found that defect incorporation produces some local changes upon the band structure of the material and also induces a metallic state. That implies n-type electrical conductivity in the Ti-doped α-Cr 2 O 3 crystals and relates our work directly to a number of experimental studies in this area. Our results provide evidence over change in magnetic moments in the vicinity of defect, which means that the chromium oxide doped with Ti impurity might not act as an antiferromagnetic substance.
Ab initio calculation of chromium oxide containing Ti dopant
Energy Technology Data Exchange (ETDEWEB)
Maldonado, Frank [Grupo de Fisicoquimica de Materiales, Universidad Tecnica Particular de Loja, Apartado 11-01-608, Loja (Ecuador); Novillo, Corina [Escuela de Ingenieria Quimica, Universidad Tecnica Particular de Loja, Apartado 11-01-608, Loja (Ecuador); Stashans, Arvids, E-mail: arvids@utpl.edu.ec [Grupo de Fisicoquimica de Materiales, Universidad Tecnica Particular de Loja, Apartado 11-01-608, Loja (Ecuador)
2012-01-17
Highlights: Black-Right-Pointing-Pointer Microstructure changes in chromium oxide due to the Ti doping. Black-Right-Pointing-Pointer Discovery of magnetism in Ti-doped {alpha}-Cr{sub 2}O{sub 3} crystal. Black-Right-Pointing-Pointer Explanation of the origin of n-type electrical conductivity. Black-Right-Pointing-Pointer Detailed analysis of electronic properties and density of states. Black-Right-Pointing-Pointer As to authors' knowledge, Ti-doped crystal is studied for the first time by the DFT. - Abstract: First-principles computations based on the density functional theory within the generalised gradient approximation and introduced intra-atomic interaction term for strongly correlated electrons (DFT + U method) has been used in this work. Ti impurity doping in the {alpha}-Cr{sub 2}O{sub 3} crystal has been carried out considering single defect model within the periodic crystalline structure. Atomic displacements, Bader charges on atoms have been computed showing that Ti dopant converts the chemical bonding in its neighbourhood into more ionic one. The defect-local microstructure is such as there exist general tendency of atomic rearrangements away with respect to the Ti imperfection. It is found that defect incorporation produces some local changes upon the band structure of the material and also induces a metallic state. That implies n-type electrical conductivity in the Ti-doped {alpha}-Cr{sub 2}O{sub 3} crystals and relates our work directly to a number of experimental studies in this area. Our results provide evidence over change in magnetic moments in the vicinity of defect, which means that the chromium oxide doped with Ti impurity might not act as an antiferromagnetic substance.
A comparative ab initio study of Br2*- and Br2 water clusters.
Pathak, A K; Mukherjee, T; Maity, D K
2006-01-14
The work presents ab initio results on structure and electronic properties of Br2*-.nH2O(n=1-10) and Br2.nH2O(n=1-8) hydrated clusters to study the effects of an excess electron on the microhydration of the halide dimer. A nonlocal density functional, namely, Becke's half-and-half hybrid exchange-correlation functional is found to perform well on the present systems with a split valence 6-31++G(d,p) basis function. Geometry optimizations for all the clusters are carried out with several initial guess structures and without imposing any symmetry restriction. Br2*-.nH2O clusters prefer to have symmetrical double hydrogen-bonding structures. Results on Br2.nH2O(n>or=2) cluster show that the O atom of one H2O is oriented towards one Br atom and the H atom of another H2O is directed to other Br atom making Br2 to exist as Br+-Br- entity in the cluster. The binding and solvation energies are calculated for the Br2*-.nH2O and Br2.nH2O clusters. Calculations of the vibrational frequencies show that the formation of Br2*- and Br2 water clusters induces significant shifts from the normal modes of isolated water. Excited-state calculations are carried out on Br2*-.nH2O clusters following configuration interaction with single electron excitation procedure and UV-VIS absorption profiles are simulated. There is an excellent agreement between the present theoretical UV-VIS spectra of Br2*-.10H2O cluster and the reported transient optical spectra for Br2*- in aqueous solution.
Ab initio and matrix isolation study of the acetylene-furan dimer
International Nuclear Information System (INIS)
Sanchez-Garcia, Elsa; Mardyukov, Artur; Tekin, Adem; Crespo-Otero, Rachel; Montero, Luis A.; Sander, Wolfram; Jansen, Georg
2008-01-01
Five acetylene-furan dimer structures are identified using ab initio calculations at the second-order Moller-Plesset (MP2) level of theory. The structures are stabilized by two basic types of intermolecular interactions: the CH...O and the CH...π interaction. The CH...π interaction appears in two variants, depending on which molecule provides the hydrogen atom and which molecule the π system. The MP2 results indicate that the CH...π interaction between one of the hydrogen atoms of acetylene and the π system of furan as found in structure A is the strongest interaction, followed by the in-plane CH...O interaction in the second most stable acetylene-furan dimer structure B. A matrix isolation study shows the acetylene-furan dimer to exist in an argon matrix, but likely rather as structure B than as A. High level coupled cluster calculations with up to triple excitations (CCSD(T)) yield the interaction energy of structure A as about -2.4 kcal/mol in the complete basis set limit and find structure B to be nearly isoenergetic with -2.3 kcal/mol. This is confirmed in calculations employing the density functional theory combined with symmetry adapted intermolecular perturbation theory (DFT-SAPT) approach yielding interaction energies of -2.3 and -2.0 kcal/mol for A and B, respectively. DFT-SAPT also helps to understand the importance of the electrostatic, induction and dispersion interaction energies and their respective exchange counterparts for the stability of the various acetylene-furan dimer structures. The CH...O and CH...π interactions are furthermore analyzed with the help of the atoms in molecules (AIM) theory
Absolute acidity of clay edge sites from ab-initio simulations
Tazi, Sami; Rotenberg, Benjamin; Salanne, Mathieu; Sprik, Michiel; Sulpizi, Marialore
2012-10-01
We provide a microscopic understanding of the solvation structure and reactivity of the edges of neutral clays. In particular we address the tendency to deprotonation of the different reactive groups on the (0 1 0) face of pyrophyllite. Such information cannot be inferred directly from titration experiments, which do not discriminate between different sites and whose interpretation resorts to macroscopic models. The determination of the corresponding pKa then usually relies on bond valence models, sometimes improved by incorporating some structural information from ab-initio simulations. Here we use density functional theory based molecular dynamics simulations, combined with thermodynamic integration, to compute the free energy of the reactions of water with the different surface groups, leading to a deprotonated site and an aqueous hydronium ion. Our approach consistently describes the clay and water sides of the interface and includes naturally electronic polarization effects. It also allows to investigate the structure and solvation of all sites separately. We find that the most acidic group is SiOH, due to its ability to establish strong hydrogen bonds with adsorbed water, as it also happens on the quartz and amorphous silica surfaces. The acidity constant of AlOH2 is only 1 pKa unit larger. Finally, the pKa of AlOH is outside the possible range in water and this site should not deprotonate in aqueous solution. We show that the solvation of surface sites and hence their acidity is strongly affected by the proximity of other sites, in particular for AlOH and AlOH2 which share the same Al. We discuss the implications of our findings on the applicability of bond valence models to predict the acidity of edge sites of clays.
International Nuclear Information System (INIS)
Demchenko, I.N.; Chernyshova, M.; Stolte, W.C.; Speaks, D.T.; Derkachova, A.
2012-01-01
The electronic structure of cadmium dichloride has been studied by X-ray absorption near edge structure (XANES) and, for the first time, by resonant inelastic X-ray scattering (RIXS) at the Cl K edge. Good agreement was obtained between the non-resonant X-ray emission (XES) along with XANES experimental spectra and the calculated Cl 3p local partial density of states (DOS). The calculations were performed using the full-potential linearized-augmented-plane-wave with the local orbitals (FP-(L)APW l o) method utilized in the WIEN2k code. It was shown that the position of the RIXS band in CdCl 2 follows a linear dispersion according to the Raman–Stokes law if the excitation energy is tuned below the absorption threshold. The situation changes for core excitation above the photoabsorption threshold where the dispersion relation is split into two branches. The position of the resonant contribution does not depend on the excitation energy, while the excitonic sideband follows the Raman–Stoke law. Combined XANES and RIXS measurements compared to calculated band structure allowed us to determine the direct band gap of CdCl 2 to be at 5.7 ± 0.05 eV. -- Highlights: ► XANES at the K edge of Cl and related emission KV band interpreted within the ab initio DFT formalism. ► Two dominant contributions observed in RIXS data: the resonant and the excitonic ones. ► The dispersion relation below the absorption threshold follows Raman–Stokes law. ► Dispersion above the threshold splits into two qualitatively different relations. ► Overlapping of XAS spectrum with RIXS one makes possible to estimate direct band gap value to be 5.7 eV.
Ab Initio Prediction of Piezoelectricity in Two-Dimensional Materials.
Blonsky, Michael N; Zhuang, Houlong L; Singh, Arunima K; Hennig, Richard G
2015-10-27
Two-dimensional (2D) materials present many unique materials concepts, including material properties that sometimes differ dramatically from those of their bulk counterparts. One of these properties, piezoelectricity, is important for micro- and nanoelectromechanical systems applications. Using symmetry analysis, we determine the independent piezoelectric coefficients for four groups of predicted and synthesized 2D materials. We calculate with density-functional perturbation theory the stiffness and piezoelectric tensors of these materials. We determine the in-plane piezoelectric coefficient d11 for 37 materials within the families of 2D metal dichalcogenides, metal oxides, and III-V semiconductor materials. A majority of the structures, including CrSe2, CrTe2, CaO, CdO, ZnO, and InN, have d11 coefficients greater than 5 pm/V, a typical value for bulk piezoelectric materials. Our symmetry analysis shows that buckled 2D materials exhibit an out-of-plane coefficient d31. We find that d31 for 8 III-V semiconductors ranges from 0.02 to 0.6 pm/V. From statistical analysis, we identify correlations between the piezoelectric coefficients and the electronic and structural properties of the 2D materials that elucidate the origin of the piezoelectricity. Among the 37 2D materials, CdO, ZnO, and CrTe2 stand out for their combination of large piezoelectric coefficient and low formation energy and are recommended for experimental exploration.
