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Sample records for ab initio calculations

  1. 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

  2. Ab Initio Calculations of Oxosulfatovanadates

    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 stable...... with anO-V-O angle of 72.5 degrees . The calculated spectrum shows bands in reasonable agreement with anexperimental spectrum which has been attributed to (VO2SO4)-. The geometry and the electron density fortwo binuclear vanadium complexes proposed as intermediates in the vanadium catalyzed SO2...

  3. Ab initio calculations of material strength

    Šob, Mojmír; Friák, Martin; Vitek, V.

    Tokyo : The Japan Society of Mechanical Engineers, 2003, s. 467-475. [International Symposium on Micro-Mechanical Engineering - Heat Transfer, Fluid Dynamics, Reliability and Mechanotronics.. Tsuchiura and Tsukuba (JP), 01.12.2003-03.12.2003] 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

  4. Guiding ab initio calculations by alchemical derivatives

    to Baben, M.; Achenbach, J. O.; von Lilienfeld, O. A.

    2016-03-01

    We assess the concept of alchemical transformations for predicting how a further and not-tested change in composition would change materials properties. This might help to guide ab initio calculations through multidimensional property-composition spaces. Equilibrium volumes, bulk moduli, and relative lattice stability of fcc and bcc 4d transition metals Zr, Nb, Mo, Tc, Ru, Rh, Pd, and Ag are calculated using density functional theory. Alchemical derivatives predict qualitative trends in lattice stability while equilibrium volumes and bulk moduli are predicted with less than 9% and 28% deviation, respectively. Predicted changes in equilibrium volume and bulk moduli for binary and ternary mixtures of Rh-Pd-Ag are in qualitative agreement even for predicted bulk modulus changes as large as +100% or -50%. Based on these results, it is suggested that alchemical transformations could be meaningful for enhanced sampling in the context of virtual high-throughput materials screening projects.

  5. Cyanogen Azide. Ionization Potentials and Ab Initio SCF MO Calculation

    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 are fo...

  6. Ab-initio calculations for dilute magnetic semiconductors

    Belhadji, Brahim

    2008-01-01

    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 approximatio...

  7. Augmented wave ab initio EFG calculations: some methodological warnings

    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.

  8. Augmented wave ab initio EFG calculations: some methodological warnings

    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 SnO2. 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

  9. Ab-initio calculations on melting of thorium

    Mukherjee, D.; Sahoo, B. D.; Joshi, K. D.; Kaushik, T. C.; Gupta, Satish C.

    2016-05-01

    Ab-initio molecular dynamics study has been performed on face centered cubic structured thorium to determine its melting temperature at room pressure. The ion-electron interaction potential energy calculated as a function of temperature for three volumes (a0)3 and (1.02a0)3 and (1.04a0)3 increases gradually with temperature and undergoes a sharp jump at ~2200 K, ~2100 K and ~1800 K, respectively. Here, a0 = 5.043 Å is the equilibrium lattice parameter at 0 K obtained from ab-initio calculations. These jumps in interaction energy are treated as due to the onset of melting and corresponding temperatures as melting point. The melting point of 2100 K is close to the experimental value of 2023K. Further, the same has been verified by plotting the atomic arrangement evolved at various temperatures and corresponding pair correlation functions.

  10. Molecular symmetry in ab initio calculations

    A scheme is presented for the construction of the Fock matrix in LCAO-SCF calculations and for the transformation of basis integrals to LCAO-MO integrals that can utilize several symmetry unique lists of integrals corresponding to different symmetry groups. The algorithm is fully compatible with vector processing machines and is especially suited for parallel processing machines. copyright 1987 Academic Press, Inc

  11. Ab initio calculations for industrial materials engineering: successes and challenges

    Wimmer, Erich; Freeman, Clive; Christensen, Mikael; Wolf, Walter; Saxe, Paul [Materials Design, Inc., PO Box 2000, Angel Fire, NM 87710 (United States); Najafabadi, Reza; Young Jr, George A; Ballard, Jake D; Angeliu, Thomas M; Vollmer, James [Knolls Atomic Power Laboratory, PO Box 1072, Schenectady, NY 12301-1072 (United States); Chambers, James J; Niimi, Hiroaki; Shaw, Judy B, E-mail: ewimmer@materialsdesign.co [Advanced CMOS, Texas Instruments Incorporated, Dallas, TX 75243 (United States)

    2010-09-29

    Computational materials science based on ab initio calculations has become an important partner to experiment. This is demonstrated here for the effect of impurities and alloying elements on the strength of a Zr twist grain boundary, the dissociative adsorption and diffusion of iodine on a zirconium surface, the diffusion of oxygen atoms in a Ni twist grain boundary and in bulk Ni, and the dependence of the work function of a TiN-HfO{sub 2} junction on the replacement of N by O atoms. In all of these cases, computations provide atomic-scale understanding as well as quantitative materials property data of value to industrial research and development. There are two key challenges in applying ab initio calculations, namely a higher accuracy in the electronic energy and the efficient exploration of large parts of the configurational space. While progress in these areas is fueled by advances in computer hardware, innovative theoretical concepts combined with systematic large-scale computations will be needed to realize the full potential of ab initio calculations for industrial applications.

  12. Ab initio calculations for industrial materials engineering: successes and challenges

    Computational materials science based on ab initio calculations has become an important partner to experiment. This is demonstrated here for the effect of impurities and alloying elements on the strength of a Zr twist grain boundary, the dissociative adsorption and diffusion of iodine on a zirconium surface, the diffusion of oxygen atoms in a Ni twist grain boundary and in bulk Ni, and the dependence of the work function of a TiN-HfO2 junction on the replacement of N by O atoms. In all of these cases, computations provide atomic-scale understanding as well as quantitative materials property data of value to industrial research and development. There are two key challenges in applying ab initio calculations, namely a higher accuracy in the electronic energy and the efficient exploration of large parts of the configurational space. While progress in these areas is fueled by advances in computer hardware, innovative theoretical concepts combined with systematic large-scale computations will be needed to realize the full potential of ab initio calculations for industrial applications.

  13. Ab initio calculations of reactions with light nuclei

    Quaglioni, Sofia; Hupin, Guillaume; Calci, Angelo; Navrátil, Petr; Roth, Robert

    2016-03-01

    An ab initio (i.e., from first principles) theoretical framework capable of providing a unified description of the structure and low-energy reaction properties of light nuclei is desirable to further our understanding of the fundamental interactions among nucleons, and provide accurate predictions of crucial reaction rates for nuclear astrophysics, fusion-energy research, and other applications. In this contribution we review ab initio calculations for nucleon and deuterium scattering on light nuclei starting from chiral two- and three-body Hamiltonians, obtained within the framework of the ab initio no-core shell model with continuum. This is a unified approach to nuclear bound and scattering states, in which square-integrable energy eigenstates of the A-nucleon system are coupled to (A-a)+a target-plus-projectile wave functions in the spirit of the resonating group method to obtain an efficient description of the many-body nuclear dynamics both at short and medium distances and at long ranges.

  14. Accelerating Ab Initio Nuclear Physics Calculations with GPUs

    Potter, Hugh; Maris, Pieter; Sosonkina, Masha; Vary, James; Binder, Sven; Calci, Angelo; Langhammer, Joachim; Roth, Robert; Çatalyürek, Ümit; Saule, Erik

    2014-01-01

    This paper describes some applications of GPU acceleration in ab initio nuclear structure calculations. Specifically, we discuss GPU acceleration of the software package MFDn, a parallel nuclear structure eigensolver. We modify the matrix construction stage to run partly on the GPU. On the Titan supercomputer at the Oak Ridge Leadership Computing Facility, this produces a speedup of approximately 2.2x - 2.7x for the matrix construction stage and 1.2x - 1.4x for the entire run.

  15. Ab initio calculation of tensile strength in iron

    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

  16. Ab Initio Calculations of Co Shielding in Model Complexes

    Elaine A. Moore

    2002-08-01

    Full Text Available Abstract: Recent ab initio calculations of cobalt NMR shielding show that DFT-GIAO calculations using hybrid functionals are found to reproduce experimental values well. This method is used to calculate the variation of the cobalt NMR shielding tensor of sqaure pyramidal nitrosyl complexes with respect to the CoNO geometry and to differing basal ligands. The isotropic shielding is shown to have a large negative derivative with respect to CoX distance where X is a ligating atom.; the derivative with respect to NO distance is smaller but still significant. The zz component where z is along the CoN(NO bond is more sensitive to the basal ligands but the other two principal components are sensitive to the CoNO geometry.

  17. Transport coefficients in diamond from ab-initio calculations

    Löfâs, Henrik; Grigoriev, Anton; Isberg, Jan; Ahuja, Rajeev

    2013-03-01

    By combining the Boltzmann transport equation with ab-initio electronic structure calculations, we obtain transport coefficients for boron-doped diamond. We find the temperature dependence of the resistivity and the hall coefficients in good agreement with experimental measurements. Doping in the samples is treated via the rigid band approximation and scattering is treated in the relaxation time approximation. In contrast to previous results, the acoustic phonon scattering is the dominating scattering mechanism for the considered doping range. At room temperature, we find the thermopower, S, in the range 1-1.6 mV/K and the power factor, S2σ, in the range 0.004-0.16 μW /cm K2.

  18. Relativistic ab initio calculations for ion-atom collisions

    Within the independent particle model we solve the time---dependent single-particle equation using ab initio SCF-DIRAC-FOCK-SLATER wavefunctions as a basis. To reinstate the many-particle aspect of the collision system we use the inclusive probability formalism to answer experimental questions. As an example we show an application to the case of S15+ on Ar where experimental data on the K-K charge transfer are available for a wide range of impact energies from 4.7 to 90 MeV. Our molecular adiabatic calculations and the evaluation using the inclusive probability formalism show good results in the low energy range from 4.7 to 16 MeV impact energy

  19. Ab-initio calculations for dilute magnetic semiconductors

    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.)

  20. Ab initio calculations of mechanical properties: Methods and applications

    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: 27.417, year: 2014

  1. Engineering Room-temperature Superconductors Via ab-initio Calculations

    Gulian, Mamikon; Melkonyan, Gurgen; Gulian, Armen

    The BCS, or bosonic model of superconductivity, as Little and Ginzburg have first argued, can bring in superconductivity at room temperatures in the case of high-enough frequency of bosonic mode. It was further elucidated by Kirzhnitset al., that the condition for existence of high-temperature superconductivity is closely related to negative values of the real part of the dielectric function at finite values of the reciprocal lattice vectors. In view of these findings, the task is to calculate the dielectric function for real materials. Then the poles of this function will indicate the existence of bosonic excitations which can serve as a "glue" for Cooper pairing, and if the frequency is high enough, and the dielectric matrix is simultaneously negative, this material is a good candidate for very high-Tc superconductivity. Thus, our approach is to elaborate a methodology of ab-initio calculation of the dielectric function of various materials, and then point out appropriate candidates. We used the powerful codes (TDDF with the DP package in conjunction with ABINIT) for computing dielectric responses at finite values of the wave vectors in the reciprocal lattice space. Though our report is concerned with the particular problem of superconductivity, the application range of the data processing methodology is much wider. The ability to compute the dielectric function of existing and still non-existing (though being predicted!) materials will have many more repercussions not only in fundamental sciences but also in technology and industry.

  2. Ab initio quantum transport calculations using plane waves

    Garcia-Lekue, A.; Vergniory, M. G.; Jiang, X. W.; Wang, L. W.

    2015-08-01

    We present an ab initio method to calculate elastic quantum transport at the nanoscale. The method is based on a combination of density functional theory using plane wave nonlocal pseudopotentials and the use of auxiliary periodic boundary conditions to obtain the scattering states. The method can be applied to any applied bias voltage and the charge density and potential profile can either be calculated self-consistently, or using an approximated self-consistent field (SCF) approach. Based on the scattering states one can straightforwardly calculate the transmission coefficients and the corresponding electronic current. The overall scheme allows us to obtain accurate and numerically stable solutions for the elastic transport, with a computational time similar to that of a ground state calculation. This method is particularly suitable for calculations of tunneling currents through vacuum, that some of the nonequilibrium Greens function (NEGF) approaches based on atomic basis sets might have difficulty to deal with. Several examples are provided using this method from electron tunneling, to molecular electronics, to electronic devices: (i) On a Au nanojunction, the tunneling current dependence on the electrode-electrode distance is investigated. (ii) The tunneling through field emission resonances (FERs) is studied via an accurate description of the surface vacuum states. (iii) Based on quantum transport calculations, we have designed a molecular conformational switch, which can turn on and off a molecular junction by applying a perpendicular electric field. (iv) Finally, we have used the method to simulate tunnel field-effect transistors (TFETs) based on two-dimensional transition-metal dichalcogenides (TMDCs), where we have studied the performance and scaling limits of such nanodevices and proposed atomic doping to enhance the transistor performance.

  3. Ab Initio Nuclear Structure and Reaction Calculations for Rare Isotopes

    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).

  4. Ab Initio Nuclear Structure and Reaction Calculations for Rare Isotopes

    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).

  5. Emergence of rotational bands in ab initio no-core configuration interaction calculations

    Caprio, M A; Vary, J P; Smith, R

    2015-01-01

    Rotational bands have been observed to emerge in ab initio no-core configuration interaction (NCCI) calculations for p-shell nuclei, as evidenced by rotational patterns for excitation energies, electromagnetic moments, and electromagnetic transitions. We investigate the ab initio emergence of nuclear rotation in the Be isotopes, focusing on 9Be for illustration, and make use of basis extrapolation methods to obtain ab initio predictions of rotational band parameters for comparison with experiment. We find robust signatures for rotational motion, which reproduce both qualitative and quantitative features of the experimentally observed bands.

  6. Ab initio calculations of grain boundaries in bcc metals

    Scheiber, Daniel; Pippan, Reinhard; Puschnig, Peter; Romaner, Lorenz

    2016-03-01

    In this study, we compute grain boundary (GB) properties for a large set of GBs in bcc transition metals with a special focus on W, Mo and Fe using ab initio density functional theory (DFT) and semi-empirical second nearest neighbour modified embedded atom method (2NN-MEAM) potentials. The GB properties include GB energies, surface energies, GB excess volume and work of separation, which we analyse and then compare to experimental data. We find that the used 2NN-MEAM potentials can predict general trends of GB properties, but do not always reproduce the GB ground state structure and energy found with DFT. In particular, our results explain the experimental finding that W and Mo prefer intergranular fracture, while other bcc metals prefer transgranular cleavage.

  7. Interatomic Coulombic decay widths of helium trimer: Ab initio calculations

    Kolorenč, Přemysl, E-mail: kolorenc@mbox.troja.mff.cuni.cz [Charles University in Prague, Faculty of Mathematics and Physics, Institute of Theoretical Physics, V Holešovičkách 2, 180 00 Prague (Czech Republic); Sisourat, Nicolas [Sorbonne Universités, UPMC Univ Paris 06, UMR 7614, Laboratoire de Chimie Physique Matière et Rayonnement, F-75005 Paris (France); CNRS, UMR 7614, Laboratoire de Chimie Physique Matière et Rayonnement, F-75005 Paris (France)

    2015-12-14

    We report on an extensive study of interatomic Coulombic decay (ICD) widths in helium trimer computed using a fully ab initio method based on the Fano theory of resonances. Algebraic diagrammatic construction for one-particle Green’s function is utilized for the solution of the many-electron problem. An advanced and universal approach to partitioning of the configuration space into discrete states and continuum subspaces is described and employed. Total decay widths are presented for all ICD-active states of the trimer characterized by one-site ionization and additional excitation of an electron into the second shell. Selected partial decay widths are analyzed in detail, showing how three-body effects can qualitatively change the character of certain relaxation transitions. Previously unreported type of three-electron decay processes is identified in one class of the metastable states.

  8. Ab initio molecular dynamics calculations of ion hydration free energies

    We apply ab initio molecular dynamics (AIMD) methods in conjunction with the thermodynamic integration or 'λ-path' technique to compute the intrinsic hydration free energies of Li+, Cl-, and Ag+ ions. Using the Perdew-Burke-Ernzerhof functional, adapting methods developed for classical force field applications, and with consistent assumptions about surface potential (φ) contributions, we obtain absolute AIMD hydration free energies (ΔGhyd) within a few kcal/mol, or better than 4%, of Tissandier et al.'s [J. Phys. Chem. A 102, 7787 (1998)] experimental values augmented with the SPC/E water model φ predictions. The sums of Li+/Cl- and Ag+/Cl- AIMD ΔGhyd, which are not affected by surface potentials, are within 2.6% and 1.2 % of experimental values, respectively. We also report the free energy changes associated with the transition metal ion redox reaction Ag++Ni+→Ag+Ni2+ in water. The predictions for this reaction suggest that existing estimates of ΔGhyd for unstable radiolysis intermediates such as Ni+ may need to be extensively revised.

  9. Ab initio calculations versus polarized neutron diffraction for the spin density of free radicals

    The determination of the magnetization distribution using polarized neutron diffraction has played a key role during the last twenty years in the field of molecular magnetism. This distribution can also be obtained by first principle ab initio calculations. Such calculations always rely on approximations and the question that arises is to know whether the obtained results are reliable enough to represent accurately the properties of these molecules. The comparison between polarized neutron experimental results and ab initio calculations has turned to provide stringent tests for these methods. In the resent article a comparison between experimental and theoretical results is made and is illustrated by examples based on magnetic free radicals. (author)

  10. Study on the surface hydroxyl group on solid breeding materials by ab-initio calculations

    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)

  11. Transport and optical properties of warm dense aluminum in the two-temperature regime: Ab initio calculation and semiempirical approximation

    Knyazev, D. V.; Levashov, P. R.

    2014-01-01

    This work is devoted to the investigation of transport and optical properties of liquid aluminum in the two-temperature case. At first optical properties, static electrical and thermal conductivities were obtained in the \\textit{ab initio} calculation. The \\textit{ab initio} calculation is based on the quantum molecular dynamics, density functional theory and the Kubo-Greenwood formula. The semiempirical approximation was constructed based on the results of the \\textit{ab initio} caculation. ...

  12. Efficient ab initio free energy calculations by classically assisted trajectory sampling

    Wilson, Hugh F.

    2015-12-01

    A method for efficiently performing ab initio free energy calculations based on coupling constant thermodynamic integration is demonstrated. By the use of Boltzmann-weighted sums over states generated from a classical ensemble, the free energy difference between the classical and ab initio ensembles is readily available without the need for time-consuming integration over molecular dynamics trajectories. Convergence and errors in this scheme are discussed and characterised in terms of a quantity representing the degree of misfit between the classical and ab initio systems. Smaller but still substantial efficiency gains over molecular dynamics are also demonstrated for the calculation of average properties such as pressure and total energy for systems in equilibrium.

  13. Ab initio calculation of molecular energies including parity violating interactions

    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, Epv. 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 Epv values in the RHF-CIS framework and those in the RHF-SDE framework: the Epv 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 EH (DZ** basis set) while the maximal Epv value for the RHF-SDE formalism is just 3.635 X 10-20 EH (TZ basis set). It is remarkable that both in the RFH-CIS and in the RHF-SDE approaches the diagonal tensor components of Epv strictly follow the geometry of a molecule and are always different from zero at chiral conformations. The zeros of the total Epv 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 Epv. 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 Epv 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 violating energy

  14. Ab initio calculations of phosphorus and arsenic clustering parameters for the improvement of process simulation models

    Sahli, Beat [Integrated Systems Laboratory, ETH Zurich, Gloriastrasse 35, 8092 Zurich (Switzerland)], E-mail: sahli@iis.ee.ethz.ch; Vollenweider, Kilian [Integrated Systems Laboratory, ETH Zurich, Gloriastrasse 35, 8092 Zurich (Switzerland); Zographos, Nikolas; Zechner, Christoph [Synopsys Switzerland LLC, Affolternstrasse 52, 8050 Zurich (Switzerland)

    2008-12-05

    We present the results of extensive ab initio simulations for phosphorus clusters, arsenic clusters and mixed phosphorus/arsenic clusters in silicon. The specific defects and the parameters that are investigated are selected according to the needs of state-of-the-art diffusion and activation models, taking into account the availability of experimental data, the capabilities of current ab initio methods and the requirements for advanced technology development. The calculated binding energies are used to determine a good starting point for the calibration of a new clustering model implemented in an atomistic process simulator. The defect species V, I, P, PV, PI, As, AsV, AsI and clusters containing up to four dopant atoms and up to one V or I are considered in all relevant charge states. The ab initio results are discussed as well as the challenges arising in the transfer of this information into the process simulation model.

  15. Ab initio calculation of the lifetimes of 4p and 3d levels of Ca+

    We have done an ab initio calculation based on the Brueckner approximation for the lifetimes of 4p2P and 3d2D levels of Ca+. The results of the Brueckner approximation differ from experiment by 2.5%. With leading third-order corrections included, our results agree with the latest accurate experiment within a 1% difference

  16. Mechanisms for catalytic carbon nanofiber growth studied by ab initio density functional theory calculations

    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...

  17. Ab initio Calculations of Charge Symmetry Breaking in the A=4 Hypernuclei

    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: 7.512, year: 2014

  18. Ab Initio Calculations of Deuterium Isotope Effects on Chemical Shifts of Salt-Bridged Lysines

    Ullah, Saif; Ishimoto, Takayoshi; Williamson, Mike P.;

    2011-01-01

    Deuterium isotope effects measure the change in chemical shift on substitution of a proton by deuterium. They have been calculated by direct treatment of the H/D nuclear quantum effect using a multicomponent ab initio molecular orbital method based on a non-Born−Oppenheimer approximation. This me...

  19. \\textit{Ab initio} calculation of transport and optical properties of aluminum: influence of simulation parameters

    Knyazev, D. V.; Levashov, P. R.

    2013-01-01

    This work is devoted to the \\textit{ab initio} calculation of transport and optical properties of aluminum. The calculation is based on the quantum molecular dynamics simulation, density functional theory and the Kubo-Greenwood formula. Mainly the calculations are performed for liquid aluminum at near-normal densities for the temperatures from melting up to 20000 K. The results on dynamic electrical conductivity, static electrical conductivity and thermal conductivity are obtained and compare...

  20. Ab initio calculation of positron distribution, ACAR and lifetime in TTF-TCNQ

    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.

  1. Ab initio calculation of positron distribution, ACAR and lifetime in TTF-TCNQ

    Ishibashi, Shoji; Kohyama, Masanori

    2000-06-01

    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.

  2. On limits of ab initio calculations of pairing gap in nuclei

    Saperstein, E. E.; Baldo, M.; Lombardo, U.; Pankratov, S. S.; Zverev, M. V.

    2010-01-01

    A brief review of recent microscopic calculations of nuclear pairing gap is given. A semi-microscopic model is suggested in which the ab-initio effective pairing interaction is supplemented with a small phenomenological addendum. It involves a parameter which is universal for all medium and heavy nuclei. Calculations for several isotopic and isotonic chains of semi-magic nuclei confirm the relevance of the model.

  3. Ab Initio Calculations for the BaTiO3 (001) Surface Structure

    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.

  4. Raman spectroscopy, ab-initio model calculations, and conformational, equilibria in ionic liquids

    Berg, Rolf W.

    hoped that the structural resolving power of Raman spectroscopy will be appreciated by the reader, when used on crystals of known conformation and on the corresponding liquids, especially in combination with modern quantum mechanics calculations. It is hoped that these inetrdisciplinary methods will be...... 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...... instrumentation ...... 311 12.3 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 [C4...

