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Sample records for ab-initio calculations based

  1. Full Dimensional Vibrational Calculations for Methane Using AN Accurate New AB Initio Based Potential Energy Surface

    NASA Astrophysics Data System (ADS)

    Majumder, Moumita; Dawes, Richard; Wang, Xiao-Gang; Carrington, Tucker; Li, Jun; Guo, Hua; Manzhos, Sergei

    2014-06-01

    New potential energy surfaces for methane were constructed, represented as analytic fits to about 100,000 individual high-level ab initio data. Explicitly-correlated multireference data (MRCI-F12(AE)/CVQZ-F12) were computed using Molpro [1] and fit using multiple strategies. Fits with small to negligible errors were obtained using adaptations of the permutation-invariant-polynomials (PIP) approach [2,3] based on neural-networks (PIP-NN) [4,5] and the interpolative moving least squares (IMLS) fitting method [6] (PIP-IMLS). The PESs were used in full-dimensional vibrational calculations with an exact kinetic energy operator by representing the Hamiltonian in a basis of products of contracted bend and stretch functions and using a symmetry adapted Lanczos method to obtain eigenvalues and eigenvectors. Very close agreement with experiment was produced from the purely ab initio PESs. References 1- H.-J. Werner, P. J. Knowles, G. Knizia, 2012.1 ed. 2012, MOLPRO, a package of ab initio programs. see http://www.molpro.net. 2- Z. Xie and J. M. Bowman, J. Chem. Theory Comput 6, 26, 2010. 3- B. J. Braams and J. M. Bowman, Int. Rev. Phys. Chem. 28, 577, 2009. 4- J. Li, B. Jiang and Hua Guo, J. Chem. Phys. 139, 204103 (2013). 5- S Manzhos, X Wang, R Dawes and T Carrington, JPC A 110, 5295 (2006). 6- R. Dawes, X-G Wang, A.W. Jasper and T. Carrington Jr., J. Chem. Phys. 133, 134304 (2010).

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

    NASA Astrophysics Data System (ADS)

    He, Yuping

    2015-03-01

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

  3. Effect of composition on antiphase boundary energy in Ni3Al based alloys: Ab initio calculations

    NASA Astrophysics Data System (ADS)

    Gorbatov, O. I.; Lomaev, I. L.; Gornostyrev, Yu. N.; Ruban, A. V.; Furrer, D.; Venkatesh, V.; Novikov, D. L.; Burlatsky, S. F.

    2016-06-01

    The effect of composition on the antiphase boundary (APB) energy of Ni-based L 12-ordered alloys is investigated by ab initio calculations employing the coherent potential approximation. The calculated APB energies for the {111} and {001} planes reproduce experimental values of the APB energy. The APB energies for the nonstoichiometric γ' phase increase with Al concentration and are in line with the experiment. The magnitude of the alloying effect on the APB energy correlates with the variation of the ordering energy of the alloy according to the alloying element's position in the 3 d row. The elements from the left side of the 3 d row increase the APB energy of the Ni-based L 12-ordered alloys, while the elements from the right side slightly affect it except Ni. The way to predict the effect of an addition on the {111} APB energy in a multicomponent alloy is discussed.

  4. A modified W-W interatomic potential based on ab initio calculations

    NASA Astrophysics Data System (ADS)

    Wang, J.; Zhou, Y. L.; Li, M.; Hou, Q.

    2014-01-01

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

  5. A new Fe–He interatomic potential based on ab initio calculations in α-Fe

    SciTech Connect

    Gao, Fei; Deng, Huiqiu; Heinisch, Howard L.; Kurtz, Richard J.

    2011-11-01

    A new interatomic potential for Fe−He interactions has been developed by fitting to the results obtained from ab initio calculations. Based on the electronic hybridization between Fe d-electrons and He s-electrons, an s-band model, along with a repulsive pair potential, has been developed to describe the Fe−He interaction. The atomic configurations and formation energies of single He defects and small interstitial He clusters are utilized in the fitting process. The binding properties and relative stabilities of the He-vacancy and interstitial He clusters are studied. The present Fe−He potential is also applied to study the emission of self-interstitial atoms from small He clusters in alpha-Fe matrices. It is found that the di-He cluster dissociates when the temperature is higher than 400K, but the larger He clusters can create an interstitial Fe atom. The temperature for kicking out an interstitial Fe atom is found to decrease with increasing size of the He clusters.

  6. Guiding ab initio calculations by alchemical derivatives.

    PubMed

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

    2016-03-14

    We assess the concept of alchemical transformations for predicting how a further and not-tested change in composition would change materials properties. This might help to guide ab initio calculations through multidimensional property-composition spaces. Equilibrium volumes, bulk moduli, and relative lattice stability of fcc and bcc 4d transition metals Zr, Nb, Mo, Tc, Ru, Rh, Pd, and Ag are calculated using density functional theory. Alchemical derivatives predict qualitative trends in lattice stability while equilibrium volumes and bulk moduli are predicted with less than 9% and 28% deviation, respectively. Predicted changes in equilibrium volume and bulk moduli for binary and ternary mixtures of Rh-Pd-Ag are in qualitative agreement even for predicted bulk modulus changes as large as +100% or -50%. Based on these results, it is suggested that alchemical transformations could be meaningful for enhanced sampling in the context of virtual high-throughput materials screening projects. PMID:26979677

  7. Guiding ab initio calculations by alchemical derivatives

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  8. Ab Initio Calculation of the Hoyle State

    SciTech Connect

    Epelbaum, Evgeny; Krebs, Hermann; Lee, Dean; Meissner, Ulf-G.

    2011-05-13

    The Hoyle state plays a crucial role in the helium 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 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 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 the properties of the Hoyle state and in agreement with the experimentally observed energy.

  9. Ab initio based calculations of vacancy formation and clustering energies including lattice relaxation in Fe{sub 3}Al

    SciTech Connect

    Muratov, L.S.; Cooper, B.R.; Wills, J.M.

    1999-07-01

    Vacancy formation and clustering significantly affect structural properties of transition-metal aluminides. Ab-initio quantum mechanical total-energy calculations using a full-potential linear combination of muffin-tin orbitals (LMTO) technique provide a convenient method of studying relevant characteristics such as changes in density of states, and charge redistribution around defects. Augmented with Hellmann-Feymann forces, LMTO allows calculations of relaxation geometries and relaxation energies. The authors have performed such calculations for vacancies and antisite substitutional point defects in Fe{sub 3}Al with DO{sub 3} crystallographic structure. There are two limiting factors complicating calculations of defect formation energies directly from ab-initio calculations. The first is that a single defect, due to the lattice periodicity necessitated by the use of ab-initio total energy techniques, cannot be considered as an isolated defect, even in the maximum computable simulation cell. The second complication is the fact that chemical potentials of elements cannot be directly extracted from the total energy calculations for the compound. To deal with this problem, the authors considered two possible approximations and compared results, which were found to be quite similar for iron vacancies.

  10. Ab Initio Calculations Of Light-Ion Reactions

    SciTech Connect

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

    2012-03-12

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

  11. Molecular structure, spectroscopic characterization of (S)-2-Oxopyrrolidin-1-yl Butanamide and ab initio, DFT based quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Ramya, T.; Gunasekaran, S.; Ramkumaar, G. R.

    2015-10-01

    The experimental and theoretical spectra of (S)-2-Oxopyrrolidin-1-yl Butanamide (S2OPB) were studied. FT-IR and FT-Raman spectra of S2OPB in the solid phase were recorded and analyzed in the range 4000-450 and 5000-50 cm-1 respectively. The structural and spectroscopic analyses of S2OPB were calculated using ab initio Hartree Fock (HF) and density functional theory calculations (B3PW91, B3LYP) with 6-31G(d,p) basis set. A complete vibrational interpretation has been made on the basis of the calculated Potential Energy Distribution (PED). The HF, B3LYP and B3PW91 methods based NMR calculation has been used to assign the 1H NMR and 13C NMR chemical shift of S2OPB. Comparative study on UV-Vis spectral analysis between the experimental and theoretical (B3PW91, B3LYP) methods and the global chemical parameters and local descriptor of reactivity through the Fukui function were performed. Finally the thermodynamic properties of S2OPB were calculated at different temperatures and the corresponding relations between the properties and temperature were also studied.

  12. Molecular structure, spectroscopic characterization of (S)-2-Oxopyrrolidin-1-yl Butanamide and ab initio, DFT based quantum chemical calculations.

    PubMed

    Ramya, T; Gunasekaran, S; Ramkumaar, G R

    2015-10-01

    The experimental and theoretical spectra of (S)-2-Oxopyrrolidin-1-yl Butanamide (S2OPB) were studied. FT-IR and FT-Raman spectra of S2OPB in the solid phase were recorded and analyzed in the range 4000-450 and 5000-50 cm(-1) respectively. The structural and spectroscopic analyses of S2OPB were calculated using ab initio Hartree Fock (HF) and density functional theory calculations (B3PW91, B3LYP) with 6-31G(d,p) basis set. A complete vibrational interpretation has been made on the basis of the calculated Potential Energy Distribution (PED). The HF, B3LYP and B3PW91 methods based NMR calculation has been used to assign the (1)H NMR and (13)C NMR chemical shift of S2OPB. Comparative study on UV-Vis spectral analysis between the experimental and theoretical (B3PW91, B3LYP) methods and the global chemical parameters and local descriptor of reactivity through the Fukui function were performed. Finally the thermodynamic properties of S2OPB were calculated at different temperatures and the corresponding relations between the properties and temperature were also studied. PMID:25956325

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

    PubMed

    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

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

  15. Ab-initio calculations for a realistic sensor: A study of CO sensors based on nitrogen-rich carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Souza, A. M.; Rocha, A. R.; Fazzio, A.; da Silva, A. J. R.

    2012-09-01

    The use of nanoscale low-dimensional systems could boost the sensitivity of gas sensors. In this work we simulate a nanoscopic sensor based on carbon nanotubes with a large number of binding sites using ab initio density functional electronic structure calculations coupled to the Non-Equilibrium Green's Function formalism. We present a recipe where the adsorption process is studied followed by conductance calculations of a single defect system and of more realistic disordered system considering different coverages of molecules as one would expect experimentally. We found that the sensitivity of the disordered system is enhanced by a factor of 5 when compared to the single defect one. Finally, our results from the atomistic electronic transport are used as input to a simple model that connects them to experimental parameters such as temperature and partial gas pressure, providing a procedure for simulating a realistic nanoscopic gas sensor. Using this methodology we show that nitrogen-rich carbon nanotubes could work at room temperature with extremely high sensitivity.

  16. Ab-initio based calculations of vacancy formation and clustering energies including lattice relaxation in Fe{sub 3}Al

    SciTech Connect

    Muratov, L.S.; Cooper, B.R.; Wills, J.M.

    1999-03-01

    Vacancy formation and clustering significantly affect structural properties of transition-metal aluminides. Ab-initio quantum mechanical total-energy calculations using a full-potential linear combination of muffin-tin orbitals (LMTO) technique provide a convenient method of studying relevant characteristics such as changes in density of states, and charge redistribution around defects. Augmented with Hellmann-Feymann forces, LMTO allows calculations of relaxation geometries and relaxation energies. The authors have performed such calculations for vacancies and antisite substitutional point defects in Fe{sub 3}Al with DO{sub 3} crystallographic structure. There are two limiting factors complicating calculations of defect formation energies directly from ab-initio calculations. The first is that a single defect, due to the lattice periodicity necessitated by the use of ab-initio total energy techniques, cannot be considered as an isolated defect, even in the maximum computable simulation cell. Unlike previous calculations, which did not find a dependency on the size of the simulation cell, the calculations have shown a significant difference in results for 32- and 16- atom cells. This difference provides information about vacancy clustering since it can be explained by a relatively small attractive interaction energy {approximately} 0.2 eV between two vacancies located in adjacent simulation cells and separated by the lattice constant distance (5.52 {angstrom}). By comparing the internal energies for two configurations of 30 atom cells (32 atom--2 vacancies), the authors were able to estimate that the attractive interaction between two vacancies could reach 1.2 eV. The second complication is the fact that chemical potentials of elements cannot be directly extracted from the total energy calculations for the compound. To deal with this problem, they considered two possible approximations and compared results, which were found to be quite similar for iron vacancies.

