The interaction of MnH(X 7Σ+) with He: Ab initio potential energy surface and bound states

Science.gov (United States)

Turpin, Florence; Halvick, Philippe; Stoecklin, Thierry

2010-06-01

The potential energy surface of the ground state of the He-MnH(X Σ7+) van der Waals complex is presented. Within the supermolecular approach of intermolecular energy calculations, a grid of ab initio points was computed at the multireference configuration interaction level using the aug-cc-pVQZ basis set for helium and hydrogen and the relativistic aug-cc-pVQZ-DK basis set for manganese. The potential energy surface was then fitted to a global analytical form which main features are discussed. As a first application of this potential energy surface, we present accurate calculations of bound energy levels of the H3e-MnH and H4e-MnH complexes.

Fast vibrational configuration interaction using generalized curvilinear coordinates and self-consistent basis.

Science.gov (United States)

Scribano, Yohann; Lauvergnat, David M; Benoit, David M

2010-09-07

In this paper, we couple a numerical kinetic-energy operator approach to the direct-vibrational self-consistent field (VSCF)/vibrational configuration interaction (VCI) method for the calculation of vibrational anharmonic frequencies. By combining this with fast-VSCF, an efficient direct evaluation of the ab initio potential-energy surface (PES), we introduce a general formalism for the computation of vibrational bound states of molecular systems exhibiting large-amplitude motion such as methyl-group torsion. We validate our approach on an analytical two-dimensional model and apply it to the methanol molecule. We show that curvilinear coordinates lead to a significant improvement in the VSCF/VCI description of the torsional frequency in methanol, even for a simple two-mode coupling expansion of the PES. Moreover, we demonstrate that a curvilinear formulation of the fast-VSCF/VCI scheme improves its speed by a factor of two and its accuracy by a factor of 3.

Interactive Cost Configuration Over Decision Diagrams

DEFF Research Database (Denmark)

Andersen, Henrik Reif; Hadzic, Tarik; Pisinger, David

2010-01-01

interaction online. In particular,binary decision diagrams (BDDs) have been successfully used as a compilation target for product and service configuration. In this paper we discuss how to extend BDD-based configuration to scenarios involving cost functions which express user preferences. We first show...... that an efficient, robust and easy to implement extension is possible if the cost function is additive, and feasible solutions are represented using multi-valued decision diagrams (MDDs). We also discuss the effect on MDD size if the cost function is non-additive or if it is encoded explicitly into MDD. We...... then discuss interactive configuration in the presence of multiple cost functions. We prove that even in its simplest form, multiple-cost configuration is NP-hard in the input MDD. However, for solving two-cost configuration we develop a pseudo-polynomial scheme and a fully polynomial approximation scheme...

Co-Configuration in Interaction Work

DEFF Research Database (Denmark)

Fischer, Louise Harder; Pries-Heje, Lene

2015-01-01

How to increase knowledge workers productivity is still a puzzle. While knowledge work has become increasingly virtual, collaborative and interactive, we still witness challenges in the area of productivity. We challenge the widespread perception of the causal relationship between high autonomy...... and high productivity in knowledge work and the fact that configuration and standardization for improving productivity is logical impossible. With a hermeneutical approach we describe and interpret “what is going on” in two different context of interaction knowledge work. Findings suggests that knowledge...... workers often feel caught in counter-productive practices with technology, due to the autonomous use of Interaction-IT and the challenge of configuring work. We witness different behaviors related to “the autonomy paradox” and we see something interesting happening, when introducing Interaction IT. While...

Ab initio study of Cr interactions with point defects in bcc Fe

International Nuclear Information System (INIS)

Olsson, P.; Domain, Ch.; Wallenius, J.

2008-01-01

Full text of publication follows. Ferritic martensitic steels are candidate structural materials for fast neutron reactors, and in particular high-Cr reduced-activation steels. In Fe-Cr alloys, Cr plays a major role in the radiation-induced evolution of the mechanical properties. Using ab initio calculations based on density functional theory, the properties of Cr in α-Fe have been investigated. The intrinsic point defect formation energies were found to be larger in model bcc Cr as compared to those in ferromagnetic bcc Fe. The interactions of Cr with point defects (vacancy and self interstitials) have been characterised. Single Cr atoms interact weakly with vacancies but significantly with self-interstitial atoms. Mixed interstitials of any interstitial symmetry are bound. Configurations where two Cr atoms are in nearest neighbour position are generally unfavourable in bcc Fe except when they are a part of a interstitial complex. Mixed interstitials do not have as strong directional stability as pure Fe interstitials have. The effects on the results using the atom description scheme of either the ultrasoft pseudo-potential (USPP) or the projector augmented wave (PAW) formalisms are connected to the differences in local magnetic moments that the two methods predict. As expected for the Fe-Cr system, the results obtained using the PAW method are more reliable than the ones obtained with USPP. (authors)

Speed-up of ab initio hybrid Monte Carlo and ab initio path integral hybrid Monte Carlo simulations by using an auxiliary potential energy surface

International Nuclear Information System (INIS)

Nakayama, Akira; Taketsugu, Tetsuya; Shiga, Motoyuki

2009-01-01

Efficiency of the ab initio hybrid Monte Carlo and ab initio path integral hybrid Monte Carlo methods is enhanced by employing an auxiliary potential energy surface that is used to update the system configuration via molecular dynamics scheme. As a simple illustration of this method, a dual-level approach is introduced where potential energy gradients are evaluated by computationally less expensive ab initio electronic structure methods. (author)

Ab initio calculation atomics ground state wave function for interactions Ion- Atom

International Nuclear Information System (INIS)

Shojaee, F.; Bolori zadeh, M. A.

2007-01-01

Ab initio calculation atomics ground state wave function for interactions Ion- Atom Atomic wave function expressed in a Slater - type basis obtained within Roothaan- Hartree - Fock for the ground state of the atoms He through B. The total energy is given for each atom.

Ab initio study of H + + H 2 collisions: Elastic/inelastic and charge transfer processes

Science.gov (United States)

Saieswari, A.; Kumar, Sanjay

2007-12-01

An ab initio full configuration interaction study has been undertaken to obtain the global potential energy surfaces for the ground and the first excited electronic state of the H + + H 2 system employing Dunning's cc-pVQZ basis set. Using the ab initio approach the corresponding quasi-diabatic potential energy surfaces and coupling potentials have been obtained. A time-independent quantum mechanical study has been also undertaken for both the inelastic and charge transfer processes at the experimental collision energy Ec.m. = 20.0 eV and the preliminary results show better agreement with the experimental data as compared to the earlier available theoretical studies.

Ab initio nuclear structure - the large sparse matrix eigenvalue problem

Energy Technology Data Exchange (ETDEWEB)

Vary, James P; Maris, Pieter [Department of Physics, Iowa State University, Ames, IA, 50011 (United States); Ng, Esmond; Yang, Chao [Computational Research Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Sosonkina, Masha, E-mail: jvary@iastate.ed [Scalable Computing Laboratory, Ames Laboratory, Iowa State University, Ames, IA, 50011 (United States)

2009-07-01

The structure and reactions of light nuclei represent fundamental and formidable challenges for microscopic theory based on realistic strong interaction potentials. Several ab initio methods have now emerged that provide nearly exact solutions for some nuclear properties. The ab initio no core shell model (NCSM) and the no core full configuration (NCFC) method, frame this quantum many-particle problem as a large sparse matrix eigenvalue problem where one evaluates the Hamiltonian matrix in a basis space consisting of many-fermion Slater determinants and then solves for a set of the lowest eigenvalues and their associated eigenvectors. The resulting eigenvectors are employed to evaluate a set of experimental quantities to test the underlying potential. For fundamental problems of interest, the matrix dimension often exceeds 10{sup 10} and the number of nonzero matrix elements may saturate available storage on present-day leadership class facilities. We survey recent results and advances in solving this large sparse matrix eigenvalue problem. We also outline the challenges that lie ahead for achieving further breakthroughs in fundamental nuclear theory using these ab initio approaches.

Ab initio nuclear structure - the large sparse matrix eigenvalue problem

International Nuclear Information System (INIS)

Vary, James P; Maris, Pieter; Ng, Esmond; Yang, Chao; Sosonkina, Masha

2009-01-01

The structure and reactions of light nuclei represent fundamental and formidable challenges for microscopic theory based on realistic strong interaction potentials. Several ab initio methods have now emerged that provide nearly exact solutions for some nuclear properties. The ab initio no core shell model (NCSM) and the no core full configuration (NCFC) method, frame this quantum many-particle problem as a large sparse matrix eigenvalue problem where one evaluates the Hamiltonian matrix in a basis space consisting of many-fermion Slater determinants and then solves for a set of the lowest eigenvalues and their associated eigenvectors. The resulting eigenvectors are employed to evaluate a set of experimental quantities to test the underlying potential. For fundamental problems of interest, the matrix dimension often exceeds 10 10 and the number of nonzero matrix elements may saturate available storage on present-day leadership class facilities. We survey recent results and advances in solving this large sparse matrix eigenvalue problem. We also outline the challenges that lie ahead for achieving further breakthroughs in fundamental nuclear theory using these ab initio approaches.

Specific interactions between DNA and regulatory protein controlled by ligand-binding: Ab initio molecular simulation

Energy Technology Data Exchange (ETDEWEB)

Matsushita, Y., E-mail: kurita@cs.tut.ac.jp; Murakawa, T., E-mail: kurita@cs.tut.ac.jp; Shimamura, K., E-mail: kurita@cs.tut.ac.jp; Oishi, M., E-mail: kurita@cs.tut.ac.jp; Ohyama, T., E-mail: kurita@cs.tut.ac.jp; Kurita, N., E-mail: kurita@cs.tut.ac.jp [Department of Computer Science and Engineering, Toyohashi University of Technology, Tempaku-cho, Toyohashi, Aichi, 441-8580 (Japan)

2015-02-27

The catabolite activator protein (CAP) is one of the regulatory proteins controlling the transcription mechanism of gene. Biochemical experiments elucidated that the complex of CAP with cyclic AMP (cAMP) is indispensable for controlling the mechanism, while previous molecular simulations for the monomer of CAP+cAMP complex revealed the specific interactions between CAP and cAMP. However, the effect of cAMP-binding to CAP on the specific interactions between CAP and DNA is not elucidated at atomic and electronic levels. We here considered the ternary complex of CAP, cAMP and DNA in solvating water molecules and investigated the specific interactions between them at atomic and electronic levels using ab initio molecular simulations based on classical molecular dynamics and ab initio fragment molecular orbital methods. The results highlight the important amino acid residues of CAP for the interactions between CAP and cAMP and between CAP and DNA.

Specific interactions between DNA and regulatory protein controlled by ligand-binding: Ab initio molecular simulation

International Nuclear Information System (INIS)

Matsushita, Y.; Murakawa, T.; Shimamura, K.; Oishi, M.; Ohyama, T.; Kurita, N.

2015-01-01

The catabolite activator protein (CAP) is one of the regulatory proteins controlling the transcription mechanism of gene. Biochemical experiments elucidated that the complex of CAP with cyclic AMP (cAMP) is indispensable for controlling the mechanism, while previous molecular simulations for the monomer of CAP+cAMP complex revealed the specific interactions between CAP and cAMP. However, the effect of cAMP-binding to CAP on the specific interactions between CAP and DNA is not elucidated at atomic and electronic levels. We here considered the ternary complex of CAP, cAMP and DNA in solvating water molecules and investigated the specific interactions between them at atomic and electronic levels using ab initio molecular simulations based on classical molecular dynamics and ab initio fragment molecular orbital methods. The results highlight the important amino acid residues of CAP for the interactions between CAP and cAMP and between CAP and DNA

Gauge-Invariant Formulation of Time-Dependent Configuration Interaction Singles Method

Directory of Open Access Journals (Sweden)

Takeshi Sato

2018-03-01

Full Text Available We propose a gauge-invariant formulation of the channel orbital-based time-dependent configuration interaction singles (TDCIS method [Phys. Rev. A, 74, 043420 (2006], one of the powerful ab initio methods to investigate electron dynamics in atoms and molecules subject to an external laser field. In the present formulation, we derive the equations of motion (EOMs in the velocity gauge using gauge-transformed time-dependent, not fixed, orbitals that are equivalent to the conventional EOMs in the length gauge using fixed orbitals. The new velocity-gauge EOMs avoid the use of the length-gauge dipole operator, which diverges at large distance, and allows us to exploit computational advantages of the velocity-gauge treatment over the length-gauge one, e.g., a faster convergence in simulations with intense and long-wavelength lasers, and the feasibility of exterior complex scaling as an absorbing boundary. The reformulated TDCIS method is applied to an exactly solvable model of one-dimensional helium atom in an intense laser field to numerically demonstrate the gauge invariance. We also discuss the consistent method for evaluating the time derivative of an observable, which is relevant, e.g., in simulating high-harmonic generation.

Electronic structure of Ge-2 and Ge-2 and thermodynamic properties of Ge-2 from all electron ab initio investigations and Knudsen effusion mass spectroscopic measurements

DEFF Research Database (Denmark)

Shim, Irene; Baba, M. Sai; Gingerich, K.A.

2002-01-01

The low-lying states of the molecule Ge-2 and of the ion Ge-2(-) have been investigated by all electron ab initio multiconfiguration self-consistent field (CASSCF) and multi-reference configuration interaction (MRCI) calculations. The relativistic corrections for the Darwin contact term and for t......The low-lying states of the molecule Ge-2 and of the ion Ge-2(-) have been investigated by all electron ab initio multiconfiguration self-consistent field (CASSCF) and multi-reference configuration interaction (MRCI) calculations. The relativistic corrections for the Darwin contact term...... excited states are presented. Thermal functions based on the theoretically determined molecular parameters were used to derive the thermodynamic properties of the Ge-2 molecule from new mass spectrometric equilibrium data. The literature value for the dissociation energy of Ge-2 has been re...

Electron correlation effects on the N2--N2 interaction

International Nuclear Information System (INIS)

Hay, P.J.; Pack, R.T.; Martin, R.L.

1984-01-01

Ab initio self-consistent field, configuration interaction, and many-body perturbation theory methods are used to calculate the intermolecular potential between two nitrogen molecules. The emphasis is placed on the repulsive region important at the temperatures and pressures encountered in detonations. In addition, electron gas calculations are employed to fit and extend the ab initio data. We also generate effective spherical potentials which fit dilute gas virial, viscosity, and differential scattering data while being constrained by Hugoniot or ab initio data in the repulsive region. Finally, we discuss the roles of electron correlation and of many-body effects on the N 2 --N 2 interaction. Comparisons are also made to the Ar 2 potential where similar ab initio calculations are compared to an accurate empirical potential

Ab initio quantum chemistry in parallel-portable tools and applications

International Nuclear Information System (INIS)

Harrison, R.J.; Shepard, R.; Kendall, R.A.

1991-01-01

In common with many of the computational sciences, ab initio chemistry faces computational constraints to which a partial solution is offered by the prospect of highly parallel computers. Ab initio codes are large and complex (O(10 5 ) lines of FORTRAN), representing a significant investment of communal effort. The often conflicting requirements of portability and efficiency have been successfully resolved on vector computers by reliance on matrix oriented kernels. This proves inadequate even upon closely-coupled shared-memory parallel machines. We examine the algorithms employed during a typical sequence of calculations. Then we investigate how efficient portable parallel implementations may be derived, including the complex multi-reference singles and doubles configuration interaction algorithm. A portable toolkit, modeled after the Intel iPSC and the ANL-ACRF PARMACS, is developed, using shared memory and TCP/IP sockets. The toolkit is used as an initial platform for programs portable between LANS, Crays and true distributed-memory MIMD machines. Timings are presented. 53 refs., 4 tabs

Kramers Pairs in configuration interaction

DEFF Research Database (Denmark)

Avery, John Scales; Avery, James Emil

2003-01-01

The theory of symmetry-preserving Kramers pair creation operators is reviewed and formulas for applying these operators to configuration interaction calculations are derived. A new and more general type of symmetry-preserving pair creation operator is proposed and shown to commute with the total ...

Improving the Performance of Interactive Configuration with Regular String Constraints

DEFF Research Database (Denmark)

Hansen, Esben Rune; Tiedemann, Peter

2008-01-01

A generalization of the problem of interactive configuration has previously been presented in [1]. This generalization utilized decomposition to extend the standard finite domain interactive configuration framework to deal with unbounded string variables and provided features such as prefix auto...

Ab initio molecular-orbital study on electron correlation effects in CuO6 clusters relating to high-Tc superconductivity

International Nuclear Information System (INIS)

Yamamoto, S.; Yamaguchi, K.; Nasu, K.

1990-01-01

Ab initio molecular-orbital calculations for CuO 6 clusters have been performed to elucidate the electronic structures of undoped and doped copper oxides, which are of current interest in relation to high-T c superconductivity. The electron correlation effects for these species are thoroughly investigated by the full-valence configuration-interaction method and the complete-active-space self-consistent-field method. The electron correlation effect is relatively simple for the A g state (σ hole), whereas pair excitations and spin-flip excitations give sizable contributions to the configuration-interaction wave function for the B state (in-plane π hole). Implications of these results are discussed in relation to the mechanisms of the high-T c superconductivity

Configuration interaction wave functions: A seniority number approach

International Nuclear Information System (INIS)

Alcoba, Diego R.; Torre, Alicia; Lain, Luis; Massaccesi, Gustavo E.; Oña, Ofelia B.

2014-01-01

This work deals with the configuration interaction method when an N-electron Hamiltonian is projected on Slater determinants which are classified according to their seniority number values. We study the spin features of the wave functions and the size of the matrices required to formulate states of any spin symmetry within this treatment. Correlation energies associated with the wave functions arising from the seniority-based configuration interaction procedure are determined for three types of molecular orbital basis: canonical molecular orbitals, natural orbitals, and the orbitals resulting from minimizing the expectation value of the N-electron seniority number operator. The performance of these bases is analyzed by means of numerical results obtained from selected N-electron systems of several spin symmetries. The comparison of the results highlights the efficiency of the molecular orbital basis which minimizes the mean value of the seniority number for a state, yielding energy values closer to those provided by the full configuration interaction procedure

Configuration interaction wave functions: A seniority number approach

Energy Technology Data Exchange (ETDEWEB)

Alcoba, Diego R. [Departamento de Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires and Instituto de Física de Buenos Aires, Consejo Nacional de Investigaciones Científicas y Técnicas, Ciudad Universitaria, 1428 Buenos Aires (Argentina); Torre, Alicia; Lain, Luis, E-mail: qfplapel@lg.ehu.es [Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco, Apdo. 644, E-48080 Bilbao (Spain); Massaccesi, Gustavo E. [Departamento de Ciencias Exactas, Ciclo Básico Común, Universidad de Buenos Aires, Ciudad Universitaria, 1428 Buenos Aires (Argentina); Oña, Ofelia B. [Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas, Universidad Nacional de La Plata, CCT La Plata, Consejo Nacional de Investigaciones Científicas y Técnicas, Diag. 113 y 64 (S/N), Sucursal 4, CC 16, 1900 La Plata (Argentina)

2014-06-21

This work deals with the configuration interaction method when an N-electron Hamiltonian is projected on Slater determinants which are classified according to their seniority number values. We study the spin features of the wave functions and the size of the matrices required to formulate states of any spin symmetry within this treatment. Correlation energies associated with the wave functions arising from the seniority-based configuration interaction procedure are determined for three types of molecular orbital basis: canonical molecular orbitals, natural orbitals, and the orbitals resulting from minimizing the expectation value of the N-electron seniority number operator. The performance of these bases is analyzed by means of numerical results obtained from selected N-electron systems of several spin symmetries. The comparison of the results highlights the efficiency of the molecular orbital basis which minimizes the mean value of the seniority number for a state, yielding energy values closer to those provided by the full configuration interaction procedure.

Spin-orbit interaction effects in zincblende semiconductors: Ab initio pseudopotential calculations

International Nuclear Information System (INIS)

Li, Ming-Fu; Surh, M.P.; Louie, S.G.

1988-06-01

Ab initio band structure calculations have been performed for the spin-orbit interaction effects at the top of the valence bands for GaAs and InSb. Relativistic, norm-conserving pseudopotentials are used with no correction made for the gaps from the local density approximation. The spin-orbit splitting at Γ and linear terms in the /rvec char/k dependence of the splitting are found to be in excellent agreement with existing experiments and previous theoretical results. The effective mass and the cubic splitting terms are also examined. 6 refs., 1 fig., 2 tabs

Pushing configuration-interaction to the limit

DEFF Research Database (Denmark)

Vogiatzis, Konstantinos D.; Ma, Dongxia; Olsen, Jeppe

2017-01-01

A new large-scale parallel multiconfigurational self-consistent field (MCSCF) implementation in the open-source NWChem computational chemistry code is presented. The generalized active space (GAS) approach is used to partition large configuration interaction (CI) vectors and generate a sufficient...

Molecular structure and interactions of nucleic acid components in nanoparticles: ab initio calculations

International Nuclear Information System (INIS)

Rubin, Yu.V.; Belous, L.F.

2012-01-01

Self-associates of nucleic acid components (stacking trimers and tetramers of the base pairs of nucleic acids) and short fragments of nucleic acids are nanoparticles (linear sizes of these particles are more than 10 A). Modern quantum-mechanical methods and softwares allow one to perform ab initio calculations of the systems consisting of 150-200 atoms with enough large basis sets (for example, 6-31G * ). The aim of this work is to reveal the peculiarities of molecular and electronic structures, as well as the energy features of nanoparticles of nucleic acid components. We had carried out ab initio calculations of the molecular structure and interactions in the stacking dimer, trimer, and tetramer of nucleic base pairs and in the stacking (TpG)(ApC) dimer and (TpGpC) (ApCpG) trimer of nucleotides, which are small DNA fragments. The performed calculations of molecular structures of dimers and trimers of nucleotide pairs showed that the interplanar distance in the structures studied is equal to 3.2 A on average, and the helical angle in a trimer is approximately equal to 30 o : The distance between phosphor atoms in neighboring chains is 13.1 A. For dimers and trimers under study, we calculated the horizontal interaction energies. The analysis of interplanar distances and angles between nucleic bases and their pairs in the calculated short oligomers of nucleic acid base pairs (stacking dimer, trimer, and tetramer) has been carried out. Studies of interactions in the calculated short oligomers showed a considerable role of the cross interaction in the stabilization of the structures. The contribution of cross interactions to the horizontal interactions grows with the length of an oligomer. Nanoparticle components get electric charges in nanoparticles. Longwave low-intensity bands can appear in the electron spectra of nanoparticles.

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

DEFF Research Database (Denmark)

Shim, Irene; Kingcade, Joseph E. , Jr.; Gingerich, Karl A.

1986-01-01

In the present work we present all-electron ab initio Hartree–Fock (HF) and configuration interaction (CI) calculations of six electronic states of the PdGe molecule. The molecule is predicted to have a 3Pi ground state and two low-lying excited states 3Sigma− and 1Sigma+. The electronic structure...

Simulations of the dissociation of small helium clusters with ab initio molecular dynamics in electronically excited states

International Nuclear Information System (INIS)

Closser, Kristina D.; Head-Gordon, Martin; Gessner, Oliver

2014-01-01

The dynamics resulting from electronic excitations of helium clusters were explored using ab initio molecular dynamics. The simulations were performed with configuration interaction singles and adiabatic classical dynamics coupled to a state-following algorithm. 100 different configurations of He 7 were excited into the 2s and 2p manifold for a total of 2800 trajectories. While the most common outcome (90%) was complete fragmentation to 6 ground state atoms and 1 excited state atom, 3% of trajectories yielded bound, He 2 * , and <0.5% yielded an excited helium trimer. The nature of the dynamics, kinetic energy release, and connections to experiments are discussed

Theoretical studies of molecular interactions

Energy Technology Data Exchange (ETDEWEB)

Lester, W.A. Jr. [Univ. of California, Berkeley (United States)

1993-12-01

This research program is directed at extending fundamental knowledge of atoms and molecules including their electronic structure, mutual interaction, collision dynamics, and interaction with radiation. The approach combines the use of ab initio methods--Hartree-Fock (HF) multiconfiguration HF, configuration interaction, and the recently developed quantum Monte Carlo (MC)--to describe electronic structure, intermolecular interactions, and other properties, with various methods of characterizing inelastic and reaction collision processes, and photodissociation dynamics. Present activity is focused on the development and application of the QMC method, surface catalyzed reactions, and reorientation cross sections.

Ab initio intermolecular potential energy surface and thermophysical properties of nitrous oxide.

Science.gov (United States)

Crusius, Johann-Philipp; Hellmann, Robert; Hassel, Egon; Bich, Eckard

2015-06-28

We present an analytical intermolecular potential energy surface (PES) for two rigid nitrous oxide (N2O) molecules derived from high-level quantum-chemical ab initio calculations. Interaction energies for 2018 N2O-N2O configurations were computed utilizing the counterpoise-corrected supermolecular approach at the CCSD(T) level of theory using basis sets up to aug-cc-pVQZ supplemented with bond functions. A site-site potential function with seven sites per N2O molecule was fitted to the pair interaction energies. We validated our PES by computing the second virial coefficient as well as shear viscosity and thermal conductivity in the dilute-gas limit. The values of these properties are substantiated by the best experimental data.

Ab initio modeling of Al adsorption on CaF2 surfaces

International Nuclear Information System (INIS)

Barzilai, S.; Argaman, N.; Froumin, N.; Fuks, D.; Frage, N.

2008-01-01

Ab initio simulations of the adsorption of Al atoms on CaF 2 (0 0 1) and (1 1 1) surfaces have been performed for supercells with 7 different atomic configurations, using density functional theory. For (1 1 1) surfaces, a repulsive interaction was observed for most configurations, while a weak attraction was obtained when the Al atom was placed above F atoms. For the Ca-terminated (0 0 1) surface, the adsorption energy was about 5 times larger, whereas for the F-terminated (0 0 1) surface it was about 20 times greater. The comparative analysis indicates that the (0 0 1) surfaces are reactive and have a strong Al adatom bonding (chemisorption), especially for the F-terminated substrate. On the contrary, the (1 1 1) plane may be considered as non-reactive (physisorption), having a weak bonding of the Al adatom above the F site

Ab Initio Molecular Dynamics Simulations of Furfural at the Liquid-Solid Interface

OpenAIRE

Sanwu Wang; Hongli Dang; Wenhua Xue; Darwin Shields; Xin Liu; Friederike C. Jentoft; Daniel E. Resasco

2013-01-01

The bonding configuration and the heat of adsorption of a furfural molecule on the Pd(111) surface were determined by ab initio density-functional-theory calculations. The dynamics of pure liquid water, the liquid-solid interface formed by liquid water and the Pd(111) surface, as well as furfural at the water-Pd interface, were investigated by ab initio molecular dynamics simulations at finite temperatures. Calculations and simulations suggest that the bonding configurati...

An Activity-Centric Approach to Configuration Work in Distributed Interaction

DEFF Research Database (Denmark)

Houben, Steven

The widespread introduction of new types of computing devices, such as smartphones, tablet computers, large interactive displays or even wearable devices, has led to setups in which users are interacting with a rich ecology of devices. These new device ecologies have the potential to introduce...... and captures the problems and challenges of distributed interaction. Using both empirical data and related work, I argue that configuration work is composed of: curation work, task resumption lag, mobility work, physical handling and articulation work. Using configuration work as a problem description, I...

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

Science.gov (United States)

You, Y.; Yan, M. F.

2013-05-01

C and N atoms are the most frequent foreign interstitial atoms (FIAs), and often incorporated into the surface layers of steels to enhance their properties by thermochemical treatments. Al, Si, Ti, V, Cr, Mn, Co, Ni, Cu, Nb and Mo are the most common alloying elements in steels, also can be called foreign substitutional atoms (FSAs). The FIA and FSA interactions play an important role in the diffusion of C and N atoms, and the microstructures and mechanical properties of surface modified layers. Ab initio calculations based on the density functional theory are carried out to investigate FIA interactions with FSA in ferromagnetic bcc iron. The FIA-FSA interactions are analyzed systematically from five aspects, including interaction energies, density of states (DOS), bond populations, electron density difference maps and local magnetic moments.

An Interaction Measure for Control Configuration Selection for Multivariable Bilinear Systems

DEFF Research Database (Denmark)

Shaker, Hamid Reza; Stoustrup, Jakob

2013-01-01

are needed to be controlled, are nonlinear and linear models are insufficient to describe the behavior of the processes. The focus of this paper is on the problem of control configuration selection for a class of nonlinear systems which is known as bilinear systems. A gramian-based interaction measure...... for control configuration selection of MIMO bilinear processes is described. In general, most of the results on the control configuration selection, which have been proposed so far, can only support linear systems. The proposed gramian-based interaction measure not only supports bilinear processes but also...

Many-body perturbation theory for ab initio nuclear structure

International Nuclear Information System (INIS)

Tichai, Alexander

2017-01-01

The solution of the quantum many-body problem for medium-mass nuclei using realistic nuclear interactions poses a superbe challenge for nuclear structure research. Because an exact solution can only be provided for the lightest nuclei, one has to rely on approximate solutions when proceeding to heavier systems. Over the past years, tremendous progress has been made in the development and application of systematically improvable expansion methods and an accurate description of nuclear observables has become viable up to mass number A ∼ 100. While closed-shell systems are consistently described via a plethora of different many-body methods, the extension to genuine open-shell systems still remains a major challenge and up to now there is no ab initio many-body method which applies equally well to systems with even and odd mass numbers. The goal of this thesis is the development and implementation of innovative perturbative approaches with genuine open-shell capabilities. This requires the extension of well-known single-reference approaches to more general vacua. In this work we choose two complementary routes for the usage of generalized reference states. First, we derive a new ab initio approach based on multi-configurational reference states that are conveniently derived from a prior no-core shell model calculation. Perturbative corrections are derived via second-order many-body perturbation theory, thus, merging configuration interaction and many-body perturbation theory. The generality of this ansatz enables for a treatment of medium-mass systems with arbitrary mass number, as well as the extension to low-lying excited states such that ground and excited states are treated on an equal footing. In a complementary approach, we use reference states that break a symmetry of the underlying Hamiltonian. In the simplest case this corresponds to the expansion around a particle-number-broken Hartree-Fock-Bogolyubov vacuum which is obtained from a mean-field calculation

H3+: Ab initio calculation of the vibration spectrum

International Nuclear Information System (INIS)

Carney, G.D.; Porter, R.N.

1976-01-01

The vibration spectrum of H 3 + is calculated from the representation of a previously reported [J. Chem Phys. 60, 4251 (1974)] ab initio potential-energy surface in a fifth degree Simons--Parr--Finlan (SPF) expansion. Morse- and harmonic-oscillator basis functions are used to describe the motions of the three oscillators and the Harris--Engerholm--Gwinn quadrature technique is used to obtain matrix elements of the Hamiltonian in the basis of vibrational configurations. Our variational method is thus analogous to configuration--interaction calculations for electronic states. The ground state is found to have a zero-point energy of 4345 cm -1 and a vibrationally averaged geometry of R 1 =R 2 =0.91396 A, theta=60.0012degree, where theta is the angle between the two equivalent bonds. The transition frequencies for the E and A 1 fundamentals are nu-bar/sub E/=2516 cm -1 and nu-bar/sub A/=3185 cm -1 and those for the corresponding first overtones of the bending mode are 2nu-bar/sub E/=5004 +- 4 cm -1 and 2nu-bar/sub A/=4799 cm -1 . The first overtone of the breathing mode is 6264 cm -1 . The first-excited A 1 vibration state is metastable with a dipole--radiation lifetime of 3 sec. Transition frequencies, Einstein coefficients, and lifetimes are reported for a total of 21 transitions. Analysis of results for Dunham number and normal-coordinate expansions in comparison with those for SPF expansion show the latter to be superior for ab initio vibrational calculations. A scheme for possible direct measurement of the fundamental A 1 and E vibrational bands is suggested

Implementation of $ab$ $initio$ perturbed angular correlation observables for analysis of fluctuating quadrupole interactions

CERN Document Server

Barbosa, Marcelo

A review about the nuclear properties, namely the nuclear moments (magnetic dipole moment and electric quadrupole moment) and their interaction with electromagnetic fields external to the nucleus (hyperfine interactions), as well as the angular distribution of radiation produced by $\\gamma$-decay, is presented. A detailed description about the theory of Perturbed Angular Correlations was done, including the comparison between $\\gamma-\\gamma$- correlations and $e^{-}- \\gamma$ correlations. For dynamic nuclear interactions, an introduction to the theory of stochastic states in PAC was performed. We focused on ab-initio implementation of observables for analyzing fluctuating quadrupole hyperfine interactions on time dependent perturbed angular correlations experiments. The development of computacional codes solving the full problem, adapted to fit data obtained on single crystals or polycrystals for two-state transient fields with any axial symmetry and orientation was the main purpose of this work. The final pa...

Mutual influence between triel bond and cation-π interactions: an ab initio study

Science.gov (United States)

Esrafili, Mehdi D.; Mousavian, Parisasadat

2017-12-01

Using ab initio calculations, the cooperative and solvent effects on cation-π and B...N interactions are studied in some model ternary complexes, where these interactions coexist. The nature of the interactions and the mechanism of cooperativity are investigated by means of quantum theory of atoms in molecules (QTAIM), noncovalent interaction (NCI) index and natural bond orbital analysis. The results indicate that all cation-π and B...N binding distances in the ternary complexes are shorter than those of corresponding binary systems. The QTAIM analysis reveals that ternary complexes have higher electron density at their bond critical points relative to the corresponding binary complexes. In addition, according to the QTAIM analysis, the formation of cation-π interaction increases covalency of B...N bonds. The NCI analysis indicates that the cooperative effects in the ternary complexes make a shift in the location of the spike associated with each interaction, which can be regarded as an evidence for the reinforcement of both cation-π and B...N interactions in these systems. Solvent effects on the cooperativity of cation-π and B...N interactions are also investigated.

Molecular equilibrium structures from experimental rotational constants and calculated vibration-rotation interaction constants

DEFF Research Database (Denmark)

Pawlowski, F; Jorgensen, P; Olsen, Jeppe

2002-01-01

A detailed study is carried out of the accuracy of molecular equilibrium geometries obtained from least-squares fits involving experimental rotational constants B(0) and sums of ab initio vibration-rotation interaction constants alpha(r)(B). The vibration-rotation interaction constants have been...... calculated for 18 single-configuration dominated molecules containing hydrogen and first-row atoms at various standard levels of ab initio theory. Comparisons with the experimental data and tests for the internal consistency of the calculations show that the equilibrium structures generated using Hartree......-Fock vibration-rotation interaction constants have an accuracy similar to that obtained by a direct minimization of the CCSD(T) energy. The most accurate vibration-rotation interaction constants are those calculated at the CCSD(T)/cc-pVQZ level. The equilibrium bond distances determined from these interaction...

Ab initio calculation of diffusion barriers for Cu adatom hopping on Cu(1 0 0) surface and evolution of atomic configurations

Science.gov (United States)

Zhang, Wei; Gan, Jie; Li, Qian; Gao, Kun; Sun, Jian; Xu, Ning; Ying, Zhifeng; Wu, Jiada

2011-06-01

The self-diffusion dynamics of Cu adatoms on Cu(1 0 0) surface has been studied based on the calculation of the energy barriers for various hopping events using lattice-gas based approach and a modified model. To simplify the description of the interactions and the calculation of the energy barrier, a three-tier hierarchy of description of atomic configurations was conceived in which the active adatom and its nearest atoms were chosen to constitute basic configuration and taken as a whole to study many-body interactions of the atoms in various atomic configurations, whereas the impacts of the next nearest atoms on the diffusion of the active adatom were considered as multi-site interactions. Besides the simple hopping of single adatoms, the movements of dimers and trimers as the results of multiple hopping events have also been examined. Taking into account the hopping events of all adatoms, the stability of atomic configurations has been examined and the evolution of atomic configurations has also been analyzed.

Ab initio calculation of diffusion barriers for Cu adatom hopping on Cu(1 0 0) surface and evolution of atomic configurations

International Nuclear Information System (INIS)

Zhang Wei; Gan Jie; Li Qian; Gao Kun; Sun Jian; Xu Ning; Ying Zhifeng; Wu Jiada

2011-01-01

The self-diffusion dynamics of Cu adatoms on Cu(1 0 0) surface has been studied based on the calculation of the energy barriers for various hopping events using lattice-gas based approach and a modified model. To simplify the description of the interactions and the calculation of the energy barrier, a three-tier hierarchy of description of atomic configurations was conceived in which the active adatom and its nearest atoms were chosen to constitute basic configuration and taken as a whole to study many-body interactions of the atoms in various atomic configurations, whereas the impacts of the next nearest atoms on the diffusion of the active adatom were considered as multi-site interactions. Besides the simple hopping of single adatoms, the movements of dimers and trimers as the results of multiple hopping events have also been examined. Taking into account the hopping events of all adatoms, the stability of atomic configurations has been examined and the evolution of atomic configurations has also been analyzed.

All Electron ab initio Investigations of the Three Lowest Lying Electronic States of the RuC Molecule

DEFF Research Database (Denmark)

Shim, Irene; Gingerich, K. A.

2000-01-01

The three lowest-lying electronic states of RuC, (1)Sigma(+), (3)Delta, and (1)Delta, have been investigated by performing all-electron ab initio multi-configuration self-consistent-field (CASSCF) and multi-reference configuration interaction (MRCI) calculations including relativistic corrections....... The electronic ground state is derived as (1)Sigma(+) with the spectroscopic constants r(e) = 1.616 Angstrom and omega(e) = 1085 cm(-1). The lowest-lying excited state, (3)Delta, has r(e) = 1.632 Angstrom, omega(e) = 1063 cm(-1), and T-e = 912 cm(-1). These results are consistent with recent spectroscopic values....... The chemical bonds in all three lowest-lying states are triple bonds composed of one sigma and two pi bonds. (C) 2000 Elsevier Science B.V. All rights reserved....

Ab initio study of vibronic transitions between x2π and 12Σ+ electronic states of HCP+ ion

Directory of Open Access Journals (Sweden)

Stojanović Ljiljana

2013-01-01

Full Text Available The ground and low-lying excited doublet electronic states of the HCP+ ion were studied by means of multireference configuration interaction method. Vibronic energy levels of the X2Π state of Σ, Π, Δ, and Φ symmetry, up to the 2500 cm-1, have been calculated variationally, employing previously developed ab initio methods which take into account vibronic and spin-orbit interactions. Obtained vibronic wave functions were used to estimate transition moments between vibronic energy levels of the X2Π and 12Σ+ electronic states. Results were compared to available experimental and theoretical data. [Projekat Ministarstva nauke Republike Srbije, br. 172040

Interaction of single-walled carbon nanotubes and saxitoxin: Ab initio simulations and biological responses in hippocampal cell line HT-22.

Science.gov (United States)

Ramos, Patrícia; Schmitz, Marcos; Filgueira, Daza; Votto, Ana Paula; Durruthy, Michael; Gelesky, Marcos; Ruas, Caroline; Yunes, João; Tonel, Mariana; Fagan, Solange; Monserrat, José

2017-07-01

Saxitoxins (STXs) are potent neurotoxins that also induce cytotoxicity through the generation of reactive oxygen species. Carbon nanotubes (CNTs) are nanomaterials that can promote a Trojan horse effect, facilitating the entry of toxic molecules to cells when adsorbed to nanomaterials. The interaction of pristine single-walled (SW)CNTs and carboxylated (SWCNT-COOH) nanotubes with STX was evaluated by ab initio simulation and bioassays using the cell line HT-22. Cells (5 × 10 4  cells/mL) were exposed to SWCNT and SWCNT-COOH (5 μg mL -1 ), STX (200 μg L -1 ), SWCNT+STX, and SWCNT-COOH+STX for 30 min or 24 h. Results of ab initio simulation showed that the interaction between SWCNT and SWCNT-COOH with STX occurs in a physisorption. The interaction of SWCNT+STX induced a decrease in cell viability. Cell proliferation was not affected in any treatment after 30 min or 24 h of exposure (p > 0.05). Treatment with SWCNT-COOH induced high reactive oxygen species levels, an effect attenuated in SWCNT-COOH+STX treatment. In terms of cellular oxygen consumption, both CNTs when coexposed with STX antagonize the toxin effect. Based on these results, it can be concluded that the results obtained in vitro corroborate the semiempirical evidence found using density functional theory ab initio simulation. Environ Toxicol Chem 2017;36:1728-1737. © 2016 SETAC. © 2016 SETAC.

Control configuration selection for bilinear systems via generalised Hankel interaction index array

DEFF Research Database (Denmark)

Shaker, Hamid Reza; Tahavori, Maryamsadat

2015-01-01

configuration selection. It is well known that a suitable control configuration selection is an important prerequisite for a successful industrial control. In this paper the problem of control configuration selection for multiple-input and multiple-output (MIMO) bilinear processes is addressed. First...... way, an iterative method for solving the generalised Sylvester equation is proposed. The generalised cross-gramian is used to form the generalised Hankel interaction index array. The generalised Hankel interaction index array is used for control configuration selection of MIMO bilinear processes. Most......Decentralised and partially decentralised control strategies are very popular in practice. To come up with a suitable decentralised or partially decentralised control structure, it is important to select the appropriate input and output pairs for control design. This procedure is called control...

Configuration interaction in LTE spectra of heavy elements

International Nuclear Information System (INIS)

Bar-Shalom, A.; Oreg, J.; Goldstein, W.

1992-11-01

We present a method for including the effects of configuration interaction (CI) between relativistic subconfigurations of an electron configuration in the calculation of emission and absorption spectra of plasmas in local thermodynamic equilibrium (LTE). Analytical expressions for the correction to the intensities, owing to Cl, of an unresolved transition array (UTA) and of a supertransition array (STA) are obtained when the correction is small compared to the spin-orbit splitting, bypassing the need to diagonalize energy matrices. These expressions serve as working formulas in the STA model and, in addition, reveal a priori the conditions under which CI effects are significant. Examples of the effect are presented

Using full configuration interaction quantum Monte Carlo in a seniority zero space to investigate the correlation energy equivalence of pair coupled cluster doubles and doubly occupied configuration interaction

International Nuclear Information System (INIS)

Shepherd, James J.; Henderson, Thomas M.; Scuseria, Gustavo E.

2016-01-01

Over the past few years, pair coupled cluster doubles (pCCD) has shown promise for the description of strong correlation. This promise is related to its apparent ability to match results from doubly occupied configuration interaction (DOCI), even though the latter method has exponential computational cost. Here, by modifying the full configuration interaction quantum Monte Carlo algorithm to sample only the seniority zero sector of Hilbert space, we show that the DOCI and pCCD energies are in agreement for a variety of 2D Hubbard models, including for systems well out of reach for conventional configuration interaction algorithms. Our calculations are aided by the sign problem being much reduced in the seniority zero space compared with the full space. We present evidence for this and then discuss the sign problem in terms of the wave function of the system which appears to have a simplified sign structure.

Ab initio study of He-He interactions in homogeneous electron gas

Energy Technology Data Exchange (ETDEWEB)

Wang, Jinlong; Niu, Liang-Liang; Zhang, Ying, E-mail: zhyi@buaa.edu.cn

2017-02-15

Highlights: • Helium atoms interact via the He induced Friedel oscillations of electron densities. • He-He global binding energy minimum of ∼−0.09 eV is reached at an optimal electron density of 0.04 e/Å{sup 3}, corresponding to an optimal He-He separation of ∼1.7 Å. • The present results can qualitatively interpret the well-known He self-trapping behavior in metals. - Abstract: We have investigated the immersion energy of a single He and the He-He interactions in homogeneous electron gas using ab initio calculations. It is found that He dislikes electrons and He-He interact via the He induced Friedel oscillations of electron densities. A critical electron density at which the global binding energy extremum shifts from the first minimum to the second one is identified. We also discover that the He-He global binding energy minimum of ∼−0.09 eV is reached at an optimal electron density of 0.04 e/Å{sup 3}, corresponding to an optimal He-He separation of ∼1.7 Å. Further, the He atoms are found to gain a trivial amount of 2s and 2p states from the free electrons, inducing a hybridization between the He s- and p-states. The present results can qualitatively interpret the well-known He self-trapping behavior in metals.

All-electron ab initio investigations of the electronic states of the NiC molecule

DEFF Research Database (Denmark)

Shim, Irene; Gingerich, Karl. A.

1999-01-01

The low-lying electronic states of NiC are investigated by all-electron ab initio multi-configuration self-consistent-field (CASSCF) calculations including relativistic corrections. The electronic structure of NiC is interpreted as perturbed antiferromagnetic couplings of the localized angular...

Ab initio study of the adducts of carbon monoxide with alkaline cations

Science.gov (United States)

Ferrari, A. M.; Ugliengo, P.; Garrone, E.

1996-09-01

The interaction between CO (either via the C or the O end) and the alkaline cations (Li+, Na+, K+, Rb+, and Cs+) has been studied by means of six ab initio methods, featuring the classical Hartree-Fock, the second order Møller-Plesset treatment of electron correlation, one local density functional and two gradient-corrected methods as well as a quadratic configuration interaction inclusive of single and double substitutions with a noniterative triples contribution to the energy. Basis sets adopted for CO, Li+, Na+, and K+ and the corresponding adducts are of triple-ζ valence quality augmented with a double set of polarization functions (d on C and O; p on the cations). For Rb+ and Cs+, Hay-Wadt effective core potential basis sets have been adopted. Calculated features are the binding energy, the frequency and intensity of the CO stretch, the bending mode, the cation-carbon (or oxygen) stretch, and the equilibrium geometry. Gradient-corrected density functional methods yield results nearly as good as the most expensive correlated method based on configurations interaction. A number of correlations are established among the observables. The role of electrostatics in the interaction is analyzed both by studying the molecular electrostatic potential of CO and by replacing the cation with a proton in the same position. Binding through the C end is invariably preferred, though, with increasing size of the cation, binding through the O end become progressively less unfavored. Experimental data concerning alkaline-cation substituted zeolites are compared with computational results, and an overall agreement is observed.

Virtual synthesis of crystals using ab initio MD: Case study on LiFePO4

Science.gov (United States)

Mishra, S. B.; Nanda, B. R. K.

2017-05-01

Molecular dynamics simulation technique is fairly successful in studying the structural aspects and dynamics of fluids. Here we study the ability of ab initio molecular dynamics (ab initio MD) to carry out virtual experiments to synthesize new crystalline materials and to predict their structures. For this purpose the olivine phosphate LiFePO4 (LFPO) is used as an example. As transition metal oxides in general are stabilized with layered geometry, we carried out ab initio MD simulations over a hypothetical layered configuration consisting of alternate LiPO2 and FeO2 layers. With intermittent steps of electron minimization, the resulted equilibrium lattice consist of PO4 tetrahedra and distorted Fe-O complexes similar to the one observed in the experimental lattice.

X-ray absorption near-edge structure in alpha-quartz and stishovite: Ab initio calculation with core - hole interaction

International Nuclear Information System (INIS)

Mo, Shang-Di; Ching, W. Y.

2001-01-01

Ab initio calculation of the XANSE/ELNES spectra for α quartz and stishovite were carried out using a large-supercell approach that includes the electron - core - hole interaction. Excellent agreements with experimental spectra were obtained for Si - K, Si - L 2,3 , and O - K edges. The usual interpretation using orbital-resolved local density of states in the conduction band is unsatisfactory. [copyright] 2001 American Institute of Physics

All Electron ab initio Investigations of the Electronic States of the MoN Molecule

DEFF Research Database (Denmark)

Shim, Irene; Gingerich, Karl A.

1999-01-01

The low lying electronic states of the molecule MoN have been investigated by performing all electron ab initio multi-configuration self-consistent-field (CASSCF) calculations. The relativistic corrections for the one electron Darwin contact term and the relativistic mass-velocity correction have...

High-precision, systematic study of hyperfine structure in the 4f/sup N/6s2 configuration of the neutral rare earths

International Nuclear Information System (INIS)

Childs, W.J.; Goodman, L.S.; Pfeufer, V.

1983-01-01

Although the hyperfine structure (hfs) of many-electron atoms has been studied intensively in recent years, it is still difficult to distinguish between the competing effects of relativity and configuration interaction. The 4f/sup N/6s 2 configuration of the neutral rare earths is of particular interest because (a) the low-lying terms are relatively free of configuration interaction, and (b) trends can be examined systematically as one proceeds through the long 4f-shell. The procedure is to deduce, from the measured hfs constants of low levels, the underlying hyperfine radial integrals for comparison with ab initio predictions. Since some of these integrals are extremely sensitive to any configuration interaction and others are not, it is possible to determine both the extent and type of configuration interaction present in some cases. Prior to the start of the present research no precise hfs information existed for the entire second half of the 4f shell of the rare earths. The present measurements were designed both to provide such data and to make possible a systematic study of the hfs throughout the 4f shell. The atomic-beam, laser-rf, double-resonance method was used for the measurements. With this technique, the occurrence of a radiofrequency transition between atomic hfs levels is detected by noting an increase in the laser-induced fluorescence

Electronic structure and bonding in the RhC molecule by all-electron ab initio HF–Cl calculations and mass spectrometric measurements

DEFF Research Database (Denmark)

Shim, Irene; Gingerich, K. A.

1984-01-01

In the present study we present all-electron ab initio Hartree–Fock (HF) and configuration interaction (CI) calculations of the 2Sigma+ ground state as well as of 16 excited states of the RhC molecule. The calculated spectroscopic constants of the lowest lying states are in good agreement...... with the experimental data. The chemical bond in the electronic ground state is mainly due to interaction of the 4d orbitals of Rh with the 2s and 2p orbitals of C. The bond is a triple bond composed of two pi bonds and one sigma bond. The 5s electron of Rh hardly participates in the bond formation. It is located...

Ab initio modeling of plasticity in HCP metals: pure zirconium and titanium and effect of oxygen

International Nuclear Information System (INIS)

Chaari, Nermine

2015-01-01

We performed atomistic simulations to determine screw dislocations properties in pure zirconium and titanium and to explain the hardening effect attributed to oxygen alloying in both hexagonal close-packed transition metals. We used two energetic models: ab initio calculations based on the density functional theory and calculations with an empirical potential. The complete energetic profile of the screw dislocation when gliding in the different slip planes is obtained in pure Zr. Our calculations reveal the existence of a metastable configuration of the screw dislocation partially spread in the first order pyramidal plane. This configuration is responsible for the cross slip of screw dislocations from prismatic planes, the easiest glide planes, to pyramidal or basal planes. This energy profile is affected by oxygen addition. Ab initio calculations reveal two main effects: oxygen enhances pyramidal cross slip by modifying the dislocation core structure, and pins the dislocation in its metastable sessile configuration. The same modeling approach is applied to titanium. In pure Ti, the same configurations of the screw dislocation in Zr are obtained, but with different energy levels. This leads to a different gliding mechanism. The same way as in Zr, oxygen enhances pyramidal glide in Ti by modifying the dislocation core structure. Besides, oxygen atom lowers the energy of the metastable configuration but not enough to pin the dislocation in this sessile configuration. (author) [fr

Hydrogen interaction with ferrite/cementite interface: ab initio calculations and thermodynamics

Science.gov (United States)

Mirzoev, A. A.; Verkhovykh, A. V.; Okishev, K. Yu.; Mirzaev, D. A.

2018-02-01

The paper presents the results of ab initio modelling of the interaction of hydrogen atoms with ferrite/cementite interfaces in steels and thermodynamic assessment of the ability of interfaces to trap hydrogen atoms. Modelling was performed using the density functional theory with generalised gradient approximation (GGA'96), as implemented in WIEN2k package. An Isaichev-type orientation relationship between the two phases was accepted, with a habit plane (101)c ∥ (112)α. The supercell contained 64 atoms (56 Fe and 8 C). The calculated formation energies of ferrite/cementite interface were 0.594 J/m2. The calculated trapping energy at cementite interstitial was 0.18 eV, and at the ferrite/cementite interface - 0.30 eV. Considering calculated zero-point energy, the trapping energies at cementite interstitial and ferrite/cementite interface become 0.26 eV and 0.39 eV, respectively. The values are close to other researchers' data. These results were used to construct a thermodynamic description of ferrite/cementite interface-hydrogen interaction. Absorption calculations using the obtained trapping energy values showed that even thin lamellar ferrite/cementite mixture with an interlamellar spacing smaller than 0.1 μm has noticeable hydrogen trapping ability at a temperature below 400 K.

Configuration mixing in the sdg interacting boson model

International Nuclear Information System (INIS)

Bouldjedri, A; Van Isacker, P; Zerguine, S

2005-01-01

A wavefunction analysis of the strong-coupling limits of the sdg interacting boson model is presented. The analysis is carried out for two-boson states and allows us to characterize the boson configuration mixing in the different limits. Based on these results and those of a shell-model analysis of the sdg IBM, qualitative conclusions are drawn about the range of applicability of each limit

Configuration mixing in the sdg interacting boson model

Energy Technology Data Exchange (ETDEWEB)

Bouldjedri, A [Department of Physics, Faculty of Science, University of Batna, Avenue Boukhelouf M El Hadi, 05000 Batna (Algeria); Van Isacker, P [GANIL, BP 55027, F-14076 Caen cedex 5 (France); Zerguine, S [Department of Physics, Faculty of Science, University of Batna, Avenue Boukhelouf M El Hadi, 05000 Batna (Algeria)

2005-11-01

A wavefunction analysis of the strong-coupling limits of the sdg interacting boson model is presented. The analysis is carried out for two-boson states and allows us to characterize the boson configuration mixing in the different limits. Based on these results and those of a shell-model analysis of the sdg IBM, qualitative conclusions are drawn about the range of applicability of each limit.

Convergence of configuration-interaction single-center calculations of positron-atom interactions

International Nuclear Information System (INIS)

Mitroy, J.; Bromley, M. W. J.

2006-01-01

The configuration interaction (CI) method using orbitals centered on the nucleus has recently been applied to calculate the interactions of positrons interacting with atoms. Computational investigations of the convergence properties of binding energy, phase shift, and annihilation rate with respect to the maximum angular momentum of the orbital basis for the e + Cu and PsH bound states, and the e + -H scattering system were completed. The annihilation rates converge very slowly with angular momentum, and moreover the convergence with radial basis dimension appears to be slower for high angular momentum. A number of methods of completing the partial wave sum are compared; an approach based on a ΔX J =a(J+(1/2)) -n +b(J+(1/2)) -(n+1) form [with n=4 for phase shift (or energy) and n=2 for the annihilation rate] seems to be preferred on considerations of utility and underlying physical justification

Spectroscopic study of uracil, 1-methyluracil and 1-methyl-4-thiouracil: Hydrogen bond interactions in crystals and ab-initio molecular dynamics

Science.gov (United States)

Brela, Mateusz Z.; Boczar, Marek; Malec, Leszek M.; Wójcik, Marek J.; Nakajima, Takahito

2018-05-01

Hydrogen bond networks in uracil, 1-methyluracil and 1-methyl-4-thiouracil were studied by ab initio molecular dynamics as well as analysis of the orbital interactions. The power spectra calculated by ab initio molecular dynamics for atoms involved in hydrogen bonds were analyzed. We calculated spectra by using anharmonic approximation based on the autocorrelation function of the atom positions obtained from the Born-Oppenheimer simulations. Our results show the differences between hydrogen bond networks in uracil and its methylated derivatives. The studied methylated derivatives, 1-methyluracil as well as 1-methyl-4-thiouracil, form dimeric structures in the crystal phase, while uracil does not form that kind of structures. The presence of sulfur atom instead oxygen atom reflects weakness of the hydrogen bonds that build dimers.

Dominant Modes in Light Nuclei - Ab Initio View of Emergent Symmetries

International Nuclear Information System (INIS)

Draayer, J P; Dytrych, T; Launey, K D; Dreyfuss, A C; Langr, D

2015-01-01

An innovative symmetry-guided concept is discussed with a focus on emergent symmetry patterns in complex nuclei. In particular, the ab initio symmetry-adapted no-core shell model (SA-NCSM), which capitalizes on exact as well as partial symmetries that underpin the structure of nuclei, provides remarkable insight into how simple symmetry patterns emerge in the many-body nuclear dynamics from first principles. This ab initio view is complemented by a fully microscopic no-core symplectic shell-model framework (NCSpM), which, in turn, informs key features of the primary physics responsible for the emergent phenomena of large deformation and alpha-cluster substructures in studies of the challenging Hoyle state in Carbon-12 and enhanced collectivity in intermediate-mass nuclei. Furthermore, by recognizing that deformed configurations often dominate the low-energy regime, the SA-NCSM provides a strategy for determining the nature of bound states of nuclei in terms of a relatively small subspace of the symmetry-reorganized complete model space, which opens new domains of nuclei for ab initio investigations, namely, the intermediate-mass region, including isotopes of Ne, Mg, and Si

Semiempirical study of the interacting potentials for H+ + CO and H+ + NO+

International Nuclear Information System (INIS)

Canuto, S.

1983-01-01

Semiempirical INDO molecular orbital calculations of the minimum energy path for the formation of HCO + , HOC + , HNO ++ and HON ++ from the proton reactions H + + CO and H + + NO + are presented. Energy barriers, geometry relaxations and stabilization energies are given. Comparisons with ab initio SCF (Self-Consistent Field) and CI (Configuration Interaction) calculations are performed in order to assess the reliability of the calculations. (Author) [pt

Ab Initio Calculations Of Light-Ion Reactions

International Nuclear Information System (INIS)

Navratil, P.; Quaglioni, S.; Roth, R.; Horiuchi, W.

2012-01-01

The exact treatment of nuclei starting from the constituent nucleons and the fundamental interactions among them has been a long-standing goal in nuclear physics. In addition to the complex nature of nuclear forces, one faces the quantum-mechanical many-nucleon problem governed by an interplay between bound and continuum states. In recent years, significant progress has been made in ab initio nuclear structure and reaction calculations based on input from QCD employing Hamiltonians constructed within chiral effective field theory. In this contribution, we present one of such promising techniques capable of describing simultaneously both bound and scattering states in light nuclei. By combining the resonating-group method (RGM) with the ab initio no-core shell model (NCSM), we complement a microscopic cluster approach with the use of realistic interactions and a microscopic and consistent description of the clusters. We discuss applications to light nuclei scattering, radiative capture and fusion reactions.

Theoretical level energies and transition data for 4p64d4, 4p64d34f and 4p54d5 configurations of W34+ ion

Science.gov (United States)

Karpuškienė, R.; Bogdanovich, P.; Kisielius, R.

2017-05-01

The ab initio quasirelativistic approach developed specifically for the calculation of spectral parameters of highly charged ions was used to derive transition data for the tungsten ion W34+. The configuration interaction method was applied to include electron correlation effects. The relativistic effects were taken into account in the Breit-Pauli approximation. The level energies, radiative lifetimes τ, Landé g-factors are determined for the ground configuration 4p64d4 and two excited configurations 4p64d34f and 4p54d5. The radiative transition wavelengths λ and emission transition probabilities A for the electric dipole, electric quadrupole, electric octupole, magnetic dipole, and magnetic quadrupole transitions among the levels of these configurations are produced.

Ab initio and Gordon--Kim intermolecular potentials for two nitrogen molecules

International Nuclear Information System (INIS)

Ree, F.H.; Winter, N.W.

1980-01-01

Both ab initio MO--LCAO--SCF and the electron-gas (or Gordon--Kim) methods have been used to compute the intermolecular potential (Phi) of N 2 molecules for seven different N 2 --N 2 orientations. The ab initio calculations were carried out using a [4s3p] contracted Gaussian basis set with and without 3d polarization functions. The larger basis set provides adequate results for Phi>0.002 hartree or intermolecular separations less than 6.5--7 bohr. We use a convenient analytic expression to represent the ab initio data in terms of the intermolecular distance and three angles defining the orientations of the two N 2 molecules. The Gordon--Kim method with Rae's self-exchange correction yields Phi, which agrees reasonably well over a large repulsive range. However, a detailed comparison of the electron kinetic energy contributions shows a large difference between the ab initio and the Gordon--Kim calculations. Using the ab initio data we derive an atom--atom potential of the two N 2 molecules. Although this expression does not accurately fit the data at some orientations, its spherical average agrees with the corresponding average of the ab initio Phi remarkably well. The spherically averaged ab initio Phi is also compared with the corresponding quantities derived from experimental considerations. The approach of the ab initio Phi to the classical quadrupole--quadrupole interaction at large intermolecular separation is also discussed

Quasirelativistic calculation of 4s24p5, 4s24p44d and 4s4p6 configuration spectroscopic parameters for the W39+ ion

International Nuclear Information System (INIS)

Bogdanovich, P; Karpuškienė, R; Kisielius, R

2015-01-01

The ab initio quasirelativistic Hartree–Fock method developed specifically for the calculation of spectral parameters of heavy atoms and highly charged ions is used to derive spectral data for the 4s 2 4p 5 , 4s 2 4p 4 4d and 4s4p 6 configurations of the multicharged tungsten ion W 39+ . The relativistic effects are taken into account in the Breit–Pauli approximation for the quasirelativistic Hartree–Fock radial orbitals. The configuration interaction method is applied to include the electron correlation effects. Produced data are compared with existing experimental measurements and theoretical calculations. (paper)

A hybrid configuration interaction treatment based on seniority number and excitation schemes

International Nuclear Information System (INIS)

Alcoba, Diego R.; Capuzzi, Pablo; Torre, Alicia; Lain, Luis; Oña, Ofelia B.; Van Raemdonck, Mario; Bultinck, Patrick; Van Neck, Dimitri

2014-01-01

We present a configuration interaction method in which the Hamiltonian of an N-electron system is projected on Slater determinants selected according to the seniority-number criterion along with the traditional excitation-based procedure. This proposed method is especially useful to describe systems which exhibit dynamic (weak) correlation at determined geometric arrangements (where the excitation-based procedure is more suitable) but show static (strong) correlation at other arrangements (where the seniority-number technique is preferred). The hybrid method amends the shortcomings of both individual determinant selection procedures, yielding correct shapes of potential energy curves with results closer to those provided by the full configuration interaction method

A hybrid configuration interaction treatment based on seniority number and excitation schemes

Energy Technology Data Exchange (ETDEWEB)

Alcoba, Diego R.; Capuzzi, Pablo [Departamento de Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires and Instituto de Física de Buenos Aires, Consejo Nacional de Investigaciones Científicas y Técnicas, Ciudad Universitaria, 1428 Buenos Aires (Argentina); Torre, Alicia; Lain, Luis, E-mail: qfplapel@lg.ehu.es [Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco, Apdo. 644 E-48080 Bilbao (Spain); Oña, Ofelia B. [Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas, Universidad Nacional de La Plata, CCT La Plata, Consejo Nacional de Investigaciones Científicas y Técnicas, Diag. 113 y 64 (S/N), Sucursal 4, CC 16, 1900 La Plata (Argentina); Van Raemdonck, Mario; Bultinck, Patrick [Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281 (S3), 9000 Gent (Belgium); Van Neck, Dimitri [Center for Molecular Modelling, Ghent University, Technologiepark 903, 9052 Zwijnaarde (Belgium)

2014-12-28

We present a configuration interaction method in which the Hamiltonian of an N-electron system is projected on Slater determinants selected according to the seniority-number criterion along with the traditional excitation-based procedure. This proposed method is especially useful to describe systems which exhibit dynamic (weak) correlation at determined geometric arrangements (where the excitation-based procedure is more suitable) but show static (strong) correlation at other arrangements (where the seniority-number technique is preferred). The hybrid method amends the shortcomings of both individual determinant selection procedures, yielding correct shapes of potential energy curves with results closer to those provided by the full configuration interaction method.