  5. Dissipative Particle Dynamics interaction parameters from ab initio calculations

    Sepehr, Fatemeh; Paddison, Stephen J.

    2016-02-01

    Dissipative Particle Dynamics (DPD) is a commonly employed coarse-grained method to model complex systems. Presented here is a pragmatic approach to connect atomic-scale information to the meso-scale interactions defined between the DPD particles or beads. Specifically, electronic structure calculations were utilized for the calculation of the DPD pair-wise interaction parameters. An implicit treatment of the electrostatic interactions for charged beads is introduced. The method is successfully applied to derive the parameters for a hydrated perfluorosulfonic acid ionomer with absorbed vanadium cations.

  6. Large-scale ab initio configuration interaction calculations for light nuclei

    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 12C including emerging collective phenomena such as rotational band structures using SRG evolved chiral N3LO interactions.

  7. Ab initio calculations on the magnetic properties of transition metal complexes

    We present a protocol for the ab initio determination of the magnetic properties of mono- and polynuclear transition metal compounds. First, we obtain the low lying electronic states by multireference methods. Then, we include spin-orbit coupling and an external magnetic field for the determination of zero-field splitting and g-tensors. For the polynuclear complexes the magnetic exchange coupling constants are determined by a modified complete active space self consistent field method. Based on the results of the ab initio calculations, magnetic data such as magnetic susceptibility or magnetization are simulated and compared to experimental data. The results obtained for the polynuclear complexes are further analysed by calculations on model complexes where part of the magnetic centers are substituted by diamagnetic ions. The methods are applied to different Co and Ni containing transition metal complexes

  8. Ab initio calculations on twisted graphene/hBN: Electronic structure and STM image simulation

    Correa, J. D.; Cisternas, E.

    2016-09-01

    By performing ab initio calculations we obtained theoretical scanning tunneling microscopy (STM) images and studied the electronic properties of graphene on a hexagonal boron-nitrite (hBN) layer. Three different stack configurations and four twisted angles were considered. All calculations were performed using density functional theory, including van der Waals interactions as implemented in the SIESTA ab initio package. Our results show that the electronic structure of graphene is preserved, although some small changes are induced by the interaction with the hBN layer, particularly in the total density of states at 1.5 eV under the Fermi level. When layers present a twisted angle, the density of states shows several van Hove singularities under the Fermi level, which are associated to moiré patterns observed in theoretical STM images.

  9. Ultracold mixtures of metastable He and Rb: Scattering lengths from ab initio calculations and thermalization measurements

    Knoop, S.; Żuchowski, P. S.; KÈ©dziera, D.; Mentel, Ł.; Puchalski, M.; Mishra, H. P.; Flores, A. S.; Vassen, W.

    2014-08-01

    We have investigated the ultracold interspecies scattering properties of metastable triplet He and Rb. We performed state-of-the-art ab initio calculations of the relevant interaction potential, and measured the interspecies elastic cross section for an ultracold mixture of metastable triplet He4 and Rb87 in a quadrupole magnetic trap at a temperature of 0.5 mK. Our combined theoretical and experimental study gives an interspecies scattering length a4+87=+17-4+1a0, which prior to this work was unknown. More general, our work shows the possibility of obtaining accurate scattering lengths using ab initio calculations for a system containing a heavy, many-electron atom, such as Rb.

  10. Experimental studies and ab initio calculations on characteristics of the C state of SF2 radical

    SF2 radicals were generated by a pulsed dc discharge in the mixture gas beam of SF2 and Ar. The (2+1) resonance-enhanced multiphoton ionization (REMPI) excitation spectroscopy of SF2 radical was obtained between 325 and 365 nm. The SF+ ion signals were also observed in the same wavelength range. The analysis shows that the spectrum can be assigned as the two-photon resonant excitation of SF2 radical (B-tilde1 B1 and (C-tilde1 A1 states). And also, ab initio calculations suggest that the C-tilde state is a bonding state with Rydberg characteristic. The potential energy surfaces (PESs) of SF2 and SF2+ by ab initio calculations suggest that SF+ ions originate from dissociation processes of excited SF2+ ions. (author)

  11. Ab Initio Calculations and Raman and SERS Spectral Analyses of Amphetamine Species

    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...... with internal bonds (sulfates, hydrogen phosphates, etc.) need to be taken into account when employing these spectra for identification purposes. These results also show how Raman spectroscopy can assist the forensic community in drug profiling studies. Furthermore, because their spectra are different...

  12. Ab initio calculations and modelling of atomic cluster structure

    Solov'yov, Ilia; Lyalin, Andrey G.; Solov'yov, Andrey V.;

    2004-01-01

    framework for modelling the fusion process of noble gas clusters is presented. We report the striking correspondence of the peaks in the experimentally measured abundance mass spectra with the peaks in the size-dependence of the second derivative of the binding energy per atom calculated for the chain...

  13. Ab Initio Calculations of Hydrocarbon Thermochemistry and Reaction Kinetics

    Aguilera Iparraguirre, Jorge

    2009-01-01

    In the framework of the SFB 551 "Carbon from the Gas Phase: Elementary Reactions, Structures, Materials" several areas of carbon related chemistry have been studied with help of computational tools. They include the exploration of different ways of building PAHs, the attempt to check the limits of quantum chemistry methods in hydrocarbon chemistry using explicitly-correlated methods and the calculation of accurate reaction rates.

  14. Towards Microscopic Ab Initio Calculations of Astrophysical S-Factors

    Neff, Thomas; Langanke, Karlheinz

    2010-01-01

    Low energy capture cross sections are calculated within a microscopic many-body approach using an effective Hamiltonian derived from the Argonne V18 potential. The dynamics is treated within Fermionic Molecular Dynamics (FMD) which uses a Gaussian wave-packet basis to represent the many-body states. A phase-shift equivalent effective interaction derived within the Unitary Correlation Operator Method (UCOM) that treats explicitly short-range central and tensor correlations is employed. As a first application the 3He(alpha,gamma)7Be reaction is presented. Within the FMD approach the microscopic many-body wave functions of the 3/2- and 1/2- bound states in 7Be as well as the many-body scattering states in the 1/2+, 3/2+ and 5/2+ channels are calculated as eigenstates of the same microscopic effective Hamiltonian. Finally the S-factor is calculated from E1 transition matrix elements between the many-body scattering and bound states. For 3He(alpha,gamma)7Be the S-factor agrees very well, both in absolute normaliza...

  15. Hyperfine tensors of nitrogen-vacancy center in diamond from \\emph{ab initio} calculations

    Gali, Adam

    2009-01-01

    We determine and analyze the charge and spin density distributions of nitrogen-vacancy (N-V) center in diamond for both the ground and excited states by \\emph{ab initio} supercell calculations. We show that the hyperfine tensor of $^{15}$N nuclear spin is negative and strongly anisotropic in the excited state, in contrast to previous models used extensively to explain electron spin resonance measurements. In addition, we detect a significant redistribution of the spin density due to excitatio...

  16. The onset of ion solvation by ab initio calculations: Comparison of water and methanol

    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

  17. Capillary affinity electrophoresis and ab initio calculation studies on complexation of valinomycin with Na+ ion

    Ehala, Sille; Dybal, Jiří; Makrlík, E.; Kašička, Václav

    2009-01-01

    Roč. 32, č. 4 (2009), s. 597-604. ISSN 1615-9306 R&D Projects: GA ČR(CZ) GA203/06/1044; GA ČR(CZ) GA203/08/1428; GA AV ČR 1ET400500402 Institutional research plan: CEZ:AV0Z40550506; CEZ:AV0Z40500505 Keywords : capillary affinity electrophoresis * valinomycin * ab initio calculation Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 2.551, year: 2009

  18. Electronic transport properties of fullerene functionalized carbon nanotubes: Ab initio and tight-binding calculations

    Fürst, Joachim Alexander; J Hashemi; Markussen, Troels; Brandbyge, Mads; Jauho, Antti-Pekka; Nieminen, R. M.

    2009-01-01

    Fullerene functionalized carbon nanotubes-NanoBuds-form a novel class of hybrid carbon materials, which possesses many advantageous properties as compared to the pristine components. Here, we report a theoretical study of the electronic transport properties of these compounds. We use both ab initio techniques and tight-binding calculations to illustrate these materials' transmission properties and give physical arguments to interpret the numerical results. Specifically, above the Fermi energy...

  19. Electronic transport properties of fullerene functionalized carbon nanotubes: Ab initio and tight-binding calculations

    Fürst, J. A.; J Hashemi; Markussen, T.; Brandbyge, M.; Jauho, A.P.; Nieminen, Risto M.

    2009-01-01

    Fullerene functionalized carbon nanotubes—NanoBuds—form a novel class of hybrid carbon materials, which possesses many advantageous properties as compared to the pristine components. Here, we report a theoretical study of the electronic transport properties of these compounds. We use both ab initio techniques and tight-binding calculations to illustrate these materials’ transmission properties and give physical arguments to interpret the numerical results. Specifically, above the Fermi energy...

  20. Ab initio Calculations of Optical Properties of Clusters

    Shinde, Ravindra

    2016-01-01

    We have performed systematic large-scale all-electron correlated calculations on boron Bn, aluminum Aln and magnesium Mgn clusters (n=2--5), to study their linear optical absorption spectra. Several possible isomers of each cluster were considered, and their geometries were optimized at the coupled-cluster singles doubles (CCSD) level of theory. Using the optimized ground-state geometries, excited states of different clusters were computed using the multi-reference singles-doubles configuration interaction (MRSDCI) approach, which includes electron correlation effects at a sophisticated level. These CI wavefunctions were used to compute the transition dipole matrix elements connecting the ground and various excited states of different clusters, eventually leading to their linear absorption spectra. The convergence of our results with respect to the basis sets, and the size of the CI expansion was carefully examined. Isomers of a given cluster show a distinct signature spectrum, indicating a strong structure p...

  1. Ab Initio Calculations Of Nuclear Reactions And Exotic Nuclei

    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.

  2. Ab Initio Calculations Of Nuclear Reactions And Exotic Nuclei

    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.

  3. Electronic Structure of Silicon Nanowires Matrix from Ab Initio Calculations.

    Monastyrskii, Liubomyr S; Boyko, Yaroslav V; Sokolovskii, Bogdan S; Potashnyk, Vasylyna Ya

    2016-12-01

    An investigation of the model of porous silicon in the form of periodic set of silicon nanowires has been carried out. The electronic energy structure was studied using a first-principle band method-the method of pseudopotentials (ultrasoft potentials in the basis of plane waves) and linearized mode of the method of combined pseudopotentials. Due to the use of hybrid exchange-correlation potentials (B3LYP), the quantitative agreement of the calculated value of band gap in the bulk material with experimental data is achieved. The obtained results show that passivation of dangling bonds with hydrogen atoms leads to substantial transformation of electronic energy structure. At complete passivation of the dangling silicon bonds by hydrogen atoms, the band gap value takes the magnitude which substantially exceeds that for bulk silicon. The incomplete passivation gives rise to opposite effect when the band gap value decreases down the semimetallic range. PMID:26768147

  4. Structure and lattice dynamics of PrFe3(BO3)4: Ab initio calculation

    Chernyshev, V. A.; Nikiforov, A. E.; Petrov, V. P.

    2016-06-01

    The crystal structure and phonon spectrum of PrFe3(BO3)4 are ab initio calculated in the context of the density functional theory. The ion coordinates in the unit cell of a crystal and the lattice parameters are evaluated from the calculations. The types and frequencies of the fundamental vibrations, as well as the line intensities of the IR spectrum, are determined. The elastic constants of the crystal are calculated. A "seed" frequency of the vibration strongly interacting with the electron excitation on the praseodymium ion is obtained for low-frequency A 2 mode. The calculated results are in agreement with the known experimental data.

  5. Ab initio calculation of valley splitting in monolayer δ-doped phosphorus in silicon.

    Drumm, Daniel W; Budi, Akin; Per, Manolo C; Russo, Salvy P; L Hollenberg, Lloyd C

    2013-01-01

    : The differences in energy between electronic bands due to valley splitting are of paramount importance in interpreting transport spectroscopy experiments on state-of-the-art quantum devices defined by scanning tunnelling microscope lithography. Using vasp, we develop a plane-wave density functional theory description of systems which is size limited due to computational tractability. Nonetheless, we provide valuable data for the benchmarking of empirical modelling techniques more capable of extending this discussion to confined disordered systems or actual devices. We then develop a less resource-intensive alternative via localised basis functions in siesta, retaining the physics of the plane-wave description, and extend this model beyond the capability of plane-wave methods to determine the ab initio valley splitting of well-isolated δ-layers. In obtaining an agreement between plane-wave and localised methods, we show that valley splitting has been overestimated in previous ab initio calculations by more than 50%. PMID:23445785

  6. Ab Initio No-Core Shell Model Calculations Using Realistic Two- and Three-Body Interactions

    Navratil, P; Ormand, W E; Forssen, C; Caurier, E

    2004-11-30

    There has been significant progress in the ab initio approaches to the structure of light nuclei. One such method is the ab initio no-core shell model (NCSM). Starting from realistic two- and three-nucleon interactions this method can predict low-lying levels in p-shell nuclei. In this contribution, we present a brief overview of the NCSM with examples of recent applications. We highlight our study of the parity inversion in {sup 11}Be, for which calculations were performed in basis spaces up to 9{Dirac_h}{Omega} (dimensions reaching 7 x 10{sup 8}). We also present our latest results for the p-shell nuclei using the Tucson-Melbourne TM three-nucleon interaction with several proposed parameter sets.

  7. Iron -chromium alloys and free surfaces: from ab initio calculations to thermodynamic modeling

    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

  8. Phonon spectrum of lead oxychloride Pb3O2Cl2: Ab initio calculation and experiment

    Zakir'yanov, D. O.; Chernyshev, V. A.; Zakir'yanova, I. D.

    2016-02-01

    IR and Raman spectra of Pb3O2Cl2 in the range of 50-600 cm-1 have been detected for the first time. Ab initio calculations of the crystal structure and the phonon spectrum of Pb3O2Cl2 in the framework of LCAO approach have been performed by the Hartree-Fock method and in the framework of the density functional theory with the use of hybrid functionals. The results of calculations have made it possible to interpret the experimental vibration spectra and reveal silent modes, which do not manifest themselves in these spectra but influence the optical properties of the crystal.

  9. Superior thermal conductivity and extremely high mechanical strength in polyethylene chains from {\\it ab initio} calculation

    Jiang, Jin-Wu; Zhao, Junhua; Zhou, Kun; Rabczuk, Timon

    2012-01-01

    The upper limit of the thermal conductivity and the mechanical strength are predicted for the polyethylene chain, by performing the {\\it ab initio} calculation and applying the quantum mechanical non-equilibrium Green's function approach. Specially, there are two main findings from our calculation: (1). the thermal conductivity can reach a high value of 310 W/K/m in a 100 nm polyethylene chain at room temperature; (2). the Young's modulus in the polyethylene chain is as high as 374.5 GPa, and...

  10. Ab initio molecular orbital calculations on ion pair-water complexes of metal halides and oxides

    Mohandas, P; Singh, S.; Chandrasekhar, J

    1994-01-01

    Ab initio MO calculations are performed on a series of ion-molecular and ion pair-molecular complexes of H2O + MX (MX = LiF, LiCl, NaCl, BeO and MgO) systems. BSSE-corrected stabilization energies, optimized geometrical parameters, internal force constants and harmonic vibrational frequencies have been evaluated for all the structures of interest. The trends observed in the geometrical parameters and other properties calculated for the mono-hydrated contact ion pair complexes parallel those c...

  11. Ionization of aqueous cations: Photoelectron spectroscopy and ab initio calculations of protonated imidazole

    Jagoda-Cwiklik, Barbara; Slavíček, P.; Nolting, D.; Winter, B.; Jungwirth, Pavel

    2008-01-01

    Roč. 112, č. 25 (2008), s. 7355-7358. ISSN 1520-6106 R&D Projects: GA MŠk LC512; GA ČR GA203/07/1006 Grant ostatní: DFG(DE) WI1327/3-1; GA ČR(CZ) GP203/07/P449 Institutional research plan: CEZ:AV0Z40550506 Keywords : protenated imidazole * ab initio calculations * photoelectron spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.189, year: 2008

  12. Experimental and ab initio DFT calculated Raman Spectrum of Sudan I, a Red Dye

    Kunov-Kruse, Andreas Jonas; Kristensen, Steffen Buus; Liu, Chuan;

    2011-01-01

    . 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......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...

  13. 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.

  14. Ab initio calculations of 14N and 15N hyperfine structures

    Jönsson, P; Nemouchi, M; Godefroid, M

    2010-01-01

    Hyperfine structure parameters are calculated for the 2p2(3P)3s 4P_J, 2p2(3P)3p 4Po_J and 2p2(3P)3p 4Do_J levels, using the ab initio multiconfiguration Hartree-Fock method. The theoretical hyperfine coupling constants are in complete disagreement with the experimental values of Jennerich et al. (EPJD 40(2006), 81) deduced from the analysis of the near-infrared Doppler-free saturated absorption spectra.

  15. Efficient Use of an Adapting Database of Ab Initio Calculations To Generate Accurate Newtonian Dynamics.

    Shaughnessy, M C; Jones, R E

    2016-02-01

    We develop and demonstrate a method to efficiently use density functional calculations to drive classical dynamics of complex atomic and molecular systems. The method has the potential to scale to systems and time scales unreachable with current ab initio molecular dynamics schemes. It relies on an adapting dataset of independently computed Hellmann-Feynman forces for atomic configurations endowed with a distance metric. The metric on configurations enables fast database lookup and robust interpolation of the stored forces. We discuss mechanisms for the database to adapt to the needs of the evolving dynamics, while maintaining accuracy, and other extensions of the basic algorithm. PMID:26669825

  16. Real-space ab-initio electronic structure calculations using SfePy

    Cimrman, R.; Novák, Matyáš; Kolman, Radek; Vackář, Jiří

    Plzeň: University of West Bohemia, 2015 - (Adámek, V.). s. 21-22 ISBN 978-80-261-0568-8. [Computational Mechanics 2015 /31./- conference with international participation /31./. 09.11.2015-11.11.2015, Špičák] R&D Projects: GA ČR(CZ) GAP108/11/0853; GA ČR(CZ) GAP101/12/2315 Institutional support: RVO:61388998 ; RVO:68378271 Keywords : real-space ab-initio electronic structure calculations * finite element method * isogeometric analysis Subject RIV: BE - Theoretical Physics

  17. Structural Features of Boron-Doped Si(113) Surfaces Simulated by ab initio Calculations

    LIAO Long-Zhong; LIU Zheng-Hui; ZHANG Zhao-Hui

    2008-01-01

    Based on ab initio calculations, boron-doped Si(113) surfaces have been simulated and atomic structures of the surfaces have been proposed. It has been determined that surface features of empty and filled states that are separately localized at pentamers and adatoms indicates a low surface density of B atoms, while it is attributed to heavy doping of B atoms at the second layer that pentamers and adatoms are both present in an image of scanning tunnelling microscopy. B doping at the second layer should be balanced by adsorbed B or Si atoms beside the adatoms and inserted B interstitials below the adatoms.

  18. \\textit{Ab initio} calculation of transport and optical properties of aluminum: influence of simulation parameters

    Knyazev, D V

    2013-01-01

    This work is devoted to the \\textit{ab initio} calculation of transport and optical properties of aluminum. The calculation is based on the quantum molecular dynamics simulation, density functional theory and the Kubo-Greenwood formula. Mainly the calculations are performed for liquid aluminum at near-normal densities for the temperatures from melting up to 20000 K. The results on dynamic electrical conductivity, static electrical conductivity and thermal conductivity are obtained and compared with available reference and experimental data and the calculations of other authors. The influence of the technical parameters on the results is investigated in detail. The error of static electrical conductivity calculation is estimated to be about 20%; more accurate results require bigger number of atoms.

  19. Recent progress with large-scale ab initio calculations: the CONQUEST code

    Bowler, D. R.; Choudhury, R.; Gillan, M. J.; Miyazaki, T.

    While the success of density functional theory (DFT) has led to its use in a wide variety of fields such as physics, chemistry, materials science and biochemistry, it has long been recognised that conventional methods are very inefficient for large complex systems, because the memory requirements scale as N 2 and the cpu requirements as N 3 (where N is the number of atoms). The principles necessary to develop methods with linear scaling of the cpu and memory requirements with system size (O(N ) methods) have been established for more than ten years, but only recently have practical codes showing this scaling for DFT started to appear. We report recent progress in the development of the Conquest code, which performs O(N ) DFT calculations on parallel computers, and has a demonstrated ability to handle systems of over 10000 atoms. The code can be run at different levels of precision, ranging from empirical tight-binding, through ab initio tight-binding, to full ab initio , and techniques for calculating ionic forces in a consistent way at all levels of precision will be presented. Illustrations are given of practical Conquest calculations in the strained Ge/Si(001) system.

  20. Ab initio calculations of the optical properties of crystalline and liquid InSb

    Ab initio calculations of the electronic and optical properties of InSb were performed for both the crystalline and liquid states. Two sets of atomic structure models for liquid InSb at 900 K were obtained by ab initio molecular dynamics simulations. To reduce the effect of structural peculiarities in the liquid models, an averaging of the two sets of the calculated electronic and optical properties corresponding to the two liquid models was performed. The calculated results indicate that, owing to the phase transition from crystal to liquid, the density of states around the Fermi level increases. As a result, the energy band gap opening near the Fermi level disappears. Consequently, the optical properties change from semiconductor to metallic behavior. Namely, owing to the melting of InSb, the interband transition peaks disappear and a Drude-like dispersion is observed in the optical dielectric functions. The optical absorption at a photon energy of 3.06 eV, which is used in Blu-ray Disc systems, increases owing to the melting of InSb. This increase in optical absorption is proposed to result from the increased optical transitions below 2 eV

  1. A-dependence of the Spectra of the F Isotopes from ab initio Calculations

    Barrett, Bruce R.; Dikmen, Erdal; Maris, Pieter; Vary, James P.; Shirokov, Andrey M.

    2016-03-01

    Using a succession of Okubo-Lee-Suzuki transformations within the No Core Shell Model (NCSM) formalism, we derive an ab initio, non-perturbative procedure for calculating the input for standard shell-model (SSM) calculations within one major shell. We have used this approach for calculating the spectra of the F isotopes from A=18 to A=25, so as to study the A-dependence of the results. In particular, we are interested in seeing if the theoretical input is weak enough, so that a single set of two-body effective interactions can be used for all of the F isotopes investigated. We will present results from SSM calculations based on input obtained with the JISP16 nucleon-nucleon interaction in an initial 4 ℏΩ NCSM basis space. This work supported in part by TUBITAK-BIDEB, the US DOE, the US NSF, NERSC, and the Russian Ministry of Education and Science.