  17. Ab initio Calculations of Electronic Fingerprints of DNA bases on Graphene

    NASA Astrophysics Data System (ADS)

    Ahmed, Towfiq; Rehr, John J.; Kilina, Svetlana; Das, Tanmoy; Haraldsen, Jason T.; Balatsky, Alexander V.

    2012-02-01

    We have carried out first principles DFT calculations of the electronic local density of states (LDOS) of DNA nucleotide bases (A,C,G,T) adsorbed on graphene using LDA with ultra-soft pseudo-potentials. We have also calculated the longitudinal transmission currents T(E) through graphene nano-pores as an individual DNA base passes through it, using a non-equilibrium Green's function (NEGF) formalism. We observe several dominant base-dependent features in the LDOS and T(E) in an energy range within a few eV of the Fermi level. These features can serve as electronic fingerprints for the identification of individual bases from dI/dV measurements in scanning tunneling spectroscopy (STS) and nano-pore experiments. Thus these electronic signatures can provide an alternative approach to DNA sequencing.

  18. Heats of Segregation of BCC Binaries from ab Initio and Quantum Approximate Calculations

    NASA Technical Reports Server (NTRS)

    Good, Brian S.

    2004-01-01

    We compare dilute-limit heats of segregation for selected BCC transition metal binaries computed using ab initio and quantum approximate energy methods. Ab initio calculations are carried out using the CASTEP plane-wave pseudopotential computer code, while quantum approximate results are computed using the Bozzolo-Ferrante-Smith (BFS) method with the most recent LMTO-based parameters. Quantum approximate segregation energies are computed with and without atomistic relaxation, while the ab initio calculations are performed without relaxation. Results are discussed within the context of a segregation model driven by strain and bond-breaking effects. We compare our results with full-potential quantum calculations and with available experimental results.

  19. Thermodynamic Properties of Elements and Compounds in Al-Sc Binary System from Ab Initio Calculations Based on Density Functional Theory

    NASA Astrophysics Data System (ADS)

    Zhou, Zeyou; Wu, Bo; Dou, Shushi; Zhao, Chunfeng; Xiong, Yuanpeng; Wu, Yufeng; Yang, Shangjin; Wei, Zhenyi

    2014-04-01

    The thermodynamic properties of FCC Al, HCP Sc, B2 AlSc, C15 Al2Sc, B82 AlSc2, and L12 Al3Sc were studied using ab initio calculations based on density functional theory. The 0 K (-273 °C) total energies were calculated using the ab initio plane-wave pseudopotential method within the generalized gradient approximation. The ab initio calculations of the phonon dispersion curves and the density of state of FCC Al, HCP Sc, B2 AlSc, C15 Al2Sc, B82 AlSc2, and L12 Al3Sc have been performed using the density functional theory and the direct method. Deduced from Helmholtz free energy, the thermal expansion, enthalpy, heat capacity, and entropy as a function of temperature were calculated and compared considerably with the experimental data and other computational results. Our calculations show that the enthalpies of formation are temperature-dependent, and the slope is about -3.4 J/mol/K for B2 AlSc, -2.3 J/mol/K for C15 Al2Sc, -0.8 J/mol/K for B82 AlSc2, and -2.7 J/mol/K for L12 Al3Sc, respectively.

  20. Spinel compounds as multivalent battery cathodes: A systematic evaluation based on ab initio calculations

    DOE PAGESBeta

    Liu, Miao; Rong, Ziqin; Malik, Rahul; Canepa, Pieremanuele; Jain, Anubhav; Ceder, Gerbrand; Persson, Kristin A.

    2014-12-16

    In this study, batteries that shuttle multivalent ions such as Mg2+ and Ca2+ ions are promising candidates for achieving higher energy density than available with current Li-ion technology. Finding electrode materials that reversibly store and release these multivalent cations is considered a major challenge for enabling such multivalent battery technology. In this paper, we use recent advances in high-throughput first-principles calculations to systematically evaluate the performance of compounds with the spinel structure as multivalent intercalation cathode materials, spanning a matrix of five different intercalating ions and seven transition metal redox active cations. We estimate the insertion voltage, capacity, thermodynamic stabilitymore » of charged and discharged states, as well as the intercalating ion mobility and use these properties to evaluate promising directions. Our calculations indicate that the Mn2O4 spinel phase based on Mg and Ca are feasible cathode materials. In general, we find that multivalent cathodes exhibit lower voltages compared to Li cathodes; the voltages of Ca spinels are ~0.2 V higher than those of Mg compounds (versus their corresponding metals), and the voltages of Mg compounds are ~1.4 V higher than Zn compounds; consequently, Ca and Mg spinels exhibit the highest energy densities amongst all the multivalent cation species. The activation barrier for the Al³⁺ ion migration in the Mn₂O₄ spinel is very high (~1400 meV for Al3+ in the dilute limit); thus, the use of an Al based Mn spinel intercalation cathode is unlikely. Amongst the choice of transition metals, Mn-based spinel structures rank highest when balancing all the considered properties.« less

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

    NASA Technical Reports Server (NTRS)

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

    1994-01-01

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

  2. Langevin spin dynamics based on ab initio calculations: numerical schemes and applications.

    PubMed

    Rózsa, L; Udvardi, L; Szunyogh, L

    2014-05-28

    A method is proposed to study the finite-temperature behaviour of small magnetic clusters based on solving the stochastic Landau-Lifshitz-Gilbert equations, where the effective magnetic field is calculated directly during the solution of the dynamical equations from first principles instead of relying on an effective spin Hamiltonian. Different numerical solvers are discussed in the case of a one-dimensional Heisenberg chain with nearest-neighbour interactions. We performed detailed investigations for a monatomic chain of ten Co atoms on top of a Au(0 0 1) surface. We found a spiral-like ground state of the spins due to Dzyaloshinsky-Moriya interactions, while the finite-temperature magnetic behaviour of the system was well described by a nearest-neighbour Heisenberg model including easy-axis anisotropy. PMID:24806308

  3. Theoretical study of dehydration-carbonation reaction on brucite surface based on ab initio quantum mechanic calculations

    NASA Astrophysics Data System (ADS)

    Churakov, S. V.; Parrinello, M.

    2003-04-01

    The carbonation of brucite (Mg(OH)2) has been considered as a potential technology for cleaning industrial carbon dioxide waste. The kinetics of the reaction Mg(OH)2 + CO2 -> MgCO3 + H2O have been studied experimentally at 573°C by Bearat at al. [1]. Their experiments suggest that the carbonation of magnesium hydroxide proceeds by the reaction Mg(OH)2 -> MgO + H2O followed by the adsorption of CO2 molecules on the dehydrated brucite surface. Due to the large difference in volumes between Mg(OH)2 and MgO, dehydration causes the formation of dislocations and cracks, allowing water molecules to leave the brucite surface and facilitating the advance of the carbonation front in the bulk solid. The detailed mechanism of this process is however unknown. We used the Car-Parrinello ab initio molecular dynamics method to study the structure and dynamics of the (0001), (1-100) and (11-20) surfaces of brucit and calculated the enthalpy and activation barrier of H2O nucleation and dehydration on different surfaces. The results obtained are in agreement with previous studies of brucite dehydration by Masini and Bernasconi [2]. The reactive Car-Parrinello molecular dynamics method [3] has been applied to investigate the detailed mechanism of the dehydration-carbonation reaction at the (1-100) interface of brucite with the gas phase. Based on the results of our MD simulations and the calculated enthalpy of CO2 adsorption on the dehydrated brucite surfaces we propose a mechanism for the dehydration/carbonation reaction. [1] Bearat H, McKelvy MJ, Chizmeshya AVG, Sharma R, Carpenter RW (2002) J. Amer. Ceram. Soc. 85(4):742 [2] Masini P and Bernasconi M (2001) J. Phys. Cond. Mat. 13: 1-12 [3] Iannuzzi M, Laio A and Parrinello M (2003) Phys. Rev. Lett. (submitted)

  4. Ab initio calculation and anharmonic force field of hypochlorous acid, HOCl

    NASA Astrophysics Data System (ADS)

    Halonen, L.; Ha, T.-K.

    1988-03-01

    Ab initio calculations on HOCl have been performed at the third-order Møller-Plesset perturbation theory level to determine the equilibrium structure and the anharmonic force field. An empirical anharmonic force field based on the ab initio results is obtained using available experimental vibration-rotation data. Four of the six harmonic and six of the ten cubic force constants have been determined experimentally, the remaining values being fixed at the ab initio values. A good fit to the experimental vibration-rotation data of four isotopic species is obtained.

  5. Ab initio calculations and crystal symmetry considerations for novel FeSe-based superconductors

    NASA Astrophysics Data System (ADS)

    Mazin, Igor

    2013-03-01

    Density functional calculations disagree with the ARPES measurements on both K0.3Fe2Se2 superconducting phase and FeSe/SrTiO3 monolayers. Yet they can still be dramatically useful for the reason that they respect full crystallographic symmetry and take good account of electron-ion interaction. Using just symmetry analysis, it is shown that nodeless d-wave superconductivity is not an option in these systems, and a microscopic framework is derived that leads to a novel s-wave sign-reversal state, qualitatively different from the already familiar s+/- state in pnictides and bulk binary selenides. Regarding the FeSe monolayer, bonding and charge transfer between the film and the substrate is analyzed and it is shown that the former is weak and the latter negligible, which sets important restrictions on possible mechanisms of doping and superconductivity in these monolayers. In particular, the role of the so-called ``Se etching,'' necessary for superconductivity in FeSe monolayers, is analyzed in terms of electronic structure and bonding with the substrate.

  6. Porphyrin-based polymeric nanostructures for light harvesting applications: Ab initio calculations

    NASA Astrophysics Data System (ADS)

    Orellana, Walter

    The capture and conversion of solar energy into electricity is one of the most important challenges to the sustainable development of mankind. Among the large variety of materials available for this purpose, porphyrins concentrate great attention due to their well-known absorption properties in the visible range. However, extended materials like polymers with similar absorption properties are highly desirable. In this work, we investigate the stability, electronic and optical properties of polymeric nanostructures based on free-base porphyrins and phthalocyanines (H2P, H2Pc), within the framework of the time-dependent density functional perturbation theory. The aim of this work is the stability, electronic, and optical characterization of polymeric sheets and nanotubes obtained from H2P and H2Pc monomers. Our results show that H2P and H2Pc sheets exhibit absorption bands between 350 and 400 nm, slightly different that the isolated molecules. However, the H2P and H2Pc nanotubes exhibit a wide absorption in the visible and near-UV range, with larger peaks at 600 and 700 nm, respectively, suggesting good characteristic for light harvesting. The stability and absorption properties of similar structures obtained from ZnP and ZnPc molecules is also discussed. Departamento de Ciencias Físicas, República 220, 037-0134 Santiago, Chile.

  7. Ab initio pseudopotential band calculation of organic conductors

    SciTech Connect

    Ishibashi, Shoji; Kohyama, Masanori

    1999-12-01

    The authors have calculated the band structures of organic conductors TTF-TCNQ and {beta}-(BEDT-TTF){sub 2}I{sub 3} using the ab initio plane-wave pseudopotential method within the local-density approximation (LDA). The Fermi-surface shape and the origin of bands near the Fermi level are investigated for each compound.