Higher-order resonant electronic recombination as a manifestation of configuration interaction

International Nuclear Information System (INIS)

Beilmann, C; Amaro, P; Tashenov, S; Bekker, H; Harman, Z; Crespo López-Urrutia, J R

2013-01-01

Theoretical and experimental investigations of higher-order electron–ion recombination resonances including inter-shell excitations are presented for L-shell ions of Kr with the aim of examining details of atomic structure calculations. The particular importance of electron–electron interaction and configuration mixing effects for these recombination processes enables their use for detailed tests of electron correlation effects. A test of the required level of considered mixing configurations is presented and further experiments involving higher-order recombination channels are motivated. (paper)

Configurational energies and effective cluster interactions in substitutionally disordered binary alloys

International Nuclear Information System (INIS)

Gonis, A.; Zhang, X.h.; Freeman, A.J.; Turchi, P.; Stocks, G.M.; Nicholson, D.M.

1987-01-01

The determination of configurational energies in terms of effective cluster interactions in substitutionally disordered alloys from a knowledge of the alloy electronic structure is examined within the methods of concentration waves (CW) and the generalized perturbation method (GPM), and for the first time within the embedded-cluster method (ECM). It is shown that the ECM provides the exact summation to all orders of the effective cluster interaction expansions obtained in the partially renormalized GPM. The connection between the various methods (CW, GPM, and ECM) is discussed and illustrated by means of numerical calculations for model one-dimensional tight-binding (TB) systems and for TB Hamiltonians chosen to describe Pd-V alloys. These calculations, and the formal considerations presented in the body of the paper, show the complete equivalence of converged GPM summations within specific clusters and the ECM. In addition, it is shown that an exact expansion of the configurational energy can be obtained in terms of fully renormalized effective cluster interactions. In principle, these effective cluster interactions can be used in conjunction with statistical models to determine stable ordered structures at low temperatures and alloy phase diagrams

Intermolecular interactions of trifluorohalomethanes with Lewis bases in the gas phase: an ab initio study.

Science.gov (United States)

Wang, Yi-Siang; Yin, Chih-Chien; Chao, Sheng D

2014-10-07

We perform an ab initio computational study of molecular complexes with the general formula CF3X-B that involve one trifluorohalomethane CF3X (X = Cl or Br) and one of a series of Lewis bases B in the gas phase. The Lewis bases are so chosen that they provide a range of electron-donating abilities for comparison. Based on the characteristics of their electron pairs, we consider the Lewis bases with a single n-pair (NH3 and PH3), two n-pairs (H2O and H2S), two n-pairs with an unsaturated bond (H2CO and H2CS), and a single π-pair (C2H4) and two π-pairs (C2H2). The aim is to systematically investigate the influence of the electron pair characteristics and the central atom substitution effects on the geometries and energetics of the formed complexes. The counterpoise-corrected supermolecule MP2 and coupled-cluster single double with perturbative triple [CCSD(T)] levels of theory have been employed, together with a series of basis sets up to aug-cc-pVTZ. The angular and radial configurations, the binding energies, and the electrostatic potentials of the stable complexes have been compared and discussed as the Lewis base varies. For those complexes where halogen bonding plays a significant role, the calculated geometries and energetics are consistent with the σ-hole model. Upon formation of stable complexes, the C-X bond lengths shorten, while the C-X vibrational frequencies increase, thus rendering blueshifting halogen bonds. The central atom substitution usually enlarges the intermolecular bond distances while it reduces the net charge transfers, thus weakening the bond strengths. The analysis based on the σ-hole model is grossly reliable but requires suitable modifications incorporating the central atom substitution effects, in particular, when interaction components other than electrostatic contributions are involved.

Ab Initio Predictions of Structures and Densities of Energetic Solids

National Research Council Canada - National Science Library

Rice, Betsy M; Sorescu, Dan C

2004-01-01

We have applied a powerful simulation methodology known as ab initio crystal prediction to assess the ability of a generalized model of CHNO intermolecular interactions to predict accurately crystal...

Ab Initio Symmetry-Adapted No-Core Shell Model

International Nuclear Information System (INIS)

Draayer, J P; Dytrych, T; Launey, K D

2011-01-01

A multi-shell extension of the Elliott SU(3) model, the SU(3) symmetry-adapted version of the no-core shell model (SA-NCSM), is described. The significance of this SA-NCSM emerges from the physical relevance of its SU(3)-coupled basis, which – while it naturally manages center-of-mass spuriosity – provides a microscopic description of nuclei in terms of mixed shape configurations. Since typically configurations of maximum spatial deformation dominate, only a small part of the model space suffices to reproduce the low-energy nuclear dynamics and hence, offers an effective symmetry-guided framework for winnowing of model space. This is based on our recent findings of low-spin and high-deformation dominance in realistic NCSM results and, in turn, holds promise to significantly enhance the reach of ab initio shell models.

Phase diagrams from ab-initio calculations: Re-W and Fe-B

Energy Technology Data Exchange (ETDEWEB)

Hammerschmidt, Thomas; Bialon, Arthur; Palumbo, Mauro; Fries, Suzana G.; Drautz, Ralf [ICAMS, Ruhr-Universitaet Bochum (Germany)

2011-07-01

The CALPHAD (CaLculation of Phase Diagrams) method relies on Gibbs energy databases and is of limited predictive power in cases where only limited experimental data is available for constructing the Gibbs energy databases. This is problematic for, e.g., the calculation of the phase transformation kinetics within phase field simulations that not only require the thermodynamic equilibrium data but also information on metastable phases. Such information is difficult to obtain directly from experiment but ab-initio calculations may supplement experimental databases as they comprise metastable phases and arbitrary chemical compositions. We present simulations for two prototypical systems: Re-W and Fe-B. For both systems we calculate the heat of formation for an extensive set of structures using ab-initio calculations and employ the total energies in CALPHAD in order to determine the corresponding phase diagrams. We account for the configurational entropy within the Bragg-Williams approximation and neglect the phenomenological excess-term that is commonly used in CALPHAD as well as the contribution of phonons and electronic excitations to the free energy. According to our calculations the complex intermetallic phases in Re-W are stabilized by the configurational entropy. For Fe-B, we calculate metastable and stable phase diagrams including recently predicted new stable phases.

Energy level properties of 4p64d3, 4p64d24f, and 4p54d4 configurations of the W35+ ion

International Nuclear Information System (INIS)

Bogdanovich, P.; Kisielius, R.

2014-01-01

The ab initio quasirelativistic Hartree–Fock method developed specifically for the calculation of spectroscopic parameters of heavy atoms and highly charged ions was used to derive spectral data for the multicharged tungsten ion W 35+ . The configuration interaction method was applied to include the electron-correlation effects. The relativistic effects were taken into account in the Breit–Pauli approximation for quasirelativistic Hartree–Fock radial orbitals. The energy level spectra, radiative lifetimes τ, and Lande g-factors have been calculated for the 4p 6 4d 3 , 4p 6 4d 2 4f, and 4p 5 4d 4 configurations of the W 35+ ion

Multiple time step integrators in ab initio molecular dynamics

International Nuclear Information System (INIS)

Luehr, Nathan; Martínez, Todd J.; Markland, Thomas E.

2014-01-01

Multiple time-scale algorithms exploit the natural separation of time-scales in chemical systems to greatly accelerate the efficiency of molecular dynamics simulations. Although the utility of these methods in systems where the interactions are described by empirical potentials is now well established, their application to ab initio molecular dynamics calculations has been limited by difficulties associated with splitting the ab initio potential into fast and slowly varying components. Here we present two schemes that enable efficient time-scale separation in ab initio calculations: one based on fragment decomposition and the other on range separation of the Coulomb operator in the electronic Hamiltonian. We demonstrate for both water clusters and a solvated hydroxide ion that multiple time-scale molecular dynamics allows for outer time steps of 2.5 fs, which are as large as those obtained when such schemes are applied to empirical potentials, while still allowing for bonds to be broken and reformed throughout the dynamics. This permits computational speedups of up to 4.4x, compared to standard Born-Oppenheimer ab initio molecular dynamics with a 0.5 fs time step, while maintaining the same energy conservation and accuracy

Perspective: Ab initio force field methods derived from quantum mechanics

Science.gov (United States)

Xu, Peng; Guidez, Emilie B.; Bertoni, Colleen; Gordon, Mark S.

2018-03-01

It is often desirable to accurately and efficiently model the behavior of large molecular systems in the condensed phase (thousands to tens of thousands of atoms) over long time scales (from nanoseconds to milliseconds). In these cases, ab initio methods are difficult due to the increasing computational cost with the number of electrons. A more computationally attractive alternative is to perform the simulations at the atomic level using a parameterized function to model the electronic energy. Many empirical force fields have been developed for this purpose. However, the functions that are used to model interatomic and intermolecular interactions contain many fitted parameters obtained from selected model systems, and such classical force fields cannot properly simulate important electronic effects. Furthermore, while such force fields are computationally affordable, they are not reliable when applied to systems that differ significantly from those used in their parameterization. They also cannot provide the information necessary to analyze the interactions that occur in the system, making the systematic improvement of the functional forms that are used difficult. Ab initio force field methods aim to combine the merits of both types of methods. The ideal ab initio force fields are built on first principles and require no fitted parameters. Ab initio force field methods surveyed in this perspective are based on fragmentation approaches and intermolecular perturbation theory. This perspective summarizes their theoretical foundation, key components in their formulation, and discusses key aspects of these methods such as accuracy and formal computational cost. The ab initio force fields considered here were developed for different targets, and this perspective also aims to provide a balanced presentation of their strengths and shortcomings. Finally, this perspective suggests some future directions for this actively developing area.

Parallel implementation and performance optimization of the configuration-interaction method

Energy Technology Data Exchange (ETDEWEB)

Shan, H; Williams, S; Johnson, C; McElvain, K; Ormand, WE

2015-11-20

The configuration-interaction (CI) method, long a popular approach to describe quantum many-body systems, is cast as a very large sparse matrix eigenpair problem with matrices whose dimension can exceed one billion. Such formulations place high demands on memory capacity and memory bandwidth - - two quantities at a premium today. In this paper, we describe an efficient, scalable implementation, BIGSTICK, which, by factorizing both the basis and the interaction into two levels, can reconstruct the nonzero matrix elements on the fly, reduce the memory requirements by one or two orders of magnitude, and enable researchers to trade reduced resources for increased computational time. We optimize BIGSTICK on two leading HPC platforms - - the Cray XC30 and the IBM Blue Gene/Q. Specifically, we not only develop an empirically-driven load balancing strategy that can evenly distribute the matrix-vector multiplication across 256K threads, we also developed techniques that improve the performance of the Lanczos reorthogonalization. Combined, these optimizations improved performance by 1.3-8× depending on platform and configuration.

Cooperative effects in the structuring of fluoride water clusters: Ab initio hybrid quantum mechanical/molecular mechanical model incorporating polarizable fluctuating charge solvent

Science.gov (United States)

Bryce, Richard A.; Vincent, Mark A.; Malcolm, Nathaniel O. J.; Hillier, Ian H.; Burton, Neil A.

1998-08-01

A new hybrid quantum mechanical/molecular mechanical model of solvation is developed and used to describe the structure and dynamics of small fluoride/water clusters, using an ab initio wave function to model the ion and a fluctuating charge potential to model the waters. Appropriate parameters for the water-water and fluoride-water interactions are derived, with the fluoride anion being described by density functional theory and a large Gaussian basis. The role of solvent polarization in determining the structure and energetics of F(H2O)4- clusters is investigated, predicting a slightly greater stability of the interior compared to the surface structure, in agreement with ab initio studies. An extended Lagrangian treatment of the polarizable water, in which the water atomic charges fluctuate dynamically, is used to study the dynamics of F(H2O)4- cluster. A simulation using a fixed solvent charge distribution indicates principally interior, solvated states for the cluster. However, a preponderance of trisolvated configurations is observed using the polarizable model at 300 K, which involves only three direct fluoride-water hydrogen bonds. Ab initio calculations confirm this trisolvated species as a thermally accessible state at room temperature, in addition to the tetrasolvated interior and surface structures. Extension of this polarizable water model to fluoride clusters with five and six waters gave less satisfactory agreement with experimental energies and with ab initio geometries. However, our results do suggest that a quantitative model of solvent polarization is fundamental for an accurate understanding of the properties of anionic water clusters.

Nuclear deformation in the configuration-interaction shell model

Science.gov (United States)

Alhassid, Y.; Bertsch, G. F.; Gilbreth, C. N.; Mustonen, M. T.

2018-02-01

We review a method that we recently introduced to calculate the finite-temperature distribution of the axial quadrupole operator in the laboratory frame using the auxiliary-field Monte Carlo technique in the framework of the configuration-interaction shell model. We also discuss recent work to determine the probability distribution of the quadrupole shape tensor as a function of intrinsic deformation β,γ by expanding its logarithm in quadrupole invariants. We demonstrate our method for an isotope chain of samarium nuclei whose ground states describe a crossover from spherical to deformed shapes.

Materials Screening for the Discovery of New Half-Heuslers: Machine Learning versus ab Initio Methods.

Science.gov (United States)

Legrain, Fleur; Carrete, Jesús; van Roekeghem, Ambroise; Madsen, Georg K H; Mingo, Natalio

2018-01-18

Machine learning (ML) is increasingly becoming a helpful tool in the search for novel functional compounds. Here we use classification via random forests to predict the stability of half-Heusler (HH) compounds, using only experimentally reported compounds as a training set. Cross-validation yields an excellent agreement between the fraction of compounds classified as stable and the actual fraction of truly stable compounds in the ICSD. The ML model is then employed to screen 71 178 different 1:1:1 compositions, yielding 481 likely stable candidates. The predicted stability of HH compounds from three previous high-throughput ab initio studies is critically analyzed from the perspective of the alternative ML approach. The incomplete consistency among the three separate ab initio studies and between them and the ML predictions suggests that additional factors beyond those considered by ab initio phase stability calculations might be determinant to the stability of the compounds. Such factors can include configurational entropies and quasiharmonic contributions.

Theoretical energy level spectra and transition data for 4p64d, 4p64f and 4p54d2 configurations of W37+ ion

International Nuclear Information System (INIS)

Bogdanovich, P.; Kisielius, R.

2012-01-01

The ab initio quasirelativistic Hartree–Fock method developed specifically for the calculation of spectral parameters of heavy atoms and highly charged ions was applied to determine atomic data for tungsten ions. The correlation effects were included by adopting the configuration interaction method. The Breit–Pauli approximation for quasirelativistic Hartree–Fock radial orbitals was employed to take into account relativistic effects. The energy level spectra, radiative lifetimes, Lande factors g were calculated for the 4p 6 4d, 4p 6 4f and 4p 5 4d 2 configurations of W 37+ ion. The atomic data, namely, the transition wavelengths, spontaneous emission rates and oscillator strengths for the electric dipole, electric quadrupole and magnetic dipole transitions among and within the levels of these configurations are tabulated.

Amino acids interacting with defected carbon nanotubes: ab initio calculations

Directory of Open Access Journals (Sweden)

M. Darvish Ganji

2016-09-01

Full Text Available The adsorption of a number of amino acids on a defected single-walled carbon nanotube (SWCNT is investigated by using the density-functional theory (DFT calculations. The adsorption energies and equilibrium distances are calculated for various configurations such as amino acid attaching to defect sites heptagon, pentagon and hexagon in defective tube and also for several molecular orientations with respect to the nanotube surface. The results showed that amino acids prefer to be physisorbed on the outer surface of the defected nanotube with different interaction strength following the hierarchy histidine > glycine > phenylalanine > cysteine. Comparing these findings with those obtained for perfect SWCNTs reveals that the adsorption energy of the amino acids increase for adsorption onto defected CNTs. The adsorption nature has also been evaluated by means of electronics structures analysis within the Mulliken population and DOS spectra for the interacting entities.

The Relationship Between Spatial Configuration and Social Interaction in High-Rise Flats: A Case Study On The Jatinegara Barat in Jakarta.

Directory of Open Access Journals (Sweden)

Ridwana Rifan

2018-01-01

The results of this study indicate that: (1 the relationship of spatial configuration to social interaction level in Jatinegara Barat flats can be positive or negative. (2 Positive relationships are found on the1st and 2ndfloor areas. High configuration values with high interaction levels are found in shared spaces on the 1st and 2nd floors with characteristics such as open space, large space, and availability of interaction supporting elements, while low configuration values with low interaction levels are found in more confined spaces such as private spaces and narrow corridors. (3 Negative relationships are found in the corridor and shared space in front of the elevator on each typical floors. Shared space in front of the elevator that has high spatial configuration value with large area show a low level of social interaction. While corridor with lower configuration value with the narrow area but have supporting elements such as chairs, mats, and shops have a higher level of social interaction. (4 This study shows that in the case of the relationship between spatial configuration and social interaction, availability of interaction supporting elements has greater influence rather than any other spatial factors.

Decomposition of the configuration-interaction coefficients in the multiconfiguration time-dependent Hartree-Fock method

Energy Technology Data Exchange (ETDEWEB)

Lötstedt, Erik, E-mail: lotstedt@chem.s.u-tokyo.ac.jp; Kato, Tsuyoshi; Yamanouchi, Kaoru [Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan)

2016-04-21

An approximate implementation of the multiconfiguration time-dependent Hartree-Fock method is proposed, in which the matrix of configuration-interaction coefficients is decomposed into a product of matrices of smaller dimension. The applicability of this method in which all the configurations are kept in the expansion of the wave function, while the configuration-interaction coefficients are approximately calculated, is discussed by showing the results on three model systems: a one-dimensional model of a beryllium atom, a one-dimensional model of a carbon atom, and a one-dimensional model of a chain of four hydrogen atoms. The time-dependent electronic dynamics induced by a few-cycle, long-wavelength laser pulse is found to be well described at a lower computational cost compared to the standard multiconfiguration time-dependent Hartree-Fock treatment. Drawbacks of the method are also discussed.

Ab initio calculations of 3H(d,n)4He fusion

International Nuclear Information System (INIS)

Navratil, Petr; Quaglioni, Sofia

2012-01-01

We build a new ab initio many-body approach capable of describing simultaneously both bound and scattering states in light nuclei, by combining the resonating-group method with the ab initio no-core shell model. In this way, we complement a microscopic-cluster technique with the use of realistic interactions, and a microscopic and consistent description of the nucleon clusters. We will present the first results of the d- 3 H and d- 3 He fusion calculation obtained within our ab initio approach. We will also discuss our d- 4 He, 3 H- 4 He and 3 H- 3 H scattering calculations and the outline of the extension of the formalism to include three-cluster final states with the goal to calculate the 3 H( 3 H,2n) 4 He cross section

Driving spin transition at interface: Role of adsorption configurations

Science.gov (United States)

Zhang, Yachao

2018-01-01

A clear insight into the electrical manipulation of molecular spins at interface is crucial to the design of molecule-based spintronic devices. Here we report on the electrically driven spin transition in manganocene physisorbed on a metallic surface in two different adsorption configurations predicted by ab initio techniques, including a Hubbard-U correction at the manganese site and accounting for the long-range van der Waals interactions. We show that the application of an electric field at the interface induces a high-spin to low-spin transition in the flat-lying manganocene, while it could hardly alter the high-spin ground state of the standing-up molecule. This phenomenon cannot be explained by either the molecule-metal charge transfer or the local electron correlation effects. We demonstrate a linear dependence of the intra-molecular spin-state splitting on the energy difference between crystal-field splitting and on-site Coulomb repulsion. After considering the molecule-surface binding energy shifts upon spin transition, we reproduce the obtained spin-state energetics. We find that the configuration-dependent responses of the spin-transition originate from the binding energy shifts instead of the variation of the local ligand field. Through these analyses, we obtain an intuitive understanding of the effects of molecule-surface contact on spin-crossover under electrical bias.

A Force Balanced Fragmentation Method for ab Initio Molecular Dynamic Simulation of Protein

Directory of Open Access Journals (Sweden)

Mingyuan Xu

2018-05-01

Full Text Available A force balanced generalized molecular fractionation with conjugate caps (FB-GMFCC method is proposed for ab initio molecular dynamic simulation of proteins. In this approach, the energy of the protein is computed by a linear combination of the QM energies of individual residues and molecular fragments that account for the two-body interaction of hydrogen bond between backbone peptides. The atomic forces on the caped H atoms were corrected to conserve the total force of the protein. Using this approach, ab initio molecular dynamic simulation of an Ace-(ALA9-NME linear peptide showed the conservation of the total energy of the system throughout the simulation. Further a more robust 110 ps ab initio molecular dynamic simulation was performed for a protein with 56 residues and 862 atoms in explicit water. Compared with the classical force field, the ab initio molecular dynamic simulations gave better description of the geometry of peptide bonds. Although further development is still needed, the current approach is highly efficient, trivially parallel, and can be applied to ab initio molecular dynamic simulation study of large proteins.

Electron affinities: theoretical

International Nuclear Information System (INIS)

Kaufman, J.J.

1976-01-01

A brief description is given of the conceptual background and formalism of the various ab-initio and semi-ab-initio quantum computational techniques for calculating atomic and molecular electron affinities: Hartree--Fock--Roothaan SCF, configuration interaction (CI), multiconfiguration SCF (MC-SCF), Bethe--Goldstone, superposition of configurations (SOC), ab-initio effective core model potentials, Xα-MS, plus other less common methods. Illustrative and comparative examples of electron affinities calculated by these various methods are presented

Ab initio study of interaction of helium with edge and screw dislocations in tungsten

Energy Technology Data Exchange (ETDEWEB)

Bakaev, Alexander, E-mail: bakaev_vic@mail.ru [SCK-CEN, Nuclear Materials Science Institute, Boeretang 200, Mol 2400 (Belgium); Department of Experimental Nuclear Physics K-89, Institute of Physics, Nanotechnology and Telecommunications, Peter the Great St. Petersburg Polytechnic University, 29 Polytekhnicheskaya str., 195251 St. Petersburg (Russian Federation); Institute of Ion Beam Physics and Materials Research, Helmholtz-Zentrum Dresden-Rossendorf, Bautzner Landstrasse 400, 01328 Dresden (Germany); Terentyev, Dmitry [SCK-CEN, Nuclear Materials Science Institute, Boeretang 200, Mol 2400 (Belgium); Grigorev, Petr [SCK-CEN, Nuclear Materials Science Institute, Boeretang 200, Mol 2400 (Belgium); Department of Experimental Nuclear Physics K-89, Institute of Physics, Nanotechnology and Telecommunications, Peter the Great St. Petersburg Polytechnic University, 29 Polytekhnicheskaya str., 195251 St. Petersburg (Russian Federation); Ghent University, Applied Physics EA17 FUSION-DC, St. Pietersnieuwstraat, 41 B4, B-9000 Gent (Belgium); Posselt, Matthias [Institute of Ion Beam Physics and Materials Research, Helmholtz-Zentrum Dresden-Rossendorf, Bautzner Landstrasse 400, 01328 Dresden (Germany); Zhurkin, Evgeny E. [Department of Experimental Nuclear Physics K-89, Institute of Physics, Nanotechnology and Telecommunications, Peter the Great St. Petersburg Polytechnic University, 29 Polytekhnicheskaya str., 195251 St. Petersburg (Russian Federation)

2017-02-15

Highlights: • Both screw (SD) and edge dislocations (ED) offer trapping sites for He in tungsten. • He atom is attracted to SD and ED with the interaction energy of ~1.3 and ~3.0 eV, respectively. • The attraction of He to dislocations can contribute to the nucleation of He clusters at high T. - Abstract: The interaction of a single He atom with edge and screw dislocations in tungsten has been studied using ab initio calculations. It was revealed that He is strongly attracted to the core of both dislocations with the interaction energy of −1.3 and −3.0 eV for screw and edge dislocations, respectively, which corresponds to the detrapping temperature in thermal desorption spectroscopy experiments of about 500 K and 1050 K, respectively. The lowest energy positions for He around the dislocation cores are identified and the atomic structures are rationalized on the basis of elasticity theory considerations. Both types of dislocations exhibit a higher binding energy for He as compared to the He-He binding (known as self-trapping) and are weaker traps as compared to a single vacancy. It is, thus, concluded that the strong attraction to dislocation lines can contribute to the nucleation of He clusters in the temperature range which already excludes He self-trapping.

Ab initio study of interaction of helium with edge and screw dislocations in tungsten

International Nuclear Information System (INIS)

Bakaev, Alexander; Terentyev, Dmitry; Grigorev, Petr; Posselt, Matthias; Zhurkin, Evgeny E.

2017-01-01

Highlights: • Both screw (SD) and edge dislocations (ED) offer trapping sites for He in tungsten. • He atom is attracted to SD and ED with the interaction energy of ~1.3 and ~3.0 eV, respectively. • The attraction of He to dislocations can contribute to the nucleation of He clusters at high T. - Abstract: The interaction of a single He atom with edge and screw dislocations in tungsten has been studied using ab initio calculations. It was revealed that He is strongly attracted to the core of both dislocations with the interaction energy of −1.3 and −3.0 eV for screw and edge dislocations, respectively, which corresponds to the detrapping temperature in thermal desorption spectroscopy experiments of about 500 K and 1050 K, respectively. The lowest energy positions for He around the dislocation cores are identified and the atomic structures are rationalized on the basis of elasticity theory considerations. Both types of dislocations exhibit a higher binding energy for He as compared to the He-He binding (known as self-trapping) and are weaker traps as compared to a single vacancy. It is, thus, concluded that the strong attraction to dislocation lines can contribute to the nucleation of He clusters in the temperature range which already excludes He self-trapping.

Particle-two particle interaction in configuration space

International Nuclear Information System (INIS)

Kuzmichev, V.E.

1982-07-01

The problem if three indentical particles with zero-range two-particle interaction is considered. An explicit expression for the effective potential between one particle and the remaining two-particle system is obtained in the coordinate representation. It is shown that for arbitrary energies, at small and, for zero energy, at large distances rho between the one particle and centre of mass of the other two particles the diagonal matrix element of the effective potential is attractive and proportional to 1/rho 2 . This property of the effective potenial explains both the Thomas singularity and the Efimov effect. In the case of zero total energy of the system the general form of the solution of the three-particle integral equation is found in configuration space. (orig.)

Resolution-of-identity stochastic time-dependent configuration interaction for dissipative electron dynamics in strong fields.

Science.gov (United States)

Klinkusch, Stefan; Tremblay, Jean Christophe

2016-05-14

In this contribution, we introduce a method for simulating dissipative, ultrafast many-electron dynamics in intense laser fields. The method is based on the norm-conserving stochastic unraveling of the dissipative Liouville-von Neumann equation in its Lindblad form. The N-electron wave functions sampling the density matrix are represented in the basis of singly excited configuration state functions. The interaction with an external laser field is treated variationally and the response of the electronic density is included to all orders in this basis. The coupling to an external environment is included via relaxation operators inducing transition between the configuration state functions. Single electron ionization is represented by irreversible transition operators from the ionizing states to an auxiliary continuum state. The method finds its efficiency in the representation of the operators in the interaction picture, where the resolution-of-identity is used to reduce the size of the Hamiltonian eigenstate basis. The zeroth-order eigenstates can be obtained either at the configuration interaction singles level or from a time-dependent density functional theory reference calculation. The latter offers an alternative to explicitly time-dependent density functional theory which has the advantage of remaining strictly valid for strong field excitations while improving the description of the correlation as compared to configuration interaction singles. The method is tested on a well-characterized toy system, the excitation of the low-lying charge transfer state in LiCN.

Resolution-of-identity stochastic time-dependent configuration interaction for dissipative electron dynamics in strong fields

Energy Technology Data Exchange (ETDEWEB)

Klinkusch, Stefan; Tremblay, Jean Christophe [Institute for Chemistry and Biochemistry, Freie Universität Berlin, Takustr. 3, D-14195 Berlin (Germany)

2016-05-14

In this contribution, we introduce a method for simulating dissipative, ultrafast many-electron dynamics in intense laser fields. The method is based on the norm-conserving stochastic unraveling of the dissipative Liouville-von Neumann equation in its Lindblad form. The N-electron wave functions sampling the density matrix are represented in the basis of singly excited configuration state functions. The interaction with an external laser field is treated variationally and the response of the electronic density is included to all orders in this basis. The coupling to an external environment is included via relaxation operators inducing transition between the configuration state functions. Single electron ionization is represented by irreversible transition operators from the ionizing states to an auxiliary continuum state. The method finds its efficiency in the representation of the operators in the interaction picture, where the resolution-of-identity is used to reduce the size of the Hamiltonian eigenstate basis. The zeroth-order eigenstates can be obtained either at the configuration interaction singles level or from a time-dependent density functional theory reference calculation. The latter offers an alternative to explicitly time-dependent density functional theory which has the advantage of remaining strictly valid for strong field excitations while improving the description of the correlation as compared to configuration interaction singles. The method is tested on a well-characterized toy system, the excitation of the low-lying charge transfer state in LiCN.

Determination of orbitals for use in configuration interaction calculations

International Nuclear Information System (INIS)

Dunning, T.H. Jr.; Davidson, E.R.; Ruedenberg, K.; Hinze, J.

1978-01-01

For a full configuration interaction (CI) calculation the choice of orbitals is completely irrelevant, i.e., the calculated wavefunction is unaffected by an arbitrary unitary transformation of the orbitals; it depends only on the space spanned by the original basis set. For most chemical systems it is not possible to realistically carry out a full CI calculation, so that specification of the orbital set is important. Even for less-than-full CI calculations, it can be shown, however, that for certain types of calculations the wavefunction is unaffected by restricted transformations among the orbital set. For example, for CI calculations based on a single configuration plus a complete set of excitations of a given type (single, double, etc.), the calculated wavefunction is independent of transformations among the set of occupied orbitals and among the set of virtual orbitals. The wavefunction does, however, depend on transformations which mix the occupied and virtual orbitals

Threshold and channel interaction in cochlear implant users: evaluation of the tripolar electrode configuration.

Science.gov (United States)

Bierer, Julie Arenberg

2007-03-01

The efficacy of cochlear implants is limited by spatial and temporal interactions among channels. This study explores the spatially restricted tripolar electrode configuration and compares it to bipolar and monopolar stimulation. Measures of threshold and channel interaction were obtained from nine subjects implanted with the Clarion HiFocus-I electrode array. Stimuli were biphasic pulses delivered at 1020 pulses/s. Threshold increased from monopolar to bipolar to tripolar stimulation and was most variable across channels with the tripolar configuration. Channel interaction, quantified by the shift in threshold between single- and two-channel stimulation, occurred for all three configurations but was largest for the monopolar and simultaneous conditions. The threshold shifts with simultaneous tripolar stimulation were slightly smaller than with bipolar and were not as strongly affected by the timing of the two channel stimulation as was monopolar. The subjects' performances on clinical speech tests were correlated with channel-to-channel variability in tripolar threshold, such that greater variability was related to poorer performance. The data suggest that tripolar channels with high thresholds may reveal cochlear regions of low neuron survival or poor electrode placement.

Ab initio study of phase equilibria in TiCx

DEFF Research Database (Denmark)

Korzhavyi, P.A.; Pourovskii, L.V.; Hugosson, H.W.

2002-01-01

The phase diagram for the vacancy-ordered structures in the substoichiometric TiCx (x = 0.5-1.0) has been established from Monte Carlo simulations with the long-range pair and multisite effective interactions obtained from ab initio calculations. Three ordered superstructures of vacancies (Ti2C, Ti...

Bridging a gap between continuum-QCD and ab initio predictions of hadron observables

Energy Technology Data Exchange (ETDEWEB)

Binosi, Daniele [European Centre for Theoretical Studies in Nuclear Physics and Related Areas - ECT* and Fondazione Bruno Kessler, Villa Tambosi, Strada delle Tabarelle 286, I-38123 Villazzano (Italy); Chang, Lei [CSSM, School of Chemistry and Physics, University of Adelaide, Adelaide, SA 5005 (Australia); Papavassiliou, Joannis [Department of Theoretical Physics and IFIC, University of Valencia and CSIC, E-46100, Valencia (Spain); Roberts, Craig D., E-mail: cdroberts@anl.gov [Physics Division, Argonne National Laboratory, Argonne, IL 60439 (United States)

2015-03-06

Within contemporary hadron physics there are two common methods for determining the momentum-dependence of the interaction between quarks: the top-down approach, which works toward an ab initio computation of the interaction via direct analysis of the gauge-sector gap equations; and the bottom-up scheme, which aims to infer the interaction by fitting data within a well-defined truncation of those equations in the matter sector that are relevant to bound-state properties. We unite these two approaches by demonstrating that the renormalisation-group-invariant running-interaction predicted by contemporary analyses of QCD's gauge sector coincides with that required in order to describe ground-state hadron observables using a nonperturbative truncation of QCD's Dyson–Schwinger equations in the matter sector. This bridges a gap that had lain between nonperturbative continuum-QCD and the ab initio prediction of bound-state properties.

Configuration interaction calculations of positron binding to Be(3P )

International Nuclear Information System (INIS)

Bromley, M.W.J.; Mitroy, J.

2006-01-01

The configuration interaction method is applied to investigate the possibility of positron binding to the metastable beryllium (1s 2 2s2p 3 P ) state. The largest calculation obtained an estimated energy that was unstable by 0.00014 Hartree with respect to the Ps + Be + (2s) lowest dissociation channel. It is likely that positron binding to parent states with non-zero angular momentum is inhibited by centrifugal barriers

The ionic states of iodobenzene studied by photoionization and ab initio configuration interaction and DFT computations

International Nuclear Information System (INIS)

Palmer, Michael H.; Ridley, Trevor; Hoffmann, Søren Vrønning; Jones, Nykola C.; Coreno, Marcello; Simone, Monica de; Grazioli, Cesare; Biczysko, Malgorzata; Baiardi, Alberto

2015-01-01

New valence electron photoelectron spectra of iodobenzene obtained using synchrotron radiation have been recorded. Ionization energies (IEs) determined using multi-configuration SCF calculation (MCSCF) procedures confirmed the adiabatic IE order as: X 2 B 1

Ab Initio Nuclear Structure and Reaction Calculations for Rare Isotopes

Energy Technology Data Exchange (ETDEWEB)

Draayer, Jerry P. [Louisiana State Univ., Baton Rouge, LA (United States)

2014-09-28

We have developed a novel ab initio symmetry-adapted no-core shell model (SA-NCSM), which has opened the intermediate-mass region for ab initio investigations, thereby providing an opportunity for first-principle symmetry-guided applications to nuclear structure and reactions for nuclear isotopes from the lightest p-shell systems to intermediate-mass nuclei. This includes short-lived proton-rich nuclei on the path of X-ray burst nucleosynthesis and rare neutron-rich isotopes to be produced by the Facility for Rare Isotope Beams (FRIB). We have provided ab initio descriptions of high accuracy for low-lying (including collectivity-driven) states of isotopes of Li, He, Be, C, O, Ne, Mg, Al, and Si, and studied related strong- and weak-interaction driven reactions that are important, in astrophysics, for further understanding stellar evolution, X-ray bursts and triggering of s, p, and rp processes, and in applied physics, for electron and neutrino-nucleus scattering experiments as well as for fusion ignition at the National Ignition Facility (NIF).

Ab Initio Nuclear Structure and Reaction Calculations for Rare Isotopes

International Nuclear Information System (INIS)

Draayer, Jerry P.

2014-01-01

We have developed a novel ab initio symmetry-adapted no-core shell model (SA-NCSM), which has opened the intermediate-mass region for ab initio investigations, thereby providing an opportunity for first-principle symmetry-guided applications to nuclear structure and reactions for nuclear isotopes from the lightest p-shell systems to intermediate-mass nuclei. This includes short-lived proton-rich nuclei on the path of X-ray burst nucleosynthesis and rare neutron-rich isotopes to be produced by the Facility for Rare Isotope Beams (FRIB). We have provided ab initio descriptions of high accuracy for low-lying (including collectivity-driven) states of isotopes of Li, He, Be, C, O, Ne, Mg, Al, and Si, and studied related strong- and weak-interaction driven reactions that are important, in astrophysics, for further understanding stellar evolution, X-ray bursts and triggering of s, p, and rp processes, and in applied physics, for electron and neutrino-nucleus scattering experiments as well as for fusion ignition at the National Ignition Facility (NIF).

Formation of Field-reversed-Configuration Plasma with Punctuated-betatron-orbit Electrons

International Nuclear Information System (INIS)

Welch, D.R.; Cohen, S.A.; Genoni, T.C.; Glasser, A.H.

2010-01-01

We describe ab initio, self-consistent, 3D, fully electromagnetic numerical simulations of current drive and field-reversed-configuration plasma formation by odd-parity rotating magnetic fields (RMFo). Magnetic-separatrix formation and field reversal are attained from an initial mirror configuration. A population of punctuated-betatron-orbit electrons, generated by the RMFo, carries the majority of the field-normal azimuthal electrical current responsible for field reversal. Appreciable current and plasma pressure exist outside the magnetic separatrix whose shape is modulated by the RMFo phase. The predicted plasma density and electron energy distribution compare favorably with RMFo experiments.

Deterministic alternatives to the full configuration interaction quantum Monte Carlo method for strongly correlated systems

Science.gov (United States)

Tubman, Norm; Whaley, Birgitta

The development of exponential scaling methods has seen great progress in tackling larger systems than previously thought possible. One such technique, full configuration interaction quantum Monte Carlo, allows exact diagonalization through stochastically sampling of determinants. The method derives its utility from the information in the matrix elements of the Hamiltonian, together with a stochastic projected wave function, which are used to explore the important parts of Hilbert space. However, a stochastic representation of the wave function is not required to search Hilbert space efficiently and new deterministic approaches have recently been shown to efficiently find the important parts of determinant space. We shall discuss the technique of Adaptive Sampling Configuration Interaction (ASCI) and the related heat-bath Configuration Interaction approach for ground state and excited state simulations. We will present several applications for strongly correlated Hamiltonians. This work was supported through the Scientific Discovery through Advanced Computing (SciDAC) program funded by the U.S. Department of Energy, Office of Science, Advanced Scientific Computing Research and Basic Energy Sciences.

Character of intermolecular interaction in pyridine-argon complex: Ab initio potential energy surface, internal dynamics, and interrelations between SAPT energy components

Energy Technology Data Exchange (ETDEWEB)

Makarewicz, Jan, E-mail: jama@amu.edu.pl; Shirkov, Leonid [Faculty of Chemistry, Adam Mickiewicz University, Umultowska 89b, 61-614 Poznań (Poland)

2016-05-28

The pyridine-Ar (PAr) van der Waals (vdW) complex is studied using a high level ab initio method. Its structure, binding energy, and intermolecular vibrational states are determined from the analytical potential energy surface constructed from interaction energy (IE) values computed at the coupled cluster level of theory with single, double, and perturbatively included triple excitations with the augmented correlation consistent polarized valence double-ζ (aug-cc-pVDZ) basis set complemented by midbond functions. The structure of the complex at its global minimum with Ar at a distance of 3.509 Å from the pyridine plane and shifted by 0.218 Å from the center of mass towards nitrogen agrees well with the corresponding equilibrium structure derived previously from the rotational spectrum of PAr. The PAr binding energy D{sub e} of 392 cm{sup −1} is close to that of 387 cm{sup −1} calculated earlier at the same ab initio level for the prototypical benzene-Ar (BAr) complex. However, under an extension of the basis set, D{sub e} for PAr becomes slightly lower than D{sub e} for BAr. The ab initio vdW vibrational energy levels allow us to estimate the reliability of the methods for the determination of the vdW fundamentals from the rotational spectra. To disclose the character of the intermolecular interaction in PAr, the symmetry-adapted perturbation theory (SAPT) is employed for the analysis of different physical contributions to IE. It is found that SAPT components of IE can be approximately expressed in the binding region by only two of them: the exchange repulsion and dispersion energy. The total induction effect is negligible. The interrelations between various SAPT components found for PAr are fulfilled for a few other complexes involving aromatic molecules and Ar or Ne, which indicates that they are valid for all rare gas (Rg) atoms and aromatics.

Variational configuration interaction methods and comparison with perturbation theory

International Nuclear Information System (INIS)

Pople, J.A.; Seeger, R.; Krishnan, R.

1977-01-01

A configuration interaction (CI) procedure which includes all single and double substitutions from an unrestricted Hartree-Fock single determinant is described. This has the feature that Moller-Plesset perturbation results to second and third order are obtained in the first CI iterative cycle. The procedure also avoids the necessity of a full two-electron integral transformation. A simple expression for correcting the final CI energy for lack of size consistency is proposed. Finally, calculations on a series of small molecules are presented to compare these CI methods with perturbation theory

Augmented wave ab initio EFG calculations: some methodological warnings

International Nuclear Information System (INIS)

Errico, Leonardo A.; Renteria, Mario; Petrilli, Helena M.

2007-01-01

We discuss some accuracy aspects inherent to ab initio electronic structure calculations in the understanding of nuclear quadrupole interactions. We use the projector augmented wave method to study the electric-field gradient (EFG) at both Sn and O sites in the prototype cases SnO and SnO 2 . The term ab initio is used in the standard context of the also called first principles methods in the framework of the Density Functional Theory. As the main contributions of EFG calculations to problems in condensed matter physics are related to structural characterizations on the atomic scale, we discuss the 'state of the art' on theoretical EFG calculations and make a brief critical review on the subject, calling attention to some fundamental theoretical aspects

Augmented wave ab initio EFG calculations: some methodological warnings

Energy Technology Data Exchange (ETDEWEB)

Errico, Leonardo A. [Departamento de Fisica-IFLP (CONICET), Facultad de Ciencias Exactas, Universidad Nacional de La Plata, CC67 (1900) La Plata (Argentina); Renteria, Mario [Departamento de Fisica-IFLP (CONICET), Facultad de Ciencias Exactas, Universidad Nacional de La Plata, CC67 (1900) La Plata (Argentina); Petrilli, Helena M. [Instituto de Fisica-DFMT, Universidade de Sao Paulo, C.P. 66318, 05315-970 Sao Paulo, SP (Brazil)]. E-mail: hmpetril@macbeth.if.usp.br

2007-02-01

We discuss some accuracy aspects inherent to ab initio electronic structure calculations in the understanding of nuclear quadrupole interactions. We use the projector augmented wave method to study the electric-field gradient (EFG) at both Sn and O sites in the prototype cases SnO and SnO{sub 2}. The term ab initio is used in the standard context of the also called first principles methods in the framework of the Density Functional Theory. As the main contributions of EFG calculations to problems in condensed matter physics are related to structural characterizations on the atomic scale, we discuss the 'state of the art' on theoretical EFG calculations and make a brief critical review on the subject, calling attention to some fundamental theoretical aspects.

Ab initio vel ex eventu

Science.gov (United States)

Thiessen, P. A.; Treder, H.-J.

Der gegenwärtige Stand der physikalischen Erkenntnis, in Sonderheit die Atomistik und die Quantentheorie, ermöglicht (in wohldefinierten Energie-Bereichen) eine ab initio-Berechnung aller physikalischen und chemischen Prozesse und Strukturen. Die Schrödinger-Gleichung erlaubt zusammen mit den Prinzipien der Quantenstatistik (Pauli-Prinzip) aus dem Planckschen Wirkungsquantum h und den atomischen Konstanten die Berechnung aller Energieumsätze, Zeitabläufe etc., die insbesondere die chemische Physik bestimmen. Die Rechenresultate gelten auch quantitativ bis auf die unvermeidliche Stochastik.Die ab initio-Berechnungen korrespondieren einerseits und sind andererseits komplementär zu den auf den Methoden der theoretischen Chemie und der klassischen Thermodynamik beruhenden Ergebnissen ex eventu. Die theoretische Behandlung ab initio führt zu mathematischen Experimenten, die die Laboratoriums-Experimente ergänzen oder auch substituieren.Translated AbstractAb initio vel ex eventuThe present state of physical knowledge, in peculiar atomistic and quantum theory, makes an ab initio calculation of all physical and chemical processes and structures possible (in well defined reaches of energy). The Schrödinger equation together with the principles of quantum statistics (Pauli principle) permits from the Planck and atomistic constants to calculate all exchanges of energy, courses of time, etc. which govern chemical physics. The calculated results are valid even quantitatively apart from the unavoidable stochastics.These ab initio calculations on the one hand correspond and are on the other complimentary to results ex eventu based on the methods of theoretical chemistry and classical thermodynamics. Theoretical treatment ab initio leads to mathematical experiments which add to or even substitute experiments in the laboratory.

Electric dipole moment of diatomic molecules by configuration interaction. IV.

Science.gov (United States)

Green, S.

1972-01-01

The theory of basis set dependence in configuration interaction calculations is discussed, taking into account a perturbation model which is valid for small changes in the self-consistent field orbitals. It is found that basis set corrections are essentially additive through first order. It is shown that an error found in a previously published dipole moment calculation by Green (1972) for the metastable first excited state of CO was indeed due to an inadequate basis set as claimed.

Accelerating nuclear configuration interaction calculations through a preconditioned block iterative eigensolver

Science.gov (United States)

Shao, Meiyue; Aktulga, H. Metin; Yang, Chao; Ng, Esmond G.; Maris, Pieter; Vary, James P.

2018-01-01

We describe a number of recently developed techniques for improving the performance of large-scale nuclear configuration interaction calculations on high performance parallel computers. We show the benefit of using a preconditioned block iterative method to replace the Lanczos algorithm that has traditionally been used to perform this type of computation. The rapid convergence of the block iterative method is achieved by a proper choice of starting guesses of the eigenvectors and the construction of an effective preconditioner. These acceleration techniques take advantage of special structure of the nuclear configuration interaction problem which we discuss in detail. The use of a block method also allows us to improve the concurrency of the computation, and take advantage of the memory hierarchy of modern microprocessors to increase the arithmetic intensity of the computation relative to data movement. We also discuss the implementation details that are critical to achieving high performance on massively parallel multi-core supercomputers, and demonstrate that the new block iterative solver is two to three times faster than the Lanczos based algorithm for problems of moderate sizes on a Cray XC30 system.

Ab-initio perturbed-cluster study of carbon monoxide adsorption at a stepped LiF(001) surface

Science.gov (United States)

Pisani, C.; Corà, F.; Orlando, R.; Nada, R.

1993-02-01

The perturbed-cluster ab-initio Hartree-Fock approach to the study of local defects in crystals [J. Chem. Phys. 92(1990)7448] is applied to the study of CO adsorption at a stepped LiF(001) surface. The step is simulated by a tablet of four ions superimposed on an infinite LiF(001) monolayer. The geometry of the step is first optimized, and corresponds to an important relaxation of cations and anions of the tablet inwards and outwards, respectively. The equilibrium configuration, adsorption energy and vibrational frequency of CO at a corner of the tablet occupied by a lithium cation are calculated. With respect to adsorption at a perfect (100) face, there is a large increase in interaction energy, especially when adsorption occurs via the oxygen atom. This difference is essentially related to modifications of the electrostatic field experienced by the adsorbed molecule.

Effects of configuration interaction on photoabsorption spectra in the continuum

International Nuclear Information System (INIS)

Komninos, Yannis; Nicolaides, Cleanthes A.

2004-01-01

It is pointed out that the proper interpretation of a recently published experimental spectrum from the multilaser photoionization of Sr [Eichmann et al., Phys. Rev. Lett. 90, 233004 (2003)] must account for a radiative transition between two autoionizing states. The application of orthonormality selection rules and of configuration-interaction theory involving the continuous spectrum and the quasicontinuum of the upper part of Rydberg series explains quantitatively the appearance, the shape, and the variation of heights of the observed peaks of resonances

CONFIGURATION-INTERACTION IN NI METAL AND NI-ALLOYS AND HIGH-ENERGY SPECTROSCOPY

NARCIS (Netherlands)

TANAKA, A; JO, T; SAWATZKY, GA

We discuss the electronic state of Ni atoms in Ni metal and of Ni impurity in Cu and Au metals from the viewpoint of 3d configuration interaction (CI) using the Anderson impurity model including atomic multiplets. On the basis of the discussion, we give an interpretation for the Ni 2p-core X-ray

Parallel multireference configuration interaction calculations on mini-beta-carotenes and beta-carotene.

Science.gov (United States)

Kleinschmidt, Martin; Marian, Christel M; Waletzke, Mirko; Grimme, Stefan

2009-01-28

We present a parallelized version of a direct selecting multireference configuration interaction (MRCI) code [S. Grimme and M. Waletzke, J. Chem. Phys. 111, 5645 (1999)]. The program can be run either in ab initio mode or as semiempirical procedure combined with density functional theory (DFT/MRCI). We have investigated the efficiency of the parallelization in case studies on carotenoids and porphyrins. The performance is found to depend heavily on the cluster architecture. While the speed-up on the older Intel Netburst technology is close to linear for up to 12-16 processes, our results indicate that it is not favorable to use all cores of modern Intel Dual Core or Quad Core processors simultaneously for memory intensive tasks. Due to saturation of the memory bandwidth, we recommend to run less demanding tasks on the latter architectures in parallel to two (Dual Core) or four (Quad Core) MRCI processes per node. The DFT/MRCI branch has been employed to study the low-lying singlet and triplet states of mini-n-beta-carotenes (n=3, 5, 7, 9) and beta-carotene (n=11) at the geometries of the ground state, the first excited triplet state, and the optically bright singlet state. The order of states depends heavily on the conjugation length and the nuclear geometry. The (1)B(u) (+) state constitutes the S(1) state in the vertical absorption spectrum of mini-3-beta-carotene but switches order with the 2 (1)A(g) (-) state upon excited state relaxation. In the longer carotenes, near degeneracy or even root flipping between the (1)B(u) (+) and (1)B(u) (-) states is observed whereas the 3 (1)A(g) (-) state is found to remain energetically above the optically bright (1)B(u) (+) state at all nuclear geometries investigated here. The DFT/MRCI method is seen to underestimate the absolute excitation energies of the longer mini-beta-carotenes but the energy gaps between the excited states are reproduced well. In addition to singlet data, triplet-triplet absorption energies are

Parallel multireference configuration interaction calculations on mini-β-carotenes and β-carotene

Science.gov (United States)

Kleinschmidt, Martin; Marian, Christel M.; Waletzke, Mirko; Grimme, Stefan

2009-01-01

We present a parallelized version of a direct selecting multireference configuration interaction (MRCI) code [S. Grimme and M. Waletzke, J. Chem. Phys. 111, 5645 (1999)]. The program can be run either in ab initio mode or as semiempirical procedure combined with density functional theory (DFT/MRCI). We have investigated the efficiency of the parallelization in case studies on carotenoids and porphyrins. The performance is found to depend heavily on the cluster architecture. While the speed-up on the older Intel Netburst technology is close to linear for up to 12-16 processes, our results indicate that it is not favorable to use all cores of modern Intel Dual Core or Quad Core processors simultaneously for memory intensive tasks. Due to saturation of the memory bandwidth, we recommend to run less demanding tasks on the latter architectures in parallel to two (Dual Core) or four (Quad Core) MRCI processes per node. The DFT/MRCI branch has been employed to study the low-lying singlet and triplet states of mini-n-β-carotenes (n =3, 5, 7, 9) and β-carotene (n =11) at the geometries of the ground state, the first excited triplet state, and the optically bright singlet state. The order of states depends heavily on the conjugation length and the nuclear geometry. The B1u+ state constitutes the S1 state in the vertical absorption spectrum of mini-3-β-carotene but switches order with the 2 A1g- state upon excited state relaxation. In the longer carotenes, near degeneracy or even root flipping between the B1u+ and B1u- states is observed whereas the 3 A1g- state is found to remain energetically above the optically bright B1u+ state at all nuclear geometries investigated here. The DFT/MRCI method is seen to underestimate the absolute excitation energies of the longer mini-β-carotenes but the energy gaps between the excited states are reproduced well. In addition to singlet data, triplet-triplet absorption energies are presented. For β-carotene, where these transition

Propulsion and airframe aerodynamic interactions of supersonic V/STOL configurations. Volume 2: Wind tunnel test force and moment data report

Science.gov (United States)

Zilz, D. E.

1985-01-01

A wind tunnel model of a supersonic V/STOL fighter configuration has been tested to measure the aerodynamic interaction effects which can result from geometrically close-coupled propulsion system/airframe components. The approach was to configure the model to represent two different test techniques. One was a conventional test technique composed of two test modes. In the Flow-Through mode, absolute configuration aerodynamics are measured, including inlet/airframe interactions. In the Jet-Effects mode, incremental nozzle/airframe interactions are measured. The other test technique is a propulsion simulator approach, where a sub-scale, externally powered engine is mounted in the model. This allows proper measurement of inlet/airframe and nozzle/airframe interactions simultaneously. This is Volume 2 of 2: Wind Tunnel Test Force and Moment Data Report.

Ab‐initio study of germanium di-interstitial using a hybrid functional (HSE)

Energy Technology Data Exchange (ETDEWEB)

Igumbor, E., E-mail: elgumuk@gmail.com [Department of Physics, University of Pretoria, Pretoria 0002 (South Africa); Department of Mathematics and Physical Sciences, Samuel Adegboyega University, Km 1 Ogwa/Ehor Rd, Ogwa, Edo State (Nigeria); Ouma, C.N.M.; Webb, G. [Department of Physics, University of Pretoria, Pretoria 0002 (South Africa); Meyer, W.E., E-mail: wmeyer@up.ac.za [Department of Physics, University of Pretoria, Pretoria 0002 (South Africa)

2016-01-01

In this work, we present ab‐initio calculation results of Ge di-interstitials (I{sub 2(Ge)}) in the framework of the density functional theory (DFT) using the Heyd, Scuseria, and Ernzerhof (HSE) hybrid functional. The formation energy, transition levels and minimum energy configurations were obtained for I{sub 2(Ge)} −2, −1, 0, +1 and +2 charge states. The calculated formation energies show that for all charge states of I{sub 2(Ge)}, the double tetrahedral (T) configuration formed the most stable defect with a binding energy of 1.24 eV in the neutral state. We found the (+2/+1) charge state transition level for the T lying below the conduction band minimum and (+2/+1) for the split[110]-tetrahedral configuration lying deep at 0.41 eV above the valence band maximum. The di-interstitials in Ge exhibited the properties of both shallow and deep donor levels at (+2/+1) within the band gap and depending on the configurations. I{sub 2(Ge)} gave rise to negative-U, with effective-U values of −0.61 and −1.6 eV in different configurations. We have compared our results with calculations of di-interstitials in silicon and available experimental data.

DFT Study of Azole Corrosion Inhibitors on Cu2O Model of Oxidized Copper Surfaces: II. Lateral Interactions and Thermodynamic Stability

Directory of Open Access Journals (Sweden)

Dunja Gustinčič

2018-05-01

Full Text Available The adsorption of imidazole, triazole, and tetrazole—used as simple models of azole corrosion inhibitors—on various Cu 2 O(111- and Cu 2 O(110-type surfaces was characterized using density functional theory (DFT calculations with the focus on lateral intermolecular interactions and the thermodynamic stability of various adsorption structures. To this end, an ab initio thermodynamics approach was used to construct two-dimensional phase diagrams for all three molecules. The impact of van der Waals dispersion interactions on molecular adsorption bonding was also addressed. Lateral intermolecular interactions were found to be the most repulsive for imidazole and the least for tetrazole, for which they are usually even slightly attractive. Both non-dissociative and dissociative adsorption modes were considered and although dissociated molecules bind to surfaces more strongly, none of the considered structures that involve dissociated molecules appear on the phase diagrams. Our results show that the three azole molecules display a strong tendency to preferentially adsorb at reactive coordinatively unsaturated (CUS Cu surface sites and stabilize them. According to the calculated phase diagrams for Cu 2 O(111-type surfaces, the three azole molecules adsorb to specific CUS sites, designated as Cu CUS , under all conditions at which molecular adsorption is stable. This tentatively suggests that their corrosion inhibition capability may stem, at least in part, from their ability to passivate reactive surface sites. We further comment on a specific drawback due to neglect of configurational entropy that is usually utilized within the ab initio thermodynamics approach. We analyze the issue for Langmuir and Frumkin adsorption models and show that when configurational entropy is neglected, the ab initio thermodynamics approach is too hasty to predict phase-transition like behavior.

Non-equilibrium quantum dynamics of ultra-cold atomic mixtures: the multi-layer multi-configuration time-dependent Hartree method for bosons

International Nuclear Information System (INIS)

Krönke, Sven; Cao, Lushuai; Schmelcher, Peter; Vendrell, Oriol

2013-01-01

We develop and apply the multi-layer multi-configuration time-dependent Hartree method for bosons, which represents an ab initio method for investigating the non-equilibrium quantum dynamics of multi-species bosonic systems. Its multi-layer feature allows for tailoring the wave function ansatz to describe intra- and inter-species correlations accurately and efficiently. To demonstrate the beneficial scaling and efficiency of the method, we explored the correlated tunneling dynamics of two species with repulsive intra- and inter-species interactions, to which a third species with vanishing intra-species interaction was weakly coupled. The population imbalances of the first two species can feature a temporal equilibration and their time evolution significantly depends on the coupling to the third species. Bosons of the first and second species exhibit a bunching tendency, whose strength can be influenced by their coupling to the third species. (paper)

Optical spectroscopy and system–bath interactions in molecular aggregates with full configuration interaction Frenkel exciton model

Energy Technology Data Exchange (ETDEWEB)

Seibt, Joachim; Sláma, Vladislav; Mančal, Tomáš, E-mail: mancal@karlov.mff.cuni.cz

2016-12-20

Highlights: • Standard Frenkel exciton model is extended to include inter-band coupling. • It is formally linked with configuration interaction method of quantum chemistry. • Spectral shifts due to inter-band coupling are found in molecular aggregates. • Effects of peak amplitude redistribution in two-dimensional spectra are found. - Abstract: Standard application of the Frenkel exciton model neglects resonance coupling between collective molecular aggregate states with different number of excitations. These inter-band coupling terms are, however, of the same magnitude as the intra-band coupling between singly excited states. We systematically derive the Frenkel exciton model from quantum chemical considerations, and identify it as a variant of the configuration interaction method. We discuss all non-negligible couplings between collective aggregate states, and provide compact formulae for their calculation. We calculate absorption spectra of molecular aggregate of carotenoids and identify significant band shifts as a result of inter-band coupling. The presence of inter-band coupling terms requires renormalization of the system–bath coupling with respect to standard formulation, but renormalization effects are found to be weak. We present detailed discussion of molecular dimer and calculate its time-resolved two-dimensional Fourier transformed spectra to find weak but noticeable effects of peak amplitude redistribution due to inter-band coupling.

Ground state analytical ab initio intermolecular potential for the Cl2-water system

International Nuclear Information System (INIS)

Hormain, Laureline; Monnerville, Maurice; Toubin, Céline; Duflot, Denis; Pouilly, Brigitte; Briquez, Stéphane; Bernal-Uruchurtu, Margarita I.; Hernández-Lamoneda, Ramón

2015-01-01

The chlorine/water interface is of crucial importance in the context of atmospheric chemistry. Modeling the structure and dynamics at this interface requires an accurate description of the interaction potential energy surfaces. We propose here an analytical intermolecular potential that reproduces the interaction between the Cl 2 molecule and a water molecule. Our functional form is fitted to a set of high level ab initio data using the coupled-cluster single double (triple)/aug-cc-p-VTZ level of electronic structure theory for the Cl 2 − H 2 O complex. The potential fitted to reproduce the three minima structures of 1:1 complex is validated by the comparison of ab initio results of Cl 2 interacting with an increasing number of water molecules. Finally, the model potential is used to study the physisorption of Cl 2 on a perfectly ordered hexagonal ice slab. The calculated adsorption energy, in the range 0.27 eV, shows a good agreement with previous experimental results

Configuration interaction calculations of positron binding to Be({sup 3}P )

Energy Technology Data Exchange (ETDEWEB)

Bromley, M.W.J. [Department of Physics, San Diego State University, San Diego, CA 92182 (United States)]. E-mail: mbromley@physics.sdsu.edu; Mitroy, J. [Faculty of Technology, Charles Darwin University, Darwin, NT 0909 (Australia)]. E-mail: jxm107@rsphysse.anu.edu.au

2006-06-15

The configuration interaction method is applied to investigate the possibility of positron binding to the metastable beryllium (1s{sup 2}2s2p {sup 3}P ) state. The largest calculation obtained an estimated energy that was unstable by 0.00014 Hartree with respect to the Ps + Be{sup +}(2s) lowest dissociation channel. It is likely that positron binding to parent states with non-zero angular momentum is inhibited by centrifugal barriers.

Ab initio and DFT study of hydrogen bond interactions between ascorbic acid and dimethylsulfoxide based on FT-IR and FT-Raman spectra

Science.gov (United States)

Niazazari, Naser; Zatikyan, Ashkhen L.; Markarian, Shiraz A.

2013-06-01

The hydrogen bonding of 1:1 complexes formed between L-ascorbic acid (LAA) and dimethylsulfoxide (DMSO) has been studied by means of ab initio and density functional theory (DFT) calculations. Solutions of L-ascorbic acid (AA) in dimethylsulfoxide (DMSO) have been studied by means of both FT-IR (4000-220 cm-1) and FT-Raman spectroscopy. Ab initio Hartree-Fock (HF) and DFT methods have been used to determine the structure and energies of stable conformers of various types of L-AA/DMSO complexes in gas phase and solution. The basis sets 6-31++G∗∗ and 6-311+G∗ were used to describe the structure, energy, charges and vibrational frequencies of interacting complexes in the gas phase. The optimized geometric parameters and interaction energies for various complexes at different theories have been estimated. Binding energies have been corrected for basis set superposition error (BSSE) and harmonic vibrational frequencies of the structures have been calculated to obtain the stable forms of the complexes. The self-consistent reaction field (SCRF) has been used to calculate the effect of DMSO as the solvent on the geometry, energy and charges of complexes. The solvent effect has been studied using the Onsager models. It is shown that the polarity of the solvent plays an important role on the structures and relative stabilities of different complexes. The results obtained show that there is a satisfactory correlation between experimental and theoretical predictions.

Nuclear structure calculations in $^{20}$Ne with No-Core Configuration-Interaction model

OpenAIRE

Konieczka, Maciej; Satuła, Wojciech

2016-01-01

Negative parity states in $^{20}$Ne and Gamow-Teller strength distribution for the ground-state beta-decay of $^{20}$Na are calculated for the very first time using recently developed No-Core Configuration-Interaction model. The approach is based on multi-reference density functional theory involving isospin and angular-momentum projections. Advantages and shortcomings of the method are briefly discussed.

Configuration Management

International Nuclear Information System (INIS)

Morcos, A.; Taylor, H. S.

1989-01-01

This paper will briefly discuss the reason for and content of configuration management both for new plants and, when adapted, for older plants. It will then address three types of activities a utility may undertake as part of a nuclear CAM program and with which Sargent and Leyden has been actively involved. The first activity is a methodology for preparing design-basis documentation. The second is the identification of essential data required to be kept by the utility in support of the operation of a nuclear plant. The third activity is a computerized classification system of plant components, allowing ready identification of plant functional and physical characteristics. Plant configuration documentation describes plant components, the ways they arranged to interact, and the ways they are enabled to interact. Configuration management, on the other hand, is more than the control of such documentation. It is a dynamic process for ensuring that a plant configuration meets all relevant requirements for safety and economy, even while the configuration changes and even while the requirements change. Configuration management for a nuclear plant is so complex that it must be implemented in phases and modules. It takes advantage of and integrates existing programs. Managing complexity and streamlining the change process become important additional objectives of configuration management. The example activities fulfill essential goals of an overall CAM program: definition of design baseline, definition of essential plant data, and classification of plant components

Ab initio study of weakly bound halogen complexes: RX⋯PH3.

