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Sample records for ab-initio many-body perturbation

  1. Ab initio study of temporary anions of benzene and fluorobenzenes using the multipartitioning many-body perturbation theory.

    Science.gov (United States)

    Izmaylov, Artur F; Shchegoleva, Lyudmila N; Scuseria, Gustavo E; Zaitsevskii, Andréi

    2005-12-01

    We present an ab initio study of the lowest states of five temporary anions: C6H6(-), C6H5F(-), 1,4-C6H4F2(-), 1,2,3-C6H3F3(-), and 1,3,5-C6H3F3(-). Vertical positions and widths of anionic resonances have been calculated within the stabilization graph approach using the multipartitioning form of the many-body perturbation theory for state-selective effective Hamiltonians restricted to second order (MPPT-R). Good agreement with experimentally derived estimates justifies application of the MPPT-R method for theoretical investigation of haloaromatic temporary anion radicals. PMID:19810321

  2. Effects of quantum confinement on excited state properties of SrTiO3 from ab initio many-body perturbation theory

    Science.gov (United States)

    Reyes-Lillo, Sebastian E.; Rangel, Tonatiuh; Bruneval, Fabien; Neaton, Jeffrey B.

    2016-07-01

    The Ruddlesden-Popper (RP) homologous series Srn +1TinO3 n +1 provides a useful template for the study and control of the effects of dimensionality and quantum confinement on the excited state properties of the complex oxide SrTiO3. We use ab initio many-body perturbation theory within the G W approximation and the Bethe-Salpeter equation approach to calculate quasiparticle energies and absorption spectra of Srn +1TinO3 n +1 for n =1 -5 and ∞ . Our computed direct and indirect optical gaps are in excellent agreement with spectroscopic measurements. The calculated optical spectra reproduce the main experimental features and reveal excitonic structure near the gap edge. We find that electron-hole interactions are important across the series, leading to significant exciton binding energies that increase for small n and reach a value of 330 meV for n =1 , a trend attributed to increased quantum confinement. We find that the lowest-energy singlet exciton of Sr2TiO4 (n =1 ) localizes in the two-dimensional plane defined by the TiO2 layer, and we explain the origin of its localization.

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

    CERN Document Server

    Quaglioni, Sofia

    2009-01-01

    We develop a new ab initio many-body approach capable of describing simultaneously both bound and scattering states in light nuclei, by combining the resonating-group method with the use of realistic interactions, and a microscopic and consistent description of the nucleon clusters. This approach preserves translational symmetry and Pauli principle. We outline technical details and present phase shift results for neutron scattering on 3H, 4He and 10Be and proton scattering on 3He and 4He, using realistic nucleon-nucleon (NN) potentials. Our A=4 scattering results are compared to earlier ab initio calculations. We find that the CD-Bonn NN potential in particular provides an excellent description of nucleon-4He S-wave phase shifts. On the contrary, the experimental nucleon-4He P-wave phase shifts are not well reproduced by any NN potential we use. We demonstrate that a proper treatment of the coupling to the n-10Be continuum is successful in explaining the parity-inverted ground state in 11Be.

  4. Ab initio calculations of many-body interactions for compressed solid argon.

    Science.gov (United States)

    Tian, Chunling; Liu, Fusheng; Cai, Lingcang; Yuan, Hongkuan; Chen, Hong; Zhong, Mingmin

    2015-11-01

    An investigation on many-body effects of solid argon at high pressure was conducted based on a many-body expansion of interaction energy. The three- and four-body terms in the expansion were calculated using the coupled-cluster method with single, double, and noniterative triple theory and incremental method, in which the configurations of argon trimers and tetramers were chosen as the same as those in the actual lattice. The four-body interactions in compressed solid argon were estimated for the first time, and the three-body interaction ab initio calculations were extended to a small distance. It shows that the four-body contribution is repulsive at high densities and effectively cancels the three-body lattice energy. The dimer potential plus three-body interaction can well reproduce the measurements of equation of state at pressure approximately lower than ∼60 GPa, when including the four-body effects extends the agreement up to the maximum experimental pressure of 114 GPa. PMID:26547175

  5. Many-body effects on the electronic and optical properties of Si nanowires from ab initio approaches

    Energy Technology Data Exchange (ETDEWEB)

    Palummo, M.; Del Sole, R. [European Theoretical Spectroscopy Facility (ETSF), CNR-INFM-SMC, Roma (Italy); Dipartimento di Fisica - Universita di Roma, ' Tor Vergata' , Roma (Italy); Ossicini, S. [European Theoretical Spectroscopy Facility (ETSF), Reggio Emilia (Italy); Dipartimento di Scienze e Metodi dell' Ingegneria, Universita di Modena e Reggio Emilia (Italy)

    2010-08-15

    The study of semiconducting nanowires is one of the most rapidly growing research areas in materials science and nanotechnology, not only from the point of view of the possible applications, but also regarding the use of the latest developments in the theory. In this paper, we review the general ab initio many-body theory and methods and resume some of our very recent results regarding the structural, electronic, and optical properties of Silicon nanowires (Si-NWs), outlining both the reached achievements and some of the technical aspects necessary to obtain them. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

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

    CERN Document Server

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

    2013-01-01

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

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

    Science.gov (United States)

    Kong, Bo; Zhang, Yachao

    2016-07-01

    The electronic structures of the cubic GdH3 are extensively investigated using the ab initio many-body GW calculations treating the Gd 4f electrons either in the core (4f-core) or in the valence states (4f-val). Different degrees of quasiparticle (QP) self-consistent calculations with the different starting points are used to correct the failures of the GGA/GGA + U/HSE03 calculations. In the 4f-core case, GGA + G0W0 calculations give a fundamental band gap of 1.72 eV, while GGA+ GW0 or GGA + GW calculations present a larger band gap. In the 4f-val case, the nonlocal exchange-correlation (xc) functional HSE03 can account much better for the strong localization of the 4f states than the semilocal or Hubbard U corrected xc functional in the Kohn-Sham equation. We show that the fundamental gap of the antiferromagnetic (AFM) or ferromagnetic (FM) GdH3 can be opened up by solving the QP equation with improved starting point of eigenvalues and wave functions given by HSE03. The HSE03 + G0W0 calculations present a fundamental band gap of 2.73 eV in the AFM configuration, and the results of the corresponding GW0 and GW calculations are 2.89 and 3.03 eV, respectively. In general, for the cubic structure, the fundamental gap from G0W0 calculations in the 4f-core case is the closest to the real result. By G0W0 calculations in the 4f-core case, we find that H or Gd defects can strongly affect the band structure, especially the H defects. We explain the mechanism in terms of the possible electron correlation on the hydrogen site. Under compression, the insulator-to-metal transition in the cubic GdH3 occurs around 40 GPa, which might be a satisfied prediction.

  8. Ab Initio Many-Body Calculations of n-3H, n-4He, p-{3,4}He, and n-10Be Scattering

    CERN Document Server

    Quaglioni, Sofia

    2008-01-01

    We develop a new ab initio many-body approach capable of describing simultaneously both bound and scattering states in light nuclei, by combining the resonating-group method with the use of realistic interactions, and a microscopic and consistent description of the nucleon clusters. This approach preserves translational symmetry and Pauli principle. We present phase shifts for neutron scattering on 3H, 4He and 10Be and proton scattering on {3,4}He, using realistic nucleon-nucleon potentials. Our A=4 scattering results are compared to earlier ab initio calculations. We demonstrate that a proper treatment of the coupling to the n-10Be continuum is essential to explain the parity-inverted ground state in 11Be.

  9. Exploring the ab initio/classical free energy perturbation method: The hydration free energy of water

    Science.gov (United States)

    Sakane, Shinichi; Yezdimer, Eric M.; Liu, Wenbin; Barriocanal, Jose A.; Doren, Douglas J.; Wood, Robert H.

    2000-08-01

    The ab initio/classical free energy perturbation (ABC-FEP) method proposed previously by Wood et al. [J. Chem. Phys. 110, 1329 (1999)] uses classical simulations to calculate solvation free energies within an empirical potential model, then applies free energy perturbation theory to determine the effect of changing the empirical solute-solvent interactions to corresponding interactions calculated from ab initio methods. This approach allows accurate calculation of solvation free energies using an atomistic description of the solvent and solute, with interactions calculated from first principles. Results can be obtained at a feasible computational cost without making use of approximations such as a continuum solvent or an empirical cavity formation energy. As such, the method can be used far from ambient conditions, where the empirical parameters needed for approximate theories of solvation may not be available. The sources of error in the ABC-FEP method are the approximations in the ab initio method, the finite sample of configurations, and the classical solvent model. This article explores the accuracy of various approximations used in the ABC-FEP method by comparing to the experimentally well-known free energy of hydration of water at two state points (ambient conditions, and 973.15 K and 600 kg/m3). The TIP4P-FQ model [J. Chem. Phys. 101, 6141 (1994)] is found to be a reliable solvent model for use with this method, even at supercritical conditions. Results depend strongly on the ab initio method used: a gradient-corrected density functional theory is not adequate, but a localized MP2 method yields excellent agreement with experiment. Computational costs are reduced by using a cluster approximation, in which ab initio pair interaction energies are calculated between the solute and up to 60 solvent molecules, while multi-body interactions are calculated with only a small cluster (5 to 12 solvent molecules). Sampling errors for the ab initio contribution to

  10. Simultaneous description of conductance and thermopower in single-molecule junctions from many-body ab initio calculations

    DEFF Research Database (Denmark)

    Jin, Chengjun; Markussen, Troels; Thygesen, Kristian Sommer

    2014-01-01

    We investigate the electronic conductance and thermopower of a single-molecule junction consisting of bis-(4-aminophenyl) acetylene (B4APA) connected to gold electrodes. We use nonequilibrium Green's function methods in combination with density-functional theory (DFT) and the many-body GW...... approximation. To simulate recent break junction experiments, we calculate the transport properties of the junction as it is pulled apart. For all junction configurations, DFT with a standard semilocal functional overestimates the conductance by almost an order of magnitude, while the thermopower...

  11. Ab initio geometry and bright excitation of carotenoids: Quantum Monte Carlo and Many Body Green's Function Theory calculations on peridinin

    CERN Document Server

    Coccia, Emanuele; Guidoni, Leonardo

    2014-01-01

    In this letter we report the singlet ground state structure of the full carotenoid peridinin by means of variational Monte Carlo (VMC) calculations. The VMC relaxed geometry has an average bond length alternation of 0.1165(10) {\\AA}, larger than the values obtained by DFT (PBE, B3LYP and CAM-B3LYP) and shorter than that calculated at the Hartree-Fock (HF) level. TDDFT and EOM-CCSD calculations on a reduced peridinin model confirm the HOMO-LUMO major contribution of the Bu+-like (S2) bright excited state. Many Body Green's Function Theory (MBGFT) calculations of the vertical excitation energy of the Bu+-like state for the VMC structure (VMC/MBGFT) provide excitation energy of 2.62 eV, in agreement with experimental results in n-hexane (2.72 eV). The dependence of the excitation energy on the bond length alternation in the MBGFT and TDDFT calculations with different functionals is discussed.

  12. Many-body ab initio diffusion quantum Monte Carlo applied to the strongly correlated oxide NiO

    Energy Technology Data Exchange (ETDEWEB)

    Mitra, Chandrima; Krogel, Jaron T.; Santana, Juan A.; Reboredo, Fernando A., E-mail: reboredofa@ornl.gov [Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 (United States)

    2015-10-28

    We present a many-body diffusion quantum Monte Carlo (DMC) study of the bulk and defect properties of NiO. We find excellent agreement with experimental values, within 0.3%, 0.6%, and 3.5% for the lattice constant, cohesive energy, and bulk modulus, respectively. The quasiparticle bandgap was also computed, and the DMC result of 4.72 (0.17) eV compares well with the experimental value of 4.3 eV. Furthermore, DMC calculations of excited states at the L, Z, and the gamma point of the Brillouin zone reveal a flat upper valence band for NiO, in good agreement with Angle Resolved Photoemission Spectroscopy results. To study defect properties, we evaluated the formation energies of the neutral and charged vacancies of oxygen and nickel in NiO. A formation energy of 7.2 (0.15) eV was found for the oxygen vacancy under oxygen rich conditions. For the Ni vacancy, we obtained a formation energy of 3.2 (0.15) eV under Ni rich conditions. These results confirm that NiO occurs as a p-type material with the dominant intrinsic vacancy defect being Ni vacancy.

  13. 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...

  14. Many-body perturbation procedure for energy-dependent perturbation: Merging many-body perturbation theory with QED

    OpenAIRE

    Lindgren, Ingvar; Salomonson, Sten; Hedendahl, Daniel

    2006-01-01

    A formalism for energy-dependent many-body perturbation theory (MBPT), previously indicated in our recent review articles (Lindgren et al., Phys.Rep. 389,161(2004), Can.J.Phys. 83,183(2005)), is developed in more detail. The formalism allows for a mixture of energy-dependent (retarded) and energy-independent (instantaneous) interactions and hence for a merger of QED and standard (relativistic) MBPT. This combination is particularly important for light elements, such as light heliumlike ions, ...

  15. Hartree-Fock Many-Body Perturbation Theory for Nuclear Ground-States

    CERN Document Server

    Tichai, Alexander; Binder, Sven; Roth, Robert

    2016-01-01

    We investigate the order-by-order convergence behavior of many-body perturbation theory (MBPT) as a simple and efficient tool to approximate the ground-state energy of closed-shell nuclei. To address the convergence properties directly, we explore perturbative corrections up to 30th order and highlight the role of the partitioning for convergence. The use of a simple Hartree-Fock solution to construct the unperturbed basis leads to a convergent MBPT series for soft interactions, in contrast to, e.g., a harmonic oscillator basis. For larger model spaces and heavier nuclei, where a direct high-order MBPT calculation in not feasible, we perform third-order calculation and compare to advanced ab initio coupled-cluster calculations for the same interactions and model spaces. We demonstrate that third-order MBPT provides ground-state energies for nuclei up into tin isotopic chain that are in excellent agreement with the best available coupled-cluster results at a fraction of the computational cost.

  16. Hartree-Fock many-body perturbation theory for nuclear ground-states

    Science.gov (United States)

    Tichai, Alexander; Langhammer, Joachim; Binder, Sven; Roth, Robert

    2016-05-01

    We investigate the order-by-order convergence behavior of many-body perturbation theory (MBPT) as a simple and efficient tool to approximate the ground-state energy of closed-shell nuclei. To address the convergence properties directly, we explore perturbative corrections up to 30th order and highlight the role of the partitioning for convergence. The use of a simple Hartree-Fock solution for the unperturbed basis leads to a convergent MBPT series for soft interactions, in contrast to the divergent MBPT series obtained with a harmonic oscillator basis. For larger model spaces and heavier nuclei, where a direct high-order MBPT calculation is not feasible, we perform third-order calculations and compare to advanced ab initio coupled-cluster results for the same interactions and model spaces. We demonstrate that third-order MBPT provides ground-state energies for nuclei up into the tin isotopic chain in excellent agreement with the best available coupled-cluster calculations at a fraction of the computational cost.

  17. Photoemission spectra of aqueous solutions of salts from many-body perturbation theory

    Science.gov (United States)

    Gaiduk, Alex P.; Skone, Jonathan H.; Govoni, Marco; Galli, Giulia

    The computational design of electrode materials for energy conversion and storage processes requires an accurate description of the energy levels of the electrolyte and of electrolyte/electrode interfaces. Conventional density-functional approximations are in general not well suited for this task as they yield inaccurate orbital energies. Many-body perturbation theory (MBPT) predicts vertical ionization potentials and energy gaps in better agreement with experiments, providing the possibility for an accurate description of the electronic properties of electrolytes. We coupled ab initio molecular dynamics with MBPT calculations to investigate the photoemission spectra of a 1 M aqueous solution of NaCl. For the first time we were able to determine the absolute positions of the spectra peaks, with excellent agreement with experiments for both the solute and solvent peak positions. The best results were obtained using wavefunctions obtained from dielectric-dependent hybrid calculations as a starting point for MBPT. Work supported by DOE BES DE-SC0008938. Computer time provided by the Argonne Leadership Computing Facility through the INCITE program.

  18. Non-relativistic many-body problem perturbation theory calculation: toward relativistic many-body problem perturbation theory

    International Nuclear Information System (INIS)

    Non-relativistic many-body perturbation theory is discussed. Methods and results in the solution of inhomogeneous 1- and 2-particle equations are presented. B. Similar programs for the Dirac equation are considered. The 1-particle equation is equivalent to the relativistic random phase approximation (work by A.-M. Martensson-Pendrill), and the 2-particle equation is under study. C. Matrix diagonalization of the Dirac equation is being explored as a method of isolating positive energy solutions. For a weak external field, the upper components of the diagonal equation correspond to positive energy solutions

  19. Classical ab initio van der Waals interactions from many-body dispersion and multipole machine learning models trained in chemical space

    CERN Document Server

    Bereau, Tristan; von Lilienfeld, O Anatole

    2015-01-01

    Accurate predictions of van der Waals forces require faithful models of dispersion, permanent and induced multipole-moments, as well as penetration and repulsion. We introduce a universal combined physics- and data-driven model of dispersion and multipole-moment contributions, respectively. Atomic multipoles are estimated "on-the-fly" for any organic molecule in any conformation using a machine learning approach trained on quantum chemistry results for tens of thousands of atoms in varying chemical environments drawn from thousands of organic molecules. Globally neutral, cationic, and anionic molecular charge states can be treated with individual models. Dispersion interactions are included via recently-proposed classical many-body potentials. For nearly one thousand intermolecular dimers, this approximate van der Waals model is found to reach an accuracy similar to that of state-of-the-art force fields, while bypassing the need for parametrization. Estimates of cohesive energies for the benzene crystal confi...

  20. Energy-dependent many-body perturbation theory: a road towards a many-body-QED procedure

    International Nuclear Information System (INIS)

    A rigorous procedure for energy-dependent many-body perturbation theory (MBPT) is presented. This can be applied for numerical evaluation of many-body-QED effects by combining QED with electron correlation to arbitrary order. So far, it has been used only for the exchange of a single retarded photon together with an arbitrary number of instantaneous Coulomb interactions. For heliumlike neon this represents more than 99% of the nonradiative effect on the energy beyond standard MBPT. (author)

  1. Ab Initio Atom-Atom Potentials Using CamCASP: Theory and Application to Many-Body Models for the Pyridine Dimer.

    Science.gov (United States)

    Misquitta, Alston J; Stone, Anthony J

    2016-09-13

    Creating accurate, analytic atom-atom potentials for small organic molecules from first principles can be a time-consuming and computationally intensive task, particularly if we also require them to include explicit polarization terms, which are essential in many systems. We describe how the CamCASP suite of programs can be used to generate such potentials using some of the most accurate electronic structure methods currently applicable. We derive the long-range terms from monomer properties and determine the short-range anisotropy parameters by a novel and robust method based on the iterated stockholder atom approach. Using these techniques, we develop distributed multipole models for the electrostatic, polarization, and dispersion interactions in the pyridine dimer and develop a series of many-body potentials for the pyridine system. Even the simplest of these potentials exhibits root mean square errors of only about 0.6 kJ mol(-1) for the low-energy pyridine dimers, significantly surpassing the best empirical potentials. Our best model is shown to support eight stable minima, four of which have not been reported before in the literature. Further, the functional form can be made systematically more elaborate so as to improve the accuracy without a significant increase in the human-time spent in their generation. We investigate the effects of anisotropy, rank of multipoles, and choice of polarizability and dispersion models.

  2. Ab Initio Atom-Atom Potentials Using CamCASP: Theory and Application to Many-Body Models for the Pyridine Dimer.

    Science.gov (United States)

    Misquitta, Alston J; Stone, Anthony J

    2016-09-13

    Creating accurate, analytic atom-atom potentials for small organic molecules from first principles can be a time-consuming and computationally intensive task, particularly if we also require them to include explicit polarization terms, which are essential in many systems. We describe how the CamCASP suite of programs can be used to generate such potentials using some of the most accurate electronic structure methods currently applicable. We derive the long-range terms from monomer properties and determine the short-range anisotropy parameters by a novel and robust method based on the iterated stockholder atom approach. Using these techniques, we develop distributed multipole models for the electrostatic, polarization, and dispersion interactions in the pyridine dimer and develop a series of many-body potentials for the pyridine system. Even the simplest of these potentials exhibits root mean square errors of only about 0.6 kJ mol(-1) for the low-energy pyridine dimers, significantly surpassing the best empirical potentials. Our best model is shown to support eight stable minima, four of which have not been reported before in the literature. Further, the functional form can be made systematically more elaborate so as to improve the accuracy without a significant increase in the human-time spent in their generation. We investigate the effects of anisotropy, rank of multipoles, and choice of polarizability and dispersion models. PMID:27467814

  3. Conformers of CL-20 explosive and ab initio refinement using perturbation theory: implications to detonation mechanisms.

    Science.gov (United States)

    Molt, Robert W; Bartlett, Rodney J; Watson, Thomas; Bazanté, Alexandre P

    2012-12-13

    We have identified the major conformers of CL-20 explosive, otherwise known as 2,4,6,8,10,12-hexanitrohexaazaisowurtzitane, more formally known as 2,4,6,8,10,12-hexanitrohexaazatetracyclo[5.5.0.0]-dodecane, via Monte Carlo search in conformational space through molecular mechanics and subsequent quantum mechanical refinement using perturbation theory. Our search produced enough conformers to account for all of the various forms of CL-20 found in crystals. This suggests that our methodology will be useful in studying the conformational landscape of other nitramines. The energy levels of the conformers found are all within 0.25 eV of one another based on MBPT(2)/6-311G(d,p); consequently, without further refinement from a method such as coupled cluster theory, all conformers may reasonably be populated at STP in the gas phase. We also report the harmonic vibrational frequencies of conformers, including the implications on the mechanism of detonation. In particular, we establish that the weakest N-N nitramine of CL-20 is the cyclohexane equatorial nitramine. This preliminary mapping of the conformers of CL-20 makes it possible to study the mechanism of detonation of this explosive rigorously in future work. PMID:23136867

  4. An investigation of ab initio shell-model interactions derived by no-core shell model

    Science.gov (United States)

    Wang, XiaoBao; Dong, GuoXiang; Li, QingFeng; Shen, CaiWan; Yu, ShaoYing

    2016-09-01

    The microscopic shell-model effective interactions are mainly based on the many-body perturbation theory (MBPT), the first work of which can be traced to Brown and Kuo's first attempt in 1966, derived from the Hamada-Johnston nucleon-nucleon potential. However, the convergence of the MBPT is still unclear. On the other hand, ab initio theories, such as Green's function Monte Carlo (GFMC), no-core shell model (NCSM), and coupled-cluster theory with single and double excitations (CCSD), have made many progress in recent years. However, due to the increasing demanding of computing resources, these ab initio applications are usually limited to nuclei with mass up to A = 16. Recently, people have realized the ab initio construction of valence-space effective interactions, which is obtained through a second-time renormalization, or to be more exactly, projecting the full-manybody Hamiltonian into core, one-body, and two-body cluster parts. In this paper, we present the investigation of such ab initio shell-model interactions, by the recent derived sd-shell effective interactions based on effective J-matrix Inverse Scattering Potential (JISP) and chiral effective-field theory (EFT) through NCSM. In this work, we have seen the similarity between the ab initio shellmodel interactions and the interactions obtained by MBPT or by empirical fitting. Without the inclusion of three-body (3-bd) force, the ab initio shell-model interactions still share similar defects with the microscopic interactions by MBPT, i.e., T = 1 channel is more attractive while T = 0 channel is more repulsive than empirical interactions. The progress to include more many-body correlations and 3-bd force is still badly needed, to see whether such efforts of ab initio shell-model interactions can reach similar precision as the interactions fitted to experimental data.

  5. Many-body-QED perturbation theory: Connection to the Bethe-Salpeter equation

    OpenAIRE

    Lindgren, Ingvar

    2005-01-01

    The connection between many-body theory (MBPT)--in perturbative and non-perturbative form--and quantum-electrodynamics (QED) is reviewed for systems of two fermions in an external field. The treatment is mainly based upon the recently developed covariant-evolution-operator method for QED calculations [Lindgren et al. Phys. Rep. 389, 161 (2004)], which has a structure quite akin to that of many-body perturbation theory. At the same time this procedure is closely connected to the S-matrix and t...

  6. Relativistic multireference many-body perturbation theory calculations on Au64+ - Au69+ ions

    Energy Technology Data Exchange (ETDEWEB)

    Vilkas, M J; Ishikawa, Y; Trabert, E

    2006-03-31

    Many-body perturbation theory (MBPT) calculations are an adequate tool for the description of the structure of highly charged multi-electron ions and for the analysis of their spectra. They demonstrate this by way of a re-investigation of n=3, {Delta}n=0 transitions in the EUV spectra of Na-, Mg-, Al-like, and Si-like ions of Au that have been obtained previously by heavy-ion accelerator based beam-foil spectroscopy. They discuss the evidence and propose several revisions on the basis of the multi-reference many-body perturbation theory calculations of Ne- through P-like ions of Au.

  7. 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...... framework for modelling the fusion process of noble gas clusters is presented. We report the striking correspondence of the peaks in the experimentally measured abundance mass spectra with the peaks in the size-dependence of the second derivative of the binding energy per atom calculated for the chain...... of the noble gas clusters up to 150 atoms....

  8. Ab initio effective rotational and rovibrational Hamiltonians for non-rigid systems via curvilinear second order vibrational M{\\o}ller-Plesset perturbation theory

    CERN Document Server

    Changala, P Bryan

    2016-01-01

    We present a perturbative method for ab initio calculations of rotational and rovibrational effective Hamiltonians of both rigid and non-rigid molecules. Our approach is based on a curvilinear implementation of second order vibrational M{\\o}ller-Plesset perturbation theory (VMP2) extended to include rotational effects via a second order contact transformation. Though more expensive, this approach is significantly more accurate than standard second order vibrational perturbation theory (VPT2) for systems that are poorly described to zeroth order by rectilinear normal mode harmonic oscillators. We apply this method and demonstrate its accuracy on two molecules: Si$_2$C, a quasilinear triatomic with significant bending anharmonicity, and CH$_3$NO$_2$, which contains a completely unhindered methyl rotor. In addition to these two examples, we discuss several key technical aspects of the method, including an efficient implementation of Eckart and quasi-Eckart frame embedding that does not rely on numerical finite d...

  9. Green functions in the renormalized many-body perturbation theory for correlated and disordered electrons

    Directory of Open Access Journals (Sweden)

    V.Janiš

    2006-01-01

    Full Text Available The ways of introducing and handling renormalizations in the many-body perturbation theory are reviewed. We stress the indispensable role the technique of Green functions plays in extrapolating the weak-coupling perturbative approaches to intermediate and strong couplings. We separately discuss mass and charge renormalizations. The former is incorporated in a self-consistent equation for the self-energy derived explicitly from generating Feynman diagrams within the Baym and Kadanoff approach. The latter amounts to self-consistent equations for two-particle irreducible vertices. We analyze the charge renormalization initiated by De Dominicis and Martin and demonstrate that its realization via the parquet approach may become a powerful and viable way of using the many-body diagrammatic approach reliably in non-perturbative regimes with cooperative phenomena induced by either strong interaction or strong static randomness.

  10. Ab-Initio Molecular Dynamics

    CERN Document Server

    Kühne, Thomas D

    2012-01-01

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

  11. Self-consistent many-body perturbation theory in range-separated density-functional theory

    DEFF Research Database (Denmark)

    Fromager, Emmanuel; Jensen, Hans Jørgen Aagaard

    2008-01-01

    effects adequately which, on the other hand, can be described by many-body perturbation theory MBPT. It is therefore of interest to develop a hybrid model which combines the best of both the MBPT and DFT approaches. This can be achieved by splitting the two-electron interaction into long-range and short......In many cases, density-functional theory (DFT) with current standard approximate functionals offers a relatively accurate and computationally cheap description of the short-range dynamic electron correlation effects. However, in general, standard DFT does not treat the dispersion interaction...

  12. An universal algorithm of calculating terms of atomic many-body perturbation theory

    CERN Document Server

    Dzuba, V A

    2007-01-01

    An algorithm, based on numerical description of the terms of many-body perturbation theory (Goldstone diagrams), is presented. The algorithm assumes a basis set of orthogonal single-electron orbitals supplied by the user. These orbitals are the eigenstates of the Dirac operator in the spherically-symmetric case. Apart from this the algorithm is practically free from any limitations and can be used for calculating of wide range of atomic properties in any order of the perturbation theory and with any external field applied to the atom. The use of the algorithm is illustrated by calculating of the second and third order correlation corrections to the ground state energies of sodium, copper and gallium.

  13. Particle-hole configuration interaction and many-body perturbation theory: application to Hg+

    CERN Document Server

    Berengut, J C

    2016-01-01

    The combination of configuration interaction and many-body perturbation theory methods (CI+MBPT) is extended to non-perturbatively include configurations with electron holes below the designated Fermi level, allowing us to treat systems where holes play an important role. For example, the method can treat valence-hole systems like Ir$^{17+}$, particle-hole excitations in noble gases, and difficult transitions such as the $6s \\rightarrow 5d^{-1}6s^2$ optical clock transition in Hg$^+$. We take the latter system as our test case for the method and obtain very good accuracy (~1%) for the low-lying transition energies. The $\\alpha$-dependence of these transitions is calculated and used to reinterpret the existing best laboratory limits on the time-dependence of the fine-structure constant.

  14. Second-order many-body perturbation theory: an eternal frontier.

    Science.gov (United States)

    Hirata, So; He, Xiao; Hermes, Matthew R; Willow, Soohaeng Y

    2014-01-30

    Second-order many-body perturbation theory [MBPT(2)] is the lowest-ranked member of a systematic series of approximations convergent at the exact solutions of the Schrödinger equations. It has served and continues to serve as the testing ground for new approximations, algorithms, and even theories. This article introduces this basic theory from a variety of viewpoints including the Rayleigh-Schrödinger perturbation theory, the many-body Green's function theory based on the Dyson equation, and the related Feynman-Goldstone diagrams. It also explains the important properties of MBPT(2) such as size consistency, its ability to describe dispersion interactions, and divergence in metals. On this basis, this article surveys three major advances made recently by the authors to this theory. They are a finite-temperature extension of MBPT(2) and the resolution of the Kohn-Luttinger conundrum, a stochastic evaluation of the correlation and self-energies of MBPT(2) using the Monte Carlo integration of their Laplace-transformed expressions, and an extension to anharmonic vibrational zero-point energies and transition frequencies based on the Dyson equation.

  15. Finite-temperature second-order many-body perturbation theory revisited

    CERN Document Server

    Santra, Robin

    2016-01-01

    We present an algebraic, nondiagrammatic derivation of finite-temperature second-order many-body perturbation theory [FT-MBPT(2)], using techniques and concepts accessible to theoretical chemical physicists. We give explicit expressions not just for the grand potential but particularly for the mean energy of an interacting many-electron system. The framework presented is suitable for computing the energy of a finite or infinite system in contact with a heat and particle bath at finite temperature and chemical potential. FT-MBPT(2) may be applied if the system, at zero temperature, may be described using standard (i.e., zero-temperature) second-order many-body perturbation theory [ZT-MBPT(2)] for the energy. We point out that in such a situation, FT-MBPT(2) reproduces, in the zero-temperature limit, the energy computed within ZT-MBPT(2). In other words, the difficulty that has been referred to as the Kohn--Luttinger conundrum, does not occur. We comment, in this context, on a "renormalization" scheme recently ...

  16. Post-Wick theorems for symbolic manipulation of second-quantized expressions in atomic many-body perturbation theory

    Energy Technology Data Exchange (ETDEWEB)

    Derevianko, Andrei [Physics Department, University of Nevada, Reno, NV 89557 (United States)

    2010-04-14

    Manipulating expressions in many-body perturbation theory becomes unwieldy with increasing order of the perturbation theory. Here I derive a set of theorems for efficient simplification of such expressions. The derived rules are specifically designed for implementing with symbolic algebra tools. As an illustration, we count the numbers of Brueckner-Goldstone diagrams in the first several orders of many-body perturbation theory for matrix elements between two states of a mono-valent system.

  17. Post-Wick theorems for symbolic manipulation of second-quantized expressions in atomic many-body perturbation theory

    CERN Document Server

    Derevianko, Andrei

    2009-01-01

    Manipulating expressions in many-body perturbation theory becomes unwieldily with increasing order of the perturbation theory. Here I derive a set of theorems for efficient simplification of such expressions. The derived rules are specifically designed for implementing with symbolic algebra tools. As an illustration, we count the numbers of Brueckner-Goldstone diagrams in the first several orders of many-body perturbation theory for matrix elements between two states of a mono-valent system.

  18. Many-body-QED perturbation theory: Connection to the two-electron Bethe-Salpeter equation

    Science.gov (United States)

    Lindgren, I.; Salomonson, S.; Hedendahl, D.

    2005-03-01

    The connection between many-body perturbation theory (MBPT) and quantum electrodynamics (QED) is reviewed for systems of two fermions in an external field. The treatment is mainly based on the recently developed covariant-evolution-operator method for QED calculations (I. Lindgren, S. Salomonson, and B. Asen. Phys. Rep. 389, 161 (2004)), which is quite similar in structure to MBPT. At the same time, this procedure is closely related to the S-matrix and Green's-function formalisms and can therefore serve as a bridge connecting various approaches. It is demonstrated that the MBPT-QED scheme, when carried to all orders, leads to a Schrodinger-like equation, equivalent to the Bethe-Salpeter (BS) equation. A Bloch equation in commutator form that can be used for an "extended" or quasi-degenerate model space is derived. This is a multi-state equation that has the same relation to the single-state BS equation as the standard Bloch equation has to the ordinary Schrodinger equation. It can be used to generate a perturbation expansion compatible with the BS equation even in the case of a quasi-degenerate model space.

  19. From long- to short-range correlations in the many-body perturbation theory

    International Nuclear Information System (INIS)

    Exfoliated layered solids commonly exhibit unusual properties in comparison to their bulk counterparts. Reliable theoretical studies of these materials often require more than just the standard density functional theory. Then, it is desirable to apply methods of the many-body perturbation theory, but they converge slowly with respect to the basis size. We argue that this problem stems from the electron-electron interaction cusp of correlated wave functions. Our analysis of the uniform electron gas shows that RPA correlation energies as well as GW quasi particle energies converge as the negative third power of the cut-off wave vector, and also a further asymptotic expansion is possible. This result is applied for a study of binding in 30 layered solids and the quasi particle band structure of BN and MoS2. Obtained exfoliation energies are surprisingly similar with the typical value of 20 meV/A2. The quasi particle calculations show that the band gaps strongly depend on the width of the vacuum gap between periodic images of single layers, which is another long-range correlation effect along with the van der Waals interaction. The accuracy of these results is strongly influenced by the treatment of the short-range electron correlations.

  20. Second-order many-body perturbation study of ice Ih

    Science.gov (United States)

    He, Xiao; Sode, Olaseni; Xantheas, Sotiris S.; Hirata, So

    2012-11-01

    Ice Ih is arguably the most important molecular crystal in nature, yet our understanding of its structural and dynamical properties is still far from complete. We present embedded-fragment calculations of the structures and vibrational spectra of the three-dimensional, proton-disordered phase of ice Ih performed at the level of second-order many-body perturbation theory with a basis-set superposition error correction. Our calculations address previous controversies such as the one related to the O-H bond length as well as the existence of two types of hydrogen bonds with strengths differing by a factor of two. For the latter, our calculations suggest that the observed spectral features arise from the directionality or the anisotropy of collective hydrogen-bond stretching vibrations rather than the previously suggested vastly different force constants. We also report a capability to efficiently compute infrared and Raman intensities of a periodic solid. Our approach reproduces the infrared and Raman spectra, the variation of inelastic neutron scattering spectra with deuterium concentration, and the anomaly of heat capacities at low temperatures for ice Ih.

  1. Interactions of ThO(X) with He, Ne and Ar from the ab initio coupled cluster and symmetry adapted perturbation theory calculations

    International Nuclear Information System (INIS)

    Graphical abstract: ThO–He potential energy surface has a peculiar topology with the global minimum in the bent He–OTh configuration, local minimum in the collinear He–ThO arrangement and two saddle points separating the minima. Vibrational wave functions reflect increasing delocalization of He atom within the complex. Complexes with Ne and Ar have similar potentials, but are increasingly more rigid. Highlights: ► CCSD(T): ThO–RG – floppy van der Waals complexes with bent equilibrium structure. ► Rovibrational energy levels: spatial RG localization decreases from He to Ar. ► SAPT qualitative: delicate balance between exchange and dispersion forces. ► SAPT quantitative: problems with intramonomer correlation and core potentials. ► Long-range interactions: peculiar reduction of the dispersion anisotropy. - Abstract: Two-dimensional interaction potential energy surfaces for the ground-state ThO complexes with RG atoms from He to Ar are calculated ab initio at the coupled cluster CCSD(T) level of theory. The global minimum for all complexes is related to a bent geometry, with the RG atom closer to the oxygen end. Parallel symmetry adapted perturbation theory (SAPT) calculations for the ThO–He complex showed that this configuration is favored by the exchange interaction that slightly prevails over the dispersion and induction contributions which prefer the collinear arrangement. Variational calculations of rovibrational energy levels provided the dissociation energies of 9, 15 and 184 cm−1, for the 3He, Ne and Ar complexes, respectively. The He and Ne complexes in the ground state resemble linear molecules as their zero-point energies exceed the barrier at the linear RG–OTh arrangement. Vibrationally-averaged structure of the Ar–ThO complex better reflects the bent geometry of the equilibrium point.

  2. Band alignment of semiconductors from density-functional theory and many-body perturbation theory

    Science.gov (United States)

    Hinuma, Yoyo; Grüneis, Andreas; Kresse, Georg; Oba, Fumiyasu

    2014-10-01

    The band lineup, or alignment, of semiconductors is investigated via first-principles calculations based on density functional theory (DFT) and many-body perturbation theory (MBPT). Twenty-one semiconductors including C, Si, and Ge in the diamond structure, BN, AlP, AlAs, AlSb, GaP, GaAs, GaSb, InP, InAs, InSb, ZnS, ZnSe, ZnTe, CdS, CdSe, and CdTe in the zinc-blende structure, and GaN and ZnO in the wurtzite structure are considered in view of their fundamental and technological importance. Band alignments are determined using the valence and conduction band offsets from heterointerface calculations, the ionization potential (IP) and electron affinity (EA) from surface calculations, and the valence band maximum and conduction band minimum relative to the branch point energy, or charge neutrality level, from bulk calculations. The performance of various approximations to DFT and MBPT, namely the Perdew-Burke-Ernzerhof (PBE) semilocal functional, the Heyd-Scuseria-Ernzerhof (HSE) hybrid functional, and the GW approximation with and without vertex corrections in the screened Coulomb interaction, is assessed using the GWΓ1 approximation as a reference, where first-order vertex corrections are included in the self-energy. The experimental IPs, EAs, and band offsets are well reproduced by GWΓ1 for most of the semiconductor surfaces and heterointerfaces considered in this study. The PBE and HSE functionals show sizable errors in the IPs and EAs, in particular for group II-VI semiconductors with wide band gaps, but are much better in the prediction of relative band positions or band offsets due to error cancellation. The performance of the GW approximation is almost on par with GWΓ1 as far as relative band positions are concerned. The band alignments based on average interfacial band offsets for all pairs of 17 semiconductors and branch point energies agree with explicitly calculated interfacial band offsets with small mean absolute errors of both ˜0.1eV, indicating a

  3. Red and blue shift of liquid water's excited states: A many body perturbation study

    Science.gov (United States)

    Ziaei, Vafa; Bredow, Thomas

    2016-08-01

    In the present paper, accurate optical absorption spectrum of liquid H2O is calculated in the energy range of 5-20 eV to probe the nature of water's excited states by means of many body perturbation approach. Main features of recent inelastic X-ray measurements are well reproduced, such as a bound excitonic peak at 7.9 eV with a shoulder at 9.4 eV as well as the absorption maximum at 13.9 eV, followed by a broad shoulder at 18.4 eV. The spectrum is dominated by excitonic effects impacting the structures of the spectrum at low and higher energy regimes mixed by single particle effects at high energies. The exciton distribution of the low-energy states, in particular of S1, is highly anisotropic and localized mostly on one water molecule. The S1 state is essentially a HOCO-LUCO (highest occupied crystal orbital - lowest unoccupied crystal orbital) transition and of intra-molecular type, showing a localized valence character. Once the excitation energy is increased, a significant change in the character of the electronically excited states occurs, characterized through emergence of multiple quasi-particle peaks at 7.9 eV in the quasi-particle (QP) transition profile and in the occurring delocalized exciton density distribution, spread over many more water molecules. The exciton delocalization following a change of the character of excited states at around 7.9 eV causes the blue shift of the first absorption band with respect to water monomer S1. However, due to reduction of the electronic band gap from gas to liquid phase, following enhanced screening upon condensation, the localized S1 state of liquid water is red-shifted with respect to S1 state of water monomer. For higher excitations, near vertical ionization energy (11 eV), quasi-free electrons emerge, in agreement with the conduction band electron picture. Furthermore, the occurring red and blue shift of the excited states are independent of the coupling of resonant and anti-resonant contributions to the

  4. Ab initio studies of ionization potentials of hydrated hydroxide and hydronium

    CERN Document Server

    Swartz, Charles W

    2013-01-01

    The ionization potential distributions of hydrated hydroxide and hydronium are computed with many-body approach for electron excitations with configurations generated by {\\it ab initio} molecular dynamics. The experimental features are well reproduced and found to be closely related to the molecular excitations. In the stable configurations, the ionization potential is mainly perturbed by water molecules within the first solvation shell. On the other hand, electron excitation is delocalized on both proton receiving and donating complex during proton transfer, which shifts the excitation energies and broadens the spectra for both hydrated ions.

  5. Towards new horizons in ab initio nuclear structure theory

    International Nuclear Information System (INIS)

    We review recent advances in ab initio nuclear structure theory, which have changed the horizons of this field. Starting from chiral effective field theory to construct the nuclear Hamiltonian and the similarity renormalization group to further soften it, we address several many-body approaches that have seen major developments over the past few years. We show that the domain of ab initio nuclear structure theory has been pushed well beyond the p-shell and that quantitative QCD-based predictions are becoming possible all the way from the proton to the neutron drip line up into the medium-mass regime. (authors)

  6. Many-body perturbation-theory formulas for energy levels of excited states of closed-shell atoms

    Energy Technology Data Exchange (ETDEWEB)

    Avgoustoglou, E.; Johnson, W.R.; Plante, D.R.; Sapirstein, J.; Sheinerman, S. (Department of Physics, University of Notre Dame, Notre Dame, Indiana 46556 (United States)); Blundell, S.A. (University of California, Lawrence Livermore National Laboratory, P.O. Box 808, Livermore, California 94550 (United States))

    1992-11-01

    Many-body perturbation-theory formulas are derived for one-particle--one-hole excited states of closed-shell atoms. Both analytic results and Goldstone diagrams complete through third order are presented, and a sample calculation of a transition energy in neonlike xenon is carried out.

  7. Accurate ionization potential of gold anionic clusters from density functional theory and many-body perturbation theory

    CERN Document Server

    Tanwar, A; Trevisanutto, P E; Chiodo, L; Della Sala, F; 10.1140/epjb/e2013-40016-5

    2013-01-01

    We present a theoretical study of the ionization potential in small anionic gold clusters, using density functional theory, with and without exact-exchange, and many body perturbation theory, namely the G0W0 approach. We find that G0W0 is the best approach and correctly describes the first ionization potential with an accuracy of about 0.1 eV.

  8. Ab Initio No-Core Shell Model

    Energy Technology Data Exchange (ETDEWEB)

    Barrett, B R; Navratil, P; Vary, J P

    2011-04-11

    A long-standing goal of nuclear theory is to determine the properties of atomic nuclei based on the fundamental interactions among the protons and neutrons (i.e., nucleons). By adopting nucleon-nucleon (NN), three-nucleon (NNN) and higher-nucleon interactions determined from either meson-exchange theory or QCD, with couplings fixed by few-body systems, we preserve the predictive power of nuclear theory. This foundation enables tests of nature's fundamental symmetries and offers new vistas for the full range of complex nuclear phenomena. Basic questions that drive our quest for a microscopic predictive theory of nuclear phenomena include: (1) What controls nuclear saturation; (2) How the nuclear shell model emerges from the underlying theory; (3) What are the properties of nuclei with extreme neutron/proton ratios; (4) Can we predict useful cross sections that cannot be measured; (5) Can nuclei provide precision tests of the fundamental laws of nature; and (6) Under what conditions do we need QCD to describe nuclear structure, among others. Along with other ab initio nuclear theory groups, we have pursued these questions with meson-theoretical NN interactions, such as CD-Bonn and Argonne V18, that were tuned to provide high-quality descriptions of the NN scattering phase shifts and deuteron properties. We then add meson-theoretic NNN interactions such as the Tucson-Melbourne or Urbana IX interactions. More recently, we have adopted realistic NN and NNN interactions with ties to QCD. Chiral perturbation theory within effective field theory ({chi}EFT) provides us with a promising bridge between QCD and hadronic systems. In this approach one works consistently with systems of increasing nucleon number and makes use of the explicit and spontaneous breaking of chiral symmetry to expand the strong interaction in terms of a dimensionless constant, the ratio of a generic small momentum divided by the chiral symmetry breaking scale taken to be about 1 GeV/c. The

  9. Ab Initio No-Core Shell Model

    International Nuclear Information System (INIS)

    A long-standing goal of nuclear theory is to determine the properties of atomic nuclei based on the fundamental interactions among the protons and neutrons (i.e., nucleons). By adopting nucleon-nucleon (NN), three-nucleon (NNN) and higher-nucleon interactions determined from either meson-exchange theory or QCD, with couplings fixed by few-body systems, we preserve the predictive power of nuclear theory. This foundation enables tests of nature's fundamental symmetries and offers new vistas for the full range of complex nuclear phenomena. Basic questions that drive our quest for a microscopic predictive theory of nuclear phenomena include: (1) What controls nuclear saturation; (2) How the nuclear shell model emerges from the underlying theory; (3) What are the properties of nuclei with extreme neutron/proton ratios; (4) Can we predict useful cross sections that cannot be measured; (5) Can nuclei provide precision tests of the fundamental laws of nature; and (6) Under what conditions do we need QCD to describe nuclear structure, among others. Along with other ab initio nuclear theory groups, we have pursued these questions with meson-theoretical NN interactions, such as CD-Bonn and Argonne V18, that were tuned to provide high-quality descriptions of the NN scattering phase shifts and deuteron properties. We then add meson-theoretic NNN interactions such as the Tucson-Melbourne or Urbana IX interactions. More recently, we have adopted realistic NN and NNN interactions with ties to QCD. Chiral perturbation theory within effective field theory (χEFT) provides us with a promising bridge between QCD and hadronic systems. In this approach one works consistently with systems of increasing nucleon number and makes use of the explicit and spontaneous breaking of chiral symmetry to expand the strong interaction in terms of a dimensionless constant, the ratio of a generic small momentum divided by the chiral symmetry breaking scale taken to be about 1 GeV/c. The resulting NN

  10. Ab Initio Path to Heavy Nuclei

    CERN Document Server

    Binder, Sven; Calci, Angelo; Roth, Robert

    2014-01-01

    We present the first ab initio calculations of nuclear ground states up into the domain of heavy nuclei, spanning the range from 16-O to 132-Sn based on two- plus three-nucleon interactions derived within chiral effective field theory. We employ the similarity renormalization group for preparing the Hamiltonian and use coupled-cluster theory to solve the many-body problem for nuclei with closed sub-shells. Through an analysis of theoretical uncertainties resulting from various truncations in this framework, we identify and eliminate the technical hurdles that previously inhibited the step beyond medium-mass nuclei, allowing for reliable validations of nuclear Hamiltonians in the heavy regime. Following this path we show that chiral Hamiltonians qualitatively reproduce the systematics of nuclear ground-state energies up to the neutron-rich Sn isotopes.

  11. Third-order many-body perturbation theory calculations for the beryllium and magnesium isoelectronic sequences

    CERN Document Server

    Ho, H C; Blundell, S A; Safronova, M S

    2006-01-01

    Relativistic third-order MBPT is applied to obtain energies of ions with two valence electrons in the no virtual-pair approximation (NVPA). A total of 302 third-order Goldstone diagrams are organized into 12 one-body and 23 two-body terms. Only third-order two-body terms and diagrams are presented here, owing to the fact that the one-body terms are identical to the previously studied third-order terms in monovalent ions. Dominant classes of diagrams are identified. The model potential is a Dirac-Hartree-Fock $V^{N-2}$ potential, and B-spline basis functions in a cavity of finite radius are employed in the numerical calculations. The Breit interaction is taken into account through second order of perturbation theory and the lowest-order Lamb shift is also evaluated. Sample calculations are performed for berylliumlike ions with Z = 4--7, and for the magnesiumlike ion P IV. The third-order energies are in excellent agreement with measurement with an accuracy at 0.2% level for the cases considered. Comparisons ar...

  12. Finite-temperature second-order many-body perturbation and Hartree-Fock theories for one-dimensional solids: an application to Peierls and charge-density-wave transitions in conjugated polymers.

    Science.gov (United States)

    He, Xiao; Ryu, Shinsei; Hirata, So

    2014-01-14

    Finite-temperature extensions of ab initio Gaussian-basis-set spin-restricted Hartree-Fock (HF) and second-order many-body perturbation (MP2) theories are implemented for infinitely extended, periodic, one-dimensional solids and applied to the Peierls and charge-density-wave (CDW) transitions in polyyne and all-trans polyacetylene. The HF theory predicts insulating CDW ground states for both systems in their equidistant structures at low temperatures. In the same structures, they turn metallic at high temperatures. Starting from the "dimerized" low-temperature equilibrium structures, the systems need even higher temperatures to undergo a Peierls transition, which is accompanied by geometric as well as electronic distortions from dimerized to non-dimerized forms. The conventional finite-temperature MP2 theory shows a sign of divergence in any phase at any nonzero temperature and is useless. The renormalized finite-temperature MP2 (MP2R) theory is divergent only near metallic electronic structures, but is well behaved elsewhere. MP2R also predicts CDW and Peierls transitions occurring at two different temperatures. The effect of electron correlation is primarily to lower the Peierls transition temperature.

  13. Ultra-sensitive pressure dependence of bandgap of rutile-GeO{sub 2} revealed by many body perturbation theory

    Energy Technology Data Exchange (ETDEWEB)

    Samanta, Atanu; Singh, Abhishek K. [Materials Research Centre, Indian Institute of Science, Bangalore 560012 (India); Jain, Manish [Department of Physics, Indian Institute of Science, Bangalore 560012 (India)

    2015-08-14

    The reported values of bandgap of rutile GeO{sub 2} calculated by the standard density functional theory within local-density approximation (LDA)/generalized gradient approximation (GGA) show a wide variation (∼2 eV), whose origin remains unresolved. Here, we investigate the reasons for this variation by studying the electronic structure of rutile-GeO{sub 2} using many-body perturbation theory within the GW framework. The bandgap as well as valence bandwidth at Γ-point of rutile phase shows a strong dependence on volume change, which is independent of bandgap underestimation problem of LDA/GGA. This strong dependence originates from a change in hybridization among O-p and Ge-(s and p) orbitals. Furthermore, the parabolic nature of first conduction band along X-Γ-M direction changes towards a linear dispersion with volume expansion.

  14. The density matrix renormalization group for ab initio quantum chemistry

    CERN Document Server

    Wouters, Sebastian

    2014-01-01

    During the past 15 years, the density matrix renormalization group (DMRG) has become increasingly important for ab initio quantum chemistry. Its underlying wavefunction ansatz, the matrix product state (MPS), is a low-rank decomposition of the full configuration interaction tensor. The virtual dimension of the MPS, the rank of the decomposition, controls the size of the corner of the many-body Hilbert space that can be reached with the ansatz. This parameter can be systematically increased until numerical convergence is reached. The MPS ansatz naturally captures exponentially decaying correlation functions. Therefore DMRG works extremely well for noncritical one-dimensional systems. The active orbital spaces in quantum chemistry are however often far from one-dimensional, and relatively large virtual dimensions are required to use DMRG for ab initio quantum chemistry (QC-DMRG). The QC-DMRG algorithm, its computational cost, and its properties are discussed. Two important aspects to reduce the computational co...

  15. Toward the Ab-initio Description of Medium Mass Nuclei

    CERN Document Server

    Barbieri, C; Soma, V; Duguet, T; Navratil, P

    2012-01-01

    As ab-initio calculations of atomic nuclei enter the A=40-100 mass range, a great challenge is how to approach the vast majority of open-shell (degenerate) isotopes. We add realistic three-nucleon interactions to the state of the art many-body Green's function theory of closed-shells, and find that physics of neutron driplines is reproduced with very good quality. Further, we introduce the Gorkov formalism to extend ab-initio theory to semi-magic, fully open-shell, isotopes. Proof-of-principle calculations for Ca-44 and Ni-74 confirm that this approach is indeed feasible. Combining these two advances (open-shells and three-nucleon interactions) requires longer, technical, work but it is otherwise within reach.