  8. Dialkylimidazolium chloroaluminates: Ab initio calculations, Raman and neutron scattering measurements

    SciTech Connect

    Takahasi, S. ); Curtiss, L.A.; Gosztola, D.; Koura, N. ); Loong, C.K.; Saboungi, M.L. . Materials Science Div.)

    1993-04-01

    The Raman and neutron scattering spectra of 46 mol% AlCl[sub 3] -54 mol% 1-ethyl-3-methyl imidazolium chloride (EMIC) and 67 mol% AlCl[sub 3] - 33 mol% EMIC melts are presented. Ab initio molecular orbital calculations have been carried out on structures of chloroaluminate anion and EMI cation and the interaction between anion and cation.

  9. Ab initio correlated calculations of rare-gas dimer quadrupoles

    NASA Astrophysics Data System (ADS)

    Donchev, Alexander G.

    2007-10-01

    This paper reports ab initio calculations of rare gas ( RG=Kr , Ar, Ne, and He) dimer quadrupoles at the second order of Møller-Plesset perturbation theory (MP2). The study reveals the crucial role of the dispersion contribution to the RG2 quadrupole in the neighborhood of the equilibrium dimer separation. The magnitude of the dispersion quadrupole is found to be much larger than that predicted by the approximate model of Hunt. As a result, the total MP2 quadrupole moment is significantly smaller than was assumed in virtually all previous related studies. An analytical model for the distance dependence of the RG2 quadrupole is proposed. The model is based on the effective-electron approach of Jansen, but replaces the original Gaussian approximation to the electron density in an RG atom by an exponential one. The role of the nonadditive contribution in RG3 quadrupoles is discussed.

  10. Ab Initio Path-Integral Calculations of Kinetic and Equilibrium Isotope Effects on Base-Catalyzed RNA Transphosphorylation Models

    PubMed Central

    Wong, Kin-Yiu; Yuqing, Xu; York, Darrin M.

    2014-01-01

    Detailed understandings of the reaction mechanisms of RNA catalysis in various environments can have profound importance for many applications, ranging from the design of new biotechnologies to the unraveling of the evolutionary origin of life. An integral step in the nucleolytic RNA catalysis is self-cleavage of RNA strands by 2′-O-transphosphorylation. Key to elucidating a reaction mechanism is determining the molecular structure and bonding characteristics of transition state. A direct and powerful probe of transition state is measuring isotope effects on biochemical reactions, particularly if we can reproduce isotope effect values from quantum calculations. This paper significantly extends the scope of our previous joint experimental and theoretical work in examining isotope effects on enzymatic and non-enzymatic 2′-O-transphosphorylation reaction models that mimic reactions catalyzed by RNA enzymes (ribozymes), and protein enzymes such as ribonuclease A (RNase A). Native reactions are studied, as well as reactions with thio substitutions representing chemical modifications often used in experiments to probe mechanism. Here, we report and compare results from eight levels of electronic-structure calculations for constructing the potential energy surfaces in kinetic and equilibrium isotope effects (KIE and EIE) computations, including a “gold-standard” coupled-cluster level of theory [CCSD(T)]. In addition to the widely-used Bigeleisen equation for estimating KIE and EIE values, internuclear anharmonicity and quantum tunneling effects were also computed using our recently-developed ab initio path-integral method, i.e., automated integration-free path-integral (AIF-PI) method. The results of this work establish an important set of benchmarks that serve to guide calculations of KIE and EIE for RNA catalysis. PMID:24841935

  11. Towards AB Initio Calculation of the Circular Dichroism of Peptides

    NASA Astrophysics Data System (ADS)

    Molteni, E.; Onida, G.; Tiana, G.

    2012-08-01

    In this work we plan to use ab initio spectroscopy calculations to compute circular dichroism (CD) spectra of peptides. CD provides information on protein secondary structure content; peptides, instead, remain difficult to address, due to their tendency to adopt multiple conformations in equilibrium. Therefore peptides are an interesting test-case for ab initio calculation of CD spectra. As a first application, we focus on the (83-92) fragment of HIV-1 protease, which is known to be involved in the folding and dimerization of this protein. As a preliminary step, we performed classical molecular dynamics (MD) simulations, in order to obtain a set of representative conformers of the peptide. Then, on some of the obtained conformations, we calculated absorption spectra at the independent particle, RPA and TDLDA levels, showing the presence of charge transfer excitations, and their influence on spectral features.

  12. Ab-initio calculations on melting of thorium

    NASA Astrophysics Data System (ADS)

    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.

  13. Thermochemical data for CVD modeling from ab initio calculations

    SciTech Connect

    Ho, P.; Melius, C.F.

    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.

  14. Revised vibrational band assignments for the experimental IR and Raman spectra of 2,3,4-trifluorobenzonitrile based on ab initio, DFT and normal coordinate calculations

    NASA Astrophysics Data System (ADS)

    Hiremath, C. S.; Kalkoti, G. B.; Aralakkanavar, M. K.

    2009-09-01

    In the present study, a systematic vibrational spectroscopic investigation for the experimental IR and Raman spectra of 2,3,4-trifluorobenzonitrile (TFB), aided by electronic structure calculations has been carried out. The electronic structure calculations - ab initio (RHF) and hybrid density functional methods (B3LYP) - have been performed with 6-31G* basis set. Molecular equilibrium geometries, electronic energies, IR intensities, harmonic vibrational frequencies, depolarization ratios and Raman activities have been computed. The results of the calculations have been used to simulate IR and Raman spectra for TFB that showed excellent agreement with the observed spectra. Potential energy distribution (PED) and normal mode analysis have also been performed. The assignments proposed based on the experimental IR and Raman spectra have been reviewed. A complete assignment of the observed spectra has been proposed.

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

    NASA Astrophysics Data System (ADS)

    Wilson, Hugh F.

    2015-12-01

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

  16. Ab initio calculations of reactions with light nuclei

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  17. Ab initio DFT calculations of vibrational properties

    NASA Astrophysics Data System (ADS)

    Story, S. M.; Vila, F. D.; Kas, J. J.; Rehr, J. J.

    2014-03-01

    Vibrational properties such as EXAFS and crystallographic Debye-Waller factors, vibrational free energies, phonon self-energies, and phonon contributions to the electron spectral function, are key to understanding many aspects of materials beyond ground state electronic structure. Thus, their simulation using first principles methods is of particular importance. Many of these vibrational properties can be calculated from the dynamical matrix and electron-phonon coupling coefficients obtained from DFT calculations. Here we present a code DMVP that calculates these properties from the output of electronic structure codes such as ABINIT, Gaussian, Quantum Espresso and VASP. Our modular interfacing tool AI2PS allows us to translate the different outputs into a DMVP compatible format and generate vibrational properties in an automated way. Finally, we present some current applications that take advantage of the modular form of AI2PS to extend its capabilities to the calculation of coefficients of thermal expansion and other properties of interest such as infrared spectra. This work was supported by DOE Grant DE-FG02-97ER45623.

  18. Ab Initio Calculations Applied to Problems in Metal Ion Chemistry

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.; Partridge, Harry; Arnold, James O. (Technical Monitor)

    1994-01-01

    Electronic structure calculations can provide accurate spectroscopic data (such as molecular structures) vibrational frequencies, binding energies, etc.) that have been very useful in explaining trends in experimental data and in identifying incorrect experimental measurements. In addition, ab initio calculations. have given considerable insight into the many interactions that make the chemistry of transition metal systems so diverse. In this review we focus on cases where calculations and experiment have been used to solve interesting chemical problems involving metal ions. The examples include cases where theory was used to differentiate between disparate experimental values and cases where theory was used to explain unexpected experimental results.

  19. Ab initio quantum transport calculations using plane waves

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

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

  20. Potential Dependence of Electrochemical Barriers from ab Initio Calculations.

    PubMed

    Chan, Karen; Nørskov, Jens K

    2016-05-01

    We present a simple and computationally efficient method to determine the potential dependence of the activation energies for proton-electron transfer from a single ab initio barrier calculation. We show that the potential dependence of the activation energy is given by the partial charge transferred at the transition state. The method is evaluated against the potential dependence determined explicitly through multiple calculations at varying potential. We show that the transfer coefficient is given by the charge transferred from the initial to transition state, which has significant implications for electrochemical kinetics. PMID:27088442

  1. Electronic coupling calculation and pathway analysis of electron transfer reaction using ab initio fragment-based method. I. FMO-LCMO approach

    NASA Astrophysics Data System (ADS)

    Nishioka, Hirotaka; Ando, Koji

    2011-05-01

    By making use of an ab initio fragment-based electronic structure method, fragment molecular orbital-linear combination of MOs of the fragments (FMO-LCMO), developed by Tsuneyuki et al. [Chem. Phys. Lett. 476, 104 (2009)], 10.1016/j.cplett.2009.05.069, we propose a novel approach to describe long-distance electron transfer (ET) in large system. The FMO-LCMO method produces one-electron Hamiltonian of whole system using the output of the FMO calculation with computational cost much lower than conventional all-electron calculations. Diagonalizing the FMO-LCMO Hamiltonian matrix, the molecular orbitals (MOs) of the whole system can be described by the LCMOs. In our approach, electronic coupling TDA of ET is calculated from the energy splitting of the frontier MOs of whole system or perturbation method in terms of the FMO-LCMO Hamiltonian matrix. Moreover, taking into account only the valence MOs of the fragments, we can considerably reduce computational cost to evaluate TDA. Our approach was tested on four different kinds of model ET systems with non-covalent stacks of methane, non-covalent stacks of benzene, trans-alkanes, and alanine polypeptides as their bridge molecules, respectively. As a result, it reproduced reasonable TDA for all cases compared to the reference all-electron calculations. Furthermore, the tunneling pathway at fragment-based resolution was obtained from the tunneling current method with the FMO-LCMO Hamiltonian matrix.

  2. Ab initio calculation of thermodynamic properties of silicon

    NASA Astrophysics Data System (ADS)

    Wei, Siqing; Li, Changlin; Chou, M. Y.

    1994-11-01

    We present a fully ab initio calculation of the thermodynamic properties for silicon within the quasiharmonic approximation, making use of volume-dependent phonon frequencies obtained from pseudopotential local-density calculations. The temperature dependence of the thermal-expansion coefficient, specific heat (at constant volume), and other related quantities are studied. We confirm that the thermal-expansion coefficient behaves differently in three temperature regions: positive for temperature below 15 K, negative between 15 and 125 K, and positive again above 125 K. This finding agrees with experiment. The abnormal (negative) thermal-expansion coefficient at low temperatures is explained through a detailed study of mode Grüneisen parameters. Both specific-heat and thermal-expansion-coefficient values calculated are in excellent agreement with experiment up to a few hundred kelvin.

  3. Motif based Hessian matrixfor ab initio geometry optimization ofnanostructures

    SciTech Connect

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

    2006-04-05

    A simple method to estimate the atomic degree Hessian matrixof a nanosystem is presented. The estimated Hessian matrix, based on themotif decomposition of the nanosystem, can be used to accelerate abinitio atomic relaxations with speedups of 2 to 4 depending on the sizeof the system. In addition, the programing implementation for using thismethod in a standard ab initio package is trivial.