Science.gov (United States)

Georg, Herbert C; Fileti, Eudes E; Malaspina, Thaciana

2013-01-01

Ab initio calculations were employed to study the role of ipso carbon hybridization in halogenated compounds RX (R=methyl, phenyl, acetyl, H and X=F, Cl, Br and I) and its interaction with a phosphorus atom, as occurs in the halogen bonded complex type RX⋯PH3. The analysis was performed using ab initio MP2, MP4 and CCSD(T) methods. Systematic energy analysis found that the interaction energies are in the range -4.14 to -11.92 kJ mol(-1) (at MP2 level without ZPE correction). Effects of electronic correlation levels were evaluated at MP4 and CCSD(T) levels and a reduction of up to 27% in interaction energy obtained in MP2 was observed. Analysis of the electrostatic maps confirms that the PhCl⋯PH3 and all MeX⋯PH3 complexes are unstable. NBO analysis suggested that the charge transfer between the moieties is bigger when using iodine than bromine and chlorine. The electrical properties of these complexes (dipole and polarizability) were determined and the most important observed aspect was the systematic increase at the dipole polarizability, given by the interaction polarizability. This increase is in the range of 0.7-6.7 u.a. (about 3-7%).

Investigation of polarization effects in the gramicidin A channel from ab initio molecular dynamics simulations.

Science.gov (United States)

Timko, Jeff; Kuyucak, Serdar

2012-11-28

Polarization is an important component of molecular interactions and is expected to play a particularly significant role in inhomogeneous environments such as pores and interfaces. Here we investigate the effects of polarization in the gramicidin A ion channel by performing quantum mechanics/molecular mechanics molecular dynamics (MD) simulations and comparing the results with those obtained from classical MD simulations with non-polarizable force fields. We consider the dipole moments of backbone carbonyl groups and channel water molecules as well as a number of structural quantities of interest. The ab initio results show that the dipole moments of the carbonyl groups and water molecules are highly sensitive to the hydrogen bonds (H-bonds) they participate in. In the absence of a K(+) ion, water molecules in the channel are quite mobile, making the H-bond network highly dynamic. A central K(+) ion acts as an anchor for the channel waters, stabilizing the H-bond network and thereby increasing their average dipole moments. In contrast, the K(+) ion has little effect on the dipole moments of the neighboring carbonyl groups. The weakness of the ion-peptide interactions helps to explain the near diffusion-rate conductance of K(+) ions through the channel. We also address the sampling issue in relatively short ab initio MD simulations. Results obtained from a continuous 20 ps ab initio MD simulation are compared with those generated by sampling ten windows from a much longer classical MD simulation and running each window for 2 ps with ab initio MD. Both methods yield similar results for a number of quantities of interest, indicating that fluctuations are fast enough to justify the short ab initio MD simulations.

Gamow-Teller response in the configuration space of a density-functional-theory-rooted no-core configuration-interaction model

Science.gov (United States)

Konieczka, M.; Kortelainen, M.; Satuła, W.

2018-03-01

Background: The atomic nucleus is a unique laboratory in which to study fundamental aspects of the electroweak interaction. This includes a question concerning in medium renormalization of the axial-vector current, which still lacks satisfactory explanation. Study of spin-isospin or Gamow-Teller (GT) response may provide valuable information on both the quenching of the axial-vector coupling constant as well as on nuclear structure and nuclear astrophysics. Purpose: We have performed a seminal calculation of the GT response by using the no-core configuration-interaction approach rooted in multireference density functional theory (DFT-NCCI). The model treats properly isospin and rotational symmetries and can be applied to calculate both the nuclear spectra and transition rates in atomic nuclei, irrespectively of their mass and particle-number parity. Methods: The DFT-NCCI calculation proceeds as follows: First, one builds a configuration space by computing relevant, for a given physical problem, (multi)particle-(multi)hole Slater determinants. Next, one applies the isospin and angular-momentum projections and performs the isospin and K mixing in order to construct a model space composed of linearly dependent states of good angular momentum. Eventually, one mixes the projected states by solving the Hill-Wheeler-Griffin equation. Results: The method is applied to compute the GT strength distribution in selected N ≈Z nuclei including the p -shell 8Li and 8Be nuclei and the s d -shell well-deformed nucleus 24Mg. In order to demonstrate a flexibility of the approach we present also a calculation of the superallowed GT β decay in doubly-magic spherical 100Sn and the low-spin spectrum in 100In. Conclusions: It is demonstrated that the DFT-NCCI model is capable of capturing the GT response satisfactorily well by using a relatively small configuration space, exhausting simultaneously the GT sum rule. The model, due to its flexibility and broad range of applicability, may

Ab initio lattice stability of fcc and hcp Fe-Mn random alloys

International Nuclear Information System (INIS)

Gebhardt, T; Music, D; Hallstedt, B; Schneider, J M; Ekholm, M; Abrikosov, I A; Vitos, L

2010-01-01

We have studied the lattice stability of face centred cubic (fcc) versus hexagonal close packed (hcp) Fe-Mn random alloys using ab initio calculations. In the calculations we considered the antiferromagnetic order of local moments, which for fcc alloys models the magnetic configuration of this phase at room temperature (below its Neel temperature) as well as their complete disorder, corresponding to paramagnetic fcc and hcp alloys. For both cases, the results are consistent with our thermodynamic calculations, obtained within the Calphad approach. For the room temperature magnetic configuration, the cross-over of the total energies of the hcp phase and the fcc phase of Fe-Mn alloys is at the expected Mn content, whereas for the magnetic configuration above the fcc Neel temperature, the hcp lattice is more stable within the whole composition range studied. The increase of the total energy difference between hcp and antiferromagnetic fcc due to additions of Mn as well as the stabilizing effect of antiferromagnetic ordering on the fcc phase are well displayed. These results are of relevance for understanding the deformation mechanisms of these random alloys.

Ab initio lattice stability of fcc and hcp Fe-Mn random alloys

Energy Technology Data Exchange (ETDEWEB)

Gebhardt, T; Music, D; Hallstedt, B; Schneider, J M [Materials Chemistry, RWTH Aachen University, D-52056 Aachen (Germany); Ekholm, M; Abrikosov, I A [Department of Physics, Chemistry and Biology (IFM), Linkoeping University, SE-581 83 Linkoeping (Sweden); Vitos, L, E-mail: gebhardt@mch.rwth-aachen.d [Department of Materials Science and Engineering, Applied Materials Physics, oyal Institute of Technology, SE-10044 Stockholm (Sweden)

2010-07-28

We have studied the lattice stability of face centred cubic (fcc) versus hexagonal close packed (hcp) Fe-Mn random alloys using ab initio calculations. In the calculations we considered the antiferromagnetic order of local moments, which for fcc alloys models the magnetic configuration of this phase at room temperature (below its Neel temperature) as well as their complete disorder, corresponding to paramagnetic fcc and hcp alloys. For both cases, the results are consistent with our thermodynamic calculations, obtained within the Calphad approach. For the room temperature magnetic configuration, the cross-over of the total energies of the hcp phase and the fcc phase of Fe-Mn alloys is at the expected Mn content, whereas for the magnetic configuration above the fcc Neel temperature, the hcp lattice is more stable within the whole composition range studied. The increase of the total energy difference between hcp and antiferromagnetic fcc due to additions of Mn as well as the stabilizing effect of antiferromagnetic ordering on the fcc phase are well displayed. These results are of relevance for understanding the deformation mechanisms of these random alloys.

Nanoscale multireference quantum chemistry: full configuration interaction on graphical processing units.

Science.gov (United States)

Fales, B Scott; Levine, Benjamin G

2015-10-13

Methods based on a full configuration interaction (FCI) expansion in an active space of orbitals are widely used for modeling chemical phenomena such as bond breaking, multiply excited states, and conical intersections in small-to-medium-sized molecules, but these phenomena occur in systems of all sizes. To scale such calculations up to the nanoscale, we have developed an implementation of FCI in which electron repulsion integral transformation and several of the more expensive steps in σ vector formation are performed on graphical processing unit (GPU) hardware. When applied to a 1.7 × 1.4 × 1.4 nm silicon nanoparticle (Si72H64) described with the polarized, all-electron 6-31G** basis set, our implementation can solve for the ground state of the 16-active-electron/16-active-orbital CASCI Hamiltonian (more than 100,000,000 configurations) in 39 min on a single NVidia K40 GPU.

The multi-reference retaining the excitation degree perturbation theory: A size-consistent, unitary invariant, and rapidly convergent wavefunction based ab initio approach

International Nuclear Information System (INIS)

Fink, Reinhold F.

2009-01-01

The retaining the excitation degree (RE) partitioning [R.F. Fink, Chem. Phys. Lett. 428 (2006) 461(20 September)] is reformulated and applied to multi-reference cases with complete active space (CAS) reference wave functions. The generalised van Vleck perturbation theory is employed to set up the perturbation equations. It is demonstrated that this leads to a consistent and well defined theory which fulfils all important criteria of a generally applicable ab initio method: The theory is proven numerically and analytically to be size-consistent and invariant with respect to unitary orbital transformations within the inactive, active and virtual orbital spaces. In contrast to most previously proposed multi-reference perturbation theories the necessary condition for a proper perturbation theory to fulfil the zeroth order perturbation equation is exactly satisfied with the RE partitioning itself without additional projectors on configurational spaces. The theory is applied to several excited states of the benchmark systems CH 2 , SiH 2 , and NH 2 , as well as to the lowest states of the carbon, nitrogen and oxygen atoms. In all cases comparisons are made with full configuration interaction results. The multi-reference (MR)-RE method is shown to provide very rapidly converging perturbation series. Energy differences between states of similar configurations converge even faster

Electric dipole moment of diatomic molecules by configuration interaction. V - Two states of /2/Sigma/+/ symmetry in CN.

Science.gov (United States)

Green, S.

1972-01-01

Previous accurate dipole moment calculation techniques are modified to be applicable to higher excited states of symmetry. The self-consistent fields and configuration interactions are calculated for the X(2)Sigma(+) and B(2)Sigma(+) states of CN. Spin hyperfine constants and spin density at the nucleus are considered in the context of one-electron operator properties. The values of the self-consistent field and configuration interaction for the spin density are compared with experimental values for several diatomic molecules.

Ab initio study of interstitial cluster interaction with Re, Os, and Ta in W

Energy Technology Data Exchange (ETDEWEB)

Setyawan, Wahyu, E-mail: wahyu.setyawan@pnnl.gov; Nandipati, Giridhar; Kurtz, Richard J.

2017-02-15

The stability of tungsten self-interstitial atom (SIA) clusters is studied using first-principles methods. Clusters from one to seven SIAs are systematically explored from 1264 unique configurations. Finite-size effect of the simulation cell is corrected based on the scaling of formation energy versus inverse volume cell. Furthermore, the accuracy of the calculations is improved by treating the 5p semicore states as valence states. Configurations of the three most stable clusters in each cluster size n are presented, which consist of parallel [111] dumbbells. The evolution of these clusters leading to small dislocation loops is discussed. The binding energy of size-n clusters is analyzed relative to an n → (n-1) + 1 dissociation and is shown to increase with size. Extrapolation for n > 7 is presented using a dislocation loop model. In addition, the interaction of these clusters with a substitutional Re, Os, or Ta solute is explored by replacing one of the dumbbells with the solute. Re and Os strongly attract these clusters, but Ta strongly repels. The strongest interaction is found when the solute is located on the periphery of the cluster rather than in the middle. The magnitude of this interaction decreases with cluster size. Empirical fits to describe the trend of the solute binding energy are presented. - Highlights: • Systematic DFT exploration of tungsten SIA clusters from 1264 configurations. • Detailed structures of several most stable clusters are presented. • Novel finding of the trend of solute binding of Re, Os, and Ta with SIA clusters. • Empirical models that describe the trends of the solute binding energies.

Ab initio study of interstitial cluster interaction with Re, Os, and Ta in W

International Nuclear Information System (INIS)

Setyawan, Wahyu; Nandipati, Giridhar; Kurtz, Richard J.

2017-01-01

The stability of tungsten self-interstitial atom (SIA) clusters is studied using first-principles methods. Clusters from one to seven SIAs are systematically explored from 1264 unique configurations. Finite-size effect of the simulation cell is corrected based on the scaling of formation energy versus inverse volume cell. Furthermore, the accuracy of the calculations is improved by treating the 5p semicore states as valence states. Configurations of the three most stable clusters in each cluster size n are presented, which consist of parallel [111] dumbbells. The evolution of these clusters leading to small dislocation loops is discussed. The binding energy of size-n clusters is analyzed relative to an n → (n-1) + 1 dissociation and is shown to increase with size. Extrapolation for n > 7 is presented using a dislocation loop model. In addition, the interaction of these clusters with a substitutional Re, Os, or Ta solute is explored by replacing one of the dumbbells with the solute. Re and Os strongly attract these clusters, but Ta strongly repels. The strongest interaction is found when the solute is located on the periphery of the cluster rather than in the middle. The magnitude of this interaction decreases with cluster size. Empirical fits to describe the trend of the solute binding energy are presented. - Highlights: • Systematic DFT exploration of tungsten SIA clusters from 1264 configurations. • Detailed structures of several most stable clusters are presented. • Novel finding of the trend of solute binding of Re, Os, and Ta with SIA clusters. • Empirical models that describe the trends of the solute binding energies.

Mixing of the lowest-lying qqq configurations with JP =1/2- in different hyperfine interaction models

Science.gov (United States)

Chen, Jia; An, Chunsheng; Chen, Hong

2018-02-01

We investigate mixing of the lowest-lying qqq configurations with JP = 1/2- caused by the hyperfine interactions between quarks mediated by Goldstone Boson Exchange, One Gluon Exchange, and both Goldstone Boson and One Gluon exchange, respectively. The first orbitally excited nucleon, Σ, Λ and Ξ states are considered. Contributions of both the contact term and tensor term are taken into account. Our numerical results show that mixing of the studied configurations in the two employed hyperfine interaction models are very different. Therefore, the present results, which should affect the strong and electromagnetic decays of baryon resonances, may be used to examine the present employed hyperfine interaction models. Supported by National Natural Science Foundation of China (11675131,11645002), Chongqing Natural Science Foundation (cstc2015jcyjA00032) and Fundamental Research Funds for the Central Universities (SWU115020)

Ab Initio Modeling Of Friction Reducing Agents Shows Quantum Mechanical Interactions Can Have Macroscopic Manifestation.

Science.gov (United States)

Hernández Velázquez, J D; Barroso-Flores, J; Gama Goicochea, A

2016-11-23

Two of the most commonly encountered friction-reducing agents used in plastic sheet production are the amides known as erucamide and behenamide, which despite being almost identical chemically, lead to markedly different values of the friction coefficient. To understand the origin of this contrasting behavior, in this work we model brushes made of these two types of linear-chain molecules using quantum mechanical numerical simulations under the density functional theory at the B97D/6-31G(d,p) level of theory. Four chains of erucamide and behenamide were linked to a 2 × 10 zigzag graphene sheet and optimized both in vacuum and in continuous solvent using the SMD implicit solvation model. We find that erucamide chains tend to remain closer together through π-π stacking interactions arising from the double bonds located at C13-C14, a feature behenamide lacks, and thus a more spread configuration is obtained with the latter. It is argued that this arrangement of the erucamide chains is responsible for the lower friction coefficient of erucamide brushes, compared with behenamide brushes, which is a macroscopic consequence of cooperative quantum mechanical interactions. While only quantum level interactions are modeled here, we show that behenamide chains are more spread out in the brush than erucamide chains as a consequence of those interactions. The spread-out configuration allows more solvent particles to penetrate the brush, leading in turn to more friction, in agreement with macroscopic measurements and mesoscale simulations of the friction coefficient reported in the literature.

Ab-initio approach to the effect of Fe on the diffusion in hcp Zr

International Nuclear Information System (INIS)

Perez, Rodolfo Ariel; Weissmann, Mariana

2008-01-01

The role of Fe in the hcp Zr diffusion process is analyzed, given its ultra-fast diffusion (up to nine orders of magnitude higher than the self-diffusion in the temperature range 779-1128 K) and the enhancement observed in the self and substitutional diffusion induced by its unavoidable presence as impurity. Ab-initio calculations using SIESTA and WIEN2K codes were performed in order to find the actual Fe minimum energy configuration within the hcp Zr matrix and its interaction with vacancies. Several off-centre quasi-interstitial positions with energies similar to substitutional Fe were encountered. The comparison with diffusion coefficient measurements and Moessbauer experiments allows us to discard the substitutional position of the Fe atom as well as to affirm that its presence creates a considerable lattice distortion together with an increment in the number of vacancies. The above effects could be responsible for the enhancement in the self and substitutional diffusion, whereas the large amount of quasi-interstitial positions for Fe could be, at least partially, responsible for the ultra-fast Fe diffusion

A nonlocal, ab initio model of dissociative electron attachment and vibrational excitation of NO

International Nuclear Information System (INIS)

Trevisan, Cynthia S.; Houfek, Karel; Zhang, Zhiyong; Orel, Ann E.; McCurdy, C. William; Rescigno, Thomas N.

2005-01-01

We present the results of an ab initio study of elastic scattering and vibrational excitation of NO by electron impact in the loW--energy (0-2 eV) region where the cross sections are dominated by resonance contributions. The 3Sigma-, 1Delta and 1Sigma+ NO- resonance lifetimes are taken from our earlier study [Phys. Rev. A 69, 062711 (2004)], but the resonance energies used here are obtained from new configuration-interaction studies. Here we employ a more elaborate nonlocal treatment of the nuclear dynamics, which is found to remedy the principal deficiencies of the local complex potential model we employed in our earlier study, and gives cross sections in better agreement with the most recent experiments. We also present cross sections for dissociative electron attachment to NO leading to groundstate products. The calculations show that, while the peak cross sections starting from NO in its ground vibrational state are very small, the cross sections are extremely sensitive to vibrational excitation of the target and should be readily observable for target NO molecules excited to v = 10 and above

Multireference configuration interaction calculations of the first six ionization potentials of the uranium atom

Energy Technology Data Exchange (ETDEWEB)

Bross, David H.; Parmar, Payal; Peterson, Kirk A., E-mail: kipeters@wsu.edu [Department of Chemistry, Washington State University, Pullman, Washington 99164-4630 (United States)

2015-11-14

The first 6 ionization potentials (IPs) of the uranium atom have been calculated using multireference configuration interaction (MRCI+Q) with extrapolations to the complete basis set limit using new all-electron correlation consistent basis sets. The latter was carried out with the third-order Douglas-Kroll-Hess Hamiltonian. Correlation down through the 5s5p5d electrons has been taken into account, as well as contributions to the IPs due to the Lamb shift. Spin-orbit coupling contributions calculated at the 4-component Kramers restricted configuration interaction level, as well as the Gaunt term computed at the Dirac-Hartree-Fock level, were added to the best scalar relativistic results. The final ionization potentials are expected to be accurate to at least 5 kcal/mol (0.2 eV) and thus more reliable than the current experimental values of IP{sub 3} through IP{sub 6}.

Coupled-Cluster and Configuration-Interaction Calculations for Heavy Nuclei

International Nuclear Information System (INIS)

Horoi, M.; Gour, J. R.; Wloch, M.; Lodriguito, M. D.; Brown, B. A.; Piecuch, P.

2007-01-01

We compare coupled-cluster (CC) and configuration-interaction (CI) results for 56 Ni obtained in the pf-shell basis, focusing on practical CC approximations that can be applied to systems with dozens or hundreds of correlated fermions. The weight of the reference state and the strength of correlation effects are controlled by the gap between the f 7/2 orbit and the f 5/2 , p 3/2 , p 1/2 orbits. Independent of the gap, the CC method with 1p-1h and 2p-2h clusters and a noniterative treatment of 3p-3h clusters is as accurate as the more demanding CI approach truncated at the 4p-4h level

Watermelon configurations with wall interaction: exact and asymptotic results

Energy Technology Data Exchange (ETDEWEB)

Krattenthaler, C [Institut Camille Jordan, Universite Claude Bernard Lyon-I, 21, avenue Claude Bernard, F-69622 Villeurbanne Cedex (France)

2006-06-15

We perform an exact and asymptotic analysis of the model of n vicious walkers interacting with a wall via contact potentials, a model introduced by Brak, Essam and Owczarek. More specifically, we study the partition function of watermelon configurations which start on the wall, but may end at arbitrary height, and their mean number of contacts with the wall. We improve and extend the earlier (partially nonrigorous) results by Brak, Essam and Owczarek, providing new exact results, and more precise and more general asymptotic results, in particular full asymptotic expansions for the partition function and the mean number of contacts. Furthermore, we relate this circle of problems to earlier results in the combinatorial and statistical literature.

Watermelon configurations with wall interaction: exact and asymptotic results

International Nuclear Information System (INIS)

Krattenthaler, C

2006-01-01

We perform an exact and asymptotic analysis of the model of n vicious walkers interacting with a wall via contact potentials, a model introduced by Brak, Essam and Owczarek. More specifically, we study the partition function of watermelon configurations which start on the wall, but may end at arbitrary height, and their mean number of contacts with the wall. We improve and extend the earlier (partially nonrigorous) results by Brak, Essam and Owczarek, providing new exact results, and more precise and more general asymptotic results, in particular full asymptotic expansions for the partition function and the mean number of contacts. Furthermore, we relate this circle of problems to earlier results in the combinatorial and statistical literature

Watermelon configurations with wall interaction: exact and asymptotic results

Science.gov (United States)

Krattenthaler, C.

2006-06-01

We perform an exact and asymptotic analysis of the model of n vicious walkers interacting with a wall via contact potentials, a model introduced by Brak, Essam and Owczarek. More specifically, we study the partition function of watermelon configurations which start on the wall, but may end at arbitrary height, and their mean number of contacts with the wall. We improve and extend the earlier (partially nonrigorous) results by Brak, Essam and Owczarek, providing new exact results, and more precise and more general asymptotic results, in particular full asymptotic expansions for the partition function and the mean number of contacts. Furthermore, we relate this circle of problems to earlier results in the combinatorial and statistical literature.

Optical absorption spectra and g factor of MgO: Mn2+explored by ab initio and semi empirical methods

Science.gov (United States)

Andreici Eftimie, E.-L.; Avram, C. N.; Brik, M. G.; Avram, N. M.

2018-02-01

In this paper we present a methodology for calculations of the optical absorption spectra, ligand field parameters and g factor for the Mn2+ (3d5) ions doped in MgO host crystal. The proposed technique combines two methods: the ab initio multireference (MR) and the semi empirical ligand field (LF) in the framework of the exchange charge model (ECM) respectively. Both methods of calculations are applied to the [MnO6]10-cluster embedded in an extended point charge field of host matrix ligands based on Gellé-Lepetit procedure. The first step of such investigations was the full optimization of the cubic structure of perfect MgO crystal, followed by the structural optimization of the doped of MgO:Mn2+ system, using periodic density functional theory (DFT). The ab initio MR wave functions approaches, such as complete active space self-consistent field (CASSCF), N-electron valence second order perturbation theory (NEVPT2) and spectroscopy oriented configuration interaction (SORCI), are used for the calculations. The scalar relativistic effects have also been taken into account through the second order Douglas-Kroll-Hess (DKH2) procedure. Ab initio ligand field theory (AILFT) allows to extract all LF parameters and spin-orbit coupling constant from such calculations. In addition, the ECM of ligand field theory (LFT) has been used for modelling theoptical absorption spectra. The perturbation theory (PT) was employed for the g factor calculation in the semi empirical LFT. The results of each of the aforementioned types of calculations are discussed and the comparisons between the results obtained and the experimental results show a reasonable agreement, which justifies this new methodology based on the simultaneous use of both methods. This study establishes fundamental principles for the further modelling of larger embedded cluster models of doped metal oxides.

Ab initio O(N) elongation-counterpoise method for BSSE-corrected interaction energy analyses in biosystems

Energy Technology Data Exchange (ETDEWEB)

Orimoto, Yuuichi; Xie, Peng; Liu, Kai [Department of Material Sciences, Faculty of Engineering Sciences, Kyushu University, 6-1 Kasuga-Park, Fukuoka 816-8580 (Japan); Yamamoto, Ryohei [Department of Molecular and Material Sciences, Interdisciplinary Graduate School of Engineering Sciences, Kyushu University, 6-1 Kasuga-Park, Fukuoka 816-8580 (Japan); Imamura, Akira [Hiroshima Kokusai Gakuin University, 6-20-1 Nakano, Aki-ku, Hiroshima 739-0321 (Japan); Aoki, Yuriko, E-mail: aoki.yuriko.397@m.kyushu-u.ac.jp [Department of Material Sciences, Faculty of Engineering Sciences, Kyushu University, 6-1 Kasuga-Park, Fukuoka 816-8580 (Japan); Japan Science and Technology Agency, CREST, 4-1-8 Hon-chou, Kawaguchi, Saitama 332-0012 (Japan)

2015-03-14

An Elongation-counterpoise (ELG-CP) method was developed for performing accurate and efficient interaction energy analysis and correcting the basis set superposition error (BSSE) in biosystems. The method was achieved by combining our developed ab initio O(N) elongation method with the conventional counterpoise method proposed for solving the BSSE problem. As a test, the ELG-CP method was applied to the analysis of the DNAs’ inter-strands interaction energies with respect to the alkylation-induced base pair mismatch phenomenon that causes a transition from G⋯C to A⋯T. It was found that the ELG-CP method showed high efficiency (nearly linear-scaling) and high accuracy with a negligibly small energy error in the total energy calculations (in the order of 10{sup −7}–10{sup −8} hartree/atom) as compared with the conventional method during the counterpoise treatment. Furthermore, the magnitude of the BSSE was found to be ca. −290 kcal/mol for the calculation of a DNA model with 21 base pairs. This emphasizes the importance of BSSE correction when a limited size basis set is used to study the DNA models and compare small energy differences between them. In this work, we quantitatively estimated the inter-strands interaction energy for each possible step in the transition process from G⋯C to A⋯T by the ELG-CP method. It was found that the base pair replacement in the process only affects the interaction energy for a limited area around the mismatch position with a few adjacent base pairs. From the interaction energy point of view, our results showed that a base pair sliding mechanism possibly occurs after the alkylation of guanine to gain the maximum possible number of hydrogen bonds between the bases. In addition, the steps leading to the A⋯T replacement accompanied with replications were found to be unfavorable processes corresponding to ca. 10 kcal/mol loss in stabilization energy. The present study indicated that the ELG-CP method is promising for

Analytic nuclear forces and molecular properties from full configuration interaction quantum Monte Carlo

International Nuclear Information System (INIS)

Thomas, Robert E.; Overy, Catherine; Opalka, Daniel; Alavi, Ali; Knowles, Peter J.; Booth, George H.

2015-01-01

Unbiased stochastic sampling of the one- and two-body reduced density matrices is achieved in full configuration interaction quantum Monte Carlo with the introduction of a second, “replica” ensemble of walkers, whose population evolves in imaginary time independently from the first and which entails only modest additional computational overheads. The matrices obtained from this approach are shown to be representative of full configuration-interaction quality and hence provide a realistic opportunity to achieve high-quality results for a range of properties whose operators do not necessarily commute with the Hamiltonian. A density-matrix formulated quasi-variational energy estimator having been already proposed and investigated, the present work extends the scope of the theory to take in studies of analytic nuclear forces, molecular dipole moments, and polarisabilities, with extensive comparison to exact results where possible. These new results confirm the suitability of the sampling technique and, where sufficiently large basis sets are available, achieve close agreement with experimental values, expanding the scope of the method to new areas of investigation

Serious Gaming for Test & Evaluation of Clean-Slate (Ab Initio) National Airspace System (NAS) Designs

Science.gov (United States)

Allen, B. Danette; Alexandrov, Natalia

2016-01-01

Incremental approaches to air transportation system development inherit current architectural constraints, which, in turn, place hard bounds on system capacity, efficiency of performance, and complexity. To enable airspace operations of the future, a clean-slate (ab initio) airspace design(s) must be considered. This ab initio National Airspace System (NAS) must be capable of accommodating increased traffic density, a broader diversity of aircraft, and on-demand mobility. System and subsystem designs should scale to accommodate the inevitable demand for airspace services that include large numbers of autonomous Unmanned Aerial Vehicles and a paradigm shift in general aviation (e.g., personal air vehicles) in addition to more traditional aerial vehicles such as commercial jetliners and weather balloons. The complex and adaptive nature of ab initio designs for the future NAS requires new approaches to validation, adding a significant physical experimentation component to analytical and simulation tools. In addition to software modeling and simulation, the ability to exercise system solutions in a flight environment will be an essential aspect of validation. The NASA Langley Research Center (LaRC) Autonomy Incubator seeks to develop a flight simulation infrastructure for ab initio modeling and simulation that assumes no specific NAS architecture and models vehicle-to-vehicle behavior to examine interactions and emergent behaviors among hundreds of intelligent aerial agents exhibiting collaborative, cooperative, coordinative, selfish, and malicious behaviors. The air transportation system of the future will be a complex adaptive system (CAS) characterized by complex and sometimes unpredictable (or unpredicted) behaviors that result from temporal and spatial interactions among large numbers of participants. A CAS not only evolves with a changing environment and adapts to it, it is closely coupled to all systems that constitute the environment. Thus, the ecosystem that

High pressure studies of configuration interaction and crystal field effects in Sm2+

International Nuclear Information System (INIS)

Shen, Y.; Bray, K.L.

1998-01-01

Full text: Divalent rare earth ions are interesting luminescence centres because of the low energy of the excited 4f n-1 5d 1 configuration relative to the 4f n ground configuration. The low energy difference between these two configurations leads to two principle effects which distinguish the luminescence properties of divalent rare earth ions from those of trivalent rare earth ions. First, a significant amount of 5d state mixing into the electronic states of the 4f n configuration occurs and second, the thermal activation barrier to 4f n → 4f n-1 5d 1 crossing is greatly reduced. The first effect introduces opposite parity character into the emitting levels of divalent rare earth ions and acts to shorten lifetimes and increase f-f luminescence intensity, while the second effect acts to enhance thermal quenching of 4f n excited electronic states closest in energy to the 4f n-1 5d 1 configuration. The interaction between the 4f n and 4f n-1 5d 1 configurations and crystal field properties are typically studied by considering the luminescence properties of divalent rare earth ions in a series of host crystals. We are currently developing a new approach, based on high pressure luminescence spectroscopy, for understanding con-figuration interaction and crystal field properties of divalent rare earth ions. The strategy of our approach is to use high pressure as a tool of structural perturbation. By applying hydrostatic pressure to solids, we have an opportunity to continuously vary the nearest neighbour coordination environment of divalent rare earth dopants. Our general goal is to correlate pressure-induced changes in local structure with pressure-induced changes in luminescence properties in an attempt to better understand structure-property-composition relations in solid state luminescent materials. In this paper we present recent results on Sm 2+ in a series of MFCl (M = Sr, Ba, Ca) host lattices. Luminescence spectra and decay properties as a function of

Ab initio study of charge transfer between lithium and aromatic hydrocarbons. Can the results be directly transferred to the lithium-graphene interaction?

Science.gov (United States)

Sadlej-Sosnowska, N

2014-08-28

We have used electronic density calculations to study neutral complexes of Li with aromatic hydrocarbons. The charge transferred between a Li atom and benzene, coronene, circumcoronene, and circumcircumcoronene has been studied by ab initio methods (at the HF and MP2 level). Toward this aim, the method of integrating electron density in two cuboid fragments of space was applied. One of the fragments was constructed so that it enclosed the bulk of the electron density of lithium; the second, the bulk of the electron density of hydrocarbon. It was found that for each complex two conformations were identified: the most stable with a greater vertical Li-hydrocarbon distance, on the order of 2.5 Å, and another of higher energy with a corresponding distance less than 2 Å. In all cases the transfer of a fractional number, 0.1-0.3 electrons, between Li and hydrocarbon was found; however, the direction of the transfer was not the same in all complexes investigated. The structures of complexes of the first configuration could be represented as Li(σ-)···AH(σ+), whereas the opposite direction of charge transfer was found for complexes of the second configuration, with higher energy. The directions of the dipole moments in the complexes supported these conclusions because they directly measure the redistribution of electron density in a complex with respect to substrates.

Simple synthesis, structure and ab initio study of 1,4-benzodiazepine-2,5-diones

Science.gov (United States)

Jadidi, Khosrow; Aryan, Reza; Mehrdad, Morteza; Lügger, Thomas; Ekkehardt Hahn, F.; Ng, Seik Weng

2004-04-01

A simple procedure for the synthesis of pyrido[2,1-c][1,4] benzodiazepine-6,12-dione ( 1) and 1,4-benzodiazepine-2,5-diones ( 2a- 2d), using microwave irradiation and/or conventional heating is reported. The configuration of 1 was determined by single-crystal X-ray diffraction. A detailed ab initio B3LYP/6-31G* calculation of structural parameters and substituent effects on ring inversion barriers (Δ G#) and also free energy differences (Δ G0) for benzodiazepines are reported.

Relativistic configuration-interaction calculations of electric dipole n=2−n=3 transitions for medium-charge Li-like ions

Energy Technology Data Exchange (ETDEWEB)

Deng, Banglin, E-mail: banglindeng@yahoo.cn [Department of Applied Physics, Chengdu University of Technology, Chengdu 610059, Sichuan (China); Jiang, Gang [Institute of Atomic and Molecular Physics, Sichuan University, Chengdu 610065, Sichuan (China); Zhang, Chuanyu [Department of Applied Physics, Chengdu University of Technology, Chengdu 610059, Sichuan (China)

2014-09-15

In this work, the multi-configuration Dirac–Fock and relativistic configuration-interaction methods have been used to calculate the transition wavelengths, electric dipole transition probabilities, line strengths, and absorption oscillator strengths for the 2s–3p, 2p–3s, and 2p–3d transitions in Li-like ions with nuclear charge Z=7–30. Our calculated values are in good agreement with previous experimental and theoretical results. We took the contributions from Breit interaction, finite nuclear mass corrections, and quantum electrodynamics corrections to the initial and final levels into account, and also found that the contributions from Breit interaction, self-energy, and vacuum polarization grow fast with increasing nuclear charge for a fixed configuration. The ratio of the velocity to length form of the transition rate (A{sub v}/A{sub l}) was used to estimate the accuracy of our calculations.

Configuration interaction calculations for the region of 76Ge

Science.gov (United States)

Brown, Alex

2017-09-01

I will present a short history of the configuration interaction Hamiltonians that have been developed for the (0f5 / 2 , 1p3 / 2 , 1p1 / 2 , 0g9 / 2) (jj 44) model space. This model space is appropriate for the region of nuclei bounded by the nickel isotopes for Z = 28 and the isotones with N = 50 . I will discuss results for the double-beta decay of 76Ge that lies in the jj 44 region. I will show results for the structure of nuclei around 76Ge for some selected data from gamma decay, Gamow-Teller beta decay, charge-exchange reactions, one-nucleon transfer reactions, and two-nucleon transfer reactions. This work was supported by NSF Grant PHY-1404442.

Accelerating Full Configuration Interaction Calculations for Nuclear Structure

International Nuclear Information System (INIS)

Yang, Chao; Sternberg, Philip; Maris, Pieter; Ng, Esmond; Sosonkina, Masha; Le, Hung Viet; Vary, James; Yang, Chao

2008-01-01

One of the emerging computational approaches in nuclear physics is the full configuration interaction (FCI) method for solving the many-body nuclear Hamiltonian in a sufficiently large single-particle basis space to obtain exact answers - either directly or by extrapolation. The lowest eigenvalues and corresponding eigenvectors for very large, sparse and unstructured nuclear Hamiltonian matrices are obtained and used to evaluate additional experimental quantities. These matrices pose a significant challenge to the design and implementation of efficient and scalable algorithms for obtaining solutions on massively parallel computer systems. In this paper, we describe the computational strategies employed in a state-of-the-art FCI code MFDn (Many Fermion Dynamics - nuclear) as well as techniques we recently developed to enhance the computational efficiency of MFDn. We will demonstrate the current capability of MFDn and report the latest performance improvement we have achieved. We will also outline our future research directions

Ab initio results for intermediate-mass, open-shell nuclei

Science.gov (United States)

Baker, Robert B.; Dytrych, Tomas; Launey, Kristina D.; Draayer, Jerry P.

2017-01-01

A theoretical understanding of nuclei in the intermediate-mass region is vital to astrophysical models, especially for nucleosynthesis. Here, we employ the ab initio symmetry-adapted no-core shell model (SA-NCSM) in an effort to push first-principle calculations across the sd-shell region. The ab initio SA-NCSM's advantages come from its ability to control the growth of model spaces by including only physically relevant subspaces, which allows us to explore ultra-large model spaces beyond the reach of other methods. We report on calculations for 19Ne and 20Ne up through 13 harmonic oscillator shells using realistic interactions and discuss the underlying structure as well as implications for various astrophysical reactions. This work was supported by the U.S. NSF (OCI-0904874 and ACI -1516338) and the U.S. DOE (DE-SC0005248), and also benefitted from the Blue Waters sustained-petascale computing project and high performance computing resources provided by LSU.

Ab Initio Many-Body Calculations Of Nucleon-Nucleus Scattering

Energy Technology Data Exchange (ETDEWEB)

Quaglioni, S; Navratil, P

2008-12-17

We develop a new ab initio many-body approach capable of describing simultaneously both bound and scattering states in light nuclei, by combining the resonating-group method with the use of realistic interactions, and a microscopic and consistent description of the nucleon clusters. This approach preserves translational symmetry and Pauli principle. We outline technical details and present phase shift results for neutron scattering on {sup 3}H, {sup 4}He and {sup 10}Be and proton scattering on {sup 3,4}He, using realistic nucleon-nucleon (NN) potentials. Our A = 4 scattering results are compared to earlier ab initio calculations. We find that the CD-Bonn NN potential in particular provides an excellent description of nucleon-{sup 4}He S-wave phase shifts. We demonstrate that a proper treatment of the coupling to the n-{sup 10}Be continuum is successful in explaining the parity-inverted ground state in {sup 11}Be.

Exploring proton transfer in 1,2,3-triazole-triazolium dimer with ab initio method

Science.gov (United States)

Li, Ailin; Yan, Tianying; Shen, Panwen

Ab initio calculations are utilized to search for transition state structures for proton transfer in the 1,2,3-triazole-triazolium complexes on the basis of optimized dimers. The result suggests six transition state structures for single proton transfer in the complexes, most of which are coplanar. The energy barriers, between different stable and transition states structures with zero point energy (ZPE) corrections, show that proton transfer occurs at room temperature with coplanar configuration that has the lowest energy. The results clearly support that reorientation gives triazole flexibility for proton transfer.

Exploring proton transfer in 1,2,3-triazole-triazolium dimer with ab initio method

Energy Technology Data Exchange (ETDEWEB)

Li, Ailin; Yan, Tianying; Shen, Panwen [Department of Material Chemistry, Institute of New Energy Material Chemistry, Nankai University, Tianjin, 300071 (China)

2011-02-01

Ab initio calculations are utilized to search for transition state structures for proton transfer in the 1,2,3-triazole-triazolium complexes on the basis of optimized dimers. The result suggests six transition state structures for single proton transfer in the complexes, most of which are coplanar. The energy barriers, between different stable and transition states structures with zero point energy (ZPE) corrections, show that proton transfer occurs at room temperature with coplanar configuration that has the lowest energy. The results clearly support that reorientation gives triazole flexibility for proton transfer. (author)

Ab initio theories of electric transport in solid systems with reduced dimensions

International Nuclear Information System (INIS)

Weinberger, Peter

2003-01-01

Ab initio theories of electric transport in solid systems with reduced dimensions, i.e., systems that at best are characterized by two-dimensional translational invariance, are reviewed in terms of a fully relativistic description of the Kubo-Greenwood equation. As the use of this equation requires concepts such as collinearity and non-collinearity in order to properly define resistivities or resistances corresponding to particular magnetic configurations, respective consequences of the (local) density functional theory are recalled in quite a detailed manner. Furthermore, since theoretical descriptions of solid systems with reduced dimensions require quantum mechanical methods different from bulk systems (three-dimensional periodicity), the so-called Screened Korringa-Kohn-Rostoker (SKKR-) method for layered systems is introduced together with a matching coherent potential approximation (inhomogeneous CPA). The applications shown are mainly meant to illustrate various aspects of electric transport in solid systems with reduced dimensions and comprise not only current-in-plane (CIP) experiments, but also current perpendicular to the planes of atoms geometries, consequences of tunneling, and finite nanostructures at or on metallic substrates. In order to give a more complete view of available ab initio methods also a non-relativistic approach based on the Tight Binding Linear Combination of muffin tin orbitals (TB-LMTO-) method and the so-called Kubo-Landauer equation in terms of transmission and reflection matrices is presented. A compilation of references with respect to ab-initio type approaches not explicitly discussed in here finally concludes the discussion of electric properties in solid systems with reduced dimensions

Simulation of Molten Core-Concrete Interaction in oxide/metal stratified configuration with the TOLBIAC-ICB code

International Nuclear Information System (INIS)

Tourniaire, B.; Spindler, B.

2005-01-01

The frame of this work is the validation of the TOLBIAC-ICB code which is devoted to the simulation of Molten Core-Concrete Interaction (MCCI) for reactor safety analysis. Attention focuses here on the validation of TOLBIAC-ICB in configurations expected to be representative of the long term phase of MCCI i.e. during an interaction between an oxide/metal stratified corium melt and a concrete structure. Up to now the BETA tests performed at the Forschungszentrum Karlsruhe (FzK) are the only tests available to study such kind of interaction. The BETA tests are first described and the operating conditions are reminded. The TOLBIAC-ICB code is then briefly described, with emphasis on the models used for stratified configurations. The results of the simulations are discussed. A sensitivity study is also performed with the power generated in the oxide layer instead of the metal layer as in the test. This last calculation shows that the large axial ablation observed in the tests is probably due to the peculiar configuration of the test with input power in the bottom metal layer. Since in the reactor case the residual power would be mainly concentrated in the upper oxide layer, the conclusions of the BETA tests for the reactor applications, in term of axial ablation, must be derived with caution. (author)

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

Energy Technology Data Exchange (ETDEWEB)

Liu, Hanchao; Wang, Yimin; Bowman, Joel M. [Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, Georgia 30322 (United States)

2015-05-21

The calculation and characterization of the IR spectrum of liquid water have remained a challenge for theory. In this paper, we address this challenge using a combination of ab initio approaches, namely, a quantum treatment of IR spectrum using the ab initio WHBB water potential energy surface and a refined ab initio dipole moment surface. The quantum treatment is based on the embedded local monomer method, in which the three intramolecular modes of each embedded H{sub 2}O monomer are fully coupled and also coupled singly to each of six intermolecular modes. The new dipole moment surface consists of a previous spectroscopically accurate 1-body dipole moment surface and a newly fitted ab initio intrinsic 2-body dipole moment. A detailed analysis of the new dipole moment surface in terms of the coordinate dependence of the effective atomic charges is done along with tests of it for the water dimer and prism hexamer double-harmonic spectra against direct ab initio calculations. The liquid configurations are taken from previous molecular dynamics calculations of Skinner and co-workers, using the TIP4P plus E3B rigid monomer water potential. The IR spectrum of water at 300 K in the range of 0–4000 cm{sup −1} is calculated and compared with experiment, using the ab initio WHBB potential and new ab initio dipole moment, the q-TIP4P/F potential, which has a fixed-charged description of the dipole moment, and the TTM3-F potential and dipole moment surfaces. The newly calculated ab initio spectrum is in very good agreement with experiment throughout the above spectral range, both in band positions and intensities. This contrasts to results with the other potentials and dipole moments, especially the fixed-charge q-TIP4P/F model, which gives unrealistic intensities. The calculated ab initio spectrum is analyzed by examining the contribution of various transitions to each band.

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

International Nuclear Information System (INIS)

Liu, Hanchao; Wang, Yimin; Bowman, Joel M.

2015-01-01

The calculation and characterization of the IR spectrum of liquid water have remained a challenge for theory. In this paper, we address this challenge using a combination of ab initio approaches, namely, a quantum treatment of IR spectrum using the ab initio WHBB water potential energy surface and a refined ab initio dipole moment surface. The quantum treatment is based on the embedded local monomer method, in which the three intramolecular modes of each embedded H 2 O monomer are fully coupled and also coupled singly to each of six intermolecular modes. The new dipole moment surface consists of a previous spectroscopically accurate 1-body dipole moment surface and a newly fitted ab initio intrinsic 2-body dipole moment. A detailed analysis of the new dipole moment surface in terms of the coordinate dependence of the effective atomic charges is done along with tests of it for the water dimer and prism hexamer double-harmonic spectra against direct ab initio calculations. The liquid configurations are taken from previous molecular dynamics calculations of Skinner and co-workers, using the TIP4P plus E3B rigid monomer water potential. The IR spectrum of water at 300 K in the range of 0–4000 cm −1 is calculated and compared with experiment, using the ab initio WHBB potential and new ab initio dipole moment, the q-TIP4P/F potential, which has a fixed-charged description of the dipole moment, and the TTM3-F potential and dipole moment surfaces. The newly calculated ab initio spectrum is in very good agreement with experiment throughout the above spectral range, both in band positions and intensities. This contrasts to results with the other potentials and dipole moments, especially the fixed-charge q-TIP4P/F model, which gives unrealistic intensities. The calculated ab initio spectrum is analyzed by examining the contribution of various transitions to each band

Contextual interactions in grating plaid configurations are explained by natural image statistics and neural modeling

Directory of Open Access Journals (Sweden)

Udo Alexander Ernst

2016-10-01

Full Text Available Processing natural scenes requires the visual system to integrate local features into global object descriptions. To achieve coherent representations, the human brain uses statistical dependencies to guide weighting of local feature conjunctions. Pairwise interactions among feature detectors in early visual areas may form the early substrate of these local feature bindings. To investigate local interaction structures in visual cortex, we combined psychophysical experiments with computational modeling and natural scene analysis. We first measured contrast thresholds for 2x2 grating patch arrangements (plaids, which differed in spatial frequency composition (low, high or mixed, number of grating patch co-alignments (0, 1 or 2, and inter-patch distances (1° and 2° of visual angle. Contrast thresholds for the different configurations were compared to the prediction of probability summation (PS among detector families tuned to the four retinal positions. For 1° distance the thresholds for all configurations were larger than predicted by PS, indicating inhibitory interactions. For 2° distance, thresholds were significantly lower compared to PS when the plaids were homogeneous in spatial frequency and orientation, but not when spatial frequencies were mixed or there was at least one misalignment. Next, we constructed a neural population model with horizontal laminar structure, which reproduced the detection thresholds after adaptation of connection weights. Consistent with prior work, contextual interactions were medium-range inhibition and long-range, orientation-specific excitation. However, inclusion of orientation-specific, inhibitory interactions between populations with different spatial frequency preferences were crucial for explaining detection thresholds. Finally, for all plaid configurations we computed their likelihood of occurrence in natural images. The likelihoods turned out to be inversely related to the detection thresholds obtained

Determination of the electronic energy levels of colloidal nanocrystals using field-effect transistors and Ab-initio calculations.

Science.gov (United States)

Bisri, Satria Zulkarnaen; Degoli, Elena; Spallanzani, Nicola; Krishnan, Gopi; Kooi, Bart Jan; Ghica, Corneliu; Yarema, Maksym; Heiss, Wolfgang; Pulci, Olivia; Ossicini, Stefano; Loi, Maria Antonietta

2014-08-27

Colloidal nanocrystals electronic energy levels are determined by strong size-dependent quantum confinement. Understanding the configuration of the energy levels of nanocrystal superlattices is vital in order to use them in heterostructures with other materials. A powerful method is reported to determine the energy levels of PbS nanocrystal assemblies by combining the utilization of electric-double-layer-gated transistors and advanced ab-initio theory. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cr interaction in the formation of nano cluster of Y, Ti and O in bcc Fe an ab initio study

International Nuclear Information System (INIS)

Murali, D.; Panigrahi, B.K.; Valsakumar, M.C.; Chandra, Sharath; Sundar, C.S.

2008-01-01

Nanostructured ferritic alloys containing highly stable fine dispersion of yttrium oxide nano particles, produced by mechanical alloying, are promising structural materials for fast fission and fusion environments. Formation of Cr depleted and O enriched Y-Ti-O nanoclusters are observed in the atom probe analysis. Ab initio calculations based on density functional theory are carried out to understand the role of Cr atom interactions with other solute atoms (Y, Ti, O) and vacancies in the formation of nanocluster. The binding energy of clusters of Y-Ti-O in bcc Fe is found to be very high in the presence of vacancies. Our calculations are consistent with the atom probe observation of depletion of Cr atoms and enrichment of O atoms in the nanoclusters. (author)

Is HO3 minimum cis or trans? An analytic full-dimensional ab initio isomerization path.

Science.gov (United States)

Varandas, A J C

2011-05-28

The minimum energy path for isomerization of HO(3) has been explored in detail using accurate high-level ab initio methods and techniques for extrapolation to the complete basis set limit. In agreement with other reports, the best estimates from both valence-only and all-electron single-reference methods here utilized predict the minimum of the cis-HO(3) isomer to be deeper than the trans-HO(3) one. They also show that the energy varies by less than 1 kcal mol(-1) or so over the full isomerization path. A similar result is found from valence-only multireference configuration interaction calculations with the size-extensive Davidson correction and a correlation consistent triple-zeta basis, which predict the energy difference between the two isomers to be of only Δ = -0.1 kcal mol(-1). However, single-point multireference calculations carried out at the optimum triple-zeta geometry with basis sets of the correlation consistent family but cardinal numbers up to X = 6 lead upon a dual-level extrapolation to the complete basis set limit of Δ = (0.12 ± 0.05) kcal mol(-1). In turn, extrapolations with the all-electron single-reference coupled-cluster method including the perturbative triples correction yield values of Δ = -0.19 and -0.03 kcal mol(-1) when done from triple-quadruple and quadruple-quintuple zeta pairs with two basis sets of increasing quality, namely cc-cpVXZ and aug-cc-pVXZ. Yet, if added a value of 0.25 kcal mol(-1) that accounts for the effect of triple and perturbative quadruple excitations with the VTZ basis set, one obtains a coupled cluster estimate of Δ = (0.14 ± 0.08) kcal mol(-1). It is then shown for the first time from systematic ab initio calculations that the trans-HO(3) isomer is more stable than the cis one, in agreement with the available experimental evidence. Inclusion of the best reported zero-point energy difference (0.382 kcal mol(-1)) from multireference configuration interaction calculations enhances further the relative

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

International Nuclear Information System (INIS)

Levesque, M.

2010-11-01

Ferritic steels possibly strengthened by oxide dispersion are candidates as structural materials for generation IV and fusion nuclear reactors. Their use is limited by incomplete knowledge of the iron-chromium phase diagram at low temperatures and of the phenomena inducing preferential segregation of one element at grain boundaries or at surfaces. In this context, this work contributes to the multi-scale study of the model iron-chromium alloy and their free surfaces by numerical simulations. This study begins with ab initio calculations of properties related to the mixture of atoms of iron and chromium. We highlight complex dependency of the magnetic moments of the chromium atoms on their local chemical environment. Surface properties are also proving sensitive to magnetism. This is the case of impurity segregation of chromium in iron and of their interactions near the surface. In a second step, we construct a simple energy model for high numerical efficiency. It is based on pair interactions on a rigid lattice to which are given local chemical environment and temperature dependencies. With this model, we reproduce the ab initio results at zero temperature and experimental results at high temperature. We also deduce the solubility limits at all intermediate temperatures with mean field approximations that we compare to Monte Carlo simulations. The last step of our work is to introduce free surfaces in our model. We then study the effect of ab initio calculated bulk and surface properties on surface segregation.Finally, we calculate segregation isotherms. We therefore propose an evolution model of surface composition of iron-chromium alloys as a function of bulk composition. which are given local chemical environment and temperature dependencies. With this model, we reproduce the ab initio results at zero temperature and experimental results at high temperature. We also deduce the solubility limits at all intermediate temperatures with mean field approximations that

Configuration interaction in charge exchange spectra of tin and xenon

Science.gov (United States)

D'Arcy, R.; Morris, O.; Ohashi, H.; Suda, S.; Tanuma, H.; Fujioka, S.; Nishimura, H.; Nishihara, K.; Suzuki, C.; Kato, T.; Koike, F.; O'Sullivan, G.

2011-06-01

Charge-state-specific extreme ultraviolet spectra from both tin ions and xenon ions have been recorded at Tokyo Metropolitan University. The electron cyclotron resonance source spectra were produced from charge exchange collisions between the ions and rare gas target atoms. To identify unknown spectral lines of tin and xenon, atomic structure calculations were performed for Sn14+-Sn17+ and Xe16+-Xe20+ using the Hartree-Fock configuration interaction code of Cowan (1981 The Theory of Atomic Structure and Spectra (Berkeley, CA: University of California Press)). The energies of the capture states involved in the single-electron process that occurs in these slow collisions were estimated using the classical over-barrier model.

New ab initio adiabatic potential energy surfaces and bound state calculations for the singlet ground X˜ 1A1 and excited C˜ 1B2(21A') states of SO2

Science.gov (United States)

Kłos, Jacek; Alexander, Millard H.; Kumar, Praveen; Poirier, Bill; Jiang, Bin; Guo, Hua

2016-05-01

We report new and more accurate adiabatic potential energy surfaces (PESs) for the ground X˜ 1A1 and electronically excited C˜ 1B2(21A') states of the SO2 molecule. Ab initio points are calculated using the explicitly correlated internally contracted multi-reference configuration interaction (icMRCI-F12) method. A second less accurate PES for the ground X ˜ state is also calculated using an explicitly correlated single-reference coupled-cluster method with single, double, and non-iterative triple excitations [CCSD(T)-F12]. With these new three-dimensional PESs, we determine energies of the vibrational bound states and compare these values to existing literature data and experiment.

Non-orthogonal configuration interaction for the calculation of multielectron excited states

Energy Technology Data Exchange (ETDEWEB)

Sundstrom, Eric J., E-mail: eric.jon.sundstrom@berkeley.edu; Head-Gordon, Martin [Department of Chemistry, University of California Berkeley, Berkeley, California 94720, USA and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)

2014-03-21

We apply Non-orthogonal Configuration Interaction (NOCI) to molecular systems where multielectron excitations, in this case double excitations, play a substantial role: the linear polyenes and β-carotene. We demonstrate that NOCI when applied to systems with extended conjugation, provides a qualitatively correct wavefunction at a fraction of the cost of many other multireference treatments. We also present a new extension to this method allowing for purification of higher-order spin states by utilizing Generalized Hartree-Fock Slater determinants and the details for computing 〈S{sup 2}〉 for the ground and excited states.

Ab Initio Values of the Thermophysical Properties of Helium as Standards

Science.gov (United States)

Hurly, John J.; Moldover, Michael R.

2000-01-01

Recent quantum mechanical calculations of the interaction energy of pairs of helium atoms are accurate and some include reliable estimates of their uncertainty. We combined these ab initio results with earlier published results to obtain a helium-helium interatomic potential that includes relativistic retardation effects over all ranges of interaction. From this potential, we calculated the thermophysical properties of helium, i.e., the second virial coefficients, the dilute-gas viscosities, and the dilute-gas thermal conductivities of 3He, 4He, and their equimolar mixture from 1 K to 104 K. We also calculated the diffusion and thermal diffusion coefficients of mixtures of 3He and 4He. For the pure fluids, the uncertainties of the calculated values are dominated by the uncertainties of the potential; for the mixtures, the uncertainties of the transport properties also include contributions from approximations in the transport theory. In all cases, the uncertainties are smaller than the corresponding experimental uncertainties; therefore, we recommend the ab initio results be used as standards for calibrating instruments relying on these thermophysical properties. We present the calculated thermophysical properties in easy-to-use tabular form. PMID:27551630

Ab initio investigation of barium-scandium-oxygen coatings on tungsten for electron emitting cathodes

Science.gov (United States)

Vlahos, Vasilios; Booske, John H.; Morgan, Dane

2010-02-01

Microwave, x-ray, and radio-frequency radiation sources require a cathode emitting electrons into vacuum. Thermionic B-type dispenser cathodes consist of BaxOz coatings on tungsten (W), where the surface coatings lower the W work function and enhance electron emission. The new and promising class of scandate cathodes modifies the B-type surface through inclusion of Sc, and their superior emissive properties are also believed to stem from the formation of a low work function surface alloy. In order to better understand these cathode systems, density-functional theory (DFT)-based ab initio modeling is used to explore the stability and work function of BaxScyOz on W(001) monolayer-type surface structures. It is demonstrated how surface depolarization effects can be calculated easily using ab initio calculations and fitted to an analytic depolarization equation. This approach enables the rapid extraction of the complete depolarization curve (work function versus coverage relation) from relatively few DFT calculations, useful for understanding and characterizing the emitting properties of novel cathode materials. It is generally believed that the B-type cathode has some concentration of Ba-O dimers on the W surface, although their structure is not known. Calculations suggest that tilted Ba-O dimers are the stable dimer surface configuration and can explain the observed work function reduction corresponding to various dimer coverages. Tilted Ba-O dimers represent a new surface coating structure not previously proposed for the activated B-type cathode. The thermodynamically stable phase of Ba and O on the W surface was identified to be the Ba0.25O configuration, possessing a significantly lower Φ value than any of the Ba-O dimer configurations investigated. The identification of a more stable Ba0.25O phase implies that if Ba-O dimers cover the surface of emitting B-type cathodes, then a nonequilibrium steady state must dominate the emitting surface. The identification of

Critical comparison between equation of motion-Green's function methods and configuration interaction methods: analysis of methods and applications

International Nuclear Information System (INIS)

Freed, K.F.; Herman, M.F.; Yeager, D.L.

1980-01-01

A description is provided of the common conceptual origins of many-body equations of motion and Green's function methods in Liouville operator formulations of the quantum mechanics of atomic and molecular electronic structure. Numerical evidence is provided to show the inadequacies of the traditional strictly perturbative approaches to these methods. Nonperturbative methods are introduced by analogy with techniques developed for handling large configuration interaction calculations and by evaluating individual matrix elements to higher accuracy. The important role of higher excitations is exhibited by the numerical calculations, and explicit comparisons are made between converged equations of motion and configuration interaction calculations for systems where a fundamental theorem requires the equality of the energy differences produced by these different approaches. (Auth.)

Core structure of screw dislocations in Fe from first-principles; Simulation ab initio des coeurs de dislocation vis dans le fer

Energy Technology Data Exchange (ETDEWEB)

Ventelon, L

2008-11-15

The various methods appropriate for the simulation of dislocations within first-principles calculations have been set up, improved and compared between them. They have been applied to study screw dislocations in body-centered cubic iron using the SIESTA code. A non-degenerate core structure is obtained; its detailed analysis reveals a dilatation effect. Taking it into account in an anisotropic elasticity model, allows explaining the cell-size dependence of the energetics, obtained within the dipole approach. The Peierls potential obtained in ab initio suggests that the metastable core configuration at halfway position in the Peierls barrier, predicted by empirical potential, does not exist. We show how to construct tri-periodic cells optimized to study kinked dislocations. Using empirical potential, we demonstrate the feasibility of ab initio calculations of Peierls stress and kink formation. (author)

Electronic spectra of DyF studied by four-component relativistic configuration interaction methods

Energy Technology Data Exchange (ETDEWEB)

Yamamoto, Shigeyoshi, E-mail: syamamot@lets.chukyo-u.ac.jp [School of International Liberal Studies, Chukyo University, 101-2 Yagoto-Honmachi, Showa-ku, Nagoya 466-8666 (Japan); Tatewaki, Hiroshi [Institute of Advanced Studies in Artificial Intelligence, Chukyo University, Toyota 470-0393 (Japan); Graduate School of Natural Sciences, Nagoya City University, Aichi 467-8501 (Japan)

2015-03-07

The electronic states of the DyF molecule below 3.0 eV are studied using 4-component relativistic CI methods. Spinors generated by the average-of-configuration Hartree-Fock method with the Dirac-Coulomb Hamiltonian were used in CI calculations by the KRCI (Kramers-restricted configuration interaction) program. The CI reference space was generated by distributing 11 electrons among the 11 Kramers pairs composed mainly of Dy [4f], [6s], [6p] atomic spinors, and double excitations are allowed from this space to the virtual molecular spinors. The CI calculations indicate that the ground state has the dominant configuration (4f{sup 9})(6s{sup 2})(Ω = 7.5). Above this ground state, 4 low-lying excited states (Ω = 8.5, 7.5, 7.5, 7.5) are found with dominant configurations (4f{sup 10})(6s). These results are consistent with the experimental studies of McCarthy et al. Above these 5 states, 2 states were observed at T{sub 0} = 2.39 eV, 2.52 eV by McCarthy et al. and were named as [19.3]8.5 and [20.3]8.5. McCarthy et al. proposed that both states have dominant configurations (4f{sup 9})(6s)(6p), but these configurations are not consistent with the large R{sub e}’s (∼3.9 a.u.) estimated from the observed rotational constants. The present CI calculations provide near-degenerate states of (4f{sup 10})(6p{sub 3/2,1/2}), (4f{sup 10})(6p{sub 3/2,3/2}), and (4f{sup 9})(6s)(6p{sub 3/2,1/2}) at around 3 eV. The former two states have larger R{sub e} (3.88 a.u.) than the third, so that it is reasonable to assign (4f{sup 10})(6p{sub 3/2,1/2}) to [19.3]8.5 and (4f{sup 10})(6p{sub 3/2,3/2}) to [20.3]8.5.

Understanding and improving the efficiency of full configuration interaction quantum Monte Carlo.

Science.gov (United States)

Vigor, W A; Spencer, J S; Bearpark, M J; Thom, A J W

2016-03-07

Within full configuration interaction quantum Monte Carlo, we investigate how the statistical error behaves as a function of the parameters which control the stochastic sampling. We define the inefficiency as a measure of the statistical error per particle sampling the space and per time step and show there is a sizeable parameter regime where this is minimised. We find that this inefficiency increases sublinearly with Hilbert space size and can be reduced by localising the canonical Hartree-Fock molecular orbitals, suggesting that the choice of basis impacts the method beyond that of the sign problem.

Understanding and improving the efficiency of full configuration interaction quantum Monte Carlo

Energy Technology Data Exchange (ETDEWEB)

Vigor, W. A.; Bearpark, M. J. [Department of Chemistry, Imperial College London, Exhibition Road, London SW7 2AZ (United Kingdom); Spencer, J. S. [Department of Physics, Imperial College London, Exhibition Road, London SW7 2AZ (United Kingdom); Department of Materials, Imperial College London, Exhibition Road, London SW7 2AZ (United Kingdom); Thom, A. J. W. [Department of Chemistry, Imperial College London, Exhibition Road, London SW7 2AZ (United Kingdom); University Chemical Laboratory, Lensfield Road, Cambridge CB2 1EW (United Kingdom)

2016-03-07

Within full configuration interaction quantum Monte Carlo, we investigate how the statistical error behaves as a function of the parameters which control the stochastic sampling. We define the inefficiency as a measure of the statistical error per particle sampling the space and per time step and show there is a sizeable parameter regime where this is minimised. We find that this inefficiency increases sublinearly with Hilbert space size and can be reduced by localising the canonical Hartree–Fock molecular orbitals, suggesting that the choice of basis impacts the method beyond that of the sign problem.

Hydrogen bonding interactions in PN...HX complexes: DFT and ab initio studies of structure, properties and topology.

Science.gov (United States)

Varadwaj, Pradeep Risikrishna

2010-05-01

Spin-restricted DFT (X3LYP and B3LYP) and ab initio (MP2(fc) and CCSD(fc)) calculations in conjunction with the Aug-CC-pVDZ and Aug-CC-pVTZ basis sets were performed on a series of hydrogen bonded complexes PN...HX (X = F, Cl, Br) to examine the variations of their equilibrium gas phase structures, energetic stabilities, electronic properties, and vibrational characteristics in their electronic ground states. In all cases the complexes were predicted to be stable with respect to the constituent monomers. The interaction energy (Delta E) calculated using a super-molecular model is found to be in this order: PN...HF > PN...HCl > PN...HBr in the series examined. Analysis of various physically meaningful contributions arising from the Kitaura-Morokuma (KM) and reduced variational space self-consistent-field (RVS-SCF) energy decomposition procedures shows that the electrostatic energy has significant contribution to the over-all interaction energy. Dipole moment enhancement (Delta mu) was observed in these complexes expected of predominant dipole-dipole electrostatic interaction and was found to follow the trend PN...HF > PN...HCl > PN...HBr at the CCSD level. However, the DFT (X3LYP and B3LYP) and MP2 levels less accurately determined these values (in this order HF 0, nabla(2)rho(c) > 0 and H(c) > 0 at the BCP) whilst the bonds in PN (rho(c) > 0, nabla(2)rho(c) > 0 and H(c) 0, nabla(2)rho(c) BD*(HX) delocalization.

