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...
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...
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...
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 ([...
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
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.
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
In-medium no-core shell model for ab initio nuclear structure calculations
International Nuclear Information System (INIS)
Gebrerufael, Eskendr
2017-01-01
In this work, we merge two successful ab initio nuclear-structure methods, the no-core shell model (NCSM) and the multi-reference in-medium similarity renormalization group (IM-SRG), to define a novel many-body approach for the comprehensive description of ground and excited states of closed- and open-shell medium-mass nuclei. Building on the key advantages of the two methods - the decoupling of excitations at the many-body level in the IM-SRG, and the exact diagonalization in the NCSM applicable up to medium-light nuclei - their combination enables fully converged no-core calculations for an unprecedented range of nuclei and observables at moderate computational cost. The efficiency and rapid model-space convergence of the new approach make it ideally suited for ab initio studies of ground and low-lying excited states of nuclei up to the medium-mass regime. Interactions constructed within the framework of chiral effective field theory provide an excellent opportunity to describe properties of nuclei from first principles, i.e., rooted in quantum chromodynamics, they overcome the lack of predictive power of phenomenological potentials. The hard core of these interactions causes strong short-range correlations, which we soften by using the similarity-renormalization-group transformation that accelerates the model-space convergence of many-body calculations. Three-nucleon effects, which are mandatory for the correct description of bulk properties of nuclei, are included in our calculations by using the normal-ordered two-body approximation, which has been shown to be sufficient to capture the main effects of the three-nucleon interaction. Using these interactions, we analyze energies of ground and excited states in the carbon and oxygen isotopic chains, where conventional NCSM calculations are still feasible and provide an important benchmark. Furthermore, we study the Hoyle state in 12 C - a three-alpha cluster state that cannot be converged in standard NCSM
Cluster form factor calculation in the ab initio no-core shell model
International Nuclear Information System (INIS)
Navratil, Petr
2004-01-01
We derive expressions for cluster overlap integrals or channel cluster form factors for ab initio no-core shell model (NCSM) wave functions. These are used to obtain the spectroscopic factors and can serve as a starting point for the description of low-energy nuclear reactions. We consider the composite system and the target nucleus to be described in the Slater determinant (SD) harmonic oscillator (HO) basis while the projectile eigenstate to be expanded in the Jacobi coordinate HO basis. This is the most practical case. The spurious center of mass components present in the SD bases are removed exactly. The calculated cluster overlap integrals are translationally invariant. As an illustration, we present results of cluster form factor calculations for 5 He vertical bar 4 He+n>, 5 He vertical bar 3 H+d>, 6 Li vertical bar 4 He+d>, 6 Be vertical bar 3 He+ 3 He>, 7 Li vertical bar 4 He+ 3 H>, 7 Li vertical bar 6 Li+n>, 8 Be vertical bar 6 Li+d>, 8 Be vertical bar 7 Li+p>, 9 Li vertical bar 8 Li+n>, and 13 C vertical bar 12 C+n>, with all the nuclei described by multi-(ℎ/2π)Ω NCSM wave functions
Determination of a silane intermolecular force field potential model from an ab initio calculation
International Nuclear Information System (INIS)
Li, Arvin Huang-Te; Chao, Sheng D.; Chang, Chien-Cheng
2010-01-01
Intermolecular interaction potentials of the silane dimer in 12 orientations have been calculated by using the Hartree-Fock (HF) self-consistent theory and the second-order Moeller-Plesset (MP2) perturbation theory. We employed basis sets from Pople's medium-size basis sets [up to 6-311++G(3df, 3pd)] and Dunning's correlation consistent basis sets (up to the triply augmented correlation-consistent polarized valence quadruple-zeta basis set). We found that the minimum energy orientations were the G and H conformers. We have suggested that the Si-H attractions, the central silicon atom size, and electronegativity play essential roles in weakly binding of a silane dimer. The calculated MP2 potential data were employed to parametrize a five-site force field for molecular simulations. The Si-Si, Si-H, and H-H interaction parameters in a pairwise-additive, site-site potential model for silane molecules were regressed from the ab initio energies.
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
Energy Technology Data Exchange (ETDEWEB)
Liu, Hanchao; Wang, Yimin; Bowman, Joel M. [Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, Georgia 30322 (United States)
2015-05-21
The calculation and characterization of the IR spectrum of liquid water have remained a challenge for theory. In this paper, we address this challenge using a combination of ab initio approaches, namely, a quantum treatment of IR spectrum using the ab initio WHBB water potential energy surface and a refined ab initio dipole moment surface. The quantum treatment is based on the embedded local monomer method, in which the three intramolecular modes of each embedded H{sub 2}O monomer are fully coupled and also coupled singly to each of six intermolecular modes. The new dipole moment surface consists of a previous spectroscopically accurate 1-body dipole moment surface and a newly fitted ab initio intrinsic 2-body dipole moment. A detailed analysis of the new dipole moment surface in terms of the coordinate dependence of the effective atomic charges is done along with tests of it for the water dimer and prism hexamer double-harmonic spectra against direct ab initio calculations. The liquid configurations are taken from previous molecular dynamics calculations of Skinner and co-workers, using the TIP4P plus E3B rigid monomer water potential. The IR spectrum of water at 300 K in the range of 0–4000 cm{sup −1} is calculated and compared with experiment, using the ab initio WHBB potential and new ab initio dipole moment, the q-TIP4P/F potential, which has a fixed-charged description of the dipole moment, and the TTM3-F potential and dipole moment surfaces. The newly calculated ab initio spectrum is in very good agreement with experiment throughout the above spectral range, both in band positions and intensities. This contrasts to results with the other potentials and dipole moments, especially the fixed-charge q-TIP4P/F model, which gives unrealistic intensities. The calculated ab initio spectrum is analyzed by examining the contribution of various transitions to each band.
International Nuclear Information System (INIS)
Liu, Hanchao; Wang, Yimin; Bowman, Joel M.
2015-01-01
The calculation and characterization of the IR spectrum of liquid water have remained a challenge for theory. In this paper, we address this challenge using a combination of ab initio approaches, namely, a quantum treatment of IR spectrum using the ab initio WHBB water potential energy surface and a refined ab initio dipole moment surface. The quantum treatment is based on the embedded local monomer method, in which the three intramolecular modes of each embedded H 2 O monomer are fully coupled and also coupled singly to each of six intermolecular modes. The new dipole moment surface consists of a previous spectroscopically accurate 1-body dipole moment surface and a newly fitted ab initio intrinsic 2-body dipole moment. A detailed analysis of the new dipole moment surface in terms of the coordinate dependence of the effective atomic charges is done along with tests of it for the water dimer and prism hexamer double-harmonic spectra against direct ab initio calculations. The liquid configurations are taken from previous molecular dynamics calculations of Skinner and co-workers, using the TIP4P plus E3B rigid monomer water potential. The IR spectrum of water at 300 K in the range of 0–4000 cm −1 is calculated and compared with experiment, using the ab initio WHBB potential and new ab initio dipole moment, the q-TIP4P/F potential, which has a fixed-charged description of the dipole moment, and the TTM3-F potential and dipole moment surfaces. The newly calculated ab initio spectrum is in very good agreement with experiment throughout the above spectral range, both in band positions and intensities. This contrasts to results with the other potentials and dipole moments, especially the fixed-charge q-TIP4P/F model, which gives unrealistic intensities. The calculated ab initio spectrum is analyzed by examining the contribution of various transitions to each band
Ab initio calculation of the sound velocity of dense hydrogen: implications for models of Jupiter
Alavi, A.; Parrinello, M.; Frenkel, D.
1995-01-01
First-principles molecular dynamics simulations were used to calculate the sound velocity of dense hydrogen, and the results were compared with extrapolations of experimental data that currently conflict with either astrophysical models or data obtained from recent global oscillation measurements of
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
International Nuclear Information System (INIS)
Freire, Ricardo O.; Rocha, Gerd B.; Albuquerque, Rodrigo Q.; Simas, Alfredo M.
2005-01-01
The second version of the sparkle model for the calculation of lanthanide complexes (SMLC II) as well as ab-initio calculations (HF/STO-3G and HF/3-21G) have been used to calculate the geometries of a series of europium (III) complexes with different coordination numbers (CN=7, 8 and 9), ligating atoms (O and N) and ligands (mono, bi and polydentate). The so-called ligand field parameters, Bqk's, have been calculated from both SMLC II and ab-initio optimized structures and compared to the ones calculated from crystallographic data. The results show that the SMLC II model represents a significant improvement over the previous version (SMLC) and has given good results when compared to ab-initio methods, which demand a much higher computational effort. Indeed, ab-initio methods take around a hundred times more computing time than SMLC. As such, our results indicate that our sparkle model can be a very useful and a fast tool when applied to the prediction of both ground state geometries and ligand field parameters of europium (III) complexes
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...
Czech Academy of Sciences Publication Activity Database
Čurík, Roman; Šulc, M.
2010-01-01
Roč. 43, č. 17 (2010), s. 175205 ISSN 0953-4075 R&D Projects: GA MŠk(CZ) OC10046; GA MŠk OC09079; GA AV ČR KJB400400803; GA ČR GA202/08/0631 Institutional research plan: CEZ:AV0Z40400503 Keywords : Ab initio calculations * Commonly used * DFT potential Subject RIV: CF - Physical ; The oretical Chemistry Impact factor: 1.902, year: 2010
International Nuclear Information System (INIS)
Olsson, Paer
2004-04-01
The efficiency of fast neutron reactors, such as for fusion, breeding and transmutation, depend strongly on the neutron radiation resistance of the materials used in the reactors. The binary Fe-Cr alloy, which has many attractive properties in this regard, is the base for the best steels of today which are, however, still not up to the required standards. Therefore, substantial effort has been devoted to finding new materials that can cope with the demands better. Experimental studies must be complemented with extensive theoretical modelling in order to understand the effects that different alloying elements has on the resistance properties of materials. To this end, the first steps of multi-scale modelling has been taken, starting out with ab initio calculations of the electronic structure of the complete concentration range range of the disordered binary Fe-C alloy. The mixing enthalpy of Fe-Cr has been quantitatively predicted and has, together with data from literature, been used in order to fit two sets of interatomic potentials for the purpose of simulating defect evolution with molecular dynamics and kinetic Monte-Carlo codes. These dedicated Fe-Cr alloy potentials are new and represent important additions to the pure element potentials that can be found in literature
Energy Technology Data Exchange (ETDEWEB)
Olsson, Paer
2004-04-01
The efficiency of fast neutron reactors, such as for fusion, breeding and transmutation, depend strongly on the neutron radiation resistance of the materials used in the reactors. The binary Fe-Cr alloy, which has many attractive properties in this regard, is the base for the best steels of today which are, however, still not up to the required standards. Therefore, substantial effort has been devoted to finding new materials that can cope with the demands better. Experimental studies must be complemented with extensive theoretical modelling in order to understand the effects that different alloying elements has on the resistance properties of materials. To this end, the first steps of multi-scale modelling has been taken, starting out with ab initio calculations of the electronic structure of the complete concentration range range of the disordered binary Fe-C alloy. The mixing enthalpy of Fe-Cr has been quantitatively predicted and has, together with data from literature, been used in order to fit two sets of interatomic potentials for the purpose of simulating defect evolution with molecular dynamics and kinetic Monte-Carlo codes. These dedicated Fe-Cr alloy potentials are new and represent important additions to the pure element potentials that can be found in literature.
Swerts, Ben; Chibotaru, Liviu F; Lindh, Roland; Seijo, Luis; Barandiaran, Zoila; Clima, Sergiu; Pierloot, Kristin; Hendrickx, Marc F A
2008-04-01
In this article, we present a fragment model potential approach for the description of the crystalline environment as an extension of the use of embedding ab initio model potentials (AIMPs). The biggest limitation of the embedding AIMP method is the spherical nature of its model potentials. This poses problems as soon as the method is applied to crystals containing strongly covalently bonded structures with highly nonspherical electron densities. The newly proposed method addresses this problem by keeping the full electron density as its model potential, thus allowing one to group sets of covalently bonded atoms into fragments. The implementation in the MOLCAS 7.0 quantum chemistry package of the new method, which we call the embedding fragment ab inito model potential method (embedding FAIMP), is reported here, together with results of CASSCF/CASPT2 calculations. The developed methodology is applied for two test problems: (i) the investigation of the lowest ligand field states (2)A1 and (2)B1 of the Cr(V) defect in the YVO4 crystal and (ii) the investigation of the lowest ligand field and ligand-metal charge transfer (LMCT) states at the Mn(II) substitutional impurity doped into CaCO3. Comparison with similar calculations involving AIMPs for all environmental atoms, including those from covalently bounded units, shows that the FAIMP treatment of the YVO4 units surrounding the CrO4(3-) cluster increases the excitation energy (2)B1 → (2)A1 by ca. 1000 cm(-1) at the CASSCF level of calculation. In the case of the Mn(CO3)6(10-) cluster, the FAIMP treatment of the CO3(2-) units of the environment give smaller corrections, of ca. 100 cm(-1), for the ligand-field excitation energies, which is explained by the larger ligands of this cluster. However, the correction for the energy of the lowest LMCT transition is found to be ca. 600 cm(-1) for the CASSCF and ca. 1300 cm(-1) for the CASPT2 calculation.
DEFF Research Database (Denmark)
Singla, Mallika; Rasmussen, Morten Lund; Hashemi, Hamid
2018-01-01
. In the present work, the thermal conversion of CH3Cl under gasification conditions was investigated. A detailed chemical kinetic model for pyrolysis and oxidation of methyl chloride was developed and validated against selected experimental data from the literature. Key reactions of CH2Cl with O2 and C2H4......Limitations in current hot gas cleaning methods for chlorine species from biomass gasification may be a challenge for end use such as gas turbines, engines, and fuel cells, all requiring very low levels of chlorine. During devolatilization of biomass, chlorine is released partly as methyl chloride...... in low-temperature gasification. The present work illustrates how ab initio theory and chemical kinetic modeling can help to resolve emission issues for thermal processes in industrial scale....
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 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.
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)
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
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.
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...
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
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)
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 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
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...
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...
International Nuclear Information System (INIS)
Medišauskas, Lukas; Ivanov, Misha Yu; Morales, Felipe; Plimak, Lev; Smirnova, Olga; Palacios, Alicia; González-Castrillo, Alberto; Martín, Fernando
2015-01-01
We present an analytical model based on the time-dependent WKB approximation to reproduce the photoionization spectra of an H 2 molecule in the autoionization region. We explore the nondissociative channel, which is the major contribution after one-photon absorption, and we focus on the features arising in the energy differential spectra due to the interference between the direct and the autoionization pathways. These features depend on both the timescale of the electronic decay of the autoionizing state and the time evolution of the vibrational wavepacket created in this state. With full ab initio calculations and with a one-dimensional approach that only takes into account the nuclear wavepacket associated to the few relevant electronic states we compare the ground state, the autoionizing state, and the background continuum electronic states. Finally, we illustrate how these features transform from molecular-like to atomic-like by increasing the mass of the system, thus making the electronic decay time shorter than the nuclear wavepacket motion associated with the resonant state. In other words, autoionization then occurs faster than the molecular dissociation into neutrals. (paper)
Ab initio calculations of cross luminescence materials
International Nuclear Information System (INIS)
Kanchana, V.
2016-01-01
Abintio calculations have been performed to study the structural, electronic, and optical properties of ABX 3 (A=alkali, B=alkaline-earth, and X=halide) compounds. The ground state properties are calculated using the pseudopotential method with the inclusion of van der Waals interaction, which we find inevitable in reproducing the experimental structure properties in alkali iodides because of its layered structure. All calculations were performed using the Full-Potential Linearized Augmented Plane Wave method. The band structures are plotted with various functionals and we find the newly developed Tran and Blaha modified Becke-Johnson potential to improve the band gap significantly. The optical properties such as complex dielectric function, refractive index, and absorption spectra are calculated which clearly reveal the optically isotropic nature of these materials though being structurally anisotropic, which is the key requirement for ceramic scintillators. Cross luminescence materials are very interesting because of its fast decay. One of the major criteria for the cross luminescence to happen is the energy difference between valence band and next deeper core valence band being lesser when compared to energy gap of the compound, so that radiative electronic transition may occur between valence band and core valence band. We found this criteria to be satisfied in all the studied compounds leading to cross luminescence except for KSrI 3 , RbSrI 3 . The present study suggest that among the six compounds studied, CsSrI 3 , CsMgCl 3 , CsCaCl 3 , and CsSrCl 3 compounds are cross luminescence materials, which is well explained from the band structure, optical properties calculations. Chlorides are better scintillators that iodides and CsMgCl 3 is found to be promising one among the studied compounds. Apart from these materials we have also discussed electronic structure and optical properties of other scintillator compounds. (author)
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.
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
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...
Ciofi degli Atti, Claudio; Mezzetti, Chiara Benedetta; Morita, Hiko
2017-04-01
Background: Two-nucleon (2 N ) short-range correlations (SRC) in nuclei have been recently thoroughly investigated, both theoretically and experimentally and the study of three-nucleon (3 N ) SRC, which could provide important information on short-range hadronic structure, is underway. Novel theoretical ideas concerning 2 N and 3 N SRC are put forward in the present paper. Purpose: The general features of a microscopic one-nucleon spectral function which includes the effects of both 2 N and 3 N SRC and its comparison with ab initio spectral functions of the three-nucleon systems are illustrated. Methods: A microscopic and parameter-free one-nucleon spectral function expressed in terms of a convolution integral involving ab initio relative and center-of-mass (c.m.) momentum distributions of a 2 N pair and aimed at describing two- and three-nucleon short-range correlations, is obtained by using: (i) the two-nucleon momentum distributions obtained within ab initio approaches based upon nucleon-nucleon interactions of the Argonne family; (ii) the exact relation between one- and two-nucleon momentum distributions; (iii) the fundamental property of factorization of the nuclear wave function at short internucleon ranges. Results: The comparison between the ab initio spectral function of 3He and the one based upon the convolution integral shows that when the latter contains only two-nucleon short-range correlations the removal energy location of the peaks and the region around them exhibited by the ab initio spectral function are correctly predicted, unlike the case of the high and low removal energy tails; the inclusion of the effects of three-nucleon correlations brings the convolution model spectral function in much better agreement with the ab initio one; it is also found that whereas the three-nucleon short-range correlations dominate the high energy removal energy tail of the spectral function, their effects on the one-nucleon momentum distribution are almost one
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
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
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...
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 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).
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
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.)
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....
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.)
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
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
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
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.
Efficacy of the SU(3) scheme for ab initio large-scale calculations beyond the lightest nuclei
Energy Technology Data Exchange (ETDEWEB)
Dytrych, T. [Academy of Sciences of the Czech Republic (ASCR), Prague (Czech Republic); Louisiana State Univ., Baton Rouge, LA (United States); Maris, Pieter [Iowa State Univ., Ames, IA (United States); Launey, K. D. [Louisiana State Univ., Baton Rouge, LA (United States); Draayer, J. P. [Louisiana State Univ., Baton Rouge, LA (United States); Vary, James [Iowa State Univ., Ames, IA (United States); Langr, D. [Czech Technical Univ., Prague (Czech Republic); Aerospace Research and Test Establishment, Prague (Czech Republic); Saule, E. [Univ. of North Carolina, Charlotte, NC (United States); Caprio, M. A. [Univ. of Notre Dame, IN (United States); Catalyurek, U. [The Ohio State Univ., Columbus, OH (United States). Dept. of Electrical and Computer Engineering; Sosonkina, M. [Old Dominion Univ., Norfolk, VA (United States)
2016-06-09
We report on the computational characteristics of ab initio nuclear structure calculations in a symmetry-adapted no-core shell model (SA-NCSM) framework. We examine the computational complexity of the current implementation of the SA-NCSM approach, dubbed LSU3shell, by analyzing ab initio results for ^{6}Li and ^{12}C in large harmonic oscillator model spaces and SU(3)-selected subspaces. We demonstrate LSU3shell's strong-scaling properties achieved with highly-parallel methods for computing the many-body matrix elements. Results compare favorably with complete model space calculations and signi cant memory savings are achieved in physically important applications. In particular, a well-chosen symmetry-adapted basis a ords memory savings in calculations of states with a fixed total angular momentum in large model spaces while exactly preserving translational invariance.
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
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)
Zhandun, V.; Zamkova, N.; Ovchinnikov, S.; Sandalov, I.
2017-11-01
To accurately translate the results obtained within density functional theory (DFT) to the language of many-body theory we suggest and test the following approach: the parameters of the formulated model are to be found from the requirement that the model self-consistent electron density and density of electron states are as close as possible to the ones found from the DFT-based calculations. The investigation of the phase diagram of the model allows us to find the critical regions in magnetic properties. Then the behavior of the real system in these regions is checked by the ab initio calculations. As an example, we studied the physics of magnetic moment (MM) formation due to substitutions of Si by Fe-atoms or vice versa in the otherwise non-magnetic alloy α-FeSi2. We find that the MM formation is essentially controlled by the interaction of Fe atoms with its next nearest atoms (NNN) and by their particular arrangement. The latter may result in different magnetic states at the same concentrations of constituents. Moreover, one of arrangements produces the counterintuitive result: a ferromagnetism arises due to an increase in Si concentration in Fe1-xSi2+ x ordered alloy. The existing phenomenological models associate the destruction of magnetic moment only with the number of Fe-Si nearest neighbors. The presented results show that the crucial role in MM formation is played by the particular local NNN environment of the metal atom in the transition metal-metalloid alloy.
(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.
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.
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)
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.
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.
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)
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
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.
Dos, Alexandra; Schimming, Volkmar; Tosoni, Sergio; Limbach, Hans-Heinrich
2008-12-11
The interactions of the 15N-labeled amino groups of dry solid poly-L-lysine (PLL) with various halogen and oxygen acids HX and the relation to the secondary structure have been studied using solid-state 15N and 13C CPMAS NMR spectroscopy (CP = cross polarization and MAS = magic angle spinning). For comparison, 15N NMR spectra of an aqueous solution of PLL were measured as a function of pH. In order to understand the effects of protonation and hydration on the 15N chemical shifts of the amino groups, DFT and chemical shielding calculations were performed on isolated methylamine-acid complexes and on periodic halide clusters of the type (CH3NH3(+)X(-))n. The combined experimental and computational results reveal low-field shifts of the amino nitrogens upon interaction with the oxygen acids HX = HF, H2SO4, CH3COOH, (CH3)2POOH, H3PO4, HNO3, and internal carbamic acid formed by reaction of the amino groups with gaseous CO2. Evidence is obtained that only hydrogen-bonded species of the type (Lys-NH2***H-X)n are formed in the absence of water. 15N chemical shifts are maximum when H is located in the hydrogen bond center and then decrease again upon full protonation, as found for aqueous solution at low pH. By contrast, halogen acids interact in a different way. They form internal salts of the type (Lys-NH3(+)X(-))n via the interaction of many acid-base pairs. This salt formation is possible only in the beta-sheet conformation. By contrast, the formation of hydrogen-bonded complexes can occur both in beta-sheet domains as well as in alpha-helical domains. The 15N chemical shifts of the protonated ammonium groups increase when the size of the interacting halogen anions is increased from chloride to iodide and when the number of the interacting anions is increased. Thus, the observed high-field 15N shift of ammonium groups upon hydration is the consequence of replacing interacting halogen atoms by oxygen atoms.
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.
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 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 ...
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 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)
Gunde, R.; Ha, T.-K.; Günthard, H. H.
1990-08-01
In this paper results of consistent force field modeling (CFF) of the potential function to conversion of the gauche (g) to the trans (t) conformer of 1,2-difluoroethane (DFE) isolated in an argon matrix will be reported. Starting point are locally stable configurations gDFE:Ar 364 (defect GH1) and tDFE:Ar 364 (TH1) obtained in previous work from CFF modeling of a cube shaped Ar 364 fragment containing one DFE molecule in its center. Using the dihedral angle of DFE as an independent parameter the minimum energy path of the conversion process gDFE:Ar 364→tDFE:Ar 364 will be determined by CFF energy minimization. Determination of the minimum energy path is found to require large numbers of energy minimization steps and to lead to a rather complicated motion of the molecule with respect to the crystal fragment. Surprisingly the molecule-matrix interactions lead to a reduction of the g-t barrier by ≈500 cal/mol and to a stabilization of the trans species by ≈500 cal/mol. This finding is a consequence of a delicate interplay of matrix-molecule and matrix-matrix interactions. Calculation of the electric polarization energy (induced dipole-first-order polarization approximation) is based on extended ab initio calculations of dipole and quadrupole moments and a bond polarizability estimate of the first-order polarizability of DFE as a function of the internal rotation angle, on Fourier expansion of multipole components and use of symmetry for reduction of the order of the linear system defining the (self-consistent) induced dipole moments of all Ar atoms. Electric polarization is found to alter the potential function of the conversion process in a profound way: the g-t barrier and the t-g energy difference are increased to ≈3000 cal/mol and to ≈1500 cal/mol respectively (≈2500 and ≈530 cal/mol respectively for free DFE). Further applications of the technique developed in this work to related problems of matrix isolated molecules, e.g., vibrational matrix
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.
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)
Ab initio calculation of hyperfine splitting constants of molecules
Ohta, K.; Nakatsuji, H.; Hirao, K.; Yonezawa, T.
1980-08-01
Hyperfine splitting (hfs) constants of molecules, methyl, ethyl, vinyl, allyl, cyclopropyl, formyl, O3-, NH2, NO2, and NF2 radicals have been calculated by the pseudo-orbital (PO) theory, the unrestricted HF (UHF), projected UHF (PUHF) and single excitation (SE) CI theories. The pseudo-orbital (PO) theory is based on the symmetry-adapted-cluster (SAC) expansion proposed previously. Several contractions of the Gaussian basis sets of double-zeta accuracy have been examined. The UHF results were consistently too large to compare with experiments and the PUHF results were too small. For molecules studied here, the PO theory and SECI theory gave relatively close results. They were in fair agreement with experiments. The first-order spin-polarization self-consistency effect, which was shown to be important for atoms, is relatively small for the molecules. The present result also shows an importance of eliminating orbital-transformation dependence from conventional first-order perturbation calculations. The present calculations have explained well several important variations in the experimental hfs constants.
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 calculation of electron excitation energies in solids
International Nuclear Information System (INIS)
Louie, S.G.
1996-02-01
Progress in the first-principles calculation of electron excitation energies in solids is discussed. Quasiparticle energies are computed by expanding the electron self energy to first order in the screened Coulomb interaction in the so-called GW approximation. The method was applied to explain and predict spectroscopic properties of a variety of systems. Several illustrative applications to semiconductors, materials under pressure, chemisorption, and point defects in solids are presented. A recent reformulation of the method employing mixed- space functions and imaginary time techniques is also discussed
Ab Initio Calculations Of Nuclear Reactions And Exotic Nuclei
Energy Technology Data Exchange (ETDEWEB)
Quaglioni, S. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
2014-05-05
Our ultimate goal is to develop a fundamental theory and efficient computational tools to describe dynamic processes between nuclei and to use such tools toward supporting several DOE milestones by: 1) performing predictive calculations of difficult-to-measure landmark reactions for nuclear astrophysics, such as those driving the neutrino signature of our sun; 2) improving our understanding of the structure of nuclei near the neutron drip line, which will be the focus of the DOE’s Facility for Rare Isotope Beams (FRIB) being constructed at Michigan State University; but also 3) helping to reveal the true nature of the nuclear force. Furthermore, these theoretical developments will support plasma diagnostic efforts at facilities dedicated to the development of terrestrial fusion energy.
Ab initio MCHF structural calculations of Mg-like cerium
Wajid, Abdul; Jabeen, S.; Husain, Abid
2018-05-01
Energy levels and emission line wavelengths of high-Z materials are useful for impurity diagnostics in the next generation fusion devices. For this here we have calculated E1, M2 transitions, oscillator strengths, and transition probabilities for transitions among the terms belonging to the 2p63s2, 2p63s3p, 2p63p2 and 2p63s3d for the Magnesium like cerium (Ce XLVII) using the GRASP2K package based on the fully relativistic multi-configuration Dirac-Fock method. The electron correlation effects, Breit interaction and quantum electrodynamics effects to the atomic state wave functions and the corresponding energies have been taken into account.
Ab Initio Calculations of Transport Properties of Vanadium Oxides
Lamsal, Chiranjivi; Ravindra, N. M.
2018-04-01
The temperature-dependent transport properties of vanadium oxides have been studied near the Fermi energy using the Kohn-Sham band structure approach combined with Boltzmann transport equations. V2O5 exhibits significant thermoelectric properties, which can be attributed to its layered structure and stability. Highly anisotropic electrical conduction in V2O5 is clearly manifested in the calculations. Due to specific details of the band structure and anisotropic electron-phonon interactions, maxima and crossovers are also seen in the temperature-dependent Seebeck coefficient of V2O5. During the phase transition of VO2, the Seebeck coefficient changes by 18.9 µV/K, which is close to (within 10% of) the observed discontinuity of 17.3 µV/K.
Ab initio calculation of the electronic absorption spectrum of liquid water
International Nuclear Information System (INIS)
Martiniano, Hugo F. M. C.; Galamba, Nuno; Cabral, Benedito J. Costa
2014-01-01
The electronic absorption spectrum of liquid water was investigated by coupling a one-body energy decomposition scheme to configurations generated by classical and Born-Oppenheimer Molecular Dynamics (BOMD). A Frenkel exciton Hamiltonian formalism was adopted and the excitation energies in the liquid phase were calculated with the equation of motion coupled cluster with single and double excitations method. Molecular dynamics configurations were generated by different approaches. Classical MD were carried out with the TIP4P-Ew and AMOEBA force fields. The BLYP and BLYP-D3 exchange-correlation functionals were used in BOMD. Theoretical and experimental results for the electronic absorption spectrum of liquid water are in good agreement. Emphasis is placed on the relationship between the structure of liquid water predicted by the different models and the electronic absorption spectrum. The theoretical gas to liquid phase blue-shift of the peak positions of the electronic absorption spectrum is in good agreement with experiment. The overall shift is determined by a competition between the O–H stretching of the water monomer in liquid water that leads to a red-shift and polarization effects that induce a blue-shift. The results illustrate the importance of coupling many-body energy decomposition schemes to molecular dynamics configurations to carry out ab initio calculations of the electronic properties in liquid phase
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
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.
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...
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
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.
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 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.
International Nuclear Information System (INIS)
Ito, A.; Kenmotsu, T.; Kikuhara, Y.; Inai, K.; Ohya, K.; Wang, Y.; Irle, S.; Morokuma, K.; Nakamura, H.
2009-01-01
Full text: To understand the plasma-wall interaction on divertor plates, we investigate the interaction of hydrogen atoms and carbon materials used in the high heat flux components by the use of the following simulations. Monte-Carlo (MC) method based on binary collision approximation can calculate the sputtering process of hydrogen atoms on the carbon material quickly. Classical molecular dynamics (MD) method employs multi-body potential models and can treat realistic structures of crystal and molecule. The ab-initio method can calculate electron energy in quantum mechanics, which is regarded as realistic potential for atoms. In the present paper, the interaction of the hydrogen and the carbon material is investigated using the multi-scale (MC, MD and ab-initio) methods. The bombardment of hydrogen atoms onto the carbon material is simulated by the ACAT-code of the MC method, which cannot represent the structure of crystal, and the MD method using modified reactive empirical bond order (REBO) potential, which treats single crystal graphite and amorphous carbon. Consequently, we clarify that the sputtering yield and the reflection rate calculated by the ACAT-code agree with those on the amorphous carbon calculated by the MD. Moreover, there are many kinds of REBO potential for the MD. Adsorption, reflection and penetration rates between a hydrogen atom and a graphene surface are calculated by the MD simulations using the two kinds of potential model. For the incident energy of less than 1 eV, the MD simulation using the modified REBO potential, which is based on Brenner's REBO potential in 2002, shows that reflection is dominant, while the most popular Brenner's REBO potential in 1990 shows that adsorption is dominant. This reflection of the low energy injection is caused by a small potential barrier for the hydrogen atom in the modified REBO potential. The small potential barrier is confirmed by the ab-initio calculations, which are hybrid DFT (B3LYP/cc-pVDZ), ab-initio
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.
Hutchinson, Bevis; Malmström, Mikael; Lönnqvist, Johan; Bate, Pete; Ehteshami, Hossein; Korzhavyi, Pavel A
2018-07-01
High temperature crystal elasticity constants for face centred cubic austenite are important for interpreting the ultrasonic properties of iron and steels but cannot be determined by normal single crystal methods. Values of these constants have recently been calculated using an ab-initio approach and the present work was carried out to test their applicability using laser-ultrasonic measurements. Steel samples having a known texture were examined at temperatures between 800 °C and 1100 °C to measure the velocity of longitudinal P-waves which were found to be in good agreement with modelled values. Copyright © 2018 Elsevier B.V. All rights reserved.
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.
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.
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.
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.
The role of ab initio electronic structure calculations in studies of the strength of materials
International Nuclear Information System (INIS)
Sob, M.; Friak, M.; Legut, D.; Fiala, J.; Vitek, V.
2004-01-01
In this paper we give an account of applications of quantum-mechanical (first-principles) electronic structure calculations to the problem of theoretical tensile strength in metals and intermetallics. First, we review previous as well as ongoing research on this subject. We then describe briefly the electronic structure calculational methods and simulation of the tensile test. This approach is then illustrated by calculations of theoretical tensile strength in iron and in the intermetallic compound Ni 3 Al. The anisotropy of calculated tensile strength is explained in terms of higher-symmetry structures encountered along the deformation paths studied. The table summarizing values of theoretical tensile strengths calculated up to now is presented and the role of ab initio electronic structure calculations in contemporary studies of the strength of material is discussed
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.
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
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
Vigil-Fowler, Derek; Lischner, Johannes; Louie, Steven
2013-03-01
Understanding many-electron interaction effects and the influence of the substrate in graphene-on-substrate systems is of great theoretical and practical interest. Thus far, both model Hamiltonian and ab initio GW calculations for the quasiparticle properties of such systems have employed crude models for the effect of the substrate, often approximating the complicated substrate dielectric matrix by a single constant. We develop a method in which the spatially-dependent dielectric matrix of the substrate (e.g., SiC) is incorporated into that of doped graphene to obtain an accurate total dielectric matrix. We present ab initio GW + cumulant expansion calculations, showing that both the cumulant expansion (to include higher-order electron correlations) and a proper account of the substrate screening are needed to achieve agreement with features seen in ARPES. We discuss how this methodology could be used in other systems. This work was supported by NSF Grant No. DMR10-1006184 and U.S. DOE Contract No. DE-AC02-05CH11231. Computational resources have been provided by the NERSC and NICS. D.V-F. acknowledges funding from the DOD's NDSEG fellowship.
Ab Initio Calculations of the Electronic Structures and Biological Functions of Protein Molecules
Zheng, Haoping
2003-04-01
The self-consistent cluster-embedding (SCCE) calculation method reduces the computational effort from M3 to about M1 (M is the number of atoms in the system) with unchanged calculation precision. So the ab initio, all-electron calculation of the electronic structure and biological function of protein molecule becomes a reality, which will promote new proteomics considerably. The calculated results of two real protein molecules, the trypsin inhibitor from the seeds of squash Cucurbita maxima (CMTI-I, 436 atoms) and the Ascaris trypsin inhibitor (912 atoms, two three-dimensional structures), are presented. The reactive sites of the inhibitors are determined and explained. The precision of structure determination of inhibitors are tested theoretically.
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
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.
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 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.
Ab initio molecular orbital calculations on the associated complexes of lithium cyanide with ammonia
International Nuclear Information System (INIS)
Mohandas, P.; Shivaglal, M.C.; Chandrasekhar, J.
1995-01-01
Ab initio molecular orbital (MO) calculations with the 3-21G and 6-31G basis sets are carried out on a series of complexes of NH 3 with Li + , C triple-bond N - , LiCN, and its isomer LiNC. The BSSE-corrected interaction energies, geometrical parameters, internal force constants, and harmonic vibrational frequencies are evaluated for 15 species. Complexes with trifurcated (C 3v ) structures are calculated to be saddle points on the potential energy surfaces and have one imaginary frequency each. Calculated energies, geometrical parameters, internal force constants, and harmonic vibrational frequencies of the various species considered are discussed in terms of the nature of association of LiCN with ammonia. The vibrational frequencies of the relevant complexed species are compared with the experimental frequencies reported earlier for solutions of lithium cyanide in liquid ammonia. 40 refs., 1 fig., 4 tabs
Böhm, Karl-Heinz; Banert, Klaus; Auer, Alexander A
2014-04-23
We present ab-initio calculations of secondary isotope effects on NMR chemical shieldings. The change of the NMR chemical shift of a certain nucleus that is observed if another nucleus is replaced by a different isotope can be calculated by computing vibrational corrections on the NMR parameters using electronic structure methods. We demonstrate that the accuracy of the computational results is sufficient to even distinguish different conformers. For this purpose, benchmark calculations for fluoro(2-2H)ethane in gauche and antiperiplanar conformation are carried out at the HF, MP2 and CCSD(T) level of theory using basis sets ranging from double- to quadruple-zeta quality. The methodology is applied to the secondary isotope shifts for 2-fluoronorbornane in order to resolve an ambiguity in the literature on the assignment of endo- and exo-2-fluoronorbornanes with deuterium substituents in endo-3 and exo-3 positions, also yielding insight into mechanistic details of the corresponding synthesis.
Directory of Open Access Journals (Sweden)
Karl-Heinz Böhm
2014-04-01
Full Text Available We present ab-initio calculations of secondary isotope effects on NMR chemical shieldings. The change of the NMR chemical shift of a certain nucleus that is observed if another nucleus is replaced by a different isotope can be calculated by computing vibrational corrections on the NMR parameters using electronic structure methods. We demonstrate that the accuracy of the computational results is sufficient to even distinguish different conformers. For this purpose, benchmark calculations for fluoro(2-2Hethane in gauche and antiperiplanar conformation are carried out at the HF, MP2 and CCSD(T level of theory using basis sets ranging from double- to quadruple-zeta quality. The methodology is applied to the secondary isotope shifts for 2-fluoronorbornane in order to resolve an ambiguity in the literature on the assignment of endo- and exo-2-fluoronorbornanes with deuterium substituents in endo-3 and exo-3 positions, also yielding insight into mechanistic details of the corresponding synthesis.
International Nuclear Information System (INIS)
Rubin, Yu.V.; Belous, L.F.
2012-01-01
Self-associates of nucleic acid components (stacking trimers and tetramers of the base pairs of nucleic acids) and short fragments of nucleic acids are nanoparticles (linear sizes of these particles are more than 10 A). Modern quantum-mechanical methods and softwares allow one to perform ab initio calculations of the systems consisting of 150-200 atoms with enough large basis sets (for example, 6-31G * ). The aim of this work is to reveal the peculiarities of molecular and electronic structures, as well as the energy features of nanoparticles of nucleic acid components. We had carried out ab initio calculations of the molecular structure and interactions in the stacking dimer, trimer, and tetramer of nucleic base pairs and in the stacking (TpG)(ApC) dimer and (TpGpC) (ApCpG) trimer of nucleotides, which are small DNA fragments. The performed calculations of molecular structures of dimers and trimers of nucleotide pairs showed that the interplanar distance in the structures studied is equal to 3.2 A on average, and the helical angle in a trimer is approximately equal to 30 o : The distance between phosphor atoms in neighboring chains is 13.1 A. For dimers and trimers under study, we calculated the horizontal interaction energies. The analysis of interplanar distances and angles between nucleic bases and their pairs in the calculated short oligomers of nucleic acid base pairs (stacking dimer, trimer, and tetramer) has been carried out. Studies of interactions in the calculated short oligomers showed a considerable role of the cross interaction in the stabilization of the structures. The contribution of cross interactions to the horizontal interactions grows with the length of an oligomer. Nanoparticle components get electric charges in nanoparticles. Longwave low-intensity bands can appear in the electron spectra of nanoparticles.
International Nuclear Information System (INIS)
Kucharczyk, M.; Olszewski, S.
1982-01-01
The Grueneisen parameter of alkali halides is calculated by an ab initio quantum-statistical method and then compared with the experimental data. The crystal model applied assumes the crystal ions to be compressible but impenetrable spheres. The ions are described with the aid of a modified Thomas-Fermi theory with exchange. At the next step it is possible to calculate the energy needed to transform the system of the non-interacting ions into the ionic system represented by the crystal lattice. This calculation allows for an ab initio estimate of the parameters entering the Born, or the Born-Mayer, repulsive part of the crystal energy. The parameters are then used in the calculation of the Grueneisen parameter and its dependence on the crystal compression. (author)
All-electron ab initio calculations of YBa2Cu3O7 with self-consistence crystal field
Institute of Scientific and Technical Information of China (English)
刘洪霖; 陈念贻
1995-01-01
The quantum chemical calculations of cluster YBa2Cu3O7 considering all electrons have been per-formed by using the ab initio HF method with self-consistence crystal field.A Hartree-Fork surface potentialis proposed to make an asymmetric duster model possess a relatively symmetric potential field and to obtaina relatively symmetric electronic structure,electronic distributions,frontier orbitals,and bond order,etc.Thesuggestions that there exists a covalent bonding complex,[CuO2-O-CuO-O-Cu2]6,8-,in the cell unit ofthe crystal,and the cell units are connected with each other by ionic bonds along the c direction of the crys-tal lattice are offered based on the chemical bonding characteristics from the calculated results.The importantcontribution of the apical oxygen to superconductivities is emphasized as well.
International Nuclear Information System (INIS)
Wadt, W.R.; Hay, P.J.
1985-01-01
A consistent set of ab initio effective core potentials (ECP) has been generated for the main group elements from Na to Bi using the procedure originally developed by Kahn. The ECP's are derived from all-electron numerical Hartree--Fock atomic wave functions and fit to analytical representations for use in molecular calculations. For Rb to Bi the ECP's are generated from the relativistic Hartree--Fock atomic wave functions of Cowan which incorporate the Darwin and mass--velocity terms. Energy-optimized valence basis sets of (3s3p) primitive Gaussians are presented for use with the ECP's. Comparisons between all-electron and valence-electron ECP calculations are presented for NaF, NaCl, Cl 2 , Cl 2 - , Br 2 , Br 2 - , and Xe 2 + . The results show that the average errors introduced by the ECP's are generally only a few percent
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.
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.
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].
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.
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)
Ab initio electronic band structure calculation of InP in the wurtzite phase
Dacal, Luis C. O.; Cantarero, Andrés
2011-05-01
We present ab initio calculations of the InP band structure in the wurtzite phase and compare it with that of the zincblende phase. In both calculations, we use the full potential linearized augmented plane wave method as implemented in the WIEN2k code and the modified Becke-Johnson exchange potential, which provides an improved value of the bandgap. The structural optimization of the wurtizte InP gives a=0.4150 nm, c=0.6912 nm, and an internal parameter u=0.371, showing the existence of a spontaneous polarization along the growth axis. As compared to the ideal wurtzite structure (that with the lattice parameter derived from the zincblende structure calculations), the actual wurtzite structure is compressed (-1.3%) in plane and expanded (0.7%) along the c-direction. The value of the calculated band gaps agrees well with recent optical experiments. The calculations are also consistent with the optical transitions found using polarized light.
Verevkin, Sergey P; Emel'yanenko, Vladimir N; Kozlova, Svetlana A
2008-10-23
This work has been undertaken in order to obtain data on thermodynamic properties of organic carbonates and to revise the group-additivity values necessary for predicting their standard enthalpies of formation and enthalpies of vaporization. The standard molar enthalpies of formation of dibenzyl carbonate, tert-butyl phenyl carbonate, and diphenyl carbonate were measured using combustion calorimetry. Molar enthalpies of vaporization of these compounds were obtained from the temperature dependence of the vapor pressure measured by the transpiration method. Molar enthalpy of sublimation of diphenyl carbonate was measured in the same way. Ab initio calculations of molar enthalpies of formation of organic carbonates have been performed using the G3MP2 method, and results are in excellent agreement with the available experiment. Then the group-contribution method has been developed to predict values of the enthalpies of formation and enthalpies of vaporization of organic carbonates.
Stress reduction of Cu-doped diamond-like carbon films from ab initio calculations
Directory of Open Access Journals (Sweden)
Xiaowei Li
2015-01-01
Full Text Available Structure and properties of Cu-doped diamond-like carbon films (DLC were investigated using ab initio calculations. The effect of Cu concentrations (1.56∼7.81 at.% on atomic bond structure was mainly analyzed to clarify the residual stress reduction mechanism. Results showed that with introducing Cu into DLC films, the residual compressive stress decreased firstly and then increased for each case with the obvious deterioration of mechanical properties, which was in agreement with the experimental results. Structural analysis revealed that the weak Cu-C bond and the relaxation of both the distorted bond angles and bond lengths accounted for the significant reduction of residual compressive stress, while at the higher Cu concentration the increase of residual stress attributed to the existence of distorted Cu-C structures and the increased fraction of distorted C-C bond lengths.
Ab Initio Calculations on Halogen Bond Between N-Br and Electron-donating Groups
Institute of Scientific and Technical Information of China (English)
WANG Yan-hua; CHEN Xue-song; ZOU Jian-wei; YU Qing-sen
2007-01-01
Ab initio calculations of complexes formed between N-bromosuccinimide and a series of electron-donating groups were performed at the level of MP2/Lanl2DZ* to gain a deeper insight into the nature of the N-Br halogen stronger halogen-bonding complex than the C-Br. A comparison of neutral hydrogen bond complex series reveals that the electron-donating capacities of the atoms decrease in the order, N＞O＞S; O(sp3)＞O(sp2), which is adequate for the C-Br halogen bonding. Interaction energies, in conjunction with the geometrical parameters show that the affinitive capacity of trihalide anions X-3 with N-bromosuccinimide are markedly lower than that of the corresponding X- with N-bromosuccinimide, even lower than those of neutral molecules with N-bromosuccinimide. AIM analyses further confirmed the above results.
Guo, Guang-Yu; Ishibashi, Shoji; Tamura, Tomoyuki; Terakura, Kiyoyuki
2007-03-01
Since the discovery of carbon nanotubes (CNTs) in 1991 by Iijima, carbon and other nanotubes have attracted considerable interest worldwide because of their unusual properties and also great potentials for technological applications. Though CNTs continue to attract great interest, other nanotubes such as BN nanotubes (BN-NTs) may offer different opportunities that CNTs cannot provide. In this contribution, we present the results of our recent systematic ab initio calculations of the static dielectric constant, electric polarizability, Born dynamical charge, electrostriction coefficient and piezoelectric constant of BN-NTs using the latest crystalline finite electric field theory [1]. [1] I. Souza, J. Iniguez, and D. Vanderbilt, Phys. Rev. Lett. 89, 117602 (2002); P. Umari and A. Pasquarello, Phys. Rev. Lett. 89, 157602 (2002).
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.
Magnetization, resistivity, specific heat and ab initio calculations of Gd5Sb3.
Samatham, S Shanmukharao; Patel, Akhilesh Kumar; Lukoyanov, Alexey V; Suresh, K G
2018-06-07
We report on the combined results of structural, magnetic, transport and calorimetric properties of Mn_{5}Si_{3}-type hexagonal Gd_{5}Sb_{3}, together with ab-initio calculations. It exhibits a ferromagnetic (FM)-like transition at 265 K, antiferromagnetic (AFM) Néel transition at 95.5 K followed by a spin-orientation transition at 62 K. The system is found to be in AFM state down to 2 K in a field of 70 kOe. The FM-AFM phase coexistence is not noticeable despite large positive Curie-Weiss temperature (θ_{CW} = 223.5 ± 0.2 K). Instead, low-temperature AFM and high-temperature FM-like phases are separated in large temperatures. Temperature-magnetic field (H-T) phase diagram reveals field-driven complex magnetic phases. Within the AFM phase, the system is observed to undergo field-driven spin-orientation transitions. Field-induced tricritical and quantum critical points appear to be absent due to strong AFM nature and by the intervention of FM-like state between paramagnetic and AFM states, respectively. The metallic behavior of the compound is inferred from resistivity along with large Sommerfeld parameter. However, no sign of strong electron-correlations is reasoned from the Kadowaki-Wood's ratio A/γ^{2} ∼ 1.9×10^{-6} μΩ.cm.(mol.K)^{2}(mJ)^{-2}, despite heavy γ. Essentially, ab initio calculations accounting for electronic correlations confirm AFM nature of low-temperature magnetic state in Gd_{5}Sb_{3} and attainable FM ordering in agreement with experimental data. © 2018 IOP Publishing Ltd.