  4. Ab Initio Calculations of Excited Carrier Dynamics in Gallium Nitride

    NASA Astrophysics Data System (ADS)

    Jhalani, Vatsal; Bernardi, Marco

    Bulk wurtzite GaN is the primary material for blue light-emission technology. The radiative processes in GaN are regulated by the dynamics of excited (or so-called ``hot'') carriers, through microscopic processes not yet completely understood. We present ab initio calculations of electron-phonon (e-ph) scattering rates for hot carriers in GaN. Our work combines density functional theory to compute the electronic states, and density functional perturbation theory to obtain the phonon dispersions and e-ph coupling matrix elements. These quantities are interpolated on fine Brillouin zone grids with maximally localized Wannier functions, to converge the e-ph scattering rates within 5 eV of the band edges. We resolve the contribution of the different phonon modes to the total scattering rate, and study the impact on the relaxation times of the long-range Fröhlich interaction due to the longitudinal-optical phonon modes.

  5. Transport coefficients in diamond from ab-initio calculations

    NASA Astrophysics Data System (ADS)

    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. An ab initio-based Er–He interatomic potential in hcp Er

    SciTech Connect

    Yang, Li; ye, Yeting; Fan, K. M.; Shen, Huahai; Peng, Shuming; Long, XG; Zhou, X. S.; Zu, Xiaotao; Gao, Fei

    2014-09-01

    We have developed an empirical erbium-helium (Er-He) potential by fitting to the results calculated from ab initio method. Based on the electronic hybridization between Er and He atoms, an s-band model, along with a repulsive pair potential, has been derived to describe the Er-He interaction. The atomic configurations and the formation energies of single He defects, small He interstitial clusters (Hen) and He-vacancy (HenV ) clusters obtained by ab initio calculations are used as the fitting database. The binding energies and relative stabilities of the HnVm clusters are studied by the present potential and compared with the ab initio calculations. The Er-He potential is also applied to study the migration of He in hcp-Er at different temperatures, and He clustering is found to occur at 600 K in hcp Er crystal, which may be due to the anisotropic migration behavior of He interstitials.

  7. Ab initio calculation of the shock Hugoniot of bulk silicon

    NASA Astrophysics Data System (ADS)

    Strickson, Oliver; Artacho, Emilio

    2016-03-01

    We describe how ab initio molecular dynamics can be used to determine the Hugoniot locus (states accessible by a shock wave) for materials with a number of stable phases, and with an approximate treatment of plasticity and yield, without having to simulate these phenomena directly. We consider the case of bulk silicon, with forces from density-functional theory, up to 70 GPa. The fact that shock waves can split into multiple waves due to phase transitions or yielding is taken into account here by specifying the strength of any preceding waves explicitly based on their yield strain. Points corresponding to uniaxial elastic compression along three crystal axes and a number of postshock phases are given, including a plastically yielded state, approximated by an isotropic stress configuration following an elastic wave of predetermined strength. The results compare well to existing experimental data for shocked silicon.

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

    SciTech Connect

    Kolorenč, Přemysl; Sisourat, Nicolas

    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.

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

    PubMed

    Kolorenč, Přemysl; Sisourat, Nicolas

    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. PMID:26671378

  10. HfO_2and ZrO2 : Comparison of Structures and Thermodynamic and Electronic Properties Based on Ab Initio Calculations and Experiment

    NASA Astrophysics Data System (ADS)

    Demkov, Alexander A.; Navrotsky, Alexandra

    2001-03-01

    The International Technology Roadmap for Semiconductors (ITRS) predicts that the strategy of scaling complementary metal-oxide-semiconductor (CMOS) devices will come to an abrupt end around the year 2012. The main reason for this will be the unacceptably high leakage current through the silicon dioxide gate with a thickness below 20 ÅFinding a gate insulator alternative to SiO2 has proven to be far from trivial. Hafnium and zirconium dioxides and silicates have been recently considered as gate dielectrics with intermediate dielectric constants. Hafnia and ziconia are important ceramic materials as well, and their phase relations are rather well studied. There is also interest in hafnia as a constituent of ceramic waste forms for plutonium, based on its refractory nature and high neutron absorption cross section. We use a combination of the ab-initio calculations and calorimetry to investigate thermodynamic and electronic properties of hafnia and zirconia. We describe the cubic to tetragonal phase transition in the fluorite structure by computing the total energy surface for zone-edge distortions correct to fourth order in the soft-mode displacement with the strain coupling renormalization included. We compare the two materials using some simple chemical concepts.

  11. Surface Segregation Energies of BCC Binaries from Ab Initio and Quantum Approximate Calculations

    NASA Technical Reports Server (NTRS)

    Good, Brian S.

    2003-01-01

    We compare dilute-limit segregation energies for selected BCC transition metal binaries computed using ab initio and quantum approximate energy method. Ab initio calculations are carried out using the CASTEP plane-wave pseudopotential computer code, while quantum approximate results are computed using the Bozzolo-Ferrante-Smith (BFS) method with the most recent parameterization. Quantum approximate segregation energies are computed with and without atomistic relaxation. The ab initio calculations are performed without relaxation for the most part, but predicted relaxations from quantum approximate calculations are used in selected cases to compute approximate relaxed ab initio segregation energies. Results are discussed within the context of segregation models driven by strain and bond-breaking effects. We compare our results with other quantum approximate and ab initio theoretical work, and available experimental results.

  12. Electron-ejection cross sections in electron- and ion impact ionization: ab initio and semiempirical calculations

    SciTech Connect

    Manson, S.T.; Miller, J.H.

    1987-01-01

    Ab initio calculations of single and double differential cross sections for ionization by fast, charged particles within the framework of the Born approximation are presented. In addition, a semi-empirical method based on the asymptotic Bethe-Born expansion is also discussed. Both are applied to ionization of helium by electrons and protons in an effort to assess their accuracy and validity. Agreement with experiment is quite good. The implications for other targets is discussed.

  13. Ab initio calculations in a uniform magnetic field using periodic supercells

    SciTech Connect

    Cai, W; Galli, G

    2003-10-21

    We present a formulation of ab initio electronic structure calculations in a finite magnetic field, which retains the simplicity and efficiency of techniques widely used in first principles molecular dynamics simulations, based on plane-wave basis sets and Fourier transforms. In addition we discuss results obtained with this method for the energy spectrum of interacting electrons in quantum wells, and for the electronic properties of dense fluid deuterium in a uniform magnetic field.

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

    SciTech Connect

    Bodenstein, Tilmann; Fink, Karin

    2015-12-31

    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.

  15. Development of an ab-initio calculation method for 2D layered materials-based optoelectronic devices

    NASA Astrophysics Data System (ADS)

    Kim, Han Seul; Kim, Yong-Hoon

    We report on the development of a novel first-principles method for the calculation of non-equilibrium nanoscale device operation process. Based on region-dependent Δ self-consistent field method beyond the standard density functional theory (DFT), we will introduce a novel method to describe non-equilibrium situations such as external bias and simultaneous optical excitations. In particular, we will discuss the limitation of conventional method and advantage of our scheme in describing 2D layered materials-based devices operations. Then, we investigate atomistic mechanism of optoelectronic effects from 2D layered materials-based devices and suggest the optimal material and architecture for such devices.

  16. Ab initio SCF calculations on hydrogen bonded cresol isomers

    NASA Astrophysics Data System (ADS)

    Pohl, M.; Kleinermanns, K.

    1988-12-01

    Ab initio GAUSSIAN 80 calculations with two different basis sets (STO-3G and 4 31 G*) were performed on hydrogen bonded cresol isomers for comparison with experimental data from free jet fluorescence excitation spectroscopy. For m-cresol, the calculated barriers for hindered internal rotation of the OH-group and the CH3-group are in good agreement with experiment. The calculations show the trans-linear configuration of p-cresol· B-clusters ( B = H2O, CH3OH) to be more stable than the all-planar configuration. This agrees with CI calculations and microwave spectroscopic investigations of the water dimer. Calculations of both the intermolecular stretch and bend frequencies of p-cresol· B-clusters show little dependence on the all-planar or trans-linear configuration but a strong dependence on the choice of the basis set. With the minimal basis set STO-3G, the vibrational energies are generally too high. The agreement between the calculated vibrational frequencies from the 4 31 G* basis set and the experimental values is fair.

  17. Accurate high level ab initio-based global potential energy surface and dynamics calculations for ground state of CH{sub 2}{sup +}

    SciTech Connect

    Li, Y. Q.; Zhang, P. Y.; Han, K. L.

    2015-03-28

    A global many-body expansion potential energy surface is reported for the electronic ground state of CH{sub 2}{sup +} by fitting high level ab initio energies calculated at the multireference configuration interaction level with the aug-cc-pV6Z basis set. The topographical features of the new global potential energy surface are examined in detail and found to be in good agreement with those calculated directly from the raw ab initio energies, as well as previous calculations available in the literature. In turn, in order to validate the potential energy surface, a test theoretical study of the reaction CH{sup +}(X{sup 1}Σ{sup +})+H({sup 2}S)→C{sup +}({sup 2}P)+H{sub 2}(X{sup 1}Σ{sub g}{sup +}) has been carried out with the method of time dependent wavepacket on the title potential energy surface. The total integral cross sections and the rate coefficients have been calculated; the results determined that the new potential energy surface can both be recommended for dynamics studies of any type and as building blocks for constructing the potential energy surfaces of larger C{sup +}/H containing systems.

  18. FTIR, Raman spectra and ab initio calculations of 2-mercaptobenzothiazole.

    PubMed

    Rai, Amareshwar K; Singh, Rachana; Singh, K N; Singh, V B

    2006-02-01

    FTIR and Raman spectra of a rubber vulcanization accelerator, 2-mercaptobenzothiazole (MBT), were recorded in the solid phase. The harmonic vibrational wavenumbers, for both the toutomeric forms of MBT, as well as for its dimeric complex, have been calculated, using ab initio RHF and density functional B3LYP methods invoking different basis sets upto RHF/6-31G** and B3LYP/6-31G** and the results were compared with the experimental values. Conformational studies have been also carried out regarding its toutomeric monomer forms and its dimer form. With all the basis sets the thione form of MBT (II) is predicted to be more stable than thiol form (I) and dimeric conformation (III) is predicted to be more stable with monomeric conformations (I) and (II). Vibrational assignments have been made, and it has been found that the calculated normal mode frequencies of dimeric conformation (III) are required for the analysis of IR and Raman bands of the MBT. The predicted shift in NH- stretching vibration towards the lower wave number side with the B3LYP/6-31G** calculations for the most stable dimer form (III), is in better agreement with experimental results. The intermolecular sulfur-nitrogen distance in N-H...S hydrogen bond was found to be 3.35 angstroms from these calculations, is also in agreement to the experimental value. PMID:16098806

  19. Ab initio calculation of infrared intensities for hydrogen peroxide

    NASA Technical Reports Server (NTRS)

    Rogers, J. D.; Hillman, J. J.

    1982-01-01

    Results of an ab initio SCF quantum mechanical study are used to derive estimates for the infrared intensities of the fundamental vibrations of hydrogen peroxide. Atomic polar tensors (APTs) were calculated on the basis of a 4-31G basis set, and used to derive absolute intensities for the vibrational transitions. Comparison of the APTs calculated for H2O2 with those previously obtained for H2O and CH3OH, and of the absolute intensities derived from the H2O2 APTs with those derived from APTs transferred from H2O and CH3OH, reveals the sets of values to differ by no more than a factor of two, supporting the validity of the theoretical calculation. Values of the infrared intensities obtained correspond to A1 = 14.5 km/mol, A2 = 0.91 km/mol, A3 = 0.058 km/mol, A4 = 123 km/mol, A5 = 46.2 km/mol, and A6 = 101 km/mol. Charge, charge flux and overlap contributions to the dipole moment derivatives are also computed.