Relativistic configuration-interaction calculation of the correlation energies of heliumlike ions. Revision 1

International Nuclear Information System (INIS)

Cheng, K.T.; Chen, M.H.; Johnson, W.R.

1994-04-01

A new relativistic configuration-interaction (CI) method using B-spline basis functions has been developed to study the correlation energies of two-electron heliumlike ions. Based on the relativistic no-pair Hamiltonian, the CI equation leads to a symmetric eigenvalue problem involving large, dense matrices. Davidson's method is used to obtain the lowest few eigenenergies and eigenfunctions. Results on transition energies and finite structure splittings for heliumlike ions are in very good agreement with experiment throughout the periodic table

Interaction potentials for multiquark states from instantons and other background gauge field configurations

International Nuclear Information System (INIS)

Warner, R.C.; Joshi, G.C.

1979-01-01

A simple rule is presented for calculating the contributions to the interaction potentials between constituent particles for a family of multiquark states, due to the presence of a semi-classical gauge field configuration which exists in a single SU(2) subgroup of colour SU(3). In multiquark states beyond the baryon many-body potential terms are found. The static (Wilson loop) limit is sufficient to elucidate the dependence of the potential on the colour structure of the multiquark state

Weak interactions in Graphane/BN systems under static electric fields—A periodic ab-initio study.

Science.gov (United States)

Steinkasserer, Lukas Eugen Marsoner; Gaston, Nicola; Paulus, Beate

2015-04-21

Ab-initio calculations via periodic Hartree-Fock (HF) and local second-order Møller-Plesset perturbation theory (LMP2) are used to investigate the adsorption properties of combined Graphane/boron nitride systems and their response to static electric fields. It is shown how the latter can be used to alter both structural as well as electronic properties of these systems.

Electronic properties of liquid Hg-In alloys : Ab-initio molecular dynamics study

International Nuclear Information System (INIS)

Sharma, Nalini; Ahluwalia, P. K.; Thakur, Anil

2016-01-01

Ab-initio molecular dynamics simulations are performed to study the structural properties of liquid Hg-In alloys. The interatomic interactions are described by ab-initio pseudopotentials given by Troullier and Martins. Three liquid Hg-In alloys (Hg_1_0In_9_0, Hg_3_0In_7_0_,_. Hg_5_0In_5_0, Hg_7_0In_3_0, and Hg_9_0Pb_1_0) at 299 K are considered. The calculated results for liquid Hg (l-Hg) and lead (l-In) are also drawn. Along with the calculated results of considered five liquid alloys of Hg-In alloy. The results obtained from electronic properties namely total density of state and partial density of states help to find the local arrangement of Hg and In atoms and the presence of liquid state in the considered five alloys.

Ab initio calculation of the electronic absorption spectrum of liquid water

International Nuclear Information System (INIS)

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

2014-01-01

The electronic absorption spectrum of liquid water was investigated by coupling a one-body energy decomposition scheme to configurations generated by classical and Born-Oppenheimer Molecular Dynamics (BOMD). A Frenkel exciton Hamiltonian formalism was adopted and the excitation energies in the liquid phase were calculated with the equation of motion coupled cluster with single and double excitations method. Molecular dynamics configurations were generated by different approaches. Classical MD were carried out with the TIP4P-Ew and AMOEBA force fields. The BLYP and BLYP-D3 exchange-correlation functionals were used in BOMD. Theoretical and experimental results for the electronic absorption spectrum of liquid water are in good agreement. Emphasis is placed on the relationship between the structure of liquid water predicted by the different models and the electronic absorption spectrum. The theoretical gas to liquid phase blue-shift of the peak positions of the electronic absorption spectrum is in good agreement with experiment. The overall shift is determined by a competition between the O–H stretching of the water monomer in liquid water that leads to a red-shift and polarization effects that induce a blue-shift. The results illustrate the importance of coupling many-body energy decomposition schemes to molecular dynamics configurations to carry out ab initio calculations of the electronic properties in liquid phase

Ab initio model of porous periclase

International Nuclear Information System (INIS)

Drummond, Neil D.; Swift, Damian C.; Ackland, Graeme J.

2004-01-01

A two-phase equilibrium equation of state (EOS) for periclase (MgO) was constructed using ab initio quantum mechanics, including a rigorous calculation of quasiharmonic phonon modes. Much of the shock wave data reported for periclase is on porous material. We compared the theoretical EOS with porous data using a simple 'snowplough' treatment and also a model using finite equilibration rates suitable for continuum mechanics simulations. (This model has been applied previously to various heterogeneous explosives as well as other porous materials.) The results were consistent and matched the data well at pressures above the regime affected by strength - and ramp-wave formation - during compaction. Ab initio predictions of the response of porous material have been cited recently as a novel and advanced capability; we feel that this is a fairly routine extension to established ab initio techniques

Ab initio derivation of model energy density functionals

International Nuclear Information System (INIS)

Dobaczewski, Jacek

2016-01-01

I propose a simple and manageable method that allows for deriving coupling constants of model energy density functionals (EDFs) directly from ab initio calculations performed for finite fermion systems. A proof-of-principle application allows for linking properties of finite nuclei, determined by using the nuclear nonlocal Gogny functional, to the coupling constants of the quasilocal Skyrme functional. The method does not rely on properties of infinite fermion systems but on the ab initio calculations in finite systems. It also allows for quantifying merits of different model EDFs in describing the ab initio results. (letter)

Large-scale parallel configuration interaction. I. Nonrelativisticand scalar-relativistic general active space implementationwith application to (Rb-Ba)+

DEFF Research Database (Denmark)

Knecht, Stefan; Jensen, Hans Jørgen Aagaard; Fleig, Timo

2008-01-01

We present a parallel implementation of a string-driven general active space configuration interaction program for nonrelativistic and scalar-relativistic electronic-structure calculations. The code has been modularly incorporated in the DIRAC quantum chemistry program package. The implementation...

Spin-Orbit Effect on the Molecular Properties of TeXn (X = F, Cl, Br, and I; n = 1, 2, and 4): A Density Functional Theory and Ab Initio Study.

Science.gov (United States)

Moon, Jiwon; Kim, Joonghan

2016-09-29

Density functional theory (DFT) and ab initio calculations, including spin-orbit coupling (SOC), were performed to investigate the spin-orbit (SO) effect on the molecular properties of tellurium halides, TeXn (X = F, Cl, Br, and I; n = 1, 2, and 4). SOC elongates the Te-X bond and slightly reduces the vibrational frequencies. Consideration of SOC leads to better agreement with experimental values. Møller-Plesset second-order perturbation theory (MP2) seriously underestimates the Te-X bond lengths. In contrast, B3LYP significantly overestimates them. SO-PBE0 and multireference configuration interactions with the Davidson correction (MRCI+Q), which include SOC via a state-interaction approach, give the Te-I bond length of TeI2 that matches the experimental value. On the basis of the calculated thermochemical energy and optimized molecular structure, TeI4 is unlikely to be stable. The use of PBE0 including SOC is strongly recommended for predicting the molecular properties of Te-containing compounds.

Ab initio van der waals interactions in simulations of water alter structure from mainly tetrahedral to high-density-like

DEFF Research Database (Denmark)

Møgelhøj, Andreas; Kelkkanen, Kari André; Wikfeldt, K Thor

2011-01-01

The structure of liquid water at ambient conditions is studied in ab initio molecular dynamics simulations in the NVE ensemble using van der Waals (vdW) density-functional theory, i.e., using the new exchange-correlation functionals optPBE-vdW and vdW-DF2, where the latter has softer nonlocal...... protocol could cause the deviation. An O-O PCF consisting of a linear combination of 70% from vdW-DF2 and 30% from low-density liquid water, as extrapolated from experiments, reproduces near-quantitatively the experimental O-O PCF for ambient water. This suggests the possibility that the new functionals...... shows some resemblance with experiment for high-density water ( Soper , A. K. and Ricci , M. A. Phys. Rev. Lett. 2000 , 84 , 2881 ), but not directly with experiment for ambient water. Considering the accuracy of the new functionals for interaction energies, we investigate whether the simulation...

Ab-initio investigation of spin-dependent transport properties in Fe-doped armchair graphyne nanoribbons

Energy Technology Data Exchange (ETDEWEB)

GolafroozShahri, S.; Roknabadi, M.R., E-mail: roknabad@um.ac.ir; Shahtahmasebi, N.; Behdani, M.

2016-12-15

An ab-initio study on the spin-polarized transport properties of H-passivated Fe-doped graphyne nanoribbons is presented. All the calculations were based on density functional theory (DFT). Doping single magnetic atom on graphyne nanoribbons leads to metallicity which can significantly improve the conductivity. The currents are not degenerate for both up and down spin electrons and they are considerably spin-polarized. Therefore a relatively good spin-filtering can be expected. For configurations with geometric symmetry spin-rectifying is also observed. Therefore they can be applied as a dual spin-filter or a dual spin-diode in spintronic equipment. - Highlights: • The existence of Fe additional electrons lead to metallicity. • Doping magnetic atom on studied n-AGyNRs, has improved the conductance of nanoribbons. • The current for both spin electrons is considerably spin-polarized. • Threshold voltage decreased by increasing the width of ribbon. • For configurations with geometric symmetry spin-rectifying effect was also observed.

Proposal for novel curcumin derivatives as potent inhibitors against Alzheimer's disease: Ab initio molecular simulations on the specific interactions between amyloid-beta peptide and curcumin

Science.gov (United States)

Ota, Shintaro; Fujimori, Mitsuki; Ishimura, Hiromi; Shulga, Sergiy; Kurita, Noriyuki

2017-10-01

Accumulation of amyloid-β (Aβ) peptides in a brain is closely related with the pathogenesis of Alzheimer's disease. To suppress the production of Aβ peptides, we propose novel curcumin derivatives and investigate their binding properties with the amyloid precursor protein (APP), using protein-ligand docking as well as ab initio molecular simulations. Our proposed derivative (curcumin XIV) is found to have a large binding energy with APP and interacts strongly with the cleavage site Ala19 by secretase. It is thus expected that curcumin XIV can protect APP from the secretase attack and be a potent inhibitor against the production of Aβ peptides.

A sparse matrix based full-configuration interaction algorithm

International Nuclear Information System (INIS)

Rolik, Zoltan; Szabados, Agnes; Surjan, Peter R.

2008-01-01

We present an algorithm related to the full-configuration interaction (FCI) method that makes complete use of the sparse nature of the coefficient vector representing the many-electron wave function in a determinantal basis. Main achievements of the presented sparse FCI (SFCI) algorithm are (i) development of an iteration procedure that avoids the storage of FCI size vectors; (ii) development of an efficient algorithm to evaluate the effect of the Hamiltonian when both the initial and the product vectors are sparse. As a result of point (i) large disk operations can be skipped which otherwise may be a bottleneck of the procedure. At point (ii) we progress by adopting the implementation of the linear transformation by Olsen et al. [J. Chem Phys. 89, 2185 (1988)] for the sparse case, getting the algorithm applicable to larger systems and faster at the same time. The error of a SFCI calculation depends only on the dropout thresholds for the sparse vectors, and can be tuned by controlling the amount of system memory passed to the procedure. The algorithm permits to perform FCI calculations on single node workstations for systems previously accessible only by supercomputers

Study of wide band-gap crystal LiCaAlF6 by IR-reflection spectroscopy and ab initio calculations

International Nuclear Information System (INIS)

Novikova, N.N.; Klimin, S.A.; Mavrin, B.N.

2017-01-01

Polarized IR-reflection spectra and results of ab initio calculations of vibrational and electronic properties of LiCaAlF6 single crystal are presented. It is shown that the crystal band gap is direct. Experimental and theoretical parameters are obtained for dipole-active and all phonons, respectively, including silent modes. Experimental IR-reflection and Raman spectra are well described in the frame of results obtained by ab initio calculations. The peculiarities are discussed concerning the structure of electronic bands, the interatomic interactions, the character of lattice vibrations, and the phonon dispersion.

Magnetic properties of point defect interaction with impurity atoms in Fe-Cr alloys

Science.gov (United States)

Nguyen-Manh, D.; Lavrentiev, M. Yu.; Dudarev, S. L.

2009-04-01

An integrated ab initio and statistical Monte Carlo investigation has been recently carried out to model the thermodynamic and kinetic properties of Fe-Cr alloys. We found that the conventional Fe-Cr phase diagram is not adequate at low temperature region where the magnetic contribution to the free energy plays an important role in the prediction of an ordered Fe 15Cr phase and its negative enthalpy of formation. The origin of the anomalous thermodynamic and magnetic properties of Fe-Cr alloys can be understood using a tight-binding Stoner model combined with the charge neutrality condition. We investigate the environmental dependence of magnetic moment distributions for various self-interstitial atom dumbbells configurations using spin density maps found using density functional theory calculations. The mixed dumbbell Fe-Cr and Fe-Mn binding energies are found to be positive due to magnetic interactions. Finally, we discuss the relationship between the migration energy of vacancy in Fe-Cr alloys and magnetism at the saddle point configuration.

An ab initio model of electron transport in hematite (a-Fe2O3) basal planes

International Nuclear Information System (INIS)

Rosso, Kevin M.; Smith, Dayle MA; Dupuis, Michel

2003-01-01

Transport of conduction electrons through basal planes of the hematite lattice was modeled as a valence alternation of iron cations using ab initio molecular orbital calculations and electron transfer theory. A cluster approach was successfully implemented to compute electron transfer rate-controlling quantities such as the reorganization energy and electronic coupling matrix element. Localization of a conduction electron at an iron lattice site is accompanied by large iron/oxygen bond length increases that give rise to a large inner-sphere component of the reorganization energy. The interaction between the reactant and product electronic states in the crossing?point configuration is substantial and leads to an adiabatic electron transfer system. Electron transfer is predicted to possess a small positive activation energy that turns out to be in excellent agreement with values deduced from conductivity measurements. Measured electron mobility can be explained in terms of nearest neighbor electron hops without significant contribution from iron atoms further away. Comparison of the predicted maximum polaron binding energy with the predicted half bandwidth indicates compliance with the small polaron condition. Therefore the localized electron treatment is appropriate to describe electron transport in this system

An ab initio molecular

Indian Academy of Sciences (India)

mechanisms of two molecular crystals: An ab initio molecular dynamics ... for Computation in Molecular and Materials Science and Department of Chemistry, School of ..... NSAF Foundation of National Natural Science Foun- ... Matter 14 2717.

Coupling of ab initio density functional theory and molecular dynamics for the multiscale modeling of carbon nanotubes

International Nuclear Information System (INIS)

Ng, T Y; Yeak, S H; Liew, K M

2008-01-01

A multiscale technique is developed that couples empirical molecular dynamics (MD) and ab initio density functional theory (DFT). An overlap handshaking region between the empirical MD and ab initio DFT regions is formulated and the interaction forces between the carbon atoms are calculated based on the second-generation reactive empirical bond order potential, the long-range Lennard-Jones potential as well as the quantum-mechanical DFT derived forces. A density of point algorithm is also developed to track all interatomic distances in the system, and to activate and establish the DFT and handshaking regions. Through parallel computing, this multiscale method is used here to study the dynamic behavior of single-walled carbon nanotubes (SWCNTs) under asymmetrical axial compression. The detection of sideways buckling due to the asymmetrical axial compression is reported and discussed. It is noted from this study on SWCNTs that the MD results may be stiffer compared to those with electron density considerations, i.e. first-principle ab initio methods

Configuration interaction calculations and excitation rates of X-ray and EUV transitions in sulfurlike manganese

Energy Technology Data Exchange (ETDEWEB)

El-Maaref, A.A., E-mail: ahmed.maaref@azhar.edu.eg; Saddeek, Y.B.; Abou halaka, M.M.

2017-02-15

Highlights: • Fine-structure calculations of sulfurlike Mn have been performed using configuration interaction technique, CI. • The relativistic effects, Breit-Pauli Hameltonian, have been correlated to the CI calculations. • Excitation rates by electron impact of the Mn X ion have been evaluated up to ionization potential. - Abstract: Fine-structure calculations of energies and transition parameters have been performed using the configuration interaction technique (CI) as implemented in CIV3 code for sulfurlike manganese, Mn X. The calculations are executed in an intermediate coupling scheme using the Breit-Pauli Hamiltonian. As well as, energy levels and oscillator strengths are calculated using LANL code, where the calculations by LANL have been used to estimate the accuracy of the present CI calculations. The calculated energy levels, oscillator strengths, and lifetimes are in reasonable agreement with the published experimental and theoretical values. Electron impact excitation rates of the transitions emit soft X-ray and extreme ultraviolet (EUV) wavelengths have been evaluated. The level population densities are calculated using the collisional radiative model (CRM), as well. The collisional excitation rates and collision strengths have been calculated in the electron temperature range ≤ the ionization potential, ∼1–250 eV.

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

International Nuclear Information System (INIS)

Ito, A.; Kenmotsu, T.; Kikuhara, Y.; Inai, K.; Ohya, K.; Wang, Y.; Irle, S.; Morokuma, K.; Nakamura, H.

2009-01-01

Full text: To understand the plasma-wall interaction on divertor plates, we investigate the interaction of hydrogen atoms and carbon materials used in the high heat flux components by the use of the following simulations. Monte-Carlo (MC) method based on binary collision approximation can calculate the sputtering process of hydrogen atoms on the carbon material quickly. Classical molecular dynamics (MD) method employs multi-body potential models and can treat realistic structures of crystal and molecule. The ab-initio method can calculate electron energy in quantum mechanics, which is regarded as realistic potential for atoms. In the present paper, the interaction of the hydrogen and the carbon material is investigated using the multi-scale (MC, MD and ab-initio) methods. The bombardment of hydrogen atoms onto the carbon material is simulated by the ACAT-code of the MC method, which cannot represent the structure of crystal, and the MD method using modified reactive empirical bond order (REBO) potential, which treats single crystal graphite and amorphous carbon. Consequently, we clarify that the sputtering yield and the reflection rate calculated by the ACAT-code agree with those on the amorphous carbon calculated by the MD. Moreover, there are many kinds of REBO potential for the MD. Adsorption, reflection and penetration rates between a hydrogen atom and a graphene surface are calculated by the MD simulations using the two kinds of potential model. For the incident energy of less than 1 eV, the MD simulation using the modified REBO potential, which is based on Brenner's REBO potential in 2002, shows that reflection is dominant, while the most popular Brenner's REBO potential in 1990 shows that adsorption is dominant. This reflection of the low energy injection is caused by a small potential barrier for the hydrogen atom in the modified REBO potential. The small potential barrier is confirmed by the ab-initio calculations, which are hybrid DFT (B3LYP/cc-pVDZ), ab-initio

Ab initio calculation of molecular energies including parity violating interactions

International Nuclear Information System (INIS)

Bakasov, A.; Ha Taekyu; Quack, M.

1995-01-01

A new approach, RHF-CIS, based on the perturbation of the ground state RHF wave function by the CIS excitations, has been implemented for evaluation of energy of parity violating interaction in molecules, E pv . The earlier approach, RHF-SDE, was based on the perturbation of the RHF ground states by the single-determinant ''excitations'' (SDE). The results obtained show the dramatic difference between E pv values in the RHF-CIS framework and those in the RHF-SDE framework: the E pv values of the RHF-CIS formalism are more than one order of magnitude greater compared to the RHF-SDE formalism as well as the corresponding tensor components. The maximal total value obtained for hydrogen peroxide in the RHF-CIS framework is 3.661 X 10 -19 E H (DZ ** basis set) while the maximal E pv value for the RHF-SDE formalism is just 3.635 X 10 -20 E H (TZ basis set). It is remarkable that both in the RFH-CIS and in the RHF-SDE approaches the diagonal tensor components of E pv strictly follow the geometry of a molecule and are always different from zero at chiral conformations. The zeros of the total E pv at chiral geometries are now found to be the results of the interplay between the diagonal tensor components values. We have carried out exhaustive analysis of the RHF-SDE formalism and found that it is not sufficiently accurate for studies of E pv . To this end, we have completely reproduced the previous work, which has been done in the RHF-SDE frame-work, and developed it further, studying how the RHF-SDE results vary when changing size and quality of basis sets. This last resource does not save the RHF-SDE formalism for evaluations of E pv from the general failure. Packages of FORTRAN routines called ENWEAK/RHFSDE-93 and ENWEAK/RHFCIS-94 have been developed which run on top of an ab initio MO package. We used 6-31G and 6-31G**, DZ and DZ**, TZ and TZ**, and (10s, 6p,**) basis sets. We will discuss the importance of the present results for possible measurement of the parity

Equations of state of heavy metals: ab initio approaches; Equations d'etat des metaux lourds: approches ab initio

Energy Technology Data Exchange (ETDEWEB)

Bernard, S.; Jollet, F.; Jomard, G.; Siberchicot, B.; Torrent, M.; Zerah, G.; Amadon, B.; Bouchet, J.; Richard, N.; Robert, G. [CEA Bruyeres-le-Chatel, 91 (France)

2005-07-01

The determination of equations of states of heavy metals through ab initio calculation, i.e. without any adjustable parameter, allows to access to pressure and temperature thermodynamic conditions sometimes inaccessible to experiment. To perform such calculations, density functional theory (DFT) is a good starting point: when electronic densities are homogeneous enough, the local density approximation (LDA) remarkably accounts for thermodynamic properties of heavy metals, such as tantalum, or the light actinides, as well for static properties - equilibrium volume, elastic constants - as for dynamical quantities like phonon spectra. For heavier elements, like neptunium or plutonium, relativistic effects and strong electronic interactions must be taken into account, which requires more sophisticated theoretical approaches. (authors)

A permutationally invariant full-dimensional ab initio potential energy surface for the abstraction and exchange channels of the H + CH4 system

International Nuclear Information System (INIS)

Li, Jun; Chen, Jun; Zhao, Zhiqiang; Zhang, Dong H.; Xie, Daiqian; Guo, Hua

2015-01-01

We report a permutationally invariant global potential energy surface (PES) for the H + CH 4 system based on ∼63 000 data points calculated at a high ab initio level (UCCSD(T)-F12a/AVTZ) using the recently proposed permutation invariant polynomial-neural network method. The small fitting error (5.1 meV) indicates a faithful representation of the ab initio points over a large configuration space. The rate coefficients calculated on the PES using tunneling corrected transition-state theory and quasi-classical trajectory are found to agree well with the available experimental and previous quantum dynamical results. The calculated total reaction probabilities (J tot = 0) including the abstraction and exchange channels using the new potential by a reduced dimensional quantum dynamic method are essentially the same as those on the Xu-Chen-Zhang PES [Chin. J. Chem. Phys. 27, 373 (2014)

Explicit polarization (X-Pol) potential using ab initio molecular orbital theory and density functional theory.

Science.gov (United States)

Song, Lingchun; Han, Jaebeom; Lin, Yen-lin; Xie, Wangshen; Gao, Jiali

2009-10-29

The explicit polarization (X-Pol) method has been examined using ab initio molecular orbital theory and density functional theory. The X-Pol potential was designed to provide a novel theoretical framework for developing next-generation force fields for biomolecular simulations. Importantly, the X-Pol potential is a general method, which can be employed with any level of electronic structure theory. The present study illustrates the implementation of the X-Pol method using ab initio Hartree-Fock theory and hybrid density functional theory. The computational results are illustrated by considering a set of bimolecular complexes of small organic molecules and ions with water. The computed interaction energies and hydrogen bond geometries are in good accord with CCSD(T) calculations and B3LYP/aug-cc-pVDZ optimizations.

Ab Initio Liquid Water Dynamics in Aqueous TMAO Solution.

Science.gov (United States)

Usui, Kota; Hunger, Johannes; Sulpizi, Marialore; Ohto, Tatsuhiko; Bonn, Mischa; Nagata, Yuki

2015-08-20

Ab initio molecular dynamics (AIMD) simulations in trimethylamine N-oxide (TMAO)-D2O solution are employed to elucidate the effects of TMAO on the reorientational dynamics of D2O molecules. By decomposing the O-D groups of the D2O molecules into specific subensembles, we reveal that water reorientational dynamics are retarded considerably in the vicinity of the hydrophilic TMAO oxygen (O(TMAO)) atom, due to the O-D···O(TMAO) hydrogen-bond. We find that this reorientational motion is governed by two distinct mechanisms: The O-D group rotates (1) after breaking the O-D···O(TMAO) hydrogen-bond, or (2) together with the TMAO molecule while keeping this hydrogen-bond intact. While the orientational slow-down is prominent in the AIMD simulation, simulations based on force field models exhibit much faster dynamics. The simulated angle-resolved radial distribution functions illustrate that the O-D···O(TMAO) hydrogen-bond has a strong directionality through the sp(3) orbital configuration in the AIMD simulation, and this directionality is not properly accounted for in the force field simulation. These results imply that care must be taken when modeling negatively charged oxygen atoms as single point charges; force field models may not adequately describe the hydration configuration and dynamics.

Benchmarks for electronically excited states: Time-dependent density functional theory and density functional theory based multireference configuration interaction

DEFF Research Database (Denmark)

Silva-Junior, Mario R.; Schreiber, Marko; Sauer, Stephan P. A.

2008-01-01

Time-dependent density functional theory (TD-DFT) and DFT-based multireference configuration interaction (DFT/MRCI) calculations are reported for a recently proposed benchmark set of 28 medium-sized organic molecules. Vertical excitation energies, oscillator strengths, and excited-state dipole...

The controlled formation and cleavage of an intramolecular d8-d8 Pt-Pt interaction in a dinuclear cycloplatinated molecular "pivot-hinge".

Science.gov (United States)

Koo, Chi-Kin; Wong, Ka-Leung; Lau, Kai-Cheung; Wong, Wai-Yeung; Lam, Michael Hon-Wah

2009-08-03

The bis(diphenylphosphino)methane (dppm)-bridged dinuclear cycloplatinated complex {[Pt(L)](2)(mu-dppm)}(2+) (Pt(2)dppm; HL: 2-phenyl-6-(1H-pyrazol-3-yl)-pyridine) demonstrates interesting reversible "pivot-hinge"-like intramolecular motions in response to the protonation/deprotonation of L. In its protonated "closed" configuration, the two platinum(II) centers are held in position by intramolecular d(8)-d(8) Pt-Pt interaction. In its deprotonated "open" configuration, such Pt-Pt interaction is cleaved. To further understand the mechanism behind this hingelike motion, an analogous dinuclear cycloplatinated complex, {[Pt(L)](2)(mu-dchpm)}(2+) (Pt(2)dchpm) with bis(dicyclohexylphosphino)methane (dchpm) as the bridging ligand, was synthesized. From its protonation/deprotonation responses, it was revealed that aromatic pi-pi interactions between the phenyl moieties of the mu-dppm and the deprotonated pyrazolyl rings of L was essential to the reversible cleavage of the intramolecular Pt-Pt interaction in Pt(2)dppm. In the case of Pt(2)dchpm, spectroscopic and spectrofluorometric titrations as well as X-ray crystallography indicated that the distance between the two platinum(II) centers shrank upon deprotonation, thus causing a redshift in its room-temperature triplet metal-metal-to-ligand charge-transfer emission from 614 to 625 nm. Ab initio calculations revealed the presence of intramolecular hydrogen bonding between the deprotonated and negatively charged 1-pyrazolyl-N moiety and the methylene CH and phenyl C-H of the mu-dppm. The "open" configuration of the deprotonated Pt(2)dppm was estimated to be 19 kcal mol(-1) more stable than its alternative "closed" configuration. On the other hand, the open configuration of the deprotonated Pt(2)dchpm was 6 kcal mol(-1) less stable than its alternative closed configuration.

Ab Initio Potential Energy Surfaces for Both the Ground (X̃1A′ and Excited (A∼1A′′ Electronic States of HSiBr and the Absorption and Emission Spectra of HSiBr/DSiBr

Directory of Open Access Journals (Sweden)

Anyang Li

2012-01-01

Full Text Available Ab initio potential energy surfaces for the ground (X̃1A′ and excited (A˜A′′1 electronic states of HSiBr were obtained by using the single and double excitation coupled-cluster theory with a noniterative perturbation treatment of triple excitations and the multireference configuration interaction with Davidson correction, respectively, employing an augmented correlation-consistent polarized valence quadruple zeta basis set. The calculated vibrational energy levels of HSiBr and DSiBr of the ground and excited electronic states are in excellent agreement with the available experimental band origins. In addition, the absorption and emission spectra of HSiBr and DSiBr were calculated using an efficient single Lanczos propagation method and are in good agreement with the available experimental observations.

Criticality in the configuration-mixed interacting boson model: (1) U(5)-Q(χ)Q(χ) mixing

International Nuclear Information System (INIS)

Hellemans, V.; Van Isacker, P.; De Baerdemacker, S.; Heyde, K.

2007-01-01

The case of U(5)-Q(χ)Q(χ) mixing in the configuration-mixed interacting boson model is studied in its mean-field approximation. Phase diagrams with analytical and numerical solutions are constructed and discussed. Indications for first-order and second-order shape phase transitions can be obtained from binding energies and from critical exponents, respectively

Fish-robot interactions in a free-swimming environment: Effects of speed and configuration of robots on live fish

Science.gov (United States)

Butail, Sachit; Polverino, Giovanni; Phamduy, Paul; Del Sette, Fausto; Porfiri, Maurizio

2014-03-01

We explore fish-robot interactions in a comprehensive set of experiments designed to highlight the effects of speed and configuration of bioinspired robots on live zebrafish. The robot design and movement is inspired by salient features of attraction in zebrafish and includes enhanced coloration, aspect ratio of a fertile female, and carangiform/subcarangiformlocomotion. The robots are autonomously controlled to swim in circular trajectories in the presence of live fish. Our results indicate that robot configuration significantly affects both the fish distance to the robots and the time spent near them.

Ab initio valence calculations in chemistry

CERN Document Server

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

Ab initio adiabatic and quasidiabatic potential energy surfaces of H ...

Indian Academy of Sciences (India)

by protons and electrons has been studied to rational- ize the cosmic ... reference configuration interaction (icMRCI) to study .... total number of contracted configurations was 292058 .... numerical integration of dynamical equations. To cir-.

Bicanonical ab Initio Molecular Dynamics for Open Systems.

Science.gov (United States)

Frenzel, Johannes; Meyer, Bernd; Marx, Dominik

2017-08-08

Performing ab initio molecular dynamics simulations of open systems, where the chemical potential rather than the number of both nuclei and electrons is fixed, still is a challenge. Here, drawing on bicanonical sampling ideas introduced two decades ago by Swope and Andersen [ J. Chem. Phys. 1995 , 102 , 2851 - 2863 ] to calculate chemical potentials of liquids and solids, an ab initio simulation technique is devised, which introduces a fictitious dynamics of two superimposed but otherwise independent periodic systems including full electronic structure, such that either the chemical potential or the average fractional particle number of a specific chemical species can be kept constant. As proof of concept, we demonstrate that solvation free energies can be computed from these bicanonical ab initio simulations upon directly superimposing pure bulk water and the respective aqueous solution being the two limiting systems. The method is useful in many circumstances, for instance for studying heterogeneous catalytic processes taking place on surfaces where the chemical potential of reactants rather than their number is controlled and opens a pathway toward ab initio simulations at constant electrochemical potential.

Global characteristics of atomic spectra and their use for the analysis of spectra. IV. Configuration interaction effects

International Nuclear Information System (INIS)

Kucas, S.; Jonauskas, V.; Karazija, R.

1997-01-01

For pt.III see ibid., vol.52, p.639, 1995. Changes of the moments of atomic spectrum due to configuration interaction (CI), the CI strength, the average shift of the energy of a level due to its interaction with all levels of distant configuration and other global characteristics of CI effects in atoms are systematised and their expressions presented. The results of the calculation of those characteristics for the energy level spectra of the 3s3p 3 + 3s 2 3p3d configurations in Si isoelectronic series, 3p 5 3d N + 3p 6 3d N-2 4p + 3p 6 3d N-2 4f (N = 5, 6, 7, 8) in Cr, Mn, Fe and Co isoelectronic series, ns 2 np N + np N+2 at n = 2 - 5 and N = 2 - 4 in neutral atoms as well as for the characteristic emission spectra corresponding to the 3p 5 3d 9 + 3d 7 4p → 3d 8 transitions as well as for the Auger M 4.3 N 1 N 2.3 spectra in Kr and N 4.5 O 1 O 2.3 in Xe are given and compared with the same characteristics of the more complete experimental spectra. (orig.)

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

Czech Academy of Sciences Publication Activity Database

Čurík, Roman; Šulc, M.

2010-01-01

Roč. 43, č. 17 (2010), s. 175205 ISSN 0953-4075 R&D Projects: GA MŠk(CZ) OC10046; GA MŠk OC09079; GA AV ČR KJB400400803; GA ČR GA202/08/0631 Institutional research plan: CEZ:AV0Z40400503 Keywords : Ab initio calculations * Commonly used * DFT potential Subject RIV: CF - Physical ; The oretical Chemistry Impact factor: 1.902, year: 2010

PAC study of dynamic hyperfine interactions at {sup 111}In-doped Sc{sub 2}O{sub 3} semiconductor and comparison with ab initio calculations

Energy Technology Data Exchange (ETDEWEB)

Munoz, E. L., E-mail: munoz@fisica.unlp.edu.ar; Richard, D. [Departamento de Fisica and Instituto de Fisica La Plata (IFLP, CCT La Plata, CONICET) (Argentina); Carbonari, A. W. [Instituto de Pesquisas Energeticas y Nucleares-IPEN-CNEN/SP (Brazil); Errico, L. A.; Renteria, M. [Departamento de Fisica and Instituto de Fisica La Plata (IFLP, CCT La Plata, CONICET) (Argentina)

2010-04-15

Time-Differential {gamma}-{gamma} Perturbed-Angular-Correlation (PAC) measurements were performed in {sup 111}In-difussed Sc{sub 2}O{sub 3} polycrystals in order to characterize the electric-field-gradient tensor at {sup 111}Cd nuclei located at the two non-equivalent cation sites of the host lattice. The experimental data were compared with ab initio calculations performed using the Full-Potential Augmented Plane Wave plus local orbital (FP-APW+lo) method in the framework of the Density Functional Theory. The PAC experiments were carried out in air in the temperature range 10-900 K. The spectra present a strong damping below 650 K. This damping is associated with dynamic hyperfine interactions that were analyzed with the perturbation factor proposed by Baeverstam et al.. A model based in the population of impurity levels that are introduced by the Cd probes (supported by FP-APW+lo results) is proposed in order to explain the origin of the observed dynamic interactions.

Bayesian optimization for constructing potential energy surfaces of polyatomic molecules with the smallest number of ab initio calculations

Science.gov (United States)

Vargas-Hernandez, Rodrigo A.; v Krems, Roman

2017-04-01

We examine the application of kernel methods of machine learning for constructing potential energy surfaces (PES) of polyatomic molecules. In particular, we illustrate the application of Bayesian optimization with Gaussian processes as an efficient method for sampling the configuration space of polyatomic molecules. Bayesian optimization relies on two key components: a prior over an objective function and a mechanism for sampling the configuration space. We use Gaussian processes to model the objective function and various acquisition functions commonly used in computer science to quantify the accuracy of sampling. The PES is obtained through an iterative process of adding ab initio points at the locations maximizing the acquisition function and re-trainig the Gaussian process with new points added. We sample different PESs with one or many acquisition functions and show how the acquisition functions affect the construction of the PESs.

Adaptive jump barrier height in Monte Carlo configuration kinetics.

Energy Technology Data Exchange (ETDEWEB)

Leitner, Martin; Pfeiler, Wolfgang; Pueschl, Wolfgang [Dynamics of Condensed Systems, Faculty of Physics, University of Vienna, Strudlhofgasse 4, A-1090 Wien (Austria); Vogtenhuber, Doris [Computational Materials Science, Faculty of Physics, University of Vienna, Sensengasse 8, A-1090 Wien (Austria)

2008-07-01

In usual MC simulations of configuration kinetics atom jump probabilities are calculated from energies of the initial and/or final bound states of the moving atom, leaving aside the exact energy of the intermediate saddle point state. This energy may however be critically influenced by the local atomic environment. We propose a strategy to explicitly take account of this influence. The basis is ab initio calculation of representative jump paths in the framework of the nudged elastic band method. From these results, an influence function is derived which modifies the energy of the saddle point and therefore the effective jump barrier height as calculated from the initial and final states according to a cluster expansion scheme. The overall effect is demonstrated on the NiAl system.

Thermal transport in nanocrystalline Si and SiGe by ab initio based Monte Carlo simulation.

Science.gov (United States)

Yang, Lina; Minnich, Austin J

2017-03-14

Nanocrystalline thermoelectric materials based on Si have long been of interest because Si is earth-abundant, inexpensive, and non-toxic. However, a poor understanding of phonon grain boundary scattering and its effect on thermal conductivity has impeded efforts to improve the thermoelectric figure of merit. Here, we report an ab-initio based computational study of thermal transport in nanocrystalline Si-based materials using a variance-reduced Monte Carlo method with the full phonon dispersion and intrinsic lifetimes from first-principles as input. By fitting the transmission profile of grain boundaries, we obtain excellent agreement with experimental thermal conductivity of nanocrystalline Si [Wang et al. Nano Letters 11, 2206 (2011)]. Based on these calculations, we examine phonon transport in nanocrystalline SiGe alloys with ab-initio electron-phonon scattering rates. Our calculations show that low energy phonons still transport substantial amounts of heat in these materials, despite scattering by electron-phonon interactions, due to the high transmission of phonons at grain boundaries, and thus improvements in ZT are still possible by disrupting these modes. This work demonstrates the important insights into phonon transport that can be obtained using ab-initio based Monte Carlo simulations in complex nanostructured materials.

Network configuration of global R&D networks

DEFF Research Database (Denmark)

Hansen, Zaza Nadja Lee; Srai, Jagjit Singh

2011-01-01

, network configuration of global R&D has tended to focus on strategic elements with limited attention given operational effectiveness, or to interfaces with downstream manufacturing operations. Within OM literature, the drivers of configuration of global networks within, engineering, production, supply...... to R&D networks emerged, e.g. product features were more prominent in R&D networks. Furthermore, the study has shown extensive interaction with other operations, including many downstream manufacturing operations. By extending the OM configuration concepts to the configuration of R&D networks......Companies are increasingly globalising their R&D activities, both within the firms and with external partners, with consequent implications for their interaction with manufacturing operations. Previous research in R&D networks has focused on coordination, governance and support elements. However...

Communication: An adaptive configuration interaction approach for strongly correlated electrons with tunable accuracy

Energy Technology Data Exchange (ETDEWEB)

Schriber, Jeffrey B.; Evangelista, Francesco A. [Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, Georgia 30322 (United States)

2016-04-28

We introduce a new procedure for iterative selection of determinant spaces capable of describing highly correlated systems. This adaptive configuration interaction (ACI) determines an optimal basis by an iterative procedure in which the determinant space is expanded and coarse grained until self-consistency. Two importance criteria control the selection process and tune the ACI to a user-defined level of accuracy. The ACI is shown to yield potential energy curves of N{sub 2} with nearly constant errors, and it predicts singlet-triplet splittings of acenes up to decacene that are in good agreement with the density matrix renormalization group.

Communication: A benchmark-quality, full-dimensional ab initio potential energy surface for Ar-HOCO

International Nuclear Information System (INIS)

Conte, Riccardo; Bowman, Joel M.; Houston, Paul L.

2014-01-01

A full-dimensional, global ab initio potential energy surface (PES) for the Ar-HOCO system is presented. The PES consists of a previous intramolecular ab initio PES for HOCO [J. Li, C. Xie, J. Ma, Y. Wang, R. Dawes, D. Xie, J. M. Bowman, and H. Guo, J. Phys. Chem. A 116, 5057 (2012)], plus a new permutationally invariant interaction potential based on fitting 12 432 UCCSD(T)-F12a/aVDZ counterpoise-corrected energies. The latter has a total rms fitting error of about 25 cm −1 for fitted interaction energies up to roughly 12 000 cm −1 . Two additional fits are presented. One is a novel very compact permutational invariant representation, which contains terms only involving the Ar-atom distances. The rms fitting error for this fit is 193 cm −1 . The other fit is the widely used pairwise one. The pairwise fit to the entire data set has an rms fitting error of 427 cm −1 . All of these potentials are used in preliminary classical trajectory calculations of energy transfer with a focus on comparisons with the results using the benchmark potential

Communication: A benchmark-quality, full-dimensional ab initio potential energy surface for Ar-HOCO

Energy Technology Data Exchange (ETDEWEB)

Conte, Riccardo, E-mail: riccardo.conte@emory.edu, E-mail: jmbowma@emory.edu; Bowman, Joel M., E-mail: riccardo.conte@emory.edu, E-mail: jmbowma@emory.edu [Department of Chemistry and Cherry L. Emerson Center for Scientific Calculation, Emory University, Atlanta, Georgia 30322 (United States); Houston, Paul L., E-mail: paul.houston@cos.gatech.edu [School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332 (United States)

2014-04-21

A full-dimensional, global ab initio potential energy surface (PES) for the Ar-HOCO system is presented. The PES consists of a previous intramolecular ab initio PES for HOCO [J. Li, C. Xie, J. Ma, Y. Wang, R. Dawes, D. Xie, J. M. Bowman, and H. Guo, J. Phys. Chem. A 116, 5057 (2012)], plus a new permutationally invariant interaction potential based on fitting 12 432 UCCSD(T)-F12a/aVDZ counterpoise-corrected energies. The latter has a total rms fitting error of about 25 cm{sup −1} for fitted interaction energies up to roughly 12 000 cm{sup −1}. Two additional fits are presented. One is a novel very compact permutational invariant representation, which contains terms only involving the Ar-atom distances. The rms fitting error for this fit is 193 cm{sup −1}. The other fit is the widely used pairwise one. The pairwise fit to the entire data set has an rms fitting error of 427 cm{sup −1}. All of these potentials are used in preliminary classical trajectory calculations of energy transfer with a focus on comparisons with the results using the benchmark potential.

Ab initio study of stability and migration of H and He in hcp-Sc

International Nuclear Information System (INIS)

Yang, L; Zu, X T; Peng, S M; Long, X G; Gao, F; Heinisch, H L; Kurtz, R J

2011-01-01

Ab initio calculations based on density functional theory have been performed to determine the relative stabilities and migration of H and He atoms in hcp-Sc. The results show that the formation energy of an interstitial H or He atom is smaller than that of a corresponding substitutional atom. The tetrahedral (T) interstitial position is more stable than an octahedral (O) position for both He and H interstitials. The nudged elastic band method has been used to study the migration of interstitial H and He atoms in hcp-Sc. It is found that the migration energy barriers for H interstitials in hcp-Sc are significantly different from those for He interstitials, but their migration mechanisms are similar. In addition, the formation energies of five different configurations of a H-H pair were determined, revealing that the most stable configuration consists of two H atoms located at the second-neighbor tetrahedral interstitial sites along the hexagonal direction. The formation and relative stabilities of some small He clusters have also been investigated.

Relativistic configuration interaction treatment of generalized oscillator strength for krypton

International Nuclear Information System (INIS)

Wang Huangchun; Qu Yizhi; Liu Chunhua

2007-01-01

A fully relativistic configuration interaction method is developed to investigate the transition energies and general oscillator strengths of the lower lying states of krypton, for both optically allowed and optically forbidden transitions. The calculated results are in agreement with the recent experimental measurements. The calculated transition energies for the 5s and 5s' transitions are 9.970 and 10.717 eV, which agree with the experimental data of 10.033 and 10.643 eV. The calculated oscillator strengths are 0.211 and 0.170, comparable with the experimental results 0.214(±0.012) and 0.194 (±0.012), respectively. The momentum transfer positions (K 2 in a.u.) of the minimum and maximum GOSs in the 4s 2 4p 6 →4s 2 4p 5 (5s + 5s') transitions are 1.105 and 2.225, comparable with the measurements results 1.24 and 2.97. (authors)

Relativistic Configuration Interaction Treatment of Generalized Oscillator Strength for Krypton

Institute of Scientific and Technical Information of China (English)

WANG Huang-Chun; QU Yi-Zhi; LIU Chun-Hua

2007-01-01

A fully relativistic configuration interaction method is developed to investigate the transition energies and general oscillator strengths of the lower lying states of krypton, for both optically allowed and optically forbidden transitions. The calculated results are in agreement with the recent experimental measurements. The calculated transition energies for the 5s and 5s' transitions are 9.970 and 10.717eV, which agree with the experimental data of 10.033 and 10.643 eV. The calculated oscillator strengths are 0.211 and 0.170, comparable with the experimental results 0.214(±0.012) and 0.194 (±0.012), respectively. The momentum transfer positions ( K2 in a.u.) of the minimum and maximum GOSs in the 4s24p6 → 4s24p5 (5s + 5s') transitions are 1.105 and 2.225, comparable with the measurements results 1.24 and 2.97 [Phys. Rev. A 67 (2003) 062708].

Symmetries of cluster configurations

International Nuclear Information System (INIS)

Kramer, P.

1975-01-01

A deeper understanding of clustering phenomena in nuclei must encompass at least two interrelated aspects of the subject: (A) Given a system of A nucleons with two-body interactions, what are the relevant and persistent modes of clustering involved. What is the nature of the correlated nucleon groups which form the clusters, and what is their mutual interaction. (B) Given the cluster modes and their interaction, what systematic patterns of nuclear structure and reactions emerge from it. Are there, for example, families of states which share the same ''cluster parents''. Which cluster modes are compatible or exclude each other. What quantum numbers could characterize cluster configurations. There is no doubt that we can learn a good deal from the experimentalists who have discovered many of the features relevant to aspect (B). Symmetries specific to cluster configurations which can throw some light on both aspects of clustering are discussed

Adaptive vibrational configuration interaction (A-VCI): A posteriori error estimation to efficiently compute anharmonic IR spectra

Science.gov (United States)

Garnier, Romain; Odunlami, Marc; Le Bris, Vincent; Bégué, Didier; Baraille, Isabelle; Coulaud, Olivier

2016-05-01

A new variational algorithm called adaptive vibrational configuration interaction (A-VCI) intended for the resolution of the vibrational Schrödinger equation was developed. The main advantage of this approach is to efficiently reduce the dimension of the active space generated into the configuration interaction (CI) process. Here, we assume that the Hamiltonian writes as a sum of products of operators. This adaptive algorithm was developed with the use of three correlated conditions, i.e., a suitable starting space, a criterion for convergence, and a procedure to expand the approximate space. The velocity of the algorithm was increased with the use of a posteriori error estimator (residue) to select the most relevant direction to increase the space. Two examples have been selected for benchmark. In the case of H2CO, we mainly study the performance of A-VCI algorithm: comparison with the variation-perturbation method, choice of the initial space, and residual contributions. For CH3CN, we compare the A-VCI results with a computed reference spectrum using the same potential energy surface and for an active space reduced by about 90%.

Positron-attachment to small molecules: Vibrational enhancement of positron affinities with configuration interaction level of multi-component molecular orbital approach

Energy Technology Data Exchange (ETDEWEB)

Tachikawa, Masanori [Quantum Chemistry Division, Graduate School of NanoBioScience, Yokohama City University, 22-2 Seto, Kanazawa, Yokohama 236-0027 (Japan)

2015-12-31

To theoretically demonstrate the binding of a positron to small polarized molecules, we have calculated the vibrational averaged positron affinity (PA) values along the local vibrational contribution with the configuration interaction level of multi-component molecular orbital method. This method can take the electron-positron correlation contribution into account through single electronic - single positronic excitation configurations. The PA values are enhanced by including the local vibrational contribution from vertical PA values due to the anharmonicity of the potential.

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

Energy Technology Data Exchange (ETDEWEB)

Masrour, R., E-mail: rachidmasrour@hotmail.com [Laboratory of Materials, Processes, Environment and Quality, Cady Ayyed University, National School of Applied Sciences, BP. 63, 46000 Safi (Morocco); LMPHE (URAC 12), Faculty of Science, Mohammed V-Agdal University, Rabat (Morocco); Hlil, E.K. [Institut Néel, CNRS et Université Joseph Fourier, BP 166, F-38042 Grenoble Cedex 9 (France); Hamedoun, M. [Institute of Nanomaterials and Nanotechnologies, MAScIR, Rabat (Morocco); Benyoussef, A. [LMPHE (URAC 12), Faculty of Science, Mohammed V-Agdal University, Rabat (Morocco); Institute of Nanomaterials and Nanotechnologies, MAScIR, Rabat (Morocco); Hassan II Academy of Science and Technology, Rabat (Morocco); Mounkachi, O.; El Moussaoui, H. [Institute of Nanomaterials and Nanotechnologies, MAScIR, Rabat (Morocco)

2014-06-01

Self-consistent ab initio calculations, based on DFT (Density Functional Theory) approach and using FLAPW (Full potential Linear Augmented Plane Wave) method, are performed to investigate both electronic and magnetic properties of the MnSe lattice. Polarized spin and spin–orbit coupling are included in calculations within the framework of the antiferromagnetic state between two adjacent Mn lattices. Magnetic moments considered to lie along (001) axes are computed. Obtained data from ab initio calculations are used as input for the high temperature series expansions (HTSEs) calculations to compute other magnetic parameters. The zero-field high temperature static susceptibility series of the spin −4.28 nearest-neighbor Ising model on face centered cubic (fcc) and lattices is thoroughly analyzed by means of a power series coherent anomaly method (CAM). The exchange interaction between the magnetic atoms and the Néel temperature are deduced using the mean filed and HTSEs theories. - Highlights: • Ab initio calculations are used to investigate both electronic and magnetic properties of the MnSe alloys. • Obtained data from ab initio calculations are used as input for the HTSEs. • The Néel temperature is obtained for MnSe alloys.

Manipulating magnetism and conductance of an adatom-molecule junction on a metal surface: An ab initio study

DEFF Research Database (Denmark)

Tao, Kun; Stepanyuk, V.S.; Bruno, P.

2008-01-01

The state of the art ab initio calculations reveal the effect of a scanning tunneling microscopy tip on magnetic properties and conductance of a benzene-adatom sandwich on Cu(001). We concentrate on a benzene-Co system interacting with a Cr tip. Our studies give a clear evidence that magnetism...

Ab-initio ZORA calculations

NARCIS (Netherlands)

Faas, S.; Snijders, Jaap; van Lenthe, J.H.; HernandezLaguna, A; Maruani, J; McWeeny, R; Wilson, S

2000-01-01

In this paper we present the first application of the ZORA (Zeroth Order Regular Approximation of the Dirac Fock equation) formalism in Ab Initio electronic structure calculations. The ZORA method, which has been tested previously in the context of Density Functional Theory, has been implemented in

Ab initio study of point defects in magnesium oxide

International Nuclear Information System (INIS)

Gilbert, C. A.; Kenny, S. D.; Smith, R.; Sanville, E.

2007-01-01

Energetics of a variety of point defects in MgO have been considered from an ab initio perspective using density functional theory. The considered defects are isolated Schottky and Frenkel defects and interstitial pairs, along with a number of Schottky defects and di-interstitials. Comparisons were made between the density functional theory results and results obtained from empirical potential simulations and these generally showed good agreement. Both methodologies predicted the first nearest neighbor Schottky defects to be the most energetically favorable of the considered Schottky defects and that the first, second, and fifth nearest neighbor di-interstitials were of similar energy and were favored over the other di-interstitial configurations. Relaxed structures of the defects were analyzed, which showed that empirical potential simulations were accurately predicting the displacements of atoms surrounding di-interstitials, but were overestimating O atom displacement for Schottky defects. Transition barriers were computed for the defects using the nudged elastic band method. Vacancies and Schottky defects were found to have relatively high energy barriers, the majority of which were over 2 eV, in agreement with conclusions reached using empirical potentials. The lowest barriers for di-interstitial transitions were found to be for migration into a first nearest neighbor configuration. Charges were calculated using a Bader analysis and this found negligible charge transfer during the defect transitions and only small changes in the charges on atoms surrounding defects, indicating why fixed charge models work as well as they do

Leadership Class Configuration Interaction Code - Status and Opportunities

Science.gov (United States)

Vary, James

2011-10-01

With support from SciDAC-UNEDF (www.unedf.org) nuclear theorists have developed and are continuously improving a Leadership Class Configuration Interaction Code (LCCI) for forefront nuclear structure calculations. The aim of this project is to make state-of-the-art nuclear structure tools available to the entire community of researchers including graduate students. The project includes codes such as NuShellX, MFDn and BIGSTICK that run a range of computers from laptops to leadership class supercomputers. Codes, scripts, test cases and documentation have been assembled, are under continuous development and are scheduled for release to the entire research community in November 2011. A covering script that accesses the appropriate code and supporting files is under development. In addition, a Data Base Management System (DBMS) that records key information from large production runs and archived results of those runs has been developed (http://nuclear.physics.iastate.edu/info/) and will be released. Following an outline of the project, the code structure, capabilities, the DBMS and current efforts, I will suggest a path forward that would benefit greatly from a significant partnership between researchers who use the codes, code developers and the National Nuclear Data efforts. This research is supported in part by DOE under grant DE-FG02-87ER40371 and grant DE-FC02-09ER41582 (SciDAC-UNEDF).

Ab initio modeling of interactions between screw dislocations and interstitial solutes in body-centered cubic transition metals

International Nuclear Information System (INIS)

Luthi, Berengere

2017-01-01

In order to improve our understanding of alloy plasticity, it is important to describe at the atomic scale the dislocation-solute interactions and their effect on the dislocation mobility. This work focuses on the body-centered cubic (BCC) transition metals in presence of interstitial solute atoms, in particular the Fe-C system. Using Density Functional Theory (DFT) calculations, the core structure of the screw dislocation of Burgers vector b=1/2<111> was investigated in iron in presence of boron, carbon, nitrogen and oxygen solute atoms, and in BCC metals from group 5 (V, Nb, Ta) and 6 (Mo, W) in presence of carbon solutes. A core reconstruction is evidenced in iron and group 6 metals, along with a strong attractive dislocation-solute interaction energy: the dislocation goes from easy to hard configuration where the solute atoms are at the center of trigonal prisms along the dislocation line. A different behavior is observed in group 5 metals, for which the most stable configuration for the carbon atom is an octahedral site in the vicinity of the dislocation, without any core reconstruction. This group tendency is linked to the structure of mono-carbides. Consequences of the strongly attractive dislocation-solute interactions in Fe(C) were then investigated. First the equilibrium segregation close to the dislocation core was studied using a mean-field model and Monte Carlo simulations. Over a wide temperature range, from 200 to 700 K, a strong segregation is predicted with every other prismatic site occupied by a carbon atom. Then, the mobility of the dislocation in presence of carbon atoms was investigated by modeling the double-kink mechanism with DFT, in relation with experimental data obtained with transmission electron microscopy. The activation energy obtained for this atomic scale mechanism is in good agreement with experimental values for the dynamic strain aging. (author) [fr

Ab initio calculation of the interaction potentials of helium, neon, and methane as well as theoretical studies on their thermophysical properties and those of water vapor

International Nuclear Information System (INIS)

Hellmann, Robert

2009-01-01

Thermophysical properties of the pure gases helium, neon, methane and water vapor were calculated for low densities over wide temperature ranges. Statistical thermodynamics was used for the determination of the pressure virial coefficients. The kinetic theory of gases was utilized for the calculation of the transport and relaxation properties. So far kinetic theory was limited to linear molecules and has now been extended to molecules of arbitrary geometry to enable calculations on methane and water vapor. The interaction potentials, which are needed for all computations, were determined for helium, neon and methane from the supermolecular approach using quantum chemical ab initio methods. For water the interaction potentials were taken from the literature. The calculated values of the thermophysical properties for the four gases show very good agreement with the best experimental data. At very low and very high temperatures the theoretical values are more accurate than experimental data. (orig.)

Electronic configuration of nFe/3Cr/nFe (n=1-6) trilayers in FM state

International Nuclear Information System (INIS)

Botana, J.; Pereiro, M.; Baldomir, D.; Arias, J.E.; Warda, K.; Wojtczak, L.

2007-01-01

Ab initio calculations have been performed on several ultrathin Fe/Cr/Fe trilayer systems in ferromagnetic configuration, with a fixed width of the spacer chromium slab of three atomic monolayers, and both iron slabs symmetrically varying in a range from 1 to 6 atomic monolayers. We have calculated the charge distribution of these trilayers and calculated and plotted the density of states of every one of them. We have identified Friedel-like oscillations of the charge distribution from the Mulliken population analysis in the Fe slabs

Study of the stabilization energies of halide-water clusters: An application of first-principles interaction potentials based on a polarizable and flexible model

International Nuclear Information System (INIS)

Ayala, Regla; Martinez, Jose M.; Pappalardo, Rafael R.; Sanchez Marcos, Enrique

2004-01-01

The aim of this work is to compute the stabilization energy E stab (n) of [X(H 2 O) n ] - (X≡F, Br, and I for n=1-60) clusters from Monte Carlo simulations using first-principles ab initio potentials. Stabilization energy of [X(H 2 O) n ] - clusters is defined as the difference between the vertical photodeachment energy of the cluster and the electron affinity of the isolated halide. On one hand, a study about the relation between cluster structure and the E stab (n) value, as well as the dependence of the latter with temperature is performed, on the other hand, a test on the reliability of our recently developed first-principles halide ion-water interaction potentials is carried out. Two different approximations were applied: (1) the Koopmans' theorem and (2) calculation of the difference between the interaction energy of [X(H 2 O) n ] - and [X(H 2 O) n ] clusters using the same ab initio interaction potentials. The developed methodology allows for using the same interaction potentials in the case of the ionic and neutral clusters with the proviso that the charge of the halide anion was switched off in the latter. That is, no specific parametrization of the interaction potentials to fit the magnitude under study was done. The good agreement between our predicted E stab (n) and experimental data allows us to validate the first-principles interaction potentials developed elsewhere and used in this study, and supports the fact that this magnitude is mainly determined by electrostatic factors, which can be described by our interaction potentials. No relation between the value of E stab (n) and the structure of clusters has been found. The diversity of E stab (n) values found for different clusters with similar interaction energy indicates the need for statistical information to properly estimate the stabilization energy of the halide anions. The effect of temperature in the prediction of the E stab (n) is not significant as long as it was high enough to avoid

Ab initio methods for electron-molecule collisions

International Nuclear Information System (INIS)

Collins, L.A.; Schneider, B.I.

1987-01-01

This review concentrates on the recent advances in treating the electronic aspect of the electron-molecule interaction and leaves to other articles the description of the rotational and vibrational motions. Those methods which give the most complete treatment of the direct, exchange, and correlation effects are focused on. Such full treatments are generally necessary at energies below a few Rydbergs (≅ 60 eV). This choice unfortunately necessitates omission of those active and vital areas devoted to the development of model potentials and approximate scattering formulations. The ab initio and model approaches complement each other and are both extremely important to the full explication of the electron-scattering process. Due to the rapid developments of recent years, the approaches that provide the fullest treatment are concentrated on. 81 refs

Improved parametric fits for the HeH2 ab initio energy surface

International Nuclear Information System (INIS)

Muchnick, P.

1992-01-01

A brief history of the development of ab initio calculations for the HeH 2 quasi-molecule energy surface, and the parametric fits to these ab initio calculations, is presented. The concept of 'physical reasonableness' of the parametric fit is discussed. Several new improved parametric fits for the energy surface, meeting these requirements, are then proposed. One fit extends the Russek-Garcia parametric fit for the deep repulsion region to include r-dependent parameters, resulting in a more physically reasonable fit with smaller average error. This improved surface fit is applied to quasi-elastic collisions of He on H 2 in the impulse approximation. Previous classical calculations of the scaled inelastic vibrorotational excitation energy distributions are improved with this more accurate parametric fit of the energy surface and with the incorporation of quantum effects in vibrational excitation. It is shown that Sigmund's approach in developing his scaling law is incomplete in the contribution of the three-body interactions to vibrational excitation of the H 2 molecule is concerned. The Sigmund theory is extended to take into account for r-dependency of three-body interactions. A parametric fit for the entire energy surface from essentially 0 ≤R≤∞ and 1.2≤r≤1.6 a.u., where R is the intermolecular spacing and r is the hydrogen bonding length, is also presented. This fit is physically reasonable in all asymptotic limits. This first, full surface parametric fit is based primarily upon a composite of ab initio studies by Russek and Garcia and Meyer, Hariharan and Kutzelnigg. Parametric fits for the H 2 (1sσ g ) 2 , H 2 + (1sσ g ), H 2 + (2pσ u ) and (LiH 2 ) + energy surfaces are also presented. The new parametric fits for H 2 , H 2 + (1sσ g ) are shown to be improvements over the well-known Morse potentials for these surfaces

A Initio Theoretical Studies of Surfaces of Semiconductors

Science.gov (United States)

Wang, Jing

1993-01-01

The first semiconductor which we study with these techniques is the archetypal elemental semiconductor, silicon. We present the first extensive study of point defects on Si(100). We identify the principal defects and two primary mechanisms responsible for their dominance: the need to eliminate dangling bonds on the surface and the need to compensate the strain induced by topological effects. Furthermore, we present evidence that the presence of point defects on the Si(100) surface is not intrinsic to the ground state of the surface as a stress relieving mechanism but rather is due merely to thermal fluctuations. We address materials issues associated with the identification of the lowest energy surfaces of GaAs and the determination of the geometric structure of a GaAs crystallite growing freely in three dimensions. The fracture energies associated with (110), (100) and (111) interface planes are calculated and a Wulff construction indicates that an ideal stoichiometric GaAs crystal should be terminated with (110) surfaces. We investigate the more complex issues that arise on surfaces when aspects of these two semiconductors are mixed. We investigate the problem of growing GaAs on the Si(100) surface and demonstrate how and why the most fundamental properties of the resulting bulk GaAs material, such as its crystalline orientation, may depend sensitively on the interplay between growth conditions such as temperature and the properties of the Si surface. For stepped Si(100) -As, we show that the growth of As directly on top of the Si surface produces a metastable state, while the replacement of the original top Si layer leads to a lower energy configuration, with the rearrangement of the surface driven by the relaxation of stress by surface steps. Finally, we study delta -doping, where one attempts to grow a single layer of Si on a GaAs surface before continuing with the growth of bulk GaAs. We shall employ a slightly different modality of the ab initio approach. We

Molecular modeling studies of interactions between sodium polyacrylate polymer and calcite surface

Energy Technology Data Exchange (ETDEWEB)

Ylikantola, A. [University of Jyväskylä, Department of Chemistry, P.O. Box 35, University of Jyväskylä, FI-40014 (Finland); Linnanto, J., E-mail: juha.m.linnanto@gmail.com [University of Jyväskylä, Department of Chemistry, P.O. Box 35, University of Jyväskylä, FI-40014 (Finland); University of Tartu, Institute of Physics, Riia 142, EE-51014 Tartu (Estonia); Knuutinen, J.; Oravilahti, A. [University of Jyväskylä, Department of Chemistry, P.O. Box 35, University of Jyväskylä, FI-40014 (Finland); Toivakka, M. [Åbo Akademi University, Laboratory of Paper Coating and Converting and Center for Functional Materials, FI-20500 Turku/Åbo (Finland)

2013-07-01

The interactions between calcite pigment and sodium polyacrylate dispersing agent, widely used in papermaking as paper coating components, were investigated using classical force field and quantum chemical approaches. The objective was to understand interactions between the calcite surface and sodium polyacrylate polymer at 300 K using molecular dynamics simulations. A quantum mechanical ab initio Hartree–Fock method was also used to obtain detailed information about the sodium polyacrylate polymer structure. The effect of water molecules (moisture) on the interactions was also examined. Calculations showed that molecular weight, branching and the orientation of sodium polyacrylate polymers influence the interactions between the calcite surface and the polymer. The force field applied, and also water molecules, were found to have an impact on all systems studied. Ab initio Hartree–Fock calculations indicated that there are two types of coordination between sodium atoms and carboxylate groups of the sodium polyacrylate polymer, inter- and intra-carboxylate group coordination. In addition, ab initio Hartree–Fock calculations of the structure of the sodium polyacrylate polymer produced important information regarding interactions between the polymers and carboxylated styrene-butadiene latex particles.