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.
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 .
International Nuclear Information System (INIS)
Kim, Jiwoong; Kang, Shinhoo
2012-01-01
Highlights: ► Elastic properties of TiC, TiN and their alloys were calculated by ab initio calculations. ► Debye temperature and Gruneisen constant of TiC, TiN and their alloys were calculated as a function of nitrogen content. ► Thermo-physical properties were calculated as a function of nitrogen content. ► Thermal expansion of the alloys was fitted in different temperature range. - Abstract: The equilibrium lattice parameters, elastic properties, material brittleness, heat capacities, and thermal expansion coefficients of TiC, TiN, and their intermediate composition alloys (Ti(C 1−x N x ), x = 0.25, 0.5, and 0.75) were calculated using ab initio density functional theory (DFT) methods. We employed the Debye–Gruneisen model to calculate a finite temperature heat capacity and thermal expansion coefficient. The calculated elastic moduli and thermal expansion coefficients agreed well with the experimental data and with other DFT calculations. Accurate heat capacities of TiC, TiN, and their intermediate composition alloys were obtained by calculating not only the phonon contributions but also the electron contributions to the heat capacity. Our calculations indicated that the heat capacity differences between each composition originated mainly from the electronic contributions.
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
Ab initio calculations of the structure and conformations of 2,6-lutidine
International Nuclear Information System (INIS)
Porcinai, S.; Foggi, P.
1997-01-01
Ab initio molecular orbital calculations at the SCF level have been utilized to determine the structure and the electronic and vibrational properties of 2,6-lutidine (2,6-dimethyl-pyridine) in the ground electronic state. Comparative calculations have been performed on the parent molecule pyridine. Structure predictions of both molecules are in good agreement with experimental data. The most stable rotamer of 2,6-lutidine has C 2v symmetry with one of the C-H bonds of both the methyl groups lying in the plane of the aromatic ring and pointing in the opposite direction with respect to the nitrogen atom. This is the result of the minimization of competing forces deriving from steric hindrance and electronic stabilization. Vibrational frequencies and oscillator strengths of C-H stretching in the fundamental region have been calculated for both pyridine and the most stable rotamer of 2,6-lutidine and compared to IR data obtained in pure liquids. The potential energy profile of the C-H bond in and out of plane has been investigated up to five times the equilibrium distance. The trend of the potential curves confirms that the C-H bond lying in the plane has a higher dissociation energy than that of the in-plane bonds as observed in experiments on vibrational overtones
A program system for ab initio MO calculations on vector and parallel processing machines. Pt. 1
International Nuclear Information System (INIS)
Ernenwein, R.; Rohmer, M.M.; Benard, M.
1990-01-01
We present a program system for ab initio molecular orbital calculations on vector and parallel computers. The present article is devoted to the computation of one- and two-electron integrals over contracted Gaussian basis sets involving s-, p-, d- and f-type functions. The McMurchie and Davidson (MMD) algorithm has been implemented and parallelized by distributing over a limited number of logical tasks the calculation of the 55 relevant classes of integrals. All sections of the MMD algorithm have been efficiently vectorized, leading to a scalar/vector ratio of 5.8. Different algorithms are proposed and compared for an optimal vectorization of the contraction of the 'intermediate integrals' generated by the MMD formalism. Advantage is taken of the dynamic storage allocation for tuning the length of the vector loops (i.e. the size of the vectorization buffer) as a function of (i) the total memory available for the job, (ii) the number of logical tasks defined by the user (≤13), and (iii) the storage requested by each specific class of integrals. Test calculations carried out on a CRAY-2 computer show that the average number of finite integrals computed over a (s, p, d, f) CGTO basis set is about 1180000 per second and per processor. The combination of vectorization and parallelism on this 4-processor machine reduces the CPU time by a factor larger than 20 with respect to the scalar and sequential performance. (orig.)
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.
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
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
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 calculation of Ti NMR shieldings for titanium oxides and halides
Tossell, J. A.
Titanium NMR shielding constants have been calculated using ab initio coupled Hartree-Fock perturbation theory and polarized double-zeta basis sets for TiF 4, TiF 62-, TiCI 4, Ti(OH) 4, Ti(OH 2) 64+, Ti(OH) 4O, and Ti(OH) 3O -. In all cases the calculations were performed at Hartree-Fuck energy-optimized geometries. For Ti(OH) 4 a S4-symmetry geometry with nonlinear ∠ TiOH was employed. Relative shieldings are in reasonable agreement with experiment for TiF 62-, TiCI 4, and Ti(OR) 4, where R = H or alkyl. Ti(OH 2) 64+ is predicted to be more highly shielded than Ti(OH) 4 by about 340 ppm. The five-coordinate complex Ti(OH) 4O, whose calculated structure matches well that measured by extended X-ray absorption fine structure in K 2O · TiO 2 · SiO 2 glass, is actually deshielded compared to Ti(OH) 4 by about 40 ppm. X-ray absorption-near-edge spectral energies have also been calculated for TiF 4, TiCI 4, Ti(OH) 4, and Ti(OH) 4O using an equivalent ionic core virtual-orbital method and the observed reduction in term energy for the five-coordinate species compared to Ti(OH) 4 has been reproduced. Replacement of the H atoms in Ti(OH) 4 by point charges has only a slight effect upon σTi, suggesting a possible means of incorporating second-neighbor effects in NMR calculations for condensed phases.
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.
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.
Au55, a stable glassy cluster: results of ab initio calculations
Directory of Open Access Journals (Sweden)
Dieter Vollath
2017-10-01
Full Text Available Structure and properties of small nanoparticles are still under discussion. Moreover, some thermodynamic properties and the structural behavior still remain partially unknown. One of the best investigated nanoparticles is the Au55 cluster, which has been analyzed experimentally and theoretically. However, up to now, the results of these studies are still inconsistent. Consequently, we have carried out the present ab initio study of the Au55 cluster, using up-to-date computational concepts, in order to clarify these issues. Our calculations have confirmed the experimental result that the thermodynamically most stable structure is not crystalline, but it is glassy. The non-crystalline structure of this cluster was validated by comparison of the coordination numbers with those of a crystalline cluster. It was found that, in contrast to bulk materials, glass formation is connected to an energy release that is close to the melting enthalpy of bulk gold. Additionally, the surface energy of this cluster was calculated using two different theoretical approaches resulting in values close to the surface energy for bulk gold. It shall be emphasized that it is now possible to give a confidence interval for the value of the surface energy.
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.
Barabash, Sergey V.; Pramanik, Dipankar
2015-03-01
Development of low-leakage dielectrics for semiconductor industry, together with many other areas of academic and industrial research, increasingly rely upon ab initio tunneling and transport calculations. Complex band structure (CBS) is a powerful formalism to establish the nature of tunneling modes, providing both a deeper understanding and a guided optimization of materials, with practical applications ranging from screening candidate dielectrics for lowest ``ultimate leakage'' to identifying charge-neutrality levels and Fermi level pinning. We demonstrate that CBS is prone to a particular type of spurious ``phantom'' solution, previously deemed true but irrelevant because of a very fast decay. We demonstrate that (i) in complex materials, phantom modes may exhibit very slow decay (appearing as leading tunneling terms implying qualitative and huge quantitative errors), (ii) the phantom modes are spurious, (iii) unlike the pseudopotential ``ghost'' states, phantoms are an apparently unavoidable artifact of large numerical basis sets, (iv) a presumed increase in computational accuracy increases the number of phantoms, effectively corrupting the CBS results despite the higher accuracy achieved in resolving the true CBS modes and the real band structure, and (v) the phantom modes cannot be easily separated from the true CBS modes. We discuss implications for direct transport calculations. The strategy for dealing with the phantom states is discussed in the context of optimizing high-quality high- κ dielectric materials for decreased tunneling leakage.
van der Horst, J.W.; Bobbert, P.A.; Bobbert, Peter A.; Michels, M.A.J.; Brocks, G.; Kelly, Paul J.
1999-01-01
We use the ab-initio many-body GW method to calculate the quasi-particle spectrum of polythiophene. For the isolated chain, we find a large increase of the gap compared to DFT-LDA calculations (1.2 eV). The result (4.1 eV) exceeds experimental values, due to the absence of long-range screening in
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
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
International Nuclear Information System (INIS)
Reeh, S; Kasprzak, M; Klusmann, C D; Stalf, F; Music, D; Schneider, J M; Ekholm, M; Abrikosov, I A
2013-01-01
The elastic properties of fcc Fe–Mn–X (X = Cr, Co, Ni, Cu) alloys with additions of up to 8 at.% X were studied by combinatorial thin film growth and characterization and by ab initio calculations using the disordered local moments (DLM) approach. The lattice parameter and Young’s modulus values change only marginally with X. The calculations and experiments are in good agreement. We demonstrate that the elastic properties of transition metal alloyed Fe–Mn can be predicted by the DLM model. (paper)
Reeh, S; Kasprzak, M; Klusmann, C D; Stalf, F; Music, D; Ekholm, M; Abrikosov, I A; Schneider, J M
2013-06-19
The elastic properties of fcc Fe-Mn-X (X = Cr, Co, Ni, Cu) alloys with additions of up to 8 at.% X were studied by combinatorial thin film growth and characterization and by ab initio calculations using the disordered local moments (DLM) approach. The lattice parameter and Young's modulus values change only marginally with X. The calculations and experiments are in good agreement. We demonstrate that the elastic properties of transition metal alloyed Fe-Mn can be predicted by the DLM model.
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.
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)
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.
Characterization of adsorbed water in MIL-53(Al) by FTIR spectroscopy and ab-initio calculations.
Salazar, J M; Weber, G; Simon, J M; Bezverkhyy, I; Bellat, J P
2015-03-28
Here, we report ab-initio calculations developed with a twofold purpose: understand how adsorbed water molecules alter the infrared spectrum of the metal-organic framework MIL-53(Al) and to investigate which are the associated physico-chemical processes. The analyzed structures are the two anhydrous narrow (np⊘) and large (lp⊘) pore forms and the hydrated narrow pore form (np-H2O) of the MIL-53(Al). For these structures, we determined their corresponding infrared spectra (FTIR) and we identified the vibrational modes associated to the dominant spectral lines. We show that wagging and scissoring modes of CO2 give flexibility to the structure for facilitating the lp⊘- np⊘ transition. In our studies, this transition is identified by eight vibrational modes including the δCH(18a) vibrational mode currently used to identify the mentioned transition. We report an exhaustive band identification of the infrared spectra associated to the analyzed structures. Moreover, the FTIR for the np-H2O structure allowed us to identify four types of water molecules linked to the host structure by one to three hydrogen bonds.
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...
Directory of Open Access Journals (Sweden)
Lei Li
2015-01-01
Full Text Available The ab initio calculations about the properties of the interstitials doping in the rutile TiO2 and their impact on the transport coefficients are reported. As the doping of the Zr or Ti interstitials in the TiO2, the lattice Ti4+ ions acquire the excess electrons so reduced to the Ti3+ or Ti2+ ions. However, the Cu interstitials could not lose enough electrons to reduce the lattice Ti4+ ions. Furthermore, the Ti or Cu interstitials in the ZrO2 also are unable to promote the lattice Zr4+ ions to form the lattice Zr3+ or Zr2+ ions. The high transport coefficients are observed in the defected TiO2 with the Ti or Zr interstitials as the high concentration of the Ti3+ or Ti2+ ions. So, the Zr interstitials are the favorable choice for the extra-doping to improve the transport properties in the TiO2-based resistive random access memory.
Input/Output of ab-initio nuclear structure calculations for improved performance and portability
International Nuclear Information System (INIS)
Laghave, Nikhil
2010-01-01
Many modern scientific applications rely on highly computation intensive calculations. However, most applications do not concentrate as much on the role that input/output operations can play for improved performance and portability. Parallelizing input/output operations of large files can significantly improve the performance of parallel applications where sequential I/O is a bottleneck. A proper choice of I/O library also offers a scope for making input/output operations portable across different architectures. Thus, use of parallel I/O libraries for organizing I/O of large data files offers great scope in improving performance and portability of applications. 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. 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 I/O of large datasets along with their portability and ease of use in the down-stream processing. Even situations where the amount of data to be written is not huge, proper use of input/output operations can boost the performance of scientific applications. Application checkpointing offers enormous performance improvement and flexibility by doing a negligible amount of I/O to disk. Checkpointing saves and resumes application state in such a manner that in most cases the application is unaware that there has been an interruption to its execution. This helps in saving large amount of work that has been previously done and continue application execution. This small amount of I/O provides substantial time saving by offering restart/resume capability to applications. The need for checkpointing in optimization code NEWUOA has been identified and checkpoint/restart capability has been implemented in NEWUOA by using simple file I/O.
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)
Czech Academy of Sciences Publication Activity Database
Čársky, Petr
2010-01-01
Roč. 43, č. 17 (2010), s. 175204 ISSN 0953-4075 R&D Projects: GA MŠk OC09079; GA MŠk(CZ) OC10046; GA ČR GA202/08/0631 Institutional research plan: CEZ:AV0Z40400503 Keywords : ab initio calculations * electron scattering * polyatomic molecules Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.902, year: 2010
Czech Academy of Sciences Publication Activity Database
Šob, Mojmír; Kroupa, Aleš; Pavlů, Jana; Vřešťál, Jan
2009-01-01
Roč. 150, č. 1 (2009), s. 1-28 ISSN 1012-0394 R&D Projects: GA MŠk OC 147; GA ČR GA106/07/1078 Institutional research plan: CEZ:AV0Z20410507 Keywords : Ab initio calculations * CALPHAD method * Laves phases * sigma phase * ternary systems * super-austenitic steels Subject RIV: BM - Solid Matter Physics ; Magnetism
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.
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)
Manson, S.T.; Miller, J.H.; Pacific Northwest Lab., Richland, WA)
1983-01-01
Ionization cross sections for heavy ions and electrons incident on various atoms and molecules are required in the modeling of the interaction of radiation with matter. For each case, the energy distribution of secondary electrons (the single differential cross section, SDCS) is needed over a broad range of projectile and secondary electron (delta-ray) energies. In many cases the energy and angular distribution of secondary electrons (the double differential cross section, DDCS) is also necessary. Clearly, it would be desirable to have laboratory SDCS and DDCS measurements for all of the cases required. For a variety of reasons, this is not yet possible. Thus, one must turn elsewhere to obtain the needed cross sections. In this paper, we discuss cross sections obtained in two different ways; ab initio theory based on the first Born approximation, and a semi-empirical method based on the Bethe-Born Approximation. In both cases, results on helium will be presented since the largest amount of data is available in this case. Applications of both methods to other target species are given in the references. The accuracy of the methods and plans for the near future are also discussed. 23 references, 6 figures
A program system for ab initio MO calculations on vector and parallel processing machines. Pt. 3
International Nuclear Information System (INIS)
Wiest, R.; Demuynck, J.; Benard, M.; Rohmer, M.M.; Ernenwein, R.
1991-01-01
This series of three papers presents a program system for ab initio molecular orbital calculations on vector and parallel computers. Part III is devoted to the four-index transformation on a molecular orbital basis of size NMO of the file of two-electorn integrals (pqparallelrs) generated by a contracted Gaussian set of size NATO (number of atomic orbitals). A fast Yoshimine algorithm first sorts the (pqparallelrs) integrals with respect to index pq only. This file of half-sorted integrals labelled by their rs-index can be processed without further modification to generate either the transformed integrals or the supermatrix elements. The large memory available on the CRAY-2 hase made possible to implement the transformation algorithm proposed by Bender in 1972, which requires a core-storage allocation varying as (NATO) 3 . Two versions of Bender's algorithm are included in the present program. The first version is an in-core version, where the complete file of accumulated contributions to transformed integrals in stored and updated in central memory. This version has been parallelized by distributing over a limited number of logical tasks the NATO steps corresponding to the scanning of the most external loop. The second version is an out-of-core version, in which twin files are alternatively used as input and output for the accumulated contributions to transformed integrals. This version is not parallel. The choice of one or another version and (for version 1) the determination of the number of tasks depends upon the balance between the available and the requested amounts of storage. The storage management and the choice of the proper version are carried out automatically using dynamic storage allocation. Both versions are vectorized and take advantage of the molecular symmetry. (orig.)
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
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.
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
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...
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.
Energy Technology Data Exchange (ETDEWEB)
Kroes, Geert-Jan, E-mail: g.j.kroes@chem.leidenuniv.nl; Pavanello, Michele [Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA Leiden (Netherlands); Blanco-Rey, María [Departamento de Física de Materiales, Facultad de Químicas UPV/EHU, Apartado 1072, 20080 Donostia-San Sebastián (Spain); Donostia International Physics Center, Paseo Manuel de Lardizabal 4, 20018 Donostia-San Sebastián (Spain); Alducin, Maite [Donostia International Physics Center, Paseo Manuel de Lardizabal 4, 20018 Donostia-San Sebastián (Spain); Centro de Física de Materiales, Centro Mixto CSIC-UPV/EHU, Paseo Manuel de Lardizabal 5, 20018 Donostia-San Sebastián (Spain); Auerbach, Daniel J. [Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA Leiden (Netherlands); Max Planck Institute for Biophysical Chemistry, Göttingen (Germany); Institute for Physical Chemistry, Georg-August University of Göttingen, Göttingen (Germany)
2014-08-07
Energy loss from the translational motion of an atom or molecule impinging on a metal surface to the surface may determine whether the incident particle can trap on the surface, and whether it has enough energy left to react with another molecule present at the surface. Although this is relevant to heterogeneous catalysis, the relative extent to which energy loss of hot atoms takes place to phonons or electron-hole pair (ehp) excitation, and its dependence on the system's parameters, remain largely unknown. We address these questions for two systems that present an extreme case of the mass ratio of the incident atom to the surface atom, i.e., H + Cu(111) and H + Au(111), by presenting adiabatic ab initio molecular dynamics (AIMD) predictions of the energy loss and angular distributions for an incidence energy of 5 eV. The results are compared to the results of AIMDEFp calculations modeling energy loss to ehp excitation using an electronic friction (“EF”) model applied to the AIMD trajectories, so that the energy loss to the electrons is calculated “post” (“p”) the computation of the AIMD trajectory. The AIMD calculations predict average energy losses of 0.38 eV for Cu(111) and 0.13-0.14 eV for Au(111) for H-atoms that scatter from these surfaces without penetrating the surface. These energies closely correspond with energy losses predicted with Baule models, which is suggestive of structure scattering. The predicted adiabatic integral energy loss spectra (integrated over all final scattering angles) all display a lowest energy peak at an energy corresponding to approximately 80% of the average adiabatic energy loss for non-penetrative scattering. In the adiabatic limit, this suggests a way of determining the approximate average energy loss of non-penetratively scattered H-atoms from the integral energy loss spectrum of all scattered H-atoms. The AIMDEFp calculations predict that in each case the lowest energy loss peak should show additional energy
Kroes, Geert-Jan; Pavanello, Michele; Blanco-Rey, María; Alducin, Maite; Auerbach, Daniel J
2014-08-07
Energy loss from the translational motion of an atom or molecule impinging on a metal surface to the surface may determine whether the incident particle can trap on the surface, and whether it has enough energy left to react with another molecule present at the surface. Although this is relevant to heterogeneous catalysis, the relative extent to which energy loss of hot atoms takes place to phonons or electron-hole pair (ehp) excitation, and its dependence on the system's parameters, remain largely unknown. We address these questions for two systems that present an extreme case of the mass ratio of the incident atom to the surface atom, i.e., H + Cu(111) and H + Au(111), by presenting adiabatic ab initio molecular dynamics (AIMD) predictions of the energy loss and angular distributions for an incidence energy of 5 eV. The results are compared to the results of AIMDEFp calculations modeling energy loss to ehp excitation using an electronic friction ("EF") model applied to the AIMD trajectories, so that the energy loss to the electrons is calculated "post" ("p") the computation of the AIMD trajectory. The AIMD calculations predict average energy losses of 0.38 eV for Cu(111) and 0.13-0.14 eV for Au(111) for H-atoms that scatter from these surfaces without penetrating the surface. These energies closely correspond with energy losses predicted with Baule models, which is suggestive of structure scattering. The predicted adiabatic integral energy loss spectra (integrated over all final scattering angles) all display a lowest energy peak at an energy corresponding to approximately 80% of the average adiabatic energy loss for non-penetrative scattering. In the adiabatic limit, this suggests a way of determining the approximate average energy loss of non-penetratively scattered H-atoms from the integral energy loss spectrum of all scattered H-atoms. The AIMDEFp calculations predict that in each case the lowest energy loss peak should show additional energy loss in the
Recent Developments in No-Core Shell-Model Calculations
International Nuclear Information System (INIS)
Navratil, P.; Quaglioni, S.; Stetcu, I.; Barrett, B.R.
2009-01-01
We present an overview of recent results and developments of the no-core shell model (NCSM), an ab initio approach to the nuclear many-body problem for light nuclei. In this aproach, we start from realistic two-nucleon or two- plus three-nucleon interactions. Many-body calculations are performed using a finite harmonic-oscillator (HO) basis. To facilitate convergence for realistic inter-nucleon interactions that generate strong short-range correlations, we derive effective interactions by unitary transformations that are tailored to the HO basis truncation. For soft realistic interactions this might not be necessary. If that is the case, the NCSM calculations are variational. In either case, the ab initio NCSM preserves translational invariance of the nuclear many-body problem. In this review, we, in particular, highlight results obtained with the chiral two- plus three-nucleon interactions. We discuss efforts to extend the applicability of the NCSM to heavier nuclei and larger model spaces using importance-truncation schemes and/or use of effective interactions with a core. We outline an extension of the ab initio NCSM to the description of nuclear reactions by the resonating group method technique. A future direction of the approach, the ab initio NCSM with continuum, which will provide a complete description of nuclei as open systems with coupling of bound and continuum states is given in the concluding part of the review.
Recent Developments in No-Core Shell-Model Calculations
Energy Technology Data Exchange (ETDEWEB)
Navratil, P; Quaglioni, S; Stetcu, I; Barrett, B R
2009-03-20
We present an overview of recent results and developments of the no-core shell model (NCSM), an ab initio approach to the nuclear many-body problem for light nuclei. In this aproach, we start from realistic two-nucleon or two- plus three-nucleon interactions. Many-body calculations are performed using a finite harmonic-oscillator (HO) basis. To facilitate convergence for realistic inter-nucleon interactions that generate strong short-range correlations, we derive effective interactions by unitary transformations that are tailored to the HO basis truncation. For soft realistic interactions this might not be necessary. If that is the case, the NCSM calculations are variational. In either case, the ab initio NCSM preserves translational invariance of the nuclear many-body problem. In this review, we, in particular, highlight results obtained with the chiral two- plus three-nucleon interactions. We discuss efforts to extend the applicability of the NCSM to heavier nuclei and larger model spaces using importance-truncation schemes and/or use of effective interactions with a core. We outline an extension of the ab initio NCSM to the description of nuclear reactions by the resonating group method technique. A future direction of the approach, the ab initio NCSM with continuum, which will provide a complete description of nuclei as open systems with coupling of bound and continuum states is given in the concluding part of the review.
Kim, Ji-Su; Kim, Byung-Kook; Kim, Yeong-Cheol
2015-10-01
We investigated the effect of Cu alloying on S poisoning of Ni surfaces and nanoparticle morphologies using ab-initio thermodynamics calculations. Based on the Cu segregation energy and the S adsorption energy, the surface energy and nanoparticle morphology of pure Ni, pure Cu, and NiCu alloys were evaluated as functions of the chemical potential of S and the surface orientations of (100), (110), and (111). The constructed nanoparticle morphology was varied as a function of chemical potential of S. We find that the Cu added to Ni for NiCu alloys is strongly segregated into the top surface, and increases the S tolerance of the NiCu nanoparticles.
International Nuclear Information System (INIS)
Hay, P.J.; Wadt, W.R.
1985-01-01
Ab initio effective core potentials (ECP's) have been generated to replace the Coulomb, exchange, and core-orthogonality effects of the chemically inert core electron in the transition metal atoms Sc to Hg. For the second and third transition series relative ECP's have been generated which also incorporate the mass--velocity and Darwin relativistic effects into the potential. The ab initio ECP's should facilitate valence electron calculations on molecules containing transition-metal atoms with accuracies approaching all-electron calculations at a fraction of the computational cost. Analytic fits to the potentials are presented for use in multicenter integral evaluation. Gaussian orbital valence basis sets are developed for the (3d,4s,4p), (4d,5s,5p), and (5d,6s,6p) orbitals of the first, second, and third transition series atoms, respectively. All-electron and valence-electron atomic excitation energies are also compared for the low-lying states of Sc--Hg, and the valence-electron calculations are found to reproduce the all-electron excitation energies (typically within a few tenths of an eV)
Ab initio calculation of the bcc Fe-Al phase diagram including magnetic interactions
International Nuclear Information System (INIS)
Gonzales-Ormeno, Pablo Guillermo; Petrilli, Helena Maria; Schoen, Claudio Geraldo
2006-01-01
The metastable phase diagram of the body-centered cubic-based ordering equilibria in the Fe-Al system has been calculated by the cluster expansion method, through the combination of the full potential-linear augmented plane wave and cluster variation methods. The results are discussed with reference to the effect of including the spin polarizations of Fe in the thermodynamic model
Ab initio calculations of fundamental properties of SrTe1−xOx alloys
Indian Academy of Sciences (India)
dielectric constant was studied by different models. On the other hand, the ... system in the framework of the density-functional theory. ∗ ... first principles calculations. Earlier ... by Vegard's law [19], but this is not the case of the band gap value.
Ab initio calculation of mechanical and thermal properties of U{sub 2}Mo intermetallic
Energy Technology Data Exchange (ETDEWEB)
Jaroszewicz, S., E-mail: jaroszew@tandar.cnea.gov.ar [Gerencia de Investigación y Aplicaciones, Comisión Nacional de Energía Atómica (Argentina); Losada, E.L.; Garcés, J.E. [DAEE, Centro Atómico Bariloche, Comisión Nacional de Energía Atómica (Argentina); Mosca, H.O. [Gerencia de Investigación y Aplicaciones, Comisión Nacional de Energía Atómica (Argentina)
2013-10-15
We present a study of structural, elastic and thermodynamic properties of tetragonal (C11{sub b}) U{sub 2}Mo by means of density-functional theory based calculations using full-potential linearized augmented plane wave method. In this approach the generalized gradient approximation were used for the exchange–correlation potential calculation. The optimized lattice parameters are in excellent agreement with the experimental data. Through the Debye–Grüneisen model the temperature and pressure dependence of equation of state, bulk modulus, thermal expansion and specific heat have been obtained and discussed in the range of pressure 0–20 GPa and the temperature 0–800 K.
Mastail, C.; David, M.; Nita, F.; Michel, A.; Abadias, G.
2017-11-01
We use ab initio calculations to determine the preferred nucleation sites and migration pathways of Ti, Al and N adatoms on cubic NaCl-structure (B1) AlN surfaces, primary inputs towards a further thin film growth modelling of the TiAlN alloy system. The potential energy landscape is mapped out for both metallic species and nitrogen adatoms for two different AlN surface orientations, (001) and (110), using density functional theory. For all species, the adsorption energies on AlN(011) surface are larger than on AlN(001) surface. Ti and Al adatom adsorption energy landscapes determined at 0 K by ab initio show similar features, with stable binding sites being located in, or near, epitaxial surface positions, with Ti showing a stronger binding compared to Al. In direct contrast, N adatoms (Nad) adsorb preferentially close to N surface atoms (Nsurf), thus forming strong N2-molecule-like bonds on both AlN(001) and (011). Similar to N2 desorption mechanisms reported for other cubic transition metal nitride surfaces, in the present work we investigate Nad/Nsurf desorption on AlN(011) using a drag calculation method. We show that this process leaves a Nsurf vacancy accompanied with a spontaneous surface reconstruction, highlighting faceting formation during growth.
Directory of Open Access Journals (Sweden)
Basso Ernani A.
2001-01-01
Full Text Available Axial-equatorial conformational proportions for cyclohexyl-N,N-dimethyl carbamate have been measured, for the first time, by the Eliel method, ¹H and 13C dynamic nuclear magnetic resonance (DNMR. The results were compared against those determined by theoretical calculations. By the Eliel method at least five experimentally independent measureables were used in CCl4, CDCl3 and CD3CN. The ¹H and 13C low temperature experiments were performed in CF2Br2/CD2Cl2 . Semiempirical methods MNDO, AM1 and PM3 and ab initio molecular orbital calculations at the HF/STO-3G and HF/6-31G(d,p levels have been performed on the axial and equatorial conformers populations. All applied methods correctly predict the equatorial conformer preference over the axial one. The resulting equatorial preferences determined by NMR data and theoretical calculations are in good agreement.
International Nuclear Information System (INIS)
Termentzidis, K; Pokropivny, A; Xiong, S-Y; Chumakov, Y; Volz, S; Woda, M; Cortona, P
2012-01-01
We use molecular dynamics and ab-initio methods to predict the thermal and electronic properties of new materials with high figures of merit. The simulated systems are bulk bismuth tellurides with antisite and vacancy defects. Optimizations of the materials under investigation are performed by the SIESTA code for subsequent calculations of force constants, electronic properties, and Seebeck coefficients. The prediction of the thermal conductivity is made by Non-Equilibrium Molecular Dynamics (NEMD) using the LAMMPS code. The thermal conductivity of bulk bismuth telluride with different stoichiometry and with a number of substitution defects is calculated. We have found that the thermal conductivity can be decreased by 60% by introducing vacancy defects. The calculated thermal conductivities for the different structures are compared with the available experimental and theoretical results.
International Nuclear Information System (INIS)
He, J.; Behera, R.K.; Finnis, M.W.; Li, X.; Dickey, E.C.; Phillpot, S.R.; Sinnott, S.B.
2007-01-01
A computational approach that integrates ab initio electronic structure and thermodynamic calculations is used to determine point defect stability in rutile TiO 2 over a range of temperatures, oxygen partial pressures and stoichiometries. Both donors (titanium interstitials and oxygen vacancies) and acceptors (titanium vacancies) are predicted to have shallow defect transition levels in the electronic-structure calculations. The resulting defect formation energies for all possible charge states are then used in thermodynamic calculations to predict the influence of temperature and oxygen partial pressure on the relative stabilities of the point defects. Their ordering is found to be the same as temperature increases and oxygen partial pressure decreases: titanium vacancy → oxygen vacancy → titanium interstitial. The charges on these defects, however, are quite sensitive to the Fermi level. Finally, the combined formation energies of point defect complexes, including Schottky, Frenkel and anti-Frenkel defects, are predicted to limit the further formation of point defects
Torres, V. J. B.; Hajj Hussein, R.; Pagès, O.; Rayson, M. J.
2017-02-01
We test a presumed ability behind the phenomenological percolation scheme used for the basic description of the multi-mode Raman spectra of mixed crystals at one dimension along the linear chain approximation, to determine, via the Raman intensities, the nature of the atom substitution, as to whether this is random or due to local clustering/anticlustering. For doing so, we focus on the model percolation-type GeySi1-y system characterized by six oscillators { 1 × ( G e - G e ) , 3 × ( G e - S i ) , 2 × ( S i - S i ) } and place the study around the critical compositions y ˜ (0.16, 0.71, and 0.84) corresponding to nearly matching of intensities between the like Raman modes from a given multiplet ( G e - S i triplet or S i - S i doublet). The interplay between the GeySi1-y Raman intensities predicted by the percolation scheme depending on a suitable order parameter κ of local clustering/anticlustering is found to be consistent with ab initio calculations of the GeySi1-y Raman spectra done with the Ab Initio Modeling PROgram code using large (64-, 216-, and 512-atoms) disordered cubic supercells matching the required ( y , κ ) values. The actual "percolation vs. ab initio" comparative insight at moderate/dilute-(Ge,Si) limits, with an emphasis on the κ -induced intra-bond transfer of oscillator strength, extends a pioneering one earlier achieved at an intermediate composition ( y ˜ 0.50) by using small (32-atom) supercells [O. Pagès et al., J. Appl. Phys. 114, 033513 (2013)], mainly concerned with the inter-bond transfer of oscillator strength, providing altogether a complete picture.
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.
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)
Numerical Exact Ab Initio Four-Nucleon Scattering Calculations: from Dream to Reality
Fonseca, A. C.; Deltuva, A.
2017-03-01
In the present manuscript we review the work of the last ten years on the pursuit to obtain numerical exact solutions of the four-nucleon scattering problem using the most advanced force models that fit two nucleon data up to pion production threshold with a χ ^2 per data point approximately one, together with the Coulomb interaction between protons; three- and four-nucleon forces are also included in the framework of a meson exchange potential model where NN couples to NΔ. Failure to describe the world data on four-nucleon scattering observables in the framework of a non relativistic scattering approach falls necessarily on the force models one uses. Four-nucleon observables pose very clear challenges, particular in the low energy region where there are a number of resonances whose position and width needs to be dynamically generated by the nucleon-nucleon (NN) interactions one uses. In addition, our calculations constitute the most advance piece of work where observables for all four-nucleon reactions involving isospin I=0, I=0 coupled to I=1 and isospin I=1 initial states are calculated at energies both below and above breakup threshold. We also present a very extensive comparison between calculated results and data for cross sections and spin observables. Therefore the present work reveals both the shortcomings and successes of some of the present NN force models in describing four-nucleon data and serve as a benchmark for future developments.
Ab-initio calculations of the Ruddlesden-Popper phases CaMnO3, CaO(CaMnO3) and CaO(CaMnO3)2
International Nuclear Information System (INIS)
Cardoso, C; Borges, R P; Gasche, T; Godinho, M
2008-01-01
The present work reports ab-initio density functional theory calculations for the Ruddlesden-Popper phase CaO(CaMnO 3 ) n compounds. In order to study the evolution of the properties with the number of perovskite layers, a detailed analysis of the densities of states calculated for each compound and for several magnetic configurations was performed. The effect of distortions of the crystal structure on the magnetic ground state is also analysed and the exchange constants and transition temperatures are calculated for the three compounds using a mean field model. The calculated magnetic ground state structures and magnetic moments are in good agreement with experimental results and previous calculations
Ab Initio Calculation of XAFS Debye-Waller Factors for Crystalline Materials
Dimakis, Nicholas
2007-02-01
A direct an accurate technique for calculating the thermal X-ray absorption fine structure (XAFS) Debye-Waller factors (DWF) for materials of crystalline structure is presented. Using the Density Functional Theory (DFT) under the hybrid X3LYP functional, a library of MnO spin—optimized clusters are built and their phonon spectrum properties are calculated; these properties in the form of normal mode eigenfrequencies and eigenvectors are in turn used for calculation of the single and multiple scattering XAFS DWF. DWF obtained via this technique are temperature dependent expressions and can be used to substantially reduce the number of fitting parameters when experimental spectra are fitted with a hypothetical structure without any ad hoc assumptions. Due to the high computational demand a hybrid approach of mixing the DFT calculated DWF with the correlated Debye model for inner and outer shells respectively is presented. DFT obtained DWFs are compared with corresponding values from experimental XAFS spectra on manganosite. The cluster size effect and the spin parameter on the DFT calculated DWFs are discussed.
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.
Eggenberger, Rolf; Gerber, Stefan; Huber, Hanspeter; Searles, Debra; Welker, Marc
1992-08-01
The shear viscosity is calculated ab initio for the liquid and hypercritical state, i.e. a previously published potential for Ne 2, obtained from ab initio calculations including electron correlation, is used in classical equilibrium molecular dynamics simulations to obtain the shear viscosity from a Green-Kubo integral. The quality of the results is quite uniform over a large pressure range up to 1000 MPa and a wide temperature range from 26 to 600 K. In most cases the calculated shear viscosity deviates by less than 10% from the experimental value, in general the error being only a few percent.
Pohl, Gábor; Beke, Tamás; Borbély, János; Perczel, András
2006-11-15
Because of their great flexibility and strength resistance, both spider silks and silkworm silks are of increasing scientific and commercial interest. Despite numerous spectroscopic and theoretical studies, several structural properties at the atomic level have yet to be identified. The present theoretical investigation focuses on these issues by studying three silk-like model peptides: (AG)(64), [(AG)(4)EG](16), and [(AG)(4)PEG](16), using a Lego-type approach to construct these polypeptides. On the basis of these examples it is shown that thermoneutral isodesmic reactions and ab initio calculations provide a capable method to investigate structural properties of repetitive polypeptides. The most probable overall fold schema of these molecules with respect to the type of embedded hairpin structures were determined at the ab initio level of theory (RHF/6-311++G(d,p)//RHF/3-21G). Further on, analysis is carried out on the possible hairpin and turn regions and on their effect on the global fold. In the case of the (AG)(64) model peptide, the optimal beta-sheet/turn ratio was also determined, which provided good support for experimental observations. In addition, lateral shearing of a hairpin "folding unit" was investigated at the quantum chemical level to explain the mechanical properties of spider silk. The unique mechanical characteristics of silk bio-compounds are now investigated at the atomic level.
Energy Technology Data Exchange (ETDEWEB)
Dane Morgan
2010-06-10
The project began March 13, 2006, allocated for three years, and received a one year extension from March 13, 2009 to March 12, 2010. It has now completed 48 of 48 total months. The project was focused on using ab initio methods to gain insights into radiation induced segregation (RIS) in Ni-Fe-Cr alloys. The project had the following key accomplishments • Development of a large database of ab initio energetics that can be used by many researchers in the future for increased understanding of this system. For example, we have the first calculations showing a dramatic stabilization effect of Cr-Cr interstitial dumbbells in Ni. • Prediction of both vacancy and interstitial diffusion constants for Ni-Cr and Ni-Fe for dilute Cr and Fe. This work included generalization of widely used multifrequency models to make use of ab initio derived energetics and thermodynamics. • Prediction of qualitative trends of RIS from vacancy and interstitial mechanisms, suggesting the two types of defect fluxes drive Cr RIS in opposite directions. • Detailed kinetic Monte Carlo modeling of diffusion by vacancy mechanism in Ni-Cr as a function of Cr concentration. The results demonstrate that Cr content can have a significant effect on RIS. • Development of a quantitative RIS transport model, including models for thermodynamic factors and boundary conditions.
Electric field gradient in FeTiO3 by nuclear magnetic resonance and ab initio calculations.
Procházka, V; Stěpánková, H; Chlan, V; Tuček, J; Cuda, J; Kouřil, K; Filip, J; Zbořil, R
2011-05-25
Temperature dependence of nuclear magnetic resonance (NMR) spectra of (47)Ti and (49)Ti in polycrystalline ilmenite FeTiO(3) was measured in the range from 5 to 300 K under an external magnetic field of 9.401 T. NMR spectra collected between 300 and 77 K exhibit a resolved quadrupole splitting. The electric field gradient (EFG) tensor was evaluated for Ti nuclei and the ratio of (47)Ti and (49)Ti nuclear quadrupole moments was refined during the fitting procedure. Below 77 K, the fine structure of quadrupole splitting disappears due to the enormous increase of anisotropy. As a counterpart, ab initio calculations were performed using full potential augmented plane waves + local orbitals. The calculated EFG tensors for Ti and Fe were compared to the experimental ones evaluated from NMR and the Mössbauer spectroscopy experiments.
Phonon spectra of elpasolites Cs{sub 2}NaRF{sub 6} (R=Y,Yb): Ab initio calculations
Energy Technology Data Exchange (ETDEWEB)
Chernyshev, Vladimir, E-mail: Vladimir.Chernyshev@urfu.ru; Petrov, Vladislav; Nikiforov, Anatoliy; Zakiryanov, Dmitriy [Ural Federal University, Ekaterinburg (Russian Federation)
2015-12-07
The influence of hydrostatic pressure on structure and dynamics of a crystal lattice of elpasolites Cs{sub 2}NaYbF{sub 6} and Cs{sub 2}NaYF{sub 6} (S.G. 225) within ab initio approach is investigated. Frequencies and irreducible representations (irreps) of phonon modes are determined. Elastic constants are calculated. The calculations are carried out within MO LCAO approach using DFT method with hybrid functionalities of B3LYP and PBE0 in CRYSTAL09 periodic code. For the description of rare earth ion the pseudopotential replacing internal orbitals including 4f orbitals was used. External 5s and 5p orbitals defining chemical bond were described by valence basis sets.
International Nuclear Information System (INIS)
Gil, T.J.; McCurdy, C.W.; Rescigno, T.N.; Lengsfield, B.H. III
1994-01-01
The authors are reporting results of ab-initio calculations of electron-impact excitation of water and methane occurring at scattering energies up to 60 eV. The authors consider dissociative excited states of both systems since the understanding of their chemistry has considerable importance in plasma technology and atmospheric research. In the case of methane the authors are dealing with the promotion of a valence electron into Rydberg orbitals, while in water the excited states have one electron in an antibonding unoccupied valence orbital and support Feshbach resonances. The authors discuss issues related to convergence of the close-coupling expansion in the case of Rydberg excitation, where the authors have coupled up to 16 channels. The practical realization of the calculation within the framework of the complex Kohn variational principle represents merging of quantum chemistry and quantum scattering theory and is also discussed
Thermodynamic and mechanical properties of TiC from ab initio calculation
International Nuclear Information System (INIS)
Dang, D. Y.; Fan, J. L.; Gong, H. R.
2014-01-01
The temperature-dependent thermodynamic and mechanical properties of TiC are systematically investigated by means of a combination of density-functional theory, quasi-harmonic approximation, and thermal electronic excitation. It is found that the quasi-harmonic Debye model should be pertinent to reflect thermodynamic properties of TiC, and the elastic properties of TiC decease almost linearly with the increase of temperature. Calculations also reveal that TiC possesses a pronounced directional pseudogap across the Fermi level, mainly due to the strong hybridization of Ti 3d and C 2p states. Moreover, the strong covalent bonding of TiC would be enhanced (reduced) with the decrease (increase) of temperature, while the change of volume (temperature) should have negligible effect on density of states at the Fermi level. The calculated results agree well with experimental observations in the literature.
Ab-initio calculations of Co-based diluted magnetic semiconductors Cd 1-xCoxX (X=S, Se, Te)
Saeed, Yasir; Nazir, Safdar; Shaukat, Ali; Reshak, A. H.
2010-01-01
Ab-initio calculations are performed to investigate the structural, electronic and magnetic properties of spin-polarized diluted magnetic semiconductors composed of IIVI compounds Cd1-xCoxX (X=S, Se, Te) at x=0.25. From the calculated results
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.
International Nuclear Information System (INIS)
Chen, Yongchang; Sun, Zhaolin; Song, Lijuan; Li, Qiang; Xu, Ming
2012-01-01
Ethene hydrogenation reaction, catalyzed by an iridium atom adsorbed on γ-Al 2 O 3 (001) surface, is studied via ab initio calculations based on density functional theory (DFT). The catalyzed reaction process and activation energy are compared with the counterparts of a reaction occurs in vacuum condition. It is found that the activation energy barrier is substantially lowered by the adsorbed Ir atom on the γ-Al 2 O 3 (001). The catalyzed reaction is modeled in two steps: (1) Hydrogen molecular dissolution and then bonded with C 2 H 4 molecular. (2) Desorption of the C 2 H 6 molecular from the surface. -- Highlights: ► The ethene hydrogenation reaction is simulated with nudged elastic band methods. ► The catalytic effect of the Ir atom on γ-Al 2 O 3 (001) surface is modeled. ► Details of the catalytic reaction are exhibited.
International Nuclear Information System (INIS)
Wimmer, E
2008-01-01
A workshop, 'Theory Meets Industry', was held on 12-14 June 2007 in Vienna, Austria, attended by a well balanced number of academic and industrial scientists from America, Europe, and Japan. The focus was on advances in ab initio solid state calculations and their practical use in industry. The theoretical papers addressed three dominant themes, namely (i) more accurate total energies and electronic excitations (ii) more complex systems, and (iii) more diverse and accurate materials properties. Hybrid functionals give some improvements in energies, but encounter difficulties for metallic systems. Quantum Monte Carlo methods are progressing, but no clear breakthrough is on the horizon. Progress in order-N methods is steady, as is the case for efficient methods for exploring complex energy hypersurfaces and large numbers of structural configurations. The industrial applications were dominated by materials issues in energy conversion systems, the quest for hydrogen storage materials, improvements of electronic and optical properties of microelectronic and display materials, and the simulation of reactions on heterogeneous catalysts. The workshop is a clear testimony that ab initio computations have become an industrial practice with increasingly recognized impact
Wimmer, E.
2008-02-01
A workshop, 'Theory Meets Industry', was held on 12-14 June 2007 in Vienna, Austria, attended by a well balanced number of academic and industrial scientists from America, Europe, and Japan. The focus was on advances in ab initio solid state calculations and their practical use in industry. The theoretical papers addressed three dominant themes, namely (i) more accurate total energies and electronic excitations, (ii) more complex systems, and (iii) more diverse and accurate materials properties. Hybrid functionals give some improvements in energies, but encounter difficulties for metallic systems. Quantum Monte Carlo methods are progressing, but no clear breakthrough is on the horizon. Progress in order-N methods is steady, as is the case for efficient methods for exploring complex energy hypersurfaces and large numbers of structural configurations. The industrial applications were dominated by materials issues in energy conversion systems, the quest for hydrogen storage materials, improvements of electronic and optical properties of microelectronic and display materials, and the simulation of reactions on heterogeneous catalysts. The workshop is a clear testimony that ab initio computations have become an industrial practice with increasingly recognized impact.
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
Emel'yanenko, Vladimir N; Verevkin, Sergey P; Heintz, Andreas
2007-04-04
Ionic liquids are attracting growing interest as alternatives to conventional molecular solvents. Experimental values of vapor pressure, enthalpy of vaporization, and enthalpy of formation of ionic liquids are the key thermodynamic quantities, which are required for the validation and development of the molecular modeling and ab initio methods toward this new class of solvents. In this work, the molar enthalpy of formation of the liquid 1-butyl-3-methylimidazolium dicyanamide, 206.2 +/- 2.5 kJ.mol-1, was measured by means of combustion calorimetry. The molar enthalpy of vaporization of 1-butyl-3-methylimidazolium dicyanamide, 157.2 +/- 1.1 kJ.mol-1, was obtained from the temperature dependence of the vapor pressure measured using the transpiration method. The latter method has been checked with measurements of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide, where data are available from the effusion technique. The first experimental determination of the gaseous enthalpy of formation of the ionic liquid 1-butyl-3-methylimidazolium dicyanamide, 363.4 +/- 2.7 kJ.mol-1, from thermochemical measurements (combustion and transpiration) is presented. Ab initio calculations of the enthalpy of formation in the gaseous phase have been performed for 1-butyl-3-methylimidazolium dicyanamide using the G3MP2 theory. Excellent agreement with experimental results has been observed. The method developed opens a new way to obtain thermodynamic properties of ionic liquids which have not been available so far.
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.
Equilibrium fission model calculations
International Nuclear Information System (INIS)
Beckerman, M.; Blann, M.
1976-01-01
In order to aid in understanding the systematics of heavy ion fission and fission-like reactions in terms of the target-projectile system, bombarding energy and angular momentum, fission widths are calculated using an angular momentum dependent extension of the Bohr-Wheeler theory and particle emission widths using angular momentum coupling
International Nuclear Information System (INIS)
Schatz, G.C.; Walch, S.P.; Wagner, A.F.