Defective pyrite (100) surface: An ab initio study
International Nuclear Information System (INIS)
Stirling, Andras; Bernasconi, Marco; Parrinello, Michele
2007-01-01
The structural and electronic properties of sulfur monomeric defects at the FeS 2 (100) surface have been studied by periodic density-functional calculations. We have shown that for a monomeric sulfur bound to an originally fivefold coordinated surface Fe site, the defect core features a triplet electronic ground state with unpaired spins localized on the exposed Fe-S unit. At this site, the iron and sulfur ions have oxidation states +4 and -2, respectively. This defect can be seen as produced via heterolytic bond breaking of the S-S sulfur dimer followed by a Fe-S redox reaction. The calculated sulfur 2p core-level shifts of the monomeric defects are in good agreement with experimental photoemission spectra, which allow a compelling assignment of the different spectroscopic features. The effect of water on the stability of the defective surface has also been studied, and it has been shown that the triplet state is stable against the wetting of the surface. The most important implications of the presence of the monomeric sulfur defect on the reactivity are also discussed
Ab- initio investigation of physical properties of KTP and RTP
Directory of Open Access Journals (Sweden)
Marzieh Ghoohestani
2017-09-01
Full Text Available In this work,the physical properties of KTP and RTP single-crystals have been investigated by performing accurate total energy calculations in the framework of density functional theory by using the full-potential linearized augmented plane wave method. The effects of Rb substitution on structural, electronic and optical properties of KTP are discussed. The structural properties have been calculated by using different exchange correlation including LDA, PBE, WC and PBEsol. Also PBEsol approximation and and more accurate approximation mBJ are employed to calculate the energy gap values. The Pseudoinversion values of both crystals have been calculated by using PseudoSymmetry software . Rb substitution effect on pseudosymmetry of KTP and also relation between second-order susceptibility of crystals and the Pseudoinversion values are discussed. The optical coefficients such as refractive index, birefringence values and absorption coefficients have been calculated by using the dielectric function. The anisotropy in the linear optical properties of KTP and RTP crystals have been demonstrated. Then calculated results have been compared.
Ab-initio electronic band structure calculations for beryllium chalcogenides
International Nuclear Information System (INIS)
Kalpana, G.; Pari, G.; Yousuf, Mohammad
1997-01-01
The first principle tight-binding linear muffin-tin orbital method within the local density approximation (LDA) has been used to calculate the ground state properties, structural phase transition and pressure dependence of band gap of BeS, BeSe and BeTe. We have calculated the energy-volume relations for these compounds in the B3 and B8 phases. The calculated lattice parameters, bulk modulus and the pressure-volume relation were found to be in good agreement with the recent experimental results. The calculated B3→B8 structural transition pressure for BeS, BeSe and BeTe agree well with the recent experimental results. Our calculations show that these compounds are indirect band gap (Γ-X) semiconductors at ambient conditions. The calculated band gap values are found to be underestimated by 20-30% which is due to the usage of LDA. After the structural transition to the B8 phase, BeS continues to be indirect band gap semiconductors and ultimately above 100 GPa it metallises, BeSe and BeTe are metallic at the B3→B8 structural transition. (author)
Ab initio study of isomerism in molecular Li2AB+ ions with 12 and 14 valence electrons
International Nuclear Information System (INIS)
Charkin, O.P.; Klimenko, N.M.; Mak-Ki, M.L.; Shlojer, P.R.
1997-01-01
Ab initio calculations of potential energy surfaces (PES) of molecular ions Li 2 AB + with 12 and 14 valence electrons have been made in the framework of approximations MP2/6-31G*//HF/6-31G*+ZPE(HF/6-31G*) and MP4SDTQ/6-31*//MP2/6-31G*+ZPE(MP2/6-31G*). The following most favourable structures have been found: a double-terminal linear for LiNO + (a triplet); a plane bicyclic one for Li 2 OF + , Li 2 SCl + , Li 2 NO + (a singlet) and Li 2 PS + (a singlet), where both cations are coordinated to A-B bond; rectangular (T-shaped) for Li 2 OCl + and SFLi + , as well as for LiNS + and POLi 2 + ions in singlet and triplet states; in the form of a half-opened butterfly for Li 2 PS + (a triplet) and Li 2 SCl +
International Nuclear Information System (INIS)
Almeida, Wagner B. de
2000-01-01
The determination of the molecular structure of molecules is of fundamental importance in chemistry. X-rays and electron diffraction methods constitute in important tools for the elucidation of the molecular structure of systems in the solid state and gas phase, respectively. The use of quantum mechanical molecular orbital ab initio methods offer an alternative for conformational analysis studies. Comparison between theoretical results and those obtained experimentally in the gas phase can make a significant contribution for an unambiguous determination of the geometrical parameters. In this article the determination for an unambiguous determination of the geometrical parameters. In this article the determination of the molecular structure of the cyclooctane molecule by electron diffraction in the gas phase an initio calculations will be addressed, providing an example of a comparative analysis of theoretical and experimental predictions. (author)
AB initio energetics of lanthanum substitution in ferroelectric bismuth titanate
International Nuclear Information System (INIS)
Shah, S.H.
2012-01-01
Density functional theory based electronic structure calculations play a vital role in understanding, controlling and optimizing physical properties of materials at microscopic level. In present study system of interest is bismuth titanate (Bi/sub 4/Ti/sub 3/O/sub 12/)/(BIT) which has wide range of applications such as a high temperature piezoelectric and one of the best material for memory devices. However, it also suffers from serious issues such as oxygen vacancies which degrade its performance as a memory element and piezoelectric material. In this context, the bulk and defect properties of orthorhombic bismuth titanate (Bi/sub 4/Ti/sub 3/O/sub 12/) and bismuth lanthanum titanate (Bi/sub 3.25/La/sub 0.75/Ti/sub 3/O/sub 12/)/(BLT, x=0.75) were investigated by using first principles calculations and atomistic thermodynamics. Heats of formation, valid chemical conditions for synthesis, lanthanum substitution energies and oxygen and bismuth vacancy formation energies were computed. The study improves understanding of how native point defects and substitutional impurities influence the ferroelectric properties of these layered perovskite materials. It was found that lanthanum incorporation could occur on either of the two distinct bismuth sites in the structure and that the effect of substitution is to increase the formation energy of nearby native oxygen vacancies. The results provide direct atomistic evidence over a range of chemical conditions for the suggestion that lanthanum incorporation reduces the oxygen vacancy concentration. Oxygen vacancies contribute to ferroelectric fatigue by interacting strongly with domain walls and therefore a decrease in their concentration is beneficial. (orig./A.B.)
2015-05-08
Supplementary material for “Finding the stable structures of N1−xWX with an ab - initio high-throughput approach” Michael J. Mehl∗ Center for...AND SUBTITLE Supplementary Material for ’Finding the Stable Structures of N1-xWX with an ab - initio High-throughput Approach’ 5a. CONTRACT NUMBER 5b...and J. Hafner, Ab initio molecular dynamics for open-shell transition metals, Phys. Rev. B 48, 13115–13118 (1993). 2 G. Kresse and J. Hafner, Ab initio
Ab initio simulations and neutron scattering studies of structure and dynamics in PdH
International Nuclear Information System (INIS)
Totolici, I.E.
2001-07-01
The work presented in this PhD thesis is concerned with the interpretation of the neutron scattering measurements from the palladium hydrogen system by means of ab initio electronic structure calculations. The motivation of performing such calculations was due to recent neutron scattering studies on this system that showed a strong directional dependence to the dynamical structure factor together with a complex dependence on energy. Here we attempt to describe the origin of these features by ab initio simulations of the dynamical structure factor. The method assumes an adiabatic separation of the motion of the proton and palladium atoms. The proton wave functions are calculated by a direct solution of the associated single-particle Schroedinger equation using a plane wave basis set method and a mapping of the adiabatic surface. The Fourier components of the adiabatic potential are obtained from LDA pseudopotential calculations. Using Fermi's golden rule within the Born approximation we were then able to calculate the dynamical structure factor, S(Q,ω), for exciting the proton from its ground state to various excited states as a function of the magnitude and direction of the scattering wave vector. The results are in agreement with the inelastic neutron scattering spectra and allow us to identify the origin of previous inexplicable features, in particular the strong directional dependence to the experimental data. The method was extended to investigate the expansion of the equilibrium lattice constant as a function of the H isotope when the zero-point energy of the proton/deuterium is explicitly taken into account in the relaxation process. The results we obtained predicted a bigger lattice constant for the hydride, as expected. Furthermore, other complex ab initio calculations were carried out in order to describe the origin of the large optic dispersion, seen previously in the coherent neutron scattering data. Our calculated dispersion proved to be in good
Using Ab-Initio Calculations to Appraise Stm-Based - and Kink-Formation Energies
Feibelman, Peter J.
2001-03-01
Ab-initio total energies can and should be used to test the typically model-dependent results of interpreting STM morphologies. The benefits of such tests are illustrated here by ab-initio energies of step- and kink-formation on Pb and Pt(111) which show that the STM-based values of the kink energies must be revised. On Pt(111), the computed kink-energies for (100)- and (111)-microfacet steps are about 0.25 and 0.18 eV. These results imply a specific ratio of formation energies for the two step types, namely 1.14, in excellent agreement with experiment. If kink-formation actually cost the same energy on the two step types, an inference drawn from scanning probe observations of step wandering,(M. Giesen et al., Surf. Sci. 366, 229(1996).) this ratio ought to be 1. In the case of Pb(111), though computed energies to form (100)- and (111)-microfacet steps agree with measurement, the ab-initio kink-formation energies for the two step types, 41 and 60 meV, are 40-50% below experimental values drawn from STM images.(K. Arenhold et al., Surf. Sci. 424, 271(1999).) The discrepancy results from interpreting the images with a step-stiffness vs. kink-energy relation appropriate to (100) but not (111) surfaces. Good agreement is found when proper account of the trigonal symmetry of Pb(111) is taken in reinterpreting the step-stiffness data.