Configuration Path Integral Monte Carlo. Ab initio simulations of fermions in the warm dense matter regime

Energy Technology Data Exchange (ETDEWEB)

Schoof, Tim

2017-03-08

The reliable quantum mechanical description of thermodynamic properties of fermionic many-body systems at high densities and strong degeneracy is of increasing interest due to recent experimental progress in generating systems that exhibit a non-trivial interplay of quantum, temperature, and coupling effects. While quantum Monte Carlo methods are among the most accurate approaches for the description of the ground state, finite-temperature path integral Monte Carlo (PIMC) simulations cannot correctly describe weakly to moderately coupled and strongly degenerate Fermi systems due to the so-called fermion sign problem. By switching from the coordinate representation to a basis of anti-symmetric Slater-determinants, the Configuration Path Integral Monte Carlo (CPIMC) approach greatly reduces the sign problem and allows for the exact computation of thermodynamic properties in this regime. During this work, the CPIMC algorithm was greatly improved in terms of efficiency and accessible observables. The first successful implementation of the diagrammatic worm algorithm for a general Hamiltonian in Fock space with arbitrary pair interactions gives direct access to the Matsubara Green function. This allows for the reconstruction of dynamic properties from simulations in thermodynamic equilibrium and significantly reduces the statistical variance of derived estimators, such as the one-particle density. The strongly improved MC sampling, the much more efficient calculation of update probabilities, and the successful parallelization to thousands of CPU cores, which have been achieved as part of the new implementation, are essential for the subsequent application of the method to much larger systems than in previous works. This thesis demonstrates the capabilities of the CPIMC approach for a model system of Coulomb interacting fermions in a two-dimensional harmonic trap. The correctness of the CPIMC implementation is verified by rigorous comparisons with an exact

Ab initio interaction potentials for X and B excited states of He-I2 for studying dynamics

International Nuclear Information System (INIS)

Prosmiti, Rita; Garcia-Gutierrez, Leonor; Delgado-Tellez, Laura; Valdes, Alvaro; Villarreal, Pablo; Delgado-Barrio, Gerardo

2009-01-01

Ab initio CCSD(T) and MRCI approaches were employed to construct potential energy surfaces of the ground and the B electronic excited states of He-I 2 complex, while full quantum mechanical methods were applied to study its spectroscopy and dynamics. A description of the approach adopted, together with the results obtained and their comparison with recent experimental data, as well as further improvements are presented.

An excited-state approach within full configuration interaction quantum Monte Carlo

International Nuclear Information System (INIS)

Blunt, N. S.; Smart, Simon D.; Booth, George H.; Alavi, Ali

2015-01-01

We present a new approach to calculate excited states with the full configuration interaction quantum Monte Carlo (FCIQMC) method. The approach uses a Gram-Schmidt procedure, instantaneously applied to the stochastically evolving distributions of walkers, to orthogonalize higher energy states against lower energy ones. It can thus be used to study several of the lowest-energy states of a system within the same symmetry. This additional step is particularly simple and computationally inexpensive, requiring only a small change to the underlying FCIQMC algorithm. No trial wave functions or partitioning of the space is needed. The approach should allow excited states to be studied for systems similar to those accessible to the ground-state method due to a comparable computational cost. As a first application, we consider the carbon dimer in basis sets up to quadruple-zeta quality and compare to existing results where available

Highly scalable Ab initio genomic motif identification

KAUST Repository

Marchand, Benoit; Bajic, Vladimir B.; Kaushik, Dinesh

2011-01-01

We present results of scaling an ab initio motif family identification system, Dragon Motif Finder (DMF), to 65,536 processor cores of IBM Blue Gene/P. DMF seeks groups of mutually similar polynucleotide patterns within a set of genomic sequences and builds various motif families from them. Such information is of relevance to many problems in life sciences. Prior attempts to scale such ab initio motif-finding algorithms achieved limited success. We solve the scalability issues using a combination of mixed-mode MPI-OpenMP parallel programming, master-slave work assignment, multi-level workload distribution, multi-level MPI collectives, and serial optimizations. While the scalability of our algorithm was excellent (94% parallel efficiency on 65,536 cores relative to 256 cores on a modest-size problem), the final speedup with respect to the original serial code exceeded 250,000 when serial optimizations are included. This enabled us to carry out many large-scale ab initio motiffinding simulations in a few hours while the original serial code would have needed decades of execution time. Copyright 2011 ACM.

A full-configuration-interaction nuclear orbital approach and application for small doped He clusters

Energy Technology Data Exchange (ETDEWEB)

Lara-Castells, M. P. de, E-mail: delara@iff.csic.es; Aguirre, N. F., E-mail: delara@iff.csic.es; Delgado-Barrio, G., E-mail: delara@iff.csic.es; Villarreal, P., E-mail: delara@iff.csic.es [Instituto de Física Fundamental (CSIC), Serrano 123, 28006 Madrid (Spain); Mitrushchenkov, A. O. [Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallée (France)

2015-01-22

An efficient full-configuration-interaction 'nuclear orbital' treatment was developed as a benchmark quantum-chemistry-like method to calculate, ground and excited, fermionic 'solvent' wave-functions and applied to {sup 3}He{sub N} clusters with atomic or molecular impurities [J. Chem. Phys. (Communication) 125, 221101 (2006)]. The main difficulty in handling doped {sup 3}He{sub N} clusters lies in the Fermi-Dirac nuclear statistics, the wide amplitudes of the He-dopant and He-He motions, and the hard-core He-He interaction at short distances. This paper overviews the theoretical approach and its recent applications to energetic, structural and spectroscopic aspects of different dopant-{sup 3}He{sub N} clusters. Preliminary results by using the latest version of the FCI-NO computational implementation, to bosonic Cl{sub 2}(X)-({sup 4}He){sub N} clusters, are also shown.

Summary of workshop 'Theory Meets Industry' - the impact of ab initio solid state calculations on industrial materials research

International Nuclear Information System (INIS)

Wimmer, E

2008-01-01

A workshop, 'Theory Meets Industry', was held on 12-14 June 2007 in Vienna, Austria, attended by a well balanced number of academic and industrial scientists from America, Europe, and Japan. The focus was on advances in ab initio solid state calculations and their practical use in industry. The theoretical papers addressed three dominant themes, namely (i) more accurate total energies and electronic excitations (ii) more complex systems, and (iii) more diverse and accurate materials properties. Hybrid functionals give some improvements in energies, but encounter difficulties for metallic systems. Quantum Monte Carlo methods are progressing, but no clear breakthrough is on the horizon. Progress in order-N methods is steady, as is the case for efficient methods for exploring complex energy hypersurfaces and large numbers of structural configurations. The industrial applications were dominated by materials issues in energy conversion systems, the quest for hydrogen storage materials, improvements of electronic and optical properties of microelectronic and display materials, and the simulation of reactions on heterogeneous catalysts. The workshop is a clear testimony that ab initio computations have become an industrial practice with increasingly recognized impact

Large-dimension configuration-interaction calculations of positron binding to the group-II atoms

International Nuclear Information System (INIS)

Bromley, M. W. J.; Mitroy, J.

2006-01-01

The configuration-interaction (CI) method is applied to the calculation of the structures of a number of positron binding systems, including e + Be, e + Mg, e + Ca, and e + Sr. These calculations were carried out in orbital spaces containing about 200 electron and 200 positron orbitals up to l=12. Despite the very large dimensions, the binding energy and annihilation rate converge slowly with l, and the final values do contain an appreciable correction obtained by extrapolating the calculation to the l→∞ limit. The binding energies were 0.00317 hartree for e + Be, 0.0170 hartree for e + Mg, 0.0189 hartree for e + Ca, and 0.0131 hartree for e + Sr

Pseudo Jahn–Teller effect in distortion and restoration of planar configurations of tetra-heterocyclic 1,2-diazetes C{sub 2}N{sub 2}E{sub 4}, E = H, F, Cl, Br

Energy Technology Data Exchange (ETDEWEB)

Ilkhani, Ali R. [Institute for Theoretical Chemistry, University of Texas at Austin, Austin, TX 78712 (United States); Department of Chemistry, Yazd Branch, Islamic Azad University, Yazd (Iran, Islamic Republic of); Gorinchoy, Natalia N. [Institute of Chemistry, Academy of Sciences of Moldova, Chisinau, Republic of Moldova (Moldova, Republic of); Bersuker, Isaac B., E-mail: bersuker@cm.utexas.edu [Institute for Theoretical Chemistry, University of Texas at Austin, Austin, TX 78712 (United States); Institute of Chemistry, Academy of Sciences of Moldova, Chisinau, Republic of Moldova (Moldova, Republic of)

2015-10-16

Highlights: • The pseudo Jahn–Teller mechanism of puckering of tetracyclic 1,2-diazetes is revealed. • Vibronic constants are extracted from ab initio calculations versus PJTE equations. • Methods of restoring the planar configuration by external perturbations are suggested. - Abstract: The pseudo Jahn–Teller effect (PJTE) is employed to explain the origin of the puckered structures of tetra-heterocyclic 1,2-diazetes, C{sub 2}N{sub 2}E{sub 4}, E = H, F, Cl, Br, and to reveal the conditions of restoration of their planar configuration. The high-symmetry C{sub 2v} planar configuration of all these compounds is unstable with respect to puckering, a{sub 2}-type distortions produced by the PJT coupling between their ground {sup 1}A{sub 1} and excited {sup 1}A{sub 2} electronic states. The PJTE coupling constants are estimated by fitting ab initio calculated energy profiles to the formulas of the vibronic coupling problem (A{sub 1} + A{sub 2}) ⊗ a{sub 2}. The conditions for the restoration of the planar configurations of the C{sub 2}N{sub 2}E{sub 4} cycles were revealed: the PJTE can be quenched by removing the outer two electrons, e.g. by producing a “triple-decker sandwich” structure with two electron acceptors on both sides of the neutral cycle.

Quantitative verification of ab initio self-consistent laser theory.

Science.gov (United States)

Ge, Li; Tandy, Robert J; Stone, A D; Türeci, Hakan E

2008-10-13

We generalize and test the recent "ab initio" self-consistent (AISC) time-independent semiclassical laser theory. This self-consistent formalism generates all the stationary lasing properties in the multimode regime (frequencies, thresholds, internal and external fields, output power and emission pattern) from simple inputs: the dielectric function of the passive cavity, the atomic transition frequency, and the transverse relaxation time of the lasing transition.We find that the theory gives excellent quantitative agreement with full time-dependent simulations of the Maxwell-Bloch equations after it has been generalized to drop the slowly-varying envelope approximation. The theory is infinite order in the non-linear hole-burning interaction; the widely used third order approximation is shown to fail badly.

Modeling Disordered Materials with a High Throughput ab-initio Approach

Science.gov (United States)

2015-11-13

Modeling Disordered Materials with a High Throughput ab - initio Approach Kesong Yang,1 Corey Oses,2 and Stefano Curtarolo3, 4 1Department of...J. Furthmüller, Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set, Phys. Rev. B 54, 11169–11186 (1996

Embedded atom approach for gold–silicon system from ab initio

Indian Academy of Sciences (India)

In the present paper, an empirical embedded atom method (EAM) potential for gold–silicon (Au–Si) is developed by fitting to ab initio force (the 'force matching' method) and experimental data. The force database is generated within ab initio molecular dynamics (AIMD). The database includes liquid phase at various ...

Two-component, ab initio potential energy surface for CO2-H2O, extension to the hydrate clathrate, CO2@(H2O)20, and VSCF/VCI vibrational analyses of both.

Science.gov (United States)

Wang, Qingfeng Kee; Bowman, Joel M

2017-10-28

We report an ab initio, full-dimensional, potential energy surface (PES) for CO 2 -H 2 O, in which two-body interaction energies are fit using a basis of permutationally invariant polynomials and combined with accurate potentials for the non-interacting monomers. This approach which we have termed "plug and play" is extended here to improve the precision of the 2-body fit in the long range. This is done by combining two separate fits. One is a fit to 47 593 2-body energies in the region of strong interaction and approaching the long range, and the second one is a fit to 6244 2-body energies in the long range. The two fits have a region of overlap which permits a smooth switch from one to the other. All energies are obtained at the CCSD(T)-F12b/aug-cc-pVTZ level of theory. Properties of the full PES, i.e., stationary points, harmonic frequencies of the global minimum, etc., are shown to be in excellent agreement with direct CCSD(T)-F12b/aug-cc-pVTZ results. Diffusion Monte Carlo calculations of the dimer zero-point energy (ZPE) are performed, and a dissociation energy, D 0 , of 787 cm -1 is obtained using that ZPE, D e , and the rigorous ZPEs of the monomers. Using a benchmark D e , D 0 is 758 cm -1 . Vibrational self-consistent field (VSCF)/virtual state configuration interaction (VCI) MULTIMODE calculations of intramolecular fundamentals are reported and are in good agreement with available experimental results. Finally, the full dimer PES is combined with an existing ab initio water potential to develop a potential for the CO 2 hydrate clathrate CO 2 (H 2 O) 20 (5 12 water cage). A full normal-mode analysis of this hydrate clathrate is reported as are local-monomer VSCF/VCI calculations of the fundamentals of CO 2 .

A configural dominant account of contextual cueing: Configural cues are stronger than colour cues.

Science.gov (United States)

Kunar, Melina A; John, Rebecca; Sweetman, Hollie

2014-01-01

Previous work has shown that reaction times to find a target in displays that have been repeated are faster than those for displays that have never been seen before. This learning effect, termed "contextual cueing" (CC), has been shown using contexts such as the configuration of the distractors in the display and the background colour. However, it is not clear how these two contexts interact to facilitate search. We investigated this here by comparing the strengths of these two cues when they appeared together. In Experiment 1, participants searched for a target that was cued by both colour and distractor configural cues, compared with when the target was only predicted by configural information. The results showed that the addition of a colour cue did not increase contextual cueing. In Experiment 2, participants searched for a target that was cued by both colour and distractor configuration compared with when the target was only cued by colour. The results showed that adding a predictive configural cue led to a stronger CC benefit. Experiments 3 and 4 tested the disruptive effects of removing either a learned colour cue or a learned configural cue and whether there was cue competition when colour and configural cues were presented together. Removing the configural cue was more disruptive to CC than removing colour, and configural learning was shown to overshadow the learning of colour cues. The data support a configural dominant account of CC, where configural cues act as the stronger cue in comparison to colour when they are presented together.

Improving the iterative Linear Interaction Energy approach using automated recognition of configurational transitions.

Science.gov (United States)

Vosmeer, C Ruben; Kooi, Derk P; Capoferri, Luigi; Terpstra, Margreet M; Vermeulen, Nico P E; Geerke, Daan P

2016-01-01

Recently an iterative method was proposed to enhance the accuracy and efficiency of ligand-protein binding affinity prediction through linear interaction energy (LIE) theory. For ligand binding to flexible Cytochrome P450s (CYPs), this method was shown to decrease the root-mean-square error and standard deviation of error prediction by combining interaction energies of simulations starting from different conformations. Thereby, different parts of protein-ligand conformational space are sampled in parallel simulations. The iterative LIE framework relies on the assumption that separate simulations explore different local parts of phase space, and do not show transitions to other parts of configurational space that are already covered in parallel simulations. In this work, a method is proposed to (automatically) detect such transitions during the simulations that are performed to construct LIE models and to predict binding affinities. Using noise-canceling techniques and splines to fit time series of the raw data for the interaction energies, transitions during simulation between different parts of phase space are identified. Boolean selection criteria are then applied to determine which parts of the interaction energy trajectories are to be used as input for the LIE calculations. Here we show that this filtering approach benefits the predictive quality of our previous CYP 2D6-aryloxypropanolamine LIE model. In addition, an analysis is performed of the gain in computational efficiency that can be obtained from monitoring simulations using the proposed filtering method and by prematurely terminating simulations accordingly.

Magnetization reversal in magnetic dot arrays: Nearest-neighbor interactions and global configurational anisotropy

Energy Technology Data Exchange (ETDEWEB)

Van de Wiele, Ben [Department of Electrical Energy, Systems and Automation, Ghent University, Technologiepark 913, B-9052 Ghent-Zwijnaarde (Belgium); Fin, Samuele [Dipartimento di Fisica e Scienze della Terra, Università degli Studi di Ferrara, 44122 Ferrara (Italy); Pancaldi, Matteo [CIC nanoGUNE, E-20018 Donostia-San Sebastian (Spain); Vavassori, Paolo [CIC nanoGUNE, E-20018 Donostia-San Sebastian (Spain); IKERBASQUE, Basque Foundation for Science, E-48013 Bilbao (Spain); Sarella, Anandakumar [Physics Department, Mount Holyoke College, 211 Kendade, 50 College St., South Hadley, Massachusetts 01075 (United States); Bisero, Diego [Dipartimento di Fisica e Scienze della Terra, Università degli Studi di Ferrara, 44122 Ferrara (Italy); CNISM, Unità di Ferrara, 44122 Ferrara (Italy)

2016-05-28

Various proposals for future magnetic memories, data processing devices, and sensors rely on a precise control of the magnetization ground state and magnetization reversal process in periodically patterned media. In finite dot arrays, such control is hampered by the magnetostatic interactions between the nanomagnets, leading to the non-uniform magnetization state distributions throughout the sample while reversing. In this paper, we evidence how during reversal typical geometric arrangements of dots in an identical magnetization state appear that originate in the dominance of either Global Configurational Anisotropy or Nearest-Neighbor Magnetostatic interactions, which depends on the fields at which the magnetization reversal sets in. Based on our findings, we propose design rules to obtain the uniform magnetization state distributions throughout the array, and also suggest future research directions to achieve non-uniform state distributions of interest, e.g., when aiming at guiding spin wave edge-modes through dot arrays. Our insights are based on the Magneto-Optical Kerr Effect and Magnetic Force Microscopy measurements as well as the extensive micromagnetic simulations.

Ab initio calculation of the interaction potentials of helium, neon, and methane as well as theoretical studies on their thermophysical properties and those of water vapor; Ab initio-Berechnung der Wechselwirkungspotentiale von Helium, Neon und Methan sowie theoretische Untersuchungen zu ihren thermophysikalischen Eigenschaften und denen von Wasserdampf

Energy Technology Data Exchange (ETDEWEB)

Hellmann, Robert

2009-06-16

Thermophysical properties of the pure gases helium, neon, methane and water vapor were calculated for low densities over wide temperature ranges. Statistical thermodynamics was used for the determination of the pressure virial coefficients. The kinetic theory of gases was utilized for the calculation of the transport and relaxation properties. So far kinetic theory was limited to linear molecules and has now been extended to molecules of arbitrary geometry to enable calculations on methane and water vapor. The interaction potentials, which are needed for all computations, were determined for helium, neon and methane from the supermolecular approach using quantum chemical ab initio methods. For water the interaction potentials were taken from the literature. The calculated values of the thermophysical properties for the four gases show very good agreement with the best experimental data. At very low and very high temperatures the theoretical values are more accurate than experimental data. (orig.)

Ab initio R-matrix/Multi-channel Quantum Defect Theory applied to Molecular Core Excitation and Ionization

International Nuclear Information System (INIS)

Hiyama, M.; Kosugi, N.

2004-01-01

Full text: Ab initio R-matrix/MQDT approach, which is a combination of ab initio R-matrix techniques and the multi channel quantum defect theory (MQDT), has recently been developed by one of the present authors (MH) and Child, to successfully obtain the potential energy curves of Rydberg states converging to not only the lowest but also the higher ionized states. This approach is also applied to estimate the valence state interaction with Rydberg and continuum (ionization) channels. Very recently we have made an original ab initio polyatomic R-matrix/MQDT program package, GSCF4R based on Gaussian type basis functions for the bound and continuum states, to extensively study molecular excitation and ionization in the X-ray region as well as in the VUV region. We are going to report the results for core excitation and ionization of diatomic molecules such as NO and O 2 to show that the R-matrix/MQDT method is indispensable to describe the core-to-Rydberg states with the higher quantum number and the continuum states. These results lead us to the conclusion that the close-coupling approximation augmented with the correlation term within the R-matrix/MQDT formalism is powerful to calculate the Rydberg-valence mixing and the interchannel coupling between several core-ionized states

Ab initio folding of mixed-fold FSD-EY protein using formula-based polarizable hydrogen bond (PHB) charge model

Science.gov (United States)

Zhang, Dawei; Lazim, Raudah; Mun Yip, Yew

2017-09-01

We conducted an all-atom ab initio folding of FSD-EY, a protein with a ββα configuration using non-polarizable (AMBER) and polarizable force fields (PHB designed by Gao et al.) in implicit solvent. The effect of reducing the polarization effect integrated into the force field by the PHB model, termed the PHB0.7 was also examined in the folding of FSD-EY. This model incorporates into the force field 70% of the original polarization effect to minimize the likelihood of over-stabilizing the backbone hydrogen bonds. Precise folding of the β-sheet of FSD-EY was further achieved by relaxing the REMD structure obtained in explicit water.

Lessons Learned in Designing User-configurable Modular Robotics

DEFF Research Database (Denmark)

Lund, Henrik Hautop

2013-01-01

User-configurable robotics allows users to easily configure robotic systems to perform task-fulfilling behaviors as desired by the users. With a user configurable robotic system, the user can easily modify the physical and func-tional aspect in terms of hardware and software components of a robotic...... with the semi-autonomous com-ponents of the user-configurable robotic system in interaction with the given environment. Components constituting such a user-configurable robotic system can be characterized as modules in a modular robotic system. Several factors in the definition and implementation...

The 3d8-(3d74p + 3p53d9) transitions in Br X: A striking case of configuration interaction

International Nuclear Information System (INIS)

Kleef, T.A.M. van; Uylings, P.H.M.; Ryabtsev, A.N.; Podobedova, L.I.; Joshi, Y.N.

1988-01-01

The spectrum of nine times ionized bromine (Br X) was photographed in the 90-120 A wavelength region on a variety of grazing incidence spectrographs using an open spark and a triggered spark as light sources. The analysis of the 3d 8 -(3d 7 4p + 3p 5 3d 9 ) transitions has resulted in establishing all 9 levels of the 3d 8 configuration, all 12 levels of the 3p 5 3d 9 configuration and 99 out of 110 levels of the 3d 7 4p configuration. The excitation probability of the 3p inner-shell electron increases with nuclear charge and in Br X is comparable with the excitation probability of the optical electrons resulting in a very strong configuration interaction between the 3p 5 3d 9 and 3d 7 4p configurations. Parametric calculations treating these configurations as one super configuration support the analysis. Two hundred and thirty two lines have been classified in this spectrum. (orig.)

Ab initio study of the EFG at the N sites in imidazole

Energy Technology Data Exchange (ETDEWEB)

Brown Goncalves, Marcos, E-mail: browngon@if.usp.br [Universidade de Sao Paulo, Instituto de Fisica (Brazil); Di Felice, R. [National Center on Nanostructures and Biosystems at Surfaces (S3) of INFM-CNR (Italy); Poleshchuk, O. Kh. [Tomsk State Pedagogical University (Russian Federation); Petrilli, H. M. [Universidade de Sao Paulo, Instituto de Fisica (Brazil)

2008-01-15

We study the nuclear quadrupole interaction at the nitrogen sites in the molecular and crystalline phases of the imidazole compound. We use PAW which is a state-of-the-art method to calculate the electronic structure and electric field gradient at the nucleus in the framework of the density functional theory. The quadrupole frequencies at both imino and amino N sites are in excellent agreement with measurements. This is the first time that the electric field gradient at crystalline imidazole is correctly treated by an ab initio theoretical approach.

Ab initio modelling of methane hydrate thermophysical properties.

Science.gov (United States)

Jendi, Z M; Servio, P; Rey, A D

2016-04-21

The key thermophysical properties of methane hydrate were determined using ab initio modelling. Using density functional theory, the second-order elastic constants, heat capacity, compressibility, and thermal expansion coefficient were calculated. A wide and relevant range of pressure-temperature conditions were considered, and the structures were assessed for stability using the mean square displacement and radial distribution functions. Methane hydrate was found to be elastically isotropic with a linear dependence of the bulk modulus on pressure. Equally significant, multi-body interactions were found to be important in hydrates, and water-water interactions appear to strongly influence compressibility like in ice Ih. While the heat capacity of hydrate was found to be higher than that of ice, the thermal expansion coefficient was significantly lower, most likely due to the lower rigidity of hydrates. The mean square displacement gave important insight into stability, heat capacity, and elastic moduli, and the radial distribution functions further confirmed stability. The presented results provide a much needed atomistic thermoelastic characterization of methane hydrates and are essential input for the large-scale applications of hydrate detection and production.

From empirical to ab initio: transferable potentials in the atomistic simulation of amorphous carbons

International Nuclear Information System (INIS)

Marks, N.A.; Goringe, C.M.; McKenzie, D.R.; McCulloch, D.G.; Royal Melbourne Institute of Technology University, Melbourne, VIC

2000-01-01

Full text: Silicon is often described as the prototype covalent material, and when it comes to developing atomistic models this situation is well described by the sentiment that 'everything works for silicon'. The same cannot be said for carbon though, where the interaction potential has always proved problematical, be it with empirical, tight-binding or ab initio methods. Thus far the most decisive contributions to understanding amorphous carbon networks have come from ab initio simulations using the Car-Parrinello method, where the fully quantum treatment of the valence electrons has provided unexpected insight into the local structure. However such first principles calculations are restricted spatially and temporally to systems with approximately 100 atoms and times of order one picosecond. There is therefore demand for less expensive techniques capable of resolving important questions whose solution can only to found with larger simulations running for longer times. In the case of tetrahedral amorphous carbon, such issues include the release of compressive stress through annealing, the origin of graphitic surface layers and the nature of the film growth process and thermal spike. Against this background tight-binding molecular dynamics has emerged as a popular alternative to first principles methods, and our group has an ongoing program to understand film growth using one of the efficient variants of tight-binding. Another direction of research is a new empirical potential based on the Environment Dependent Interaction Potential (EDIP) recently developed for silicon. The EDIP approach represents a promising direction for empirical potentials through its use of ab initio data to motivate the functional form as well as the more conventional parametrisation. By inverting ab initio cohesive energy curves the authors of EDIP arrived at a pair potential expression which reduces to the well-known Stillinger-Weber form at integer coordination, while providing

Two-component, ab initio potential energy surface for CO2—H2O, extension to the hydrate clathrate, CO2@(H2O)20, and VSCF/VCI vibrational analyses of both

Science.gov (United States)

Wang, Qingfeng Kee; Bowman, Joel M.

2017-10-01

We report an ab initio, full-dimensional, potential energy surface (PES) for CO2—H2O, in which two-body interaction energies are fit using a basis of permutationally invariant polynomials and combined with accurate potentials for the non-interacting monomers. This approach which we have termed "plug and play" is extended here to improve the precision of the 2-body fit in the long range. This is done by combining two separate fits. One is a fit to 47 593 2-body energies in the region of strong interaction and approaching the long range, and the second one is a fit to 6244 2-body energies in the long range. The two fits have a region of overlap which permits a smooth switch from one to the other. All energies are obtained at the CCSD(T)-F12b/aug-cc-pVTZ level of theory. Properties of the full PES, i.e., stationary points, harmonic frequencies of the global minimum, etc., are shown to be in excellent agreement with direct CCSD(T)-F12b/aug-cc-pVTZ results. Diffusion Monte Carlo calculations of the dimer zero-point energy (ZPE) are performed, and a dissociation energy, D0, of 787 cm-1 is obtained using that ZPE, De, and the rigorous ZPEs of the monomers. Using a benchmark De, D0 is 758 cm-1. Vibrational self-consistent field (VSCF)/virtual state configuration interaction (VCI) MULTIMODE calculations of intramolecular fundamentals are reported and are in good agreement with available experimental results. Finally, the full dimer PES is combined with an existing ab initio water potential to develop a potential for the CO2 hydrate clathrate CO2(H2O)20(512 water cage). A full normal-mode analysis of this hydrate clathrate is reported as are local-monomer VSCF/VCI calculations of the fundamentals of CO2.

Distinct configurations of protein complexes and biochemical pathways revealed by epistatic interaction network motifs

LENUS (Irish Health Repository)

Casey, Fergal

2011-08-22

Abstract Background Gene and protein interactions are commonly represented as networks, with the genes or proteins comprising the nodes and the relationship between them as edges. Motifs, or small local configurations of edges and nodes that arise repeatedly, can be used to simplify the interpretation of networks. Results We examined triplet motifs in a network of quantitative epistatic genetic relationships, and found a non-random distribution of particular motif classes. Individual motif classes were found to be associated with different functional properties, suggestive of an underlying biological significance. These associations were apparent not only for motif classes, but for individual positions within the motifs. As expected, NNN (all negative) motifs were strongly associated with previously reported genetic (i.e. synthetic lethal) interactions, while PPP (all positive) motifs were associated with protein complexes. The two other motif classes (NNP: a positive interaction spanned by two negative interactions, and NPP: a negative spanned by two positives) showed very distinct functional associations, with physical interactions dominating for the former but alternative enrichments, typical of biochemical pathways, dominating for the latter. Conclusion We present a model showing how NNP motifs can be used to recognize supportive relationships between protein complexes, while NPP motifs often identify opposing or regulatory behaviour between a gene and an associated pathway. The ability to use motifs to point toward underlying biological organizational themes is likely to be increasingly important as more extensive epistasis mapping projects in higher organisms begin.

The benefits of ITER for the portfolio of fusion configurations

International Nuclear Information System (INIS)

Goldston, R.J.

2002-01-01

Recent plasma science challenges are 1) what limits the pressure in plasmas? (macroscopic stability), 2) how do hot particles and plasma waves interact in the non-linear regime? (wave-particle interactions), 3) what causes plasma transport? (microscopic turbulence and transport) and 4) how can high-temperature plasma and material surface co-exist? (plasma-material interactions). This fusion plasma science is addressed using a 'Portfolio' of configurations, like Stellarator, Tokamak, Spherical Torus, Reversed Field Pinch, Spheromak, and Field Reversed Configuration. Namely, the scientific results from one configuration benefit progress in others. Recent example of this effort can be found in NCSX, NSTX and RFP. ITER will provide very significant benefits to the development of the full fusion portfolio; macroscopic stability, wave-particle interactions, microturbulence and transport, plasma-material interactions, and technical demonstration of an integrated fusion system. (author)

The benefits of ITER for the portfolio of fusion configurations

Energy Technology Data Exchange (ETDEWEB)

Goldston, R.J. [Princeton Plasma Physics Lab., NJ (United States)

2002-10-01

Recent plasma science challenges are 1) what limits the pressure in plasmas? (macroscopic stability), 2) how do hot particles and plasma waves interact in the non-linear regime? (wave-particle interactions), 3) what causes plasma transport? (microscopic turbulence and transport) and 4) how can high-temperature plasma and material surface co-exist? (plasma-material interactions). This fusion plasma science is addressed using a 'Portfolio' of configurations, like Stellarator, Tokamak, Spherical Torus, Reversed Field Pinch, Spheromak, and Field Reversed Configuration. Namely, the scientific results from one configuration benefit progress in others. Recent example of this effort can be found in NCSX, NSTX and RFP. ITER will provide very significant benefits to the development of the full fusion portfolio; macroscopic stability, wave-particle interactions, microturbulence and transport, plasma-material interactions, and technical demonstration of an integrated fusion system. (author)

Summation of Parquet diagrams as an ab initio method in nuclear structure calculations

International Nuclear Information System (INIS)

Bergli, Elise; Hjorth-Jensen, Morten

2011-01-01

Research highlights: → We present a Green's function based approach for doing ab initio nuclear structure calculations. → In particular the sum the subset of so-called Parquet diagrams. → Applying the theory to a simple but realistic model, results in good agreement with other ab initio methods. → This opens up for ab initio calculations for medium-heavy nuclei. - Abstract: In this work we discuss the summation of the Parquet class of diagrams within Green's function theory as a possible framework for ab initio nuclear structure calculations. The theory is presented and some numerical details are discussed, in particular the approximations employed. We apply the Parquet method to a simple model, and compare our results with those from an exact solution. The main conclusion is that even at the level of approximation presented here, the results shows good agreement with other comparable ab initio approaches.

A classic case of Jahn–Teller effect theory revisited: Ab initio simulation of hyperfine coupling and pseudorotational tunneling in the 1"2E′ state of Na_3

International Nuclear Information System (INIS)

Hauser, Andreas W.; Pototschnig, Johann V.; Ernst, Wolfgang E.

2015-01-01

Highlights: • Multireference and Coupled Cluster methods are applied to Na_3. • The PES is characterized by an analytical function fitted to ab initio data. • An effective rovibrational Hamiltonian is set up, with all parameters derived ab initio. • The coupling of pseudorotational tunneling and hyperfine interactions is investigated. • The theoretical predictions are compared to microwave spectra. - Abstract: The predictive capabilities of current ab initio approaches are tested in a benchmark study on the well known case of the Na_3 ground state. This molecule is small enough to be treated with computationally demanding methods, but also shows an interesting interplay between Jahn–Teller-, spin-orbit-, rovibrational- and hyperfine-interactions. The necessary parameters for the effective Hamiltonian are derived from the potential energy surface of the 1"2E′ ground state and from spin density evaluations at selected geometries, without any fitting adjustments to experimental data. We compare our results to highly resolved microwave spectra, with the aim to improve previous assignment attempts, where some parameters had to be estimated from fits to measured spectra.

Dynamic hyperfine interactions in {sup 111}In({sup 111}Cd)-doped ZnO semiconductor: PAC results supported by ab initio calculations

Energy Technology Data Exchange (ETDEWEB)

Munoz, Emiliano L., E-mail: munoz@fisica.unlp.edu.ar [Departamento de Fisica and Instituto de Fisica La Plata (IFLP, CONICET La Plata), Facultad de Ciencias Exactas, Universidad Nacional de La Plata, CC 67, 1900 La Plata (Argentina); Mercurio, Marcio E.; Cordeiro, Moacir R.; Pereira, Luciano F.D.; Carbonari, Artur W. [Instituto de Pesquisas Energeticas y Nucleares-IPEN-CNEN/SP, Sao Paulo (Brazil); Renteria, Mario [Departamento de Fisica and Instituto de Fisica La Plata (IFLP, CONICET La Plata), Facultad de Ciencias Exactas, Universidad Nacional de La Plata, CC 67, 1900 La Plata (Argentina)

2012-08-15

In this work, we present results of Time-Differential {gamma}-{gamma} Perturbed-Angular-Correlations (PAC) experiments performed in {sup 111}Cd-doped ZnO semiconductor. The PAC technique has been applied in order to characterize the electric-field-gradient (EFG) tensor at ({sup 111}In (EC){yields}) {sup 111}Cd nuclei located, as was later demonstrated, at defect-free cation sites of the ZnO host structure. The PAC experiments were performed in the temperature range of 77-1075 K. At first glance, the unexpected presence of low-intensity dynamic hyperfine interactions was observed, which were analyzed with a perturbation factor based on the Baeverstam and Othaz model. The experimental EFG results were compared with ab initio calculations performed with the Full-Potential Augmented Plane Wave plus local orbital (FP-APW+lo) method, in the framework of the Density Functional Theory (DFT), using the Wien2K code. The presence of the dynamic hyperfine interactions has been analyzed enlightened by the FP-APW+lo calculations of the EFG performed as a function of the charge state of the cell. We could correlate the large strength of the dynamic hyperfine interaction with the strong variation of the EFG due to changes in the electronic charge distribution in the Cd vicinity during the time-window of the PAC measurement. It was also revealed that the Cd impurity decays to a final stable neutral charge state (Cd{sup 2+}) fast enough (in few ns) to produce the nearly undamped observed PAC spectra.

Summary of workshop 'Theory Meets Industry'—the impact of ab initio solid state calculations on industrial materials research

Science.gov (United States)

Wimmer, E.

2008-02-01

A workshop, 'Theory Meets Industry', was held on 12-14 June 2007 in Vienna, Austria, attended by a well balanced number of academic and industrial scientists from America, Europe, and Japan. The focus was on advances in ab initio solid state calculations and their practical use in industry. The theoretical papers addressed three dominant themes, namely (i) more accurate total energies and electronic excitations, (ii) more complex systems, and (iii) more diverse and accurate materials properties. Hybrid functionals give some improvements in energies, but encounter difficulties for metallic systems. Quantum Monte Carlo methods are progressing, but no clear breakthrough is on the horizon. Progress in order-N methods is steady, as is the case for efficient methods for exploring complex energy hypersurfaces and large numbers of structural configurations. The industrial applications were dominated by materials issues in energy conversion systems, the quest for hydrogen storage materials, improvements of electronic and optical properties of microelectronic and display materials, and the simulation of reactions on heterogeneous catalysts. The workshop is a clear testimony that ab initio computations have become an industrial practice with increasingly recognized impact.

Spin-flip configuration interaction singles with exact spin-projection: Theory and applications to strongly correlated systems.

Science.gov (United States)

Tsuchimochi, Takashi

2015-10-14

Spin-flip approaches capture static correlation with the same computational scaling as the ordinary single reference methods. Here, we extend spin-flip configuration interaction singles (SFCIS) by projecting out intrinsic spin-contamination to make it spin-complete, rather than by explicitly complementing it with spin-coupled configurations. We give a general formalism of spin-projection for SFCIS, applicable to any spin states. The proposed method is viewed as a natural unification of SFCIS and spin-projected CIS to achieve a better qualitative accuracy at a low computational cost. While our wave function ansatz is more compact than previously proposed spin-complete SF approaches, it successfully offers more general static correlation beyond biradicals without sacrificing good quantum numbers. It is also shown that our method is invariant with respect to open-shell orbital rotations, due to the uniqueness of spin-projection. We will report benchmark calculations to demonstrate its qualitative performance on strongly correlated systems, including conical intersections that appear both in ground-excited and excited-excited degeneracies.

Towards hydrogen metallization: an Ab initio approach; Vers la metallisation de l`hydrogene: approche AB initio

Energy Technology Data Exchange (ETDEWEB)

Bernard, St

1998-12-31

The quest for metallic hydrogen is a major goal for both theoretical and experimental condensed matter physics. Hydrogen and deuterium have been compressed up to 200 GPa in diamond anvil cells, without any clear evidence for a metallic behaviour. Loubeyere has recently suggested that hydrogen could metallize, at pressures within experimental range, in a new Van der Waals compound: Ar(H{sub 2}){sub 2} which is characterized at ambient pressure by an open and anisotropic sublattice of hydrogen molecules, stabilized by an argon skeleton. This thesis deals with a detailed ab initio investigation, by Car-Parrinello molecular dynamics methods, of the evolution under pressure of this compound. In a last chapter, we go to much higher pressures and temperatures, in order to compare orbital and orbital free ab initio methods for the dense hydrogen plasma. (author) 109 refs.

Towards hydrogen metallization: an Ab initio approach; Vers la metallisation de l`hydrogene: approche AB initio

Energy Technology Data Exchange (ETDEWEB)

Bernard, St

1999-12-31

The quest for metallic hydrogen is a major goal for both theoretical and experimental condensed matter physics. Hydrogen and deuterium have been compressed up to 200 GPa in diamond anvil cells, without any clear evidence for a metallic behaviour. Loubeyere has recently suggested that hydrogen could metallize, at pressures within experimental range, in a new Van der Waals compound: Ar(H{sub 2}){sub 2} which is characterized at ambient pressure by an open and anisotropic sublattice of hydrogen molecules, stabilized by an argon skeleton. This thesis deals with a detailed ab initio investigation, by Car-Parrinello molecular dynamics methods, of the evolution under pressure of this compound. In a last chapter, we go to much higher pressures and temperatures, in order to compare orbital and orbital free ab initio methods for the dense hydrogen plasma. (author) 109 refs.

Isotope shift and configuration interaction in U I

International Nuclear Information System (INIS)

King, W.H.

1979-01-01

Recent calculations by Rajnak and Fred (J. Opt. Soc. Am.; 67:1314 (1977)) show that the transitions studied by Gagne et al (J. Opt. Soc. Am.; 66:1415 (1976)) have upper levels of mixed configurations. The amount of mixing and the probability of mass shifts due to 5f electrons is discussed. (author)

Comparison of fully internally and strongly contracted multireference configuration interaction procedures

Science.gov (United States)

Sivalingam, Kantharuban; Krupicka, Martin; Auer, Alexander A.; Neese, Frank

2016-08-01

Multireference (MR) methods occupy an important class of approaches in quantum chemistry. In many instances, for example, in studying complex magnetic properties of transition metal complexes, they are actually the only physically satisfactory choice. In traditional MR approaches, single and double excitations are performed with respect to all reference configurations (or configuration state functions, CSFs), which leads to an explosive increase of computational cost for larger reference spaces. This can be avoided by the internal contraction scheme proposed by Meyer and Siegbahn, which effectively reduces the number of wavefunction parameters to their single-reference counterpart. The "fully internally contracted" scheme (FIC) is well known from the popular CASPT2 approach. An even shorter expansion of the wavefunction is possible with the "strong contraction" (SC) scheme proposed by Angeli and Malrieu in their NEVPT2 approach. Promising multireference configuration interaction formulations (MRCI) employing internal contraction and strong contraction have been reported by several authors. In this work, we report on the implementation of the FIC-MRCI and SC-MRCI methodologies, using a computer assisted implementation strategy. The methods are benchmarked against the traditional uncontracted MRCI approach for ground and excited states of small molecules (N2, O2, CO, CO+, OH, CH, and CN). For ground states, the comparison includes the "partially internally contracted" MRCI based on the Celani-Werner ansatz (PC-MRCI). For the three contraction schemes, the average errors range from 2% to 6% of the uncontracted MRCI correlation energies. Excitation energies are reproduced with ˜0.2 eV accuracy. In most cases, the agreement is better than 0.2 eV, even in cases with very large differential correlation contributions as exemplified for the d-d and ligand-to-metal charge transfer transitions of a Cu [NH 3 ] 4 2 + model complex. The benchmark is supplemented with the

A combined photoelectron spectroscopy and relativistic ab initio studies of the electronic structures of UFO and UFO-

Science.gov (United States)

Roy, Soumendra K.; Jian, Tian; Lopez, Gary V.; Li, Wei-Li; Su, Jing; Bross, David H.; Peterson, Kirk A.; Wang, Lai-Sheng; Li, Jun

2016-02-01

The observation of the gaseous UFO- anion is reported, which is investigated using photoelectron spectroscopy and relativisitic ab initio calculations. Two strong photoelectron bands are observed at low binding energies due to electron detachment from the U-7sσ orbital. Numerous weak detachment bands are also observed due to the strongly correlated U-5f electrons. The electron affinity of UFO is measured to be 1.27(3) eV. High-level relativistic quantum chemical calculations have been carried out on the ground state and many low-lying excited states of UFO to help interpret the photoelectron spectra and understand the electronic structure of UFO. The ground state of UFO- is linear with an O-U-F structure and a 3H4 spectral term derived from a U 7sσ25fφ15fδ1 electron configuration, whereas the ground state of neutral UFO has a 4H7/2 spectral term with a U 7sσ15fφ15fδ1 electron configuration. Strong electron correlation effects are found in both the anionic and neutral electronic configurations. In the UFO neutral, a high density of electronic states with strong configuration mixing is observed in most of the scalar relativistic and spin-orbit coupled states. The strong electron correlation, state mixing, and spin-orbit coupling of the electronic states make the excited states of UFO very challenging for accurate quantum chemical calculations.

A combined photoelectron spectroscopy and relativistic ab initio studies of the electronic structures of UFO and UFO(-).

Science.gov (United States)

Roy, Soumendra K; Jian, Tian; Lopez, Gary V; Li, Wei-Li; Su, Jing; Bross, David H; Peterson, Kirk A; Wang, Lai-Sheng; Li, Jun

2016-02-28

The observation of the gaseous UFO(-) anion is reported, which is investigated using photoelectron spectroscopy and relativisitic ab initio calculations. Two strong photoelectron bands are observed at low binding energies due to electron detachment from the U-7sσ orbital. Numerous weak detachment bands are also observed due to the strongly correlated U-5f electrons. The electron affinity of UFO is measured to be 1.27(3) eV. High-level relativistic quantum chemical calculations have been carried out on the ground state and many low-lying excited states of UFO to help interpret the photoelectron spectra and understand the electronic structure of UFO. The ground state of UFO(-) is linear with an O-U-F structure and a (3)H4 spectral term derived from a U 7sσ(2)5fφ(1)5fδ(1) electron configuration, whereas the ground state of neutral UFO has a (4)H(7/2) spectral term with a U 7sσ(1)5fφ(1)5fδ(1) electron configuration. Strong electron correlation effects are found in both the anionic and neutral electronic configurations. In the UFO neutral, a high density of electronic states with strong configuration mixing is observed in most of the scalar relativistic and spin-orbit coupled states. The strong electron correlation, state mixing, and spin-orbit coupling of the electronic states make the excited states of UFO very challenging for accurate quantum chemical calculations.

Rosetta FlexPepDock ab-initio: simultaneous folding, docking and refinement of peptides onto their receptors.

Science.gov (United States)

Raveh, Barak; London, Nir; Zimmerman, Lior; Schueler-Furman, Ora

2011-04-29

Flexible peptides that fold upon binding to another protein molecule mediate a large number of regulatory interactions in the living cell and may provide highly specific recognition modules. We present Rosetta FlexPepDock ab-initio, a protocol for simultaneous docking and de-novo folding of peptides, starting from an approximate specification of the peptide binding site. Using the Rosetta fragments library and a coarse-grained structural representation of the peptide and the receptor, FlexPepDock ab-initio samples efficiently and simultaneously the space of possible peptide backbone conformations and rigid-body orientations over the receptor surface of a given binding site. The subsequent all-atom refinement of the coarse-grained models includes full side-chain modeling of both the receptor and the peptide, resulting in high-resolution models in which key side-chain interactions are recapitulated. The protocol was applied to a benchmark in which peptides were modeled over receptors in either their bound backbone conformations or in their free, unbound form. Near-native peptide conformations were identified in 18/26 of the bound cases and 7/14 of the unbound cases. The protocol performs well on peptides from various classes of secondary structures, including coiled peptides with unusual turns and kinks. The results presented here significantly extend the scope of state-of-the-art methods for high-resolution peptide modeling, which can now be applied to a wide variety of peptide-protein interactions where no prior information about the peptide backbone conformation is available, enabling detailed structure-based studies and manipulation of those interactions. © 2011 Raveh et al.

Ab initio potential for solids

DEFF Research Database (Denmark)

Chetty, N.; Stokbro, Kurt; Jacobsen, Karsten Wedel

1992-01-01

. At the most approximate level, the theory is equivalent to the usual effective-medium theory. At all levels of approximation, every term in the total-energy expression is calculated ab initio, that is, without any fitting to experiment or to other calculations. Every step in the approximation procedure can...

Ab initio investigation of superconductivity in orthorhombic MgPtSi

Energy Technology Data Exchange (ETDEWEB)

Tütüncü, H.M., E-mail: tutuncu@sakarya.edu.tr [Sakarya Üniversitesi, Fen-Edebiyat Fakültesi, Fizik Bölümü, 54187, Adapazarı (Turkey); Sakarya Üniversitesi, BIMAYAM Biyomedikal, Manyetik ve Yarıiletken Malzemeler Araştırma Merkezi, 54187, Adapazarı (Turkey); Ertuǧrul Karaca [Sakarya Üniversitesi, Fen-Edebiyat Fakültesi, Fizik Bölümü, 54187, Adapazarı (Turkey); Srivastava, G.P. [School of Physics, University of Exeter, Stocker Road, Exeter EX4 4QL (United Kingdom)

2016-07-15

We have performed an ab initio study of electronic, vibrational and superconducting properties of the orthorhombic MgPtSi by employing the density functional theory, a linear-response formalism, and the plane-wave pseudopotential method. Our electronic results suggest that the density of states at the Fermi level is primarily contributed by Pt 5d and Si 3p states with much smaller contribution from Mg electronic states. Phonon anomalies have been found for all three acoustic branches. Due to these phonon anomalies, the acoustic branches make large contributions to the average electron-phonon coupling parameter. From the Eliashberg spectral function, the value of average electron-phonon coupling parameter is found to 0.707. Using this value, the superconducting critical temperature is obtained to be 2.4 K, in excellent accordance with its experimental value of 2.5 K. - Highlights: • The electronic structure of MgPtSi is studied using ab initio pseudopotential method. • Phonons and electron–phonon interaction in MgPtSi are studied using a linear response theory. • The acoustic phonon modes couple more strongly with electrons. • The value of λ is found to be 0.707 which shows that MgPtSi is a conventional honon-mediated superconductor. • The calculated T{sub c} of 2.4 K is in excellent accordance with its experimental value of 2.5 K.

Ab initio study of C14 laves phases in Fe-based systems

Directory of Open Access Journals (Sweden)

Pavlu J.

2012-01-01

Full Text Available Structural properties and energetics of Fe-based C14 Laves phases at various compositions (i.e. Fe2Fe, Fe2X, X2Fe, X2X, where X stands for Si, Cr, Mo, W, Ta were investigated using the pseudopotential VASP (Vienna Ab initio Simulation Package code employing the PAW-PBE (Projector Augmented Wave - Perdew Burke-Ernzerhof pseudopotentials. Full relaxation was performed for all structures studied including the reference states of elemental constituents and the equilibrium structure parameters as well as bulk moduli were found. The structure parameters of experimentally found structures were very well reproduced by our calculations. It was also found that the lattice parameters and volumes of the unit cell decrease with increasing molar fraction of iron. Thermodynamic analysis shows that the Fe2X configurations of Laves phases are more stable than the X2Fe ones. Some of the X2Fe configurations are even unstable with respect to the weighted average of the Laves phases of elemental constituents. Our calculations predict the stability of Fe2Ta. On the other hand, Fe2Mo and Fe2W are slightly unstable (3.19 and 0.68 kJ.mol-1, respectively and hypothetical structures Fe2Cr and Fe2Si are found unstable as well.

Criticality in the configuration-mixed interacting boson model (1) $U(5)-\\hat{Q}(\\chi)\\cdot\\hat{Q}(\\chi)$ mixing

CERN Document Server

Hellemans, V; De Baerdemacker, S; Heyde, K

2008-01-01

The case of U(5)--$\\hat{Q}(\\chi)\\cdot\\hat{Q}(\\chi)$ mixing in the configuration-mixed Interacting Boson Model is studied in its mean-field approximation. Phase diagrams with analytical and numerical solutions are constructed and discussed. Indications for first-order and second-order shape phase transitions can be obtained from binding energies and from critical exponents, respectively.

Ab initio Eliashberg Theory: Making Genuine Predictions of Superconducting Features

Science.gov (United States)

Sanna, Antonio; Flores-Livas, José A.; Davydov, Arkadiy; Profeta, Gianni; Dewhurst, Kay; Sharma, Sangeeta; Gross, E. K. U.

2018-04-01

We present an application of Eliashberg theory of superconductivity to study a set of novel superconducting systems with a wide range of structural and chemical properties. The set includes three intercalated group-IV honeycomb layered structures, SH3 at 200 GPa (the superconductor with the highest measured critical temperature), the similar system SeH3 at 150 GPa, and a lithium doped mono-layer of black phosphorus. The theoretical approach we adopt is a recently developed, fully ab initio Eliashberg approach that takes into account the Coulomb interaction in a full energy-resolved fashion avoiding any free parameters like μ*. This method provides reasonable estimations of superconducting properties, including TC and the excitation spectra of superconductors.

Ab initio theory for current-induced molecular switching: Melamine on Cu(001)

KAUST Repository

Ohto, Tatsuhiko

2013-05-28

Melamine on Cu(001) is mechanically unstable under the current of a scanning tunneling microscope tip and can switch among configurations. However, these are not equally accessible, and the switching critical current depends on the bias polarity. In order to explain such rich phenomenology, we have developed a scheme to evaluate the evolution of the reaction paths and activation barriers as a function of bias, which is rooted in the nonequilibrium Green\\'s function method implemented within density functional theory. This, combined with the calculation of the inelastic electron tunneling spectroscopy signal, allows us to identify the vibrational modes promoting the observed molecular conformational changes. Finally, once our ab initio results are used within a resonance model, we are able to explain the details of the switching behavior, such as its dependence on the bias polarity, and the noninteger power relation between the reaction rate constants and both the bias voltage and the electric current. © 2013 American Physical Society.

Ab initio theory for current-induced molecular switching: Melamine on Cu(001)

KAUST Repository

Ohto, Tatsuhiko; Rungger, Ivan; Yamashita, Koichi; Nakamura, Hisao; Sanvito, Stefano

2013-01-01

Melamine on Cu(001) is mechanically unstable under the current of a scanning tunneling microscope tip and can switch among configurations. However, these are not equally accessible, and the switching critical current depends on the bias polarity. In order to explain such rich phenomenology, we have developed a scheme to evaluate the evolution of the reaction paths and activation barriers as a function of bias, which is rooted in the nonequilibrium Green's function method implemented within density functional theory. This, combined with the calculation of the inelastic electron tunneling spectroscopy signal, allows us to identify the vibrational modes promoting the observed molecular conformational changes. Finally, once our ab initio results are used within a resonance model, we are able to explain the details of the switching behavior, such as its dependence on the bias polarity, and the noninteger power relation between the reaction rate constants and both the bias voltage and the electric current. © 2013 American Physical Society.

Configuration interaction effect on open M shell Fe and Ni LTE spectral opacities, Rosseland and Planck means

International Nuclear Information System (INIS)

Gilles, D; Busquet, M; Gilleron, F; Pain, J-C; Klapisch, M

2016-01-01

We have recently shown that iron and nickel open M-shell opacity spectra, up to Δn = 2 are very sensitive to Configuration Interaction (CI) treatments at temperature around 15 eV and for various densities. To do so we had compared extensive CI calculations obtained with two opacity codes HULLAC-v9 and SCO-RCG. In this work we extend these comparisons to a first evaluation of CI effects on Rosseland and Planck means. (paper)

Repulsive energy and the Grueneisen parameter of alkali halides calculated on the basis of a quantum-statistical ab initio theory

International Nuclear Information System (INIS)

Kucharczyk, M.; Olszewski, S.

1982-01-01

The Grueneisen parameter of alkali halides is calculated by an ab initio quantum-statistical method and then compared with the experimental data. The crystal model applied assumes the crystal ions to be compressible but impenetrable spheres. The ions are described with the aid of a modified Thomas-Fermi theory with exchange. At the next step it is possible to calculate the energy needed to transform the system of the non-interacting ions into the ionic system represented by the crystal lattice. This calculation allows for an ab initio estimate of the parameters entering the Born, or the Born-Mayer, repulsive part of the crystal energy. The parameters are then used in the calculation of the Grueneisen parameter and its dependence on the crystal compression. (author)

Ab initio study on the thermal properties of the fcc Al3Mg and Al3Sc alloys

International Nuclear Information System (INIS)

Li Donglin; Chen Ping; Yi Jianxiong; Tang Biyu; Peng Liming; Ding Wenjiang

2009-01-01

Ab initio density functional theory (DFT) and density function perturbation theory (DFPT) have been used to investigate the thermal properties of the fcc Al 3 Mg and Al 3 Sc alloys over a wide range of pressure and temperature, in comparison with fcc Al. Phonon dispersions were obtained at equilibrium and strained configurations by density functional perturbation theory. Using the quasiharmonic approximation for the free energy, several thermal quantities of interest, such as the thermal Grueneisen parameter, heat capacity, thermal expansion coefficient and entropy, were calculated as a function of temperature and pressure, and the variation features of these quantities were discussed in detail. This investigation provides useful information for design and applications of technologically relevant Al-based alloys.

Transition state theory thermal rate constants and RRKM-based branching ratios for the N((2)D) + CH(4) reaction based on multi-state and multi-reference ab initio calculations of interest for the Titan's chemistry.

Science.gov (United States)

Ouk, Chanda-Malis; Zvereva-Loëte, Natalia; Scribano, Yohann; Bussery-Honvault, Béatrice

2012-10-30

Multireference single and double configuration interaction (MRCI) calculations including Davidson (+Q) or Pople (+P) corrections have been conducted in this work for the reactants, products, and extrema of the doublet ground state potential energy surface involved in the N((2)D) + CH(4) reaction. Such highly correlated ab initio calculations are then compared with previous PMP4, CCSD(T), W1, and DFT/B3LYP studies. Large relative differences are observed in particular for the transition state in the entrance channel resolving the disagreement between previous ab initio calculations. We confirm the existence of a small but positive potential barrier (3.86 ± 0.84 kJ mol(-1) (MR-AQCC) and 3.89 kJ mol(-1) (MRCI+P)) in the entrance channel of the title reaction. The correlation is seen to change significantly the energetic position of the two minima and five saddle points of this system together with the dissociation channels but not their relative order. The influence of the electronic correlation into the energetic of the system is clearly demonstrated by the thermal rate constant evaluation and it temperature dependance by means of the transition state theory. Indeed, only MRCI values are able to reproduce the experimental rate constant of the title reaction and its behavior with temperature. Similarly, product branching ratios, evaluated by means of unimolecular RRKM theory, confirm the NH production of Umemoto et al., whereas previous works based on less accurate ab initio calculations failed. We confirm the previous findings that the N((2)D) + CH(4) reaction proceeds via an insertion-dissociation mechanism and that the dominant product channels are CH(2)NH + H and CH(3) + NH. Copyright © 2012 Wiley Periodicals, Inc.

Large-scale parallel configuration interaction. II. Two- and four-component double-group general active space implementation with application to BiH

DEFF Research Database (Denmark)

Knecht, Stefan; Jensen, Hans Jørgen Aagaard; Fleig, Timo

2010-01-01

We present a parallel implementation of a large-scale relativistic double-group configuration interaction CIprogram. It is applicable with a large variety of two- and four-component Hamiltonians. The parallel algorithm is based on a distributed data model in combination with a static load balanci...

Disordered crystals from first principles I: Quantifying the configuration space

Science.gov (United States)

Kühne, Thomas D.; Prodan, Emil

2018-04-01

This work represents the first chapter of a project on the foundations of first-principle calculations of the electron transport in crystals at finite temperatures. We are interested in the range of temperatures, where most electronic components operate, that is, room temperature and above. The aim is a predictive first-principle formalism that combines ab-initio molecular dynamics and a finite-temperature Kubo-formula for homogeneous thermodynamic phases. The input for this formula is the ergodic dynamical system (Ω , G , dP) defining the thermodynamic crystalline phase, where Ω is the configuration space for the atomic degrees of freedom, G is the space group acting on Ω and dP is the ergodic Gibbs measure relative to the G-action. The present work develops an algorithmic method for quantifying (Ω , G , dP) from first principles. Using the silicon crystal as a working example, we find the Gibbs measure to be extremely well characterized by a multivariate normal distribution, which can be quantified using a small number of parameters. The latter are computed at various temperatures and communicated in the form of a table. Using this table, one can generate large and accurate thermally-disordered atomic configurations to serve, for example, as input for subsequent simulations of the electronic degrees of freedom.

Ab-initio calculations for dilute magnetic semiconductors

Energy Technology Data Exchange (ETDEWEB)

Belhadji, Brahim

2008-03-03

This thesis focusses on ab-initio calculations for the electronic structure and the magnetic properties of dilute magnetic semiconductors (DMS). In particular we aim at the understanding of the complex exchange interactions in these systems. Our calculations are based on density functional theory, being ideally suited for a description of the material specific properties of the considered DMS. Moreover we use the KKR Green function method in connection with the coherent potential approximation (CPA), which allows to include the random substitutional disorder in a mean field-like approximation for the electronic structure. Finally we calculate the exchange coupling constants J{sub ij} between two impurities in a CPA medium by using the Lichtenstein formula and from this calculate the Curie temperature by a numerically exact Monte Carlo method. Based on this analysis we found and investigated four different exchange mechanisms being of importance in DMS systems: Double exchange, p-d exchange, antiferromagnetic superexchanges, and ferromagnetic superexchange. A second topic we have investigated in this thesis is the pressure dependence of the exchange interactions and the Curie temperatures in (Ga,Mn)As and (In,Mn)As, using the LDA and the LDA+U approximations. Exact calculations of T{sub C} by Monte Carlo simulations show a somehow different behavior. (orig.)

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

International Nuclear Information System (INIS)

Saha, H.P.

1993-01-01

The multiconfiguration Hartree-Fock method for continuum wave functions has been used to calculate the scattering length and phase shifts over extremely low energies ranging from 0 to 1 eV very accurately for electron-helium scattering. The scattering length is calculated very accurately with wave functions computed exactly at zero energy, resulting in an upper bound of 1.1784. The electron correlation and polarization of the target by the scattering electron, which are very important in these calculations, have been taken into account in an accurate ab initio manner through the configuration-interaction procedure by optimizing both bound and continuum orbitals simultaneously at each kinetic energy of the scattered electron. Detailed results for scattering length, differential, total, and momentum-transfer cross sections obtained from the phase shifts are presented. The present scattering length is found to be in excellent agreement with the experimental result of Andrick and Bitsch [J. Phys. B 8, 402 (1975)] and the theoretical result of O'Malley, Burke, and Berrington [J. Phys. B 12, 953 (1979)]. There is excellent agreement between the present total cross sections and the corresponding experimental measurements of Buckman and Lohmann [J. Phys. B 19, 2547 (1986)]. The present momentum-transfer cross sections also show remarkable agreement with the experimental results of Crompton, Elford, and Robertson [Aust. J. Phys. 23, 667 (1970)

On the physical interpretation of torsion-rotation parameters in methanol and acetaldehyde: Comparison of global fit and ab initio results

International Nuclear Information System (INIS)

Xu, L.; Lees, R.M.; Hougen, J.T.

1999-01-01

Equilibrium structural constants and certain torsion endash rotation interaction parameters have been determined for methanol and acetaldehyde from ab initio calculations using GAUSSIAN 94. The substantial molecular flexing which occurs in going from the bottom to the top of the torsional potential barrier can be quantitatively related to coefficients of torsion endash rotation terms having a (1-cos ampersand hthinsp;3γ) dependence on torsional angle γ. The barrier height, six equilibrium structural constants characterizing the bottom of the potential well, and six torsion endash rotation constants are all compared to experimental parameters obtained from global fits to large microwave and far-infrared data sets for methanol and acetaldehyde. The rather encouraging agreement between the Gaussian and global fit results for methanol seems both to validate the accuracy of ab initio calculations of these parameters, and to demonstrate that the physical origin of these torsion endash rotation interaction terms in methanol lies primarily in structural relaxation with torsion. The less satisfactory agreement between theory and experiment for acetaldehyde requires further study. copyright 1999 American Institute of Physics

Theoretical study of the interaction of N2 with water molecules. (H2O)/sub n/:N2, n = 1--8

International Nuclear Information System (INIS)

Curtiss, L.A.; Eisgruber, C.L.