1980-01-01
We present ab initio (GVB--POL--CI) calculations for enough of the region about the abstraction and exchange saddle points for H(T)+CH 4 (CD 4 ) to perform a full normal mode analysis of the transition states. The resulting normal mode frequencies are compared to four other published surfaces: an ab initio UHF--SCF calculation by Carsky and Zahradnik, a semiempirical surface by Raff, and two semiempirical surfaces by Kurylo, Hollinden, and Timmons. Significant quantitative and qualitative differences exist between the POL--CI results and those of the other surfaces. Transition state theory rate constants and vibrationally adiabatic reaction threshold energies were computed for all surfaces and compared to available experimental values. For abstraction, the POL--CI rates are in good agreement with experimental rates and in better agreement than are the rates of any of the other surfaces. For exchange, uncertainties in the experimental values and in the importance of vibrationally nonadiabatic effects cloud the comparison of theory to experiment. Tentative conclusions are that the POL--CI barrier is too low by several kcal. Unless vibrationaly nonadiabatic effects are severe, the POL--CI surface is still in better agreement with experiment than are the other surfaces. The rates for a simple 3-atom transition state theory model (where CH 3 is treated as an atom) are compared to the rates for the full 6-atom model. The kinetic energy coupling of reaction coordinate modes to methyl group modes is identified as being of primary importance in determining the accuracy of the 3-atom model for this system. Substantial coupling in abstraction, but not exchange, causes the model to fail for abstraction but succeed for exchange
Directory of Open Access Journals (Sweden)
K. A. Pestka II
2011-09-01
Full Text Available The complete elastic tensors of SmScO3 and NdScO3 were measured using resonant ultrasound spectroscopy (RUS in combination with ab-initio calculations. Measurement of the elastic tensor of these recently synthesized single crystal RE scandates is essential for understanding dynamic lattice applications including phonon confinement, strain induced thin film growth and superlattice construction. On average, the experimental elastic constants differed by less than 5% of the theoretical values, further validating the accuracy of modern ab-initio calculations as a means of estimating the initial elastic constants used in RUS measurements.
Study of wide band-gap crystal LiCaAlF6 by IR-reflection spectroscopy and ab initio calculations
International Nuclear Information System (INIS)
Novikova, N.N.; Klimin, S.A.; Mavrin, B.N.
2017-01-01
Polarized IR-reflection spectra and results of ab initio calculations of vibrational and electronic properties of LiCaAlF6 single crystal are presented. It is shown that the crystal band gap is direct. Experimental and theoretical parameters are obtained for dipole-active and all phonons, respectively, including silent modes. Experimental IR-reflection and Raman spectra are well described in the frame of results obtained by ab initio calculations. The peculiarities are discussed concerning the structure of electronic bands, the interatomic interactions, the character of lattice vibrations, and the phonon dispersion.
Mankodi, T K; Bhandarkar, U V; Puranik, B P
2017-08-28
A new ab initio based chemical model for a Direct Simulation Monte Carlo (DSMC) study suitable for simulating rarefied flows with a high degree of non-equilibrium is presented. To this end, Collision Induced Dissociation (CID) cross sections for N 2 +N 2 →N 2 +2N are calculated and published using a global complete active space self-consistent field-complete active space second order perturbation theory N 4 potential energy surface and quasi-classical trajectory algorithm for high energy collisions (up to 30 eV). CID cross sections are calculated for only a selected set of ro-vibrational combinations of the two nitrogen molecules, and a fitting scheme based on spectroscopic weights is presented to interpolate the CID cross section for all possible ro-vibrational combinations. The new chemical model is validated by calculating equilibrium reaction rate coefficients that can be compared well with existing shock tube and computational results. High-enthalpy hypersonic nitrogen flows around a cylinder in the transition flow regime are simulated using DSMC to compare the predictions of the current ab initio based chemical model with the prevailing phenomenological model (the total collision energy model). The differences in the predictions are discussed.
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
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 electronic structure calculations for Mn linear chains deposited on CuN/Cu(001) surfaces
International Nuclear Information System (INIS)
Barral, Maria Andrea; Weht, Ruben; Lozano, Gustavo; Maria Llois, Ana
2007-01-01
In a recent experiment, scanning tunneling microscopy has been used to obtain a direct probe of the magnetic interaction in linear manganese chains arranged by atomic manipulation on thin insulating copper nitride islands grown on Cu(001). The local spin excitation spectra of these chains have been measured with inelastic electron tunneling spectroscopy. Analyzing the spectroscopic results with a Heisenberg Hamiltonian the interatomic coupling strength within the chains has been obtained. It has been found that the coupling strength depends on the deposition sites of the Mn atoms on the islands. In this contribution, we perform ab initio calculations for different arrangements of infinite Mn chains on CuN in order to understand the influence of the environment on the value of the magnetic interactions
Energy Technology Data Exchange (ETDEWEB)
Lucas, G
2006-10-15
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)
International Nuclear Information System (INIS)
Errico, L.A.; Renteria, M.; Bibiloni, A.G.; Darriba, G.N.
2005-01-01
We report an ab initio study of the temperature dependence of the electric-field gradient (EFG) tensor at Cd impurities replacing cations in Lu 2 O 3 . Calculations were performed with the Full-Potential Linearized-Augmented Plane Wave method that allows us to treat the electronic structure and the processes induced by the impurity in the host-lattice without the use of external parameters. In this new insight, the EFG thermal dependence arises from the ionization of an impurity acceptor level introduced in the band-gap of Lu 2 O 3 by Cd impurities, in good agreement with a previously proposed two state model. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)
Energy Technology Data Exchange (ETDEWEB)
Errico, L.A.; Renteria, M.; Bibiloni, A.G.; Darriba, G.N. [Departamento de Fisica, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, CC 67, 1900 La Plata (Argentina)
2005-08-01
We report an ab initio study of the temperature dependence of the electric-field gradient (EFG) tensor at Cd impurities replacing cations in Lu{sub 2}O{sub 3}. Calculations were performed with the Full-Potential Linearized-Augmented Plane Wave method that allows us to treat the electronic structure and the processes induced by the impurity in the host-lattice without the use of external parameters. In this new insight, the EFG thermal dependence arises from the ionization of an impurity acceptor level introduced in the band-gap of Lu{sub 2}O{sub 3} by Cd impurities, in good agreement with a previously proposed two state model. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)
Energy Technology Data Exchange (ETDEWEB)
Ortenzi, Luciano
2013-10-17
In this thesis I study the interplay between magnetism and superconductivity in itinerant magnets and superconductors. I do this by applying a semiphenomenological method to four representative compounds. In particular I use the discrepancies (whenever present) between density functional theory (DFT) calculations and the experiments in order to construct phenomenological models which explain the magnetic, superconducting and optical properties of four representative systems. I focus my attention on the superconducting and normal state properties of the recently discovered APt3P superconductors, on superconducting hole-doped CuBiSO, on the optical properties of LaFePO and finally on the ferromagnetic-paramagnetic transition of Ni3Al under pressure. At the end I present a new method which aims to describe the effect of spin fluctuations in itinerant magnets and superconductors that can be used to monitor the evolution of the electronic structure from non magnetic to magnetic in systems close to a quantum critical point.
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.
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.
Ab initio calculation on the low-lying excited states of Si2+ cation including spin–orbit coupling
International Nuclear Information System (INIS)
Liu, Yanlei; Zhai, Hongsheng; Zhang, Xiaomei; Liu, Yufang
2013-01-01
Highlights: • 24 Λ–S states are correlated to the dissociation limit of Si( 3 P g ) + Si + ( 2 P u ) are first reported. • The dissociation energies of the calculated electronic states are predicted in our work. • It is first time that the entire 54 Ω states generated from the 24 Λ–S states have been studied. • PECs of Λ–S and Ω states are depicted with the aid of avoided crossing rule between the same symmetry. - Abstract: Ab initio all-electron relativistic calculations of the low-lying excited states of Si 2 + have been performed at MRCI+Q/AVQZ level. The calculated electronic states, including 12 doublet and 12 quartet Λ–S states, are correlated to the dissociation limit of Si( 3 P g ) + Si + ( 2 P u ). Spin–orbit interaction is taken into account via the state interaction approach with the full Breit-Pauli Hamiltonian, which causes the entire 24 Λ–S states to split into 54 Ω states. This is the first time that spin–orbit coupling (SOC) calculation has been performed on Si 2 + . The obtained potential energy curves (PECs) of Λ–S and Ω states are respectively depicted with the aid of the avoided crossing rule between the same symmetry. The spectroscopic constants of the bound Λ–S and Ω states are determined, and excellent agreements with the latest theoretical results are achieved
Energy gap of extended states in SiC-doped graphene nanoribbon: Ab initio calculations
Energy Technology Data Exchange (ETDEWEB)
Liu, Xiaoshi; Wu, Yong [College of Science, University of Shanghai for Science and Technology, Shanghai 200093 (China); Shanghai Key Lab of Modern Optical System, Shanghai 200093 (China); Li, Zhongyao, E-mail: lizyusst@gmail.com [College of Science, University of Shanghai for Science and Technology, Shanghai 200093 (China); Shanghai Key Lab of Modern Optical System, Shanghai 200093 (China); Gao, Yong [School of Science, Shanghai Second Polytechnic University, Shanghai 201209 (China)
2017-04-01
Highlights: • The gap of isolated ribbon is inversely proportional to the width of ribbon. • The gap of doped ribbon cannot be modeled by effective width approximation. • The fitted energy gap can match the experimental observations. • The doping results in a spin-polarized metallic-like band structure. - Abstract: The energy gap of extended states in zigzag graphene nanoribbons (ZGNRs) was examined on the basis of density-functional theory. In isolated ZGNRs, the energy gap is inversely proportional to the width of ribbon. It agrees well with the results from the Dirac equation in spin-unpolarized ZGNRs, although the considered ZGNRs have spin-polarized edges. However, the energy gap in SiC-doped ZGNRs cannot be modeled by effective width approximation. The doping also lifts the spin-degenerate of edge states and results in a metallic-like band structure near the Fermi level in SiC-doped ZGNRs. Our calculations may be helpful for understanding the origin of the reported single-channel ballistic transport in epitaxial graphene nanoribbons.
Insights inot the atomic many-particle dynamics of scattering processes by ab-initio calculations
International Nuclear Information System (INIS)
Zapukhlyak, Myroslav
2008-01-01
The present thesis gives a theoretical contribution to the understanding of the many-particle dynamics in inelastic ion-atom collisions. Many-electron dynamics in ion-helium collisions and proton-sodium collisions was theoretically studied. The description is based on the semiclassical approximation with the straight orbit for the projectile motion. The ion-atom collision problem is by this reduced to a time-dependent many-electron problem and in the non-relativistic approximation described by the time-dependent Schroedinger equation. The solution of the many-electron problem pursues in the framework of the time-dependent density functional theory. The time-dependent Schroedinger equation for the interacting many-electron problem is transformed to the system of the time-dependent Kohn-Sham equations and solved by the two-center-basis generator method. The unknown time-dependent exchange-correlation one-particle potential forces different approximation int he time-dependent Kohn-Shan scheme. In this thesis the model of the independent electrons was applied as basis model, in which the electron-electron correlation is consistently neglected in all parts and in all steps. Differential cross sections for different one- and two-electron processes were calculated in the so-called eikonal approximation for the collisional systems p-He, He 2+ -He, and Ar q+ -He (q=15-18) [de
DEFF Research Database (Denmark)
Shim, Irene; Kingcade, Joseph E. , Jr.; Gingerich, Karl A.
1986-01-01
In the present work we present all-electron ab initio Hartree–Fock (HF) and configuration interaction (CI) calculations of six electronic states of the PdGe molecule. The molecule is predicted to have a 3Pi ground state and two low-lying excited states 3Sigma− and 1Sigma+. The electronic structure...
Czech Academy of Sciences Publication Activity Database
Chalupský, Jakub; Rokob, Tibor András; Kurashige, Y.; Yanai, T.; Solomon, E. I.; Rulíšek, Lubomír; Srnec, Martin
2014-01-01
Roč. 136, č. 45 (2014), s. 15977-15991 ISSN 0002-7863 R&D Projects: GA ČR(CZ) GA14-31419S Institutional support: RVO:61388963 ; RVO:61388955 Keywords : DMRG-CASPT2 * ab initio calculations * reaction mechanisms Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 12.113, year: 2014
Czech Academy of Sciences Publication Activity Database
Adler, R. W.; Allen, P. R.; Hnyk, Drahomír; Rankin, D. W. H.; Robertson, H. E.; Smart, B. A.; Gillespie, R. J.; Bytheway, I.
1999-01-01
Roč. 64, č. 12 (1999), s. 4226-4232 ISSN 0022-3263 Institutional research plan: CEZ:AV0Z4032918 Keywords : structure * initio calculations * 3,3-Diethylpentane Subject RIV: CC - Organic Chemistry Impact factor: 3.440, year: 1999
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.
International Nuclear Information System (INIS)
Saha, H.P.
1993-01-01
The multiconfiguration Hartree-Fock method for continuum wave functions has been used to calculate the scattering length and phase shifts over extremely low energies ranging from 0 to 1 eV very accurately for electron-helium scattering. The scattering length is calculated very accurately with wave functions computed exactly at zero energy, resulting in an upper bound of 1.1784. The electron correlation and polarization of the target by the scattering electron, which are very important in these calculations, have been taken into account in an accurate ab initio manner through the configuration-interaction procedure by optimizing both bound and continuum orbitals simultaneously at each kinetic energy of the scattered electron. Detailed results for scattering length, differential, total, and momentum-transfer cross sections obtained from the phase shifts are presented. The present scattering length is found to be in excellent agreement with the experimental result of Andrick and Bitsch [J. Phys. B 8, 402 (1975)] and the theoretical result of O'Malley, Burke, and Berrington [J. Phys. B 12, 953 (1979)]. There is excellent agreement between the present total cross sections and the corresponding experimental measurements of Buckman and Lohmann [J. Phys. B 19, 2547 (1986)]. The present momentum-transfer cross sections also show remarkable agreement with the experimental results of Crompton, Elford, and Robertson [Aust. J. Phys. 23, 667 (1970)
DEFF Research Database (Denmark)
Åstrand, Per-Olof; Ramanujam, P.S.; Hvilsted, Søren
2000-01-01
Electronic excitation energies of 16 azobenzene dyes have been calculated by ab initio methods within the second-order polarization propagator approximation (SOPPA). Good agreement with expriment is found for the lowest singlet and triplet states for both the trans- and cis-azobenzene molecules......, the experimental singlet π → π* transitions are reproduced for a set of azobenzene dyes with different electron donor and acceptor groups and the correct shifts in excitation energy are obtained for the different substituents. It has also been demonstrated that ab initio methods can be used to determine suitable...
Hahn, Seungsoo
2016-10-28
The Hamiltonian matrix for the first excited vibrational states of a protein can be effectively represented by local vibrational modes constituting amide III, II, I, and A modes to simulate various vibrational spectra. Methods for obtaining the Hamiltonian matrix from ab initio quantum calculation results are discussed, where the methods consist of three steps: selection of local vibrational mode coordinates, calculation of a reduced Hessian matrix, and extraction of the Hamiltonian matrix from the Hessian matrix. We introduce several methods for each step. The methods were assessed based on the density functional theory calculation results of 24 oligopeptides with four different peptide lengths and six different secondary structures. The completeness of a Hamiltonian matrix represented in the reduced local mode space is improved by adopting a specific atom group for each amide mode and reducing the effect of ignored local modes. The calculation results are also compared to previous models using C=O stretching vibration and transition dipole couplings. We found that local electric transition dipole moments of the amide modes are mainly bound on the local peptide planes. Their direction and magnitude are well conserved except amide A modes, which show large variation. Contrary to amide I modes, the vibrational coupling constants of amide III, II, and A modes obtained by analysis of a dipeptide are not transferable to oligopeptides with the same secondary conformation because coupling constants are affected by the surrounding atomic environment.
Ab initio calculation of conformation and vibrational spectrum for the pyrosulfate ion
DEFF Research Database (Denmark)
Dyekjær, Jane Dannow; Berg, Rolf W.; Johansen, Helge
2003-01-01
Theoretical calculations have been performed and applied to determine the most likely geometry for the pyrosulfate ion. The main question was to determine as to whether the system has C-2 or C-2, conformation. The present study favors C-2 symmetry. Bond lengths and angles have been calculated for...
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
Vargas-Hernandez, Rodrigo A.; v Krems, Roman
2017-04-01
We examine the application of kernel methods of machine learning for constructing potential energy surfaces (PES) of polyatomic molecules. In particular, we illustrate the application of Bayesian optimization with Gaussian processes as an efficient method for sampling the configuration space of polyatomic molecules. Bayesian optimization relies on two key components: a prior over an objective function and a mechanism for sampling the configuration space. We use Gaussian processes to model the objective function and various acquisition functions commonly used in computer science to quantify the accuracy of sampling. The PES is obtained through an iterative process of adding ab initio points at the locations maximizing the acquisition function and re-trainig the Gaussian process with new points added. We sample different PESs with one or many acquisition functions and show how the acquisition functions affect the construction of the PESs.
Ab initio calculation of pentacene-PbSe hybrid interface for photovoltaic applications.
Roy, P; Nguyen, Thao P
2016-07-21
We perform density functional theory (DFT) quantum chemical calculations for the pentacene-PbSe hybrid interface at both molecular and crystal levels. At the interface, the parallel orientation of pentacene on the PbSe surface is found to be the most favorable, analogous to a pentacene-gold interface. The molecule-surface distance and the value of charge transfer from one pentacene molecule to the PbSe surface are estimated at around 4.15 Å and 0.12 e(-) respectively. We found that, standard-LDA/GGA-PBE/hybrid/meta-GGA xc-functionals incorrectly determine the band gaps of both pentacene and PbSe and leads to a failed prediction of the energy alignment in this system. So, we use a relativistic G0W0 functional and accurately model the electronic properties of pentacene and PbSe in both bulk material and near the interface. An energy shift of 0.23 eV, due to the difference in work function at the interface was supplemented after a detailed analysis of the electrostatic potential. The highest occupied molecular orbital level of pentacene is 0.01 eV above PbSe while the lowest unoccupied molecular orbital of pentacene lies 1.70 eV above PbSe, allowing both electrons and holes to transfer along the donor-acceptor junction. Our results provide additional insights into the electronic structure properties of the pentacene-PbSe heterojunction and establish it as a promising and efficient candidate for photovoltaic applications.
Ab initio calculations on collisions of low energy electrons with polyatomic molecules
International Nuclear Information System (INIS)
Rescigno, T.N.
1991-01-01
The Kohn variational method is one of simplest, and oldest, techniques for performing scattering calculations. Nevertheless, a number of formal problems, as well as practical difficulties associated with the computation of certain required matrix elements, delayed its application to electron--molecule scattering problems for many years. This paper will describe the recent theoretical and computational developments that have made the ''complex'' Kohn variational method a practical tool for carrying out calculations of low energy electron--molecule scattering. Recent calculations on a number of target molecules will also be summarized. 41 refs., 7 figs
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.
Mohamed, Tarek A; Shaltout, I; Al Yahyaei, K M
2006-05-01
Systems of iron tellurite glasses were prepared by melt quenching with compositions of [85%TeO2+5%Fe2O3+10%TMO], where transition metal oxides (TMO) are TiO2, V2O5, MnO, CoO, NiO and CuO. Furthermore, the main structural units of these samples have been characterized by means of Raman spectra (150-1200 cm(-1)) as well as wavenumber predictions by means of Gaussian 98 ab initio calculations for the proposed site symmetries of TeO4(4-) triagonal bipyramid (C2v) and Te2O7(6-) bridged tetrahedra (Cs and C1). Aided by normal coordinate analysis, calculated vibrational frequencies, Raman scattering activities, force constants in internal coordinates and potential energy distributions (PEDs), revised vibrational assignments for the fundamental modes have been proposed. The main structural features are correlated to the dominant units of triagonal bipyramid (tbp) or bridged tetrahedral (TeO3+1 binds to TeO3 through TeOTe bridge; corner sharing). Moreover, the Raman spectra of the investigated tellurites reflect a structural change from tbp (coordination number is four) to triagonal pyramidal (coordination number is three).
Directory of Open Access Journals (Sweden)
Todd M. Alam
2002-08-01
Full Text Available Abstract: Ring formation in phosphate systems is expected to influence both the magnitude and orientation of the phosphorus (31P nuclear magnetic resonance (NMR chemical shielding anisotropy (CSA tensor. Ab initio calculations of the 31P CSA tensor in both cyclic and acyclic phosphate clusters were performed as a function of the number of phosphate tetrahedral in the system. The calculation of the 31P CSA tensors employed the GAUSSIAN 98 implementation of the gauge-including atomic orbital (GIAO method at the Hartree-Fock (HF level. It is shown that both the 31P CSA tensor anisotropy, and the isotropic chemical shielding can be used for the identification of cyclic phosphates. The differences between the 31P CSA tensor in acyclic and cyclic phosphate systems become less pronounced with increasing number of phosphate groups within the ring. The orientation of the principal components for the 31P CSA tensor shows some variation due to cyclization, most notably with the smaller, highly strained ring systems.
Gorenstein, D G; Taira, K
1984-01-01
Ab initio molecular orbital calculations have been performed on the reaction profile for the addition/elimination reaction between ammonia and formic acid, proceeding via a tetrahedral intermediate: NH3 + HCO2H----H2NCH(OH)2----NH2CHO + H2O. Calculated transition state energies for the first addition step of the reaction revealed that a lone pair on the oxygen of the OH group, which is antiperiplanar to the attacking nitrogen, stabilized the transition state by 3.9 kcal/mol, thus supporting the hypothesis of stereoelectronic control for this reaction. In addition, a secondary, counterbalancing stereoelectronic effect stabilizes the second step, water elimination, transition state by 3.1 kcal/mol if the lone pair on the leaving water oxygen is not antiperiplanar to the C-N bond. The best conformation for the transition states was thus one with a lone pair antiperiplanar to the adjacent scissile bond and also one without a lone-pair orbital on the scissile bond oxygen or nitrogen antiperiplanar to the adjacent polar bond. The significance of these stereoelectronic effects for the mechanism of action of serine proteases is discussed. PMID:6394065
Bakowies, Dirk
2009-04-01
A theoretical composite approach, termed ATOMIC for Ab initio Thermochemistry using Optimal-balance Models with Isodesmic Corrections, is introduced for the calculation of molecular atomization energies and enthalpies of formation. Care is taken to achieve optimal balance in accuracy and cost between the various components contributing to high-level estimates of the fully correlated energy at the infinite-basis-set limit. To this end, the energy at the coupled-cluster level of theory including single, double, and quasiperturbational triple excitations is decomposed into Hartree-Fock, low-order correlation (MP2, CCSD), and connected-triples contributions and into valence-shell and core contributions. Statistical analyses for 73 representative neutral closed-shell molecules containing hydrogen and at least three first-row atoms (CNOF) are used to devise basis-set and extrapolation requirements for each of the eight components to maintain a given level of accuracy. Pople's concept of bond-separation reactions is implemented in an ab initio framework, providing for a complete set of high-level precomputed isodesmic corrections which can be used for any molecule for which a valence structure can be drawn. Use of these corrections is shown to lower basis-set requirements dramatically for each of the eight components of the composite model. A hierarchy of three levels is suggested for isodesmically corrected composite models which reproduce atomization energies at the reference level of theory to within 0.1 kcal/mol (A), 0.3 kcal/mol (B), and 1 kcal/mol (C). Large-scale statistical analysis shows that corrections beyond the CCSD(T) reference level of theory, including coupled-cluster theory with fully relaxed connected triple and quadruple excitations, first-order relativistic and diagonal Born-Oppenheimer corrections can normally be dealt with using a greatly simplified model that assumes thermoneutral bond-separation reactions and that reduces the estimate of these
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.
Energy Technology Data Exchange (ETDEWEB)
Kong, Bo, E-mail: kong79@yeah.net, E-mail: yachao.zhang@pku.edu.cn [School of Physics and Electronic Sciences, Guizhou Education University, Guiyang 550018 (China); Guizhou Provincial Key Laboratory of Computational Nano-Material Science, Guizhou Education University, Guiyang 550018 (China); Zhang, Yachao, E-mail: kong79@yeah.net, E-mail: yachao.zhang@pku.edu.cn [Guizhou Provincial Key Laboratory of Computational Nano-Material Science, Guizhou Education University, Guiyang 550018 (China)
2016-07-07
The electronic structures of the cubic GdH{sub 3} are extensively investigated using the ab initio many-body GW calculations treating the Gd 4f electrons either in the core (4f-core) or in the valence states (4f-val). Different degrees of quasiparticle (QP) self-consistent calculations with the different starting points are used to correct the failures of the GGA/GGA + U/HSE03 calculations. In the 4f-core case, GGA + G{sub 0}W{sub 0} calculations give a fundamental band gap of 1.72 eV, while GGA+ GW{sub 0} or GGA + GW calculations present a larger band gap. In the 4f-val case, the nonlocal exchange-correlation (xc) functional HSE03 can account much better for the strong localization of the 4f states than the semilocal or Hubbard U corrected xc functional in the Kohn–Sham equation. We show that the fundamental gap of the antiferromagnetic (AFM) or ferromagnetic (FM) GdH{sub 3} can be opened up by solving the QP equation with improved starting point of eigenvalues and wave functions given by HSE03. The HSE03 + G{sub 0}W{sub 0} calculations present a fundamental band gap of 2.73 eV in the AFM configuration, and the results of the corresponding GW{sub 0} and GW calculations are 2.89 and 3.03 eV, respectively. In general, for the cubic structure, the fundamental gap from G{sub 0}W{sub 0} calculations in the 4f-core case is the closest to the real result. By G{sub 0}W{sub 0} calculations in the 4f-core case, we find that H or Gd defects can strongly affect the band structure, especially the H defects. We explain the mechanism in terms of the possible electron correlation on the hydrogen site. Under compression, the insulator-to-metal transition in the cubic GdH{sub 3} occurs around 40 GPa, which might be a satisfied prediction.
Ab-initio calculation of ZnGeAs{sub 2} semiconductor
Energy Technology Data Exchange (ETDEWEB)
Tripathy, S. K., E-mail: susanta96@gmail.com; Kumar, V., E-mail: susanta96@gmail.com [Department of Electronics Engineering, Indian School of Mines, Dhanbad 826004 (India)
2014-04-24
The structural, electronic, optical and elastic properties of ZnGeAs{sub 2} semiconductor have been investigated using pseudopotential plane wave method within the density functional theory (DFT). The optimized lattice constants, energy gap and crystal field splitting parameter are calculated. The optical properties such as dielectric function, optical reflectivity,, extinction coefficient, absorption spectra, refractive index and electron energy loss spectrum have been studied. The values of bulk modulus (B), elastic constants (C{sub ij}), Young’s modulus (Y), Zener anisotropic factor (A), Poisson’s ratio (ν) and Debye temperature (Θ{sub D}) have been calculated. The calculated values of all these parameters are compared with the available experimental values and the values reported by different workers. A fairly good agreement has been found between them.
Abs-initio, Predictive Calculations for Optoelectronic and Advanced Materials Research
Bagayoko, Diola
2010-10-01
Most density functional theory (DFT) calculations find band gaps that are 30-50 percent smaller than the experimental ones. Some explanations of this serious underestimation by theory include self-interaction and the derivative discontinuity of the exchange correlation energy. Several approaches have been developed in the search for a solution to this problem. Most of them entail some modification of DFT potentials. The Green function and screened Coulomb approximation (GWA) is a non-DFT formalism that has led to some improvements. Despite these efforts, the underestimation problem has mostly persisted in the literature. Using the Rayleigh theorem, we describe a basis set and variational effect inherently associated with calculations that employ a linear combination of atomic orbitals (LCAO) in a variational approach of the Rayleigh-Ritz type. This description concomitantly shows a source of large underestimation errors in calculated band gaps, i.e., an often dramatic lowering of some unoccupied energies on account of the Rayleigh theorem as opposed to a physical interaction. We present the Bagayoko, Zhao, and Williams (BZW) method [Phys. Rev. B 60, 1563 (1999); PRB 74, 245214 (2006); and J. Appl. Phys. 103, 096101 (2008)] that systematically avoids this effect and leads (a) to DFT and LDA calculated band gaps of semiconductors in agreement with experiment and (b) theoretical predictions of band gaps that are confirmed by experiment. Unlike most calculations, BZW computations solve, self-consistently, a system of two coupled equations. DFT-BZW calculated effective masses and optical properties (dielectric functions) also agree with measurements. We illustrate ten years of success of the BZW method with its results for GaN, C, Si, 3C-SIC, 4H-SiC, ZnO, AlAs, Ge, ZnSe, w-InN, c-InN, InAs, CdS, AlN and nanostructures. We conclude with potential applications of the BZW method in optoelectronic and advanced materials research.
Electronic, vibrational and related properties of group IV metal oxides by ab initio calculations
International Nuclear Information System (INIS)
Leite Alves, H.W.; Silva, C.C.; Lino, A.T.; Borges, P.D.; Scolfaro, L.M.R.; Silva, E.F. da
2008-01-01
We present our theoretical results for the structural, electronic, vibrational and optical properties of MO 2 (M = Sn, Zr, Hf and Ti) obtained by first-principles calculations. Relativistic effects are demonstrated to be important for a realistic description of the detailed structure of the electronic frequency-dependent dielectric function, as well as of the carrier effective masses. Based on our results, we found that the main contribution of the high values calculated for the oxides dielectric constants arises from the vibrational properties of these oxides, and the vibrational static dielectric constant values diminish with increasing pressure
Ab Initio Calculations of Deuterium Isotope Effects on Chemical Shifts of Salt-Bridged Lysines
DEFF Research Database (Denmark)
Ullah, Saif; Ishimoto, Takayoshi; Williamson, Mike P.
2011-01-01
(D), in ammonium and amines decrease as a counterion or water molecule moves closer to the nitrogen. 1Δ15N(D) and 2Δ1H(D) of the NH3+ groups of lysine residues in the B1 domain of protein G have been calculated using truncated side chains and also determined experimentally by NMR. Comparisons show...
Ab-initio calculations of electric field gradient in Ru compounds and ...
Indian Academy of Sciences (India)
Home; Journals; Pramana – Journal of Physics; Volume 89; Issue 2. A b − i n i t i o calculations of electric field gradient in Ru compounds and their implication on the nuclear quadrupole moments of 99 Ru and 101 Ru. S N MISHRA. Research Article Volume 89 Issue 2 August 2017 Article ID 22 ...
DEFF Research Database (Denmark)
Bludsky, O.; Bak, Keld L.; JORGENSEN, P
1995-01-01
The quartic force field and the cubic dipole moment surface are calculated for trans-2,3-dideuteriooxirane at the self-consistent field and the second order Moller-Plesset levels of theory using a triple zeta plus two polarization functions basis set. Contact transformation theory is used to dete...
Ab initio calculations of partial molar properties in the single-site approximation
DEFF Research Database (Denmark)
Ruban, Andrei; Skriver, Hans Lomholt
1997-01-01
We discuss the application of the single-site approximation in calculations of partial molar quantities, e.g., impurity solution energy, segregation energy, and effective chemical potential, which are related to a variation of the composition of an alloy or its nonequivalent parts. We demonstrate...
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 Calculations of Electronic Fingerprints of DNA bases on Graphene
Ahmed, Towfiq; Rehr, John J.; Kilina, Svetlana; Das, Tanmoy; Haraldsen, Jason T.; Balatsky, Alexander V.
2012-02-01
We have carried out first principles DFT calculations of the electronic local density of states (LDOS) of DNA nucleotide bases (A,C,G,T) adsorbed on graphene using LDA with ultra-soft pseudo-potentials. We have also calculated the longitudinal transmission currents T(E) through graphene nano-pores as an individual DNA base passes through it, using a non-equilibrium Green's function (NEGF) formalism. We observe several dominant base-dependent features in the LDOS and T(E) in an energy range within a few eV of the Fermi level. These features can serve as electronic fingerprints for the identification of individual bases from dI/dV measurements in scanning tunneling spectroscopy (STS) and nano-pore experiments. Thus these electronic signatures can provide an alternative approach to DNA sequencing.
International Nuclear Information System (INIS)
Gohaud, Neil; Begue, Didier; Pouchan, Claude
2005-01-01
The complete quartic force field of methyllithium (CH 3 Li) is computed at the B3LYP/cc-pVTZ level of theory. The vibrational energy levels calculated from a perturbational and a variational procedure are in agreement with the observed spectra except for the C-Li stretching and the symmetric methyl deformation modes for which a disagreement with the experimental assignment given by Andrews is apparent. This discrepancy between experiment and theory is so large that questions are raised either about a correct characterization of, or correct calculations for the monomeric species CH 3 Li. Our theoretical study of methyllithium aggregates (CH 3 Li) n , with n = 2, 3, 4 and 6, gives a new interpretation of the experimental data
Ab initio calculations of torsionally mediated hyperfine splittings in E states of acetaldehyde
Xu, Li-Hong; Reid, E. M.; Guislain, B.; Hougen, J. T.; Alekseev, E. A.; Krapivin, I.
2017-12-01
Quantum chemistry packages can be used to predict with reasonable accuracy spin-rotation hyperfine interaction constants for methanol, which contains one methyl-top internal rotor. In this work we use one of these packages to calculate components of the spin-rotation interaction tensor for acetaldehyde. We then use torsion-rotation wavefunctions obtained from a fit to the acetaldehyde torsion-rotation spectrum to calculate the expected magnitude of hyperfine splittings analogous to those observed at relatively high J values in the E symmetry states of methanol. We find that theory does indeed predict doublet splittings at moderate J values in the acetaldehyde torsion-rotation spectrum, which closely resemble those seen in methanol, but that the factor of three decrease in hyperfine spin-rotation constants compared to methanol puts the largest of the acetaldehyde splittings a factor of two below presently available Lamb-dip resolution.
Energy Technology Data Exchange (ETDEWEB)
Mokhtari, A.; Akbarzadeh, H
2003-09-01
The electronic and structural properties of beryllium nitride (alpha and beta), magnesium- and calcium-nitrides were investigated using first principle full potential-linearized augmented plane wave method within density functional theory. We used Perdew and Wang-generalized gradient approximation, which is based on exchange correlation energy optimization, to calculate the total energy and the Engel-Vosko's GGA formalism, which optimize the corresponding potential, for band structure calculations. We also optimized internal parameters by relaxing the atomic positions in the force directions. Our results including lattice parameter, bulk modulus and it's pressure derivative, cohesive energy, band structure and density of states are compared with the experimental and other theoretical (Hartree-Fock approximation with a posteriori density functional correction) data.
International Nuclear Information System (INIS)
Mokhtari, A.; Akbarzadeh, H.
2003-01-01
The electronic and structural properties of beryllium nitride (alpha and beta), magnesium- and calcium-nitrides were investigated using first principle full potential-linearized augmented plane wave method within density functional theory. We used Perdew and Wang-generalized gradient approximation, which is based on exchange correlation energy optimization, to calculate the total energy and the Engel-Vosko's GGA formalism, which optimize the corresponding potential, for band structure calculations. We also optimized internal parameters by relaxing the atomic positions in the force directions. Our results including lattice parameter, bulk modulus and it's pressure derivative, cohesive energy, band structure and density of states are compared with the experimental and other theoretical (Hartree-Fock approximation with a posteriori density functional correction) data
International Nuclear Information System (INIS)
Albrecht, Stefan
1999-01-01
A method for the inclusion of self-energy and excitonic effects in first-principle calculations of absorption spectra, within the state-of-the-art plane wave pseudopotential approach, is presented. Starting from a ground state calculation, using density functional theory (DFT) in the local density approximation (LDA), we correct the exchange-correlation potential of DFT-LDA with the self-energy applying Hedin's GW approximation to obtain the physical quasiparticles states. The electron-hole interaction is treated solving an effective two-particle equation, which we derive from Hedin's coupled integral equations, leading to the fundamental Bethe-Salpeter equation in an intermediate step. The interaction kernel contains the screened electron-hole Coulomb interaction and the electron-hole exchange effects, which reflect the microscopic structure of the system and are thus also called local-field effects. We obtain the excitonic eigenstates through diagonalization. This allows us a detailed analysis of the optical properties. The application of symmetry properties enables us to reduce the size of the two-particle Hamiltonian matrix, thus minimizing the computational effort. We apply our method to silicon, diamond, lithium oxide and the sodium tetramer. Good agreement with experiment is obtained for the absorption spectra of Si and diamond, the static dielectric constant of diamond, and for the onset of optical absorption of Li 2 O due to discrete bound excitons. We discuss various approximations of our method and show the strong mixing of independent particle transitions to a bound excitonic state in the Na 4 cluster. The influence of ground state calculations on optical spectra is investigated under particular consideration of the pseudopotential generation and we discuss the use of different Brillouin zone point sampling schemes for spectral calculations. (author) [fr
Magnetic properties of polar ZnO surfaces from ab-initio calculations
Energy Technology Data Exchange (ETDEWEB)
Fischer, Guntram; Adeagbo, Waheed; Hergert, Wolfram [University Halle, Halle (Germany); Ernst, Arthur [Max-Planck-Institute of Microstructure Physics, Halle (Germany); Sanchez, Nadia; Mu noz, Carmen [Instituto de Ciencia de Materiales de Madrid, Madrid (Spain); Szotek, Zdzislawa; Temmerman, Walter [Daresbury Laboratory, Warrington (United Kingdom)
2011-07-01
We have investigated a magnetic moment formation of three oxygen-terminated polar ZnO surfaces. Specifically, these are the (000-1) surface, the (0001) surface with an oxygen atom on top of the Zn atom [(0001)-t], and the (0001) surface with an oxygen atom in a threefold hollow site [(0001)-h]. In this study we have used a multi-code approach allowing us to relax the surface structure and calculate the Heisenberg exchange parameters via a magnetic force theorem. Also, the influence of applying self-interaction corrections (SIC) to the oxygen p orbitals has been investigated. Our calculations show that all three surfaces are magnetic. In addition, we find that applying SIC is necessary to correctly describe the top oxygen atom of the (0001)-h and (0001)-t surfaces, for both of which we find Curie temperatures to be larger than room temperature. The latter have been derived from Monte Carlo simulations based on the calculated exchange parameters.
The ab initio model potential method. Second series transition metal elements
International Nuclear Information System (INIS)
Barandiaran, Z.; Seijo, L.; Huzinaga, S.
1990-01-01
The ab initio core method potential model (AIMP) has already been presented in its nonrelativistic version and applied to the main group and first series transition metal elements [J. Chem. Phys. 86, 2132 (1987); 91, 7011 (1989)]. In this paper we extend the AIMP method to include relativistic effects within the Cowan--Griffin approximation and we present relativistic Zn-like core model potentials and valence basis sets, as well as their nonrelativistic Zn-like core and Kr-like core counterparts. The pilot molecular calculations on YO, TcO, AgO, and AgH reveal that the 4p orbital is indeed a core orbital only at the end part of the series, whereas the 4s orbital can be safely frozen from Y to Cd. The all-electron and model potential results agree in 0.01--0.02 A in R e and 25--50 cm -1 in bar ν e if the same type of valence part of the basis set is used. The comparison of the relativistic results on AgH with those of the all-electron Dirac--Fock calculations by Lee and McLean is satisfactory: the absolute value of R e is reproduced within the 0.01 A margin and the relativistic contraction of 0.077 A is also very well reproduced (0.075 A). Finally, the relative magnitude of the effects of the core orbital change, mass--velocity potential, and Darwin potential on the net relativistic effects are analyzed in the four molecules studied
International Nuclear Information System (INIS)
Koehler, W.E.; Schaefer, J.
1983-01-01
The temperature dependence of the effective Waldmann--Snider cross sections determining the Senftleben--Beenakker effects of viscosity and heat conductivity has been studied for pH 2 gas between 10 and 200 K. From ab initio nonspherical potentials of H 2 --H 2 , scattering matrices have been determined in close-coupling calculations. From these, the elements of the scattering amplitude matrix have been obtained and used as input quantities for the evaluation of the various Waldmann--Snider collision integrals. The results of these first ab initio numerical calculations of anisotropic transport coefficients show excellent agreement of calculated and measured effective cross sections, especially for the most recent improved version of the interaction potential. In addition, it has been shown that the polarization production cross sections are quite sensitive to the potential anisotropy
Bakkari, Karim; Fersi, Riadh; Kebir Hlil, El; Bessais, Lotfi; Thabet Mliki, Najeh
2018-03-01
First-principle calculations combining density functional theory and the full-potential linearized augmented plane wave (FP-LAPW) method are performed to investigate the electronic and magnetic structure of Pr2Co7 in its two polymorphic forms, (2:7 H) and (2:7 R), for the first time. This type of calculation was also performed for PrCo5 and PrCo2 intermetallics. We have computed the valence density of states separately for spin-up and spin-down states in order to investigate the electronic band structure. This is governed by the strong contribution of the partial DOS of 3d-Co bands compared to the partial DOS of the 4f-Pr bands. Such a high ferromagnetic state is discussed in terms of the strong spin polarization observed in the total DOS. The magnetic moments carried by the Co and Pr atoms located in several sites for all compounds are computed. These results mainly indicate that cobalt atoms make a dominant contribution to the magnetic moments. The notable difference in the atomic moments of Pr and Co atoms between different structural slabs is explained in terms of the magnetic characteristics of the PrCo2 and PrCo5 compounds and the local chemical environments of the Pr and Co atoms in different structural slabs of Pr2Co7. From spin-polarized calculations we have simulated the 3d and 4f band population to estimate the local magnetic moments. These results are in accordance with the magnetic moments calculated using the FP-LAPW method. In addition, the exchange interactions J ij are calculated and used as input for M(T) simulations. Involving the data obtained from the electronic structure calculations, the appropriate Padé Table is applied to simulate the magnetization M(T) and to estimate the mean-field Curie temperature. We report a fairly good agreement between the ab initio calculation of magnetization and Curie temperature with the experimental data.
Rotational study of the CH4–CO complex: Millimeter-wave measurements and ab initio calculations
International Nuclear Information System (INIS)
Surin, L. A.; Tarabukin, I. V.; Panfilov, V. A.; Schlemmer, S.; Kalugina, Y. N.; Faure, A.; Rist, C.; Avoird, A. van der
2015-01-01
The rotational spectrum of the van der Waals complex CH 4 –CO has been measured with the intracavity OROTRON jet spectrometer in the frequency range of 110–145 GHz. Newly observed and assigned transitions belong to the K = 2–1 subband correlating with the rotationless j CH4 = 0 ground state and the K = 2–1 and K = 0–1 subbands correlating with the j CH4 = 2 excited state of free methane. The (approximate) quantum number K is the projection of the total angular momentum J on the intermolecular axis. The new data were analyzed together with the known millimeter-wave and microwave transitions in order to determine the molecular parameters of the CH 4 –CO complex. Accompanying ab initio calculations of the intermolecular potential energy surface (PES) of CH 4 –CO have been carried out at the explicitly correlated coupled cluster level of theory with single, double, and perturbative triple excitations [CCSD(T)-F12a] and an augmented correlation-consistent triple zeta (aVTZ) basis set. The global minimum of the five-dimensional PES corresponds to an approximately T-shaped structure with the CH 4 face closest to the CO subunit and binding energy D e = 177.82 cm −1 . The bound rovibrational levels of the CH 4 –CO complex were calculated for total angular momentum J = 0–6 on this intermolecular potential surface and compared with the experimental results. The calculated dissociation energies D 0 are 91.32, 94.46, and 104.21 cm −1 for A (j CH4 = 0), F (j CH4 = 1), and E (j CH4 = 2) nuclear spin modifications of CH 4 –CO, respectively
Nahar, S. N.
2003-01-01
Most astrophysical plasmas entail a balance between ionization and recombination. We present new results from a unified method for self-consistent and ab initio calculations for the inverse processes of photoionization and (e + ion) recombination. The treatment for (e + ion) recombination subsumes the non-resonant radiative recombination and the resonant dielectronic recombination processes in a unified scheme (S.N. Nahar and A.K. Pradhan, Phys. Rev. A 49, 1816 (1994);H.L. Zhang, S.N. Nahar, and A.K. Pradhan, J.Phys.B, 32,1459 (1999)). Calculations are carried out using the R-matrix method in the close coupling approximation using an identical wavefunction expansion for both processes to ensure self-consistency. The results for photoionization and recombination cross sections may also be compared with state-of-the-art experiments on synchrotron radiation sources for photoionization, and on heavy ion storage rings for recombination. The new experiments display heretofore unprecedented detail in terms of resonances and background cross sections and thereby calibrate the theoretical data precisely. We find a level of agreement between theory and experiment at about 10% for not only the ground state but also the metastable states. The recent experiments therefore verify the estimated accuracy of the vast amount of photoionization data computed under the OP, IP and related works. features. Present work also reports photoionization cross sections including relativistic effects in the Breit-Pauli R-matrix (BPRM) approximation. Detailed features in the calculated cross sections exhibit the missing resonances due to fine structure. Self-consistent datasets for photoionization and recombination have so far been computed for approximately 45 atoms and ions. These are being reported in a continuing series of publications in Astrophysical J. Supplements (e.g. references below). These data will also be available from the electronic database TIPTOPBASE (http://heasarc.gsfc.nasa.gov)
A nonlocal, ab initio model of dissociative electron attachment and vibrational excitation of NO
International Nuclear Information System (INIS)
Trevisan, Cynthia S.; Houfek, Karel; Zhang, Zhiyong; Orel, Ann E.; McCurdy, C. William; Rescigno, Thomas N.
2005-01-01
We present the results of an ab initio study of elastic scattering and vibrational excitation of NO by electron impact in the loW--energy (0-2 eV) region where the cross sections are dominated by resonance contributions. The 3Sigma-, 1Delta and 1Sigma+ NO- resonance lifetimes are taken from our earlier study [Phys. Rev. A 69, 062711 (2004)], but the resonance energies used here are obtained from new configuration-interaction studies. Here we employ a more elaborate nonlocal treatment of the nuclear dynamics, which is found to remedy the principal deficiencies of the local complex potential model we employed in our earlier study, and gives cross sections in better agreement with the most recent experiments. We also present cross sections for dissociative electron attachment to NO leading to groundstate products. The calculations show that, while the peak cross sections starting from NO in its ground vibrational state are very small, the cross sections are extremely sensitive to vibrational excitation of the target and should be readily observable for target NO molecules excited to v = 10 and above
Kim, Jaehyun; Kang, Jiyoung; Nishigami, Hiroshi; Kino, Hiori; Tateno, Masaru
2018-03-01
Hydrogenases catalyze both the dissociation and production of dihydrogen (H2). Most hydrogenases are inactivated rapidly and reactivated slowly (in vitro), in the presence of dioxygen (O2) and H2, respectively. However, membrane-bound [NiFe] hydrogenases (MBHs) sustain their activity even together with O2, which is termed "O2 tolerance". In previous experimental analyses, an MBH was shown to include a hydroxyl ion (OH-) bound to an Fe of the super-oxidized [4Fe-3S]5+ cluster in the proximity of the [NiFe] catalytic cluster. In this study, the functional role of the OH- in the O2 tolerance was investigated by ab initio electronic structure calculation of the [4Fe-3S] proximal cluster. The analysis revealed that the OH- significantly altered the electronic structure, thereby inducing the delocalization of the lowest unoccupied molecular orbital (LUMO) toward the [NiFe] catalytic cluster, which may intermediate the electron transfer between the catalytic and proximal clusters. This can promote the O2-tolerant catalytic cycle in the hydrogenase reaction.
Accuracy and Transferability of Ab Initio Electronic Band Structure Calculations for Doped BiFeO3
Gebhardt, Julian; Rappe, Andrew M.