  16. Electron correlation effects in the half-metallic NiMnSb within a cluster-perturbation approach with ab-initio parameters

    Directory of Open Access Journals (Sweden)

    H. Allmaier

    2008-06-01

    Full Text Available  Using a combination of electronic-structure and many-body calculations, we investigate correlations effects in the halfmetallic ferromagnet NiMnSb. A realistic many-body Hamiltonian, containing only Mn-d orbitals shows the importance of non-quasiparticle states just above the Fermi level. Our results suggest that for a better description of low energy states around Fermi level, Ni-d orbitals should be explicitly included.

  17. $\\it{Ab}$ $\\it{initio}$ nuclear many-body perturbation calculations in the Hartree-Fock basis

    CERN Document Server

    Hu, Baishan; Sun, Zhonghao; Vary, James P; Li, Tong

    2016-01-01

    Starting from realistic nuclear forces, the chiral N$^3$LO and JISP16, we have applied many-body perturbation theory (MBPT) to the structure of closed-shell nuclei, $^4$He and $^{16}$O. The two-body N$^3$LO interaction is softened by a similarity renormalization group transformation while JISP16 is adopted without renormalization. The MBPT calculations are performed within the Hartree-Fock (HF) bases. The angular momentum coupled scheme is used, which can reduce the computational task. Corrections up to the third order in energy and up to the second order in radius are evaluated. Higher-order corrections in the HF basis are small relative to the leading-order perturbative result. Using the anti-symmetrized Goldstone diagram expansions of the wave function, we directly correct the one-body density for the calculation of the radius, rather than calculate corrections to the occupation propabilities of single-particle orbits as found in other treatments. We compare our results with other methods where available a...

  18. Ab initio electronic and optical spectra of free-base porphyrins: The role of electronic correlation.

    Science.gov (United States)

    Palummo, Maurizia; Hogan, Conor; Sottile, Francesco; Bagalá, Paolo; Rubio, Angel

    2009-08-28

    We present a theoretical investigation of electronic and optical properties of free-base porphyrins based on density functional theory and many-body perturbation theory. The electronic levels of free-base porphine (H(2)P) and its phenyl derivative, free-base tetraphenylporphyrin (H(2)TPP) are calculated using the ab initio GW approximation for the self-energy. The approach is found to yield results that compare favorably with the available photoemission spectra. The excitonic nature of the optical peaks is revealed by solving the Bethe-Salpeter equation, which provides an accurate description of the experimental absorption spectra. The lowest triplet transition energies are in good agreement with the measured values. PMID:19725603

  19. Relativistic Many-body Moller-Plesset Perturbation Theory Calculations of the Energy Levels and Transition Probabilities in Na- to P-like Xe Ions

    Energy Technology Data Exchange (ETDEWEB)

    Vilkas, M J; Ishikawa, Y; Trabert, E

    2007-03-27

    Relativistic multireference many-body perturbation theory calculations have been performed on Xe{sup 43+}-Xe{sup 39+} ions, resulting in energy levels, electric dipole transition probabilities, and level lifetimes. The second-order many-body perturbation theory calculation of energy levels included mass shifts, frequency-dependent Breit correction and Lamb shifts. The calculated transition energies and E1 transition rates are used to present synthetic spectra in the extreme ultraviolet range for some of the Xe ions.

  20. Acoustic magnons in the long-wavelength limit: Investigating the Goldstone violation in many-body perturbation theory

    Science.gov (United States)

    Müller, Mathias C. T. D.; Friedrich, Christoph; Blügel, Stefan

    2016-08-01

    Collective spin excitations in magnetic materials arise from the correlated motion of electron-hole pairs with opposite spins. The pair propagation is described by the transverse magnetic susceptibility, which we calculate within many-body perturbation theory from first principles employing the full-potential linearized augmented-plane-wave formalism. Ferromagnetic materials exhibit a spontaneously broken global rotation symmetry in spin space leading to the appearance of acoustic magnons (zero gap) in the long-wavelength limit. However, due to approximations used in the numerical scheme, the acoustic magnon dispersion exhibits a small but finite gap at Γ . We analyze this violation of the Goldstone mode and present an approach that implements the magnetic susceptibility using a renormalized Green function instead of the Kohn-Sham one. This much more expensive approach shows substantial improvement of the Goldstone-mode condition. In addition, we discuss a possible correction scheme, which involves an adjustment of the Kohn-Sham exchange splitting, which is motivated by the spin-wave solution of the one-band Hubbard model. The new exchange splittings turn out to be closer to experiment. We present corrected magnon spectra for the elementary ferromagnets Fe, Co, and Ni.

  1. The In-Medium Similarity Renormalization Group: A novel ab initio method for nuclei

    Science.gov (United States)

    Hergert, H.; Bogner, S. K.; Morris, T. D.; Schwenk, A.; Tsukiyama, K.

    2016-03-01

    We present a comprehensive review of the In-Medium Similarity Renormalization Group (IM-SRG), a novel ab initio method for nuclei. The IM-SRG employs a continuous unitary transformation of the many-body Hamiltonian to decouple the ground state from all excitations, thereby solving the many-body problem. Starting from a pedagogical introduction of the underlying concepts, the IM-SRG flow equations are developed for systems with and without explicit spherical symmetry. We study different IM-SRG generators that achieve the desired decoupling, and how they affect the details of the IM-SRG flow. Based on calculations of closed-shell nuclei, we assess possible truncations for closing the system of flow equations in practical applications, as well as choices of the reference state. We discuss the issue of center-of-mass factorization and demonstrate that the IM-SRG ground-state wave function exhibits an approximate decoupling of intrinsic and center-of-mass degrees of freedom, similar to Coupled Cluster (CC) wave functions. To put the IM-SRG in context with other many-body methods, in particular many-body perturbation theory and non-perturbative approaches like CC, a detailed perturbative analysis of the IM-SRG flow equations is carried out. We conclude with a discussion of ongoing developments, including IM-SRG calculations with three-nucleon forces, the multi-reference IM-SRG for open-shell nuclei, first non-perturbative derivations of shell-model interactions, and the consistent evolution of operators in the IM-SRG. We dedicate this review to the memory of Gerry Brown, one of the pioneers of many-body calculations of nuclei.

  2. Finite-temperature coupled-cluster, many-body perturbation, and restricted and unrestricted Hartree–Fock study on one-dimensional solids: Luttinger liquids, Peierls transitions, and spin- and charge-density waves

    International Nuclear Information System (INIS)

    One-dimensional (1D) solids exhibit a number of striking electronic structures including charge-density wave (CDW) and spin-density wave (SDW). Also, the Peierls theorem states that at zero temperature, a 1D system predicted by simple band theory to be a metal will spontaneously dimerize and open a finite fundamental bandgap, while at higher temperatures, it will assume the equidistant geometry with zero bandgap (a Peierls transition). We computationally study these unique electronic structures and transition in polyyne and all-trans polyacetylene using finite-temperature generalizations of ab initio spin-unrestricted Hartree–Fock (UHF) and spin-restricted coupled-cluster doubles (CCD) theories, extending upon previous work [He et al., J. Chem. Phys. 140, 024702 (2014)] that is based on spin-restricted Hartree–Fock (RHF) and second-order many-body perturbation (MP2) theories. Unlike RHF, UHF can predict SDW as well as CDW and metallic states, and unlike MP2, CCD does not diverge even if the underlying RHF reference wave function is metallic. UHF predicts a gapped SDW state with no dimerization at low temperatures, which gradually becomes metallic as the temperature is raised. CCD, meanwhile, confirms that electron correlation lowers the Peierls transition temperature. Furthermore, we show that the results from all theories for both polymers are subject to a unified interpretation in terms of the UHF solutions to the Hubbard–Peierls model using different values of the electron-electron interaction strength, U/t, in its Hamiltonian. The CCD wave function is shown to encompass the form of the exact solution of the Tomonaga–Luttinger model and is thus expected to describe accurately the electronic structure of Luttinger liquids

  3. Collective rotation from ab initio theory

    CERN Document Server

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

    2015-01-01

    Through ab initio approaches in nuclear theory, we may now seek to quantitatively understand the wealth of nuclear collective phenomena starting from the underlying internucleon interactions. No-core configuration interaction (NCCI) calculations for p-shell nuclei give rise to rotational bands, as evidenced by rotational patterns for excitation energies, electromagnetic moments, and electromagnetic transitions. In this review, NCCI calculations of 7-9Be are used to illustrate and explore ab initio rotational structure, and the resulting predictions for rotational band properties are compared with experiment. We highlight the robustness of ab initio rotational predictions across different choices for the internucleon interaction.

  4. Aspects of linked cluster expansion in general model space many-body perturbation and coupled-cluster theory

    International Nuclear Information System (INIS)

    In this paper, a method of generating separable forms of the wave-operator for incomplete model spaces is discussed. With a time-dependent access to the many-body perturbation and coupled-cluster theories, it is shown how one can extract the regular part of the wave-operator which consists of linked cluster-operators only in the adiabatic limit. The procedure naturally suggests a hierarchy of lower valence model spaces P/sup (k)/, once a particular m-valence incomplete model space P/sup (m) is specified. The wave-operator Omega and the effective Hamiltonian H/sub eff/ are linked in this development and are valence-universal in the sense of being valid for P/sup (k)/'s, o ≤ k ≤ m. They have derived two distinct forms for Omega: (i) Omega = {exp(S)}, with {} as normal order with respect to suitable vacuum, where S are open operators inducing transitions from P(m) to outside it; (ii) Omega/sub N/ = {exp(S + X)}, where X are additional closed operators which are introduced to maintain isometry of Omega/sub N/: P/sup (k)/Omega/sub N/ + Omega/sub N/P/sup (k)/ = P/sub (k)/. In neither of these choices do we have intermediate normalization. It is also possible to develop an alternative strategy with the complete model spaces, such that an effective valence-universal operator H may be found which generates roots, only a subset of which are equal to the eigenvalues of H. These subsets are the ones that H/sub eff/ would have furnished. This may thus be viewed as a Fock-space realization of the intermediate Hamiltonian approach

  5. exciting: a full-potential all-electron package implementing density-functional theory and many-body perturbation theory

    Science.gov (United States)

    Gulans, Andris; Kontur, Stefan; Meisenbichler, Christian; Nabok, Dmitrii; Pavone, Pasquale; Rigamonti, Santiago; Sagmeister, Stephan; Werner, Ute; Draxl, Claudia

    2014-09-01

    Linearized augmented planewave methods are known as the most precise numerical schemes for solving the Kohn-Sham equations of density-functional theory (DFT). In this review, we describe how this method is realized in the all-electron full-potential computer package, exciting. We emphasize the variety of different related basis sets, subsumed as (linearized) augmented planewave plus local orbital methods, discussing their pros and cons and we show that extremely high accuracy (microhartrees) can be achieved if the basis is chosen carefully. As the name of the code suggests, exciting is not restricted to ground-state calculations, but has a major focus on excited-state properties. It includes time-dependent DFT in the linear-response regime with various static and dynamical exchange-correlation kernels. These are preferably used to compute optical and electron-loss spectra for metals, molecules and semiconductors with weak electron-hole interactions. exciting makes use of many-body perturbation theory for charged and neutral excitations. To obtain the quasi-particle band structure, the GW approach is implemented in the single-shot approximation, known as G0W0. Optical absorption spectra for valence and core excitations are handled by the solution of the Bethe-Salpeter equation, which allows for the description of strongly bound excitons. Besides these aspects concerning methodology, we demonstrate the broad range of possible applications by prototypical examples, comprising elastic properties, phonons, thermal-expansion coefficients, dielectric tensors and loss functions, magneto-optical Kerr effect, core-level spectra and more.

  6. A highly accurate ab initio potential energy surface for methane

    Science.gov (United States)

    Owens, Alec; Yurchenko, Sergei N.; Yachmenev, Andrey; Tennyson, Jonathan; Thiel, Walter

    2016-09-01

    A new nine-dimensional potential energy surface (PES) for methane has been generated using state-of-the-art ab initio theory. The PES is based on explicitly correlated coupled cluster calculations with extrapolation to the complete basis set limit and incorporates a range of higher-level additive energy corrections. These include core-valence electron correlation, higher-order coupled cluster terms beyond perturbative triples, scalar relativistic effects, and the diagonal Born-Oppenheimer correction. Sub-wavenumber accuracy is achieved for the majority of experimentally known vibrational energy levels with the four fundamentals of 12CH4 reproduced with a root-mean-square error of 0.70 cm-1. The computed ab initio equilibrium C-H bond length is in excellent agreement with previous values despite pure rotational energies displaying minor systematic errors as J (rotational excitation) increases. It is shown that these errors can be significantly reduced by adjusting the equilibrium geometry. The PES represents the most accurate ab initio surface to date and will serve as a good starting point for empirical refinement.

  7. Cd hyperfine interactions in DNA bases and DNA of mouse strains infected with Trypanosoma cruzi investigated by perturbed angular correlation spectroscopy and ab initio calculations.

    Science.gov (United States)

    Petersen, Philippe A D; Silva, Andreia S; Gonçalves, Marcos B; Lapolli, André L; Ferreira, Ana Maria C; Carbonari, Artur W; Petrilli, Helena M

    2014-06-01

    In this work, perturbed angular correlation (PAC) spectroscopy is used to study differences in the nuclear quadrupole interactions of Cd probes in DNA molecules of mice infected with the Y-strain of Trypanosoma cruzi. The possibility of investigating the local genetic alterations in DNA, which occur along generations of mice infected with T. cruzi, using hyperfine interactions obtained from PAC measurements and density functional theory (DFT) calculations in DNA bases is discussed. A comparison of DFT calculations with PAC measurements could determine the type of Cd coordination in the studied molecules. To the best of our knowledge, this is the first attempt to use DFT calculations and PAC measurements to investigate the local environment of Cd ions bound to DNA bases in mice infected with Chagas disease. The obtained results also allowed the detection of local changes occurring in the DNA molecules of different generations of mice infected with T. cruzi, opening the possibility of using this technique as a complementary tool in the characterization of complicated biological systems.

  8. 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

  9. Ab initio determination of bond length dependence of the correlated valence shell Hamiltonian of CH: Comparison with semiempirical theories

    Science.gov (United States)

    Sun, Hosung; Freed, Karl F.

    1984-01-01

    The exact ab initio effective valence shell Hamiltonian, which is mimicked by semiempirical theories of valence, is calculated for CH at 11 bond lengths using quasidegenerate many-body perturbation theory to incorporate extensive correlation contributions. Least squares fits of the bond length dependence of the calculated CH matrix elements provide simple formulas which are compared with the intuitive forms introduced into semiempirical theories. Some of the semiempirical formulas, e.g., one-center, one-electron integrals and two-center, two-electron integrals, are in good agreement with our correlated ab initio calculations, while others display substantial departures. For example, the bond length dependence of one-center, two-electron integrals, which are assumed to be independent of bond length in semiempirical theories, is substantial but physically understandable. Corrections are found to the assumed proportionality of resonance and overlap integrals. The bond length dependence of nonclassical three-electron integrals is presented along with the hybrid and exchange integrals that are ignored in zero differential overlap methods.

  10. Unified ab initio approaches to nuclear structure and reactions

    Science.gov (United States)

    Navrátil, Petr; Quaglioni, Sofia; Hupin, Guillaume; Romero-Redondo, Carolina; Calci, Angelo

    2016-05-01

    The description of nuclei starting from the constituent nucleons and the realistic interactions among them has been a long-standing goal in nuclear physics. In addition to the complex nature of the nuclear forces, with two-, three- and possibly higher many-nucleon components, 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. After a brief overview of the field, we focus on ab initio many-body approaches—built upon the no-core shell model—that are capable of simultaneously describing both bound and scattering nuclear states, and present results for resonances in light nuclei, reactions important for astrophysics and fusion research. In particular, we review recent calculations of resonances in the 6He halo nucleus, of five- and six-nucleon scattering, and an investigation of the role of chiral three-nucleon interactions in the structure of 9Be. Further, we discuss applications to the 7Be {({{p}},γ )}8{{B}} radiative capture. Finally, we highlight our efforts to describe transfer reactions including the 3H{({{d}},{{n}})}4He fusion.

  11. Three-cluster dynamics within an ab initio framework

    CERN Document Server

    Quaglioni, S; Navrátil, P

    2013-01-01

    We introduce a fully antisymmetrized treatment of three-cluster dynamics within the ab initio framework of the no-core shell model/resonating-group method (NCSM/RGM). Energy-independent non-local interactions among the three nuclear fragments are obtained from realistic nucleon-nucleon interactions and consistent ab initio many-body wave functions of the clusters. The three-cluster Schr\\"odinger equation is solved with bound-state boundary conditions by means of the hyperspherical-harmonic method on a Lagrange mesh. We discuss the formalism in detail and give algebraic expressions for systems of two single nucleons plus a nucleus. Using a soft similarity-renormalization-group evolved chiral nucleon-nucleon potential, we apply the method to an $^4$He+$n+n$ description of $^6$He and compare the results to experiment and to a six-body diagonalization of the Hamiltonian performed within the harmonic-oscillator expansions of the NCSM. Differences between the two calculations provide a measure of core ($^4$He) pola...

  12. Unified ab initio approaches to nuclear structure and reactions

    CERN Document Server

    Navratil, Petr; Hupin, Guillaume; Romero-Redondo, Carolina; Calci, Angelo

    2016-01-01

    The description of nuclei starting from the constituent nucleons and the realistic interactions among them has been a long-standing goal in nuclear physics. In addition to the complex nature of the nuclear forces, with two-, three- and possibly higher many-nucleon components, 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 {\\em ab initio} nuclear structure and reaction calculations based on input from QCD-employing Hamiltonians constructed within chiral effective field theory. After a brief overview of the field, we focus on ab initio many-body approaches - built upon the No-Core Shell Model - that are capable of simultaneously describing both bound and scattering nuclear states, and present results for resonances in light nuclei, reactions important for astrophysics and fusion research. In particular, we review recent calculations of resonances in the $^6$He halo nucleus, of five- and six...

  13. Diagrammatic many-body perturbation expansion for atoms and molecules: VI Experiments in vector processing and parallel processing for second-order energy calculations

    Science.gov (United States)

    Moncrieff, David; Baker, David J.; Wilson, Stephen

    1989-08-01

    The efficient evaluation of the second-order expression in the many-body perturbation theory expansion for the correlation energy on vector processing and parallel processing computers is discussed. It is argued that the linked diagram theorem not only leads to the well known theoretical advantages of the many-body perturbation theory approach which allows the calculation of correlation energies for large (i.e. extended molecules or species containing heavy atoms) systems but also decouples the many-electron problem allowing efficient implementation on parallel processing machines. Furthermore, the computation associated with each of the resulting subproblems is very well suited to vector processing machines. Timing tests are reported for the CRAY 1 and CDC Cyber 205 vector processors, for a 1 processor implementation on the CRAY X-MP/48 and the ETA-10E, and for a 4 processor implementation on the Cray X-MP/48.

  14. Application of complete space multireference many-body perturbation theory to N2: Dependence on reference space and H0

    Science.gov (United States)

    Finley, James P.; Freed, Karl F.

    1995-01-01

    We study the wide latitude available in choosing the reference space and the zeroth order Hamiltonian H0 for complete reference space multireference perturbation theory. This effective Hamiltonian Heff method employs a general one-body form of H0 which is varied by using different molecular orbitals and orbital energies. An energy gap is imposed between the zeroth order reference and secondary space states by forcing the valence orbitals to be degenerate. The forced valence orbital degeneracy removes the occurrence of detrimentally small perturbation energy denominators. Extensive computations are provided for the nitrogen molecule, where calculated ground state spectroscopic constants are compared with full configuration interaction computations and calculated vertical excitation energies are compared with multireference coupled cluster computations. It is demonstrated that the forced reference space degeneracy can lead to certain perturbation denominators becoming too small for practical convergence. This characteristic is illustrated by a simple two-orbital model which stresses the need for important zeroth order excitation energies (equivalent to the factors appearing in the perturbation energy denominators) to exceed those in an Epstein-Nesbet perturbation partitioning. This simple model illustrates the general behavior found in all the more extensive Heff computations. In many cases where zeroth order excitation energies are too small for satisfactory third order results, improvements are obtained by using an H0 which redefines the orbital energies in order to increase problematic zeroth order excitation energies. The necessary orbital energy shifts are identified by examining the first order wave functions from larger reference spaces and the zeroth order energies. Frequently, fractional occupancy Fock-type operators are employed to provide the requisite orbital energy shifts. Some of the reference spaces investigated deviate extremely from quasidegeneracy

  15. Ab Initio Calculations of Oxosulfatovanadates

    DEFF Research Database (Denmark)

    Frøberg, Torben; Johansen, Helge

    1996-01-01

    Restricted Hartree-Fock and multi-configurational self-consistent-field calculations together with secondorder perturbation theory have been used to study the geometry, the electron density, and the electronicspectrum of (VO2SO4)-. A bidentate sulphate attachment to vanadium was found to be stable...... with anO-V-O angle of 72.5 degrees . The calculated spectrum shows bands in reasonable agreement with anexperimental spectrum which has been attributed to (VO2SO4)-. The geometry and the electron density fortwo binuclear vanadium complexes proposed as intermediates in the vanadium catalyzed SO2...

  16. Ab initio mass tensor molecular dynamics

    OpenAIRE

    Tsuchida, Eiji

    2010-01-01

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

  17. Reciprocity Theorems for Ab Initio Force Calculations

    CERN Document Server

    Wei, C; Mele, E J; Rappe, A M; Lewis, Steven P.; Rappe, Andrew M.

    1996-01-01

    We present a method for calculating ab initio interatomic forces which scales quadratically with the size of the system and provides a physically transparent representation of the force in terms of the spatial variation of the electronic charge density. The method is based on a reciprocity theorem for evaluating an effective potential acting on a charged ion in the core of each atom. We illustrate the method with calculations for diatomic molecules.

  18. 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...

  19. Highly scalable Ab initio genomic motif identification

    KAUST Repository

    Marchand, Benoît

    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.

  20. Random Phase Approximation For allowed and Parity Non-conserving Electric Dipole Transition Amplitudes and its connection with Many-Body Perturbation Theory and Coupled Cluster Theory

    CERN Document Server

    Gopakumar, G; Das, B P; Chaudhuri, R K; Mukherjee, D; Hirao, K; Gopakumar, Geetha; Sur, Chirajib; Das, Bhanu Pratap; Chaudhuri, Rajat K.; Hirao, Kimihiko

    2005-01-01

    The connections between the Random Phase Approximation (RPA) and Many-Body Perturbation Theory (MBPT) and its all order generalisation, the Coupled- Cluster Theory (CCT) have been explored. Explicit expressions have been derived for the electric dipole amplitudes for allowed and forbidden transitions induced by the parity non-conserving neutral weak interaction. The Goldstone diagrams associated with the RPA terms in both cases are shown to arise in MBPT and CCT and the numerical verification of this relationship is made for the allowed electric dipole transitions.

  1. Relativistic multireference many-body perturbation theory calculations on F-, Ne-, Na-, Mg-, Al-, Si-, and P-like xenon ions

    Energy Technology Data Exchange (ETDEWEB)

    Vilkas, M J; Ishikawa, Y; Trabert, E

    2005-12-22

    Many-Body Perturbation Theory (MBPT) has been employed to calculate with high wavelength accuracy the extreme ultraviolet (EUV) spectra of F-like to P-like Xe ions. They discuss the reliability of the new calculations using the example of EUV beam-foil spectra of Xe, in which n = 3, {Delta}n = 0 transitions of Na-, Mg-, Al-like, and Si-like ions have been found to dominate. A further comparison is made with spectra from an electron beam ion trap, that is, from a device with a very different (low density) excitation balance.

  2. Ab Initio Molecular Dynamics: A Virtual Laboratory

    OpenAIRE

    Hobbi Mobarhan, Milad

    2014-01-01

    In this thesis, we perform ab initio molecular dynamics (MD) simulations at the Hartree-Fock level, where the forces are computed on-the-fly using the Born-Oppenheimer approximation. The theory behind the Hartree-Fock method is discussed in detail and an implementation of this method based on Gaussian basis functions is explained. We also demonstrate how to calculate the analytic energy derivatives needed for obtaining the forces acting on the nuclei. Hartree-Fock calculations on the ground s...

  3. Ab Initio Study on Hypothetical Silver Nitride

    Institute of Scientific and Technical Information of China (English)

    DELIGOZ Engin; COLAKOGLU Kemal; CIFTCI Yasemin Oztekin

    2008-01-01

    We perform the ab initio calculations based on norm-conserving pseudopotentials and density functional theory to investigate the structural, elastic, and thermodynamical properties for silver nitride (AgN) compound that is a member of the 4d transition metal group and has not been synthesized yet. The obtained results are compared with the other available theoretical data, and the agreement is, generally, quite good. We also present the pressure-dependent behaviour of some mechanical and thermodynamical properties for the same compounds.

  4. Ab-initio molecular dynamics simulation of liquid water by Quantum Monte Carlo

    CERN Document Server

    Zen, Andrea; Mazzola, Guglielmo; Guidoni, Leonardo; Sorella, Sandro

    2014-01-01

    Despite liquid water is ubiquitous in chemical reactions at roots of life and climate on earth, the prediction of its properties by high-level ab initio molecular dynamics simulations still represents a formidable task for quantum chemistry. In this article we present a room temperature simulation of liquid water based on the potential energy surface obtained by a many-body wave function through quantum Monte Carlo (QMC) methods. The simulated properties are in excellent agreement with recent neutron scattering and X-ray experiments, particularly concerning the position of the oxygen-oxygen peak in the radial distribution function, at variance of previous Density Functional Theory attempts. Given the excellent performances of QMC on large scale supercomputers, this work opens new perspectives for predictive and reliable ab-initio simulations of complex chemical systems.

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

    Science.gov (United States)

    Maris, Pieter; Metin Aktulga, H.; Caprio, Mark A.; Çatalyürek, Ümit V.; Ng, Esmond G.; Oryspayev, Dossay; Potter, Hugh; Saule, Erik; Sosonkina, Masha; Vary, James P.; Yang, Chao; Zhou, Zheng

    2012-12-01

    In ab-initio Configuration Interaction calculations, the nuclear wavefunction is expanded in Slater determinants of single-nucleon wavefunctions and the many-body Schrodinger equation becomes a large sparse matrix problem. The challenge is to reach numerical convergence to within quantified numerical uncertainties for physical observables using finite truncations of the infinite-dimensional basis space. We discuss strategies for constructing and solving the resulting large sparse matrix eigenvalue problems on current multicore computer architectures. Several of these strategies have been implemented in the code MFDn, a hybrid MPI/OpenMP Fortran code for ab-initio nuclear structure calculations that can scale to 100,000 cores and more. Finally, we will conclude with some recent results for 12C including emerging collective phenomena such as rotational band structures using SRG evolved chiral N3LO interactions.

  6. Ab initio molecular dynamics simulation of liquid water by quantum Monte Carlo

    Energy Technology Data Exchange (ETDEWEB)

    Zen, Andrea, E-mail: a.zen@ucl.ac.uk [Dipartimento di Fisica, “La Sapienza” - Università di Roma, piazzale Aldo Moro 5, 00185 Rome (Italy); London Centre for Nanotechnology, University College London, London WC1E 6BT (United Kingdom); Luo, Ye, E-mail: xw111luoye@gmail.com; Mazzola, Guglielmo, E-mail: gmazzola@phys.ethz.ch; Sorella, Sandro, E-mail: sorella@sissa.it [SISSA–International School for Advanced Studies, Via Bonomea 26, 34136 Trieste (Italy); Democritos Simulation Center CNR–IOM Istituto Officina dei Materiali, 34151 Trieste (Italy); Guidoni, Leonardo, E-mail: leonardo.guidoni@univaq.it [Dipartimento di Fisica, “La Sapienza” - Università di Roma, piazzale Aldo Moro 5, 00185 Rome (Italy); Dipartimento di Scienze Fisiche e Chimiche, Università degli Studi dell’ Aquila, via Vetoio, 67100 L’ Aquila (Italy)

    2015-04-14

    Although liquid water is ubiquitous in chemical reactions at roots of life and climate on the earth, the prediction of its properties by high-level ab initio molecular dynamics simulations still represents a formidable task for quantum chemistry. In this article, we present a room temperature simulation of liquid water based on the potential energy surface obtained by a many-body wave function through quantum Monte Carlo (QMC) methods. The simulated properties are in good agreement with recent neutron scattering and X-ray experiments, particularly concerning the position of the oxygen-oxygen peak in the radial distribution function, at variance of previous density functional theory attempts. Given the excellent performances of QMC on large scale supercomputers, this work opens new perspectives for predictive and reliable ab initio simulations of complex chemical systems.

  7. Computer simulation of acetonitrile and methanol with ab initio-based pair potentials

    Science.gov (United States)

    Hloucha, M.; Sum, A. K.; Sandler, S. I.

    2000-10-01

    This study address the adequacy of ab initio pair interaction energy potentials for the prediction of macroscopic properties. Recently, Bukowski et al. [J. Phys. Chem. A 103, 7322 (1999)] performed a comprehensive study of the potential energy surfaces for several pairs of molecules using symmetry-adapted perturbation theory. These ab initio energies were then fit to an appropriate site-site potential form. In an attempt to bridge the gap between ab initio interaction energy information and macroscopic properties prediction, we performed Gibbs ensemble Monte Carlo (GEMC) simulations using their developed pair potentials for acetonitrile and methanol. The simulations results show that the phase behavior of acetonitrile is well described by just the pair interaction potential. For methanol, on the other hand, pair interactions are insufficient to properly predict its vapor-liquid phase behavior, and its saturated liquid density. We also explored simplified forms for representing the ab initio interaction energies by refitting a selected range of the data to a site-site Lennard-Jones and to a modified Buckingham (exponential-6) potentials plus Coulombic interactions. These were also used in GEMC simulations in order to evaluate the quality and computational efficiency of these different potential forms. It was found that the phase behavior prediction for acetonitrile and methanol are highly dependent on the details of the interaction potentials developed.

  8. Ab initio phonon properties of half-Heusler NiTiSn, NiZrSn and NiHfSn.

    Science.gov (United States)

    Andrea, Luc; Hug, Gilles; Chaput, Laurent

    2015-10-28

    A theoretical investigation of phonon properties from first-principles calculations is carried out for the half-Heusler compounds NiXSn, [Formula: see text], Zr and Hf. The crystal structures are optimised via ab initio calculations within the framework of density functional theory. The phonon properties are retrieved from harmonic and anharmonic interatomic force constants calculations using the finite size displacements method and many-body perturbation theory. A solution to the linearized phonon Boltzmann transport equation is then used to compute the ab initio thermal conductivities. For X   =   Ti, Zr and Hf, we found 15.4, 13.3 and 15.8 W m(-1) K(-1) at 300 K, respectively. Thanks to a spectral analysis of the velocities and lifetimes we were able appreciate the differences in the thermal conductivities between the three compounds under study. Our results provide insights to understand the behaviour of the thermal conductivity and therefore to improve the thermoelectric figure of merit for such materials.

  9. Kopplung von Dichtefunktional- und ab-initio-Methoden

    OpenAIRE

    Goll, Erich

    2008-01-01

    Im Rahmen der Doktorarbeit wurde untersucht, inwieweit die Kopplung von Dichtefunktionalmethoden und ab-initio-Korrelationsmethoden der Quantenchemie eine Verbesserung bezüglich beider Grenzmethoden erbringt. Die Kopplung erfolgt durch eine Aufspaltung des interelektronischen Hamiltonoperators (abstoßende Coulombwechselwirkung). Die kurzreichweitige Wechselwirkung wird mit Dichtefunktionaltheorie behandelt, die langreichweitige mit Hilfe von ab-initio-Methoden. Diese Aufteilung soll dazu dien...

  10. Ab initio alpha-alpha scattering

    CERN Document Server

    Elhatisari, Serdar; Rupak, Gautam; Epelbaum, Evgeny; Krebs, Hermann; Lähde, Timo A; Luu, Thomas; Meißner, Ulf-G

    2015-01-01

    Processes involving alpha particles and alpha-like nuclei comprise a major part of stellar nucleosynthesis and hypothesized mechanisms for thermonuclear supernovae. In an effort towards understanding alpha processes from first principles, we describe in this letter the first ab initio calculation of alpha-alpha scattering. We use lattice effective field theory to describe the low-energy interactions of nucleons and apply a technique called the adiabatic projection method to reduce the eight-body system to an effective two-cluster system. We find good agreement between lattice results and experimental phase shifts for S-wave and D-wave scattering. The computational scaling with particle number suggests that alpha processes involving heavier nuclei are also within reach in the near future.

  11. Ab initio molar volumes and Gaussian radii.

    Science.gov (United States)

    Parsons, Drew F; Ninham, Barry W

    2009-02-12

    Ab initio molar volumes are calculated and used to derive radii for ions and neutral molecules using a spatially diffuse model of the electron distribution with Gaussian spread. The Gaussian radii obtained can be used for computation of nonelectrostatic ion-ion dispersion forces that underlie Hofmeister specific ion effects. Equivalent hard-sphere radii are also derived, and these are in reasonable agreement with crystalline ionic radii. The Born electrostatic self-energy is derived for a Gaussian model of the electronic charge distribution. It is shown that the ionic volumes used in electrostatic calculations of strongly hydrated cosmotropic ions ought best to include the first hydration shell. Ionic volumes for weakly hydrated chaotropic metal cations should exclude electron overlap (in electrostatic calculations). Spherical radii are calculated as well as nonisotropic ellipsoidal radii for nonspherical ions, via their nonisotropic static polarizability tensors. PMID:19140766

  12. Ab initio alpha-alpha scattering

    Science.gov (United States)

    Elhatisari, Serdar; Lee, Dean; Rupak, Gautam; Epelbaum, Evgeny; Krebs, Hermann; Lähde, Timo A.; Luu, Thomas; Meißner, Ulf-G.

    2015-12-01

    Processes such as the scattering of alpha particles (4He), the triple-alpha reaction, and alpha capture play a major role in stellar nucleosynthesis. In particular, alpha capture on carbon determines the ratio of carbon to oxygen during helium burning, and affects subsequent carbon, neon, oxygen, and silicon burning stages. It also substantially affects models of thermonuclear type Ia supernovae, owing to carbon detonation in accreting carbon-oxygen white-dwarf stars. In these reactions, the accurate calculation of the elastic scattering of alpha particles and alpha-like nuclei—nuclei with even and equal numbers of protons and neutrons—is important for understanding background and resonant scattering contributions. First-principles calculations of processes involving alpha particles and alpha-like nuclei have so far been impractical, owing to the exponential growth of the number of computational operations with the number of particles. Here we describe an ab initio calculation of alpha-alpha scattering that uses lattice Monte Carlo simulations. We use lattice effective field theory to describe the low-energy interactions of protons and neutrons, and apply a technique called the ‘adiabatic projection method’ to reduce the eight-body system to a two-cluster system. We take advantage of the computational efficiency and the more favourable scaling with system size of auxiliary-field Monte Carlo simulations to compute an ab initio effective Hamiltonian for the two clusters. We find promising agreement between lattice results and experimental phase shifts for s-wave and d-wave scattering. The approximately quadratic scaling of computational operations with particle number suggests that it should be possible to compute alpha scattering and capture on carbon and oxygen in the near future. The methods described here can be applied to ultracold atomic few-body systems as well as to hadronic systems using lattice quantum chromodynamics to describe the interactions of

  13. Ab initio alpha-alpha scattering.

    Science.gov (United States)

    Elhatisari, Serdar; Lee, Dean; Rupak, Gautam; Epelbaum, Evgeny; Krebs, Hermann; Lähde, Timo A; Luu, Thomas; Meißner, Ulf-G

    2015-12-01

    Processes such as the scattering of alpha particles ((4)He), the triple-alpha reaction, and alpha capture play a major role in stellar nucleosynthesis. In particular, alpha capture on carbon determines the ratio of carbon to oxygen during helium burning, and affects subsequent carbon, neon, oxygen, and silicon burning stages. It also substantially affects models of thermonuclear type Ia supernovae, owing to carbon detonation in accreting carbon-oxygen white-dwarf stars. In these reactions, the accurate calculation of the elastic scattering of alpha particles and alpha-like nuclei--nuclei with even and equal numbers of protons and neutrons--is important for understanding background and resonant scattering contributions. First-principles calculations of processes involving alpha particles and alpha-like nuclei have so far been impractical, owing to the exponential growth of the number of computational operations with the number of particles. Here we describe an ab initio calculation of alpha-alpha scattering that uses lattice Monte Carlo simulations. We use lattice effective field theory to describe the low-energy interactions of protons and neutrons, and apply a technique called the 'adiabatic projection method' to reduce the eight-body system to a two-cluster system. We take advantage of the computational efficiency and the more favourable scaling with system size of auxiliary-field Monte Carlo simulations to compute an ab initio effective Hamiltonian for the two clusters. We find promising agreement between lattice results and experimental phase shifts for s-wave and d-wave scattering. The approximately quadratic scaling of computational operations with particle number suggests that it should be possible to compute alpha scattering and capture on carbon and oxygen in the near future. The methods described here can be applied to ultracold atomic few-body systems as well as to hadronic systems using lattice quantum chromodynamics to describe the interactions of

  14. Tensor contraction engine: Abstraction and automated parallel implementation of configuration-interaction, coupled-cluster, and many-body perturbation theories

    International Nuclear Information System (INIS)

    We develop a symbolic manipulation program and program generator (Tensor Contraction Engine or TCE) that automatically derives the working equations of a well-defined model of second-quantized many-electron theories and synthesizes efficient parallel computer programs on the basis of these equations. Provided an ansatz of a many-electron theory model, TCE performs valid contractions of creation and annihilation operators according to Wick's theorem, consolidates identical terms, and reduces the expressions into the form of multiple tensor contractions acted by permutation operators. Subsequently, it determines the binary contraction order for each multiple tensor contraction with the minimal operation and memory cost, factorizes common binary contractions (defines intermediate tensors), and identifies reusable intermediates. The resulting ordered list of binary tensor contractions, additions, and index permutations is translated into an optimized program that is combined with the NWChem and UTChem computational chemistry software packages. The programs synthesized by TCE take advantage of spin symmetry, Abelian point-group symmetry, and index permutation symmetry at every stage of calculations to minimize the number of arithmetic operations and storage requirement, adjust the peak local memory usage by index range tiling, and support parallel I/O interfaces and dynamic load balancing for parallel executions. We demonstrate the utility of TCE through automatic derivation and implementation of parallel programs for various models of configuration-interaction theory (CISD, CISDT, CISDTQ), many-body perturbation theory[MBPT(2), MBPT(3), MBPT(4)], and coupled-cluster theory (LCCD, CCD, LCCSD, CCSD, QCISD, CCSDT, and CCSDTQ)

  15. Electronic structure and bond length dependence of the effective valence shell Hamiltonian of S2 as studied by quasidegenerate many-body perturbation theory

    Science.gov (United States)

    Wang, Xiao-Chuan; Freed, Karl F.

    1987-03-01

    The effective valence shell Hamiltonian (Hv) of S2 is calculated as a function of internuclear distance using quasidegenerate many-body perturbation theory with the full valence space spanned by eight valence orbitals. Calculated potential curves and excitation energies for several valence states are in good agreement with experiment and are compared with configuration interaction calculations using the same primitive basis. In order to test assumptions of semiempirical theories, we also perform a more approximate calculation of Hv in which the valence space is constructed as the union of the atomic valence spaces with the atomic orbitals taken from atomic SCF calculations. A new and important feature of this approximate, correlated Hv is the use of optimized valence and excited orbitals as determined from a constrained SCF procedure. The matrix elements of this approximate, correlated Hv are transformed to the original nonorthogonal atomic valence basis, and their bond length dependences are fit with simple analytical functions. Some calculated Hv matrix elements agree with the forms commonly postulated for semiempirical integrals, while others display quite different behavior. An example of the latter are the one-center, two-electron integrals which depend significantly on bond length in marked contrast to semiempirical theories which assume them to be bond length independent.

  16. On the hierarchical parallelization of ab initio simulations

    CERN Document Server

    Ruiz-Barragan, Sergi; Shiga, Motoyuki

    2016-01-01

    A hierarchical parallelization has been implemented in a new unified code PIMD-SMASH for ab initio simulation where the replicas and the Born-Oppenheimer forces are parallelized. It is demonstrated that ab initio path integral molecular dynamics simulations can be carried out very efficiently for systems up to a few tens of water molecules. The code was then used to study a Diels-Alder reaction of cyclopentadiene and butenone by ab initio string method. A reduction in the reaction energy barrier is found in the presence of hydrogen-bonded water, in accordance with experiment.

  17. Ab initio derivation of model energy density functionals

    Science.gov (United States)

    Dobaczewski, Jacek

    2016-08-01

    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.

  18. The Many-Body Expansion Combined with Neural Networks

    CERN Document Server

    Yao, Kun; Parkhill, John

    2016-01-01

    Fragmentation methods such as the many-body expansion (MBE) are a common strategy to model large systems by partitioning energies into a hierarchy of decreasingly significant contributions. The number of fragments required for chemical accuracy is still prohibitively expensive for ab-initio MBE to compete with force field approximations for applications beyond single-point energies. Alongside the MBE, empirical models of ab-initio potential energy surfaces have improved, especially non-linear models based on neural networks (NN) which can reproduce ab-initio potential energy surfaces rapidly and accurately. Although they are fast, NNs suffer from their own curse of dimensionality; they must be trained on a representative sample of chemical space. In this paper we examine the synergy of the MBE and NN's, and explore their complementarity. The MBE offers a systematic way to treat systems of arbitrary size and intelligently sample chemical space. NN's reduce, by a factor in excess of $10^6$ the computational ove...

  19. Ab initio no core calculations of light nuclei and preludes to Hamiltonian quantum field theory

    Energy Technology Data Exchange (ETDEWEB)

    Vary, J.P.; Maris, P.; /Iowa State U.; Shirokov, A.M.; /Iowa State U. /SINP, Moscow; Honkanen, H.; li, J.; /Iowa State U.; Brodsky, S.J.; /SLAC; Harindranath, A.; /Saha Inst.; Teramond, G.F.de; /Costa Rica U.

    2009-08-03

    Recent advances in ab initio quantum many-body methods and growth in computer power now enable highly precise calculations of nuclear structure. The precision has attained a level sufficient to make clear statements on the nature of 3-body forces in nuclear physics. Total binding energies, spin-dependent structure effects, and electroweak properties of light nuclei play major roles in pinpointing properties of the underlying strong interaction. Eventually,we anticipate a theory bridge with immense predictive power from QCD through nuclear forces to nuclear structure and nuclear reactions. Light front Hamiltonian quantum field theory offers an attractive pathway and we outline key elements.

  20. Dynamical screening effects in correlated electron materials-a progress report on combined many-body perturbation and dynamical mean field theory: 'GW + DMFT'.

    Science.gov (United States)

    Biermann, Silke

    2014-04-30

    We give a summary of recent progress in the field of electronic structure calculations for materials with strong electronic Coulomb correlations. The discussion focuses on developments beyond the by now well established combination of density functional and dynamical mean field theory dubbed 'LDA + DMFT'. It is organized around the description of dynamical screening effects in the solid. Indeed, screening in the solid gives rise to dynamical local Coulomb interactions U(ω) (Aryasetiawan et al 2004 Phys. Rev. B 70 195104), and this frequency dependence leads to effects that cannot be neglected in a truly first principles description. We review the recently introduced extension of LDA + DMFT to dynamical local Coulomb interactions 'LDA + U(ω) + DMFT' (Casula et al 2012 Phys. Rev. B 85 035115, Werner et al 2012 Nature Phys. 1745-2481). A reliable description of dynamical screening effects is also a central ingredient of the 'GW + DMFT' scheme (Biermann et al 2003 Phys. Rev. Lett. 90 086402), a combination of many-body perturbation theory in Hedin's GW approximation and dynamical mean field theory. Recently, the first GW + DMFT calculations including dynamical screening effects for real materials have been achieved, with applications to SrV O3 (Tomczak et al 2012 Europhys. Lett. 100 67001, Tomczak et al Phys. Rev. B submitted (available electronically as arXiv:1312.7546)) and adatom systems on surfaces (Hansmann et al 2013 Phys. Rev. Lett. 110 166401). We review these and comment on further perspectives in the field. This review is an attempt to put elements of the original works into the broad perspective of the development of truly first principles techniques for correlated electron materials. PMID:24722486

  1. Electronic and optical properties of pure and modified diamondoids studied by many-body perturbation theory and time-dependent density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Demján, Tamás [Institute of Physics, Loránd Eötvös University, Pázmány Péter sétány 1/A, H-1117 Budapest (Hungary); Institute for Solid State Physics and Optics, Wigner Research Center for Physics, Hungarian Academy of Sciences, P.O. Box 49, H-1525 Budapest (Hungary); Vörös, Márton [Department of Atomic Physics, Budapest University of Technology and Economics, Budafoki út 8., H-1111 Budapest (Hungary); Palummo, Maurizia [Dipartimento di Fisica, Universitá di Roma “Tor Vergata”, Via della Ricerca Scientifica 1, 00133 Roma (Italy); Gali, Adam [Institute for Solid State Physics and Optics, Wigner Research Center for Physics, Hungarian Academy of Sciences, P.O. Box 49, H-1525 Budapest (Hungary); Department of Atomic Physics, Budapest University of Technology and Economics, Budafoki út 8., H-1111 Budapest (Hungary)

    2014-08-14

    Diamondoids are small diamond nanoparticles (NPs) that are built up from diamond cages. Unlike usual semiconductor NPs, their atomic structure is exactly known, thus they are ideal test-beds for benchmarking quantum chemical calculations. Their usage in spintronics and bioimaging applications requires a detailed knowledge of their electronic structure and optical properties. In this paper, we apply density functional theory (DFT) based methods to understand the electronic and optical properties of a few selected pure and modified diamondoids for which accurate experimental data exist. In particular, we use many-body perturbation theory methods, in the G{sub 0}W{sub 0} and G{sub 0}W{sub 0}+BSE approximations, and time-dependent DFT in the adiabatic local density approximation. We find large quasiparticle gap corrections that can exceed thrice the DFT gap. The electron-hole binding energy can be as large as 4 eV but it is considerably smaller than the GW corrections and thus G{sub 0}W{sub 0}+BSE optical gaps are about 50% larger than the Kohn-Sham (KS) DFT gaps. We find significant differences between KS time-dependent DFT and GW+BSE optical spectra on the selected diamondoids. The calculated G{sub 0}W{sub 0} quasiparticle levels agree well with the corresponding experimental vertical ionization energies. We show that nuclei dynamics in the ionization process can be significant and its contribution may reach about 0.5 eV in the adiabatic ionization energies.

  2. Volumic omit maps in ab initio dual-space phasing.

    Science.gov (United States)

    Oszlányi, Gábor; Sütő, András

    2016-07-01

    Alternating-projection-type dual-space algorithms have a clear construction, but are susceptible to stagnation and, thus, inefficient for solving the phase problem ab initio. To improve this behaviour new omit maps are introduced, which are real-space perturbations applied periodically during the iteration process. The omit maps are called volumic, because they delete some predetermined subvolume of the unit cell without searching for atomic regions or analysing the electron density in any other way. The basic algorithms of positivity, histogram matching and low-density elimination are tested by their solution statistics. It is concluded that, while all these algorithms based on weak constraints are practically useless in their pure forms, appropriate volumic omit maps can transform them to practically useful methods. In addition, the efficiency of the already useful reflector-type charge-flipping algorithm can be further improved. It is important that these results are obtained by using non-sharpened structure factors and without any weighting scheme or reciprocal-space perturbation. The mathematical background of volumic omit maps and their expected applications are also discussed. PMID:27357850

  3. A highly accurate {\\it ab initio} potential energy surface for methane

    CERN Document Server

    Owens, Alec; Yachmenev, Andrey; Tennyson, Jonathan; Thiel, Walter

    2016-01-01

    A new nine-dimensional potential energy surface (PES) for methane has been generated using state-of-the-art \\textit{ab initio} theory. The PES is based on explicitly correlated coupled cluster calculations with extrapolation to the complete basis set limit and incorporates a range of higher-level additive energy corrections. These include: core-valence electron correlation, higher-order coupled cluster terms beyond perturbative triples, scalar relativistic effects and the diagonal Born-Oppenheimer correction. Sub-wavenumber accuracy is achieved for the majority of experimentally known vibrational energy levels with the four fundamentals of $^{12}$CH$_4$ reproduced with a root-mean-square error of $0.70{\\,}$cm$^{-1}$. The computed \\textit{ab initio} equilibrium C{--}H bond length is in excellent agreement with previous values despite pure rotational energies displaying minor systematic errors as $J$ (rotational excitation) increases. It is shown that these errors can be significantly reduced by adjusting the e...

  4. An ab initio potential function for the ν13 vibrational mode of 1,3-butadiene

    Science.gov (United States)

    Senent, M. L.

    1995-06-01

    The restricted potential of the ν13 torsional mode of 1,3-butadiene has been determined from ab initio calculations. The relative energy and geometry of the second rotamer were calculated with the optimized couple cluster method with double substitutions. This ab initio level provides that the second stable structure attaches to a gauche form situated at 140.8°. The potential energy function was obtained by fitting to a symmetry-adapted Fourier series the total electronic energies of several selected conformations. These energies were calculated by the Möller-Plesset perturbation theory up to the second order (MP2) with full and partial optimization of the geometry. Torsional Raman band positions and fundamental frequencies were determined from the periodic potentials with a good agreement with experimental data. The convenience of performing fully optimized calculations to determine the restricted function is also refuted.

  5. Ab initio calculation of the Hoyle state

    CERN Document Server

    Epelbaum, Evgeny; Lee, Dean; Meißner, Ulf-G

    2011-01-01

    The Hoyle state plays a crucial role in the hydrogen burning of stars heavier than our sun and in the production of carbon and other elements necessary for life. This excited state of the carbon-12 nucleus was postulated by Hoyle^{1} as a necessary ingredient for the fusion of three alpha particles to produce carbon at stellar temperatures. Although the Hoyle state was seen experimentally more than a half century ago^{2,3}, nuclear theorists have not yet uncovered the nature of this state from first principles. In this letter we report the first ab initio calculation of the low-lying states of carbon-12 using supercomputer lattice simulations and a theoretical framework known as effective field theory. In addition to the ground state and excited spin-2 state, we find a resonance at -85(3) MeV with all of properties of the Hoyle state and in agreement with the experimentally observed energy. These lattice simulations provide insight into the structure of this unique state and new clues as to the amount of fine...

  6. In pursuit of the ab initio limit for conformational energy prototypes

    Science.gov (United States)

    Császár, Attila G.; Allen, Wesley D.; Schaefer, Henry F.

    1998-06-01

    The convergence of ab initio predictions to the one- and n-particle limits has been systematically explored for several conformational energy prototypes: the inversion barriers of ammonia, water, and isocyanic acid, the torsional barrier of ethane, the E/Z rotamer separation of formic acid, and the barrier to linearity of silicon dicarbide. Explicit ab initio results were obtained with atomic-orbital basis sets as large as [7s6p5d4f3g2h1i/6s5p4d3f2g1h] and electron correlation treatments as extensive as fifth-order Møller-Plesset perturbation theory (MP5), the full coupled-cluster method through triple excitations (CCSDT), and Brueckner doubles theory including perturbational corrections for both triple and quadruple excitations [BD(TQ)]. Subsequently, basis set and electron correlation extrapolation schemes were invoked to gauge any further variations in arriving at the ab initio limit. Physical effects which are tacitly neglected in most theoretical work have also been quantified by computations of non-Born-Oppenheimer (BODC), relativistic, and core correlation shifts of relative energies. Instructive conclusions are drawn for the pursuit of spectroscopic accuracy in theoretical conformational analyses, and precise predictions for the key energetic quantities of the molecular prototypes are advanced.

  7. Young Modulus of Crystalline Polyethylene from ab Initio Molecular Dynamics

    OpenAIRE

    Hageman, J.C.L.; Meier, Robert J.; M. Heinemann; de Groot, R. A.

    1997-01-01

    The Young modulus for crystalline polyethylene is calculated using ab initio molecular dynamics based on density functional theory in the local density approximation (DFT-LDA). This modulus, which can be seen as the ultimate value for the Young modulus of polyethylene fibers, is found to be 334 GPa. For the first time the modulus is evaluated ab initio (no bias from experimental data) with demonstrated basis set convergence.