1984-01-01

Ab initio molecular orbital calculations including correlation energy have been carried out on the interaction of a single H 2 O molecule with N 2 . The potential energy surface for H 2 O:N 2 is found to have a minimum corresponding to a HOH xxx N 2 structure with a weak ( -1 ) hydrogen bond. A second, less stable, configuration corresponding to a H 2 O xxx N 2 structure with N 2 bonded side on to the oxygen of H 2 O was found to be either a minimum or a saddle point in the potential energy surface depending on the level of calculation. The minimal STO-3G basis set was used to investigate the interaction of up to eight H 2 O molecules with N 2 . Two types of clusters, one containing only HOH xxx N 2 interactions and the other containing both HOH xxxN 2 and H 2 O xxx N 2 interactions, were investigated for [N 2 :(H 2 O)/sub n/, n = 2--8

Many-body optimization using an ab initio monte carlo method.

Science.gov (United States)

Haubein, Ned C; McMillan, Scott A; Broadbelt, Linda J

2003-01-01

Advances in computing power have made it possible to study solvated molecules using ab initio quantum chemistry. Inclusion of discrete solvent molecules is required to determine geometric information about solute/solvent clusters. Monte Carlo methods are well suited to finding minima in many-body systems, and ab initio methods are applicable to the widest range of systems. A first principles Monte Carlo (FPMC) method was developed to find minima in many-body systems, and emphasis was placed on implementing moves that increase the likelihood of finding minimum energy structures. Partial optimization and molecular interchange moves aid in finding minima and overcome the incomplete sampling that is unavoidable when using ab initio methods. FPMC was validated by studying the boron trifluoride-water system, and then the method was used to examine the methyl carbenium ion in water to demonstrate its application to solvation problems.

Use of a finite range nucleon-nucleon interaction in the continuum shell model

International Nuclear Information System (INIS)

Faes, Jean-Baptiste

2007-01-01

The unification of nuclear structure and nuclear reactions was always a great challenge of nuclear physics. The extreme complexity of finite quantum systems lead in the past to a separate development of the nuclear structure and the nuclear reactions. A unified description of structure and reactions is possible within the continuum shell model. All previous applications of this model used the zero-range residual interaction and the finite depth local potential to generate the single-particle basis. In the thesis, we have presented an extension of the continuum shell model for finite-range nucleon-nucleon interaction and an arbitrary number of nucleons in the scattering continuum. The great advantage of the present formulation is the same two-body interaction used both to generate the single-particle basis and to describe couplings to the continuum states. This formulation opens a possibility for an ab initio continuum shell model studies with the same nucleon-nucleon interaction generating the nuclear mean field, the configuration mixing and the coupling to the scattering continuum. First realistic applications of the above model has been shown for spectra of "1"7F and "1"7O, and elastic phase-shifts in the reaction "1"6O(p, p)"1"6O. (author)

Evaluation of the Stillinger-Weber classical interaction potential for tetragonal semiconductors in nonideal atomic configurations

International Nuclear Information System (INIS)

Dodson, B.W.

1986-01-01

A classical potential incorporating two- and three-body interaction terms has recently been introduced by Stillinger and Weber (SW) for simulation of the liquefaction transition of silicon. The equilibrium mechanical properties of this potential are determined and found to agree well with experimental values. The potential also seems to be adequate for problems involving computation of defect energies, such as the stability of strained-layer superlattice interfaces. However, inadequate treatment of configurations with low coordination number makes modeling of the epitaxial growth of (111) silicon impossible. Simple modifications of the SW potential form do allow for (111) epitaxial growth, but the earliest stages of growth then become unphysical

Ab initio density functional theory investigation of structural and electronic properties of silicon carbide nanotube bundles

Science.gov (United States)

Moradian, Rostam; Behzad, Somayeh; Chegel, Raad

2008-10-01

By using ab initio density functional theory the structural and electronic properties of isolated and bundled (8,0) and (6,6) silicon carbide nanotubes (SiCNTs) are investigated. Our results show that for such small diameter nanotubes the inter-tube interaction causes a very small radial deformation, while band splitting and reduction of the semiconducting energy band gap are significant. We compared the equilibrium interaction energy and inter-tube separation distance of (8,0) SiCNT bundle with (10,0) carbon nanotube (CNT) bundle where they have the same radius. We found that there is a larger inter-tube separation and weaker inter-tube interaction in the (8,0) SiCNT bundle with respect to (10,0) CNT bundle, although they have the same radius.

Ab initio density functional theory investigation of structural and electronic properties of silicon carbide nanotube bundles

International Nuclear Information System (INIS)

Moradian, Rostam; Behzad, Somayeh; Chegel, Raad

2008-01-01

By using ab initio density functional theory the structural and electronic properties of isolated and bundled (8,0) and (6,6) silicon carbide nanotubes (SiCNTs) are investigated. Our results show that for such small diameter nanotubes the inter-tube interaction causes a very small radial deformation, while band splitting and reduction of the semiconducting energy band gap are significant. We compared the equilibrium interaction energy and inter-tube separation distance of (8,0) SiCNT bundle with (10,0) carbon nanotube (CNT) bundle where they have the same radius. We found that there is a larger inter-tube separation and weaker inter-tube interaction in the (8,0) SiCNT bundle with respect to (10,0) CNT bundle, although they have the same radius

Calculations of configurations of doubly ionized copper (Cu III)

International Nuclear Information System (INIS)

Sugar, J.; Martin, W.C.

1976-01-01

The energy levels belonging to the configurations 3d 7 4s 2 and 3d 8 nl (nl = 4s, 5s, 4p, 5p, 4d, 5d, 4f, and 5g) have been calculated. The radial energy integrals were treated as parameters and adjusted to give a least-squares fit to the observed levels. Two- and three-body effective electrostatic interactions for equivalent electrons were included, as well as two-body effective interactions for inequivalent electrons. Strong configuration interaction between 3d 7 4s 2 and 3d 8 4d was taken into account. Values of the parameters are given for all the above configurations, and the calculated levels are given for all except 3d 8 4s and 3d 8 4p (for which essentially equivalent results have been published). Leading eigenvector percentages are given in appropriate coupling schemes

Configuring the development space for conceptualization

DEFF Research Database (Denmark)

Brønnum, Louise; Clausen, Christian

2013-01-01

This paper addresses issues of conceptualization in the early stages of concept development noted as the Front End of Innovation [FEI]. We examine this particular development space as a socio technical space where a diversity of technological knowledge, user perspectives and organizational agendas...... meet and interact. Based on a case study from an industrial medical company, the paper addresses and analyses the configuration of the development space in a number of projects aiming to take up user oriented perspectives in their activities. It presents insights on how the FEI was orchestrated...... and staged and how different elements and objects contributed to the configuration of the space in order to make it perform in a certain way. The analysis points at the importance of the configuration processes and indicate how these configurations often may act as more or less hidden limitations on concept...

Magnetic properties of vanadium doped CdTe: Ab initio calculations

Energy Technology Data Exchange (ETDEWEB)

Goumrhar, F. [Laboratory of Physics of High Energy, Modeling & Simulations (LPHE-MS), Faculty of Sciences, Mohammed V University of Rabat, Av. Ibn Batouta, B.P. 1014 Rabat (Morocco); Bahmad, L., E-mail: bahmad@fsr.ac.ma [Laboratory of Magnetism and High Energy Physics (LMPHE-URAC12), Faculty of Sciences, Mohammed V University of Rabat, Av. Ibn Batouta, B.P. 1014 Rabat (Morocco); Mounkachi, O. [Material and Nanomaterial Center, MAScIR Fondation, Rabat (Morocco); Benyoussef, A. [Laboratory of Magnetism and High Energy Physics (LMPHE-URAC12), Faculty of Sciences, Mohammed V University of Rabat, Av. Ibn Batouta, B.P. 1014 Rabat (Morocco); Material and Nanomaterial Center, MAScIR Fondation, Rabat (Morocco); Hassan II Academy of Sciences and Technology, Rabat (Morocco)

2017-04-15

In this paper, we are applying the ab initio calculations to study the magnetic properties of vanadium doped CdTe. This study is based on the Korringa–Kohn–Rostoker method (KKR) combined with the coherent potential approximation (CPA), within the local density approximation (LDA). This method is called KKR-CPA-LDA. We have calculated and plotted the density of states (DOS) in the energy diagram for different concentrations of dopants. We have also investigated the magnetic and half-metallic properties of this compound and shown the mechanism of exchange interaction. Moreover, we have estimated the Curie temperature T{sub c} for different concentrations. Finally, we have shown how the crystal field and the exchange splittings vary as a function of the concentrations.

Relativity and Electron Correlation in Chemistry

NARCIS (Netherlands)

Visscher, Lucas

1993-01-01

In this thesis we describe a method for relativistic quantum mechanical calculations on molecules. We obtain relativistic zero order wave functions by the use of the Dirac-Fock method and improve these by relativistic Configuration Interaction. This opens the way for an accurate ab initio treatment

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

International Nuclear Information System (INIS)

Koehler, W.E.; Schaefer, J.

1983-01-01

The temperature dependence of the effective Waldmann--Snider cross sections determining the Senftleben--Beenakker effects of viscosity and heat conductivity has been studied for pH 2 gas between 10 and 200 K. From ab initio nonspherical potentials of H 2 --H 2 , scattering matrices have been determined in close-coupling calculations. From these, the elements of the scattering amplitude matrix have been obtained and used as input quantities for the evaluation of the various Waldmann--Snider collision integrals. The results of these first ab initio numerical calculations of anisotropic transport coefficients show excellent agreement of calculated and measured effective cross sections, especially for the most recent improved version of the interaction potential. In addition, it has been shown that the polarization production cross sections are quite sensitive to the potential anisotropy

Towards hydrogen metallization: an Ab initio approach

International Nuclear Information System (INIS)

Bernard, St.

1998-01-01

The quest for metallic hydrogen is a major goal for both theoretical and experimental condensed matter physics. Hydrogen and deuterium have been compressed up to 200 GPa in diamond anvil cells, without any clear evidence for a metallic behaviour. Loubeyere has recently suggested that hydrogen could metallize, at pressures within experimental range, in a new Van der Waals compound: Ar(H 2 ) 2 which is characterized at ambient pressure by an open and anisotropic sublattice of hydrogen molecules, stabilized by an argon skeleton. This thesis deals with a detailed ab initio investigation, by Car-Parrinello molecular dynamics methods, of the evolution under pressure of this compound. In a last chapter, we go to much higher pressures and temperatures, in order to compare orbital and orbital free ab initio methods for the dense hydrogen plasma. (author)

Single-ion 4f element magnetism: an ab-initio look at Ln(COT)2(-).

Science.gov (United States)

Gendron, Frédéric; Pritchard, Benjamin; Bolvin, Hélène; Autschbach, Jochen

2015-12-14

The electron densities associated with the Ln 4f shell, and spin and orbital magnetizations ('magnetic moment densities'), are investigated for the Ln(COT)2(-) series. The densities are obtained from ab-initio calculations including spin-orbit coupling. For Ln = Ce, Pr the magnetizations are also derived from crystal field models and shown to agree with the ab-initio results. Analysis of magnetizations from ab-initio calculations may be useful in assisting research on single molecule magnets.

Microscopic nucleon spectral function for finite nuclei featuring two- and three-nucleon short-range correlations: The model versus ab initio calculations for three-nucleon systems

Science.gov (United States)

Ciofi degli Atti, Claudio; Mezzetti, Chiara Benedetta; Morita, Hiko

2017-04-01

Background: Two-nucleon (2 N ) short-range correlations (SRC) in nuclei have been recently thoroughly investigated, both theoretically and experimentally and the study of three-nucleon (3 N ) SRC, which could provide important information on short-range hadronic structure, is underway. Novel theoretical ideas concerning 2 N and 3 N SRC are put forward in the present paper. Purpose: The general features of a microscopic one-nucleon spectral function which includes the effects of both 2 N and 3 N SRC and its comparison with ab initio spectral functions of the three-nucleon systems are illustrated. Methods: A microscopic and parameter-free one-nucleon spectral function expressed in terms of a convolution integral involving ab initio relative and center-of-mass (c.m.) momentum distributions of a 2 N pair and aimed at describing two- and three-nucleon short-range correlations, is obtained by using: (i) the two-nucleon momentum distributions obtained within ab initio approaches based upon nucleon-nucleon interactions of the Argonne family; (ii) the exact relation between one- and two-nucleon momentum distributions; (iii) the fundamental property of factorization of the nuclear wave function at short internucleon ranges. Results: The comparison between the ab initio spectral function of 3He and the one based upon the convolution integral shows that when the latter contains only two-nucleon short-range correlations the removal energy location of the peaks and the region around them exhibited by the ab initio spectral function are correctly predicted, unlike the case of the high and low removal energy tails; the inclusion of the effects of three-nucleon correlations brings the convolution model spectral function in much better agreement with the ab initio one; it is also found that whereas the three-nucleon short-range correlations dominate the high energy removal energy tail of the spectral function, their effects on the one-nucleon momentum distribution are almost one

Interaction of ICRF power and edge plasma in Tore Supra ergodic divertor configuration

International Nuclear Information System (INIS)

Nguyen, F.; Grosman, A.; Basiuk, V.; Fraboulet, D.; Beaumont, B.; Becoulet, A.; Ghendrih, Ph.; Ladurelle, L.; Meslin, B.

2000-01-01

The coupling of ICRF power to plasma is a crucial problem in Tore Supra for high power and long pulse operations and depends greatly on the edge parameters, in particular on the edge density. Conversely, the behaviour of the bulk plasma is related to the edge conditions and the injection of RF power also induces major modifications on the edge plasma. Moreover, the Ergodic Divertor (ED) of Tore Supra imposes a complex configuration at the edge due to the presence of the magnetic perturbation. Several diagnostics are available to study the interaction of ICRF power with the edge plasma: Langmuir probes on the ED modules, infra red (IR) cameras, charge exchange neutral analysers. In minority heating scheme, the edge density is very sensitive to any perturbation in the high recycling regime which is always found in the ED configuration for relevant plasma parameters. Partially detached regimes, with or without inhomogeneities of density and temperature induced by the flux tubes of the laminar layer, are obtained for high resistance coupling values. The coupling is then not very robust and feedback control or antenna automatic matching techniques are developed. In fast wave electron heating scheme with ED, various fast wave absorption mechanisms (minority heating, Mode Conversion, Alfven resonance) are present at the plasma edge due to the large size of the plasma. The ICRF coupling is difficult due to the low fast wave direct electron damping, even with high hydrogen minority scheme. An increase of the injected ICRF power could improve this situation

Photoabsorption in sodium clusters: first principles configuration interaction calculations

Science.gov (United States)

Priya, Pradip Kumar; Rai, Deepak Kumar; Shukla, Alok

2017-05-01

We present systematic and comprehensive correlated-electron calculations of the linear photoabsorption spectra of small neutral closed- and open-shell sodium clusters (Nan, n = 2 - 6), as well as closed-shell cation clusters (Nan+, n = 3, 5). We have employed the configuration interaction (CI) methodology at the full CI (FCI) and quadruple CI (QCI) levels to compute the ground, and the low-lying excited states of the clusters. For most clusters, besides the minimum energy structures, we also consider their energetically close isomers. The photoabsorption spectra were computed under the electric-dipole approximation, employing the dipole-matrix elements connecting the ground state with the excited states of each isomer. Our calculations were tested rigorously for convergence with respect to the basis set, as well as with respect to the size of the active orbital space employed in the CI calculations. These calculations reveal that as far as electron-correlation effects are concerned, core excitations play an important role in determining the optimized ground state geometries of various clusters, thereby requiring all-electron correlated calculations. But, when it comes to low-lying optical excitations, only valence electron correlation effects play an important role, and excellent agreement with the experimental results is obtained within the frozen-core approximation. For the case of Na6, the largest cluster studied in this work, we also discuss the possibility of occurrence of plasmonic resonance in the optical absorption spectrum. Supplementary material in the form of one pdf file available from the Journal web page at http://https://doi.org/10.1140/epjd/e2017-70728-3

Robust and Efficient Spin Purification for Determinantal Configuration Interaction.

Science.gov (United States)

Fales, B Scott; Hohenstein, Edward G; Levine, Benjamin G

2017-09-12

The limited precision of floating point arithmetic can lead to the qualitative and even catastrophic failure of quantum chemical algorithms, especially when high accuracy solutions are sought. For example, numerical errors accumulated while solving for determinantal configuration interaction wave functions via Davidson diagonalization may lead to spin contamination in the trial subspace. This spin contamination may cause the procedure to converge to roots with undesired ⟨Ŝ 2 ⟩, wasting computer time in the best case and leading to incorrect conclusions in the worst. In hopes of finding a suitable remedy, we investigate five purification schemes for ensuring that the eigenvectors have the desired ⟨Ŝ 2 ⟩. These schemes are based on projection, penalty, and iterative approaches. All of these schemes rely on a direct, graphics processing unit-accelerated algorithm for calculating the S 2 c matrix-vector product. We assess the computational cost and convergence behavior of these methods by application to several benchmark systems and find that the first-order spin penalty method is the optimal choice, though first-order and Löwdin projection approaches also provide fast convergence to the desired spin state. Finally, to demonstrate the utility of these approaches, we computed the lowest several excited states of an open-shell silver cluster (Ag 19 ) using the state-averaged complete active space self-consistent field method, where spin purification was required to ensure spin stability of the CI vector coefficients. Several low-lying states with significant multiply excited character are predicted, suggesting the value of a multireference approach for modeling plasmonic nanomaterials.

Control of divertor configuration in JT-60

International Nuclear Information System (INIS)

Yoshino, R.; Kukuchi, M.; Ninomiya, H.; Yoshida, H.; Tsuji, S.; Hosogane, N.; Seki, S.

1985-01-01

The control algorithm of JT-60 divertor configuration is presented. JT-60 has five types of poloidal magnetic field coil with each power supply in order to regulate the control objectives mentioned above. However, if one controls each objective by each coil current independently, there must inevitably occur large interaction between control objectives. Because the relation between control objectives and coil currents is complicated. This situation may be the same with a fusion reactor device. For making it possible to control each objective independently without causing large interaction, the authors adopt the noninteracting control algorithm. Hence, this report demonstrates the availability of this method to the control of JT-60 divertor configuration

Study of half-metallic behavior in Sr2CoWO6 perovskite by ab initio DFT calculations

International Nuclear Information System (INIS)

Bonilla, M.; Landinez Tellez, D.A.; Arbey Rodriguez, J.; Aguiar, J. Albino; Roa-Rojas, J.

2008-01-01

In this work, we report several ab initio calculations performed for Sr 2 CoWO 6 by means of the density functional theory and the linearized augmented plane wave method for both spin orientations. For calculations, the exchange and correlation potential were treated into the generalized gradient approximation, which permits to consider from the beginning the difference between the electronic densities for both up and down spin orientations. The densities of states are calculated by the histogram method and the positions of Fermi levels are found by integrating over the density of states for both spin configurations. Our results reveal that Sr 2 CoWO 6 material behaves as insulators for the spin-up orientation and conductor for the spin down, as expected for the half-metallic systems. Results of partial densities of states permit to conclude that the conduction band has predominant contributions of d x 2 -y 2 and d xz+yz states of Co for the spin-down orientation. A magnetic moment of 3 μ B was calculated. From the Murnaghan equation state, we also calculate the cell dimensions that minimize the total energy for several configurations

Multireference configuration interaction treatment of potential energy surfaces: symmetric dissociation of H/sub 2/O in a double-zeta basis

Energy Technology Data Exchange (ETDEWEB)

Brown, F B; Shavitt, I; Shepard, R

1984-03-23

Multiconfiguration self-consistent fields (SCF) and multireference configurational interaction (CI) calculations have been performed for the H/sub 2/O molecule in a double-zeta basis for four symmetric geometries, for comparison with full CI results. Unlike single-reference results, the energy errors are almost independent of geometry, allowing unbiased treatments of potential energy surfaces. 35 references, 1 figure, 2 tables.

Ab Initio periodic Hartree-Fock study of group IA cations in ANA-type zeolites

International Nuclear Information System (INIS)

Anchell, J.L.; White, J.C.; Thompson, M.R.; Hess, A.C.

1994-01-01

This study investigates the electronic structure of Group IA cations intercalated into zeolites with the analcime (ANA) framework using ab initio periodic Hartree-Fock theory. The purpose of the study is to gain a better understanding of the role played by electron-donating species in zeolites in general, with specific applications to materials that have been suggested as storage matrices for radioactive materials. The effect of the intercalated species (Na, K, Rb, and Cs) on the electronic structure of the zeolite is presented on the basis of an analysis of the total and projected density of states, Mulliken charges, and charge density differences. The results of those analyses indicate that, relative to a charge neutral atomic state, the Group IA species donate an electron to the zeolite lattice and interact most strongly with the s and p atomic states of oxygen as the species are moved through the lattice. In addition, estimates of the self-diffusion constants of Na, K, Rb, and Cs based upon a one-dimensional diffusion model parameterized from the ab initio total energy data will be presented. 24 refs., 8 figs., 4 tabs

Experimental evidence for blue-shifted hydrogen bonding in the fluoroform-hydrogen chloride complex: a matrix-isolation infrared and ab initio study.

Science.gov (United States)

Gopi, R; Ramanathan, N; Sundararajan, K

2014-07-24

The 1:1 hydrogen-bonded complex of fluoroform and hydrogen chloride was studied using matrix-isolation infrared spectroscopy and ab initio computations. Using B3LYP and MP2 levels of theory with 6-311++G(d,p) and aug-cc-pVDZ basis sets, the structures of the complexes and their energies were computed. For the 1:1 CHF3-HCl complexes, ab initio computations showed two minima, one cyclic and the other acyclic. The cyclic complex was found to have C-H · · · Cl and C-F · · · H interactions, where CHF3 and HCl sub-molecules act as proton donor and proton acceptor, respectively. The second minimum corresponded to an acyclic complex stabilized only by the C-F · · · H interaction, in which CHF3 is the proton acceptor. Experimentally, we could trap the 1:1 CHF3-HCl cyclic complex in an argon matrix, where a blue-shift in the C-H stretching mode of the CHF3 sub-molecule was observed. To understand the nature of the interactions, Atoms in Molecules and Natural Bond Orbital analyses were carried out to unravel the reasons for blue-shifting of the C-H stretching frequency in these complexes.

The spherical-harmonics representation for the interaction between diatomic molecules: The general case and applications to COsbnd CO and COsbnd HF

Science.gov (United States)

Barreto, Patricia R. P.; Cruz, Ana Claudia P. S.; Barreto, Rodrigo L. P.; Palazzetti, Federico; Albernaz, Alessandra F.; Lombardi, Andrea; Maciel, Glauciete S.; Aquilanti, Vincenzo

2017-07-01

The spherical-harmonics expansion is a mathematically rigorous procedure and a powerful tool for the representation of potential energy surfaces of interacting molecular systems, determining their spectroscopic and dynamical properties, specifically in van der Waals clusters, with applications also to classical and quantum molecular dynamics simulations. The technique consists in the construction (by ab initio or semiempirical methods) of the expanded potential interaction up to terms that provide the generation of a number of leading configurations sufficient to account for faithful geometrical representations. This paper reports the full general description of the method of the spherical-harmonics expansion as applied to diatomic-molecule - diatomic-molecule systems of increasing complexity: the presentation of the mathematical background is given for providing both the application to the prototypical cases considered previously (O2sbnd O2, N2sbnd N2, and N2sbnd O2 systems) and the generalization to: (i) the COsbnd CO system, where a characteristic feature is the lower symmetry order with respect to the cases studied before, requiring a larger number of expansion terms necessary to adequately represent the potential energy surface; and (ii) the COsbnd HF system, which exhibits the lowest order of symmetry among this class of aggregates and therefore the highest number of leading configurations.

On the performance of atomic natural orbital basis sets: A full configuration interaction study

International Nuclear Information System (INIS)

Illas, F.; Ricart, J.M.; Rubio, J.; Bagus, P.S.

1990-01-01

The performance of atomic natural orbital (ANO) basis sets has been studied by comparing self-consistant field (SCF) and full configuration interaction (CI) results obtained for the first row atoms and hydrides. The ANO results have been compared with those obtained using a segmented basis set containing the same number of contracted basis functions. The total energies obtained with the ANO basis sets are always lower than the one obtained by using the segmented one. However, for the hydrides, differential electronic correlation energy obtained with the ANO basis set may be smaller than the one recovered with the segmented set. We relate this poorer differential correlation energy for the ANO basis set to the fact that only one contracted d function is used for the ANO and segmented basis sets

An ab initio and TD DFT

Indian Academy of Sciences (India)

The photophysical behaviour of N-(2-hydroxy benzylidene) aniline or most commonly known as salicylideneaniline (SA) has been investigated using the ab initio and DFT levels of theory. The quantum chemical calculations show that the optimized non planar enol (1) form of the SA molecule is the most stable conformer ...

The 4s24p3-4s4p4 transition in AsI-like AgXV

International Nuclear Information System (INIS)

Dong Chenzhong; Zhao Jinbao

1992-01-01

Some terms of the 4s 4p 4 configuration in RuXII, RhXIII and PdXIV ions can be improved and all the energy values of the configuration in AgXV can be predicted theoretically by means of a configuration-interaction ab initio analysis for the level structure of the 4s 4p 4 configuration along the AsI sequence of KrIV-AgXV ions. Calculations of the wavelengths and oscillator strenghts are presented for the 4s 2 4p 3 -4s 4p 4 transition in AgXV. (orig.)

Nonlinear effects in evolution - an ab initio study: A model in which the classical theory of evolution occurs as a special case.

Science.gov (United States)

Clerc, Daryl G

2016-07-21

An ab initio approach was used to study the molecular-level interactions that connect gene-mutation to changes in an organism׳s phenotype. The study provides new insights into the evolutionary process and presents a simplification whereby changes in phenotypic properties may be studied in terms of the binding affinities of the chemical interactions affected by mutation, rather than by correlation to the genes. The study also reports the role that nonlinear effects play in the progression of organs, and how those effects relate to the classical theory of evolution. Results indicate that the classical theory of evolution occurs as a special case within the ab initio model - a case having two attributes. The first attribute: proteins and promoter regions are not shared among organs. The second attribute: continuous limiting behavior exists in the physical properties of organs as well as in the binding affinity of the associated chemical interactions, with respect to displacements in the chemical properties of proteins and promoter regions induced by mutation. Outside of the special case, second-order coupling contributions are significant and nonlinear effects play an important role, a result corroborated by analyses of published activity levels in binding and transactivation assays. Further, gradations in the state of perfection of an organ may be small or large depending on the type of mutation, and not necessarily closely-separated as maintained by the classical theory. Results also indicate that organs progress with varying degrees of interdependence, the likelihood of successful mutation decreases with increasing complexity of the affected chemical system, and differences between the ab initio model and the classical theory increase with increasing complexity of the organism. Copyright © 2016 The Author. Published by Elsevier Ltd.. All rights reserved.

A deterministic alternative to the full configuration interaction quantum Monte Carlo method

Energy Technology Data Exchange (ETDEWEB)

Tubman, Norm M.; Lee, Joonho; Takeshita, Tyler Y.; Head-Gordon, Martin; Whaley, K. Birgitta [University of California, Berkeley, Berkeley, California 94720 (United States)

2016-07-28

Development of exponentially scaling methods has seen great progress in tackling larger systems than previously thought possible. One such technique, full configuration interaction quantum Monte Carlo, is a useful algorithm that allows exact diagonalization through stochastically sampling determinants. The method derives its utility from the information in the matrix elements of the Hamiltonian, along with a stochastic projected wave function, to find the important parts of Hilbert space. However, the stochastic representation of the wave function is not required to search Hilbert space efficiently, and here we describe a highly efficient deterministic method that can achieve chemical accuracy for a wide range of systems, including the difficult Cr{sub 2} molecule. We demonstrate for systems like Cr{sub 2} that such calculations can be performed in just a few cpu hours which makes it one of the most efficient and accurate methods that can attain chemical accuracy for strongly correlated systems. In addition our method also allows efficient calculation of excited state energies, which we illustrate with benchmark results for the excited states of C{sub 2}.

Ab initio modelling of transition metals in diamond

International Nuclear Information System (INIS)

Watkins, M; Mainwood, A

2003-01-01

Transition metals (TM) from the first transition series are commonly used as solvent catalysts in the synthesis of diamond by high pressure, high temperature processes. Ab initio calculations on these metals, in finite clusters of tetrahedrally coordinated carbon, enable us to investigate trends in their stability and properties. By carrying out systematic studies of interstitial, substitutional and semi-vacancy TM defects, we show that the electronic structure of the TMs is complicated by the presence of 'dangling bonds' when the TM disrupts the crystal lattice: interstitial defects conform to the Ludwig-Woodbury (LW) model, whilst substitutional and semi-vacancy defects move from approximating the LW model early in the transition series to approaching the vacancy model for the heavier metals. Multi-configurational self-consistent field methods allow genuine many-electron states to be modelled; for neutral interstitial, and all substitutional TMs, the crystal fields are found to exceed the exchange energies in strength. Consequently, low spin states are found for these defects. We find substitutional defects to be the most stable, but that semi-vacancy TMs are very similar in energy to the substitutional defects late in the transition series; interstitial defects are only metastable in diamond. Given appropriate charge compensators neutral and positively charged interstitial TM defects were stable, while negatively charged species appeared to be strongly disfavoured

Simulations of two sedimenting-interacting spheres with different sizes and initial configurations using immersed boundary method

Science.gov (United States)

Liao, Chuan-Chieh; Hsiao, Wen-Wei; Lin, Ting-Yu; Lin, Chao-An

2015-06-01

Numerical investigations are carried out for the drafting, kissing and tumbling (DKT) phenomenon of two freely falling spheres within a long container by using an immersed-boundary method. The method is first validated with flows induced by a sphere settling under gravity in a small container for which experimental data are available. The hydrodynamic interactions of two spheres are then studied with different sizes and initial configurations. When a regular sphere is placed below the larger one, the duration of kissing decreases in pace with the increase in diameter ratio. On the other hand, the time duration of the kissing stage increases in tandem with the increase in diameter ratio as the large sphere is placed below the regular one, and there is no DKT interactions beyond threshold diameter ratio. Also, the gap between homogeneous spheres remains constant at the terminal velocity, whereas the gaps between the inhomogeneous spheres increase due to the differential terminal velocity.

Ab initio electronic structure of quasi-two-dimensional materials: A “native” Gaussian–plane wave approach

Energy Technology Data Exchange (ETDEWEB)

Trevisanutto, Paolo E. [Graphene Research Centre and CA2DM, National University of Singapore, Singapore 117542, Singapore and Singapore Synchrotron Light Source, National University of Singapore, Singapore 117603 (Singapore); Vignale, Giovanni, E-mail: vignaleg@missouri.edu [Department of Physics and Astronomy, University of Missouri, Columbia, Missouri 65211 (United States)

2016-05-28

Ab initio electronic structure calculations of two-dimensional layered structures are typically performed using codes that were developed for three-dimensional structures, which are periodic in all three directions. The introduction of a periodicity in the third direction (perpendicular to the layer) is completely artificial and may lead in some cases to spurious results and to difficulties in treating the action of external fields. In this paper we develop a new approach, which is “native” to quasi-2D materials, making use of basis function that are periodic in the plane, but atomic-like in the perpendicular direction. We show how some of the basic tools of ab initio electronic structure theory — density functional theory, GW approximation and Bethe-Salpeter equation — are implemented in the new basis. We argue that the new approach will be preferable to the conventional one in treating the peculiarities of layered materials, including the long range of the unscreened Coulomb interaction in insulators, and the effects of strain, corrugations, and external fields.

Ab-initio calculations of superconducting properties of YBa2Cu3O7

International Nuclear Information System (INIS)

Zhao, G.L.; Bagayoko, D.

1999-01-01

The authors present ab-initio calculations for the electronic structure and superconducting properties of YBa 2 Cu 3 O 7 (YBCO). The electronic structure was calculated using a self-consistent ab-initio LCAO method. They solved the anisotropic Eliashberg gap equation numerically. The strong coupling of the high energy optical phonons around 60--73 meV, with the electrons at the Fermi surface, leads to a high Tc in YBCO. The calculated Tc is about 89 K for μ* = 0.1. The good agreement of the calculated results with experimental measurements and the ab-initio nature of the calculations support the scenario of an anisotropic s-wave superconductor for YBCO

The accuracy of ab initio calculations without ab initio calculations for charged systems: Kriging predictions of atomistic properties for ions in aqueous solutions

Science.gov (United States)

Di Pasquale, Nicodemo; Davie, Stuart J.; Popelier, Paul L. A.

2018-06-01

Using the machine learning method kriging, we predict the energies of atoms in ion-water clusters, consisting of either Cl- or Na+ surrounded by a number of water molecules (i.e., without Na+Cl- interaction). These atomic energies are calculated following the topological energy partitioning method called Interacting Quantum Atoms (IQAs). Kriging predicts atomic properties (in this case IQA energies) by a model that has been trained over a small set of geometries with known property values. The results presented here are part of the development of an advanced type of force field, called FFLUX, which offers quantum mechanical information to molecular dynamics simulations without the limiting computational cost of ab initio calculations. The results reported for the prediction of the IQA components of the energy in the test set exhibit an accuracy of a few kJ/mol, corresponding to an average error of less than 5%, even when a large cluster of water molecules surrounding an ion is considered. Ions represent an important chemical system and this work shows that they can be correctly taken into account in the framework of the FFLUX force field.

Use of ab initio quantum chemical methods in battery technology

Energy Technology Data Exchange (ETDEWEB)

Deiss, E [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

1997-06-01

Ab initio quantum chemistry can nowadays predict physical and chemical properties of molecules and solids. An attempt should be made to use this tool more widely for predicting technologically favourable materials. To demonstrate the use of ab initio quantum chemistry in battery technology, the theoretical energy density (energy per volume of active electrode material) and specific energy (energy per mass of active electrode material) of a rechargeable lithium-ion battery consisting of a graphite electrode and a nickel oxide electrode has been calculated with this method. (author) 1 fig., 1 tab., 7 refs.

Density matrix-based time-dependent configuration interaction approach to ultrafast spin-flip dynamics

Science.gov (United States)

Wang, Huihui; Bokarev, Sergey I.; Aziz, Saadullah G.; Kühn, Oliver

2017-08-01

Recent developments in attosecond spectroscopy yield access to the correlated motion of electrons on their intrinsic timescales. Spin-flip dynamics is usually considered in the context of valence electronic states, where spin-orbit coupling is weak and processes related to the electron spin are usually driven by nuclear motion. However, for core-excited states, where the core-hole has a nonzero angular momentum, spin-orbit coupling is strong enough to drive spin-flips on a much shorter timescale. Using density matrix-based time-dependent restricted active space configuration interaction including spin-orbit coupling, we address an unprecedentedly short spin-crossover for the example of L-edge (2p→3d) excited states of a prototypical Fe(II) complex. This process occurs on a timescale, which is faster than that of Auger decay (∼4 fs) treated here explicitly. Modest variations of carrier frequency and pulse duration can lead to substantial changes in the spin-state yield, suggesting its control by soft X-ray light.

NH2- in a cold ion trap with He buffer gas: Ab initio quantum modeling of the interaction potential and of state-changing multichannel dynamics

Science.gov (United States)

Hernández Vera, Mario; Yurtsever, Ersin; Wester, Roland; Gianturco, Franco A.

2018-05-01

We present an extensive range of accurate ab initio calculations, which map in detail the spatial electronic potential energy surface that describes the interaction between the molecular anion NH2 - (1A1) in its ground electronic state and the He atom. The time-independent close-coupling method is employed to generate the corresponding rotationally inelastic cross sections, and then the state-changing rates over a range of temperatures from 10 to 30 K, which is expected to realistically represent the experimental trapping conditions for this ion in a radio frequency ion trap filled with helium buffer gas. The overall evolutionary kinetics of the rotational level population involving the molecular anion in the cold trap is also modelled during a photodetachment experiment and analyzed using the computed rates. The present results clearly indicate the possibility of selectively detecting differences in behavior between the ortho- and para-anions undergoing photodetachment in the trap.

Ab Initio molecular dynamics with excited electrons

NARCIS (Netherlands)

Alavi, A.; Kohanoff, J.; Parrinello, M.; Frenkel, D.

1994-01-01

A method to do ab initio molecular dynamics suitable for metallic and electronically hot systems is described. It is based on a density functional which is costationary with the finite-temperature functional of Mermin, with state being included with possibly fractional occupation numbers.

Laser-induced electron dynamics including photoionization: A heuristic model within time-dependent configuration interaction theory.

Science.gov (United States)

Klinkusch, Stefan; Saalfrank, Peter; Klamroth, Tillmann

2009-09-21

We report simulations of laser-pulse driven many-electron dynamics by means of a simple, heuristic extension of the time-dependent configuration interaction singles (TD-CIS) approach. The extension allows for the treatment of ionizing states as nonstationary states with a finite, energy-dependent lifetime to account for above-threshold ionization losses in laser-driven many-electron dynamics. The extended TD-CIS method is applied to the following specific examples: (i) state-to-state transitions in the LiCN molecule which correspond to intramolecular charge transfer, (ii) creation of electronic wave packets in LiCN including wave packet analysis by pump-probe spectroscopy, and, finally, (iii) the effect of ionization on the dynamic polarizability of H(2) when calculated nonperturbatively by TD-CIS.

Control Configuration Selection for Multivariable Descriptor Systems

DEFF Research Database (Denmark)

Shaker, Hamid Reza; Stoustrup, Jakob

2012-01-01

Control configuration selection is the procedure of choosing the appropriate input and output pairs for the design of SISO (or block) controllers. This step is an important prerequisite for a successful industrial control strategy. In industrial practices it is often the case that the system, whi...... is that it can be used to propose a richer sparse or block diagonal controller structure. The interaction measure is used for control configuration selection of the linearized CSTR model with descriptor from....

Photochemistry of ethylene: A multireference configuration interaction investigation of the excited-state energy surfaces

International Nuclear Information System (INIS)

Barbatti, M.; Paier, J.; Lischka, H.

2004-01-01

Multireference configuration interaction with singles and doubles (MR-CISD) calculations have been performed for the optimization of conical intersections and stationary points on the ethylene excited-state energy surfaces using recently developed methods for the computation of analytic gradients and nonadiabatic coupling terms. Basis set dependence and the effect of various choices of reference spaces for the MR-CISD calculations have been investigated. The crossing seam between the S 0 and S 1 states has been explored in detail. This seam connects all conical intersections presently known for ethylene. Major emphasis has been laid on the hydrogen-migration path. Starting in the V state of twisted-orthogonal ethylene, a barrierless path to ethylidene was found. The feasibility of ethylidene formation will be important for the explanation of the relative yield of cis and trans H 2 elimination

Interaction between benzenedithiolate and gold: Classical force field for chemical bonding

Science.gov (United States)

Leng, Yongsheng; Krstić, Predrag S.; Wells, Jack C.; Cummings, Peter T.; Dean, David J.

2005-06-01

We have constructed a group of classical potentials based on ab initio density-functional theory (DFT) calculations to describe the chemical bonding between benzenedithiolate (BDT) molecule and gold atoms, including bond stretching, bond angle bending, and dihedral angle torsion involved at the interface between the molecule and gold clusters. Three DFT functionals, local-density approximation (LDA), PBE0, and X3LYP, have been implemented to calculate single point energies (SPE) for a large number of molecular configurations of BDT-1, 2 Au complexes. The three DFT methods yield similar bonding curves. The variations of atomic charges from Mulliken population analysis within the molecule/metal complex versus different molecular configurations have been investigated in detail. We found that, except for bonded atoms in BDT-1, 2 Au complexes, the Mulliken partial charges of other atoms in BDT are quite stable, which significantly reduces the uncertainty in partial charge selections in classical molecular simulations. Molecular-dynamics (MD) simulations are performed to investigate the structure of BDT self-assembled monolayer (SAM) and the adsorption geometry of S adatoms on Au (111) surface. We found that the bond-stretching potential is the most dominant part in chemical bonding. Whereas the local bonding geometry of BDT molecular configuration may depend on the DFT functional used, the global packing structure of BDT SAM is quite independent of DFT functional, even though the uncertainty of some force-field parameters for chemical bonding can be as large as ˜100%. This indicates that the intermolecular interactions play a dominant role in determining the BDT SAMs global packing structure.

Ab initio and matrix isolation study of the acetylene-furan dimer

International Nuclear Information System (INIS)

Sanchez-Garcia, Elsa; Mardyukov, Artur; Tekin, Adem; Crespo-Otero, Rachel; Montero, Luis A.; Sander, Wolfram; Jansen, Georg

2008-01-01

Five acetylene-furan dimer structures are identified using ab initio calculations at the second-order Moller-Plesset (MP2) level of theory. The structures are stabilized by two basic types of intermolecular interactions: the CH...O and the CH...π interaction. The CH...π interaction appears in two variants, depending on which molecule provides the hydrogen atom and which molecule the π system. The MP2 results indicate that the CH...π interaction between one of the hydrogen atoms of acetylene and the π system of furan as found in structure A is the strongest interaction, followed by the in-plane CH...O interaction in the second most stable acetylene-furan dimer structure B. A matrix isolation study shows the acetylene-furan dimer to exist in an argon matrix, but likely rather as structure B than as A. High level coupled cluster calculations with up to triple excitations (CCSD(T)) yield the interaction energy of structure A as about -2.4 kcal/mol in the complete basis set limit and find structure B to be nearly isoenergetic with -2.3 kcal/mol. This is confirmed in calculations employing the density functional theory combined with symmetry adapted intermolecular perturbation theory (DFT-SAPT) approach yielding interaction energies of -2.3 and -2.0 kcal/mol for A and B, respectively. DFT-SAPT also helps to understand the importance of the electrostatic, induction and dispersion interaction energies and their respective exchange counterparts for the stability of the various acetylene-furan dimer structures. The CH...O and CH...π interactions are furthermore analyzed with the help of the atoms in molecules (AIM) theory

Hydration structure and dynamics of a hydroxide ion in water clusters of varying size and temperature: Quantum chemical and ab initio molecular dynamics studies

International Nuclear Information System (INIS)

Bankura, Arindam; Chandra, Amalendu

2012-01-01

Highlights: ► A theoretical study of hydroxide ion-water clusters is carried for varying cluster size and temperature. ► The structures of OH − (H 2 O) n are found out through quantum chemical calculations for n = 4, 8, 16 and 20. ► The finite temperature behavior of the clusters is studied through ab initio dynamical simulations. ► The spectral features of OH modes (deuterated) and their dependence on hydrogen bonding states of water are discussed. ► The mechanism and kinetics of proton transfer processes in these anionic clusters are also investigated. - Abstract: We have investigated the hydration structure and dynamics of OH − (H 2 O) n clusters (n = 4, 8, 16 and 20) by means of quantum chemical and ab initio molecular dynamics calculations. Quantum chemical calculations reveal that the solvation structure of the hydroxide ion transforms from three and four-coordinated surface states to five-coordinated interior state with increase in cluster size. Several other isomeric structures with energies not very different from the most stable isomer are also found. Ab initio simulations show that the most probable configurations at higher temperatures need not be the lowest energy isomeric structure. The rates of proton transfer in these clusters are found to be slower than that in bulk water. The vibrational spectral calculations reveal distinct features for free OH (deuterated) stretch modes of water in different hydrogen bonding states. Effects of temperature on the structural and dynamical properties are also investigated for the largest cluster considered here.

Integrating configuration workflows with project management system

International Nuclear Information System (INIS)

Nilsen, Dimitri; Weber, Pavel

2014-01-01

The complexity of the heterogeneous computing resources, services and recurring infrastructure changes at the GridKa WLCG Tier-1 computing center require a structured approach to configuration management and optimization of interplay between functional components of the whole system. A set of tools deployed at GridKa, including Puppet, Redmine, Foreman, SVN and Icinga, provides the administrative environment giving the possibility to define and develop configuration workflows, reduce the administrative effort and improve sustainable operation of the whole computing center. In this presentation we discuss the developed configuration scenarios implemented at GridKa, which we use for host installation, service deployment, change management procedures, service retirement etc. The integration of Puppet with a project management tool like Redmine provides us with the opportunity to track problem issues, organize tasks and automate these workflows. The interaction between Puppet and Redmine results in automatic updates of the issues related to the executed workflow performed by different system components. The extensive configuration workflows require collaboration and interaction between different departments like network, security, production etc. at GridKa. Redmine plugins developed at GridKa and integrated in its administrative environment provide an effective way of collaboration within the GridKa team. We present the structural overview of the software components, their connections, communication protocols and show a few working examples of the workflows and their automation.

Few-Nucleon Research at TUNL: Probing Two- and Three-Nucleon Interactions with Neutrons

Science.gov (United States)

Howell, C. R.; Tornow, W.; Witała, H.

2016-03-01

The central goal of few-nucleon research at the Triangle Universities Nuclear Laboratory (TUNL) is to perform measurements that contribute to advancing ab-initio calculations of nuclear structure and reactions. The program aims include evaluating theoretical treatments of few-nucleon reaction dynamics through strategically comparing theory predictions to data, determining properties of the neutron-neutron interaction that are not accessible in two-nucleon reactions, and searching for evidence of longrange features of three-nucleon interactions, e.g., spin and isospin dependence. This paper will review studies of three- and four-nucleon systems at TUNL conducted using unpolarized and polarized neutron beams. Measurements of neutron-induced reactions performed by groups at TUNL over the last six years are described in comparison with theory predictions. The results are discussed in the context of the program goals stated above. Measurements of vector analyzing powers for elastic scattering in A=3 and A=4 systems, differential cross sections for neutron-deuteron elastic scattering and neutrondeuteron breakup in several final-state configurations are described. The findings from these studies and plans for the coming three years are presented in the context of worldwide activities in this front, in particular, research presented in this session.

Neutron star equilibrium configurations within a fully relativistic theory with strong, weak, electromagnetic, and gravitational interactions

International Nuclear Information System (INIS)

Belvedere, Riccardo; Pugliese, Daniela; Rueda, Jorge A.; Ruffini, Remo; Xue, She-Sheng

2012-01-01

We formulate the equations of equilibrium of neutron stars taking into account strong, weak, electromagnetic, and gravitational interactions within the framework of general relativity. The nuclear interactions are described by the exchange of the σ, ω, and ρ virtual mesons. The equilibrium conditions are given by our recently developed theoretical framework based on the Einstein–Maxwell–Thomas–Fermi equations along with the constancy of the general relativistic Fermi energies of particles, the “Klein potentials”, throughout the configuration. The equations are solved numerically in the case of zero temperatures and for selected parameterizations of the nuclear models. The solutions lead to a new structure of the star: a positively charged core at supranuclear densities surrounded by an electronic distribution of thickness ∼ℏ/(m e c)∼10 2 ℏ/(m π c) of opposite charge, as well as a neutral crust at lower densities. Inside the core there is a Coulomb potential well of depth ∼m π c 2 /e. The constancy of the Klein potentials in the transition from the core to the crust, imposes the presence of an overcritical electric field ∼(m π /m e ) 2 E c , the critical field being E c =m e 2 c 3 /(eℏ). The electron chemical potential and the density decrease, in the boundary interface, until values μ e crust e core and ρ crust core . For each central density, an entire family of core–crust interface boundaries and, correspondingly, an entire family of crusts with different mass and thickness, exist. The configuration with ρ crust =ρ drip ∼4.3×10 11 gcm −3 separates neutron stars with and without inner crust. We present here the novel neutron star mass–radius for the especial case ρ crust =ρ drip and compare and contrast it with the one obtained from the traditional Tolman–Oppenheimer–Volkoff treatment.

State-of-the-art ab initio potential energy curve for the xenon atom pair and related spectroscopic and thermophysical properties

Science.gov (United States)

Hellmann, Robert; Jäger, Benjamin; Bich, Eckard

2017-07-01

A new ab initio interatomic potential energy curve for two ground-state xenon atoms is presented. It is based on supermolecular calculations at the coupled-cluster level with single, double, and perturbative triple excitations [CCSD(T)] employing basis sets up to sextuple-zeta quality, which were developed as part of this work. In addition, corrections were determined for higher coupled-cluster levels up to CCSDTQ as well as for scalar and spin-orbit relativistic effects at the CCSD(T) level. A physically motivated analytical function was fitted to the calculated interaction energies and used to compute the vibrational spectrum of the dimer, the second virial coefficient, and the dilute gas transport properties. The agreement with the best available experimental data for the investigated properties is excellent; the new potential function is superior not only to previous ab initio potentials but also to the most popular empirical ones.

State-of-the-art ab initio potential energy curve for the xenon atom pair and related spectroscopic and thermophysical properties.

Science.gov (United States)

Hellmann, Robert; Jäger, Benjamin; Bich, Eckard

2017-07-21

A new ab initio interatomic potential energy curve for two ground-state xenon atoms is presented. It is based on supermolecular calculations at the coupled-cluster level with single, double, and perturbative triple excitations [CCSD(T)] employing basis sets up to sextuple-zeta quality, which were developed as part of this work. In addition, corrections were determined for higher coupled-cluster levels up to CCSDTQ as well as for scalar and spin-orbit relativistic effects at the CCSD(T) level. A physically motivated analytical function was fitted to the calculated interaction energies and used to compute the vibrational spectrum of the dimer, the second virial coefficient, and the dilute gas transport properties. The agreement with the best available experimental data for the investigated properties is excellent; the new potential function is superior not only to previous ab initio potentials but also to the most popular empirical ones.

Strong influence of coadsorbate interaction on CO desorption dynamics on Ru(0001) probed by ultrafast x-ray spectroscopy and ab initio simulations

Energy Technology Data Exchange (ETDEWEB)

Xin, H. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States); LaRue, J. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Oberg, H. [Stockholm Univ., Stockholm (Sweden); Beye, M. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Dell' Angela, M. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); Turner, J. J. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Gladh, J. [Stockholm Univ., Stockholm (Sweden); Ng, M. L. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Sellberg, J. A. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Kaya, S. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Mercurio, G. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); Hieke, F. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); Nordlund, D. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Schlotter, W. F. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Dakovski, G. L. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Minitti, M. P. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Fohlisch, A. [Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Univ. Potsdam, Potsdam (Germany); Wolf, M. [Fritz-Haber Institute of the Max-Planck-Society, Berlin (Germany); Wurth, W. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); DESY Photon Science, Hamburg (Germany); Ogasawara, H. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Norskov, J. K. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States); Ostrom, H. [Stockholm Univ., Stockholm (Sweden); Pettersson, L. G. M. [Stockholm Univ., Stockholm (Sweden); Nilsson, A. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Stockholm Univ., Stockholm (Sweden); Ablid-Pedersen, F. [SLAC National Accelerator Lab., Menlo Park, CA (United States)

2015-04-16

We show that coadsorbed oxygen atoms have a dramatic influence on the CO desorption dynamics from Ru(0001). In contrast to the precursor-mediated desorption mechanism on Ru(0001), the presence of surface oxygen modifies the electronic structure of Ru atoms such that CO desorption occurs predominantly via the direct pathway. This phenomenon is directly observed in an ultrafast pump-probe experiment using a soft x-ray free-electron laser to monitor the dynamic evolution of the valence electronic structure of the surface species. This is supported with the potential of mean force along the CO desorption path obtained from density-functional theory calculations. Charge density distribution and frozen-orbital analysis suggest that the oxygen-induced reduction of the Pauli repulsion, and consequent increase of the dative interaction between the CO 5σ and the charged Ru atom, is the electronic origin of the distinct desorption dynamics. Ab initio molecular dynamics simulations of CO desorption from Ru(0001) and oxygen-coadsorbed Ru(0001) provide further insights into the surface bond-breaking process.

Ab initio electronic structure calculations for Mn linear chains deposited on CuN/Cu(001) surfaces

International Nuclear Information System (INIS)

Barral, Maria Andrea; Weht, Ruben; Lozano, Gustavo; Maria Llois, Ana

2007-01-01

In a recent experiment, scanning tunneling microscopy has been used to obtain a direct probe of the magnetic interaction in linear manganese chains arranged by atomic manipulation on thin insulating copper nitride islands grown on Cu(001). The local spin excitation spectra of these chains have been measured with inelastic electron tunneling spectroscopy. Analyzing the spectroscopic results with a Heisenberg Hamiltonian the interatomic coupling strength within the chains has been obtained. It has been found that the coupling strength depends on the deposition sites of the Mn atoms on the islands. In this contribution, we perform ab initio calculations for different arrangements of infinite Mn chains on CuN in order to understand the influence of the environment on the value of the magnetic interactions

Rabi like angular splitting in Surface Plasmon Polariton - Exciton interaction in ATR configuration

Science.gov (United States)

Hassan, Heba; Abdallah, T.; Negm, S.; Talaat, H.

2018-05-01

We have studied the coupling of propagating Surface Plasmon Polaritons (SPP) on silver films and excitons in CdS quantum dots (QDs). We employed the Kretschmann-Raether configuration of the attenuated total reflection (ATR) to propagate the SPP on silver film of thickness 47.5 nm at three different wavelengths. The CdS QD have been chemically synthesized with particular size such that its exciton of energy would resonate with SPP. High resolution transmission electron microscopy (HRTEM) and scan tunneling microscopy (STM) were used to measure the corresponding QDs size and confirm its shape. Further confirmation of the size has been performed by the effective mass approximation (EMA) model utilizing the band gap of the prepared QDs. The band gaps have been measured through UV-vis absorption spectra as well as scan tunneling spectroscopy (STS). The coupling has been observed as two branching dips in the ATR spectra indicating Rabi like splitting. To the best of our knowledge, this is the first time that Rabi interaction is directly observed in an ATR angular spectra. This observation is attributed to the use a high resolution angular scan (±0.005°), in addition to the Doppler width of the laser line as well as the energy distribution of the excitons. The effect of three different linker molecules (TOPO, HDA), (Pyridine) and (Tri-butylamine) as surface ligands, on SPP-Exciton interaction has been examined.

Exponentially more precise quantum simulation of fermions in the configuration interaction representation

Science.gov (United States)

Babbush, Ryan; Berry, Dominic W.; Sanders, Yuval R.; Kivlichan, Ian D.; Scherer, Artur; Wei, Annie Y.; Love, Peter J.; Aspuru-Guzik, Alán

2018-01-01

We present a quantum algorithm for the simulation of molecular systems that is asymptotically more efficient than all previous algorithms in the literature in terms of the main problem parameters. As in Babbush et al (2016 New Journal of Physics 18, 033032), we employ a recently developed technique for simulating Hamiltonian evolution using a truncated Taylor series to obtain logarithmic scaling with the inverse of the desired precision. The algorithm of this paper involves simulation under an oracle for the sparse, first-quantized representation of the molecular Hamiltonian known as the configuration interaction (CI) matrix. We construct and query the CI matrix oracle to allow for on-the-fly computation of molecular integrals in a way that is exponentially more efficient than classical numerical methods. Whereas second-quantized representations of the wavefunction require \\widetilde{{ O }}(N) qubits, where N is the number of single-particle spin-orbitals, the CI matrix representation requires \\widetilde{{ O }}(η ) qubits, where η \\ll N is the number of electrons in the molecule of interest. We show that the gate count of our algorithm scales at most as \\widetilde{{ O }}({η }2{N}3t).

The Pu–U–Am system: An ab initio informed CALPHAD thermodynamic study

International Nuclear Information System (INIS)

Perron, A.; Turchi, P.E.A.; Landa, A.; Söderlind, P.; Ravat, B.; Oudot, B.; Delaunay, F.

2015-01-01

Highlights: • The ab initio informed CALPHAD assessment of the Am–U system has been realized. • A strong tendency toward phase separation across the whole composition range is predicted. • The ab initio informed Pu–U–Am thermodynamic database has been developed. • The solubility of Am and U in the liquid phase is improved by adding Pu. • The δ-Pu (fcc) phase is strongly stabilized by Am, on the contrary to the bcc phase. - Abstract: Phase diagram and thermodynamic properties of the Am–U system, that are experimentally unknown, are calculated using the CALPHAD method with input from ab initio electronic-structure calculations for the fcc and bcc phases. A strong tendency toward phase separation across the whole composition range is predicted. In addition, ab initio informed Pu–U and Am–Pu thermodynamic assessments are combined to build a Pu–U–Am thermodynamic database. Regarding the Pu-rich corner of the ternary system, predictions indicate that Am acts as a powerful δ-Pu (fcc) stabilizer. In the U-rich corner, similar predictions are made but to a lesser extent. In both cases, the bcc phase is destabilized and the fcc phase is enhanced. Finally, results and methodology are discussed and compared with previous assessments and guidelines are provided for further experimental studies

The Pu–U–Am system: An ab initio informed CALPHAD thermodynamic study

Energy Technology Data Exchange (ETDEWEB)

Perron, A., E-mail: perron1@llnl.gov [Lawrence Livermore National Laboratory, Livermore, CA 94550 (United States); Turchi, P.E.A.; Landa, A.; Söderlind, P. [Lawrence Livermore National Laboratory, Livermore, CA 94550 (United States); Ravat, B.; Oudot, B.; Delaunay, F. [CEA-Centre de Valduc, 21120 Is sur Tille (France)

2015-03-15

Highlights: • The ab initio informed CALPHAD assessment of the Am–U system has been realized. • A strong tendency toward phase separation across the whole composition range is predicted. • The ab initio informed Pu–U–Am thermodynamic database has been developed. • The solubility of Am and U in the liquid phase is improved by adding Pu. • The δ-Pu (fcc) phase is strongly stabilized by Am, on the contrary to the bcc phase. - Abstract: Phase diagram and thermodynamic properties of the Am–U system, that are experimentally unknown, are calculated using the CALPHAD method with input from ab initio electronic-structure calculations for the fcc and bcc phases. A strong tendency toward phase separation across the whole composition range is predicted. In addition, ab initio informed Pu–U and Am–Pu thermodynamic assessments are combined to build a Pu–U–Am thermodynamic database. Regarding the Pu-rich corner of the ternary system, predictions indicate that Am acts as a powerful δ-Pu (fcc) stabilizer. In the U-rich corner, similar predictions are made but to a lesser extent. In both cases, the bcc phase is destabilized and the fcc phase is enhanced. Finally, results and methodology are discussed and compared with previous assessments and guidelines are provided for further experimental studies.

Surface chemistry and bonding configuration of ultrananocrystalline diamond surfaces and their effects on nanotribological properties

International Nuclear Information System (INIS)

Sumant, A. V.; Grierson, D. S.; Carpick, R. W.; Gerbi, J. E.; Carlisle, J. A.; Auciello, O.

2007-01-01

We present a comprehensive study of surface composition and nanotribology for ultrananocrystalline diamond (UNCD) surfaces, including the influence of film nucleation on these properties. We describe a methodology to characterize the underside of the films as revealed by sacrificial etching of the underlying substrate. This enables the study of the morphology and composition resulting from the nucleation and initial growth of the films, as well as the characterization of nanotribological properties which are relevant for applications including micro-/nanoelectromechanical systems. We study the surface chemistry, bonding configuration, and nanotribological properties of both the topside and the underside of the film with synchrotron-based x-ray absorption near-edge structure spectroscopy to identify the bonding state of the carbon atoms, x-ray photoelectron spectroscopy to determine the surface chemical composition, Auger electron spectroscopy to further verify the composition and bonding configuration, and quantitative atomic force microscopy to study the nanoscale topography and nanotribological properties. The films were grown on SiO 2 after mechanically polishing the surface with detonation synthesized nanodiamond powder, followed by ultrasonication in a methanol solution containing additional nanodiamond powder. The sp 2 fraction, morphology, and chemistry of the as-etched underside are distinct from the topside, exhibiting a higher sp 2 fraction, some oxidized carbon, and a smoother morphology. The nanoscale single-asperity work of adhesion between a diamond nanotip and the as-etched UNCD underside is far lower than for a silicon-silicon interface (59.2±2 vs 826±186 mJ/m 2 , respectively). Exposure to atomic hydrogen dramatically reduces nanoscale adhesion to 10.2±0.4 mJ/m 2 , at the level of van der Waals' interactions and consistent with recent ab initio calculations. Friction is substantially reduced as well, demonstrating a direct link between the

Ab Initio Atomistic Thermodynamics for Surfaces: A Primer

National Research Council Canada - National Science Library

Rogal, Jutta; Reuter, Karsten

2006-01-01

.... These techniques are referred to as first-principles (or in latin: ab initio) to indicate that they do not rely on empirical or fitted parameters, which then makes them applicable for a wide range of realistic conditions...

Two-electron states of a group-V donor in silicon from atomistic full configuration interactions

Science.gov (United States)

Tankasala, Archana; Salfi, Joseph; Bocquel, Juanita; Voisin, Benoit; Usman, Muhammad; Klimeck, Gerhard; Simmons, Michelle Y.; Hollenberg, Lloyd C. L.; Rogge, Sven; Rahman, Rajib

2018-05-01

Two-electron states bound to donors in silicon are important for both two-qubit gates and spin readout. We present a full configuration interaction technique in the atomistic tight-binding basis to capture multielectron exchange and correlation effects taking into account the full band structure of silicon and the atomic-scale granularity of a nanoscale device. Excited s -like states of A1 symmetry are found to strongly influence the charging energy of a negative donor center. We apply the technique on subsurface dopants subjected to gate electric fields and show that bound triplet states appear in the spectrum as a result of decreased charging energy. The exchange energy, obtained for the two-electron states in various confinement regimes, may enable engineering electrical control of spins in donor-dot hybrid qubits.

Interaction energies and structures of the (n 1–3) complexes

Indian Academy of Sciences (India)

JAMAL N DAWOUD

Lithium ion complexes; ab initio calculations; bond dissociation energy; electrostatic interaction; carbon oxide. 1. Introduction. The chemistry of alkali metal interactions with lig- ands has been the subject of considerable attention in the last twenty years. It has decisive implications in biology, chemistry and physics.1–3 The ...

Evaluation of Early Ground Control Station Configurations for Interacting with a UAS Traffic Management (UTM) System

Science.gov (United States)

Dao, Arik-Quang V.; Martin, Lynne; Mohlenbrink, Christoph; Bienert, Nancy; Wolte, Cynthia; Gomez, Ashley; Claudatos, Lauren; Mercer, Joey

2017-01-01

The purpose of this paper is to report on a human factors evaluation of ground control station design concepts for interacting with an unmanned traffic management system. The data collected for this paper comes from recent field tests for NASA's Unmanned Traffic Management (UTM) project, and covers the following topics; workload, situation awareness, as well as flight crew communication, coordination, and procedures. The goal of this evaluation was to determine if the various software implementations for interacting with the UTM system can be described and classified into design concepts to provide guidance for the development of future UTM interfaces. We begin with a brief description of NASA's UTM project, followed by a description of the test range configuration related to a second development phase. We identified (post hoc) two classes in which the ground control stations could be grouped. This grouping was based on level of display integration. The analysis was exploratory and informal. It was conducted to compare ground stations across those two classes and against the aforementioned topics. Herein, we discuss the results.

Time-resolved photoelectron spectroscopy and ab initio multiple spawning studies of hexamethylcyclopentadiene

DEFF Research Database (Denmark)

Wolf, T. J. A.; Kuhlman, Thomas Scheby; Schalk, O.

2014-01-01

Time-resolved photoelectron spectroscopy and ab initio multiple spawning were applied to the ultrafast non-adiabatic dynamics of hexamethylcyclopentadiene. The high level of agreement between experiment and theory associates wavepacket motion with a distinct degree of freedom.......Time-resolved photoelectron spectroscopy and ab initio multiple spawning were applied to the ultrafast non-adiabatic dynamics of hexamethylcyclopentadiene. The high level of agreement between experiment and theory associates wavepacket motion with a distinct degree of freedom....

Theoretical study of the process of chelate ring scission in β-diketonates of metals. Basic state of lithium β-diketonates

International Nuclear Information System (INIS)

Sirenko, N.S.; L'vov, I.B.; Vovna, V.I.