Ab initio Hartree-Fock study on surface desorption process in tritium release
International Nuclear Information System (INIS)
Taniguchi, M.; Tanaka, S.
1998-01-01
Dissociative adsorption of hydrogen on Li 2 O (110) surface has been investigated with ab initio Hartree-Fock quantum chemical calculation technique. Heat of adsorption and surface potential energy for H 2 dissociative adsorption were evaluated by calculating the total energy of the system. The calculated results on adsorption heat indicated that H 2 adsorption is endothermic. However, when an oxygen vacancy exists adjacent to the adsorption site, the heat of adsorption became less endothermic and the activation energy required to dissociate the H-H bonding was smaller than that for the terrace site. This is considered to be caused by the excess charge localized near the defect. (orig.)
Simple synthesis, structure and ab initio study of 1,4-benzodiazepine-2,5-diones
Jadidi, Khosrow; Aryan, Reza; Mehrdad, Morteza; Lügger, Thomas; Ekkehardt Hahn, F.; Ng, Seik Weng
2004-04-01
A simple procedure for the synthesis of pyrido[2,1-c][1,4] benzodiazepine-6,12-dione ( 1) and 1,4-benzodiazepine-2,5-diones ( 2a- 2d), using microwave irradiation and/or conventional heating is reported. The configuration of 1 was determined by single-crystal X-ray diffraction. A detailed ab initio B3LYP/6-31G* calculation of structural parameters and substituent effects on ring inversion barriers (Δ G#) and also free energy differences (Δ G0) for benzodiazepines are reported.
The role of Metals in Amyloid Aggregation: A Test Case for ab initio Simulations
International Nuclear Information System (INIS)
Minicozzi, V.; Rossi, G. C.; Stellato, F.; Morante, S.
2007-01-01
First principle ab initio molecular dynamics simulations of the Car-Parrinello type have proved to be of invaluable help in understanding the microscopic mechanisms of chemical bonding both in solid state physics and in structural biophysics. In this work we present as test cases the study of the Cu coordination mode in two especially important examples: Prion protein and β-amyloids. Using medium size PC-clusters as well as larger parallel platforms, we are able to deal with systems comprising 300 to 500 atoms and 1000 to 1500 electrons for as long as 2-3 ps. We present structural results which confirm indications coming from NMR and XAS data
Quantum chemistry the development of ab initio methods in molecular electronic structure theory
Schaefer III, Henry F
2004-01-01
This guide is guaranteed to prove of keen interest to the broad spectrum of experimental chemists who use electronic structure theory to assist in the interpretation of their laboratory findings. A list of 150 landmark papers in ab initio molecular electronic structure methods, it features the first page of each paper (which usually encompasses the abstract and introduction). Its primary focus is methodology, rather than the examination of particular chemical problems, and the selected papers either present new and important methods or illustrate the effectiveness of existing methods in predi
Charge carrier motion in disordered conjugated polymers: a multiscale ab-initio study
Energy Technology Data Exchange (ETDEWEB)
Vukmirovic, Nenad; Wang, Lin-Wang
2009-11-10
We developed an ab-initio multiscale method for simulation of carrier transport in large disordered systems, based on direct calculation of electronic states and electron-phonon coupling constants. It enabled us to obtain the never seen before rich microscopic details of carrier motion in conjugated polymers, which led us to question several assumptions of phenomenological models, widely used in such systems. The macroscopic mobility of disordered poly(3- hexylthiophene) (P3HT) polymer, extracted from our simulation, is in agreement with experimental results from the literature.
Energy Technology Data Exchange (ETDEWEB)
Fujiwara, Y [Department of Mathematical and Life Sciences, Graduate School of Science, Hiroshima University, Higashi-Hiroshima, Hiroshima 739-8526 (Japan); Tanimoto, Y [Faculty of Pharmacy, Osaka Ohtani University, Nishikiorikita, Tondabayashi 584-8540 (Japan)], E-mail: fuji0710@sci.hiroshima-u.ac.jp
2009-03-01
On magnetic force evaluation necessary for magnetically levitated diamagnetic substances, isotropic diamagnetic susceptibility estimation by the ab initio quantum chemical calculation using Gaussian03W was verified for more than 300 molecules in a viewpoint of the accuracy in the absolute value and the calculation level affording good cost performance. From comparison, the method of B3PW91 / 6-311+G(d,p) was found to give the adequate absolute value by the relation of (observed) = (1.03 {+-} 0.005) x (calculated) - (1.22 {+-} 0.60) x 10{sup -6} in a unit of cm{sup 3} mol{sup -1} and good cost performance.
Benefits of Parallel I/O in Ab Initio Nuclear Physics Calculations
International Nuclear Information System (INIS)
Laghave, Nikhil; Sosonkina, Masha; Maris, Pieter; Vary, James P.
2009-01-01
Many modern scientific applications rely on highly parallel calculations, which scale to 10's of thousands processors. However, most applications do not concentrate on parallelizing input/output operations. In particular, sequential I/O has been identified as a bottleneck for the highly scalable MFDn (Many Fermion Dynamics for nuclear structure) code performing ab initio nuclear structure calculations. In this paper, we develop interfaces and parallel I/O procedures to use a well-known parallel I/O library in MFDn. As a result, we gain efficient input/output of large datasets along with their portability and ease of use in the downstream processing.
Pietrucci, Fabio; Andreoni, Wanda
2011-08-01
Social permutation invariant coordinates are introduced describing the bond network around a given atom. They originate from the largest eigenvalue and the corresponding eigenvector of the contact matrix, are invariant under permutation of identical atoms, and bear a clear signature of an order-disorder transition. Once combined with ab initio metadynamics, these coordinates are shown to be a powerful tool for the discovery of low-energy isomers of molecules and nanoclusters as well as for a blind exploration of isomerization, association, and dissociation reactions.
Double ionization in Helium. Ab initio calculations beyond the one dimensional approximation
International Nuclear Information System (INIS)
Camilo Ruiz; Luis Plaja; Luis Roso; Andreas Becker
2006-01-01
Complete test of publication follows. We present ab-initio computations of the ionization of two-electron atoms by short pulses of coherent radiation beyond the one-dimensional approximation. In the model the electron correlation is included in its full dimensionality, while the center-of-mass motion is restricted along the polarization axis. We show some result for Non Sequential Double Ionization (NSDI) as well as for SDI for high intensity low IR frequency. Some recent applications for this correlated system is also presented.
International Nuclear Information System (INIS)
Marks, N.A.; Goringe, C.M.; McKenzie, D.R.; McCulloch, D.G.; Royal Melbourne Institute of Technology University, Melbourne, VIC
2000-01-01
Full text: Silicon is often described as the prototype covalent material, and when it comes to developing atomistic models this situation is well described by the sentiment that 'everything works for silicon'. The same cannot be said for carbon though, where the interaction potential has always proved problematical, be it with empirical, tight-binding or ab initio methods. Thus far the most decisive contributions to understanding amorphous carbon networks have come from ab initio simulations using the Car-Parrinello method, where the fully quantum treatment of the valence electrons has provided unexpected insight into the local structure. However such first principles calculations are restricted spatially and temporally to systems with approximately 100 atoms and times of order one picosecond. There is therefore demand for less expensive techniques capable of resolving important questions whose solution can only to found with larger simulations running for longer times. In the case of tetrahedral amorphous carbon, such issues include the release of compressive stress through annealing, the origin of graphitic surface layers and the nature of the film growth process and thermal spike. Against this background tight-binding molecular dynamics has emerged as a popular alternative to first principles methods, and our group has an ongoing program to understand film growth using one of the efficient variants of tight-binding. Another direction of research is a new empirical potential based on the Environment Dependent Interaction Potential (EDIP) recently developed for silicon. The EDIP approach represents a promising direction for empirical potentials through its use of ab initio data to motivate the functional form as well as the more conventional parametrisation. By inverting ab initio cohesive energy curves the authors of EDIP arrived at a pair potential expression which reduces to the well-known Stillinger-Weber form at integer coordination, while providing
Czech Academy of Sciences Publication Activity Database
Slavíček, Petr; Winter, B.; Faubel, M.; Bradforth, S. E.; Jungwirth, Pavel
2009-01-01
Roč. 131, č. 18 (2009), s. 6460-6467 ISSN 0002-7863 R&D Projects: GA MŠk LC512; GA ČR GA203/08/0114 Grant - others:GA ČR(CZ) GP203/07/P449 Institutional research plan: CEZ:AV0Z40550506; CEZ:AV0Z40400503 Keywords : DNA bases * photoelectron spectroscopy * ab initio calculations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 8.580, year: 2009
Ramsdellite-structured LiTiO 2: A new phase predicted from ab initio calculations
Koudriachova, M. V.
2008-06-01
A new phase of highly lithiated titania with potential application as an anode in Li-rechargeable batteries is predicted on the basis of ab initio calculations. This phase has a composition LiTiO2 and may be accessed through electrochemical lithiation of ramsdellite-structured TiO2 at the lowest potential reported for titanium dioxide based materials. The potential remains constant over a wide range of Li-concentrations. The new phase is metastable with respect to a tetragonally distorted rock salt structure, which hitherto has been the only known polymorph of LiTiO2.
International Nuclear Information System (INIS)
Fujiwara, Y; Tanimoto, Y
2009-01-01
On magnetic force evaluation necessary for magnetically levitated diamagnetic substances, isotropic diamagnetic susceptibility estimation by the ab initio quantum chemical calculation using Gaussian03W was verified for more than 300 molecules in a viewpoint of the accuracy in the absolute value and the calculation level affording good cost performance. From comparison, the method of B3PW91 / 6-311+G(d,p) was found to give the adequate absolute value by the relation of (observed) = (1.03 ± 0.005) x (calculated) - (1.22 ± 0.60) x 10 -6 in a unit of cm 3 mol -1 and good cost performance.