  2. Minimal parameter implicit solvent model for ab initio electronic structure calculations

    Dziedzic, Jacek; Skylaris, Chris-Kriton; Mostofi, Arash A; Payne, Mike C

    2011-01-01

    We present an implicit solvent model for ab initio electronic structure calculations which is fully self-consistent and is based on direct solution of the nonhomogeneous Poisson equation. The solute cavity is naturally defined in terms of an isosurface of the electronic density according to the formula of Fattebert and Gygi (J. Comp. Chem. 23, 6 (2002)). While this model depends on only two parameters, we demonstrate that by using appropriate boundary conditions and dispersion-repulsion contributions, solvation energies obtained for an extensive test set including neutral and charged molecules show dramatic improvement compared to existing models. Our approach is implemented in, but not restricted to, a linear-scaling density functional theory (DFT) framework, opening the path for self-consistent implicit solvent DFT calculations on systems of unprecedented size, which we demonstrate with calculations on a 2615-atom protein-ligand complex.

  3. High-pressure physical properties of magnesium silicate post-perovskite from ab initio calculations

    Zi-Jiang Liu; Xiao-Wei Sun; Cai-Rong Zhang; Jian-Bu Hu; Ling-Cang Cai; Qi-Feng Chen

    2012-08-01

    The structure, thermodynamic and elastic properties of magnesium silicate (MgSiO3) post-perovskite at high pressure are investigated with quasi-harmonic Debye model and ab initio method based on the density functional theory (DFT). The calculated structural parameters of MgSiO3 post-perovskite are consistent with the available experimental results and the recent theoretical results. The Debye temperature, heat capacity and thermal expansion coefficient at high pressures and temperatures are predicted using the quasi-harmonic Debye model. The elastic constants are calculated using stress–strain relations. A complete elastic tensor of MgSiO3 post-perovskite is determined in the wide pressure range. The calculated elastic anisotropic factors and directional bulk modulus show that MgSiO3 post-perovskite possesses high elastic anisotropy.

  4. Identifying Stereoisomers by ab-initio Calculation of Secondary Isotope Shifts on NMR Chemical Shieldings

    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.

  5. Atomic and Electronic Structures of C_60+BN Nanopeapods from ab initio Pseudopotential Calculations

    Trave, Andrea; Ribeiro, Filipe; Louie, Steven G.; Cohen, Marvin L.

    2004-03-01

    Nanopeapods are structures of nanometric size consisting of an external carbon nanotube encapsulating a chain or complex array of fullerenes. Recent calculations and experiments have proven that nanopeapods can be obtained assembling fullerenes within boron nitride nanotubes, creating novel materials of possible interest for electronic transport applications. To improve the understanding of the properties of these composite systems, as compared to empty nanotubes and carbon nanopeapods, ab-initio total energy calculations have been performed within the pseudopotential Density Functional Theory in local density approximation. Results of these calculations on the energetics and geometrical deformations involved in the encapsulation will be presented, followed by a discussion of the consequences on the electronic structures of these systems, with particular focus on aspects relevant to electronic transport phenomena. This work is supported by NFS (Grant DMR00-87088) and DOE (Contract DE-AC03-76SF00098), using computational resources at NERSC and NPACI.

  6. The Crystal Structure of Impurity Centers Tm^{2+} and Eu^{2+} in SrCl2 : Ab Initio Calculations

    Chernyshev, V. A.; Serdcev, A. V.; Petrov, V. P.; Nikiforov, A. E.

    2016-01-01

    Ab initio calculations of the impurity centers Tm^{2+} thulium and europium Eu^{2+} in SrCl2 and MeF2 (Me = Ca, Sr, Ba) were carried out at low (zero) temperature. The crystal structure of impurity centers was investigated. Charge density maps show that the bonds formed by the rare-earth ions have an ionic character. The crystal structures, lattice dynamics, and band structures of MeF2 and SrCl2 were calculated at low temperature. Ab initio calculations were performed in periodic CRYSTAL code within the framework of the MO LCAO approach by using hybrid DFT functionals.

  7. Unrestricted compact model potentials for ab initio embedded cluster calculations: Magnetic interactions in KNiF3

    Mejías, J. A.; Sanz, Javier Fernández

    1995-01-01

    Compact model potentials to introduce the effect of spin-dependent environments in ab initio embedded cluster calculations are reported. The groups forming the environment are described by unrestricted Hartree-Fock wave functions. The method is tested for the magnetic description of KNiF3 by using different model clusters. The cluster calculations are done at the unrestricted Hartree-Fock and unrestricted second-order perturbation levels. The obtained values are in excellent agreement with other more sophisticated ab initio calculations if some Ni-F delocalization is allowed. How the superexchange interaction is accounted for in our method is also discussed.

  8. Ab initio many-body calculations of nucleon-nucleus scattering

    Quaglioni, Sofia

    2009-01-01

    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 3H, 4He and 10Be and proton scattering on 3He and 4He, 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-4He S-wave phase shifts. On the contrary, the experimental nucleon-4He P-wave phase shifts are not well reproduced by any NN potential we use. We demonstrate that a proper treatment of the coupling to the n-10Be continuum is successful in explaining the parity-inverted ground state in 11Be.

  9. Ab initio many-body calculations of nucleon scattering on ^16O

    Navratil, Petr; Quaglioni, Sofia; Roth, Robert

    2008-10-01

    We develop a new ab initio many-body approachootnotetextS. Quaglioni and P. Navratil, arXiv:0804.1560. capable of describing simultaneously both bound and scattering states in light nuclei, by combining the resonating-group methodootnotetextY. C. Tang et al., Phys. Rep. 47, 167 (1978); K. Langanke and H. Friedrich, Advances in Nuclear Physics, Plenum, New York, 1987. with the ab initio no-core shell model (NCSM).ootnotetextP. Navratil, J. P. Vary, and B. R. Barrett, Phys. Rev. Lett. 84, 5728 (2000); Phys. Rev. C 62, 054311 (2000). 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, while preserving Pauli principle and translational symmetry. We will present results for low-energy nucleon scattering on ^16O and for A=17 bound states obtained using realistic nucleon-nucleon potentials. The ^16O wave functions are calculated within the importance-truncated NCSMootnotetextR. Roth and P. Navratil, Phys. Rev. Lett. 99, 092501 (2007). that allows the use of model spaces up to 18φ and ultimately enables to reach convergence of phase-shifts and other observables. Prepared by LLNL under Contract DE-AC52-07NA27344. Support from the U.S. DOE/SC/NP (Work Proposal No. SCW0498), and from the U. S. Department of Energy Grant DE-FC02-07ER41457 is acknowledged.

  10. Ab-initio Calculations of Electronic Properties of Boron Phosphide (BP)

    Ejembi, John; Franklin, Lashaunda; Malozovsky, Yuriy; Bagayoko, Diola

    2014-03-01

    We present results from ab-initio, self consistent local density approximation (LDA) calculations of electronic and related properties of zinc blende boron phosphide (BP). We employed a local density approximation (LDA) potential and implemented the linear combination of atomic orbitals (LCAO) formalism. This implementation followed the Bagayoko, Zhao, and Williams (BZW) method, as enhanced by Ekuma and Franklin (BZW-EF). We discuss our preliminary results for the indirect band gap, from Γ to X, of Boron Phosphide. We also report calculated electron and hole effective masses for Boron Phosphide and total (DOS) and partial (pDOS) density of states. Acknowledgments: This research is funded in part by the National Science Foundation (NSF) and the Louisiana Board of Regents, through LASiGMA [Award Nos. EPS- 1003897, NSF (2010-15)-RII-SUBR] and NSF HRD-1002541, the US Department of Energy - National, Nuclear Security Administration (NNSA) (Award No. DE-NA0001861), LaSPACE, and LONI-SUBR.

  11. Ab-initio calculations of electronic, transport, and structural properties of boron phosphide

    Ejembi, J. I.; Nwigboji, I. H.; Franklin, L.; Malozovsky, Y.; Zhao, G. L.; Bagayoko, D., E-mail: diola-bagayoko@subr.edu [Department of Physics, Southern University and A and M College, Baton Rouge, Louisiana 70813 (United States)

    2014-09-14

    We present results from ab-initio, self-consistent density functional theory calculations of electronic and related properties of zinc blende boron phosphide (zb-BP). We employed a local density approximation potential and implemented the linear combination of atomic orbitals formalism. This technique follows the Bagayoko, Zhao, and Williams method, as enhanced by the work of Ekuma and Franklin. The results include electronic energy bands, densities of states, and effective masses. The calculated band gap of 2.02 eV, for the room temperature lattice constant of a=4.5383 Å, is in excellent agreement with the experimental value of 2.02±0.05 eV. Our result for the bulk modulus, 155.7 GPa, agrees with experiment (152–155 GPa). Our predictions for the equilibrium lattice constant and the corresponding band gap, for very low temperatures, are 4.5269 Å and 2.01 eV, respectively.

  12. Electronic Curves Crossing in Methyl Iodide by Spin–Orbit Ab Initio Calculation

    An ab initio investigation of electronic curve crossing in a methyl iodide molecule is carried out using Spin–Orbit multiconfigurational quasidegenerate perturbation theory. The one-dimensional rigid potential curves and optimized effective curves of low-lying states, including Spin–Orbit coupling and relativistic effects, are calculated. The Spin–Orbit electronic curve crossing between 3Q0+and 1Q1, and the shadow minimum in potential energy curve of 3Q0+ at large internuclear distance are found in both sets of the curves according to the present calculations. The crossing position is in the range of RC–I = 0.2370 ± 00001 nm. Comparisons with other reports are presented. (atomic and molecular physics)

  13. Ab Initio Calculation of Structure and Thermodynamic Properties of Zintl Aluminide SrAl2

    Fu, Zhi-Jian; Jia, Li-Jun; Xia, Ji-Hong; Tang, Ke; Li, Zhao-Hong; Sun, Xiao-Wei; Chen, Qi-Feng

    2015-12-01

    The structural and thermodynamic properties of the orthorhombic and cubic structure SrAl2 at pressure and temperature are investigated by using the ab initio plane-wave pseudopotential density functional theory methodwithin the generalised gradient approximation (GGA). The calculated lattice parameters are in agreement with the available experimental data and other theoretical results. The phase transition predicted takes place at 0.5 GPa from the orthorhombic to the cubic structure at zero temperature. The thermodynamic properties of the zinc-blende structure SrAl2 are calculated by the quasi-harmonic Debye model. The pressure-volume relationship and the variations inthe thermal expansion α are obtained systematically in the pressure and temperature ranges of 0-5 GPa and 0-500 K, respectively.

  14. Ab-initio calculations on two-electron ions in strongly coupled plasma environment

    Bhattacharyya, S; Mukherjee, T K

    2015-01-01

    In this work, the controversy between the interpretations of recent measurements on dense aluminum plasma created with Linac coherent light sources (LCLS) X-ray free electron laser (FEL) and Orion laser has been addressed. In both kind of experiments, helium-like and hydrogen-like spectral lines are used for plasma diagnostics . However, there exist no precise theoretical calculations for He-like ions within dense plasma environment. The strong need for an accurate theoretical estimates for spectral properties of He-like ions in strongly coupled plasma environment leads us to perform ab initio calculations in the framework of Rayleigh-Ritz variation principle in Hylleraas coordinates where ion-sphere potential is used. An approach to resolve the long-drawn problem of numerical instability for evaluating two-electron integrals with extended basis inside a finite domain is presented here. The present values of electron densities corresponding to disappearance of different spectral lines obtained within the fram...

  15. Study of the atomic rare gas behaviour by ab initio calculations

    The atomic behaviour of helium and krypton in uranium dioxide has been studied using an ab initio simulation technique. Incorporation energies and solution energies of these two rare gases have been calculated. Krypton atoms are found to be insoluble in this nuclear fuel whatever the trap considered and their presence in the lattice induces swelling when they are located in interstitial sites or in oxygen vacancies. Due to its small atomic size, the predicted helium behaviour is very different. Indeed, helium is found to be soluble in stoichiometric and hyper-stoichiometric uranium dioxide in the presence of uranium vacancies or divacancies constituted by one uranium and one oxygen vacancy. Moreover helium atoms induce a lattice parameter contraction except in interstitial sites where a slight expansion is calculated. (author)

  16. Ab initio calculation of ionization potential and electron affinity in solid-state organic semiconductors

    Kang, Youngho; Jeon, Sang Ho; Cho, Youngmi; Han, Seungwu

    2016-01-01

    We investigate the vertical ionization potential (IP) and electron affinity (EA) of organic semiconductors in the solid state that govern the optoelectrical property of organic devices using a fully ab initio way. The present method combines the density functional theory and many-body perturbation theory based on G W approximations. To demonstrate the accuracy of this approach, we carry out calculations on several prototypical organic molecules. Since IP and EA depend on the molecular orientation at the surface, the molecular geometry of the surface is explicitly considered through the slab model. The computed IP and EA are in reasonable and consistent agreements with spectroscopic data on organic surfaces with various molecular arrangements. However, the transport gaps are slightly underestimated in calculations, which can be explained by different screening effects between surface and bulk regions.

  17. Modeling and Ab initio Calculations of Thermal Transport in Si-Based Clathrates and Solar Perovskites

    He, Yuping

    2015-03-01

    We present calculations of the thermal transport coefficients of Si-based clathrates and solar perovskites, as obtained from ab initio calculations and models, where all input parameters derived from first principles. We elucidated the physical mechanisms responsible for the measured low thermal conductivity in Si-based clatherates and predicted their electronic properties and mobilities, which were later confirmed experimentally. We also predicted that by appropriately tuning the carrier concentration, the thermoelectric figure of merit of Sn and Pb based perovskites may reach values ranging between 1 and 2, which could possibly be further increased by optimizing the lattice thermal conductivity through engineering perovskite superlattices. Work done in collaboration with Prof. G. Galli, and supported by DOE/BES Grant No. DE-FG0206ER46262.

  18. Ab-initio calculations of charge symmetry breaking in the A=4 hypernuclei

    Gazda, Daniel

    2015-01-01

    We report on ab-initio NCSM calculations of the A=4 mirror Lambda hypernuclei Lambda-4H and Lambda-4He, using the Bonn-Juelich LO chiral EFT YN potentials plus a CSB Lambda0--Sigma0 mixing vertex. In addition to reproducing rather well the 0+ (g.s.) and 1+ (exc.) binding energies, these four-body calculations demonstrate for the first time that the observed CSB splitting of mirror levels, reaching hundreds of keV for 0+ (g.s.), can be reproduced using realistic theoretical interaction models, although with a non-negligible momentum cutoff dependence. Our results are discussed in relation to recent measurements of the Lambda-4H (0+ g.s.) binding energy [MAMI A1 Collaboration, Phys. Rev. Lett. 114, 232501 (2015)] and the Lambda-4He (1+ exc.) excitation energy [J-PARC E13 Collaboration, Phys. Rev. Lett. 115, 222501 (2015)].

  19. Raman Spectroscopy and Ab-Initio Model Calculations on Ionic Liquids

    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 ([C4mim][X]) salts. The rotational isomerism of the [C4mim]þ cation is described: the presence of anti and...... gauche conformers that has been elucidated in remarkable papers by Hamaguchi et al. Such presence of a conformational equilibrium seems to be a general feature of the room temperature liquids. Then the ‘‘localized structure features’’ that apparently exist in ionic liquids are described. It is hoped that...

  20. Ab Initio Calculations on Halogen Bond Between N-Br and Electron-donating Groups

    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.

  1. Stress reduction of Cu-doped diamond-like carbon films from ab initio calculations

    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.

  2. A set of molecular models based on quantum mechanical ab initio calculations and thermodynamic data

    Eckl, Bernhard; Hasse, Hans

    2009-01-01

    A parameterization strategy for molecular models on the basis of force fields is proposed, which allows a rapid development of models for small molecules by using results from quantum mechanical (QM) ab initio calculations and thermodynamic data. The geometry of the molecular models is specified according to the atom positions determined by QM energy minimization. The electrostatic interactions are modeled by reducing the electron density distribution to point dipoles and point quadrupoles located in the center of mass of the molecules. Dispersive and repulsive interactions are described by Lennard-Jones sites, for which the parameters are iteratively optimized to experimental vapor-liquid equilibrium (VLE) data, i.e. vapor pressure, saturated liquid density, and enthalpy of vaporization of the considered substance. The proposed modeling strategy was applied to a sample set of ten molecules from different substance classes. New molecular models are presented for iso-butane, cyclohexane, formaldehyde, dimethyl...

  3. Determination of absolute configuration using ab initio calculation of optical rotation.

    Stephens, P J; Devlin, F J; Cheeseman, J R; Frisch, M J; Bortolini, O; Besse, P

    2003-01-01

    Ab initio Density Functional Theory (DFT) calculations of transparent spectral region, discrete frequency specific rotations were used to assign the absolute configurations (ACs) of: 1, 2H-naphtho[1,8-bc]thiophene 1-oxide; 2, m-F-phenyl glycidic acid methyl ester; 3, o-Br-phenyl glycidic acid methyl ester; 4, p-CH(3)-phenyl glycidic acid methyl ester; 5, 2-(1-hydroxyethyl)-chromen-4-one; and 6, 6-Br-2-(1-hydroxyethyl)-chromen-4-one. The ACs of 5 and 6 were previously determined via X-ray crystallography to be: 5, R(-)/S(+); 6, R(+)/S(-). The ACs obtained using [alpha](D) are the same for both 5 and 6: R(+)/S(-). We conclude that the previously reported AC of 5 is incorrect. PMID:12884375

  4. Interactions of foreign interstitial and substitutional atoms in bcc iron from ab initio calculations

    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

  5. High-pressure study of ScVO4 by Raman scattering and ab initio calculations

    Panchal, V.; Manjón, F. J.; Errandonea, D.; Rodriguez-Hernandez, P.; López-Solano, J.; Muñoz, A.; Achary, S. N.; Tyagi, A. K.

    2011-02-01

    We report results of experimental and theoretical lattice-dynamics studies on scandium orthovanadate up to 35 GPa. Raman-active modes of the low-pressure zircon phase are measured up to 8.2 GPa, where the onset of an irreversible zircon-to-scheelite phase transition is detected. Raman-active modes in the scheelite structure are observed up to 16.5 GPa. Beyond 18.2 GPa we detected a gradual splitting of the Eg modes of the scheelite phase, indicating the onset of a second phase transition. Raman symmetries, frequencies, and pressure coefficients in the three phases of ScVO4 are discussed in the light of ab initio lattice-dynamics calculations that support the experimental results. The results on all the three phases of ScVO4 are compared with those previously reported for related orthovanadates.

  6. Pressure-induced semimetallic behavior of calcium from ab initio calculations

    A loss of metallic properties in fcc calcium under high pressure is studied ab initio using the density functional theory (DFT) and GW approximation. It is found that a more correct description of many-electron effects given by GW method does not provide significant changes in the behavior of electronic spectrum in comparison with DFT approach. We note that the obtained width of (pseudo)gap is highly sensitive to the k-point sampling used for density of states calculation. The analysis of fcc calcium's band structure at p ∼ 20 GPa shows that the crossing of bands at the Fermi level is removed if the spin-orbit coupling is taken into account.

  7. Elastic constants of Al and TiN calculated by ab initio method

    张铭; 申江; 何家文

    2001-01-01

    The elastic constants of Al single crystal were calculated by ab initio method for calibration. Three deformation directions were selected in order to obtain the different constants of c11, c12 and c44. The cohesion energy curves of the three deformation directions were calculated. The results of the second order partial differential at the equilibrium point of the cohesion energy curve provide the elastic constants of the Al single crystal. The changes of crystal symmetry and lattice can lead to the deviations of the calculated cohesion energy curves and the accurate elastic constants can not be obtained, but when the correction is taken into calculation, the calculated results are very close to the literature data. It is very difficult to obtain the elastic constants of thin films by experiment and the data from the handbook are scattered in a large scale. However, the elastic constants calculated by this method can be served as a standard. Though the errors of TiN elastic constants calculated by this method are a little higher than that for Al, the results are acceptable.

  8. Ab-Initio Calculations of Electronic Properties of InP and GaP

    Malozovsky, Y.; Franklin, L.; Ekuma, E. C.; Zhao, G. L.; Bagayoko, D.

    2013-06-01

    We present results from ab-initio, self-consistent local density approximation (LDA) calculations of electronic and related properties of zinc blende indium phosphide (InP) and gallium phosphide (GaP). We employed a LDA potential and implemented the linear combination of atomic orbitals (LCAO) formalism. This implementation followed the Bagayoko, Zhao and Williams (BZW) method, as enhanced by Ekuma and Franklin (BZW-EF). This method searches for the optimal basis set that yields the minima of the occupied energies. This search entails increases of the size of the basis set and the related modifications of angular symmetry and of radial orbitals. Our calculated, direct band gap of 1.398 eV (1.40 eV), at the Γ point, is in excellent agreement with experimental values, for InP, and our preliminary result for the indirect gap of GaP is 2.135 eV, from the Γ to X high symmetry points. We have also calculated electron and hole effective masses for both InP and GaP. These calculated properties also agree with experimental findings. We conclude that the BZW-EF method could be employed in calculations of electronic properties of high-Tc superconducting materials to explain their complex properties.

  9. Energy and diffusion of hydrogen atoms in titanium substituted vanadium hydrides from ab initio calculations

    The equilibrium lattice parameters, formation energy, and diffusion behavior of hydrogen atoms in vanadium hydrides with and without Ti substitution were calculated by ab initio calculations and quantum correction by zero point energy was achieved using phonon vibration calculations. The calculated formation energies indicated that Ti substitution induces instability in the vanadium hydrides and electron density calculations showed that hydrogen has strong electrochemical affinity with Ti. The diffusion behavior was examined by the nudged elastic band (NEB) method to investigate the transition states of the hydrides. It revealed that Ti substitution is shown to reduce the diffusion coefficient and this effect was decreased with increasing temperature. The results of this study are expected to provide useful guidelines for understanding hydrogen absorption and desorption properties of hydrogen storage materials. - Highlights: • Ti substitution expands any crystal structure of vanadium metal or hydride. • H atoms are repulsed by Ti atoms despite their high electrochemical affinity. • Strong electrochemical bonding between Ti and H lowers the formation energy. • Ti substitution reduces hydrogen diffusion by over 90% at room temperature

  10. Energy and diffusion of hydrogen atoms in titanium substituted vanadium hydrides from ab initio calculations

    Kim, Jiwoong, E-mail: jwk@kigam.re.kr; Yoo, Jeong-Hyun, E-mail: yjh0010@naver.com; Cho, Sung-Wook, E-mail: cho@kigam.re.kr

    2014-12-15

    The equilibrium lattice parameters, formation energy, and diffusion behavior of hydrogen atoms in vanadium hydrides with and without Ti substitution were calculated by ab initio calculations and quantum correction by zero point energy was achieved using phonon vibration calculations. The calculated formation energies indicated that Ti substitution induces instability in the vanadium hydrides and electron density calculations showed that hydrogen has strong electrochemical affinity with Ti. The diffusion behavior was examined by the nudged elastic band (NEB) method to investigate the transition states of the hydrides. It revealed that Ti substitution is shown to reduce the diffusion coefficient and this effect was decreased with increasing temperature. The results of this study are expected to provide useful guidelines for understanding hydrogen absorption and desorption properties of hydrogen storage materials. - Highlights: • Ti substitution expands any crystal structure of vanadium metal or hydride. • H atoms are repulsed by Ti atoms despite their high electrochemical affinity. • Strong electrochemical bonding between Ti and H lowers the formation energy. • Ti substitution reduces hydrogen diffusion by over 90% at room temperature.