2017-11-01
BiFeO3 is a multiferroic material and, therefore, highly interesting with respect to future oxide electronics. In order to realize such devices, pn junctions need to be fabricated, which are currently impeded by the lack of successful p-type doping in this material. In order to guide the numerous research efforts in this field, we recently finished a comprehensive computational study, investigating the influence of many dopants onto the electronic structure of BiFeO3. In order to allow for this large scale ab initio study, the computational setup had to be accurate and efficient. Here we discuss the details of this assessment, showing that standard density-functional theory (DFT) yields good structural properties. The obtained electronic structure, however, suffers from well-known shortcomings. By comparing the conventional DFT results for alkali and alkaline-earth metal doping with more accurate hybrid-DFT calculations, we show that, in this case, the problems of standard DFT go beyond a simple systematic error. Conventional DFT shows bad transferability and the more reliable hybrid-DFT has to be chosen for a qualitatively correct prediction of doping induced changes in the electronic structure of BiFeO3.
Bovino, S; Zhang, P; Kharchenko, V; Dalgarno, A
2011-07-14
In this paper, we report our investigation of the translational energy relaxation of fast S((1)D) atoms in a Xe thermal bath. The interaction potential of Xe-S was constructed using ab initio methods. Total and differential cross sections were then calculated. The latter have been incorporated into the construction of the kernel of the Boltzmann equation describing the energy relaxation process. The solution of the Boltzmann equation was obtained and results were compared with those reported in experiments [G. Nan, and P. L. Houston, J. Chem. Phys. 97, 7865 (1992)]. Good agreement with the measured time-dependent relative velocity of fast S((1)D) atoms was obtained except at long relaxation times. The discrepancy may be due to the error accumulation caused by the use of hard sphere approximation and the Monte Carlo analysis of the experimental data. Our accurate description of the energy relaxation process led to an increase in the number of collisions required to achieve equilibrium by an order of magnitude compared to the number given by the hard-sphere approximation.
International Nuclear Information System (INIS)
Hay, P.J.; Wadt, W.R.
1985-01-01
Ab initio effective core potentials (ECP's) have been generated to replace the innermost core electron for third-row (K--Au), fourth-row (Rb--Ag), and fifth-row (Cs--Au) atoms. The outermost core orbitals: corresponding to the ns 2 np 6 configuration for the three rows here: are not replaced by the ECP but are treated on an equal footing with the nd, (n+1)s and (n+1)p valence orbitals. These ECP's have been derived for use in molecular calculations where these outer core orbitals need to be treated explicitly rather than to be replaced by an ECP. The ECP's for the forth and fifth rows also incorporate the mass--velocity and Darwin relativistic effects into the potentials. Analytic fits to the potentials are presented for use in multicenter integral evaluation. Gaussian orbital valence basis sets are developed for the (3s, 3p, 3d, 4s, 4p), (4s, 4p, 4d, 5s, 5p), and (5s, 5p, 5d, 6s, 6p) ortibals of the three respective rows
International Nuclear Information System (INIS)
Dacal, Luis C O; Cantarero, A
2014-01-01
Most III–V semiconductors, which acquire the zinc-blende phase as bulk materials, adopt the metastable wurtzite phase when grown in the form of nanowires. These are new semiconductors with new optical properties, in particular, a different electronic band gap when compared with that grown in the zinc-blende phase. The electronic gap of wurtzite InAs at the Γ–point of the Brillouin zone (E 0 gap) has been recently measured, E 0 =0.46 eV at low temperature. The electronic gap at the A–point of the Brillouin zone (equivalent to the L–point in the zinc-blende structure, E 1 ) has also been obtained recently based on a resonant Raman scattering experiment. In this work, we calculate the band structure of InAs in the zinc-blende and wurtzite phases, using the full potential linearized augmented plane wave method, including spin-orbit interaction. The electronic band gap has been improved through the modified Becke–Johnson exchange-correlation potential. Both the E 0 and E 1 gaps agree very well with the experiment. From the calculations, a crystal field splitting of 0.122 eV and a spin-orbit splitting of 0.312 eV (the experimental value in zinc-blende InAs is 0.4 eV) has been obtained. Finally, we calculate the dielectric function of InAs in both the zinc-blende and wurtzite phases and a comparative discussion is given. (paper)
Dacal, Luis C. O.; Cantarero, A.
2014-03-01
Most III-V semiconductors, which acquire the zinc-blende phase as bulk materials, adopt the metastable wurtzite phase when grown in the form of nanowires. These are new semiconductors with new optical properties, in particular, a different electronic band gap when compared with that grown in the zinc-blende phase. The electronic gap of wurtzite InAs at the \\Gamma -point of the Brillouin zone ({{E}_{0}} gap) has been recently measured, {{E}_{0}}=0.46 eV at low temperature. The electronic gap at the A-point of the Brillouin zone (equivalent to the L-point in the zinc-blende structure, {{E}_{1}}) has also been obtained recently based on a resonant Raman scattering experiment. In this work, we calculate the band structure of InAs in the zinc-blende and wurtzite phases, using the full potential linearized augmented plane wave method, including spin-orbit interaction. The electronic band gap has been improved through the modified Becke-Johnson exchange-correlation potential. Both the {{E}_{0}} and {{E}_{1}} gaps agree very well with the experiment. From the calculations, a crystal field splitting of 0.122 eV and a spin-orbit splitting of 0.312 eV (the experimental value in zinc-blende InAs is 0.4 eV) has been obtained. Finally, we calculate the dielectric function of InAs in both the zinc-blende and wurtzite phases and a comparative discussion is given.
Optimizing porphyrins for dye sensitized solar cells using large-scale ab initio calculations
DEFF Research Database (Denmark)
Ørnsø, Kristian Baruël; Pedersen, Christian S.; García Lastra, Juan Maria
2014-01-01
different side and anchoring groups. Based on the calculated frontier orbital energies and optical gaps we quantify the energy level alignment with the TiO2 conduction band and different redox mediators. An analysis of the energy level-structure relationship reveals a significant structural diversity among...... the dyes with the highest level alignment quality, demonstrating the large degree of flexibility in porphyrin dye design. As a specific example of dye optimization, we show that the level alignment of the high efficiency record dye YD2-o-C8 [Yella et al., Science, 2011, 334, 629-634] can be significantly...
DEFF Research Database (Denmark)
Bak, KL; Bludsky, O.; Jorgensen, P
1995-01-01
A priori theory is derived for anharmonic calculations of vibrational circular dichroism (VCD). The anharmonic VCD expression is gauge origin independent and reduce to the magnetic field perturbation theory expression in the double-harmonic approximation. The theory has been implemented using...... for the atomic axial tensors and using second-order Moller-Plesset theory for the atomic polar tensors and the force fields, The changes of the vibrational rotatory strengths from anharmonicities are small, and do not explain the previously observed large discrepancies between the double-harmonic results...
Ab initio calculation of the electronic and optical properties of solid pentacene
International Nuclear Information System (INIS)
Tiago, Murilo L.; Northrup, John E.; Louie, Steve G.
2002-01-01
The optical and electronic properties of crystalline pentacene are studied, using a first-principles Green's-function approach. The quasiparticle energies are calculated within the GW approximation and the electron-hole excitations are computed by solving the Bethe-Salpeter equation. We investigate the role of polymorphism on the electronic energy gap and linear optical spectrum by studying two different crystalline phases: the solution-phase structure and the vapor-phase structure. charge-transfer excitons are found to dominate the optical spectrum. Excitons with sizable binding energies are predicted for both phases
Energy Technology Data Exchange (ETDEWEB)
Benrekia, A.R., E-mail: benrekia.ahmed@yahoo.com [Faculty of Science and Technology, University of Medea (Algeria); Benkhettou, N. [Laboratoire des Materiaux Magnetiques, Faculte des Sciences, Universite Djillali Liabes de Sidi Bel Abbes (Algeria); Nassour, A. [Laboratoire de Cristallographie, Resonance Magnetique et Modelisations (CRM2, UMR CNRS 7036) Institut Jean Barriol, Nancy Universite BP 239, Boulevard des Aiguillettes, 54506 Vandoeuvre-les-Nancy (France); Driz, M. [Applied Material Laboratory (AML), Electronics Department, University of Sidi bel Abbes (DZ 22000) (Algeria); Sahnoun, M. [Laboratoire de Physique Quantique de la Matiere et Modelisations Mathematique (LPQ3M), Faculty of Science and Technology,University of Mascara (Algeria); Lebegue, S. [Laboratoire de Cristallographie, Resonance Magnetique et Modelisations (CRM2, UMR CNRS 7036) Institut Jean Barriol, Nancy Universite BP 239, Boulevard des Aiguillettes, 54506 Vandoeuvre-les-Nancy (France)
2012-07-01
We present first-principles VASP calculations of the structural, electronic, vibrational, and optical properties of paraelectric SrTiO{sub 3} and KTaO{sub 3}. The ab initio calculations are performed in the framework of density functional theory with different exchange-correlation potentials. Our calculated lattice parameters, elastic constants, and vibrational frequencies are found to be in good agreement with the available experimental values. Then, the bandstructures are calculated with the GW approximation, and the corresponding band gap is used to obtain the optical properties of SrTiO{sub 3} and KTaO{sub 3}.
Ab initio calculation of transport properties between PbSe quantum dots facets with iodide ligands
Wang, B.; Patterson, R.; Chen, W.; Zhang, Z.; Yang, J.; Huang, S.; Shrestha, S.; Conibeer, G.
2018-01-01
The transport properties between Lead Selenide (PbSe) quantum dots decorated with iodide ligands has been studied using density functional theory (DFT). Quantum conductance at each selected energy levels has been calculated along with total density of states and projected density of states. The DFT calculation is carried on using a grid-based planar augmented wave (GPAW) code incorporated with the linear combination of atomic orbital (LCAO) mode and Perdew Burke Ernzerhof (PBE) exchange-correlation functional. Three iodide ligand attached low index facets including (001), (011), (111) are investigated in this work. P-orbital of iodide ligand majorly contributes to density of state (DOS) at near top valence band resulting a significant quantum conductance, whereas DOS of Pb p-orbital shows minor influence. Various values of quantum conductance observed along different planes are possibly reasoned from a combined effect electrical field over topmost surface and total distance between adjacent facets. Ligands attached to (001) and (011) planes possess similar bond length whereas it is significantly shortened in (111) plane, whereas transport between (011) has an overall low value due to newly formed electric field. On the other hand, (111) plane with a net surface dipole perpendicular to surface layers leading to stronger electron coupling suggests an apparent increase of transport probability. Apart from previously mentioned, the maximum transport energy levels located several eVs (1 2 eVs) from the edge of valence band top.
Laser Spectroscopy and AB Initio Calculations on the TaF Molecule
Ng, Kiu Fung; Zou, Wenli; Liu, Wenjian; Cheung, Allan S. C.
2016-06-01
Electronic transition spectrum of the tantalum monoflouride (TaF) molecule in the spectral region between 448 and 520 nm has been studied using the technique of laser-ablation/reaction free jet expansion and laser induced fluorescence spectroscopy. TaF molecule was produced by reacting laser-ablated tantalum atoms with sulfur hexafluoride gas seeded in argon. Sixteen vibrational bands with resolved rotational structure have been recorded and analyzed, which were organized into six electronic transition systems and the ground state has been identified to be the X3Σ-(0+) state with bond length, ro, and equilibrium vibrational frequency, ωe, determined to be 1.8209 Å and 700.1 wn respectively. In addition, four vibrational bands belong to another transition system involving lower state with Ω = 2 component has also been analyzed. All observed transitions are with ΔΩ = 0. Least-squares fit of the measured line positions yielded molecular constants for the electronic states involved. The Λ-S and Ω states of TaF were calculated at the state-averaged complete active space self-consistent field (SA-CASSCF) and the subsequent internally contracted multi-reference configuration interaction with singles and doubles and Davidson's cluster correction (MRCISD+Q) levels of theory with the active space of 4 electrons in 6 orbitals, that is, the molecular orbitals corresponding to Ta 5d6s are active. The spin-orbit coupling (SOC) is calculated by the state-interaction approach at the SA-CASSCF level via the relativistic effective core potentials (RECPs) spin-orbit operator, where the diagonal elements of the spin-orbit matrix are replaced by the above MRCISD+Q energies. The spectroscopic properties of the ground and many low-lying electronic states of the TaF molecule will be reported. With respect to the observed electronic states in this work, the calculated results are in good agreement with our experimental determinations. This work represents the first experimental
Determining the phase diagram of lithium via ab initio calculation and ramp compression
Shulenburger, Luke; Seagle, Chris; Haill, Thomas; Harding, Eric
2015-06-01
Diamond anvil cell experiments have shown elemental lithium to have an extraordinarily complex phase diagram under pressure exhibiting numerous solid phases at pressures below 1 Mbar, as well as a complicated melting behavior. We explore this phase diagram utilizing a combination of quantum mechanical calculations and ramp compression experiments performed on Sandia National Laboratories' Z-machine. We aim to extend our knowledge of the high pressure behavior to moderate temperatures at pressures above 50 GPa with a specific focus on the melt line above 70 GPa. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Company, for the US Dept of Energy's Natl. Nuclear Security Administration under Contract DE-AC04-94AL85000.
Ab initio calculation of the thermodynamic properties of InSb under intense laser irradiation
International Nuclear Information System (INIS)
Feng, ShiQuan; Cheng, XinLu; Zhao, JianLing; Zhang, Hong
2013-01-01
In this paper, phonon spectra of InSb at different electronic temperatures are presented. Based on the phonon dispersion relationship, we further perform a theoretical investigation of the thermodynamic properties of InSb under intense laser irradiation. The phonon entropy, phonon heat capacity, and phonon contribution to Helmholtz free energy and internal energy of InSb are calculated as functions of temperature at different electronic temperatures. The abrupt change in the phonon entropy- temperature curve from T e = 0.75 to 1.0 eV provides an indication of InSb undergoing a phase transition from solid to liquid. It can be considered as a collateral evidence of non-thermal melting for InSb under intense electronic excitation effect
Ab initio calculation of the thermodynamic properties of InSb under intense laser irradiation
Feng, ShiQuan; Zhao, JianLing; Cheng, XinLu; Zhang, Hong
2013-07-01
In this paper, phonon spectra of InSb at different electronic temperatures are presented. Based on the phonon dispersion relationship, we further perform a theoretical investigation of the thermodynamic properties of InSb under intense laser irradiation. The phonon entropy, phonon heat capacity, and phonon contribution to Helmholtz free energy and internal energy of InSb are calculated as functions of temperature at different electronic temperatures. The abrupt change in the phonon entropy- temperature curve from Te = 0.75 to 1.0 eV provides an indication of InSb undergoing a phase transition from solid to liquid. It can be considered as a collateral evidence of non-thermal melting for InSb under intense electronic excitation effect.
Application of ab initio calculations and molecular dynamics to collagen and brome mosaic virus
Eifler, Jay Quinson
In bio-related research, large proteins are of important interest. We study two such proteins. Collagen is one such protein which forms part of the structural matrix for animals, such as in their bones and teeth. 1JS9 is another protein that is a component of the protein shell of the brome mosaic virus (BMV). And BMV is important for drug delivery and imaging. To better understand the properties of these proteins, quantum mechanically (QM) based results are needed, however computationally feasible methods are also necessary. The Orthogonalized Linear Combination of Atomic Orbitals (OLCAO) method is well-suited for application to such large proteins. However, a new approach to reduce the computational cost is required and this extension to the method we call the Amino-Acid Based Method (AAPM) of OLCAO. The AAPM roughly calculates electronic, self-consistent field (scf) potentials for individual amino-acids with their neighboring amino-acids included as a boundary condition. This allows the costly scf part of the calculation to be skipped out. Additionally, the number of potentials used to describe the how protein i s also minimized. Results for effective charge and bond order are obtained and analyzed for Collagen and preliminary effective charge results are obtained for 1JS9. The effective charge results reproduce those already obtained with other QM based methods but without reduced cost and preserved accuracy that are characteristically different than the formal charges mostly still in use to describe the charge properties of proteins. The bond order results for Collagen nicely reproduce the observed experimentally-derived hydrogen bonding between the individual chains of the collagen triple-helix as well as the observed hydrogen bonding network.
Ab initio calculations of non-stoichiometric copper nitride, pure and with palladium
International Nuclear Information System (INIS)
Moreno-Armenta, Maria G.; Soto, Gerardo; Takeuchi, Noboru
2011-01-01
Research highlights: → The most stable arrangement corresponds to the Cu 3 N-anti ReO 3 structure. → Formation energy of Cu 32 Vac 0 N 8 and Cu 24 Pd 8 Vac 0 N 8 are very similar. → The biggest volume in the compound is Cu 31 Pd 1 Vac 0 N 8/ . → Small amount introduction of extra metal atoms in copper nitride is possible. - Abstract: We present first principles calculations of copper nitride by using periodic density functional theory within a plane-wave ultrasoft pseudopotential scheme. The insertions of extra Cu and/or Pd atoms in the empty sites, vacancy reorganization, and substitution of Cu by Pd atoms were studied. We have used an equivalent reduced-symmetry 2 x 2 x 2 Cu 3 N-like cubic super-cell. Small Cu and/or Pd concentrations and vacancy rearrangements in the copper sub-lattice were conveniently calculated in these low-symmetry cells. We cover probable situations like: the occupation of the initially empty copper sites by (1) copper atoms, and by (2) palladium; (3) the relocation of vacancies in the copper sub-lattice; and (4) the substitution of small quantities of copper by palladium atoms in the copper sub-lattice. The equilibrium volumes and energies after relaxing the atomic positions are compared to those of intrinsic copper nitride. We found that the most stable arrangement corresponds to the ideal stoichiometric Cu 3 N. We also found that any deviation from this ideal configuration shift the semiconductor state to a metallic or semi-metallic one.
Speciation of magnesium in monohydrocalcite: XANES, ab initio and geochemical modeling
Fukushi, Keisuke; Suzuki, Yuma; Kawano, Jun; Ohno, Takeshi; Ogawa, Masahiro; Yaji, Toyonari; Takahashi, Yoshio
2017-09-01
Monohydrocalcite (MHC: CaCO3·H2O), a rare carbonate mineral formed under surface conditions, is usually observed in nature as containing a variable amount of Mg, with a 0.007-0.45 Mg/Ca mole ratio. The variable Mg composition in MHC is anticipated as a promising proxy to assess paleo-hydrochemistry especially in saline lakes. Although the roles of Mg on the formation and stability of MHC have been studied intensively, the Mg speciation in MHC has remained unclear and controversial. This study examined Mg speciation in MHC using X-ray absorption near edge structure (XANES), ab initio molecular simulation, and geochemical modeling. Mg-XANES spectra of MHC with different Mg/Ca ratios prepared from mixing solutions of Na2CO3, CaCl2 and MgCl2 revealed that the Mg in MHC is a mixture of amorphous Mg carbonate (AMC) and other Mg containing phase. The contribution of AMC to total Mg is negatively correlated to the crystallinity of MHC. Results show that AMC might play a protective role in the crystallization and the transformation to stable calcium carbonates. Ab initio calculation of Mg2+ substitution into MHC showed that a limited amount of Mg2+ can be incorporated into the MHC structure. Six-fold coordination of Mg2+ is substituted for eight-fold coordination of Ca2+ in the MHC structure. The other type of Mg in MHC revealed from the XANES analyses most likely corresponds to the structural Mg in MHC. The contribution of the structural Mg is almost constant at 0.06 in Mg/Ca, representing the limit of solid solubility of Mg in MHC. The solubility products of the MHC with the limit of solid solubility of Mg and the AMC associated with MHC were estimated from the reacted solution compositions. Prediction of the Mg/Ca ratio as a function of the initial solution conditions using solubility reasonably reproduces the observed apparent Mg/Ca ratios in MHC from the present study and earlier studies. The apparent Mg/Ca ratio of MHC is useful to elucidate water chemistry
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.
Czech Academy of Sciences Publication Activity Database
Řezníček, R.; Chlan, V.; Štěpánková, H.; Novák, Pavel; Żukrowski, J.; Kozlowski, A.; Kakol, Z.; Tarnawski, Z.; Honig, J.M.
2017-01-01
Roč. 96, č. 19 (2017), s. 1-10, č. článku 195124. ISSN 2469-9950 Institutional support: RVO:68378271 Keywords : magnetite * Mossbauer effect * density functional theory * modelling Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 3.836, year: 2016
Chemical trend of exchange coupling in diluted magnetic II-VI semiconductors: Ab initio calculations
Chanier, T.; Virot, F.; Hayn, R.
2009-05-01
We have calculated the chemical trend of magnetic exchange parameters ( Jdd , Nα , and Nβ ) of Zn-based II-VI semiconductors ZnA ( A=O , S, Se, and Te) doped with Co or Mn. We show that a proper treatment of electron correlations by the local spin-density approximation (LSDA)+U method leads to good agreement between experimental and theoretical values of the nearest-neighbor exchange coupling Jdd between localized 3d spins in contrast to the LSDA method. The exchange couplings between localized spins and doped electrons in the conduction band Nα are in good agreement with experiment as well. But the values for Nβ (coupling to doped holes in the valence band) indicate a crossover from weak coupling (for A=Te and Se) to strong coupling (for A=O ) and a localized hole state in ZnO:Mn. This hole localization explains the apparent discrepancy between photoemission and magneto-optical data for ZnO:Mn.
Attractive PHHP interactions revealed by state-of-the-art ab initio calculations.
Yourdkhani, Sirous; Jabłoński, Mirosław; Echeverría, Jorge
2017-10-25
We report in this work a combined structural and state-of-the-art computational study of homopolar P-HH-P intermolecular contacts. Database surveys have shown the abundance of such surprisingly unexplored contacts, which are usually accompanied by other weak interactions in the solid state. By means of a detailed theoretical study utilizing SAPT(DFT), MP2, SCS-MP2, MP2C and CCSD(T) methods and both aug-cc-pVXZ and aug-cc-pCVXZ (X = D, T, Q, 5) basis sets as well as extrapolation to the CBS limit, we have shown that P-HH-P contacts are indeed attractive and considerably strong. SAPT(DFT) calculations have revealed the dispersive nature of the P-HH-P interaction with only minor contribution of the inductive term, whereas the first-order electrostatic term is clearly overbalanced by the first-order exchange energy. In general the computed interaction energies follow the trend: E ≈ E < E < E. Our results have also shown that the aug-cc-pVDZ (or aug-cc-pCVDZ) basis set is not yet well balanced and that the second-order dispersion energy term is the slowest converging among all SAPT(DFT) energy components. Compared to aug-cc-pVXZ basis sets, their core-correlation counterparts have a modest influence on all supermolecular interaction energies and a negligible influence on both the SAPT(DFT) interaction energy and its components.
International Nuclear Information System (INIS)
Ma, Duancheng; Friák, Martin; Pezold, Johann von; Raabe, Dierk; Neugebauer, Jörg
2015-01-01
We propose an approach for the computationally efficient and quantitatively accurate prediction of solid-solution strengthening. It combines the 2-D Peierls–Nabarro model and a recently developed solid-solution strengthening model. Solid-solution strengthening is examined with Al–Mg and Al–Li as representative alloy systems, demonstrating a good agreement between theory and experiments within the temperature range in which the dislocation motion is overdamped. Through a parametric study, two guideline maps of the misfit parameters against (i) the critical resolved shear stress, τ 0 , at 0 K and (ii) the energy barrier, ΔE b , against dislocation motion in a solid solution with randomly distributed solute atoms are created. With these two guideline maps, τ 0 at finite temperatures is predicted for other Al binary systems, and compared with available experiments, achieving good agreement
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
Energy Technology Data Exchange (ETDEWEB)
Bryant, Pamela L.; Harwell, Chris; Mrse, Anthony A.; Emery, Earl F.; Gan, Zhedong; Caldwell, Tod; Reyes, Arneil P.; Kuhns, Philip; Hoyt, David W.; Simeral, Larry S.; Hall, Randall W.; Butler, Leslie G.
2001-11-07
Aminato and propanolato aluminum clusters with 3-, 4-, and 6-coordinate aluminum sites are studied with three 27Al NMR techniques optimized for large 27Al Quadrupole coupling constants: field-swept, frequency-stepped, and high-field MAS NMR. The 27Al quadrupole coupling constants and asymmetry parameters of molecular species, both experimental and derived from ab initio molecular orbital calculations, are correlated with structure.
Negative ions of p-nitroaniline: Photodetachment, collisions, and ab initio calculations
Smith, Byron H.; Buonaugurio, Angela; Chen, Jing; Collins, Evan; Bowen, Kit H.; Compton, Robert N.; Sommerfeld, Thomas
2013-06-01
The structures of parent anion, M-, and deprotonated molecule, [M-H]-, anions of the highly polar p-nitroaniline (pNA) molecule are studied experimentally and theoretically. Photoelectron spectroscopy (PES) of the parent anion is employed to estimate the adiabatic electron affinity (EAa = 0.75 ± 0.1 eV) and vertical detachment energy (VDE = 1.1 eV). These measured energies are in good agreement with computed values of 0.73 eV for the EAa and the range of 0.85 to 1.0 eV for the VDE at the EOM-CCSD/Aug-cc-pVTZ level. Collision induced dissociation (CID) of deprotonated pNA, [pNA - H]-, with argon yielded [pNA - H - NO]- (i.e., rearrangement to give loss of NO) with a threshold energy of 2.36 eV. Calculations of the energy difference between [pNA - H]- and [pNA - H - NO]- give 1.64 eV, allowing an estimate of a 0.72 eV activation barrier for the rearrangement reaction. Direct dissociation of [pNA - H]- yielding NO_2^ - occurs at a threshold energy of 3.80 eV, in good agreement with theory (between 3.39 eV and 4.30 eV). As a result of the exceedingly large dipole moment for pNA (6.2 Debye measured in acetone), we predict two dipole-bound states, one at ˜110 meV and an excited state at 2 meV. No dipole-bound states are observed in the photodetachment experiments due the pronounced mixing between states with dipole-bound and valence character similar to what has been observed in other nitro systems. For the same reason, dipole-bound states are expected to provide highly efficient "doorway states" for the formation of the pNA- valence anion, and these states should be observable as resonances in the reverse process, that is, in the photodetachment spectrum of pNA- near the photodetachment threshold.
International Nuclear Information System (INIS)
Stroppa, Daniel G.; Montoro, Luciano A.; Ramirez, Antonio J.; Beltran, Armando; Andres, Juan; Conti, Tiago G.; Silva, Rafael O. da; Longo, Elson; Leite, Edson R.
2009-01-01
Modeling of nanocrystals supported by advanced morphological and chemical characterization is a unique tool for the development of reliable nanostructured devices, which depends on the ability to synthesize and characterize material on the atomic scale. Among the most significant challenges in nanostructural characterization is the evaluation of crystal growth mechanisms and their dependence on the shape of nanoparticles and the distribution of doping elements. This work presents a new strategy to characterize nanocrystals, applied here to antimony-doped tin oxide (Sb-SnO 2 ) (ATO) by the combined use of experimental and simulated high-resolution transmission electron microscopy (HRTEM) images and surface energy ab initio calculations. The results show that the Wulff construction can not only describe the shape of nanocrystals as a function of surface energy distribution but also retrieve quantitative information on dopant distribution by the dimensional analysis of nanoparticle shapes. In addition, a novel three-dimensional evaluation of an oriented attachment growth mechanism is provided in the proposed methodology. This procedure is a useful approach for faceted nanocrystal shape modeling and indirect quantitative evaluation of dopant spatial distribution, which are difficult to evaluate by other techniques. (author)
Bryant, P L; Harwell, C R; Mrse, A A; Emery, E F; Gan, Z; Caldwell, T; Reyes, A P; Kuhns, P; Hoyt, D W; Simeral, L S; Hall, R W; Butler, L G
2001-12-05
Experimental and ab initio molecular orbital techniques are developed for study of aluminum species with large quadrupole coupling constants to test structural models for methylaluminoxanes (MAO). The techniques are applied to nitrogen- and oxygen-containing complexes of aluminum and to solid MAO isolated from active commercial MAO preparations. (Aminato)- and (propanolato)aluminum clusters with 3-, 4-, and 6-coordinate aluminum sites are studied with three (27)Al NMR techniques optimized for large (27)Al quadrupole coupling constants: field-swept, frequency-stepped, and high-field MAS NMR. Four-membered (aminato)aluminum complexes with AlN(4) coordination yield slightly smaller C(q) values than similar AlN(2)C(2) sites: 12.2 vs 15.8 MHz. Planar 3-coordinate AlN(2)C sites have the largest C(q) values, 37 MHz. In all cases, molecular orbital calculations of the electric field gradient tensors yields C(q) and eta values that match with experiment, even for a large hexameric (aminato)aluminum cage. A D(3d) symmetry hexaaluminum oxane cluster, postulated as a model for MAO, yields a calculated C(q) of -23.7 MHz, eta = 0.7474, and predicts a spectrum that is too broad to match the field-swept NMR of methylaluminoxane, which shows at least three sites, all with C(q) values greater than 15 MHz but less than 21 MHz. Thus, the proposed hexaaluminum cluster, with its strained four-membered rings, is not a major component of MAO. However, calculations for dimers of the cage complex, either edge-bridged or face-bridged, show a much closer match to experiment. Also, MAO preparations differ, with a gel form of MAO having significantly larger (27)Al C(q) values than a nongel form, a conclusion reached on the basis of (27)Al NMR line widths in field-swept NMR spectra acquired from 13 to 24 T.
Conformers and non-covalent interactions studied by laser spectroscopies and ab initio calculations
Energy Technology Data Exchange (ETDEWEB)
Ullrich, Susanne
2001-07-01
The model peptides, formanilide and acetanilide, and their weakly bound complexes were studied in the gas-phase using resonance enhanced multi-photon ionisation (REMPI) and zero electron kinetic energy (ZEKE) photoelectron spectroscopy. Both, cis- and trans-isomers of formanilide, were observed under molecular beam conditions. Trans-formanilide displayed predominantly in-plane vibrational excitation indicative of a planar geometry with modest geometry changes upon excitation and ionisation. In cis-formanilide the side-chain is twisted compared to the phenyl plane in the S{sub 0} state, but planar in the S{sub 1} and D{sub 0} states, revealed in characteristic side-chain torsional and out-of-plane bending excitations. Additionally, the ZEKE spectra provide evidence that excess cationic charge is delocalised from the aromatic ring to the side chain. The work on trans-formanilide was extended to its van der Waals complex with Argon with the purpose of investigating the torsional potential of the side-chain and probing charge delocalisation. Complexation of amides with water is of considerable interest since water is not only present as a bulk solvent surrounding a peptide but also attached to specific binding sites in its interior. Evidence was found for the existence of a NH- and CO-bound isomer of trans-formanilide in the neutral, S{sub 0} and S{sub 1}, states, with the ZEKE spectrum of the cationic 'CO-bound' complex indicating a strong preference for the NH binding site. (author)
International Nuclear Information System (INIS)
Ghosh, G.; Olson, G.B.
2007-01-01
An optimal integration of modern computational tools and efficient experimentation is presented for the accelerated design of Nb-based superalloys. Integrated within a systems engineering framework, we have used ab initio methods along with alloy theory tools to predict phase stability of solid solutions and intermetallics to accelerate assessment of thermodynamic and kinetic databases enabling comprehensive predictive design of multicomponent multiphase microstructures as dynamic systems. Such an approach is also applicable for the accelerated design and development of other high performance materials. Based on established principles underlying Ni-based superalloys, the central microstructural concept is a precipitation strengthened system in which coherent cubic aluminide phase(s) provide both creep strengthening and a source of Al for Al 2 O 3 passivation enabled by a Nb-based alloy matrix with required ductile-to-brittle transition temperature, atomic transport kinetics and oxygen solubility behaviors. Ultrasoft and PAW pseudopotentials, as implemented in VASP, are used to calculate total energy, density of states and bonding charge densities of aluminides with B2 and L2 1 structures relevant to this research. Characterization of prototype alloys by transmission and analytical electron microscopy demonstrates the precipitation of B2 or L2 1 aluminide in a (Nb) matrix. Employing Thermo-Calc and DICTRA software systems, thermodynamic and kinetic databases are developed for substitutional alloying elements and interstitial oxygen to enhance the diffusivity ratio of Al to O for promotion of Al 2 O 3 passivation. However, the oxidation study of a Nb-Hf-Al alloy, with enhanced solubility of Al in (Nb) than in binary Nb-Al alloys, at 1300 deg. C shows the presence of a mixed oxide layer of NbAlO 4 and HfO 2 exhibiting parabolic growth
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)
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)
International Nuclear Information System (INIS)
Joubert, J.-M.; Colinet, C.; Rodrigues, G.; Suzuki, P.A.; Nunes, C.A.; Coelho, G.C.; Tedenac, J.-C.
2012-01-01
The solid solution based on Nb 5 Si 3 (Cr 5 B 3 structure type, D8 l , tI32, I4/mcm, No140, a=6.5767 Å, c=11.8967 Å) in the Nb–Si–B system was studied from the structural and thermodynamic point of view both experimentally and by ab initio calculations. Rietveld refinement of powder X-ray synchrotron data allowed to determine the boron to silicon substitution mechanism and the structural parameters. Ab initio calculations of different ordered compounds and selected disordered alloys allowed to obtain in addition to the enthalpy of formation of the solution, substitution mechanism and structural parameters which are in excellent agreement with the experimental data. The stability of the phase is discussed. - Graphial abstract: Valence-charge electron localization function in the z=0 plane of the D8 l structure for the ordered compound Nb 5 SiB 2 . Highlights: ► Coupling between ab initio data and experimental results from synchrotron powder diffraction. ► Excellent agreement between the two techniques for the site occupancies and internal coordinates. ► Explanation of the phase stability up to Nb 5 SiB 2 .
Martins, Luan Carvalho; Torres, Pedro Henrique Monteiro; de Oliveira, Renata Barbosa; Pascutti, Pedro Geraldo; Cino, Elio A.; Ferreira, Rafaela Salgado
2018-05-01
Chagas disease remains a major health problem in South America, and throughout the world. The two drugs clinically available for its treatment have limited efficacy and cause serious adverse effects. Cruzain is an established therapeutic target of Trypanosoma cruzi, the protozoan that causes Chagas disease. Our group recently identified a competitive cruzain inhibitor (compound 1) with an IC50 = 15 µM that is also more synthetically accessible than the previously reported lead, compound 2. Prior studies, however, did not propose a binding mode for compound 1, hindering understanding of the structure-activity relationship and optimization. Here, the cruzain binding mode of compound 1 was investigated using docking, molecular dynamics (MD) simulations with ab initio derived parameters, ab initio calculations, and MM/PBSA. Two ligand protonation states and four binding poses were evaluated. A careful ligand parameterization method was employed to derive more physically meaningful parameters than those obtained by automated tools. The poses of unprotonated 1 were unstable in MD, showing large conformational changes and diffusing away from the binding site, whereas the protonated form showed higher stability and interaction with negatively charged residues Asp161 and Cys25. MM/PBSA also suggested that these two residues contribute favorably to binding of compound 1. By combining results from MD, ab initio calculations, and MM/PBSA, a binding mode of 1 is proposed. The results also provide insights for further optimization of 1, an interesting lead compound for the development of new cruzain inhibitors.
International Nuclear Information System (INIS)
González-Lavado, Eloisa; Corchado, Jose C.; Espinosa-Garcia, Joaquin
2014-01-01
Based exclusively on high-level ab initio calculations, a new full-dimensional analytical potential energy surface (PES-2014) for the gas-phase reaction of hydrogen abstraction from methane by an oxygen atom is developed. The ab initio information employed in the fit includes properties (equilibrium geometries, relative energies, and vibrational frequencies) of the reactants, products, saddle point, points on the reaction path, and points on the reaction swath, taking especial caution respecting the location and characterization of the intermediate complexes in the entrance and exit channels. By comparing with the reference results we show that the resulting PES-2014 reproduces reasonably well the whole set of ab initio data used in the fitting, obtained at the CCSD(T) = FULL/aug-cc-pVQZ//CCSD(T) = FC/cc-pVTZ single point level, which represents a severe test of the new surface. As a first application, on this analytical surface we perform an extensive dynamics study using quasi-classical trajectory calculations, comparing the results with recent experimental and theoretical data. The excitation function increases with energy (concave-up) reproducing experimental and theoretical information, although our values are somewhat larger. The OH rotovibrational distribution is cold in agreement with experiment. Finally, our results reproduce experimental backward scattering distribution, associated to a rebound mechanism. These results lend confidence to the accuracy of the new surface, which substantially improves the results obtained with our previous surface (PES-2000) for the same system
Energy Technology Data Exchange (ETDEWEB)
Munoz, E. L., E-mail: munoz@fisica.unlp.edu.ar; Richard, D. [Departamento de Fisica and Instituto de Fisica La Plata (IFLP, CCT La Plata, CONICET) (Argentina); Carbonari, A. W. [Instituto de Pesquisas Energeticas y Nucleares-IPEN-CNEN/SP (Brazil); Errico, L. A.; Renteria, M. [Departamento de Fisica and Instituto de Fisica La Plata (IFLP, CCT La Plata, CONICET) (Argentina)
2010-04-15
Time-Differential {gamma}-{gamma} Perturbed-Angular-Correlation (PAC) measurements were performed in {sup 111}In-difussed Sc{sub 2}O{sub 3} polycrystals in order to characterize the electric-field-gradient tensor at {sup 111}Cd nuclei located at the two non-equivalent cation sites of the host lattice. The experimental data were compared with ab initio calculations performed using the Full-Potential Augmented Plane Wave plus local orbital (FP-APW+lo) method in the framework of the Density Functional Theory. The PAC experiments were carried out in air in the temperature range 10-900 K. The spectra present a strong damping below 650 K. This damping is associated with dynamic hyperfine interactions that were analyzed with the perturbation factor proposed by Baeverstam et al.. A model based in the population of impurity levels that are introduced by the Cd probes (supported by FP-APW+lo results) is proposed in order to explain the origin of the observed dynamic interactions.
Wood, Geoffrey P F; Sreedhara, Alavattam; Moore, Jamie M; Wang, John; Trout, Bernhardt L
2016-05-12
An assessment of the mechanisms of (•)OH and (•)OOH radical-mediated oxidation of tryptophan was performed using density functional theory calculations and ab initio plane-wave Quantum Mechanics/Molecular Mechanics (QM/MM) molecular dynamics simulations. For the (•)OH reactions, addition to the pyrrole ring at position 2 is the most favored site with a barrierless reaction in the gas phase. The subsequent degradation of this adduct through a H atom transfer to water was intermittently observed in aqueous-phase molecular dynamics simulations. For the (•)OOH reactions, addition to the pyrrole ring at position 2 is the most favored pathway, in contrast to the situation in the model system ethylene, where concerted addition to the double bond is preferred. From the (•)OOH position 2 adduct QM/MM simulations show that formation of oxy-3-indolanaline occurs readily in an aqueous environment. The observed transformation starts from an initial rupture of the O-O bond followed by a H atom transfer with the accompanying loss of an (•)OH radical to solution. Finally, classical molecular dynamics simulations were performed to equate observed differential oxidation rates of various tryptophan residues in monoclonal antibody fragments. It was found that simple parameters derived from simulation correlate well with the experimental data.
Ab initio calculations of PbTiO{sub 3}/SrTiO{sub 3} (001) heterostructures
Energy Technology Data Exchange (ETDEWEB)
Eglitis, R.I.; Piskunov, S.; Zhukovskii, Yu.F. [Institute of Solid State Physics, University of Latvia, 8 Kengaraga Str., 1063 Riga (Latvia)
2016-12-15
We performed ab initio calculations for the PbTiO{sub 3}/SrTiO{sub 3} (001) heterostructures. For both PbO and TiO{sub 2}-terminations of the PbTiO{sub 3} (001) thin film, augmented on the SrTiO{sub 3} (001) substrate, the magnitudes of atomic relaxations Δz increases as a function of the number of augmented monolayers. For both terminations of the augmented PbTiO{sub 3} (001) nanothin film, all upper, third and fifth monolayers are displaced inwards (Δz is negative), whereas all second, fourth and sixth monolayers are displaced outwards (Δz is positive). The B3PW calculated PbTiO{sub 3}/SrTiO{sub 3} (001) heterostructure band gaps, independently from the number of augmented layers, are always smaller than the PbTiO{sub 3} and SrTiO{sub 3} bulk band gaps. For both PbO and TiO{sub 2}-terminated PbTiO{sub 3}/SrTiO{sub 3}(001) heterostructures, their band gaps are reduced due to the increased number of PbTiO{sub 3} (001) monolayers. The band gaps of PbO-terminated augmented PbTiO{sub 3} (001) films are always larger than those for TiO{sub 2}-terminated PbTiO{sub 3} (001) thin films. The only exception is the case of 7-layer PbO-terminated and 8-layer TiO{sub 2}-terminated augmented PbTiO{sub 3} (001) thin films, where their band gaps both are equal to 2.99 eV. For each monolayer of the SrTiO{sub 3} (001) substrate, charge magnitudes always are more than several times larger, than for each monolayer in the augmented PbTiO{sub 3} (001) thin film. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)
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.
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.
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
Energy Technology Data Exchange (ETDEWEB)
Wang, Yuezhong, E-mail: wyzphysics@163.com [Department of Physics and Key Laboratory for Radiation Physics and Technology of Ministry of Education, Sichuan University, Chengdu 610064 (China); Tianjin Jinhang Institute of Technical Physics, Tianjin 300192 (China); Lu, Tiecheng, E-mail: lutiecheng@scu.edu.cn [Department of Physics and Key Laboratory for Radiation Physics and Technology of Ministry of Education, Sichuan University, Chengdu 610064 (China); International Center for Material Physics, Chinese Academy of Sciences, Shenyang 110015 (China); Zhang, Rongshi [Tianjin Jinhang Institute of Technical Physics, Tianjin 300192 (China); Jiang, Shengli; Qi, Jianqi; Wang, Ying [Department of Physics and Key Laboratory for Radiation Physics and Technology of Ministry of Education, Sichuan University, Chengdu 610064 (China); Chen, Qingyun [Department of Physics and Key Laboratory for Radiation Physics and Technology of Ministry of Education, Sichuan University, Chengdu 610064 (China); National Defense Key Discipline Laboratory of Nuclear Waste and Environmental Safety, Southwest University of Science and Technology, Mianyang 621010 (China); Miao, Naihua [Physique Theorique des Materiaux, Universite de Liege, Sart Tilman B-4000 (Belgium); He, Duanwei [Institute of Atomic and Molecular Physics, Sichuan University, Chengdu 610064 (China)
2013-01-25
Highlights: Black-Right-Pointing-Pointer We reassess the chemical bonding character of {gamma}-AlON which shows strong ionicity. Black-Right-Pointing-Pointer {gamma}-AlON single-crystals exhibit highly elastic anisotropy. Black-Right-Pointing-Pointer The thermodynamic properties are investigated in a wider temperature/pressure range. Black-Right-Pointing-Pointer {gamma}-AlON is an O/N partially disordered structure. - Abstract: Spinel aluminium oxynitride ({gamma}-AlON), as a kind of transparent ceramic material expectable, is studied using the ab initio density functional method, in terms of electronic, elastic, thermodynamic properties and structure disorder. The results show that {gamma}-AlON exhibits strong ionicity, as quantitatively expressed by (Al{sub O}{sup 2.43+}){sub 15}(Al{sub T}{sup 2.41+}){sub 8}(O{sup 1.64-}){sub 27}(N{sup 2.27-}){sub 5} from our reassessment of the ionic character. We summarize and speculate that the considered oxynitride single-crystals exhibit highly elastic anisotropy. The interpretation of the thermodynamic properties of {gamma}-AlON according to quasi-harmonic Debye model confirm the available experiments and are extended to a wider temperature/pressure range. This material holds high elastic strength under extreme environments, where dB/dT absolute value is less than 0.03 GPa/K, independent of the pressure. Finally, we study the O/N structure disorder character of {gamma}-AlON solid solution by investigating nine possible crystal structures. It is found that {gamma}-AlON should be partially disordered, and in fact, the O/N ordering has a significant effect on the properties.
International Nuclear Information System (INIS)
Wang, Yuezhong; Lu, Tiecheng; Zhang, Rongshi; Jiang, Shengli; Qi, Jianqi; Wang, Ying; Chen, Qingyun; Miao, Naihua; He, Duanwei
2013-01-01
Highlights: ► We reassess the chemical bonding character of γ-AlON which shows strong ionicity. ► γ-AlON single-crystals exhibit highly elastic anisotropy. ► The thermodynamic properties are investigated in a wider temperature/pressure range. ► γ-AlON is an O/N partially disordered structure. - Abstract: Spinel aluminium oxynitride (γ-AlON), as a kind of transparent ceramic material expectable, is studied using the ab initio density functional method, in terms of electronic, elastic, thermodynamic properties and structure disorder. The results show that γ-AlON exhibits strong ionicity, as quantitatively expressed by (Al O 2.43+ ) 15 (Al T 2.41+ ) 8 (O 1.64- ) 27 (N 2.27- ) 5 from our reassessment of the ionic character. We summarize and speculate that the considered oxynitride single-crystals exhibit highly elastic anisotropy. The interpretation of the thermodynamic properties of γ-AlON according to quasi-harmonic Debye model confirm the available experiments and are extended to a wider temperature/pressure range. This material holds high elastic strength under extreme environments, where dB/dT absolute value is less than 0.03 GPa/K, independent of the pressure. Finally, we study the O/N structure disorder character of γ-AlON solid solution by investigating nine possible crystal structures. It is found that γ-AlON should be partially disordered, and in fact, the O/N ordering has a significant effect on the properties.
Energy Technology Data Exchange (ETDEWEB)
Pigozzi, Giancarlo; Janczak-Rusch, Jolanta; Passerone, Daniele; Antonio Pignedoli, Carlo; Patscheider, Joerg; Jeurgens, Lars P. H. [Empa, Swiss Federal Laboratories for Materials Science and Technology, Ueberlandstrasse 129, CH-8600 Duebendorf (Switzerland); Antusek, Andrej [Empa, Swiss Federal Laboratories for Materials Science and Technology, Ueberlandstrasse 129, CH-8600 Duebendorf (Switzerland); Faculty of Materials Science and Technology, Slovak University of Technology in Bratislava, Paulinska 16, 917 24 Trnava (Slovakia); Parlinska-Wojtan, Magdalena [Empa, Swiss Federal Laboratories for Materials Science and Technology, Ueberlandstrasse 129, CH-8600 Duebendorf (Switzerland); University of Rzeszow, Institute of Physics, ul. Rejtana 16a, 35-959 Rzeszow (Poland); Bissig, Vinzenz [Kirsten Soldering AG, Hinterbergstrasse 32, CH-6330 Cham (Switzerland)
2012-10-29
Nano-sized Ag-Cu{sub 8nm}/AlN{sub 10nm} multilayers were deposited by reactive DC sputtering on {alpha}-Al{sub 2}O{sub 3}(0001) substrates. Investigation of the phase constitution and interface structure of the multilayers evidences a phase separation of the alloy sublayers into nanosized grains of Ag and Cu. The interfaces between the Ag grains and the quasi-single-crystalline AlN sublayers are semi-coherent, whereas the corresponding Cu/AlN interfaces are incoherent. The orientation relationship between Ag and AlN is constant throughout the entire multilayer stack. These observations are consistent with atomistic models of the interfaces as obtained by ab initio calculations.
International Nuclear Information System (INIS)
Forssen, C.; Caurier, E.; Navratil, P.