2000-01-01

By the methods of Mndo and ab initio with configuration interaction (CI) accounting among them two variants of torsion scission of chelate ring in lithium malonodialdeginate and acetylacetonate are investigated. Effect of used approximation and optimization on calculated barriers of rotation and scission energies of metallocycle is estimated. It is shown that value of rotation barrier in ab initio approximation (2.0-2.5 eV) is for 30-100 % more then in MNDO approximation. Accounting of CI leads to insignificant changes of chelate ring scission energies and energy barriers as in direction of increase so in decrease one [ru

In-medium no-core shell model for ab initio nuclear structure calculations

International Nuclear Information System (INIS)

Gebrerufael, Eskendr

2017-01-01

In this work, we merge two successful ab initio nuclear-structure methods, the no-core shell model (NCSM) and the multi-reference in-medium similarity renormalization group (IM-SRG), to define a novel many-body approach for the comprehensive description of ground and excited states of closed- and open-shell medium-mass nuclei. Building on the key advantages of the two methods - the decoupling of excitations at the many-body level in the IM-SRG, and the exact diagonalization in the NCSM applicable up to medium-light nuclei - their combination enables fully converged no-core calculations for an unprecedented range of nuclei and observables at moderate computational cost. The efficiency and rapid model-space convergence of the new approach make it ideally suited for ab initio studies of ground and low-lying excited states of nuclei up to the medium-mass regime. Interactions constructed within the framework of chiral effective field theory provide an excellent opportunity to describe properties of nuclei from first principles, i.e., rooted in quantum chromodynamics, they overcome the lack of predictive power of phenomenological potentials. The hard core of these interactions causes strong short-range correlations, which we soften by using the similarity-renormalization-group transformation that accelerates the model-space convergence of many-body calculations. Three-nucleon effects, which are mandatory for the correct description of bulk properties of nuclei, are included in our calculations by using the normal-ordered two-body approximation, which has been shown to be sufficient to capture the main effects of the three-nucleon interaction. Using these interactions, we analyze energies of ground and excited states in the carbon and oxygen isotopic chains, where conventional NCSM calculations are still feasible and provide an important benchmark. Furthermore, we study the Hoyle state in 12 C - a three-alpha cluster state that cannot be converged in standard NCSM

Supplementary Material for Finding the Stable Structures of N1-xWX with an Ab-initio High-Throughput Approach

Science.gov (United States)

2015-05-08

Supplementary material for “Finding the stable structures of N1−xWX with an ab - initio high-throughput approach” Michael J. Mehl∗ Center for...AND SUBTITLE Supplementary Material for ’Finding the Stable Structures of N1-xWX with an ab - initio High-throughput Approach’ 5a. CONTRACT NUMBER 5b...and J. Hafner, Ab initio molecular dynamics for open-shell transition metals, Phys. Rev. B 48, 13115–13118 (1993). 2 G. Kresse and J. Hafner, Ab initio

A comparative ab initio study of Br2*- and Br2 water clusters.

Science.gov (United States)

Pathak, A K; Mukherjee, T; Maity, D K

2006-01-14

The work presents ab initio results on structure and electronic properties of Br2*-.nH2O(n=1-10) and Br2.nH2O(n=1-8) hydrated clusters to study the effects of an excess electron on the microhydration of the halide dimer. A nonlocal density functional, namely, Becke's half-and-half hybrid exchange-correlation functional is found to perform well on the present systems with a split valence 6-31++G(d,p) basis function. Geometry optimizations for all the clusters are carried out with several initial guess structures and without imposing any symmetry restriction. Br2*-.nH2O clusters prefer to have symmetrical double hydrogen-bonding structures. Results on Br2.nH2O(n>or=2) cluster show that the O atom of one H2O is oriented towards one Br atom and the H atom of another H2O is directed to other Br atom making Br2 to exist as Br+-Br- entity in the cluster. The binding and solvation energies are calculated for the Br2*-.nH2O and Br2.nH2O clusters. Calculations of the vibrational frequencies show that the formation of Br2*- and Br2 water clusters induces significant shifts from the normal modes of isolated water. Excited-state calculations are carried out on Br2*-.nH2O clusters following configuration interaction with single electron excitation procedure and UV-VIS absorption profiles are simulated. There is an excellent agreement between the present theoretical UV-VIS spectra of Br2*-.10H2O cluster and the reported transient optical spectra for Br2*- in aqueous solution.

SGO: A fast engine for ab initio atomic structure global optimization by differential evolution

Science.gov (United States)

Chen, Zhanghui; Jia, Weile; Jiang, Xiangwei; Li, Shu-Shen; Wang, Lin-Wang

2017-10-01

As the high throughout calculations and material genome approaches become more and more popular in material science, the search for optimal ways to predict atomic global minimum structure is a high research priority. This paper presents a fast method for global search of atomic structures at ab initio level. The structures global optimization (SGO) engine consists of a high-efficiency differential evolution algorithm, accelerated local relaxation methods and a plane-wave density functional theory code running on GPU machines. The purpose is to show what can be achieved by combining the superior algorithms at the different levels of the searching scheme. SGO can search the global-minimum configurations of crystals, two-dimensional materials and quantum clusters without prior symmetry restriction in a relatively short time (half or several hours for systems with less than 25 atoms), thus making such a task a routine calculation. Comparisons with other existing methods such as minima hopping and genetic algorithm are provided. One motivation of our study is to investigate the properties of magnetic systems in different phases. The SGO engine is capable of surveying the local minima surrounding the global minimum, which provides the information for the overall energy landscape of a given system. Using this capability we have found several new configurations for testing systems, explored their energy landscape, and demonstrated that the magnetic moment of metal clusters fluctuates strongly in different local minima.

A High Performance Block Eigensolver for Nuclear Configuration Interaction Calculations

International Nuclear Information System (INIS)

Aktulga, Hasan Metin; Afibuzzaman, Md.; Williams, Samuel; Buluc, Aydin; Shao, Meiyue

2017-01-01

As on-node parallelism increases and the performance gap between the processor and the memory system widens, achieving high performance in large-scale scientific applications requires an architecture-aware design of algorithms and solvers. We focus on the eigenvalue problem arising in nuclear Configuration Interaction (CI) calculations, where a few extreme eigenpairs of a sparse symmetric matrix are needed. Here, we consider a block iterative eigensolver whose main computational kernels are the multiplication of a sparse matrix with multiple vectors (SpMM), and tall-skinny matrix operations. We then present techniques to significantly improve the SpMM and the transpose operation SpMM T by using the compressed sparse blocks (CSB) format. We achieve 3-4× speedup on the requisite operations over good implementations with the commonly used compressed sparse row (CSR) format. We develop a performance model that allows us to correctly estimate the performance of our SpMM kernel implementations, and we identify cache bandwidth as a potential performance bottleneck beyond DRAM. We also analyze and optimize the performance of LOBPCG kernels (inner product and linear combinations on multiple vectors) and show up to 15× speedup over using high performance BLAS libraries for these operations. The resulting high performance LOBPCG solver achieves 1.4× to 1.8× speedup over the existing Lanczos solver on a series of CI computations on high-end multicore architectures (Intel Xeons). We also analyze the performance of our techniques on an Intel Xeon Phi Knights Corner (KNC) processor.

Atomic carbon chains as spin-transmitters: An ab initio transport study

DEFF Research Database (Denmark)

Fürst, Joachim Alexander; Brandbyge, Mads; Jauho, Antti-Pekka

2010-01-01

An atomic carbon chain joining two graphene flakes was recently realized in a ground-breaking experiment by Jin et al. (Phys. Rev. Lett., 102 (2009) 205501). We present ab initio results for the electron transport properties of such chains and demonstrate complete spin-polarization of the transmi......An atomic carbon chain joining two graphene flakes was recently realized in a ground-breaking experiment by Jin et al. (Phys. Rev. Lett., 102 (2009) 205501). We present ab initio results for the electron transport properties of such chains and demonstrate complete spin...

Transition-metal interactions in aluminum-rich intermetallics

International Nuclear Information System (INIS)

Al-Lehyani, Ibrahim; Widom, Mike; Wang, Yang; Moghadam, Nassrin; Stocks, G. Malcolm; Moriarty, John A.

2001-01-01

The extension of the first-principles generalized pseudopotential theory (GPT) to transition-metal (TM) aluminides produces pair and many-body interactions that allow efficient calculations of total energies. In aluminum-rich systems treated at the pair-potential level, one practical limitation is a transition-metal overbinding that creates an unrealistic TM-TM attraction at short separations in the absence of balancing many-body contributions. Even with this limitation, the GPT pair potentials have been used effectively in total-energy calculations for Al-TM systems with TM atoms at separations greater than 4 Aa. An additional potential term may be added for systems with shorter TM atom separations, formally folding repulsive contributions of the three- and higher-body interactions into the pair potentials, resulting in structure-dependent TM-TM potentials. Towards this end, we have performed numerical ab initio total-energy calculations using the Vienna ab initio simulation package for an Al-Co-Ni compound in a particular quasicrystalline approximant structure. The results allow us to fit a short-ranged, many-body correction of the form a(r 0 /r) b to the GPT pair potentials for Co-Co, Co-Ni, and Ni-Ni interactions

Dispersion and Solvation Effects on the Structure and Dynamics of N719 Adsorbed to Anatase Titania (101) Surfaces in Room-Temperature Ionic Liquids: An ab Initio Molecular Simulation Study

KAUST Repository

Byrne, Aaron

2015-12-24

Ab initio, density functional theory (DFT)-based molecular dynamics (MD) has been carried out to investigate the effect of explicit solvation on the dynamical and structural properties of a [bmim][NTf2] room-temperature ionic liquid (RTIL), solvating a N719 sensitizing dye adsorbed onto an anatase titania (101) surface. The effect of explicit dispersion on the properties of this dye-sensitized solar cell (DSC) interface has also been studied. Upon inclusion of dispersion interactions in simulations of the solvated system, the average separation between the cations and anions decreases by 0.6 Å; the mean distance between the cations and the surface decreases by about 0.5 Å; and the layering of the RTIL is significantly altered in the first layer surrounding the dye, with the cation being on average 1.5 Å further from the center of the dye. Inclusion of dispersion effects when a solvent is not explicitly included (to dampen longer-range interactions) can result in unphysical "kinking" of the adsorbed dye\\'s configuration. The inclusion of solvent shifts the HOMO and LUMO levels of the titania surface by +3 eV. At this interface, the interplay between the effects of dispersion and solvation combines in ways that are often subtle, such as enhancement or inhibition of specific vibrational modes. © 2015 American Chemical Society.

AB INITIO calculations of magneto-optical effects

Czech Academy of Sciences Publication Activity Database

Kuneš, Jan; Oppeneer, P. M.

2002-01-01

Roč. 2, - (2002), s. 141-146 ISSN 1346-7948 R&D Projects: GA AV ČR IAA1010214 Institutional research plan: CEZ:AV0Z1010914 Keywords : electronic structure * ab initio calculation * polar magneto-optical Kerr effect * transitiom metal * uranium intermetallics * CrO 2 Subject RIV: BM - Solid Matter Physics ; Magnetism

Unraveling the structure of the h-BN/Rh(111) nanomesh with ab initio calculations

International Nuclear Information System (INIS)

Laskowski, R; Blaha, P

2008-01-01

The properties of a single layer of h-BN on top of a Rh(111) surface are discussed in terms of an ab initio generated force field approach as well as by direct ab initio density-functional theory (DFT) calculations. A single-layer model for the h-BN/Rh(111) nanomesh, in contrast to a previously considered (incomplete) double-layer model of h-BN, can explain the experimental data. The main focus of this work is to compare a force field approach described earlier in (Laskowski et al 2007 Phys. Rev. Lett. 98 106802) with direct ab initio calculations. The calculated geometry of the h-BN layer is very similar to the structure predicted by the force field approach. The ab initio calculated density of states projected on N-p x,y of BN corresponding to 'low' and 'high' regions with respect to the Rh surface shows a 1 eV splitting and thus explains the observed σ-band splitting. Moreover, we find good agreement between calculated and experimental scanning tunneling microscope (STM) images of this system

Oscillator strengths for transitions among Fe III levels belonging to the three lowest configurations

International Nuclear Information System (INIS)

Deb, N C; Hibbert, A

2008-01-01

Accurate oscillator strengths and Einstein A-coefficients for some El and E2 transitions among 3d 6 , 3d 5 4s and 3d 5 4p levels of FeIII are presented and compared with other available results. The present results comprise by far the largest configuration interaction calculation for this astrophysically important ion, and include relativistic effects through the Breit-Pauli operator. The core-valence effects from a large number of 3d 6 and 3d 5 cores are carefully treated by optimising 4d, 4f, 5s, 5p, 5d, 5f and 6p orbitals either as a correction or as a correlation orbital while 1s, 2s, 2p, 3s, 3p and 3d Hartree-Fock functions are used. The 4s and 4p functions are optimised as spectroscopic orbitals. Fine-tuning of the ab initio energies was done through adjusting by a small amount some diagonal elements of the Hamiltonian matrix. It is found that for many of the relatively strong dipole transitions, our calculated oscillator strengths agree with available calculations, while for the weaker transitions our results often disagree with the previously determined results. We also present gA values for five E2 transitions for the multiplets 3d 6 5 DJ → 3d 5 ( 6 S)4s 5 S 2. The present results for these transitions show a 30-40% increase over the results previously published.

Spectral distributions of mixed configurations of identical nucleons in the seniority scheme II. Configuration-seniority scheme

International Nuclear Information System (INIS)

Quesne, C.; Spitz, S.

1978-01-01

Configuration-seniority spectral distributions as well as fixed seniority and fixed total seniority and parity distributions are studied in detail for mixed configurations of identitical nucleons. The decomposition of any (1+2) -body Hamiltonian into irreducible tensors with respect to the unitary and symplectic groups in each subshell is obtained. Group theoretical methods based on the Wigner-Eckart theorem for the higher unitary groups are used to get analytical expressions for the partial widths of configuration-seniority distributions. During this derivation, various isoscalar factors for the chain SU (2Ω) is contained inSp (2Ω) are determined. Numerical calculations of centroid energies, partial widths, and mixing parameters are performed in the Sn and Pb nuclei with a surface delta and a gaussian interactions. Average ordinary and total seniority breaking is studied. Total seniority space truncations in the ground state region are discussed in the Pb nuclei in connections with various approximation schemes

Ab initio ground state phenylacetylene-argon intermolecular potential energy surface and rovibrational spectrum

DEFF Research Database (Denmark)

Cybulski, Hubert; Fernandez, Berta; Henriksen, Christian

2012-01-01

to the axis perpendicular to the phenylacetylene plane and containing the center of mass. The calculated interaction energy is -418.9 cm(-1). To check further the potential, we obtain the rovibrational spectrum of the complex and the results are compared to the available experimental data. (C) 2012 American......We evaluate the phenylacetylene-argon intermolecular potential energy surface by fitting a representative number of ab initio interaction energies to an analytic function. These energies are calculated at a grid of intermolecular geometries, using the CCSD(T) method and the aug-cc-pVDZ basis set...... extended with a series of 3s3p2d1flg midbond functions. The potential is characterized by two equivalent global minima where the Ar atom is located above and below the phenylacetylene plane at a distance of 3.5781 angstrom from the molecular center of mass and at an angle of 9.08 degrees with respect...

Ab initio STM and STS simulations on magnetic and nonmagnetic metallic surfaces

Energy Technology Data Exchange (ETDEWEB)

Dick, Alexey

2008-04-14

The aim of this work was to provide an in-depth understanding of a new generation of scan- ning tunneling microscopy experiments, performed employing different regimes of the STM: the spectroscopy-mode (the so-called Fourier Transformed STM, FT-STM), and the spin-sensitive mode (the so-called spin-polarized STM, SP-STM). In the present thesis ab initio tools are proposed that are based on DFT calculations to theoretically predict and analyze such types of the STM. The first part of this thesis focusses on the simulation of FT-STM, the mode that allows to probe local dispersion properties of the electrons at the surface. In order to provide the theoretical counterpart of the experimental FT-STM spectra we have introduced a new implicit approach that is derived from Tersoff-Hamann theory of the STM. The importance of an accurate description of surface wavefunctions at 5-15 A above the surface as well as the spurious quantum- size effects have been discussed in detail together with approaches to obtain converged FT-STM images. We applied our method to FT-STM experiments performed on Ag(110) surfaces. In the second part of the thesis we discuss the modeling of the spin-resolved STM, the mode that allows to characterize the magnetic structure of a surface. As a case system we studied here the magnetically-ordered transition-metal nitride surface Mn{sub 3}N{sub 2}(010). Because SP-STM experiments did not allow a conclusive understanding of the surface structure, we have first employed ab initio thermodynamics to figure out the most stable magnetic and atomic configuration of the surface that are consistent with experiments. To simulate SP-STM images on the most stable Mn{sub 3}N{sub 2}(010) surface we have employed the spin-generalized transfer-Hamiltonian formalism, assuming that the tip wavefunctions have dominant radial symmetry (s-like tip). (orig.)

The Periodic Table as a Mnemonic Device for Writing Electronic Configurations.

Science.gov (United States)

Mabrouk, Suzanne T.

2003-01-01

Presents an interactive method for using the periodic table as an effective mnemonic for writing electronic configurations. Discusses the intrinsic relevance of configurations to chemistry by building upon past analogies. Addresses pertinent background information, describes the hands-on method, and demonstrates its use. Transforms the traditional…

Unbiased reduced density matrices and electronic properties from full configuration interaction quantum Monte Carlo

International Nuclear Information System (INIS)

Overy, Catherine; Blunt, N. S.; Shepherd, James J.; Booth, George H.; Cleland, Deidre; Alavi, Ali

2014-01-01

Properties that are necessarily formulated within pure (symmetric) expectation values are difficult to calculate for projector quantum Monte Carlo approaches, but are critical in order to compute many of the important observable properties of electronic systems. Here, we investigate an approach for the sampling of unbiased reduced density matrices within the full configuration interaction quantum Monte Carlo dynamic, which requires only small computational overheads. This is achieved via an independent replica population of walkers in the dynamic, sampled alongside the original population. The resulting reduced density matrices are free from systematic error (beyond those present via constraints on the dynamic itself) and can be used to compute a variety of expectation values and properties, with rapid convergence to an exact limit. A quasi-variational energy estimate derived from these density matrices is proposed as an accurate alternative to the projected estimator for multiconfigurational wavefunctions, while its variational property could potentially lend itself to accurate extrapolation approaches in larger systems

Ab initio transport across bismuth selenide surface barriers

KAUST Repository

Narayan, Awadhesh; Rungger, Ivan; Droghetti, Andrea; Sanvito, Stefano

2014-01-01

© 2014 American Physical Society. We investigate the effect of potential barriers in the form of step edges on the scattering properties of Bi2Se3(111) topological surface states by means of large-scale ab initio transport simulations. Our results

Investigation on electronic and magnetic properties of Mn2NiAl by ab initio calculations and Monte Carlo simulations

International Nuclear Information System (INIS)

Masrour, R.; Jabar, A.; Hlil, E.K.; Hamedoun, M.; Benyoussef, A.; Hourmatallah, A.; Rezzouk, A.; Bouslykhane, K.; Benzakour, N.

2017-01-01

Self-consistent ab initio calculations, based on Density Functional Theory (DFT) approach and using Full potential Linear Augmented Plane Wave (FLAPW) method, are performed to investigate both electronic and magnetic properties of the Mn 2 NiAl. Magnetic moment considered to lie along (001) axes are computed. Obtained data from ab initio calculations are used as input for Monte Carlo simulations to compute other magnetic parameters. Also, the magnetic properties of Mn 2 NiAl are studied using the Monte Carlo simulations. The variation of magnetization and magnetic susceptibility with the reduced temperature of Mn 2 NiAl are investigated. The transition temperature of this system is deduced for different values exchange interaction and crystal field. The thermal total magnetization has been obtained, and the magnetic hysteresis cycle is established. The total magnetic moment is superior to those obtained by the other method and is mainly determined by the antiparallel aligned Mn I , Mn II and Ni spin moments. The superparamagnetic phase is found at the neighborhood of transition temperature. - Highlights: • Ab initio calculations are used to study magnetic and electronic properties of Mn 2 NiX. • The transition temperature of Mn 2 NiX is established. • The magnetic hysteresis cycle of M n2 NiX (X = Al, Ga, In, Sn) is deduced. • The magnetic coercive field of Mn 2 NiX (X = Al, Ga, In, Sn) is given.

Relation between properties of long-range diatomic bound states

Czech Academy of Sciences Publication Activity Database

Špirko, Vladimír; Sauer, S. P. A.; Szalewicz, K.

2013-01-01

Roč. 87, č. 1 (2013), 012510/1-012510/6 ISSN 1050-2947 R&D Projects: GA ČR GAP208/11/0436; GA MŠk(CZ) LH11022 Institutional research plan: CEZ:AV0Z40550506 Keywords : potential-energy curve * ab-initio calculations * configuration-interaction calculations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.991, year: 2013

Interaction of Fast Ions with Global Plasma Modes in the C-2 Field Reversed Configuration Experiment

Science.gov (United States)

Smirnov, Artem; Dettrick, Sean; Clary, Ryan; Korepanov, Sergey; Thompson, Matthew; Trask, Erik; Tuszewski, Michel

2012-10-01

A high-confinement operating regime [1] with plasma lifetimes significantly exceeding past empirical scaling laws was recently obtained by combining plasma gun edge biasing and tangential Neutral Beam Injection (NBI) in the C-2 field-reversed configuration (FRC) experiment [2, 3]. We present experimental and computational results on the interaction of fast ions with the n=2 rotational and n=1 wobble modes in the C-2 FRC. It is found that the n=2 mode is similar to quadrupole magnetic fields in its detrimental effect on the fast ion transport due to symmetry breaking. The plasma gun generates an inward radial electric field, thus stabilizing the n=2 rotational instability without applying the quadrupole magnetic fields. The resultant FRCs are nearly axisymmetric, which enables fast ion confinement. The NBI further suppresses the n=2 mode, improves the plasma confinement characteristics, and increases the plasma configuration lifetime [4]. The n=1 wobble mode has relatively little effect on the fast ion transport, likely due to the approximate axisymmetry about the displaced plasma column. [4pt] [1] M. Tuszewski et al., Phys. Rev. Lett. 108, 255008 (2012).[0pt] [2] M. Binderbauer et al., Phys. Rev. Lett. 105, 045003 (2010).[0pt] [3] H.Y. Guo et al., Phys. Plasmas 18, 056110 (2011).[0pt] [4] M. Tuszewski et al., Phys. Plasmas 19, 056108 (2012)

State-of-the-art ab initio potential energy curve for the krypton atom pair and thermophysical properties of dilute krypton gas.

Science.gov (United States)

Jäger, Benjamin; Hellmann, Robert; Bich, Eckard; Vogel, Eckhard

2016-03-21

A new reference krypton-krypton interatomic potential energy curve was developed by means of quantum-chemical ab initio calculations for 36 interatomic separations. Highly accurate values for the interaction energies at the complete basis set limit were obtained using the coupled-cluster method with single, double, and perturbative triple excitations as well as t-aug-cc-pV5Z and t-aug-cc-pV6Z basis sets including mid-bond functions, with the 6Z basis set being newly constructed for this study. Higher orders of coupled-cluster terms were considered in a successive scheme up to full quadruple excitations. Core-core and core-valence correlation effects were included. Furthermore, relativistic effects were studied not only at a scalar relativistic level using second-order direct perturbation theory, but also utilizing full four-component and Gaunt-effect computations. An analytical pair potential function was fitted to the interaction energies, which is characterized by a depth of 200.88 K with an estimated standard uncertainty of 0.51 K. Thermophysical properties of low-density krypton were calculated for temperatures up to 5000 K. Second and third virial coefficients were obtained from statistical thermodynamics. Viscosity and thermal conductivity as well as the self-diffusion coefficient were computed using the kinetic theory of gases. The theoretical results are compared with experimental data and with results for other pair potential functions from the literature, especially with those calculated from the recently developed ab initio potential of Waldrop et al. [J. Chem. Phys. 142, 204307 (2015)]. Highly accurate experimental viscosity data indicate that both the present ab initio pair potential and the one of Waldrop et al. can be regarded as reference potentials, even though the quantum-chemical methods and basis sets differ. However, the uncertainties of the present potential and of the derived properties are estimated to be considerably lower.

Ab initio lattice dynamics of metal surfaces

International Nuclear Information System (INIS)

Heid, R.; Bohnen, K.-P.

2003-01-01

Dynamical properties of atoms on surfaces depend sensitively on their bonding environment and thus provide valuable insight into the local geometry and chemical binding at the boundary of a solid. Density-functional theory provides a unified approach to the calculation of structural and dynamical properties from first principles. Its high accuracy and predictive power for lattice dynamical properties of semiconductor surfaces has been demonstrated in a previous article by Fritsch and Schroeder (Phys. Rep. 309 (1999) 209). In this report, we review the state-of-the-art of these ab initio approaches to surface dynamical properties of metal surfaces. We give a brief introduction to the conceptual framework with focus on recent advances in computational procedures for the ab initio linear-response approach, which have been a prerequisite for an efficient treatment of surface dynamics of noble and transition metals. The discussed applications to clean and adsorbate-covered surfaces demonstrate the high accuracy and reliability of this approach in predicting detailed microscopic properties of the phonon dynamics for a wide range of metallic surfaces

Ab initio study of the positronation of the CaO and SrO molecules including calculation of annihilation rates.

Science.gov (United States)

Buenker, Robert J; Liebermann, Heinz-Peter

2012-07-15

Ab initio multireference single- and double-excitation configuration interaction calculations have been performed to compute potential curves for ground and excited states of the CaO and SrO molecules and their positronic complexes, e(+)CaO, and e(+)SrO. The adiabatic dissociation limit for the (2)Σ(+) lowest states of the latter systems consists of the positive metal ion ground state (M(+)) and the OPs complex (e(+)O(-)), although the lowest energy limit is thought to be e(+)M + O. Good agreement is found between the calculated and experimental spectroscopic constants for the neutral diatomics wherever available. The positron affinity of the closed-shell X (1)Σ(+) ground states of both systems is found to lie in the 0.16-0.19 eV range, less than half the corresponding values for the lighter members of the alkaline earth monoxide series, BeO and MgO. Annihilation rates (ARs) have been calculated for all four positronated systems for the first time. The variation with bond distance is generally similar to what has been found earlier for the alkali monoxide series of positronic complexes, falling off gradually from the OPs AR value at their respective dissociation limits. The e(+)SrO system shows some exceptional behavior, however, with its AR value reaching a minimum at a relatively large bond distance and then rising to more than twice the OPs value close to its equilibrium distance. Copyright © 2012 Wiley Periodicals, Inc.

Ab initio study of alanine polypeptide chain twisting

DEFF Research Database (Denmark)

Solov'yov, Ilia; Yakubovich, Alexander V.; Solov'yov, Andrey V.

2006-01-01

chains. These particular degrees of freedom are essential for the characterization of the proteins folding process. Calculations have been carried out within the ab initio theoretical framework based on the density functional theory and accounting for all the electrons in the system. We have determined...

Ab initio simulation of dislocation cores in metals

International Nuclear Information System (INIS)

Ventelon, L.

2008-01-01

In the framework of the multi scale simulation of metals and alloys plasticity, the aim of this study is to develop a methodology of ab initio dislocations study and to apply it to the [111] screw dislocation in the bc iron. (A.L.B.)

Steel — ab Initio: Quantum Mechanics Guided Design of New Fe-Based Materials

Science.gov (United States)

Prahl, Ulrich; Bleck, Wolfgang; Saeed-Akbari, Alireza

This contribution reports the results of the collaborative research unit SFB 761 "Steel — ab initio", a cooperative project between RWTH Aachen University and the Max-Planck-Institute for Iron Research in Düsseldorf (MPIE) financed by the German Research Foundation (DFG). For the first time, it is exploited how ab initio approaches may lead to a detailed understanding and thus to a specific improvement of material development. The challenge lies in the combination of abstract natural science theories with rather engineering-like established concepts. Aiming at the technological target of the development of a new type of structural materials based on Fe-Mn-C alloys, the combination of ab initio and engineering methods is new, but could be followed quite successfully. Three major topics are treated in this research unit: a) development of a new method for material- and process-development based on ab initio calculations; b) design of a new class of structural materials with extraordinary property combinations; c) acceleration of development time and reduction of experimental efforts and complexity for material- and process-development. In the present work, an overview of the results of the first five years as well as an outlook for the upcoming three-year period is given.

A Review of Solid-Solution Models of High-Entropy Alloys Based on Ab Initio Calculations

Directory of Open Access Journals (Sweden)

Fuyang Tian

2017-11-01

Full Text Available Similar to the importance of XRD in experiments, ab initio calculations, as a powerful tool, have been applied to predict the new potential materials and investigate the intrinsic properties of materials in theory. As a typical solid-solution material, the large degree of uncertainty of high-entropy alloys (HEAs results in the difficulty of ab initio calculations application to HEAs. The present review focuses on the available ab initio based solid-solution models (virtual lattice approximation, coherent potential approximation, special quasirandom structure, similar local atomic environment, maximum-entropy method, and hybrid Monte Carlo/molecular dynamics and their applications and limits in single phase HEAs.

Realization of prediction of materials properties by ab initio ...

Indian Academy of Sciences (India)

Unknown

alization of the results of ab initio molecular dynamics simulation on atom insertion process to C60 and to carbon nanotube ... micro-clusters to estimate absolute highest occupied mo- .... To analyse the observed properties theoretically,.

Carbon diffusion in molten uranium: an ab initio molecular dynamics study

Science.gov (United States)

Garrett, Kerry E.; Abrecht, David G.; Kessler, Sean H.; Henson, Neil J.; Devanathan, Ram; Schwantes, Jon M.; Reilly, Dallas D.

2018-04-01

In this work we used ab initio molecular dynamics within the framework of density functional theory and the projector-augmented wave method to study carbon diffusion in liquid uranium at temperatures above 1600 K. The electronic interactions of carbon and uranium were described using the local density approximation (LDA). The self-diffusion of uranium based on this approach is compared with literature computational and experimental results for liquid uranium. The temperature dependence of carbon and uranium diffusion in the melt was evaluated by fitting the resulting diffusion coefficients to an Arrhenius relationship. We found that the LDA calculated activation energy for carbon was nearly twice that of uranium: 0.55 ± 0.03 eV for carbon compared to 0.32 ± 0.04 eV for uranium. Structural analysis of the liquid uranium-carbon system is also discussed.

A Configuration Model of Organizational Culture

Directory of Open Access Journals (Sweden)

Daniel Dauber

2012-01-01

Full Text Available The article proposes a configuration model of organizational culture, which explores dynamic relationships between organizational culture, strategy, structure, and operations of an organization (internal environment and maps interactions with the external environment (task and legitimization environment. A major feature of the configuration model constitutes its well-defined processes, which connect the elements of the model systematically to each other, such as single- and double-loop learning, operationalization of strategies, legitimization management, and so on. The model is grounded in a large review of literature in different research areas and builds on widely recognized models in the field of organization and culture theory. It constitutes a response to the call for new models, which are able to explain and facilitate the exploration of the empirical complexity that organizations face today. The configuration model of organizational culture is of particular interest to scholars who investigate into cultural phenomena and change over time.

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

DEFF Research Database (Denmark)

Berg, Rolf W.; Nørbygaard, Thomas; White, Peter C.

2011-01-01

For the first time, the differences between the spectra of amphetamine and amphetamine-H+ and between different conformers are thoroughly studied by ab initio model calculations, and Raman and surface-enhanced Raman spectroscopy (SERS) spectra are measured for different species of amphetamine....... The spectra of amphetamine and amphetamine-H+ sampleswere obtained and assigned according to a comparison of the experimental spectra and the ab initio MO calculations, performed using the Gaussian 03W program (Gaussian, Inc., Pittsburgh, PA). The analyses were based on complete geometry minimization...

Ab-initio calculations of the Ruddlesden-Popper phases CaMnO3, CaO(CaMnO3) and CaO(CaMnO3)2

International Nuclear Information System (INIS)

Cardoso, C; Borges, R P; Gasche, T; Godinho, M

2008-01-01

The present work reports ab-initio density functional theory calculations for the Ruddlesden-Popper phase CaO(CaMnO 3 ) n compounds. In order to study the evolution of the properties with the number of perovskite layers, a detailed analysis of the densities of states calculated for each compound and for several magnetic configurations was performed. The effect of distortions of the crystal structure on the magnetic ground state is also analysed and the exchange constants and transition temperatures are calculated for the three compounds using a mean field model. The calculated magnetic ground state structures and magnetic moments are in good agreement with experimental results and previous calculations

Systematic ab initio study of half-Heusler materials for optoelectronic applications

Energy Technology Data Exchange (ETDEWEB)

Gruhn, Thomas; Felser, Claudia [Institute of Inorganic and Analytical Chemistry, Johannes Gutenberg University, Mainz (Germany)

2010-07-01

The development of new, optimized optoelectronic devices depends crucially on the availability of semiconductors with taylored electronic and structural properties. At the moment, the majority of applications is based on a rather small set of semiconducting materials, while many more semiconductors exist in the huge class of ternary compounds. Especially, the class of 8-electron half-Heusler materials comprises a large number semiconducters with various properties. With the help of ab initio density functional theory we have studied essentially all 8-electron half-Heusler compounds that are of technological relevance. For more than 650 compounds we have determined the optimum configuration by varying the lattice constant and permuting the elements over the sublattices. Within this exceptionally large data set we have studied the band structure and the lattice constants as a function of the electronegativities of the elements, the arrangement of the atoms, and the atomic radii. The results are used to select suitable materials for the buffer layer in thin-film solar cells with a Cu(In,Ga)Se{sub 2} (CIGS) absorber layer. Considering the bandgap and the geometrical matching with the CIGS film, we have obtained a set of 29 compounds that are promissing materials for cadmium-free CIGS buffer layer.

Ab initio atomic simulation of hydrogen and iodine effects in zirconium

International Nuclear Information System (INIS)

Domain, Ch.

2002-03-01

In this work we present ab initio atomic simulations concerning the effects of hydrogen and iodine in hexagonal zirconium. We first studied the point defects in the dilute Zr-H (and to a less extend Zr-H-O) systems and concluded that it is better described within the generalised gradient approximation for the exchange and correlation functional. We calculated the hydrogen thermal diffusion coefficient in solid solution that agree very well with the experimental values. The calculated formation energy of different self-interstitial configuration are rather small (around 3 eV) and close to each other indicating the high complexity of these defects. We studied the core structure of the screw dislocation that has a preferential prismatic spreading. We also calculated the gamma surface for different gliding planes. The influence of hydrogen, that induces a significant reduction of the gamma surfaces excess energies, allows to qualitatively explain experimental results regarding some hydrogen effects on hexagonal zirconium plastic deformation. We also discussed the effect of zirconium hydride stoichiometry on gamma surfaces. The results concerning the iodine and oxygen adsorption on zirconium surfaces, inducing the evaluation of the effective surface energy reduction as a function of the iodine partial pressure allow for a better description of iodine induced stress corrosion cracking of zirconium. (author)

Ab Initio Calculations of Transport in Titanium and Aluminum Mixtures

Science.gov (United States)

Walker, Nicholas; Novak, Brian; Tam, Ka Ming; Moldovan, Dorel; Jarrell, Mark

In classical molecular dynamics simulations, the self-diffusion and shear viscosity of titanium about the melting point have fallen within the ranges provided by experimental data. However, the experimental data is difficult to collect and has been rather scattered, making it of limited value for the validation of these calculations. By using ab initio molecular dynamics simulations within the density functional theory framework, the classical molecular dynamics data can be validated. The dynamical data from the ab initio molecular dynamics can also be used to calculate new potentials for use in classical molecular dynamics, allowing for more accurate classical dynamics simulations for the liquid phase. For metallic materials such as titanium and aluminum alloys, these calculations are very valuable due to an increasing demand for the knowledge of their thermophysical properties that drive the development of new materials. For example, alongside knowledge of the surface tension, viscosity is an important input for modeling the additive manufacturing process at the continuum level. We are developing calculations of the viscosity along with the self-diffusion for aluminum, titanium, and titanium-aluminum alloys with ab initio molecular dynamics. Supported by the National Science Foundation through cooperative agreement OIA-1541079 and the Louisiana Board of Regents.

Substrate Screening Effects in ab initio Many-body Green's Function Calculations of Doped Graphene on SiC

Science.gov (United States)

Vigil-Fowler, Derek; Lischner, Johannes; Louie, Steven

2013-03-01

Understanding many-electron interaction effects and the influence of the substrate in graphene-on-substrate systems is of great theoretical and practical interest. Thus far, both model Hamiltonian and ab initio GW calculations for the quasiparticle properties of such systems have employed crude models for the effect of the substrate, often approximating the complicated substrate dielectric matrix by a single constant. We develop a method in which the spatially-dependent dielectric matrix of the substrate (e.g., SiC) is incorporated into that of doped graphene to obtain an accurate total dielectric matrix. We present ab initio GW + cumulant expansion calculations, showing that both the cumulant expansion (to include higher-order electron correlations) and a proper account of the substrate screening are needed to achieve agreement with features seen in ARPES. We discuss how this methodology could be used in other systems. This work was supported by NSF Grant No. DMR10-1006184 and U.S. DOE Contract No. DE-AC02-05CH11231. Computational resources have been provided by the NERSC and NICS. D.V-F. acknowledges funding from the DOD's NDSEG fellowship.

Optimizing Sparse Matrix-Multiple Vectors Multiplication for Nuclear Configuration Interaction Calculations

Energy Technology Data Exchange (ETDEWEB)

Aktulga, Hasan Metin [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Buluc, Aydin [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Williams, Samuel [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Yang, Chao [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

2014-08-14

Obtaining highly accurate predictions on the properties of light atomic nuclei using the configuration interaction (CI) approach requires computing a few extremal Eigen pairs of the many-body nuclear Hamiltonian matrix. In the Many-body Fermion Dynamics for nuclei (MFDn) code, a block Eigen solver is used for this purpose. Due to the large size of the sparse matrices involved, a significant fraction of the time spent on the Eigen value computations is associated with the multiplication of a sparse matrix (and the transpose of that matrix) with multiple vectors (SpMM and SpMM-T). Existing implementations of SpMM and SpMM-T significantly underperform expectations. Thus, in this paper, we present and analyze optimized implementations of SpMM and SpMM-T. We base our implementation on the compressed sparse blocks (CSB) matrix format and target systems with multi-core architectures. We develop a performance model that allows us to understand and estimate the performance characteristics of our SpMM kernel implementations, and demonstrate the efficiency of our implementation on a series of real-world matrices extracted from MFDn. In particular, we obtain 3-4 speedup on the requisite operations over good implementations based on the commonly used compressed sparse row (CSR) matrix format. The improvements in the SpMM kernel suggest we may attain roughly a 40% speed up in the overall execution time of the block Eigen solver used in MFDn.

Transferability of polarizable models for ion-water electrostatic interaction

International Nuclear Information System (INIS)

Masia, Marco

2009-01-01

Studies of ion-water systems at condensed phase and at interfaces have pointed out that molecular and ionic polarization plays an important role for many phenomena ranging from hydrogen bond dynamics to water interfaces' structure. Classical and ab initio Molecular Dynamics simulations reveal that induced dipole moments at interfaces (e.g. air-water and water-protein) are usually high, hinting that polarizable models to be implemented in classical force fields should be very accurate in reproducing the electrostatic properties of the system. In this paper the electrostatic properties of three classical polarizable models for ion-water interaction are compared with ab initio results both at gas and condensed phase. For Li + - water and Cl - -water dimers the reproducibility of total dipole moments obtained with high level quantum chemical calculations is studied; for the same ions in liquid water, Car-Parrinello Molecular Dynamics simulations are used to compute the time evolution of ionic and molecular dipole moments, which are compared with the classical models. The PD2-H2O model developed by the author and coworkers [Masia et al. J. Chem. Phys. 2004, 121, 7362] together with the gaussian intermolecular damping for ion-water interaction [Masia et al. J. Chem. Phys. 2005, 123, 164505] showed to be the fittest in reproducing the ab initio results from gas to condensed phase, allowing for force field transferability.

(4)He Thermophysical Properties: New Ab Initio Calculations.

Science.gov (United States)

Hurly, John J; Mehl, James B

2007-01-01

Since 2000, atomic physicists have reduced the uncertainty of the helium-helium "ab initio" potential; for example, from approximately 0.6 % to 0.1 % at 4 bohr, and from 0.8 % to 0.1 % at 5.6 bohr. These results led us to: (1) construct a new inter-atomic potential ϕ 07, (2) recalculate values of the second virial coefficient, the viscosity, and the thermal conductivity of (4)He from 1 K to 10,000 K, and (3), analyze the uncertainties of the thermophysical properties that propagate from the uncertainty of ϕ 07 and from the Born-Oppenheimer approximation of the electron-nucleon quantum mechanical system. We correct minor errors in a previous publication [J. J. Hurly and M. R. Moldover, J. Res. Nat. Inst. Standards Technol. 105, 667 (2000)] and compare our results with selected data published after 2000. The ab initio results tabulated here can serve as standards for the measurement of thermophysical properties.

Matrix product operators, matrix product states, and ab initio density matrix renormalization group algorithms

Science.gov (United States)

Chan, Garnet Kin-Lic; Keselman, Anna; Nakatani, Naoki; Li, Zhendong; White, Steven R.

2016-07-01

Current descriptions of the ab initio density matrix renormalization group (DMRG) algorithm use two superficially different languages: an older language of the renormalization group and renormalized operators, and a more recent language of matrix product states and matrix product operators. The same algorithm can appear dramatically different when written in the two different vocabularies. In this work, we carefully describe the translation between the two languages in several contexts. First, we describe how to efficiently implement the ab initio DMRG sweep using a matrix product operator based code, and the equivalence to the original renormalized operator implementation. Next we describe how to implement the general matrix product operator/matrix product state algebra within a pure renormalized operator-based DMRG code. Finally, we discuss two improvements of the ab initio DMRG sweep algorithm motivated by matrix product operator language: Hamiltonian compression, and a sum over operators representation that allows for perfect computational parallelism. The connections and correspondences described here serve to link the future developments with the past and are important in the efficient implementation of continuing advances in ab initio DMRG and related algorithms.

Interactive effects of size, contrast, intensity and configuration of background objects in evoking disruptive camouflage in cuttlefish.

Science.gov (United States)

Chiao, Chuan-Chin; Chubb, Charles; Hanlon, Roger T

2007-07-01

Disruptive body coloration is a primary camouflage tactic of cuttlefish. Because rapid changeable coloration of cephalopods is guided visually, we can present different visual backgrounds (e.g., computer-generated, two-dimensional prints) and video record the animal's response by describing and grading its body pattern. We showed previously that strength of cuttlefish disruptive patterning depends on the size, contrast, and density of discrete light elements on a homogeneous dark background. Here we report five experiments on the interactions of these and other features. Results show that Weber contrast of light background elements is--in combination with element size--a powerful determinant of disruptive response strength. Furthermore, the strength of disruptive patterning decreases with increasing mean substrate intensity (with other factors held constant). Interestingly, when element size, Weber contrast and mean substrate intensity are kept constant, strength of disruptive patterning depends on the configuration of clusters of small light elements. This study highlights the interactions of multiple features of natural microhabitats that directly influence which camouflage pattern a cuttlefish will choose.

Hylleraas-Configuration Interaction study of the 1S ground state of the negative Li ion.

Science.gov (United States)

Sims, James S

2017-12-28

In a previous work Sims and Hagstrom [J. Chem. Phys. 140, 224312 (2014)] reported Hylleraas-Configuration Interaction (Hy-CI) method variational calculations for the neutral atom and positive ion 1 S ground states of the beryllium isoelectronic sequence. The Li - ion, nominally the first member of this series, has a decidedly different electronic structure. This paper reports the results of a large, comparable calculation for the Li - ground state to explore how well the Hy-CI method can represent the more diffuse L shell of Li - which is representative of the Be(2sns) excited states as well. The best non-relativistic energy obtained was -7.500 776 596 hartree, indicating that 10 - 20 nh accuracy is attainable in Hy-CI and that convergence of the r 12 r 34 double cusp is fast and that this correlation type can be accurately represented within the Hy-CI model.

Nanomechanics modeling of carbon nanotubes interacting with surfaces in various configurations

Science.gov (United States)

Wu, Yu-Chiao

Carbon nanotubes (CNTs) have been widely used as potential components in reported nanoelectromechanical (NEM) devices due to their excellent mechanical and electrical properties. This thesis models the experiments by the continuum mechanics in two distinct scenarios. In the first situation, measurements are made of CNT configurations after manipulations. Modeling is then used to determine the interfacial properties during the manipulation which led to the observed configuration. This technique is used to determine the shear stress between a SWNT bundle and other materials. During manipulation, a SWNT bundle slipped on two micro-cantilevers. According to the slack due to the slippage after testing and the device configuration, the shear stress between a SWNT bundle and other materials can be determined. In another model, the work of adhesion was determined on two accidentally fabricated devices. Through the configuration of two SWNT adhered bundles and the force-distance curves measured by an atomic force microscope (AFM), modeling was used to determine the work of adhesion between two bundles and the shear stress at the SWNT-substrate interface. In the second situation, modeling is used in a more traditional fashion to make theoretical predictions as to how a device will operate. Using this technique, the actuation mechanism of a single-trench SWNT-based switch was investigated. During the actuation, the deflection-induced tension causes the SWNT bundle to slip on both platforms and to be partially peeled from two side recessed electrodes. These effects produce a slack which reduces the threshold voltages subsequent to the first actuation. The result shows excellent agreement between the theory and the measurement. Furthermore, the operation of a double-trenched SWNT-based switch was investigated. A slack is produced in the 1st actuated trench region by the slip and peeling effects. This slack reduces the 2nd actuation voltage in the neighbor trench. Finally, the

Role of electronic correlations in photoionization of NO2 in the vicinity of the 2A1/2B2 conical intersection.

Science.gov (United States)

Brambila, Danilo S; Harvey, Alex G; Houfek, Karel; Mašín, Zdeněk; Smirnova, Olga

2017-08-02

We present the first ab initio multi-channel photoionization calculations for NO 2 in the vicinity of the 2 A 1 / 2 B 2 conical intersection, for a range of nuclear geometries, using our newly developed set of tools based on the ab initio multichannel R-matrix method. Electronic correlation is included in both the neutral and the scattering states of the molecule via configuration interaction. Configuration mixing is especially important around conical intersections and avoided crossings, both pertinent for NO 2 , and manifests itself via significant variations in photoelectron angular distributions. The method allows for a balanced and accurate description of the photoionization/photorecombination for a number of different ionic channels in a wide range of photoelectron energies up to 100 eV. Proper account of electron correlations is crucial for interpreting time-resolved signals in photoelectron spectroscopy and high harmonic generation (HHG) from polyatomic molecules.

Investigation of the binding mode of a novel cruzain inhibitor by docking, molecular dynamics, ab initio and MM/PBSA calculations

Science.gov (United States)

Martins, Luan Carvalho; Torres, Pedro Henrique Monteiro; de Oliveira, Renata Barbosa; Pascutti, Pedro Geraldo; Cino, Elio A.; Ferreira, Rafaela Salgado

2018-05-01

Chagas disease remains a major health problem in South America, and throughout the world. The two drugs clinically available for its treatment have limited efficacy and cause serious adverse effects. Cruzain is an established therapeutic target of Trypanosoma cruzi, the protozoan that causes Chagas disease. Our group recently identified a competitive cruzain inhibitor (compound 1) with an IC50 = 15 µM that is also more synthetically accessible than the previously reported lead, compound 2. Prior studies, however, did not propose a binding mode for compound 1, hindering understanding of the structure-activity relationship and optimization. Here, the cruzain binding mode of compound 1 was investigated using docking, molecular dynamics (MD) simulations with ab initio derived parameters, ab initio calculations, and MM/PBSA. Two ligand protonation states and four binding poses were evaluated. A careful ligand parameterization method was employed to derive more physically meaningful parameters than those obtained by automated tools. The poses of unprotonated 1 were unstable in MD, showing large conformational changes and diffusing away from the binding site, whereas the protonated form showed higher stability and interaction with negatively charged residues Asp161 and Cys25. MM/PBSA also suggested that these two residues contribute favorably to binding of compound 1. By combining results from MD, ab initio calculations, and MM/PBSA, a binding mode of 1 is proposed. The results also provide insights for further optimization of 1, an interesting lead compound for the development of new cruzain inhibitors.

Investigation on electronic and magnetic properties of Mn{sub 2}NiAl by ab initio calculations and Monte Carlo simulations

Energy Technology Data Exchange (ETDEWEB)

Masrour, R., E-mail: rachidmasrour@hotmail.com [Laboratory of Materials, Processes, Environment and Quality, Cady Ayyed University, National School of Applied Sciences, PB 63 46000 Safi (Morocco); Jabar, A. [Laboratory of Materials, Processes, Environment and Quality, Cady Ayyed University, National School of Applied Sciences, PB 63 46000 Safi (Morocco); Hlil, E.K. [Institut Néel, CNRS, Université Grenoble Alpes, BP 166, F-38042 Grenoble cedex 9 (France); Hamedoun, M. [Institute of Nanomaterials and Nanotechnologies, MAScIR, Rabat (Morocco); Benyoussef, A. [Institute of Nanomaterials and Nanotechnologies, MAScIR, Rabat (Morocco); Hassan II Academy of Science and Technology, Rabat (Morocco); Hourmatallah, A. [Equipe de Physique du Solide, Laboratoire LIPI, Ecole Normale Supérieure, BP 5206, Bensouda, Fes (Morocco); Rezzouk, A.; Bouslykhane, K.; Benzakour, N. [Laboratoire de Physique du Solide, Université Sidi Mohammed Ben Abdellah, Faculté des sciences DharMahraz, BP 1796, Fes (Morocco)

2017-04-15

Self-consistent ab initio calculations, based on Density Functional Theory (DFT) approach and using Full potential Linear Augmented Plane Wave (FLAPW) method, are performed to investigate both electronic and magnetic properties of the Mn{sub 2}NiAl. Magnetic moment considered to lie along (001) axes are computed. Obtained data from ab initio calculations are used as input for Monte Carlo simulations to compute other magnetic parameters. Also, the magnetic properties of Mn{sub 2}NiAl are studied using the Monte Carlo simulations. The variation of magnetization and magnetic susceptibility with the reduced temperature of Mn{sub 2}NiAl are investigated. The transition temperature of this system is deduced for different values exchange interaction and crystal field. The thermal total magnetization has been obtained, and the magnetic hysteresis cycle is established. The total magnetic moment is superior to those obtained by the other method and is mainly determined by the antiparallel aligned Mn{sub I}, Mn{sub II} and Ni spin moments. The superparamagnetic phase is found at the neighborhood of transition temperature. - Highlights: • Ab initio calculations are used to study magnetic and electronic properties of Mn{sub 2}NiX. • The transition temperature of Mn{sub 2}NiX is established. • The magnetic hysteresis cycle of M{sub n2}NiX (X = Al, Ga, In, Sn) is deduced. • The magnetic coercive field of Mn{sub 2}NiX (X = Al, Ga, In, Sn) is given.

Relativistic configuration interaction calculation on the ground and excited states of iridium monoxide

International Nuclear Information System (INIS)

Suo, Bingbing; Yu, Yan-Mei; Han, Huixian

2015-01-01

We present the fully relativistic multi-reference configuration interaction calculations of the ground and low-lying excited electronic states of IrO for individual spin-orbit component. The lowest-lying state is calculated for Ω = 1/2, 3/2, 5/2, and 7/2 in order to clarify the ground state of IrO. Our calculation suggests that the ground state is of Ω = 1/2, which is highly mixed with 4 Σ − and 2 Π states in Λ − S notation. The two low-lying states 5/2 and 7/2 are nearly degenerate with the ground state and locate only 234 and 260 cm −1 above, respectively. The equilibrium bond length 1.712 Å and the harmonic vibrational frequency 903 cm −1 of the 5/2 state are close to the experimental measurement of 1.724 Å and 909 cm −1 , which suggests that the 5/2 state should be the low-lying state that contributes to the experimental spectra. Moreover, the electronic states that give rise to the observed transition bands are assigned for Ω = 5/2 and 7/2 in terms of the obtained excited energies and oscillator strengths

Seniority and orbital symmetry as tools for establishing a full configuration interaction hierarchy.

Science.gov (United States)

Bytautas, Laimutis; Henderson, Thomas M; Jiménez-Hoyos, Carlos A; Ellis, Jason K; Scuseria, Gustavo E

2011-07-28

We explore the concept of seniority number (defined as the number of unpaired electrons in a determinant) when applied to the problem of electron correlation in atomic and molecular systems. Although seniority is a good quantum number only for certain model Hamiltonians (such as the pairing Hamiltonian), we show that it provides a useful partitioning of the electronic full configuration interaction (FCI) wave function into rapidly convergent Hilbert subspaces whose weight diminishes as its seniority number increases. The primary focus of this study is the adequate description of static correlation effects. The examples considered are the ground states of the helium, beryllium, and neon atoms, the symmetric dissociation of the N(2) and CO(2) molecules, as well as the symmetric dissociation of an H(8) hydrogen chain. It is found that the symmetry constraints that are normally placed on the spatial orbitals greatly affect the convergence rate of the FCI expansion. The energy relevance of the seniority zero sector (determinants with all paired electrons) increases dramatically if orbitals of broken spatial symmetry (as those commonly used for Hubbard Hamiltonian studies) are allowed in the wave function construction. © 2011 American Institute of Physics

Inelastic neutron scattering an ab-initio calculation of negative thermal expansion in Ag2O

International Nuclear Information System (INIS)

Gupta, M.K.; Mittal, R.; Rols, S.; Chaplot, S.L.

2012-01-01

The compound Ag 2 O undergoes large and isotropic negative thermal expansion over 0-500 K. We report temperature dependent inelastic neutron scattering measurements and ab-initio calculations of the phonon spectrum. The temperature dependence of the experimental phonon spectrum shows strong anharmonic nature of phonon modes of energy around 2.4 meV. The ab-initio calculations reveal that the maximum negative Grüneisen parameter, which is a measure of the relevant anharmonicity, occurs for the transverse phonon modes that involve bending motions of the Ag 4 O tetrahedra. The thermal expansion is evaluated from the ab-initio calculation of the pressure dependence of the phonon modes, and found in good agreement with available experimental data.

Local random configuration-tree theory for string repetition and facilitated dynamics of glass

Science.gov (United States)

Lam, Chi-Hang

2018-02-01

We derive a microscopic theory of glassy dynamics based on the transport of voids by micro-string motions, each of which involves particles arranged in a line hopping simultaneously displacing one another. Disorder is modeled by a random energy landscape quenched in the configuration space of distinguishable particles, but transient in the physical space as expected for glassy fluids. We study the evolution of local regions with m coupled voids. At a low temperature, energetically accessible local particle configurations can be organized into a random tree with nodes and edges denoting configurations and micro-string propagations respectively. Such trees defined in the configuration space naturally describe systems defined in two- or three-dimensional physical space. A micro-string propagation initiated by a void can facilitate similar motions by other voids via perturbing the random energy landscape, realizing path interactions between voids or equivalently string interactions. We obtain explicit expressions of the particle diffusion coefficient and a particle return probability. Under our approximation, as temperature decreases, random trees of energetically accessible configurations exhibit a sequence of percolation transitions in the configuration space, with local regions containing fewer coupled voids entering the non-percolating immobile phase first. Dynamics is dominated by coupled voids of an optimal group size, which increases as temperature decreases. Comparison with a distinguishable-particle lattice model (DPLM) of glass shows very good quantitative agreements using only two adjustable parameters related to typical energy fluctuations and the interaction range of the micro-strings.

An ab initio potential energy surface for the formic acid dimer: zero-point energy, selected anharmonic fundamental energies, and ground-state tunneling splitting calculated in relaxed 1-4-mode subspaces.

Science.gov (United States)

Qu, Chen; Bowman, Joel M

2016-09-14

We report a full-dimensional, permutationally invariant potential energy surface (PES) for the cyclic formic acid dimer. This PES is a least-squares fit to 13475 CCSD(T)-F12a/haTZ (VTZ for H and aVTZ for C and O) energies. The energy-weighted, root-mean-square fitting error is 11 cm -1 and the barrier for the double-proton transfer on the PES is 2848 cm -1 , in good agreement with the directly-calculated ab initio value of 2853 cm -1 . The zero-point vibrational energy of 15 337 ± 7 cm -1 is obtained from diffusion Monte Carlo calculations. Energies of fundamentals of fifteen modes are calculated using the vibrational self-consistent field and virtual-state configuration interaction method. The ground-state tunneling splitting is computed using a reduced-dimensional Hamiltonian with relaxed potentials. The highest-level, four-mode coupled calculation gives a tunneling splitting of 0.037 cm -1 , which is roughly twice the experimental value. The tunneling splittings of (DCOOH) 2 and (DCOOD) 2 from one to three mode calculations are, as expected, smaller than that for (HCOOH) 2 and consistent with experiment.

Nonequilibrium Chemical Effects in Single-Molecule SERS Revealed by Ab Initio Molecular Dynamics Simulations

Energy Technology Data Exchange (ETDEWEB)

Fischer, Sean A.; Apra, Edoardo; Govind, Niranjan; Hess, Wayne P.; El-Khoury, Patrick Z.

2017-02-03

Recent developments in nanophotonics have paved the way for achieving significant advances in the realm of single molecule chemical detection, imaging, and dynamics. In particular, surface-enhanced Raman scattering (SERS) is a powerful analytical technique that is now routinely used to identify the chemical identity of single molecules. Understanding how nanoscale physical and chemical processes affect single molecule SERS spectra and selection rules is a challenging task, and is still actively debated. Herein, we explore underappreciated chemical phenomena in ultrasensitive SERS. We observe a fluctuating excited electronic state manifold, governed by the conformational dynamics of a molecule (4,4’-dimercaptostilbene, DMS) interacting with a metallic cluster (Ag20). This affects our simulated single molecule SERS spectra; the time trajectories of a molecule interacting with its unique local environment dictates the relative intensities of the observable Raman-active vibrational states. Ab initio molecular dynamics of a model Ag20-DMS system are used to illustrate both concepts in light of recent experimental results.

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

International Nuclear Information System (INIS)

Li, Arvin Huang-Te; Chao, Sheng D.; Chang, Chien-Cheng

2010-01-01

Intermolecular interaction potentials of the silane dimer in 12 orientations have been calculated by using the Hartree-Fock (HF) self-consistent theory and the second-order Moeller-Plesset (MP2) perturbation theory. We employed basis sets from Pople's medium-size basis sets [up to 6-311++G(3df, 3pd)] and Dunning's correlation consistent basis sets (up to the triply augmented correlation-consistent polarized valence quadruple-zeta basis set). We found that the minimum energy orientations were the G and H conformers. We have suggested that the Si-H attractions, the central silicon atom size, and electronegativity play essential roles in weakly binding of a silane dimer. The calculated MP2 potential data were employed to parametrize a five-site force field for molecular simulations. The Si-Si, Si-H, and H-H interaction parameters in a pairwise-additive, site-site potential model for silane molecules were regressed from the ab initio energies.

Origins of Singlet Fission in Solid Pentacene from an ab initio Green's Function Approach

Science.gov (United States)

Refaely-Abramson, Sivan; da Jornada, Felipe H.; Louie, Steven G.; Neaton, Jeffrey B.

2017-12-01

We develop a new first-principles approach to predict and understand rates of singlet fission with an ab initio Green's-function formalism based on many-body perturbation theory. Starting with singlet and triplet excitons computed from a G W plus Bethe-Salpeter equation approach, we calculate the exciton-biexciton coupling to lowest order in the Coulomb interaction, assuming a final state consisting of two noninteracting spin-correlated triplets with finite center-of-mass momentum. For crystalline pentacene, symmetries dictate that the only purely Coulombic fission decay process from a bright singlet state requires a final state consisting of two inequivalent nearly degenerate triplets of nonzero, equal and opposite, center-of-mass momenta. For such a process, we predict a singlet lifetime of 30-70 fs, in very good agreement with experimental data, indicating that this process can dominate singlet fission in crystalline pentacene. Our approach is general and provides a framework for predicting and understanding multiexciton interactions in solids.

Few-Nucleon Research at TUNL: Probing Two- and Three-Nucleon Interactions with Neutrons

Directory of Open Access Journals (Sweden)

Howell C.R.

2016-01-01

Full Text Available The central goal of few-nucleon research at the Triangle Universities Nuclear Laboratory (TUNL is to perform measurements that contribute to advancing ab-initio calculations of nuclear structure and reactions. The program aims include evaluating theoretical treatments of few-nucleon reaction dynamics through strategically comparing theory predictions to data, determining properties of the neutron-neutron interaction that are not accessible in two-nucleon reactions, and searching for evidence of longrange features of three-nucleon interactions, e.g., spin and isospin dependence. This paper will review studies of three- and four-nucleon systems at TUNL conducted using unpolarized and polarized neutron beams. Measurements of neutron-induced reactions performed by groups at TUNL over the last six years are described in comparison with theory predictions. The results are discussed in the context of the program goals stated above. Measurements of vector analyzing powers for elastic scattering in A=3 and A=4 systems, differential cross sections for neutron-deuteron elastic scattering and neutrondeuteron breakup in several final-state configurations are described. The findings from these studies and plans for the coming three years are presented in the context of worldwide activities in this front, in particular, research presented in this session.

Potential energies for the two lowest 1A' electronic states of H3+

International Nuclear Information System (INIS)

Ichihara, Akira; Yokoyama, Keiichi; Iwamoto, Osamu

1998-11-01

Potential energies for the two lowest 1 A' states of H 3 + at 701 different spatial geometries are tabulated. These energies have been calculated by the ab initio full configuration interaction method with a (8s6p2d1f) Gaussian type basis set. Features of avoided crossing of two surfaces as well as the potential well in the ground state can be produced by interpolating calculated energies. These ab initio energies are expressed as a function of three internuclear distances in the range from 0.6 to 10.0 bohr, and they are applicable to the molecular dynamics study for the H + + H 2 system. (author)

Geometry optimization of supersymmetrical molecules in quantum chemical ab-initio calculations

International Nuclear Information System (INIS)

Gruenbichler, H.

1985-01-01

One-dimensional geometry optimizations in ab-initio SCF-calculations are investigated. It is shown, that the well known standard algorithms are sometimes too expensive and can be replaced or accompanied by more recent algorithms. Two alternatives were realized in the molecule calculating program GAUSSIAN 80, basing on the Fibonacci algorithm and Kryachco potential adjustment. The algorithms were compared in terms of accuracy of results, CPU-time used and reliability of the method. The results are presented in various tables, showing the efficiency of the various methods. A survey of the usual model potentials is given and the compatibility with ab-initio data is evaluated. (Author, shortened and translated by A.N.)

Sensitivity of core-level spectroscopy to electrostatic environments of nitrile groups: An ab initio study

Directory of Open Access Journals (Sweden)

Abid Hussain

2017-09-01

Full Text Available Ab initio quantum chemistry calculations have been performed to probe the influence of hydrogen bonding on the electronic structure of hydrogen cyanide (HCN. Our calculations determine the origin of nitrogen-specific Raman spectral features from resonant inelastic X-ray scattering occurring in the presence of a water molecule and an electric dipole field. The similarity of the two interactions in altering the electronic structure of the nitrogen atom differs only in the covalent contributions from the water molecule. The CN stretching mode as a structural probe was also investigated to study the electronic origin of the anomalous frequency shift of the nitrile group when subjected to hydrogen bonding and an electrostatic dipole field. The major changes in the electronic structure of HCN are electrostatic in nature and originate from dipole-dipole interactions. The relative shifts of the CN stretching frequency are in good agreement with those experimentally observed.

Sphinx: merging knowledge-based and ab initio approaches to improve protein loop prediction.