  11. Using ab initio calculations in designing bcc Mg-Li alloys for ultra-lightweight applications

    Ab initio calculations are becoming increasingly useful to engineers interested in designing new alloys, because these calculations are able to accurately predict basic material properties only knowing the atomic composition of the material. In this paper, single crystal elastic constants of 11 bcc Mg-Li alloys are calculated using density functional theory (DFT) and compared with available experimental data. Based on DFT determined properties, engineering parameters such as the ratio of bulk modulus over shear modulus (B/G) and the ratio of Young's modulus over mass density (Y/ρ) are calculated. Analysis of B/G and Y/ρ shows that bcc Mg-Li alloys with 30-50 at.% Li offer the most potential as lightweight structural material. Compared with fcc Al-Li alloys, bcc Mg-Li alloys have a lower B/G ratio, but a comparable Y/ρ ratio. An Ashby map containing Y/ρ vs B/G shows that it is not possible to increase both Y/ρ and B/G by changing only the composition of a binary alloy

  12. Ab initio calculations for the far infrared collision induced absorption by N2 gas.

    Bussery-Honvault, Béatrice; Hartmann, Jean-Michel

    2014-02-01

    We present (far-infrared) Collision Induced Absorption (CIA) spectra calculations for pure gaseous N2 made for the first time, from first-principles. They were carried out using classical molecular dynamics simulations based on ab initio predictions of both the intermolecular potential and the induced-dipole moment. These calculations reproduce satisfactory well the experimental values (intensity and band profile) with agreement within 3% at 149 K. With respect to results obtained with only the long range (asymptotic) dipole moment (DM), including the short range overlap contribution improves the band intensity and profile at 149 K, but it deteriorates them at 296 K. The results show that the relative contribution of the short range DM to the band intensity is typically around 10%. We have also examined the sensitivity of the calculated CIA to the intermolecular potential anisotropy, providing a test of the so-called isotropic approximation used up to now in all N2 CIA calculations. As all these effects interfere simultaneously with quantitatively similar influences (around 10%), it is rather difficult to assert which one could explain remaining deviations with the experimental results. Furthermore, the rather large uncertainties and sometimes inconsistencies of the available measurements forbid any definitive conclusion, stressing the need for new experiments. PMID:24511942

  13. Ab-initio calculation of the photonuclear cross section of $^{10}$B

    Kruse, M K G; Johnson, C W

    2015-01-01

    We present for the first-time the photonuclear cross section of $^{10}$B calculated within the ab-initio No Core Shell Model framework. Realistic two-nucleon (NN) chiral forces up to next-to-next-to-next-order (N3LO), which have been softened by the similarity renormalization group method (SRG) to $\\lambda=2.02$ fm$^{-1}$, were utilized. The electric-dipole response function is calculated using the Lanczos method. The effects of the continuum were accounted for by including neutron escape widths derived from R-matrix theory. The calculated cross section agrees well with experimental data in terms of structure as well as in absolute peak height, $\\sigma_{\\rm max}=4.85~{\\rm mb}$ at photon energy $\\omega=23.61~{\\rm MeV}$, and integrated cross section $85.36\\, {\\rm MeV \\cdotp mb}$. We test the Brink hypothesis by calculating the electric-dipole response for the first five positive-parity states in $^{10}$B and verify that dipole excitations built upon the ground- and excited states have similar characteristics.

  14. Mechanical properties of carbynes investigated by ab initio total-energy calculations

    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...

  15. Optical Spectroscopy of the Bulk and Interfacial Hydrated Electron from Ab Initio Calculations

    Uhlig, Frank; Herbert, J. M.; Coons, M. P.; Jungwirth, Pavel

    2014-01-01

    Roč. 118, č. 35 (2014), s. 7507-7515. ISSN 1089-5639 R&D Projects: GA ČR GBP208/12/G016 Institutional support: RVO:61388963 Keywords : hydrated electron * optical spectrum * ab initio molecular dynamics Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.693, year: 2014

  16. Computationally efficient and quantitatively accurate multiscale simulation of solid-solution strengthening by ab initio calculation

    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 alloy s Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 4.465, year: 2014

  17. Ab-initio Calculations of Accurate Electronic Properties of Wurzite AlN

    Nwigboji, Ifeanyi; Malozovsky, Yuriy; Bagayoko, Diola; Bagayoko Research Group Team

    2014-03-01

    We present results from ab-initio, self consistent local density approximation (LDA) calculations of electronic and related properties of wurtzite Aluminum Nitride (w-AlN). Our non-relativistic computations employed the Ceperley and Alder LDA potential and the linear combination of atomic orbital (LCAO) formalism. The implementation of the LCAO formalism followed the Bagayoko, Zhao, and Williams' method as enhanced by Ekuma and Franklin (BZW-EF). The BZW-EF method verifiably obtains the minima of the occupied energies; these minima provide the most variationally and physically valid density functional theory (DFT) description of the ground states of materials under study. Our preliminary results for w-AlN show that w-AlN has a direct band gap of 5.82 eV at the Γ point. The preliminary energy bands were obtained with a basis set comprising 48 functions. None of the several, larger basis sets tested to date led to occupied energies lower than those obtained with the above 48. While most previous LDA calculations are 2 eV smaller or more than the experimental value of 5.9 eV that is in excellent agreement with our finding, considering the typical experimental uncertainty of 0.2 eV for absorption measurements on AlN. We also discuss our calculated density of states (DOS) and partial densities of states (pDOS).

  18. Ab-initio Calculations of Accurate Electronic Properties of ZnS

    Khamala, Bethuel; Franklin, Loushanda; Malozovski, Yuriy; Stewart, Anthony; Bagayoko, Diola; Bagayoko Research Group Team

    2014-03-01

    We present the results from ab-initio, self consistent, local density approximation (LDA) calculations of the electronic and related properties of zinc-blende zinc sulphide (zb-ZnS). We employed the Ceperley and Alder LDA potential and the linear combination of atomic orbital (LCAO) formalism in our non-relativistic computations. The implementation of the LCAO formalism followed the Bagayoko, Zhao, and Williams method as enhanced by Ekuma and Franklin (BZW-EF). The BZW-EF method includes a methodical search for the optimal basis set that yields the minima of the occupied energies. This search entails increasing the size of the basis set and related modifications of angular symmetry and of radial orbitals. Our calculated, direct gap of 3.725 eV, at the Γ point, is in excellent agreement with experiment. We have also calculated the total (DOS) and partial (pDOS) densities of states, electron and hole effective masses and total energies that agree very well with available, corresponding experimental results. Acknowledgement: This research is funded in part by the National Science Foundation (NSF) and the Louisiana Board of Regents, through LASiGMA [Award Nos. EPS- 1003897, NSF (2010-15)-RII-SUBR] and NSF HRD-1002541, the US Department of Energy - National, Nuclear Security Administration (NNSA) (Award No. DE-NA0001861), LaSPACE, and LONI-SUBR.

  19. Potential energy surface and second virial coefficient of methane-water from ab initio calculations

    Akin-Ojo, Omololu; Szalewicz, Krzysztof

    2005-10-01

    Six-dimensional intermolecular potential energy surfaces (PESs) for the interaction of CH4 with H2O are presented, obtained from ab initio calculations using symmetry-adapted perturbation theory (SAPT) at two different levels of intramonomer correlation and the supermolecular approach at three different levels of electron correlation. Both CH4 and H2O are assumed to be rigid molecules with interatomic distances and angles fixed at the average values in the ground-state vibration. A physically motivated analytical expression for each PES has been developed as a sum of site-site functions. The PES of the CH4-H2O dimer has only two symmetry-distinct minima. From the SAPT calculations, the global minimum has an energy of -1.03kcal /mol at a geometry where H2O is the proton donor, HO -H⋯CH4, with the O-H-C angle of 165°, while the secondary minimum, with an energy of -0.72kcal/mol, has CH4 in the role of the proton donor (H3C -H⋯OH2). We estimated the complete basis set limit of the SAPT interaction energy at the global minimum to be -1.06kcal/mol. The classical cross second virial coefficient B12(T) has been calculated for the temperature range 298-653K. Our best results agree well with some experiments, allowing an evaluation of the quality of experimental results.

  20. Ab-initio Calculation of Optoelectronic and Structural Properties of Cubic Lithium Oxide (Li2O)

    Ziegler, Joshua; Polin, Daniel; Malozovsky, Yuriy; Bagayoko, Diola

    Using the Bagayoko, Zhao, and Williams (BZW) method, as enhanced by Ekuma and Franklin (BZW-EF), we performed ab-initio, density functional theory (DFT) calculations of optoelectronic, transport, and bulk properties of Li2S. In so doing, we avoid ``band gap'' and problems plaguing many DET calculations [AIP Advances 4, 127104 (2014)]. We employed a local density approximation (LDA) potential and the linear combination of atomic orbitals (LCAO). With the BZW-EF method, our results possess the full, physical content of DFT and agree with available, corresponding experimental ones. In particular, we found a room temperature indirect band gap of 6.659 eV that compares favorably with experimental values ranging from 5 to 7.99 eV. We also calculated total and partial density of states (DOS and PDOS), effective masses of charge carriers, the equilibrium lattice constant, and the bulk modulus. Acknowledgments: This work was funded in part by the National Science Foundation (NSF) and the Louisiana Board of Regents, through LASiGMA [Award Nos. EPS- 1003897, NSF (2010-15)-RII-SUBR] and NSF HRD-1002541, the US Department of Energy - National, Nuclear Security Administration (NNSA) (Award Nos. DE-NA0001861 and DE- NA0002630), LaSPACE, and LONI-SUBR.

  1. Ab initio calculation of molecular field interactions in rare-earth transition-metal intermetallics (invited)

    Brooks, M. S. S.; Gasche, T.; Auluck, S.; Nordström, L.; Severin, L.; Trygg, J.; Johansson, B.

    1991-11-01

    The interaction, KRM, between the rare-earth 4f moment and the transition-metal 3d moments in rare-earth transition-metal intermetallics is shown to depend upon the R-5d moment, which is due to 3d-5d hybridization, and local 4f-5d exchange integrals. Both the R-5d moment and KRM may be calculated ab initio from the local spin-density approximation to density functional theory in self-consistent energy-band calculations with the localized 4f-moments fixed at their Russel-Saunders values. Detailed examples are given for the RFe2 (R=Gd-Yb) series. The exchange integrals are similar to those entering into the density functional version of Stoner theory and their energy dependence must be treated carefully. The calculated local exchange integrals are shown to be related to the molecular fields derived from spin Hamiltonians, hence to the spin-wave spectra. Reasonable agreement with values of the molecular fields extracted from inelastic neutron scattering and high field susceptibility measurements is obtained.

  2. Integration of ab-initio nuclear calculation with derivative free optimization technique

    Sharda, Anurag [Iowa State Univ., Ames, IA (United States)

    2008-01-01

    Optimization techniques are finding their inroads into the field of nuclear physics calculations where the objective functions are very complex and computationally intensive. A vast space of parameters needs searching to obtain a good match between theoretical (computed) and experimental observables, such as energy levels and spectra. Manual calculation defies the scope of such complex calculation and are prone to error at the same time. This body of work attempts to formulate a design and implement it which would integrate the ab initio nuclear physics code MFDn and the VTDIRECT95 code. VTDIRECT95 is a Fortran95 suite of parallel code implementing the derivative-free optimization algorithm DIRECT. Proposed design is implemented for a serial and parallel version of the optimization technique. Experiment with the initial implementation of the design showing good matches for several single-nucleus cases are conducted. Determination and assignment of appropriate number of processors for parallel integration code is implemented to increase the efficiency and resource utilization in the case of multiple nuclei parameter search.

  3. Ab initio calculation of the pair potentials of MgB2

    Ab initio calculations on model clusters of MgB2 are presented to estimate the pairing potentials of superconductivity. The total energies of the clusters for the restricted Hartree-Fock (RHF) type and unrestricted Hartree-Fock (UHF) type singlet ground states and the triplet state are calculated by the hybrid DFT method of Gaussian G03 program. The energy difference between the UHF singlet state and the triplet state is correlated to the superconducting energy gap 2Δ. The highest occupied molecular orbital (HOMO) and the next HOMO are composed of mostly the 2pσ and the 3s orbitals of boron and 3pσ orbitals of magnesium. These orbitals constitute the spin polarized singlet state which represent the superconducting state. The vibrational frequencies of the singlet and the triplet states are calculated on a model cluster, Mg8B16H10, to find vibrational frequencies, and the results are used to interpret the isotope effects of 10B and 11B for the transition temperatures

  4. Geometry of an Isolated Dimer of Imidazole Characterised by Rotational Spectroscopy and Ab Initio Calculations.

    Mullaney, John C; Zaleski, Daniel P; Tew, David P; Walker, Nicholas R; Legon, Anthony C

    2016-04-18

    An isolated, gas-phase dimer of imidazole is generated through laser vaporisation of a solid rod containing a 1:1 mixture of imidazole and copper in the presence of an argon buffer gas undergoing supersonic expansion. The complex is characterised through broadband rotational spectroscopy and is shown to have a twisted, hydrogen-bonded geometry. Calculations at the CCSD(T)(F12*)/cc-pVDZ-F12 level of theory confirm this to be the lowest-energy conformer of the imidazole dimer. The distance between the respective centres of mass of the imidazole monomer subunits is determined to be 5.2751(1) Å, and the twist angle γ describing rotation of one monomer with respect to the other about a line connecting the centres of mass of the monomers is determined to be 87.9(4)°. Four out of six intermolecular parameters in the model geometry are precisely determined from the experimental rotational constants and are consistent with results calculated ab initio. PMID:26812549

  5. A modified W–W interatomic potential based on ab initio calculations

    In this paper we have developed a Finnis–Sinclair-type interatomic potential for W–W interactions that is based on ab initio calculations. The modified potential is able to reproduce the correct formation energies of self-interstitial atom (SIA) defects in tungsten, offering a significant improvement over the Ackland–Thetford tungsten potential. Using the modified potential, the thermal expansion is calculated in a temperature range from 0 to 3500 K. The results are in reasonable agreement with the experimental data, thus overcoming the shortcomings of the negative thermal expansion using the Derlet–Nguyen–Manh–Dudarev tungsten potential. The W–W potential presented here is also applied to study in detail the diffusion of SIAs in tungsten. We reveal that the initial SIA initiates a sequence of tungsten atom displacements and replacements in the 〈1 1 1〉 direction. An Arrhenius fit to the diffusion data at temperatures below 550 K indicates a migration energy of 0.022 eV, which is in reasonable agreement with the experimental data. (paper)

  6. Insights into photodissociation dynamics of acetaldehyde from ab initio calculations and molecular dynamics simulations

    In the present paper we report a theoretical study on mechanistic photodissociation of acetaldehyde (CH3CHO). Stationary structures for H2 and CO eliminations in the ground state (S0) have been optimized with density functional theory method, which is followed by the intrinsic reaction coordinate and ab initio molecular dynamics calculations to confirm the elimination mechanism. Equilibrium geometries, transition states, and intersection structures for the C-C and C-H dissociations in excited states were determined by the complete-active-space self-consistent field (CASSCF) method. Based on the CASSCF optimized structures, the potential energy profiles for the dissociations were refined by performing the single-point calculations using the multireference configuration interaction method. Upon the low-energy irradiation of CH3CHO (265 nm1 C-C bond fission following intersystem crossing from the S1 state is the predominant channel and the minor channel, the ground-state elimination to CH4+CO after internal conversion (IC) from S1 to S0, could not be excluded. With the photon energy increasing, another pathway of IC, achieved via an S1/S0 intersection point resulting from the S1 C-C bond fission, becomes accessible and increases the yield of CH4+CO.

  7. Ab initio calculation of the electronic absorption spectrum of liquid water

    Martiniano, Hugo F. M. C.; Galamba, Nuno; Cabral, Benedito J. Costa

    2014-04-01

    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.

  8. Determination of a silane intermolecular force field potential model from an ab initio calculation

    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.

  9. Ab initio calculation of the electronic absorption spectrum of liquid water

    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

  10. Ab initio calculation of the electronic absorption spectrum of liquid water

    Martiniano, Hugo F. M. C.; Galamba, Nuno [Grupo de Física Matemática da Universidade de Lisboa, Av. Professor Gama Pinto 2, 1649-003 Lisboa (Portugal); Cabral, Benedito J. Costa, E-mail: ben@cii.fc.ul.pt [Grupo de Física Matemática da Universidade de Lisboa, Av. Professor Gama Pinto 2, 1649-003 Lisboa (Portugal); Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, 1749-016 Lisboa (Portugal); Instituto de Física da Universidade de São Paulo, CP 66318, 05314-970 São Paulo, SP (Brazil)

    2014-04-28

    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.

  11. A theoretical study of benzaldehyde derivatives as tyrosinase inhibitors using Ab initio calculated NQCC parameters

    Marjan Rafiee

    2015-09-01

    Full Text Available Tyrosinase is a multifunctional copper-containing enzyme. It can catalyze two distinct reactions of melanin synthesis and benzaldehyde derivatives, which are potential tyrosinase inhibitors. To find the relationships between charge distributions of benzaldehyde and their pharmaceutical behavior, the present study aimed at investigating nuclear quadrupole coupling constants of quadrupolare nuclei in the functional benzaldehyde group and calculating some its derivatives. In addition, the differences between the electronic structures of various derivatives of this depigmenting drug were examined. All ab initio calculations were carried out using Gaussian 03. The results predicted benzaldehyde derivatives to be bicentral inhibitors; nevertheless, the oxygen or hydrogen contents of the aldehyde group were not found to be the only active sites. Furthermore with the presence of the aldehyde group, the terminal methoxy group in C4 was found to contribute to tyrosinase inhibitory activities. In addition, an oxygen atom with high charge density in the side chain was found to play an important role in its inhibitory effect.

  12. Ab initio Calculations of Charge Symmetry Breaking in the A =4 Hypernuclei

    Gazda, Daniel; Gal, Avraham

    2016-03-01

    We report on ab initio no-core shell model calculations of the mirror Λ hypernuclei H4Λ and He4Λ , using the Bonn-Jülich leading-order chiral effective field theory hyperon-nucleon potentials plus a charge symmetry breaking Λ -Σ0 mixing vertex. In addition to reproducing rather well the 0g.s . + and 1exc+ binding energies, these four-body calculations demonstrate for the first time that the observed charge symmetry breaking splitting of mirror levels, reaching hundreds of keV for 0g.s . +, can be reproduced using realistic theoretical interaction models, although with a non-negligible momentum cutoff dependence. Our results are discussed in relation to recent measurements of the H4Λ(0g.s . +) binding energy at the Mainz Microtron [A. Esser et al. (A1 Collaboration), Phys. Rev. Lett. 114, 232501 (2015)] and the He4Λ(1exc+) excitation energy [T.O. Yamamoto et al. (J-PARC E13 Collaboration), Phys. Rev. Lett. 115, 222501 (2015)].

  13. The ab initio calculation of molecular electric, magnetic and geometric properties.

    Bast, Radovan; Ekström, Ulf; Gao, Bin; Helgaker, Trygve; Ruud, Kenneth; Thorvaldsen, Andreas J

    2011-02-21

    We give an account of some recent advances in the development of ab initio methods for the calculation of molecular response properties, involving electric, magnetic, and geometric perturbations. Particular attention is given to properties in which the basis functions depend explicitly both on time and on the applied perturbations such as perturbations involving nuclear displacements or external magnetic fields when London atomic orbitals are used. We summarize a general framework based on the quasienergy for the calculation of arbitrary-order molecular properties using the elements of the density matrix in the atomic-orbital basis as the basic variables. We demonstrate that the necessary perturbed density matrices of arbitrary order can be determined from a set of linear equations that have the same formal structure as the set of linear equations encountered when determining the linear response equations (or time-dependent self-consistent-field equations). Additional components needed to calculate properties involving perturbation-dependent basis sets are flexible one- and two-electron integral techniques for geometric or magnetic-field differentiated integrals; in Kohn-Sham density-functional theory (KS-DFT), we also need to calculate derivatives of the exchange-correlation functional. We describe a recent proposal for evaluating these contributions based on automatic differentiation. Within this framework, it is now possible to calculate any molecular property for an arbitrary self-consistent-field reference state, including two- and four-component relativistic self-consistent-field wave functions. Examples of calculations that can be performed with this formulation are presented. PMID:21180690

  14. 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 ∠ TiOH 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.

  15. Emergent properties of nuclei from ab initio coupled-cluster calculations

    Hagen, G; Hjorth-Jensen, M; Papenbrock, T

    2016-01-01

    Emergent properties such as nuclear saturation and deformation, and the effects on shell structure due to the proximity of the scattering continuum and particle decay channels are fascinating phenomena in atomic nuclei. In recent years, ab initio approaches to nuclei have taken the first steps towards tackling the computational challenge of describing these phenomena from Hamiltonians with microscopic degrees of freedom. This endeavor is now possible due to ideas from effective field theories, novel optimization strategies for nuclear interactions, ab initio methods exhibiting a soft scaling with mass number, and ever-increasing computational power. This paper reviews some of the recent accomplishments. We also present new results. The recently optimized chiral interaction NNLO$_{\\rm sat}$ is shown to provide an accurate description of both charge radii and binding energies in selected light- and medium-mass nuclei up to $^{56}$Ni. We derive an efficient scheme for including continuum effects in coupled-clust...

  16. Direct calculation of equilibrium constants for isotopic exchange reactions by ab initio molecular orbital theory

    The ability of simple levels of ab initio molecular orbital theory to describe with reasonable accuracy the energetics of isotopic exchange processes is demonstrated. Three levels of ab initio molecular orbital theory have been surveyed. The first two levels are single-determinant Hartree-Foch methods utilizing the 3-21G split-valence and 6-31G* polarization basis sets. The third level, which is computationally the most complex, uses the 6-31G* basis set but allows for partial account of electron correlation by way of Moller-Plesset perturbation theory terminated at second order. Theoretical and spectroscopic equilibrium constants for reactions XH + XD reversible XD + H2 where XD is a hydride of the first row of the periodic table are tabulated

  17. An effective scheme for selecting basis sets for ab initio calculations

    2000-01-01

    An effective scheme for selecting economical basis sets for ab initio calculations has been proposed for wide-range systems based on the analysis of different functions in the currently used basis sets. Accordingly, the selection of the basis sets should be made according to the different properties and real chemical surrounding of the atoms in the systems. For normal systems, the size and level of the basis sets used for the descriptions of the constituent atoms should be increased from left to right according to the position of the atom in the periodic table. Moreover, the more the atom is negatively charged, the more the basis functions and suitable polarization functions and diffuse functions should be utilized. Whereas, for the positively charged atoms, the size of basis set may be reduced. It is not necessary to use the polarization and diffuse functions for the covalently saturated atoms with normal valence states. However, for the system involving hydrogen-bonding, weak interactions, functional groups, metallic bonding with zero valence or low positive valence, and other sensitive interactions, the polarization and diffuse functions must be used. With this scheme, reliable calculation results may be obtained with suitable basis sets and smaller computational capability. By detailed analysis of a series of systems, it has been demonstrated that this scheme is very practical and effective. This scheme may be used in Hartree-Fock, M?ller-Plesset and density functional theoretical calculations. It is expected that the scheme would find important applications in the extensive calculations of large systems in chemistry, materials science, and life and biological sciences.

  18. Determination of the orientation of azathioprine adsorbed on a silver electrode by SERS and ab initio calculations

    Chen, Shi-Ping; Qiao, Zhuahong; Vivoni, Alberto; Hosten, Charles M.