  20. Spinel compounds as multivalent battery cathodes: A systematic evaluation based on ab initio calculations

    SciTech Connect

    Liu, Miao; Rong, Ziqin; Malik, Rahul; Canepa, Pieremanuele; Jain, Anubhav; Ceder, Gerbrand; Persson, Kristin A.

    2014-12-16

    In this study, batteries that shuttle multivalent ions such as Mg2+ and Ca2+ ions are promising candidates for achieving higher energy density than available with current Li-ion technology. Finding electrode materials that reversibly store and release these multivalent cations is considered a major challenge for enabling such multivalent battery technology. In this paper, we use recent advances in high-throughput first-principles calculations to systematically evaluate the performance of compounds with the spinel structure as multivalent intercalation cathode materials, spanning a matrix of five different intercalating ions and seven transition metal redox active cations. We estimate the insertion voltage, capacity, thermodynamic stability of charged and discharged states, as well as the intercalating ion mobility and use these properties to evaluate promising directions. Our calculations indicate that the Mn2O4 spinel phase based on Mg and Ca are feasible cathode materials. In general, we find that multivalent cathodes exhibit lower voltages compared to Li cathodes; the voltages of Ca spinels are ~0.2 V higher than those of Mg compounds (versus their corresponding metals), and the voltages of Mg compounds are ~1.4 V higher than Zn compounds; consequently, Ca and Mg spinels exhibit the highest energy densities amongst all the multivalent cation species. The activation barrier for the Al³⁺ ion migration in the Mn₂O₄ spinel is very high (~1400 meV for Al3+ in the dilute limit); thus, the use of an Al based Mn spinel intercalation cathode is unlikely. Amongst the choice of transition metals, Mn-based spinel structures rank highest when balancing all the considered properties.

  1. Melting curves of metals by ab initio calculations

    NASA Astrophysics Data System (ADS)

    Minakov, Dmitry; Levashov, Pavel

    2015-06-01

    In this work we used several ab initio approaches to reproduce melting curves and discussed their abilities, advantages and drawbacks. We used quasiharmonic appoximation and Lindemann criterion to build melting curves in wide region of pressures. This approach allows to calculate the total free energy of electrons and phonons, so it is possible to obtain all thermodynamic properties in the crystalline state. We also used quantum molecular dynamics simulations to investigate melting at various pressures. We explored the size-effect of the heat until it melts (HUM) method in detail. Special attention was paid to resolve the boundaries of the melting region on density. All calculations were performed for aluminum, copper and gold. Results were in good agreement with available experimental data. Also we studied the influence of electronic temperature on melting curves. It turned out that the melting temperature increased with the rise of electron temperature at normal density and had non-monotonic behavior at higher densities. This work is supported by the Ministry of Education and Science of the Russian Federation (Project No. 3.522.2014/K).

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

    NASA Astrophysics Data System (ADS)

    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.

  3. Ab initio calculation of double ionization of atoms

    SciTech Connect

    Serov, V. V.

    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.

  4. Ab initio simulations on rutile-based titania nanowires

    NASA Astrophysics Data System (ADS)

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

    2012-08-01

    The rod symmetry groups for monoperiodic (1D) nanostructures have been applied for construction of models for bulk-like TiO2 nanowires (NWs) cut from a rutile-based 3D crystal along the chosen [001] and [110] directions of crystallographic axes. In this study, we have considered nanowires described by both the Ti-atom centered rotation axes as well as the hollow site centered axes passing through the interstitial positions between the Ti and O atoms closest to the axes. The most stable [001]-oriented TiO2 NWs with rhombic cross sections are found to display the energetically preferable {110} facets only while the nanowires with quasi-square sections across the [110] axis are formed by the alternating { 1bar 10 } and {001} facets. For simulations on rutile-based nanowires possessing different diameters for each NW type, we have performed large-scale ab initio Density Functional Theory (DFT) and hybrid DFT-Hartree Fock (DFT-HF) calculations with total geometry optimization within the Generalized Gradient Approximation (GGA) in the form of the Perdew-Becke-Ernzenhof (PBE) exchange-correlation functionals (PBE and PBE0, respectively), using the formalism of linear combination of localized atomic functions (LCAO). We have simulated both structural and electronic properties of TiO2 NWs depending both on orientation and position of symmetry axes as well as on diameter and morphology of nanowires.

  5. Ab initio calculation of excitonic Hamiltonian of light-harvesting complex LH1 of Thermochromatium tepidum

    NASA Astrophysics Data System (ADS)

    Kozlov, Maxim I.; Poddubnyy, Vladimir V.; Glebov, Ilya O.; Belov, Aleksandr S.; Khokhlov, Daniil V.

    2016-02-01

    The electronic properties of light-harvesting complexes determine the efficiency of energy transfer in photosynthetic antennae. Ab initio calculations of the electronic properties of bacteriochlorophylls (composing the LH1 complex of the purple bacteria Thermochromatium tepidum) were performed. Based on these calculations, the excitonic Hamiltonian of a native cyclic complex and the Hamiltonians of open complexes with several removed bacteriochlorophylls were constructed. Absorption spectra calculated based on these Hamiltonians agree well with the experimental data. We found that the parameters of interaction between the neighboring bacteriochlorophylls are significantly larger than the empirical parameters suggested previously.

  6. Vortices of polarization in BaTiO3 core-shell nanoceramics: Calculations based on ab initio derived Hamiltonian versus Landau theory

    NASA Astrophysics Data System (ADS)

    Anoufa, M.; Kiat, J. M.; Kornev, I.; Bogicevic, C.

    2013-10-01

    In this paper, we want to emphasize the fact that many experimental properties of ceramics can be explained by the existence of a core-shell structure of the grains, particularly at small sizes. In this framework, we have studied BaTiO3 (BT) ceramics constituted of core-shell nanoparticles, nanowires, or nanoplanes by using ab initio derived effective Hamiltonian calculations whose application range is for large values of shell thickness and low values of shell permittivity. Many differences and new features compared to the situation of nanodots are induced by the core-shell structure. For instance, phase sequences are different; there is also a coexistence of vortices found by Naumov, Bellaiche, and Fu [I. I. Naumov, L. Bellaiche, and H. Fu, Nature (London)10.1038/nature03107 432, 737 (2004)] in the case of isolated dots with a homogeneous polarization, a transition from cubic paraelectric phase towards nonpolar rhombohedral phase, anomalies in dielectric permittivity associated with the onset of toroidal moments, etc. Afterwards, we compare these results with those obtained by the Landau theory of core-shell ceramics we have recently published. However, the ab initio calculations fail to capture the physics at small shell thickness and/or high shell permittivity, whereas the Landau theory fails to predict the peculiar properties of the phases in which vortices exist. Therefore, in a tentative way to build a global theory, we have constructed a Landau potential using both the polarization and the toroidal moment as competing order parameters, which allows us to propose a phase diagram, whatever the thickness and permittivity of the shell are.

  7. Electronic states of Zn2 - Ab initio calculations of a prototype for Hg2

    NASA Technical Reports Server (NTRS)

    Hay, P. J.; Dunning, T. H., Jr.; Raffenetti, R. C.

    1976-01-01

    The electronic states of Zn2 are investigated by ab initio polarization configuration-interaction calculations. Molecular states dissociating to Zn(1S) + Zn(1S, 3P, 1P) and Zn(3P) + Zn(3P) are treated. Important effects from states arising from Zn(+)(25) + Zn(-)(2P) are found in the potential-energy curves and electronic-transition moments. A model calculation for Hg2 based on the Zn2 curves and including spin-orbit coupling leads to a new interpretation of the emission bands in Hg vapor.

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

    SciTech Connect

    Draayer, Jerry P.

    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).

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

    SciTech Connect

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

    2015-05-21

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

    The calculation and characterization of the IR spectrum of liquid water have remained a challenge for theory. In this paper, we address this challenge using a combination of ab initio approaches, namely, a quantum treatment of IR spectrum using the ab initio WHBB water potential energy surface and a refined ab initio dipole moment surface. The quantum treatment is based on the embedded local monomer method, in which the three intramolecular modes of each embedded H2O monomer are fully coupled and also coupled singly to each of six intermolecular modes. The new dipole moment surface consists of a previous spectroscopically accurate 1-body dipole moment surface and a newly fitted ab initio intrinsic 2-body dipole moment. A detailed analysis of the new dipole moment surface in terms of the coordinate dependence of the effective atomic charges is done along with tests of it for the water dimer and prism hexamer double-harmonic spectra against direct ab initio calculations. The liquid configurations are taken from previous molecular dynamics calculations of Skinner and co-workers, using the TIP4P plus E3B rigid monomer water potential. The IR spectrum of water at 300 K in the range of 0-4000 cm-1 is calculated and compared with experiment, using the ab initio WHBB potential and new ab initio dipole moment, the q-TIP4P/F potential, which has a fixed-charged description of the dipole moment, and the TTM3-F potential and dipole moment surfaces. The newly calculated ab initio spectrum is in very good agreement with experiment throughout the above spectral range, both in band positions and intensities. This contrasts to results with the other potentials and dipole moments, especially the fixed-charge q-TIP4P/F model, which gives unrealistic intensities. The calculated ab initio spectrum is analyzed by examining the contribution of various transitions to each band.

  11. Ramsdellite-structured LiTiO 2: A new phase predicted from ab initio calculations

    NASA Astrophysics Data System (ADS)

    Koudriachova, M. V.

    2008-06-01

    A new phase of highly lithiated titania with potential application as an anode in Li-rechargeable batteries is predicted on the basis of ab initio calculations. This phase has a composition LiTiO2 and may be accessed through electrochemical lithiation of ramsdellite-structured TiO2 at the lowest potential reported for titanium dioxide based materials. The potential remains constant over a wide range of Li-concentrations. The new phase is metastable with respect to a tetragonally distorted rock salt structure, which hitherto has been the only known polymorph of LiTiO2.

  12. Ab Initio Calculations of the Interaction between CO 2 and the Acetate Ion

    SciTech Connect

    Steckel, Janice A.

    2012-11-29

    A series of ab initio calculations designed to investigate the interaction of CO{sub 2} with acetate are presented. The lowest energy structure, AC–CO{sub 2}-η{sup 2}, is predicted by CCSD(T)/aVTZ to be bound by -10.6 kcal/mol. Six of the bound complexes have binding energies on the order of -8 kcal/mol, but analysis shows that the η{sup 1}-CT complex is fundamentally different from the others. The η{sup 1}-CT complex is characterized by geometric distortion, large polarization and induction effects and charge transfer whereas the other five complexes have little geometric distortion and negligible charge transfer. The amount of charge that is transferred from the anion to the CO{sub 2} in the η{sup 1}-CT complex is estimated to be about half an electron by NPA, DMA, CHELPG, and Mulliken analyses, whereas the EDA-ALMO-CTA (B3LYP) approach predicts a charge transfer of 75 me{sup –}. However, the transfer of this small amount of charge leads to an energy lowering of -56 kcal/mol, without which the complex would not be bound. The RI-MP2 geometries closely approximate those resulting from the CCSD optimizations, and the optimized second-order opposite spin (O2) method performs well for all the complexes except for the η{sup 1}-CT complex. DFT methods do not reproduce all the ab initio geometries, binding energies and/or energy ordering of these complexes although the range-separated hybrid meta-GGA (M11) and nonlocal (VV10 and vdwDF10) functionals are shown to yield results significantly better than other functionals considered for this system. The fact that there is such variation among DFT methods has implications for DFT-based ab initio molecular dynamics simulations and for the parametrization of classical force fields based on DFT calculations.