2009-01-01
Recently, charge radii and ground-state electromagnetic moments of Li and Be isotopes were measured precisely. We have performed large-scale ab initio no-core shell model calculations for these isotopes using high-precision nucleon-nucleon potentials. The isotopic trends of our computed charge radii and quadrupole and magnetic-dipole moments are in good agreement with experimental results with the exception of the 11 Li charge radius. The magnetic moments are in particular well described, whereas the absolute magnitudes of the quadrupole moments are about 10% too small. The small magnitude of the 6 Li quadrupole moment is reproduced, and with the CD-Bonn NN potential, also its correct sign
Energy Technology Data Exchange (ETDEWEB)
Zapukhlyak, Myroslav
2008-12-05
The present thesis gives a theoretical contribution to the understanding of the many-particle dynamics in inelastic ion-atom collisions. Many-electron dynamics in ion-helium collisions and proton-sodium collisions was theoretically studied. The description is based on the semiclassical approximation with the straight orbit for the projectile motion. The ion-atom collision problem is by this reduced to a time-dependent many-electron problem and in the non-relativistic approximation described by the time-dependent Schroedinger equation. The solution of the many-electron problem pursues in the framework of the time-dependent density functional theory. The time-dependent Schroedinger equation for the interacting many-electron problem is transformed to the system of the time-dependent Kohn-Sham equations and solved by the two-center-basis generator method. The unknown time-dependent exchange-correlation one-particle potential forces different approximation in the time-dependent Kohn-Shan scheme. In this thesis the model of the independent electrons was applied as basis model, in which the electron-electron correlation is consistently neglected in all parts and in all steps. Differential cross sections for different one- and two-electron processes were calculated in the so-called eikonal approximation for the collisional systems p-He, He{sup 2+}-He, and Ar{sup q+}-He (q=15-18). [German] Die vorliegende Arbeit leistet einen theoretischen Beitrag zum Verstaendnis der Vielteilchendynamik in inelastischen Ion-Atom-Stoessen. Vielelektronendynamik in Ion-Helium-Stoessen und Proton-Natrium-Stoessen wurde theoretisch untersucht. Die Beschreibung basiert auf der semiklassischen Naeherung mit der geraden Bahn fuer die Projektilbewegung. Das Ion-Atom- Stossproblem wird damit auf ein zeitabhaengiges Vielelektronenproblem reduziert und in der nichtrelativistischen Naeherung mit der zeitabhaengigen Schroedinger-Gleichung beschrieben. Die Loesung des Vielelektronenproblems erfolgt im
International Nuclear Information System (INIS)
Harding, L.B.; Wagner, A.F.; Bowman, J.M.; Schatz, G.C.; Christoffel, K.
1982-01-01
GVB-POL-CI ab initio calculations of the geometries, energetics, and normal mode frequencies of C 2 H 2 , C 2 H 3 , and the transition state for the addition reaction of H + C 2 H 2 are presented. In addition, normal mode frequencies for the isotopic variants D + C 2 D 2 , D + C 2 H 2 , and H + C 2 D 2 are preented. These results are compared to experimental values for C 2 H 2 and to ab initio values of Hagase and Kern, and semiempirical values of Keil, Lynch, Cowfer, and Michael. The results are also used to calculate the apparent bimolecular addition rate constant using conventional RRKM theory for chemical activation. The calculated rate constants and their isotopic variants are compared as a function of temperature and pressure to available experimental information. The agreement is little different from that obtained by Keil et al. with a similar calculation using semiempirical values for acetylene, transition-state, and vinyl radical properties. In particular, the calculated high-pressure limit of the rate constant appears to be at least 1 order of magnitude higher than the experimental limit. Several possible reasons for this discrepancy are discussed
International Nuclear Information System (INIS)
Awasthi, Neha; Ritschel, Thomas; Lipowsky, Reinhard; Knecht, Volker
2013-01-01
Highlights: • ΔG and K eq for NO 2 dimerization and NH 3 synthesis calculated via ab-initio methods. • Vis-á-vis experiments, W1 and CCSD(T) are accurate and G3B3 also does quite well. • CBS-APNO most accurate for NH 3 reaction but shows limitations in modeling NO 2 . • Temperature dependence of ΔG and K eq is calculated for the NH 3 reaction. • Good agreement of calculated K eq with experiments and the van’t Hoff approximation. -- Abstract: Standard quantum chemical methods are used for accurate calculation of thermochemical properties such as enthalpies of formation, entropies and Gibbs energies of formation. Equilibrium reactions are widely investigated and experimental measurements often lead to a range of reaction Gibbs energies and equilibrium constants. It is useful to calculate these equilibrium properties from quantum chemical methods in order to address the experimental differences. Furthermore, most standard calculation methods differ in accuracy and feasibility of the system size. Hence, a systematic comparison of equilibrium properties calculated with different numerical algorithms would provide a useful reference. We select two well-known gas phase equilibrium reactions with small molecules: covalent dimer formation of NO 2 (2NO 2 ⇌ N 2 O 4 ) and the synthesis of NH 3 (N 2 + 3 H 2 ⇌ 2NH 3 ). We test four quantum chemical methods denoted by G3B3, CBS-APNO, W1 and CCSD(T) with aug-cc-pVXZ basis sets (X = 2, 3, and 4), to obtain thermochemical data for NO 2 , N 2 O 4 , and NH 3 . The calculated standard formation Gibbs energies Δ f G° are used to calculate standard reaction Gibbs energies Δ r G° and standard equilibrium constants K eq for the two reactions. Standard formation enthalpies Δ f H° are calculated in a more reliable way using high-level methods such as W1 and CCSD(T). Standard entropies S° for the molecules are calculated well within the range of experiments for all methods, however, the values of standard formation
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.
Quantum-Chemical ab initio Calculations on the Three Isomers of Diborabenzene (C4H4B2)
Singh, Jaswinder; Wang, Yuekui; Raabe, Gerhard
2010-01-01
Quantum-chemical ab initio calculations up to the ZPE+CCSD(T)/aug-cc-pVTZ//MP2/6- 311++G** level were performed on three possible structural isomers of diborabenzene (C4H4B2). All three molecules were found to be local minima on the C4H4B2 energy surface and to have closed shell singlet ground states. While the ground states of the 1,3- and 1,4-isomer are planar and of C2v and D2h symmetry, respectively, 1,2-diborabenzene is non-planar with a C2 axis passing through the center of the BB bond and the middle of the opposite carbon-carbon bond as the only symmetry element. The energetically most favourable 1,3-diborabenzene was found to be about 19 and 36 kcal/mol lower in energy than the 1,2- and the 1,4-isomer. Planar 1,3- and 1,4-diborabenzene have three doubly occupied π orbitals while non-planar 1,2-diborabenzene has also three doubly occupied orbitals which can be derived from the π orbitals of its 3.7 kcal/mol energetically less favourable planar form ("π-like" orbitals). The lowest unoccupied orbitals of all three isomers have σ symmetry with large coefficients at the two boron atoms. These orbitals are lower in energy than the lowest unoccupied molecular orbitals (LUMOs) of e. g. benzene and pyridine and might cause pronounced acceptor properties which could be one of the reasons for the elusiveness of the title compounds. The results of bond separation reactions show that cyclic conjugation stabilizes all three diborabenzenes relative to their isolated fragments. The most effective stabilization energy of about 24 kcal/mol was found for the energetically lowest 1,3-isomer. This value amounts to approximately one third of the experimental value for the bond separation energy of pyridine. In all cases the energetically lowest triplet states are significantly (16 - 24 kcal/mol) higher in energy than the singlet ground states. Also among the triplets the 1,3-isomer is the energetically most fabourable species.
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.
Energy Technology Data Exchange (ETDEWEB)
Munoz, Emiliano L., E-mail: munoz@fisica.unlp.edu.ar [Departamento de Fisica and Instituto de Fisica La Plata (IFLP, CONICET La Plata), Facultad de Ciencias Exactas, Universidad Nacional de La Plata, CC 67, 1900 La Plata (Argentina); Mercurio, Marcio E.; Cordeiro, Moacir R.; Pereira, Luciano F.D.; Carbonari, Artur W. [Instituto de Pesquisas Energeticas y Nucleares-IPEN-CNEN/SP, Sao Paulo (Brazil); Renteria, Mario [Departamento de Fisica and Instituto de Fisica La Plata (IFLP, CONICET La Plata), Facultad de Ciencias Exactas, Universidad Nacional de La Plata, CC 67, 1900 La Plata (Argentina)
2012-08-15
In this work, we present results of Time-Differential {gamma}-{gamma} Perturbed-Angular-Correlations (PAC) experiments performed in {sup 111}Cd-doped ZnO semiconductor. The PAC technique has been applied in order to characterize the electric-field-gradient (EFG) tensor at ({sup 111}In (EC){yields}) {sup 111}Cd nuclei located, as was later demonstrated, at defect-free cation sites of the ZnO host structure. The PAC experiments were performed in the temperature range of 77-1075 K. At first glance, the unexpected presence of low-intensity dynamic hyperfine interactions was observed, which were analyzed with a perturbation factor based on the Baeverstam and Othaz model. The experimental EFG results were compared with ab initio calculations performed with the Full-Potential Augmented Plane Wave plus local orbital (FP-APW+lo) method, in the framework of the Density Functional Theory (DFT), using the Wien2K code. The presence of the dynamic hyperfine interactions has been analyzed enlightened by the FP-APW+lo calculations of the EFG performed as a function of the charge state of the cell. We could correlate the large strength of the dynamic hyperfine interaction with the strong variation of the EFG due to changes in the electronic charge distribution in the Cd vicinity during the time-window of the PAC measurement. It was also revealed that the Cd impurity decays to a final stable neutral charge state (Cd{sup 2+}) fast enough (in few ns) to produce the nearly undamped observed PAC spectra.
Förner, Wolfgang
1992-03-01
Ab initio investigations of the bond alternation in butadiene are presented. The atomic basis sets applied range from minimal to split valence plus polarization quality. With the latter one the Hartree-Fock limit for the bond alternation is reached. Correlation is considered on Møller-Plesset many-body perturbation theory of second order (MP2), linear coupled cluster doubles (L-CCD) and coupled cluster doubles (CCD) level. For the smaller basis sets it is shown that for the bond alternation π-π correlations are essential while the effects of σ-σ and σ-π correlations are, though large, nearly independent of bond alternation. On MP2 level the variation of σ-π correlation with bond alternation is surprisingly large. This is discussed as an artefact of MP2. Comparative Su-Schrieffer-Heeger (SSH) and Pariser-Parr-Pople (PPP) calculations show that these models in their usual parametrizations cannot reproduce the ab initio results.
Ab initio modeling of 2D layered organohalide lead perovskites
Energy Technology Data Exchange (ETDEWEB)
Fraccarollo, Alberto; Cantatore, Valentina; Boschetto, Gabriele; Marchese, Leonardo; Cossi, Maurizio, E-mail: maurizio.cossi@uniupo.it [Dipartimento di Scienze e Innovazione Tecnologica (DISIT), Università del Piemonte Orientale, via T. Michel 11, I-15121 Alessandria (Italy)
2016-04-28
A number of 2D layered perovskites A{sub 2}PbI{sub 4} and BPbI{sub 4}, with A and B mono- and divalent ammonium and imidazolium cations, have been modeled with different theoretical methods. The periodic structures have been optimized (both in monoclinic and in triclinic systems, corresponding to eclipsed and staggered arrangements of the inorganic layers) at the DFT level, with hybrid functionals, Gaussian-type orbitals and dispersion energy corrections. With the same methods, the various contributions to the solid stabilization energy have been discussed, separating electrostatic and dispersion energies, organic-organic intralayer interactions and H-bonding effects, when applicable. Then the electronic band gaps have been computed with plane waves, at the DFT level with scalar and full relativistic potentials, and including the correlation energy through the GW approximation. Spin orbit coupling and GW effects have been combined in an additive scheme, validated by comparing the computed gap with well known experimental and theoretical results for a model system. Finally, various contributions to the computed band gaps have been discussed on some of the studied systems, by varying some geometrical parameters and by substituting one cation in another’s place.
Vanicek, Jiri
2014-03-01
Rigorous quantum-mechanical calculations of coherent ultrafast electronic spectra remain difficult. I will present several approaches developed in our group that increase the efficiency and accuracy of such calculations: First, we justified the feasibility of evaluating time-resolved spectra of large systems by proving that the number of trajectories needed for convergence of the semiclassical dephasing representation/phase averaging is independent of dimensionality. Recently, we further accelerated this approximation with a cellular scheme employing inverse Weierstrass transform and optimal scaling of the cell size. The accuracy of potential energy surfaces was increased by combining the dephasing representation with accurate on-the-fly ab initio electronic structure calculations, including nonadiabatic and spin-orbit couplings. Finally, the inherent semiclassical approximation was removed in the exact quantum Gaussian dephasing representation, in which semiclassical trajectories are replaced by communicating frozen Gaussian basis functions evolving classically with an average Hamiltonian. Among other examples I will present an on-the-fly ab initio semiclassical dynamics calculation of the dispersed time-resolved stimulated emission spectrum of the 54-dimensional azulene. This research was supported by EPFL and by the Swiss National Science Foundation NCCR MUST (Molecular Ultrafast Science and Technology) and Grant No. 200021124936/1.
International Nuclear Information System (INIS)
Marshall, T.S.; Wilson, T.M.
1992-01-01
The authors report on the results of electronic band structure calculations of bulk ZnSe, bulk ZnS and the (ZnSe) 1 (ZnS) 1 , strained-layer superlattice (SLS) using the ab initio factorized linear combination of atomic orbitals method. The bulk calculations were done using the standard primitive nonrectangular 2-atom zinc blende unit cell, while the SLS calculation was done using a primitive tetragonal 4-atom unit cell modeled from the CuAu I structure. The analytic fit to the SLS crystalline potential was determined by using the nonlinear coefficients from the bulk fits. The CPU time saved by factorizing the energy matrix integrals and using a rectangular unit cell is discussed
Bisri, Satria Zulkarnaen; Degoli, Elena; Spallanzani, Nicola; Krishnan, Gopi; Kooi, Bart Jan; Ghica, Corneliu; Yarema, Maksym; Heiss, Wolfgang; Pulci, Olivia; Ossicini, Stefano; Loi, Maria Antonietta
2014-08-27
Colloidal nanocrystals electronic energy levels are determined by strong size-dependent quantum confinement. Understanding the configuration of the energy levels of nanocrystal superlattices is vital in order to use them in heterostructures with other materials. A powerful method is reported to determine the energy levels of PbS nanocrystal assemblies by combining the utilization of electric-double-layer-gated transistors and advanced ab-initio theory. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
International Nuclear Information System (INIS)
Hellmann, Robert
2009-01-01
Thermophysical properties of the pure gases helium, neon, methane and water vapor were calculated for low densities over wide temperature ranges. Statistical thermodynamics was used for the determination of the pressure virial coefficients. The kinetic theory of gases was utilized for the calculation of the transport and relaxation properties. So far kinetic theory was limited to linear molecules and has now been extended to molecules of arbitrary geometry to enable calculations on methane and water vapor. The interaction potentials, which are needed for all computations, were determined for helium, neon and methane from the supermolecular approach using quantum chemical ab initio methods. For water the interaction potentials were taken from the literature. The calculated values of the thermophysical properties for the four gases show very good agreement with the best experimental data. At very low and very high temperatures the theoretical values are more accurate than experimental data. (orig.)
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, PB 63 46000 Safi (Morocco); Jabar, A. [Laboratory of Materials, Processes, Environment and Quality, Cady Ayyed University, National School of Applied Sciences, PB 63 46000 Safi (Morocco); Hlil, E.K. [Institut Néel, CNRS, Université Grenoble Alpes, BP 166, F-38042 Grenoble cedex 9 (France); Hamedoun, M. [Institute of Nanomaterials and Nanotechnologies, MAScIR, Rabat (Morocco); Benyoussef, A. [Institute of Nanomaterials and Nanotechnologies, MAScIR, Rabat (Morocco); Hassan II Academy of Science and Technology, Rabat (Morocco); Hourmatallah, A. [Equipe de Physique du Solide, Laboratoire LIPI, Ecole Normale Supérieure, BP 5206, Bensouda, Fes (Morocco); Rezzouk, A.; Bouslykhane, K.; Benzakour, N. [Laboratoire de Physique du Solide, Université Sidi Mohammed Ben Abdellah, Faculté des sciences DharMahraz, BP 1796, Fes (Morocco)
2017-04-15
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{sub 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{sub 2}NiAl are studied using the Monte Carlo simulations. The variation of magnetization and magnetic susceptibility with the reduced temperature of Mn{sub 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{sub I}, Mn{sub 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{sub 2}NiX. • The transition temperature of Mn{sub 2}NiX is established. • The magnetic hysteresis cycle of M{sub n2}NiX (X = Al, Ga, In, Sn) is deduced. • The magnetic coercive field of Mn{sub 2}NiX (X = Al, Ga, In, Sn) is given.
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.
Denning, Elizabeth J; Mackerell, Alexander D
2011-04-20
Deoxyribonucleic acid (DNA) is composed of five major elements carbon, hydrogen, nitrogen, oxygen, and phosphorus. The substitution of any of these elements in DNA would be anticipated to have major biological implications. However, recent studies have suggested that the substitution of arsenic into DNA (As-DNA) in bacteria may be possible. To help evaluate this possibility, ab initio quantum mechanical calculations are used to show that arsenodiester and phosphodiester linkages have similar geometric and conformational properties. Based on these results, it is suggested that the As-DNA will have similar conformational properties to phosphorus-based DNA, including the maintenance of base stacking.
Bokarev, Sergey I; Dantz, Marcus; Suljoti, Edlira; Kühn, Oliver; Aziz, Emad F
2013-08-23
Nonradiative decay channels in the L-edge fluorescence yield spectra from transition-metal-aqueous solutions give rise to spectral distortions with respect to x-ray transmission spectra. Their origin is unraveled here using partial and inverse partial fluorescence yields on the microjet combined with multireference ab initio electronic structure calculations. Comparing Fe2+, Fe3+, and Co2+ systems we demonstrate and quantify unequivocally the state-dependent electron delocalization within the manifold of d orbitals as one origin of this observation.
Yu, Hua-Gen; Han, Huixian; Guo, Hua
2016-04-14
Vibrational energy levels of the ammonium cation (NH4(+)) and its deuterated isotopomers are calculated using a numerically exact kinetic energy operator on a recently developed nine-dimensional permutation invariant semiglobal potential energy surface fitted to a large number of high-level ab initio points. Like CH4, the vibrational levels of NH4(+) and ND4(+) exhibit a polyad structure, characterized by a collective quantum number P = 2(v1 + v3) + v2 + v4. The low-lying vibrational levels of all isotopomers are assigned and the agreement with available experimental data is better than 1 cm(-1).
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.
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
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)
Lavenir, E.; Pic, J.M.; Alibran, P.; Leclercq, J.M.
1987-01-01
The QUANTUM I project is a three-stage device. The stages are respectively dedicated to particular steps of the ab initio determination of a point on the hypersurface. The first stage deals with the computation of the integrals between the basis functions, the second with the S.C.F. (or M.C.S.C.F.) process and the third with the C.I treatment. Each step is developed in terms of parallel mode (M.I.M.D.), the whole device working following a pipeline mode: the three stages works simultaneously for different points
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.
Luitel, Homnath; Chakrabarti, Mahuya; Sarkar, A.; Dechoudhury, S.; Bhowmick, D.; Naik, V.; Sanyal, D.
2018-02-01
Room temperature magnetic properties of 50 keV N4+ ion beam implanted rutile TiO2 have been theoretically and experimentally studied. Ab-initio calculation under the frame work of density functional theory has been carried out to study the magnetic properties of the different possible nitrogen related defects in TiO2. Spin polarized density of states calculation suggests that both Ninst and NO can induce ferromagnetic ordering in rutile TiO2. In both cases the 2p orbital electrons of nitrogen atom give rise to the magnetic moment in TiO2. The possibility of the formation of N2 molecule in TiO2 system is also studied but in this case no significant magnetic moment has been observed. The magnetic measurements, using SQUID magnetometer, results a ferromagnetic ordering even at room temperature for the 50 keV N4+ ion beam implanted rutile TiO2.
Partovi-Azar, Pouya; Kühne, Thomas D
2015-11-05
We present a novel computational method to accurately calculate Raman spectra from first principles. Together with an extension of the second-generation Car-Parrinello method of Kühne et al. (Phys. Rev. Lett. 2007, 98, 066401) to propagate maximally localized Wannier functions together with the nuclei, a speed-up of one order of magnitude can be observed. This scheme thus allows to routinely calculate finite-temperature Raman spectra "on-the-fly" by means of ab-initio molecular dynamics simulations. To demonstrate the predictive power of this approach we investigate the effect of hydrophobic and hydrophilic solutes in water solution on the infrared and Raman spectra. © 2015 Wiley Periodicals, Inc.
DEFF Research Database (Denmark)
Shim, Irene; Gingerich, K. A.
1984-01-01
In the present study we present all-electron ab initio Hartree–Fock (HF) and configuration interaction (CI) calculations of the 2Sigma+ ground state as well as of 16 excited states of the RhC molecule. The calculated spectroscopic constants of the lowest lying states are in good agreement...... with the experimental data. The chemical bond in the electronic ground state is mainly due to interaction of the 4d orbitals of Rh with the 2s and 2p orbitals of C. The bond is a triple bond composed of two pi bonds and one sigma bond. The 5s electron of Rh hardly participates in the bond formation. It is located...
Orce, J. N.; Djongolov, M.; Navratil, P.; Ball, G.; Garnsworthy, A. B.; Hackman, G.; Lassen, J.; Meissner, J.; Pearson, C. J.; Li, R.; Milovanovic, L.; Sjue, S. K. L.; Teigelhoefer, A.; Triambak, S.; Williams, S. J.; Falou, H. Al; Drake, T. E.; Andreoiu, C.; Cross, D.; Kshetri, R.; Finlay, P.; Garrett, P. E.; Leach, K. G.; Rand, E. T.; Sumithrarachchi, C. S.; Svensson, C. E.; Tardiff, E. R.; Wong, J.; Forssen, C.; Hayes, A. B.; Sarazin, F.; Stoyer, M. A.; Wu, C. Y.
2013-03-01
The highly efficient and segmented TIGRESS HPGe γ-ray array at TRIUMF has been used to perform a reorientation effect Coulomb excitation study of the 2+1 state at 3.368 MeV in 10Be. This is the first Coulomb excitation measurement that provides information on diagonal matrix elements for such a high lying first excited state from μ-ray data. With the availability of accurate lifetime data, a restriction on the diagonal matrix element is determined. This result is compared to a no core shell model calculation with the CD-Bonn 2000 two nucleon potential.
Burnham, Christian J.; Futera, Zdenek; English, Niall J.
2018-03-01
The force-matching method has been applied to parameterise an empirical potential model for water-water and water-hydrogen intermolecular interactions for use in clathrate-hydrate simulations containing hydrogen guest molecules. The underlying reference simulations constituted ab initio molecular dynamics (AIMD) of clathrate hydrates with various occupations of hydrogen-molecule guests. It is shown that the resultant model is able to reproduce AIMD-derived free-energy curves for the movement of a tagged hydrogen molecule between the water cages that make up the clathrate, thus giving us confidence in the model. Furthermore, with the aid of an umbrella-sampling algorithm, we calculate barrier heights for the force-matched model, yielding the free-energy barrier for a tagged molecule to move between cages. The barrier heights are reasonably large, being on the order of 30 kJ/mol, and are consistent with our previous studies with empirical models [C. J. Burnham and N. J. English, J. Phys. Chem. C 120, 16561 (2016) and C. J. Burnham et al., Phys. Chem. Chem. Phys. 19, 717 (2017)]. Our results are in opposition to the literature, which claims that this system may have very low barrier heights. We also compare results to that using the more ad hoc empirical model of Alavi et al. [J. Chem. Phys. 123, 024507 (2005)] and find that this model does very well when judged against the force-matched and ab initio simulation data.
International Nuclear Information System (INIS)
Pham Van, Tat; Deiters, Ulrich K.
2015-01-01
Highlights: • We construct the angular orientations of dimers H 2 −H 2 and H 2 −O 2 . • We calculate the ab initio intermolecular interaction energies for all built orientations. • Extrapolating the interaction energies to the complete basis set limit aug-cc-pV23Z. • We develop two 5-site ab initio intermolecular potentials of dimers H 2 −H 2 , H 2 −O 2 . • Calculating the virial coefficients of dimer H 2 −H 2 and H 2 −O 2 . - Abstract: The intermolecular interaction potentials of the dimers H 2 −H 2 and H 2 −O 2 were calculated from quantum mechanics, using coupled-cluster theory CCSD(T) and correlation-consistent basis sets aug-cc-pVmZ (m = 2, 3); the results were extrapolated to the basis set limit aug-cc-pV23Z. The interaction energies were corrected for the basis set superposition error with the counterpoise scheme. For comparison also Møller–Plesset perturbation theory (at levels 2–4) with the basis sets aug-cc-pVTZ were considered, but the results proved inferior. The quantum mechanical results were used to construct analytical pair potential functions. From these functions the second virial coefficients of hydrogen and the cross virial coefficients of the hydrogen–oxygen system were obtained by integration; in both cases corrections for quantum effects were included. The results agree well with experimental data, if available, or with empirical correlations
Energy Technology Data Exchange (ETDEWEB)
Matar, Samir F. [CNRS, ICMCB, UPR 9048, Pessac (France); Bordeaux Univ., Pessac (France). ICMCB, UPR 9048; Al Alam, Adel F.; Ouaini, Naim [Univ. Saint Esprit de Kaslik (USEK), Jounieh (Lebanon). URA GREVE, CSR-USEK
2013-01-15
For equiatomic MgNi which can be hydrogenated up to the composition MgNiH{sub 1.6} at an absorption/desorption temperature of 200 C, the effects of hydrogen absorption are approached with the model structures MgNiH, MgNiH{sub 2} and MgNiH{sub 3}. From full geometry optimization and calculated cohesive energies obtained within DFT, the MgNiH{sub 2} composition close to the experimental limit is identified as most stable. Charge density analysis shows an increasingly covalent character of hydrogen: MgNiH(H{sup -0.67}) {yields} MgNiH{sub 2}(H{sup -0.63}) {yields} MgNiH{sub 3}(H{sup -0.55}). While Mg-Ni bonding prevails in MgNi and hydrogenated model phases, extra itinerant low-energy Ni states appear when hydrogen is introduced signaling Ni-H bonding which prevails over Mg-H as evidenced from total energy calculations and chemical bonding analyses. (orig.)
Konstantinou, Konstantinos; Sushko, Peter V; Duffy, Dorothy M
2016-09-21
The nature of chemical bonding of molybdenum in high level nuclear waste glasses has been elucidated by ab initio molecular dynamics simulations. Two compositions, (SiO 2 ) 57.5 -(B 2 O 3 ) 10 -(Na 2 O) 15 -(CaO) 15 -(MoO 3 ) 2.5 and (SiO 2 ) 57.3 -(B 2 O 3 ) 20 -(Na 2 O) 6.8 -(Li 2 O) 13.4 -(MoO 3 ) 2.5 , were considered in order to investigate the effect of ionic and covalent components on the glass structure and the formation of the crystallisation precursors (Na 2 MoO 4 and CaMoO 4 ). The coordination environments of Mo cations and the corresponding bond lengths calculated from our model are in excellent agreement with experimental observations. The analysis of the first coordination shell reveals two different types of molybdenum host matrix bonds in the lithium sodium borosilicate glass. Based on the structural data and the bond valence model, we demonstrate that the Mo cation can be found in a redox state and the molybdate tetrahedron can be connected with the borosilicate network in a way that inhibits the formation of crystalline molybdates. These results significantly extend our understanding of bonding in Mo-containing nuclear waste glasses and demonstrate that tailoring the glass composition to specific heavy metal constituents can facilitate incorporation of heavy metals at high concentrations.
Recommendations for DSD model calculations
International Nuclear Information System (INIS)
Cvelbar, F.
1999-01-01
The latest achievements of the DSD (direct-semidirect) capture model, such as the extension to unbound final states or to densely distributed bound states, and the introduction of the consistent DSD model are reviewed. Recommendations for the future use of the model are presented. (author)
Ferreira da Silva, F.; Lange, E.; Limão-Vieira, P.; Jones, N. C.; Hoffmann, S. V.; Hubin-Franskin, M.-J.; Delwiche, J.; Brunger, M. J.; Neves, R. F. C.; Lopes, M. C. A.; de Oliveira, E. M.; da Costa, R. F.; Varella, M. T. do N.; Bettega, M. H. F.; Blanco, F.; García, G.; Lima, M. A. P.; Jones, D. B.
2015-10-01
The electronic spectroscopy of isolated furfural (2-furaldehyde) in the gas phase has been investigated using high-resolution photoabsorption spectroscopy in the 3.5-10.8 eV energy-range, with absolute cross section measurements derived. Electron energy loss spectra are also measured over a range of kinematical conditions. Those energy loss spectra are used to derive differential cross sections and in turn generalised oscillator strengths. These experiments are supported by ab initio calculations in order to assign the excited states of the neutral molecule. The good agreement between the theoretical results and the measurements allows us to provide the first quantitative assignment of the electronic state spectroscopy of furfural over an extended energy range.
International Nuclear Information System (INIS)
Ferreira da Silva, F.; Lange, E.; Limão-Vieira, P.; Jones, N. C.; Hoffmann, S. V.; Hubin-Franskin, M.-J.; Delwiche, J.; Brunger, M. J.
2015-01-01
The electronic spectroscopy of isolated furfural (2-furaldehyde) in the gas phase has been investigated using high-resolution photoabsorption spectroscopy in the 3.5–10.8 eV energy-range, with absolute cross section measurements derived. Electron energy loss spectra are also measured over a range of kinematical conditions. Those energy loss spectra are used to derive differential cross sections and in turn generalised oscillator strengths. These experiments are supported by ab initio calculations in order to assign the excited states of the neutral molecule. The good agreement between the theoretical results and the measurements allows us to provide the first quantitative assignment of the electronic state spectroscopy of furfural over an extended energy range
International Nuclear Information System (INIS)
Ziyu Wu; Paris, E.; Langenhorst, F.; Seifert, F.
2002-01-01
The O K-edge spectra of a series of Ti-bearing compounds with Ti in diffrent structural and chemical environments have been measured using electron energy-loss spectroscopy and analyzed using ab initio full multiple-scattering (MS) calculations. The near-edge structures arise mainly from covalency by direct and/or indirect interaction between O and metal atoms and between O and Si atoms. The coordination number of the cation and the site symmetry also influence the spectral shape and structures. Using different size clusters around the excited atom in the full MS simulation, it is possible to interpret and assign the features present in the spectra of each compund to its specific atomic arrangement and electronic structure. (au)
Energy Technology Data Exchange (ETDEWEB)
Ferreira da Silva, F.; Lange, E. [Laboratório de Colisões Atómicas e Moleculares, CEFITEC, Departamento de Física, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica (Portugal); Limão-Vieira, P., E-mail: plimaovieira@fct.unl.pt, E-mail: michael.brunger@flinders.edu.au, E-mail: maplima@ifi.unicamp.br [Laboratório de Colisões Atómicas e Moleculares, CEFITEC, Departamento de Física, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica (Portugal); School of Chemical and Physical Sciences, Flinders University, GPO Box 2100, Adelaide, South Australia 5001 (Australia); Jones, N. C.; Hoffmann, S. V. [ISA, Department of Physics and Astronomy, Aarhus University, Ny Munkegade, DK-8000 Århus C (Denmark); Hubin-Franskin, M.-J.; Delwiche, J. [Départment de Chimie, Institut de Chimie-Bât. B6C, Université de Liège, B-4000 Liège 1 (Belgium); Brunger, M. J., E-mail: plimaovieira@fct.unl.pt, E-mail: michael.brunger@flinders.edu.au, E-mail: maplima@ifi.unicamp.br [School of Chemical and Physical Sciences, Flinders University, GPO Box 2100, Adelaide, South Australia 5001 (Australia); Institute of Mathematical Sciences, University of Malaya, 50603 Kuala Lumpur (Malaysia); and others
2015-10-14
The electronic spectroscopy of isolated furfural (2-furaldehyde) in the gas phase has been investigated using high-resolution photoabsorption spectroscopy in the 3.5–10.8 eV energy-range, with absolute cross section measurements derived. Electron energy loss spectra are also measured over a range of kinematical conditions. Those energy loss spectra are used to derive differential cross sections and in turn generalised oscillator strengths. These experiments are supported by ab initio calculations in order to assign the excited states of the neutral molecule. The good agreement between the theoretical results and the measurements allows us to provide the first quantitative assignment of the electronic state spectroscopy of furfural over an extended energy range.
International Nuclear Information System (INIS)
Willaime, F.; Fu, C.C.; Marinica, M.C.; Dalla Torre, J.
2005-01-01
The stability and mobility of self-interstitials and small interstitial clusters, I n , in α-Fe is investigated by means of calculations performed in the framework of the density functional theory using the SIESTA code. The mono-, di- and tri-interstitials are shown to be made of (parallel) dumbbells and to migrate by nearest-neighbor translation-rotation jumps, according to Johnson's mechanism. The orientation of the dumbbells becomes energetically more favourable for I 5 and larger clusters. The performance of a semi-empirical potential recently developed for Fe, including ab initio self-interstitial data in the fitted properties, is evaluated over the present results. The superiority over previous semi-empirical potentials is confirmed. Finally the impact of the present results on the formation mechanism of loops, observed experimentally in α-Fe is discussed
International Nuclear Information System (INIS)
Vivie-Riedle, R. de; Hering, P.; Kompa, K.L.
1990-01-01
CARS has been used to analyze the rovibronic state distribution of H 2 after collision with Na(3 2 P). New lines, which do not correspond to H 2 lines are observed in the CARS spectrum. The experiments point to the formation of a complex of Na(3 2 P)H 2 in A 2 B 2 symmetry. Ab initio calculations of the A 2 B 2 potential were performed. On this surface the vibrational spectra of the exciplex is evaluated. The observed lines can be attributed to vibrational transitions in the complex, in which combinational modes are involved. The connection of experimental and theoretical results indicates that a collisionally stabilized exciplex molecule is formed during the quenching process. (orig.)
Karaminkov, Rosen; Chervenkov, Sotir; Neusser, Hans J
2008-05-21
The para-fluorinated flexible neurotransmitter analogue 2-phenylethanol has been investigated by highly resolved resonance-enhanced two-photon ionisation two-colour UV laser spectroscopy with mass resolution and ab initio structural optimisations and energy calculations. Two stable conformations, gauche and anti, separated by a high potential barrier have been identified in the cold molecular beam by rotational analysis of the vibronic band structures. The theoretically predicted higher-lying conformations most likely relax to these two structures during the adiabatic expansion. The lowest-energy gauche conformer is stabilised by an intramolecular nonconventional OH...pi-type hydrogen bond between the terminal OH group of the side chain and the pi electrons of the phenyl ring. The good agreement between the experimental and theoretical results demonstrates that even the substitution with a strongly electronegative atom of 2-phenylethanol at the para position has no noticeable effect on the strength and orientation of the OH...pi bond.
Bowman, Joel M.; Gazdy, Bela; Bentley, Joseph A.; Lee, Timothy J.; Dateo, Christopher E.
1993-01-01
A potential energy surface for the HCN/HNC system which is a fit to extensive, high-quality ab initio, coupled-cluster calculations is presented. All HCN and HNC states with energies below the energy of the first delocalized state are reported and characterized. Vibrational transition energies are compared with all available experimental data on HCN and HNC, including high CH-overtone states up to 23,063/cm. A simulation of the (A-tilde)-(X-tilde) stimulated emission pumping (SEP) spectrum is also reported, and the results are compared to experiment. Franck-Condon factors are reported for odd bending states of HCN, with one quantum of vibrational angular momentum, in order to compare with the recent assignment by Jonas et al. (1992), on the basis of axis-switching arguments of a number of previously unassigned states in the SEP spectrum.
Energy Technology Data Exchange (ETDEWEB)
Tamarany, Rizcky; Lee, Seung-Cheol [Korea Institute of Science and Technology, Seoul 136-791 (Korea, Republic of); Department of Nanomaterials Science and Engineering, University of Science and Technology, Daejeon 305-350 (Korea, Republic of); Kim, Hyung-Jun; Choi, Jung-Hae [Korea Institute of Science and Technology, Seoul 136-791 (Korea, Republic of)
2013-02-07
Ab initio calculations were performed to investigate the initial deposition of epitaxial MgO on GaAs(001)-{beta}2(2 Multiplication-Sign 4). The differences between the chemical bonding of Mg-As and O-As were characterized by the adsorption energies of atomic O and Mg at several symmetrically distinct sites, and O bonding was substantially stronger than that of Mg. Thermodynamics were analyzed through the introduction of environmental chemical potentials simulating in situ growth conditions by the sputtering of a stoichiometric MgO target. A surface phase diagram was generated under Mg and O environments with constrained equilibrium, and the results explained the initial formation of an epitaxial MgO phase on GaAs(001)-{beta}2(2 Multiplication-Sign 4).
International Nuclear Information System (INIS)
Tamarany, Rizcky; Lee, Seung-Cheol; Kim, Hyung-Jun; Choi, Jung-Hae
2013-01-01
Ab initio calculations were performed to investigate the initial deposition of epitaxial MgO on GaAs(001)-β2(2 × 4). The differences between the chemical bonding of Mg-As and O-As were characterized by the adsorption energies of atomic O and Mg at several symmetrically distinct sites, and O bonding was substantially stronger than that of Mg. Thermodynamics were analyzed through the introduction of environmental chemical potentials simulating in situ growth conditions by the sputtering of a stoichiometric MgO target. A surface phase diagram was generated under Mg and O environments with constrained equilibrium, and the results explained the initial formation of an epitaxial MgO phase on GaAs(001)-β2(2 × 4).
International Nuclear Information System (INIS)
Nomura, Kenji; Ohta, Hiromichi; Hirano, Masahiro; Kamiya, Toshio; Uruga, Tomoya; Hosono, Hideo
2007-01-01
Ionic amorphous oxide semiconductors (IAOSs) are new materials for flexible thin film transistors that exhibit field-effect mobilities of ∼10 cm 2 V -1 s -1 [K. Nomura et al., Nature 488, 432 (2004)]. The local coordination structure in an IAOS, In-Ga-Zn-O (a-IGZO), was examined using extended x-ray absorption fine structure analysis combined with ab initio calculations. The short-range ordering and coordination structures in a-IGZO are similar to those in the corresponding crystalline phase, InGaZnO 4 , and edge-sharing structures consisting of In-O polyhedra remain in the amorphous structure. The In 3+ 5s orbitals form an extended state with a band effective mass of ∼0.2m e at the conduction band bottom
CONFOLD2: improved contact-driven ab initio protein structure modeling.
Adhikari, Badri; Cheng, Jianlin
2018-01-25
Contact-guided protein structure prediction methods are becoming more and more successful because of the latest advances in residue-residue contact prediction. To support contact-driven structure prediction, effective tools that can quickly build tertiary structural models of good quality from predicted contacts need to be developed. We develop an improved contact-driven protein modelling method, CONFOLD2, and study how it may be effectively used for ab initio protein structure prediction with predicted contacts as input. It builds models using various subsets of input contacts to explore the fold space under the guidance of a soft square energy function, and then clusters the models to obtain the top five models. CONFOLD2 obtains an average reconstruction accuracy of 0.57 TM-score for the 150 proteins in the PSICOV contact prediction dataset. When benchmarked on the CASP11 contacts predicted using CONSIP2 and CASP12 contacts predicted using Raptor-X, CONFOLD2 achieves a mean TM-score of 0.41 on both datasets. CONFOLD2 allows to quickly generate top five structural models for a protein sequence when its secondary structures and contacts predictions at hand. The source code of CONFOLD2 is publicly available at https://github.com/multicom-toolbox/CONFOLD2/ .
Ab-initio calculations of semiconductor MgGeP{sub 2} and MgGeAs{sub 2}
Energy Technology Data Exchange (ETDEWEB)
Kocak, B.; Ciftci, Y.O., E-mail: yasemin@gazi.edu.tr
2016-05-15
Highlights: • MgGeP{sub 2} and MgGeAs{sub 2} are semiconductor compounds. • MgGeP{sub 2} and MgGeAs{sub 2} are energetically, mechanically and dynamically stable. • The electronic charge density contour plot shows that the nature of bonding is a mixture of ionic-covalent. - Abstract: In this study, we focus on structural, electronic, elastic, lattice dynamic and optic properties of MgGeP{sub 2} and MgGeAs{sub 2} using ab-initio density-functional theory (DFT) within Armiento-Mattson 2005 (AM05) scheme of the generalized gradient approximation (GGA) for the exchange-correlation potential. Our computed structural results are in reasonable agreement with the literature. The band gap of these compounds is predicted to be direct. Our elastic results prove that these compounds are mechanically stable. The obtained phonon spectra of MgGeP{sub 2} and MgGeAs{sub 2} do not exhibit any significant imaginary branches using GGA-AM05 for the exchange-correlation approximation. Further analysis of the optical response of the dielectric functions, optical reflectivity, refractive index, extinction coefficient and electron energy loss delves into for the energy range of 0–22.5 eV. It motivated that there exists an optical polarization anisotropy of these compounds for optoelectronic device applications.
Grabowski, Ireneusz; Lotrich, Victor
2005-08-01
A new approximate non-iterative procedure to obtain accurate correlation and exchange-correlation potentials of Kohn-Sham (KS) density functional theory (DFT) is presented. By carrying out only one step of the correlated optimized effective potential (OEP) iterations following the standard iterative exchange-only OEP, one can recover accurate correlation potentials corresponding to the orbital-dependent second-order many-body perturbation theory [MBPT(2)] energy functional that are hardly discernible from those obtained by the more expensive, fully iterative procedure. This new 'one-step' OEP-MBPT(2) algorithm reflects the non-iterative, perturbative algorithm of standard, canonical MBPT(2) of ab initio wave function theory, while it allows the correlation potentials to readjust and include the majority of the MBPT(2) correlation effect. It is also flexible in the treatment of exchange and the Hartree-Fock orbitals may be used in lieu of the exchange-only OEP orbitals, when the correlation or exchange-correlation potential is of interest.
Masrour, R.; Jabar, A.; Hlil, E. K.
2018-05-01
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 the electronic and magnetic properties of the Fe4N compound. Polarized spin and spin-orbit coupling are included in calculations within the framework of the ferromagnetic state between Fe(I) and Fe(II) in Fe4N compound. We have used the obtained data from abinitio calculations as an input in Monte Carlo simulation to calculate the magnetic properties of this compounds such as the ground state phase diagrams, total and partial magnetization of Fe(I) and Fe(II) as well as the transition temperatures are computed. The variation of magnetization with the crystal field are also studied. The magnetic hysteresis cycle of the same Fe4N compound are determined for different values of temperatures and crystal field values. The two-step hysteresis loop are evidenced, which is typical for Fe4N structure. The ferromagnetic and superparamagnetic phase is observed as well.
Ab-initio calculations of Co-based diluted magnetic semiconductors Cd 1-xCoxX (X=S, Se, Te)
Saeed, Yasir
2010-10-01
Ab-initio calculations are performed to investigate the structural, electronic and magnetic properties of spin-polarized diluted magnetic semiconductors composed of IIVI compounds Cd1-xCoxX (X=S, Se, Te) at x=0.25. From the calculated results of band structure and density of states, the half-metallic character and stability of ferromagnetic state for Cd1-xCoxS, Cd1-xCoxSe and Cd 1-xCoxTe alloys are determined. It is found that the tetrahedral crystal field gives rise to triple degeneracy t2g and double degeneracy eg. Furthermore, we predict the values of spin-exchange splitting energies Δx(d) and Δ x(p-d) and exchange constants N0α and N 0β produced by the Co 3d states. Calculated total magnetic moments and the robustness of half-metallicity of Cd1-xCo xX (X=S, Se, Te) with respect to the variation in lattice parameters are also discussed. We also extend our calculations to x=0.50, 0.75 for S compounds in order to observe the change due to increase in Co. © 2010 Elsevier B.V.
Moloto, K. D.; Engelbrecht, N. E.; Burger, R. A.
2018-06-01
A simplified ab initio approach is followed to model cosmic-ray proton modulation, using a steady-state three-dimensional stochastic solver of the Parker transport equation that simulates some effects of time dependence. Standard diffusion coefficients based on Quasilinear Theory and Nonlinear Guiding Center Theory are employed. The spatial and temporal dependences of the various turbulence quantities required as inputs for the diffusion, as well as the turbulence-reduced drift coefficients, follow from parametric fits to results from a turbulence transport model as well as from spacecraft observations of these turbulence quantities. Effective values are used for the solar wind speed, magnetic field magnitude, and tilt angle in the modulation model to simulate temporal effects due to changes in the large-scale heliospheric plasma. The unusually high cosmic-ray intensities observed during the 2009 solar minimum follow naturally from the current model for most of the energies considered. This demonstrates that changes in turbulence contribute significantly to the high intensities during that solar minimum. We also discuss and illustrate how this model can be used to predict future cosmic-ray intensities, and comment on the reliability of such predictions.
Transition Models for Engineering Calculations
Fraser, C. J.
2007-01-01
While future theoretical and conceptual developments may promote a better understanding of the physical processes involved in the latter stages of boundary layer transition, the designers of rotodynamic machinery and other fluid dynamic devices need effective transition models now. This presentation will therefore center around the development of of some transition models which have been developed as design aids to improve the prediction codes used in the performance evaluation of gas turbine blading. All models are based on Narasimba's concentrated breakdown and spot growth.
An ab initio model of electron transport in hematite (a-Fe2O3) basal planes
International Nuclear Information System (INIS)
Rosso, Kevin M.; Smith, Dayle MA; Dupuis, Michel
2003-01-01
Transport of conduction electrons through basal planes of the hematite lattice was modeled as a valence alternation of iron cations using ab initio molecular orbital calculations and electron transfer theory. A cluster approach was successfully implemented to compute electron transfer rate-controlling quantities such as the reorganization energy and electronic coupling matrix element. Localization of a conduction electron at an iron lattice site is accompanied by large iron/oxygen bond length increases that give rise to a large inner-sphere component of the reorganization energy. The interaction between the reactant and product electronic states in the crossing?point configuration is substantial and leads to an adiabatic electron transfer system. Electron transfer is predicted to possess a small positive activation energy that turns out to be in excellent agreement with values deduced from conductivity measurements. Measured electron mobility can be explained in terms of nearest neighbor electron hops without significant contribution from iron atoms further away. Comparison of the predicted maximum polaron binding energy with the predicted half bandwidth indicates compliance with the small polaron condition. Therefore the localized electron treatment is appropriate to describe electron transport in this system
Temperature Calculations in the Coastal Modeling System
2017-04-01
ERDC/CHL CHETN-IV-110 April 2017 Approved for public release; distribution is unlimited . Temperature Calculations in the Coastal Modeling...tide) and river discharge at model boundaries, wave radiation stress, and wind forcing over a model computational domain. Physical processes calculated...calculated in the CMS using the following meteorological parameters: solar radiation, cloud cover, air temperature, wind speed, and surface water temperature
Casali, R. A.; Lasave, J.; Caravaca, M. A.; Koval, S.; Ponce, C. A.; Migoni, R. L.
2013-04-01
The pressure dependences of the structural, thermoelastic and vibrational properties of SnO2 in its rutile phase are studied, as well as the pressure-induced transition to a CaCl2-type phase. These studies have been performed by means of ab initio (AI) density functional theory calculations using the localized basis code SIESTA. The results are employed to develop a shell model (SM) for application in future studies of nanostructured SnO2. A good agreement of the SM results for the pressure dependences of the above properties with the ones obtained from present and previous AI calculations as well as from experiments is achieved. The transition is characterized by a rotation of the Sn-centered oxygen octahedra around the tetragonal axis through the Sn. This rotation breaks the tetragonal symmetry of the lattice and an orthorhombic distortion appears above the critical pressure Pc. A zone-center phonon of B1g symmetry in the rutile phase involves such rotation and softens on approaching Pc. It becomes an Ag mode which stabilizes with increasing pressure in the CaCl2 phase. This behavior, together with the softening of the shear modulus (C11-C12)/2 related to the orthorhombic distortion, allows a precise determination of a value for Pc. An additional determination is provided by the splitting of the basal plane lattice parameters. Both the AI and the experimentally observed softening of the B1g mode are incomplete, indicating a small discontinuity at the transition. However, all results show continuous changes in volume and lattice parameters, indicating a second-order transition. All these results indicate that there should be sufficient confidence for the future employment of the shell model.