    2003-10-01

    We report the SERS spectrum of azthioprine (AZA) on a silver electrode surface and the results of normal mode calculations using empirical and ab initio calculations of the 6-mercaptopurione (6-MP) component of AZA. The empirical calculations were done with a Urey-Bradley force field (UBFF) and the ab initio calculations with the STO-3G basis set using the UHF, MP2 and BLYP methods. From the difference between the SERS and solid spectra, we determined that AZA attaches edge-on to the surface through the N3 site on the 6-MP component of the molecule. The UBFF calculation on an Ag adatom-molecule model reproduced most of the main observed frequency shifts in the SERS spectrum. With a similar model, the ab initio calculations yielded frequency shifts in the same direction as the one observed for the in-plane normal modes, but they yielded opposite shifts for the out-of-plane normal modes. This phenomenon may be attributed to a face-on interaction of the 6-MP component with a neighboring adatom made possible by an inclination of the molecule on the surface.

  19. The vibrational behavior of silica clusters at the glass transition: Ab initio calculations and thermodynamic implications.

    Ottonello, G; Zuccolini, M Vetuschi; Belmonte, D

    2010-09-14

    We present the results of a computational investigation with ab initio procedures of the structure-energy and vibrational properties of silica clusters in a dielectric continuum with dielectric constant ε=3.8, through density functional theory/B3LYP gas phase calculations coupled with a polarized continuum model approach [integral equation formalism applied to a polarized continuum (IEFPCM)] and those of the periodical structure D(6h) which leads to the α-cristobalite polymorph of silica when subjected to symmetry operations with the same functional within the linear combination of atomic orbitals (LCAO) approximation and in the framework of Bloch's theorem. Based on the computed energies and vibrational features, an aggregate of the D(6h) network and the monomer locally ordered in the short-medium range and both present in the glass in a mutual arrangement lacking of spatial continuity reproduces satisfactorily the experimentally observed low T heat capacity and the deviation from the Debye T(3) law. Above T(g), the experimental heat capacity of the liquid is perfectly reproduced summing to the internal modes the translational and rotational contributions to the bulk heat capacity and subtracting the (acoustic) terms arising from coherent motion (no longer existent). PMID:20849179

  20. Modern ab initio valence bond theory calculations reveal charge shift bonding in protic ionic liquids.

    Patil, Amol Baliram; Bhanage, Bhalchandra Mahadeo

    2016-06-21

    The nature of bonding interactions between the cation and the anion of an ionic liquid is at the heart of understanding ionic liquid properties. A particularly interesting case is a special class of ionic liquids known as protic ionic liquids. The extent of proton transfer in protic ionic liquids has been observed to vary according to the interacting species. Back proton transfer renders protic ionic liquids volatile and to be considered as inferior ionic liquids. We try to address this issue by employing modern ab initio valence bond theory calculations. The results indicate that the bonding in the cation and the anion of a prototypical ionic liquid, ethylammonium nitrate, is fundamentally different. It is neither characteristic of covalent/polar covalent bonding nor ionic bonding but rather charge shift bonding as a resonance hybrid of two competing ionic molecular electronic structure configurations. An investigation of other analogous protic ionic liquids reveals that this charge shift bonding seems to be a typical characteristic of protic ionic liquids while the ionic solid analogue compound ammonium nitrate has less charge shift bonding character as compared to protic ionic liquids. Further the extent of charge shift bonding character has been found to be congruent with the trends in many physicochemical properties such as melting point, conductivity, viscosity, and ionicity of the studied ionic liquids indicating that percentage charge shift character may serve as a key descriptor for large scale computational screening of ionic liquids with desired properties. PMID:27229870

  1. An effective scheme for selecting basis sets for ab initio calculations

    张瑞勤; 黄建华; 步宇翔; 韩克利; 李述汤; 何国钟

    2000-01-01

    An effective scheme for selecting economical basis sets for ab initio calculations has been proposed for wide-range systems based on the analysis of different functions in the currently used basis sets. Accordingly, the selection of the basis sets should be made according to the different properties and real chemical surrounding of the atoms in the systems. For normal systems, the size and level of the basis sets used for the descriptions of the constituent atoms should be increased from left to right according to the position of the atom in the periodic table. Moreover, the more the atom is negatively charged, the more the basis functions and suitable polarization functions and diffuse functions should be utilized. whereas, for the positively charged atoms, the size of basis set may be reduced. it is not necessary to use the polarization and diffuse functions for the covalently saturated atoms with normal valence states. However, for the system involving hy-drogen-bonding, weak interactions, functional

  2. Electromechanical effects in carbon nanotubes: Ab initio and analytical tight-binding calculations

    Verissimo-Alves, M.; Koiller, Belita; Chacham, H.; Capaz, R. B.

    2003-04-01

    We perform ab initio calculations of charged graphene and single-wall carbon nanotubes (CNTs). A wealth of electromechanical behaviors is obtained. (1) Both nanotubes and graphene expand upon electron injection. (2) Upon hole injection, metallic nanotubes and graphene display a nonmonotonic behavior. Upon increasing hole densities, the lattice constant initially contracts, reaches a minimum, and then starts to expand. The hole densities at minimum lattice constants are 0.3 |e|/atom for graphene and between 0.1 and 0.3|e|/atom for the metallic nanotubes studied. (3) Semiconducting CNT’s with small diameters (d≲20 Å) always expand upon hole injection. (4) Semiconducting CNT’s with large diameters (d≳20 Å) display a behavior intermediate between those of metallic and large-gap CNT’s. (5) The strain versus extra charge displays a linear plus power-law behavior, with characteristic exponents for graphene, metallic, and semiconducting CNT’s. All these features are physically understood within a simple tight-binding total-energy model.

  3. Nature of the Interstitials in Titanium Dioxide and Their Impact on Transmission Coefficient: Ab Initio Calculations

    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.

  4. Ab initio many-body calculations of nucleon-4He scattering with three-nucleon forces

    Hupin, Guillaume; Navrátil, Petr; Quaglioni, Sofia; Calci, Angelo; Roth, Robert

    2013-01-01

    We extend the ab initio no-core shell model/resonating-group method to include three-nucleon (3N) interactions for the description of nucleon-nucleus collisions. We outline the formalism, give algebraic expressions for the 3N-force integration kernels, and discuss computational aspects of two alternative implementations. The extended theoretical framework is then applied to nucleon-4He scattering using similarity-renormalization-group (SRG) evolved nucleon-nucleon plus three-nucleon potentials derived from chiral effective field theory. We analyze the convergence properties of the calculated phase shifts and explore their dependence upon the SRG evolution parameter. We include up to six excited states of the 4He target and find significant effects from the inclusion of the chiral 3N force, e.g., it enhances the spin-orbit splitting between the 3/2- and 1/2- resonances and leads to an improved agreement with the phase shifts obtained from an accurate R-matrix analysis of the five-nucleon experimental data. We ...

  5. Ab initio calculations of the forbidden Bragg reflections energy spectra in wurtzites versus temperature.

    Oreshko, A P; Ovchinnikova, E N; Beutier, G; Collins, S P; Nisbet, G; Kolchinskaya, A M; Dmitrienko, V E

    2012-06-20

    Thermal-motion induced (TMI) scattering is caused by the influence of atomic displacements on electronic states in crystals and strongly depends on temperature. It corresponds to dipole-dipole resonant x-ray scattering, but is usually accompanied by dipole-quadrupole scattering. The phenomenological theory supposes the dipole-quadrupole term to be temperature independent (TI). As a result, the transformation of the energy spectra with temperature observed experimentally in ZnO and GaN corresponds to the interference between the TMI and TI terms. In the present paper the direct confirmation of this theoretical prediction is given. Ab initio molecular dynamics was used to simulate the sets of atomic sites at various temperatures followed by quantum mechanical calculation of resonant Bragg reflection energy spectra. The results of simulation are in excellent coincidence with experimental energy spectra of forbidden reflections and confirm the earlier phenomenological conjecture about the interference between the TI dipole-quadrupole and TMI dipole-dipole contributions to the resonant atomic factor. PMID:22627099

  6. Role of ab-initio calculations in elucidating properties of hydrated and ammoniated electrons

    The properties of solvated electrons are analyzed in terms of a self-consistent modified continuum model based on the techniques of ab initio molecular quantum mechanics. The model is semiclassical in spirit, employing the quantum mechanical density for the excess charge and the first solvation shell in conjunction with classical electrostatics, and is developed in a general form which can be straightforwardly applied to special cases of interest, such as the solvated mono- and dielectron complexes. The advantages and disadvantages of the technique are discussed in relation to other more empirical approaches. Computational results are presented for excess electrons (mono- and dielectrons) in water and ammonia, and the role of long-range polarization of the medium in localizing the excess charge is analyzed. The variationally determined ground states are characterized in terms of equilibrium solvation shell geometry (appreciable cavities are implied for both water and ammonia), solvation energy, photoionization energy, and charge distribution. The finding of negative spin densities at the first solvent shell protons underscores the importance of a many electron theoretical treatment. Preliminary results for excited states are also reported. The calculated results are compared with experimental and other theoretical data, and the sensitivity of the results to various features of the model is discussed. Particular attention is paid to the number of solvent molecules required to trap the excess electron

  7. Trans-difluoroethylene ozonide: microwave spectrum, structure, dipole moment, ab initio calculations, and anomeric effect

    The rotational spectra of six isotopic species of trans-difluoroethylene ozonide (trans-3,5-difluoro-1,2,4-trioxolane) were assigned. These included the parent species, the single- and double-substituted deuterium species, the double 18O/sub p/, the triple 18O, and and 13C species. The spectrum consisted of b-type transitions with a 10:6 intensity alternation. The electric dipole moment was determined from Stark effect measurements to be μ/sub b/ = 0.994 (5) D. These results support an average structure having an O/sub p/-O/sub p/ twist ring conformation with C2 symmetry and diaxial fluorine substituents. The shortening of the C-O/sub p/ bonds (1.368 A) relative to the C-O/sub c/ bonds (1.401 A) is very apparent in this member of the fluoroozonide series. Ab initio calculations were performed at the HG/6-31G/sup */ level and analyzed in terms of electron density distributions. Experimental and theoretical results are rationalized in terms of anomeric interactions with the peroxy oxygen atoms

  8. Trans-difluoroethylene ozonide: microwave spectrum, structure, dipole moment, ab initio calculations, and anomeric effect

    LaBarge, M.S.; Hillig, K.W. II; Kuczkowski, R.L.; Cremer, D.

    1986-07-03

    The rotational spectra of six isotopic species of trans-difluoroethylene ozonide (trans-3,5-difluoro-1,2,4-trioxolane) were assigned. These included the parent species, the single- and double-substituted deuterium species, the double /sup 18/O/sub p/, the triple /sup 18/O, and and /sup 13/C species. The spectrum consisted of b-type transitions with a 10:6 intensity alternation. The electric dipole moment was determined from Stark effect measurements to be ..mu../sub b/ = 0.994 (5) D. These results support an average structure having an O/sub p/-O/sub p/ twist ring conformation with C/sub 2/ symmetry and diaxial fluorine substituents. The shortening of the C-O/sub p/ bonds (1.368 A) relative to the C-O/sub c/ bonds (1.401 A) is very apparent in this member of the fluoroozonide series. Ab initio calculations were performed at the HG/6-31G/sup */ level and analyzed in terms of electron density distributions. Experimental and theoretical results are rationalized in terms of anomeric interactions with the peroxy oxygen atoms.

  9. Ab initio calculations of the magnetic properties of perovskites under deformation

    Maznichenko, Igor [Institut fuer Physik, Martin-Luther-Universitaet Halle-Wittenberg, Halle (Saale) (Germany); Etz, Corina; Ernst, Arthur [Max-Planck-Institut fuer Mikrostrukturphysik, Halle (Saale) (Germany); Lueders, Martin; Szotek, Zdzislawa; Temmerman, Walter [Daresbury Laboratory, Daresbury, Warrington, Cheshire (United Kingdom); Mertig, Ingrid [Institut fuer Physik, Martin-Luther-Universitaet Halle-Wittenberg, Halle (Saale) (Germany); Max-Planck-Institut fuer Mikrostrukturphysik, Halle (Saale) (Germany)

    2010-07-01

    Materials with perovskite and perovskite-like structures demonstrate a broad spectrum of physical properties. Colossal magnetoresistance, ferroelectricity, multiferroicity, superconductivity, charge ordering, metal-insulator transition, Jahn-Teller and other effects are observed in perovskites. These properties of the mentioned materials with the common formula ABO{sub 3} are very sensitive to the type of the cations A and B. La{sub 2/3}Sr{sub 1/3}MnO{sub 3} (LSMO) is a strongly correlated 3d transition metal oxide with a Curie temperature (T{sub C}) above RT (370 K). For other La/Sr ratios different types of antiferromagnetism are observed. Other perovskite, ruthenate SrRuO{sub 3} (SRO) is a 4d ferromagnet with T{sub C} = 160 K. Here we perform ab initio calculations for LSMO and SRO in ideal cubic, tetragonally distorted, and different orthorhombic structures. We focus on magnetic order and Curie temperature of the above mentioned structures in the different structural phases.

  10. Large scale ab initio calculations based on three levels of parallelization

    Bottin, François; Leroux, Stéphane; Knyazev, Andrew; Zérah, Gilles

    2007-01-01

    We suggest and implement a parallelization scheme based on an efficient multiband eigenvalue solver, called the locally optimal block preconditioned conjugate gradient LOBPCG method, and using an optimized three-dimensional (3D) fast Fourier transform (FFT) in the ab initio}plane-wave code ABINIT. In addition to the standard data partitioning over processors corresponding to different k-points, we introduce data partitioning with respect to blocks of bands as well as spatial partitioning in t...

  11. Ab initio excited states calculations of Kr3+, probing semi-empirical modelling

    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

  12. Efficient Ab-Initio Electron Transport Calculations for Heterostructures by the Nonequilibrium Green’s Function Method

    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.

  13. Efficacy of the SU(3) scheme for ab initio large-scale calculations beyond the lightest nuclei

    Dytrych, T; Launey, K D; Draayer, J P; Vary, J P; Langr, D; Saule, E; Caprio, M A; Catalyurek, U; Sosonkina, M

    2016-01-01

    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 6Li and 12C 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 significant memory savings are achieved in physically important applications. In particular, a well-chosen symmetry-adapted basis affords memory savings in calculations of states with a fixed total angular momentum in large model spaces while exactly preserving translational invariance.

  14. Rotational study of the CH4-CO complex: Millimeter-wave measurements and ab initio calculations.

    Surin, L A; Tarabukin, I V; Panfilov, V A; Schlemmer, S; Kalugina, Y N; Faure, A; Rist, C; van der Avoird, A

    2015-10-21

    The rotational spectrum of the van der Waals complex CH4-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 jCH4 = 0 ground state and the K = 2-1 and K = 0-1 subbands correlating with the jCH4 = 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 CH4-CO complex. Accompanying ab initio calculations of the intermolecular potential energy surface (PES) of CH4-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 CH4 face closest to the CO subunit and binding energy De = 177.82 cm(-1). The bound rovibrational levels of the CH4-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 D0 are 91.32, 94.46, and 104.21 cm(-1) for A (jCH4 = 0), F (jCH4 = 1), and E (jCH4 = 2) nuclear spin modifications of CH4-CO, respectively. PMID:26493903

  15. Structure and vibrational modes of AgI-doped AsSe glasses: Raman scattering and ab initio calculations

    We report an investigation of the structure and vibrational modes of (AgI)x (AsSe)100-x, bulk glasses using Raman spectroscopy and first principles calculations. The short- and medium-range structural order of the glasses was elucidated by analyzing the reduced Raman spectra, recorded at off-resonance conditions. Three distinct local environments were revealed for the AsSe glass including stoichiometric-like and As-rich network sub-structures, and cage-like molecules (As4Sen, n=3, 4) decoupled from the network. To facilitate the interpretation of the Raman spectra ab initio calculations are employed to study the geometric and vibrational properties of As4Sen molecular units that are parts of the glass structure. The incorporation of AgI causes appreciable structural changes into the glass structure. AgI is responsible for the population reduction of molecular units and for the degradation of the As-rich network-like sub-structure via the introduction of As-I terminal bonds. Ab initio calculations of mixed chalcohalide pyramids AsSemI3-m provided useful information augmenting the interpretation of the Raman spectra. -- Graphical abstract: Raman scattering and ab initio calculations are employed to study the structure of AgI-AsSe superionic glasses. The role of mixed chalcohalide pyramidal units as illustrated in the figure is elucidated. Display Omitted Research highlights: → Doping binary As-Se glasses with AgI cause dramatic changes in glass structure. → Raman scattering and ab initio calculations determine changes in short- and medium-range order. → Three local environments exist in AsSe glass including a network sub-structure and cage-like molecules. → Mixed chalcohalide pyramids AsSemI3-m dominate the AgI-doped glass structure.

  16. Ab initio calculation of thermodynamic, transport, and optical properties of CH{sub 2} plastics

    Knyazev, D. V. [Joint Institute for High Temperatures RAS, Izhorskaya 13 bldg. 2, Moscow 125412 (Russian Federation); Moscow Institute of Physics and Technology (State University), Institutskiy per. 9, Dolgoprudny, Moscow Region 141700 (Russian Federation); State Scientific Center of the Russian Federation – Institute for Theoretical and Experimental Physics of National Research Centre “Kurchatov Institute,” Bolshaya Cheremushkinskaya 25, 117218 Moscow (Russian Federation); Levashov, P. R. [Joint Institute for High Temperatures RAS, Izhorskaya 13 bldg. 2, Moscow 125412 (Russian Federation); Tomsk State University, Lenin Prospekt 36, Tomsk 634050 (Russian Federation)

    2015-05-15

    This work covers an ab initio calculation of thermodynamic, transport, and optical properties of plastics of the effective composition CH{sub 2} at density 0.954 g/cm{sup 3} in the temperature range from 5 kK up to 100 kK. The calculation is based on the quantum molecular dynamics, density functional theory, and the Kubo-Greenwood formula. The temperature dependence of the static electrical conductivity σ{sub 1{sub D{sub C}}}(T) has a step-like shape: σ{sub 1{sub D{sub C}}}(T) grows rapidly for 5 kK ≤ T ≤ 10 kK and is almost constant for 20 kK ≤ T ≤ 60 kK. The additional analysis based on the investigation of the electron density of states (DOS) is performed. The rapid growth of σ{sub 1{sub D{sub C}}}(T) at 5 kK ≤ T ≤ 10 kK is connected with the increase of DOS at the electron energy equal to the chemical potential ϵ = μ. The frequency dependence of the dynamic electrical conductivity σ{sub 1}(ω) at 5 kK has the distinct non-Drude shape with the peak at ω ≈ 10 eV. This behavior of σ{sub 1}(ω) was explained by the dip at the electron DOS.

  17. Input/Output of ab-initio nuclear structure calculations for improved performance and portability

    Laghave, Nikhil [Iowa State Univ., Ames, IA (United States)

    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.

  18. Vacancy–solute interactions in ferromagnetic and paramagnetic bcc iron: Ab initio calculations

    Highlights: ► Interactions of vacancies with 3p, 3d, and 4d impurities in bcc Fe are calculated ab initio. ► Ferromagnetic and disordered paramagnetic states of the Fe matrix are considered. ► Three groups of impurities whose interactions with vacancies strongly depend on magnetic order. ► Compound-formers (Al, Si, P, S), insoluble elements (Cu, Ag), and magnetic elements (Mn, Co, Ni). ► The results are applied to interpret anomalies of vacancy trapping and impurity diffusion. - Abstract: Vacancy–solute interactions play a crucial role in diffusion-controlled processes, such as ordering or decomposition, which occur in alloys under heat treatment or under irradiation. Detailed knowledge of these interactions is important for predicting long-term behavior of nuclear materials (such as reactor steels and nuclear-waste containers) as well as for advancing our general understanding of kinetic processes in alloys. Using first-principles calculations based on the density functional theory and employing the locally self-consistent Green’s function technique, we develop a database of vacancy–solute interactions in dilute alloys of bcc Fe with 3p (Al, Si, P, S), 3d (Sc–Cu), and 4d (Y–Ag) elements. Unrelaxed interactions within the first three coordination shells have been computed in the ferromagnetic state as well as in the paramagnetic (disordered local moment) state of the iron matrix. Magnetism is found to have a strong effect on the vacancy–solute interactions. Implications of the obtained results for interpreting the effects of vacancy trapping and enhanced impurity diffusion are discussed.

  19. Input/Output of ab-initio nuclear structure calculations for improved performance and portability

    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.

  20. Towards efficient ab initio calculations of electron scattering by polyatomic molecules: II. Efficient evaluation of exchange integrals

    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

  1. Finite temperature elastic constants of paramagnetic materials within the disordered local moment picture from ab initio molecular dynamics calculations

    Mozafari, Elham; Shulumba, Nina; Steneteg, Peter; Alling, Björn; Abrikosov, Igor A.

    2016-01-01

    We present a theoretical scheme to calculate the elastic constants of magnetic materials in the high-temperature paramagnetic state. Our approach is based on a combination of disordered local moments picture and ab initio molecular dynamics (DLM-MD). Moreover, we investigate a possibility to enhance the efficiency of the simulations using recently introduced method: symmetry imposed force constant temperature dependent effective potential (SIFC-TDEP). We have chosen cubic paramagnetic CrN as ...

  2. Ab initio calculations of optical properties of silver clusters: Cross-over from molecular to nanoscale behavior

    Titantah, John T.; Karttunen, Mikko

    2016-01-01

    Electronic and optical properties of silver clusters were calculated using two different \\textit{ab initio} approaches: 1) based on all-electron full-potential linearized-augmented plane-wave method and 2) local basis function pseudopotential approach. Agreement is found between the two methods for small and intermediate sized clusters for which the former method is limited due to its all-electron formulation. The latter, due to non-periodic boundary conditions, is the more natural approach t...

  3. Towards efficient ab initio calculations of electron scattering by polyatomic molecules: III. Modelling correlation-polarization interactions

    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 ; Theoretical Chemistry Impact factor: 1.902, year: 2010

  4. Single- and double-wall carbon nanotubes fully covered with tetraphenylporphyrins: Stability and optoelectronic properties from ab-initio calculations

    Orellana, Walter

    2015-01-01

    The optoelectronic properties of single- and double-wall carbon nanotubes (CNTs) noncovalently functionalized with tetraphenylporphyrins (TPPs) are addressed by dispersion-corrected ab initio calculations. Five CNT species with different chiralities were considered. We find that the most stable configurations are those where the CNTs are fully covered by TPPs, exhibiting binding energy of about 2~eV/TPP. The semiconducting CNT-TPP compounds show optical response characterized by a strong abso...

  5. Multi-scale modeling of materials: from ab-initio calculations to kinetic simulations; Modelisation multiechelle des materiaux de l'ab-initio a la cinetique

    Willaime, F. [Division de l' energie nucleaire, CEA Centre de Saclay, 91191 Gif-sur-Yvette (France); Deutsch, T.; Pochet, P. [INAC, Direction des sciences de la matiere, CEA Centre de Grenoble, 38054 Grenoble Cedex 9 (France)

    2010-07-01

    Ab-initio calculation methods, for the purposes of computing electronic structures, have made it possible, since the early nineties, to simulate the properties of perfect crystalline materials (materials free of any defect). By improving such methods, and with the increasing power of supercomputers, it has now become feasible to simulate the properties of elementary defects, which may seldom be accessed directly through experiments. This has opened up a vast, fruitful field of multi-scale simulations, where such data yield the basis for realistic simulations of the kinetics of materials evolution. The kinetic Monte-Carlo method thus provides the means to model phenomena acting at the scale of a second, or even of a year. In the issue of self-diffusion in silicon, multi-scale simulation has been successful in predicting an asymmetrical behaviour: a speeding up of vacancy diffusion under compression and a tailing off under tension, and conversely, a speeding up of interstitial diffusion under tension and a falling off under compression. Multi-scale modeling has also been successful in simulating irradiation defects in iron. (A.C.)