Science.gov (United States)

Marks, Claire; Nowak, Jaroslaw; Klostermann, Stefan; Georges, Guy; Dunbar, James; Shi, Jiye; Kelm, Sebastian; Deane, Charlotte M

2017-05-01

Loops are often vital for protein function, however, their irregular structures make them difficult to model accurately. Current loop modelling algorithms can mostly be divided into two categories: knowledge-based, where databases of fragments are searched to find suitable conformations and ab initio, where conformations are generated computationally. Existing knowledge-based methods only use fragments that are the same length as the target, even though loops of slightly different lengths may adopt similar conformations. Here, we present a novel method, Sphinx, which combines ab initio techniques with the potential extra structural information contained within loops of a different length to improve structure prediction. We show that Sphinx is able to generate high-accuracy predictions and decoy sets enriched with near-native loop conformations, performing better than the ab initio algorithm on which it is based. In addition, it is able to provide predictions for every target, unlike some knowledge-based methods. Sphinx can be used successfully for the difficult problem of antibody H3 prediction, outperforming RosettaAntibody, one of the leading H3-specific ab initio methods, both in accuracy and speed. Sphinx is available at http://opig.stats.ox.ac.uk/webapps/sphinx. deane@stats.ox.ac.uk. Supplementary data are available at Bioinformatics online. © The Author 2017. Published by Oxford University Press.

Ab initio molecular dynamics simulations of low energy recoil events in MgO

International Nuclear Information System (INIS)

Petersen, B. A.; Liu, B.; Weber, W. J.; Oak Ridge National Laboratory; Zhang, Y.; Oak Ridge National Laboratory

2017-01-01

In this paper, low-energy recoil events in MgO are studied using ab initio molecular dynamics simulations to reveal the dynamic displacement processes and final defect configurations. Threshold displacement energies, E_d, are obtained for Mg and O along three low-index crystallographic directions, [100], [110], and [111]. The minimum values for E_d are found along the [110] direction consisting of the same element, either Mg or O atoms. Minimum threshold values of 29.5 eV for Mg and 25.5 eV for O, respectively, are suggested from the calculations. For other directions, the threshold energies are considerably higher, 65.5 and 150.0 eV for O along [111] and [100], and 122.5 eV for Mg along both [111] and [100] directions, respectively. These results show that the recoil events in MgO are partial-charge transfer assisted processes where the charge transfer plays an important role. Finally, there is a similar trend found in other oxide materials, where the threshold displacement energy correlates linearly with the peak partial-charge transfer, suggesting this behavior might be universal in ceramic oxides.

Shear stiffness in nanolaminar Ti3SiC2 challenges ab initio calculations

International Nuclear Information System (INIS)

Kisi, E H; Zhang, J F; Kirstein, O; Riley, D P; Styles, M J; Paradowska, A M

2010-01-01

Nanolaminates such as the M n+1 AX n (MAX) phases are a material class with ab initio derived elasticity tensors published for over 250 compounds. We have for the first time experimentally determined the full elasticity tensor of the archetype MAX phase, Ti 3 SiC 2 , using polycrystalline samples and in situ neutron diffraction. The experimental elastic constants show extreme shear stiffness, with c 44 more than five times greater than expected for an isotropic material. Such shear stiffness is quite rare in hexagonal materials and strongly contradicts the predictions of all published MAX phase elastic constants derived from ab initio calculations. It is concluded that second order properties such as elastic moduli derived from ab initio calculations require careful experimental verification. The diffraction technique used currently provides the only method of verification for the elasticity tensor for the majority of new materials where single crystals are not available. (fast track communication)

Ab initio study on the reaction between uranium and O2

International Nuclear Information System (INIS)

Shuai Maobing; Zhao Pengji; Tian Anmin

2000-08-01

Optimized geometries, total energies and electronic structures of some gaseous atoms and molecules of uranium-oxygen system are calculated with harmonic vibration analysis using ab initio method. The potential energy surfaces (PESs) of the uranium oxidation process are also constructed. The calculated optimized geometries, infrared vibrational frequencies and the first ionized potential energies are in well accordance with available experimental data. Although U6p, U7s and U6d valence orbital electrons take part in the formation of U - O bond, the U5f electrons play an dominant role in this process and because the energies of U5f, U6d, U7s and Uds atomic orbitals are close to each other, these orbitals may hybrid and interact with O2p orbital, simultaneously, to form molecular orbitals of uranium oxides. The PESs show that different reaction modes result in different product geometries

Interactive baby feeding bottle

NARCIS (Netherlands)

2013-01-01

An interactive baby bottle with an electronic unit is disclosed. The electronic unit comprises a sensor unit configured to sense the heart beat of a person bottle feeding a baby and an actuator unit configured to transmit the sensed heart beat to the baby. The disclosed interactive baby bottle can

Compensation of the long-range beam-beam interactions as a path towards new configurations for the high luminosity LHC

Directory of Open Access Journals (Sweden)

Stéphane Fartoukh

2015-12-01

Full Text Available Colliding bunch trains in a circular collider demands a certain crossing angle in order to separate the two beams transversely after the collision. The magnitude of this crossing angle is a complicated function of the bunch charge, the number of long-range beam-beam interactions, of β^{*} and type of optics (flat or round, and possible compensation or additive effects between several low-β insertions in the ring depending on the orientation of the crossing plane at each interaction point. About 15 years ago, the use of current bearing wires was proposed at CERN in order to mitigate the long-range beam-beam effects [J. P. Koutchouk, CERN Report No. LHC-Project-Note 223, 2000], therefore offering the possibility to minimize the crossing angle with all the beneficial effects this might have: on the luminosity performance by reducing the need for crab-cavities or lowering their voltage, on the required aperture of the final focus magnets, on the strength of the orbit corrector involved in the crossing bumps, and finally on the heat load and radiation dose deposited in the final focus quadrupoles. In this paper, a semianalytical approach is developed for the compensation of the long-range beam-beam interactions with current wires. This reveals the possibility of achieving optimal correction through a careful adjustment of the aspect ratio of the β functions at the wire position. We consider the baseline luminosity upgrade plan of the Large Hadron Collider (HL-LHC project, and compare it to alternative scenarios, or so-called “configurations,” where modifications are applied to optics, crossing angle, or orientation of the crossing plane in the two low-β insertions of the ring. For all these configurations, the beneficial impact of beam-beam compensation devices is then demonstrated on the tune footprint, the dynamical aperture, and/or the frequency map analysis of the nonlinear beam dynamics as the main figures of merit.

Computational methods for ab initio detection of microRNAs

Directory of Open Access Journals (Sweden)

Malik eYousef

2012-10-01

Full Text Available MicroRNAs are small RNA sequences of 18-24 nucleotides in length, which serve as templates to drive post transcriptional gene silencing. The canonical microRNA pathway starts with transcription from DNA and is followed by processing via the Microprocessor complex, yielding a hairpin structure. Which is then exported into the cytosol where it is processed by Dicer and then incorporated into the RNA induced silencing complex. All of these biogenesis steps add to the overall specificity of miRNA production and effect. Unfortunately, their modes of action are just beginning to be elucidated and therefore computational prediction algorithms cannot model the process but are usually forced to employ machine learning approaches. This work focuses on ab initio prediction methods throughout; and therefore homology-based miRNA detection methods are not discussed. Current ab initio prediction algorithms, their ties to data mining, and their prediction accuracy are detailed.

Configurational Information as Potentially Negative Entropy: The Triple Helix Model

Directory of Open Access Journals (Sweden)

Loet Leydesdorff

2008-10-01

Full Text Available Configurational information is generated when three or more sources of variance interact. The variations not only disturb each other relationally, but by selecting upon each other, they are also positioned in a configuration. A configuration can be stabilized and/or globalized. Different stabilizations can be considered as second-order variation, and globalization as a second-order selection. The positive manifestations and the negative selections operate upon one another by adding and reducing uncertainty, respectively. Reduction of uncertainty in a configuration can be measured in bits of information. The variables can also be considered as dimensions of the probabilistic entropy in the system(s under study. The configurational information then provides us with a measure of synergy within a complex system. For example, the knowledge base of an economy can be considered as such a synergy in the otherwise virtual (that is, fourth dimension of a regime

Ab initio study of perovskite type oxide materials for solid oxide fuel cells

Science.gov (United States)

Lee, Yueh-Lin

2011-12-01

Perovskite type oxides form a family of materials of significant interest for cathodes and electrolytes of solid oxide fuel cells (SOFCs). These perovskites not only are active catalysts for surface oxygen reduction (OR) reactions but also allow incorporating the spilt oxygen monomers into their bulk, an unusual and poorly understood catalytic mechanism that couples surface and bulk properties. The OR mechanisms can be influenced strongly by defects in perovskite oxides, composition, and surface defect structures. This thesis work initiates a first step in developing a general strategy based on first-principles calculations for detailed control of oxygen vacancy content, transport rates of surface and bulk oxygen species, and surface/interfacial reaction kinetics. Ab initio density functional theory methods are used to model properties relevant for the OR reactions on SOFC cathodes. Three main research thrusts, which focus on bulk defect chemistry, surface defect structures and surface energetics, and surface catalytic properties, are carried to investigate different level of material chemistry for improved understanding of key physics/factors that govern SOFC cathode OR activity. In the study of bulk defect chemistry, an ab initio based defect model is developed for modeling defect chemistry of LaMnO 3 under SOFC conditions. The model suggests an important role for defect interactions, which are typically excluded in previous defect models. In the study of surface defect structures and surface energetics, it is shown that defect energies change dramatically (1˜2 eV lower) from bulk values near surfaces. Based on the existing bulk defect model with the calculated ab initio surface defect energetics, we predict the (001) MnO 2 surface oxygen vacancy concentration of (La0.9Sr0.1 )MnO3 is about 5˜6 order magnitude higher than that of the bulk under typical SOFC conditions. Finally, for surface catalytic properties, we show that area specific resistance, oxygen

Conceptualizing Embedded Configuration

DEFF Research Database (Denmark)

Oddsson, Gudmundur Valur; Hvam, Lars; Lysgaard, Ole

2006-01-01

and services. The general idea can be named embedded configuration. In this article we intend to conceptualize embedded configuration, what it is and is not. The difference between embedded configuration, sales configuration and embedded software is explained. We will look at what is needed to make embedded...... configuration systems. That will include requirements to product modelling techniques. An example with consumer electronics will illuminate the elements of embedded configuration in settings that most can relate to. The question of where embedded configuration would be relevant is discussed, and the current...

Quantum Szilard Engine with Attractively Interacting Bosons

Science.gov (United States)

Bengtsson, J.; Tengstrand, M. Nilsson; Wacker, A.; Samuelsson, P.; Ueda, M.; Linke, H.; Reimann, S. M.

2018-03-01

We show that a quantum Szilard engine containing many bosons with attractive interactions enhances the conversion between information and work. Using an ab initio approach to the full quantum-mechanical many-body problem, we find that the average work output increases significantly for a larger number of bosons. The highest overshoot occurs at a finite temperature, demonstrating how thermal and quantum effects conspire to enhance the conversion between information and work. The predicted effects occur over a broad range of interaction strengths and temperatures.

Ab initio calculations and modelling of atomic cluster structure

DEFF Research Database (Denmark)

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

2004-01-01

The optimized structure and electronic properties of small sodium and magnesium clusters have been investigated using it ab initio theoretical methods based on density-functional theory and post-Hartree-Fock many-body perturbation theory accounting for all electrons in the system. A new theoretical...

Modeling of nuclear glasses by classical and ab initio molecular dynamics

International Nuclear Information System (INIS)

Ganster, P.

2004-01-01

A calcium aluminosilicate glass of molar composition 67 % SiO 2 - 12 % Al 2 O 3 - 21 % CaO was modelled by classical and ab initio molecular dynamics. The size effect study in classical MD shows that the systems of 100 atoms are more ordered than the larger ones. These effects are mainly due to the 3-body terms in the empirical potentials. Nevertheless, these effects are small and the structures generated are in agreement with experimental data. In such kind of glass, we denote an aluminium avoidance and an excess of non bridging oxygens which can be compensated by tri-coordinated oxygens. When the dynamics of systems of 100 and 200 atoms is followed by ab initio MD, some local arrangements occurs (bond length, angular distributions). Thus, more realistic vibrational properties are obtained in ab initio MD. The modelling of thin films shows that aluminum atoms extend to the most external part of the surface and they are all tri-coordinated. Calcium atoms are set in the sub layer part of the surface and they produce a depolymerization of the network. In classical MD, tri-coordinated aluminium atoms produce an important electric field above the surface. With non bridging oxygens, they constitute attractive sites for single water molecules. (author) [fr

Modelling of nuclear glasses by classical and ab initio molecular dynamics

International Nuclear Information System (INIS)

Ganster, P.

2004-10-01

A calcium aluminosilicate glass of molar composition 67 % SiO 2 - 12 % Al 2 O 3 - 21 % CaO was modelled by classical and ab initio molecular dynamics. The size effect study in classical MD shows that the systems of 100 atoms are more ordered than the larger ones. These effects are mainly due to the 3-body terms in the empirical potentials. Nevertheless, these effects are small and the structures generated are in agreement with experimental data. In such kind of glass, we denote an aluminium avoidance and an excess of non bridging oxygens which can be compensated by tri coordinated oxygens. When the dynamics of systems of 100 and 200 atoms is followed by ab initio MD, some local arrangements occurs (bond length, angular distributions). Thus, more realistic vibrational properties are obtained in ab initio MD. The modelling of thin films shows that aluminium atoms extend to the most external part of the surface and they are all tri-coordinated. Calcium atoms are set in the sub layer part of the surface and they produce a depolymerization of the network. In classical MD, tri-coordinated aluminium atoms produce an important electric field above the surface. With non bridging oxygens, they constitute attractive sites for single water molecules. (author)

A configural dominant account of contextual cueing : configural cues are stronger than colour cues

OpenAIRE

Kunar, Melina A.; Johnston, Rebecca; Sweetman, Hollie

2013-01-01

Previous work has shown that reaction times to find a target in displays that have been repeated are faster than those for displays that have never been seen before. This learning effect, termed “contextual cueing” (CC), has been shown using contexts such as the configuration of the distractors in the display and the background colour. However, it is not clear how these two contexts interact to facilitate search. We investigated this here by comparing the strengths of these two cues when they...

Exploring the speed and performance of molecular replacement with AMPLE using QUARK ab initio protein models

Energy Technology Data Exchange (ETDEWEB)

Keegan, Ronan M. [STFC Rutherford Appleton Laboratory, Didcot OX11 0FA (United Kingdom); Bibby, Jaclyn; Thomas, Jens [University of Liverpool, Liverpool L69 7ZB (United Kingdom); Xu, Dong [Sanford-Burnham Medical Research Institute, 10901 North Torrey Pines Road, La Jolla, CA 92037 (United States); Zhang, Yang [University of Michigan, Ann Arbor, MI 48109 (United States); Mayans, Olga [University of Liverpool, Liverpool L69 7ZB (United Kingdom); Winn, Martyn D. [Science and Technology Facilities Council Daresbury Laboratory, Warrington WA4 4AD (United Kingdom); Rigden, Daniel J., E-mail: drigden@liv.ac.uk [University of Liverpool, Liverpool L69 7ZB (United Kingdom); STFC Rutherford Appleton Laboratory, Didcot OX11 0FA (United Kingdom)

2015-02-01

Two ab initio modelling programs solve complementary sets of targets, enhancing the success of AMPLE with small proteins. AMPLE clusters and truncates ab initio protein structure predictions, producing search models for molecular replacement. Here, an interesting degree of complementarity is shown between targets solved using the different ab initio modelling programs QUARK and ROSETTA. Search models derived from either program collectively solve almost all of the all-helical targets in the test set. Initial solutions produced by Phaser after only 5 min perform surprisingly well, improving the prospects for in situ structure solution by AMPLE during synchrotron visits. Taken together, the results show the potential for AMPLE to run more quickly and successfully solve more targets than previously suspected.

Insertion of Mono- vs. Bi- vs. Trivalent Atoms in Prospective Active Electrode Materials for Electrochemical Batteries: An ab Initio Perspective

Directory of Open Access Journals (Sweden)

Vadym V. Kulish

2017-12-01

Full Text Available Rational design of active electrode materials is important for the development of advanced lithium and post-lithium batteries. Ab initio modeling can provide mechanistic understanding of the performance of prospective materials and guide design. We review our recent comparative ab initio studies of lithium, sodium, potassium, magnesium, and aluminum interactions with different phases of several actively experimentally studied electrode materials, including monoelemental materials carbon, silicon, tin, and germanium, oxides TiO2 and VxOy as well as sulphur-based spinels MS2 (M = transition metal. These studies are unique in that they provided reliable comparisons, i.e., at the same level of theory and using the same computational parameters, among different materials and among Li, Na, K, Mg, and Al. Specifically, insertion energetics (related to the electrode voltage and diffusion barriers (related to rate capability, as well as phononic effects, are compared. These studies facilitate identification of phases most suitable as anode or cathode for different types of batteries. We highlight the possibility of increasing the voltage, or enabling electrochemical activity, by amorphization and p-doping, of rational choice of phases of oxides to maximize the insertion potential of Li, Na, K, Mg, Al, as well as of rational choice of the optimum sulfur-based spinel for Mg and Al insertion, based on ab initio calculations. Some methodological issues are also addressed, including construction of effective localized basis sets, applications of Hubbard correction, generation of amorphous structures, and the use of a posteriori dispersion corrections.

Loop-driven graphical unitary group approach to the electron correlation problem, including configuration interaction energy gradients

International Nuclear Information System (INIS)

Brooks, B.R.

1979-09-01

The Graphical Unitary Group Approach (GUGA) was cast into an extraordinarily powerful form by restructuring the Hamiltonian in terms of loop types. This restructuring allows the adoption of the loop-driven formulation which illuminates vast numbers of previously unappreciated relationships between otherwise distinct Hamiltonian matrix elements. The theoretical/methodological contributions made here include the development of the loop-driven formula generation algorithm, a solution of the upper walk problem used to develop a loop breakdown algorithm, the restriction of configuration space employed to the multireference interacting space, and the restructuring of the Hamiltonian in terms of loop types. Several other developments are presented and discussed. Among these developments are the use of new segment coefficients, improvements in the loop-driven algorithm, implicit generation of loops wholly within the external space adapted within the framework of the loop-driven methodology, and comparisons of the diagonalization tape method to the direct method. It is also shown how it is possible to implement the GUGA method without the time-consuming full (m 5 ) four-index transformation. A particularly promising new direction presented here involves the use of the GUGA methodology to obtain one-electron and two-electron density matrices. Once these are known, analytical gradients (first derivatives) of the CI potential energy are easily obtained. Several test calculations are examined in detail to illustrate the unique features of the method. Also included is a calculation on the asymmetric 2 1 A' state of SO 2 with 23,613 configurations to demonstrate methods for the diagonalization of very large matrices on a minicomputer. 6 figures, 6 tables

Ab initio velocity-field curves in monoclinic β-Ga2O3

Science.gov (United States)

Ghosh, Krishnendu; Singisetti, Uttam

2017-07-01

We investigate the high-field transport in monoclinic β-Ga2O3 using a combination of ab initio calculations and full band Monte Carlo (FBMC) simulation. Scattering rate calculation and the final state selection in the FBMC simulation use complete wave-vector (both electron and phonon) and crystal direction dependent electron phonon interaction (EPI) elements. We propose and implement a semi-coarse version of the Wannier-Fourier interpolation method [Giustino et al., Phys. Rev. B 76, 165108 (2007)] for short-range non-polar optical phonon (EPI) elements in order to ease the computational requirement in FBMC simulation. During the interpolation of the EPI, the inverse Fourier sum over the real-space electronic grids is done on a coarse mesh while the unitary rotations are done on a fine mesh. This paper reports the high field transport in monoclinic β-Ga2O3 with deep insight into the contribution of electron-phonon interactions and velocity-field characteristics for electric fields ranging up to 450 kV/cm in different crystal directions. A peak velocity of 2 × 107 cm/s is estimated at an electric field of 200 kV/cm.

Direct pathway for sticking/desorption of H2 on Si(100)

DEFF Research Database (Denmark)

Kratzer, Peter; Hammer, Bjørk; Nørskov, Jens Kehlet

1995-01-01

The energetics of H2 interacting with the Si(100) surface is studied by means of ab initio total-energy calculations within the framework of density-functional theory. We find a direct desorption pathway from the monohydride phase that is compatible with experimental activation energies and demon......The energetics of H2 interacting with the Si(100) surface is studied by means of ab initio total-energy calculations within the framework of density-functional theory. We find a direct desorption pathway from the monohydride phase that is compatible with experimental activation energies...... and demonstrate the importance of substrate relaxation for this process. Both the transition state configuration and the barrier height depend crucially on the degree of buckling of the Si dimers on the Si(100) surface. The adsorption barrier height on the clean surface is governed by the buckling via its...

Ab initio theory and calculations of X-ray spectra

International Nuclear Information System (INIS)

Rehr, J.J.; Kas, J.J.; Prange, M.P.; Sorini, A.P.; Takimoto, Y.; Vila, F.

2009-01-01

There has been dramatic progress in recent years both in the calculation and interpretation of various x-ray spectroscopies. However, current theoretical calculations often use a number of simplified models to account for many-body effects, in lieu of first principles calculations. In an effort to overcome these limitations we describe in this article a number of recent advances in theory and in theoretical codes which offer the prospect of parameter free calculations that include the dominant many-body effects. These advances are based on ab initio calculations of the dielectric and vibrational response of a system. Calculations of the dielectric function over a broad spectrum yield system dependent self-energies and mean-free paths, as well as intrinsic losses due to multielectron excitations. Calculations of the dynamical matrix yield vibrational damping in terms of multiple-scattering Debye-Waller factors. Our ab initio methods for determining these many-body effects have led to new, improved, and broadly applicable x-ray and electron spectroscopy codes. (authors)

Ab initio multiple cloning algorithm for quantum nonadiabatic molecular dynamics

Energy Technology Data Exchange (ETDEWEB)

Makhov, Dmitry V.; Shalashilin, Dmitrii V. [Department of Chemistry, University of Leeds, Leeds LS2 9JT (United Kingdom); Glover, William J.; Martinez, Todd J. [Department of Chemistry and The PULSE Institute, Stanford University, Stanford, California 94305, USA and SLAC National Accelerator Laboratory, Menlo Park, California 94025 (United States)

2014-08-07

We present a new algorithm for ab initio quantum nonadiabatic molecular dynamics that combines the best features of ab initio Multiple Spawning (AIMS) and Multiconfigurational Ehrenfest (MCE) methods. In this new method, ab initio multiple cloning (AIMC), the individual trajectory basis functions (TBFs) follow Ehrenfest equations of motion (as in MCE). However, the basis set is expanded (as in AIMS) when these TBFs become sufficiently mixed, preventing prolonged evolution on an averaged potential energy surface. We refer to the expansion of the basis set as “cloning,” in analogy to the “spawning” procedure in AIMS. This synthesis of AIMS and MCE allows us to leverage the benefits of mean-field evolution during periods of strong nonadiabatic coupling while simultaneously avoiding mean-field artifacts in Ehrenfest dynamics. We explore the use of time-displaced basis sets, “trains,” as a means of expanding the basis set for little cost. We also introduce a new bra-ket averaged Taylor expansion (BAT) to approximate the necessary potential energy and nonadiabatic coupling matrix elements. The BAT approximation avoids the necessity of computing electronic structure information at intermediate points between TBFs, as is usually done in saddle-point approximations used in AIMS. The efficiency of AIMC is demonstrated on the nonradiative decay of the first excited state of ethylene. The AIMC method has been implemented within the AIMS-MOLPRO package, which was extended to include Ehrenfest basis functions.

Ab Initio Study of the Dynamical Si–O Bond Breaking Event in α-Quartz

International Nuclear Information System (INIS)

Su Rui; Zhang Hong; Han Wei; Chen Jun

2015-01-01

The Si–O bond breaking event in the α-quartz at the first triplet (T_1) excitation state is studied by using ab initio molecular dynamics (AIMD) and nudged elastic band calculations. A meta-stable non-bridging oxygen hole center and E′ center (NBOHC-E′) is observed in the AIMD which consists of a broken Si–O bond with a Si–O distance of 2.54 Å. By disallowing the re-bonding of the Si and O atoms, another defect configuration (III-Si/V-Si) is obtained and validated to be stable at both ground and excitation states. The NBOHC-E′ is found to present on the minimal energy pathway of the initial to III-Si/V-Si transition, showing that the generating of the NBOHC-E′ is an important step of the excitation induced structure defect. The energy barriers to produce the NBOHC-E′ and III-Si/V-Si defects are calculated to be 1.19 and 1.28 eV, respectively. The electronic structures of the two defects are calculated by the self-consistent GW calculations and the results show a clear electron transition from the bonding orbital to the non-bonding orbital. (paper)

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

DEFF Research Database (Denmark)

Berg, Rolf W.

2009-01-01

spectroscopy and ab-initio molecular orbital calculations. A discussion is given, based mainly on some recent FT- Raman spectroscopic results on the model ionic liquid system of 1-butyl-3-methyl-imidazolium ([C4C1Im]+X-) salts. The rotational isomerism of the [C4C1Im]+ cation is described: the presence of anti.......3 Brief introduction to ab-initio model calculations .... 312 12.4 Case study on Raman spectroscopy and structure of imidazolium-based ionic liquids ..... 312 12.5 Raman spectra and structure of [C4C1Im]+ liquids ..... 315 12.6 Normal mode analysis and rotational isomerism of the [C4C1Im]+ cation...

Facet-specific interaction between methanol and TiO2 probed by sum-frequency vibrational spectroscopy.

Science.gov (United States)

Yang, Deheng; Li, Yadong; Liu, Xinyi; Cao, Yue; Gao, Yi; Shen, Y Ron; Liu, Wei-Tao

2018-04-24

The facet-specific interaction between molecules and crystalline catalysts, such as titanium dioxides (TiO 2 ), has attracted much attention due to possible facet-dependent reactivity. Using surface-sensitive sum-frequency vibrational spectroscopy, we have studied how methanol interacts with different common facets of crystalline TiO 2 , including rutile(110), (001), (100), and anatase(101), under ambient temperature and pressure. We found that methanol adsorbs predominantly in the molecular form on all of the four surfaces, while spontaneous dissociation into methoxy occurs preferentially when these surfaces become defective. Extraction of Fermi resonance coupling between stretch and bending modes of the methyl group in analyzing adsorbed methanol spectra allows determination of the methanol adsorption isotherm. The isotherms obtained for the four surfaces are nearly the same, yielding two adsorbed Gibbs free energies associated with two different adsorption configurations singled out by ab initio calculations. They are ( i ) ∼-20 kJ/mol for methanol with its oxygen attached to a low-coordinated surface titanium, and ( ii ) ∼-5 kJ/mol for methanol hydrogen-bonded to a surface oxygen and a neighboring methanol molecule. Despite similar adsorption energetics, the Fermi resonance coupling strength for adsorbed methanol appears to depend sensitively on the surface facet and coverage.

Ab initio intermolecular potential energy surface and thermophysical properties of hydrogen sulfide.

Science.gov (United States)

Hellmann, Robert; Bich, Eckard; Vogel, Eckhard; Vesovic, Velisa

2011-08-14

A six-dimensional potential energy hypersurface (PES) for two interacting rigid hydrogen sulfide molecules was determined from high-level quantum-mechanical ab initio computations. A total of 4016 points for 405 different angular orientations of two molecules were calculated utilizing the counterpoise-corrected supermolecular approach at the CCSD(T) level of theory and extrapolating the calculated interaction energies to the complete basis set limit. An analytical site-site potential function with eleven sites per hydrogen sulfide molecule was fitted to the interaction energies. The PES has been validated by computing the second pressure virial coefficient, shear viscosity, thermal conductivity and comparing with the available experimental data. The calculated values of volume viscosity were not used to validate the potential as the low accuracy of the available data precluded such an approach. The second pressure virial coefficient was evaluated by means of the Takahashi and Imada approach, while the transport properties, in the dilute limit, were evaluated by utilizing the classical trajectory method. In general, the agreement with the primary experimental data is within the experimental error for temperatures higher than 300 K. For lower temperatures the lack of reliable data indicates that the values of the second pressure virial coefficient and of the transport properties calculated in this work are currently the most accurate estimates for the thermophysical properties of hydrogen sulfide.

Adsorption of ethanol on V2O5 (010) surface for gas-sensing applications: Ab initio investigation

International Nuclear Information System (INIS)

Qin, Yuxiang; Cui, Mengyang; Ye, Zhenhua

2016-01-01

Highlights: • Ethanol adsorbed on V 2 O 5 (010) surface was investigated by ab initio calculations. • Ethanol prefers to adsorb on “Hill”-like surface, rather than“Valley”-like region. • Surface O 1(H) site plays a key role to dominate the ethanol adsorption process. • Sensing mechanism is related with electronic structure and electron redistribution. • Gas sensitivity is reflected by quantitative electron population analysis. - Abstract: The adsorption of ethanol on V 2 O 5 (010) surface was investigated by means of density functional theory (DFT) with a combined generalized gradient approximation (GGA) plus Hubbard U approach to exploit the potential sensing applications. The adsorption configurations were first constructed by considering different orientations of ethanol molecule to V and O sites on the “Hill”- and “Valley”-like regions of corrugated (010) surface. It is found that ethanol molecule can adsorb on whole surface in multiple stable configurations. Nevertheless the molecular adsorption on the “Hill”-like surface is calculated to occur preferentially, and the single coordinated oxygen on “Hill”-like surface (O 1(H) ) acting as the most energetically favorable adsorption site shows the strongest adsorption ability to ethanol molecule. Surface adsorption of ethanol tunes the electronic structure of V 2 O 5 and cause an n-doping effect. As a consequence, the Fermi levels shift toward the conductive bond increasing the charge carrier concentration of electrons in adsorbed V 2 O 5 . The sensitive electronic structure and the multiple stable configurations to ethanol adsorption highlight the high adsorption activity and then the potential of V 2 O 5 (010) surface applied to high sensitive sensor for ethanol vapor detection. Further Mulliken population and Natural bond orbital (NBO) calculations quantify the electron transfer from the adsorbed ethanol to the surface, and correlates the adsorption ability of surface sites

Ab initio assisted process modeling for Si-based nanoelectronic devices

International Nuclear Information System (INIS)

Windl, Wolfgang

2005-01-01

In this paper, we discuss concepts and examples of ab initio calculations assisting physics-based process simulation. We focus on how to determine diffusion and reaction constants, where modern methods such as the nudged elastic band method allow a systematic and reliable search for the minimum energy migration path and barrier. We show that once the saddle point is determined, the underlying harmonic transition state theory also allows to calculate the prefactors. The discussed examples include nitrogen diffusion, boron deactivation and boron interface segregation. Finally, some concepts are discussed for future device technologies such as molecular devices, where the currently prevalent multiscale approach (kinetic parameters used in higher level models like diffusion-reaction or kinetic Monte Carlo modeling) would not be sensible anymore. As an example, we described the ab initio temperature-accelerated dynamics modeling of contact formation in carbon nanotube devices

Ab initio and empirical studies on the asymmetry of molecular current-voltage characteristics

International Nuclear Information System (INIS)

Hoft, R C; Armstrong, N; Ford, M J; Cortie, M B

2007-01-01

We perform theoretical calculations of the tunnelling current through various small organic molecules sandwiched between gold electrodes by using both a tunnel barrier model and an ab initio transport code. The height of the tunnelling barrier is taken to be the work function of gold as modified by the adsorbed molecule and calculated from an ab initio electronic structure code. The current-voltage characteristics of these molecules are compared. Asymmetry is introduced into the system in two ways: an asymmetric molecule and a gap between the molecule and the right electrode. The latter is a realistic situation in scanning probe experiments. The asymmetry is also realized in the tunnel barrier model by two distinct work functions on the left and right electrodes. Significant asymmetry is observed in the ab initio i(V) curves. The tunnel barrier i(V) curves show much less pronounced asymmetry. The relative sizes of the currents through the molecules are compared. In addition, the performance of the WKB approximation is compared to the results obtained from the exact Schroedinger solution to the tunnelling barrier problem

A nine-dimensional ab initio global potential energy surface for the H2O+ + H2 → H3O+ + H reaction

Science.gov (United States)

Li, Anyang; Guo, Hua

2014-06-01

An accurate full-dimensional global potential energy surface (PES) is developed for the title reaction. While the long-range interactions in the reactant asymptote are represented by an analytical expression, the interaction region of the PES is fit to more than 81 000 of ab initio points at the UCCSD(T)-F12b/AVTZ level using the permutation invariant polynomial neural network approach. Fully symmetric with respect to permutation of all four hydrogen atoms, the PES provides a faithful representation of the ab initio points, with a root mean square error of 1.8 meV or 15 cm-1. The reaction path for this exoergic reaction features an attractive and barrierless entrance channel, a submerged saddle point, a shallow H4O+ well, and a barrierless exit channel. The rate coefficients for the title reaction and kinetic isotope effect have been determined on this PES using quasi-classical trajectories, and they are in good agreement with available experimental data. It is further shown that the H2O+ rotational enhancement of reactivity observed experimentally can be traced to the submerged saddle point. Using our recently proposed Sudden Vector Projection model, we demonstrate that a rotational degree of freedom of the H2O+ reactant is strongly coupled with the reaction coordinate at this saddle point, thus unraveling the origin of the pronounced mode specificity in this reaction.

A nine-dimensional ab initio global potential energy surface for the H2O+ + H2 → H3O+ + H reaction

International Nuclear Information System (INIS)

Li, Anyang; Guo, Hua

2014-01-01

An accurate full-dimensional global potential energy surface (PES) is developed for the title reaction. While the long-range interactions in the reactant asymptote are represented by an analytical expression, the interaction region of the PES is fit to more than 81 000 of ab initio points at the UCCSD(T)-F12b/AVTZ level using the permutation invariant polynomial neural network approach. Fully symmetric with respect to permutation of all four hydrogen atoms, the PES provides a faithful representation of the ab initio points, with a root mean square error of 1.8 meV or 15 cm −1 . The reaction path for this exoergic reaction features an attractive and barrierless entrance channel, a submerged saddle point, a shallow H 4 O + well, and a barrierless exit channel. The rate coefficients for the title reaction and kinetic isotope effect have been determined on this PES using quasi-classical trajectories, and they are in good agreement with available experimental data. It is further shown that the H 2 O + rotational enhancement of reactivity observed experimentally can be traced to the submerged saddle point. Using our recently proposed Sudden Vector Projection model, we demonstrate that a rotational degree of freedom of the H 2 O + reactant is strongly coupled with the reaction coordinate at this saddle point, thus unraveling the origin of the pronounced mode specificity in this reaction

Calculation of intermolecular potentials for H2−H2 and H2−O2 dimers ab initio and prediction of second virial coefficients

International Nuclear Information System (INIS)

Pham Van, Tat; Deiters, Ulrich K.

2015-01-01

Highlights: • We construct the angular orientations of dimers H 2 −H 2 and H 2 −O 2 . • We calculate the ab initio intermolecular interaction energies for all built orientations. • Extrapolating the interaction energies to the complete basis set limit aug-cc-pV23Z. • We develop two 5-site ab initio intermolecular potentials of dimers H 2 −H 2 , H 2 −O 2 . • Calculating the virial coefficients of dimer H 2 −H 2 and H 2 −O 2 . - Abstract: The intermolecular interaction potentials of the dimers H 2 −H 2 and H 2 −O 2 were calculated from quantum mechanics, using coupled-cluster theory CCSD(T) and correlation-consistent basis sets aug-cc-pVmZ (m = 2, 3); the results were extrapolated to the basis set limit aug-cc-pV23Z. The interaction energies were corrected for the basis set superposition error with the counterpoise scheme. For comparison also Møller–Plesset perturbation theory (at levels 2–4) with the basis sets aug-cc-pVTZ were considered, but the results proved inferior. The quantum mechanical results were used to construct analytical pair potential functions. From these functions the second virial coefficients of hydrogen and the cross virial coefficients of the hydrogen–oxygen system were obtained by integration; in both cases corrections for quantum effects were included. The results agree well with experimental data, if available, or with empirical correlations

Software configuration management

International Nuclear Information System (INIS)

Arribas Peces, E.; Martin Faraldo, P.

1993-01-01

Software Configuration Management is directed towards identifying system configuration at specific points of its life cycle, so as to control changes to the configuration and to maintain the integrity and traceability of the configuration throughout its life. SCM functions and tasks are presented in the paper

GAS PHASE STRUCTURE AND STABILITY OF COMPLEX FORMED BY H2O, NH3, H2S AND THEIR METHYL DERIVATIVES WITH THE CATION CO2+

Directory of Open Access Journals (Sweden)

Cahyorini Kusumawardani

2010-06-01

Full Text Available Ab initio molecular orbital calculations at the Hartree-Fock-Self Consistent Field (HF-SCF have been performed in order to determine the structure and gas phase energies of complex formed by the Lewis bases of H2O, NH3, H2S and their methyl derivatives with the cation Co2+. The relative basicities of the base studied depend on both the substituent. The gas-phase interaction energies computed by the SCF method including electron correlation Møller-Plesset 2 (MP2 dan Configuration Iteration (CI were comparable in accuracy. The binding energies computed by these two methods reach the targeted chemical accuracy.   Keywords: ab initio calculation, cobalt complex, structure stability

Vortex configuration in the presence of local magnetic field and locally applied stress

Energy Technology Data Exchange (ETDEWEB)

Wissberg, Shai; Kremen, Anna; Shperber, Yishai; Kalisky, Beena, E-mail: beena@biu.ac.il

2017-02-15

Highlights: • We discuss different ways to determine vortex configuration using a scanning SQUID. • We determined the vortex configuration by approaching the sample during cooling. • We observed an accumulation of vortices when contact was made with the sample. • We show how we can manipulate local vortex configuration using contact. - Abstract: Vortex configuration is determined by the repulsive interaction, which becomes dominant with increasing vortex density, by the pinning potential, and by other considerations such as the local magnetic fields, currents flowing in the sample, or as we showed recently, by local stress applied on the sample. In this work we describe different ways to control vortex configuration using scanning SQUID microscopy.

Vortex configuration in the presence of local magnetic field and locally applied stress

International Nuclear Information System (INIS)

Wissberg, Shai; Kremen, Anna; Shperber, Yishai; Kalisky, Beena

2017-01-01

Highlights: • We discuss different ways to determine vortex configuration using a scanning SQUID. • We determined the vortex configuration by approaching the sample during cooling. • We observed an accumulation of vortices when contact was made with the sample. • We show how we can manipulate local vortex configuration using contact. - Abstract: Vortex configuration is determined by the repulsive interaction, which becomes dominant with increasing vortex density, by the pinning potential, and by other considerations such as the local magnetic fields, currents flowing in the sample, or as we showed recently, by local stress applied on the sample. In this work we describe different ways to control vortex configuration using scanning SQUID microscopy.

Valence configurations in 214Rn

International Nuclear Information System (INIS)

Dracoulis, G.D.; Byrne, A.P.; Stuchbery, A.E.; Bark, R.A.; Poletti, A.R.

1987-01-01

Excited states of 214 Rn, up to spins of ≅ 24 ℎ have been studied using γ-ray and electron spectroscopy following the 208 Pb( 9 Be,3n) 214 Rn reaction. The level scheme (which differs substantially from earlier work) is compared with the results of a semi-empirical shell model calculation. The availability of high-spin orbitals for the four valence protons and two valence neutrons, and the effect of the attractive proton-neutron interaction, leads to the prediction of high-spin states at an unusually low excitation energy. Experimentally, the high level density leads to difficulties in the level scheme assignments at high spin. Nevertheless, configuration assignments, supported by transition strengths deduced from the measured lifetimes (in the nanosecond region) are suggested for the main yrast states. The decay properties also suggest that configuration mixing is important. The possibility of a gradual transition to octupole deformation, implied by the decay properties of the 11 - and 10 + yrast states is also discussed. (orig.)

Modelling of nuclear glasses by classical and ab initio molecular dynamics; Modelisation de verres intervenant dans le conditionnement des dechets radioactifs par dynamiques moleculaires classique et ab initio

Energy Technology Data Exchange (ETDEWEB)

Ganster, P

2004-10-15

A calcium aluminosilicate glass of molar composition 67 % SiO{sub 2} - 12 % Al{sub 2}O{sub 3} - 21 % CaO was modelled by classical and ab initio molecular dynamics. The size effect study in classical MD shows that the systems of 100 atoms are more ordered than the larger ones. These effects are mainly due to the 3-body terms in the empirical potentials. Nevertheless, these effects are small and the structures generated are in agreement with experimental data. In such kind of glass, we denote an aluminium avoidance and an excess of non bridging oxygens which can be compensated by tri coordinated oxygens. When the dynamics of systems of 100 and 200 atoms is followed by ab initio MD, some local arrangements occurs (bond length, angular distributions). Thus, more realistic vibrational properties are obtained in ab initio MD. The modelling of thin films shows that aluminium atoms extend to the most external part of the surface and they are all tri-coordinated. Calcium atoms are set in the sub layer part of the surface and they produce a depolymerization of the network. In classical MD, tri-coordinated aluminium atoms produce an important electric field above the surface. With non bridging oxygens, they constitute attractive sites for single water molecules. (author)

New Theoretical Developments in Exploring Electronically Excited States: Including Localized Configuration Interaction Singles and Application to Large Helium Clusters

Science.gov (United States)

Closser, Kristina Danielle

This thesis presents new developments in excited state electronic structure theory. Contrasted with the ground state, the electronically excited states of atoms and molecules often are unstable and have short lifetimes, exhibit a greater diversity of character and are generally less well understood. The very unusual excited states of helium clusters motivated much of this work. These clusters consist of large numbers of atoms (experimentally 103--109 atoms) and bands of nearly degenerate excited states. For an isolated atom the lowest energy excitation energies are from 1s → 2s and 1s → 2 p transitions, and in clusters describing the lowest energy band minimally requires four states per atom. In the ground state the clusters are weakly bound by van der Waals interactions, however in the excited state they can form well-defined covalent bonds. The computational cost of quantum chemical calculations rapidly becomes prohibitive as the size of the systems increase. Standard excited-state methods such as configuration interaction singles (CIS) and time-dependent density functional theory (TD-DFT) can be used with ≈100 atoms, and are optimized to treat only a few states. Thus, one of our primary aims is to develop a method which can treat these large systems with large numbers of nearly degenerate excited states. Additionally, excited states are generally formed far from their equilibrium structures. Vertical excitations from the ground state induce dynamics in the excited states. Thus, another focus of this work is to explore the results of these forces and the fate of the excited states. Very little was known about helium cluster excited states when this work began, thus we first investigated the excitations in small helium clusters consisting of 7 or 25 atoms using CIS. The character of these excited states was determined using attachment/detachment density analysis and we found that in the n = 2 manifold the excitations could generally be interpreted as

Shapes of nuclear configurations in a cranked harmonic oscillator model

International Nuclear Information System (INIS)

Troudet, T.; Arvieu, R.

1980-05-01

The shapes of nuclear configurations are calculated using Slater determinants built with cranked harmonic oscillator single particle states. The nuclear forces role is played by a volume conservation condition (of the potential or of the density) in a first part. In a second part, we have used the finite range, density dependent interaction of Cogny. A very simple classification of configurations emerges in the first part, the relevant parameter being the equatorial eccentricity of the nuclear density. A critical equatorial eccentricity is obtained which governs the accession to the case for which the nucleus is oblate and symmetric around its axis of rotation. Nuclear configurations calculated in the second part observe remarkably well these behaviors

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

Institute of Scientific and Technical Information of China (English)

WANG Yan-hua; CHEN Xue-song; ZOU Jian-wei; YU Qing-sen

2007-01-01

Ab initio calculations of complexes formed between N-bromosuccinimide and a series of electron-donating groups were performed at the level of MP2/Lanl2DZ* to gain a deeper insight into the nature of the N-Br halogen stronger halogen-bonding complex than the C-Br. A comparison of neutral hydrogen bond complex series reveals that the electron-donating capacities of the atoms decrease in the order, N＞O＞S; O(sp3)＞O(sp2), which is adequate for the C-Br halogen bonding. Interaction energies, in conjunction with the geometrical parameters show that the affinitive capacity of trihalide anions X-3 with N-bromosuccinimide are markedly lower than that of the corresponding X- with N-bromosuccinimide, even lower than those of neutral molecules with N-bromosuccinimide. AIM analyses further confirmed the above results.

Ab initio path-integral molecular dynamics and the quantum nature of hydrogen bonds

International Nuclear Information System (INIS)

Feng Yexin; Chen Ji; Wang Enge; Li Xin-Zheng

2016-01-01

The hydrogen bond (HB) is an important type of intermolecular interaction, which is generally weak, ubiquitous, and essential to life on earth. The small mass of hydrogen means that many properties of HBs are quantum mechanical in nature. In recent years, because of the development of computer simulation methods and computational power, the influence of nuclear quantum effects (NQEs) on the structural and energetic properties of some hydrogen bonded systems has been intensively studied. Here, we present a review of these studies by focussing on the explanation of the principles underlying the simulation methods, i.e., the ab initio path-integral molecular dynamics. Its extension in combination with the thermodynamic integration method for the calculation of free energies will also be introduced. We use two examples to show how this influence of NQEs in realistic systems is simulated in practice. (topical review)

Configuration-interaction relativistic-many-body-perturbation-theory calculations of photoionization cross sections from quasicontinuum oscillator strengths

International Nuclear Information System (INIS)

Savukov, I. M.; Filin, D. V.

2014-01-01

Many applications are in need of accurate photoionization cross sections, especially in the case of complex atoms. Configuration-interaction relativistic-many-body-perturbation theory (CI-RMBPT) has been successful in predicting atomic energies, matrix elements between discrete states, and other properties, which is quite promising, but it has not been applied to photoionization problems owing to extra complications arising from continuum states. In this paper a method that will allow the conversion of discrete CI-(R)MPBT oscillator strengths (OS) to photoionization cross sections with minimal modifications of the codes is introduced and CI-RMBPT cross sections of Ne, Ar, Kr, and Xe are calculated. A consistent agreement with experiment is found. RMBPT corrections are particularly significant for Ar, Kr, and Xe and improve agreement with experimental results compared to the particle-hole CI method. As a result, the demonstrated conversion method can be applied to CI-RMBPT photoionization calculations for a large number of multivalence atoms and ions

Quantifying transition voltage spectroscopy of molecular junctions: Ab initio calculations

DEFF Research Database (Denmark)

Chen, Jingzhe; Markussen, Troels; Thygesen, Kristian Sommer

2010-01-01

Transition voltage spectroscopy (TVS) has recently been introduced as a spectroscopic tool for molecular junctions where it offers the possibility to probe molecular level energies at relatively low bias voltages. In this work we perform extensive ab initio calculations of the nonlinear current...

Isobar configurations in nuclei and short range correlations

CERN Document Server

Weber, H J

1979-01-01

Recent results on short range correlations and isobar configurations are reviewed, and in particular a unitary version of the isobar model, coupling constants and rho -meson transition potentials, a comparison with experiments, the CERN N*-knockout from /sup 4/He, QCD and the NN interaction of short range. (42 refs).

Ab Initio Calculations for the BaTiO3 (001) Surface Structure

Institute of Scientific and Technical Information of China (English)

XUE Xu-Yan; WANG Chun-Lei; ZHONG Wei-Lie

2004-01-01

@@ The ab initio method within the local density approximation is applied to calculate cubic BaTiO3 (001) surface relaxation and rumpling for two different terminations (BaO and TiO2). Our calculations demonstrate that cubic perovskite BaTiO3 crystals possess surface polarization, accompanied by the presence of the relevant electric field.We analyse their electronic structures (band structure, density of states and the electronic density redistribution with emphasis on the covalency effects). The results are also compared with that of the previous ab initio calculations. Considerable increases of Ti-O chemical bond covalency nearby the surface have been observed.The band gap reduces especially for the TiO2 termination.

An atomistic geometrical model of the B-DNA configuration for DNA-radiation interaction simulations

Science.gov (United States)

Bernal, M. A.; Sikansi, D.; Cavalcante, F.; Incerti, S.; Champion, C.; Ivanchenko, V.; Francis, Z.

2013-12-01

In this paper, an atomistic geometrical model for the B-DNA configuration is explained. This model accounts for five organization levels of the DNA, up to the 30 nm chromatin fiber. However, fragments of this fiber can be used to construct the whole genome. The algorithm developed in this work is capable to determine which is the closest atom with respect to an arbitrary point in space. It can be used in any application in which a DNA geometrical model is needed, for instance, in investigations related to the effects of ionizing radiations on the human genetic material. Successful consistency checks were carried out to test the proposed model. Catalogue identifier: AEPZ_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEPZ_v1_0.html Program obtainable from: CPC Program Library, Queen’s University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 1245 No. of bytes in distributed program, including test data, etc.: 6574 Distribution format: tar.gz Programming language: FORTRAN. Computer: Any. Operating system: Multi-platform. RAM: 2 Gb Classification: 3. Nature of problem: The Monte Carlo method is used to simulate the interaction of ionizing radiation with the human genetic material in order to determine DNA damage yields per unit absorbed dose. To accomplish this task, an algorithm to determine if a given energy deposition lies within a given target is needed. This target can be an atom or any other structure of the genetic material. Solution method: This is a stand-alone subroutine describing an atomic-resolution geometrical model of the B-DNA configuration. It is able to determine the closest atom to an arbitrary point in space. This model accounts for five organization levels of the human genetic material, from the nucleotide pair up to the 30 nm chromatin fiber. This subroutine carries out a series of coordinate transformations

Permanent and induced dipole requirements in ab initio calculations of electron affinities of polar molecules

International Nuclear Information System (INIS)

Garrett, W.R.

1979-01-01

Through the use of a molecular pseudopotential method, we determine the a approximate magnitudes of errors that result when electron affinity determinations of polar negative ions are made through ab initio calculations in which the use of a given basis set yields inappropriate values for permanent and induced dipole moments of the neutral molecule. These results should prove useful in assessing the adequacy of basis sets in ab initio calculations of molecular electron affinities for simple linear polar molecules

Common lines modeling for reference free Ab-initio reconstruction in cryo-EM.

Science.gov (United States)

Greenberg, Ido; Shkolnisky, Yoel

2017-11-01

We consider the problem of estimating an unbiased and reference-free ab initio model for non-symmetric molecules from images generated by single-particle cryo-electron microscopy. The proposed algorithm finds the globally optimal assignment of orientations that simultaneously respects all common lines between all images. The contribution of each common line to the estimated orientations is weighted according to a statistical model for common lines' detection errors. The key property of the proposed algorithm is that it finds the global optimum for the orientations given the common lines. In particular, any local optima in the common lines energy landscape do not affect the proposed algorithm. As a result, it is applicable to thousands of images at once, very robust to noise, completely reference free, and not biased towards any initial model. A byproduct of the algorithm is a set of measures that allow to asses the reliability of the obtained ab initio model. We demonstrate the algorithm using class averages from two experimental data sets, resulting in ab initio models with resolutions of 20Å or better, even from class averages consisting of as few as three raw images per class. Copyright © 2017 Elsevier Inc. All rights reserved.

Software control and system configuration management - A process that works

Science.gov (United States)

Petersen, K. L.; Flores, C., Jr.

1983-01-01

A comprehensive software control and system configuration management process for flight-crucial digital control systems of advanced aircraft has been developed and refined to insure efficient flight system development and safe flight operations. Because of the highly complex interactions among the hardware, software, and system elements of state-of-the-art digital flight control system designs, a systems-wide approach to configuration control and management has been used. Specific procedures are implemented to govern discrepancy reporting and reconciliation, software and hardware change control, systems verification and validation testing, and formal documentation requirements. An active and knowledgeable configuration control board reviews and approves all flight system configuration modifications and revalidation tests. This flexible process has proved effective during the development and flight testing of several research aircraft and remotely piloted research vehicles with digital flight control systems that ranged from relatively simple to highly complex, integrated mechanizations.

Software control and system configuration management: A systems-wide approach

Science.gov (United States)

Petersen, K. L.; Flores, C., Jr.

1984-01-01

A comprehensive software control and system configuration management process for flight-crucial digital control systems of advanced aircraft has been developed and refined to insure efficient flight system development and safe flight operations. Because of the highly complex interactions among the hardware, software, and system elements of state-of-the-art digital flight control system designs, a systems-wide approach to configuration control and management has been used. Specific procedures are implemented to govern discrepancy reporting and reconciliation, software and hardware change control, systems verification and validation testing, and formal documentation requirements. An active and knowledgeable configuration control board reviews and approves all flight system configuration modifications and revalidation tests. This flexible process has proved effective during the development and flight testing of several research aircraft and remotely piloted research vehicles with digital flight control systems that ranged from relatively simple to highly complex, integrated mechanizations.

Early stage precipitation in aluminum alloys : An ab initio study

NARCIS (Netherlands)

Zhang, X.

2017-01-01

Multiscale computational materials science has reached a stage where many complicated phenomena or properties that are of great importance to manufacturing can be predicted or explained. The word “ab initio study” becomes commonplace as the development of density functional theory has enabled the

Ab initio electronic properties of dual phosphorus monolayers in silicon

DEFF Research Database (Denmark)

Drumm, Daniel W.; Per, Manolo C.; Budi, Akin

2014-01-01

In the midst of the epitaxial circuitry revolution in silicon technology, we look ahead to the next paradigm shift: effective use of the third dimension - in particular, its combination with epitaxial technology. We perform ab initio calculations of atomically thin epitaxial bilayers in silicon...

Ab initio calculations of mechanical properties: Methods and applications

Czech Academy of Sciences Publication Activity Database

Pokluda, J.; Černý, Miroslav; Šob, Mojmír; Umeno, Y.

2015-01-01

Roč. 73, AUG (2015), s. 127-158 ISSN 0079-6425 R&D Projects: GA ČR(CZ) GAP108/12/0311 Institutional support: RVO:68081723 Keywords : Ab initio methods * Elastic moduli * Intrinsic hardness * Stability analysis * Theoretical strength * Intrinsic brittleness/ductility Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 31.083, year: 2015

Ab initio study of single-crystalline and polycrystalline elastic properties of Mg-substituted calcite crystals.

Science.gov (United States)

Zhu, L-F; Friák, M; Lymperakis, L; Titrian, H; Aydin, U; Janus, A M; Fabritius, H-O; Ziegler, A; Nikolov, S; Hemzalová, P; Raabe, D; Neugebauer, J

2013-04-01

We employ ab initio calculations and investigate the single-crystalline elastic properties of (Ca,Mg)CO3 crystals covering the whole range of concentrations from pure calcite CaCO3 to pure magnesite MgCO3. Studying different distributions of Ca and Mg atoms within 30-atom supercells, our theoretical results show that the energetically most favorable configurations are characterized by elastic constants that nearly monotonously increase with the Mg content. Based on the first principles-derived single-crystalline elastic anisotropy, the integral elastic response of (Ca,Mg)CO3 polycrystals is determined employing a mean-field self-consistent homogenization method. As in case of single-crystalline elastic properties, the computed polycrystalline elastic parameters sensitively depend on the chemical composition and show a significant stiffening impact of Mg atoms on calcite crystals in agreement with the experimental findings. Our analysis also shows that it is not advantageous to use a higher-scale two-phase mix of stoichiometric calcite and magnesite instead of substituting Ca atoms by Mg ones on the atomic scale. Such two-phase composites are not significantly thermodynamically favorable and do not provide any strong additional stiffening effect. Copyright © 2013 Elsevier Ltd. All rights reserved.

MAP, MAC, and vortex-rings configurations in the Weinberg-Salam model

Science.gov (United States)

Teh, Rosy; Ng, Ban-Loong; Wong, Khai-Ming

2015-11-01

We report on the presence of new axially symmetric monopoles, antimonopoles and vortex-rings solutions of the SU(2)×U(1) Weinberg-Salam model of electromagnetic and weak interactions. When the ϕ-winding number n = 1, and 2, the configurations are monopole-antimonopole pair (MAP) and monopole-antimonopole chain (MAC) with poles of alternating sign magnetic charge arranged along the z-axis. Vortex-rings start to appear from the MAP and MAC configurations when the winding number n = 3. The MAP configurations possess zero net magnetic charge whereas the MAC configurations possess net magnetic charge of 4 πn / e. In the MAP configurations, the monopole-antimonopole pair is bounded by the Z0 field flux string and there is an electromagnetic current loop encircling it. The monopole and antimonopole possess magnetic charges ± 4πn/e sin2θW respectively. In the MAC configurations there is no string connecting the monopole and the adjacent antimonopole and they possess magnetic charges ± 4 πn/e respectively. The MAC configurations possess infinite total energy and zero magnetic dipole moment whereas the MAP configurations which are actually sphalerons possess finite total energy and magnetic dipole moment. The configurations were investigated for varying values of Higgs self-coupling constant 0 ≤ λ ≤ 40 at Weinberg angle θW = π/4.

CONFIGURATION GENERATOR MODEL

International Nuclear Information System (INIS)

Alsaed, A.

2004-01-01

''The Disposal Criticality Analysis Methodology Topical Report'' prescribes an approach to the methodology for performing postclosure criticality analyses within the monitored geologic repository at Yucca Mountain, Nevada. An essential component of the methodology is the ''Configuration Generator Model for In-Package Criticality'' that provides a tool to evaluate the probabilities of degraded configurations achieving a critical state. The configuration generator model is a risk-informed, performance-based process for evaluating the criticality potential of degraded configurations in the monitored geologic repository. The method uses event tree methods to define configuration classes derived from criticality scenarios and to identify configuration class characteristics (parameters, ranges, etc.). The probabilities of achieving the various configuration classes are derived in part from probability density functions for degradation parameters. The NRC has issued ''Safety Evaluation Report for Disposal Criticality Analysis Methodology Topical Report, Revision 0''. That report contained 28 open items that required resolution through additional documentation. Of the 28 open items, numbers 5, 6, 9, 10, 18, and 19 were concerned with a previously proposed software approach to the configuration generator methodology and, in particular, the k eff regression analysis associated with the methodology. However, the use of a k eff regression analysis is not part of the current configuration generator methodology and, thus, the referenced open items are no longer considered applicable and will not be further addressed

Ab initio molecular crystal structures, spectra, and phase diagrams.

Science.gov (United States)

Hirata, So; Gilliard, Kandis; He, Xiao; Li, Jinjin; Sode, Olaseni

2014-09-16

Conspectus Molecular crystals are chemists' solids in the sense that their structures and properties can be understood in terms of those of the constituent molecules merely perturbed by a crystalline environment. They form a large and important class of solids including ices of atmospheric species, drugs, explosives, and even some organic optoelectronic materials and supramolecular assemblies. Recently, surprisingly simple yet extremely efficient, versatile, easily implemented, and systematically accurate electronic structure methods for molecular crystals have been developed. The methods, collectively referred to as the embedded-fragment scheme, divide a crystal into monomers and overlapping dimers and apply modern molecular electronic structure methods and software to these fragments of the crystal that are embedded in a self-consistently determined crystalline electrostatic field. They enable facile applications of accurate but otherwise prohibitively expensive ab initio molecular orbital theories such as Møller-Plesset perturbation and coupled-cluster theories to a broad range of properties of solids such as internal energies, enthalpies, structures, equation of state, phonon dispersion curves and density of states, infrared and Raman spectra (including band intensities and sometimes anharmonic effects), inelastic neutron scattering spectra, heat capacities, Gibbs energies, and phase diagrams, while accounting for many-body electrostatic (namely, induction or polarization) effects as well as two-body exchange and dispersion interactions from first principles. They can fundamentally alter the role of computing in the studies of molecular crystals in the same way ab initio molecular orbital theories have transformed research practices in gas-phase physical chemistry and synthetic chemistry in the last half century. In this Account, after a brief summary of formalisms and algorithms, we discuss applications of these methods performed in our group as compelling

Effects of confinement on the Rydberg molecule NeH

International Nuclear Information System (INIS)

Lo, J M H; Klobukowski, M; Bielinska-Waz, D; Diercksen, G H F; Schreiner, E W S

2005-01-01

Ab initio potential energy curves of the Rydberg NeH molecule in the presence of cylindrical spatial confinement were computed by the method of multi-reference configuration interaction with extended basis sets. The influence of the applied potential to the structures and spectra of the ground and excited states of NeH was analysed in terms of perturbation theory. In addition, the phenomenon of field-induced ionization was discussed

Studies of urea geometry by means of ab initio methods and computer simulations of liquids

OpenAIRE

Cirino, José Jair Vianna; Bertran, Celso Aparecido

2002-01-01

A study was carried out on the urea geometries using ab initio calculation and Monte Carlo computational simulation of liquids. The ab initio calculated results showed that urea has a non-planar conformation in the gas phase in which the hydrogen atoms are out of the plane formed by the heavy atoms. Free energies associated to the rotation of the amino groups of urea in water were obtained using the Monte Carlo method in which the thermodynamic perturbation theory is implemented. The magnitud...

New developments in multireference and complete configuration interaction calculations

International Nuclear Information System (INIS)

Knowles, P.J.; Werner, H.J.

1987-01-01

Some recently developed techniques for the calculation of Hamiltonian matrix elements in molecular electronic structure calculations are described. These techniques allow the very rapid calculation, in any desired order, of one particle coupling coefficients between spin symmetry adapted basis functions of arbitrary structure. The matrix elements that are required, for either internally contracted multireference CI calculations, or full CI calculations, are then obtainable from suitable summations over resolutions of the identity, which has been shown previously to be rather efficient; this is especially true on vector computers, since all arithmetic can be formulated as matrix multiplications. These ideas have culminated in the preparation of a new multireference CI program which is capable of handling very large numbers of reference configurations. Application of the new techniques to full CI calculations are also presented

Interaction of Al with O2 exposed Mo2BC

International Nuclear Information System (INIS)

Bolvardi, Hamid; Music, Denis; Schneider, Jochen M.

2015-01-01

Highlights: • Al adheres to many surfaces. • Solid–solid interactions challenging for real (oxidized) surfaces. • Dissociative O 2 adsorption on Mo 2 BC(0 4 0). • Al nonamer is disrupted on oxidized Mo 2 BC(0 4 0). • Adhesion of a residual Al on the native oxide. - Abstract: A Mo 2 BC(0 4 0) surface was exposed to O 2 . The gas interaction was investigated using ab initio molecular dynamics and X-ray photoelectron spectroscopy (XPS) of air exposed surfaces. The calculations suggest that the most dominating physical mechanism is dissociative O 2 adsorption whereby Mo−O, O−Mo−O and Mo 2 −C−O bond formation is observed. To validate these results, Mo 2 BC thin films were synthesized utilizing high power pulsed magnetron sputtering and air exposed surfaces were probed by XPS. MoO 2 and MoO 3 bond formation is observed and is consistent with here obtained ab initio data. Additionally, the interfacial interactions of O 2 exposed Mo 2 BC(0 4 0) surface with an Al nonamer is studied with ab initio molecular dynamics to describe on the atomic scale the interaction between this surface and Al to mimic the interface present during cold forming processes of Al based alloys. The Al nonamer was disrupted and Al forms chemical bonds with oxygen contained in the O 2 exposed Mo 2 BC(0 4 0) surface. Based on the comparison of here calculated adsorption energy with literature data, Al−Al bonds are shown to be significantly weaker than the Al−O bonds formed across the interface. Hence, Al−Al bond rupture is expected for a mechanically loaded interface. Therefore the adhesion of a residual Al on the native oxide layer is predicted. This is consistent with experimental observations. The data presented here may also be relevant for other oxygen containing surfaces in a contact with Al or Al based alloys for example during forming operations

Ab initio molecular dynamics simulation of laser melting of silicon

NARCIS (Netherlands)

Silvestrelli, P.-L.; Alavi, A.; Parrinello, M.; Frenkel, D.

1996-01-01

The method of ab initio molecular dynamics, based on finite temperature density functional theory, is used to simulate laser heating of crystal silicon. We have found that a high concentration of excited electrons dramatically weakens the covalent bond. As a result, the system undergoes a melting

Ab initio I-V characteristics of short C-20 chains

DEFF Research Database (Denmark)

Roland, C.; Larade, B.; Taylor, Jeremy Philip