  8. Ab initio no-core shell model with continuum

    Science.gov (United States)

    Navratil, Petr

    2008-04-01

    The ab initio no-core shell model (NCSM) is a many-body approach to nuclear structure of light nuclei. The NCSM adopts an effective interaction theory to transform fundamental inter-nucleon interactions into effective interactions for a specified nucleus in a selected harmonic oscillator basis space [1]. The method is capable of predicting nuclear structure from inter-nucleon forces derived from quantum chromodynamics by means of chiral effective field theory [2]. NCSM extensions to the microscopic description of nuclear reactions are now under development. In my talk, I will first discuss our recent calculations of the ^4He total photo-absorption cross section using two- and three-nucleon interactions from chiral effective field theory [3]. I will then outline our effort to augment the NCSM by the resonating group method (RGM) technique to develop a new method capable of describing simultaneously both bound states and nuclear reactions on light nuclei [4]. This approach, which preserves translational symmetry and the Pauli principle, will allow us to calculate cross sections of reactions important for astrophysics and describe weakly-bound systems from first principles. I will present our first phase shift results for neutron scattering off ^3H, ^4He and ^7Li and proton scattering off ^3He, ^4He and ^7Be using realistic nucleon-nucleon potentials. 3mm [1] P. Navr'atil, J. P. Vary and B. R. Barrett, Phys. Rev. C 62, 054311 (2000). [2] P. Navr'atil and V. G. Gueorguiev and J. P. Vary, W. E. Ormand and A. Nogga, Phys. Rev. Lett. 99, 042501 (2007). [3] S. Quaglioni and P. Navr'atil, Phys. Lett. B 652, 370 (2007). [4] S. Quaglioni and P. Navr'atil, arXiv:0712.0855.

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

    Science.gov (United States)

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

    2016-01-28

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

  10. Quantum many body systems

    Energy Technology Data Exchange (ETDEWEB)

    Rivasseau, Vincent [Paris-Sud Univ. Orsay (France). Laboratoire de Physique Theorique; Seiringer, Robert [McGill Univ., Montreal, QC (Canada). Dept. of Mathematics and Statistics; Solovej, Jan Philip [Copenhagen Univ. (Denmark). Dept. of Mathematics; Spencer, Thomas [Institute for Advanced Study, Princeton, NJ (United States). School of Mathematics

    2012-11-01

    The book is based on the lectures given at the CIME school ''Quantum many body systems'' held in the summer of 2010. It provides a tutorial introduction to recent advances in the mathematics of interacting systems, written by four leading experts in the field: V. Rivasseau illustrates the applications of constructive Quantum Field Theory to 2D interacting electrons and their relation to quantum gravity; R. Seiringer describes a proof of Bose-Einstein condensation in the Gross-Pitaevski limit and explains the effects of rotating traps and the emergence of lattices of quantized vortices; J.-P. Solovej gives an introduction to the theory of quantum Coulomb systems and to the functional analytic methods used to prove their thermodynamic stability; finally, T. Spencer explains the supersymmetric approach to Anderson localization and its relation to the theory of random matrices. All the lectures are characterized by their mathematical rigor combined with physical insights.

  11. Ab Initio Studies of Stratospheric Ozone Depletion Chemistry

    Science.gov (United States)

    Lee, Timothy J.; Head-Gordon, Martin; Langhoff, Stephen R. (Technical Monitor)

    1995-01-01

    An overview of the current understanding of ozone depletion chemistry, particularly with regards the formation of the so-called Antarctic ozone hole, will be presented together with an outline as to how ab initio quantum chemistry can be used to further our understanding of stratospheric chemistry. The ability of modern state-of-the art ab initio quantum chemical techniques to characterize reliably the gas-phase molecular structure, vibrational spectrum, electronic spectrum, and thermal stability of fluorine, chlorine, bromine and nitrogen oxide species will be demonstrated by presentation of some example studies. The ab initio results will be shown to be in excellent agreement with the available experimental data, and where the experimental data are either not known or are inconclusive, the theoretical results are shown to fill in the gaps and to resolve experimental controversies. In addition, ab initio studies in which the electronic spectra and the characterization of excited electronic states of halogen oxide species will also be presented. Again where available, the ab initio results are compared to experimental observations, and are used to aid in the interpretation of experimental studies.

  12. Ab initio simulation of transport phenomena in rarefied gases.

    Science.gov (United States)

    Sharipov, Felix; Strapasson, José L

    2012-09-01

    Ab initio potentials are implemented into the direct simulation Monte Carlo (DSMC) method. Such an implementation allows us to model transport phenomena in rarefied gases without any fitting parameter of intermolecular collisions usually extracted from experimental data. Applying the method proposed by Sharipov and Strapasson [Phys. Fluids 24, 011703 (2012)], the use of ab initio potentials in the DSMC requires the same computational efforts as the widely used potentials such as hard spheres, variable hard sphere, variable soft spheres, etc. At the same time, the ab initio potentials provide more reliable results than any other one. As an example, the transport coefficients of a binary mixture He-Ar, viz., viscosity, thermal conductivity, and thermal diffusion factor, have been calculated for several values of the mole fraction. PMID:23030889

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

    Energy Technology Data Exchange (ETDEWEB)

    Dytrych, T. [Academy of Sciences of the Czech Republic (ASCR), Prague (Czech Republic); Louisiana State Univ., Baton Rouge, LA (United States); Maris, Pieter [Iowa State Univ., Ames, IA (United States); Launey, K. D. [Louisiana State Univ., Baton Rouge, LA (United States); Draayer, J. P. [Louisiana State Univ., Baton Rouge, LA (United States); Vary, James [Iowa State Univ., Ames, IA (United States); Langr, D. [Czech Technical Univ., Prague (Czech Republic); Aerospace Research and Test Establishment, Prague (Czech Republic); Saule, E. [Univ. of North Carolina, Charlotte, NC (United States); Caprio, M. A. [Univ. of Notre Dame, IN (United States); Catalyurek, U. [The Ohio State Univ., Columbus, OH (United States). Dept. of Electrical and Computer Engineering; Sosonkina, M. [Old Dominion Univ., Norfolk, VA (United States)

    2016-06-09

    We report on the computational characteristics of ab initio nuclear structure calculations in a symmetry-adapted no-core shell model (SA-NCSM) framework. We examine the computational complexity of the current implementation of the SA-NCSM approach, dubbed LSU3shell, by analyzing ab initio results for 6Li and 12C in large harmonic oscillator model spaces and SU(3)-selected subspaces. We demonstrate LSU3shell's strong-scaling properties achieved with highly-parallel methods for computing the many-body matrix elements. Results compare favorably with complete model space calculations and signi cant memory savings are achieved in physically important applications. In particular, a well-chosen symmetry-adapted basis a ords memory savings in calculations of states with a fixed total angular momentum in large model spaces while exactly preserving translational invariance.

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

    Science.gov (United States)

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

    2016-10-01

    We report on the computational characteristics of ab initio nuclear structure calculations in a symmetry-adapted no-core shell model (SA-NCSM) framework. We examine the computational complexity of the current implementation of the SA-NCSM approach, dubbed LSU3shell, by analyzing ab initio results for 6Li and 12C in large harmonic oscillator model spaces and SU3-selected subspaces. We demonstrate LSU3shell's strong-scaling properties achieved with highly-parallel methods for computing the many-body matrix elements. Results compare favorably with complete model space calculations and significant memory savings are achieved in physically important applications. In particular, a well-chosen symmetry-adapted basis affords memory savings in calculations of states with a fixed total angular momentum in large model spaces while exactly preserving translational invariance.

  15. The Yambo code: a comprehensive tool to perform ab-initio simulations of equilibrium and out-of-equilibrium properties

    Science.gov (United States)

    Marini, Andrea

    Density functional theory and many-body perturbation theory methods (such as GW and Bethe-Selpether equation) are standard approaches to the equilibrium ground and excited state properties of condensed matter systems, surfaces, molecules and other several kind of materials. At the same time ultra-fast optical spectroscopy is becoming a widely used and powerful tool for the observation of the out-of-equilibrium dynamical processes. In this case the theoretical tools (such as the Baym-Kadanoff equation) are well known but, only recently, have been merged with the ab-Initio approach. And, for this reason, highly parallel and efficient codes are lacking. Nevertheless, the combination of these two areas of research represents, for the ab-initio community, a challenging prespective as it requires the development of advanced theoretical, methodological and numerical tools. Yambo is a popular community software implementing the above methods using plane-waves and pseudo-potentials. Yambo is available to the community as open-source software, and oriented to high-performance computing. The Yambo project aims at making the simulation of these equilibrium and out-of-equilibrium complex processes available to a wide community of users. Indeed the code is used, in practice, in many countries and well beyond the European borders. Yambo is a member of the suite of codes of the MAX European Center of Excellence (Materials design at the exascale) . It is also used by the user facilities of the European Spectroscopy Facility and of the NFFA European Center (nanoscience foundries & fine analysis). In this talk I will discuss some recent numerical and methodological developments that have been implemented in Yambo towards to exploitation of next generation HPC supercomputers. In particular, I will present the hybrid MPI+OpenMP parallelization and the specific case of the response function calculation. I will also discuss the future plans of the Yambo project and its potential use as

  16. Molecular transport in the language of many-body states

    Science.gov (United States)

    Galperin, Michael

    2009-03-01

    Recent advancements in experimental techniques at nanoscale caused a surge in research of transport through molecular junctions. Nonlinearity of current-voltage characteristic at resonance makes this regime particularly important for potential molecular based memory, switchers and logic devices. One of important differences of molecular junctions (compared e.g. to semiconductor QDs) is sensitivity of electronic and vibrational structure of the junction to oxidation/reduction of the molecule. This implies necessity of treating the transport at resonance in the language of molecular states rather than single particle orbitals. The latter are the choice of majority of available ab initio approaches. We consider two possible schemes capable of incorporating isolated molecule (many-body) states as a basis for transport calculations. The schemes utilize Hubbard operators for description of single electron transitions between many-body states and go beyond previously proposed scattering theory and standard quantum master equation approaches.

  17. P-V Relation for Mercuric Calcogenides: Ab Initio Method

    Directory of Open Access Journals (Sweden)

    G. Misra

    2011-01-01

    Full Text Available Mercuric Calcogenides found many applications in electronic and optical devices as semiconducting materials. An equation of state provides useful information about the relationship between pressure (P, volume (V and temperature (T that helps to understand the behaviour of materials under the effect of high pressure and high temperature. The present paper sheds light on the electronic structure of Mercuric Calcogenides by simulating its electronic properties through ab initio method. This ab initio method is extended to derive the equation of state for Mercuric Calcogenides. The present equation of state has also been tested for the prediction of End Point. The computed results compare well with Quantum statistical data.

  18. Recent achievements in ab initio modelling of liquid water

    CERN Document Server

    Khaliullin, Rustam Z

    2013-01-01

    The application of newly developed first-principle modeling techniques to liquid water deepens our understanding of the microscopic origins of its unusual macroscopic properties and behaviour. Here, we review two novel ab initio computational methods: second-generation Car-Parrinello molecular dynamics and decomposition analysis based on absolutely localized molecular orbitals. We show that these two methods in combination not only enable ab initio molecular dynamics simulations on previously inaccessible time and length scales, but also provide unprecedented insights into the nature of hydrogen bonding between water molecules. We discuss recent applications of these methods to water clusters and bulk water.

  19. 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.

  20. Precise Ab-initio prediction of terahertz vibrational modes in crystalline systems

    DEFF Research Database (Denmark)

    Jepsen, Peter Uhd; Clark, Stewart J.

    2007-01-01

    We use a combination of experimental THz time-domain spectroscopy and ab-initio density functional perturbative theory to accurately predict the terahertz vibrational spectrum of molecules in the crystalline phase. Our calculations show that distinct vibrational modes found in solid-state materials...... are best described as phonon modes with strong coupling to the intramolecular degrees of freedom. Hence a computational method taking the periodicity of the crystal lattice as well as intramolecular motion into account is a prerequisite for the correct prediction of vibrational modes in such materials....

  1. An accurate potential energy curve for helium based on ab initio calculations

    Science.gov (United States)

    Janzen, A. R.; Aziz, R. A.

    1997-07-01

    Korona, Williams, Bukowski, Jeziorski, and Szalewicz [J. Chem. Phys. 106, 1 (1997)] constructed a completely ab initio potential for He2 by fitting their calculations using infinite order symmetry adapted perturbation theory at intermediate range, existing Green's function Monte Carlo calculations at short range and accurate dispersion coefficients at long range to a modified Tang-Toennies potential form. The potential with retardation added to the dipole-dipole dispersion is found to predict accurately a large set of microscopic and macroscopic experimental data. The potential with a significantly larger well depth than other recent potentials is judged to be the most accurate characterization of the helium interaction yet proposed.

  2. All electron ab initio investigations of the electronic states of the FeC molecule

    DEFF Research Database (Denmark)

    Shim, Irene; Gingerich, Karl A.

    1999-01-01

    The low lying electronic states of the molecule FeC have been investigated by performing all electron ab initio multi-configuration self-consistent-field (CASSCF) and multi reference configuration interaction (MRCI) calculations. The relativistic corrections for the one electron Darwin contact term...... and the relativistic mass-velocity correction have been determined in perturbation calculations. The electronic structure of the FeC molecule is interpreted as antiferromagnetic couplings of the localized angular momenta of the ions Fe+ and C resulting in a triple bond in the valence bond sense. The electronic ground...

  3. Symmetry-Adapted Ab Initio Shell Model for Nuclear Structure Calculations

    Science.gov (United States)

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

    2012-05-01

    An innovative concept, the symmetry-adapted ab initio shell model, that capitalizes on partial as well as exact symmetries that underpin the structure of nuclei, is discussed. This framework is expected to inform the leading features of nuclear structure and reaction data for light and medium mass nuclei, which are currently inaccessible by theory and experiment and for which predictions of modern phenomenological models often diverge. We use powerful computational and group-theoretical algorithms to perform ab initio CI (configuration-interaction) calculations in a model space spanned by SU(3) symmetry-adapted many-body configurations with the JISP16 nucleon-nucleon interaction. We demonstrate that the results for the ground states of light nuclei up through A = 16 exhibit a strong dominance of low-spin and high-deformation configurations together with an evident symplectic structure. This, in turn, points to the importance of using a symmetry-adapted framework, one based on an LS coupling scheme with the associated spatial configurations organized according to deformation.

  4. 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 tr

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

    DEFF Research Database (Denmark)

    Bak, Börge; Jansen, Peter; Stafast, Herbert

    1975-01-01

    The Ne(I) and He(I) photoelectron(PE) spectra of cyanogen azide, NCN3, have been recorded at high resolution. Their interpretation is achieved by comparison with the PE spectrum of HN3 and an ab initio LCGO SCF MO calculation. Deviations from Koopmans' theorem of quite different magnitudes are fo...

  6. Relaxation of Small Molecules: an ab initio Study

    Institute of Scientific and Technical Information of China (English)

    CAO Yi-Gang; JIAO Zheng-Kuan; A. Antons; K. Schroeder; S. Blügel2

    2002-01-01

    Using an ab initio total energy and force method, we have relaxed several group IV and group V elementalclusters, in detail the arsenic and antimony dimers, silicon, phosphorus, arsenic and antimony tetramers. The obtainedbond lengths and cohesive energies are more accurate than other calculating methods, and in excellent agreement withthe experimental results.

  7. Young Modulus of Crystalline Polyethylene from ab Initio Molecular Dynamics

    NARCIS (Netherlands)

    Hageman, J.C.L.; Meier, Robert J.; Heinemann, M.; Groot, R.A. de

    1997-01-01

    The Young modulus for crystalline polyethylene is calculated using ab initio molecular dynamics based on density functional theory in the local density approximation (DFT-LDA). This modulus, which can be seen as the ultimate value for the Young modulus of polyethylene fibers, is found to be 334 GPa.

  8. Atomic many-body theory

    Energy Technology Data Exchange (ETDEWEB)

    Lindgren, I.; Morrison, J.

    1982-01-01

    The unified description of atomic theory provided in this book bridges the gap between elementary books on quantum mechanics and present-day research in the field. Angular-momentum theory and the Hartree-Fock model are developed systematically and then applied to a number of physical problems. The treatment of many-body theory which then follows is based on a general form of the Rayleigh-Schroedinger perturbation theory, applicable to open-shell as well as closed-shell systems. The presentation in the book is based largely on graphical methods. Angular momentum graphs are used to represent the coupling between the spin and orbital angular momenta of the electrons, and the different terms in the perturbation expansion are expressed by means of 'Feynman-like' - or Goldstone - diagrams. These diagrams are evaluated using the angular-momentum graphs developed in the early part of the book. The formalism is applied to a number of problems in atomic physics, such as the electron-correlation energy, the electrostatic term structure and the spin-orbit and hyperfine interactions. The final chapter deals with the exp(S) or coupled-cluster formalism in the pair approximation, which appears to be the most promising approach for accurate calculations of the structure of real atomic and molecular systems.

  9. Ab initio Investigations of the Equilibria between Trichlorothioacetyl Chloride, Tetrachlorothiirane, and Trichloroethenesulfenyl Chloride, their Reactants and Decomposition Products

    DEFF Research Database (Denmark)

    Pedersen, Kim Vestergaard; Christensen, Henrik; Shim, Irene;

    2004-01-01

    Trichlorothioacetyl chloride 1, tetrachlorothiirane 2, and trichloroethenesulfenyl chloride 3 and the equilibria between them have been investigated by ab initio Hartree-Fock (HF), Møller-Plesset second order perturbation (MP2) calculations, and by Gaussian-3 theory, G3(MP2). The transition state...... of the isomerization reactions have been identified. Also investigated were possible reactions leading to the isomers and their possible decomposition products. The results show that the unobserved isomerization reactions are feasible....

  10. Mapping Enzymatic Catalysis using the Effective Fragment Molecular Orbital Method: Towards all ab initio Biochemistry

    CERN Document Server

    Steinmann, Casper; Jensen, Jan H

    2012-01-01

    We extend the Effective Fragment Molecular Orbital (EFMO) method to the frozen domain approach where only the geometry of an active part is optimized, while the many-body polarization effects are considered for the whole system. The new approach efficiently mapped out the entire reaction path of chorismate mutase in less than four days using 80 cores on 20 nodes, where the whole system containing 2398 atoms is treated in the ab initio fashion without using any force fields. The reaction path is constructed automatically with the only assumption of defining the reaction coordinate a priori. We determine the reaction barrier of chorismate mutase to be $18.3\\pm 3.6$ kcal mol$^{-1}$ using ONIOM with MP2/cc-pVDZ and EFMO/6-31G(d) for the high and low layers, respectively.

  11. Modern Ab Initio Approaches and Applications in Few-Nucleon Physics with A \\ge 4

    CERN Document Server

    Leidemann, Winfried

    2012-01-01

    We present an overview of the evolution of ab initio methods for few-nucleon systems with A \\ge 4, tracing the progress made that today allows precision calculations for these systems. First a succinct description of the diverse approaches is given. In order to identify analogies and differences the methods are grouped according to different formulations of the quantum mechanical many-body problem. Various significant applications from the past and present are described. We discuss the results with emphasis on the developments following the original implementations of the approaches. In particular we highlight benchmark results which represent important milestones towards setting an ever growing standard for theoretical calculations. This is relevant for meaningful comparisons with experimental data. Such comparisons may reveal whether a specific force model is appropriate for the description of nuclear dynamics.

  12. Liquid chloroform structure from computer simulation with a full ab initio intermolecular interaction potential

    International Nuclear Information System (INIS)

    We have calculated the intermolecular interaction energies of the chloroform dimer in 12 orientations using the second-order Møller-Plesset perturbation theory. Single point energies of important geometries were calibrated by the coupled cluster with single and double and perturbative triple excitation method. Dunning's correlation consistent basis sets up to aug-cc-pVQZ have been employed in extrapolating the interaction energies to the complete basis set limit values. With the ab initio potential data we constructed a 5-site force field model for molecular dynamics simulations. We compared the simulation results with recent experiments and obtained quantitative agreements for the detailed atomwise radial distribution functions. Our results were also consistent with previous results using empirical force fields with polarization effects. Moreover, the calculated diffusion coefficients reproduced the experimental data over a wide range of thermodynamic conditions. To the best of our knowledge, this is the first ab initio force field which is capable of competing with existing empirical force fields for liquid chloroform

  13. Estudo da geometria da uréia por métodos ab initio e simulação computacional de líquidos

    Directory of Open Access Journals (Sweden)

    Cirino José Jair Vianna

    2002-01-01

    Full Text Available 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 magnitude of the free energy obtained from this simulation did not permit us to conclude that urea is non-planar in water.

  14. 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.

  15. Understanding phonon transport in thermoelectric materials using ab initio approaches

    Science.gov (United States)

    Broido, David

    Good thermoelectric materials have low phonon thermal conductivity, kph. Accurate theories to describe kph are important components in developing predictive models of thermoelectric efficiency that can help guide synthesis and measurement efforts. We have developed ab initio approaches to calculate kph, in which phonon modes and phonon scattering rates are computed using interatomic force constants determined from density functional theory, and a full solution of the Boltzmann transport equation for phonons is implemented. A recent approach to calculate interatomic force constants using ab initio molecular dynamics has yielded a good description of the thermal properties of Bi2Te3. But, the complexity of new promising candidate thermoelectric materials introduces computational challenges in assessing their thermal properties. An example is germanane, a germanium based hydrogen-terminated layered semiconductor, which we will discuss in this talk.

  16. Ab-initio calculations on melting of thorium

    Science.gov (United States)

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

    2016-05-01

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

  17. Serine Proteases an Ab Initio Molecular Dynamics Study

    CERN Document Server

    De Santis, L

    1999-01-01

    In serine proteases (SP's), the H-bond between His-57 and Asp-102, and that between Gly-193 and the transition state intermediate play a crucial role for enzymatic function. To shed light on the nature of these interactions, we have carried out ab initio molecular dynamics simulations on complexes representing adducts between the reaction intermediate and elastase (one protein belonging to the SP family). Our calculations indicate the presence of a low--barrier H-bond between His-57 and Asp-102, in complete agreement with NMR experiments on enzyme--transition state analog complexes. Comparison with an ab initio molecular dynamics simulation on a model of the substrate--enzyme adduct indicates that the Gly-193--induced strong stabilization of the intermediate is accomplished by charge/dipole interactions and not by H-bonding as previously suggested. Inclusion of the protein electric field in the calculations does not affect significantly the charge distribution.

  18. The density matrix renormalization group for ab initio quantum chemistry

    OpenAIRE

    Wouters, Sebastian

    2015-01-01

    During the past 15 years, the density matrix renormalization group (DMRG) has become increasingly important for ab initio quantum chemistry. It is used as a numerically exact solver for highly correlated regions in molecules. While the method works extremely well for one-dimensional systems, the correlated regions of interest are often far from one-dimensional. In this introductory talk, I will discuss the DMRG algorithm from a quantum information perspective, how quantum information theory h...

  19. Molexpl: a tool for ab initio data exploration and visualization

    OpenAIRE

    Wang, Xueying; Onofrio, Nicolas,; Strachan, Alejandro

    2015-01-01

    Density functional theory (DFT) based on ab initio theory, is a powerful method to resolve the electronic structure of atoms, molecules and solids. However, in practical, DFT is limited to few hundreds of atoms. To overcome this limitation, researchers have developed empirical interatomic potentials implemented in molecular dynamics (MD) simulations. MD ignores the movements of electrons and describes bonding and non-bonding interaction as a function of the distance between atoms called force...

  20. Ab initio calculation of tight-binding parameters

    Energy Technology Data Exchange (ETDEWEB)

    McMahan, A.K.; Klepeis, J.E.

    1997-12-01

    We calculate ab initio values of tight-binding parameters for the f- electron metal Ce and various phases of Si, from local-density functional one-electron Hamiltonian and overlap matrix elements. Our approach allows us to unambiguously test the validity of the common minimal basis and two-center approximations as well as to determine the degree of transferability of both nonorthogonal and orthogonal hopping parameters in the cases considered.

  1. GAUSSIAN 76: an ab initio molecular orbital program

    Energy Technology Data Exchange (ETDEWEB)

    Binkley, J. S.; Whiteside, R.; Hariharan, P. C.; Seeger, R.; Hehre, W. J.; Lathan, W. A.; Newton, M. D.; Ditchfield, R.; Pople, J. A.

    1978-06-01

    Gaussian 76 is a general-purpose computer program for ab initio Hartree-Fock molecular orbital calculations. It can handle basis sets involving s, p and d-type gaussian functions. Certain standard sets (STO-3G, 4-31G, 6-31G*, etc.) are stored internally for easy use. Closed shell (RHF) or unrestricted open shell (UHF) wave functions can be obtained. Facilities are provided for geometry optimization to potential minima and for limited potential surface scans.

  2. P-V Relation for Mercuric Calcogenides: Ab Initio Method

    OpenAIRE

    G. Misra; S. Tenguria; Gautam, M.

    2011-01-01

    Mercuric Calcogenides found many applications in electronic and optical devices as semiconducting materials. An equation of state provides useful information about the relationship between pressure (P), volume (V) and temperature (T) that helps to understand the behaviour of materials under the effect of high pressure and high temperature. The present paper sheds light on the electronic structure of Mercuric Calcogenides by simulating its electronic properties through ab initio method. This a...

  3. Ab-initio calculations for dilute magnetic semiconductors

    OpenAIRE

    Belhadji, Brahim

    2008-01-01

    This thesis focusses on ab-initio calculations for the electronic structure and the magnetic properties of dilute magnetic semiconductors (DMS). In particular we aim at the understanding of the complex exchange interactions in these systems. Our calculations are based on density functional theory, being ideally suited for a description of the material specific properties of the considered DMS. Moreover we use the KKR Green function method in connection with the coherent potential approximatio...

  4. Thermochemical data for CVD modeling from ab initio calculations

    Energy Technology Data Exchange (ETDEWEB)

    Ho, P. [Sandia National Labs., Albuquerque, NM (United States); Melius, C.F. [Sandia National Labs., Livermore, CA (United States)

    1993-12-31

    Ab initio electronic-structure calculations are combined with empirical bond-additivity corrections to yield thermochemical properties of gas-phase molecules. A self-consistent set of heats of formation for molecules in the Si-H, Si-H-Cl, Si-H-F, Si-N-H and Si-N-H-F systems is presented, along with preliminary values for some Si-O-C-H species.

  5. 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).

  6. Acceleration of the Convergence in ab initio Atomic Relaxations

    Science.gov (United States)

    Zhao, Zhengji; Wang, Lin-Wang; Meza, Juan

    2006-03-01

    Atomic relaxations is often required to accurately describe the properties of nanosystems. In ab initio calculations, a common practice is to use a standard search algorithm, such as BFGS (Broyden-Fletcher-Goldfarb-Shanno) or CG (conjugate gradient) method, which starts the atomic relaxations without any knowledge of the Hessian matrix of the system. For example, the initial Hessian in BFGS method is often set to identity, and there is no preconditioning to CG method. One way to accelerate the convergence of the atomic relaxations is to estimate an approximate Hessian matrix of the system and then use it as the initial Hessian in BFGS method or a preconditioner in CG method. Previous attempts to obtain the approximated Hessian were focused on the use of classical force field models which rely on the existence of good parameters. Here, we present an alternative method to estimate the Hessian matrix of a nanosystem. First, we decompose the system into motifs which consist of a few atoms, then calculate the Hessian matrix elements on different motif types from ab initio calculations for small prototype systems. Then we generate the Hessian Matrix of the whole system by putting together these motif Hessians. We have applied our motif-based Hessian matrix in ab initio atomic relaxations in several bulk (with/without impurity) and quantum dot systems, and have found a speed up factor of 2 to 4 depending on the system size.

  7. Ab initio multiple cloning algorithm for quantum nonadiabatic molecular dynamics

    Science.gov (United States)

    Makhov, Dmitry V.; Glover, William J.; Martinez, Todd J.; Shalashilin, Dmitrii V.

    2014-08-01

    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.

  8. 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.

  9. A Complete and Accurate Ab Initio Repeat Finding Algorithm.

    Science.gov (United States)

    Lian, Shuaibin; Chen, Xinwu; Wang, Peng; Zhang, Xiaoli; Dai, Xianhua

    2016-03-01

    It has become clear that repetitive sequences have played multiple roles in eukaryotic genome evolution including increasing genetic diversity through mutation, changes in gene expression and facilitating generation of novel genes. However, identification of repetitive elements can be difficult in the ab initio manner. Currently, some classical ab initio tools of finding repeats have already presented and compared. The completeness and accuracy of detecting repeats of them are little pool. To this end, we proposed a new ab initio repeat finding tool, named HashRepeatFinder, which is based on hash index and word counting. Furthermore, we assessed the performances of HashRepeatFinder with other two famous tools, such as RepeatScout and Repeatfinder, in human genome data hg19. The results indicated the following three conclusions: (1) The completeness of HashRepeatFinder is the best one among these three compared tools in almost all chromosomes, especially in chr9 (8 times of RepeatScout, 10 times of Repeatfinder); (2) in terms of detecting large repeats, HashRepeatFinder also performed best in all chromosomes, especially in chr3 (24 times of RepeatScout and 250 times of Repeatfinder) and chr19 (12 times of RepeatScout and 60 times of Repeatfinder); (3) in terms of accuracy, HashRepeatFinder can merge the abundant repeats with high accuracy. PMID:26272474

  10. Ab initio nuclear structure - the large sparse matrix eigenvalue problem

    International Nuclear Information System (INIS)

    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 1010 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.

  11. A systematic benchmark of the ab initio Bethe-Salpeter equation approach for low-lying optical excitations of small organic molecules

    OpenAIRE

    Bruneval, Fabien; Hamed, Samia M.; Neaton, Jeffrey B.

    2015-01-01

    The predictive power of the ab initio Bethe-Salpeter equation (BSE) approach, rigorously based on many-body Green's function theory but incorporating information from density functional theory, has already been demonstrated for the optical gaps and spectra of solid-state systems. Interest in photoactive hybrid organic/inorganic systems has recently increased, and so has the use of the BSE for computing neutral excitations of organic molecules. However, no systematic benchmarks of the BSE for ...

  12. Relativistic Multireference Many-body Perturbation Theory for Open-shell Ions with Multiple Valence Shell Electrons: the Transition Rates and Lifetimes of the Excited Levels in Chlorinelike Fe X

    Energy Technology Data Exchange (ETDEWEB)

    Ishikawa, Y; Santana, J A; Trabert, E

    2009-09-30

    A recently developed relatistic multireference many-body perturbation theory based on multireference configuration-interaction wavefunctions as zeroth order wavefunctions is outlined. The perturbation theory employs a general class of configuration-interaction wve functions as reference functions, and thus is applciable to multiple open valence shell systems with near degeneracy of a manifold of strongly interacting configurations. Multireference many-body perturbation calculations are reported for the ground and excited states of chlorine-like Fe X in which the near degeneracy of a manifold of strongly interacting configurations mandates a multireference treatment. Term energies of a total of 83 excited levels arising from the 3s{sup 2}3p{sup 5}, 3s3p{sup 6}, 3s{sup 2}3p{sup 4}3d, 3s3p{sup 5}3d, and 3s{sup 2}3p{sup 3}3d{sup 2} configurations of the ion are evaluated to high accuracy. Transition rates associated with E1/M1/E2/M2/E3 radiative decays and lifetimes of a number of excited levels are calculated and compared with laboratory measurements to critically evaluate recent experiments.

  13. Accelerating Ab Initio Path Integral Simulations via Imaginary Multiple-Timestepping.

    Science.gov (United States)

    Cheng, Xiaolu; Herr, Jonathan D; Steele, Ryan P

    2016-04-12

    This work investigates the use of multiple-timestep schemes in imaginary time for computationally efficient ab initio equilibrium path integral simulations of quantum molecular motion. In the simplest formulation, only every n(th) path integral replica is computed at the target level of electronic structure theory, whereas the remaining low-level replicas still account for nuclear motion quantum effects with a more computationally economical theory. Motivated by recent developments for multiple-timestep techniques in real-time classical molecular dynamics, both 1-electron (atomic-orbital basis set) and 2-electron (electron correlation) truncations are shown to be effective. Structural distributions and thermodynamic averages are tested for representative analytic potentials and ab initio molecular examples. Target quantum chemistry methods include density functional theory and second-order Møller-Plesset perturbation theory, although any level of theory is formally amenable to this framework. For a standard two-level splitting, computational speedups of 1.6-4.0x are observed when using a 4-fold reduction in time slices; an 8-fold reduction is feasible in some cases. Multitiered options further reduce computational requirements and suggest that quantum mechanical motion could potentially be obtained at a cost not significantly different from the cost of classical simulations. PMID:26966920

  14. 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.

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

    CERN Document Server

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

    2016-01-01

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

  16. A systematic benchmark of the ab initio Bethe-Salpeter equation approach for low-lying optical excitations of small organic molecules

    Energy Technology Data Exchange (ETDEWEB)

    Bruneval, Fabien [CEA, DEN, Service de Recherches de Métallurgie Physique, F-91191 Gif-sur-Yvette (France); Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Department of Physics, University of California, Berkeley, California 94720 (United States); Hamed, Samia M. [Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Department of Physics, University of California, Berkeley, California 94720 (United States); Department of Chemistry, University of California, Berkeley, California 94720 (United States); Kavli Energy Nanosciences Institute at Berkeley, Berkeley, California 94720 (United States); Neaton, Jeffrey B. [Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Department of Physics, University of California, Berkeley, California 94720 (United States); Kavli Energy Nanosciences Institute at Berkeley, Berkeley, California 94720 (United States)

    2015-06-28

    The predictive power of the ab initio Bethe-Salpeter equation (BSE) approach, rigorously based on many-body Green’s function theory but incorporating information from density functional theory, has already been demonstrated for the optical gaps and spectra of solid-state systems. Interest in photoactive hybrid organic/inorganic systems has recently increased and so has the use of the BSE for computing neutral excitations of organic molecules. However, no systematic benchmarks of the BSE for neutral electronic excitations of organic molecules exist. Here, we study the performance of the BSE for the 28 small molecules in Thiel’s widely used time-dependent density functional theory benchmark set [Schreiber et al., J. Chem. Phys. 128, 134110 (2008)]. We observe that the BSE produces results that depend critically on the mean-field starting point employed in the perturbative approach. We find that this starting point dependence is mainly introduced through the quasiparticle energies obtained at the intermediate GW step and that with a judicious choice of starting mean-field, singlet excitation energies obtained from BSE are in excellent quantitative agreement with higher-level wavefunction methods. The quality of the triplet excitations is slightly less satisfactory.

  17. A systematic benchmark of the ab initio Bethe-Salpeter equation approach for low-lying optical excitations of small organic molecules

    International Nuclear Information System (INIS)

    The predictive power of the ab initio Bethe-Salpeter equation (BSE) approach, rigorously based on many-body Green’s function theory but incorporating information from density functional theory, has already been demonstrated for the optical gaps and spectra of solid-state systems. Interest in photoactive hybrid organic/inorganic systems has recently increased and so has the use of the BSE for computing neutral excitations of organic molecules. However, no systematic benchmarks of the BSE for neutral electronic excitations of organic molecules exist. Here, we study the performance of the BSE for the 28 small molecules in Thiel’s widely used time-dependent density functional theory benchmark set [Schreiber et al., J. Chem. Phys. 128, 134110 (2008)]. We observe that the BSE produces results that depend critically on the mean-field starting point employed in the perturbative approach. We find that this starting point dependence is mainly introduced through the quasiparticle energies obtained at the intermediate GW step and that with a judicious choice of starting mean-field, singlet excitation energies obtained from BSE are in excellent quantitative agreement with higher-level wavefunction methods. The quality of the triplet excitations is slightly less satisfactory

  18. Ab initio structure determination via powder X-ray diffraction

    Indian Academy of Sciences (India)

    Digamber G Porob; T N Guru Row

    2001-10-01

    Structure determination by powder X-ray diffraction data has gone through a recent surge since it has become important to get to the structural information of materials which do not yield good quality single crystals. Although the method of structure completion when once the starting model is provided is facile through the Rietveld refinement technique, the structure solution ab initio os still not push-button technology. In this article a survey of the recent development in this area is provided with an illustration of the structure determination of -NaBi3V2O10.

  19. Electrostriction coefficient of ferroelectric materials from ab initio computation

    Directory of Open Access Journals (Sweden)

    Z. Jiang

    2016-06-01

    Full Text Available Electrostriction is an important material property that characterizes how strain changes with the development of polarization inside a material. We show that ab initio techniques developed in recent years can be exploited to compute and understand electrostriction of ferroelectric materials. Here, electrostriction coefficients of ferroelectric BaTiO3, PbTiO3, as well as dielectric BaZrO3, are obtained and analyzed. Possible causes of the difference between experimental and numerical results are discussed. We also identified that relative displacements between certain ions at a given polarization could be a good indicator of a material’s electrostriction property.

  20. Tailoring magnetoresistance at the atomic level: An ab initio study

    KAUST Repository

    Tao, Kun

    2012-01-05

    The possibility of manipulating the tunneling magnetoresistance (TMR) of antiferromagnetic nanostructures is predicted in the framework of ab initio calculations. By the example of a junction composed of an antiferromagnetic dimer and a spin-polarized scanning tunneling microscopy tip we show that the TMR can be tuned and even reversed in sign by lateral and vertical movements of the tip. Moreover, our finite-bias calculations demonstrate that the magnitude and the sign of the TMR can also be tuned by an external voltage. © 2012 American Physical Society.

  1. Ab initio study of neutron drops with chiral Hamiltonians

    Directory of Open Access Journals (Sweden)

    H.D. Potter

    2014-12-01

    Full Text Available We report ab initio calculations for neutron drops in a 10 MeV external harmonic-oscillator trap using chiral nucleon–nucleon plus three-nucleon interactions. We present total binding energies, internal energies, radii and odd–even energy differences for neutron numbers N=2–18 using the no-core shell model with and without importance truncation. Furthermore, we present total binding energies for N=8,16,20,28,40,50 obtained in a coupled-cluster approach. Comparisons with quantum Monte Carlo results, where available, using Argonne v8′ with three-nucleon interactions reveal important dependences on the chosen Hamiltonian.

  2. Accelerating ab initio molecular dynamics simulations by linear prediction methods

    Science.gov (United States)

    Herr, Jonathan D.; Steele, Ryan P.

    2016-09-01

    Acceleration of ab initio molecular dynamics (AIMD) simulations can be reliably achieved by extrapolation of electronic data from previous timesteps. Existing techniques utilize polynomial least-squares regression to fit previous steps' Fock or density matrix elements. In this work, the recursive Burg 'linear prediction' technique is shown to be a viable alternative to polynomial regression, and the extrapolation-predicted Fock matrix elements were three orders of magnitude closer to converged elements. Accelerations of 1.8-3.4× were observed in test systems, and in all cases, linear prediction outperformed polynomial extrapolation. Importantly, these accelerations were achieved without reducing the MD integration timestep.

  3. Equations of state of heavy metals: ab initio approaches

    International Nuclear Information System (INIS)

    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)

  4. Ab initio Study of He Stability in hcp-Ti

    Institute of Scientific and Technical Information of China (English)

    DAI Yun-Ya; YANG Li; PENG Shu-Ming; LONG Xing-Gui; GAO Fei; ZU Xiao-Tao

    2010-01-01

    @@ The stability of He in hcp-Ti is studied using the ab initio method based on the density functional theory.The results indicate that a single He atom prefers to occupy the tetrahedral site rather than the octahedral site.The interaction of He defects with Ti atoms is employed to explain the relative stabilities of He point defects in hcp-Ti.The relative stability of He defects in hcp-Ti is useful for He clustering and bubble nucleation in metal tritides,which provides the basis for development of improved atomistic models.

  5. Polymeric nitrogen in a graphene matrix: An ab initio study

    Science.gov (United States)

    Timoshevskii, V.; Ji, Wei; Abou-Rachid, Hakima; Lussier, Louis-Simon; Guo, H.

    2009-09-01

    A hybrid material where polymeric nitrogen chains are sandwiched between graphene sheets in the form of a three-dimensional crystal, is predicted by means of ab initio simulations. It is demonstrated that chainlike polymeric nitrogen phase becomes stable at ambient pressure when intercalated in a multilayer graphene matrix. The physical origin of this stabilization is identified by studying the electronic properties of the system. This approach of stabilizing polymeric nitrogen by means of external three-dimensional matrix constitutes a path toward synthesizing different types of nitrogen-based high-energy materials.

  6. Ab-initio study of transition metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Ramesh [Dept. of Physics, Feroze Gandhi Insititute of Engineering and Technology, Raebareli-229001 (India); Shukla, Seema, E-mail: sharma.yamini62@gmail.com; Dwivedi, Shalini, E-mail: sharma.yamini62@gmail.com; Sharma, Yamini, E-mail: sharma.yamini62@gmail.com [Theoretical Condensed Matter Physics Laboratory, Dept. of Physics Feroze Gandhi College, Raebareli-229001 (India)

    2014-04-24

    We have performed ab initio self consistent calculations based on Full potential linearized augmented plane wave (FP-LAPW) method to investigate the optical and thermal properties of yttrium hydrides. From the band structure and density of states, the optical absorption spectra and specific heats have been calculated. The band structure of Yttrium metal changes dramatically due to hybridization of Y sp orbitals with H s orbitals and there is a net charge transfer from metal to hydrogen site. The electrical resistivity and specific heats of yttrium hydrides are lowered but the thermal conductivity is slightly enhanced due to increase in scattering from hydrogen sites.

  7. 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......3C2, and Ti6C5) are found to be ground state configurations. Their stability has been verified by full-potential total energy calculations of the fully relaxed structures....

  8. Accelerating Ab Initio Nuclear Physics Calculations with GPUs

    CERN Document Server

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

    2014-01-01

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

  9. Ab initio intermolecular potential energy surface of He-LiH

    Institute of Scientific and Technical Information of China (English)

    鄢国森; 杨明晖; 谢代前

    1997-01-01

    The intermolecular potential energy surface of He-LiH complex was studied using the full-electronic complete forth-order Miller-Plesset perturbation (MPPT) method.In ab initio calculations,the bond length of LiH was fixed at 0 159 5 nm.The potential has two local minima of Vm=-179.93 cm for the linear He LiH geormetrv at Rm=0.227 nm and Vm=-10.44 cm-1 for the linear He-HL1 geometry at Rm=0.516 nm The potemal exhibits strong anisotropy The analytic potential function with 31 parameters was determined by fitting to the calculated ab,mtio potentials The influence of variation of LiH bond length on the potential energy surface was also studied

  10. Ab initio and phenomenological studies of the static response of neutron matter

    CERN Document Server

    Buraczynski, Mateusz

    2016-01-01

    We investigate the problem of periodically modulated strongly interacting neutron matter. We carry out ab initio non-perturbative auxiliary-field diffusion Monte Carlo calculations using an external sinusoidal potential in addition to phenomenological two- and three-nucleon interactions. Several choices for the wave function ansatz are explored and special care is taken to extrapolate finite-sized results to the thermodynamic limit. We perform calculations at various densities as well as at different strengths and periodicities of the one-body potential. Our microscopic results are then used to constrain the isovector term from energy-density functional theories of nuclei at many different densities, while making sure to separate isovector contributions from bulk properties. Lastly, we use our results to extract the static density-density linear response function of neutron matter at different densities. Our findings provide insights into inhomogeneous neutron matter and are related to the physics of neutron-...

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

    Science.gov (United States)

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

    2016-03-01

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

  12. 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...... been determined in perturbation calculations. The electronic ground state is confirmed as being 4 . The chemical bond of MoN has triple bond character due to the approximately fully occupied delocalized bonding and orbitals. The spectroscopic constants for the ground state and ten excited states have...... been derived. The excited doublet states, 2 , 2 , 2 , and 2 + are found to be lower lying than the 4 state that has been investigated experimentally. Elaborate multi configuration configuration interaction (MRCI) calculations have been carried out for the states 4 and 4 using various basis sets...

  13. Ab Initio Protein Structure Prediction Using Pathway Models

    Directory of Open Access Journals (Sweden)

    Christopher Bystroff

    2006-04-01

    Full Text Available Ab initio prediction is the challenging attempt to predict protein structures based only on sequence information and without using templates. It is often divided into two distinct sub-problems: (a the scoring function that can distinguish native, or native-like structures, from non-native ones; and (b the method of searching the conformational space. Currently, there is no reliable scoring function that can always drive a search to the native fold, and there is no general search method that can guarantee a significant sampling of near-natives. Pathway models combine the scoring function and the search. In this short review, we explore some of the ways pathway models are used in folding, in published works since 2001, and present a new pathway model, HMMSTR-CM, that uses a fragment library and a set of nucleation/propagation-based rules. The new method was used for ab initio predictions as part of CASP5. This work was presented at the Winter School in Bioinformatics, Bologna, Italy, 10–14 February 2003.

  14. Ab initio dynamics of the cytochrome P450 hydroxylation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Elenewski, Justin E.; Hackett, John C, E-mail: jchackett@vcu.edu [Department of Physiology and Biophysics and The Massey Cancer Center, School of Medicine, Virginia Commonwealth University, 401 College Street, Richmond, Virginia 23219-1540 (United States)

    2015-02-14

    The iron(IV)-oxo porphyrin π-cation radical known as Compound I is the primary oxidant within the cytochromes P450, allowing these enzymes to affect the substrate hydroxylation. In the course of this reaction, a hydrogen atom is abstracted from the substrate to generate hydroxyiron(IV) porphyrin and a substrate-centered radical. The hydroxy radical then rebounds from the iron to the substrate, yielding the hydroxylated product. While Compound I has succumbed to theoretical and spectroscopic characterization, the associated hydroxyiron species is elusive as a consequence of its very short lifetime, for which there are no quantitative estimates. To ascertain the physical mechanism underlying substrate hydroxylation and probe this timescale, ab initio molecular dynamics simulations and free energy calculations are performed for a model of Compound I catalysis. Semiclassical estimates based on these calculations reveal the hydrogen atom abstraction step to be extremely fast, kinetically comparable to enzymes such as carbonic anhydrase. Using an ensemble of ab initio simulations, the resultant hydroxyiron species is found to have a similarly short lifetime, ranging between 300 fs and 3600 fs, putatively depending on the enzyme active site architecture. The addition of tunneling corrections to these rates suggests a strong contribution from nuclear quantum effects, which should accelerate every step of substrate hydroxylation by an order of magnitude. These observations have strong implications for the detection of individual hydroxylation intermediates during P450 catalysis.

  15. AB INITIO SIMULATIONS FOR MATERIAL PROPERTIES ALONG THE JUPITER ADIABAT

    International Nuclear Information System (INIS)

    We determine basic thermodynamic and transport properties of hydrogen-helium-water mixtures for the extreme conditions along Jupiter's adiabat via ab initio simulations, which are compiled in an accurate and consistent data set. In particular, we calculate the electrical and thermal conductivity, the shear and longitudinal viscosity, and diffusion coefficients of the nuclei. We present results for associated quantities like the magnetic and thermal diffusivity and the kinematic shear viscosity along an adiabat that is taken from a state-of-the-art interior structure model. Furthermore, the heat capacities, the thermal expansion coefficient, the isothermal compressibility, the Grüneisen parameter, and the speed of sound are calculated. We find that the onset of dissociation and ionization of hydrogen at about 0.9 Jupiter radii marks a region where the material properties change drastically. In the deep interior, where the electrons are degenerate, many of the material properties remain relatively constant. Our ab initio data will serve as a robust foundation for applications that require accurate knowledge of the material properties in Jupiter's interior, e.g., models for the dynamo generation.

  16. Ab initio and kinetic modeling studies of formic acid oxidation

    DEFF Research Database (Denmark)

    Marshall, Paul; Glarborg, Peter

    2015-01-01

    A detailed chemical kinetic model for oxidation of formic acid (HOCHO) in flames has been developed, based on theoretical work and data from literature. Ab initio calculations were used to obtain rate coefficients for reactions of HOCHO with H, O, and HO2. Modeling predictions with the mechanism ...... as the fate of HOCO, determines the oxidation rate of formic acid. At lower temperatures HO2, formed from HOCO + O2, is an important chain carrier and modeling predictions become sensitive to the HOCHO + HO2 reaction. © 2014 The Combustion Institute.......A detailed chemical kinetic model for oxidation of formic acid (HOCHO) in flames has been developed, based on theoretical work and data from literature. Ab initio calculations were used to obtain rate coefficients for reactions of HOCHO with H, O, and HO2. Modeling predictions with the mechanism...... on calculations with the kinetic model. Formic acid is consumed mainly by reaction with OH, yielding OCHO, which dissociates rapidly to CO2 + H, and HOCO, which may dissociate to CO + OH or CO2 + H, or react with H, OH, or O2 to form more stable products. The branching fraction of the HOCHO + OH reaction, as well...

  17. Toward Chemical Accuracy in the Description of Ion-Water Interactions through Many-Body Representations. I. Halide-Water Dimer Potential Energy Surfaces.

    Science.gov (United States)

    Bajaj, Pushp; Götz, Andreas W; Paesani, Francesco

    2016-06-14

    Despite recent progress, a unified understanding of how ions affect the structure and dynamics of water across different phases remains elusive. Here, we report the development of full-dimensional many-body potential energy functions, called MB-nrg (Many-Body-energy), for molecular simulations of halide ion-water systems from the gas phase to the condensed phase. The MB-nrg potentials are derived entirely from "first-principles" calculations carried out at the F12 explicitly correlated coupled-cluster level including single, double, and perturbative triple excitations, CCSD(T)-F12, in the complete basis set limit. Building upon the functional form of the MB-pol water potential, the MB-nrg potentials are expressed through the many-body expansion of the total energy in terms of explicit contributions representing one-body, two-body, and three-body interactions, with all higher-order contributions being described by classical induction. The specific focus of this study is on the MB-nrg two-body terms representing the full-dimensional potential energy surfaces (PESs) of the corresponding H2O-X(-) dimers, with X(-)= F(-), Cl(-), Br(-), and I(-). The accuracy of the MB-nrg PESs is systematically assessed through extensive comparisons with results obtained using both ab initio models and polarizable force fields for energies, structures, and harmonic frequencies of the H2O-X(-) dimers. PMID:27145081

  18. Ab Initio Many-Electron Calculation of Hyperfast Time-Resolved Coherent Excitation and Decay Of Polyelectronic Atoms

    International Nuclear Information System (INIS)

    The theoretical quantitative understanding of time-resolved processes of coherent excitation and decay in polyelectronic atoms, induced by hypershort electromagnetic pulses, is a prerequisite for their possible control. We review key elements of an approach to the ab initio determination of perturbative as well as of nonperturbative solutions of the time-dependent Schroedinger equation describing such processes. The essential element of this approach is the development of formalism and methods that utilize physically relevant state-specific wavefunctions of stationary states of the discrete and the continuous spectrum

  19. Many-body Propagator Theory with Three-Body Interactions: a Path to Exotic Open Shell Isotopes

    CERN Document Server

    Barbieri, C

    2014-01-01

    Ab-initio predictions of nuclei with masses up to A~100 or more is becoming possible thanks to novel advances in computations and in the formalism of many-body physics. Some of the most fundamental issues include how to deal with many-nucleon interactions, how to calculate degenerate--open shell--systems, and pursuing ab-initio approaches to reaction theory. Self-consistent Green's function (SCGF) theory is a natural approach to address these challenges. Its formalism has recently been extended to three- and many-body interactions and reformulated within the Gorkov framework to reach semi-magic open shell isotopes. These exciting developments, together with the predictive power of chiral nuclear Hamiltonians, are opening the path to understanding large portions of the nuclear chart, especially within the $sd$ and $pf$ shells. The present talk reviews the most recent advances in ab-initio nuclear structure and many-body theory that have been possible through the SCGF approach.

  20. Three-particle correlation from a Many-Body Perspective: Trions in a Carbon Nanotube

    OpenAIRE

    Deilmann, Thorsten; Drüppel, Matthias; Rohlfing, Michael

    2016-01-01

    Trion states of three correlated particles (e.g., two electrons and one hole) are essential to understand the optical spectra of doped or gated nanostructures, like carbon nanotubes or transition-metal dichalcogenides. We develop a theoretical many-body description for such correlated states using an ab-initio approach. It can be regarded as an extension of the widely used $GW$ method and Bethe-Salpeter equation, thus allowing for a direct comparison with excitons. We apply this method to a s...