International Nuclear Information System (INIS)
Casali, R A; Ponce, C A; Lasave, J; Koval, S; Migoni, R L; Caravaca, M A
2013-01-01
The pressure dependences of the structural, thermoelastic and vibrational properties of SnO 2 in its rutile phase are studied, as well as the pressure-induced transition to a CaCl 2 -type phase. These studies have been performed by means of ab initio (AI) density functional theory calculations using the localized basis code SIESTA. The results are employed to develop a shell model (SM) for application in future studies of nanostructured SnO 2 . A good agreement of the SM results for the pressure dependences of the above properties with the ones obtained from present and previous AI calculations as well as from experiments is achieved. The transition is characterized by a rotation of the Sn-centered oxygen octahedra around the tetragonal axis through the Sn. This rotation breaks the tetragonal symmetry of the lattice and an orthorhombic distortion appears above the critical pressure P c . A zone-center phonon of B 1g symmetry in the rutile phase involves such rotation and softens on approaching P c . It becomes an A g mode which stabilizes with increasing pressure in the CaCl 2 phase. This behavior, together with the softening of the shear modulus (C 11 −C 12 )/2 related to the orthorhombic distortion, allows a precise determination of a value for P c . An additional determination is provided by the splitting of the basal plane lattice parameters. Both the AI and the experimentally observed softening of the B 1g mode are incomplete, indicating a small discontinuity at the transition. However, all results show continuous changes in volume and lattice parameters, indicating a second-order transition. All these results indicate that there should be sufficient confidence for the future employment of the shell model. (paper)
Rhyman, Lydia; Armata, Nerina; Ramasami, Ponnadurai; Dyke, John M
2012-06-14
The atmospherically relevant reactions between dimethyl selenide (DMSe) and the molecular halogens (X(2) = Cl(2), Br(2), and I(2)) have been studied with ab initio calculations at the MP2/aug-cc-pVDZ level of theory. Geometry optimization calculations showed that the reactions proceed from the reagents to the products (CH(3)SeCH(2)X + HX) via three minima, a van der Waals adduct (DMSe:X(2)), a covalently bound intermediate (DMSeX(2)), and a product-like complex (CH(3)SeCH(2)X:HX). The computed potential energy surfaces are used to predict what molecular species are likely to be observed in spectroscopic experiments such as gas-phase photoelectron spectroscopy and infrared matrix isolation spectroscopy. It is concluded that, for the reactions of DMSe with Cl(2) and Br(2), the covalent intermediate should be seen in spectroscopic experiments, whereas, in the DMSe + I(2) reaction, the van der Waals adduct DMSe:I(2) should be observed. Comparison is made with previous related calculations and experiments on dimethyl sulfide (DMS) with molecular halogens. The relevance of the results to atmospheric chemistry is discussed. The DMSeX(2) and DMSe:X(2) intermediates are likely to be reservoirs of molecular halogens in the atmosphere which will lead on photolysis to ozone depletion.
Buenker, Robert J; Liebermann, Heinz-Peter
2012-07-15
Ab initio multireference single- and double-excitation configuration interaction calculations have been performed to compute potential curves for ground and excited states of the CaO and SrO molecules and their positronic complexes, e(+)CaO, and e(+)SrO. The adiabatic dissociation limit for the (2)Σ(+) lowest states of the latter systems consists of the positive metal ion ground state (M(+)) and the OPs complex (e(+)O(-)), although the lowest energy limit is thought to be e(+)M + O. Good agreement is found between the calculated and experimental spectroscopic constants for the neutral diatomics wherever available. The positron affinity of the closed-shell X (1)Σ(+) ground states of both systems is found to lie in the 0.16-0.19 eV range, less than half the corresponding values for the lighter members of the alkaline earth monoxide series, BeO and MgO. Annihilation rates (ARs) have been calculated for all four positronated systems for the first time. The variation with bond distance is generally similar to what has been found earlier for the alkali monoxide series of positronic complexes, falling off gradually from the OPs AR value at their respective dissociation limits. The e(+)SrO system shows some exceptional behavior, however, with its AR value reaching a minimum at a relatively large bond distance and then rising to more than twice the OPs value close to its equilibrium distance. Copyright © 2012 Wiley Periodicals, Inc.
International Nuclear Information System (INIS)
Sun Jizhong; Stirner, Thomas
2009-01-01
Ab initio supercell calculations employing the periodic Hartree-Fock formalism are presented of the (0001) α-Cr 2 O 3 surface with a partially or totally Al-substituted external layer. In the simulations a fraction of the Cr atoms at the surface of the chromia slab are replaced by Al atoms, and the Al surface coverage is varied between zero (pure chromia) and 100% (Al-terminated chromia). The surface Al atoms are found to relax inwards considerably, with the magnitude of the relaxation decreasing with increasing Al surface coverage. The calculations also reveal that the surface energy of the slab decreases with increasing Al coverage. Finally, the electronic properties at the surface of the Al-substituted (0001) α-Cr 2 O 3 slabs are investigated. Here the calculations show that the substitution of Cr by Al gives rise to an increase in the covalency of the Al-O bonds compared to slabs of pure alumina. In contrast, the influence of the surface Al atoms on the electrostatic potential in the (0001) plane of metal ions is relatively small. These findings support the utilisation of α-chromia substrates for the templated growth of α-alumina, which is consistent with recent experiments.
Ab Initio Enhanced calphad Modeling of Actinide-Rich Nuclear Fuels
Energy Technology Data Exchange (ETDEWEB)
Morgan, Dane [Univ. of Wisconsin, Madison, WI (United States); Yang, Yong Austin [Univ. of Wisconsin, Madison, WI (United States)
2013-10-28
The process of fuel recycling is central to the Advanced Fuel Cycle Initiative (AFCI), where plutonium and the minor actinides (MA) Am, Np, and Cm are extracted from spent fuel and fabricated into new fuel for a fast reactor. Metallic alloys of U-Pu-Zr-MA are leading candidates for fast reactor fuels and are the current basis for fast spectrum metal fuels in a fully recycled closed fuel cycle. Safe and optimal use of these fuels will require knowledge of their multicomponent phase stability and thermodynamics (Gibbs free energies). In additional to their use as nuclear fuels, U-Pu-Zr-MA contain elements and alloy phases that pose fundamental questions about electronic structure and energetics at the forefront of modern many-body electron theory. This project will validate state-of-the-art electronic structure approaches for these alloys and use the resulting energetics to model U-Pu-Zr-MA phase stability. In order to keep the work scope practical, researchers will focus on only U-Pu-Zr-{Np,Am}, leaving Cm for later study. The overall objectives of this project are to: Provide a thermodynamic model for U-Pu-Zr-MA for improving and controlling reactor fuels; and, Develop and validate an ab initio approach for predicting actinide alloy energetics for thermodynamic modeling.
International Nuclear Information System (INIS)
Lu Xiaogang; Selleby, Malin; Sundman, Bo
2007-01-01
The thermal expansivities and heat capacities of MX (M = Ti, Zr, Hf, V, Nb, Ta; X = C, N) carbides and nitrides with NaCl structure were calculated using the Debye-Grueneisen model combined with ab initio calculations. Two different approximations for the Grueneisen parameter γ were used in the Debye-Grueneisen model, i.e. the expressions proposed by Slater and by Dugdale and MacDonald. The thermal electronic contribution was evaluated from ab initio calculations of the electronic density of states. The calculated results were compared with CALPHAD assessments and experimental data. It was found that the calculations using the Dugdale-MacDonald γ can account for most of the experimental data. By fitting experimental heat capacity and thermal expansivity data below the Debye temperatures, an estimation of Poisson's ratio was obtained and Young's and shear moduli were evaluated. In order to reach a reasonable agreement with experimental data, it was necessary to use the logarithmic averaged mass of the constituent atoms. The agreements between the calculated and the experimental values for the bulk and Young's moduli are generally better than the agreement for shear modulus
Li, Xiaojie; Schönecker, Stephan; Li, Ruihuan; Li, Xiaoqing; Wang, Yuanyuan; Zhao, Jijun; Johansson, Börje; Vitos, Levente
2016-06-03
To examine the effect of neutron transmutation on tungsten as the first wall material of fusion reactors, the elastic properties of W 1-x-y Re x Os y (0 ⩽ x, y ⩽ 6%) random alloys in body centered cubic (bcc) structure are investigated systematically using the all-electron exact muffin-tin orbitals (EMTO) method in combination with the coherent-potential approximation (CPA). The calculated lattice constant and elastic properties of pure W are consistent with available experiments. Both Os and Re additions reduce the lattice constant and increase the bulk modulus of W, with Os having the stronger effect. The polycrystalline shear modulus, Young's modulus and the Debye temperature increase (decrease) with the addition of Re (Os). Except for C 11 , the other elastic parameters including C 12 , C 44 , Cauchy pressure, Poisson ratio, B/G, increase as a function of Re and Os concentration. The variations of the latter three parameters and the trend in the ratio of cleavage energy to shear modulus for the most dominant slip system indicate that the ductility of the alloy enhances with increasing Re and Os content. The calculated elastic anisotropy of bcc W slightly increases with the concentration of both alloying elements. The estimated melting temperatures of the W-Re-Os alloy suggest that Re or Os addition will reduce the melting temperature of pure W solid. The classical Labusch-Nabarro model for solid-solution hardening predicts larger strengthening effects in W 1-y Os y than in W 1-x Re x . A strong correlation between C' and the fcc-bcc structural energy difference for W 1-x-y Re x Os y is revealed demonstrating that canonical band structure dictates the alloying effect on C'. The structural energy difference is exploited to estimate the alloying effect on the ideal tensile strength in the [0 0 1] direction.
Energy Technology Data Exchange (ETDEWEB)
Kubas, Adam; Blumberger, Jochen, E-mail: j.blumberger@ucl.ac.uk [Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT (United Kingdom); Hoffmann, Felix [Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT (United Kingdom); Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, Universitätsstr. 150, 44801 Bochum (Germany); Heck, Alexander; Elstner, Marcus [Institute of Physical Chemistry, Karlsruhe Institute of Technology, Fritz-Haber-Weg 6, 76131 Karlsruhe (Germany); Oberhofer, Harald [Department of Chemistry, Technical University of Munich, Lichtenbergstr. 4, 85747 Garching (Germany)
2014-03-14
We introduce a database (HAB11) of electronic coupling matrix elements (H{sub ab}) for electron transfer in 11 π-conjugated organic homo-dimer cations. High-level ab inito calculations at the multireference configuration interaction MRCI+Q level of theory, n-electron valence state perturbation theory NEVPT2, and (spin-component scaled) approximate coupled cluster model (SCS)-CC2 are reported for this database to assess the performance of three DFT methods of decreasing computational cost, including constrained density functional theory (CDFT), fragment-orbital DFT (FODFT), and self-consistent charge density functional tight-binding (FODFTB). We find that the CDFT approach in combination with a modified PBE functional containing 50% Hartree-Fock exchange gives best results for absolute H{sub ab} values (mean relative unsigned error = 5.3%) and exponential distance decay constants β (4.3%). CDFT in combination with pure PBE overestimates couplings by 38.7% due to a too diffuse excess charge distribution, whereas the economic FODFT and highly cost-effective FODFTB methods underestimate couplings by 37.6% and 42.4%, respectively, due to neglect of interaction between donor and acceptor. The errors are systematic, however, and can be significantly reduced by applying a uniform scaling factor for each method. Applications to dimers outside the database, specifically rotated thiophene dimers and larger acenes up to pentacene, suggests that the same scaling procedure significantly improves the FODFT and FODFTB results for larger π-conjugated systems relevant to organic semiconductors and DNA.
Mancini, John S; Bowman, Joel M
2013-03-28
We report a global, full-dimensional, ab initio potential energy surface describing the HCl-H2O dimer. The potential is constructed from a permutationally invariant fit, using Morse-like variables, to over 44,000 CCSD(T)-F12b∕aug-cc-pVTZ energies. The surface describes the complex and dissociated monomers with a total RMS fitting error of 24 cm(-1). The normal modes of the minima, low-energy saddle point and separated monomers, the double minimum isomerization pathway and electronic dissociation energy are accurately described by the surface. Rigorous quantum mechanical diffusion Monte Carlo (DMC) calculations are performed to determine the zero-point energy and wavefunction of the complex and the separated fragments. The calculated zero-point energies together with a De value calculated from CCSD(T) with a complete basis set extrapolation gives a D0 value of 1348 ± 3 cm(-1), in good agreement with the recent experimentally reported value of 1334 ± 10 cm(-1) [B. E. Casterline, A. K. Mollner, L. C. Ch'ng, and H. Reisler, J. Phys. Chem. A 114, 9774 (2010)]. Examination of the DMC wavefunction allows for confident characterization of the zero-point geometry to be dominant at the C(2v) double-well saddle point and not the C(s) global minimum. Additional support for the delocalized zero-point geometry is given by numerical solutions to the 1D Schrödinger equation along the imaginary-frequency out-of-plane bending mode, where the zero-point energy is calculated to be 52 cm(-1) above the isomerization barrier. The D0 of the fully deuterated isotopologue is calculated to be 1476 ± 3 cm(-1), which we hope will stand as a benchmark for future experimental work.
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)
Kellö, Vladimir [Department of Physical Chemistry, Comenius University, SK-842 15 Bratislava (Slovakia)
2015-01-22
Highly correlated scalar relativistic calculations of electric field gradients at nuclei in diatomic molecules in combination with accurate nuclear quadrupole coupling constants obtained from microwave spectroscopy are used for determination of nuclear quadrupole moments.
He, Zhili; Feng, Gang; Yang, Bin; Yang, Lijiang; Liu, Cheng-Wen; Xu, Hong-Guang; Xu, Xi-Ling; Zheng, Wei-Jun; Gao, Yi Qin
2018-06-14
To understand the initial hydration processes of CaCl 2 , we performed molecular simulations employing the force field based on the theory of electronic continuum correction with rescaling. Integrated tempering sampling molecular dynamics were combined with ab initio calculations to overcome the sampling challenge in cluster structure search and refinement. The calculated vertical detachment energies of CaCl 2 (H 2 O) n - (n = 0-8) were compared with the values obtained from photoelectron spectra, and consistency was found between the experiment and computation. Separation of the Cl-Ca ion pair is investigated in CaCl 2 (H 2 O) n - anions, where the first Ca-Cl ionic bond required 4 water molecules, and both Ca-Cl bonds are broken when the number of water molecules is larger than 7. For neutral CaCl 2 (H 2 O) n clusters, breaking of the first Ca-Cl bond starts at n = 5, and 8 water molecules are not enough to separate the two ion pairs. Comparing with the observations on magnesium chloride, it shows that separating one ion pair in CaCl 2 (H 2 O) n requires fewer water molecules than those for MgCl 2 (H 2 O) n . Coincidentally, the solubility of calcium chloride is higher than that of magnesium chloride in bulk solutions.
Directory of Open Access Journals (Sweden)
Gümüs Hacer Pir
2015-06-01
Full Text Available Quantum chemical calculations have been performed to study the molecular geometry, 1H and 13C NMR chemical shifts, conformational, natural bond orbital (NBO and nonlinear optical (NLO properties of the 2-chloro-5-(2-hydroxyethyl-4- methoxy-6-methylpyrimidine molecule in the ground state using DFT and HF methods with 6-311++G(d,p basis set. The optimized geometric parameters and 1H and 13C NMR chemical shifts have been compared with the experimental values of the title molecule. The results of the calculations show excellent agreement between the experimental and calculated frequencies at B3LYP/6-311++G(d,p level. In order to provide a full understanding of the properties of the title molecule in the context of molecular orbital picture, the highest occupied molecular energy level (EHOMO, the lowest unoccupied molecular energy level (ELUMO, the energy difference (DE between EHOMO and ELUMO, electronegativity (χ, hardness (η and softness (S have been calculated using B3LYP/6-311++G(d,p and HF/6-311++G(d,p levels. The calculated HOMO and LUMO energies show that the charge transfer occurs within the title molecule.
Stephens, Susanna L; Bittner, Dror M; Mikhailov, Victor A; Mizukami, Wataru; Tew, David P; Walker, Nicholas R; Legon, Anthony C
2014-10-06
The molecular geometries of isolated complexes in which a single molecule of C2H4 or C2H2 is bound to CuCl have been determined through pure rotational spectroscopy and ab-initio calculations. The C2H2···CuCl and C2H4···CuCl complexes are generated through laser vaporization of a copper rod in the presence of a gas sample undergoing supersonic expansion and containing C2H2 (or C2H4), CCl4, and Ar. Results are presented for five isotopologues of C2H2···CuCl and six isotopologues of C2H4···CuCl. Both of these complexes adopt C(2v), T-shaped geometries in which the hydrocarbon binds to the copper atom through its π electrons such that the metal is equidistant from all H atoms. The linear and planar geometries of free C2H2 and C2H4, respectively, are observed to distort significantly on attachment to the CuCl unit, and the various changes are quantified. The ∠(*-C-H) parameter in C2H2 (where * indicates the midpoint of the C≡C bond) is measured to be 192.4(7)° in the r0 geometry of the complex representing a significant change from the linear geometry of the free molecule. This distortion of the linear geometry of C2H2 involves the hydrogen atoms moving away from the copper atom within the complex. Ab-initio calculations at the CCSD(T)(F12*)/AVTZ level predict a dihedral ∠(HCCCu) angle of 96.05° in C2H4···CuCl, and the experimental results are consistent with such a distortion from planarity. The bonds connecting the carbon atoms within each of C2H2 and C2H4, respectively, extend by 0.027 and 0.029 Å relative to the bond lengths in the isolated molecules. Force constants, k(σ), and nuclear quadrupole coupling constants, χ(aa)(Cu), [χ(bb)(Cu) - χ(cc)(Cu)], χ(aa)(Cl), and [χ(bb)(Cl) - χ(cc)(Cl)], are independently determined for all isotopologues of C2H2···CuCl studied and for four isotopologues of C2H4···CuCl.
Ab initio calculation of the electronic structure and spectroscopic properties of spinel γ-Sn3N4
International Nuclear Information System (INIS)
Ching, W. Y.; Rulis, Paul
2006-01-01
The electronic structure and physical properties of γ-Sn 3 N 4 in the spinel structure are investigated by first-principles calculations. The calculated band structure, electronic bonding, and optical properties are compared with two well-studied spinel nitrides γ-Si 3 N 4 and γ-Ge 3 N 4 . γ-Sn 3 N 4 is a semiconductor with a direct band gap of 1.40 eV and an attractive small electron effective mass of 0.17. Its optical properties are different from that of γ-Si 3 N 4 and γ-Ge 3 N 4 because of the difference in the conduction band minimum. The Sn K, Sn L 3 , Sn M 5 , and N K edges of the x-ray-absorption near-edge structure spectra in γ-Sn 3 N 4 are calculated using a supercell approach and are found to be rich in structures. These spectra are discussed in the context of the electronic structure of the unoccupied conduction band in the presence of the electron core-hole interaction. These calculated spectra can be used for the characterization of this novel compound
International Nuclear Information System (INIS)
Vincent, E.; Becquart, C.S.; Domain, C.
2007-01-01
The embrittlement of pressure vessel steels under radiation has been long ago correlated with the presence of Cu solutes. Other solutes such as Ni, Mn and Si are now suspected to contribute also to the embrittlement. The interactions of these solutes with radiation induced point defects thus need to be characterized properly in order to understand the elementary mechanisms behind the formation of the clusters formed upon radiation. Ab initio calculations based on the density functional theory have been performed to determine the interactions of point defects with solute atoms in dilute FeX alloys (X = Cu, Mn, Ni or Si) in order to build a database used to parameterise an atomic kinetic Monte Carlo model. Some results of irradiation damage in dilute Fe-CuNiMnSi alloys obtained with this model are presented
Vincent, E.; Becquart, C. S.; Domain, C.
2007-02-01
The embrittlement of pressure vessel steels under radiation has been long ago correlated with the presence of Cu solutes. Other solutes such as Ni, Mn and Si are now suspected to contribute also to the embrittlement. The interactions of these solutes with radiation induced point defects thus need to be characterized properly in order to understand the elementary mechanisms behind the formation of the clusters formed upon radiation. Ab initio calculations based on the density functional theory have been performed to determine the interactions of point defects with solute atoms in dilute FeX alloys (X = Cu, Mn, Ni or Si) in order to build a database used to parameterise an atomic kinetic Monte Carlo model. Some results of irradiation damage in dilute Fe-CuNiMnSi alloys obtained with this model are presented.
Calculation models for a nuclear reactor
International Nuclear Information System (INIS)
Tashanii, Ahmed Ali
2010-01-01
Determination of different parameters of nuclear reactors requires neutron transport calculations. Due to complicity of geometry and material composition of the reactor core, neutron calculations were performed for simplified models of the real arrangement. In frame of the present work two models were used for calculations. First, an elementary cell model was used to prepare cross section data set for a homogenized-core reactor model. The homogenized-core reactor model was then used to perform neutron transport calculation. The nuclear reactor is a tank-shaped thermal reactor. The semi-cylindrical core arrangement consists of aluminum made fuel bundles immersed in water which acts as a moderator as well as a coolant. Each fuel bundle consists of aluminum cladded fuel rods arranged in square lattices. (author)
Precipitates/Salts Model Sensitivity Calculation
International Nuclear Information System (INIS)
Mariner, P.
2001-01-01
The objective and scope of this calculation is to assist Performance Assessment Operations and the Engineered Barrier System (EBS) Department in modeling the geochemical effects of evaporation on potential seepage waters within a potential repository drift. This work is developed and documented using procedure AP-3.12Q, ''Calculations'', in support of ''Technical Work Plan For Engineered Barrier System Department Modeling and Testing FY 02 Work Activities'' (BSC 2001a). The specific objective of this calculation is to examine the sensitivity and uncertainties of the Precipitates/Salts model. The Precipitates/Salts model is documented in an Analysis/Model Report (AMR), ''In-Drift Precipitates/Salts Analysis'' (BSC 2001b). The calculation in the current document examines the effects of starting water composition, mineral suppressions, and the fugacity of carbon dioxide (CO 2 ) on the chemical evolution of water in the drift
Energy Technology Data Exchange (ETDEWEB)
Holland, D.M.P., E-mail: david.holland@stfc.ac.uk [Daresbury Laboratory, Daresbury, Warrington, Cheshire WA4 4AD (United Kingdom); Shaw, D.A. [Daresbury Laboratory, Daresbury, Warrington, Cheshire WA4 4AD (United Kingdom); Stener, M.; Decleva, P. [Dipartimento di Scienze Chimiche e Farmaceutiche, Università degli Studi di Trieste, Via L. Giorgieri, I-34127 Trieste (Italy); Consorzio Interuniversitario Nazionale per la Scienze e Tecnologia dei Materiali, INSTM, Unità di Trieste (Italy); CNR-IOM, Trieste (Italy); Coriani, S. [Dipartimento di Scienze Chimiche e Farmaceutiche, Università degli Studi di Trieste, Via L. Giorgieri, I-34127 Trieste (Italy); Consorzio Interuniversitario Nazionale per la Scienze e Tecnologia dei Materiali, INSTM, Unità di Trieste (Italy); Aarhus Institute of Advanced Studies, Aarhus University, 8000 Aarhus C (Denmark)
2016-09-30
Highlights: • The valence shell photoabsorption spectrum of s-triazine has been measured. • Electronic structure calculated with TDDFT and coupled cluster approaches. • Assignments proposed for Rydberg and valence states. • Mixing between Rydberg and valence states important. - Abstract: The absolute photoabsorption cross section of s-triazine has been measured between 4 and 40 eV, and is dominated by bands associated with valence states. Structure due to Rydberg excitations is both weak and irregular. Jahn-Teller interactions affect the vibronic structure observed in the Rydberg absorption bands due to excitation from the 1e″ or 6e′ orbitals. The interpretation of the experimental spectrum has been guided by transition energies and oscillator strengths, for Rydberg and valence states, calculated with the time-dependent version of density functional theory and with the coupled cluster linear response approach. The theoretical studies indicate that Rydberg/Rydberg and Rydberg/valence mixing is important.
Energy Technology Data Exchange (ETDEWEB)
Sarmiento-Pérez, Rafael; Botti, Silvana, E-mail: silvana.botti@univ-lyon1.fr [Institut Lumière Matière and ETSF, UMR5306 Université Lyon 1-CNRS, Université de Lyon, F-69622 Villeurbanne Cedex (France); Schnohr, Claudia S., E-mail: c.schnohr@uni-jena.de [Institut für Festkörperphysik, Friedrich-Schiller-Universität Jena, Max-Wien-Platz 1, 07743 Jena (Germany); Lauermann, Iver [Helmholtz-Zentrum Berlin für Materialien und Energie, Hahn-Meitner Platz 1, 14109 Berlin (Germany); Rubio, Angel [Nano-Bio Spectroscopy Group and ETSF Scientific Development Centre, Departamento de Física de Materiales, Centro de Física de Materiales CSIC-MPC and DIPC, Universidad del País Vasco UPV/EHU, Avenida de Tolosa 72, E-20018 San Sebastián (Spain); Fritz Haber Institute, Max Planck Society, Faradayweg 4-6, 14195 Berlin (Germany); Johnson, Benjamin, E-mail: benjamin.johnson@alumni.tu-berlin.de [Fritz Haber Institute, Max Planck Society, Faradayweg 4-6, 14195 Berlin (Germany)
2014-09-07
Element-specific unoccupied electronic states of Cu(In, Ga)S{sub 2} were studied as a function of the In/Ga ratio by combining X-ray absorption spectroscopy with density functional theory calculations. The S absorption edge shifts with changing In/Ga ratio as expected from the variation of the band gap. In contrast, the cation edge positions are largely independent of composition despite the changing band gap. This unexpected behavior is well reproduced by our calculations and originates from the dependence of the electronic states on the local atomic environment. The changing band gap arises from a changing spatial average of these localized states with changing alloy composition.
Ab initio calculations of the magnetic properties of TM (Ti, V)-doped zinc-blende ZnO
Goumrhar, F.; Bahmad, L.; Mounkachi, O.; Benyoussef, A.
2018-01-01
In order to promote suitable material to be used in spintronics devices, this study purposes to evaluate the magnetic properties of the titanium and vanadium-doped zinc-blende ZnO from first-principles. The calculations of these properties are based on the Korringa-Kohn-Rostoker (KKR) method combined with the coherent potential approximation (CPA), using the local density approximation (LDA). We have calculated and discussed the density of states (DOSs) in the energy phase diagrams for different concentration values, of the dopants. We have also investigated the magnetic and half-metallic properties of this doped compound. Additionally, we showed the mechanism of the exchange coupling interaction. Finally, we estimated and studied the Curie temperature for different concentrations.
DEFF Research Database (Denmark)
Holland, D.M.P.; Shaw, D.A.; Stener, Mauro
2016-01-01
absorption bands due to excitation from the 1e00 or 6e0 orbitals. The interpretation of the experimental spectrum has been guided by transition energies and oscillator strengths, for Rydberg and valence states, calculated with the time-dependent version of density functional theory and with the coupled...... cluster linear response approach. The theoretical studies indicate that Rydberg/Rydberg and Rydberg/valence mixing is important....
International Nuclear Information System (INIS)
Zeng Xiancheng; Hu Hao; Hu Xiangqian; Yang Weitao
2009-01-01
A quantum mechanical/molecular mechanical minimum free energy path (QM/MM-MFEP) method was developed to calculate the redox free energies of large systems in solution with greatly enhanced efficiency for conformation sampling. The QM/MM-MFEP method describes the thermodynamics of a system on the potential of mean force surface of the solute degrees of freedom. The molecular dynamics (MD) sampling is only carried out with the QM subsystem fixed. It thus avoids 'on-the-fly' QM calculations and thus overcomes the high computational cost in the direct QM/MM MD sampling. In the applications to two metal complexes in aqueous solution, the new QM/MM-MFEP method yielded redox free energies in good agreement with those calculated from the direct QM/MM MD method. Two larger biologically important redox molecules, lumichrome and riboflavin, were further investigated to demonstrate the efficiency of the method. The enhanced efficiency and uncompromised accuracy are especially significant for biochemical systems. The QM/MM-MFEP method thus provides an efficient approach to free energy simulation of complex electron transfer reactions.
International Nuclear Information System (INIS)
Vidal-Vidal, Á.; Pérez-Rodríguez, M.; Piñeiro, M.M.
2017-01-01
Highlights: • OCS hydrolysis equilibrium constants were calculated using QM composite methods. • CBS-QB3 was found to be the most adequate method for OCS thermodynamic calculations. • Calculated hydrolysis yields decrease when temperature increases. • The isotopic effect is less significant than temperature or initial concentration dependences. - Abstract: Carbonyl sulphide is the predominant sulphur compound in the atmosphere, contributing to the formation of aerosol particles affecting global climate. Human activity has significantly increased its total amount since the beginning of the Industrial Revolution due to its presence in petroleum and coal, reason why it is necessary to understand and control its emissions. On the other hand, carbonyl sulphide is an undesired substance for catalysis in important industrial processes. Hydrolysis is the most promising among the different strategies to reduce its presence, giving as products carbon dioxide and hydrogen sulphide. In the present work, the mechanism of reaction of carbonyl sulphide hydrolysis process in gas phase was studied from 400 K to 1500 K, equilibrium constants were obtained and reaction yields were estimated, by means of composite quantum-computational methods. Good agreement with literature experimental results confirms the suitability of the chosen methods, specially CBS-QB3, in supporting the reaction mechanism, giving accurate equilibrium constant values, and obtaining realistic yields. The effect of isotopic substitution in OCS was also studied, from 300 K to 1500 K, being much less significant than temperature dependence.
Sambathkumar, K; Jeyavijayan, S; Arivazhagan, M
2015-08-05
Combined experimental and theoretical studies were conducted on the molecular structure and vibrational spectra of 4-AminoPhthalhydrazide (APH). The FT-IR and FT-Raman spectra of APH were recorded in the solid phase. The molecular geometry and vibrational frequencies of APH in the ground state have been calculated by using the ab initio HF (Hartree-Fock) and density functional methods (B3LYP) invoking 6-311+G(d,p) basis set. The optimized geometric bond lengths and bond angles obtained by HF and B3LYP method show best agreement with the experimental values. Comparison of the observed fundamental vibrational frequencies of APH with calculated results by HF and density functional methods indicates that B3LYP is superior to the scaled Hartree-Fock approach for molecular vibrational problems. The difference between the observed and scaled wave number values of most of the fundamentals is very small. A detailed interpretation of the NMR spectra of APH was also reported. The theoretical spectrograms for infrared and Raman spectra of the title molecule have been constructed. UV-vis spectrum of the compound was recorded and the electronic properties, such as HOMO and LUMO energies, were performed by time dependent density functional theory (TD-DFT) approach. Finally the calculations results were applied to simulated infrared and Raman spectra of the title compound which show good agreement with observed spectra. And the temperature dependence of the thermodynamic properties of constant pressure (Cp), entropy (S) and enthalpy change (ΔH0→T) for APH were also determined. Copyright © 2015 Elsevier B.V. All rights reserved.
Moynier, Frédéric; Fujii, Toshiyuki; Wang, Kun; Foriel, Julien
2013-05-01
Iron is one of the most abundant transition metal in higher plants and variations in its isotopic compositions can be used to trace its utilization. In order to better understand the effect of plant-induced isotopic fractionation on the global Fe cycling, we have estimated by quantum chemical calculations the magnitude of the isotopic fractionation between different Fe species relevant to the transport and storage of Fe in higher plants: Fe(II)-citrate, Fe(III)-citrate, Fe(II)-nicotianamine, and Fe(III)-phytosiderophore. The ab initio calculations show firstly, that Fe(II)-nicotianamine is ˜3‰ (56Fe/54Fe) isotopically lighter than Fe(III)-phytosiderophore; secondly, even in the absence of redox changes of Fe, change in the speciation alone can create up to ˜1.5‰ isotopic fractionation. For example, Fe(III)-phytosiderophore is up to 1.5‰ heavier than Fe(III)-citrate2 and Fe(II)-nicotianamine is up to 1‰ heavier than Fe(II)-citrate. In addition, in order to better understand the Fe isotopic fractionation between different plant components, we have analyzed the iron isotopic composition of different organs (roots, seeds, germinated seeds, leaves and stems) from six species of higher plants: the dicot lentil (Lens culinaris), and the graminaceous monocots Virginia wild rye (Elymus virginicus), Johnsongrass (Sorghum halepense), Kentucky bluegrass (Poa pratensis), river oat (Uniola latifolia), and Indian goosegrass (Eleusine indica). The calculations may explain that the roots of strategy-II plants (Fe(III)-phytosiderophore) are isotopically heavier (by about 1‰ for the δ56Fe) than the upper parts of the plants (Fe transported as Fe(III)-citrate in the xylem or Fe(II)-nicotianamine in the phloem). In addition, we suggest that the isotopic variations observed between younger and older leaves could be explained by mixing of Fe received from the xylem and the phloem.
International Nuclear Information System (INIS)
Mahmood, Q; Alay-e-Abbas, S M; Mahmood, I; Noor, N A; Asif, Mahmood
2016-01-01
The mechanical, electronic and magnetic properties of non-magnetic MgTe and ferro-magnetic (FM) Mg 0.75 TM 0.25 Te (TM = Fe, Co, Ni) in the zinc-blende phase are studied by ab-initio calculations for the first time. We use the generalized gradient approximation functional for computing the structural stability, and mechanical properties, while the modified Becke and Johnson local (spin) density approximation (mBJLDA) is utilized for determining the electronic and magnetic properties. By comparing the energies of non-magnetic and FM calculations, we find that the compounds are stable in the FM phase, which is confirmed by their structural stabilities in terms of enthalpy of formation. Detailed descriptions of elastic properties of Mg 0.75 TM 0.25 Te alloys in the FM phase are also presented. For electronic properties, the spin-polarized electronic band structures and density of states are computed, showing that these compounds are direct bandgap materials with strong hybridizations of TM 3d states and Te p states. Further, the ferromagnetism is discussed in terms of the Zener free electron model, RKKY model and double exchange model. The charge density contours in the (110) plane are calculated to study bonding properties. The spin exchange splitting and crystal field splitting energies are also calculated. The distribution of electron spin density is employed in computing the magnetic moments appearing at the magnetic sites (Fe, Co, Ni), as well as at the non-magnetic sites (Mg, Te). It is found that the p–d hybridization causes not only magnetic moments on the magnetic sites but also induces negligibly small magnetic moments at the non-magnetic sites. (paper)
Model cross section calculations using LAHET
International Nuclear Information System (INIS)
Prael, R.E.
1992-01-01
The current status of LAHET is discussed. The effect of a multistage preequilibrium exciton model following the INC is examined for neutron emission benchmark calculations, as is the use of a Fermi breakup model for light nuclei rather than an evaporation model. Comparisons are made also for recent fission cross section experiments, and a discussion of helium production cross sections is presented
International Nuclear Information System (INIS)
Song, W.; Appen, J. von; Choi, P.; Dronskowski, R.; Raabe, D.; Bleck, W.
2013-01-01
Carbide precipitation during upper and lower bainite formation in high-carbon bearing steel 100Cr6 is characterized using transmission electron microscopy and atom probe tomography. The results reveal that both ε and θ carbides precipitate in lower bainite isothermally held at 260 °C and only θ precipitates form in upper bainite isothermally held at 500 °C. ε and θ precipitate under paraequilibrium condition at 260 °C in lower bainite and θ precipitates under negligible partitioning local equilibrium condition in upper bainite at 500 °C. In order to theoretically study ε and θ precipitation and the ε → θ transition in bainite, thermodynamic calculations have been carried out using ab initio techniques. We find that ε and θ carbides in ferrite have almost identical thermodynamic stability, and hence have similar formation probability. In austenite, however, cementite formation is clearly preferred: it is favored by 5 kJ mol −1 at room temperature and still by 4 kJ mol −1 at 500 °C. Hence, the thermodynamic predictions agree well with the atom probe tomography results
International Nuclear Information System (INIS)
Ghose, Subrata
2006-01-01
Full text: Until recently, inelastic neutron scattering (INS) has been extensively used to study the phonon dispersion throughout the Brillouin zone and phonon density of states in crystalline materials. The weak interaction of neutrons with matter and the typical size of the neutron beams require the use of cm-size single crystals that puts an upper limit to the measurement of phonon dispersion at high pressure to about 10-15 Gpa by INS. Inelastic X-ray scattering (IXS) using third generation synchrotron sources now makes it possible to measure the phonon dispersion at high pressures up to 50 GP A in crystals tens of microns in size mounted in a diamond-anvil cell, usually using He as the pressure transmitting medium. We have used this technique to measure the longitudinal acoustic and optic phonon branches of MgO along the Γ-X direction at 35 Gpa. The experimentally observed phonon-branches are in remarkable agreement with ab-initio quantum mechanical calculations using the density-functional perturbation theory. The derived thermodynamic properties, such as specific heat and the entropy are in very good agreement with values obtained from a thermodynamically assessed data set
Nugraha, T. A.; Rohrmueller, M.; Gerstmann, U.; Greulich-Weber, S.; Stellhorn, A.; Cantin, J. L.; von Bardeleben, J.; Schmidt, W. G.; Wippermann, S.
SiC is widely used in high-power, high-frequency electronic devices. Recently, it has also been employed as a building block in nanocomposites used as light absorbers in solar energy conversion devices. Analogous to Si, SiC features SiO2 as native oxide that can be used for passivation and insulating layers. However, a significant number of defect states are reported to form at SiC/SiO2 interfaces, limiting mobility and increasing recombination of free charge carriers. We investigated the growth of oxide on different 3C-SiC surfaces from first principles. Carbon antisite Csi defects are found to be strongly stabilized in particular at the interface, because carbon changes its hybridization from sp3 in the SiC-bulk to sp2 at the interface, creating a dangling bond inside a porous region of the SiO2 passivating layer. Combining ab initio g-tensor calculations and electron paramagnetic resonance (EPR) measurements, we show that Csi defects explain the measured EPR signatures, while the hyperfine structure allows to obtain local structural information of the oxide layer. Financial support from BMBF NanoMatFutur Grant 13N12972 and DFG priority program SPP-1601 is gratefully acknowledged.
Ab-initio calculation of the valence-band offset at strained GaAs/InAs (001) heterojunction
International Nuclear Information System (INIS)
Tit, N.; Peressi, M.
1993-06-01
We present a self consistent pseudopotential calculation of the valence band offset (VBO) at GaAs/InAs (001) strained heterojunction, which is chose as an example of the isovalent polar with common-anion lattice mismatched heterojunctions. The effects of strain are studied by looking at the variation of the VBO versus the in plane lattice constant, which is imposed by the substrate. Our results show that the VBO can be tuned by about 0.17 eV going from GaAs to InAs substrates. Comparison of our work with the available experimental and theoretical results is also discussed. (author). 25 refs, 3 figs, 5 tabs
Energy Technology Data Exchange (ETDEWEB)
Boldyrev, A I; Sukhanov, L P; Charkin, O P [AN SSSR, Moscow. Inst. Novykh Khimicheskikh Problem
1982-01-01
In approximation by the Hartree-Fock-Routine method using several Gauss type bases ionization potentials of complex hydrides LiBeH/sub 3/, NaBeH/sub 3/, LiMgH/sub 3/, LiBH/sub 4/, NaBH/sub 4/ and LiAlH/sub 4/ have been calculated. A problem of the show of structural non-rigidity of complex molecules L(MX/sub 4/) with tetrahedral anions (MX/sub 4/)/sup -/ in photoelectron spectra is considered.
Energy Technology Data Exchange (ETDEWEB)
Kostko, Oleg; Ahmed, Musahid; Metz, Ricardo B.
2008-12-05
In this work we report on the detection and vacuum-ultraviolet (VUV) photoionization of gas phase SiO2 generated in situ via laser ablation of silicon in a CO2 molecular beam. The resulting species are investigated by single photon ionization with tunable VUV synchrotron radiation and mass analyzed using reflectron mass spectrometry. Photoionization efficiency (PIE) curves are recorded for SiO and SiO2 and ionization energy estimates are revealed from such measurements. A state-to-state ionizationenergy of 12.60 (+-0.05) eV is recorded by fitting two prominent peaks in the PIE curve for the following process: 1SUM O-Si-O --> 2PRODg [O-Si-O]+. Electronic structure calculations aid in the interpretation of the photoionization process and allow for identification of the symmetric stretch of 2PRODg [O-Si-O]+ which is observed in the PIE spectrum to be 0.11 eV (890 cm-1) above the ground state of the cation and agrees with the 892 cm-1 symmetric stretch frequency calculated at the CCSD(T)/aug-cc-pVTZ level.
Veiga, R. G. A.; Miwa, R. H.; McLean, A. B.
2016-03-01
We report first-principles calculations of the energetic stability and electronic properties of metal-phthalocyanine (MPc) molecules (M = Cr, Mn, Fe, Co, Ni, Cu, and Zn) adsorbed on the δ -doped Si(111)-B (√{3 }×√{3 }) reconstructed surface. (i) It can be seen that CrPc, MnPc, FePc, and CoPc are chemically anchored to the topmost Si atom. (ii) Contrastingly, the binding of the NiPc, CuPc, and ZnPc molecules to the Si (111 ) -B (√{3 }×√{3 }) surface is exclusively ruled by van der Waals interactions, the main implication being that these molecules may diffuse and rearrange to form clusters and/or self-organized structures on this surface. The electronic structure calculations reveal that in point (i), owing to the formation of the metal-Si covalent bond, the net magnetic moment of the molecule is quenched by 1 μB , remaining unchanged in point (ii). In particular, the magnetic moment of CuPc (1 μB ) is preserved after adsorption. Finally, we verify that the formation of ZnPc, CuPc, and NiPc molecular (self-assembled) arrangements on the Si(111)-B (√{3 }×√{3 } ) surface is energetically favorable, in good agreement with recent experimental findings.
High-pressure structural behaviour of HoVO4: combined XRD experiments and ab initio calculations
International Nuclear Information System (INIS)
Garg, Alka B; Errandonea, D; Rodríguez-Hernández, P; Muñoz, A; López-Moreno, S; Popescu, C
2014-01-01
We report a high-pressure experimental and theoretical investigation of the structural properties of zircon-type HoVO 4 . Angle-dispersive x-ray diffraction measurements were carried out under quasi-hydrostatic and partial non-hydrostatic conditions up to 28 and 23.7 GPa, respectively. In the first case, an irreversible phase transition is found at 8.2 GPa. In the second case, the onset of the transition is detected at 4.5 GPa, a second (reversible) transition is found at 20.4 GPa, and a partial decomposition of HoVO 4 was observed. The structures of the different phases have been assigned and their equations of state (EOS) determined. Experimental results have also been compared to theoretical calculations which fully agree with quasi-hydrostatic experiments. Theory also suggests the possibility of another phase transition at 32 GPa; i.e. beyond the pressure limit covered by present experiments. Furthermore, calculations show that deviatoric stresses could trigger the transition found at 20.4 GPa under non-hydrostatic conditions. The reliability of the present experimental and theoretical results is supported by the consistency between the values yielded for transition pressures and EOS parameters by the two methods. (paper)
L da Silva, L F; Andrade-Filho, T; Freire, P T C; Filho, J Mendes; da Silva Filho, J G; Saraiva, G D; Moreira, S G C; de Sousa, F F
2017-06-29
A complete experimental study on the vibrational properties of palmitic and stearic acids crystallized in the B m and C forms, both belonging to the monoclinic system with the P2 1 /a (C 2h 5 ) space group, through polarized Raman and infrared spectroscopy, is reported in this paper. Density functional theory calculations were also performed to assign the normal modes and to help in the interpretation of the experimental data. The different polarizations were compared and their influence on the spectral profiles, in both the lattice and the internal mode regions, was discussed. In general, the Raman and infrared spectra exhibit accentuated differences among the polymorphic forms, which are associated with the different molecular modifications, defined as gauche and all-trans conformations. Insights about interaction among different groups are also furnished.
Ab-initio calculations of structural, electronic, and optical properties of Zn3(VO4)2
Ahmed, Nisar; Mukhtar, S.; Gao, Wei; Zafar Ilyas, Syed
2018-03-01
The structural, electronic, and optical properties of Zn3(VO4)2 are investigated using full potential linearized augmented plane wave (FP-LAPW) method within the framework of density functional theory (DFT). Various approaches are adopted to treat the exchange and correlation potential energy such as generalized gradient approximation (GGA), GGA+U, and the Tran–Blaha modified Becke–Johnson (TB-mBJ) potential. The calculated band gap of 3.424 eV by TB-mBJ is found to be close to the experimental result (3.3 eV). The optical anisotropy is analyzed through optical constants, such as dielectric function and absorption coefficient along parallel and perpendicular crystal orientations. The absorption coefficient reveals high absorption (1.5× {10}6 {cm}}-1) of photons in the ultraviolet region.
Gadret, E. G.; Dias, G. O.; Dacal, L. C. O.; de Lima, M. M., Jr.; Ruffo, C. V. R. S.; Iikawa, F.; Brasil, M. J. S. P.; Chiaramonte, T.; Cotta, M. A.; Tizei, L. H. G.; Ugarte, D.; Cantarero, A.
2010-09-01
We investigated experimentally and theoretically the valence-band structure of wurtzite InP nanowires. The wurtzite phase, which usually is not stable for III-V phosphide compounds, has been observed in InP nanowires. We present results on the electronic properties of these nanowires using the photoluminescence excitation technique. Spectra from an ensemble of nanowires show three clear absorption edges separated by 44 meV and 143 meV, respectively. The band edges are attributed to excitonic absorptions involving three distinct valence-bands labeled: A, B, and C. Theoretical results based on “ab initio” calculation gives corresponding valence-band energy separations of 50 meV and 200 meV, respectively, which are in good agreement with the experimental results.
Tanaka, Hiroshi
1998-01-01
A real-space scheme is developed to calculate matrix elements of the Green function from first principles for large disordered systems. The scheme is an extension of the particle source method, combined with the tight-binding linear muffin-tin orbitals and has the following advantages: (i) It is possible to evaluate both the diagonal and off-diagonal parts of the Green function and also their products with other quantum operators, (ii) it allows for an explicit control of the numerical accuracy and clear-cut physical interpretations of the results on the basis of the definition of the Green function, and (iii) the scheme is suitable for both vector and parallel processing and requires CPU time and memory size proportional only to the system size. The method is applied to the densities of states of bcc and amorphous Fe. The dc conductivity is also evaluated for the latter from the Kubo-Greenwood formula.