Ab-initio theoretical study of electronic excitations and optical properties in nanostructures
Marchesín, Federico
2017-01-01
218 p. La miniaturización de los dispositivos electrónicos para la transferencia de información y procesado de señales ha impulsado el estudio de las propiedades electrónicas y la dinámica de excitaciones electrónicas en nanoestructuras. En particular, los cálculos ab-initio de las repuestas ópticas y los modos plasmónicos colectivos de nanoestructuras metálicas y de grafeno, han permitido profundizar en el conocimiento de la física y así poder avanzar hacia aplicaciones industriales en mu...
Experimental and ab initio study of the photofragmentation of DNA and RNA sugars
Ha, D. T.; Huels, M. A.; Huttula, M.; Urpelainen, S.; Kukk, E.
2011-09-01
The photoelectron-photoion-photoion coincidence method is used to measure the photodissociation of doubly charged D-ribose (C5H10O5), the RNA sugar molecules, and 2-deoxy-D-ribose (C5H10O4), the DNA sugar molecules, following normal Auger decay after initial C 1s and O 1s core ionizations. The fragment identification is facilitated by measuring isotopically labeled D-ribose, such as D-ribose deuterated at C(1), and with 13C at the C(5) position. Ab initio quantum chemistry calculations are used to gain further insight into the abundant appearance of the CHO+ fragment.
Exploring proton transfer in 1,2,3-triazole-triazolium dimer with ab initio method
Li, Ailin; Yan, Tianying; Shen, Panwen
Ab initio calculations are utilized to search for transition state structures for proton transfer in the 1,2,3-triazole-triazolium complexes on the basis of optimized dimers. The result suggests six transition state structures for single proton transfer in the complexes, most of which are coplanar. The energy barriers, between different stable and transition states structures with zero point energy (ZPE) corrections, show that proton transfer occurs at room temperature with coplanar configuration that has the lowest energy. The results clearly support that reorientation gives triazole flexibility for proton transfer.
Exploring proton transfer in 1,2,3-triazole-triazolium dimer with ab initio method
Energy Technology Data Exchange (ETDEWEB)
Li, Ailin; Yan, Tianying; Shen, Panwen [Department of Material Chemistry, Institute of New Energy Material Chemistry, Nankai University, Tianjin, 300071 (China)
2011-02-01
Ab initio calculations are utilized to search for transition state structures for proton transfer in the 1,2,3-triazole-triazolium complexes on the basis of optimized dimers. The result suggests six transition state structures for single proton transfer in the complexes, most of which are coplanar. The energy barriers, between different stable and transition states structures with zero point energy (ZPE) corrections, show that proton transfer occurs at room temperature with coplanar configuration that has the lowest energy. The results clearly support that reorientation gives triazole flexibility for proton transfer. (author)
Atomic ionization of germanium by neutrinos from an ab initio approach
International Nuclear Information System (INIS)
Chen, Jiunn-Wei; Chi, Hsin-Chang; Huang, Keh-Ning; Liu, C.-P.; Shiao, Hao-Tse; Singh, Lakhwinder; Wong, Henry T.; Wu, Chih-Liang; Wu, Chih-Pan
2014-01-01
An ab initio calculation of atomic ionization of germanium by neutrinos was carried out in the framework of multiconfiguration relativistic random phase approximation and benchmarked by related atomic structure and photoabsorption data. This improves over the conventional approach based on scattering off free electrons whose validity at sub-keV energy transfer is questionable. Limits on neutrino magnetic moments are derived using reactor neutrino data taken with low threshold germanium detectors. Future applications of these atomic techniques will greatly reduce the atomic uncertainties in low-energy neutrino and dark matter detections.
Oxide nanostructures on a Nb surface and related systems: experiments and ab initio calculations
International Nuclear Information System (INIS)
Kuznetsov, Mikhail V; Razinkin, A S; Ivanovskii, Alexander L
2011-01-01
This review discusses the state of the art in two related research areas: the surfaces of niobium and of its related group IV-VI transition metals, and surface (primarily oxide) nanostructures that form on niobium (and group IV-VI d-metals) due to gas adsorption or impurity diffusion from the bulk. Experimental (X-ray photoelectron spectroscopy, photoelectron diffraction, scanning tunneling microscopy) and theoretical (ab initio simulation) results on d-metal surfaces are summarized and reviewed. (reviews of topical problems)
Ab initio predictions on the rotational spectra of carbon-chain carbene molecules
Maluendes, S. A.; McLean, A. D.; Loew, G. H. (Principal Investigator)
1992-01-01
We predict rotational constants for the carbon-chain molecules H2C=(C=)nC, n=3-8, using ab initio computations, observed values for the earlier members in the series, H2CCC and H2CCCC with n=1 and 2, and empirical geometry corrections derived from comparison of computation and experiment on related molecules. H2CCC and H2CCCC have already been observed by radioastronomy; higher members in the series, because of their large dipole moments, which we have calculated, are candidates for astronomical searches. Our predictions can guide searches and assist in both astronomical and laboratory detection.
Venâncio, Mateus F.; Rocha, Willian R.
2015-10-01
Ab initio molecular dynamics simulations were used to investigate the early chemical events involved in the dynamics of nitric oxide (NOrad), nitrosonium cation (NO+) and nitroxide anion (NO-) in aqueous solution. The NO+ ion is very reactive in aqueous solution having a lifetime of ∼4 × 10-13 s, which is shorter than the value of 3 × 10-10 s predicted experimentally. The NO+ reacts generating the nitrous acid as an intermediate and the NO2- ion as the final product. The dynamics of NOrad revealed the reversibly formation of a transient anion radical species HONOrad -.
Cr interaction in the formation of nano cluster of Y, Ti and O in bcc Fe an ab initio study
International Nuclear Information System (INIS)
Murali, D.; Panigrahi, B.K.; Valsakumar, M.C.; Chandra, Sharath; Sundar, C.S.
2008-01-01
Nanostructured ferritic alloys containing highly stable fine dispersion of yttrium oxide nano particles, produced by mechanical alloying, are promising structural materials for fast fission and fusion environments. Formation of Cr depleted and O enriched Y-Ti-O nanoclusters are observed in the atom probe analysis. Ab initio calculations based on density functional theory are carried out to understand the role of Cr atom interactions with other solute atoms (Y, Ti, O) and vacancies in the formation of nanocluster. The binding energy of clusters of Y-Ti-O in bcc Fe is found to be very high in the presence of vacancies. Our calculations are consistent with the atom probe observation of depletion of Cr atoms and enrichment of O atoms in the nanoclusters. (author)
International Nuclear Information System (INIS)
Hicks, Latorya D.; Fry, Albert J.; Kurzweil, Vanessa C.
2004-01-01
The electron affinities (EAs) of a training set of 29 monosubstituted benzalacetophenones (chalcones) were computed at the ab initio density functional B3LYP/6-31G * level of theory. The EAs and experimental reduction potentials of the training set are highly linearly correlated (correlation coefficient of 0.969 and standard deviation of 10.8 mV). An additional 72 di-, tri-, and tetrasubstituted chalcones were then synthesized. Their reduction potentials were predicted from computed EAs using the linear correlation derived from the training set. Agreement between the experimental and computed reduction potentials is remarkably good, with a standard deviation of less than 22 mV for this very large set of substances whose potentials extend over a range of almost 700 mV
Devi, Assa Aravindh Sasikala
2014-05-01
Investigations on freestanding binary and ternary clusters of Fe (x) Co (y) Ir (z) (x + y + z = 5, 6) are carried out using ab initio density functional theory techniques. The geometry, chemical order, binding energy, magnetic moment and electronic structure of the clusters are analyzed for the entire range of composition. Composition dependent structural transition is observed in the five atom clusters, while octahedral geometry prevailed in clusters with six atoms. Both the clusters show increment in binding energy with the increase in number of heterogeneous bonds. Analysis based on the chemical order parameter indicates that clusters favor mixing rather than segregation. The clusters exhibit ferromagnetic ordering and the inter-dependence of optimal cluster geometry to the magnetic moments and electronic structure is observed.
Cirino J.J.V.; Bertran C.A.
2002-01-01
A study was carried out on the urea geometries using ab initio calculation and Monte Carlo computational simulation of liquids. The ab initio calculated results showed that urea has a non-planar conformation in the gas phase in which the hydrogen atoms are out of the plane formed by the heavy atoms. Free energies associated to the rotation of the amino groups of urea in water were obtained using the Monte Carlo method in which the thermodynamic perturbation theory is implemented. The magnitud...
International Nuclear Information System (INIS)
Niranjan, Manish K
2015-01-01
We present a comparative study of the anisotropy in the elastic properties of the C49, C54 and C40 phases of TiSi 2 , as well as orthorhombic TiSi and hexagonal Ti 5 Si 3 . The elastic constants, elastic moduli, Debye temperature and sound velocities are computed within the framework of density functional theory. The computed values of the elastic constants and moduli are found to be in excellent agreement with available experimental values. The average elastic moduli, such as Young’s modulus, shear modulus, bulk modulus and Poisson’s ratio, of polycrystalline aggregates are computed using the computed elastic constants of single crystals. The anisotropy in elastic properties is analyzed using estimates of shear anisotropic factors, bulk modulus anisotropic factors and variations in Young’s and bulk moduli in different crystallographic directions. Among the Ti–Si phases, the computed directional Young’s modulus profiles of C49 TiSi 2 and C40 TiSi 2 are found to be quite similar to those of bulk Si and Ti, respectively. In addition to the elastic properties, the electronic structure of five Ti–Si phases is studied. The density of states and planar charge density profiles reveal mixed covalent–metallic bonding in all Ti–Si phases. (paper)
Ran, Shi-Ju
2016-05-01
In this work, a simple and fundamental numeric scheme dubbed as ab initio optimization principle (AOP) is proposed for the ground states of translational invariant strongly correlated quantum lattice models. The idea is to transform a nondeterministic-polynomial-hard ground-state simulation with infinite degrees of freedom into a single optimization problem of a local function with finite number of physical and ancillary degrees of freedom. This work contributes mainly in the following aspects: (1) AOP provides a simple and efficient scheme to simulate the ground state by solving a local optimization problem. Its solution contains two kinds of boundary states, one of which play the role of the entanglement bath that mimics the interactions between a supercell and the infinite environment, and the other gives the ground state in a tensor network (TN) form. (2) In the sense of TN, a novel decomposition named as tensor ring decomposition (TRD) is proposed to implement AOP. Instead of following the contraction-truncation scheme used by many existing TN-based algorithms, TRD solves the contraction of a uniform TN in an opposite way by encoding the contraction in a set of self-consistent equations that automatically reconstruct the whole TN, making the simulation simple and unified; (3) AOP inherits and develops the ideas of different well-established methods, including the density matrix renormalization group (DMRG), infinite time-evolving block decimation (iTEBD), network contractor dynamics, density matrix embedding theory, etc., providing a unified perspective that is previously missing in this fields. (4) AOP as well as TRD give novel implications to existing TN-based algorithms: A modified iTEBD is suggested and the two-dimensional (2D) AOP is argued to be an intrinsic 2D extension of DMRG that is based on infinite projected entangled pair state. This paper is focused on one-dimensional quantum models to present AOP. The benchmark is given on a transverse Ising
International Nuclear Information System (INIS)
Badaut, V.