  1. Ab initio-driven nuclear energy density functional method. A proposal for safe/correlated/improvable parametrizations of the off-diagonal EDF kernels

    Energy Technology Data Exchange (ETDEWEB)

    Duguet, T. [IRFU/Service de Physique Nucleaire, CEA, Centre de Saclay, Gif-sur-Yvette (France); Instituut voor Kern- en Stralingsfysica, KU Leuven, Leuven (Belgium); Michigan State University, National Superconducting Cyclotron Laboratory and Department of Physics and Astronomy, East Lansing, MI (United States); Bender, M. [Centre d' Etudes Nucleaires de Bordeaux Gradignan, Universite Bordeaux, UMR5797, Gradignan (France); Centre d' Etudes Nucleaires de Bordeaux Gradignan, CNRS/IN2P3, UMR5797, Gradignan (France); Ebran, J.P. [CEA, DAM, DIF, Arpajon (France); Lesinski, T.; Soma, V. [IRFU/Service de Physique Nucleaire, CEA, Centre de Saclay, Gif-sur-Yvette (France)

    2015-12-15

    This programmatic paper lays down the possibility to reconcile the necessity to resum many-body correlations into the energy kernel with the fact that safe multi-reference energy density functional (EDF) calculations cannot be achieved whenever the Pauli principle is not enforced, as is for example the case when many-body correlations are parametrized under the form of empirical density dependencies. Our proposal is to exploit a newly developed ab initio many-body formalism to guide the construction of safe, explicitly correlated and systematically improvable parametrizations of the off-diagonal energy and norm kernels that lie at the heart of the nuclear EDF method. The many-body formalism of interest relies on the concepts of symmetry breaking and restoration that have made the fortune of the nuclear EDF method and is, as such, amenable to this guidance. After elaborating on our proposal, we briefly outline the project we plan to execute in the years to come. (orig.)

  2. The ab-initio density matrix renormalization group in practice

    Energy Technology Data Exchange (ETDEWEB)

    Olivares-Amaya, Roberto; Hu, Weifeng; Sharma, Sandeep; Yang, Jun; Chan, Garnet Kin-Lic [Department of Chemistry, Princeton University, Princeton, New Jersey 08544 (United States); Nakatani, Naoki [Department of Chemistry, Princeton University, Princeton, New Jersey 08544 (United States); Catalysis Research Center, Hokkaido University, Kita 21 Nishi 10, Sapporo, Hokkaido 001-0021 (Japan)

    2015-01-21

    The ab-initio density matrix renormalization group (DMRG) is a tool that can be applied to a wide variety of interesting problems in quantum chemistry. Here, we examine the density matrix renormalization group from the vantage point of the quantum chemistry user. What kinds of problems is the DMRG well-suited to? What are the largest systems that can be treated at practical cost? What sort of accuracies can be obtained, and how do we reason about the computational difficulty in different molecules? By examining a diverse benchmark set of molecules: π-electron systems, benchmark main-group and transition metal dimers, and the Mn-oxo-salen and Fe-porphine organometallic compounds, we provide some answers to these questions, and show how the density matrix renormalization group is used in practice.

  3. Ab initio study of the transition-metal carbene cations

    Institute of Scientific and Technical Information of China (English)

    李吉海; 冯大诚; 冯圣玉

    1999-01-01

    The geometries and bonding characteristics of the first-row transition-metal carbene cations MCH2+ were investigated by ab initio molecular orbital theory (HF/LANL2DZ). All of MCH2+ are coplanar. In the closed shell structures the C bonds to M with double bonds; while in the open shell structures the partial double bonds are formed, because one of the σ and π orbitals is singly occupied. It is mainly the π-type overlap between the 2px orbital of C and 4px, 3dxz, orbitals of M+ that forms the π orbitals. The dissociation energies of C—M bond appear in periodic trend from Sc to Cu. Most of the calculated bond dissociation energies are close to the experimental ones.

  4. High-throughput ab-initio dilute solute diffusion database.

    Science.gov (United States)

    Wu, Henry; Mayeshiba, Tam; Morgan, Dane

    2016-01-01

    We demonstrate automated generation of diffusion databases from high-throughput density functional theory (DFT) calculations. A total of more than 230 dilute solute diffusion systems in Mg, Al, Cu, Ni, Pd, and Pt host lattices have been determined using multi-frequency diffusion models. We apply a correction method for solute diffusion in alloys using experimental and simulated values of host self-diffusivity. We find good agreement with experimental solute diffusion data, obtaining a weighted activation barrier RMS error of 0.176 eV when excluding magnetic solutes in non-magnetic alloys. The compiled database is the largest collection of consistently calculated ab-initio solute diffusion data in the world. PMID:27434308

  5. Transport coefficients in diamond from ab-initio calculations

    Science.gov (United States)

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

    2013-03-01

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

  6. Efficient Ab initio Modeling of Random Multicomponent Alloys

    Science.gov (United States)

    Jiang, Chao; Uberuaga, Blas P.

    2016-03-01

    We present in this Letter a novel small set of ordered structures (SSOS) method that allows extremely efficient ab initio modeling of random multicomponent alloys. Using inverse II-III spinel oxides and equiatomic quinary bcc (so-called high entropy) alloys as examples, we demonstrate that a SSOS can achieve the same accuracy as a large supercell or a well-converged cluster expansion, but with significantly reduced computational cost. In particular, because of this efficiency, a large number of quinary alloy compositions can be quickly screened, leading to the identification of several new possible high-entropy alloy chemistries. The SSOS method developed here can be broadly useful for the rapid computational design of multicomponent materials, especially those with a large number of alloying elements, a challenging problem for other approaches.

  7. Ab initio electronic structure and optical conductivity of bismuth tellurohalides

    CERN Document Server

    Schwalbe, Sebastian; Starke, Ronald; Schober, Giulio A H; Kortus, Jens

    2016-01-01

    We investigate the electronic structure, dielectric and optical properties of bismuth tellurohalides BiTeX (X = I, Cl, Br) by means of all-electron density functional theory. In particular, we present the ab initio conductivities and dielectric tensors calculated over a wide frequency range, and compare our results with the recent measurements by Akrap et al. , Makhnev et al. , and Rusinov et al. . We show how the low-frequency branch of the optical conductivity can be used to identify characteristic intra- and interband transitions between the Rashba spin-split bands in all three bismuth tellurohalides. We further calculate the refractive indices and dielectric constants, which in turn are systematically compared to previous predictions and measurements. We expect that our quantitative analysis will contribute to the general assessment of bulk Rashba materials for their potential use in spintronics devices.

  8. Ab initio H2O in realistic hydrophilic confinement.

    Science.gov (United States)

    Allolio, Christoph; Klameth, Felix; Vogel, Michael; Sebastiani, Daniel

    2014-12-15

    A protocol for the ab initio construction of a realistic cylindrical pore in amorphous silica, serving as a geometric nanoscale confinement for liquids and solutions, is presented. Upon filling the pore with liquid water at different densities, the structure and dynamics of the liquid inside the confinement can be characterized. At high density, the pore introduces long-range oscillations into the water density profile, which makes the water structure unlike that of the bulk across the entire pore. The tetrahedral structure of water is also affected up to the second solvation shell of the pore wall. Furthermore, the effects of the confinement on hydrogen bonding and diffusion, resulting in a weakening and distortion of the water structure at the pore walls and a slowdown in diffusion, are characterized. PMID:25208765

  9. Quantum plasmonics: from jellium models to ab initio calculations

    Directory of Open Access Journals (Sweden)

    Varas Alejandro

    2016-08-01

    Full Text Available Light-matter interaction in plasmonic nanostructures is often treated within the realm of classical optics. However, recent experimental findings show the need to go beyond the classical models to explain and predict the plasmonic response at the nanoscale. A prototypical system is a nanoparticle dimer, extensively studied using both classical and quantum prescriptions. However, only very recently, fully ab initio time-dependent density functional theory (TDDFT calculations of the optical response of these dimers have been carried out. Here, we review the recent work on the impact of the atomic structure on the optical properties of such systems. We show that TDDFT can be an invaluable tool to simulate the time evolution of plasmonic modes, providing fundamental understanding into the underlying microscopical mechanisms.

  10. Highly anisotropic thermal conductivity of arsenene: An ab initio study

    Science.gov (United States)

    Zeraati, Majid; Vaez Allaei, S. Mehdi; Abdolhosseini Sarsari, I.; Pourfath, Mahdi; Donadio, Davide

    2016-02-01

    Elemental two-dimensional (2D) materials exhibit intriguing heat transport and phononic properties. Here we have investigated the lattice thermal conductivity of newly proposed arsenene, the 2D honeycomb structure of arsenic, using ab initio calculations. Solving the Boltzmann transport equation for phonons, we predict a highly anisotropic thermal conductivity of 30.4 and 7.8 W/mK along the zigzag and armchair directions, respectively, at room temperature. Our calculations reveal that phonons with mean free paths between 20 nm and 1 μ m provide the main contribution to the large thermal conductivity in the zigzag direction; mean free paths of phonons contributing to heat transport in the armchair directions range between 20 and 100 nm. The obtained anisotropic thermal conductivity and feasibility of synthesis, in addition to high electron mobility reported elsewhere, make arsenene a promising material for nanoelectronic applications and thermal management.

  11. Molecular ion LiHe+: ab initio study

    International Nuclear Information System (INIS)

    Highlights: ► Excited electronic states of LiHe+ are studied. ► Potential energy curves of thirteen states are calculated. ► Dipole moment and transition dipole moment functions are determined. ► Basic spectroscopic properties of the electronic states are derived. - Abstract: High level ab initio calculations are performed on the molecular ion LiHe+. Potential energy curves for the low-lying singlet and triplet electronic states are calculated using the multi-reference configuration interaction and single-reference coupled cluster methods with large basis sets. The corresponding dipole moments and transition dipole moments functions are also determined. The basic spectroscopic properties and excitation energies of the electronic states are derived from rovibrational bound state calculations.

  12. Ab initio methods for electron-molecule collisions

    International Nuclear Information System (INIS)

    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

  13. An Efficient Approach to Ab Initio Monte Carlo Simulation

    CERN Document Server

    Leiding, Jeff

    2013-01-01

    We present a Nested Markov Chain Monte Carlo (NMC) scheme for building equilibrium averages based on accurate potentials such as density functional theory. Metropolis sampling of a reference system, defined by an inexpensive but approximate potential, is used to substantially decorrelate configurations at which the potential of interest is evaluated, thereby dramatically reducing the number needed to build ensemble averages at a given level of precision. The efficiency of this procedure is maximized on-the-fly through variation of the reference system thermodynamic state (characterized here by its inverse temperature \\beta^0), which is otherwise unconstrained. Local density approximation (LDA) results are presented for shocked states in argon at pressures from 4 to 60 GPa. Depending on the quality of the reference potential, the acceptance probability is enhanced by factors of 1.2-28 relative to unoptimized NMC sampling, and the procedure's efficiency is found to be competitive with that of standard ab initio...

  14. Ab-initio melting curve and principal Hugoniot of tantalum

    International Nuclear Information System (INIS)

    We report first principles calculations of the melting curve and principal Hugoniot (P - V curve) of body centered cubic (bcc) tantalum in the pressure range 0-300 GPa. A description of lattice dynamics and thermal properties of bcc Ta using finite temperature density functional theory (DFT) is presented. The approach works within the projector augmented wave (PAW) implementation of DFT and explicitly treats in valence the 5p, 6s and 5d electrons. The principal Hugoniot (P - V curve), obtained using the Rankine-Hugoniot equation, is investigated using the generalized gradient approximations (GGA). Very good agreement with the shock experiments is obtained with GGA in all the range of pressure. We also report the temperature-pressure relation on the shock Hugoniot and the full ab-initio melting curve of Ta

  15. Ab Initio Study of KCl and NaCl Clusters

    Science.gov (United States)

    Brownrigg, Clifton; Hira, Ajit; Pacheco, Jose; Salazar, Justin

    2013-03-01

    We continue our interest in the theoretical study of molecular clusters to examine the chemical properties of small KnCln and NanCln clusters (n = 2 - 15). The potentially important role of these molecular species in biochemical and medicinal processes is well known. This work applies the hybrid ab initio methods of quantum chemistry to derive the different alkali-halide (MnHn) geometries. Of particular interest is the competition between hexagonal ring geometries and rock salt structures. Electronic energies, rotational constants, dipole moments, and vibrational frequencies for these geometries are calculated. Magic numbers for cluster stability are identified and are related to the property of cluster compactness. Mapping of the singlet, triplet, and quintet, potential energy surfaces is performed. Calculations have been performed to examine the interactions of these clusters with some atoms and molecules of biological interest, including O, O2, and Fe. The potential for design of new medicinal drugs is explored.

  16. Ab initio electronic stopping power of protons in bulk materials

    Science.gov (United States)

    Shukri, Abdullah Atef; Bruneval, Fabien; Reining, Lucia

    2016-01-01

    The electronic stopping power is a crucial quantity for ion irradiation: it governs the deposited heat, the damage profile, and the implantation depth. Whereas experimental data are readily available for elemental solids, the data are much more scarce for compounds. Here we develop a fully ab initio computational scheme based on linear response time-dependent density-functional theory to predict the random electronic stopping power (RESP) of materials without any empirical fitting. We show that the calculated RESP compares well with experimental data, when at full convergence, with the inclusion of the core states and of the exchange correlation. We evaluate the unexpectedly limited magnitude of the nonlinear terms in the RESP by comparing with other approaches based on the time propagation of time-dependent density-functional theory. Finally, we check the validity of a few empirical rules of thumbs that are commonly used to estimate the electronic stopping power.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-12-14

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

  18. Ab initio study of II-(VI){sub 2} dichalcogenides

    Energy Technology Data Exchange (ETDEWEB)

    Olsson, P; Vidal, J; Lincot, D, E-mail: polsson@kth.se [Institut de R and D sur l' energie photovoltaique (IRDEP), UMR 7174-EDF-CNRS-ENSCP, 6 quai Watier, 78401 Chatou Cedex (France)

    2011-10-12

    The structural stabilities of the (Zn,Cd)(S,Se,Te){sub 2} dichalcogenides have been determined ab initio. These compounds are shown to be stable in the pyrite phase, in agreement with available experiments. Structural parameters for the ZnTe{sub 2} pyrite semiconductor compound proposed here are presented. The opto-electronic properties of these dichalcogenide compounds have been calculated using quasiparticle GW theory. Bandgaps, band structures and effective masses are proposed as well as absorption coefficients and refraction indices. The compounds are all indirect semiconductors with very flat conduction band dispersion and high absorption coefficients. The work functions and surface properties are predicted. The Te and Se based compounds could be of interest as absorber materials in photovoltaic applications. (paper)

  19. Ab initio Potential Energy Surface for H-H2

    Science.gov (United States)

    Partridge, Harry; Bauschlicher, Charles W., Jr.; Stallcop, James R.; Levin, Eugene

    1993-01-01

    Ab initio calculations employing large basis sets are performed to determine an accurate potential energy surface for H-H2 interactions for a broad range of separation distances. At large distances, the spherically averaged potential determined from the calculated energies agrees well with the corresponding results determined from dispersion coefficients; the van der Waals well depth is predicted to be 75 +/- (mu)E(sub h). Large basis sets have also been applied to reexamine the accuracy of theoretical repulsive potential energy surfaces. Multipolar expansions of the computed H-H2 potential energy surface are reported for four internuclear separation distances (1.2, 1.401, 1.449, and 1.7a(sub 0) of the hydrogen molecule. The differential elastic scattering cross section calculated from the present results is compared with the measurements from a crossed beam experiment.

  20. Ab initio investigation of the mechanical properties of copper

    Institute of Scientific and Technical Information of China (English)

    Liu Yue-Lin; Gui Li-Jiang; Jin Shuo

    2012-01-01

    Employing the ab initio total energy method based on the density functional theory with the generalized gradient approximation,we have systematically investigated the theoretical mechanical properties of copper (Cu).The theoretical tensile strengths are calculated to be 25.3 GPa,5.9 GPa,and 37.6 GPa for the fcc Cu single crystal in the [001],[110],and [111] directions,respectively.Among the three directions,the [110] direction is the weakest one due to the occurrence of structure transition at the lower strain and the weakest interaction of atoms between the (110) planes,while the [111] direction is the strongest direction because of the strongest interaction of atoms between the (111) planes.In terms of the elastic constants of Cu single crystal,we also estimate some mechanical quantities of polycrystalline Cu,including bulk modulus B,shear modulus G,Young's modulus Ep,and Poisson's ratio v.

  1. Ab Initio Prediction of 29Si-NMR Chemical Shifts

    Institute of Scientific and Technical Information of China (English)

    CHU Shidong; LI Yingxia; SONG Ni; GUAN Huashi

    2002-01-01

    The ability of several ab initio models to predict experimental 29Si-NMR chemical shift is examined. The shielding values of trimethylsilyl chloride (A), t-butyldimethylsilyl chloride (B) and allyltrimethylsilane (C) are calculated by GIAO, CSGT and IGAIM methods, using HF/6-31G*, B3LYP/6-31G*, HF/6-311+G**, B3LYP/6-311+G** and MPWlPW91/6-311+G** models respectively. The 29Si chemical shifts calculated by GIAO method using HF/6-311+G**model are highly in agreement with those obtained experimentally. All of the models above reproduce the trends of chemical shifts in all cases studied, suggesting that the models are of practical value.

  2. A Review on Ab Initio Approaches for Multielectron Dynamics

    CERN Document Server

    Ishikawa, Kenichi L

    2015-01-01

    In parallel with the evolution of femtosecond and attosecond laser as well as free-electron laser technology, a variety of theoretical methods have been developed to describe the behavior of atoms, molecules, clusters, and solids under the action of those laser pulses. Here we review major ab initio wave-function-based numerical approaches to simulate multielectron dynamics in atoms and molecules driven by intense long-wavelength and/or ultrashort short-wavelength laser pulses. Direct solution of the time-dependent Schr\\"odinger equation (TDSE), though its applicability is limited to He, ${\\rm H}_2$, and Li, can provide an exact description and has been greatly contributing to the understanding of dynamical electron-electron correlation. Multiconfiguration self-consistent-field (MCSCF) approach offers a flexible framework from which a variety of methods can be derived to treat both atoms and molecules, with possibility to systematically control the accuracy. The equations of motion of configuration interactio...

  3. Ab initio quantum dynamics using coupled-cluster.

    Science.gov (United States)

    Kvaal, Simen

    2012-05-21

    The curse of dimensionality (COD) limits the current state-of-the-art ab initio propagation methods for non-relativistic quantum mechanics to relatively few particles. For stationary structure calculations, the coupled-cluster (CC) method overcomes the COD in the sense that the method scales polynomially with the number of particles while still being size-consistent and extensive. We generalize the CC method to the time domain while allowing the single-particle functions to vary in an adaptive fashion as well, thereby creating a highly flexible, polynomially scaling approximation to the time-dependent Schrödinger equation. The method inherits size-consistency and extensivity from the CC method. The method is dubbed orbital-adaptive time-dependent coupled-cluster, and is a hierarchy of approximations to the now standard multi-configurational time-dependent Hartree method for fermions. A numerical experiment is also given. PMID:22612082

  4. Ab initio engineering of materials with stacked hexagonal tin frameworks

    Science.gov (United States)

    Shao, Junping; Beaufils, Clément; Kolmogorov, Aleksey N.

    2016-01-01

    The group-IV tin has been hypothesized to possess intriguing electronic properties in an atom-thick hexagonal form. An attractive pathway of producing sizable 2D crystallites of tin is based on deintercalation of bulk compounds with suitable tin frameworks. Here, we have identified a new synthesizable metal distannide, NaSn2, with a 3D stacking of flat hexagonal layers and examined a known compound, BaSn2, with buckled hexagonal layers. Our ab initio results illustrate that despite being an exception to the 8-electron rule, NaSn2 should form under pressures easily achievable in multi-anvil cells and remain (meta)stable under ambient conditions. Based on calculated Z2 invariants, the predicted NaSn2 may display topologically non-trivial behavior and the known BaSn2 could be a strong topological insulator. PMID:27387140

  5. Ab initio Molecular Dynamics Study on Small Carbon Nanotubes

    Institute of Scientific and Technical Information of China (English)

    叶林晖; 刘邦贵; 王鼎盛

    2001-01-01

    Ab initio molecular dynamics simulations are performed on small single wall nanotubes. By structural relaxation,the equilibrium C-C bond lengths and bond angles are determined. Our result shows that for both zigzag and armchair nanotubes there are two nonequivalent bond lengths. One bond stretches from that of the graphene sheet, while the other shrinks. Small variations on bond angles are also shown. Energy bands are calculated for the optimized structures. It is found that the intrinsic curvature of the very small nanotube greatly modifies the energy band which can no longer be well described in the tight-binding zone-folding picture. In our calculation very small nanotubes are metallic. The energy per atom fits quite well with the relation of E(R) = E0 + f/R2 even for the extreme small radius. The implications of the results on the properties of small nanotubes are discussed.

  6. Ab initio quasiparticle bandstructure of ABA and ABC-stacked graphene trilayers

    Science.gov (United States)

    Menezes, Marcos; Capaz, Rodrigo; Louie, Steven

    2013-03-01

    We obtain the quasiparticle band structure of ABA and ABC-stacked graphene trilayers through ab initio density functional theory (DFT) and many-body quasiparticle calculations within the GW approximation. To interpret our results, we fit the DFT and GW π bands to a low energy tight-binding model, which is found to reproduce very well the observed features near the K point. The values of the extracted hopping parameters are reported and compared with available theoretical and experimental data. For both stackings, the quasiparticle corrections lead to a renormalization of the Fermi velocity, an effect also observed in previous calculations on monolayer graphene. They also increase the separation between the higher energy bands, which is proportional to the nearest neighbor interlayer hopping parameter γ1. Both features are brought to closer agreement with experiment through the quasiparticle corrections. Finally, other effects, such as trigonal warping, electron-hole assymetry and energy gaps are discussed in terms of the associated parameters. This work was supported by the Brazilian funding agencies: CAPES, CNPq, FAPERJ and INCT-Nanomateriais de Carbono. It was also supported by NSF grant No. DMR10-1006184 and U.S. DOE under Contract No. DE-AC02-05CH11231.

  7. Ab Initio Excited States from the In-Medium Similarity Renormalization Group

    CERN Document Server

    Parzuchowski, N M; Bogner, S K

    2016-01-01

    We present two new methods for performing \\emph{ab initio} calculations of excited states for closed-shell systems within the in-medium similarity renormalization group (IMSRG) framework. Both are based on combining the IMSRG with simple many-body methods commonly used to target excited states, such as the Tamm-Dancoff approximation (TDA) and equations-of-motion (EOM) techniques. In the first approach, a two-step sequential IMSRG transformation is used to drive the Hamiltonian to a form where a simple TDA calculation (i.e., diagonalization in the space of $1$p$1$h excitations) becomes exact for a subset of eigenvalues. In the second approach, equations-of-motion (EOM) techniques are applied to the ground-state-decoupled IMSRG Hamiltonian to access excited states. We perform proof-of-principle calculations for parabolic quantum dots in two-dimensions and the closed shell nuclei $^{16}$O and $^{22}$O. We find that the TDA-IMSRG approach gives better accuracy than the EOM-IMSRG when calculations converge, but is...

  8. Ab initio modeling of the optical properties in organometallic halide perovskites for photovoltaic applications

    Science.gov (United States)

    Neukirch, Amanda; Nei, Wanyi; Pedesseau, Laurent; Even, Jacky; Katan, Claudine; Mohite, Aditya; Tretiak, Segrei

    2015-03-01

    The need for an inexpensive, clean, and plentiful source of energy has generated large amounts of research in an assortment of solution processed organic and hybrid organic-inorganic solar cells. A relative newcomer to the field of solution processed photovoltaics is the lead halide perovskite solar cell. In the past 5 years, the efficiencies of devices made from this material have increased from 3.5% to nearly 20%. Despite the rapid development of organic-inorganic perovskite solar cells, a thorough understanding of the fundamental photophysical processes driving the high performance of these devices is not well understood. I am using state-of-the-art ab initio computational techniques in order to characterize the properties at the interface of perovskite devices in order to aide in materials design and device engineering. I will present an in-depth analysis of the electronic and optical properties of bulk and surface states of pure and mixed halide systems. The high-level static quantum mechanical calculations, including spin-orbit-coupling and the many body GW approach, identify the key electronic states involved in photoinduced dynamics. This knowledge provides important information on how the optical properties change with variations to the system. Supported by the DOE, the LANL LDRD program XW11, and CNLS.

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

    International Nuclear Information System (INIS)

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

  10. Ab Initio Enhanced calphad Modeling of Actinide-Rich Nuclear Fuels

    Energy Technology Data Exchange (ETDEWEB)

    Morgan, Dane [Univ. of Wisconsin, Madison, WI (United States); Yang, Yong Austin [Univ. of Wisconsin, Madison, WI (United States)

    2013-10-28

    The process of fuel recycling is central to the Advanced Fuel Cycle Initiative (AFCI), where plutonium and the minor actinides (MA) Am, Np, and Cm are extracted from spent fuel and fabricated into new fuel for a fast reactor. Metallic alloys of U-Pu-Zr-MA are leading candidates for fast reactor fuels and are the current basis for fast spectrum metal fuels in a fully recycled closed fuel cycle. Safe and optimal use of these fuels will require knowledge of their multicomponent phase stability and thermodynamics (Gibbs free energies). In additional to their use as nuclear fuels, U-Pu-Zr-MA contain elements and alloy phases that pose fundamental questions about electronic structure and energetics at the forefront of modern many-body electron theory. This project will validate state-of-the-art electronic structure approaches for these alloys and use the resulting energetics to model U-Pu-Zr-MA phase stability. In order to keep the work scope practical, researchers will focus on only U-Pu-Zr-{Np,Am}, leaving Cm for later study. The overall objectives of this project are to: Provide a thermodynamic model for U-Pu-Zr-MA for improving and controlling reactor fuels; and, Develop and validate an ab initio approach for predicting actinide alloy energetics for thermodynamic modeling.

  11. High-level ab initio computations of the absorption spectra of organic iridium complexes.

    Science.gov (United States)

    Plasser, Felix; Dreuw, Andreas

    2015-02-12

    The excited states of fac-tris(phenylpyridinato)iridium [Ir(ppy)3] and the smaller model complex Ir(C3H4N)3 are computed using a number of high-level ab initio methods, including the recently implemented algebraic diagrammatic construction method to third-order ADC(3). A detailed description of the states is provided through advanced analysis methods, which allow a quantification of different charge transfer and orbital relaxation effects and give extended insight into the many-body wave functions. Compared to the ADC(3) benchmark an unexpected striking difference of ADC(2) is found for Ir(C3H4N)3, which derives from an overstabilization of charge transfer effects. Time-dependent density functional theory (TDDFT) using the B3LYP functional shows an analogous but less severe error for charge transfer states, whereas the ωB97 results are in good agreement with ADC(3). Multireference configuration interaction computations, which are in reasonable agreement with ADC(3), reveal that static correlation does not play a significant role. In the case of the larger Ir(ppy)3 complex, results at the TDDFT/B3LYP and TDDFT/ωB97 levels of theory are presented. Strong discrepancies between the two functionals, which are found with respect to the energies, characters, as well as the density of the low lying states, are discussed in detail and compared to experiment. PMID:25584785

  12. Extended relativistic configuration interaction and many-body perturbation calculations of spectroscopic data for the $n \\leq 6$ configurationsin ne-like ions between Cr XV and Kr XXVII

    CERN Document Server

    Wang, Kai; Si, Ran; Jönsson, Per; Ekman, Jörgen; Guo, Xue Lin; Li, Shuang; Long, Fei Yun; Dang, Wei; Zhao, Xiao Hui; Hutton, Roger; Chen, Chong Yang; Yan, Jan; Yang, Xu

    2016-01-01

    Level energies, wavelengths, electric dipole, magnetic dipole, electric quadrupole, and magnetic quadrupole transition rates, oscillator strengths, and line strengths from combined relativistic configuration interaction and many-body perturbation calculations are reported for the 201 fine-structure states of the $2s^2 2p^6$, $2s^2 2p^5 3l$, $2s 2p^6 3l$, $2s^2 2p^5 4l$, $2s 2p^6 4l$, $2s^2 2p^5 5l$, and $2s^2 2p^5 6l$ configurations in all Ne-like ions between Cr XV and Kr XXVII. Calculated level energies and transition data are compared with experiments from the NIST and CHIANTI databases, and other recent benchmark calculations. The mean energy difference with the NIST experiments is only 0.05%. The present calculations significantly increase the amount of accurate spectroscopic data for the $n >3$ states in a number of Ne-like ions of astrophysics interest. A complete dataset should be helpful in analyzing new observations from the solar and other astrophysical sources, and is also likely to be useful for ...

  13. Extended Relativistic Configuration Interaction and Many-body Perturbation Calculations of Spectroscopic Data for the N ≤ 6 Configurations in Ne-like Ions between Cr xv and Kr xxvii

    Science.gov (United States)

    Wang, K.; Chen, Z. B.; Si, R.; Jönsson, P.; Ekman, J.; Guo, X. L.; Li, S.; Long, F. Y.; Dang, W.; Zhao, X. H.; Hutton, R.; Chen, C. Y.; Yan, J.; Yang, X.

    2016-10-01

    Level energies, wavelengths, electric dipole, magnetic dipole, electric quadrupole, and magnetic quadrupole transition rates, oscillator strengths, and line strengths from combined relativistic configuration interaction and many-body perturbation calculations are reported for the 201 fine-structure states of the 2{s}22{p}6, 2{s}22{p}53l, 2s2{p}63l, 2{s}22{p}54l, 2s2{p}64l, 2{s}22{p}55l, and 2{s}22{p}56l configurations in all Ne-like ions between Cr xv and Kr xxvii. Calculated level energies and transition data are compared with experiments from the National Institute of Standards and Technology (NIST) and CHIANTI databases, and other recent benchmark calculations. The mean energy difference with the NIST experiments is only 0.05%. The present calculations significantly increase the amount of accurate spectroscopic data for the n > 3 states in a number of Ne-like ions of astrophysical interest. A complete data set should be helpful for analyzing new observations from solar and other astrophysical sources, and is also likely to be useful for modeling and diagnosing a variety of plasmas, including astronomical and fusion plasma.

  14. Structure and lattice dynamics of GaN and AlN. Ab-initio investigations of strained polytypes and superlattices

    Energy Technology Data Exchange (ETDEWEB)

    Wagner, Jan-Martin

    2004-10-14

    In this dissertation, ab-initio investigations of the strain influence on vibrational properties of GaN and AlN as well as of short-period GaN/AlN superlattices are presented. Based on densityfunctional theory and density-functional perturbation theory, for differently strained structures complete phonon spectra and related properties are calculated using the local-density approximation and norm-conserving pseudopotentials. (orig.)

  15. Communication: Towards ab initio self-energy embedding theory in quantum chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Lan, Tran Nguyen, E-mail: latran@umich.edu [Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109 (United States); Department of Physics, University of Michigan, Ann Arbor, Michigan 48109 (United States); Kananenka, Alexei A.; Zgid, Dominika [Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109 (United States)

    2015-12-28

    The self-energy embedding theory (SEET), in which the active space self-energy is embedded in the self-energy obtained from a perturbative method treating the non-local correlation effects, was recently developed in our group. In SEET, the double counting problem does not appear and the accuracy can be improved either by increasing the perturbation order or by enlarging the active space. This method was first calibrated for the 2D Hubbard lattice showing promising results. In this paper, we report an extension of SEET to quantum chemical ab initio Hamiltonians for applications to molecular systems. The self-consistent second-order Green’s function method is used to describe the non-local correlations, while the full configuration interaction method is carried out to capture strong correlation within the active space. Using few proof-of-concept examples, we show that SEET yields results of comparable quality to n-electron valence state second-order perturbation theory with the same active space, and furthermore, the full active space can be split into smaller active spaces without further implementation. Moreover, SEET avoids intruder states and does not require any high-order reduced density matrices. These advantages show that SEET is a promising method to describe physical and chemical properties of challenging molecules requiring large active spaces.

  16. Towards ab initio self-energy embedding theory in quantum chemistry

    CERN Document Server

    Lan, Tran Nguyen; Zgid, Dominika

    2015-01-01

    The self-energy embedding theory (SEET), in which the active space self-energy is embedded in the self-energy obtained from a perturbative method treating the non-local correlation effects, was recently developed in our group. In SEET the double counting problem does not appear and the accuracy can be improved either by increasing the perturbation order or by enlarging the active space. This method was first calibrated for the 2D Hubbard lattice showing promising results. In this paper, we report an extension of SEET to quantum chemical ab initio Hamiltonians for applications to molecular systems. The self-consistent second-order Green's function (GF2) method is used to describe the non-local correlations, while the full configuration interaction (FCI) method is carried out to capture strong correlation within the active space. Using few proof-of-concept examples, we show that SEET yields results of comparable quality to $n-$electron valence state second-order perturbation theory (NEVPT2) with the same active...

  17. Communication: Towards ab initio self-energy embedding theory in quantum chemistry

    International Nuclear Information System (INIS)

    The self-energy embedding theory (SEET), in which the active space self-energy is embedded in the self-energy obtained from a perturbative method treating the non-local correlation effects, was recently developed in our group. In SEET, the double counting problem does not appear and the accuracy can be improved either by increasing the perturbation order or by enlarging the active space. This method was first calibrated for the 2D Hubbard lattice showing promising results. In this paper, we report an extension of SEET to quantum chemical ab initio Hamiltonians for applications to molecular systems. The self-consistent second-order Green’s function method is used to describe the non-local correlations, while the full configuration interaction method is carried out to capture strong correlation within the active space. Using few proof-of-concept examples, we show that SEET yields results of comparable quality to n-electron valence state second-order perturbation theory with the same active space, and furthermore, the full active space can be split into smaller active spaces without further implementation. Moreover, SEET avoids intruder states and does not require any high-order reduced density matrices. These advantages show that SEET is a promising method to describe physical and chemical properties of challenging molecules requiring large active spaces

  18. Communication: Towards ab initio self-energy embedding theory in quantum chemistry.

    Science.gov (United States)

    Lan, Tran Nguyen; Kananenka, Alexei A; Zgid, Dominika

    2015-12-28

    The self-energy embedding theory (SEET), in which the active space self-energy is embedded in the self-energy obtained from a perturbative method treating the non-local correlation effects, was recently developed in our group. In SEET, the double counting problem does not appear and the accuracy can be improved either by increasing the perturbation order or by enlarging the active space. This method was first calibrated for the 2D Hubbard lattice showing promising results. In this paper, we report an extension of SEET to quantum chemical ab initio Hamiltonians for applications to molecular systems. The self-consistent second-order Green's function method is used to describe the non-local correlations, while the full configuration interaction method is carried out to capture strong correlation within the active space. Using few proof-of-concept examples, we show that SEET yields results of comparable quality to n-electron valence state second-order perturbation theory with the same active space, and furthermore, the full active space can be split into smaller active spaces without further implementation. Moreover, SEET avoids intruder states and does not require any high-order reduced density matrices. These advantages show that SEET is a promising method to describe physical and chemical properties of challenging molecules requiring large active spaces.

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

    CERN Document Server

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

    2015-01-01

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

  20. Ab initio Bogoliubov coupled cluster theory for open-shell nuclei

    Science.gov (United States)

    Signoracci, A.; Duguet, T.; Hagen, G.; Jansen, G. R.

    2015-06-01

    Background: Ab initio many-body methods have been developed over the past 10 yr to address closed-shell nuclei up to mass A ≈130 on the basis of realistic two- and three-nucleon interactions. A current frontier relates to the extension of those many-body methods to the description of open-shell nuclei. Several routes to address open-shell nuclei are currently under investigation, including ideas that exploit spontaneous symmetry breaking. Purpose: Singly open-shell nuclei can be efficiently described via the sole breaking of U(1) gauge symmetry associated with particle-number conservation as a way to account for their superfluid character. While this route was recently followed within the framework of self-consistent Green's function theory, the goal of the present work is to formulate a similar extension within the framework of coupled cluster theory. Methods: We formulate and apply Bogoliubov coupled cluster (BCC) theory, which consists of representing the exact ground-state wave function of the system as the exponential of a quasiparticle excitation cluster operator acting on a Bogoliubov reference state. Equations for the ground-state energy and the cluster amplitudes are derived at the singles and doubles level (BCCSD) both algebraically and diagrammatically. The formalism includes three-nucleon forces at the normal-ordered two-body level. The first BCC code is implemented in m scheme, which will permit the treatment of doubly open-shell nuclei via the further breaking of SU(2) symmetry associated with angular momentum conservation. Results: Proof-of-principle calculations in an Nmax=6 spherical harmonic oscillator basis for O,1816 and 18Ne in the BCCD approximation are in good agreement with standard coupled cluster results with the same chiral two-nucleon interaction, while 20O and 20Mg display underbinding relative to experiment. The breaking of U(1) symmetry, monitored by computing the variance associated with the particle-number operator, is relatively

  1. PSI3: an open-source Ab Initio electronic structure package.

    Science.gov (United States)

    Crawford, T Daniel; Sherrill, C David; Valeev, Edward F; Fermann, Justin T; King, Rollin A; Leininger, Matthew L; Brown, Shawn T; Janssen, Curtis L; Seidl, Edward T; Kenny, Joseph P; Allen, Wesley D

    2007-07-15

    PSI3 is a program system and development platform for ab initio molecular electronic structure computations. The package includes mature programming interfaces for parsing user input, accessing commonly used data such as basis-set information or molecular orbital coefficients, and retrieving and storing binary data (with no software limitations on file sizes or file-system-sizes), especially multi-index quantities such as electron repulsion integrals. This platform is useful for the rapid implementation of both standard quantum chemical methods, as well as the development of new models. Features that have already been implemented include Hartree-Fock, multiconfigurational self-consistent-field, second-order Møller-Plesset perturbation theory, coupled cluster, and configuration interaction wave functions. Distinctive capabilities include the ability to employ Gaussian basis functions with arbitrary angular momentum levels; linear R12 second-order perturbation theory; coupled cluster frequency-dependent response properties, including dipole polarizabilities and optical rotation; and diagonal Born-Oppenheimer corrections with correlated wave functions. This article describes the programming infrastructure and main features of the package. PSI3 is available free of charge through the open-source, GNU General Public License. PMID:17420978

  2. Hydrogen adsorption on boron doped graphene: an {\\it ab initio} study

    OpenAIRE

    Miwa, R. H.; Martins, T B; Fazzio, A.

    2007-01-01

    The electronic and structural properties of (i) boron doped graphene sheets, and (ii) the chemisorption processes of hydrogen adatoms on the boron doped graphene sheets have been examined by {\\it ab initio} total energy calculations.

  3. 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....

  4. Exploring the free energy surface using ab initio molecular dynamics.

    Science.gov (United States)

    Samanta, Amit; Morales, Miguel A; Schwegler, Eric

    2016-04-28

    Efficient exploration of configuration space and identification of metastable structures in condensed phase systems are challenging from both computational and algorithmic perspectives. In this regard, schemes that utilize a set of pre-defined order parameters to sample the relevant parts of the configuration space [L. Maragliano and E. Vanden-Eijnden, Chem. Phys. Lett. 426, 168 (2006); J. B. Abrams and M. E. Tuckerman, J. Phys. Chem. B 112, 15742 (2008)] have proved useful. Here, we demonstrate how these order-parameter aided temperature accelerated sampling schemes can be used within the Born-Oppenheimer and the Car-Parrinello frameworks of ab initio molecular dynamics to efficiently and systematically explore free energy surfaces, and search for metastable states and reaction pathways. We have used these methods to identify the metastable structures and reaction pathways in SiO2 and Ti. In addition, we have used the string method [W. E, W. Ren, and E. Vanden-Eijnden, Phys. Rev. B 66, 052301 (2002); L. Maragliano et al., J. Chem. Phys. 125, 024106 (2006)] within the density functional theory to study the melting pathways in the high pressure cotunnite phase of SiO2 and the hexagonal closed packed to face centered cubic phase transition in Ti. PMID:27131525

  5. Ab initio no-core solutions for $^6$Li

    CERN Document Server

    Shin, Ik Jae; Maris, Pieter; Vary, James P; Forssén, Christian; Rotureau, Jimmy; Michel, Nicolas

    2016-01-01

    We solve for properties of $^6$Li in the ab initio No-Core Full Configuration approach and we separately solve for its ground state and $J^{\\pi}=2_{2}^{+}$ resonance with the Gamow Shell Model in the Berggren basis. We employ both the JISP16 and chiral NNLO$_{opt}$ realistic nucleon-nucleon interactions and investigate the ground state energy, excitation energies, point proton root-mean-square radius and a suite of electroweak observables. We also extend and test methods to extrapolate the ground state energy, point proton root-mean-square radius, and electric quadrupole moment. We attain improved estimates of these observables in the No-Core Full Configuration approach by using basis spaces up through N$_{max}$=18 that enable more definitive comparisons with experiment. Using the Density Matrix Renormalization Group approach with the JISP16 interaction, we find that we can significantly improve the convergence of the Gamow Shell Model treatment of the $^6$Li ground state and $J^{\\pi}=2_{2}^{+}$ resonance by ...

  6. Ab initio evaluations of the He solubility in liquid Li

    Energy Technology Data Exchange (ETDEWEB)

    Sedano, Luis A. [EURATOM-CIEMAT Assoc., Materials for Fusion Program, Bd. 43 P0.04, Avda. Complutense 22, 28040 Madrid (Spain)]. E-mail: luis.sedano@ciemat.es; Hassanein, Ahmed [Argonne Nat. Lab, 9700 South Class Av., Argonne, IL (United States)]. E-mail: hassanein@anl.gov; Sanz, Javier [ETSII-UNED, c/Juan del Rosal, 12, 28040 Madrid (E) (Spain)]. E-mail: jsanz@ind.UNED.es

    2005-11-15

    Modified embedding atom methods (MEAM) are developed to have predictions of the partial molar heat of solution (-H{sub s}) by direct simulation of metal cohesion, He-metal and He-He interaction. Transitions from crystalline Li to configurations, having the liquid Li structure's factors (h-bar (q)), are simulated ab initio. Once h-bar (q) reproduced, He atoms are added, one by one, to the Li system. Parallel lines for each case, with slopes clearly independent on the number of He atoms in the system, are obtained for energy versus pressure at given temperatures. Average differences between two adjacent parallels at zero pressure, once kinetic energy of the system discounted, represents the energy gained by an He atom when added to the Li system, related to the solution energy -H{sub s}. The molar excess entropy of gas in solution (S-bar {sub l}{sup ex}) is previously evaluated following diverse fundamental approaches: a 'thermodynamic liquid-hole' (TL-H) model for alkali liquids and a statistical-mechanics (Neff and McQuarrie's) model (SMM). Between 600 and 900 deg. C, a typical range of interest for the use of Li in fusion technology, the computed values for the (He) Henry's constant in Li range from 8x10{sup -14} to 10{sup -13} at. fr. Pa{sup -1}.

  7. Ab initio simulations of pseudomorphic silicene and germanene bidimensional heterostructures

    Science.gov (United States)

    Debernardi, Alberto; Marchetti, Luigi

    2016-06-01

    Among the novel two-dimensional (2D) materials, silicene and germanene, which are two honeycomb crystal structures composed of a monolayer of Si and Ge, respectively, have attracted the attention of material scientists because they combine the advantages of the new 2D ultimate-scaled electronics with their compatibility with industrial processes presently based on Si and Ge. We envisage pseudomorphic lateral heterostructures based on ribbons of silicene and germanene, which are the 2D analogs of conventional 3D Si/Ge superlattices and quantum wells. In spite of the considerable lattice mismatch (˜4 % ) between free-standing silicene and germanene, our ab initio simulations predict that, considering striped 2D lateral heterostructures made by alternating silicene and germanene ribbons of constant width, the silicene/germanene junction remains pseudomorphic—i.e., it maintains lattice-matched edges—up to critical ribbon widths that can reach some tens of nanometers. Such critical widths are one order of magnitude larger than the critical thickness measured in 3D pseudomorphic Si/Ge heterostructures and the resolution of state-of-the-art lithography, thus enabling the possibility of lithography patterned silicene/germanene junctions. We computed how the strain produced by the pseudomorphic growth modifies the crystal structure and electronic bands of the ribbons, providing a mechanism for band-structure engineering. Our results pave the way for lithography patterned lateral heterostructures that can serve as the building blocks of novel 2D electronics.

  8. Ab initio studies of phoshorene island single electron transistor.

    Science.gov (United States)

    Ray, S J; Venkata Kamalakar, M; Chowdhury, R

    2016-05-18

    Phosphorene is a newly unveiled two-dimensional crystal with immense potential for nanoelectronic and optoelectronic applications. Its unique electronic structure and two dimensionality also present opportunities for single electron devices. Here we report the behaviour of a single electron transistor (SET) made of a phosphorene island, explored for the first time using ab initio calculations. We find that the band gap and the charging energy decrease monotonically with increasing layer numbers due to weak quantum confinement. When compared to two other novel 2D crystals such as graphene and MoS2, our investigation reveals larger adsorption energies of gas molecules on phosphorene, which indicates better a sensing ability. The calculated charge stability diagrams show distinct changes in the presence of an individual molecule which can be applied to detect the presence of different molecules with sensitivity at a single molecular level. The higher charging energies of the molecules within the SET display operational viability at room temperature, which is promising for possible ultra sensitive detection applications. PMID:27093536

  9. Ab initio studies of phosphorene island single electron transistor

    Science.gov (United States)

    Ray, S. J.; Venkata Kamalakar, M.; Chowdhury, R.

    2016-05-01

    Phosphorene is a newly unveiled two-dimensional crystal with immense potential for nanoelectronic and optoelectronic applications. Its unique electronic structure and two dimensionality also present opportunities for single electron devices. Here we report the behaviour of a single electron transistor (SET) made of a phosphorene island, explored for the first time using ab initio calculations. We find that the band gap and the charging energy decrease monotonically with increasing layer numbers due to weak quantum confinement. When compared to two other novel 2D crystals such as graphene and MoS2, our investigation reveals larger adsorption energies of gas molecules on phosphorene, which indicates better a sensing ability. The calculated charge stability diagrams show distinct changes in the presence of an individual molecule which can be applied to detect the presence of different molecules with sensitivity at a single molecular level. The higher charging energies of the molecules within the SET display operational viability at room temperature, which is promising for possible ultra sensitive detection applications.

  10. Ab initio calculation of double ionization of atoms

    Energy Technology Data Exchange (ETDEWEB)

    Serov, V. V., E-mail: vladislav.serov@mail.ru [Saratov State University, Department of Theoretical Physics (Russian Federation)

    2013-02-15

    The Solov'ev-Vinitsky method was used to perform an ab initio calculation of the triple-differential cross section for the double single-photon photoionization of helium for the case of equal emitted-electron energies. A Gaussian width {gamma} describing angular electron-electron correlations at the total electron energy E taking values in range between 0.1 and 100 eV was obtained for this cross section. The results agree with available experimental data, but they raise a doubt as to whether the well-known Wannier law {gamma} {proportional_to} E{sup 1/4} is applicable at experimentally accessible energies. The Gaussian width {gamma} was investigated as a function of the total emitted-electron energy for targets that have a strongly asymmetric configuration of the initial state-specifically, a negative atomic-hydrogen ion H{sup -} and heliumin the 1s2s{sup 1}S and 1s3s{sup 1}S excited states. It was found that this function, {gamma}(E), had a maximum at low energies. It was also shown that, at low energies, the dependence of the double-differential cross section on the angle between the emitted-electron momenta for the targets indicated above differed substantially from the Gaussian dependence, featuring maxima whose number was equal to the number of radial nodes in the initial state. This opens new possibilities for a qualitative analysis of the electron structure of targets.

  11. Accurate ab initio vibrational energies of methyl chloride

    Energy Technology Data Exchange (ETDEWEB)

    Owens, Alec, E-mail: owens@mpi-muelheim.mpg.de [Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr (Germany); Department of Physics and Astronomy, University College London, Gower Street, WC1E 6BT London (United Kingdom); Yurchenko, Sergei N.; Yachmenev, Andrey; Tennyson, Jonathan [Department of Physics and Astronomy, University College London, Gower Street, WC1E 6BT London (United Kingdom); Thiel, Walter [Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr (Germany)

    2015-06-28

    Two new nine-dimensional potential energy surfaces (PESs) have been generated using high-level ab initio theory for the two main isotopologues of methyl chloride, CH{sub 3}{sup 35}Cl and CH{sub 3}{sup 37}Cl. The respective PESs, CBS-35{sup  HL}, and CBS-37{sup  HL}, are based on explicitly correlated coupled cluster calculations with extrapolation to the complete basis set (CBS) limit, and incorporate a range of higher-level (HL) additive energy corrections to account for core-valence electron correlation, higher-order coupled cluster terms, scalar relativistic effects, and diagonal Born-Oppenheimer corrections. Variational calculations of the vibrational energy levels were performed using the computer program TROVE, whose functionality has been extended to handle molecules of the form XY {sub 3}Z. Fully converged energies were obtained by means of a complete vibrational basis set extrapolation. The CBS-35{sup  HL} and CBS-37{sup  HL} PESs reproduce the fundamental term values with root-mean-square errors of 0.75 and 1.00 cm{sup −1}, respectively. An analysis of the combined effect of the HL corrections and CBS extrapolation on the vibrational wavenumbers indicates that both are needed to compute accurate theoretical results for methyl chloride. We believe that it would be extremely challenging to go beyond the accuracy currently achieved for CH{sub 3}Cl without empirical refinement of the respective PESs.

  12. Rational design of electrolyte components by ab initio calculations

    Energy Technology Data Exchange (ETDEWEB)

    Johansson, Patrik; Jacobsson, Per [Department of Applied Physics, Chalmers University of Technology, SE-412 96 Goeteborg (Sweden)

    2006-02-28

    This paper is a small review of the use of computer simulations and especially the use of standard quantum-mechanical ab initio electronic structure calculations to rationally design and investigate different choices of chemicals/systems for lithium battery electrolytes. Covered systems and strategies to enhance the performance of electrolytes will range from assisting the interpretation of vibrational spectroscopy experiments over development of potentials for molecular dynamics simulations, to the design of new lithium salts and the lithium ion coordination in liquid, polymer, and gel polymer electrolytes. Examples of studied properties include the vibrational spectra of anions and ion pairs to characterize the nature and extent of the interactions present, the lithium ion affinities of anions, important for the salt solvation and the ability to provide a high concentration of charge carriers, the HOMO energies of the anions to estimate the stability versus oxidation, the anion volumes that correlate to the anion mobility, the lithium ion coordination and dynamics to reveal the limiting steps of lithium ion transport, etc. (author)

  13. 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.)

  14. Ab initio transport across bismuth selenide surface barriers

    KAUST Repository

    Narayan, Awadhesh

    2014-11-24

    © 2014 American Physical Society. We investigate the effect of potential barriers in the form of step edges on the scattering properties of Bi2Se3(111) topological surface states by means of large-scale ab initio transport simulations. Our results demonstrate the suppression of perfect backscattering, while all other scattering processes, which do not entail a complete spin and momentum reversal, are allowed. Furthermore, we find that the spin of the surface state develops an out-of-plane component as it traverses the barrier. Our calculations reveal the existence of quasibound states in the vicinity of the surface barriers, which appear in the form of an enhanced density of states in the energy window corresponding to the topological state. For double barriers we demonstrate the formation of quantum well states. To complement our first-principles results we construct a two-dimensional low-energy effective model and illustrate its shortcomings. Our findings are discussed in the context of a number of recent experimental works.

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

    Science.gov (United States)

    Gulian, Mamikon; Melkonyan, Gurgen; Gulian, Armen

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

  16. The Hydration Structure of Carbon Monoxide by Ab Initio Methods

    CERN Document Server

    Awoonor-Williams, Ernest

    2016-01-01

    The solvation of carbon monoxide (CO) in liquid water is important for understanding its toxicological effects and biochemical roles. In this paper, we use ab initio molecular dynamics (AIMD) and CCSD(T)-F12 calculations to assess the accuracy of the Straub and Karplus molecular mechanical (MM) model for CO(aq). The CCSD(T)-F12 CO--H2O potential energy surfaces show that the most stable structure corresponds to water donating a hydrogen bond to the C center. The MM-calculated surface it incorrectly predicts that the O atom is a stronger hydrogen bond acceptor than the C atom. The AIMD simulations indicate that CO is solvated like a hydrophobic solute, with very limited hydrogen bonding with water. The MM model tends to overestimate the degree of hydrogen bonding and overestimates the atomic radius of the C atom. The calculated Gibbs energy of hydration is in good agreement with experiment (9.3 kJ/mol calc. vs 10.7 kJ/mol exptl.). The calculated diffusivity of CO(aq) in TIP3P-model water was 5.19 x 10-5 cm2/s ...

  17. Accurate double many-body expansion potential energy surface of HS2A2A‧) by scaling the external correlation

    Science.gov (United States)

    Lu-Lu, Zhang; Yu-Zhi, Song; Shou-Bao, Gao; Yuan, Zhang; Qing-Tian, Meng

    2016-05-01

    A globally accurate single-sheeted double many-body expansion potential energy surface is reported for the first excited state of HS2 by fitting the accurate ab initio energies, which are calculated at the multireference configuration interaction level with the aug-cc-pVQZ basis set. By using the double many-body expansion-scaled external correlation method, such calculated ab initio energies are then slightly corrected by scaling their dynamical correlation. A grid of 2767 ab initio energies is used in the least-square fitting procedure with the total root-mean square deviation being 1.406 kcal·mol‑1. The topographical features of the HS2(A2A‧) global potential energy surface are examined in detail. The attributes of the stationary points are presented and compared with the corresponding ab initio results as well as experimental and other theoretical data, showing good agreement. The resulting potential energy surface of HS2(A2A‧) can be used as a building block for constructing the global potential energy surfaces of larger S/H molecular systems and recommended for dynamic studies on the title molecular system. Project supported by the National Natural Science Foundation of China (Grant No. 11304185), the Taishan Scholar Project of Shandong Province, China, the Shandong Provincial Natural Science Foundation, China (Grant No. ZR2014AM022), the Shandong Province Higher Educational Science and Technology Program, China (Grant No. J15LJ03), the China Postdoctoral Science Foundation (Grant No. 2014M561957), and the Post-doctoral Innovation Project of Shandong Province, China (Grant No. 201402013).