International Nuclear Information System (INIS)
Shukla, Anil; Bogdanov, Bogdan
2015-01-01
Small cationic and anionic clusters of lithium formate were generated by electrospray ionization and their fragmentations were studied by tandem mass spectrometry (collision-induced dissociation with N 2 ). Singly as well as multiply charged clusters were formed in both positive and negative ion modes with the general formulae, (HCOOLi) n Li + , (HCOOLi) n Li m m+ , (HCOOLi) n HCOO − , and (HCOOLi) n (HCOO) m m− . Several magic number cluster (MNC) ions were observed in both the positive and negative ion modes although more predominant in the positive ion mode with (HCOOLi) 3 Li + being the most abundant and stable cluster ion. Fragmentations of singly charged positive clusters proceed first by the loss of a dimer unit ((HCOOLi) 2 ) followed by the loss of monomer units (HCOOLi) although the former remains the dominant dissociation process. In the case of positive cluster ions, all fragmentations lead to the magic cluster (HCOOLi) 3 Li + as the most abundant fragment ion at higher collision energies which then fragments further to dimer and monomer ions at lower abundances. In the negative ion mode, however, singly charged clusters dissociated via sequential loss of monomer units. Multiply charged clusters in both positive and negative ion modes dissociated mainly via Coulomb repulsion. Quantum chemical calculations performed for smaller cluster ions showed that the trimer ion has a closed ring structure similar to the phenalenylium structure with three closed rings connected to the central lithium ion. Further additions of monomer units result in similar symmetric structures for hexamer and nonamer cluster ions. Thermochemical calculations show that trimer cluster ion is relatively more stable than neighboring cluster ions, supporting the experimental observation of a magic number cluster with enhanced stability
Ab initio calculations of ideal strength and lattice instability in W-Ta and W-Re alloys
Yang, Chaoming; Qi, Liang
2018-01-01
An important theoretical criterion to evaluate the ductility of metals with a body-centered cubic (bcc) lattice is the mechanical failure mode of their perfect crystals under tension along ; directions. When the tensile stress reaches the ideal tensile strength, the pure W crystal fails by a cleavage fracture along the {100 } plane so that it is intrinsically brittle. To discover the strategy to improve its ductility, we performed density functional theory and density functional perturbation theory calculations to study the ideal tensile strength and the lattice instability under tension for both W-Ta and W-Re alloys. Anisotropic linear elastic fracture mechanics (LEFM) theory and Rice's criterion were also applied to analyze the mechanical instability at the crack tip under tension based on the competition between cleavage propagation and dislocation emission. The results show that the intrinsic ductility can be achieved in both W-Ta and W-Re, however, by different mechanisms. Even though W-Ta alloys with low Ta concentrations are still intrinsically brittle, the intrinsic ductility of W-Ta alloys with high Ta concentrations is promoted by elastic shear instability before the cleavage failure. The intrinsic ductility of W-Re alloys is produced by unstable transverse phonon waves before the cleavage failure, and the corresponding phonon mode is related to the generation of 1/2 {2 ¯11 } dislocation in bcc crystals. The ideal tensile calculations, phonon analyses, and anisotropic LEFM examinations are mutually consistent in the evaluation of intrinsic ductility. These results bring us physical insights on the ductility-brittle mechanisms of W alloys under extreme stress conditions.
Hernández Vera, Mario; Yurtsever, Ersin; Wester, Roland; Gianturco, Franco A.
2018-05-01
We present an extensive range of accurate ab initio calculations, which map in detail the spatial electronic potential energy surface that describes the interaction between the molecular anion NH2 - (1A1) in its ground electronic state and the He atom. The time-independent close-coupling method is employed to generate the corresponding rotationally inelastic cross sections, and then the state-changing rates over a range of temperatures from 10 to 30 K, which is expected to realistically represent the experimental trapping conditions for this ion in a radio frequency ion trap filled with helium buffer gas. The overall evolutionary kinetics of the rotational level population involving the molecular anion in the cold trap is also modelled during a photodetachment experiment and analyzed using the computed rates. The present results clearly indicate the possibility of selectively detecting differences in behavior between the ortho- and para-anions undergoing photodetachment in the trap.
Zbiri, Mohamed; Viennois, Romain
2017-10-01
We report inelastic neutron scattering measurements of phonon spectra in the parent superconductor iron-tuned chalcogenide F e1 +xTe for two different x contents (x ≤0.11 ) using neutron time-of-flight technique. Thermal neutron spectroscopy allowed the collection of the low-temperature Stokes spectra over an extended Q range at 2, 40, and 120 K, hence covering both the magnetic monoclinic and the paramagnetic tetragonal phases, whereas cold neutrons allowed the measurement of high-resolution anti-Stokes spectra at 140, 220, and 300 K, thus covering the tetragonal phase. Our results evidence a spin-phonon coupling behavior towards the observed noticeable temperature-dependent change of the Stokes spectra across the transition temperatures. On the other hand, the anti-Stokes spectra reveal a pronounced hardening of the low-energy, acoustic region of the phonon spectrum upon heating, indicating a strong anharmonicity and a subtle dependence of phonons on structural evolution within the tetragonal phase. Experimental results are accompanied by ab initio calculations of phonon spectra of the tetragonal stoichiometric phase for a comparison with the high-resolution anti-Stokes spectra. Calculations included different density functional methods. Spin polarization and van der Waals interaction were either considered or neglected, individually or concomitantly, in order to study their respective effect on lattice dynamics description. Our results suggest that including van der Waals interaction has only a slight effect on phonon dynamics; however, phonon spectra are better described when spin polarization is included in a cooperative way with van der Waals interactions.
Ab initio calculations of half-metallic ferromagnetism in Cr-doped MgSe and MgTe semiconductors
Energy Technology Data Exchange (ETDEWEB)
Noor, N.A. [Department of Physics, University of the Punjab, Quaid-e-Azam Campus, 54590 Lahore (Pakistan); Alay-e-Abbas, S.M. [Department of Physics, University of Sargodha, Sargodha 40100 (Pakistan); Department of Physics, GC University Faisalabad, Allama Iqbal Road, Faisalabad 38000 (Pakistan); Sohaib, M.U. [Lahore Development Authority, 54590 Lahore (Pakistan); Ghulam Abbas, S.M. [Department of Chemistry, University of Agriculture, Faisalabad 38040 (Pakistan); Shaukat, A., E-mail: schaukat@gmail.com [Department of Physics, University of Sargodha, Sargodha 40100 (Pakistan)
2015-01-15
The full-potential linear-augmented-plane-waves plus local-orbitals (FP-LAPW+lo) method has been employed for investigation of half-metallic ferromagnetism in Cr-doped ordered zinc-blende MgSe and MgTe semiconductors. Calculations of exchange and correlation (XC) effects have been carried out using generalized gradient approximation (GGA) and orbital independent modified Becke–Johnson potential coupled with local (spin) density approximation (mBJLDA). The thermodynamic stability of the compounds and their preferred magnetic orders have been analyzed in terms of the heat of formation and minimum total energy difference in ferromagnetic (FM) and anti-ferromagnetic (AFM) ordering, respectively. Calculated electronic properties reveal that the Cr-doping induces ferromagnetism in MgSe and MgTe which gives rise to a half-metallic (HM) gap at Fermi level (E{sub F}). Further, the electronic band structure is discussed in terms of s (p)–d exchange constants that are consistent with typical magneto-optical experiment and the behavior of charge spin densities is presented for understanding the bonding nature. Our results demonstrate that the higher effective potential for the spin-down case is responsible for p–d exchange splitting. Total magnetic moment (mainly due to Cr-d states) of these compounds is 4µ{sub B}. Importantly, the electronic properties and HM gap obtained using mBJLDA show remarkable improvement as compared to the results obtained using standard GGA functional. - Highlights: • Spin effect theoretical study on Cr-doped MgSe and MgTe is performed. • Half-metallic ferromagnetism in Cr{sub x}Mg{sub 1−x}Se and Cr{sub x}Mg{sub 1−x}Te is established. • Results of WC-GGA and mBJLDA are compared for performance. • HM gaps for Cr{sub x}Mg{sub 1−x}Se and Cr{sub x}Mg{sub 1−x}Te show nonlinear variation with x. • Important values of exchange splitting/constants and moments are reported.
DEFF Research Database (Denmark)
Berg, Rolf W.
gaseous free state models. Some extreme examples are to be discussed: (1) The 1,1,3,3-tetramethyl-guanidinium chloride “molecule” [TMG-H-Cl] found [ref 1] to exist in gaseous state over its corresponding liquid in evacuated ampouls heated at ~225°C (Fig. 1); (2) the analogous bromide “molecule” [TMG...
Hybrid reduced order modeling for assembly calculations
International Nuclear Information System (INIS)
Bang, Youngsuk; Abdel-Khalik, Hany S.; Jessee, Matthew A.; Mertyurek, Ugur
2015-01-01
Highlights: • Reducing computational cost in engineering calculations. • Reduced order modeling algorithm for multi-physics problem like assembly calculation. • Non-intrusive algorithm with random sampling. • Pattern recognition in the components with high sensitive and large variation. - Abstract: While the accuracy of assembly calculations has considerably improved due to the increase in computer power enabling more refined description of the phase space and use of more sophisticated numerical algorithms, the computational cost continues to increase which limits the full utilization of their effectiveness for routine engineering analysis. Reduced order modeling is a mathematical vehicle that scales down the dimensionality of large-scale numerical problems to enable their repeated executions on small computing environment, often available to end users. This is done by capturing the most dominant underlying relationships between the model's inputs and outputs. Previous works demonstrated the use of the reduced order modeling for a single physics code, such as a radiation transport calculation. This manuscript extends those works to coupled code systems as currently employed in assembly calculations. Numerical tests are conducted using realistic SCALE assembly models with resonance self-shielding, neutron transport, and nuclides transmutation/depletion models representing the components of the coupled code system.
Hybrid reduced order modeling for assembly calculations
Energy Technology Data Exchange (ETDEWEB)
Bang, Youngsuk, E-mail: ysbang00@fnctech.com [FNC Technology, Co. Ltd., Yongin-si (Korea, Republic of); Abdel-Khalik, Hany S., E-mail: abdelkhalik@purdue.edu [Purdue University, West Lafayette, IN (United States); Jessee, Matthew A., E-mail: jesseema@ornl.gov [Oak Ridge National Laboratory, Oak Ridge, TN (United States); Mertyurek, Ugur, E-mail: mertyurek@ornl.gov [Oak Ridge National Laboratory, Oak Ridge, TN (United States)
2015-12-15
Highlights: • Reducing computational cost in engineering calculations. • Reduced order modeling algorithm for multi-physics problem like assembly calculation. • Non-intrusive algorithm with random sampling. • Pattern recognition in the components with high sensitive and large variation. - Abstract: While the accuracy of assembly calculations has considerably improved due to the increase in computer power enabling more refined description of the phase space and use of more sophisticated numerical algorithms, the computational cost continues to increase which limits the full utilization of their effectiveness for routine engineering analysis. Reduced order modeling is a mathematical vehicle that scales down the dimensionality of large-scale numerical problems to enable their repeated executions on small computing environment, often available to end users. This is done by capturing the most dominant underlying relationships between the model's inputs and outputs. Previous works demonstrated the use of the reduced order modeling for a single physics code, such as a radiation transport calculation. This manuscript extends those works to coupled code systems as currently employed in assembly calculations. Numerical tests are conducted using realistic SCALE assembly models with resonance self-shielding, neutron transport, and nuclides transmutation/depletion models representing the components of the coupled code system.
Ellis, Matthew O. A.; Stamenova, Maria; Sanvito, Stefano
2017-12-01
There exists a significant challenge in developing efficient magnetic tunnel junctions with low write currents for nonvolatile memory devices. With the aim of analyzing potential materials for efficient current-operated magnetic junctions, we have developed a multi-scale methodology combining ab initio calculations of spin-transfer torque with large-scale time-dependent simulations using atomistic spin dynamics. In this work we introduce our multiscale approach, including a discussion on a number of possible schemes for mapping the ab initio spin torques into the spin dynamics. We demonstrate this methodology on a prototype Co/MgO/Co/Cu tunnel junction showing that the spin torques are primarily acting at the interface between the Co free layer and MgO. Using spin dynamics we then calculate the reversal switching times for the free layer and the critical voltages and currents required for such switching. Our work provides an efficient, accurate, and versatile framework for designing novel current-operated magnetic devices, where all the materials details are taken into account.
Koettgen, Julius; Schmidt, Peter C.; Bučko, Tomáš; Martin, Manfred
2018-01-01
We have studied the free energy migration barriers Δ F‡ for oxygen diffusion in pure ceria and Sm-doped ceria for the temperatures 300, 700, and 1000 K. We used the density functional theory in the generalized gradient approximation and an additional Hubbard U parameter for the Ce 4 f electronic states. We compare the results for the free energy deduced from three different methods. First, a static harmonic approach is applied in which the temperature dependent vibrational contributions to energy and entropy are deduced from the phonon frequencies of supercells with a fixed volume. Second, a static quasiharmonic approach is used in which a part of the anharmonicity effect is introduced via an implicit dependence of the harmonic frequencies on the thermally expanding cell volume. Third, the free energy barriers are calculated using metadynamics and molecular dynamics in which anharmonicity effects are naturally taken into account. The three methods examined in this study lead to distinctly different results. According to the harmonic approximation, the migration free energy difference Δ F‡ increases with increasing temperature due to an increasing entropic contribution. According to the quasiharmonic approximation, the migration free energy is independent of temperature. Finally, molecular dynamics predicts a thermally induced increase in the migration free energy. We conclude that temperature dependent experimental lattice constants cancel out the increasing entropic contribution with increasing temperature in the static quasiharmonic approach. The full consideration of anharmonicity effects in the metadynamics method again leads to a temperature dependent migration free energy.
Endichi, A.; Zaari, H.; Benyoussef, A.; El Kenz, A.
2018-06-01
The magnetic behavior of LaCr2Si2C compound is investigated in this work, using first principle methods, Monte Carlo simulation (MCS) and mean field approximation (MFA). The structural, electronic and magnetic properties are described using ab initio method in the framework of the Generalized Gradient Approximation (GGA), and the Full Potential-Linearized Augmented Plane Wave (FP-LAPW) method implemented in the WIEN2K packages. We have also computed the coupling terms between magnetic atoms which are used in Hamiltonian model. A theoretical study realized by mean field approximation and Monte Carlo Simulation within the Ising model is used to more understand the magnetic properties of this compound. Thereby, our results showed a ferromagnetic ordering of the Cr magnetic moments below the Curie temperature of 30 K (Tc magnetization, the energy, the specific heat and the susceptibility. This material shows the small sign of supra-conductivity; and future researches could be focused to enhance the transport and magnetic properties of this system.
A Novel Hybrid Similarity Calculation Model
Directory of Open Access Journals (Sweden)
Xiaoping Fan
2017-01-01
Full Text Available This paper addresses the problems of similarity calculation in the traditional recommendation algorithms of nearest neighbor collaborative filtering, especially the failure in describing dynamic user preference. Proceeding from the perspective of solving the problem of user interest drift, a new hybrid similarity calculation model is proposed in this paper. This model consists of two parts, on the one hand the model uses the function fitting to describe users’ rating behaviors and their rating preferences, and on the other hand it employs the Random Forest algorithm to take user attribute features into account. Furthermore, the paper combines the two parts to build a new hybrid similarity calculation model for user recommendation. Experimental results show that, for data sets of different size, the model’s prediction precision is higher than the traditional recommendation algorithms.
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 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
A revised calculational model for fission
Energy Technology Data Exchange (ETDEWEB)
Atchison, F
1998-09-01
A semi-empirical parametrization has been developed to calculate the fission contribution to evaporative de-excitation of nuclei with a very wide range of charge, mass and excitation-energy and also the nuclear states of the scission products. The calculational model reproduces measured values (cross-sections, mass distributions, etc.) for a wide range of fissioning systems: Nuclei from Ta to Cf, interactions involving nucleons up to medium energy and light ions. (author)
Ab initio calculation of the electromagnetic and neutral-weak response functions of 4He and 12C
Energy Technology Data Exchange (ETDEWEB)
Lovato, A. [Argonne National Lab. (ANL), Argonne, IL (United States); Benhar, O. [Sapienza Univ. of Rome (Italy); Carlson, J. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Gandalfi, S. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Pieper, S. [Argonne National Lab. (ANL), Argonne, IL (United States); Rocco, N. [Sapienza Univ. of Rome (Italy); Schiavilla, Rocco [Old Dominion Univ., Norfolk, VA (United States); Thomas Jefferson National Accelerator Facility (TJNAF), Newport News, VA (United States)
2016-03-01
Precise measurement of neutrino oscillations, and hence the determination of their masses demands a quantitative understanding of neutrino-nucleus interactions. To this aim, two-body meson-exchange currents have to be accounted for along within realistic models of nuclear dynamics. We summarize our progresses towards the construction of a consistent framework, based on quantum Monte Carlo methods and on the spectral function approach, that can be exploited to accurately describe neutrino interactions with atomic nuclei over the broad kinematical region covered by neutrino experiments.
Ab Initio Study of 40Ca with an Importance Truncated No-Core Shell Model
Energy Technology Data Exchange (ETDEWEB)
Roth, R; Navratil, P
2007-05-22
We propose an importance truncation scheme for the no-core shell model, which enables converged calculations for nuclei well beyond the p-shell. It is based on an a priori measure for the importance of individual basis states constructed by means of many-body perturbation theory. Only the physically relevant states of the no-core model space are considered, which leads to a dramatic reduction of the basis dimension. We analyze the validity and efficiency of this truncation scheme using different realistic nucleon-nucleon interactions and compare to conventional no-core shell model calculations for {sup 4}He and {sup 16}O. Then, we present the first converged calculations for the ground state of {sup 40}Ca within no-core model spaces including up to 16{h_bar}{Omega}-excitations using realistic low-momentum interactions. The scheme is universal and can be easily applied to other quantum many-body problems.
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
Chrysos, Michael; Dixneuf, Sophie; Rachet, Florent
2015-07-14
This is the long-overdue answer to the discrepancies observed between theory and experiment in Ar2 regarding both the isotropic Raman spectrum and the second refractivity virial coefficient, BR [Gaye et al., Phys. Rev. A 55, 3484 (1997)]. At the origin of this progress is the advent (posterior to 1997) of advanced computational methods for weakly interconnected neutral species at close separations. Here, we report agreement between the previously taken Raman measurements and quantum lineshapes now computed with the employ of large-scale CCSD or smartly constructed MP2 induced-polarizability data. By using these measurements as a benchmark tool, we assess the degree of performance of various other ab initio computed data for the mean polarizability α, and we show that an excellent agreement with the most recently measured value of BR is reached. We propose an even more refined model for α, which is solution of the inverse-scattering problem and whose lineshape matches exactly the measured spectrum over the entire frequency-shift range probed.
Energy Technology Data Exchange (ETDEWEB)
Chrysos, Michael, E-mail: michel.chrysos@univ-angers.fr; Rachet, Florent [LUNAM Université, Université d’Angers, CNRS UMR 6200, Laboratoire MOLTECH-Anjou, 2 Bd Lavoisier, 49045 Angers (France); Dixneuf, Sophie [Centre du Commissariat à l’Énergie Atomique de Grenoble, Laboratoire CEA-bioMérieux, Bât 40.20, 17 rue des Martyrs, 38054 Grenoble (France)
2015-07-14
This is the long-overdue answer to the discrepancies observed between theory and experiment in Ar{sub 2} regarding both the isotropic Raman spectrum and the second refractivity virial coefficient, B{sub R} [Gaye et al., Phys. Rev. A 55, 3484 (1997)]. At the origin of this progress is the advent (posterior to 1997) of advanced computational methods for weakly interconnected neutral species at close separations. Here, we report agreement between the previously taken Raman measurements and quantum lineshapes now computed with the employ of large-scale CCSD or smartly constructed MP2 induced-polarizability data. By using these measurements as a benchmark tool, we assess the degree of performance of various other ab initio computed data for the mean polarizability α, and we show that an excellent agreement with the most recently measured value of B{sub R} is reached. We propose an even more refined model for α, which is solution of the inverse-scattering problem and whose lineshape matches exactly the measured spectrum over the entire frequency-shift range probed.
THERMODYNAMIC MODELING AND FIRST-PRINCIPLES CALCULATIONS
Energy Technology Data Exchange (ETDEWEB)
Turchi, P; Abrikosov, I; Burton, B; Fries, S; Grimvall, G; Kaufman, L; Korzhavyi, P; Manga, R; Ohno, M; Pisch, A; Scott, A; Zhang, W
2005-12-15
The increased application of quantum mechanical-based methodologies to the study of alloy stability has required a re-assessment of the field. The focus is mainly on inorganic materials in the solid state. In a first part, after a brief overview of the so-called ab initio methods with their approximations, constraints, and limitations, recommendations are made for a good usage of first-principles codes with a set of qualifiers. Examples are given to illustrate the power and the limitations of ab initio codes. However, despite the ''success'' of these methodologies, thermodynamics of complex multi-component alloys, as used in engineering applications, requires a more versatile approach presently afforded within CALPHAD. Hence, in a second part, the links that presently exist between ab initio methodologies, experiments, and CALPHAD approach are examined with illustrations. Finally, the issues of dynamical instability and of the role of lattice vibrations that still constitute the subject of ample discussions within the CALPHAD community are revisited in the light of the current knowledge with a set of recommendations.
Guzzo, T; Mandaliti, W; Nepravishta, R; Aramini, A; Bodo, E; Daidone, I; Allegretti, M; Topai, A; Paci, M
2016-10-11
Inclusion of drugs in cyclodextrins (CDs) is a recognized tool for modifying several properties such as solubility, stability, bioavailability, and so on. The photoreactive behavior of the β-CD/ketoprofen (KP) complex upon UV exposure showed a significant increase in photodecarboxylation, whereas the secondary degradation products by hydroxylation of the benzophenone moiety were inhibited. The results may account for an improvement of KP photophysical properties upon inclusion, thus better fostering its topical use. To correlate the structural details of the inclusion with these results, an NMR spectroscopic study of KP upon inclusion in β-CD was performed. Effects of the magnetically anisotropic centers of KP, changing their orientations upon inclusion and giving chemical shift variations, were specifically correlated with the results of the molecular dynamic simulations and ab initio calculations. In the large variety of papers focusing on the structural analysis of β-CD complexes, this work represents one of the few examples in which a detailed analysis of these simultaneous upfield-downfield NMR shifts of the same aromatic molecule upon inclusion is reported. Interestingly, the results demonstrate that the observed upfield and downfield shifts upon inclusion are not related to any direct magnetic role of β-CD. The conformational change of KP upon the inclusion process consists of a slight reduction in the angle between the two phenyl rings and in a remarkable reduction in the mobility of the carboxyl group, the latter being one of the main contributions to the NMR resonance shifts. These structural details help in understanding the features of the inclusion complex and, eventually, the driving force for its formation.
International Nuclear Information System (INIS)
Kolar, J.; Strizik, L.; Kohoutek, T.; Wagner, T.; Voyiatzis, G. A.; Chrissanthopoulos, A.; Yannopoulos, S. N.
2013-01-01
Photostructural changes—the hallmark of non-crystalline chalcogenides—are in essence the basis of a number of photoinduced effects, i.e., changes of their physical properties, which are exploited in a variety of applications, especially in photonics and optoelectronics. Despite the vast number of investigations of photostructural changes, there is currently lack of systematic studies on how the thermal history, which affects glass structure, modifies the extent of photostructural changes. In this article, we study the role of thermal history on photostructural changes in glassy As 15 S 85 . This particular sulfur-rich composition has been chosen based on the colossal photostructural response it exhibits under near-band gap light irradiation, which inherently originates from its nanoscale phase-separated nature. To control the thermal history, the glass was quenched to various temperatures and each of these quenched products was annealed under four different conditions. Off-resonant Raman scattering was used to study the equilibrium study of each product. Structural changes of interest involve changes of the sulfur atoms participating into S 8 rings and S n chains. Their ratio was found to depend on quenching/annealing conditions. Near-band gap light was used to perturb the rings-to-chain ratio and at the same time to record these changes through Raman scattering, revealing an intricate behavior of photostructural changes. Ab initio calculations were employed to determine the stability of various sulfur clusters/molecules thus aiding the correlation of the particular photo-response of glassy As 15 S 85 with its structural constituents
Precipitates/Salts Model Sensitivity Calculation
Energy Technology Data Exchange (ETDEWEB)
P. Mariner
2001-12-20
The objective and scope of this calculation is to assist Performance Assessment Operations and the Engineered Barrier System (EBS) Department in modeling the geochemical effects of evaporation on potential seepage waters within a potential repository drift. This work is developed and documented using procedure AP-3.12Q, ''Calculations'', in support of ''Technical Work Plan For Engineered Barrier System Department Modeling and Testing FY 02 Work Activities'' (BSC 2001a). The specific objective of this calculation is to examine the sensitivity and uncertainties of the Precipitates/Salts model. The Precipitates/Salts model is documented in an Analysis/Model Report (AMR), ''In-Drift Precipitates/Salts Analysis'' (BSC 2001b). The calculation in the current document examines the effects of starting water composition, mineral suppressions, and the fugacity of carbon dioxide (CO{sub 2}) on the chemical evolution of water in the drift.
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.
International Nuclear Information System (INIS)
Churakov, S.V.
2005-01-01
Pyrophyllite, Al 2 [Si 4 O 10 ](OH) 2 , is the simplest structural prototype for 2:1 dioctahedral phyllosilicate. Because the net electric charge in pyrophyllite is zero, it is the best candidate for investigating the non electrostatic contribution to sorption and transport phenomena in clays. Using ab-initio simulations, we have investigated the reactivity and structure of the water-solid interface on the basal plane and edge sites of pyrophyllite. The calculations predict slightly hydrophobic behaviour of the basal plane. For the high water coverage (100), (110) and (-110), lateral facets have a lower energy than for the (010), (130) and (-130) surfaces. Analysis of the surface reactivity reveals that the =Al-OH groups are most easily protonated on the (010), (130) and (-130) facets. The =Al-O-Si= sites will be protonated on the (100), (130), (110), (-110) and (-130) surfaces. The =Al-OH 2 complexes are more easily de-protonated than the =Si-OH and =Al-OH sites. A spontaneous, reversible exchange of the protons between the solution and the edge sites has been observed in ab-initio molecular dynamics simulations at 300 K. Such near-surface proton diffusion may result in a significant contribution to the diffusion coefficients measured in neutron scattering experiments. (author)
Govind Rajan, Ananth; Strano, Michael S; Blankschtein, Daniel
2018-04-05
Hexagonal boron nitride (hBN) is an up-and-coming two-dimensional material, with applications in electronic devices, tribology, and separation membranes. Herein, we utilize density-functional-theory-based ab initio molecular dynamics (MD) simulations and lattice dynamics calculations to develop a classical force field (FF) for modeling hBN. The FF predicts the crystal structure, elastic constants, and phonon dispersion relation of hBN with good accuracy and exhibits remarkable agreement with the interlayer binding energy predicted by random phase approximation calculations. We demonstrate the importance of including Coulombic interactions but excluding 1-4 intrasheet interactions to obtain the correct phonon dispersion relation. We find that improper dihedrals do not modify the bulk mechanical properties and the extent of thermal vibrations in hBN, although they impact its flexural rigidity. Combining the FF with the accurate TIP4P/Ice water model yields excellent agreement with interaction energies predicted by quantum Monte Carlo calculations. Our FF should enable an accurate description of hBN interfaces in classical MD simulations.
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...
EARTHWORK VOLUME CALCULATION FROM DIGITAL TERRAIN MODELS
Directory of Open Access Journals (Sweden)
JANIĆ Milorad
2015-06-01
Full Text Available Accurate calculation of cut and fill volume has an essential importance in many fields. This article shows a new method, which has no approximation, based on Digital Terrain Models. A relatively new mathematical model is developed for that purpose, which is implemented in the software solution. Both of them has been tested and verified in the praxis on several large opencast mines. This application is developed in AutoLISP programming language and works in AutoCAD environment.
Hybrid reduced order modeling for assembly calculations
Energy Technology Data Exchange (ETDEWEB)
Bang, Y.; Abdel-Khalik, H. S. [North Carolina State University, Raleigh, NC (United States); Jessee, M. A.; Mertyurek, U. [Oak Ridge National Laboratory, Oak Ridge, TN (United States)
2013-07-01
While the accuracy of assembly calculations has considerably improved due to the increase in computer power enabling more refined description of the phase space and use of more sophisticated numerical algorithms, the computational cost continues to increase which limits the full utilization of their effectiveness for routine engineering analysis. Reduced order modeling is a mathematical vehicle that scales down the dimensionality of large-scale numerical problems to enable their repeated executions on small computing environment, often available to end users. This is done by capturing the most dominant underlying relationships between the model's inputs and outputs. Previous works demonstrated the use of the reduced order modeling for a single physics code, such as a radiation transport calculation. This manuscript extends those works to coupled code systems as currently employed in assembly calculations. Numerical tests are conducted using realistic SCALE assembly models with resonance self-shielding, neutron transport, and nuclides transmutation/depletion models representing the components of the coupled code system. (authors)
Model and calculations for net infiltration
International Nuclear Information System (INIS)
Childs, S.W.; Long, A.
1992-01-01
In this paper a conceptual model for calculating net infiltration is developed and implemented. It incorporates the following important factors: viability of climate for the next 10,000 years, areal viability of net infiltration, and important soil/plant factors that affect the soil water budget of desert soils. Model results are expressed in terms of occurrence probabilities for time periods. In addition the variability of net infiltration is demonstrated both for change with time and differences among three soil/hydrologic units present at the site modeled
Mikaeilzadeh, L.; Pirgholi, M.; Tavana, A.
2018-05-01
Based on the ab-initio non-equilibrium Green's function (NEGF) formalism based on the density functional theory (DFT), we have studied the electron transport in the all-Heusler device Co2CrSi/Cu2CrAl/Co2CrSi. Results show that the calculated transmission spectra is very sensitive to the structural parameters and the interface. Also, we obtain a range for the thickness of the spacer layer for which the MR effect is optimum. Calculations also show a perfect GMR effect in this device.
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.
Reactor Thermal Hydraulic Numerical Calculation And Modeling
International Nuclear Information System (INIS)
Duong Ngoc Hai; Dang The Ba
2008-01-01
In the paper the results of analysis of thermal hydraulic state models using the numerical codes such as COOLOD, EUREKA and RELAP5 for simulation of the reactor thermal hydraulic states are presented. The calculations, analyses of reactor thermal hydraulic state and safety were implemented using different codes. The received numerical results, which were compared each to other, to experiment measurement of Dalat (Vietnam) research reactor and published results, show their appropriateness and capacity for analyses of different appropriate cases. (author)
Energy Technology Data Exchange (ETDEWEB)
Singh, Jaswinder; Raabe, Gerhard [Inst. fuer Organische Chemie, RWTH Aachen Univ. (Germany); Wang Yuekui [Key Lab. of Chemical Biology and Molecular Engineering of the Education Ministry, Inst. of Molecular Science, Shanxi Univ., Taiyuan, SH (China)
2010-01-15
Quantum-chemical ab initio calculations up to the ZPE+CCSD(T)/aug-cc-pVTZ/MP2/6-311++G** level were performed on three possible structural isomers of diborabenzene (C{sub 4}H{sub 4}B{sub 2}). All three molecules were found to be local minima on the C{sub 4}H{sub 4}B{sub 2} energy surface and to have closed shell singlet ground states. While the ground states of the 1,3- and 1,4-isomer are planar and of C{sub 2v} and D{sub 2h} symmetry, respectively, 1,2-diborabenzene is non-planar with a C{sub 2} axis passing through the center of the BB bond and the middle of the opposite carbon-carbon bond as the only symmetry element. The energetically most favourable 1,3-diborabenzene was found to be about 19 and 36 kcal/mol lower in energy than the 1,2- and the 1,4-isomer. Planar 1,3- and 1,4-diborabenzene have three doubly occupied {pi} orbitals while non-planar 1,2-diborabenzene has also three doubly occupied orbitals which can be derived from the {pi} orbitals of its 3.7 kcal/mol energetically less favourable planar form (''{pi}=like'' orbitals). The lowest unoccupied orbitals of all three isomers have {sigma} symmetry with large coefficients at the two boron atoms. These orbitals are lower in energy than the lowest unoccupied molecular orbitals (LUMOs) of e. g. benzene and pyridine and might cause pronounced acceptor properties which could be one of the reasons for the elusiveness of the title compounds. The results of bond separation reactions show that cyclic conjugation stabilizes all three diborabenzenes relative to their isolated fragments. The most effective stabilization energy of about 24 kcal/mol was found for the energetically lowest 1,3-isomer. This value amounts to approximately one third of the experimental value for the bond separation energy of pyridine. In all cases the energetically lowest triplet states are significantly (16 - 24 kcal/mol) higher in energy than the singlet ground states. Also among the triplets the 1,3-isomer is the
Energy Technology Data Exchange (ETDEWEB)
Pavloudis, Th. [Department of Physics, Aristotle University of Thessaloniki, GR-54124 Thessaloniki (Greece); Zervos, M. [Nanostructured Materials and Devices Laboratory, Department of Mechanical and Manufacturing Engineering, PO Box 20537, Nicosia 1678 (Cyprus); Komninou, Ph. [Department of Physics, Aristotle University of Thessaloniki, GR-54124 Thessaloniki (Greece); Kioseoglou, J., E-mail: sifisl@auth.gr [Department of Physics, Aristotle University of Thessaloniki, GR-54124 Thessaloniki (Greece)
2016-08-31
We carry out ab initio electronic structure calculations of (Si{sub x}Sn{sub 1−x}){sub 3}N{sub 4} using density functional theory with projector augmented-wave potentials under the generalized gradient approximation. We find that the energetically favorable structure of Sn{sub 3}N{sub 4} is the face-centered cubic spinel structure, followed by the hexagonal structure which has energy band gaps of 1.85 eV and 1.44 eV respectively. The (Si{sub x}Sn{sub 1−x}){sub 3}N{sub 4} ternary compound can exhibit both cubic and hexagonal crystal structures over the full range of x. However, the cubic structure is found to be energetically favorable for x < 0.3 above which the hexagonal structure of (Si{sub x}Sn{sub 1−x}){sub 3}N{sub 4} dominates. The energy band gap can be tuned continuously from 1.44 eV up to 5.8 eV in the case of the hexagonal crystal structure of (Si{sub x}Sn{sub 1−x}){sub 3}N{sub 4} and from 1.85 eV to 4.82 eV in the case of cubic (Si{sub x}Sn{sub 1−x}){sub 3}N{sub 4}. Nevertheless the energy gap of (Si{sub x}Sn{sub 1−x}){sub 3}N{sub 4} is direct only for x < 0.3 when it is cubic and for x < 0.5 when hexagonal. - Highlights: • (Si{sub x}Sn{sub 1−x}){sub 3}N{sub 4} exhibits both cubic and hexagonal crystal structures. • The cubic structure is favorable for x < 0.3 and the hexagonal structure for x > 0.3. • The bandgap of hexagonal (Si{sub x}Sn{sub 1−x}){sub 3}N{sub 4} may be tuned from 1.44 eV up to 5.8 eV. • The bandgap may be tuned from 1.85 eV to 4.82 eV for the cubic (Si{sub x}Sn{sub 1−x}){sub 3}N{sub 4}. • Bandgaps are direct for x < 0.3 (cubic) and for x < 0.5 3 (hexagonal (Si{sub x}Sn{sub 1−x}){sub 3}N{sub 4}).
SurfKin: an ab initio kinetic code for modeling surface reactions.
Le, Thong Nguyen-Minh; Liu, Bin; Huynh, Lam K
2014-10-05
In this article, we describe a C/C++ program called SurfKin (Surface Kinetics) to construct microkinetic mechanisms for modeling gas-surface reactions. Thermodynamic properties of reaction species are estimated based on density functional theory calculations and statistical mechanics. Rate constants for elementary steps (including adsorption, desorption, and chemical reactions on surfaces) are calculated using the classical collision theory and transition state theory. Methane decomposition and water-gas shift reaction on Ni(111) surface were chosen as test cases to validate the code implementations. The good agreement with literature data suggests this is a powerful tool to facilitate the analysis of complex reactions on surfaces, and thus it helps to effectively construct detailed microkinetic mechanisms for such surface reactions. SurfKin also opens a possibility for designing nanoscale model catalysts. Copyright © 2014 Wiley Periodicals, Inc.
Energy Technology Data Exchange (ETDEWEB)
Wiengarten, T.; Fichtner, H.; Kleimann, J.; Scherer, K. [Institut für Theoretische Physik IV, Ruhr-Universität Bochum (Germany); Oughton, S. [Department of Mathematics, University of Waikato, Hamilton 3240 (New Zealand); Engelbrecht, N. E. [Center for Space Research, North-West University, Potchefstroom 2520 (South Africa)
2016-12-10
We extend a two-component model for the evolution of fluctuations in the solar wind plasma so that it is fully three-dimensional (3D) and also coupled self-consistently to the large-scale magnetohydrodynamic equations describing the background solar wind. The two classes of fluctuations considered are a high-frequency parallel-propagating wave-like piece and a low-frequency quasi-two-dimensional component. For both components, the nonlinear dynamics is dominanted by quasi-perpendicular spectral cascades of energy. Driving of the fluctuations by, for example, velocity shear and pickup ions is included. Numerical solutions to the new model are obtained using the Cronos framework, and validated against previous simpler models. Comparing results from the new model with spacecraft measurements, we find improved agreement relative to earlier models that employ prescribed background solar wind fields. Finally, the new results for the wave-like and quasi-two-dimensional fluctuations are used to calculate ab initio diffusion mean-free paths and drift lengthscales for the transport of cosmic rays in the turbulent solar wind.
International Nuclear Information System (INIS)
Wiengarten, T.; Fichtner, H.; Kleimann, J.; Scherer, K.; Oughton, S.; Engelbrecht, N. E.
2016-01-01
We extend a two-component model for the evolution of fluctuations in the solar wind plasma so that it is fully three-dimensional (3D) and also coupled self-consistently to the large-scale magnetohydrodynamic equations describing the background solar wind. The two classes of fluctuations considered are a high-frequency parallel-propagating wave-like piece and a low-frequency quasi-two-dimensional component. For both components, the nonlinear dynamics is dominanted by quasi-perpendicular spectral cascades of energy. Driving of the fluctuations by, for example, velocity shear and pickup ions is included. Numerical solutions to the new model are obtained using the Cronos framework, and validated against previous simpler models. Comparing results from the new model with spacecraft measurements, we find improved agreement relative to earlier models that employ prescribed background solar wind fields. Finally, the new results for the wave-like and quasi-two-dimensional fluctuations are used to calculate ab initio diffusion mean-free paths and drift lengthscales for the transport of cosmic rays in the turbulent solar wind.
Ouk, Chanda-Malis; Zvereva-Loëte, Natalia; Scribano, Yohann; Bussery-Honvault, Béatrice
2012-10-30
Multireference single and double configuration interaction (MRCI) calculations including Davidson (+Q) or Pople (+P) corrections have been conducted in this work for the reactants, products, and extrema of the doublet ground state potential energy surface involved in the N((2)D) + CH(4) reaction. Such highly correlated ab initio calculations are then compared with previous PMP4, CCSD(T), W1, and DFT/B3LYP studies. Large relative differences are observed in particular for the transition state in the entrance channel resolving the disagreement between previous ab initio calculations. We confirm the existence of a small but positive potential barrier (3.86 ± 0.84 kJ mol(-1) (MR-AQCC) and 3.89 kJ mol(-1) (MRCI+P)) in the entrance channel of the title reaction. The correlation is seen to change significantly the energetic position of the two minima and five saddle points of this system together with the dissociation channels but not their relative order. The influence of the electronic correlation into the energetic of the system is clearly demonstrated by the thermal rate constant evaluation and it temperature dependance by means of the transition state theory. Indeed, only MRCI values are able to reproduce the experimental rate constant of the title reaction and its behavior with temperature. Similarly, product branching ratios, evaluated by means of unimolecular RRKM theory, confirm the NH production of Umemoto et al., whereas previous works based on less accurate ab initio calculations failed. We confirm the previous findings that the N((2)D) + CH(4) reaction proceeds via an insertion-dissociation mechanism and that the dominant product channels are CH(2)NH + H and CH(3) + NH. Copyright © 2012 Wiley Periodicals, Inc.
Energy Technology Data Exchange (ETDEWEB)
Hellmann, Robert
2009-06-16
Thermophysical properties of the pure gases helium, neon, methane and water vapor were calculated for low densities over wide temperature ranges. Statistical thermodynamics was used for the determination of the pressure virial coefficients. The kinetic theory of gases was utilized for the calculation of the transport and relaxation properties. So far kinetic theory was limited to linear molecules and has now been extended to molecules of arbitrary geometry to enable calculations on methane and water vapor. The interaction potentials, which are needed for all computations, were determined for helium, neon and methane from the supermolecular approach using quantum chemical ab initio methods. For water the interaction potentials were taken from the literature. The calculated values of the thermophysical properties for the four gases show very good agreement with the best experimental data. At very low and very high temperatures the theoretical values are more accurate than experimental data. (orig.)
Matrix model calculations beyond the spherical limit
International Nuclear Information System (INIS)
Ambjoern, J.; Chekhov, L.; Kristjansen, C.F.; Makeenko, Yu.
1993-01-01
We propose an improved iterative scheme for calculating higher genus contributions to the multi-loop (or multi-point) correlators and the partition function of the hermitian one matrix model. We present explicit results up to genus two. We develop a version which gives directly the result in the double scaling limit and present explicit results up to genus four. Using the latter version we prove that the hermitian and the complex matrix model are equivalent in the double scaling limit and that in this limit they are both equivalent to the Kontsevich model. We discuss how our results away from the double scaling limit are related to the structure of moduli space. (orig.)
Development of Dynamic Environmental Effect Calculation Model
International Nuclear Information System (INIS)
Jeong, Chang Joon; Ko, Won Il
2010-01-01
The short-term, long-term decay heat, and radioactivity are considered as main environmental parameters of SF and HLA. In this study, the dynamic calculation models for radioactivity, short-term decay heat, and long-term heat load of the SF are developed and incorporated into the Doneness code. The spent fuel accumulation has become a major issue for sustainable operation of nuclear power plants. If a once-through fuel cycle is selected, the SF will be disposed into the repository. Otherwise, in case of fast reactor or reuse cycle, the SF will be reprocessed and the high level waste will be disposed
Cost Calculation Model for Logistics Service Providers
Directory of Open Access Journals (Sweden)
Zoltán Bokor
2012-11-01
Full Text Available The exact calculation of logistics costs has become a real challenge in logistics and supply chain management. It is essential to gain reliable and accurate costing information to attain efficient resource allocation within the logistics service provider companies. Traditional costing approaches, however, may not be sufficient to reach this aim in case of complex and heterogeneous logistics service structures. So this paper intends to explore the ways of improving the cost calculation regimes of logistics service providers and show how to adopt the multi-level full cost allocation technique in logistics practice. After determining the methodological framework, a sample cost calculation scheme is developed and tested by using estimated input data. Based on the theoretical findings and the experiences of the pilot project it can be concluded that the improved costing model contributes to making logistics costing more accurate and transparent. Moreover, the relations between costs and performances also become more visible, which enhances the effectiveness of logistics planning and controlling significantly
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 Modeling of Thermomechanical Properties of Mo-Based Alloys for Fossil Energy Conversion
Energy Technology Data Exchange (ETDEWEB)
Ching, Wai-Yim
2013-12-31
In this final scientific/technical report covering the period of 3.5 years started on July 1, 2011, we report the accomplishments on the study of thermo-mechanical properties of Mo-based intermetallic compounds under NETL support. These include computational method development, physical properties investigation of Mo-based compounds and alloys. The main focus is on the mechanical and thermo mechanical properties at high temperature since these are the most crucial properties for their potential applications. In particular, recent development of applying ab initio molecular dynamic (AIMD) simulations to the T1 (Mo{sub 5}Si{sub 3}) and T2 (Mo{sub 5}SiB{sub 2}) phases are highlighted for alloy design in further improving their properties.
International Nuclear Information System (INIS)
Vincent, E.; Domain, C.; Vincent, E.; Becquart, C.S.
2008-01-01
Full text of publication follows. The embrittlement and the hardening of pressure vessel steels under radiation has been correlated with the presence solutes such as Cu, Ni, Mn and Si. Indeed it has been observed that under irradiation, these solutes tend to gather to form more or less dilute clusters. The interactions of these solutes with radiation induced point defects thus need to be characterised properly in order to understand the elementary mechanisms behind the formation of these clusters. Ab initio calculations based on the density functional theory have been performed to determine the interactions of point defects (vacancies as well as interstitials) with solute atoms in dilute FeX alloys (X Cu, Mn, Ni or Si) in order to build a database used to parameterize an atomic kinetic Monte Carlo model. The model has been applied to simulate thermal ageing as well as irradiation conditions in dilute Fe-CuNiMnSi alloys. Results obtained with this model will be presented. (authors)
Ab initio approach to the non-perturbative scalar Yukawa model
Li, YangDepartment of Physics and Astronomy, Iowa State University, Ames, IA, 50011, USA; Karmanov, V.A.(Lebedev Physical Institute, Leninsky Prospekt 53, Moscow, 119991, Russia); Maris, P.(Department of Physics and Astronomy, Iowa State University, Ames, IA, 50011, USA); Vary, J.P.(Department of Physics and Astronomy, Iowa State University, Ames, IA, 50011, USA)
2015-01-01
We report on the first non-perturbative calculation of the scalar Yukawa model in the single-nucleon sector up to four-body Fock sector truncation (one "scalar nucleon" and three "scalar pions"). The light-front Hamiltonian approach with a systematic non-perturbative renormalization is applied. We study the $n$-body norms and the electromagnetic form factor. We find that the one- and two-body contributions dominate up to coupling $\\alpha \\approx 1.7$. As we approach the coupling $\\alpha \\appr...
Effective hamiltonian calculations using incomplete model spaces
International Nuclear Information System (INIS)
Koch, S.; Mukherjee, D.
1987-01-01
It appears that the danger of encountering ''intruder states'' is substantially reduced if an effective hamiltonian formalism is developed for incomplete model spaces (IMS). In a Fock-space approach, the proof a ''connected diagram theorem'' is fairly straightforward with exponential-type of ansatze for the wave-operator W, provided the normalization chosen for W is separable. Operationally, one just needs a suitable categorization of the Fock-space operators into ''diagonal'' and ''non-diagonal'' parts that is generalization of the corresponding procedure for the complete model space. The formalism is applied to prototypical 2-electron systems. The calculations have been performed on the Cyber 205 super-computer. The authors paid special attention to an efficient vectorization for the construction and solution of the resulting coupled non-linear equations
Model for fission-product calculations
International Nuclear Information System (INIS)
Smith, A.B.
1984-01-01
Many fission-product cross sections remain unmeasurable thus considerable reliance must be placed upon calculational interpolation and extrapolation from the few available measured cross sections. The vehicle, particularly for the lighter fission products, is the conventional optical-statistical model. The applied goals generally are: capture cross sections to 7 to 10% accuracies and inelastic-scattering cross sections to 25 to 50%. Comparisons of recent evaluations and experimental results indicate that these goals too often are far from being met, particularly in the area of inelastic scattering, and some of the evaluated fission-product cross sections are simply physically unreasonable. It is difficult to avoid the conclusion that the models employed in many of the evaluations are inappropriate and/or inappropriately used. In order to alleviate the above unfortunate situations, a regional optical-statistical (OM) model was sought with the goal of quantitative prediction of the cross sections of the lighter-mass (Z = 30-51) fission products. The first step toward that goal was the establishment of a reliable experimental data base consisting of energy-averaged neutron total and differential-scattering cross sections. The second step was the deduction of a regional model from the experimental data. It was assumed that a spherical OM is appropriate: a reasonable and practical assumption. The resulting OM then was verified against the measured data base. Finally, the physical character of the regional model is examined
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)
Nicolaides, C.A.; Mercouris, T.
1996-01-01
The detailed time dependence of the decay of a three-electron autoionizing state close to threshold has been obtained ab initio by solving the time-dependent Schrodinger equation (TDSE). The theory allows the definition and computation of energy-dependent matrix elements in terms of the appropriate N-electron wavefunctions, representing the localized initial state, Ψ O , the stationary scattering states of the continuous spectrum, U( e psilon ) , and the localized excited states, Ψ n , of the effective Hamiltonian QHQ, where Q ''ident to'' |Ψ O > O |. The time-dependent wavefunction is expanded over these states and the resulting coupled equations with time-dependent coefficients (in the thousands) are solved to all orders by a Taylor series expansion technique. The robustness of the method was verified by using a model interaction in analytic form and comparing the results from two different methods for integrating the TDSE (appendix B). For the physically relevant application, the chosen state was the He - 1s2p 24 P shape resonance, about which very accurate theoretical and experimental relevant information exists. Calculations using accurate wavefunctions and an energy grid of 20.000 points in the range 0.0-21.77 eV show that the effective interaction depends on energy in a state-specific manner, thereby leading to state-specific characteristics of non-exponential decay over about 6 x 10 4 au of time, from which a width of Γ = 5.2 meV and a lifetime of 1.26 x 10 -13 s is deduced. The results suggest that either in this state or in other autoionizing states close to threshold, NED may have sufficient presence to make the violation of the law of exponential decay observable. (Author)
Energy Technology Data Exchange (ETDEWEB)
Lindenmaier, Rodica; Scharko, Nicole K.; Tonkyn, Russell G.; Nguyen, Kiet T.; Williams, Stephen D.; Johnson, Timothy J.