2010-07-01
Among the many radionuclides contained in high-level nuclear waste, 79 Se was identified as a potential threat to the safety of long term underground storage. However, siderite (FeCO 3 ) is known to form upon corrosion of the waste container, and the impact of this mineral on the fate of selenium was not accounted for. In this work, the interactions between selenium oxyanions - selenate and selenite - and siderite were investigated. To this end, both experimental characterizations (solution chemistry, X-ray Absorption Spectroscopy - XAS) and theoretical studies (ab initio modelling using Density Functional Theory - DFT ) were performed. Selenite and selenate (≤ 10 3 M) retention experiments by siderite suspensions (75 g/L ) at neutral pH in reducing glovebox (5 % H 2 ) showed that selenite is quantitatively immobilized by siderite after 48 h of reaction time, when selenate is only partly immobilized after 10 days. In the selenite case, XAS showed that immobilized selenium is initially present as Se(IV) probably sorbed on siderite surface. After 10 days of reaction, selenite ions are quantitatively reduced and form poorly crystalline elementary selenium. Selenite retention and reduction kinetics are therefore distinct. On the other hand, the fraction of immobilized selenate retained in the solid fraction does not appear to be significantly reduced over the probed timescale (10 days). For a better understanding of the reduction mechanism of selenite ions by siderite, the properties of bulk and perfect surfaces of siderite were modelled using DFT. We suggest that the properties of the valence electrons can be correctly described only if the symmetry of the fundamental state electronic density is lower than the experimental crystallographic symmetry. We then show that the retention of simple molecules as O 2 or H 2 O on siderite and magnesite (10 -14 ) perfect surfaces (perfect cleavage plane, whose surface energy is the lowest according to DFT) can be modelled with
Ab initio study of intrinsic profiles of liquid metals and their reflectivity
del Rio, B. G.; Souto, J.; Alemany, M. M. G.; González, L. E.
2017-08-01
The free surfaces of liquid metals are known to exhibit a stratified profile that, in favourable cases, shows up in experiments as a peak in the ratio between the reflectivity function and that of an ideal step-like profile. This peak is located at a wave-vector related to the distance between the layers of the profile. In fact the surface roughness produced by thermally induced capillary waves causes a depletion of the previous so called intrinsic reflectivity by a damping factor that may hinder the observation of the peak. The behaviour of the intrinsic reflectivity below the layering peak is however far from being universal, with systems as Ga or In where the reflectiviy falls uniformly towards the q → 0 value, others like Sn or Bi where a shoulder appears at intermediate wavevectors, and others like Hg which show a minimum. We have performed extensive ab initio simulations of the free liquid surfaces of Bi, Pb and Hg, that yield direct information on the structure of the profiles and found that the macroscopic capillary wave theory usually employed in order to remove the capillary wave components fails badly in some cases for the typical sample sizes affordable in ab initio simulations. However, a microscopic method for the determination of the intrinsic profile is shown to be succesful in obtaining meaningful intrinsic profiles and corresponding reflectivities which reproduce correctly the qualitative behaviour observed experimentally.
Han, Huixian; Li, Anyang; Guo, Hua
2014-12-01
A new full-dimensional global potential energy surface (PES) for the acetylene-vinylidene isomerization on the ground (S0) electronic state has been constructed by fitting ˜37 000 high-level ab initio points using the permutation invariant polynomial-neural network method with a root mean square error of 9.54 cm-1. The geometries and harmonic vibrational frequencies of acetylene, vinylidene, and all other stationary points (two distinct transition states and one secondary minimum in between) have been determined on this PES. Furthermore, acetylene vibrational energy levels have been calculated using the Lanczos algorithm with an exact (J = 0) Hamiltonian. The vibrational energies up to 12 700 cm-1 above the zero-point energy are in excellent agreement with the experimentally derived effective Hamiltonians, suggesting that the PES is approaching spectroscopic accuracy. In addition, analyses of the wavefunctions confirm the experimentally observed emergence of the local bending and counter-rotational modes in the highly excited bending vibrational states. The reproduction of the experimentally derived effective Hamiltonians for highly excited bending states signals the coming of age for the ab initio based PES, which can now be trusted for studying the isomerization reaction.
Phase diagrams from ab-initio calculations: Re-W and Fe-B
Energy Technology Data Exchange (ETDEWEB)
Hammerschmidt, Thomas; Bialon, Arthur; Palumbo, Mauro; Fries, Suzana G.; Drautz, Ralf [ICAMS, Ruhr-Universitaet Bochum (Germany)
2011-07-01
The CALPHAD (CaLculation of Phase Diagrams) method relies on Gibbs energy databases and is of limited predictive power in cases where only limited experimental data is available for constructing the Gibbs energy databases. This is problematic for, e.g., the calculation of the phase transformation kinetics within phase field simulations that not only require the thermodynamic equilibrium data but also information on metastable phases. Such information is difficult to obtain directly from experiment but ab-initio calculations may supplement experimental databases as they comprise metastable phases and arbitrary chemical compositions. We present simulations for two prototypical systems: Re-W and Fe-B. For both systems we calculate the heat of formation for an extensive set of structures using ab-initio calculations and employ the total energies in CALPHAD in order to determine the corresponding phase diagrams. We account for the configurational entropy within the Bragg-Williams approximation and neglect the phenomenological excess-term that is commonly used in CALPHAD as well as the contribution of phonons and electronic excitations to the free energy. According to our calculations the complex intermetallic phases in Re-W are stabilized by the configurational entropy. For Fe-B, we calculate metastable and stable phase diagrams including recently predicted new stable phases.
International Nuclear Information System (INIS)
Han, Huixian; Li, Anyang; Guo, Hua
2014-01-01
A new full-dimensional global potential energy surface (PES) for the acetylene-vinylidene isomerization on the ground (S 0 ) electronic state has been constructed by fitting ∼37 000 high-level ab initio points using the permutation invariant polynomial-neural network method with a root mean square error of 9.54 cm −1 . The geometries and harmonic vibrational frequencies of acetylene, vinylidene, and all other stationary points (two distinct transition states and one secondary minimum in between) have been determined on this PES. Furthermore, acetylene vibrational energy levels have been calculated using the Lanczos algorithm with an exact (J = 0) Hamiltonian. The vibrational energies up to 12 700 cm −1 above the zero-point energy are in excellent agreement with the experimentally derived effective Hamiltonians, suggesting that the PES is approaching spectroscopic accuracy. In addition, analyses of the wavefunctions confirm the experimentally observed emergence of the local bending and counter-rotational modes in the highly excited bending vibrational states. The reproduction of the experimentally derived effective Hamiltonians for highly excited bending states signals the coming of age for the ab initio based PES, which can now be trusted for studying the isomerization reaction
Chitnis, Abhishek; Chakraborty, B.; Tripathi, B. M.; Tyagi, A. K.; Garg, Nandini
2018-02-01
Lithium metatitanate (LTO) and lithium metazirconate (LZO) are lithium rich ceramics which can be used as tritium breeder materials for thermonuclear reactors. In-situ x-ray diffraction and ab-initio studies at high pressure show that LTO has a higher bulk modulus than that of LZO. In fact these studies indicate that they are the least compressible of the known lithium rich ceramics like Li2O or Li4SiO4, which are potential candidates for blanket materials. These studies show that the TiO6 octahedra are responsible for the higher bulk modulus of LTO when compared to that of LZO. It has also been shown that the compressibility and distortion of the softer LiO6 octahedra can be controlled by altering the stacking sequence of the more rigid covalently bonded octahedra. This knowledge can be used by chemists to design new lithium based ceramics with higher bulk modulus. It was observed that LTO was stable upto 34 GPa. Ab initio DFT calculations helped to understand the anisotropy in compressibility of both LZO and LTO. This study also shows, that even though the empirical potentials developed by Vijaykumar et al. successfully determine the ambient pressure structure of lithium metatitanate, they cannot be used at non ambient conditions like high pressure [1].
Xu, Dong; Zhang, Yang
2012-07-01
Ab initio protein folding is one of the major unsolved problems in computational biology owing to the difficulties in force field design and conformational search. We developed a novel program, QUARK, for template-free protein structure prediction. Query sequences are first broken into fragments of 1-20 residues where multiple fragment structures are retrieved at each position from unrelated experimental structures. Full-length structure models are then assembled from fragments using replica-exchange Monte Carlo simulations, which are guided by a composite knowledge-based force field. A number of novel energy terms and Monte Carlo movements are introduced and the particular contributions to enhancing the efficiency of both force field and search engine are analyzed in detail. QUARK prediction procedure is depicted and tested on the structure modeling of 145 nonhomologous proteins. Although no global templates are used and all fragments from experimental structures with template modeling score >0.5 are excluded, QUARK can successfully construct 3D models of correct folds in one-third cases of short proteins up to 100 residues. In the ninth community-wide Critical Assessment of protein Structure Prediction experiment, QUARK server outperformed the second and third best servers by 18 and 47% based on the cumulative Z-score of global distance test-total scores in the FM category. Although ab initio protein folding remains a significant challenge, these data demonstrate new progress toward the solution of the most important problem in the field. Copyright © 2012 Wiley Periodicals, Inc.