  18. An ab initio Non-Equilibrium Green Function Approach to Charge Transport: Dithiolethine

    Institute of Scientific and Technical Information of China (English)

    Alexander Schnurpfeil; SONG Bo; Martin Albrecht

    2006-01-01

    @@ We present a novel ab initio non-equilibrium approach to calculate the current across a molecular junction. The method rests on a wavefunction-based full ab initio description of the central region of the junction combined with a tight binding approximation for the electrodes in the frame of the Keldysh Green function formalism. Our procedure is demonstrated for a dithiolethine molecule located between silver electrodes. The main conducting channel is identified and the full current-voltage characteristic is calculated.

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

    Science.gov (United States)

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

    2011-02-21

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

  20. Tuning Many-Body Interactions in Graphene: The Effects of Doping on Excitons and Carrier Lifetimes

    Science.gov (United States)

    Mak, Kin Fai; da Jornada, Felipe H.; He, Keliang; Deslippe, Jack; Petrone, Nicholas; Hone, James; Shan, Jie; Louie, Steven G.; Heinz, Tony F.

    2014-05-01

    The optical properties of graphene are strongly affected by electron-electron (e-e) and electron-hole (e-h) interactions. Here we tune these many-body interactions through varying the density of free charge carriers. Measurements from the infrared to the ultraviolet reveal significant changes in the optical conductivity of graphene for both electron and hole doping. The shift, broadening, and modification in shape of the saddle-point exciton resonance reflect strong screening of the many-body interactions by the carriers, as well as changes in quasiparticle lifetimes. Ab initio calculations by the GW Bethe-Salpeter equation method, which take into account the modification of both the repulsive e-e and the attractive e-h interactions, provide excellent agreement with experiment. Understanding the optical properties and high-energy carrier dynamics of graphene over a wide range of doping is crucial for both fundamental graphene physics and for emerging applications of graphene in photonics.

  1. Periodic Trends in Lanthanide Compounds through the Eyes of Multireference ab Initio Theory.

    Science.gov (United States)

    Aravena, Daniel; Atanasov, Mihail; Neese, Frank

    2016-05-01

    Regularities among electronic configurations for common oxidation states in lanthanide complexes and the low involvement of f orbitals in bonding result in the appearance of several periodic trends along the lanthanide series. These trends can be observed on relatively different properties, such as bonding distances or ionization potentials. Well-known concepts like the lanthanide contraction, the double-double (tetrad) effect, and the similar chemistry along the lanthanide series stem from these regularities. Periodic trends on structural and spectroscopic properties are examined through complete active space self-consistent field (CASSCF) followed by second-order N-electron valence perturbation theory (NEVPT2) including both scalar relativistic and spin-orbit coupling effects. Energies and wave functions from electronic structure calculations are further analyzed in terms of ab initio ligand field theory (AILFT), which allows one to rigorously extract angular overlap model ligand field, Racah, and spin-orbit coupling parameters directly from high-level ab initio calculations. We investigated the elpasolite Cs2NaLn(III)Cl6 (Ln(III) = Ce-Nd, Sm-Eu, Tb-Yb) crystals because these compounds have been synthesized for most Ln(III) ions. Cs2NaLn(III)Cl6 elpasolites have been also thoroughly characterized with respect to their spectroscopic properties, providing an exceptionally vast and systematic experimental database allowing one to analyze the periodic trends across the lanthanide series. Particular attention was devoted to the apparent discrepancy in metal-ligand covalency trends between theory and spectroscopy described in the literature. Consistent with earlier studies, natural population analysis indicates an increase in covalency along the series, while a decrease in both the nephelauxetic (Racah) and relativistic nephelauxetic (spin-orbit coupling) reduction with increasing atomic number is calculated. These apparently conflicting results are discussed on the

  2. Many-body approaches to nuclear physics

    Energy Technology Data Exchange (ETDEWEB)

    Hjorth-Jensen, M.

    1993-10-01

    This thesis deals with applications of perturbative many-body theories to selected nuclear systems at low and intermediate energies. Examples are the properties of neutron stars, the calculation of shell-model effective interactions and the microscopic derivation of the optical-model potential for finite nuclei. The line of research leans on the microscopic approach, i.e. an approach which aims at describing nuclear properties from the underlying free interaction between the various hadrons where parameters like meson coupling constants define the Lagrangians. The emphasis is on the behavior of the various components of the free interaction in different nuclear media in order to understand how these components are affected by the studied nuclear correlations. 159 refs.

  3. Lithium Insertion In Silicon Nanowires: An ab Initio Study

    KAUST Repository

    Zhang, Qianfan

    2010-09-08

    The ultrahigh specific lithium ion storage capacity of Si nanowires (SiNWs) has been demonstrated recently and has opened up exciting opportunities for energy storage. However, a systematic theoretical study on lithium insertion in SiNWs remains a challenge, and as a result, understanding of the fundamental interaction and microscopic dynamics during lithium insertion is still lacking. This paper focuses on the study of single Li atom insertion into SiNWs with different sizes and axis orientations by using full ab initio calculations. We show that the binding energy of interstitial Li increases as the SiNW diameter grows. The binding energies at different insertion sites, which can be classified as surface, intermediate, and core sites, are quite different. We find that surface sites are energetically the most favorable insertion positions and that intermediate sites are the most unfavorable insertion positions. Compared with the other growth directions, the [110] SiNWs with different diameters always present the highest binding energies on various insertion locations, which indicates that [110] SiNWs are more favorable by Li doping. Furthermore, we study Li diffusion inside SiNWs. The results show that the Li surface diffusion has a much higher chance to occur than the surface to core diffusion, which is consistent with the experimental observation that the Li insertion in SiNWs is layer by layer from surface to inner region. After overcoming a large barrier crossing surface-to-intermediate region, the diffusion toward center has a higher possibility to occur than the inverse process. © 2010 American Chemical Society.

  4. A Comparative Study of Ab-Initio Thermal Conductivity Approaches: The Case of Cubic Boron Nitride

    Science.gov (United States)

    Mukhopadhyay, Saikat; Lindsay, Lucas; Broido, David; Stewart, Derek

    2013-03-01

    Given its high strength and large thermal conductivity, cubic boron nitride (cBN) provides an important complement to diamond films for heat spreading applications. However, cBN, in contrast to diamond, is a polar material with significant LO-TO splitting in the phonon dispersion. In this talk, we examine the lattice thermal conductivity of cBN using several approaches based on first principles calculations. These approaches include: (1) an analytic modified Callaway-Debye model that relies on parameters from ab-initio harmonic force constants, (2) a fully self-consistent calculation of the thermal conductivity that links an iterative solution of the phonon Boltzmann transport equation (BTE) with harmonic and anharmonic interatomic force constants. The force constants for the BTE are calculated using two approaches: density functional perturbation theory and a real-space supercell approach. We will compare the results from these approaches, highlight the role of normal phonon-phonon scattering, and also examine the impact of optical modes and LO-TO splitting. In addition, we will discuss how isotope scattering affects thermal conductivity and compare this to other boron nitride structures (hexagonal BN, BN sheets and BN nanotubes).

  5. The role of anharmonicity in the ab-initio phase diagram of calcium

    Science.gov (United States)

    di Gennaro, Marco; Saha, Srijan Kumar; Verstraete, Matthieu Jean

    2013-03-01

    In the 32-119 GPa pressure range and at room temperature, a simple cubic phase was reported for calcium in many different experiments. Standard linear response theory, both within density functional perturbation theory and frozen phonon calculations, presents dynamical instabilities for simple cubic in the whole pressure range. Many other possible candidate phases, as well as several possible stabilization mechanisms for simple cubic phase, have been proposed as the result of ab-initio predictions but the role of temperature on the relative stability of the different phases has not been investigated systematically. We revisit the stability of three candidate phases of calcium for the intermediate pressure range and for various value of temperatures, taking explicitly into account thermal corrections relative to electronic as well as phononic entropy and anharmonic contributions. This corrects the discrepancies among previous theoretical results and experiments, and presents a different picture of the temperature driven phase transition, which results from dynamical anharmonic stabilization of simple cubic and de-stabilization of the tetragonal phase. Transport quantities are calculated in the stabilized phases, to provide additional points of comparison with experiments.

  6. Role of Dynamical Instability in the Ab Initio Phase Diagram of Calcium

    Science.gov (United States)

    Di Gennaro, Marco; Saha, Srijan Kumar; Verstraete, Matthieu J.

    2013-07-01

    In the 32-119 GPa pressure range and at room temperature, a simple cubic phase was reported for calcium in many different experiments. Standard linear response theory, both within density functional perturbation theory and frozen phonon calculations, presents dynamical instabilities for the simple cubic structure in the whole pressure range. Many other possible candidate phases, as well as several possible stabilization mechanisms for the simple cubic phase, have been proposed as the result of ab initio predictions but the role of temperature on the relative stability of the different phases has not been systematically investigated. We revisit the stability of the three most important candidate phases of calcium for the intermediate pressure range and for various temperatures, taking explicitly into account thermal corrections relative to electronic as well as phononic entropy and anharmonic contributions. This corrects the discrepancies among previous theoretical results and experiments and presents a different picture of the temperature driven phase transition, which results from dynamical anharmonic stabilization of simple cubic and destabilization of the tetragonal phase.

  7. Ab initio 3D potential energy and dipole moment surfaces for the CH4-Ar complex: Collision-induced intensity and dimer content

    Science.gov (United States)

    Kalugina, Yulia N.; Lokshtanov, Sergei E.; Cherepanov, Victor N.; Vigasin, Andrey A.

    2016-02-01

    We present new three-dimensional potential energy surface (PES) and dipole moment surfaces (DMSs) for the CH4-Ar van der Waals system. Ab initio calculations of the PES and DMS were carried out using the closed-shell single- and double-excitation coupled cluster approach with non-iterative perturbative treatment of triple excitations. The augmented correlation-consistent aug-cc-pVXZ (X = D,T,Q) basis sets were employed, and the energies obtained were then extrapolated to the complete basis set limit. The dipole moment surface was obtained using aug-cc-pVTZ basis set augmented with mid-bond functions for better description of exchange interactions. The second mixed virial coefficient was calculated and compared to available experimental data. The equilibrium constant for true dimer formation was calculated using classical partition function based on the knowledge of ab initio PES. Temperature variations of the zeroth spectral moment of the rototranslational collision-induced band as well as its true dimer constituent were traced with the use of the Boltzmann-weighted squared induced dipole properly integrated over respective phase space domains. Height profiles for N2-N2, N2-H2, CH4-N2, (CH4)2, and CH4-Ar true bound dimers in Titan's atmosphere were calculated with the use of reliable ab initio PESs.

  8. Magnetic Transitions in Iron Porphyrin Halides by Inelastic Neutron Scattering and Ab Initio Studies of Zero-Field Splittings.

    Science.gov (United States)

    Stavretis, Shelby E; Atanasov, Mihail; Podlesnyak, Andrey A; Hunter, Seth C; Neese, Frank; Xue, Zi-Ling

    2015-10-19

    Zero-field splitting (ZFS) parameters of nondeuterated metalloporphyrins [Fe(TPP)X] (X = F, Br, I; H₂TPP = tetraphenylporphyrin) have been directly determined by inelastic neutron scattering (INS). The ZFS values are D = 4.49(9) cm⁻¹ for tetragonal polycrystalline [Fe(TPP)F], and D = 8.8(2) cm⁻¹, E = 0.1(2) cm⁻¹ and D = 13.4(6) cm⁻¹, E = 0.3(6) cm⁻¹ for monoclinic polycrystalline [Fe(TPP)Br] and [Fe(TPP)I], respectively. Along with our recent report of the ZFS value of D = 6.33(8) cm⁻¹ for tetragonal polycrystalline [Fe(TPP)Cl], these data provide a rare, complete determination of ZFS parameters in a metalloporphyrin halide series. The electronic structure of [Fe(TPP)X] (X = F, Cl, Br, I) has been studied by multireference ab initio methods: the complete active space self-consistent field (CASSCF) and the N-electron valence perturbation theory (NEVPT2) with the aim of exploring the origin of the large and positive zero-field splitting D of the ⁶A₁ ground state. D was calculated from wave functions of the electronic multiplets spanned by the d⁵ configuration of Fe(III) along with spin–orbit coupling accounted for by quasi degenerate perturbation theory. Results reproduce trends of D from inelastic neutron scattering data increasing in the order from F, Cl, Br, to I. A mapping of energy eigenvalues and eigenfunctions of the S = 3/2 excited states on ligand field theory was used to characterize the σ- and π-antibonding effects decreasing from F to I. This is in agreement with similar results deduced from ab initio calculations on CrX₆³⁻ complexes and also with the spectrochemical series showing a decrease of the ligand field in the same directions. A correlation is found between the increase of D and decrease of the π- and σ-antibonding energies e(λ)(X) (λ = σ, π) in the series from X = F to I. Analysis of this correlation using second-order perturbation theory expressions in terms of angular overlap parameters rationalizes the

  9. Ab Initio Description of Open-Shell Nuclei: Merging No-Core Shell Model and In-Medium Similarity Renormalization Group

    CERN Document Server

    Gebrerufael, Eskendr; Hergert, Heiko; Roth, Robert

    2016-01-01

    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 new many-body approach for the comprehensive description of ground and excited states of closed and open-shell 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 access to arbitrary nuclei, eigenstates, and observables in the NCSM---their combination enables fully converged no-core calculations for an unprecedented range of nuclei and observables at moderate computational cost. We present applications in the carbon and oxygen isotopic chains, where conventional NCSM calculations are still feasible and provide an important benchmark. The efficiency and rapid convergence of the new approach make it ideally suited for ab initio studies of the complete spectroscopy of nuclei up into the medium-mass regime.

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

    Science.gov (United States)

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

    2016-05-01

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

  11. Organic/inorganic hybrid materials: challenges for ab initio methodology.

    Science.gov (United States)

    Draxl, Claudia; Nabok, Dmitrii; Hannewald, Karsten

    2014-11-18

    CONSPECTUS: Organic/inorganic hybrid structures are most exciting since one can expect new properties that are absent in either of their building blocks. They open new perspectives toward the design and tailoring of materials with desired features and functions. Prerequisite for real progress is, however, the in-depth understanding of what happens on the atomic and electronic scale. In this respect, hybrid materials pose a challenge for electronic-structure theory. Methods that proved useful for describing one side may not be applicable for the other one, and they are likely to fail for the interfaces. In this Account, we address the question to what extent we can quantitatively describe hybrid materials and where we even miss a qualitative description. We note that we are dealing with extended systems and thus adopt a solid-state approach. Therefore, density-functional theory (DFT) and many-body perturbation theory (MBPT), the GW approach for charged and the Bethe-Salpeter equation for neutral excitations, are our methods of choice. We give a brief summary of the used methodology, focusing on those aspects where problems can be expected when materials of different character meet at an interface. These issues are then taken up when discussing hybrid materials. We argue when and why, for example, standard DFT may fall short when it comes to the electronic structure of organic/metal interfaces or where the framework of MBPT can or must take over. Selected examples of organic/inorganic interfaces, structural properties, electronic bands, optical excitation spectra, and charge-transport properties as obtained from DFT and MBPT highlight which properties can be reliably computed for such materials. The crucial role of van der Waals forces is shown for sexiphenyl films, where the subtle interplay between intermolecular and molecule-substrate interactions is decisive for growth and morphologies. With a PTCDA monolayer on metal surfaces we discuss the performance of DFT in

  12. Organic/inorganic hybrid materials: challenges for ab initio methodology.

    Science.gov (United States)

    Draxl, Claudia; Nabok, Dmitrii; Hannewald, Karsten

    2014-11-18

    CONSPECTUS: Organic/inorganic hybrid structures are most exciting since one can expect new properties that are absent in either of their building blocks. They open new perspectives toward the design and tailoring of materials with desired features and functions. Prerequisite for real progress is, however, the in-depth understanding of what happens on the atomic and electronic scale. In this respect, hybrid materials pose a challenge for electronic-structure theory. Methods that proved useful for describing one side may not be applicable for the other one, and they are likely to fail for the interfaces. In this Account, we address the question to what extent we can quantitatively describe hybrid materials and where we even miss a qualitative description. We note that we are dealing with extended systems and thus adopt a solid-state approach. Therefore, density-functional theory (DFT) and many-body perturbation theory (MBPT), the GW approach for charged and the Bethe-Salpeter equation for neutral excitations, are our methods of choice. We give a brief summary of the used methodology, focusing on those aspects where problems can be expected when materials of different character meet at an interface. These issues are then taken up when discussing hybrid materials. We argue when and why, for example, standard DFT may fall short when it comes to the electronic structure of organic/metal interfaces or where the framework of MBPT can or must take over. Selected examples of organic/inorganic interfaces, structural properties, electronic bands, optical excitation spectra, and charge-transport properties as obtained from DFT and MBPT highlight which properties can be reliably computed for such materials. The crucial role of van der Waals forces is shown for sexiphenyl films, where the subtle interplay between intermolecular and molecule-substrate interactions is decisive for growth and morphologies. With a PTCDA monolayer on metal surfaces we discuss the performance of DFT in

  13. An ab initio study of plutonium oxides surfaces; Etude ab initio des surfaces d'oxydes de Pu

    Energy Technology Data Exchange (ETDEWEB)

    Jomard, G.; Bottin, F.; Amadon, B

    2007-07-01

    By means of first-principles calculations, we have studied the atomic structure as well as the thermodynamic stability of various plutonium dioxide surfaces in function of their environment (in terms of oxygen partial pressure and temperature). All these simulations have been performed with the ABINIT code. It is well known that DFT fails to describe correctly plutonium-based materials since 5f electrons in such systems are strongly correlated. In order to go beyond DFT, we have treated PuO{sub 2} and {beta}-Pu{sub 2}O{sub 3} in a DFT+U framework. We show that the couple of parameters (U,J) that works well for pure Pu is also well designed for describing ground state (GS) properties of these two oxides. The major improvement with respect with DFT is that we are able to predict an insulating GS in agreement with experiments. The presence of a gap in the DOS (Density of States) of plutonium oxides should play a significant role in the predicted surface reactivity. However, performing DFT+U calculations on surfaces of plutonium oxide from scratch was too ambitious. That is why we decided, as a first step, to study the stability of the (100), (110) and (111) surfaces of PuO{sub 2} in a DFT-GGA framework. For each of these orientations, we considered various terminations. These ab initio results have been introduced in a thermodynamic model which allows us to predict the relative stability of the different terminations as a function of temperature and oxygen partial pressure (p{sub O{sub 2}}). We conclude that at room temperature and for p{sub O{sub 2}}{approx}10 atm., the polar O{sub 2}-(100) termination is favoured. The stabilization of such a polar stoichiometric surface is surprising and should be confirmed by DFT+U calculations before any final conclusion. (authors)

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

    OpenAIRE

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

    2014-01-01

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

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

    CERN Document Server

    Neff, Thomas; Langanke, Karlheinz

    2010-01-01

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

  16. Bandstructure meets many-body theory: the LDA+DMFT method

    Energy Technology Data Exchange (ETDEWEB)

    Held, K [Max-Planck Institut fuer Festkoerperforschung, D-70569 Stuttgart (Germany); Andersen, O K [Max-Planck Institut fuer Festkoerperforschung, D-70569 Stuttgart (Germany); Feldbacher, M [Max-Planck Institut fuer Festkoerperforschung, D-70569 Stuttgart (Germany); Yamasaki, A [Max-Planck Institut fuer Festkoerperforschung, D-70569 Stuttgart (Germany); Yang, Y-F [Max-Planck Institut fuer Festkoerperforschung, D-70569 Stuttgart (Germany)

    2008-02-13

    Ab initio calculation of the electronic properties of materials is a major challenge for solid-state theory. Whereas 40 years' experience has proven density-functional theory (DFT) in a suitable form, e.g. local approximation (LDA), to give a satisfactory description when electronic correlations are weak, materials with strongly correlated electrons, say d- or f-electrons, remain a challenge. Such materials often exhibit 'colossal' responses to small changes of external parameters such as pressure, temperature, and magnetic field, and are therefore most interesting for technical applications. Encouraged by the success of dynamical mean-field theory (DMFT) in dealing with model Hamiltonians for strongly correlated electron systems, physicists from the bandstructure and many-body communities have joined forces and developed a combined LDA+DMFT method for treating materials with strongly correlated electrons ab initio. As a function of increasing Coulomb correlations, this new approach yields a weakly correlated metal, a strongly correlated metal, or a Mott insulator. In this paper, we introduce the LDA+DMFT method by means of an example, LaMnO{sub 3}. Results for this material, including the 'colossal' magnetoresistance of doped manganites, are presented. We also discuss the advantages and disadvantages of the LDA+DMFT approach.

  17. Bandstructure meets many-body theory: the LDA+DMFT method.

    Science.gov (United States)

    Held, K; Andersen, O K; Feldbacher, M; Yamasaki, A; Yang, Y-F

    2008-02-13

    Ab initio calculation of the electronic properties of materials is a major challenge for solid-state theory. Whereas 40 years' experience has proven density-functional theory (DFT) in a suitable form, e.g. local approximation (LDA), to give a satisfactory description when electronic correlations are weak, materials with strongly correlated electrons, say d- or f-electrons, remain a challenge. Such materials often exhibit 'colossal' responses to small changes of external parameters such as pressure, temperature, and magnetic field, and are therefore most interesting for technical applications. Encouraged by the success of dynamical mean-field theory (DMFT) in dealing with model Hamiltonians for strongly correlated electron systems, physicists from the bandstructure and many-body communities have joined forces and developed a combined LDA+DMFT method for treating materials with strongly correlated electrons ab initio. As a function of increasing Coulomb correlations, this new approach yields a weakly correlated metal, a strongly correlated metal, or a Mott insulator. In this paper, we introduce the LDA+DMFT method by means of an example, LaMnO(3). Results for this material, including the 'colossal' magnetoresistance of doped manganites, are presented. We also discuss the advantages and disadvantages of the LDA+DMFT approach.

  18. Constructing ab initio and empirical potential energy surfaces for water Infrared spectrum; Vibrational and rotational energy levels; Born- Oppenheimer surface

    CERN Document Server

    Kain, J S

    2001-01-01

    The infrared spectrum of water is possibly one of the most well studied and yet portions of it are still poorly understood. Recently, significant advances have been made in assigning water spectra using variational nuclear calculations. The major factor determining the accuracy of ro-vibrational spectra of water is the accuracy of the underlying Potential Energy Surface. Even the most accurate ab initio Potential Energy Surface does not reproduce the Born-Oppenheimer surface to sufficient accuracy for spectroscopic studies. Furthermore, effects beyond this model such as the adiabatic correction, the relativistic correction and the non-adiabatic correction have to be considered. This thesis includes a discussion on how the relativistic correction was calculated, for the water molecule, from first-order perturbation theory. The relativistic correction improved vibrational stretching motion while making the prediction of the bending modes far worse. For rotational motion the relativistic effect had an increasing...

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

    DEFF Research Database (Denmark)

    Shim, Irene; Gingerich, Karl A.

    1997-01-01

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

  20. Electrical resistivity of NaPb compound-forming liquid alloy using ab initio pseudopotentials

    Indian Academy of Sciences (India)

    Anil Thakur; N S Negi; P K Ahluwalla

    2005-08-01

    The study of electrical resistivity of compound-forming liquid alloy, NaPb, is presented as a function of concentration. Hard sphere diameters of Na and Pb are obtained through the interionic pair potentials evaluated using Troullier and Martins ab initio pseudopotential, which have been used to calculate the partial structure factors (). Considering the liquid alloy to be a ternary mixture, Ziman formula, modified for complex formation has been used for calculating resistivity of binary liquid alloys. Form factors are calculated using ab initio pseudopotentials. The results suggest that Ziman formalism, when used with ab initio pseudopotentials, are quite successful in explaining the electrical resistivity data of compound-forming binary liquid alloys.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-12-05

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

  2. An Efficient Time-Stepping Scheme for Ab Initio Molecular Dynamics Simulations

    Science.gov (United States)

    Tsuchida, Eiji

    2016-08-01

    In ab initio molecular dynamics simulations of real-world problems, the simple Verlet method is still widely used for integrating the equations of motion, while more efficient algorithms are routinely used in classical molecular dynamics. We show that if the Verlet method is used in conjunction with pre- and postprocessing, the accuracy of the time integration is significantly improved with only a small computational overhead. We also propose several extensions of the algorithm required for use in ab initio molecular dynamics. The validity of the processed Verlet method is demonstrated in several examples including ab initio molecular dynamics simulations of liquid water. The structural properties obtained from the processed Verlet method are found to be sufficiently accurate even for large time steps close to the stability limit. This approach results in a 2× performance gain over the standard Verlet method for a given accuracy. We also show how to generate a canonical ensemble within this approach.

  3. 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.

  4. Matrix Product Operators, Matrix Product States, and ab initio Density Matrix Renormalization Group algorithms

    CERN Document Server

    Chan, Garnet Kin-Lic; Nakatani, Naoki; Li, Zhendong; White, Steven R

    2016-01-01

    Current descriptions of the ab initio 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 par...

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

    International Nuclear Information System (INIS)

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

  6. Exploring the speed and performance of molecular replacement with AMPLE using QUARK ab initio protein models.

    Science.gov (United States)

    Keegan, Ronan M; Bibby, Jaclyn; Thomas, Jens; Xu, Dong; Zhang, Yang; Mayans, Olga; Winn, Martyn D; Rigden, Daniel J

    2015-02-01

    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.

  7. An ab initio study on single electron transfer between ClO2 and phenol

    Institute of Scientific and Technical Information of China (English)

    崔崇威; 黄君礼

    2004-01-01

    The SET mechanism between chlorine dioxide (ClO2 ) and phenol was studied by using ab initio method at 4-31G* level. Geometries of the reactants, intermediate and products of the reaction were optimized and the single point energy calculations of the species were performed. The relative structure data of the reactants, intermediate and products are given. The SET mechanism between ClO2 and phenol was confirmed by ab initio calculations. The reaction is exothermic about 200. 88 k J/mol.

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

    DEFF Research Database (Denmark)

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

    2011-01-01

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

  9. Ab Initio Calculation on Self-Assembled Base-Functionalized Single-Walled Carbon Nanotubes

    Institute of Scientific and Technical Information of China (English)

    SONG Chen; XIA Yue-Yuan; ZHAO Ming-Wen; LIU Xiang-Dong; LI Ji-Ling; LI Li-Juan; LI Feng; HUANG Bo-Da

    2006-01-01

    @@ We perform ab initio calculations on the self-assembled base-functionalized single-walled carbon nanotubes (SWNTs) which exhibit the quasi-1D ‘ladder’ structure. The optimized configuration in the ab initio calculation is very similar to that obtainedfrom molecular dynamics simulation. We also calculate the electronic structures of the self-assembled base-functionalized SWNTs that exhibit distinct difference from the single-branch base-functionalized SWNT with a localized state lying just below the Fermi level, which may result from the coupling interaction between the bases accompanied by the self-assembly behaviour.

  10. 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)

  11. How many-body correlations and $\\alpha$-clustering shape $^6$He

    CERN Document Server

    Romero-Redondo, Carolina; Navratil, Petr; Hupin, Guillaume

    2016-01-01

    The Borromean $^6$He nucleus is an exotic system characterized by two `halo' neutrons orbiting around a compact $^4$He (or $\\alpha$) core, in which the binary subsystems are unbound. The simultaneous reproduction of its small binding energy and extended matter and point-proton radii has been a challenge for {\\em ab initio} theoretical calculations based on traditional bound-state methods. Using soft nucleon-nucleon interactions based on chiral effective field theory potentials, we show that supplementing the model space with $^4$He+$n$+$n$ cluster degrees of freedom largely solves this issue. We analyze the role played by the $\\alpha$-clustering and many-body correlations, and study the dependence of the energy spectrum on the resolution scale of the interaction.

  12. Three-particle correlation from a Many-Body Perspective: Trions in a Carbon Nanotube

    Science.gov (United States)

    Deilmann, Thorsten; Drüppel, Matthias; Rohlfing, Michael

    2016-05-01

    Trion states of three correlated particles (e.g., two electrons and one hole) are essential to understand the optical spectra of doped or gated nanostructures, like carbon nanotubes or transition-metal dichalcogenides. We develop a theoretical many-body description for such correlated states using an ab initio approach. It can be regarded as an extension of the widely used G W method and Bethe-Salpeter equation, thus allowing for a direct comparison with excitons. We apply this method to a semiconducting (8,0) carbon nanotube, and find that the lowest optically active trions are redshifted by ˜130 meV compared to the excitons, confirming experimental findings for similar tubes. Moreover, our method provides detailed insights in the physical nature of trion states. In the prototypical carbon nanotube we find a variety of different excitations, discuss the spectra, energy compositions, and correlated wave functions.

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

    Science.gov (United States)

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

    2015-10-01

    The rotational spectrum of the van der Waals complex CH4-CO has been measured with the intracavity OROTRON jet spectrometer in the frequency range of 110-145 GHz. Newly observed and assigned transitions belong to the K = 2-1 subband correlating with the rotationless jCH4 = 0 ground state and the K = 2-1 and K = 0-1 subbands correlating with the jCH4 = 2 excited state of free methane. The (approximate) quantum number K is the projection of the total angular momentum J on the intermolecular axis. The new data were analyzed together with the known millimeter-wave and microwave transitions in order to determine the molecular parameters of the CH4-CO complex. Accompanying ab initio calculations of the intermolecular potential energy surface (PES) of CH4-CO have been carried out at the explicitly correlated coupled cluster level of theory with single, double, and perturbative triple excitations [CCSD(T)-F12a] and an augmented correlation-consistent triple zeta (aVTZ) basis set. The global minimum of the five-dimensional PES corresponds to an approximately T-shaped structure with the CH4 face closest to the CO subunit and binding energy De = 177.82 cm-1. The bound rovibrational levels of the CH4-CO complex were calculated for total angular momentum J = 0-6 on this intermolecular potential surface and compared with the experimental results. The calculated dissociation energies D0 are 91.32, 94.46, and 104.21 cm-1 for A (jCH4 = 0), F (jCH4 = 1), and E (jCH4 = 2) nuclear spin modifications of CH4-CO, respectively.

  14. Ab initio calculation of Ti NMR shieldings for titanium oxides and halides

    Science.gov (United States)

    Tossell, J. A.

    Titanium NMR shielding constants have been calculated using ab initio coupled Hartree-Fock perturbation theory and polarized double-zeta basis sets for TiF 4, TiF 62-, TiCI 4, Ti(OH) 4, Ti(OH 2) 64+, Ti(OH) 4O, and Ti(OH) 3O -. In all cases the calculations were performed at Hartree-Fuck energy-optimized geometries. For Ti(OH) 4 a S4-symmetry geometry with nonlinear ∠ TiOH was employed. Relative shieldings are in reasonable agreement with experiment for TiF 62-, TiCI 4, and Ti(OR) 4, where R = H or alkyl. Ti(OH 2) 64+ is predicted to be more highly shielded than Ti(OH) 4 by about 340 ppm. The five-coordinate complex Ti(OH) 4O, whose calculated structure matches well that measured by extended X-ray absorption fine structure in K 2O · TiO 2 · SiO 2 glass, is actually deshielded compared to Ti(OH) 4 by about 40 ppm. X-ray absorption-near-edge spectral energies have also been calculated for TiF 4, TiCI 4, Ti(OH) 4, and Ti(OH) 4O using an equivalent ionic core virtual-orbital method and the observed reduction in term energy for the five-coordinate species compared to Ti(OH) 4 has been reproduced. Replacement of the H atoms in Ti(OH) 4 by point charges has only a slight effect upon σTi, suggesting a possible means of incorporating second-neighbor effects in NMR calculations for condensed phases.

  15. An ab initio cluster study of atomic oxygen chemisorption on Ga-rich GaAs(100) (2x1) and beta(4x2) surfaces

    OpenAIRE

    Mayo, Michael L.; Ray, Asok K.

    2003-01-01

    Ab initio self-consistent total energy calculations using second order Moller-Plesset perturbation theory and Hay-Wadt effective core potentials for gallium and arsenic have been used to investigate the chemisorption of atomic oxygen on the Ga-rich GaAs (100) (2 x 1) and beta(4 x 2) surfaces. Finite sized hydrogen saturated clusters with the experimental zinc-blende lattice constant of 5.654 angstroms and the energy optimized surface Ga dimer bond length of 2.758 angstroms have been used to m...

  16. Argon Interaction with Gold Surfaces: Ab Initio-Assisted Determination of Pair Ar-Au Potentials for Molecular Dynamics Simulations.

    Science.gov (United States)

    Grenier, Romain; To, Quy-Dong; de Lara-Castells, María Pilar; Léonard, Céline

    2015-07-01

    Global potentials for the interaction between the Ar atom and gold surfaces are investigated and Ar-Au pair potentials suitable for molecular dynamics simulations are derived. Using a periodic plane-wave representation of the electronic wave function, the nonlocal van-der-Waals vdW-DF2 and vdW-OptB86 approaches have been proved to describe better the interaction. These global interaction potentials have been decomposed to produce pair potentials. Then, the pair potentials have been compared with those derived by combining the dispersionless density functional dlDF for the repulsive part with an effective pairwise dispersion interaction. These repulsive potentials have been obtained from the decomposition of the repulsive interaction between the Ar atom and the Au2 and Au4 clusters and the dispersion coefficients have been evaluated by means of ab initio calculations on the Ar+Au2 complex using symmetry adapted perturbation theory. The pair potentials agree very well with those evaluated through periodic vdW-DF2 calculations. For benchmarking purposes, CCSD(T) calculations have also been performed for the ArAu and Ar+Au2 systems using large basis sets and extrapolations to the complete basis set limit. This work highlights that ab initio calculations using very small surface clusters can be used either as an independent cross-check to compare the performance of state-of-the-art vdW-corrected periodic DFT approaches or, directly, to calculate the pair potentials necessary in further molecular dynamics calculations. PMID:26046588

  17. Toward ab initio DFT: Pairing and Optimized Effective Potential

    Science.gov (United States)

    Drut, Joaquin

    2010-11-01

    The quest for a universal nuclear energy density functional has stimulated research in many different areas of quantum many-body physics. Advances in the last decade have enabled quantum chemists to explicitly construct energy density functionals for the Coulomb interaction from first principles. This task was accomplished by extending the notion of density-dependent functionals to include explicit dependence on the Kohn-Sham orbitals. The resulting approach is usually called the Optimized Effective Potential (OEP). Are these developments useful in the nuclear case? Can one extend the OEP to include pairing? In this contribution we present some first answers to these and other related questions.

  18. Ab-initio modeling of an anion $C_{60}^-$ pseudopotential for fullerene-based compounds

    CERN Document Server

    Vrubel, I I; Ivanov, V K

    2015-01-01

    A pseudopotential of $C_{60}^-$ has been constructed from ab-initio quantum-mechanical calculations. Since the obtained pseudopotential can be easily fitted by rather simple analytical approximation it can be effectively used both in classical and quantum molecular dynamics of fullerene-based compounds.

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

    DEFF Research Database (Denmark)

    Castelli, Ivano E.; Salvestrini, Paolo; Manini, Nicola

    2012-01-01

    As sp carbon chains (carbynes) are relatively rigid molecular objects, can we exploit them as construction elements in nanomechanics? To answer this question, we investigate their remarkable mechanical properties by ab initio total-energy simulations. In particular, we evaluate their linear respo...

  20. 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. PMID:27394094

  1. Ab Initio Investigations of the C2F4S Isomers and of Their Interconversions

    DEFF Research Database (Denmark)

    Shim, Irene; Vallano-Lorenzo, Sandra; Lisbona-Martin, Pilar;

    2003-01-01

    The transition states and the activation energies for the unobserved isomerization reactions between the three possible C2F4S isomers with divalent sulfur, trifluorothioacetyl fluoride 1, tetrafluorothiirane 2, and trifluoroethenesulfenyl fluoride 3, have been determined by ab initio Hartree-Fock...

  2. Ab initio prediction of vacancy properties in concentrated alloys: The case of fcc Cu-Ni

    NARCIS (Netherlands)

    Zhang, X.; Sluiter, M.H.F.

    2015-01-01

    Vacancy properties in concentrated alloys continue to be of great interest because nowadays ab initio supercell simulations reach a scale where even defect properties in disordered alloys appear to be within reach. We show that vacancy properties cannot generally be extracted from supercell total en

  3. New approaches for molecular conformer force field analysis in combination with ab initio results

    Science.gov (United States)

    Kuramshina, G. M.; Pentin, Yu. A.; Yagola, A. G.

    1999-10-01

    Ab initio and DFT results on harmonic force constants for trans- and gauche-conformers of CH 3CH 2CH 2Cl, CF 3CH 2CH 2Cl and CCl 3CH 2CH 2Cl are used for formulating constraints in molecular force field models described compounds with hindered internal rotation around the C-C bond.

  4. Ab initio and work function and surface energy anisotropy of LaB6

    NARCIS (Netherlands)

    Uijttewaal, M. A.; de Wijs, G. A.; de Groot, R. A.

    2006-01-01

    Lanthanum hexaboride is one of the cathode materials most used in high-power electronics technology, but the many experimental results do not provide a consistent picture of the surface properties. Therefore, we report the first ab initio calculations of the work functions and surface energies of th

  5. Ab initio I-V characteristics of short C-20 chains

    DEFF Research Database (Denmark)

    Roland, C.; Larade, B.; Taylor, Jeremy Philip;

    2002-01-01

    We have calculated the I-V characteristics of short chains of C-20 molecular cages between Al and Au leads with an ab initio formalism. The results indicate that a linear chain of such molecules acts primarily as metallic nanowires. The transmission, however, depends sensitively both on the...

  6. 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.

  7. Stabilization of Ab Initio Molecular Dynamics Simulations at Large Time Steps

    CERN Document Server

    Tsuchida, Eiji

    2014-01-01

    The Verlet method is still widely used to integrate the equations of motion in ab initio molecular dynamics simulations. We show that the stability limit of the Verlet method may be significantly increased by setting an upper limit on the kinetic energy of each atom with only a small loss in accuracy. The validity of this approach is demonstrated for molten lithium fluoride.

  8. New ab initio based pair potential for accurate simulation of phase transitions in ZnO

    NARCIS (Netherlands)

    Wang, Shuaiwei; Fan, Zhaochuan; Koster, Rik S.; Fang, Changming; Van Huis, Marijn A.; Yalcin, Anil O.; Tichelaar, Frans D.; Zandbergen, Henny W.; Vlugt, Thijs J H

    2014-01-01

    A set of interatomic pair potentials is developed for ZnO based on the partially charged rigid ion model (PCRIM). The derivation of the potentials combines lattice inversion, empirical fitting, and ab initio energy surface fitting. We show that, despite the low number of parameters in this model (8)

  9. Relativistic ab initio spectroscopy study of forbidden lines of singly ionized zinc

    NARCIS (Netherlands)

    Dixit, Gopal; Sahoo, Bijaya K.; Chaudhuri, Rajat K.; Majumder, Sonjoy

    2009-01-01

    The ab initio calculation has been carried out to study the astrophysically important forbidden electromagnetic transition rates of singly ionized zinc (Zn II). Electron correlations are considered to all orders using coupled-cluster theory in the relativistic framework. Calculated excitation energi

  10. Ab initio Defect Energetics in LaBO3 Perovskite Solid Oxide Fuel Cell Materials

    DEFF Research Database (Denmark)

    Lee, Yueh-Lin; Morgan, Dane; Kleis, Jesper;

    2009-01-01

    Perovskite materials of the form ABO3 are a promising family of compounds for use in solid oxide fuel cell (SOFC) cathodes. Study of the physics of these compounds under SOFC conditions with ab initio methods is particularly challenging due to high temperatures, exchange of oxygen with O2 gas, and...

  11. Raman and ab initio studies of simple and binary 1-alkyl-3-methylimidazolium ionic liquids

    DEFF Research Database (Denmark)

    Berg, R.W.; Deetlefs, M.; Seddon, K.R.;

    2005-01-01

    Raman spectra of the ionic liquids, 1-butyl-3-methylimidazolium hexafluorophosphate ([C(4)mim][PF6]), 1-hexyl-3-methylimidazolium chloride ([C(6)mim]Cl), and 1-hexyl-3-methylimidazolium hexafluorophosphate ([C(6)mim][PF6]), and binary mixtures thereof, have been assigned using ab initio MP2...

  12. Ab initio charge-carrier mobility model for amorphous molecular semiconductors

    Science.gov (United States)

    Massé, Andrea; Friederich, Pascal; Symalla, Franz; Liu, Feilong; Nitsche, Robert; Coehoorn, Reinder; Wenzel, Wolfgang; Bobbert, Peter A.

    2016-05-01

    Accurate charge-carrier mobility models of amorphous organic molecular semiconductors are essential to describe the electrical properties of devices based on these materials. The disordered nature of these semiconductors leads to percolative charge transport with a large characteristic length scale, posing a challenge to the development of such models from ab initio simulations. Here, we develop an ab initio mobility model using a four-step procedure. First, the amorphous morphology together with its energy disorder and intermolecular charge-transfer integrals are obtained from ab initio simulations in a small box. Next, the ab initio information is used to set up a stochastic model for the morphology and transfer integrals. This stochastic model is then employed to generate a large simulation box with modeled morphology and transfer integrals, which can fully capture the percolative charge transport. Finally, the charge-carrier mobility in this simulation box is calculated by solving a master equation, yielding a mobility function depending on temperature, carrier concentration, and electric field. We demonstrate the procedure for hole transport in two important molecular semiconductors, α -NPD and TCTA. In contrast to a previous study, we conclude that spatial correlations in the energy disorder are unimportant for α -NPD. We apply our mobility model to two types of hole-only α -NPD devices and find that the experimental temperature-dependent current density-voltage characteristics of all devices can be well described by only slightly decreasing the simulated energy disorder strength.

  13. Hexamethylcyclopentadiene: time-resolved photoelectron spectroscopy and ab initio multiple spawning simulations

    DEFF Research Database (Denmark)

    Wolf, T. J. A.; Kuhlman, Thomas Scheby; Schalk, O.;

    2014-01-01

    comparing time-resolved photoelectron spectroscopy (TRPES) with ab initio multiple spawning (AIMS) simulations on the MS-MR-CASPT2 level of theory. We disentangle the relationship between two phenomena that dominate the immediate molecular response upon light absorption: a spectrally dependent delay of the...

  14. Ab initio study of energy-level alignments in polymer-dye blends

    NARCIS (Netherlands)

    Pasveer, W.F.; Bobbert, P.A.; Michels, M.A.J.; Langeveld-Voss, B.M.W.; Schoo, H.F.M.; Bastiaansen, J.J.A.M.

    2003-01-01

    Polymers with a small amount of dye blended in offer an attractive possibility to change the color of the emitted light by changing the dye. We present ab initio calculations within density-functional theory of the HOMO/ LUMO energies for dipyrrolomethane dyes, polyphenylenevinylene and polyfluorene

  15. 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.

  16. 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, ...

  17. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Tanaka, Satoru; Taniguchi, Masaki [Tokyo Univ. (Japan). Faculty of Engineering

    1996-10-01

    The nature of -OH on the surface of Li{sub 2}O was analyzed with the ab-initio quantum chemical calculation technique. Calculation results showed that the stretching vibration of O-H is affected by the chemical species around the -OH. (author)

  19. Ab initio modeling of energy dissipation during chemical reactions at transition metal surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Meyer, Joerg

    2012-02-16

    In this work energy dissipation during exothermic chemical reactions in the context of heterogeneous catalysis is investigated in great detail, based on and substantially further developing ab initio methodologies. The dissociation of oxygen molecules (O{sub 2}) on the Pd(100) surface serves as a representative showcase, involving a release of about 2.6 eV of chemisorption energy. The impingement of O{sub 2} from the gas phase onto the surface occurs with randomly distributed initial molecular orientation and lateral position. In order to properly capture the breaking of the oxygen-oxygen bond, the latter is described on the level of density functional theory (DFT) with a semi-local exchange-correlation functional. Following a ''divide-and-conquer'' strategy, this description is decoupled from the dynamics to reduce the computational cost. The resulting interpolation problem is tackled with the help of neural networks using only a very limited number of data points. The initial sticking coefficient resulting from thousands of trajectories shows good agreement with available experimental data. Quite in contrast to Al(111) surfaces, the spin transition of the oxygen molecule ({sup 3}{sigma}{sup -}{sub g} spin triplet in gas phase to singlet-like state on the surface) can apparently be described adiabatically. In order to characterize this further and at the same time assess the relevance of one possible energy dissipation channel, excitations of electron-hole (e-h) pairs in the metal substrate are investigated using time-dependent perturbation theory - based on time-dependent density functional theory (TDDFT) and the Kohn-Sham band structure of the substrate. As a consequence, focus is inevitably shifted on phonons as major energy dissipation channel. A new embedding scheme called QM/Me was developed. In the present context it allows to model realistic (surface) phonons on the level of a ''modified embedded atom method'' (MEAM

  20. Negentropy in Many-Body Quantum Systems

    Directory of Open Access Journals (Sweden)

    Piero Quarati

    2016-02-01

    Full Text Available Negentropy (negative entropy is the negative contribution to the total entropy of correlated many-body environments. Negentropy can play a role in transferring its related stored mobilizable energy to colliding nuclei that participate in spontaneous or induced nuclear fusions in solid or liquid metals or in stellar plasmas. This energy transfer mechanism can explain the observed increase of nuclear fusion rates relative to the standard Salpeter screening. The importance of negentropy in these specific many-body quantum systems and its relation to many-body correlation entropy are discussed.

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

    Science.gov (United States)

    Timko, Jeff; Kuyucak, Serdar

    2012-11-01

    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.

  2. 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.

  3. Communication: Hole localization in Al-doped quartz SiO2 within ab initio hybrid-functional DFT

    International Nuclear Information System (INIS)

    We investigate the long-standing problem of hole localization at the Al impurity in quartz SiO2, using a relatively recent DFT hybrid-functional method in which the exchange fraction is obtained ab initio, based on an analogy with the static many-body COHSEX approximation to the electron self-energy. As the amount of the admixed exact exchange in hybrid functionals has been shown to be determinant for properly capturing the hole localization, this problem constitutes a prototypical benchmark for the accuracy of the method, allowing one to assess to what extent self-interaction effects are avoided. We obtain good results in terms of description of the charge localization and structural distortion around the Al center, improving with respect to the more popular B3LYP hybrid-functional approach. We also discuss the accuracy of computed hyperfine parameters, by comparison with previous calculations based on other self-interaction-free methods, as well as experimental values. We discuss and rationalize the limitations of our approach in computing defect-related excitation energies in low-dielectric-constant insulators

  4. Communication: Hole localization in Al-doped quartz SiO{sub 2} within ab initio hybrid-functional DFT

    Energy Technology Data Exchange (ETDEWEB)

    Gerosa, Matteo [Department of Energy, Politecnico di Milano, via Ponzio 34/3, 20133 Milano (Italy); Di Valentin, Cristiana; Pacchioni, Gianfranco [Dipartimento di Scienza dei Materiali, Università di Milano-Bicocca, via R. Cozzi 55, 20125 Milan (Italy); Bottani, Carlo Enrico, E-mail: carlo.bottani@polimi.it [Department of Energy, Politecnico di Milano, via Ponzio 34/3, 20133 Milano (Italy); Center for Nano Science and Technology @Polimi, Istituto Italiano di Tecnologia, via Pascoli 70/3, 20133 Milano (Italy); Onida, Giovanni [Dipartimento di Fisica dell’ Universita’ degli Studi di Milano and European Theoretical Spectroscopy Facility (ETSF), Via Celoria 16, 20133 Milan (Italy)

    2015-09-21

    We investigate the long-standing problem of hole localization at the Al impurity in quartz SiO{sub 2}, using a relatively recent DFT hybrid-functional method in which the exchange fraction is obtained ab initio, based on an analogy with the static many-body COHSEX approximation to the electron self-energy. As the amount of the admixed exact exchange in hybrid functionals has been shown to be determinant for properly capturing the hole localization, this problem constitutes a prototypical benchmark for the accuracy of the method, allowing one to assess to what extent self-interaction effects are avoided. We obtain good results in terms of description of the charge localization and structural distortion around the Al center, improving with respect to the more popular B3LYP hybrid-functional approach. We also discuss the accuracy of computed hyperfine parameters, by comparison with previous calculations based on other self-interaction-free methods, as well as experimental values. We discuss and rationalize the limitations of our approach in computing defect-related excitation energies in low-dielectric-constant insulators.

  5. Ab initio-driven nuclear energy density functional method. A proposal for safe/correlated/improvable parametrizations of the off-diagonal EDF kernels

    CERN Document Server

    Duguet, T; Ebran, J -P; Lesinski, T; Somà, V

    2015-01-01

    This programmatic paper lays down the possibility to reconcile the necessity to resum many-body correlations into the energy kernel with the fact that safe multi-reference energy density functional (EDF) calculations cannot be achieved whenever the Pauli principle is not strictly enforced, as is for example the case when many-body correlations are parametrized under the form of empirical density dependencies. Our proposal is to exploit a newly developed ab initio many-body formalism to guide the construction of safe, explicitly correlated and systematically improvable parametrizations of the {\\it off-diagonal} energy and norm kernels that lie at the heart of the nuclear EDF method. The many-body formalism of interest relies on the concepts of symmetry breaking {\\it and} restoration that have made the fortune of the nuclear EDF method and is, as such, amenable to this guidance. After elaborating on our proposal, we briefly outline the project we plan to execute in the years to come.

  6. Mathematical methods of many-body quantum field theory

    CERN Document Server

    Lehmann, Detlef

    2004-01-01

    Mathematical Methods of Many-Body Quantum Field Theory offers a comprehensive, mathematically rigorous treatment of many-body physics. It develops the mathematical tools for describing quantum many-body systems and applies them to the many-electron system. These tools include the formalism of second quantization, field theoretical perturbation theory, functional integral methods, bosonic and fermionic, and estimation and summation techniques for Feynman diagrams. Among the physical effects discussed in this context are BCS superconductivity, s-wave and higher l-wave, and the fractional quantum Hall effect. While the presentation is mathematically rigorous, the author does not focus solely on precise definitions and proofs, but also shows how to actually perform the computations.Presenting many recent advances and clarifying difficult concepts, this book provides the background, results, and detail needed to further explore the issue of when the standard approximation schemes in this field actually work and wh...

  7. 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

  8. Introduction to many-body physics

    CERN Document Server

    Coleman, Piers

    2015-01-01

    A modern, graduate-level introduction to many-body physics in condensed matter, this textbook explains the tools and concepts needed for a research-level understanding of the correlated behavior of quantum fluids. Starting with an operator-based introduction to the quantum field theory of many-body physics, this textbook presents the Feynman diagram approach, Green's functions and finite-temperature many body physics before developing the path integral approach to interacting systems. Special chapters are devoted to the concepts of Fermi liquid theory, broken symmetry, conduction in disordered systems, superconductivity and the physics of local-moment metals. A strong emphasis on concepts and numerous exercises make this an invaluable course book for graduate students in condensed matter physics. It will also interest students in nuclear, atomic and particle physics.

  9. Many-body interactions and nuclear structure

    CERN Document Server

    Hjorth-Jensen, M; Hagen, G; Kvaal, S

    2010-01-01

    This article presents several challenges to nuclear many-body theory and our understanding of the stability of nuclear matte r. In order to achieve this, we present five different cases, starting with an idealized toy model. These cases expose problems that need to be understood in order to match recent advances in nuclear theory with current experimental programs in low-energy nuclear physics. In particular, we focus on our current understanding, or lack thereof, of many-body forces, and how they evolve as functions of the number of particles . We provide examples of discrepancies between theory and experiment and outline some selected perspectives for future research directions.