  13. The implementation of ab initio quantum chemistry calculations on transporters.

    PubMed

    Cooper, M D; Hillier, I H

    1991-06-01

    The RHF and geometry optimization sections of the ab initio quantum chemistry code, GAMESS, have been optimized for a network of parallel microprocessors, Inmos T800-20 transputers, using both indirect and direct SCF techniques. The results indicate great scope for implementation of such codes on small parallel computer systems, very high efficiencies having been achieved, particularly in the cases of direct SCF and geometry optimization with large basis sets. The work, although performed upon one particular parallel system, the Meiko Computing Surface, is applicable to a wide range of parallel systems with both shared and distributed memory. PMID:1919615

  14. Relation between Magnetic, Spectroscopic and Structural Properties of Binuclear Copper(II) Complexes of Pentadentate Schiff-base Ligand, Semi-empirical and ab-initio Calculations

    NASA Astrophysics Data System (ADS)

    Elerman, Y.; Kara, H.; Elmali, A.

    2003-06-01

    The synthesis and characterization of [Cu2(L1)(3,5 prz)] (L1=1,3-Bis(2-hydroxy-3,5-chlorosalicylideneamino) propan-2-ol) 1 and of [Cu2(L2)(3,5 prz)] (L2=1,3-Bis(2-hydroxy-bromosalicylideneamino) propan-2-ol) 2 are reported. The compounds were studied by elemental analysis, infrared and electronic spectra. The structure of the Cu2(L1)(3,5 prz)] complex was determined by x-ray diffraction. The magnetochemical characteristics of these compounds were determined by temperaturedependent magnetic susceptibility measurements, revealing their antiferromagnetic coupling. The superexchange coupling constants are 210 cm-1 for 1 and 440 cm-1 for 2. The difference in the magnitude of the coupling constants was explained by the metal-ligand orbital overlaps and confirmed by ab-initio restricted Hartree-Fock (RHF) calculations. In order to determine the nature of the frontier orbitals, Extended Hückel Molecular Orbital (EHMO) calculations are also reported.

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

    SciTech Connect

    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{sup ∗}/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.

  16. Ab initio calculations of grain boundaries in bcc metals

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

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

    NASA Astrophysics Data System (ADS)

    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.

  18. Ab initio quantum Monte Carlo calculations of ground-state properties of manganese's oxides

    NASA Astrophysics Data System (ADS)

    Sharma, Vinit; Krogel, Jaron T.; Kent, P. R. C.; Reboredo, Fernando A.

    One of the critical scientific challenges of contemporary research is to obtain an accurate theoretical description of the electronic properties of strongly correlated systems such as transition metal oxides and rare-earth compounds, since state-of-art ab-initio methods based on approximate density functionals are not always sufficiently accurate. Quantum Monte Carlo (QMC) methods, which use statistical sampling to evaluate many-body wave functions, have the potential to answer this challenge. Owing to the few fundamental approximations made and the direct treatment of electron correlation, QMC methods are among the most accurate electronic structure methods available to date. We assess the accuracy of the diffusion Monte Carlo method in the case of rocksalt manganese oxide (MnO). We study the electronic properties of this strongly-correlated oxide, which has been identified as a suitable candidate for many applications ranging from catalysts to electronic devices. ``This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division.'' Ab initio quantum Monte Carlo calculations of ground-state properties of manganese's oxides.

  19. Ab initio based thermal property predictions at a low cost: An error analysis

    NASA Astrophysics Data System (ADS)

    Lejaeghere, Kurt; Jaeken, Jan; Van Speybroeck, Veronique; Cottenier, Stefaan

    2014-01-01

    Ab initio calculations often do not straightforwardly yield the thermal properties of a material yet. It requires considerable computational efforts, for example, to predict the volumetric thermal expansion coefficient αV or the melting temperature Tm from first principles. An alternative is to use semiempirical approaches. They relate the experimental values to first-principles predictors via fits or approximative models. Before applying such methods, however, it is of paramount importance to be aware of the expected errors. We therefore quantify these errors at the density-functional theory level using the Perdew-Burke-Ernzerhof functional for several semiempirical approximations of αV and Tm, and compare them to the errors from fully ab initio methods, which are computationally more intensive. We base our conclusions on a benchmark set of 71 ground-state elemental crystals. For the thermal expansion coefficient, it appears that simple quasiharmonic theory, in combination with different approximations to the Grüneisen parameter, provides a similar overall accuracy as exhaustive first-principles phonon calculations. For the melting temperature, expensive ab initio molecular-dynamics simulations still outperform semiempirical methods.

  20. Heats of Segregation of BCC Binaries from Ab Initio and Quantum Approximate Calculations

    NASA Technical Reports Server (NTRS)

    Good, Brian S.

    2003-01-01

    We compare dilute-limit segregation energies for selected BCC transition metal binaries computed using ab initio and quantum approximate energy methods. Ab initio calculations are carried out using the CASTEP plane-wave pseudopotential computer code, while quantum approximate results are computed using the Bozzolo-Ferrante-Smith (BFS) method with the most recent parameters. Quantum approximate segregation energies are computed with and without atomistic relaxation. Results are discussed within the context of segregation models driven by strain and bond-breaking effects. We compare our results with full-potential quantum calculations and with available experimental results.

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  2. Ab initio calculations on magnetism induced by composite defects in magnesium oxide

    SciTech Connect

    Zhang, Yao-Fang; Feng, Min; Shao, Bin; Lu, Yuan; Zuo, Xu; Liu, Hong

    2014-05-07

    The local magnetic state induced by the composite defects, composed of an oxygen vacancy and a nitrogen substituting oxygen, in magnesium oxide has been studied by using ab initio calculation based on density functional theory. The calculated results show that local magnetic moment can be induced by the composite defects around the oxygen vacancy, when the exchange split of the oxygen vacancy is enhanced either by the hybridization between the N-p and nearest neighbor O-p orbitals or by applying on-site Coulomb repulsion (U) and exchange interaction (J). We show that the magnetic state induced by the composite defect is energetically more stable than the non-magnetic state. In addition, we show that the U and J applied on the p-orbitals of N and O atoms may significantly impact the calculated magnetic state of the composite defect, resulting in magnetic state for a configuration that is non-magnetic by generalized gradient approximation.

  3. Infrared spectra, vibrational assignment, and ab initio calculations for N-bromo-hexafluoro-2-propanimine

    NASA Astrophysics Data System (ADS)

    Panikar, Savitha S.; Guirgis, Gamil A.; Sheehan, Tracie G.; Durig, Douglas T.; Durig, James R.

    2012-05-01

    The infrared spectra of gaseous and solid N-bromo-hexafluoro-2-propanimine, (CF3)2Cdbnd NBr, have been obtained from 2000 to 50 cm-1. The vibrational assignment for the normal modes is proposed based on infrared band contours, group frequencies and normal coordinate calculations utilizing Cs symmetry. The structural parameters have been obtained from ab initio MP2(full)/6-311 + G(d,p) calculations employing the Gaussian-03 program. Additionally, the frequencies and potential energy distributions for the normal modes have been calculated with the MP2(full)/6-31G(d). All of these results are compared to the corresponding data for some similar molecules.

  4. Infrared spectra, vibrational assignment, and ab initio calculations for N-bromo-hexafluoro-2-propanimine.

    PubMed

    Panikar, Savitha S; Guirgis, Gamil A; Sheehan, Tracie G; Durig, Douglas T; Durig, James R

    2012-05-01

    The infrared spectra of gaseous and solid N-bromo-hexafluoro-2-propanimine, (CF(3))(2)CNBr, have been obtained from 2000 to 50 cm(-1). The vibrational assignment for the normal modes is proposed based on infrared band contours, group frequencies and normal coordinate calculations utilizing C(s) symmetry. The structural parameters have been obtained from ab initio MP2(full)/6-311+G(d,p) calculations employing the Gaussian-03 program. Additionally, the frequencies and potential energy distributions for the normal modes have been calculated with the MP2(full)/6-31G(d). All of these results are compared to the corresponding data for some similar molecules. PMID:22336042

  5. 4He Thermophysical Properties: New Ab Initio Calculations

    PubMed Central

    Hurly, John J.; Mehl, James B.

    2007-01-01

    Since 2000, atomic physicists have reduced the uncertainty of the helium-helium “ab initio” potential; for example, from approximately 0.6 % to 0.1 % at 4 bohr, and from 0.8 % to 0.1 % at 5.6 bohr. These results led us to: (1) construct a new inter-atomic potential ϕ07, (2) recalculate values of the second virial coefficient, the viscosity, and the thermal conductivity of 4He from 1 K to 10,000 K, and (3), analyze the uncertainties of the thermophysical properties that propagate from the uncertainty of ϕ07 and from the Born-Oppenheimer approximation of the electron-nucleon quantum mechanical system. We correct minor errors in a previous publication [J. J. Hurly and M. R. Moldover, J. Res. Nat. Inst. Standards Technol. 105, 667 (2000)] and compare our results with selected data published after 2000. The ab initio results tabulated here can serve as standards for the measurement of thermophysical properties. PMID:27110456

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

    SciTech Connect

    Leung, Kevin; Rempe, Susan B.; Lilienfeld, O. Anatole von

    2009-05-28

    We apply ab initio molecular dynamics (AIMD) methods in conjunction with the thermodynamic integration or '{lambda}-path' technique to compute the intrinsic hydration free energies of Li{sup +}, Cl{sup -}, and Ag{sup +} ions. Using the Perdew-Burke-Ernzerhof functional, adapting methods developed for classical force field applications, and with consistent assumptions about surface potential ({phi}) contributions, we obtain absolute AIMD hydration free energies ({Delta}G{sub hyd}) within a few kcal/mol, or better than 4%, of Tissandier et al.'s [J. Phys. Chem. A 102, 7787 (1998)] experimental values augmented with the SPC/E water model {phi} predictions. The sums of Li{sup +}/Cl{sup -} and Ag{sup +}/Cl{sup -} AIMD {Delta}G{sub hyd}, which are not affected by surface potentials, are within 2.6% and 1.2 % of experimental values, respectively. We also report the free energy changes associated with the transition metal ion redox reaction Ag{sup +}+Ni{sup +}{yields}Ag+Ni{sup 2+} in water. The predictions for this reaction suggest that existing estimates of {Delta}G{sub hyd} for unstable radiolysis intermediates such as Ni{sup +} may need to be extensively revised.

  7. Correlations between ab initio and experimental data for isolated H-bonded complexes of water with nitrogen bases

    NASA Astrophysics Data System (ADS)

    Maes, G.; Smets, J.; Adamowicz, L.; McCarthy, W.; Van Bael, M. K.; Houben, L.; Schoone, K.

    1997-06-01

    Correlations between selected ab initio predicted and experimentally observed properties of 1:1 H-bonded complexes of pyridines, pyrimidines, and imidazoles with water are investigated. Relationships are found between the experimental properties of proton affinity and water frequency shift, and the ab initio calculated bond distances, interaction energies and water frequency shifts. It is also found that well-defined relations can be established between calculated and observed properties for the pyridine complexes, but these cannot be reliably extended to the other N-base systems. The similarities demonstrate that the presently available ab initio methods are useful in predicting the experimental behaviour of H-bonded systems, but only for closely related molecules.

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  9. Ab initio calculation of anisotropic magnetic properties of complexes. I. Unique definition of pseudospin Hamiltonians and their derivation

    NASA Astrophysics Data System (ADS)

    Chibotaru, L. F.; Ungur, L.