Ab initio results for intermediate-mass, open-shell nuclei
Baker, Robert B.; Dytrych, Tomas; Launey, Kristina D.; Draayer, Jerry P.
2017-01-01
A theoretical understanding of nuclei in the intermediate-mass region is vital to astrophysical models, especially for nucleosynthesis. Here, we employ the ab initio symmetry-adapted no-core shell model (SA-NCSM) in an effort to push first-principle calculations across the sd-shell region. The ab initio SA-NCSM's advantages come from its ability to control the growth of model spaces by including only physically relevant subspaces, which allows us to explore ultra-large model spaces beyond the reach of other methods. We report on calculations for 19Ne and 20Ne up through 13 harmonic oscillator shells using realistic interactions and discuss the underlying structure as well as implications for various astrophysical reactions. This work was supported by the U.S. NSF (OCI-0904874 and ACI -1516338) and the U.S. DOE (DE-SC0005248), and also benefitted from the Blue Waters sustained-petascale computing project and high performance computing resources provided by LSU.
Ab initio study of weakly bound halogen complexes: RX⋯PH3.
Georg, Herbert C; Fileti, Eudes E; Malaspina, Thaciana
2013-01-01
Ab initio calculations were employed to study the role of ipso carbon hybridization in halogenated compounds RX (R=methyl, phenyl, acetyl, H and X=F, Cl, Br and I) and its interaction with a phosphorus atom, as occurs in the halogen bonded complex type RX⋯PH3. The analysis was performed using ab initio MP2, MP4 and CCSD(T) methods. Systematic energy analysis found that the interaction energies are in the range -4.14 to -11.92 kJ mol(-1) (at MP2 level without ZPE correction). Effects of electronic correlation levels were evaluated at MP4 and CCSD(T) levels and a reduction of up to 27% in interaction energy obtained in MP2 was observed. Analysis of the electrostatic maps confirms that the PhCl⋯PH3 and all MeX⋯PH3 complexes are unstable. NBO analysis suggested that the charge transfer between the moieties is bigger when using iodine than bromine and chlorine. The electrical properties of these complexes (dipole and polarizability) were determined and the most important observed aspect was the systematic increase at the dipole polarizability, given by the interaction polarizability. This increase is in the range of 0.7-6.7 u.a. (about 3-7%).
Ground state analytical ab initio intermolecular potential for the Cl2-water system
International Nuclear Information System (INIS)
Hormain, Laureline; Monnerville, Maurice; Toubin, Céline; Duflot, Denis; Pouilly, Brigitte; Briquez, Stéphane; Bernal-Uruchurtu, Margarita I.; Hernández-Lamoneda, Ramón
2015-01-01
The chlorine/water interface is of crucial importance in the context of atmospheric chemistry. Modeling the structure and dynamics at this interface requires an accurate description of the interaction potential energy surfaces. We propose here an analytical intermolecular potential that reproduces the interaction between the Cl 2 molecule and a water molecule. Our functional form is fitted to a set of high level ab initio data using the coupled-cluster single double (triple)/aug-cc-p-VTZ level of electronic structure theory for the Cl 2 − H 2 O complex. The potential fitted to reproduce the three minima structures of 1:1 complex is validated by the comparison of ab initio results of Cl 2 interacting with an increasing number of water molecules. Finally, the model potential is used to study the physisorption of Cl 2 on a perfectly ordered hexagonal ice slab. The calculated adsorption energy, in the range 0.27 eV, shows a good agreement with previous experimental results
Vibrational inelastic and charge transfer processes in H++H2 system: An ab initio study
Amaran, Saieswari; Kumar, Sanjay
2007-12-01
State-resolved differential cross sections, total and integral cross sections, average vibrational energy transfer, and the relative probabilities are computed for the H++H2 system using the newly obtained ab initio potential energy surfaces at the full CI/cc-pVQZ level of accuracy which allow for both the direct vibrational inelastic and the charge transfer processes. The quantum dynamics is treated within the vibrational close-coupling infinite-order-sudden approximation approach using the two ab initio quasidiabatic potential energy surfaces. The computed collision attributes for both the processes are compared with the available state-to-state scattering experiments at Ec.m.=20eV. The results are in overall good agreement with most of the observed scattering features such as rainbow positions, integral cross sections, and relative vibrational energy transfers. A comparison with the earlier theoretical study carried out on the semiempirical surfaces (diatomics in molecules) is also made to illustrate the reliability of the potential energy surfaces used in the present work.
Field theoretic approach to dynamical orbital localization in ab initio molecular dynamics
International Nuclear Information System (INIS)
Thomas, Jordan W.; Iftimie, Radu; Tuckerman, Mark E.
2004-01-01
Techniques from gauge-field theory are employed to derive an alternative formulation of the Car-Parrinello ab initio molecular-dynamics method that allows maximally localized Wannier orbitals to be generated dynamically as the calculation proceeds. In particular, the Car-Parrinello Lagrangian is mapped onto an SU(n) non-Abelian gauge-field theory and the fictitious kinetic energy in the Car-Parrinello Lagrangian is modified to yield a fully gauge-invariant form. The Dirac gauge-fixing method is then employed to derive a set of equations of motion that automatically maintain orbital locality by restricting the orbitals to remain in the 'Wannier gauge'. An approximate algorithm for integrating the equations of motion that is stable and maintains orbital locality is then developed based on the exact equations of motion. It is shown in a realistic application (64 water molecules plus one hydrogen-chloride molecule in a periodic box) that orbital locality can be maintained with only a modest increase in CPU time. The ability to keep orbitals localized in an ab initio molecular-dynamics calculation is a crucial ingredient in the development of emerging linear scaling approaches
Ab initio quantum chemistry in parallel-portable tools and applications
International Nuclear Information System (INIS)
Harrison, R.J.; Shepard, R.; Kendall, R.A.
1991-01-01
In common with many of the computational sciences, ab initio chemistry faces computational constraints to which a partial solution is offered by the prospect of highly parallel computers. Ab initio codes are large and complex (O(10 5 ) lines of FORTRAN), representing a significant investment of communal effort. The often conflicting requirements of portability and efficiency have been successfully resolved on vector computers by reliance on matrix oriented kernels. This proves inadequate even upon closely-coupled shared-memory parallel machines. We examine the algorithms employed during a typical sequence of calculations. Then we investigate how efficient portable parallel implementations may be derived, including the complex multi-reference singles and doubles configuration interaction algorithm. A portable toolkit, modeled after the Intel iPSC and the ANL-ACRF PARMACS, is developed, using shared memory and TCP/IP sockets. The toolkit is used as an initial platform for programs portable between LANS, Crays and true distributed-memory MIMD machines. Timings are presented. 53 refs., 4 tabs
Ab initio study on electron excitation and electron transfer in tryptophan-tyrosine system
International Nuclear Information System (INIS)
Tong Jing; Li Xiangyuan
2002-01-01
In this article, ab initio calculation has been performed to evaluate the transition energy of electronic excitation in tryptophan and tyrosine by using semiempirical molecular orbital method AM1 and complete active space self-consistent field method. The solvent effect has been considered by means of the conductor-like screening model. After geometric optimizations of isolated tryptophan and tyrosine, and their corresponding radicals and cations, reaction heat of these electron transfer reactions have been obtained by the means of complete active space self-consistent field method. The transition energies from the ground state, respectively, to the lowest excited state and to the lowest triplet state of these two amino acids are also calculated and compared with the experimentally observed values. The ionization potential and electron affinity are also calculated for tryptophan and tyrosine employing Koopmans' theorem and ab initio calculation. Compared with the experimental measurements, the theoretical results are found satisfactory. Theoretical results give good explanations on the experimental phenomena that N 3 · can preferably oxide the side chain of tryptophan residue and then the electron transfer from tyrosine residue to tryptophan residue follows in peptides involving tryptophan and tyrosine
Ab Initio Values of the Thermophysical Properties of Helium as Standards
Hurly, John J.; Moldover, Michael R.
2000-01-01
Recent quantum mechanical calculations of the interaction energy of pairs of helium atoms are accurate and some include reliable estimates of their uncertainty. We combined these ab initio results with earlier published results to obtain a helium-helium interatomic potential that includes relativistic retardation effects over all ranges of interaction. From this potential, we calculated the thermophysical properties of helium, i.e., the second virial coefficients, the dilute-gas viscosities, and the dilute-gas thermal conductivities of 3He, 4He, and their equimolar mixture from 1 K to 104 K. We also calculated the diffusion and thermal diffusion coefficients of mixtures of 3He and 4He. For the pure fluids, the uncertainties of the calculated values are dominated by the uncertainties of the potential; for the mixtures, the uncertainties of the transport properties also include contributions from approximations in the transport theory. In all cases, the uncertainties are smaller than the corresponding experimental uncertainties; therefore, we recommend the ab initio results be used as standards for calibrating instruments relying on these thermophysical properties. We present the calculated thermophysical properties in easy-to-use tabular form. PMID:27551630
Magnuson, Martin; Mattesini, Maurizio; Bugnet, Matthieu; Eklund, Per
2015-01-01
The anisotropy in the electronic structure of the inherently nanolaminated ternary phase Cr$_{2}$GeC is investigated by bulk-sensitive and element selective soft x-ray absorption/emission spectroscopy. The angle-resolved absorption/emission measurements reveal differences between the in-plane and out-of-plane bonding at the (0001) interfaces of Cr$_{2}$GeC. The Cr $L_{2,3}$, C $K$, and Ge $M_{1}$, $M_{2,3}$ emission spectra are interpreted with first-principles density-functional theory (DFT)...
Bryce, Richard A.; Vincent, Mark A.; Malcolm, Nathaniel O. J.; Hillier, Ian H.; Burton, Neil A.