  10. Ab initio study of different structures of CaC: Magnetism, bonding, and lattice dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Nourbakhsh, Zahra, E-mail: z.nourbakhsh@ph.iut.ac.ir; Hashemifar, S. Javad, E-mail: hashemifar@cc.iut.ac.ir; Akbarzadeh, Hadi

    2013-12-05

    Highlights: •Electronic structure and phonon calculations are performed on seven CaC structures. •The more covalent structures have lower energies and nonmagnetic ground state. •Ferromagnetism in the ionic phases comes from the sharp C p band at the Fermi level. •Tendency of C atoms for dimerization may lead to structural instabilities in CaC. •Nonmagnetic B33 CaC is stable in a wide range of temperatures and pressures. -- Abstract: On the basis of ab initio pseudopotential calculations, we study structural, magnetic, dynamical, and mechanical properties of the hypothetical CaC ionic compound in the rock-salt (RS), B2, zinc-blende (ZB), wurtzite (WZ), NiAs (NA), anti-NiAs (NA{sup ∗}), and CrB (B33) structures. It is argued that the ZB, WZ, NA, and RS structures are more ionic while the NA{sup ∗}, B2, and B33 structures are more covalent systems. As a result of that, the nonmagnetic B33–CaC is the energetically preferred system, while the more ionic structures prefer a ferromagnetic ground state with high Fermi level spin polarization. The observed ferromagnetism in the more ionic systems is attributed to the sharp partially filled p states of carbon atom in the system. In the framework of density functional perturbation theory, the phonon spectra of these systems are computed and the observed dynamical instabilities of the NA{sup ∗} and B2 structures are explained in terms of the covalent bonds between carbon atoms. The calculated Helmholtz and Enthalpy free energies indicate the highest stability of the B33 structure in a wide range of temperatures and pressures. Among the ferromagnetic structures, RS–CaC and ZB–CaC are reported, respectively, to be the most and the least metastable systems in various thermodynamics conditions. Several mechanical properties of the dynamically stable structures of CaC are determined from their phonon spectra.

  11. Ab initio study of the lattice stability of β-SiC under intense laser irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Shen, Yanhong; Gao, Tao, E-mail: gaotao@scu.edu.cn

    2015-10-05

    Highlights: • The band gap of β-SiC vanishes and its metallic character is presented when T{sub e} > 6 eV. • The TA modes of β-SiC are found to be negative T{sub e} = 3.39 eV. • The LO–TO splitting degree of β-SiC at Γ point begin to decline as T{sub e} > 4.5 eV. • The ionic strength of β-SiC is related to laser radiation intensity. - Abstract: We have performed ab initio calculation of electronic properties, lattice-dynamical properties, charge density difference and charge density of β-SiC at different electronic temperatures (T{sub e}) using local density approximation (LDA) pseudopotential method within the density functional perturbation theory (DFPT). The results of electronic density of state display that β-SiC is still semiconductor with band gap of 1.51 eV at T{sub e} = 0 eV. But, beyond a temperature of 6 eV, the band gap of β-SiC vanishes and its metallic character is presented. The calculated phonon frequencies of β-SiC at T{sub e} = 0 eV show a good agreement with the experimental values and other calculations. However, when β-SiC undergoes a sharp increase of its electronic temperature, the phonon frequencies of β-SiC have a significant softening. The transverse acoustic modes of β-SiC are found to be negative T{sub e} = 3.39 eV which lead to the lattice instability. Moreover, the LO–TO splitting degree of β-SiC at Γ point increases at first and then reduces as T{sub e} is raised, the turning point is at T{sub e} = 4.5 eV. By using CUT3D, the results of the charge density difference and charge density of β-SiC indicate that when radiation intensity is only strong enough (e.g. T{sub e} > 4.5 eV), it will make the ionic strength of β-SiC weaken. Otherwise, when radiation intensity is not very high (e.g. 0–4.5 eV), the ionic strength of β-SiC will increase with the rise of T{sub e}.

  12. The ab initio model potential method with the spin-free relativistic scheme by eliminating small components Hamiltonian

    Science.gov (United States)

    Motegi, Kyosuke; Nakajima, Takahito; Hirao, Kimihiko; Seijo, Luis

    2001-04-01

    A relativistic ab initio model potential (AIMP) for Pt, Au, and Hg atoms has been developed using a relativistic scheme by eliminating small components (RESC) in which the 5p, 5d, and 6s electrons are treated explicitly. The quality of new RESC-AIMP has been tested by calculating the spectroscopic properties of the hydrides of these elements using the Hartree-Fock and coupled cluster with singles and doubles (CCSD) methods. The agreement with reference all-electron RESC calculations is excellent. The RESC-AIMP method is applied successfully in the investigation of the spectroscopic constants of Au2 and Hg2 using the CCSD method with a perturbative estimate of the contributions of triples. The ground state of Pt2 is also determined by RESC-AIMP with the second-order complete active space perturbation method. The results show that scalar relativistic effects on the valence properties are well described by the RESC-AIMP method. The effect on the basis set superposition error on the spectroscopic constants is also examined.

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

    International Nuclear Information System (INIS)

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

  14. Accelerating chemical reactions: Exploring reactive free-energy surfaces using accelerated ab initio molecular dynamics

    Science.gov (United States)

    Pierce, Levi C. T.; Markwick, Phineus R. L.; McCammon, J. Andrew; Doltsinis, Nikos L.

    2011-01-01

    A biased potential molecular dynamics simulation approach, accelerated molecular dynamics (AMD), has been implemented in the framework of ab initio molecular dynamics for the study of chemical reactions. Using two examples, the double proton transfer reaction in formic acid dimer and the hypothetical adiabatic ring opening and subsequent rearrangement reactions in methylenecyclopropane, it is demonstrated that ab initio AMD can be readily employed to efficiently explore the reactive potential energy surface, allowing the prediction of chemical reactions and the identification of metastable states. An adaptive variant of the AMD method is developed, which additionally affords an accurate representation of both the free-energy surface and the mechanism associated with the chemical reaction of interest and can also provide an estimate of the reaction rate. PMID:21548673

  15. B28: the smallest all-boron cage from an ab initio global search

    Science.gov (United States)

    Zhao, Jijun; Huang, Xiaoming; Shi, Ruili; Liu, Hongsheng; Su, Yan; King, R. Bruce

    2015-09-01

    Our ab initio global searches reveal the lowest-energy cage for B28, which is built from two B12 units and prevails over the competing structural isomers such as planar, bowl, and tube. This smallest boron cage extends the scope of all-boron fullerene and provides a new structural motif of boron clusters and nanostructures.Our ab initio global searches reveal the lowest-energy cage for B28, which is built from two B12 units and prevails over the competing structural isomers such as planar, bowl, and tube. This smallest boron cage extends the scope of all-boron fullerene and provides a new structural motif of boron clusters and nanostructures. Electronic supplementary information (ESI) available: Planar isomer structures of B28 and spatial distributions of front molecular orbitals. See DOI: 10.1039/c5nr04034e

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

    Science.gov (United States)

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

    2016-05-01

    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 (Hg10In90, Hg30In70,. Hg50In50, Hg70In30, and Hg90Pb10) 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.

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

    Science.gov (United States)

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

    2014-08-01

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

  18. Ab initio study of AlxMoNbTiV high-entropy alloys.

    Science.gov (United States)

    Cao, Peiyu; Ni, Xiaodong; Tian, Fuyang; Varga, Lajos K; Vitos, Levente

    2015-02-25

    The Al(x)MoNbTiV (x = 0-1.5) high-entropy alloys (HEAs) adopt a single solid-solution phase, having the body centered cubic (bcc) crystal structure. Here we employ the ab initio exact muffin-tin orbitals method in combination with the coherent potential approximation to investigate the equilibrium volume, elastic constants, and polycrystalline elastic moduli of Al(x)MoNbTiV HEAs. A comparison between the ab initio and experimental equilibrium volumes demonstrates the validity and accuracy of the present approach. Our results indicate that Al addition decreases the thermodynamic stability of the bcc structure with respect to face-centered cubic and hexagonal close packed lattices. For the elastically isotropic Al(0.4)MoNbTiV HEAs, the valence electron concentration (VEC) is about 4.82, which is slightly different from VEC ∼ 4.72 obtained for the isotropic Gum metals and refractory--HEAs. PMID:25640032

  19. 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.

  20. Liquid Be, Ca and Ba. An orbital-free ab-initio molecular dynamics study

    Energy Technology Data Exchange (ETDEWEB)

    Rio, B. G. del; González, L. E. [Departamento de Física Teórica, Atómica y Óptica, Universidad de Valladolid, 47011 Valladolid (Spain)

    2015-08-17

    Several static and dynamic properties of liquid beryllium (l-Be), liquid calcium (l-Ca) and liquid barium (l-Ba) near their triple point have been evaluated by the orbital-free ab initio molecular dynamics method (OF-AIMD), where the interaction between valence electrons and ions is described by means of local pseudopotentials. These local pseudopotentials used were constructed through a force-matching process with those obtained from a Kohn-Sham ab initio molecular dynamics study (KS-AIMD) of a reduced system with non-local pseudopotentials. The calculated static structures show good agreement with the available experimental data, including an asymmetric second peak in the structure factor which has been linked to the existence of a marked icosahedral short-range order in the liquid. As for the dynamic properties, we obtain collective density excitations whose associated dispersion relations exhibit a positive dispersion.

  1. Study of atomic structure of liquid Hg-In alloys using ab-initio molecular dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Nalini; Ahluwalia, P. K. [Department of Physics, Himachal Pradesh University, Shimla(HP)-171005 (India); Thakur, Anil [Department of Physics, Govt. P. G. College Solan (HP)-173212 (India)

    2015-05-15

    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. Five liquid Hg-In mixtures (Hg{sub 10}In{sub 90}, Hg{sub 30}In{sub 70}, Hg{sub 50}In{sub 50}, Hg{sub 70}In{sub 30} and Hg{sub 90}In{sub 10}) at 299K are considered. The radial distribution function g(r) and structure factor S(q) of considered alloys are compared with respective experimental results for liquid Hg (l-Hg) and (l-In). The radial distribution function g(r) shows the presence of short range order in the systems considered. Smooth curves of Bhatia-Thornton partial structure factors factor shows the presence of liquid state in the considered alloys.

  2. Study of atomic structure of liquid Hg-In alloys using ab-initio molecular dynamics

    International Nuclear Information System (INIS)

    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. Five liquid Hg-In mixtures (Hg10In90, Hg30In70, Hg50In50, Hg70In30 and Hg90In10) at 299K are considered. The radial distribution function g(r) and structure factor S(q) of considered alloys are compared with respective experimental results for liquid Hg (l-Hg) and (l-In). The radial distribution function g(r) shows the presence of short range order in the systems considered. Smooth curves of Bhatia-Thornton partial structure factors factor shows the presence of liquid state in the considered alloys

  3. Interatomic potentials for Al and Ni from experimental data and ab initio calculations

    Energy Technology Data Exchange (ETDEWEB)

    Mishin, Y.; Farkas, D.; Miehl, M.J.; Papaconstantopoulos, D.A.

    1999-07-01

    New embedded-atom potentials for Al and Ni have been developed by fitting to both experimental data and the results of ab initio calculations. The ab initio data were obtained in the form of energies of different alternative computer-generated crystalline structures of these metals. The potentials accurately reproduce basic equilibrium properties of Al and Ni such as the elastic constants, phonon dispersion curves, vacancy formation and migration energies, stacking fault energies, and surface energies. The equilibrium energies of various alternative structures not included in the fitting database are calculated with these potentials. The results are compared with predictions of total-energy tight-binding calculations for the same structures. The embedded-atom potentials correctly reproduce the structural stability trends, which suggests that they are transferable to different local environments encountered in atomistic simulations of lattice defects.

  4. Melting of sodium under high pressure. An ab-initio study

    Energy Technology Data Exchange (ETDEWEB)

    González, D. J.; González, L. E. [Departamento de Física Teórica, Atómica y Optica, Universidad de Valladolid, 47011 Valladolid (Spain)

    2015-08-17

    We report ab-initio molecular dynamics simulations of dense liquid/solid sodium for a pressure range from 0 to 100 GPa. The simulations have been performed with the orbital free ab-initio molecular dynamics method which, by using the electron density as the basic variable, allows to perform simulations with large samples and for long runs. The calculated melting curve shows a maximum at a pressure ≈ 30 GPa and it is followed by a long, steep decrease. These features are in good agreement with the experimental data. For various pressures along the melting curve, we have calculated several liquid static properties (pair distribution functions, static structure factors and short-range order parameters) in order to analyze the structural effects of pressure.

  5. An efficient time-stepping scheme for ab initio molecular dynamics simulations

    CERN Document Server

    Tsuchida, Eiji

    2015-01-01

    In ab initio molecular dynamics simulations of real-world problems, the simple Verlet method is still widely used for integrating the equations of motion, while more efficient algorithms are routinely used in classical molecular dynamics. We show that if the Verlet method is used in conjunction with pre- and postprocessing, the accuracy of the time integration is significantly improved with only a small computational overhead. The validity of the processed Verlet method is demonstrated in several examples including ab initio molecular dynamics simulations of liquid water. The structural properties obtained from the processed Verlet method are found to be sufficiently accurate even for large time steps close to the stability limit. This approach results in a 2x performance gain over the standard Verlet method for a given accuracy.

  6. 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...... of the conformational energy of the S-plus-amphetamine molecule and the S-plus-amphetamine-H+ ion. The harmonic frequency calculations provide information about the characteristic features of the Raman spectra and the nature of the bonding in the molecule. It is concluded that vibrational bands from salt anions...

  7. Electrical Resistivity of Na-K Binary Liquid Alloy Using Ab-Initio Pseudopotentials

    Institute of Scientific and Technical Information of China (English)

    Anil Thakur; P. K. Ahluwalia

    2005-01-01

    @@ The study of electrical resistivity of simple binary liquid alloy Na-K is presented as a function of concentration.Hard sphere diameters of sodium (Na) and potassium (K) are obtained through the inter ionic pair potentials evaluated using Troullier and Martins ab-initio pseudopotentials, which have been used to calculate partial structure factors S(q). The Ziman formula for calculating resistivity of binary liquid alloys has been used. Form factors are calculated using ab-initio pseudopotentials. The results suggest that the first principle approach for calculating pseudopotentials with in the frame work of Ziman formalism is quite successful in explaining the electrical resistivity data of compound forming binary liquid alloys.

  8. Ab-initio Gorkov-Green's function calculations of open-shell nuclei

    CERN Document Server

    Soma, V; Duguet, T

    2012-01-01

    We present results from a new ab-initio method that uses the self-consistent Gorkov Green's function theory to address truly open-shell systems. The formalism has been recently worked out up to second order and is implemented here in nuclei for the first time on the basis of realistic nuclear forces. We find good convergence of the results with respect to the basis size in Ca44 and Ni74 and discuss quantities of experimental interest including ground-state energies, pairing gaps and particle addition/removal spectroscopy. These results demonstrate that the Gorkov method is a valid alternative to multireference approaches for tackling degenerate or near degenerate quantum systems. In particular, it increases the number of mid-mass nuclei accessible in an ab-initio fashion from a few tens to a few hundreds.

  9. Ab initio studies of equations of state and chemical reactions of reactive structural materials

    Science.gov (United States)

    Zaharieva, Roussislava

    subject of studies of the shock or thermally induced chemical reactions of the two solids comprising these reactive materials, from first principles, is a relatively new field of study. The published literature on ab initio techniques or quantum mechanics based approaches consists of the ab initio or ab initio-molecular dynamics studies in related fields that contain a solid and a gas. One such study in the literature involves a gas and a solid. This is an investigation of the adsorption of gasses such as carbon monoxide (CO) on Tungsten. The motivation for these studies is to synthesize alternate or synthetic fuel technology by Fischer-Tropsch process. In this thesis these studies are first to establish the procedure for solid-solid reaction and then to extend that to consider the effects of mechanical strain and temperature on the binding energy and chemisorptions of CO on tungsten. Then in this thesis, similar studies are also conducted on the effect of mechanical strain and temperature on the binding energies of Titanium and hydrogen. The motivations are again to understand the method and extend the method to such solid-solid reactions. A second motivation is to seek strained conditions that favor hydrogen storage and strain conditions that release hydrogen easily when needed. Following the establishment of ab initio and ab initio studies of chemical reactions between a solid and a gas, the next step of research is to study thermally induced chemical reaction between two solids (Ni+Al). Thus, specific new studies of the thesis are as follows: (1) Ab initio Studies of Binding energies associated with chemisorption of (a) CO on W surfaces (111, and 100) at elevated temperatures and strains and (b) adsorption of hydrogen in titanium base. (2) Equations of state of mixtures of reactive material structures from ab initio methods. (3) Ab initio studies of the reaction initiation, transition states and reaction products of intermetallic mixtures of (Ni+Al) at elevated

  10. Properties of metals during the heating by intense laser irradiation using ab initio simulations

    Science.gov (United States)

    Holst, Bastian; Recoules, Vanina; Torrent, Marc; Mazevet, Stephane

    2011-10-01

    Ultrashort laser pulses irradiating a target heat the electrons to very high temperatures. In contrast, the ionic lattice is unaffected on the time scale of the laser pulse since the heat capacity of electrons is much smaller than that of the lattice. This non-equilibrium system can be described as a composition of two subsystems: one consisting of hot electrons and the other of an ionic lattice at low temperature. We studied the effect of this intense electronic excitations on the optical properties of gold using ab initio simulations. We additionally use ab initio linear response to compute the phonon spectrum and the electron-phonon coupling constant within Density Functional Theory for several electronic temperatures of few eV. LULI, Ecole Polytechnique, CNRS, CEA, UPMC, 91128 Palaiseau, France.

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

    Science.gov (United States)

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

    2013-02-27

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

  12. A fully ab initio potential energy surface for ClH2 reactive system

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    An ab initio analytical potential energy surface called BW3 for the ClH2 reactive system is presented. The fit of this surface is based on about 1 200 ab initio energy points, computed with multi-reference configuration interaction(MRCI) and scaling external correlation (SEC) method and a very large basis set. The precision in the fit is very high. The BW3 surface could reproduce correctly the dissociation energy of H2 and HCl, and the endothermicity of the Cl + H2 abstraction reaction. For the Cl + H2 abstraction reaction, the saddle point of BW3 lies in collinear geometries, and the barrier height is 32.84 kJ/mol; for the H + ClH exchange reaction, the barrier of BW3 is also linear, with a height of 77.40 kJ/mol.

  13. A fully ab initio potential energy surface for C1H2 reactive system

    Institute of Scientific and Technical Information of China (English)

    边文生; 刘成卜; H.J.Werner

    2000-01-01

    An ab initio analytical potential energy surface called BW3 for the CIH2 reactive system is presented. The fit of this surface is based on about 1 200 ab initio energy points, computed with multi-reference configuration interaction(MRCI) and scaling external correlation (SEC) method and a very large basis set. The precision in the fit is very high. The BW3 surface could reproduce correctly the dissociation energy of H2 and HCI, and the endothermicity of the Cl + H2 abstraction reaction. For the Cl + H2 abstraction reaction, the saddle point of BW3 lies in collinear geometries, and the barrier height is 32.84 kJ/mol; for the H + CIH exchange reaction, the barrier of BW3 is also linear, with a height of 77.40 kJ/mol.

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

    Science.gov (United States)

    Correa, J. D.; Cisternas, E.

    2016-09-01

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

  15. {\\it Ab initio} nuclear structure - the large sparse matrix eigenvalue problem

    CERN Document Server

    Vary, James P; 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 {\\it ab initio} methods have now emerged that provide nearly exact solutions for some nuclear properties. The {\\it 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 t...

  16. Ab initio modelling of the behaviour of point defects and fission products in nuclear fuel

    International Nuclear Information System (INIS)

    The aim of this work is to determine precisely the mechanisms of formation and migration of defects and fission products as well as the associated energies. Examples on uranium dioxide UO2 (standard nuclear fuel) and on uranium carbide UC (potential fuel for new generation reactors) are given. The obtained results are discussed and compared with the experimental results carried out. The ab initio method used is the Projector Augmented-Wave (PAW) method based on the density functional theory. The particular electronic properties of actinides are especially studied because, on account of their 5f orbitals more or less localized around the nucleus, it is difficult to model the actinide compounds by the DFT method. In particular, the modelling of the exchange-correlation interaction of the 5f electrons of UO2 requires approximations (as GGA+U) beyond those more currently used in ab initio calculations (LDA or GGA). (O.M.)

  17. Ab initio calculations to support accurate modelling of the rovibronic spectroscopy calculations of vanadium monoxide (VO)

    CERN Document Server

    McKemmish, Laura K; Tennyson, Jonathan

    2016-01-01

    Accurate knowledge of the rovibronic near-infrared and visible spectra of vanadium monoxide (VO) is very important for studies of cool stellar and hot planetary atmospheres. Here, the required ab initio dipole moment and spin-orbit coupling curves for VO are produced. This data forms the basis of a new VO line list considering 13 different electronic states and containing over 277 million transitions. Open shell transition, metal diatomics are challenging species to model through ab initio quantum mechanics due to the large number of low-lying electronic states, significant spin-orbit coupling and strong static and dynamic electron correlation. Multi-reference configuration interaction methodologies using orbitals from a complete active space self-consistent-field (CASSCF) calculation are the standard technique for these systems. We use different state-specific or minimal-state CASSCF orbitals for each electronic state to maximise the calculation accuracy. The off-diagonal dipole moment controls the intensity...

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

    International Nuclear Information System (INIS)

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

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

    CERN Document Server

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

    2016-01-01

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

  20. Necessary conditions for microscopic many-body theories

    OpenAIRE

    Jackson, A. D.; Wettig, Tilo

    1994-01-01

    Familiar necessary conditions for the saturation of many-body binding energies are reconsidered in order to provide a better understanding of the analyticity properties of the ground state energy and of the convergence properties of certain sums of Goldstone diagrams. Using these results and other elementary arguments, we identify a minimum class of diagrams which must be summed to all orders if the perturbative treatment of other diagrams is to converge.

  1. Ab initio molecular dynamics with nuclear quantum effects at classical cost: ring polymer contraction for density functional theory

    CERN Document Server

    Marsalek, Ondrej

    2015-01-01

    Path integral molecular dynamics simulations, combined with an ab initio evaluation of interactions using electronic structure theory, incorporate the quantum mechanical nature of both the electrons and nuclei, which are essential to accurately describe systems containing light nuclei. However, path integral simulations have traditionally required a computational cost around two orders of magnitude greater than treating the nuclei classically, making them prohibitively costly for most applications. Here we show that the cost of path integral simulations can be dramatically reduced by extending our ring polymer contraction approach to ab initio molecular dynamics simulations. By using density functional tight binding as a reference system, we show that our ab initio ring polymer contraction (AI-RPC) scheme gives rapid and systematic convergence to the full path integral density functional theory result. We demonstrate the efficiency of this approach in ab initio simulations of liquid water and the reactive pro...

  2. A Deep Learning Network Approach to ab initio Protein Secondary Structure Prediction

    OpenAIRE

    Spencer, Matt; Eickholt, Jesse; Cheng, Jianlin

    2014-01-01

    Ab initio protein secondary structure (SS) predictions are utilized to generate tertiary structure predictions, which are increasingly demanded due to the rapid discovery of proteins. Although recent developments have slightly exceeded previous methods of SS prediction, accuracy has stagnated around 80% and many wonder if prediction cannot be advanced beyond this ceiling. Disciplines that have traditionally employed neural networks are experimenting with novel deep learning techniques in atte...

  3. Ab Initio Study on the Anti-HIV Activities of Hydroxyflavones

    Institute of Scientific and Technical Information of China (English)

    ZHANG Yu

    2005-01-01

    Flavone and 95 hydroxyflavones have been studied with ab initio method, and their total energies, atomic charges, dipole moments, multipole moments, molecular orbital compositions, orbital energies etc. were obtained. Among them the relationship between total atomic charges and activities against HIV is basically in accordance with the experimental results. The beneficial references are provided for the extraction and synthesis of strong active anti-HIV medicines.

  4. Ab-initio simulation and experimental validation of beta-titanium alloys

    OpenAIRE

    Raabe, D.; Sander, B.; Friák, M.; Ma, D.; Neugebauer, J.

    2008-01-01

    In this progress report we present a new approach to the ab-initio guided bottom up design of beta-Ti alloys for biomedical applications using a quantum mechanical simulation method in conjunction with experiments. Parameter-free density functional theory calculations are used to provide theoretical guidance in selecting and optimizing Ti-based alloys with respect to three constraints: (i) the use of non-toxic alloy elements; (ii) the stabilization of the body centered cubic beta phase at roo...

  5. Ab Initio Studies on Hematite Surface and the Adsorption of Phosphate

    OpenAIRE

    Swati Chaudhury; Chandrika Varadachari; Kunal Ghosh

    2014-01-01

    This investigation explores the ab initio DFT method for understanding surface structure of hematite and the nature and energetics of phosphate adsorption. Using the full potential linearized plane wave method (FP-LAPW), we derived the structure and energies of various magnetic forms of hematite. The antiferromagnetic (AFM) form was observed to be the most stable. Hematite surfaces with Fe-termination, O-termination, or OH-termination were studied. The OH-terminated surface was the most stabl...

  6. Ab initio molecular dynamics simulation of hydrogen fluoride at several thermodynamic states

    DEFF Research Database (Denmark)

    Kreitmeir, M.; Bertagnolli, H.; Mortensen, Jens Jørgen;

    2003-01-01

    Liquid hydrogen fluoride is a simple but interesting system for studies of the influence of hydrogen bonds on physical properties. We have performed ab initio molecular dynamics simulations of HF at several thermodynamic states, where we examine the microscopic structure of the liquid as well...... as its static and dynamic properties. The results obtained show good agreement with well established data, and, moreover, we were able to show significant changes within the structure depending on the system's temperature and density....

  7. Surface Tension of Ab Initio Liquid Water at the Water-Air Interface

    OpenAIRE

    Nagata, Yuki; Ohto, Tatsuhiko; Bonn, Mischa; Kühne, Thomas D.

    2016-01-01

    We report calculations of the surface tension of the water-air interface using ab initio molecular dynamics (AIMD) simulations. We investigate the simulation cell size dependence of the surface tension of water from force field molecular dynamics (MD) simulations, which show that the calculated surface tension increases with increasing simulation cell size, thereby illustrating that a correction for finite size effects is required for the small system used in the AIMD simulation. The AIMD sim...

  8. First fully ab initio potential energy surface of methane with a spectroscopic accuracy

    Science.gov (United States)

    Nikitin, A. V.; Rey, M.; Tyuterev, Vl. G.

    2016-09-01

    Full 9-dimensional ab initio potential energy surfaces for the methane molecule are constructed using extended electronic structure coupled-cluster calculations with various series of basis sets following increasing X cardinal numbers: cc-pVXZ (X = 3, 4, 5, 6), aug-cc-ACVXZ (X = 3, 4, 5), and cc-pCVXZ-F12 (X = 3, 4). High-order dynamic electron correlations including triple and quadrupole excitations as well as relativistic and diagonal Born-Oppenheimer breakdown corrections were accounted for. Analytical potential functions are parametrized as non-polynomial expansions in internal coordinates in irreducible tensor representation. Vibrational energy levels are reported using global variational nuclear motion calculations with exact kinetic energy operator and a full account of the tetrahedral symmetry of CH4. Our best ab initio surface including above-mentioned contributions provides the rms (obs.-calc.) errors of less than 0.11 cm-1 for vibrational band centers below 4700 cm-1, and ˜0.3 cm-1 for all 229 assigned experimentally determined vibrational levels up to the Icosad range <7900 cm-1 without empirically adjusted parameters. These results improve the accuracy of ab initio methane vibrational predictions by more than an order of magnitude with respect to previous works. This is an unprecedented accuracy of first-principles calculations of a five-atomic molecule for such a large data set. New ab initio potential results in significantly better band center predictions even in comparison with best available empirically corrected potential energy surfaces. The issues related to the basis set extrapolation and an additivity of various corrections at this level of accuracy are discussed.

  9. Ab initio potential energy surface for the highly nonlinear dynamics of the KCN molecule

    Energy Technology Data Exchange (ETDEWEB)

    Párraga, H.; Arranz, F. J., E-mail: fj.arranz@upm.es; Benito, R. M., E-mail: rosamaria.benito@upm.es [Grupo de Sistemas Complejos, ETSI Agrónomos, Universidad Politécnica de Madrid, 28040 Madrid (Spain); Borondo, F., E-mail: f.borondo@uam.es [Departamento de Química and Instituto de Ciencias Matemáticas (ICMAT), Universidad Autónoma de Madrid, Cantoblanco, 28049-Madrid (Spain)

    2013-11-21

    An accurate ab initio quantum chemistry study at level of quadratic configuration interaction method of the electronic ground state of the KCN molecule is presented. A fitting of the results to an analytical series expansion was performed to obtain a global potential energy surface suitable for the study of the associated vibrational dynamics. Additionally, classical Poincaré surfaces of section for different energies and quantum eigenstates were calculated, showing the highly nonlinear behavior of this system.

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

    International Nuclear Information System (INIS)

    We have performed ab initio calculations of positron distribution, ACAR and lifetime in the quasi-one-dimensional organic conductor TTF-TCNQ. The electronic structure is obtained within the LDA, while the positron state is calculated either with the LDA or with the GGA. Except the positron lifetime, differences between the LDA and GGA results are rather small. The obtained results are compared with our previous experiments and calculations.

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

    Science.gov (United States)

    Ishibashi, Shoji; Kohyama, Masanori

    2000-06-01

    We have performed ab initio calculations of positron distribution, ACAR and lifetime in the quasi-one-dimensional organic conductor TTF-TCNQ. The electronic structure is obtained within the LDA, while the positron state is calculated either with the LDA or with the GGA. Except the positron lifetime, differences between the LDA and GGA results are rather small. The obtained results are compared with our previous experiments and calculations.

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

    OpenAIRE

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

    2013-01-01

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

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

    OpenAIRE

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

    2007-01-01

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

  14. Ab initio study on the magnetostructural properties of MnAs

    OpenAIRE

    Sanvito, Stefano; RUNGGER, IVAN

    2006-01-01

    The magnetic and structural properties of MnAs are studied with ab initio methods, and by mapping total energies onto a Heisenberg model. The stability of the different phases is found to depend mainly on the volume and on the amount of magnetic order, confirming previous experimental findings and phenomenological models. It is generally found that for large lattice constants the ferromagnetic state is favored, whereas for small lattice constants different antiferromagnetic states can be stab...

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

    OpenAIRE

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

    2010-01-01

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

  16. Projector augmented wave method: ab initio molecular dynamics with full wave functions

    Indian Academy of Sciences (India)

    Peter E Blöchl; Clemens J Först; Johannes Schimpl

    2003-01-01

    A brief introduction to the projector augmented wave method is given and recent developments are reviewed. The projector augmented wave method is an all-electron method for efficient ab initio molecular dynamics simulations with full wave functions. It extends and combines the traditions of existing augmented wave methods and the pseudopotential approach. Without sacrificing efficiency, the PAW method avoids transferability problems of the pseudopotential approach and it has been valuable to predict properties that depend on the full wave functions.

  17. Simulation of Ab Initio Molecular Dynamics of Shock Wave on Copper

    Institute of Scientific and Technical Information of China (English)

    张林; 蔡灵仓; 向士凯; 经福谦; 陈栋泉

    2003-01-01

    The relation between particle velocity Up, up to 4 km/s, and shock wave velocity Us in copper has been simulated with ab initio molecular dynamics. The simulated relationship without considering the correction of zero-point and finite temperature effects is Us = 4.23 + 1.53Up. After considering the correction the relation becomes Us = 4.08 + 1.53Up, which is consistent with the experimental result.

  18. Ab initio theory of galvanomagnetic phenomena in ferromagnetic metals and disordered alloys

    OpenAIRE

    Turek, Ilja; Kudrnovsky, Josef; Drchal, Vaclav

    2011-01-01

    We present an ab initio theory of transport quantities of metallic ferromagnets developed in the framework of the fully relativistic tight-binding linear muffin-tin orbital method. The approach is based on the Kubo-Streda formula for the conductivity tensor, on the coherent potential approximation for random alloys, and on the concept of interatomic electron transport. The developed formalism is applied to pure 3d transition metals (Fe, Co, Ni) and to random Ni-based ferromagnetic alloys (Ni-...

  19. Ab initio simulations of liquid NaSn alloys: Zintl anions and network formation

    OpenAIRE

    Schoene, M.; Kaschner, R.; Seifert, G

    1994-01-01

    Using the Car-Parrinello technique, ab initio molecular dynamics simulations are performed for liquid NaSn alloys in five different compositions (20, 40, 50, 57 and 80 % sodium). The obtained structure factors agree well with the data from neutron scattering experiments. The measured prepeak in the structure factor is reproduced qualitatively for most compositions. The calculated and measured positions of all peaks show the same trend as function of the composition.\\\\ The dynamic simulations ...

  20. Equations of state of magnesium perovskite and postperovskite: diagnostics from ab initio simulations

    OpenAIRE

    Belousov, Roman; Prencipe, Mauro

    2014-01-01

    The isothermal compression of magnesium perovskite and postperovskite is examined through the F-f plot and the diagnostic plot of Vinet universal model theoretically from the ab initio quantum-mechanical calculations at the hybrid Hartree-Fock / Density Functional Theory level. A purely numerical approach, first time applied in this paper, shows that the discrepancies largely observed between studies on the perovskite and criticized in geophysical applications are due to the inadequate choice...

  1. Ab initio molecular dynamics study of liquid sodium and cesium up to critical point

    Energy Technology Data Exchange (ETDEWEB)

    Yuryev, Anatoly A. [Institute of Metallurgy of Ural Branch of the Russian Academy of Sciences, Amundsen st. 101,620016, Yekaterinburg (Russian Federation); Ural Federal University, Vira st. 19, 620002, Yekaterinburg (Russian Federation); Gelchinski, Boris R. [Institute of Metallurgy of Ural Branch of the Russian Academy of Sciences, Amundsen st. 101,620016, Yekaterinburg (Russian Federation)

    2015-08-17

    Ab initio modeling of liquid metals Na and K is carried out using the program SIESTA. We have determined the parameters of the model (the optimal step, the number of particles, the initial state etc) and calculated a wide range of properties: the total energy, pair correlation function, coefficient of self-diffusion, heat capacity, statistics of Voronoi polyhedra, the density of electronic states up to the critical temperature.

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

    OpenAIRE

    Gali, Adam

    2009-01-01

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

  3. Structures of 13-atom clusters of fcc transition metals by ab initio and semiempirical calculations

    Science.gov (United States)

    Longo, R. C.; Gallego, L. J.

    2006-11-01

    We report the results of ab initio calculations of the structures and magnetic moments of Ni13 , Pd13 , Pt13 , Cu13 , Ag13 , and Au13 that were performed using a density-functional method that employs linear combinations of pseudoatomic orbitals as basis sets (SIESTA). Our structural results for Pt13 , Cu13 , Ag13 , and Au13 show that a buckled biplanar structure (BBP) is more stable than the icosahedral configuration, in keeping with results obtained recently by Chang and Chou [Phys. Rev. Lett. 93, 133401 (2004)] using the Vienna ab initio simulation package with a plane-wave basis. However, for Ni13 and Pd13 we found that the icosahedral structure is more stable than BBP. For all these clusters, two semiempirical methods based on spherically symmetric potentials both found the icosahedral structure to be the more stable, while the modified embedded atom model method, which uses a direction-dependent potential, found BBP to be the more stable structure. When low-energy structures found in recent ab initio studies of Pt13 , Cu13 , and Au13 other than Chang and Chou were optimized with SIESTA, those reported for Pt13 and Cu13 were found to be less stable than BBP, but the two-dimensional planar configuration reported for Au13 proved to be more stable than BBP.

  4. Density-matrix based determination of low-energy model Hamiltonians from ab initio wavefunctions.

    Science.gov (United States)

    Changlani, Hitesh J; Zheng, Huihuo; Wagner, Lucas K

    2015-09-14

    We propose a way of obtaining effective low energy Hubbard-like model Hamiltonians from ab initio quantum Monte Carlo calculations for molecular and extended systems. The Hamiltonian parameters are fit to best match the ab initio two-body density matrices and energies of the ground and excited states, and thus we refer to the method as ab initio density matrix based downfolding. For benzene (a finite system), we find good agreement with experimentally available energy gaps without using any experimental inputs. For graphene, a two dimensional solid (extended system) with periodic boundary conditions, we find the effective on-site Hubbard U(∗)/t to be 1.3 ± 0.2, comparable to a recent estimate based on the constrained random phase approximation. For molecules, such parameterizations enable calculation of excited states that are usually not accessible within ground state approaches. For solids, the effective Hamiltonian enables large-scale calculations using techniques designed for lattice models. PMID:26374007

  5. Accelerating ab initio path integral molecular dynamics with multilevel sampling of potential surface

    CERN Document Server

    Geng, Hua Y

    2014-01-01

    A multilevel approach to sample the potential energy surface in a path integral formalism is proposed. The purpose is to reduce the required number of ab initio evaluations of energy and forces in ab initio path integral molecular dynamics (AI-PIMD) simulation, without compromising the overall accuracy. To validate the method, the internal energy and free energy of an Einstein crystal are calculated and compared with the analytical solutions. As a preliminary application, we assess the performance of the method in a realistic model, the FCC phase of dense atomic hydrogen, in which the calculated result shows that the acceleration rate is about 3 to 4 fold for a two-level implementation, and can be increased to 10 times if extrapolation is used. With only 16 beads used for the ab initio potential sampling, this method gives a well converged internal energy. The residual error in pressure is just about 3 GPa, whereas it is about 20 GPa for a plain AI-PIMD calculation with the same number of beads. The vibration...

  6. Many-body methods in agent-based epidemic models

    CERN Document Server

    Nakamura, Gilberto M

    2016-01-01

    The susceptible-infected-susceptible (SIS) agent-based model is usually employed in the investigation of epidemics. The model describes a Markov process for a single communicable disease among susceptible (S) and infected (I) agents. However, the disease spreading forecasting is often restricted to numerical simulations, while analytic formulations lack both general results and perturbative approaches since they are subjected to asymmetric time generators. Here, we discuss perturbation theory, approximations and application of many-body techniques in epidemic models in the framework for squared norm of probability vector $|P(t)| ^2$, in which asymmetric time generators are replaced by their symmetric counterparts.

  7. Ab Initio Prediction of Piezoelectricity in Two-Dimensional Materials.

    Science.gov (United States)

    Blonsky, Michael N; Zhuang, Houlong L; Singh, Arunima K; Hennig, Richard G

    2015-10-27

    Two-dimensional (2D) materials present many unique materials concepts, including material properties that sometimes differ dramatically from those of their bulk counterparts. One of these properties, piezoelectricity, is important for micro- and nanoelectromechanical systems applications. Using symmetry analysis, we determine the independent piezoelectric coefficients for four groups of predicted and synthesized 2D materials. We calculate with density-functional perturbation theory the stiffness and piezoelectric tensors of these materials. We determine the in-plane piezoelectric coefficient d11 for 37 materials within the families of 2D metal dichalcogenides, metal oxides, and III-V semiconductor materials. A majority of the structures, including CrSe2, CrTe2, CaO, CdO, ZnO, and InN, have d11 coefficients greater than 5 pm/V, a typical value for bulk piezoelectric materials. Our symmetry analysis shows that buckled 2D materials exhibit an out-of-plane coefficient d31. We find that d31 for 8 III-V semiconductors ranges from 0.02 to 0.6 pm/V. From statistical analysis, we identify correlations between the piezoelectric coefficients and the electronic and structural properties of the 2D materials that elucidate the origin of the piezoelectricity. Among the 37 2D materials, CdO, ZnO, and CrTe2 stand out for their combination of large piezoelectric coefficient and low formation energy and are recommended for experimental exploration. PMID:26312745

  8. Ab Initio Prediction of Piezoelectricity in Two-Dimensional Materials.

    Science.gov (United States)

    Blonsky, Michael N; Zhuang, Houlong L; Singh, Arunima K; Hennig, Richard G

    2015-10-27

    Two-dimensional (2D) materials present many unique materials concepts, including material properties that sometimes differ dramatically from those of their bulk counterparts. One of these properties, piezoelectricity, is important for micro- and nanoelectromechanical systems applications. Using symmetry analysis, we determine the independent piezoelectric coefficients for four groups of predicted and synthesized 2D materials. We calculate with density-functional perturbation theory the stiffness and piezoelectric tensors of these materials. We determine the in-plane piezoelectric coefficient d11 for 37 materials within the families of 2D metal dichalcogenides, metal oxides, and III-V semiconductor materials. A majority of the structures, including CrSe2, CrTe2, CaO, CdO, ZnO, and InN, have d11 coefficients greater than 5 pm/V, a typical value for bulk piezoelectric materials. Our symmetry analysis shows that buckled 2D materials exhibit an out-of-plane coefficient d31. We find that d31 for 8 III-V semiconductors ranges from 0.02 to 0.6 pm/V. From statistical analysis, we identify correlations between the piezoelectric coefficients and the electronic and structural properties of the 2D materials that elucidate the origin of the piezoelectricity. Among the 37 2D materials, CdO, ZnO, and CrTe2 stand out for their combination of large piezoelectric coefficient and low formation energy and are recommended for experimental exploration.

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

    International Nuclear Information System (INIS)

    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

  10. Many-body effects in ionic systems

    OpenAIRE

    Wilson, Mark; Madden, Paul A.; Paul Madden

    1994-01-01

    The electron density of an ion is strongly influenced by its environment in a condensed phase. When the environment changes, for example due to thermal motion, non-trivial changes in the electron density, and hence the interionic interactions occur. These interactions give rise to many-body effects in the potential. In order to represent this phenomenon in molecular dynamics (MD) simulations a method has been developed in which the environmentally-induced changes in the ionic p...

  11. Atomic Spectral Methods for Ab Initio Molecular Electronic Energy Surfaces: Transitioning From Small-Molecule to Biomolecular-Suitable Approaches.

    Science.gov (United States)

    Mills, Jeffrey D; Ben-Nun, Michal; Rollin, Kyle; Bromley, Michael W J; Li, Jiabo; Hinde, Robert J; Winstead, Carl L; Sheehy, Jeffrey A; Boatz, Jerry A; Langhoff, Peter W

    2016-08-25

    the pairwise-atomic Hamiltonian matrices required for practical applications. These matrices can be retained as functions of scalar atomic-pair separations and employed in assembling aggregate Hamiltonian matrices, with Wigner rotation matrices providing analytical representations of their angular degrees of freedom. In this way, ab initio potential energy surfaces are obtained in the complete absence of repeated evaluations and transformations of the one- and two-electron integrals at different molecular geometries required in most ab inito molecular calculations, with large Hamiltonian matrix assembly simplified and explicit diagonalizations avoided employing partitioning and Brillouin-Wigner or Rayleigh-Schrödinger perturbation theory. Illustrative applications of the important components of the formalism, selected aspects of the scaling of the approach, and aspects of "on-the-fly" interfaces with Monte Carlo and molecular-dynamics methods are described in anticipation of subsequent applications to biomolecules and other large aggregates. PMID:27232159

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-03-21

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

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

    Science.gov (United States)

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

    2015-03-01

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

  14. Ab initio calculation of electron-phonon coupling in monoclinic β-Ga2O3 crystal

    Science.gov (United States)

    Ghosh, Krishnendu; Singisetti, Uttam

    2016-08-01

    The interaction between electrons and vibrational modes in monoclinic β-Ga2O3 is theoretically investigated using ab-initio calculations. The large primitive cell of β-Ga2O3 gives rise to 30 phonon modes all of which are taken into account in transport calculation. The electron-phonon interaction is calculated under density functional perturbation theory and then interpolated using Wannier-Fourier interpolation. The long-range interaction elements between electrons and polar optical phonon (POP) modes are calculated separately using the Born effective charge tensor. The direction dependence of the long-range POP coupling in a monoclinic crystal is explored and is included in the transport calculations. Scattering rate calculations are done using the Fermi golden rule followed by solving the Boltzmann transport equation using the Rode's method to estimate low field mobility. A room temperature mobility of 115 cm2/V s is observed. Comparison with recent experimentally reported mobility is done for a wide range of temperatures (30 K-650 K). It is also found that the POP interaction dominates the electron mobility under low electric field conditions. The relative contribution of the different POP modes is analyzed and the mode 21 meV POP is found to have the highest impact on low field electron mobility at room temperature.

  15. Ab Initio Computation of Spin Orbit Coupling Effects on Magnetic Properties of Iron-Containing Complexes and Proteins

    Science.gov (United States)

    Aquino, Fredy; Rodriguez, Jorge H.

    2007-03-01

    Zero-Field Splittings (ZFS) in metalloproteins and other metal complexes arise from the combined action of crystalline fields acting on the metal valence electrons and spin-orbit coupling (SOC), a relativistic effect. The ab-initio calculation of ZFS parameters of metal-containing (bio)molecules is a challenging computational problem of practical relevance to metalloenzyme biochemistry, inorganic chemistry, and molecular-based bio- nanotechnology. We have implemented a methodology which treats the nonrelativistic electronic structure of magnetic (bio) molecules within the framework of spin density functional theory (SDFT) and adds the relativistic effects of SOC via perturbation theory (PT). This combined SDFT-PT approach allowed us to compute the ZFS parameters of iron-containing complexes and non-heme iron proteins with a good degree of accuracy. We also developed a semiquantitative approach to elucidate the physico-chemical origin of the magnitudes of ZFS parameters. We present results for biochemically relevant iron complexes and for nitric oxide-containing non-heme iron proteins, such as isopenicillin N synthase, which have unusually large ZFS. The computed ZFS parameters are in good agreement with experiment. Supported by NSF CAREER Award CHE- 0349189 (JHR).

  16. Many-Body Basis Set Superposition Effect.

    Science.gov (United States)

    Ouyang, John F; Bettens, Ryan P A

    2015-11-10

    The basis set superposition effect (BSSE) arises in electronic structure calculations of molecular clusters when questions relating to interactions between monomers within the larger cluster are asked. The binding energy, or total energy, of the cluster may be broken down into many smaller subcluster calculations and the energies of these subsystems linearly combined to, hopefully, produce the desired quantity of interest. Unfortunately, BSSE can plague these smaller fragment calculations. In this work, we carefully examine the major sources of error associated with reproducing the binding energy and total energy of a molecular cluster. In order to do so, we decompose these energies in terms of a many-body expansion (MBE), where a "body" here refers to the monomers that make up the cluster. In our analysis, we found it necessary to introduce something we designate here as a many-ghost many-body expansion (MGMBE). The work presented here produces some surprising results, but perhaps the most significant of all is that BSSE effects up to the order of truncation in a MBE of the total energy cancel exactly. In the case of the binding energy, the only BSSE correction terms remaining arise from the removal of the one-body monomer total energies. Nevertheless, our earlier work indicated that BSSE effects continued to remain in the total energy of the cluster up to very high truncation order in the MBE. We show in this work that the vast majority of these high-order many-body effects arise from BSSE associated with the one-body monomer total energies. Also, we found that, remarkably, the complete basis set limit values for the three-body and four-body interactions differed very little from that at the MP2/aug-cc-pVDZ level for the respective subclusters embedded within a larger cluster. PMID:26574311

  17. Many-body localization in dipolar systems.

    Science.gov (United States)

    Yao, N Y; Laumann, C R; Gopalakrishnan, S; Knap, M; Müller, M; Demler, E A; Lukin, M D

    2014-12-12

    Systems of strongly interacting dipoles offer an attractive platform to study many-body localized phases, owing to their long coherence times and strong interactions. We explore conditions under which such localized phases persist in the presence of power-law interactions and supplement our analytic treatment with numerical evidence of localized states in one dimension. We propose and analyze several experimental systems that can be used to observe and probe such states, including ultracold polar molecules and solid-state magnetic spin impurities. PMID:25541771

  18. Nuclear, particle and many body physics

    CERN Document Server

    Morse, Philip M; Feshbach, Herman

    2013-01-01

    Nuclear, Particle and Many Body Physics, Volume II, is the second of two volumes dedicated to the memory of physicist Amos de-Shalit. The contributions in this volume are a testament to the respect he earned as a physicist and of the warm and rich affection he commanded as a personal friend. The book contains 41 chapters and begins with a study on the renormalization of rational Lagrangians. Separate chapters cover the scattering of high energy protons by light nuclei; approximation of the dynamics of proton-neutron systems; the scattering amplitude for the Gaussian potential; Coulomb excitati

  19. Quantum scaling in many-body systems

    CERN Document Server

    Continentino, Mucio A

    2001-01-01

    This book on quantum phase transitions has been written by one of the pioneers in the application of scaling ideas to many-body systems - a new and exciting subject that has relevance to many areas of condensed matter and theoretical physics. One of the few books on the subject, it emphasizes strongly correlated electronic systems. Although dealing with complex problems in statistical mechanics, it does not lose sight of the experiments and the actual physical systems which motivate the theoretical work. The book starts by presenting the scaling theory of quantum critical phenomena. Critical e

  20. Many-Body Physics with Trapped Ions

    CERN Document Server

    Schneider, Christian; Schaetz, Tobias

    2011-01-01

    Direct experimental access to some of the most intriguing quantum phenomena is not granted due to the lack of precise control of the relevant parameters in their naturally intricate environment. Their simulation on conventional computers is impossible, since quantum behaviour arising with superposition states or entanglement is not efficiently translatable into the classical language. However, one could gain deeper insight into complex quantum dynamics by experimentally simulating the quantum behaviour of interest in another quantum system, where the relevant parameters and interactions can be controlled and robust effects detected sufficiently well. We report on the progress in experimentally simulating quantum many-body physics with trapped ions.

  1. Non-equilibrium many body dynamics

    International Nuclear Information System (INIS)

    This Riken BNL Research Center Symposium on Non-Equilibrium Many Body Physics was held on September 23-25, 1997 as part of the official opening ceremony of the Center at Brookhaven National Lab. A major objective of theoretical work at the center is to elaborate on the full spectrum of strong interaction physics based on QCD, including the physics of confinement and chiral symmetry breaking, the parton structure of hadrons and nuclei, and the phenomenology of ultra-relativistic nuclear collisions related to the up-coming experiments at RHIC. The opportunities and challenges of nuclear and particle physics in this area naturally involve aspects of the many body problem common to many other fields. The aim of this symposium was to find common theoretical threads in the area of non-equilibrium physics and modern transport theories. The program consisted of invited talks on a variety topics from the fields of atomic, condensed matter, plasma, astrophysics, cosmology, and chemistry, in addition to nuclear and particle physics. Separate abstracts have been indexed into the database for contributions to this workshop

  2. Anharmonic force field and vibrational dynamics of CH2F2 up to 5000 cm(-1) studied by Fourier transform infrared spectroscopy and state-of-the-art ab initio calculations.

    Science.gov (United States)

    Tasinato, Nicola; Regini, Giorgia; Stoppa, Paolo; Pietropolli Charmet, Andrea; Gambi, Alberto

    2012-06-01

    Difluoromethane (CH(2)F(2), HFC-32) is a molecule used in refrigerant mixtures as a replacement of the more environmentally hazardous, ozone depleting, chlorofluorocarbons. On the other hand, presenting strong vibration-rotation bands in the 9 μm atmospheric window, it is a greenhouse gas which contributes to global warming. In the present work, the vibrational and ro-vibrational properties of CH(2)F(2), providing basic data for its atmospheric modeling, are studied in detail by coupling medium resolution Fourier transform infrared spectroscopy to high-level electronic structure ab initio calculations. Experimentally a full quantum assignment and accurate integrated absorption cross sections are obtained up to 5000 cm(-1). Ab initio calculations are carried out by using CCSD(T) theory and large basis sets of either the correlation consistent or atomic natural orbital hierarchies. By using vibrational perturbation theory to second order a complete set of vibrational and ro-vibrational parameters is derived from the ab initio quartic anharmonic force fields, which well compares with the spectroscopic constants retrieved experimentally. An excellent agreement between theory and experiment is achieved for vibrational energy levels and integrated absorption cross sections: transition frequencies up to four quanta of vibrational excitation are reproduced with a root mean square deviation (RMSD) of 7 cm(-1) while intensities are predicted within few km mol(-1) from the experiment. Basis set performances and core correlation effects are discussed throughout the paper. Particular attention is focused in the understanding of the anharmonic couplings which rule the vibrational dynamics of the |ν(1)>, |2ν(8)>, |2ν(2)> three levels interacting system. The reliability of the potential energy and dipole moment surfaces in reproducing the vibrational eigenvalues and intensities as well as in modeling the vibrational and ro-vibrational mixings over the whole 400-5000 cm(-1

  3. Benchmarking ab initio binding energies of hydrogen-bonded molecular clusters based on FTIR spectroscopy

    DEFF Research Database (Denmark)

    Bork, Nicolai Christian; Du, Lin; Reiman, Heidi;

    2014-01-01

    Gibbs free binding energies in molecular complexes and clusters based on gas phase FTIR spectroscopy. The acetonitrile-HCl molecular complex is identified via its redshifted H-Cl stretching vibrational mode. We determine the Gibbs free binding energy, ΔG°295 K, to between 4.8 and 7.9 kJ mol(-1) and......Models of formation and growth of atmospheric aerosols are highly dependent on accurate cluster binding energies. These are most often calculated by ab initio electronic structure methods but remain associated with significant uncertainties. We present a computational benchmarking study of the...