    2012-08-01

    A methodology for the rigorous nonperturbative derivation of magnetic pseudospin Hamiltonians of mononuclear complexes and fragments based on ab initio calculations of their electronic structure is described. It is supposed that the spin-orbit coupling and other relativistic effects are already taken fully into account at the stage of quantum chemistry calculations of complexes. The methodology is based on the establishment of the correspondence between the ab initio wave functions of the chosen manifold of multielectronic states and the pseudospin eigenfunctions, which allows to define the pseudospin Hamiltonians in the unique way. Working expressions are derived for the pseudospin Zeeman and zero-field splitting Hamiltonian corresponding to arbitrary pseudospins. The proposed calculation methodology, already implemented in the SINGLE_ANISO module of the MOLCAS-7.6 quantum chemistry package, is applied for a first-principles evaluation of pseudospin Hamiltonians of several complexes exhibiting weak, moderate, and very strong spin-orbit coupling effects.

  10. Electronic and thermoelectric properties of InN studied using ab initio density functional theory and Boltzmann transport calculations

    SciTech Connect

    Borges, P. D. E-mail: lscolfaro@txstate.edu; Scolfaro, L. E-mail: lscolfaro@txstate.edu

    2014-12-14

    The thermoelectric properties of indium nitride in the most stable wurtzite phase (w-InN) as a function of electron and hole concentrations and temperature were studied by solving the semiclassical Boltzmann transport equations in conjunction with ab initio electronic structure calculations, within Density Functional Theory. Based on maximally localized Wannier function basis set and the ab initio band energies, results for the Seebeck coefficient are presented and compared with available experimental data for n-type as well as p-type systems. Also, theoretical results for electric conductivity and power factor are presented. Most cases showed good agreement between the calculated properties and experimental data for w-InN unintentionally and p-type doped with magnesium. Our predictions for temperature and concentration dependences of electrical conductivity and power factor revealed a promising use of InN for intermediate and high temperature thermoelectric applications. The rigid band approach and constant scattering time approximation were utilized in the calculations.

  11. An Ab Initio Based Potential Energy Surface for Water

    NASA Technical Reports Server (NTRS)

    Partridge, Harry; Schwenke, David W.; Langhoff, Stephen R. (Technical Monitor)

    1996-01-01

    We report a new determination of the water potential energy surface. A high quality ab initio potential energy surface (PES) and dipole moment function of water have been computed. This PES is empirically adjusted to improve the agreement between the computed line positions and those from the HITRAN 92 data base. The adjustment is small, nonetheless including an estimate of core (oxygen 1s) electron correlation greatly improves the agreement with experiment. Of the 27,245 assigned transitions in the HITRAN 92 data base for H2(O-16), the overall root mean square (rms) deviation between the computed and observed line positions is 0.125/cm. However the deviations do not correspond to a normal distribution: 69% of the lines have errors less than 0.05/cm. Overall, the agreement between the line intensities computed in the present work and those contained in the data base is quite good, however there are a significant number of line strengths which differ greatly.

  12. Ab initio calculations of vacancy interactions with solute atoms in bcc Fe

    NASA Astrophysics Data System (ADS)

    Vincent, E.; Becquart, C. S.; Domain, C.

    2005-01-01

    Solute Cu plays a major role in the embrittlement of reactor pressure vessel (RPV) steels under radiation. In RPV steels and dilute FeCu alloys, the tomographic atom probe has revealed the formation of Cu atmospheres under neutron flux. More recently the role of other solutes such as Ni, Mn and Si which are also within the atmospheres has been put forward. It is thus very important to characterise the interactions of these solutes with radiation-induced point defects in order to understand the elementary mechanisms behind the formation of these atmospheres. We have investigated by ab initio calculations based on the density functional theory the interactions of point defects in dilute FeX alloys (X = Cu, Mn, Ni or Si). The structure of X-vacancy complexes has been determined, as well as their binding energies. Their relative stability is discussed and compared to experimental results obtained with model alloys.

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

    NASA Astrophysics Data System (ADS)

    You, Y.; Yan, M. F.

    2013-05-01

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

  14. Assessing the elastic properties and ductility of Fe-Cr-Al alloys from ab initio calculations

    NASA Astrophysics Data System (ADS)

    Nurmi, E.; Wang, G.; Kokko, K.; Vitos, L.

    2016-01-01

    Fe-Al is one of the best corrosion resistant alloys at high temperatures. The flip side of Al addition to Fe is the deterioration of the mechanical properties. This problem can be solved by adding a suitable amount of third alloying component. In the present work, we use ab initio calculations based on density functional theory to study the elastic properties of Fe?Cr?Al? alloys for Al and Cr contents up to 20 at.%. We assess the ductility as a function of chemistry by making use of the semi-empirical correlations between the elastic parameters and mechanical properties. In particular, we derive the bulk modulus to shear modulus ratio and the Cauchy pressure and monitor their trends in terms of chemical composition. The present findings are contrasted with the previously established oxidation resistance of Fe-Cr-Al alloys.

  15. A comparative ab initio and DFT study of polyaniline leucoemeraldine base and its oligomers.

    PubMed

    Mishra, Abhishek Kumar; Tandon, Poonam

    2009-11-01

    Ab initio Hartree-Fock (HF) and density functional theory (DFT) calculations are being performed to investigate the geometric, vibrational, and electronic properties of the polyaniline leucoemeraldine base (PANI-LB). Vibrational spectra of PANI-LB have been analyzed using the DFT oligomer approach, and complete assignments are being reported. Lower region spectral assignments of the PANI-LB which were not being reported earlier are being done in the present work. DFT calculations with the 6-31G** basis set produce very good results of not only vibrational modes but also of energy band gap. PMID:19827802

  16. Ab initio based force field and molecular dynamics simulations of crystalline TATB.

    PubMed

    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

  17. Reductive half-reaction of aldehyde oxidoreductase toward acetaldehyde: Ab initio and free energy quantum mechanical/molecular mechanical calculations

    NASA Astrophysics Data System (ADS)

    Dieterich, Johannes M.; Werner, Hans-Joachim; Mata, Ricardo A.; Metz, Sebastian; Thiel, Walter

    2010-01-01

    Energy and free energy barriers for acetaldehyde conversion in aldehyde oxidoreductase are determined for three reaction pathways using quantum mechanical/molecular mechanical (QM/MM) calculations on the solvated enzyme. Ab initio single-point QM/MM energies are obtained at the stationary points optimized at the DFT(B3LYP)/MM level. These ab initio calculations employ local correlation treatments [LMP2 and LCCSD(T0)] in combination with augmented triple- and quadruple-zeta basis sets, and the final coupled cluster results include MP2-based corrections for basis set incompleteness and for the domain approximation. Free energy perturbation (FEP) theory is used to generate free energy profiles at the DFT(B3LYP)/MM level for the most important reaction steps by sampling along the corresponding reaction paths using molecular dynamics. The ab initio and FEP QM/MM results are combined to derive improved estimates of the free energy barriers, which differ from the corresponding DFT(B3LYP)/MM energy barriers by about 3 kcal mol-1. The present results confirm the qualitative mechanistic conclusions from a previous DFT(B3LYP)/MM study. Most favorable is a three-step Lewis base catalyzed mechanism with an initial proton transfer from the cofactor to the Glu869 residue, a subsequent nucleophilic attack that yields a tetrahedral intermediate (IM2), and a final rate-limiting hydride transfer. The competing metal center activated pathway has the same final step but needs to overcome a higher barrier in the initial step on the route to IM2. The concerted mechanism has the highest free energy barrier and can be ruled out. While confirming the qualitative mechanistic scenario proposed previously on the basis of DFT(B3LYP)/MM energy profiles, the present ab initio and FEP QM/MM calculations provide corrections to the barriers that are important when aiming at high accuracy.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    SciTech Connect

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

    2011-11-15

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  3. Ab Initio Many-Body Calculations Of Nucleon-Nucleus Scattering

    SciTech Connect

    Quaglioni, S; Navratil, P

    2008-12-17

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

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

    SciTech Connect

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

    2004-11-30

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

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

    PubMed

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

    2013-01-01

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

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

    PubMed Central

    2013-01-01

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

  7. Electron transport in extended carbon-nanotube/metal contacts: Ab initio based Green function method

    NASA Astrophysics Data System (ADS)

    Fediai, Artem; Ryndyk, Dmitry A.; Cuniberti, Gianaurelio

    2015-04-01

    We have developed a new method that is able to predict the electrical properties of the source and drain contacts in realistic carbon nanotube field effect transistors (CNTFETs). It is based on large-scale ab initio calculations combined with a Green function approach. For the first time, both internal and external parts of a realistic CNT-metal contact are taken into account at the ab initio level. We have developed the procedure allowing direct calculation of the self-energy for an extended contact. Within the method, it is possible to calculate the transmission coefficient through a contact of both finite and infinite length; the local density of states can be determined in both free and embedded CNT segments. We found perfect agreement with the experimental data for Pd and Al contacts. We have explained why CNTFETs with Pd electrodes are p -type FETs with ohmic contacts, which can carry current close to the ballistic limit (provided contact length is large enough), whereas in CNT-Al contacts transmission is suppressed to a significant extent, especially for holes.

  8. Infrared and Raman spectra, conformational analysis, ab initio calculations and vibrational assignment of 2-chloroethylsilyl chloride

    NASA Astrophysics Data System (ADS)

    Pan, Chunhua; Guirgis, Gamil A.; Durig, James R.

    2005-05-01

    The infrared (3100-40 cm -1) spectra of gaseous and solid and Raman (3200-20 cm -1) spectra of liquid 2-chloroethylsilyl chloride, ClCH 2CH 2SiH 2Cl, have been recorded. There are five possible stable conformers, Gg, Tg, Gt, Tt and Gg' for this molecule where the capital letter G ( gauche) or T ( trans) refer to rotation around the C-C bond and the lower case letters to rotation around the Si-C bond. Most ab initio calculations at the MP2(full) level predicted the order of the stability as Tg>Gg>Gt>Tt>Gg' whereas all density function theory calculations with the B3LYP method predicted the stability as Tg>Tt>Gg>Gt>Gg'. The four more stable conformers have been identified in the fluid phases with the Tg rotamer the only form remaining in the solid. Variable temperature (-105 to -150 °C) studies of the infrared spectra of the samples dissolved in liquid krypton have been recorded and the enthalpy differences determined to be: 50±20 (0.59±0.24 kJ/mol), 172±17 (2.06±0.20 kJ/mol) and 290±40 cm -1 (3.45±0.48 kJ/mol) for the Tg/Gg, Tg/Gt and Tg/Tt conformer pairs with the Tg conformer the most stable form. It is estimated that there is 42±2% of the Tg form, 33±1% of the Gg form, 20±2% of the Gt form, and 5±1% of the Tt form present at ambient temperature. A relatively complete vibrational assignment is proposed for the Tg conformer and many of the fundamentals have been identified for the other three (Gg, Gt and Tt) conformers based on the ab initio MP2(full)/6-31G(d) predicted frequencies, the relative infrared and Raman spectral intensities, and infrared band contours which are supported by normal coordinate calculations. Since the predicted energies between Tg and Gg' conformers from all calculations are very large, it is not surprising that no evidence in either the infrared or Raman spectra could be found for the Gg' conformer. The geometrical parameters, harmonic force constants, vibrational frequencies, infrared intensities, Raman activities

  9. Ab initio calculations of the photoionization of diatomic molecules

    NASA Astrophysics Data System (ADS)

    Lefebvre-Brion, Helene; Raşeev, Georges

    2003-01-01

    A review is presented of the calculation of photoionization spectra, particularly in the spectral range where electron autoionization of diatomic molecules takes place. In addition to some interesting results obtained over years that compare favourably with experiment, the emphasis here is put on the relation between the methods developed for the calculation of observables associated with the continuum energy spectrum of the electrons and the Alchemy system of programs. This system of programs serves as a basis for initial and intermediate calculations. The examples presented show that diatomic molecules not only in gas phase but also oriented in space or physisorbed at surfaces may be studied readily.