1998-08-01
A new hybrid quantum mechanical/molecular mechanical model of solvation is developed and used to describe the structure and dynamics of small fluoride/water clusters, using an ab initio wave function to model the ion and a fluctuating charge potential to model the waters. Appropriate parameters for the water-water and fluoride-water interactions are derived, with the fluoride anion being described by density functional theory and a large Gaussian basis. The role of solvent polarization in determining the structure and energetics of F(H2O)4- clusters is investigated, predicting a slightly greater stability of the interior compared to the surface structure, in agreement with ab initio studies. An extended Lagrangian treatment of the polarizable water, in which the water atomic charges fluctuate dynamically, is used to study the dynamics of F(H2O)4- cluster. A simulation using a fixed solvent charge distribution indicates principally interior, solvated states for the cluster. However, a preponderance of trisolvated configurations is observed using the polarizable model at 300 K, which involves only three direct fluoride-water hydrogen bonds. Ab initio calculations confirm this trisolvated species as a thermally accessible state at room temperature, in addition to the tetrasolvated interior and surface structures. Extension of this polarizable water model to fluoride clusters with five and six waters gave less satisfactory agreement with experimental energies and with ab initio geometries. However, our results do suggest that a quantitative model of solvent polarization is fundamental for an accurate understanding of the properties of anionic water clusters.
Study of half-metallic behavior in Sr2CoWO6 perovskite by ab initio DFT calculations
International Nuclear Information System (INIS)
Bonilla, M.; Landinez Tellez, D.A.; Arbey Rodriguez, J.; Aguiar, J. Albino; Roa-Rojas, J.
2008-01-01
In this work, we report several ab initio calculations performed for Sr 2 CoWO 6 by means of the density functional theory and the linearized augmented plane wave method for both spin orientations. For calculations, the exchange and correlation potential were treated into the generalized gradient approximation, which permits to consider from the beginning the difference between the electronic densities for both up and down spin orientations. The densities of states are calculated by the histogram method and the positions of Fermi levels are found by integrating over the density of states for both spin configurations. Our results reveal that Sr 2 CoWO 6 material behaves as insulators for the spin-up orientation and conductor for the spin down, as expected for the half-metallic systems. Results of partial densities of states permit to conclude that the conduction band has predominant contributions of d x 2 -y 2 and d xz+yz states of Co for the spin-down orientation. A magnetic moment of 3 μ B was calculated. From the Murnaghan equation state, we also calculate the cell dimensions that minimize the total energy for several configurations
Magnuson, Martin; Mattesini, Maurizio; Bugnet, Matthieu; Eklund, Per
2015-10-01
The anisotropy in the electronic structure of the inherently nanolaminated ternary phase Cr2GeC is investigated by bulk-sensitive and element selective soft x-ray absorption/emission spectroscopy. The angle-resolved absorption/emission measurements reveal differences between the in-plane and out-of-plane bonding at the (0001) interfaces of Cr2GeC. The Cr L 2, 3, C K, and Ge M 1, M 2, 3 emission spectra are interpreted with first-principles density-functional theory (DFT) including core-to-valence dipole transition matrix elements. For the Ge 4s states, the x-ray emission measurements reveal two orders of magnitude higher intensity at the Fermi level than DFT within the General Gradient Approximation (GGA) predicts. We provide direct evidence of anisotropy in the electronic structure and the orbital occupation that should affect the thermal expansion coefficient and transport properties. As shown in this work, hybridization and redistribution of intensity from the shallow 3d core levels to the 4s valence band explain the large Ge density of states at the Fermi level.
International Nuclear Information System (INIS)
Bako, Imre; Megyes, Tuende; Palinkas, Gabor
2005-01-01
In this work, we present a study on water-acetonitrile (AN) mixtures by molecular dynamics ab initio and X-ray diffraction techniques. Comparison of the experimental total G(r) functions of the mixtures with the results of molecular dynamics simulation shows an overall good agreement. The properties of hydrogen bonded clusters (water clusters, and water-AN clusters) in these mixtures have been determined. Two different types of AN-water dimers were identified by ab initio quantum chemical calculation. One of these structures proved to be a true H-bonded dimer and the other a dipole bound dimer
International Nuclear Information System (INIS)
Trudeau, J.D.; Schwartz, J.L.; Farrar, T.C.
1991-01-01
The deuterium quadrupole coupling constant, χ D , in the PDO 3 2- anion has been measured in solution by NMR spin-lattice (T 1 ) relaxation time measurements and it has been calculated via ab initio methods. The experimental value of 94.7 ± 0.5 kHz is in excellent agreement with the ab initio value of 95.0 kHz. The activation energy for the ion reorientation is 2.23 ± 0.01 kJ mol -1
International Nuclear Information System (INIS)
Klevets, Ivan; Bryk, Taras
2014-01-01
Electron-ion structure factors, calculated in ab initio molecular dynamics simulations, are reported for several binary liquids with different kinds of chemical bonding: metallic liquid alloy Bi–Pb, molten salt RbF, and liquid water. We derive analytical expressions for the long-wavelength asymptotes of the partial electron-ion structure factors of binary systems and show that the analytical results are in good agreement with the ab initio simulation data. The long-wavelength behaviour of the total charge structure factors for the three binary liquids is discussed
Martinek, Tomas; Duboué-Dijon, Elise; Timr, Štěpán; Mason, Philip E.; Baxová, Katarina; Fischer, Henry E.; Schmidt, Burkhard; Pluhařová, Eva; Jungwirth, Pavel
2018-06-01
We present a combination of force field and ab initio molecular dynamics simulations together with neutron scattering experiments with isotopic substitution that aim at characterizing ion hydration and pairing in aqueous calcium chloride and formate/acetate solutions. Benchmarking against neutron scattering data on concentrated solutions together with ion pairing free energy profiles from ab initio molecular dynamics allows us to develop an accurate calcium force field which accounts in a mean-field way for electronic polarization effects via charge rescaling. This refined calcium parameterization is directly usable for standard molecular dynamics simulations of processes involving this key biological signaling ion.
Bertoldi, Dalía S.; Ramos, Susana B.; Guillermet, Armando Fernández
2017-08-01
We present a theoretical analysis of the equation of state (EOS) of metals using a quasi-harmonic Einstein model with a dimensionless cohesive energy versus distance function (F(z)) involving the Wigner-Seitz radius and a material-dependent scaling length, as suggested in classical works by Rose, Ferrante, Smith and collaborators. Using this model, and "universal" values for the function and its first and second derivatives at the equilibrium distance (z=0), three general interrelations between EOS parameters and the cohesive energy are obtained. The first correlation involves the bulk modulus, and the second, the thermal expansion coefficient. In order to test these results an extensive database is developed, which involves available experimental data, and results of current ab initio density-functional-theory calculations using the VASP code. In particular, the 0 K values for volume, bulk modulus, its pressure derivative, and the cohesive energy of 27 elements belonging to the first (Sc, Ti, V, Cr, Fe, Co, Ni, Cu, Zn), second (Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd) and third (Hf, Ta, W, Re, Os, Ir, Pt, Au) transition row of the Periodic Table are calculated ab initio and used to test the present results. The third correlation obtained, allows an evaluation of the third derivative of F(z) at z=0 for the current elements. With this new information, a discussion is presented of the possibility of finding a "universal" F(z) versus z function able to account accurately for the pressure derivative of the bulk modulus of the transition elements.
Energy Technology Data Exchange (ETDEWEB)
Bechepeche, A.P.; Nasar, R.S.; Longo, E. [Sao Carlos Univ., SP (Brazil). Dept. de Quimica; Treu Junior, O.; Varela, J.A. [UNESP, Araraquara, SP (Brazil). Inst. de Quimica
1995-12-31
The zirconia was doped with 0,113 mol of Mg O e 0,005 mol of Ti O{sub 2}, and it was calcined in 1550{sup d}eg C and it was analyzed by XRD. The results shows that pure zirconia contains 96,19% of monoclinic phase and 3,18% of cubic. However, the doping magnesia stabilizes the zirconia in 17,24 of monoclinic; 29,63 of tetragonal and 53,13% of cubic phase. The addition of titanium in zirconia gives 25,85% of tetragonal phase and 37,66% of cubic, and this shows the no stabilizing action of this transition metal. By the other side, the results with ab-initio calculating shows the same tendency resulting in the next values of total energy: pure zirconia - monoclinic -11.316,86ua; tetragonal -8742,09 ua and cubic -8742,80 ua and Zr O{sub 2} Ti O{sub 2} system - monoclinic -9463,02 ua, tetragonal -9459,39 ua and cubic -9459,97 ua (author) 3 figs., 2 tabs.
Di Pasquale, Nicodemo; Davie, Stuart J.; Popelier, Paul L. A.
2018-06-01
Using the machine learning method kriging, we predict the energies of atoms in ion-water clusters, consisting of either Cl- or Na+ surrounded by a number of water molecules (i.e., without Na+Cl- interaction). These atomic energies are calculated following the topological energy partitioning method called Interacting Quantum Atoms (IQAs). Kriging predicts atomic properties (in this case IQA energies) by a model that has been trained over a small set of geometries with known property values. The results presented here are part of the development of an advanced type of force field, called FFLUX, which offers quantum mechanical information to molecular dynamics simulations without the limiting computational cost of ab initio calculations. The results reported for the prediction of the IQA components of the energy in the test set exhibit an accuracy of a few kJ/mol, corresponding to an average error of less than 5%, even when a large cluster of water molecules surrounding an ion is considered. Ions represent an important chemical system and this work shows that they can be correctly taken into account in the framework of the FFLUX force field.
X-ray magnetic scattering in SDW Cr - ab initio study
International Nuclear Information System (INIS)
Takahashi, M.; Igarashi, J.-I.; Hirai, K.