  6. Quantum calculations of the IR spectrum of liquid water using ab initio and model potential and dipole moment surfaces and comparison with experiment

    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.

  7. On the feasibility of ab initio electronic structure calculations for Cu using a single s orbital basis

    The accuracy of a single s-orbital representation of Cu towards enabling multi-thousand atom ab initio calculations of electronic structure is evaluated in this work. If an electrostatic compensation charge of 0.3 electron per atom is used in this basis representation, the electronic transmission in bulk and nanocrystalline Cu can be made to compare accurately to that obtained with a Double Zeta Polarized basis set. The use of this representation is analogous to the use of single band effective mass representation for semiconductor electronic structure. With a basis of just one s-orbital per Cu atom, the representation is extremely computationally efficient and can be used to provide much needed ab initio insight into electronic transport in nanocrystalline Cu interconnects at realistic dimensions of several thousand atoms

  8. On the feasibility of ab initio electronic structure calculations for Cu using a single s orbital basis

    Hegde, Ganesh, E-mail: ganesh.h@ssi.samsung.com; Bowen, R. Chris [Advanced Logic Lab, Samsung Semiconductor Inc., Austin, TX 78754 (United States)

    2015-10-15

    The accuracy of a single s-orbital representation of Cu towards enabling multi-thousand atom ab initio calculations of electronic structure is evaluated in this work. If an electrostatic compensation charge of 0.3 electron per atom is used in this basis representation, the electronic transmission in bulk and nanocrystalline Cu can be made to compare accurately to that obtained with a Double Zeta Polarized basis set. The use of this representation is analogous to the use of single band effective mass representation for semiconductor electronic structure. With a basis of just one s-orbital per Cu atom, the representation is extremely computationally efficient and can be used to provide much needed ab initio insight into electronic transport in nanocrystalline Cu interconnects at realistic dimensions of several thousand atoms.

  9. Pressure dependence of magnetic coupling in ionic solids from ab initio cluster model calculations

    Casanovas, Jordi; Illas, Francesc

    1994-11-01

    The dependence of the magnetic coupling constant, J, with the pressure has been studied by an ab initio cluster model approach in a typical ionic solid such as KNiF3. By computing J at different values of the lattice parameter R, we predict a power law of the form ‖J‖≊R-n with 10.5

  10. Ab Initio Calculations of Elastic Constants of Li2O under Pressure

    LI Xiao-Feng; CHEN Xiang-Rong; JI Guang-Fu; MENG Chuan-Min

    2006-01-01

    @@ We investigate the equilibrium lattice constant, bulk modulus, elastic constants and Debye temperature of Li2 O under pressure by using ab initio unrestricted Hartree-Fock (HF) linear combination of atomic orbital (LCAO) periodic approach. The obtained results at zero pressure are well consistent with the available experimental data and other theoretical results. It is found that the elastic constants C11, C12 and C44 and bulk modulus B increase monotonously as pressure increases. Also, the anisotropy will weaken and the Debye temperature will rise with pressure increasing.

  11. Transport and optical properties of warm dense aluminum in the two-temperature regime: Ab initio calculation and semiempirical approximation

    Knyazev, D V

    2014-01-01

    This work is devoted to the investigation of transport and optical properties of liquid aluminum in the two-temperature case. At first optical properties, static electrical and thermal conductivities were obtained in the \\textit{ab initio} calculation. The \\textit{ab initio} calculation is based on the quantum molecular dynamics, density functional theory and the Kubo-Greenwood formula. The semiempirical approximation was constructed based on the results of the \\textit{ab initio} caculation. The approximation yields the dependences $\\sigma_{1_\\mathrm{DC}}\\propto1/T_i^{0.25}$ and $K\\propto T_e/T_i^{0.25}$ for the static electrical conductivity and thermal conductivity, respectively. The approximation is valid for liquid aluminum at $\\rho=2.70$~g/cm$^3$, 3~kK~$\\leq T_i\\leq T_e\\leq20$~kK. Our results are well described by the Drude model with the effective relaxation time $\\tau\\propto T_i^{-0.25}$. We have compared our results with a number of other models. They are all reduced in the low-temperature limit to th...

  12. Vibronic spectra predictions for open shell molecules - usefulness and limitations of ab initio calculations, assessed on alkali trimers

    Full text: The usefulness of standard ab initio techniques, such as coupled-cluster or multi-reference approaches, for the prediction of vibronic spectra is discussed using the example of K3 and Rb3 alkali-metal clusters. These exotic molecules, can be formed in their lowest-energy spin state (the doublet) by standard molecular beam methods; their weakly bound quartet state is easily stabilized on the surface of cold (0.4 K) helium nanodroplets. Both spin multiplicities have been characterized spectroscopically, and are good candidates to assess the quality of ab initio methods for electronic-structure calculations. The following characteristics make alkali trimers interesting in this respect: they are multi-electron systems, of moderate size, and include heavy atoms. Correlation energy and relativistic effects thus play an equally essential role for the molecular binding; at the same time, the system remains tractable by computationally expensive high-level methods. The symmetry properties of alkali trimers, in either spin multiplicity, makes them prime examples for the E.e Jahn-Teller effect, where a doubly-degenerate electronic state interacts with the doubly-degenerate vibrational mode of the system. By least-squares-fits of the ab initio points we extract parameters for the analytical description of the potential energy surfaces of several electronic states. We calculate vibronic spectra where the Jahn-Teller distortion as well as spin-orbit coupling are accounted for, which we compare with the available experimental data. (author)

  13. Emergent properties of nuclei from ab initio coupled-cluster calculations

    Hagen, G.; Hjorth-Jensen, M.; Jansen, G. R.; Papenbrock, T.

    2016-06-01

    Emergent properties such as nuclear saturation and deformation, and the effects on shell structure due to the proximity of the scattering continuum and particle decay channels are fascinating phenomena in atomic nuclei. In recent years, ab initio approaches to nuclei have taken the first steps towards tackling the computational challenge of describing these phenomena from Hamiltonians with microscopic degrees of freedom. This endeavor is now possible due to ideas from effective field theories, novel optimization strategies for nuclear interactions, ab initio methods exhibiting a soft scaling with mass number, and ever-increasing computational power. This paper reviews some of the recent accomplishments. We also present new results. The recently optimized chiral interaction NNLO{}{{sat}} is shown to provide an accurate description of both charge radii and binding energies in selected light- and medium-mass nuclei up to 56Ni. We derive an efficient scheme for including continuum effects in coupled-cluster computations of nuclei based on chiral nucleon–nucleon and three-nucleon forces, and present new results for unbound states in the neutron-rich isotopes of oxygen and calcium. The coupling to the continuum impacts the energies of the {J}π =1/{2}-,3/{2}-,7/{2}-,3/{2}+ states in {}{17,23,25}O, and—contrary to naive shell-model expectations—the level ordering of the {J}π =3/{2}+,5/{2}+,9/{2}+ states in {}{53,55,61}Ca. ).

  14. Ab initio many-body calculations of light nuclei neutron and proton scattering

    Quaglioni, Sofia

    2008-10-01

    One of the greatest challenges of nuclear physics today is the development of a quantitative microscopic theory of low-energy reactions on light nuclei. At the same time, technical progress on the theoretical front is urgent to match the major experimental advances in the study of exotic nuclei at the radioactive beam facilities. We build a new ab initio many-body approachootnotetextS. Quaglioni and P. Navratil, arXiv:0804.1560. capable of describing simultaneously both bound and scattering states in light nuclei, by combining the resonating-group methodootnotetextY. C. Tang et al., Phys. Rep. 47, 167 (1978); K. Langanke and H. Friedrich, Advances in Nuclear Physics, chapter 4., Plenum, New York, 1987. with the ab initio no-core shell model.ootnotetextP. Navratil, J. P. Vary, and B. R. Barrett, Phys. Rev. Lett. 84, 5728 (2000); Phys. Rev. C 62, 054311 (2000).. 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, while preserving Pauli principle and translational symmetry. I will present results for neutron and proton scattering on light nuclei, including n- and p-^4He phase shifts, and low-lying states of one-neutron halo p-shell nuclei, obtained using realistic nucleon-nucleon potentials. In particular, I will address the parity inversion of the ^11Be ground state.

  15. Ab initio calculation of the ro-vibrational spectrum of H2F+

    Kyuberis, Aleksandra A.; Lodi, Lorenzo; Zobov, Nikolai F.; Polyansky, Oleg L.

    2015-10-01

    An ab initio study of the rotation-vibrational spectrum of the electronic ground state of the (gas-phase) fluoronium ion H2F+ is presented. A new potential energy surface (PES) and a new dipole moment surface (DMS) were produced and used to compute rotation-vibrational energy levels, line positions and line intensities. Our computations achieve an accuracy of 0.15 cm-1 for the fundamental vibrational frequencies, which is about 50 times more accurate than previous ab initio results. The computed room-temperature line list should facilitate the experimental observations of new H2F+ lines, in particular of yet unobserved overtone transitions. The H2F+ molecular ion, which is isoelectronic to water, has a non-linear equilibrium geometry but a low-energy barrier to linearity at about 6000 cm-1. As a result the effects of so-called quantum monodromy become apparent already at low bending excitations. An analysis of excited bends in terms of quantum monodromy is presented.

  16. Stereoelectronic control in peptide bond formation. Ab initio calculations and speculations on the mechanism of action of serine proteases.

    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 t...

  17. Ab Initio Calculation of Vacancies and Interstitials in NiSi2

    WANG Tao; DAI Yong-Bing; OUYANG Si-Ke; WU Jian-Sheng; SHEN He-Sheng

    2004-01-01

    @@ An ab initio plane-wave ultrasoft pseudopotential method based on the generalized gradient approximations has been utilized to investigate the electronic structure, atomic geometry, formation energy to provide a better understanding of properties of Ni disilicide. The vacancy and interstitial formation energies largely depend on the atomic chemical potentials. The formation energies of vacancies Vsi and VNi are in the range of 0.04-0.56 eV and 1.25-2.3 eV, respectively and the formation energies of Si and Ni interstitials are 3.89-4.42 eV and 0.67-1.71 eV,respectively. The smaller Ni interstitial formation energy is in agreement with the experimental result that Ni interstitial atom is dominant diffusion species in NiSi2.

  18. The {\\it ab initio} calculation of spectra of open shell diatomic molecules

    Tennyson, Jonathan; McKemmish, Laura K; Yurchenko, Sergei N

    2016-01-01

    The spectra (rotational, rotation-vibrational or electronic) of diatomic molecules due to transitions involving only closed-shell ($^1\\Sigma$) electronic states follow very regular, simple patterns and their theoretical analysis is usually straightforward. On the other hand, open-shell electronic states lead to more complicated spectral patterns and, moreover, often appear as a manifold of closely lying electronic states, leading to perturbations with even larger complexity. This is especially true when at least one of the atoms is a transition metal. Traditionally these complex cases have been analysed using approaches based on perturbation theory, with semi-empirical parameters determined by fitting to spectral data. Recently the needs of two rather diverse scientific areas have driven the demand for improved theoretical models of open-shell diatomic systems based on an \\emph{ab initio} approach, these areas are ultracold chemistry and the astrophysics of "cool" stars, brown dwarfs and most recently extraso...

  19. Hydrogen atom injection into carbon surfaces by comparison between Monte-Carlo, molecular dynamics and ab-initio calculations

    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

  20. Ab initio calculations as a quantitative tool in the inelastic neutron scattering study of a single-molecule magnet analogue.

    Vonci, Michele; Giansiracusa, Marcus J; Gable, Robert W; Van den Heuvel, Willem; Latham, Kay; Moubaraki, Boujemaa; Murray, Keith S; Yu, Dehong; Mole, Richard A; Soncini, Alessandro; Boskovic, Colette

    2016-02-01

    Ab initio calculations carried out on the Tb analogue of the single-molecule magnet family Na9[Ln(W5O18)2] (Ln = Nd, Gd, Ho and Er) have allowed interpretation of the inelastic neutron scattering spectra. The combined experimental and theoretical approach sheds new light on the sensitivity of the electronic structure of the Tb(III) ground and excited states to small structural distortions from axial symmetry, thus revealing the subtle relationship between molecular geometry and magnetic properties of the two isostructural species that comprise the sample. PMID:26690503

  1. Theoretical studies of H2--H2 collisions. V. Ab initio calculations of relaxation phenomena in parahydrogen gas

    The temperature dependence of effective Waldmann--Snider cross sections determining relaxation and line broadening phenomena has been studied for p-H2 between 20 and 200 K. In particular, the rotational relaxation cross section and the relaxation cross sections of the rotational angular momentum vector and tensor polarizations and their respective fluxes have been calculated in an entirely ab initio treatment and close coupling formalism. As far as experimental results were available, quantitative agreement has been obtained. The rotational relaxation cross section has been proven to be quite sensitive to the potential anisotropy. Furthermore, the validity of some approximate relations between effective cross sections has been tested

  2. Electronic states and nature of bonding in the molecule MoC by all electron ab initio calculations

    Shim, Irene; Gingerich, Karl A.

    1997-01-01

    vibrational frequency as 997 cm(-1). The chemical bond in the (3) Sigma(-) electronic ground state has triple bond character due to the formation of delocalized bonding rr and a orbitals. The chemical bond in the MoC molecule is polar with charge transfer from Mo to C, giving rise to a dipole moment of 6.15 D......In the present work all electron ab initio multiconfiguration self-consistent-held (CASSCF) and multireference configuration interaction (MRCI) calculations have been carried out to determine the low-lying electronic states of the molecule MoC. The relativistic corrections for the one electron...

  3. Calculations of reduced partition function ratios of hydrated monoborate anion by the ab initio molecular orbital theory

    Based on the ab initio molecular orbital theory at the HF/6-31G(d) level, the effect of hydration on the reduced partition function ratio(RPFR) of the monoborate anion (B(OH)4-) is evaluated in order to better understand boron isotope fractionation observed in aqueous systems. Aquoborate anions up to decaaquoborate anion, B(OH)4-(H2O)10, were considered and their geometry optimization and RPFR calculations were carried out. It was induced that hydration decreased the ln(RPFR) value of B(OH)4- by ca. 1.2%. (author)

  4. Continuum-atomistic simulation of picosecond laser heating of copper with electron heat capacity from ab initio calculation

    Ji, Pengfei

    2016-01-01

    On the basis of ab initio quantum mechanics (QM) calculation, the obtained electron heat capacity is implemented into energy equation of electron subsystem in two temperature model (TTM). Upon laser irradiation on the copper film, energy transfer from the electron subsystem to the lattice subsystem is modeled by including the electron-phonon coupling factor in molecular dynamics (MD) and TTM coupled simulation. The results show temperature and thermal melting difference between the QM-MD-TTM integrated simulation and pure MD-TTM coupled simulation. The successful construction of the QM-MD-TTM integrated simulation provide a general way that is accessible to other metals in laser heating.

  5. Classical-trajectory calculations on Ar+ sputtering of a Si(001) surface using an ab initio potential

    We describe classical-trajectory calculations of sputtering yields for Ar+-ion collisions with a Si(001) surface. The Ar+-Si and short-ranged Si-Si interaction potentials were calculated using the ab initio Hartree-Fock and configuration-interaction methods. The low-energy potential describing the silicon solid is the two- and three-body form due to Stillinger and Weber. We compare the calculated sputtering yields with experiment. The potential-energy surface strongly influences the calculated sputtering yields, and it is found that the most reasonable agreement is obtained from our potentials using the (2 x 1) Si(001) reconstructed surface rather than the bulk-terminated surface. Analysis of the kinetic energy and angular distributions of the sputtered silicon atoms and of cluster yields has provided a mechanism of ejection

  6. Conformational Characteristics of Poly(tetrafluoroethylene) (PTFE) Based Upon Ab Initio Electronic Structure Calculations on Model Molecules

    Smith, Grant D.; Jaffe, R. L.; Yoon, D. Y.; Arnold, James O. (Technical Monitor)

    1994-01-01

    Conformational energy contours of perfluoroalkanes, determined from ab initio calculations, confirm the well-known spitting of trans states into two minima at plus or minus 17 degrees but also show that the gauche states split as well, with minima at plus or minus 124 degrees and plus or minus 84 in order to relieve steric crowding. The directions of such split distortions from the perfectly staggered states are strongly coupled for adjacent pairs of bonds in a manner identical to the intradyad pair for poly (isobutylene) chains. These conformational characteristics are fully represented by a six-state rotational isomeric state (RIS) model for PTFE comprised of t(+), t(-), g(sup +)+, g(sup +)-, g(sup -) + and g(sup -)-states, located at the split energy minima. The resultant 6 x 6 statistical weight matrix is described by first-order interaction parameters for the g+(+) (ca. 0.6 kcal/mol) and g+- (ca. 2.0 kcal/mol) states, and second order parameters for the g(sup +)+g(sup +)+ (ca 0.6 kcal/mol) and g(sup +)+g(sup -)+ (ca. 1.0 kcal/mol) states. This six-state RIS model, without adjustment of the geometric or energy parameters as determined from the ab initio calculations, predicts the unperturbed chain dimensions and the fraction of gauche bonds as a function of temperature for PTFE in good agreement with available experimental values.

  7. Linear optical properties and their bond length dependence of yttrium bromide from ab initio and density functional theory calculations

    Graphical abstract: The electronic properties such as the static dipole polarizability, anisotropy of the polarizability, and dipole moment of yttrium bromide, YBr (X1Σ) have been theoretically studied. Highlights: → Conventional ab initio and density functional theory methods were employed to study linear optical properties of YBr molecule. → Properties derivatives and their level of theory dependence were studied. → Electron correlation effects and rovibrational corrections have also been discussed. - Abstract: We have employed conventional ab initio and density functional theory methods to study the electronic properties such as the mean static dipole polarizability, α-bar, anisotropy of the polarizability, Δα, and dipole moment, μ, of yttrium bromide. The bond length dependence of properties is determined at different levels of theory and appropriate expansions around experimental internuclear distance have been presented. Moreover, the first and second geometrical derivatives for each property are quantified and their level of theory dependence has been analyzed. To study the effect of molecular rotation and vibration on the electronic properties, the rovibrational corrections have also been carried out. It is found that these corrections are less pronounced for considered properties of YBr. In all calculations, the electron correlation effects have been considered and discussed. The obtained results show that the electron correlation is more significant in the calculation of the mean and the anisotropy of dipole polarizability.

  8. Vibrational dynamics of single-crystal YVO4 studied by polarized micro-Raman spectroscopy and ab initio calculations

    Sanson, Andrea; Giarola, Marco; Rossi, Barbara; Mariotto, Gino; Cazzanelli, Enzo; Speghini, Adolfo

    2012-12-01

    The vibrational properties of yttrium orthovanadate (YVO4) single crystals, with tetragonal zircon structure, have been investigated by means of polarized micro-Raman spectroscopy and ab initio calculations. Raman spectra were taken at different polarizations and orientations carefully set by the use of a micromanipulator, so that all of the twelve Raman-active modes, expected on the basis of the group theory, were selected in turn and definitively assigned in wave number and symmetry. In particular the Eg(4) mode, assigned incorrectly in previous literature, has been observed at 387 cm-1. Moreover, the very weak Eg(1) mode, peaked at about 137 cm-1, was clearly observed only under some excitation wavelengths, and its peculiar Raman excitation profile was measured within a wide region of the visible. Finally, ab initio calculations based on density-functional theory have been performed in order to determine both Raman and infrared vibrational modes and to corroborate the experimental results. The rather good agreement between computational and experimental frequencies is slightly better than in previous computational works and supports our experimental symmetry assignments.

  9. Ab Initio Calculations of Differential Cross Sections for Single Charge Transfer in 3He2++4 He Collisions

    WU Yong; YAN Bing; LIU Ling; WANG Jian-Guo

    2007-01-01

    The single charge transfer process in 3 He2+ + 4He collisions is investigated using the quantum-mechanical molecularorbital close-coupling method, in which the adiabatic potentials and radial couplings are calculated by using the ab initio multireference single- and double-excitation configuration interaction methods. The differential cross sections for the single charge transfer are presented at the laboratorial energies E = 6kev and 10keV for the projectile 3He2+. Comparison with the existing data shows that the present results are better in agreement with the experimental measurements than other calculations in the dominant small angle scattering, which is attributed to the accurate calculations of the adiabatic potentials and the radial couplings.

  10. Operation Mechanism of Double-Walled Carbon Nanotubes Transistors Investigated By ab initio Calculations

    LAN nai-Ping; ZHANG Shuang

    2009-01-01

    Recently, a new switching characteristic of double-walled carbon nanotubes (DWNTs) transistors is found in during experiments. We carry out a series of ab intio calculations on DWNTs' electronic properities, together with verification on the electronic response under the electric field. Our results reveal that the peculiar energy states relation in DWNTs and related contact modes should account for the distinct switching behavior of DWNT transistors. We believe these results have important implications in the fabrication and understanding of electronic devices with DWNTs.

  11. Ab initio modelling of the behaviour of point defects and fission products in nuclear fuel; Modelisation par le calcul ab initio du comportement des defauts ponctuels et des produits de fission dans le combustible nucleaire

    Freyss, M.; Dorado, B.; Durinck, J. [CEA Cadarache (DEN/DEC/SESC/LLCC), 13 - Saint-Paul-lez-Durance (France). Dept. d' Etudes des Combustibles

    2008-07-01

    The aim of this work is to determine precisely the mechanisms of formation and migration of defects and fission products as well as the associated energies. Examples on uranium dioxide UO{sub 2} (standard nuclear fuel) and on uranium carbide UC (potential fuel for new generation reactors) are given. The obtained results are discussed and compared with the experimental results carried out. The ab initio method used is the Projector Augmented-Wave (PAW) method based on the density functional theory. The particular electronic properties of actinides are especially studied because, on account of their 5f orbitals more or less localized around the nucleus, it is difficult to model the actinide compounds by the DFT method. In particular, the modelling of the exchange-correlation interaction of the 5f electrons of UO{sub 2} requires approximations (as GGA+U) beyond those more currently used in ab initio calculations (LDA or GGA). (O.M.)

  12. Optical properties of surfaces with supercell ab initio calculations: Local-field effects

    Tancogne-Dejean, Nicolas; Giorgetti, Christine; Véniard, Valérie

    2015-12-01

    Surface optical and electronic properties are crucial for material science and have implications in fields as various as nanotechnology, nonlinear optics, and spectroscopies. In particular, the huge variation of electronic density perpendicular to the surface is expected to play a key role in absorption due to local-field effects. Numerous state-of-the-art theoretical and numerical ab initio formalisms developed for studying these properties are based on supercell approaches, in reciprocal space, due to their efficiency. In this paper, we show that the standard scheme fails for the out-of-plane optical response of the surface. This response is interpreted using the "effective-medium theory" with vacuum and also in terms of interaction between replicas, as the supercell approach implies a periodicity which is absent in the real system. We propose an alternative formulation, also based on the supercell, for computing the macroscopic dielectric function. Application to the clean Si(001) 2 ×1 surface allows us to present the effect of the local fields for both peak positions and line shape on the bulk and surface contributions. It shows how local fields built up for the in-plane and out-of-plane dielectric responses of the surface. In addition to their conceptual impact, our results explain why the standard approach gives reliable predictions for the in-plane components, leading to correct reflectance anisotropy spectra. Our scheme can be further generalized to other low-dimensional geometries, such as clusters or nanowires, and open the way to nonlinear optics for surfaces.