2017-07-25
Xylenes contain a blend of the ortho-, meta-, and para- isomers, and all are abundant contaminants in the ground, surface waters, and air. To better characterize xylene and to better enable its detection, we report high quality quantitative vapor-phase infrared spectra of all three isomers over the 540-6500 cm^{-1} range. All fundamental vibrational modes are assigned based on these vapor-phase infrared spectra, liquid-phase infrared and Raman spectra, along with density functional theory (DFT), ab initio MP2 and high energy-accuracy compound theoretical model (W1BD) calculations. Both MP2 and DFT predict a single conformer with C_{2v} symmetry for ortho-xylene, and two conformers each for meta- and para-xylene, depending on the preferred orientations of the methyl groups. For meta-xylene the two conformers have C_{s} and C_{2} symmetry, and for para-xylene these conformers have C_{2v} or C_{2h} symmetry. Since the relative population of the two conformers is approximately 50% for both isomers and predicted frequencies and intensities are very similar for each conformer, we made an arbitrary choice to discuss the C_{s} conformer for meta-xylene and the C_{2v} conformer for para-xylene. We report integrated band intensities for all isomers. Using the quantitative infrared data, we determine the global warming potential values of each isomer and discuss potential bands for atmospheric monitoring.
Acceleration methods and models in Sn calculations
International Nuclear Information System (INIS)
Sbaffoni, M.M.; Abbate, M.J.
1984-01-01
In some neutron transport problems solved by the discrete ordinate method, it is relatively common to observe some particularities as, for example, negative fluxes generation, slow and insecure convergences and solution instabilities. The commonly used models for neutron flux calculation and acceleration methods included in the most used codes were analyzed, in face of their use in problems characterized by a strong upscattering effect. Some special conclusions derived from this analysis are presented as well as a new method to perform the upscattering scaling for solving the before mentioned problems in this kind of cases. This method has been included in the DOT3.5 code (two dimensional discrete ordinates radiation transport code) generating a new version of wider application. (Author) [es
Mishra, S N
2009-03-18
Applying the time differential perturbed angular correlation (TDPAC) technique we have measured electric and magnetic hyperfine fields of the (111)Cd impurity in equi-atomic rare-earth intermetallic alloys RScGe (R = Ce, Pr and Gd) showing antiferro- and ferromagnetism with unusually high ordering temperatures. The Cd nuclei occupying the Sc site show high magnetic hyperfine fields with saturation values B(hf)(0) = 21 kG, 45 kG and 189 kG in CeScGe, PrScGe and GdScGe, respectively. By comparing the results with the hyperfine field data of Cd in rare-earth metals and estimations from the RKKY model, we find evidence for the presence of additional spin density at the probe nucleus, possibly due to spin polarization of Sc d band electrons. The principal electric field gradient component V(zz) in CeScGe, PrScGe and GdScGe has been determined to be 5.3 × 10(21) V m(-2), 5.5 × 10(21) V m(-2) and 5.6 × 10(21) V m(-2), respectively. Supplementing the experimental measurements, we have carried out ab initio calculations for pure and Cd-doped RScGe compounds with R = Ce, Pr, Nd and Gd using the full potential linearized augmented plane wave (FLAPW) method based on density functional theory (DFT). From the total energies calculated with and without spin polarization we find ferrimagnetic ground states for CeScGe and PrScGe while NdScGe and GdScGe are ferromagnetic. In addition, we find a sizable magnetic moment at the Sc site, increasing from ≈0.10 μ(B) in CeScGe to ≈0.3 μ(B) in GdScGe, confirming the spin polarization of Sc d band electrons. The calculated electric field gradient and magnetic hyperfine fields of the Cd impurity closely agree with the experimental values. We believe spin polarization of Sc 3d band electrons, strongly hybridized with spin polarized 5d band electrons of the rare-earth, enables a long range Ruderman-Kittel-Kasuya-Yosida (RKKY) interaction between RE 4f moments which in turn leads to high magnetic ordering temperatures in
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.
Ab-initio modelling of thermodynamics and kinetics of point defects in indium oxide
International Nuclear Information System (INIS)
Agoston, Peter; Klein, Andreas; Albe, Karsten; Erhart, Paul
2008-01-01
The electrical and optical properties of indium oxide films strongly vary with the processing parameters. Especially the oxygen partial pressure and temperature determine properties like electrical conductivity, composition and transparency. Since this material owes its remarkable properties like the intrinsic n-type conductivity to its defect chemistry, it is important to understand both, the equilibrium defect thermodynamics and kinetics of the intrinsic point defects. In this contribution we present a defect model based on DFT total energy calculations using the GGA+U method. Further, the nudged elastic band method is employed in order to obtain a set of migration barriers for each defect species. Due to the complicated crystal structure of indium oxide a Kinetic Monte-Carlo algorithm was implemented, which allows to determine diffusion coefficients. The bulk tracer diffusion constant is predicted as a function of oxygen partial pressure, Fermi level and temperature for the pure material
Valdes, Mateo; Dufour, Marianne; Lazauskas, Rimantas; Hervieux, Paul-Antoine
2018-01-01
The ab initio method based on the Faddeev-Merkuriev equations is used to calculate cross sections involving the (p ¯,e+,e-) three-body system, with an emphasis on antihydrogen formation (H ¯) via antiproton (p ¯) scattering on positronium. This system is studied in the energy range between the e-+H ¯(n =2 ) and the e-+H ¯(n =3 ) thresholds, where precisely calculated cross sections can be useful for future experiments (GBAR, AEGIS, etc.) aiming to produce antihydrogen atoms. A special treatment is developed to take into account the long-range charge-dipole interaction effect on the wave function. Emphasis is placed on the impact of Feshbach resonances and Gailitis-Damburg oscillations appearing in the vicinity of the p ¯+Ps (n =2 ) threshold.
Kłos, Jacek; Alexander, Millard H.; Kumar, Praveen; Poirier, Bill; Jiang, Bin; Guo, Hua
2016-05-01
We report new and more accurate adiabatic potential energy surfaces (PESs) for the ground X˜ 1A1 and electronically excited C˜ 1B2(21A') states of the SO2 molecule. Ab initio points are calculated using the explicitly correlated internally contracted multi-reference configuration interaction (icMRCI-F12) method. A second less accurate PES for the ground X ˜ state is also calculated using an explicitly correlated single-reference coupled-cluster method with single, double, and non-iterative triple excitations [CCSD(T)-F12]. With these new three-dimensional PESs, we determine energies of the vibrational bound states and compare these values to existing literature data and experiment.
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
Helium behavior in oxide dispersion strengthened (ODS) steel: Insights from ab initio modeling
Sun, Dan; Li, Ruihuan; Ding, Jianhua; Huang, Shaosong; Zhang, Pengbo; Lu, Zheng; Zhao, Jijun
2018-02-01
Using first-principles calculations, we systemically investigate the energetics and stability behavior of helium (He) atoms and small Hen (n = 2-4) clusters inside oxide dispersion strengthened (ODS) steel, as well as the incorporation of large amount of He atoms inside Y2O3 crystal. From the energetic point of view, He atom inside Y2O3 cluster is most stable, followed by the interstitial sites at the α-Fe/Y2O3 interface, and the tetrahedral interstitial sites inside α-Fe region. We further consider Hen (n = 2-4) clusters at the tetrahedral interstitial site surrounded by four Y atoms, which is the most stable site in the ODS steel model. The incorporation energies of all these Hen clusters are lower than that of single He atom in α-Fe, while the binding energy between two He atoms is relatively small. With insertion of 15 He atoms into 80-atom unit cell of Y2O3 crystal, the incorporation energy of He atoms is still lower than that of He4 cluster in α-Fe crystal. These theoretical results suggest that He atoms tend to aggregate inside Y2O3 clusters or at the α-Fe/Y2O3 interface, which is beneficial to prevent the He embrittlement in ODS steels.
Li, Mu; Wang, Weiyu; Yin, Panchao
2018-05-02
Herein, we reported a general protocol for an ab initio modeling approach to deduce structure information of polyoxometalates (POMs) in solutions from scattering data collected by the small-angle X-ray scattering (SAXS) technique. To validate the protocol, the morphologies of a serious of known POMs in either aqueous or organic solvents were analyzed. The obtained particle morphologies were compared and confirmed with previous reported crystal structures. To extend the feasibility of the protocol to an unknown system of aqueous solutions of Na 2 MoO 4 with the pH ranging from -1 to 8.35, the formation of {Mo 36 } clusters was probed, identified, and confirmed by SAXS. The approach was further optimized with a multi-processing capability to achieve fast analysis of experimental data, thereby, facilitating in situ studies of formations of POMs in solutions. The advantage of this approach is to generate intuitive 3D models of POMs in solutions without confining information such as symmetries and possible sizes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Modeling of He-N(+) clusters. II. Calculation of He-3(+) vibrational spectrum
Czech Academy of Sciences Publication Activity Database
Karlický, F.; Lepetit, B.; Kalus, R.; Paidarová, Ivana; Gadéa, F. X.
2008-01-01
Roč. 128, č. 12 (2008), 124303-1-11 ISSN 0021-9606 R&D Projects: GA ČR GA203/04/2146 Institutional research plan: CEZ:AV0Z40400503 Keywords : potential energy surface * ab-initio calculation * near-infrared spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.149, year: 2008
Qu, Chen; Bowman, Joel M
2016-09-14
We report a full-dimensional, permutationally invariant potential energy surface (PES) for the cyclic formic acid dimer. This PES is a least-squares fit to 13475 CCSD(T)-F12a/haTZ (VTZ for H and aVTZ for C and O) energies. The energy-weighted, root-mean-square fitting error is 11 cm -1 and the barrier for the double-proton transfer on the PES is 2848 cm -1 , in good agreement with the directly-calculated ab initio value of 2853 cm -1 . The zero-point vibrational energy of 15 337 ± 7 cm -1 is obtained from diffusion Monte Carlo calculations. Energies of fundamentals of fifteen modes are calculated using the vibrational self-consistent field and virtual-state configuration interaction method. The ground-state tunneling splitting is computed using a reduced-dimensional Hamiltonian with relaxed potentials. The highest-level, four-mode coupled calculation gives a tunneling splitting of 0.037 cm -1 , which is roughly twice the experimental value. The tunneling splittings of (DCOOH) 2 and (DCOOD) 2 from one to three mode calculations are, as expected, smaller than that for (HCOOH) 2 and consistent with experiment.
Concurrent algorithms for nuclear shell model calculations
International Nuclear Information System (INIS)
Mackenzie, L.M.; Macleod, A.M.; Berry, D.J.; Whitehead, R.R.
1988-01-01
The calculation of nuclear properties has proved very successful for light nuclei, but is limited by the power of the present generation of computers. Starting with an analysis of current techniques, this paper discusses how these can be modified to map parallelism inherent in the mathematics onto appropriate parallel machines. A prototype dedicated multiprocessor for nuclear structure calculations, designed and constructed by the authors, is described and evaluated. The approach adopted is discussed in the context of a number of generically similar algorithms. (orig.)
Zhang, Wei; Gan, Jie; Li, Qian; Gao, Kun; Sun, Jian; Xu, Ning; Ying, Zhifeng; Wu, Jiada
2011-06-01
The self-diffusion dynamics of Cu adatoms on Cu(1 0 0) surface has been studied based on the calculation of the energy barriers for various hopping events using lattice-gas based approach and a modified model. To simplify the description of the interactions and the calculation of the energy barrier, a three-tier hierarchy of description of atomic configurations was conceived in which the active adatom and its nearest atoms were chosen to constitute basic configuration and taken as a whole to study many-body interactions of the atoms in various atomic configurations, whereas the impacts of the next nearest atoms on the diffusion of the active adatom were considered as multi-site interactions. Besides the simple hopping of single adatoms, the movements of dimers and trimers as the results of multiple hopping events have also been examined. Taking into account the hopping events of all adatoms, the stability of atomic configurations has been examined and the evolution of atomic configurations has also been analyzed.
International Nuclear Information System (INIS)
Zhang Wei; Gan Jie; Li Qian; Gao Kun; Sun Jian; Xu Ning; Ying Zhifeng; Wu Jiada
2011-01-01
The self-diffusion dynamics of Cu adatoms on Cu(1 0 0) surface has been studied based on the calculation of the energy barriers for various hopping events using lattice-gas based approach and a modified model. To simplify the description of the interactions and the calculation of the energy barrier, a three-tier hierarchy of description of atomic configurations was conceived in which the active adatom and its nearest atoms were chosen to constitute basic configuration and taken as a whole to study many-body interactions of the atoms in various atomic configurations, whereas the impacts of the next nearest atoms on the diffusion of the active adatom were considered as multi-site interactions. Besides the simple hopping of single adatoms, the movements of dimers and trimers as the results of multiple hopping events have also been examined. Taking into account the hopping events of all adatoms, the stability of atomic configurations has been examined and the evolution of atomic configurations has also been analyzed.
Energy Technology Data Exchange (ETDEWEB)
Salmani, E., E-mail: elmehdisalmani@gmail.com [LMPHE (URAC12), Faculty of Sciences, Mohammed V University in Rabat (Morocco); Laghrissi, A.; Lamouri, R. [LMPHE (URAC12), Faculty of Sciences, Mohammed V University in Rabat (Morocco); Benchafia, E. [Department of Materials Science and Engineering, New Jersey Institute of Technology, Newark, NJ 07102 (United States); Ez-Zahraouy, H. [LMPHE (URAC12), Faculty of Sciences, Mohammed V University in Rabat (Morocco); Benyoussef, A. [Institute for Nanomaterials and Nanotechnologies, MAScIR, Rabat (Morocco)
2017-02-15
MgH{sub 2}: TM (TM: V, Cr, Mn, Fe, Co, Ni) based dilute magnetic semiconductors (DMS) are investigated using first principle calculations. Our results show that the ferromagnetic state is stable when TM introduces magnetic moments as well as intrinsic carriers in TM: Co, V, Cr, Ti; Mg{sub 0.95}TM{sub 0.05}H{sub 2}. Some of the DMS Ferro magnets under study exhibit a half-metallic behavior, which make them suitable for spintronic applications. The double exchange is shown to be the underlying mechanism responsible for the magnetism of such materials. The exchange interactions obtained from first principle calculations and used in a classical Ising model by a Monte Carlo approach resulted in ferromagnetic states with Curie temperatures within the ambient conditions. - Highlights: • The half-metallic aspect was proven to take place for Ti, Cr, Co and Ni. • The TM impurities are shown to introduce the magnetic moment that makes MgH{sub 2} good candidates for spintronic applications.
Belpassi, Leonardo; Reca, Michael L; Tarantelli, Francesco; Roncaratti, Luiz F; Pirani, Fernando; Cappelletti, David; Faure, Alexandre; Scribano, Yohann
2010-09-22
Integral cross-section measurements for the system water-H(2) in molecular-beam scattering experiments are reported. Their analysis demonstrates that the average attractive component of the water-H(2) intermolecular potential in the well region is about 30% stronger than dispersion and induction forces would imply. An extensive and detailed theoretical analysis of the electron charge displacement accompanying the interaction, over several crucial sections of the potential energy surface (PES), shows that water-H(2) interaction is accompanied by charge transfer (CT) and that the observed stabilization energy correlates quantitatively with CT magnitude at all distances. Based on the experimentally determined potential and the calculated CT, a general theoretical model is devised which reproduces very accurately PES sections obtained at the CCSD(T) level with large basis sets. The energy stabilization associated with CT is calculated to be 2.5 eV per electron transferred. Thus, CT is shown to be a significant, strongly stereospecific component of the interaction, with water functioning as electron donor or acceptor in different orientations. The general relevance of these findings for water's chemistry is discussed.
Shell model calculations for exotic nuclei
International Nuclear Information System (INIS)
Brown, B.A.; Wildenthal, B.H.
1991-01-01
A review of the shell-model approach to understanding the properties of light exotic nuclei is given. Binding energies including p and p-sd model spaces and sd and sd-pf model spaces; cross-shell excitations around 32 Mg, including weak-coupling aspects and mechanisms for lowering the ntw excitations; beta decay properties of neutron-rich sd model, of p-sd and sd-pf model spaces, of proton-rich sd model space; coulomb break-up cross sections are discussed. (G.P.) 76 refs.; 12 figs
Li, Jin-Feng; Li, Miao-Miao; Bai, Hongcun; Sun, Yin-Yin; Li, Jian-Li; Yin, Bing
2015-12-01
An ab initio study of the superhalogen properties of eighteen binuclear double-bridged [Mg2 (CN)5 ](-1) clusters is reported herein by using various theoretical methods. High-level CCSD(T) results indicate that all the clusters possess strong superhalogen properties owing to their high vertical electron detachment energies (VDEs), which exceed 6.8 eV (highest: 8.15 eV). The outer valence Green's function method provides inaccurate relative VDE values; hence, this method is not suitable for this kind of polynuclear superhalogens. Both the HF and MP2 results are generally consistent with the CCSD(T) level regarding the relative VDE values and-especially interesting-the average values of the HF and MP2 VDEs are extremely close to the CCSD(T) results. The distributions of the extra electrons of the anions are mainly aggregated into the terminal CN units. These distributions are apparently different from those of previously reported triple-bridged isomers and may be the reason for the decreased VDE values of the clusters. In addition, comparisons of the VDEs of binuclear and mononuclear superhalogens as well as studies of the thermodynamic stabilities with respect to the detachment of various CN(-1) ligands are also performed. These results confirm that polynuclear structures with pseudohalogen ligands can be considered as probable new superhalogens with enhanced properties. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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.
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
Uncertainty calculation in transport models and forecasts
DEFF Research Database (Denmark)
Manzo, Stefano; Prato, Carlo Giacomo
Transport projects and policy evaluations are often based on transport model output, i.e. traffic flows and derived effects. However, literature has shown that there is often a considerable difference between forecasted and observed traffic flows. This difference causes misallocation of (public...... implemented by using an approach based on stochastic techniques (Monte Carlo simulation and Bootstrap re-sampling) or scenario analysis combined with model sensitivity tests. Two transport models are used as case studies: the Næstved model and the Danish National Transport Model. 3 The first paper...... in a four-stage transport model related to different variable distributions (to be used in a Monte Carlo simulation procedure), assignment procedures and levels of congestion, at both the link and the network level. The analysis used as case study the Næstved model, referring to the Danish town of Næstved2...
Towards an elastic model of wurtzite AlN nanowires
International Nuclear Information System (INIS)
Mitrushchenkov, A; Chambaud, G; Yvonnet, J; He, Q-C
2010-01-01
Starting with ab initio calculations of AlN wurtzite [0001] nanowires with diameters up to 4 nm, a finite element method is developed to deal with larger nanostructures/nanoparticles. The ab initio calculations show that the structure of the nanowires can be well represented by an internal part with AlN bulk elastic properties, and one atomic surface layer with its own elastic behavior. The proposed finite element method includes surface elements with their own elastic properties using surface elastic coefficients deduced from the ab initio calculations. The elastic properties obtained with the finite element model compare very well with those obtained with the full ab initio calculations.
Shell model calculations at superdeformed shapes
International Nuclear Information System (INIS)
Nazarewicz, W.; Dobaczewski, J.; Van Isacker, P.
1991-01-01
Spectroscopy of superdeformed nuclear states opens up an exciting possibility to probe new properties of the nuclear mean field. In particular, the unusually deformed atomic nucleus can serve as a microscopic laboratory of quantum-mechanical symmetries of a three dimensional harmonic oscillator. The classifications and coupling schemes characteristic of weakly deformed systems are expected to be modified in the superdeformed world. The ''superdeformed'' symmetries lead to new quantum numbers and new effective interactions that can be employed in microscopic calculations. New classification schemes can be directly related to certain geometrical properties of the nuclear shape. 63 refs., 7 figs
Ng, Maggie; Mok, Daniel K W; Lee, Edmond P F; Dyke, John M
2013-03-15
The minimum energy path (MEP) of the reaction, CF(3)CHFCF(3) + H → transition state (TS) → CF(3)CFCF(3) + H(2), has been computed at different ab initio levels and with density functional theory (DFT) using different functionals. The computed B3LYP/6-31++G**, BH&HLYP/cc-pVDZ, BMK/6-31++G**, M05/6-31+G**, M05-2X/6-31+G**, UMP2/6-31++G**, PUMP2/6-31++G**//UMP2/6-31++G**, RCCSD(T)/aug-cc-pVDZ//UMP2/6-31++G**, RCCSD(T)/aug-cc-pVTZ(spd,sp)//UMP2//6-31++G**, RCCSD(T)/CBS//M05/6-31+G**, and RCCSD(T)/CBS//UMP2/6-31++G** MEPs, and associated gradients and Hessians, were used in reaction rate coefficient calculations based on the transition state theory (TST). Reaction rate coefficients were computed between 300 and 1500 K at various levels of TST, which include conventional TST, canonical variational TST (CVT) and improved CVT (ICVT), and with different tunneling corrections, namely, Wigner, zero-curvature, and small-curvature (SCT). The computed rate coefficients obtained at different ab initio, DFT and TST levels are compared with experimental values available in the 1000-1200 K temperature range. Based on the rate coefficients computed at the ICVT/SCT level, the highest TST level used in this study, the BH&HLYP functional performs best among all the functionals used, while the RCCSD(T)/CBS//MP2/6-31++G** level is the best among all the ab initio levels used. Comparing computed reaction rate coefficients obtained at different levels of theory shows that, the computed barrier height has the strongest effect on the computed reaction rate coefficients as expected. Variational effects on the computed rate coefficients are found to be negligibly small. Although tunneling effects are relatively small at high temperatures (~1500 K), SCT corrections are significant at low temperatures (~300 K), and both barrier heights and the magnitudes of the imaginary frequencies affect SCT corrections. Copyright © 2012 Wiley Periodicals, Inc.
Models for Automated Tube Performance Calculations
International Nuclear Information System (INIS)
Brunkhorst, C.
2002-01-01
High power radio-frequency systems, as typically used in fusion research devices, utilize vacuum tubes. Evaluation of vacuum tube performance involves data taken from tube operating curves. The acquisition of data from such graphical sources is a tedious process. A simple modeling method is presented that will provide values of tube currents for a given set of element voltages. These models may be used as subroutines in iterative solutions of amplifier operating conditions for a specific loading impedance
Non-LTE model calculations for SN 1987A and the extragalactic distance scale
Schmutz, W.; Abbott, D. C.; Russell, R. S.; Hamann, W.-R.; Wessolowski, U.
1990-01-01
This paper presents model atmospheres for the first week of SN 1987A, based on the luminosity and density/velocity structure from hydrodynamic models of Woosley (1988). The models account for line blanketing, expansion, sphericity, and departures from LTE in hydrogen and helium and differ from previously published efforts because they represent ab initio calculations, i.e., they contain essentially no free parameters. The formation of the UV spectrum is dominated by the effects of line blanketing. In the absorption troughs, the Balmer line profiles were fit well by these models, but the observed emissions are significantly stronger than predicted, perhaps due to clumping. The generally good agreement between the present synthetic spectra and observations provides independent support for the overall accuracy of the hydrodynamic models of Woosley. The question of the accuracy of the Baade-Wesselink method is addressed in a detailed discussion of its approximations. While the application of the standard method produces a distance within an uncertainty of 20 percent in the case of SN 1987A, systematic errors up to a factor of 2 are possible, particularly if the precursor was a red supergiant.
Energy Technology Data Exchange (ETDEWEB)
Falcetta, Michael F., E-mail: mffalcetta@gcc.edu; Fair, Mark C.; Tharnish, Emily M.; Williams, Lorna M.; Hayes, Nathan J. [Department of Chemistry, Grove City College, Grove City, Pennsylvania 16127 (United States); Jordan, Kenneth D. [Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260 (United States)
2016-03-14
The stabilization method is used to calculate the complex potential energy curve of the {sup 2}Π state of CO{sup −} as a function of bond length, with the refinement that separate potentials are determined for p-wave and d-wave attachment and detachment of the excess electron. Using the resulting complex potentials, absolute vibrational excitation cross sections are calculated as a function of electron energy and scattering angle. The calculated cross sections agree well with experiment.
Beyond standard model calculations with Sherpa
Energy Technology Data Exchange (ETDEWEB)
Hoeche, Stefan [SLAC National Accelerator Laboratory, Menlo Park, CA (United States); Kuttimalai, Silvan [Durham University, Institute for Particle Physics Phenomenology, Durham (United Kingdom); Schumann, Steffen [Universitaet Goettingen, II. Physikalisches Institut, Goettingen (Germany); Siegert, Frank [Institut fuer Kern- und Teilchenphysik, TU Dresden, Dresden (Germany)
2015-03-01
We present a fully automated framework as part of the Sherpa event generator for the computation of tree-level cross sections in Beyond Standard Model scenarios, making use of model information given in the Universal FeynRules Output format. Elementary vertices are implemented into C++ code automatically and provided to the matrix-element generator Comix at runtime. Widths and branching ratios for unstable particles are computed from the same building blocks. The corresponding decays are simulated with spin correlations. Parton showers, QED radiation and hadronization are added by Sherpa, providing a full simulation of arbitrary BSM processes at the hadron level. (orig.)
International Nuclear Information System (INIS)
Yan Guanghua; Liu, Chihray; Lu Bo; Palta, Jatinder R; Li, Jonathan G
2008-01-01
The purpose of this study was to choose an appropriate head scatter source model for the fast and accurate independent planar dose calculation for intensity-modulated radiation therapy (IMRT) with MLC. The performance of three different head scatter source models regarding their ability to model head scatter and facilitate planar dose calculation was evaluated. A three-source model, a two-source model and a single-source model were compared in this study. In the planar dose calculation algorithm, in-air fluence distribution was derived from each of the head scatter source models while considering the combination of Jaw and MLC opening. Fluence perturbations due to tongue-and-groove effect, rounded leaf end and leaf transmission were taken into account explicitly. The dose distribution was calculated by convolving the in-air fluence distribution with an experimentally determined pencil-beam kernel. The results were compared with measurements using a diode array and passing rates with 2%/2 mm and 3%/3 mm criteria were reported. It was found that the two-source model achieved the best agreement on head scatter factor calculation. The three-source model and single-source model underestimated head scatter factors for certain symmetric rectangular fields and asymmetric fields, but similar good agreement could be achieved when monitor back scatter effect was incorporated explicitly. All the three source models resulted in comparable average passing rates (>97%) when the 3%/3 mm criterion was selected. The calculation with the single-source model and two-source model was slightly faster than the three-source model due to their simplicity
Energy Technology Data Exchange (ETDEWEB)
Yan Guanghua [Department of Nuclear and Radiological Engineering, University of Florida, Gainesville, FL 32611 (United States); Liu, Chihray; Lu Bo; Palta, Jatinder R; Li, Jonathan G [Department of Radiation Oncology, University of Florida, Gainesville, FL 32610-0385 (United States)
2008-04-21
The purpose of this study was to choose an appropriate head scatter source model for the fast and accurate independent planar dose calculation for intensity-modulated radiation therapy (IMRT) with MLC. The performance of three different head scatter source models regarding their ability to model head scatter and facilitate planar dose calculation was evaluated. A three-source model, a two-source model and a single-source model were compared in this study. In the planar dose calculation algorithm, in-air fluence distribution was derived from each of the head scatter source models while considering the combination of Jaw and MLC opening. Fluence perturbations due to tongue-and-groove effect, rounded leaf end and leaf transmission were taken into account explicitly. The dose distribution was calculated by convolving the in-air fluence distribution with an experimentally determined pencil-beam kernel. The results were compared with measurements using a diode array and passing rates with 2%/2 mm and 3%/3 mm criteria were reported. It was found that the two-source model achieved the best agreement on head scatter factor calculation. The three-source model and single-source model underestimated head scatter factors for certain symmetric rectangular fields and asymmetric fields, but similar good agreement could be achieved when monitor back scatter effect was incorporated explicitly. All the three source models resulted in comparable average passing rates (>97%) when the 3%/3 mm criterion was selected. The calculation with the single-source model and two-source model was slightly faster than the three-source model due to their simplicity.
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).
The effects of Na on high pressure phases of CuIn0.5Ga0.5Se2 from ab initio calculation
International Nuclear Information System (INIS)
Pluengphon, P; Bovornratanaraks, T; Pinsook, U; Vannarat, S
2012-01-01
The effects of Na atoms on high pressure structural phase transitions of CuIn 0.5 Ga 0.5 Se 2 (CIGS) were studied by an ab initio method using density functional theory. At ambient pressure, CIGS is known to have chalcopyrite (I 4-bar 2 d) structure. The high pressure phase transitions of CIGS were proposed to be the same as the order in the CuInSe 2 phase transitions which are I 4-bar 2 d→F m 3-bar m→C m c m structures. By using the mixture atoms method, the Na concentration in CIGS was studied at 0.1, 1.0 and 6.25%. The positive mixing enthalpy of Na at In/Ga sites (Na InGa ) is higher than that of Na at Cu sites (Na Cu ). It confirmed previous studies that Na preferably substitutes on the Cu sites more than the (In, Ga) sites. From the energy-volume curves, we found that the effect of the Na substitutes is to reduce the hardness of CIGS under high pressure. The most significant effects occur at 6.25% Na. We also found that the electronic density of states of CIGS near the valence band maximum is increased noticeably in the chalcopyrite phase. The band gap is close in the cubic and orthorhombic phases. Also, the Na Cu -Se bond length in the chalcopyrite phase is significantly reduced at 6.25% Na, compared with the pure Cu-Se bond length. Consequently, the energy band gap in this phase is wider than in pure CIGS, and the gap increased at the rate of 31 meV GPa -1 under pressure. The Na has a small effect on the transition pressure. The path of transformation from the cubic to orthorhombic phase was derived. The Cu-Se plane in the cubic phase displaced relatively parallel to the (In, Ga)-Se plane by 18% in order to transform to the Cmcm phase. The enthalpy barrier is 0.020 eV/atom, which is equivalent to a thermal energy of 248 K. We predicted that F m 3-bar m and Cmcm can coexist in some pressure range. (paper)
Model calculations for electrochemically etched neutron detectors
International Nuclear Information System (INIS)
Pitt, E.; Scharmann, A.; Werner, B.
1988-01-01
Electrochemical etching has been established as a common method for visualisation of nuclear tracks in solid state nuclear track detectors. Usually the Mason equation, which describes the amplification of the electrical field strength at the track tip, is used to explain the treeing effect of electrochemical etching. The yield of neutron-induced tracks from electrochemically etched CR-39 track detectors was investigated with respect to the electrical parameters. A linear dependence on the response from the macroscopic field strength was measured which could not be explained by the Mason equation. It was found that the reality of a recoil proton track in the detector does not fit the boundary conditions which are necessary when the Mason equation is used. An alternative model was introduced to describe the track and detector geometry in the case of a neutron track detector. The field strength at the track tip was estimated with this model and compared with the experimental data, yielding good agreement. (author)
Model calculation of thermal conductivity in antiferromagnets
Energy Technology Data Exchange (ETDEWEB)
Mikhail, I.F.I., E-mail: ifi_mikhail@hotmail.com; Ismail, I.M.M.; Ameen, M.
2015-11-01
A theoretical study is given of thermal conductivity in antiferromagnetic materials. The study has the advantage that the three-phonon interactions as well as the magnon phonon interactions have been represented by model operators that preserve the important properties of the exact collision operators. A new expression for thermal conductivity has been derived that involves the same terms obtained in our previous work in addition to two new terms. These two terms represent the conservation and quasi-conservation of wavevector that occur in the three-phonon Normal and Umklapp processes respectively. They gave appreciable contributions to the thermal conductivity and have led to an excellent quantitative agreement with the experimental measurements of the antiferromagnet FeCl{sub 2}. - Highlights: • The Boltzmann equations of phonons and magnons in antiferromagnets have been studied. • Model operators have been used to represent the magnon–phonon and three-phonon interactions. • The models possess the same important properties as the exact operators. • A new expression for the thermal conductivity has been derived. • The results showed a good quantitative agreement with the experimental data of FeCl{sub 2}.
McKenna, Alice
One of the functions of graphite is as a moderator in several nuclear reactor designs, including the Advanced Gas-cooled Reactor (AGR). In the reactor graphite is used to thermalise the neutrons produced in the fission reaction thus allowing a self-sustained reaction to occur. The graphite blocks, acting as the moderator, are constantly irradiated and consequently suffer damage. This thesis examines the types of damage caused using molecular dynamic (MD) simulations and ab intio calculations. Neutron damage starts with a primary knock-on atom (PKA), which is travelling so fast that it creates damage through electronic and thermal excitation (this is addressed with thermal spike simulations). When the PKA has lost energy the subsequent cascade is based on ballistic atomic displacement. These two types of simulations were performed on single crystal graphite and other carbon structures such as diamond and amorphous carbon as a comparison. The thermal spike in single crystal graphite produced results which varied from no defects to a small number of permanent defects in the structure. It is only at the high energy range that more damage is seen but these energies are less likely to occur in the nuclear reactor. The thermal spike does not create damage but it is possible that it can heal damaged sections of the graphite, which can be demonstrated with the motion of the defects when a thermal spike is applied. The cascade simulations create more damage than the thermal spike even though less energy is applied to the system. A new damage function is found with a threshold region that varies with the square root of energy in excess of the energy threshold. This is further broken down in to contributions from primary and subsequent knock-on atoms. The threshold displacement energy (TDE) is found to be Ed=25eV at 300K. In both these types of simulation graphite acts very differently to the other carbon structures. There are two types of polycrystalline graphite structures
Philippov, Alexander A.; Spitkovsky, Anatoly
2018-03-01
We perform global particle-in-cell simulations of pulsar magnetospheres, including pair production, ion extraction from the surface, frame-dragging corrections, and high-energy photon emission and propagation. In the case of oblique rotators, the effects of general relativity increase the fraction of the open field lines that support active pair discharge. We find that the plasma density and particle energy flux in the pulsar wind are highly non-uniform with latitude. A significant fraction of the outgoing particle energy flux is carried by energetic ions, which are extracted from the stellar surface. Their energies may extend up to a large fraction of the open field line voltage, making them interesting candidates for ultra-high-energy cosmic rays. We show that pulsar gamma-ray radiation is dominated by synchrotron emission, produced by particles that are energized by relativistic magnetic reconnection close to the Y-point and in the equatorial current sheet. In most cases, the calculated light curves contain two strong peaks, which is in general agreement with Fermi observations. The radiative efficiency decreases with increasing pulsar inclination and increasing efficiency of pair production in the current sheet, which explains the observed scatter in L γ versus \\dot{E}. We find that the high-frequency cutoff in the spectra is regulated by the pair-loading of the current sheet. Our findings lay the foundation for quantitative interpretation of Fermi observations of gamma-ray pulsars.
Perovskite Quantum Dots Modeled Using ab Initio and Replica Exchange Molecular Dynamics
Buin, Andrei; Comin, Riccardo; Ip, Alexander H.; Sargent, Edward H.
2015-01-01
© 2015 American Chemical Society. Organometal halide perovskites have recently attracted tremendous attention at both the experimental and theoretical levels. Much of this work has been dedicated to bulk material studies, yet recent experimental work has shown the formation of highly efficient quantum-confined nanocrystals with tunable band edges. Here we investigate perovskite quantum dots from theory, predicting an upper bound of the Bohr radius of 45 Å that agrees well with literature values. When the quantum dots are stoichiometric, they are trap-free and have nearly symmetric contributions to confinement from the valence and conduction bands. We further show that surface-associated conduction bandedge states in perovskite nanocrystals lie below the bulk states, which could explain the difference in Urbach tails between mesoporous and planar perovskite films. In addition to conventional molecular dynamics (MD), we implement an enhanced phase-space sampling algorithm, replica exchange molecular dynamics (REMD). We find that in simulation of methylammonium orientation and global minima, REMD outperforms conventional MD. To the best of our knowledge, this is the first REMD implementation for realistic-sized systems in the realm of DFT calculations.
Perovskite Quantum Dots Modeled Using ab Initio and Replica Exchange Molecular Dynamics
Buin, Andrei
2015-06-18
© 2015 American Chemical Society. Organometal halide perovskites have recently attracted tremendous attention at both the experimental and theoretical levels. Much of this work has been dedicated to bulk material studies, yet recent experimental work has shown the formation of highly efficient quantum-confined nanocrystals with tunable band edges. Here we investigate perovskite quantum dots from theory, predicting an upper bound of the Bohr radius of 45 Å that agrees well with literature values. When the quantum dots are stoichiometric, they are trap-free and have nearly symmetric contributions to confinement from the valence and conduction bands. We further show that surface-associated conduction bandedge states in perovskite nanocrystals lie below the bulk states, which could explain the difference in Urbach tails between mesoporous and planar perovskite films. In addition to conventional molecular dynamics (MD), we implement an enhanced phase-space sampling algorithm, replica exchange molecular dynamics (REMD). We find that in simulation of methylammonium orientation and global minima, REMD outperforms conventional MD. To the best of our knowledge, this is the first REMD implementation for realistic-sized systems in the realm of DFT calculations.
Hernández Velázquez, J D; Barroso-Flores, J; Gama Goicochea, A
2016-11-23
Two of the most commonly encountered friction-reducing agents used in plastic sheet production are the amides known as erucamide and behenamide, which despite being almost identical chemically, lead to markedly different values of the friction coefficient. To understand the origin of this contrasting behavior, in this work we model brushes made of these two types of linear-chain molecules using quantum mechanical numerical simulations under the density functional theory at the B97D/6-31G(d,p) level of theory. Four chains of erucamide and behenamide were linked to a 2 × 10 zigzag graphene sheet and optimized both in vacuum and in continuous solvent using the SMD implicit solvation model. We find that erucamide chains tend to remain closer together through π-π stacking interactions arising from the double bonds located at C13-C14, a feature behenamide lacks, and thus a more spread configuration is obtained with the latter. It is argued that this arrangement of the erucamide chains is responsible for the lower friction coefficient of erucamide brushes, compared with behenamide brushes, which is a macroscopic consequence of cooperative quantum mechanical interactions. While only quantum level interactions are modeled here, we show that behenamide chains are more spread out in the brush than erucamide chains as a consequence of those interactions. The spread-out configuration allows more solvent particles to penetrate the brush, leading in turn to more friction, in agreement with macroscopic measurements and mesoscale simulations of the friction coefficient reported in the literature.
Brière, B; Kalinko, A; Yamada, I; Roy, P; Brubach, J B; Sopracase, R; Zaghrioui, M; Phuoc, V Ta
2016-06-27
Optical measurements were carried out by infrared spectroscopy on AA'3B4O12 A-site ordered quadruple perovskite EuCu3Fe4O12 (microscopic sample) as function of temperature. At 240 K (=TMI), EuCu3Fe4O12 undergoes a very abrupt metal to insulator transition, a paramagnetic to antiferromagnetic transition and an isostructural transformation with an abrupt large volume expansion. Above TMI, optical conductivity reveals a bad metal behavior and below TMI, an insulating phase with an optical gap of 125 meV is observed. As temperature is decreased, a large and abrupt spectral weight transfer toward an energy scale larger than 1 eV is detected. Concurrently, electronic structure calculations for both high and low temperature phases were compared to the optical conductivity results giving a precise pattern of the transition. Density of states and computed optical conductivity analysis identified Cu3dxy, Fe3d and O2p orbitals as principal actors of the spectral weight transfer. The present work constitutes a first step to shed light on EuCu3Fe4O12 electronic properties with optical measurements and ab-initio calculations.
Barragán, Patricia; Pérez de Tudela, Ricardo; Qu, Chen; Prosmiti, Rita; Bowman, Joel M
2013-07-14
Diffusion Monte Carlo (DMC) and path-integral Monte Carlo computations of the vibrational ground state and 10 K equilibrium state properties of the H7 (+)/D7 (+) cations are presented, using an ab initio full-dimensional potential energy surface. The DMC zero-point energies of dissociated fragments H5 (+)(D5 (+))+H2(D2) are also calculated and from these results and the electronic dissociation energy, dissociation energies, D0, of 752 ± 15 and 980 ± 14 cm(-1) are reported for H7 (+) and D7 (+), respectively. Due to the known error in the electronic dissociation energy of the potential surface, these quantities are underestimated by roughly 65 cm(-1). These values are rigorously determined for first time, and compared with previous theoretical estimates from electronic structure calculations using standard harmonic analysis, and available experimental measurements. Probability density distributions are also computed for the ground vibrational and 10 K state of H7 (+) and D7 (+). These are qualitatively described as a central H3 (+)/D3 (+) core surrounded by "solvent" H2/D2 molecules that nearly freely rotate.
Standard Model theory calculations and experimental tests
International Nuclear Information System (INIS)
Cacciari, M.; Hamel de Monchenault, G.
2015-01-01
To present knowledge, all the physics at the Large Hadron Collider (LHC) can be described in the framework of the Standard Model (SM) of particle physics. Indeed the newly discovered Higgs boson with a mass close to 125 GeV seems to confirm the predictions of the SM. Thus, besides looking for direct manifestations of the physics beyond the SM, one of the primary missions of the LHC is to perform ever more stringent tests of the SM. This requires not only improved theoretical developments to produce testable predictions and provide experiments with reliable event generators, but also sophisticated analyses techniques to overcome the formidable experimental environment of the LHC and perform precision measurements. In the first section, we describe the state of the art of the theoretical tools and event generators that are used to provide predictions for the production cross sections of the processes of interest. In section 2, inclusive cross section measurements with jets, leptons and vector bosons are presented. Examples of differential cross sections, charge asymmetries and the study of lepton pairs are proposed in section 3. Finally, in section 4, we report studies on the multiple production of gauge bosons and constraints on anomalous gauge couplings
Durig, James R; Pan, Chunhua; Guirgis, Gamil A
2003-03-15
The infrared (3100-40 cm(-1)) and Raman (3100-20 cm(-1)) spectra of gaseous and solid n-propylsilane, CH(3)CH(2)CH(2)SiH(3) and the Si-d(3) isotopomer, CH(3)CH(2)CH(2)SiD(3), have been recorded. Additionally, the Raman spectra of the liquids have been recorded and qualitative depolarization values obtained. Both the anti and gauche conformers have been identified in the fluid phases but only the anti conformer remains in the solid. Variable temperature (-105 to -150 degrees C) studies of the infrared spectra of n-propylsilane dissolved in liquid krypton have been recorded and the enthalpy difference has been determined to be 220+/-22 cm(-1) (2.63+/-0.26 kJ mol(-1)) with the anti conformer the more stable form. A similar value of 234+/-23 cm(-1) (2.80+/-0.28 kJ mol(-1)) was obtained for deltaH for the Si-d(3) isotopomer. At ambient temperature it is estimated that there is 30+/-2% of the gauche conformer present. The potential function governing the conformation interchange has been estimated from the far infrared spectral data, the enthalpy difference, and the dihedral angle of the gauche conformer, which is compared to the one predicted from ab initio MP2/6-31G(d) calculations. The barriers to conformational interchange are: 942, 970 and 716 cm(-1) for the anti to gauche, gauche to gauche, and gauche to anti conformers, respectively. Relatively complete vibrational assignments are proposed for both the n-propylsilane-d(0) and Si-d(3) molecules based on the relative infrared and Raman spectral intensities, infrared band contours, depolarization ratios, and normal coordinate calculations. The geometrical parameters, harmonic force constants, vibrational frequencies, infrared intensities, Raman activities and depolarization ratios, and energy differences have been obtained for the anti and gauche conformers from ab initio MP2/6-31G(d) calculations. Structural parameters and energy differences have also been obtained utilizing the larger 6-311 + G(d,p) and 6-311 + G(2
Durig, James R.; Pan, Chunhua; Guirgis, Gamil A.
2003-03-01
The infrared (3100-40 cm -1) and Raman (3100-20 cm -1) spectra of gaseous and solid n-propylsilane, CH 3CH 2CH 2SiH 3 and the Si-d 3 isotopomer, CH 3CH 2CH 2SiD 3, have been recorded. Additionally, the Raman spectra of the liquids have been recorded and qualitative depolarization values obtained. Both the anti and gauche conformers have been identified in the fluid phases but only the anti conformer remains in the solid. Variable temperature (-105 to -150 °C) studies of the infrared spectra of n-propylsilane dissolved in liquid krypton have been recorded and the enthalpy difference has been determined to be 220±22 cm -1 (2.63±0.26 kJ mol -1) with the anti conformer the more stable form. A similar value of 234±23 cm -1 (2.80±0.28 kJ mol -1) was obtained for Δ H for the Si-d 3 isotopomer. At ambient temperature it is estimated that there is 30±2% of the gauche conformer present. The potential function governing the conformation interchange has been estimated from the far infrared spectral data, the enthalpy difference, and the dihedral angle of the gauche conformer, which is compared to the one predicted from ab initio MP2/6-31G(d) calculations. The barriers to conformational interchange are: 942, 970 and 716 cm -1 for the anti to gauche, gauche to gauche, and gauche to anti conformers, respectively. Relatively complete vibrational assignments are proposed for both the n-propylsilane-d 0 and Si-d 3 molecules based on the relative infrared and Raman spectral intensities, infrared band contours, depolarization ratios, and normal coordinate calculations. The geometrical parameters, harmonic force constants, vibrational frequencies, infrared intensities, Raman activities and depolarization ratios, and energy differences have been obtained for the anti and gauche conformers from ab initio MP2/6-31G(d) calculations. Structural parameters and energy differences have also been obtained utilizing the larger 6-311+G(d,p) and 6-311+G(2d,2p) basis sets. From the isolated
Novita, Mega; Nagoshi, Hikari; Sudo, Akiho; Ogasawara, Kazuyoshi
2018-01-01
In this study, we performed an investigation on α-Al2O3: V3+ material, or the so-called color change sapphire, based on first-principles calculations without referring to any experimental parameter. The molecular orbital (MO) structure was estimated by the one-electron MO calculations using the discrete variational-Xα (DV-Xα) method. Next, the absorption spectra were estimated by the many-electron calculations using the discrete variational multi-electron (DVME) method. The effect of lattice relaxation on the crystal structures was estimated based on the first-principles band structure calculations. We performed geometry optimizations on the pure α-Al2O3 and with the impurity V3+ ion using Cambridge Serial Total Energy Package (CASTEP) code. The effect of energy corrections such as configuration dependence correction and correlation correction was also investigated in detail. The results revealed that the structural change on the α-Al2O3: V3+ resulted from the geometry optimization improved the calculated absorption spectra. By a combination of both the lattice relaxation-effect and the energy correction-effect improve the agreement to the experiment fact.
Klaa, K.; Labidi, S.; Masrour, R.; Jabar, A.; Labidi, M.; Amara, A.; Drici, A.; Hlil, E. K.; Ellouze, M.
2018-06-01
Structural, electronic, magnetic and thermodynamic main features for Ni1-xTixO ternary alloys in rock-salt structure with Ti content in the range ? were studied using the full potential Linearized augmented plane wave (FP-LAPW) method within density functional theory. The exchange-correlation potential was calculated by the generalized gradient approximation. The analysis of the electronic density of states curves allowed the computation of the magnetic moments which are considered to lie along (010) axes. The thermodynamic stability of this alloy was investigated by calculating the excess enthalpy of mixing ? as well as the phase diagram. In addition, the Monte Carlo simulations have been exploited to calculate the transition temperature and magnetic coercive field in the alloy.