2004-01-01
Full text: Resonant x-ray scattering at the K-edge of transition metal atom has attracted much attention as a powerful tool for obtaining information on magnetic or orbital properties of 3d electrons. Recently Mannix et al. performed the x-ray magnetic scattering experiment in SDW Chromium and observed the finite scattering intensity with resonant enhancement at Cr K-edge on the SDW magnetic spot (0, 0, 1 ±δ). Applying ab-initio band structure calculation based on the local spin density approximation, we analyze the scattering spectra and elucidate the mechanism of the resonant enhancement in connection with the electronic structure. We assumed the bcc structure with the lattice constant a = 5.45a 0 and the SDW wavelength λ SDW = 20a, which are nearly equilibrium value at the spin-flip temperature T SF = 122K. The K-edge x-ray absorption and scattering spectra are calculated using Fermi's golden rule. We evaluate the non-resonant scattering amplitude within the spherical and dipolar approximations for spin and orbital moment contributions, respectively. The calculated absorption spectra are in good agreement with the experiment. This may assure the validity of the calculation. We obtained finite scattering amplitude with resonant enhancement at the K-edge. The calculated photon energy dependence of the scattering intensity shows good agreement with the experiment. The contribution of the 3d and 4p orbital moments to the non-resonant scattering amplitude is negligible in consequence of the smallness of their values, which are l max d ∼ 0.006ℎ and l max p ∼ 0.00007ℎ. On the other hand, although the 3d and 4p orbital moments are infinitesimal, they play important role on the resonant enhancement, which occurs through the 1s - 4p dipole transition and reflects the 4p orbital polarization. The 4p orbital polarization is caused by the on-site spin-orbit interaction in 4p orbital itself and the hybridization of the 4p orbital with the 3d orbital at neighboring
An analysis of hydrated proton diffusion in ab initio molecular dynamics
Energy Technology Data Exchange (ETDEWEB)
Tse, Ying-Lung Steve; Voth, Gregory A., E-mail: gavoth@uchicago.edu [Department of Chemistry, James Franck Institute, and Computation Institute, University of Chicago, Chicago, Illinois 60637 (United States); Knight, Chris [Leadership Computing Facility, Argonne National Laboratory, Argonne, Illinois 60439 (United States)
2015-01-07
A detailed understanding of the inherently multiscale proton transport process raises a number of scientifically challenging questions. For example, there remain many (partially addressed) questions on the molecular mechanism for long-range proton migration and the potential for the formation of long-lived traps giving rise to burst-and-rest proton dynamics. Using results from a sizeable collection of ab initio molecular dynamics (AIMD) simulations (totaling ∼2.7 ns) with various density functional approximations (Becke-Lee-Yang-Parr (BLYP), BLYP–D3, Hamprecht-Cohen-Tozer-Handy, B3LYP) and temperatures (300–330 K), equilibrium and dynamical properties of one excess proton and 128 water molecules are studied. Two features in particular (concerted hops and weak hydrogen-bond donors) are investigated to identify modes in the system that are strongly correlated with the onset of periods of burst-and-rest dynamics. The question of concerted hops seeks to identify those time scales over which long-range proton transport can be classified as a series of sequential water hopping events or as a near-simultaneous concerted process along compressed water wires. The coupling of the observed burst-and-rest dynamics with motions of a fourth neighboring water molecule (a weak hydrogen-bond donor) solvating the protonated water molecule is also investigated. The presence (absence) of hydrogen bonds involving this fourth water molecule before and after successful proton hopping events is found to be strongly correlated with periods of burst (rest) dynamics (and consistent with pre-solvation concepts). By analyzing several realizations of the AIMD trajectories on the 100-ps time scale, convergence of statistics can be assessed. For instance, it was observed that the probability for a fourth water molecule to approach the hydronium, if not already proximal at the beginning of the lifetime of the hydronium, is very low, indicative of the formation of stable void regions
Ab initio study of isomerism of Li2AB2 molecules and Li2AB2+ ions with 16 valent electrons
International Nuclear Information System (INIS)
Charkin, O.P.; Klimenko, N.M.; MakKi, M.L.
2000-01-01
In the framework of MP2(6-31*//HF/6-31G + ZPE(HF/6-31G*) and MP4SDTQ/6-31G*//MP2/6-31G* + ZPE(MP2/6-31G*) approximations ab initio calculations of surfaces of potential energy of molecules of lithium salts of Li 2 AB 2 (Li 2 BeO 2 , L 2 MgO 2 , Li 2 BeS 2 , Li 2 MgS 2 , Li 2 CN 2 , Li 2 SiN 2 , Li 2 CP 2 ) type and ions of Li 2 AB 2 + (Li 2 BO 2 + , Li 2 AlO 2 + , Li 2 BS 2 + , Li 2 AlS 2 + , Li 2 N 3 + , Li 2 PN 2 + , Li 2 P 3 + ) type with 16 valent electrons are done. For oxide and nitride systems global minimum corresponds to symmetric linear structure D ∞h and for their sulfide and phosphorus analogues curved plane or unplane (C 2 ) structure with bond angle φ(LBA)=90-110 Deg are preferable. Equilibrium geometric parameters, relative energies and energies of isomer decomposition, frequencies and IR-intensities of normal vibrations are determined [ru
Improved parametric fits for the HeH2 ab initio energy surface
International Nuclear Information System (INIS)
Muchnick, P.
1992-01-01
A brief history of the development of ab initio calculations for the HeH 2 quasi-molecule energy surface, and the parametric fits to these ab initio calculations, is presented. The concept of 'physical reasonableness' of the parametric fit is discussed. Several new improved parametric fits for the energy surface, meeting these requirements, are then proposed. One fit extends the Russek-Garcia parametric fit for the deep repulsion region to include r-dependent parameters, resulting in a more physically reasonable fit with smaller average error. This improved surface fit is applied to quasi-elastic collisions of He on H 2 in the impulse approximation. Previous classical calculations of the scaled inelastic vibrorotational excitation energy distributions are improved with this more accurate parametric fit of the energy surface and with the incorporation of quantum effects in vibrational excitation. It is shown that Sigmund's approach in developing his scaling law is incomplete in the contribution of the three-body interactions to vibrational excitation of the H 2 molecule is concerned. The Sigmund theory is extended to take into account for r-dependency of three-body interactions. A parametric fit for the entire energy surface from essentially 0 ≤R≤∞ and 1.2≤r≤1.6 a.u., where R is the intermolecular spacing and r is the hydrogen bonding length, is also presented. This fit is physically reasonable in all asymptotic limits. This first, full surface parametric fit is based primarily upon a composite of ab initio studies by Russek and Garcia and Meyer, Hariharan and Kutzelnigg. Parametric fits for the H 2 (1sσ g ) 2 , H 2 + (1sσ g ), H 2 + (2pσ u ) and (LiH 2 ) + energy surfaces are also presented. The new parametric fits for H 2 , H 2 + (1sσ g ) are shown to be improvements over the well-known Morse potentials for these surfaces
Czech Academy of Sciences Publication Activity Database
Chocholoušová, Jana; Vacek, Jaroslav; Hobza, Pavel
2002-01-01
Roč. 4, - (2002), s. 2119-2122 ISSN 1463-9076 R&D Projects: GA MŠk LN00A032 Institutional research plan: CEZ:AV0Z4040901 Keywords : formic acid dimer * ab initio calculations * molecular dynamics simulations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.838, year: 2002
DEFF Research Database (Denmark)
Gorelik, Tatiana E; van de Streek, Jacco; Kilbinger, Andreas F M
2012-01-01
Ab-initio crystal structure analysis of organic materials from electron diffraction data is presented. The data were collected using the automated electron diffraction tomography (ADT) technique. The structure solution and refinement route is first validated on the basis of the known crystal stru...
DEFF Research Database (Denmark)
Tao, Kun; Stepanyuk, V.S.; Bruno, P.
2008-01-01
The state of the art ab initio calculations reveal the effect of a scanning tunneling microscopy tip on magnetic properties and conductance of a benzene-adatom sandwich on Cu(001). We concentrate on a benzene-Co system interacting with a Cr tip. Our studies give a clear evidence that magnetism...
International Nuclear Information System (INIS)
Nguyen Thanh Duoc; Nguyen Thi Ai Nhung; Tran Duong; Pham Van Tat
2015-01-01
The results presented in this paper are the ab initio intermolecular potentials and the second virial coefficient, B_2 (T) of the dimer Cl_2-Cl_2. These ab initio potentials were proposed by the quantum chemical calculations at high level of theory CCSD(T) with basis sets of Dunning valence correlation-consistent aug-cc-pVmZ (m = 2, 3); these results were extrapolated to complete basis set limit aug-cc-pV23Z. The ab initio energies of complete basis set limit aug-cc-pV23Z resulted from the exponential extrapolation were used to construct the 5-site pair potential functions. The second virial coefficients for this dimer were predicted from those with four-dimensional integration. The second virial coefficients were also corrected to first-order quantum effects. The results turn out to be in good agreement with experimental data, if available, or with those from empirical correlation. The quality of ab initio 5-site potentials proved the reliability for prediction of molecular thermodynamic properties. (author)
Efficacy of the SU(3) scheme for ab initio large-scale calculations beyond the lightest nuclei
Czech Academy of Sciences Publication Activity Database
Dytrych, Tomáš; Maris, P.; Launey, K. D.; Draayer, J. P.; Vary, J. P.; Langr, D.; Saule, E.; Caprio, M. A.; Catalyurek, U.; Sosonkina, M.
2016-01-01
Roč. 207, OCT (2016), s. 202-210 ISSN 0010-4655 R&D Projects: GA ČR GA16-16772S Institutional support: RVO:61389005 Keywords : nuclear structure * Ab initio methods * Shell model * models based on group theory Subject RIV: BE - Theoretical Physics Impact factor: 3.936, year: 2016
Koten, G. van; Albrecht, M.A.; Gossage, R.A.; Frey, H.; Ehlers, A.W.; Baerends, E.J.; Merbach, A.E.
2001-01-01
The detailed mechanism of the reversible binding and fast exchange of SO2 on the organoplatinum(II) complex [PtI(NCN)], 1, has been studied experimentally in solution (C2F4Br2) using low-temperature NMR spectroscopy and theoretically by ab initio calculations. Direct bonding of SO2 and formation of