  13. The ab initio calculation of spectra of open shell diatomic molecules

    Tennyson, Jonathan; Lodi, Lorenzo; McKemmish, Laura K.; Yurchenko, Sergei N.

    2016-05-01

    The spectra (rotational, rotation–vibrational or electronic) of diatomic molecules due to transitions involving only closed-shell (1Σ ) electronic states follow very regular, simple patterns and their theoretical analysis is usually straightforward. On the other hand, open-shell electronic states lead to more complicated spectral patterns and, moreover, often appear as a manifold of closely lying electronic states, leading to perturbed spectra of even greater complexity. This is especially true when at least one of the atoms is a transition metal. Traditionally these complex cases have been analysed using approaches based on perturbation theory, with semi-empirical parameters determined by fitting to spectral data. Recently the needs of two rather diverse scientific areas have driven the demand for improved theoretical models of open-shell diatomic systems based on an ab initio approach; these areas are ultracold chemistry and the astrophysics of ‘cool’ stars, brown dwarfs and most recently extrasolar planets. However, the complex electronic structure of these molecules combined with the accuracy requirements of high-resolution spectroscopy render such an approach particularly challenging. This review describes recent progress in developing methods for directly solving the effective Schrödinger equation for open-shell diatomic molecules, with a focus on molecules containing a transtion metal. It considers four aspects of the problem: (i) the electronic structure problem; (ii) non-perturbative treatments of the curve couplings; (iii) the solution of the nuclear motion Schrödinger equation; (iv) the generation of accurate electric dipole transition intensities. Examples of applications are used to illustrate these issues.

  14. Phonon spectra of elpasolites Cs2NaRF6 (R=Y,Yb): Ab initio calculations

    Chernyshev, Vladimir; Petrov, Vladislav; Nikiforov, Anatoliy; Zakiryanov, Dmitriy

    2015-12-01

    The influence of hydrostatic pressure on structure and dynamics of a crystal lattice of elpasolites Cs2NaYbF6 and Cs2NaYF6 (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.

  15. Ab initio many-body calculation of the 7Be(p,gamma)8B radiative capture

    Navratil, Petr; Quaglioni, Sofia

    2011-01-01

    We apply the ab initio no-core shell model/resonating group method (NCSM/RGM) approach to calculate the cross section of the 7Be(p,gamma)8B radiative capture. This reaction is important for understanding the solar neutrino flux. Starting from a selected similarity-transformed chiral nucleon-nucleon interaction that accurately describes two-nucleon data, we performed parameter-free many-body calculations that simultaneously predict both the normalization and the shape of the S-factor. We study the dependence on the number of 7Be eigenstates included in the coupled-channel equations and on the size of the harmonic oscillator basis used for the expansion of the eigenstates and of the localized parts of the integration kernels. Our S-factor result at zero energy is on the lower side of, but consistent with, the latest evaluation.

  16. Comparative semi-empirical and ab initio atomic structure calculations in Yb-like tungsten W4+

    In this paper, we report on extensive calculations of radiative data in Yb-like tungsten ion using several independent atomic structure methods, i.e. the relativistic Hartree–Fock approach, the flexible atomic code and the multiconfiguration Dirac–Fock method. This multi-platform approach allowed us to check the consistency of our results. Advantages and shortcomings of semi-empirical and ab initio methods for atomic structure calculations in such a complex heavy ion are also discussed in detail. A new set of transition probabilities and oscillator strengths is reported for electric dipole lines together with magnetic dipole and electric quadrupole lines in this ion of interest for fusion plasma diagnostics. (paper)

  17. High-pressure powder x-ray diffraction experiments and ab initio calculation of Ti3AlC2

    Zhang, Haibin; Wu, Xiang; Nickel, Klaus Georg; Chen, Jixin; Presser, Volker

    2009-07-01

    The structural stability of the layered ternary carbide Ti3AlC2 was studied up to 35 GPa using x-ray diffraction with a Merrill-Basset-type diamond anvil cell and ab initio calculations. The structure (P63/mmc) was stable in the present pressure range without any phase transition. The Birch-Murnaghan equation of state was employed to fit the experimental pressure-volume date, from which the isothermal bulk modulus of Ti3AlC2 was determined as 156±5 GPa, which was also supported by theoretical results. In addition, theoretical calculations described anisotropic pressure dependences of the lattice parameters, electronic structure, and bonding properties of Ti3AlC2.

  18. Theoretical calculations on atomistic behaviors in transition metals (Fe, Co, Ni) Al multilayer system: ab initio approach

    Kim, Chiho; Chung, Yong-Chae

    2006-09-01

    The energetics and the structural characteristics of atomistic behaviors for transition metal (TM; Fe, Co and Ni)-Al multiplayer systems were quantitatively investigated using ab initio calculations. The energy barriers for the surface diffusion of adatom were calculated to be 0.89, 1.01 and 1.98 eV for Fe, Co and Ni on Al (0 0 1) systems, respectively. For Al/TM (0 0 1) systems, however, the energy barriers turned out to be relatively smaller than those for the corresponding opposite systems. It could be verified that the incorporation process for TM/Al (0 0 1) system can be occurred much easier than that for the Al/TM (0 0 1) systems due to relatively small energy barriers and positive energy gains.

  19. PtMn3N0.25: A potential candidate for spintronic applications by ab initio calculations

    PtMn3N0.25 has been synthesized 36 years ago by Kren and coworkers [E. Kren, G. Kadar, M.M. Barberon, R. Fruchart, Int. J. Magn. 341 (1971) 344] but this compound remains unexplored till date. In this paper, we present a theoretical study of PtMn3N0.25 system, based on the ab initio method. We investigate the structural, electronic and magnetic properties of PtMn3N0.25 in two phases: hexagonal close packed and cubic. We find that the ferromagnetic phase is the most stable for both phases. Their metallic nature is determined through the calculations of the electronic properties. Furthermore the calculated magnetic moments hint to promising potential spintronic applications of hcp and cubic-PtMn3N0.25 as an important magnetic compound

  20. Phonon spectra of elpasolites Cs{sub 2}NaRF{sub 6} (R=Y,Yb): Ab initio calculations

    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.

  1. Ab-Initio Molecular Dynamics

    Kühne, Thomas D

    2012-01-01

    Computer simulations and molecular dynamics in particular, is a very powerful method to provide detailed and essentially exact informations of classical many-body problems. With the advent of \\textit{ab-initio} molecular dynamics, where the forces are computed on-the-fly by accurate electronic structure calculations, the scope of either method has been greatly extended. This new approach, which unifies Newton's and Schr\\"odinger's equations, allows for complex simulations without relying on any adjustable parameter. This review is intended to outline the basic principles as well as a survey of the field. Beginning with the derivation of Born-Oppenheimer molecular dynamics, the Car-Parrinello method as well as novel hybrid scheme that unifies best of either approach are discussed. The predictive power is demonstrated by a series of applications ranging from insulators to semiconductors and even metals in condensed phases.

  2. Ab-initio calculation study on the formation mechanism of boron-oxygen complexes in c-Si

    Boron-oxygen (B-O) complex in crystalline silicon (c-Si) solar cells is responsible for the light-induced efficiency degradation of solar cell. However, the formation mechanism of B-O complex is not clear yet. By Ab-initio calculation, it is found that the stagger-type oxygen dimer (O2ist) should be the component of B-O complex, whose movement occurs through its structure reconfiguration at low temperature, instead of its long-distance diffusion. The O2ist can form two stable “latent centers” with the Bs, which are recombination-inactive. The latent centers can be evolved into the metastable recombination centers via their structure transformation in the presence of excess carriers. These results can well explain the formation behaviors of B-O complexes in c-Si

  3. Ab-initio transport calculations of Fe/MgO/Fe tunnel junctions modified by Co and Cr interlayers

    Bose, Peter [Martin Luther University Halle-Wittenberg (Germany); International Max Planck Research School for Science and Technology of Nanostructures (Germany); Henk, Juergen [Max Planck Institute of Microstructure Physics, Halle (Germany); Zahn, Peter [Martin Luther University Halle-Wittenberg (Germany); Mertig, Ingrid [Martin Luther University Halle-Wittenberg (Germany); Max Planck Institute of Microstructure Physics, Halle (Germany)

    2010-07-01

    For spintronic device applications, large and tuneable tunnel magnetoresistance ratios (TMR) are inevitable. However, experimental TMR ratios of epitaxial Fe/MgO/Fe junctions can be strongly reduced by imperfect Fe/MgO interfaces. A way to increase the TMR ratio is the insertion of thin metallic layers at the Fe/MgO interfaces. With respect to their magnetic and electronic properties as well as their small lattice mismatch to Fe(001), Co and Cr interlayers have been preferably studied. We report on systematic ab-initio investigations of Co and Cr interlayers focussing on the changes of the electronic structure and the transport properties. The results of spin-dependent ballistic transport calculations reveal options to specifically manipulate the TMR ratio. The observed effects are directly addressed and interpreted by means of electronic states with complex wave vectors.

  4. Calculations of reduced partition function ratios of hydrated boric acid molecule by the ab initio molecular orbital theory

    Based on the ab initio molecular orbital theory at the HF/6-31G(d) level, the effect of hydration on the reduced partition function ratio (RPFR) of the boric acid molecule (B(OH)3) was evaluated in order to better understand boron isotope fractionation observed in aqueous systems. The B(OH)3(H2O)n species with n up to 12 were considered and their geometry optimization and RPFR calculations were carried out. It was induced that hydration decreased the RPFR of B(OH)3 and the degree of decrease in ln(RPFR) was ca. 1.5%, which was nearly equivalent to that of B(OH)4-. (author)

  5. On the full exploitation of symmetry in periodic (as well as molecular) self-consistent-field ab initio calculations

    Orlando, Roberto; De La Pierre, Marco; Zicovich-Wilson, Claudio M.; Erba, Alessandro; Dovesi, Roberto

    2014-09-01

    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.

  6. H3PAgI: generation by laser-ablation and characterization by rotational spectroscopy and ab initio calculations.

    Stephens, Susanna L; Tew, David P; Walker, Nicholas R; Legon, Anthony C

    2016-07-28

    The new compound H3PAgI has been synthesized in the gas phase by means of the reaction of laser-ablated silver metal with a pulse of gas consisting of a dilute mixture of ICF3 and PH3 in argon. Ground-state rotational spectra were detected and assigned for the two isotopologues H3P(107)AgI and H3P(109)AgI in their natural abundance by means of a chirped-pulse, Fourier-transform, microwave spectrometer. Both isotopologues exhibit rotational spectra of the symmetric-top type, analysis of which led to accurate values of the rotational constant B0, the quartic centrifugal distortion constants DJ and DJK, and the iodine nuclear quadrupole coupling constant χaa(I) = eQqaa. Ab initio calculations at the explicitly-correlated level of theory CCSD(T)(F12*)/aug-cc-pVDZ confirmed that the atoms PAg-I lie on the C3 axis in that order. The experimental rotational constants were interpreted to give the bond lengths r0(PAg) = 2.3488(20) Å and r0(Ag-I) = 2.5483(1) Å, in good agreement with the equilibrium lengths of 2.3387 Å and 2.5537 Å, respectively, obtained in the ab initio calculations. Measures of the strength of the interaction of PH3 and AgI (the dissociation energy De for the process H3PAgI = H3P + AgI and the intermolecular stretching force constant FPAg) are presented and are interpreted to show that the order of binding strength is H3PHI < H3PICl < H3PAgI for these metal-bonded molecules and their halogen-bonded and hydrogen-bonded analogues. PMID:27354204

  7. Ab initio, mean field theory and series expansions calculations study of electronic and magnetic properties of antiferromagnetic MnSe alloys

    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.

  8. Ab initio no core full configuration approach for light nuclei

    Kim, Youngman; Shin, Ik Jae; Maris, Pieter; Vary, James P.; Forssén, Christian; Rotureau, Jimmy

    2015-10-01

    Comprehensive understanding of the structure and reactions of light nuclei poses theoretical and computational challenges. Still, a number of ab initio approaches have been developed to calculate the properties of atomic nuclei using fundamental interactions among nucleons. Among them, we work with the ab initio no core full configuration (NCFC) method and ab initio no core Gamow Shell Model (GSM). We first review these approaches and present some recent results.

  9. Ab initio calculation of the electronic spectrum of azobenzene dyes and its impact on the design of optical data storage materials

    Åstrand, Per-Olof; Ramanujam, P.S.; Hvilsted, Søren; Bak, K.L.; Sauer, S.P.A.

    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......V. Furthermore, 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 candidates for azo components used in materials for data storage....

  10. Reactivity of the binuclear non-heme iron active site of delta(9) desaturase studied by large-scale multireference ab initio calculations

    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

  11. Electronic states and nature of bonding of the molecule PdGe by all electron ab initio HF–CI calculations and mass spectrometric equilibrium experiments

    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...

  12. Ab-initio Calculations of Electronic Properties of AlP, GaP and InP

    Malozovsky, Yuriy; Saliev, Azizjon; Franklin, Lashaunda; Ekuma, Chinedu; Zhao, Guang-Lin; Bagayoko, Diola

    2014-03-01

    We present results from ab-initio, self consistent local density approximation (LDA) calculations of electronic and related properties of zinc blende aluminum, gallium and indium phosphides (AlP, GaP & InP). We employed a local density approximation (LDA) potential and implemented the linear combination of atomic orbitals (LCAO) formalism. This implementation followed the Bagayoko, Zhao, and Williams (BZW) method, as enhanced by Ekuma and Franklin (BZW-EF). Our calculated, indirect band gap of 2.56 eV for AlP, and of 2.14 eV for GaP, from Γ to X, are in excellent agreement with experimental values. Our calculated direct band gap of 1.40 eV, at Γ -point for InP is also in excellent agreement with experimental value. We also report calculated electron and hole effective masses for AlP, GaP and InP and total (DOS) and partial (pDOS) densities of states. This research is funded in part by the National Science Foundation (NSF) and the Louisiana Board of Regents, through LASiGMA [Award Nos. EPS- 1003897, NSF (2010-15)-RII-SUBR] and NSF HRD-1002541, the US Department of Energy - National, Nuclear Security Administration (NNSA) (Award No. DE-NA0001861), LaSPACE, and LONI-SUBR.

  13. Ab initio calculations of the electronic structure of the low-lying states for the ultracold LiYb molecule

    Tohme, Samir N.; Korek, Mahmoud, E-mail: mahmoud.korek@bau.edu.lb, E-mail: fkorek@yahoo.com; Awad, Ramadan [Faculty of Science, Beirut Arab University, P.O. Box 11-5020 Riad El Solh, Beirut 1107 2809 (Lebanon)

    2015-03-21

    Ab initio techniques have been applied to investigate the electronic structure of the LiYb molecule. The potential energy curves have been computed in the Born–Oppenheimer approximation for the ground and 29 low-lying doublet and quartet excited electronic states. Complete active space self-consistent field, multi-reference configuration interaction, and Rayleigh Schrödinger perturbation theory to second order calculations have been utilized to investigate these states. The spectroscopic constants, ω{sub e}, R{sub e}, B{sub e}, …, and the static dipole moment, μ, have been investigated by using the two different techniques of calculation with five different types of basis. The eigenvalues, E{sub v}, the rotational constant, B{sub v}, the centrifugal distortion constant, D{sub v}, and the abscissas of the turning points, R{sub min} and R{sub max}, have been calculated by using the canonical functions approach. The comparison between the values of the present work, calculated by different techniques, and those available in the literature for several electronic states shows a very good agreement. Twenty-one new electronic states have been studied here for the first time.

  14. Ab initio calculations of the electronic structure of the low-lying states for the ultracold LiYb molecule

    Tohme, Samir N.; Korek, Mahmoud; Awad, Ramadan

    2015-03-01

    Ab initio techniques have been applied to investigate the electronic structure of the LiYb molecule. The potential energy curves have been computed in the Born-Oppenheimer approximation for the ground and 29 low-lying doublet and quartet excited electronic states. Complete active space self-consistent field, multi-reference configuration interaction, and Rayleigh Schrödinger perturbation theory to second order calculations have been utilized to investigate these states. The spectroscopic constants, ωe, Re, Be, …, and the static dipole moment, μ, have been investigated by using the two different techniques of calculation with five different types of basis. The eigenvalues, Ev, the rotational constant, Bv, the centrifugal distortion constant, Dv, and the abscissas of the turning points, Rmin and Rmax, have been calculated by using the canonical functions approach. The comparison between the values of the present work, calculated by different techniques, and those available in the literature for several electronic states shows a very good agreement. Twenty-one new electronic states have been studied here for the first time.

  15. Ab initio calculation of scattering length and cross sections at very low energies for electron-helium scattering

    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)

  16. Excitons in poly(para phenylene vinylene): a quantum-chemical perspective based on high-level ab initio calculations.

    Mewes, Stefanie A; Mewes, Jan-Michael; Dreuw, Andreas; Plasser, Felix

    2016-01-28

    Excitonic effects play a fundamental role in the photophysics of organic semiconductors such as poly(para phenylene vinylene) (PPV). The emergence of these effects is examined for PPV oligomers based on high level ab initio excited-state calculations. The computed many-body wavefunctions are subjected to our recently developed exciton analysis protocols to provide a qualitative and quantitative characterization of excitonic effects. The discussion is started by providing high-level benchmark calculations using the algebraic-diagrammatic construction for the polarization propagator in third order of perturbation theory (ADC(3)). These calculations support the general adequacy of the computationally more efficient ADC(2) method in the case of singly excited states but also reveal the existence of low-energy doubly excited states. In a next step, a series of oligomers with chains of two to eight phenyl rings is studied at the ADC(2) level showing that the confinement effects are dominant for small oligomers, while delocalized exciton bands emerge for larger systems. In the case of the largest oligomer, the first twenty singlet and triplet excited states are computed and a detailed analysis in terms of the Wannier and Frenkel models is presented. The presence of different Wannier bands becomes apparent, showing a general trend that exciton sizes are lowered with increasing quasi-momentum within the bands. PMID:26700493

  17. Virial expansion of the second layer in physical adsorption - An ab initio calculation for helium on argon crystal

    Oh, B. K.; Kim, S. K.

    1974-01-01

    A model of helium adsorption on an argon crystal is built up from the premise that local adsorption predominates in the first layer and nonlocal adsorption in the second. Application of the virial expansion theorem to the second layer gives a series in which the first term represents the motion of a single molecule in the external potential field and the second a two-body interaction under this field. The thermodynamic functions of the adsorbed phase are calculated ab initio, the gas-solid interaction potential being derived from lattice summation and the partition function from an appropriate choice of a site-spacing polynomial to describe the periodic potential. The mutual interaction of adsorbed molecules is calculated with a two-dimensional Lennard-Jones potential. The second virial coefficient is calculated and its dependence on temperature and choice of potential is studied. It is found that the second virial coefficient is very well approximated by a two-dimensional gas in free space. The adsorption isotherm, isosteric heat, and specific heat are obtained and compared with the results of Ross and Steele, giving excellent agreement.

  18. Surface structure of CdSe Nanorods revealed by combined X-rayabsorption fine structure measurements and ab-initio calculations

    Aruguete, Deborah A.; Marcus, Matthew A.; Li, Liang-shi; Williamson, Andrew; Fakra, Sirine; Gygi, Francois; Galli, Giulia; Alivisatos, A. Paul

    2006-01-27

    We report orientation-specific, surface-sensitive structural characterization of colloidal CdSe nanorods with extended X-ray absorption fine structure spectroscopy and ab-initio density functional theory calculations. Our measurements of crystallographically-aligned CdSe nanorods show that they have reconstructed Cd-rich surfaces. They exhibit orientation-dependent changes in interatomic distances which are qualitatively reproduced by our calculations. These calculations reveal that the measured interatomic distance anisotropy originates from the nanorod surface.

  19. Electronic transport properties of fullerene functionalized carbon nanotubes: Ab initio and tight-binding calculations

    Fürst, Joachim Alexander; Hashemi, J.; Markussen, Troels;

    2009-01-01

    Fullerene functionalized carbon nanotubes-NanoBuds-form a novel class of hybrid carbon materials, which possesses many advantageous properties as compared to the pristine components. Here, we report a theoretical study of the electronic transport properties of these compounds. We use both ab init...

  20. THE AB INITIO CALCULATION FOR THE BONDING STATE OF THE Hn CTUSTERS

    Liang-moMei; GuanPeng; 等

    1990-01-01

    The equilibrium geometries of several Hn(n=4,5,6,7,9,13) clsters with certain symmetry have been optimized by the ab inito Murtaug-Sargent(MS) method.We find that the stability of a centered cluster depends on the structure,the spin symmetry and the coordinate number,and the latter plays a more important role.

  1. Transport and optical properties of CH2 plastics: Ab initio calculation and density-of-states-based analysis

    Knyazev, D. V.; Levashov, P. R.

    2015-11-01

    This work covers an ab initio calculation of transport and optical properties of plastics of the effective composition CH2 at density 0.954 g/cm3 in the temperature range from 5 kK up to 100 kK. The calculation is based on the quantum molecular dynamics, density functional theory and the Kubo-Greenwood formula. The temperature dependence of the static electrical conductivity σ1DC (T) has an unusual shape: σ1DC(T) grows rapidly for 5 kK ≤ T ≤ 10 kK and is almost constant for 20 kK ≤ T ≤ 60 kK. The additional analysis based on the investigation of the electron density of states (DOS) was performed. The rapid growth of σ1DC(T) at 5 kK ≤ T ≤ 10 kK is connected with the increase of DOS at the electron energy equal to the chemical potential ɛ = μ. The frequency dependence of the dynamic electrical conductivity σ1(ω) at 5 kK has the distinct non-Drude shape with the peak at ω ≈ 10 eV. This behavior of σ1(ω) was explained by the dip at the electron DOS.

  2. Nonlocal Pseudopotentials and Long-Range Interactions in Ab Initio Finite-Element Electronic-Structure Calculations

    Pask, J. E.; Sterne, P. A.

    2004-03-01

    The finite-element (FE) method is a general approach for the solution of partial differential equations. Like the planewave (PW) method, the FE method is a systematically improvable expansion approach. Unlike the PW method, however, its basis functions are strictly local in real space, which allows for variable resolution in real space and facilitates massively parallel implementation. We discuss the application of the FE method to ab initio electronic-structure calculations.(J.E. Pask, B.M. Klein, C.Y. Fong, and P.A. Sterne, Phys. Rev. B 59), 12352 (1999). In particular, we discuss the use of nonlocal pseudopotentials in bulk calculations, and the handling of long-range interactions in the construction of the Kohn-Sham effective potential and total energy. We show that the total energy converges variationally, and at the optimal theoretical rate consistent with the cubic completeness of the basis. This work was performed under the auspices of the U.S. Department of Energy by University of California, Lawrence Livermore National Laboratory under Contract W-7405-Eng-48.