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

    OpenAIRE

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

    1994-01-01

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

  5. Monte Carlo methods in AB initio quantum chemistry quantum Monte Carlo for molecules

    CERN Document Server

    Lester, William A; Reynolds, PJ

    1994-01-01

    This book presents the basic theory and application of the Monte Carlo method to the electronic structure of atoms and molecules. It assumes no previous knowledge of the subject, only a knowledge of molecular quantum mechanics at the first-year graduate level. A working knowledge of traditional ab initio quantum chemistry is helpful, but not essential.Some distinguishing features of this book are: Clear exposition of the basic theory at a level to facilitate independent study. Discussion of the various versions of the theory: diffusion Monte Carlo, Green's function Monte Carlo, and release n

  6. Improved Ab Initio Molecular Dynamics by Minimal Biasing with Experimental Data

    CERN Document Server

    White, Andrew D; Hocky, Glen M; Voth, Gregory A

    2016-01-01

    Accounting for electrons and nuclei simultaneously is a key goal of computer simulation via ab initio molecular dynamics (AIMD). However, AIMD is often unable to accurately reproduce the properties of systems such as water due to inaccuracies in the underlying electronic density functionals, shortcomings that are often addressed by added empirical corrections and/or increasing the simulation temperature. We present here a maximum-entropy-based approach to directly incorporate limited experimental data via a minimal bias. The biased AIMD simulations of both water and of an excess proton in water are shown to give significantly improved properties for both the biased and unbiased observables.

  7. Transport coefficients of helium-argon mixture based on ab initio potential.

    Science.gov (United States)

    Sharipov, Felix; Benites, Victor J

    2015-10-21

    The viscosity, thermal conductivity, diffusion coefficient, and thermal diffusion factor of helium-argon mixtures are calculated for a wide range of temperature and for various mole fractions up to the 12th order of the Sonine polynomial expansion with an ab initio intermolecular potential. The calculated values for these transport coefficients are compared with other data available in the open literature. The comparison shows that the obtained transport coefficients of helium-argon mixture have the best accuracy for the moment. PMID:26493894

  8. Ab initio calculation of the spectrum and structure of $^{16}$O

    CERN Document Server

    Epelbaum, Evgeny; Lähde, Timo A; Lee, Dean; Meißner, Ulf-G; Rupak, Gautam

    2013-01-01

    We present ab initio lattice calculations of the low-energy even-parity states of $^{16}$O using chiral nuclear effective field theory. We find good agreement with the empirical energy spectrum, and with the electromagnetic properties and transition rates. For the ground state, we find that the nucleons are arranged in a tetrahedral configuration of alpha clusters. For the first excited spin-0 state, we find that the predominant structure is a square configuration of alpha clusters, with rotational excitations that include the first spin-2 state.

  9. Ab initio description of second-harmonic generation from crystal surfaces

    Science.gov (United States)

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

    2016-09-01

    We propose an ab initio framework to derive the dielectric and the second-order susceptibility tensors for crystal surfaces. The single-surface response is extracted from a supercell scheme. We evaluate macroscopic quantities, taking into account the local fields. The first- and second-order susceptibilities are evaluated within time-dependent density functional theory, in the long-wavelength limit. We apply our formalism to the calculation of the second-harmonic generation for clean and hydrogenated silicon surfaces. The agreement with measured second-order susceptibility components is significantly better, illustrating the importance of local-field effects.

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

    Science.gov (United States)

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

    2016-06-01

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

  11. Ab-initio GMR and current-induced torques in Au/Cr multilayers

    OpenAIRE

    Haney, P. M.; Waldron, D; Duine, R. A.; Nunez, A. S.; Guo, H; MacDonald, A.H.

    2006-01-01

    We report on an {\\em ab-initio} study of giant magnetoresistance (GMR) and current-induced-torques (CITs) in Cr/Au multilayers that is based on non-equilibrium Green's functions and spin density functional theory. We find substantial GMR due primarily to a spin-dependent resonance centered at the Cr/Au interface and predict that the CITs are strong enough to switch the antiferromagnetic order parameter at current-densities $\\sim 100$ times smaller than typical ferromagnetic metal circuit swit...

  12. Ab initio adiabatic and quasidiabatic potential energy surfaces of H++ CN system

    Indian Academy of Sciences (India)

    Bhargava Anusuri; Sanjay Kumar

    2016-02-01

    We present restricted geometry (collinear and perpendicular approaches of proton) ab initio three dimensional potential energy surfaces for H++ CN system. The calculations were performed at the internally contracted multi-reference configuration interaction level of theory using Dunning’s correlation consistent polarized valence triple zeta basis set. Adiabatic and quasidiabatic surfaces have been computed for the ground and the first excited electronic states. Nonadiabatic effects arising from radial coupling have been analyzed in terms of nonadiabatic coupling matrix elements and coupling potentials.

  13. Ab initio molecular simulations on specific interactions between amyloid beta and monosaccharides

    Science.gov (United States)

    Nomura, Kazuya; Okamoto, Akisumi; Yano, Atsushi; Higai, Shin'ichi; Kondo, Takashi; Kamba, Seiji; Kurita, Noriyuki

    2012-09-01

    Aggregation of amyloid β (Aβ) peptides, which is a key pathogenetic event in Alzheimer's disease, can be caused by cell-surface saccharides. We here investigated stable structures of the solvated complexes of Aβ with some types of monosaccharides using molecular simulations based on protein-ligand docking and classical molecular mechanics methods. Moreover, the specific interactions between Aβ and the monosaccharides were elucidated at an electronic level by ab initio fragment molecular orbital calculations. Based on the results, we proposed which type of monosaccharide prefers to have large binding affinity to Aβ and inhibit the Aβ aggregation.

  14. Temperature-Dependent Diffusion Coefficients from ab initio Computations: Hydrogen in Nickel

    Energy Technology Data Exchange (ETDEWEB)

    E Wimmer; W Wolf; J Sticht; P Saxe; C Geller; R Najafabadi; G Young

    2006-03-16

    The temperature-dependent mass diffusion coefficient is computed using transition state theory. Ab initio supercell phonon calculations of the entire system provide the attempt frequency, the activation enthalpy, and the activation entropy as a function of temperature. Effects due to thermal lattice expansion are included and found to be significant. Numerical results for the case of hydrogen in nickel demonstrate a strong temperature dependence of the migration enthalpy and entropy. Trapping in local minima along the diffusion path has a pronounced effect especially at low temperatures. The computed diffusion coefficients with and without trapping bracket the available experimental values over the entire temperature range between 0 and 1400 K.

  15. Ab initio study of beryllium-decorated fullerenes for hydrogen storage

    OpenAIRE

    Lee, Hoonkyung; Huang, Bing; Duan, Wenhui; Ihm, Jisoon

    2010-01-01

    We have found that a beryllium (Be) atom on nanostructured materials with H2 molecules generates a Kubas-like dihydrogen complex [H. Lee et al. arXiv:1002.2247v1 (2010)]. Here, we investigate the feasibility of Be-decorated fullerenes for hydrogen storage using ab initio calculations. We find that the aggregation of Be atoms on pristine fullerenes is energetically preferred, resulting in the dissociation of the dihydrogen. In contrast, for boron (B)-doped fullerenes, Be atoms prefer to be ind...

  16. Ab initio studies on the mechanic and magnetic properties of PdHx

    Institute of Scientific and Technical Information of China (English)

    Cui Xin; Liang Xi-Xia; Wang Jian-Tao; Zhao Guo-Zhong

    2011-01-01

    Based on ab initio total energy calculations, the structural, electronic, mechanic, and magnetic properties of PdHx are investigated. It is found that bulk modulus of PdHx is larger than the metal Pd with the hydrogen storage except Pd4H2. The calculated results for the magnetic moments show that the hydrogen addition weakens the magnetic properties of the PdHx systems. A strong magneto-volume effect is found in PdHx structures as well as Pd. The transition from paramagnetism to ferromagnetism is discussed. The corresponding densities of states for both structures are also shown to understand the magnetic behaviour.

  17. An ab initio molecular dynamics study of the roaming mechanism of the H2+HOC+ reaction

    Science.gov (United States)

    Yu, Hua-Gen

    2011-08-01

    We report here a direct ab initio molecular dynamics study of the p-/o-H2+HOC+ reaction on the basis of the accurate SAC-MP2 potential energy surface. The quasi-classical trajectory method was employed. This work largely focuses on the study of reaction mechanisms. A roaming mechanism was identified for this molecular ion-molecule reaction. The driving forces behind the roaming mechanism were thoroughly investigated by using a trajectory dynamics approach. In addition, the thermal rate coefficients of the H2+HOC+ reaction were calculated in the temperature range [25, 300] K and are in good agreement with experiments.

  18. Communication: GAIMS—Generalized Ab Initio Multiple Spawning for both internal conversion and intersystem crossing processes

    Science.gov (United States)

    Curchod, Basile F. E.; Rauer, Clemens; Marquetand, Philipp; González, Leticia; Martínez, Todd J.

    2016-03-01

    Full multiple spawning is a formally exact method to describe the excited-state dynamics of molecular systems beyond the Born-Oppenheimer approximation. However, it has been limited until now to the description of radiationless transitions taking place between electronic states with the same spin multiplicity. This Communication presents a generalization of the full and ab initio multiple spawning methods to both internal conversion (mediated by nonadiabatic coupling terms) and intersystem crossing events (triggered by spin-orbit coupling matrix elements) based on a spin-diabatic representation. The results of two numerical applications, a model system and the deactivation of thioformaldehyde, validate the presented formalism and its implementation.

  19. Quantum chemistry the development of ab initio methods in molecular electronic structure theory

    CERN Document Server

    Schaefer III, Henry F

    2004-01-01

    This guide is guaranteed to prove of keen interest to the broad spectrum of experimental chemists who use electronic structure theory to assist in the interpretation of their laboratory findings. A list of 150 landmark papers in ab initio molecular electronic structure methods, it features the first page of each paper (which usually encompasses the abstract and introduction). Its primary focus is methodology, rather than the examination of particular chemical problems, and the selected papers either present new and important methods or illustrate the effectiveness of existing methods in predi

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

    DEFF Research Database (Denmark)

    Abild-Pedersen, Frank; Nørskov, Jens Kehlet; Rostrup-Nielsen, Jens;

    2006-01-01

    Mechanisms and energetics of graphene growth catalyzed by nickel nanoclusters were studied using ab initio density functional theory calculations. It is demonstrated that nickel step-edge sites act as the preferential growth centers for graphene layers on the nickel surface. Carbon is transported...... from the deposition site at the free nickel surface to the perimeter of the growing graphene layer via surface or subsurface diffusion. Three different processes are identified to govern the growth of graphene layers, depending on the termination of the graphene perimeter at the nickel surface...

  1. Ab initio study of spin-dependent transport in carbon nanotubes with iron and vanadium adatoms

    DEFF Research Database (Denmark)

    Fürst, Joachim Alexander; Brandbyge, Mads; Jauho, Antti-Pekka;

    2008-01-01

    We present an ab initio study of spin-dependent transport in armchair carbon nanotubes with transition metal adsorbates: iron or vanadium. The method based on density functional theory and nonequilibrium Green's functions is used to compute the electronic structure and zero-bias conductance...... (majority or minority) being scattered depends on the adsorbate and is explained in terms of d-state filling. We contrast the single-walled carbon nanotube results to the simpler case of the adsorbate on a flat graphene sheet with periodic boundary conditions and corresponding width in the zigzag direction...

  2. Paired-permanent approach for VB theory (II) -An ab initio spin-free VB program

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Paired-permanent approach for VB theory is extensively developed. Canonical expan sion of a paired-permanent is deduced. Furthermore, it is shown that a paired-permanent may be expressed in terms of the products of sub-paired-permanents of any given order and their corre sponding minors. An ab initio spin-free valence bond program, called Xiamen, is implemented by using paired-permanent approach. Test calculation shows that Xiamen package is more efficient than some other programs based on the traditional VB algorithm, and it provides a new practical tool for quantum chemistry.

  3. A transferable ab-initio based force field for aqueous ions

    CERN Document Server

    Tazi, Sami; Rotenberg, Benjamin; Turq, Pierre; Vuilleumier, Rodolphe; Salanne, Mathieu; 10.1063/1.3692965

    2012-01-01

    We present a new polarizable force field for aqueous ions (Li+, Na+, K+, Rb+, Cs+, Mg2+, Ca2+, Sr2+ and Cl-) derived from condensed phase ab-initio calculations. We use Maximally Localized Wannier Functions together with a generalized force and dipole-matching procedure to determine the whole set of parameters. Experimental data is then used only for validation purposes and a good agreement is obtained for structural, dynamic and thermodynamic properties. The same procedure applied to crystalline phases allows to parametrize the interaction between cations and the chloride anion. Finally, we illustrate the good transferability of the force field to other thermodynamic conditions by investigating concentrated solutions.

  4. Ab-initio density functional theory study of a WO3 NH3-sensing mechanism

    Institute of Scientific and Technical Information of China (English)

    Hu Ming; Zhang Jie; Wang Wei-Dan; Qin Yu-Xiang

    2011-01-01

    WO3 bulk and various surfaces are studied by an ab-initio density functional theory technique.The band structures and electronic density states of WO3 bulk are investigated.The surface energies of different WO3 surfaces are compared and then the(002)surface with minimum energy is computed for its NH3 sensing mechanism which explains the results in the experiments.Three adsorption sites are considered.According to the comparisons of the energy and the charge change between before and after adsorption in the optimal adsorption site O1c,the NH3 sensing mechanism is obtained.

  5. Specific interactions between amyloid-β peptide and curcumin derivatives: Ab initio molecular simulations

    Science.gov (United States)

    Ishimura, Hiromi; Kadoya, Ryushi; Suzuki, Tomoya; Murakawa, Takeru; Shulga, Sergiy; Kurita, Noriyuki

    2015-07-01

    Alzheimer's disease is caused by accumulation of amyloid-β (Aβ) peptides in a brain. To suppress the production of Aβ peptides, it is effective to inhibit the cleavage of amyloid precursor protein (APP) by secretases. However, because the secretases also play important roles to produce vital proteins for human body, inhibitors for the secretases may have side effects. To propose new agents for protecting the cleavage site of APP from the attacking of the γ-secretase, we have investigated here the specific interactions between a short APP peptide and curcumin derivatives, using protein-ligand docking as well as ab initio molecular simulations.

  6. Sinteza, spektroskopska karakterizacija i ab initio istraživanje tioanaloga spirohidantoina

    OpenAIRE

    Marin MARINOV; Minchev, Stoyan; Stoyanov, Neyko; Ivanova, Galya; Spassova, Milena; Enchev, Venelin

    2005-01-01

    Ditioanalozi cikloalkan-spiro-5-hidantoina pripravljeni su reakcijama odgovarajućih spirohidantoina i Lawesson-ovoga reagensa ili P4S10. Sintetizirani su i cikloalkan-spiro-5-(2-tiohidantoini) i cikloalkan-spiro-5- -(4-tiohidantoini), uporabom različitih reakcijskih putova. Strukture dobivenih spojeva potvrđene su 1H, 13C NMR i IR spektroskopijom. Nelinearne molekularne karakteristike predviđene su kvantno-kemijskim računima na ab initio razini. U svim proučavanim strukturama, s povećanjem za...

  7. Steady state Ab-initio Theory of Lasers with Injected Signals

    OpenAIRE

    Cerjan, Alexander; Stone, A. Douglas

    2013-01-01

    We present an ab-initio treatment of the steady-state of lasers with injected signals that describes a regime, valid for micro lasers, in which the locking transition is dominated by cross-saturation and spatial hole-burning. The theory goes beyond standard approaches and treats multimode lasing with injected signals and finds the possibility of partially locked states and as well as repulsion of the free-running frequencies from the injected signal. The theory agrees well with exact integrat...

  8. Ab initio MO study of reaction mechanism for carbonyl migration of Co complex

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Ab initio method under the effective core potential (ECP) approximation is employed to study the reaction mechanism of carbonyl migration of the cycle of olefin hydroformylation catalyzed by a carbonyl cobalt HCo(CO)3 at Hartree-Fock (HF) level. The structures of the reactant, transition state and product for the reaction are determined. The energy of each stationary point is corrected at MP2/LAN2DZ//LANL2DZ+ZPE (zero-point energy) level. The calculated activation barrier is 28.89 kJ/mol.

  9. Ab initio based force field and molecular dynamics simulations of crystalline TATB.

    Science.gov (United States)

    Gee, Richard H; Roszak, Szczepan; Balasubramanian, Krishnan; Fried, Laurence E

    2004-04-15

    An all-atom force field for 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) is presented. The classical intermolecular interaction potential for TATB is based on single-point energies determined from high-level ab initio calculations of TATB dimers. The newly developed potential function is used to examine bulk crystalline TATB via molecular dynamics simulations. The isobaric thermal expansion and isothermal compression under hydrostatic pressures obtained from the molecular dynamics simulations are in good agreement with experiment. The calculated volume-temperature expansion is almost one dimensional along the c crystallographic axis, whereas under compression, all three unit cell axes participate, albeit unequally. PMID:15267608

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

    Institute of Scientific and Technical Information of China (English)

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

    2006-01-01

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

  11. An Ab initio Theoretical Study on the Nonadiabatic Coupling for Na+I2 Collision System

    Institute of Scientific and Technical Information of China (English)

    孙孝敏; 蔡政亭; 冯大诚

    2003-01-01

    The ionic and neutral state potential energy surfaces (PESs) of Na+I2 collision system have been calculated on QCISD(T) level by using ab initio method.The location and depth of the potential well,the collision radius and their fine structures have been analyzed at the equilibrium geometry of I2 molecule.The electronic transfer probabilities are also calculated in terms of Landau-Zener model.The lifetime of scattering resonance state is evaluated by the uncertainty principle.All the results have been compared with those obtained according to the Aten-Lanting-Los PES and Feng's PES.

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

    Institute of Scientific and Technical Information of China (English)

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

    2008-01-01

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

  13. Prediction of adsorption of small molecules in porous materials based on ab initio force field method

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Computational prediction of adsorption of small molecules in porous materials has great impact on the basic and applied research in chemical engineering and material sciences. In this work,we report an approach based on grand canonical ensemble Monte Carlo(GCMC) simulations and ab initio force fields. We calculated the adsorption curves of ammonia in ZSM-5 zeolite and hydrogen in MOF-5(a metal-organic-framework material). The predictions agree well with experimental data. Because the predictions are based on the first principle force fields,this approach can be used for the adsorption prediction of new molecules or materials without experimental data as guidance.

  14. Interferometric probes of many-body localization.

    Science.gov (United States)

    Serbyn, M; Knap, M; Gopalakrishnan, S; Papić, Z; Yao, N Y; Laumann, C R; Abanin, D A; Lukin, M D; Demler, E A

    2014-10-01

    We propose a method for detecting many-body localization (MBL) in disordered spin systems. The method involves pulsed coherent spin manipulations that probe the dephasing of a given spin due to its entanglement with a set of distant spins. It allows one to distinguish the MBL phase from a noninteracting localized phase and a delocalized phase. In particular, we show that for a properly chosen pulse sequence the MBL phase exhibits a characteristic power-law decay reflecting its slow growth of entanglement. We find that this power-law decay is robust with respect to thermal and disorder averaging, provide numerical simulations supporting our results, and discuss possible experimental realizations in solid-state and cold-atom systems. PMID:25325656

  15. Many-body Physics of Rydberg Polaritons

    Science.gov (United States)

    Edelman, Alexander; Littlewood, Peter

    2014-03-01

    Electromagnetically induced transparency (EIT) in cold dense atomic gasses with Rydberg states in has attracted considerable interest as a means of realizing strong nonlinear photon-photon interactions. The coherent light-matter coupling provided by the EIT medium combined with interactions between Rydberg states whose strength and shape can be engineered provide a parameter space with rich phenomenology including photon bound states and spatially ordered structures. Past theoretical treatments of these systems have relied on equations of motion to predict dynamics in particular limits. Here we present progress towards a full many-body path integral description that considers interaction effects beyond the Dicke model as well as the intrinsically non-equilibrium nature of the system, and explore a tentative phase diagram.

  16. CIME School on Quantum Many Body Systems

    CERN Document Server

    Rivasseau, Vincent; Solovej, Jan Philip; Spencer, Thomas

    2012-01-01

    The book is based on the lectures given at the CIME school "Quantum many body systems" held in the summer of 2010. It provides a tutorial introduction to recent advances in the mathematics of interacting systems, written by four leading experts in the field: V. Rivasseau illustrates the applications of constructive Quantum Field Theory to 2D interacting electrons and their relation to quantum gravity; R. Seiringer describes a proof of Bose-Einstein condensation in the Gross-Pitaevski limit and explains the effects of rotating traps and the emergence of lattices of quantized vortices; J.-P. Solovej gives an introduction to the theory of quantum Coulomb systems and to the functional analytic methods used to prove their thermodynamic stability; finally, T. Spencer explains the supersymmetric approach to Anderson localization and its relation to the theory of random matrices. All the lectures are characterized by their mathematical rigor combined with physical insights.

  17. Accurate ab initio-based adiabatic global potential energy surface for the 22A″ state of NH2 by extrapolation to the complete basis set limit

    Science.gov (United States)

    Li, Y. Q.; Ma, F. C.; Sun, M. T.

    2013-10-01

    A full three-dimensional global potential energy surface is reported first time for the title system, which is important for the photodissociation processes. It is obtained using double many-body expansion theory and an extensive set of accurate ab initio energies extrapolated to the complete basis set limit. Such a work can be recommended for dynamics studies of the N(2D) + H2 reaction, a reliable theoretical treatment of the photodissociation dynamics and as building blocks for constructing the double many-body expansion potential energy surface of larger nitrogen/hydrogen containing systems. In turn, a preliminary theoretical study of the reaction N(^2D)+H_2(X^1Σ _g^+)(ν =0,j=0)rArr NH(a^1Δ )+H(^2S) has been carried out with the method of quasi-classical trajectory on the new potential energy surface. Integral cross sections and thermal rate constants have been calculated, providing perhaps the most reliable estimate of the integral cross sections and the rate constants known thus far for such a reaction.

  18. Prediction of quantum many-body chaos in protactinium atom

    CERN Document Server

    Viatkina, A V; Flambaum, V V

    2016-01-01

    Energy level spectrum of protactinium atom (Pa, Z=91) is simulated with a CI calculation. Levels belonging to the separate manifolds of a given total angular momentum and parity $J^\\pi$ exhibit distinct properties of many-body quantum chaos. Moreover, an extremely strong enhancement of small perturbations takes place. As an example, effective three-electron interaction is investigated and found to play a significant role in the system. Chaotic properties of the eigenstates allow one to develop a statistical theory and predict probabilities of different processes in chaotic systems.

  19. Entropy Production in Isolated Quantum Many-Body Systems

    Science.gov (United States)

    Solano Carrillo, Edgardo; Millis, Andrew

    2015-03-01

    Beginning with the Liouville-von Neumann equation for the density matrix of an isolated quantum many-body system, and applying well-known projection-operator techniques, we derive an equation of motion for the rate of change of the thermodynamic entropy, valid to arbitrary order in the perturbation deviating the system from equilibrium. To lowest order, a balance equation is obtained which coincides with the one defining the entropy production in irreversible thermodynamics. A connection with fluctuation theorems is mentioned, as well as an application of the results to clarify the ``thermalization problem'' in the Jaynes-Cummings model. This work was supported by the Fulbright-Colciencias fellowship.

  20. The twofold diabatization of the KRb $(1\\sim 2)^1\\Pi$ complex in the framework of \\emph{ab initio} and deperturbation approaches

    CERN Document Server

    Kozlov, S V; Stolyarov, A V

    2016-01-01

    We performed a diabatization of the mutually perturbed $1^1\\Pi$ and $2^1\\Pi$ states of KRb based on both electronic structure calculation and direct coupled-channel deperturbation analysis of experimental energies. The potential energy curves (PECs) of the diabatic states and their scalar coupling were constructed from the \\textit{ab initio} adiabatic PECs by analytically integrating the radial $\\langle \\psi_1^{ad}|\\partial /\\partial R|\\psi_2^{ad}\\rangle$ matrix element obtained by a finite-difference method. The diabatic potentials and electronic coupling function were refined by the least squares fitting of the rovibronic termvalues of the $1^1\\Pi\\sim 2^1\\Pi$ complex. The empirical PECs combined with the coupling function as well as the diabatized spin-orbit coupling and transition dipole matrix elements are useful for further deperturbation treatment of both singlet and triplet states manifold.

  1. Spin-orbit ab initio curves of 80Se+2 ion and the assignment of photoelectron spectra of 80Se2 molecule

    Institute of Scientific and Technical Information of China (English)

    Yan Bing; Pan Shou-Fu; Guo Qing-Qun

    2008-01-01

    This paper carries out ab initio calculations to study the 80Se2(X3∑-g)state and 80Se+2(X2∏g),80Se+2(a4∏g)states by using completed active space self-consistent field and multi-reference second order perturbation theory.The electronic curves of these states including spin-orbit coupling are calculated,and then the spectroscopic parameters are obtained.The photoelectron spectra of 80Se2 molecule in gas phase are assigned according to Franck-Condon analysis based on calculated potential energy curves.The ionization energies of 80Se2 molecule are determined by the present calculation.

  2. Moderate Humidity Delays Electron-Hole Recombination in Hybrid Organic-Inorganic Perovskites: Time-Domain Ab Initio Simulations Rationalize Experiments.

    Science.gov (United States)

    Long, Run; Fang, Weihai; Prezhdo, Oleg V

    2016-08-18

    Experiments show both positive and negative changes in performance of hybrid organic-inorganic perovskite solar cells upon exposure to moisture. Ab initio nonadiabatic molecular dynamics reveals the influence of humidity on nonradiative electron-hole recombination. In small amounts, water molecules perturb perovskite surface and localize photoexcited electron close to the surface. Importantly, deep electron traps are avoided. The electron-hole overlap decreases, and the excited state lifetime increases. In large amounts, water forms stable hydrogen-bonded networks, has a higher barrier to enter perovskite, and produces little impact on charge localization. At the same time, by contributing high frequency polar vibrations, water molecules increase nonadiabatic coupling and accelerate recombination. In general, short coherence between electron and hole benefits photovoltaic response of the perovskites. The calculated recombination time scales show excellent agreement with experiment. The time-domain atomistic simulations reveal the microscopic effects of humidity on perovskite excited-state lifetimes and rationalize the conflicting experimental observations. PMID:27485025

  3. Free Energies of Chemical Reactions in Solution and in Enzymes with Ab Initio Quantum Mechanics/Molecular Mechanics Methods

    Science.gov (United States)

    Hu, Hao; Yang, Weitao

    2008-05-01

    Combined quantum mechanics/molecular mechanics (QM/MM) methods provide an accurate and efficient energetic description of complex chemical and biological systems, leading to significant advances in the understanding of chemical reactions in solution and in enzymes. Here we review progress in QM/MM methodology and applications, focusing on ab initio QM-based approaches. Ab initio QM/MM methods capitalize on the accuracy and reliability of the associated quantum-mechanical approaches, however, at a much higher computational cost compared with semiempirical quantum-mechanical approaches. Thus reaction-path and activation free-energy calculations based on ab initio QM/MM methods encounter unique challenges in simulation timescales and phase-space sampling. This review features recent developments overcoming these challenges and enabling accurate free-energy determination for reaction processes in solution and in enzymes, along with applications.

  4. Quantum supercharger library: hyper-parallel integral derivatives algorithms for ab initio QM/MM dynamics.

    Science.gov (United States)

    Renison, C Alicia; Fernandes, Kyle D; Naidoo, Kevin J

    2015-07-01

    This article describes an extension of the quantum supercharger library (QSL) to perform quantum mechanical (QM) gradient and optimization calculations as well as hybrid QM and molecular mechanical (QM/MM) molecular dynamics simulations. The integral derivatives are, after the two-electron integrals, the most computationally expensive part of the aforementioned calculations/simulations. Algorithms are presented for accelerating the one- and two-electron integral derivatives on a graphical processing unit (GPU). It is shown that a Hartree-Fock ab initio gradient calculation is up to 9.3X faster on a single GPU compared with a single central processing unit running an optimized serial version of GAMESS-UK, which uses the efficient Schlegel method for s- and l-orbitals. Benchmark QM and QM/MM molecular dynamics simulations are performed on cellobiose in vacuo and in a 39 Å water sphere (45 QM atoms and 24843 point charges, respectively) using the 6-31G basis set. The QSL can perform 9.7 ps/day of ab initio QM dynamics and 6.4 ps/day of QM/MM dynamics on a single GPU in full double precision. © 2015 Wiley Periodicals, Inc. PMID:25975864

  5. Higher-order elastic constants and megabar pressure effects of bcc tungsten: Ab initio calculations

    Science.gov (United States)

    Vekilov, Yu. Kh.; Krasilnikov, O. M.; Lugovskoy, A. V.; Lozovik, Yu. E.

    2016-09-01

    The general method for the calculation of n th (n ≥2 ) order elastic constants of the loaded crystal is given in the framework of the nonlinear elasticity theory. For the crystals of cubic symmetry under hydrostatic compression, the two schemes of calculation of the elastic constants of second, third, and fourth order from energy-finite strain relations and stress-finite strain relations are implemented. Both techniques are applied for the calculation of elastic constants of orders from second to fourth to the bcc phase of tungsten at a 0-600 GPa pressure range. The energy and stress at the various pressures and deformations are obtained ab initio in the framework of projector augmented wave+generalized gradient approximation (PAW+GGA) method, as implemented in Vienna Ab initio Simulation Package (VASP) code. Using the obtained results, we found the pressure dependence of Grüneisen parameters for long-wave acoustic modes in this interval. The Lamé constants of second and third order were estimated for polycrystalline tungsten. The proposed method is applicable for crystals with arbitrary symmetry.

  6. Estudio ab initio del mecanismo de la reacción HSO + O3

    Science.gov (United States)

    Nebot Gil, I.

    La reacción entre el radical HSO y el ozono ha sido ampliamente estudiada desde el punto de vista experimental debido a la importancia que tiene el radical HSO en la oxidación de los compuestos de azufre reductores y a que puede contribuir a la producción de H2SO4 [1-4]. Se realizaron diversos estudios teóricos sobre la cinética de la reacción entre el radical HSO y el ozono. La reacción del HSO con el ozono presenta tres canales diferentes : HSO + O3 &rightarrow &HSO2 + O2 &rightarrow &HS + 2 O2 &rightarrow &SO + OH + O2 La controversia existente entre los grupos experimentales sobre cuál de las tres vías es la predominante, se ha resuelto mediante un estudio teórico de todas ellas utilizando métodos ab initio. La estructura de todos los reactivos, productos, intermedios y estados de transición ha sido optimizada a nivel ab initio utilizando los métodos UMP2 /6-31G** y QCISD/6-31G**.

  7. Ab initio quantum chemistry in parallel-portable tools and applications

    International Nuclear Information System (INIS)

    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(105) 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

  8. Novel high-pressure phase of ZrO2: An ab initio prediction

    International Nuclear Information System (INIS)

    The high-pressure behavior of the orthorhombic cotunnite type ZrO2 is explored using an ab initio constant pressure technique. For the first time, a novel hexagonal phase (Ni2In type) within P63/mmc symmetry is predicted through the simulation. The Ni2In type crystal is the densest high-pressure phase of ZrO2 proposed so far and has not been observed in other metal dioxides at high pressure before. The phase transformation is accompanied by a small volume drop and likely to occur around 380 GPa in experiment. - Graphical abstract: Post-cotunnite Ni2In type hexagonal phase forms in zirconia at high pressure. - Highlights: • A post-cotunnite phase is predicted for ZrO2 through an ab initio simulation. • Cotunnite ZrO2 adopts the Ni2In type structure at high pressure. • The Ni2In type structure is the densest high-pressure phase of ZrO2 proposed so far. • The preferred mechanism in ZrO2 differs from the other metal dioxides

  9. Large basis ab initio shell model investigation of 9-Be and 11-Be

    CERN Document Server

    Forssén, C; Ormand, W E; Caurier, E

    2004-01-01

    We are presenting the first ab initio structure investigation of the loosely bound 11-Be nucleus, together with a study of the lighter isotope 9-Be. The nuclear structure of these isotopes is particularly interesting due to the appearance of a parity-inverted ground state in 11-Be. Our study is performed in the framework of the ab initio no-core shell model. Results obtained using four different, high-precision two-nucleon interactions, in model spaces up to 9\\hbar\\Omega, are shown. For both nuclei, and all potentials, we reach convergence in the level ordering of positive- and negative-parity spectra separately. Concerning their relative position, the positive-parity states are always too high in excitation energy, but a fast drop with respect to the negative-parity spectrum is observed when the model space is increased. This behavior is most dramatic for 11-Be. In the largest model space we were able to reach, the 1/2+ level has dropped down to become either the first or the second excited state, depending ...

  10. Thermodynamic assessment of the Ho–Te system supported by ab initio calculations

    Energy Technology Data Exchange (ETDEWEB)

    Ghamri, H.; Belgacem-Bouzida, A. [Laboratoire d’étude Physico-Chimique des Matériaux, Département de Physique, Faculté des Sciences, Université de Batna, Rue Chahid Boukhlouf, 05000 Batna (Algeria); Djaballah, Y., E-mail: ydjaballah@yahoo.fr [Laboratoire d’étude Physico-Chimique des Matériaux, Département de Physique, Faculté des Sciences, Université de Batna, Rue Chahid Boukhlouf, 05000 Batna (Algeria); Hidoussi, A. [Laboratoire d’étude Physico-Chimique des Matériaux, Département de Physique, Faculté des Sciences, Université de Batna, Rue Chahid Boukhlouf, 05000 Batna (Algeria)

    2013-03-05

    Highlights: ► We calculated enthalpies of formation of the HoTe and Ho{sub 2}Te{sub 5} compounds by using ab initio method. ► We modeled the Gibbs energy of the HoTe intermediate phase for the first time. ► The thermodynamic parameters of the all phases existing in the system were determined. ► The complete phase diagram of the system (Ho–Te) is calculated. -- Abstract: The phase diagram of the Ho–Te binary system has been assessed by using the CALPHAD (Calculation of Phase Diagrams) method on the basis of the experimental data of the phase equilibria and enthalpies of formation from ab initio electronic-structure calculations within the framework of density-functional theory. Reasonable models were constructed for all the phases of the system. The liquid phase was described as the substitutional solution model with excess energy expressed by Redlich–Kister polynomial. The compounds Ho{sub 2}Te{sub 5} and HoTe{sub 3} were expressed as stoichiometric phases. The (HoTe) phase was modeled by two-sublattices; (Ho,Va){sub 1}(Te){sub 1}. A consistent set of thermodynamic parameters has been derived, and calculated phase diagram was compared with the experimental data. A good agreement between the calculated results and experimental data was obtained.

  11. Embedding parameters in ab initio theory to develop approximations based on molecular similarity

    CERN Document Server

    Tanha, Matteus; Kaul, Shiva; Cappiello, Alexander; Gordon, Geoffrey J; Yaron, David J

    2015-01-01

    A means to take advantage of molecular similarity to lower the computational cost of electronic structure theory is explored, in which parameters are embedded into a low-cost, low-level (LL) ab initio model and adjusted to obtain agreement with results from a higher-level (HL) ab initio model. A parametrized LL (pLL) model is created by multiplying selected matrix elements of the Hamiltonian operators by scaling factors that depend on element types. Various schemes for applying the scaling factors are compared, along with the impact of making the scaling factors linear functions of variables related to bond lengths, atomic charges, and bond orders. The models are trained on ethane and ethylene, substituted with -NH2, -OH and -F, and tested on substituted propane, propylene and t-butane. Training and test datasets are created by distorting the molecular geometries and applying uniform electric fields. The fitted properties include changes in total energy arising from geometric distortions or applied fields, an...

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

    Science.gov (United States)

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

    2016-06-01

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

  13. Voltage-dependent parameter extraction for graphene nanoribbon interconnect model through ab initio approach

    Energy Technology Data Exchange (ETDEWEB)

    Yamacli, Serhan, E-mail: syamacli@nny.edu.tr

    2014-07-01

    This paper presents electrical parameter extraction for metallic graphene nanoribbon (GNR) interconnects utilizing ab initio approach. Unlike the studies taking the kinetic inductance, quantum capacitance and Fermi velocity as constant values, voltage-dependencies of these parameters are obtained for GNR transmission line model. The variations of the kinetic energy and the current by the applied voltage are taken as bases for voltage-dependent kinetic inductance calculation. Quantum capacitance and the Fermi velocity are also computed from the kinetic inductance variation. It is concluded that voltage-dependencies of the kinetic inductance and the quantum capacitance have to be taken into account for accurate GNR modelling in nanoelectronic design. - Highlights: • Metallic graphene nanoribbon interconnects are studied using ab initio approach. • Variations of the kinetic inductance (L{sub K}) and the current are obtained. • Voltage-dependency of the kinetic inductance is extracted. • The variations of quantum capacitance (C{sub Q}) and Fermi velocity are calculated. • L{sub K} and C{sub Q} change by 34% in the voltage range of 0–1 V.

  14. Ab initio quantum chemistry in parallel-portable tools and applications

    Energy Technology Data Exchange (ETDEWEB)

    Harrison, R.J.; Shepard, R. (Argonne National Lab., IL (United States)); Kendall, R.A. (Battelle Pacific Northwest Lab., Richland, WA (United States))

    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{sup 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.

  15. Vibrational spectroscopic investigations, ab initio and DFT studies on 7-bromo-5-chloro-8-hydroxyquinoline

    Science.gov (United States)

    Arjunan, V.; Mohan, S.; Ravindran, P.; Mythili, C. V.

    2009-05-01

    The Fourier transform infrared (FTIR) and FT-Raman spectra of 7-bromo-5-chloro-8-hydroxyquinoline (BCHQ) have been measured in the range 4000-400 and 4000-100 cm -1, respectively. Complete vibrational assignment and analysis of the fundamental modes of the compound were carried out using the observed FTIR and FT-Raman data. The geometry was optimised without any symmetry constrains using the DFT/B3LYP and HF methods with 6-31G** basis set. The vibrational frequencies which were determined experimentally are compared with those obtained theoretically from ab initio HF and density functional theory (DFT) gradient calculations employing the HF/6-31G** and B3LYP/6-31G** methods for the optimised geometry of the compound. The structural parameters and normal modes of vibration obtained from HF and DFT methods are in good agreement with the experimental data. Normal coordinate analysis was also carried out with ab initio force fields utilising Wilson's FG matrix method.

  16. Ab initio, density functional theory and structural studies of 4-amino-2-methylquinoline

    Science.gov (United States)

    Arjunan, V.; Saravanan, I.; Ravindran, P.; Mohan, S.

    2009-10-01

    The Fourier transform infrared (FTIR) and FT-Raman spectra of 4-amino-2-methylquinoline (AMQ) have been recorded in the range 4000-400 and 4000-100 cm -1, respectively. The experimental vibrational frequency was compared with the wavenumbers obtained theoretically by ab initio HF and DFT-B3LYP gradient calculations employing the standard 6-31G** and high level 6-311++G** basis sets for optimised geometry of the compound. The complete vibrational assignment and analysis of the fundamental modes of the compounds were carried out using the experimental FTIR and FT-Raman data, and quantum mechanical studies. The geometry and normal modes of vibration obtained from the HF and DFT methods are in good agreement with the experimental data. The potential energy distribution of the fundamental modes was calculated with ab initio force fields utilising Wilson's FG matrix method. The NH -π interactions and the influence of amino and methyl groups on the skeletal modes are investigated.

  17. Ground state analytical ab initio intermolecular potential for the Cl{sub 2}-water system

    Energy Technology Data Exchange (ETDEWEB)

    Hormain, Laureline; Monnerville, Maurice, E-mail: maurice.monnerville@univ-lille1.fr; Toubin, Céline; Duflot, Denis; Pouilly, Brigitte; Briquez, Stéphane [Laboratoire de Physique des Lasers Atomes et Molécules, Unité Mixte de Recherche (UMR) 8523, Université Lille I, Bât. P5, 59655 Villeneuve d’Ascq Cedex (France); Bernal-Uruchurtu, Margarita I.; Hernández-Lamoneda, Ramón [Centro de Investigaciones Químicas, Universidad Autónoma del Estado de Morelos, Cuernavaca 62209, México (Mexico)

    2015-04-14

    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{sub 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{sub 2} − H{sub 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{sub 2} interacting with an increasing number of water molecules. Finally, the model potential is used to study the physisorption of Cl{sub 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.

  18. Novel high-pressure phase of ZrO{sub 2}: An ab initio prediction

    Energy Technology Data Exchange (ETDEWEB)

    Durandurdu, Murat, E-mail: murat.durandurdu@agu.edu.tr

    2015-10-15

    The high-pressure behavior of the orthorhombic cotunnite type ZrO{sub 2} is explored using an ab initio constant pressure technique. For the first time, a novel hexagonal phase (Ni{sub 2}In type) within P6{sub 3}/mmc symmetry is predicted through the simulation. The Ni{sub 2}In type crystal is the densest high-pressure phase of ZrO{sub 2} proposed so far and has not been observed in other metal dioxides at high pressure before. The phase transformation is accompanied by a small volume drop and likely to occur around 380 GPa in experiment. - Graphical abstract: Post-cotunnite Ni{sub 2}In type hexagonal phase forms in zirconia at high pressure. - Highlights: • A post-cotunnite phase is predicted for ZrO{sub 2} through an ab initio simulation. • Cotunnite ZrO{sub 2} adopts the Ni{sub 2}In type structure at high pressure. • The Ni{sub 2}In type structure is the densest high-pressure phase of ZrO{sub 2} proposed so far. • The preferred mechanism in ZrO{sub 2} differs from the other metal dioxides.

  19. Ab initio calculation of oxygen self-diffusion coefficient in uranium dioxide UO2

    Science.gov (United States)

    Dorado, Boris; Garcia, Philippe; Torrent, Marc

    Uranium dioxide UO2 is the most widely used nuclear fuel worldwide and its atomic transport properties are relevant to practically all engineering aspects of the material. Although transport properties have already been studied in UO2 by means of first-principles calculations, the ab initio determination of self-diffusion coefficients has up to now remained unreachable because the relevant computational tools were neither available or adapted. The present work reports our results related to the ab initio calculation of the oxygen self-diffusion coefficient in UO2. We first determine the Gibbs free energies of formation of oxygen charged defects by calculating both the electronic and vibrational (hence entropic) contributions. Then, we use the transition state theory in order to compute the effective jump frequency of the defects, which in turn provides us with the value of the pre-exponential factor. The results are compared to self-diffusion data obtained experimentally with a careful monitoring of the relevant thermodynamic conditions (oxygen partial pressure, temperature, impurity content).

  20. 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......-polarization of the transmission in large energy ranges. The effect is due to the spin-polarized zig-zag edge terminating each graphene flake causing a spin-splitting of the graphene pi(z) bands, and the chain states. Transmission occurs when the graphene p-states resonate with similar states in the strongly hybridized edges...... and chain. This effect should in general hold for any p-conjugated molecules bridging the zig-zag edges of graphene electrodes. The polarization of the transmission can be controlled by chemically or mechanically modifying the molecule, or by applying an electrical gate....

  1. Ab initio determination of an extended Heisenberg Hamiltonian in CuO{sub 2} layers

    Energy Technology Data Exchange (ETDEWEB)

    Calzado, C.J.; Malrieu, J.P. [Lab. de Physique Quantique, IRSAMC, Univ. Paul Sabatier, Toulouse (France)

    2001-06-01

    Accurate ab initio calculations on embedded Cu{sub 4}O{sub 12} square clusters, fragments of the La{sub 2}CuO{sub 4} lattice, confirm a value of the nearest neighbor antiferromagnetic coupling (J = 124 meV) previously obtained from ab initio calculations on bicentric clusters and in good agreement with experiment. These calculations predict non negligible antiferromagnetic second-neighbor interaction (J' = 6.5 meV) and four-spin cyclic exchange (K = 14 meV), which may affect the thermodynamic and spectroscopic properties of these materials. The dependence of the magnetic coupling on local lattice distortions has also been investigated. Among them the best candidate to induce a spin-phonon effect seems to be the movement of the Cu atoms, changing the Cu-Cu distance, for which the variation of the nearest neighbor magnetic coupling with the Cu-O distance is {delta}J/{delta}d{sub Cu} {sub -} {sub O} {proportional_to} 1700 cm {sup -1} A {sup -1}. (orig.)

  2. Ab initio molecular dynamics of solvation effects on reactivity at electrified interfaces

    Science.gov (United States)

    Herron, Jeffrey A.; Morikawa, Yoshitada; Mavrikakis, Manos

    2016-08-01

    Using ab initio molecular dynamics as implemented in periodic, self-consistent (generalized gradient approximation Perdew-Burke-Ernzerhof) density functional theory, we investigated the mechanism of methanol electrooxidation on Pt(111). We investigated the role of water solvation and electrode potential on the energetics of the first proton transfer step, methanol electrooxidation to methoxy (CH3O) or hydroxymethyl (CH2OH). The results show that solvation weakens the adsorption of methoxy to uncharged Pt(111), whereas the binding energies of methanol and hydroxymethyl are not significantly affected. The free energies of activation for breaking the C-H and O-H bonds in methanol were calculated through a Blue Moon Ensemble using constrained ab initio molecular dynamics. Calculated barriers for these elementary steps on unsolvated, uncharged Pt(111) are similar to results for climbing-image nudged elastic band calculations from the literature. Water solvation reduces the barriers for both C-H and O-H bond activation steps with respect to their vapor-phase values, although the effect is more pronounced for C-H bond activation, due to less disruption of the hydrogen bond network. The calculated activation energy barriers show that breaking the C-H bond of methanol is more facile than the O-H bond on solvated negatively biased or uncharged Pt(111). However, with positive bias, O-H bond activation is enhanced, becoming slightly more facile than C-H bond activation.

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

    International Nuclear Information System (INIS)

    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)

  4. Experimental and ab initio investigations on textured Li–Mn–O spinel thin film cathodes

    Energy Technology Data Exchange (ETDEWEB)

    Fischer, J., E-mail: Julian.Fischer@kit.edu [Karlsruhe Institute of Technology (KIT), Institute for Applied Materials (IAM), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Music, D. [RWTH Aachen University, Materials Chemistry, Kopernikusstrasse 10, 52074 Aachen (Germany); Bergfeldt, T.; Ziebert, C.; Ulrich, S.; Seifert, H.J. [Karlsruhe Institute of Technology (KIT), Institute for Applied Materials (IAM), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany)

    2014-12-01

    This paper describes the tailored preparation of nearly identical lithium–manganese–oxide thin film cathodes with different global grain orientations. The thin films were synthesized by rf magnetron sputtering from a LiMn{sub 2}O{sub 4}-target in a pure argon plasma. Under appropriate processing conditions, thin films with a cubic spinel structure and a nearly similar density and surface topography but different grain orientation, i.e. (111)- and (440)-textured films, were achieved. The chemical composition was determined by inductively coupled plasma optical emission spectroscopy and carrier gas hot extraction. The constitution- and microstructure were evaluated by X-ray diffraction and Raman spectroscopy. The surface morphology and roughness were investigated by scanning electron and atomic force microscopy. The differently textured films represent an ideal model system for studying potential effects of grain orientation on the lithium ion diffusion and electrochemical behavior in LiMn{sub 2}O{sub 4}-based thin films. They are nearly identical in their chemical composition, atomic bonding behavior, surface-roughness, morphology and thickness. Our initial ab initio molecular dynamics data indicate that Li ion transport is faster in (111)-textured structure than in (440)-textured one. - Highlights: • Thin film model system of differently textured cubic Li–Mn–O spinels. • Investigation of the Li–Mn–O thin film mass density by X-ray reflectivity. • Ab initio molecular dynamics simulation on Li ion diffusion in LiMn{sub 2}O{sub 4}.

  5. Molecular potentials and wave function mapping by high-resolution electron spectroscopy and ab initio calculations

    Energy Technology Data Exchange (ETDEWEB)

    Kimberg, Victor, E-mail: victor.kimberg@pks.mpi.de [Max Planck Institute for the Physics of Complex Systems, Nöthnitzer Straße 38, 01187 Dresden (Germany); Miron, Catalin, E-mail: miron@synchrotron-soleil.fr [Synchrotron SOLEIL, l’Orme des Merisiers, Saint-Aubin, BP 48, FR-91192 Gif-sur-Yvette Cedex (France)

    2014-08-15

    Highlights: • Some studies related to the vibrational wave functions mapping phenomenon are reviewed. • The core-excited vibrational wave functions were mapped using dissociative and bound final states. • High-resolution experimental data is accompanied by ab initio calculations. • The mapping phenomenon allows one to extract constants of the molecular potentials. • The mapping techniques are general and can be applied for the study of many systems. - Abstract: The recent development of high brightness 3{sup rd} generation soft X-ray sources and high energy resolution electron spectrometers made it possible to accurately trace quantum phenomena associated to the vibrational dynamics in core-excited molecules. The present paper reviews the recent results on mapping of vibrational wave functions and molecular potentials based on electron spectroscopy. We discuss and compare the mapping phenomena in various systems, stressing the advantages of the resonant X-ray scattering for studying of the nuclear dynamics and spectroscopic constants of small molecules. The experimental results discussed in the paper are most often accompanied by state-of-the-art ab initio calculations allowing for a deeper understanding of the quantum effects. Besides its fundamental interest, the vibrational wave function mapping is shown to be useful for the analysis of core- and valence-excited molecular states based on the reflection principle.

  6. Experimental and ab initio investigations on textured Li–Mn–O spinel thin film cathodes

    International Nuclear Information System (INIS)

    This paper describes the tailored preparation of nearly identical lithium–manganese–oxide thin film cathodes with different global grain orientations. The thin films were synthesized by rf magnetron sputtering from a LiMn2O4-target in a pure argon plasma. Under appropriate processing conditions, thin films with a cubic spinel structure and a nearly similar density and surface topography but different grain orientation, i.e. (111)- and (440)-textured films, were achieved. The chemical composition was determined by inductively coupled plasma optical emission spectroscopy and carrier gas hot extraction. The constitution- and microstructure were evaluated by X-ray diffraction and Raman spectroscopy. The surface morphology and roughness were investigated by scanning electron and atomic force microscopy. The differently textured films represent an ideal model system for studying potential effects of grain orientation on the lithium ion diffusion and electrochemical behavior in LiMn2O4-based thin films. They are nearly identical in their chemical composition, atomic bonding behavior, surface-roughness, morphology and thickness. Our initial ab initio molecular dynamics data indicate that Li ion transport is faster in (111)-textured structure than in (440)-textured one. - Highlights: • Thin film model system of differently textured cubic Li–Mn–O spinels. • Investigation of the Li–Mn–O thin film mass density by X-ray reflectivity. • Ab initio molecular dynamics simulation on Li ion diffusion in LiMn2O4

  7. From ab initio quantum chemistry to molecular dynamics: The delicate case of hydrogen bonding in ammonia

    CERN Document Server

    Boese, A D; Martin, J M L; Marx, D; Chandra, Amalendu; Martin, Jan M.L.; Marx, Dominik

    2003-01-01

    The ammonia dimer (NH3)2 has been investigated using high--level ab initio quantum chemistry methods and density functional theory (DFT). The structure and energetics of important isomers is obtained to unprecedented accuracy without resorting to experiment. The global minimum of eclipsed C_s symmetry is characterized by a significantly bent hydrogen bond which deviates from linearity by about 20 degrees. In addition, the so-called cyclic C_{2h} structure is extremely close in energy on an overall flat potential energy surface. It is demonstrated that none of the currently available (GGA, meta--GGA, and hybrid) density functionals satisfactorily describe the structure and relative energies of this nonlinear hydrogen bond. We present a novel density functional, HCTH/407+, designed to describe this sort of hydrogen bond quantitatively on the level of the dimer, contrary to e.g. the widely used BLYP functional. This improved functional is employed in Car-Parrinello ab initio molecular dynamics simulations of liq...

  8. Evolved chiral NN +3N Hamiltonians for ab initio nuclear structure calculations

    Science.gov (United States)

    Roth, Robert; Calci, Angelo; Langhammer, Joachim; Binder, Sven

    2014-08-01

    We discuss the building blocks for a consistent inclusion of chiral three-nucleon (3N) interactions into ab initio nuclear structure calculations beyond the lower p shell. We highlight important technical developments, such as the similarity renormalization group (SRG) evolution in the 3N sector, a JT-coupled storage scheme for 3N matrix elements with efficient on-the-fly decoupling, and the importance-truncated no-core shell model with 3N interactions. Together, these developments make converged ab initio calculations with explicit 3N interactions possible also beyond the lower p shell. We analyze in detail the impact of various truncations of the SRG-evolved Hamiltonian, in particular the truncation of the harmonic-oscillator model space used for solving the SRG flow equations and the omission of the induced beyond-3N contributions of the evolved Hamiltonian. Both truncations lead to sizable effects in the upper p shell and beyond and we present options to remedy these truncation effects. The analysis of the different truncations is a first step towards a systematic uncertainty quantification of all stages of the calculation.