  3. Interfacial properties in ultrathin MgO films on TiN(001) surfaces: ab-initio calculations

    By using ab-initio electronic structure calculations based on the density functional theory, we systematically investigated the interfacial properties of the MgO/TiN(001) system with increasing MgO film thickness from one to three monolayers (ML). Atomic geometries and adhesion characteristics of the MgO/TiN(001) systems in the range of 1- to 3-ML MgO are presented. O-Ti and Mg-N bonds were formed across the interfaces. Our calculated energetics indicate that the interfacial adhesion of the MgO films to the TiN substrates was stronger than that for the metal-oxide systems of MgO/Ag(001) and MgO/Fe(001). An analysis of the electronic properties of the MgO/TiN(001) systems was also performed. Upon the adsorption of the MgO overlayers, the work function of the TiN(001) surface was found to exhibit a significant decrease due to the large interface dipole formed at the interface of this system. Very interestingly, the obtained work functions of 1.89 - 1.96 eV for 1- to 3-ML MgO films on TiN(001) were lower than those for other metal-supported MgO films.

  4. Plasma resonance of binary amorphous and crystalline Al-transition metal alloys: Experiments and ab initio calculations

    Stiehler, M., E-mail: martin.stiehler@mailbox.org [Technische Universität Chemnitz, Institute of Physics, 09107 Chemnitz (Germany); Kaltenborn, S. [Physics Department and Research Center OPTIMAS, University of Kaiserslautern, 67663 Kaiserslautern (Germany); Gillani, S.S.A.; Pudwell, P. [Technische Universität Chemnitz, Institute of Physics, 09107 Chemnitz (Germany); Schneider, H.C., E-mail: hcsch@physik.uni-kl.de [Physics Department and Research Center OPTIMAS, University of Kaiserslautern, 67663 Kaiserslautern (Germany); Häussler, P. [Technische Universität Chemnitz, Institute of Physics, 09107 Chemnitz (Germany)

    2015-07-15

    Highlights: • A comprehensive study of the plasma resonance of amorphous Al-transition metal alloys is given. • A characteristic fingerprint for the plasma energy versus concentration is presented. • The experimental results are supported by DFT calculations. • Amorphous alloys are found to be model systems for studying the influence of interband transitions on the plasma resonance. - Abstract: We report on measurements of the volume plasmon loss energy E{sub P} by electron energy loss spectroscopy of binary amorphous Al–(Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Y, Pd, Ce) alloys. In these systems the measured E{sub P} can be described by an effective valence of the transition metal independent of the particular transition metal. By exploiting ab initio calculations for the crystalline counterparts in the case of Al–(Ti, V, Fe, Ni) we show that this behavior can be understood in terms of the full dielectric function taking into account intra- and interband transitions mainly due to the presence of d-states close to the Fermi energy. This is validated by the comparison with published experimental data on binary Al systems with the non-transition metals Be, Mg, Ca, and Zn. Due to the absence of composition-dependent structural phase changes, amorphous alloys are found to be model-like systems for studying the influence of interband transitions on the plasma resonance.

  5. Plasma resonance of binary amorphous and crystalline Al-transition metal alloys: Experiments and ab initio calculations

    Highlights: • A comprehensive study of the plasma resonance of amorphous Al-transition metal alloys is given. • A characteristic fingerprint for the plasma energy versus concentration is presented. • The experimental results are supported by DFT calculations. • Amorphous alloys are found to be model systems for studying the influence of interband transitions on the plasma resonance. - Abstract: We report on measurements of the volume plasmon loss energy EP by electron energy loss spectroscopy of binary amorphous Al–(Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Y, Pd, Ce) alloys. In these systems the measured EP can be described by an effective valence of the transition metal independent of the particular transition metal. By exploiting ab initio calculations for the crystalline counterparts in the case of Al–(Ti, V, Fe, Ni) we show that this behavior can be understood in terms of the full dielectric function taking into account intra- and interband transitions mainly due to the presence of d-states close to the Fermi energy. This is validated by the comparison with published experimental data on binary Al systems with the non-transition metals Be, Mg, Ca, and Zn. Due to the absence of composition-dependent structural phase changes, amorphous alloys are found to be model-like systems for studying the influence of interband transitions on the plasma resonance

  6. Spin orbit coupling for molecular ab initio density matrix renormalization group calculations: Application to g-tensors

    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.

  7. Spin orbit coupling for molecular ab initio density matrix renormalization group calculations: Application to g-tensors

    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

  8. Spin orbit coupling for molecular ab initio density matrix renormalization group calculations: Application to g-tensors

    Roemelt, Michael

    2015-07-01

    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.

  9. A fast hybrid method for constructing multidimensional potential energy surfaces from ab initio calculations: A new global analytic PES of NH{sub 2} system

    Zhai, Huanchen; Lin, Shi Ying, E-mail: sylin@sdu.edu.cn

    2015-07-09

    Highlights: • A hybrid scheme to construct potential energy surfaces (PESs) is proposed. • The hybrid scheme shows enhanced stability and accuracy. • The hybrid scheme is shown to be able to construct high quality PESs. • A new analytic ab initio PES for N({sup 2}D) + H{sub 2} reactive system is constructed. - Abstract: A hybrid fitting scheme is proposed for the construction of global analytic ab initio potential energy surfaces (PESs) by means of applying reproducing kernel Hilbert space (RKHS) interpolation and cubic spline interpolation onto different dimensions of the molecular configuration space. In addition to inheriting most advantages of the pure RKHS method, this scheme offers the following extra benefits: short initiation time and enhanced stability and accuracy. We also propose a fast algorithm for the scheme allowing the PES computation time to be independent of the number of ab initio points. We have constructed an adiabatic PES of N({sup 2}D) + H{sub 2}→NH + H reactive system from more than twenty thousand ab initio points using this scheme. The accurate quantum dynamics results calculated on the constructed PES demonstrate high accuracy and efficiency of this new scheme.

  10. A fast hybrid method for constructing multidimensional potential energy surfaces from ab initio calculations: A new global analytic PES of NH2 system

    Highlights: • A hybrid scheme to construct potential energy surfaces (PESs) is proposed. • The hybrid scheme shows enhanced stability and accuracy. • The hybrid scheme is shown to be able to construct high quality PESs. • A new analytic ab initio PES for N(2D) + H2 reactive system is constructed. - Abstract: A hybrid fitting scheme is proposed for the construction of global analytic ab initio potential energy surfaces (PESs) by means of applying reproducing kernel Hilbert space (RKHS) interpolation and cubic spline interpolation onto different dimensions of the molecular configuration space. In addition to inheriting most advantages of the pure RKHS method, this scheme offers the following extra benefits: short initiation time and enhanced stability and accuracy. We also propose a fast algorithm for the scheme allowing the PES computation time to be independent of the number of ab initio points. We have constructed an adiabatic PES of N(2D) + H2→NH + H reactive system from more than twenty thousand ab initio points using this scheme. The accurate quantum dynamics results calculated on the constructed PES demonstrate high accuracy and efficiency of this new scheme

  11. Efficient "on-the-fly" calculation of Raman spectra from \\textit{ab-initio} molecular dynamics: Application to hydrophobic/hydrophilic solutes in bulk water

    Partovi-Azar, Pouya

    2015-01-01

    We present a computational method to accurately calculate Raman spectra from first principles with an at least one order of magnitude higher efficiency. This scheme thus allows to routinely calculate finite-temperature Raman spectra "on-the-fly" by means of \\textit{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.

  12. Structural stability, elastic constants, bonding characteristics and thermal properties of zincblende, rocksalt and fluorite phases in copper nitrides: plane-wave pseudo-potential ab initio calculations

    KANOUN-BOUAYED, Nawel; Kanoun, Mohammed Benali; Goumri-Said, Souraya

    2011-01-01

    We report plane-wave pseudo-potential ab initio calculations using density functional theory in order to investigate the structural parameters, elastic constants, bonding properties and polycrystalline parameters of copper nitrides in zincblende, rocksalt and fluorite structures. Total and partial densities of states indicate a metallic character of these copper nitrides. We estimate bond strengths and types of atomic bonds using Mulliken charge density population analysis and by calculating ...

  13. Ring-Puckering Motion in 1-Chloro-cyclopentene: Rotational Spectrum and ab InitioCalculations

    Caminati, Walther; Danieli, Roberto; Fantoni, Adolfo C.; Lopez, Juan C.

    1997-01-01

    The rotational spectra of 35Cl and 37Cl 1-chloro-cyclopentene have been investigated in the frequency range 26-40 GHz. The inversion splittings due to the ring-puckering motion have been determined to be 42320(10) and 42270(10) MHz for the two isotopomers, respectively. Four more vibrational states have been analyzed for the most abudant ( 35Cl) species. The barrier hindering the ring-puckering has been evaluated. According to the ab initiocalculations, it is lower than that in cyclopentene.

  14. Ab initio electronic structure calculations and optical properties of ordered and disordered Ni{sub 3}Al

    Hussain, Altaf, E-mail: altafiub@yahoo.com [Department of Physics, Islamia University of Bahawalpur, Punjab 63100 (Pakistan); Aryal, Sitaram; Rulis, Paul [Department of Physics, University of Missouri-Kansas City, MO 64110 (United States); Choudhry, M. Arshad [Department of Physics, Islamia University of Bahawalpur, Punjab 63100 (Pakistan); Chen, Jun [Institute of Applied Physics and Computational Mathematics, Beijing 10088 (China); Ching, W.Y. [Department of Physics, University of Missouri-Kansas City, MO 64110 (United States)

    2011-04-28

    The electronic structure and optical properties of the Ni{sub 3}Al intermetallic alloy are studied by the first-principles orthogonalized linear combination of atomic orbitals method. Disordered models at different temperatures were constructed using molecular dynamics and the Vienna ab initio simulation package. The average charge transfer from Al to Ni increases steadily with temperature until the liquid phase is reached. The localization index shows the presence of relatively localized states even above the Fermi level in the disordered models. The calculated optical conductivity of the ordered phase is rich in structures and in reasonable agreement with the experimental data. The spectra of the disordered Ni{sub 3}Al models show a single broadened peak at 4.96 eV in the 0 K model which shifts towards 6.62 eV at 1400 K and then down to 5.83 eV in the liquid phase. Other results on the band structure and density of states are also discussed.

  15. Multi-scale modelling of radiation damage in Fe-Cr based on ab initio electronic structure calculations

    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.

  16. Boron: a frustrated element. Physical properties at ambient conditions and under pressure from ab-initio calculations

    Ogitsu, Tadashi; Gygi, Francois; Galli, Giulia

    2004-03-01

    Boron is the only low-Z element in the periodic table whose atomic ground state structure has not yet been fully determined. For example, it is yet unclear whether perfectly pure elemental Boron is stable in an ordered crystalline form and the number of atoms in the unit cell (varying from 315 to about 325) is still the subject of debate. Using ab-initio calculations and supercells with 1260-1280 atoms, we have studied the physical properties of Boron at ambient conditions and under pressure (P). Results about the ionic and electronic structure will be presented, in particular the role of interstitial atoms and the presence of localized states right above the Fermi level will be discussed in detail. The computed equation of state under pressure is in agreement with recent experimental data. At about 120 GPa we observe amorphization, consistent with the results of Ref. [1] at l00 GPa. Amorphization occurs by random deformation of icosahedral units which remain intact; it is accompanied by a delocalization of states near the Fermi level yielding a poorly conducting system. This work was performed under the auspices of the U.S. Dept. of Energy at the University of California/ LLNL under contract no. W-7405-Eng-48. [1] Sanz et al. Phys. Rev. Lett. 89, 245501 (2002)

  17. Structure and elasticity of Cmcm CaIrO3 and their pressure dependences: Ab initio calculations

    Tsuchiya, Taku; Tsuchiya, Jun

    2007-10-01

    Cmcm CaIrO3 is isostructural to the newly discovered high-pressure postperovskite polymorph of MgSiO3 . Due to the high transition pressure in MgSiO3 over 100GPa , low-pressure analoglike CaIrO3 is substantial to investigate physical properties of the postperovskite phase experimentally. Here we perform ab initio density functional calculations of structural and elastic properties of CaIrO3 phases and compare them with the results reported for MgSiO3 phases in detail. Local spin density approximation produces a Pauli-paramagnetic metallic ground state for Pbnm CaIrO3 , while a very weak but finite antiferromagnetic moment appears in Cmcm phase at 0GPa . We also find that each component of the normalized elastic stiffness constants of CaIrO3 is largely discrepant from that of MgSiO3 particularly in shear components, though CaIrO3 shows the compression behavior roughly similar to MgSiO3 . Those contrasts in shear constants cause the different shear wave anisotropy style. Results suggest that at least regarding shear wave polarization anisotropy, CaIrO3 is unlikely to be a good low-pressure analog of MgSiO3 , and care must be taken when one extrapolates the elastic property of Cmcm CaIrO3 to the MgSiO3 postperovskite.

  18. Ab initio calculations of optical properties of silver clusters: cross-over from molecular to nanoscale behavior

    Titantah, John T.; Karttunen, Mikko

    2016-05-01

    Electronic and optical properties of silver clusters were calculated using two different ab initio approaches: (1) based on all-electron full-potential linearized-augmented plane-wave method and (2) local basis function pseudopotential approach. Agreement is found between the two methods for small and intermediate sized clusters for which the former method is limited due to its all-electron formulation. The latter, due to non-periodic boundary conditions, is the more natural approach to simulate small clusters. The effect of cluster size is then explored using the local basis function approach. We find that as the cluster size increases, the electronic structure undergoes a transition from molecular behavior to nanoparticle behavior at a cluster size of 140 atoms (diameter ~1.7 nm). Above this cluster size the step-like electronic structure, evident as several features in the imaginary part of the polarizability of all clusters smaller than Ag147, gives way to a dominant plasmon peak localized at wavelengths 350 nm ≤ λ ≤ 600 nm. It is, thus, at this length-scale that the conduction electrons' collective oscillations that are responsible for plasmonic resonances begin to dominate the opto-electronic properties of silver nanoclusters.

  19. Multi-scale modelling of radiation damage in Fe-Cr based on ab initio electronic structure calculations

    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

  20. Ab-Initio Calculated Energetics of Sigma Phase in Mo-Fe and Mo-Co Systems

    Houserová, Jana; Šob, Mojmír; Vřešťál, J.

    Brno : Brno University of Technology, Faculty of Mechanical Engeneering, 2003, s. 242-243. [JUNIORMAT'03 /4./. Brno (CZ), 23.09.2003-24.09.2003] R&D Projects: GA ČR GP106/03/P002; GA ČR GA106/02/0877 Institutional research plan: CEZ:AV0Z2041904 Keywords : sigma phase * thermodynamic ů ab initio methods Subject RIV: BM - Solid Matter Physics ; Magnetism

  1. Ab Initio Calculation of the Lattice Distortions induced by Substitutional Ag- and Cu- Impurities in Alkali Halide Crystals

    Aguado, Andrés; López, José M.; Alonso, Julio A.

    2000-01-01

    An ab initio study of the doping of alkali halide crystals (AX: A = Li, Na, K, Rb; X = F, Cl, Br, I) by ns2 anions (Ag- and Cu-) is presented. Large active clusters with 179 ions embedded in the surrounding crystalline lattice are considered in order to describe properly the lattice relaxation induced by the introduction of substitutional impurities. In all the cases considered, the lattice distortions imply the concerted movement of several shells of neighbors. The shell displacements are sm...

  2. Ab initio determination of thermodynamic properties of metals and alloys and their use in phase diagram calculations

    Vřešťál, J.; Houserová, Jana; Šob, Mojmír; Friák, Martin

    Rio de Janeiro, 2003, s. 760-770. [CONGRESSO ANUAL DA ABM /58./. Rio de Janeiro (BR), 21.07.2003-24.07.2003] R&D Projects: GA ČR GP106/03/P002; GA ČR GA106/02/0877 Institutional research plan: CEZ:AV0Z2041904 Keywords : sigma phase * phase diagram ů ab initio methods Subject RIV: BM - Solid Matter Physics ; Magnetism

  3. Phase diagram calculation in Co-Cr system using ab initio determined lattice instability of sigma phase

    Houserová, Jana; Vřešťál, J.; Friák, Martin; Šob, Mojmír

    2002-01-01

    Roč. 26, č. 4 (2002), s. 513-522. ISSN 0364-5916. [CALPHAD /31./. Stockholm, 05.05.2002-10.05.2002] R&D Projects: GA ČR GA106/02/0877 Institutional research plan: CEZ:AV0Z2041904 Keywords : phase diagram * ab initio * sigma phase Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.506, year: 2002

  4. Theoretical studies of H2--H2 collisions. IV. Ab initio calculations of anisotropic transport phenomena in para-hydrogen gas

    The temperature dependence of the effective Waldmann--Snider cross sections determining the Senftleben--Beenakker effects of viscosity and heat conductivity has been studied for pH2 gas between 10 and 200 K. From ab initio nonspherical potentials of H2--H2, 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

  5. Ab initio mass tensor molecular dynamics

    Tsuchida, Eiji

    2010-01-01

    Mass tensor molecular dynamics was first introduced by Bennett [J. Comput. Phys. 19, 267 (1975)] for efficient sampling of phase space through the use of generalized atomic masses. Here, we show how to apply this method to ab initio molecular dynamics simulations with minimal computational overhead. Test calculations on liquid water show a threefold reduction in computational effort without making the fixed geometry approximation. We also present a simple recipe for estimating the optimal ato...

  6. Ab initio calculations of phonon dispersion and lattice dynamics in TlGaTe{sub 2}

    Jafarova, Vusala; Orudzhev, Guseyn; Alekperov, Oktay; Mamedov, Nazim; Abdullayev, Nadir; Najafov, Arzu [Institute of Physics (Innovation Sector), 33 H. Javid ave, Baku 1143 (Azerbaijan); Paucar, Raul [Institute of Physics (Innovation Sector), 33 H. Javid ave, Baku 1143 (Azerbaijan); Chiba Institute of Technology, 2-17-1 Tsudanuma, Narashino, Chiba 275-0016 (Japan); Shim, YongGu [Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka 599-8531 (Japan); Wakita, Kazuki [Chiba Institute of Technology, 2-17-1 Tsudanuma, Narashino, Chiba 275-0016 (Japan)

    2015-06-15

    This work reports the results of DFT-based calculations of phonon spectra of TlGaTe{sub 2}. The dispersion of phonon bands was calculated along the directions of Brillouin zone (BZ) that include symmetry points. The calculated phonon frequencies at the centre of BZ were compared with those obtained by Raman spectroscopy with the aid of a confocal laser microscopy system. A fairly good agreement between the calculated and experimental data was found. Complimentary, molar heat capacity at constant volume and Debye temperature were calculated in the range 5/500 K on the base of the obtained phonon density of states. The obtained temperature dependencies were compared with available experimental data.The results of comparison were satisfactory. (copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  7. Four-faceted nanowires generated from densely-packed TiO2 rutile surfaces: Ab initio calculations

    Evarestov, R. A.; Zhukovskii, Yu. F.

    2013-02-01

    Two-dimensional (2D) slabs and monoperiodic (1D) nanowires orthogonal to the slab surface of rutile-based TiO2 structure terminated by densely-packed surfaces and facets, respectively, have been simulated in the current study. The procedure of structural generation of nanowires (NWs) from titania slabs (2D → 1D) is described. We have simulated: (i) (110), (100), (101) and (001) slabs of different thicknesses as well as (ii) [001]- and [110]-oriented nanowires of different diameters terminated by either four types of related {110} facets or alternating {11¯0} and {001} facets, respectively. Nanowires have been described using both the Ti atom-centered rotation axes as well as the hollow site-centered axes passing through the interstitial sites between the Ti and O atoms closest to the axes. For simulations on TiO2 slabs and NWs, we have performed large-scale ab initio Density Functional Theory (DFT) and hybrid DFT-Hartree Fock (DFT-HF) calculations with the total geometry optimization within the Generalized Gradient Approximation (GGA) in the form of the Perdew-Becke-Ernzenhof exchange-correlation functionals (PBE and PBE0, respectively), using the formalism of linear combination of localized atomic functions (LCAO) implemented in CRYSTAL09 code. Both structural and electronic properties of enumerated rutile-based titania slabs and nanowires have been calculated. According to the results of our surface energy calculations, the most stable rutile-based titania slab is terminated by (110) surfaces whereas the energetically favorable [001]-oriented NWs are also terminated by {110} facets only, thus confirming results of previous studies.

  8. Rotational study of the CH4–CO complex: Millimeter-wave measurements and ab initio calculations

    The rotational spectrum of the van der Waals complex CH4–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 jCH4 = 0 ground state and the K = 2–1 and K = 0–1 subbands correlating with the jCH4 = 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 CH4–CO complex. Accompanying ab initio calculations of the intermolecular potential energy surface (PES) of CH4–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 CH4 face closest to the CO subunit and binding energy De = 177.82 cm−1. The bound rovibrational levels of the CH4–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 D0 are 91.32, 94.46, and 104.21 cm−1 for A (jCH4 = 0), F (jCH4 = 1), and E (jCH4 = 2) nuclear spin modifications of CH4–CO, respectively

  9. Electronic structure and metallization of cubic GdH3 under pressure: Ab initio many-body GW calculations

    Kong, Bo; Zhang, Yachao

    2016-07-01

    The electronic structures of the cubic GdH3 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 + G0W0 calculations give a fundamental band gap of 1.72 eV, while GGA+ GW0 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) GdH3 can be opened up by solving the QP equation with improved starting point of eigenvalues and wave functions given by HSE03. The HSE03 + G0W0 calculations present a fundamental band gap of 2.73 eV in the AFM configuration, and the results of the corresponding GW0 and GW calculations are 2.89 and 3.03 eV, respectively. In general, for the cubic structure, the fundamental gap from G0W0 calculations in the 4f-core case is the closest to the real result. By G0W0 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 GdH3 occurs around 40 GPa, which might be a satisfied prediction.

  10. Ab-initio calculations of electronic structure and optical properties of TiAl alloy

    Hussain, Altaf [Department of Physics, The Islamia University of Bahawalpur, Bahawalpur 63120 (Pakistan); Sikandar Hayat, Sardar, E-mail: sikandariub@yahoo.co [Department of Physics, Hazara University, Mansehra 21300 (Pakistan); Choudhry, M.A. [Department of Physics, The Islamia University of Bahawalpur, Bahawalpur 63120 (Pakistan)

    2011-05-01

    The electronic structures and optical properties of TiAl intermetallic alloy system are studied by the first-principle orthogonalized linear combination of atomic orbitals method. Results on the band structure, total and partial density of states, localization index, effective atomic charges, and optical conductivity are presented and discussed in detail. Total density of states spectra reveal that (near the Fermi level) the majority of the contribution is from Ti-3d states. The effective charge calculations show an average charge transfer of 0.52 electrons from Ti to Al in primitive cell calculations of TiAl alloy. On the other hand, calculations using supercell approach reveal an average charge transfer of 0.48 electrons from Ti to Al. The localization index calculations, of primitive cell as well as of supercell, show the presence of relatively localized states even above the Fermi level for this alloy. The calculated optical conductivity spectra of TiAl alloy are rich in structures, showing the highest peak at 5.73 eV for supercell calculations. Calculations of the imaginary part of the linear dielectric function show a prominent peak at 5.71 eV and a plateau in the range 1.1-3.5 eV.