  9. Evolved Chiral NN+3N Hamiltonians for Ab Initio Nuclear Structure Calculations

    CERN Document Server

    Roth, Robert; Langhammer, Joachim; Binder, Sven

    2013-01-01

    We discuss the building blocks for a consistent inclusion of chiral three-nucleon (3N) interactions into ab initio nuclear structure calculations beyond the lower p-shell. We highlight important technical developments, such as the similarity renormalization group (SRG) evolution in the 3N sector, a JT-coupled storage scheme for 3N matrix elements with efficient on-the-fly decoupling, and the importance truncated no-core shell model with 3N interactions. Together, these developments make converged ab initio calculations with explicit 3N interactions possible also beyond the lower p-shell. We analyze in detail the impact of various truncations of the SRG-evolved Hamiltonian, in particular the truncation of the harmonic-oscillator model space used for solving the SRG flow equations and the omission of the induced beyond-3N contributions of the evolved Hamiltonian. Both truncations lead to sizable effects in the upper p-shell and beyond and we present options to remedy these truncation effects. The analysis of th...

  10. Towards an ab-initio treatment of nonlocal electronic correlations with dynamical vertex approximation

    Science.gov (United States)

    Galler, Anna; Gunacker, Patrik; Tomczak, Jan; Thunström, Patrik; Held, Karsten

    Recently, approaches such as the dynamical vertex approximation (D ΓA) or the dual-fermion method have been developed. These diagrammatic approaches are going beyond dynamical mean field theory (DMFT) by including nonlocal electronic correlations on all length scales as well as the local DMFT correlations. Here we present our efforts to extend the D ΓA methodology to ab-initio materials calculations (ab-initio D ΓA). Our approach is a unifying framework which includes both GW and DMFT-type of diagrams, but also important nonlocal correlations beyond, e.g. nonlocal spin fluctuations. In our multi-band implementation we are using a worm sampling technique within continuous-time quantum Monte Carlo in the hybridization expansion to obtain the DMFT vertex, from which we construct the reducible vertex function using the two particle-hole ladders. As a first application we show results for transition metal oxides. Support by the ERC project AbinitioDGA (306447) is acknowledged.

  11. Femtosecond dynamics of correlated many-body states in C$_{60}$ fullerenes

    CERN Document Server

    Usenko, Sergey; Azima, Armin; Jakob, Markus; Lazzarino, Leslie L; Pavlyukh, Yaroslav; Przystawik, Andreas; Drescher, Markus; Laarmann, Tim; Berakdar, Jamal

    2016-01-01

    Fullerene complexes may play a key role in the design of future molecular electronics and nanostructured devices with potential applications in light harvesting using organic solar cells. Charge and energy flow in these systems is mediated by many-body effects. We studied the structure and dynamics of laser-induced multi-electron excitations in isolated C$_{60}$ by two-photon photoionization as a function of excitation wavelength using a tunable fs UV laser and developed a corresponding theoretical framework on the basis of ab initio calculations. The measured resonance line width gives direct information on the excited state lifetime. From the spectral deconvolution we derive a lower limit for purely electronic relaxation on the order of $\\tau_\\mathrm{el}=8^{+12}_{-5}$ fs. Energy dissipation towards nuclear degrees of freedom is studied in time-resolved experiments. The evaluation of the non-linear autocorrelation trace gives a characteristic time constant of $\\tau_\\mathrm{vib}=309\\pm31$ fs for the exponenti...

  12. Ab initio interaction potentials and scattering lengths for ultracold mixtures of metastable helium and alkali-metal atoms

    Science.gov (United States)

    Kedziera, Dariusz; Mentel, Łukasz; Żuchowski, Piotr S.; Knoop, Steven

    2015-06-01

    We have obtained accurate ab initio +4Σ quartet potentials for the diatomic metastable triplet helium+alkali-metal (Li, Na, K, Rb) systems, using all-electron restricted open-shell coupled cluster singles and doubles with noniterative triples corrections CCSD(T) calculations and accurate calculations of the long-range C6 coefficients. These potentials provide accurate ab initio quartet scattering lengths, which for these many-electron systems is possible, because of the small reduced masses and shallow potentials that result in a small amount of bound states. Our results are relevant for ultracold metastable triplet helium+alkali-metal mixture experiments.

  13. Multiscale modeling of femtosecond laser irradiation on copper film with electron thermal conductivity from ab initio calculation

    CERN Document Server

    Ji, Pengfei

    2016-01-01

    By combining ab initio quantum mechanics calculation and Drude model, electron temperature and lattice temperature dependent electron thermal conductivity is calculated and implemented into a multiscale model of laser material interaction, which couples the classical molecular dynamics and two-temperature model. The results indicated that the electron thermal conductivity obtained from ab initio calculation leads to faster thermal diffusion than that using the electron thermal conductivity from empirical determination, which further induces deeper melting region, larger number of density waves travelling inside the copper film and more various speeds of atomic clusters ablated from the irradiated film surface.

  14. Ab initio ground and the first excited adiabatic and quasidiabatic potential energy surfaces of H + + CO system

    Science.gov (United States)

    George, D. X. F.; Kumar, Sanjay

    2010-08-01

    Ab initio global adiabatic as well as quasidiabatic potential energy surfaces for the ground and the first excited electronic states of the H + + CO system have been computed as a function of the Jacobi coordinates ( R, r, γ) using Dunning's cc-pVTZ basis set at the internally contracted multi-reference (single and double) configuration interaction level of accuracy. In addition, nonadiabatic coupling matrix elements arising from radial motion, mixing angle and coupling potential have been computed using the ab initio procedure [Simah et al. (1999) [66

  15. A theoretical-spectroscopy, ab-initio-based study of the electronic ground state of 121SbH3

    OpenAIRE

    Yurchenko, Sergei N.; Carvajal Zaera, Miguel; Yachmenev, Andrey; Thiel, Walter; Jensen, Per

    2010-01-01

    For the stibine isotopologue (SbH3)-Sb-121, we report improved theoretical calculations of the vibrational energies below 8000 cm- and simulations of the rovibrational spectrum in the 0-8000 cm(-1) region. The calculations are based on a refined ab initio potential energy surface and on a new dipole moment surface obtained at the coupled cluster CCSD(T) level. The theoretical results are compared with the available experimental data in order to validate the ab initio surfaces and the TROVE co...

  16. Embedded atom approach for gold–silicon system from ab initio molecular dynamics simulations using the force matching method

    Indian Academy of Sciences (India)

    A NASSOUR

    2016-09-01

    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 temperatures. Classical molecular dynamics simulations are performed to examine structural, coordination numbers, structure factors and dynamic properties of Au$_{81}$Si$_{19}$ alloy, with the interaction described via EAM model. The results are in good agreement with AIMD simulations and experimental data.

  17. Structural phase transitions in Ruddlesden-Popper phases of strontium titanate: {\\em ab initio} and inhomogeneous Ginzburg-Landau approaches

    CERN Document Server

    Lee, Jeehye

    2010-01-01

    We present the first systematic {\\em ab initio} study of anti-ferrodistortive (AFD) order in Ruddlesden-Popper (RP) phases of strontium titanate, Sr$_{1+n}$Ti$_n$O$_{3n+1}$, as a function of both compressive epitaxial strain and phase number $n$. We find all RP phases to exhibit AFD order under a significant range of strains, recovering the bulk AFD order as $\\sim 1/n^2$. A Ginzburg-Landau Hamiltonian generalized to include inter-octahedral interactions reproduces our {\\em ab initio} results well, opening a pathway to understanding other nanostructured perovskite systems.

  18. The many-body level density

    International Nuclear Information System (INIS)

    We investigate the many-body level density ρMB for fermion and boson gases. We establish its behavior as a function of the temperature and the number of particles. We deal with correction terms due to finite number of particles effects for ρMB: for fermions, it seems that it exists only one behavior. We propose a semiclassical expression of ρMB for two types of particles with an angular momentum. It is decomposed into a smooth part coming from the saddle point method plus corrective terms due to the expansion of the number of partitions for two types of particles and an oscillating part coming from the fluctuations of the single-particle level density. Our model is validated by a numerical study. For the case of the atomic nucleus, the oscillating part of ρMB is controlled by a temperature factor which depends on the chaotic or integrable nature of the system and on the fluctuation of the ground state energy. This leads to consider in more detail this last quantity. For an isolated system, we give the general expression of the mean value for fixed potentials. We treat the self-bound system case through the example of the three dimensional harmonic oscillator (3DHO). Furthermore we study the oscillating part of ρMB for bosons in the low temperature regime for billiards and for isotropic 3DHO. We note the oscillations disappear leading to a power law correction. In the case of the isotropic 3DHO, these corrections have the same order of magnitude as the smooth part. In the same way, for the high temperature regime we show the oscillating part of ρMB is exponentially negligible compared to the smooth part. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-07-01

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

  20. Ab Initio Nuclear Theory - Progress and Prospects from Quarks to the Cosmos

    International Nuclear Information System (INIS)

    The vision of solving the nuclear many-body problem with fundamental interactions tied to QCD appears to approach reality. The goals are to preserve the predictive power of the underlying theory, to test fundamental symmetries with the nucleus as laboratory and to develop new understandings of the full range of complex nuclear phenomena. Recent progress includes the derivation, within chiral perturbation theory (ChPT), of the leading terms of the nucleon-nucleon (NN), three-nucleon (3N) and four nucleon (4N) potentials. Additional substantial progress includes solving nuclear structure and reactions in nuclei up to mass 16 and selected heavier nuclei around closed shells using these ChPT interactions. Advances in theoretical frameworks (renormalization and many-body methods) as well as in computational resources (new algorithms and leadership-class parallel computers) signal a new generation of theory simulations that will yield valuable insights into origins of nuclear shell structure, collective phenomena and complex reaction dynamics. I outline some recent achievements and present ambitious consensus plans for a coming decade of research that will strengthen the links between nuclear theory and nuclear experiment, between nuclear physics and astrophysics, and between nuclear physics and nuclear energy applications. (author)

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

    International Nuclear Information System (INIS)

    Spin Orbit Coupling (SOC) is introduced to molecular ab initio density matrix renormalization group (DMRG) calculations. In the presented scheme, one first approximates the electronic ground state and a number of excited states of the Born-Oppenheimer (BO) Hamiltonian with the aid of the DMRG algorithm. Owing to the spin-adaptation of the algorithm, the total spin S is a good quantum number for these states. After the non-relativistic DMRG calculation is finished, all magnetic sublevels of the calculated states are constructed explicitly, and the SOC operator is expanded in the resulting basis. To this end, spin orbit coupled energies and wavefunctions are obtained as eigenvalues and eigenfunctions of the full Hamiltonian matrix which is composed of the SOC operator matrix and the BO Hamiltonian matrix. This treatment corresponds to a quasi-degenerate perturbation theory approach and can be regarded as the molecular equivalent to atomic Russell-Saunders coupling. For the evaluation of SOC matrix elements, the full Breit-Pauli SOC Hamiltonian is approximated by the widely used spin-orbit mean field operator. This operator allows for an efficient use of the second quantized triplet replacement operators that are readily generated during the non-relativistic DMRG algorithm, together with the Wigner-Eckart theorem. With a set of spin-orbit coupled wavefunctions at hand, the molecular g-tensors are calculated following the scheme proposed by Gerloch and McMeeking. It interprets the effective molecular g-values as the slope of the energy difference between the lowest Kramers pair with respect to the strength of the applied magnetic field. Test calculations on a chemically relevant Mo complex demonstrate the capabilities of the presented method

  2. Rotational study of the CH{sub 4}–CO complex: Millimeter-wave measurements and ab initio calculations

    Energy Technology Data Exchange (ETDEWEB)

    Surin, L. A., E-mail: surin@ph1.uni-koeln.de [I. Physikalisches Institut, University of Cologne, Zülpicher St. 77, 50937 Cologne (Germany); Institute of Spectroscopy, Russian Academy of Sciences, Fizicheskaya St. 5, 142190 Troitsk, Moscow (Russian Federation); Tarabukin, I. V.; Panfilov, V. A. [Institute of Spectroscopy, Russian Academy of Sciences, Fizicheskaya St. 5, 142190 Troitsk, Moscow (Russian Federation); Schlemmer, S. [I. Physikalisches Institut, University of Cologne, Zülpicher St. 77, 50937 Cologne (Germany); Kalugina, Y. N. [Department of Optics and Spectroscopy, Tomsk State University, 36 Lenin Ave., 634050 Tomsk (Russian Federation); Faure, A.; Rist, C. [University Grenoble Alpes, IPAG, F-38000 Grenoble (France); CNRS, IPAG, F-38000 Grenoble (France); Avoird, A. van der, E-mail: A.vanderAvoird@theochem.ru.nl [Theoretical Chemistry, Institute for Molecules and Materials, Radboud University, Heyendaalseweg 135, 6525 AJ Nijmegen (Netherlands)

    2015-10-21

    The rotational spectrum of the van der Waals complex CH{sub 4}–CO has been measured with the intracavity OROTRON jet spectrometer in the frequency range of 110–145 GHz. Newly observed and assigned transitions belong to the K = 2–1 subband correlating with the rotationless j{sub CH4} = 0 ground state and the K = 2–1 and K = 0–1 subbands correlating with the j{sub CH4} = 2 excited state of free methane. The (approximate) quantum number K is the projection of the total angular momentum J on the intermolecular axis. The new data were analyzed together with the known millimeter-wave and microwave transitions in order to determine the molecular parameters of the CH{sub 4}–CO complex. Accompanying ab initio calculations of the intermolecular potential energy surface (PES) of CH{sub 4}–CO have been carried out at the explicitly correlated coupled cluster level of theory with single, double, and perturbative triple excitations [CCSD(T)-F12a] and an augmented correlation-consistent triple zeta (aVTZ) basis set. The global minimum of the five-dimensional PES corresponds to an approximately T-shaped structure with the CH{sub 4} face closest to the CO subunit and binding energy D{sub e} = 177.82 cm{sup −1}. The bound rovibrational levels of the CH{sub 4}–CO complex were calculated for total angular momentum J = 0–6 on this intermolecular potential surface and compared with the experimental results. The calculated dissociation energies D{sub 0} are 91.32, 94.46, and 104.21 cm{sup −1} for A (j{sub CH4} = 0), F (j{sub CH4} = 1), and E (j{sub CH4} = 2) nuclear spin modifications of CH{sub 4}–CO, respectively.

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

    Science.gov (United States)

    Roemelt, Michael

    2015-07-01

    Spin Orbit Coupling (SOC) is introduced to molecular ab initio density matrix renormalization group (DMRG) calculations. In the presented scheme, one first approximates the electronic ground state and a number of excited states of the Born-Oppenheimer (BO) Hamiltonian with the aid of the DMRG algorithm. Owing to the spin-adaptation of the algorithm, the total spin S is a good quantum number for these states. After the non-relativistic DMRG calculation is finished, all magnetic sublevels of the calculated states are constructed explicitly, and the SOC operator is expanded in the resulting basis. To this end, spin orbit coupled energies and wavefunctions are obtained as eigenvalues and eigenfunctions of the full Hamiltonian matrix which is composed of the SOC operator matrix and the BO Hamiltonian matrix. This treatment corresponds to a quasi-degenerate perturbation theory approach and can be regarded as the molecular equivalent to atomic Russell-Saunders coupling. For the evaluation of SOC matrix elements, the full Breit-Pauli SOC Hamiltonian is approximated by the widely used spin-orbit mean field operator. This operator allows for an efficient use of the second quantized triplet replacement operators that are readily generated during the non-relativistic DMRG algorithm, together with the Wigner-Eckart theorem. With a set of spin-orbit coupled wavefunctions at hand, the molecular g-tensors are calculated following the scheme proposed by Gerloch and McMeeking. It interprets the effective molecular g-values as the slope of the energy difference between the lowest Kramers pair with respect to the strength of the applied magnetic field. Test calculations on a chemically relevant Mo complex demonstrate the capabilities of the presented method.

  4. Many-Body Theory of Atomic Transitions

    Science.gov (United States)

    Holmes, Charles Potter

    This dissertation presents a systematic approach to the derivation of transition widths and cross sections for atomic radiative and/or nonradiative processes. By applying the transition theory of Goldberger and Watson ^1, all transition properties are derived from proper solutions of the time-dependent Schrodinger equation. The focus is on situations where initial and final wave functions are nonorthogonal functions that belong to different self-consistent fields. This approach is particularly useful in the treatment of ionizing transitions where the outgoing free electron sees a different atomic potential from that of the initial bound state. Transition amplitudes are expressed as perturbation expansions in which singularities have been removed algebraically. These singularities are due to states which are degenerate with the initial and final states and represent the competing transition channels. The perturbation expansions show clearly the role of the nonorthogonality of the participating states leading to terms representing "shake" processes competing with higher-order electron correlation processes. Transition amplitudes including all second-order processes, are derived for the following transitions: X-ray, Auger, photoionization, radiative recombination, dielectronic recombination, radiative -Auger. Comparisons are made with the expressions frequently used by other workers. Using a Hartree-Fock-Slater model K- and L-shell X-ray and Auger transition widths are calculated for the range 5 Z Theory, (John Wiley & Sons, New York, 1964), Chapter 8, page 424.

  5. In search of the X2BO and X2BS (X = H, F) free radicals: Ab initio studies of their spectroscopic signatures

    International Nuclear Information System (INIS)

    The F2BO free radical is a known, although little studied, species but similar X2BY (X = H, D, F; Y = O, S) molecules are largely unknown. High level ab initio methods have been used to predict the molecular structures, vibrational frequencies (in cm−1), and relative energies of the ground and first two excited electronic states of these free radicals, as an aid to their eventual spectroscopic identification. The chosen theoretical methods and basis sets were tested on F2BO and found to give good agreement with the known experimental quantities. In particular, complete basis set extrapolations of coupled-cluster single and doubles with perturbative triple excitations/aug-cc-pVXZ (X = 3, 4, 5) energies gave excellent electronic term values, due to small changes in geometry between states and the lack of significant multireference character in the wavefunctions. The radicals are found to have planar C2v geometries in the X~2B2 ground state, the low-lying A~2B1 first excited state, and the higher B~2A1 state. Some of these radicals have very small ground state dipole moments hindering microwave measurements. Infrared studies in matrices or in the gas phase may be possible although the fundamentals of H2BO and H2BS are quite weak. The most promising method of identifying these species in the gas phase appears to be absorption or laser-induced fluorescence spectroscopy through the allowed B~-X~ transitions which occur in the visible-near UV region of the electromagnetic spectrum. The ab initio results have been used to calculate the Franck-Condon profiles of the absorption and emission spectra, and the rotational structure of the B~-X~000 bands has been simulated. The calculated single vibronic level emission spectra provide a unique, readily recognizable fingerprint of each particular radical, facilitating the experimental identification of new X2BY species in the gas phase

  6. The vibrational spectrum and rotational constants of difluoroethyne FC 3/4 CF. Matrix and high resolution infrared studies and ab initio calculations

    Science.gov (United States)

    Bürger, H.; Schneider, W.; Sommer, S.; Thiel, W.; Willner, H.

    1991-10-01

    Infrared spectra of the short-lived difluoroethyne molecule have been recorded in neon and argon matrices between 200 and 5000 cm-1. Fourier transform infrared spectra with a resolution of 0.004 cm-1 have been measured in the gas phase around 1350 cm-1 (ν3, ν2+ν4+ν5, hot bands) and 2150 cm-1 (ν2+ν3, ν1-ν5, hot bands). The high resolution study yields rotational parameters of the ground and all singly excited vibrational states. The interpretation of the experimental data has been guided by ab initio calculations at the SCF (self-consistent-field) level and the correlated MP2 level (Moller-Plesset second order perturbation theory) employing three different large basis sets. The theoretical calculations provide the SCF and MP2 harmonic fields as well as the SCF anharmonic force field of FCCF. The agreement between the available theoretical and experimental results is generally quite good, with the exception of the spectroscopic constants involving the trans-bending mode ν4 where more theoretical work is required. The combined use of theoretical and experimental information leads to an estimate of the equilibrium structure [D∞h, re(CC)=1.1865 Å, re(CF)=1.2832 Å] and to recommended ``best'' values for the wave numbers of all fundamental vibrations based on the matrix and high resolution infrared data and some ab initio anharmonicity constants. The present study demonstrates the advantages of a combined theoretical and experimental approach to the spectroscopy of short-lived molecules.

  7. Improved parametric fits for the HeH2 ab initio energy surface

    International Nuclear Information System (INIS)

    A brief history of the development of ab initio calculations for the HeH2 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 H2 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 H2 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 H2(1sσg)2, H2+(1sσg), H2+(2pσu) and (LiH2)+ energy surfaces are also presented. The new parametric fits for H2, H2+(1sσg) are shown to be improvements over the well-known Morse potentials for these surfaces

  8. Ab initio study of the low-lying electronic states of the CaO molecule

    International Nuclear Information System (INIS)

    Graphical abstract: Highly correlated ab initio calculations have been performed for an accurate determination of the electronic structure of the low-lying electronic states of the CaO molecule. The computations are done using the aug-cc-pV5Z basis set for O and the cc-pCV5Z for Ca. The potential energy curves for the molecular states correlating to the lowest three asymptotes are calculated at the CASSCF level. The potential curves of the lowest five molecular states, X1Σ+, a3Π, A'1Π, b3Σ+ and A1Σ+, and the corresponding dipole moment functions have been determined using internally contracted multi-reference configuration interaction approaches. The spectroscopic constants associated with these electronic states are compared to experimental values. The corresponding electronic wavefunctions have also been analyzed using the dipole moment functions. Display Omitted Highlights: → The five lowest electronic states of Cao have been determined ab initio at a high level of accuracy. → Large active space, core-valence correlation and configuration interaction are required. → The multi-configurational nature of the electronic ground state is confirmed as well as its monovalent and divalent ionic nature using dipole moment analysis. → These interacting potentials will serve for future obtention of spin-rovibronic levels. - Abstract: Highly correlated ab initio calculations have been performed for an accurate determination of the electronic structure of the low-lying electronic states of the CaO molecule. The computations are done using the aug-cc-pV5Z basis set for O and the cc-pCV5Z for Ca. The potential energy curves for the molecular states correlating to the lowest three asymptotes are calculated at the CASSCF level. The potential curves of the lowest five molecular states, X1Σ+, a3Π, A'1Π, b3Σ+ and A1Σ+, and the corresponding dipole moment functions have been determined using internally contracted multi-reference configuration interaction approaches

  9. Comparative studies of the spectroscopy of CuCl2: DFT versus standard ab initio approaches.

    Science.gov (United States)

    Ramírez-Solís, A; Poteau, R; Vela, A; Daudey, J P

    2005-04-22

    The X2Pi g-2Sigma g+, X2Pi g-2Delta g, X2Pi g-2Sigma u+, X2Pi g-2Pi u transitions on CuCl2 have been studied using several exchange-correlation functionals from the various types of density functional theory (DFT) approaches like local density approximation (LDA), generalized gradient approximation (GGA), hybrid and meta-GGA. The results are compared with the experience and with those coming from the most sophisticated nondynamic and dynamic electronic correlation treatments using the same relativistic effective core potentials and especially developed basis sets to study the electronic structure of the five lowest states and the corresponding vertical and adiabatic transition energies. The calculated transition energies for three of the hybrid functionals (B3LYP, B97-2, and PBE0) are in very good agreement with the benchmark ab initio results and experimental figures. All of the other functionals largely overestimate the X2Pi g-2Sigma g+ and X2Pi g-2Delta g transition energies, many of them even placing the 2Delta g ligand field state above the charge transfer 2Pi u and 2Sigma u+ states. The relative weight of the Hartree-Fock exchange in the definition of the functional used appears to play a key role in the accurate description of the LambdaSSigma density defined by the orientation of the 3d hole (sigma, pi, or delta) on Cu in the field of both chlorine atoms, but no simple connection of this weight with the quality of the spectra has been found. Mulliken charges and spin densities are carefully analyzed; a possible link between the extent of spin density on the metal for the X2Pi g state and the performance of the various functionals was observed, suggesting that those that lead to the largest values (close to 0.65) are the ones that best reproduce these four transitions. Most functionals lead to a remarkably low ionicity for the three ligand field states even for the best performing functionals, compared to the complete active space (SCF) (21, 14) ab initio

  10. Realization of prediction of materials properties by ab initio computer simulation

    Indian Academy of Sciences (India)

    Yoshiyuki Kawazoe

    2003-01-01

    Ab initio treatment is becoming realistic to predict physical, chemical, and even mechanical properties of academically and industrially interesting materials. There is, however, some limitation in size and time of the system up to the order of several hundred atoms and ∼ 1 pico second, even if we use the fastest supercomputer efficiently. Therefore, it is very difficult to simulate realistic materials with grain boundaries and important reactions like diffusion in materials. To improve this situation, two ways have been invented. One way is to upgrade approximations to match the necessary levels according to inhomogeneous electron gas theory beyond the present day standard, i.e. local density approximation (LDA). The reason is simply that the system we are interested in is composed of many particles interacting with Coulomb forces governed by quantum mechanics. (Complete knowledge is available, and only what we should do is to make better approximations to explain the phenomena!). Another is to extract the necessary parameters from the ab initio calculations on systems with limited number of atoms, and apply these results into cluster variation, direct, or any other sophisticated methods based on classical concepts such as statistical mechanics. In this paper, several typical examples recently worked out by our research group are introduced to indicate that these methodologies are actually possible to be successfully used to predict materials properties before experiments based on the present day state-of-art supercomputing systems. It includes scientific visualization of the results of ab initio molecular dynamics simulation on atom insertion process to C60 and to carbon nanotube, tight-binding calculation of single electron conductance properties in nanotube to create nano-scale diode virtually by computer, which will be a base of future nanoscale electric device in nanometer size, Li + H reaction without Born–Oppenheimer approximation, structural phase

  11. i-PI: A Python interface for ab initio path integral molecular dynamics simulations

    Science.gov (United States)

    Ceriotti, Michele; More, Joshua; Manolopoulos, David E.

    2014-03-01

    Recent developments in path integral methodology have significantly reduced the computational expense of including quantum mechanical effects in the nuclear motion in ab initio molecular dynamics simulations. However, the implementation of these developments requires a considerable programming effort, which has hindered their adoption. Here we describe i-PI, an interface written in Python that has been designed to minimise the effort required to bring state-of-the-art path integral techniques to an electronic structure program. While it is best suited to first principles calculations and path integral molecular dynamics, i-PI can also be used to perform classical molecular dynamics simulations, and can just as easily be interfaced with an empirical forcefield code. To give just one example of the many potential applications of the interface, we use it in conjunction with the CP2K electronic structure package to showcase the importance of nuclear quantum effects in high-pressure water. Catalogue identifier: AERN_v1_0 Program summary URL: http://cpc.cs.qub.ac.uk/summaries/AERN_v1_0.html Program obtainable from: CPC Program Library, Queen’s University, Belfast, N. Ireland Licensing provisions: GNU General Public License, version 3 No. of lines in distributed program, including test data, etc.: 138626 No. of bytes in distributed program, including test data, etc.: 3128618 Distribution format: tar.gz Programming language: Python. Computer: Multiple architectures. Operating system: Linux, Mac OSX, Windows. RAM: Less than 256 Mb Classification: 7.7. External routines: NumPy Nature of problem: Bringing the latest developments in the modelling of nuclear quantum effects with path integral molecular dynamics to ab initio electronic structure programs with minimal implementational effort. Solution method: State-of-the-art path integral molecular dynamics techniques are implemented in a Python interface. Any electronic structure code can be patched to receive the atomic

  12. Quantitative Comparison of a New Ab Initio Micrometeor Ablation Model with an Observationally Verifiable Standard Model

    Science.gov (United States)

    Meisel, David D.; Szasz, Csilla; Kero, Johan

    2008-06-01

    The Arecibo UHF radar is able to detect the head-echos of micron-sized meteoroids up to velocities of 75 km/s over a height range of 80 140 km. Because of their small size there are many uncertainties involved in calculating their above atmosphere properties as needed for orbit determination. An ab initio model of meteor ablation has been devised that should work over the mass range 10-16 kg to 10-7 kg, but the faint end of this range cannot be observed by any other method and so direct verification is not possible. On the other hand, the EISCAT UHF radar system detects micrometeors in the high mass part of this range and its observations can be fit to a “standard” ablation model and calibrated to optical observations (Szasz et al. 2007). In this paper, we present a preliminary comparison of the two models, one observationally confirmable. Among the features of the ab initio model that are different from the “standard” model are: (1) uses the experimentally based low pressure vaporization theory of O’Hanlon (A users’s guide to vacuum technology, 2003) for ablation, (2) uses velocity dependent functions fit from experimental data on heat transfer, luminosity and ionization efficiencies measured by Friichtenicht and Becker (NASA Special Publication 319: 53, 1973) for micron sized particles, (3) assumes a density and temperature dependence of the micrometeoroids and ablation product specific heats, (4) assumes a density and size dependent value for the thermal emissivity and (5) uses a unified synthesis of experimental data for the most important meteoroid elements and their oxides through least square fits (as functions of temperature, density, and/or melting point) of the tables of thermodynamic parameters given in Weast (CRC Handbook of Physics and Chemistry, 1984), Gray (American Institute of Physics Handbook, 1972), and Cox (Allen’s Astrophysical Quantities 2000). This utilization of mostly experimentally determined data is the main reason for

  13. Ab initio study of the low-lying electronic states of the CaO molecule

    Energy Technology Data Exchange (ETDEWEB)

    Khalil, Hossain; Brites, Vincent; Quere, Frederic Le [Universite Paris-Est, Laboratoire de Modelisation et Simulation Multi Echelle, UMR 8208 CNRS, Batiment Lavoisier, 5 boulevard Descartes, Champs sur Marne, 77454 Marne-la-Vallee, Cedex 2 (France); Leonard, Celine, E-mail: celine.leonard@univ-paris-est.fr [Universite Paris-Est, Laboratoire de Modelisation et Simulation Multi Echelle, UMR 8208 CNRS, Batiment Lavoisier, 5 boulevard Descartes, Champs sur Marne, 77454 Marne-la-Vallee, Cedex 2 (France)

    2011-07-28

    Graphical abstract: Highly correlated ab initio calculations have been performed for an accurate determination of the electronic structure of the low-lying electronic states of the CaO molecule. The computations are done using the aug-cc-pV5Z basis set for O and the cc-pCV5Z for Ca. The potential energy curves for the molecular states correlating to the lowest three asymptotes are calculated at the CASSCF level. The potential curves of the lowest five molecular states, X{sup 1}{Sigma}{sup +}, a{sup 3}{Pi}, A'{sup 1{Pi}}, b{sup 3}{Sigma}{sup +} and A{sup 1}{Sigma}{sup +}, and the corresponding dipole moment functions have been determined using internally contracted multi-reference configuration interaction approaches. The spectroscopic constants associated with these electronic states are compared to experimental values. The corresponding electronic wavefunctions have also been analyzed using the dipole moment functions. Display Omitted Highlights: {yields} The five lowest electronic states of Cao have been determined ab initio at a high level of accuracy. {yields} Large active space, core-valence correlation and configuration interaction are required. {yields} The multi-configurational nature of the electronic ground state is confirmed as well as its monovalent and divalent ionic nature using dipole moment analysis. {yields} These interacting potentials will serve for future obtention of spin-rovibronic levels. - Abstract: Highly correlated ab initio calculations have been performed for an accurate determination of the electronic structure of the low-lying electronic states of the CaO molecule. The computations are done using the aug-cc-pV5Z basis set for O and the cc-pCV5Z for Ca. The potential energy curves for the molecular states correlating to the lowest three asymptotes are calculated at the CASSCF level. The potential curves of the lowest five molecular states, X{sup 1}{Sigma}{sup +}, a{sup 3}{Pi}, A'{sup 1}{Pi}, b{sup 3}{Sigma}{sup +} and A{sup 1

  14. Use of scaled external correlation, a double many-body expansion, and variational transition state theory to calibrate a potential energy surface for FH2

    Science.gov (United States)

    Lynch, Gillian C.; Steckler, Rozeanne; Varandas, Antonio J. C.; Truhlar, Donald G.; Schwenke, David W.

    1991-01-01

    New ab initio results and a double many-body expansion formalism have been used to parameterize a new FH2 potential energy surface with improved properties near the saddle point and in the region of long-range attraction. The functional form of the new surface includes dispersion forces by a double many-body expansion. Stationary point properties for the new surface are calculated along with the product-valley barrier maxima of vibrationally adiabatic potential curves for F + H2 - HF(nu-prime = 3) + H, F + HD - HF(nu-prime = 3) + D, and F + D2 - DF(nu-prime = 4) + D. The new surface should prove useful for studying the effect on dynamics of a low, early barrier with a wide, flat bend potential.

  15. Structural, dynamical, electronic, and bonding properties of laser-heated silicon: An ab initio molecular-dynamics study

    NARCIS (Netherlands)

    Silvestrelli, P.-L.; Alavi, A.; Parrinello, M.; Frenkel, D.

    1997-01-01

    The method of ab initio molecular dynamics, based on finite-temperature density-functional theory, is used to simulate laser heating of crystalline silicon. We found that a high concentration of excited electrons dramatically weakens the covalent bonding. As a result the system undergoes a melting t

  16. Interplay of I-TASSER and QUARK for template-based and ab initio protein structure prediction in CASP10.

    Science.gov (United States)

    Zhang, Yang

    2014-02-01

    We develop and test a new pipeline in CASP10 to predict protein structures based on an interplay of I-TASSER and QUARK for both free-modeling (FM) and template-based modeling (TBM) targets. The most noteworthy observation is that sorting through the threading template pool using the QUARK-based ab initio models as probes allows the detection of distant-homology templates which might be ignored by the traditional sequence profile-based threading alignment algorithms. Further template assembly refinement by I-TASSER resulted in successful folding of two medium-sized FM targets with >150 residues. For TBM, the multiple threading alignments from LOMETS are, for the first time, incorporated into the ab initio QUARK simulations, which were further refined by I-TASSER assembly refinement. Compared with the traditional threading assembly refinement procedures, the inclusion of the threading-constrained ab initio folding models can consistently improve the quality of the full-length models as assessed by the GDT-HA and hydrogen-bonding scores. Despite the success, significant challenges still exist in domain boundary prediction and consistent folding of medium-size proteins (especially beta-proteins) for nonhomologous targets. Further developments of sensitive fold-recognition and ab initio folding methods are critical for solving these problems.

  17. Ab initio electronic structure and correlations in pristine and potassium-doped molecular crystals of copper phthalocyanine

    NARCIS (Netherlands)

    Giovannetti, Gianluca; Brocks, Geert; Brink, van den Jeroen

    2008-01-01

    We investigate the effect that potassium intercalation has on the electronic structure of copper phthalocyanine (CuPc) molecular crystals by means of ab initio density functional calculations. Pristine CuPc (in its alpha and beta structures) is found to be an insulator containing local magnetic mome

  18. An ab initio study of the structural and physical properties of a novel rigid-rod polymer : PIPD

    NARCIS (Netherlands)

    Hageman, J.C.L.; Horst, J.W. van der; Groot, R.A. de

    1999-01-01

    In this article, we present the first ab initio calculations on the novel rigid-rod polymer PIPD using density functional techniques. The behaviour of the molecular chain under strain is studied and the chain modulus agrees excellently with experiment. Two crystal structures are considered and hydro

  19. Ab initio treatment of the chemical reaction precursor complex Cl(P-2)-HF. 2 : Bound states and infrared spectrum

    NARCIS (Netherlands)

    Fishchuk, A.V.; Groenenboom, G.C.; Avoird, A. van der

    2006-01-01

    Bound energy levels and properties of the Cl((2)p)-HF complex were obtained from full three-dimensional (3D) calculations, with the use of the ab initio computed diabatic potential surfaces from the preceding paper and the inclusion of spin-orbit coupling. For a better understanding of the dynamics

  20. Ab-initio study of magnetic properties and phase transitions in Ga (Mn) N with Monte Carlo approach

    Energy Technology Data Exchange (ETDEWEB)

    Sbai, Y.; Ait Raiss, A.; Salmani, E. [LMPHE (URAC 12), Faculty of Science, Mohammed V University, Av. Ibn Batouta, Rabat (Morocco); Bahmad, L., E-mail: Bahmad@fsr.ac.ma [LMPHE (URAC 12), Faculty of Science, Mohammed V University, Av. Ibn Batouta, Rabat (Morocco); Benyoussef, A. [LMPHE (URAC 12), Faculty of Science, Mohammed V University, Av. Ibn Batouta, Rabat (Morocco); Institute of Nanomaterials and Nanotechnologies, MAScIR, Rabat (Morocco); Hassan II Academy of Science and Technology, Rabat (Morocco)

    2015-12-15

    On the basis of ab-initio calculations and Monte Carlo simulations the magnetic and electronic properties of Gallium nitride (GaN) doped with the transition metal Manganese (Mn) were studied. The ab initio calculations were done using the AKAI–KKR–CPA method within the Local Density Approximation (LDA) approximation. We doped our Diluted Magnetic Semiconductor (DMS), with different concentrations of magnetic impurities Mn and plotted the density of state (DOS) for each one. Showing a half-metallic behavior and ferromagnetic state especially for Ga{sub 0.95}Mn{sub 0.05}N making this DMS a strong candidate for spintronic applications. Moreover, the magnetization and susceptibility of our system as a function of the temperature has been calculated and give for various system size L to study the size effect. In addition, the transition temperature was deduced from the peak of the susceptibility. The Ab initio results are in good agreement with literature especially for (x=0.05) of Mn which gives the most interesting results. - Highlights: • The AKAI–KKR–CPA method has been applied to study the doped compound GaN:Mn. • The local density approximation (LDA) has been applied. • The ab-initio calculations have been performed. • The density of states (DOS) have been plotted for differents doping concentrations, using Monte Carlo simulations.

  1. A Photoelectron Spectroscopy and ab initio Study of B3- and B4- Anions and Their Neutrals

    Energy Technology Data Exchange (ETDEWEB)

    Zhai, Hua-Jin; Wang, Lai S.; Alexandrova, A N.; Boldyrev, Alexander I.; Zakrzewski, V G.

    2003-11-06

    The two smallest boron clusters (B3 and B4) in their neutral and anionic forms were studied by photoelectron spectroscopy and ab initio calculations. Vibrationally resolved photoelectron spectra were observed for B3- at three photon energies (355, 266, and 193 nm) and the electron affinity of B3 was measured to be+0.02 eV.

  2. AB-INITIO SIMULATION OF ELECTRONIC FEATURES OF HYPERFINE RARE EARTH OXIDE FILMS FOR SENSORY NANOSYSTEMS

    Directory of Open Access Journals (Sweden)

    A. V. Gulay

    2014-01-01

    Full Text Available Ab-Initio simulation of electronic features of sensoring nanomaterials based on rare earth oxides has been made by the example of yttrium oxide. The simulation method for thin films of nanometer scale consisted in the simulation of the material layer of the thickness equal to unit crystal cell size has been proposed within the VASP simulation package. The atomic bond breakdown in the crystal along one of the coordinate axes is simulated by the increase of a distance between the atomic layers along this axis up to values at which the value of free energy is stabilized. It has been found that the valence and conductivity bands are not revealed explicitly and the band gap is not formed in the hyperfine rare earth oxide film (at the film thickness close to 1 nm. In fact the hyperfine rare earth oxide film loses dielectric properties which were exhibited clear enough in continuum.

  3. AB INITIO STUDY ON VALENCE INDICES AND REACTIVITIES OF SOME BORAENS

    Institute of Scientific and Technical Information of China (English)

    曹阳; 王友良

    1991-01-01

    In the pressnt paper, 3-21G ab initio molecular orbital calculations arc performed on diborane B2H6 and the substituted bridged-atom species H4B2X2(X=F, C1, OH, NH2, CH3),and these geometries are optimized with the energy gradient technique. According to the quantum chemical definition of atomic valence, the valences of the bridged-atoms are calculated to studtd the characteristion of the bridging bond B-X-B. Some larger boranes B4H10, B5H9, and B5H11 are also calculated to discuss the valence indices and analyze the reactiveities of the bridged-atoms.

  4. Ab initio theory for ultrafast magnetization dynamics with a dynamic band structure

    Science.gov (United States)

    Mueller, B. Y.; Haag, M.; Fähnle, M.

    2016-09-01

    Laser-induced modifications of magnetic materials on very small spatial dimensions and ultrashort timescales are a promising field for novel storage and spintronic devices. Therefore, the contribution of electron-electron spin-flip scattering to the ultrafast demagnetization of ferromagnets after an ultrashort laser excitation is investigated. In this work, the dynamical change of the band structure resulting from the change of the magnetization in time is taken into account on an ab initio level. We find a large influence of the dynamical band structure on the magnetization dynamics and we illustrate the thermalization and relaxation process after laser irradiation. Treating the dynamical band structure yields a demagnetization comparable to the experimental one.

  5. Ab Initio Calculation of Vacancies and Interstitials in NiSi2

    Institute of Scientific and Technical Information of China (English)

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

    2004-01-01

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

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

    International Nuclear Information System (INIS)

    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

  7. ESTUDIO TEÓRICO DE LA MOLÉCULA DE HIDROGENO CALCULO AB-INITIO

    OpenAIRE

    Quitián, N.

    2010-01-01

    Utilizando la técnica LCGO-SCF-MO (Combinación Lineal de los Orbitales Moleculares en Orbitales Gausianos, en el método del Campo Auto-Coherente), se determinaron las energías de orbital, la energía electrónica total, la energía de repulsión nuclear y la energía de Hartree-Fock de la molécula de hidrógeno en su estado fundamental, mediante un cálculo ab initio y utilizando una base de funciones gausianas. Los orbitales moleculares fueron desarrollados en términos de una función Is contraída p...

  8. High-pressure elastic properties of cubic Ir2P from ab initio calculations

    Science.gov (United States)

    Sun, Xiao-Wei; Bioud, Nadhira; Fu, Zhi-Jian; Wei, Xiao-Ping; Song, Ting; Li, Zheng-Wei

    2016-10-01

    A study of the high-pressure elastic properties of new synthetic Ir2P in the anti-fluorite structure is conducted using ab initio calculations based on density functional theory. The elastic constants C11, C12 and C44 for the cubic Ir2P are obtained by the stress-strain method and the elastic stability calculations under pressure indicate that it is stable at least 100 GPa. Additionally, the electronic density of states, the aggregate elastic moduli, that is bulk modulus, shear modulus, and Young's modulus along with the Debye temperature, Poisson's ratio, and elastic anisotropy factor are all successfully obtained. Moreover, the pressure dependence of the longitudinal and shear wave velocities in three different directions [100], [110], and [111] for Ir2P are also predicted for the first time.

  9. reaxFF Reactive Force Field for Disulfide Mechanochemistry, Fitted to Multireference ab Initio Data.

    Science.gov (United States)

    Müller, Julian; Hartke, Bernd

    2016-08-01

    Mechanochemistry, in particular in the form of single-molecule atomic force microscopy experiments, is difficult to model theoretically, for two reasons: Covalent bond breaking is not captured accurately by single-determinant, single-reference quantum chemistry methods, and experimental times of milliseconds or longer are hard to simulate with any approach. Reactive force fields have the potential to alleviate both problems, as demonstrated in this work: Using nondeterministic global parameter optimization by evolutionary algorithms, we have fitted a reaxFF force field to high-level multireference ab initio data for disulfides. The resulting force field can be used to reliably model large, multifunctional mechanochemistry units with disulfide bonds as designed breaking points. Explorative calculations show that a significant part of the time scale gap between AFM experiments and dynamical simulations can be bridged with this approach. PMID:27415976

  10. Ab Initio Studies on Hematite Surface and the Adsorption of Phosphate

    Directory of Open Access Journals (Sweden)

    Swati Chaudhury

    2014-01-01

    Full Text Available This investigation explores the ab initio DFT method for understanding surface structure of hematite and the nature and energetics of phosphate adsorption. Using the full potential linearized plane wave method (FP-LAPW, we derived the structure and energies of various magnetic forms of hematite. The antiferromagnetic (AFM form was observed to be the most stable. Hematite surfaces with Fe-termination, O-termination, or OH-termination were studied. The OH-terminated surface was the most stable. Stability of hematite surfaces follows the order OH-termination > Fe-termination > O-termination. Thus, surface reaction with hematite would occur with the OH at the surface and not with Fe atoms. The structure of phosphate adsorbed on hematite was derived. Bonding is through the H atom of the OH at the surface. An alternative mechanism of phosphate adsorption on hematite has been derived. Adsorption energy is high and suggests chemisorption rather than physisorption of phosphate on hematite.

  11. Femtosecond Laser Processing of Germanium: An Ab Initio Molecular Dynamics Study

    CERN Document Server

    Ji, Pengfei

    2016-01-01

    An ab initio molecular dynamics study of femtosecond laser processing of germanium is presented in this paper. The method based on the finite temperature density functional theory is adopted to probe the structural change, thermal motion of the atoms, dynamic property of the velocity autocorrelation, and the vibrational density of states. Starting from a cubic system at room temperature (300 K) containing 64 germanium atoms with an ordered arrangement of 1.132 nm in each dimension, the femtosecond laser processing is simulated by imposing the Nose Hoover thermostat to the electronic subsystem lasting for ~100 fs and continuing with microcanonical ensemble simulation of ~200 fs. The simulation results show solid, liquid and gas phases of germanium under adjusted intensities of the femtosecond laser irradiation. We find the irradiated germanium distinguishes from the usual germanium crystal by analyzing their melting and dynamic properties.

  12. Ab initio calculation of structure and thermodynamic properties of Zintl aluminide SrAl{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Fu, Zhi-Jian [Chongqing Key Laboratory of Micro/Nano Materials Engineering and Technology, Chongqing (China); Chongqing Univ. of Arts and Sciences (China). School of Electrical and Electronic Engineering; China Academy of Engineering Physics (CAEP), Mianyang, Sichuan (China). National Key Lab. of Shock Wave and Detonation Physics; Jia, Li-Jun [Chongqing Univ. of Arts and Sciences Library (China); Xia, Ji-Hong; Tang, Ke; Li, Zhao-Hong [Chongqing Univ. of Arts and Sciences (China). School of Electrical and Electronic Engineering; Sun, Xiao-Wei [Lanzhou Jiaotong Univ. (China). School of Mathematics and Physics; Chen, Qi-Feng [China Academy of Engineering Physics (CAEP), Mianyang, Sichuan (China). National Key Lab. of Shock Wave and Detonation Physics

    2015-07-01

    The structural and thermodynamic properties of the orthorhombic and cubic structure SrAl{sub 2} at pressure and temperature are investigated by using the ab initio plane-wave pseudopotential density functional theory method within the generalised gradient approximation (GGA). The calculated lattice parameters are in agreement with the available experimental data and other theoretical results. The phase transition predicted takes place at 0.5 GPa from the orthorhombic to the cubic structure at zero temperature. The thermodynamic properties of the zinc-blende structure SrAl{sub 2} are calculated by the quasi-harmonic Debye model. The pressure-volume relationship and the variations in the thermal expansion a are obtained systematically in the pressure and temperature ranges of 0-5 GPa and 0-500 K, respectively.

  13. Ab-initio Hartree-Fock study of tritium desorption from Li{sub 2}O

    Energy Technology Data Exchange (ETDEWEB)

    Taniguchi, Masaki; Tanaka, Satoru [Tokyo Univ. (Japan). Faculty of Engineering

    1998-03-01

    Dissociative adsorption of hydrogen on Li{sub 2}O (110) surface has been investigated with ab-initio Hartree-Fock quantum chemical calculation technique. Heat of adsorption and potential energy surface for H{sub 2} dissociative adsorption was evaluated by calculating the total energy of the system. Calculation results on adsorption heat indicated that H{sub 2} adsorption is endothermic. However, when oxygen vacancy exists adjacent to the adsorption sites, heat of adsorption energy became less endothermic and the activation energy required to dissociate the H-H bonding was smaller than that for the terrace site. This is considered to be caused by the excess charge localized near the defect. (author)

  14. An efficient Monte Carlo method for calculating ab initio transition state theory reaction rates in solution

    CERN Document Server

    Iftimie, R; Schofield, J P; Iftimie, Radu; Salahub, Dennis; Schofield, Jeremy

    2003-01-01

    In this article, we propose an efficient method for sampling the relevant state space in condensed phase reactions. In the present method, the reaction is described by solving the electronic Schr\\"{o}dinger equation for the solute atoms in the presence of explicit solvent molecules. The sampling algorithm uses a molecular mechanics guiding potential in combination with simulated tempering ideas and allows thorough exploration of the solvent state space in the context of an ab initio calculation even when the dielectric relaxation time of the solvent is long. The method is applied to the study of the double proton transfer reaction that takes place between a molecule of acetic acid and a molecule of methanol in tetrahydrofuran. It is demonstrated that calculations of rates of chemical transformations occurring in solvents of medium polarity can be performed with an increase in the cpu time of factors ranging from 4 to 15 with respect to gas-phase calculations.

  15. A room temperature CO$_2$ line list with ab initio computed intensities

    CERN Document Server

    Zak, Emil; Polyansky, Oleg L; Lodi, Lorenzo; Zobov, Nikolay F; Tashkun, Sergey A; Perevalov, Valery I

    2016-01-01

    Atmospheric carbon dioxide concentrations are being closely monitored by remote sensing experiments which rely on knowing line intensities with an uncertainty of 0.5% or better. We report a theoretical study providing rotation-vibration line intensities substantially within the required accuracy based on the use of a highly accurate {\\it ab initio} dipole moment surface (DMS). The theoretical model developed is used to compute CO$_2$ intensities with uncertainty estimates informed by cross comparing line lists calculated using pairs of potential energy surfaces (PES) and DMS's of similar high quality. This yields lines sensitivities which are utilized in reliability analysis of our results. The final outcome is compared to recent accurate measurements as well as the HITRAN2012 database. Transition frequencies are obtained from effective Hamiltonian calculations to produce a comprehensive line list covering all $^{12}$C$^{16}$O$_2$ transitions below 8000 cm$^{-1}$ and stronger than 10$^{-30}$ cm / molecule at ...

  16. Electronic and optical properties of K-doped ZnO: Ab initio study

    Science.gov (United States)

    Aimouch, D. E.; Meskine, S.; Hayn, R.; Zaoui, A.; Boukortt, A.

    2016-08-01

    We present the results of ab initio calculations of K-doped ZnO in the wurtzite structure using a supercell of 32 atoms and density functional theory. A complete analysis of its electronic, optical and magnetic properties is provided. The local spin density approximation (LSDA) has been used to analyze the density of states and to understand the K influence at different concentration values. The material is revealed to become a p-type doped semiconductor. The optical constant or refractive index, the dielectric function, and the absorption coefficient were determined and show a good agreement with available experimental data. Potassium doping leads to an absorption peak at about 380 nm. That peak might improve the absorption characteristics of ZnO for solar cell or optical applications.

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

    Science.gov (United States)

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

    2004-03-01

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

  18. Lattice thermal conductivity of UO2 using ab-initio and classical molecular dynamics

    International Nuclear Information System (INIS)

    We applied the non-equilibrium ab-initio molecular dynamics and predict the lattice thermal conductivity of the pristine uranium dioxide for up to 2000 K. We also use the equilibrium classical molecular dynamics and heat-current autocorrelation decay theory to decompose the lattice thermal conductivity into acoustic and optical components. The predicted optical phonon transport is temperature independent and small, while the acoustic component follows the Slack relation and is in good agreement with the limited single-crystal experimental results. Considering the phonon grain-boundary and pore scatterings, the effective lattice thermal conductivity is reduced, and we show it is in general agreement with the sintered-powder experimental results. The charge and photon thermal conductivities are also addressed, and we find small roles for electron, surface polaron, and photon in the defect-free structures and for temperatures below 1500 K

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

    CERN Document Server

    Eckl, Bernhard; Hasse, Hans

    2009-01-01

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

  20. Precise Lifetime Measurements in Light Nuclei for Benchmarking Modern Ab-initio Nuclear Structure Models

    Energy Technology Data Exchange (ETDEWEB)

    Lister, C.J. [Department of Physics, University of Massachusetts, Lowell, Lowell MA 01854 (United States); McCutchan, E.A. [National Nuclear Data Center, Brookhaven National Laboratory, Upton, NY 11973-5000 (United States)

    2014-06-15

    A new generation of ab-initio calculations, based on realistic two- and three-body forces, is having a profound impact on our view of how nuclei work. To improve the numerical methods, and the parameterization of 3-body forces, new precise data are needed. Electromagnetic transitions are very sensitive to the dynamics which drive mixing between configurations. We have made a series of precise (< 3%) measurements of electromagnetic transitions in the A=10 nuclei {sup 10}C and {sup 10}Be by using the Doppler Shift Attenuation method carefully. Many interesting features can be reproduced including the strong α clustering. New measurements on {sup 8}Be and {sup 12}Be highlight the interplay between the alpha clusters and their valence neutrons.