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

    NASA Astrophysics Data System (ADS)

    Bussery-Honvault, Béatrice; Hartmann, Jean-Michel

    2014-02-01

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

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

    PubMed

    Bussery-Honvault, Béatrice; Hartmann, Jean-Michel

    2014-02-01

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

  12. Dissipative Particle Dynamics interaction parameters from ab initio calculations

    NASA Astrophysics Data System (ADS)

    Sepehr, Fatemeh; Paddison, Stephen J.

    2016-02-01

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

  13. Towards microscopic ab initio calculations of astrophysical S-factors

    NASA Astrophysics Data System (ADS)

    Neff, Thomas; Feldmeier, Hans; Langanke, Karlheinz

    2011-04-01

    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(α,γ)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(α, γ)7Be the S-factor agrees very well, both in absolute normalization and energy dependence, with the recent experimental data from the Weizmann, LUNA, Seattle and ERNA experiments. For the 3H(α, γ)7Li reaction the calculated S-factor is about 15% above the data.

  14. Local Current Density Calculations for Molecular Films from Ab Initio.

    PubMed

    Walz, Michael; Bagrets, Alexei; Evers, Ferdinand

    2015-11-10

    We present a formalism relying on density functional theory for the calculation of the spatially continuous electron current density j(r) and induced magnetic fields B(r) in molecular films in dc transport. The proposed method treats electron transport in graphene ribbons containing on the of order 10(3) atoms. The employed computational techniques scale efficiently when using several thousand CPUs. An application to transport through hydrogenated graphene will be presented. As we will show, the adatoms have an impact on the transmission function not only because they introduce additional states but also because their presence modifies the geometry of the carbon host lattice (lattice relaxation). PMID:26574313

  15. Ab initio density-functional calculations in materials science: from quasicrystals over microporous catalysts to spintronics.

    PubMed

    Hafner, Jürgen

    2010-09-29

    During the last 20 years computer simulations based on a quantum-mechanical description of the interactions between electrons and atomic nuclei have developed an increasingly important impact on materials science, not only in promoting a deeper understanding of the fundamental physical phenomena, but also enabling the computer-assisted design of materials for future technologies. The backbone of atomic-scale computational materials science is density-functional theory (DFT) which allows us to cast the intractable complexity of electron-electron interactions into the form of an effective single-particle equation determined by the exchange-correlation functional. Progress in DFT-based calculations of the properties of materials and of simulations of processes in materials depends on: (1) the development of improved exchange-correlation functionals and advanced post-DFT methods and their implementation in highly efficient computer codes, (2) the development of methods allowing us to bridge the gaps in the temperature, pressure, time and length scales between the ab initio calculations and real-world experiments and (3) the extension of the functionality of these codes, permitting us to treat additional properties and new processes. In this paper we discuss the current status of techniques for performing quantum-based simulations on materials and present some illustrative examples of applications to complex quasiperiodic alloys, cluster-support interactions in microporous acid catalysts and magnetic nanostructures. PMID:21386539

  16. Ab Initio Calculations on Spin Transitions in Perovskite

    NASA Astrophysics Data System (ADS)

    Brodholt, J. P.; Stackhouse, S.; Alfredsson, M.; Price, G. D.

    2006-05-01

    Spin transitions in perovskite and magnesiowustite have become the subject of considerable interest since they have been experimentally observed to occur under mantle conditions. Experimental results, however, are not always mutually consitent and a variety of transition pressures have been observed. We have, therefore, performed GGA, LDA, and hybrid-functional calculations on MgSiO3 perovskite containing 6%, 12% and 100% ferric and/or ferrous iron. Although the GGA and LDA calculations suffer from the well-know problem of predicting transition metal oxide insulators to be metallic, the hybrid-functionals do not do this. By using both methods we hope to increase confidence in the results. In agreement with previous work on Al3+ and Fe3+ bearing perovskites (Li et al, 2004) we find a wide range of transition pressures, which are related to the mechanism of iron incorporation. Compositions with just Fe2+ generally have the highest transition pressures, while compositions with just Fe3+ have the lowest. Using these results we are able to explain the spin transitions observed by different experimental groups. The spin state of iron has a small effect on the density, bulk and shear modulus of perovskite, but at the low concentrations expected in the mantle this is unlikely to be seismically visible.

  17. New Approach for Investigating Reaction Dynamics and Rates with Ab Initio Calculations.

    PubMed

    Fleming, Kelly L; Tiwary, Pratyush; Pfaendtner, Jim

    2016-01-21

    Herein, we demonstrate a convenient approach to systematically investigate chemical reaction dynamics using the metadynamics (MetaD) family of enhanced sampling methods. Using a symmetric SN2 reaction as a model system, we applied infrequent metadynamics, a theoretical framework based on acceleration factors, to quantitatively estimate the rate of reaction from biased and unbiased simulations. A systematic study of the algorithm and its application to chemical reactions was performed by sampling over 5000 independent reaction events. Additionally, we quantitatively reweighed exhaustive free-energy calculations to obtain the reaction potential-energy surface and showed that infrequent metadynamics works to effectively determine Arrhenius-like activation energies. Exact agreement with unbiased high-temperature kinetics is also shown. The feasibility of using the approach on actual ab initio molecular dynamics calculations is then presented by using Car-Parrinello MD+MetaD to sample the same reaction using only 10-20 calculations of the rare event. Owing to the ease of use and comparatively low-cost of computation, the approach has extensive potential applications for catalysis, combustion, pyrolysis, and enzymology. PMID:26690335

  18. Ab Initio Calculations Of Nuclear Reactions And Exotic Nuclei

    SciTech Connect

    Quaglioni, S.

    2014-05-05

    Our ultimate goal is to develop a fundamental theory and efficient computational tools to describe dynamic processes between nuclei and to use such tools toward supporting several DOE milestones by: 1) performing predictive calculations of difficult-to-measure landmark reactions for nuclear astrophysics, such as those driving the neutrino signature of our sun; 2) improving our understanding of the structure of nuclei near the neutron drip line, which will be the focus of the DOE’s Facility for Rare Isotope Beams (FRIB) being constructed at Michigan State University; but also 3) helping to reveal the true nature of the nuclear force. Furthermore, these theoretical developments will support plasma diagnostic efforts at facilities dedicated to the development of terrestrial fusion energy.

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

    PubMed

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

    2016-12-01

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

  20. Ab initio calculation of the thermal conductivity of indium antimonide

    NASA Astrophysics Data System (ADS)

    Miranda, Alonso L.; Xu, Bin; Hellman, Olle; Romero, Aldo H.; Verstraete, Matthieu J.

    2014-12-01

    A theoretical study based on the density functional theory and the temperature-dependent effective potential method is performed to analyze the changes in the phonon band structure as a function of temperature for indium antimonide. In particular, we show changes in the thermal expansion coefficient and the thermal resistivity that agree rather well with experimental measurements. From the theoretical side, we show a weak dependence with respect to the chosen thermostat used to obtain the inter-atomic force constants, which strengthens our conclusions.

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

    NASA Astrophysics Data System (ADS)

    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.

  2. Ab-Initio Calculations of Electronic Properties and Quantum Transport in U-Shaped Graphene Nanoribbons

    NASA Astrophysics Data System (ADS)

    Cuong, Nguyen Tien; Mizuta, Hiroshi; Cong, Bach Thanh; Otsuka, Nobuo; Chi, Dam Hieu

    2012-09-01

    Graphene is a promising candidate as a material used in nano-scale devices because of recent developments in advanced experimental techniques. Motivated by recent successful fabrications of U-shaped graphene channel transistors by using the gallium focused ion beam technology, we have performed ab-initio calculations to investigate the electronic properties and quantum transport in U-shaped graphene nanoribbons. The electronic properties are calculated using a numerical atomic orbital basis set in the framework of the density functional theory. The transport properties are investigated using the non-equilibrium Green's function method. The transmission spectra of U-shaped graphenes are analyzed in order to reveal the quantum transport of the systems. We found that the graphene nanoribbons tend to open a band gap when U-shaped structures are formed in both armchair and zigzag cases. The geometrical structures of U-shaped GNRs had enormous influences on the electron transport around the Fermi energy due to the formation of quasi-bound states at zigzag edges. The obtained results have provided valuable information for designing potential nano-scale devices based on graphenes.

  3. Band offset of the ZnO/Cu2O heterojunction from ab initio calculations

    NASA Astrophysics Data System (ADS)

    Zemzemi, M.; Alaya, S.

    2013-12-01

    The ZnO/Cu2O system has known a recent revival of interest in solar cells for its potential use as a heterojunction able to highly perform under visible light. In this work, we are interested on the characterization of the interface through nanoscale modelization based on ab initio (Density Functional Theory (DFT), Local Density Approximation (LDA), Generalized Gradient Approximation (GGA-PBE), and Pseudopotential (PP)). This work aims to build a supercell containing a heterojunction ZnO/Cu2O and study the structural properties and the discontinuity of the valence band (band offset) from a semiconductor to another. We built a zinc oxide in the wurtzite structure along the [0 0 0 1] on which we placed the copper oxide in the hexagonal structure (CdI2-type). We choose the method of Van de Walle and Martin to calculate the energy offset. This approach fits well with the DFT. Our calculations of the band offset gave us a value that corresponds to other experimental and theoretical values.

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

    SciTech Connect

    Chen Shilu; Fang Weihai

    2009-08-07

    In the present paper we report a theoretical study on mechanistic photodissociation of acetaldehyde (CH{sub 3}CHO). Stationary structures for H{sub 2} and CO eliminations in the ground state (S{sub 0}) have been optimized with density functional theory method, which is followed by the intrinsic reaction coordinate and ab initio molecular dynamics calculations to confirm the elimination mechanism. Equilibrium geometries, transition states, and intersection structures for the C-C and C-H dissociations in excited states were determined by the complete-active-space self-consistent field (CASSCF) method. Based on the CASSCF optimized structures, the potential energy profiles for the dissociations were refined by performing the single-point calculations using the multireference configuration interaction method. Upon the low-energy irradiation of CH{sub 3}CHO (265 nm<{lambda}<318 nm), the T{sub 1} C-C bond fission following intersystem crossing from the S{sub 1} state is the predominant channel and the minor channel, the ground-state elimination to CH{sub 4}+CO after internal conversion (IC) from S{sub 1} to S{sub 0}, could not be excluded. With the photon energy increasing, another pathway of IC, achieved via an S{sub 1}/S{sub 0} intersection point resulting from the S{sub 1} C-C bond fission, becomes accessible and increases the yield of CH{sub 4}+CO.

  5. Cluster form factor calculation in the ab initio no-core shell model

    SciTech Connect

    Navratil, Petr

    2004-11-01

    We derive expressions for cluster overlap integrals or channel cluster form factors for ab initio no-core shell model (NCSM) wave functions. These are used to obtain the spectroscopic factors and can serve as a starting point for the description of low-energy nuclear reactions. We consider the composite system and the target nucleus to be described in the Slater determinant (SD) harmonic oscillator (HO) basis while the projectile eigenstate to be expanded in the Jacobi coordinate HO basis. This is the most practical case. The spurious center of mass components present in the SD bases are removed exactly. The calculated cluster overlap integrals are translationally invariant. As an illustration, we present results of cluster form factor calculations for <{sup 5}He vertical bar{sup 4}He+n>, <{sup 5}He vertical bar{sup 3}H+d>, <{sup 6}Li vertical bar{sup 4}He+d>, <{sup 6}Be vertical bar{sup 3}He+{sup 3}He>, <{sup 7}Li vertical bar{sup 4}He+{sup 3}H>, <{sup 7}Li vertical bar{sup 6}Li+n>, <{sup 8}Be vertical bar{sup 6}Li+d>, <{sup 8}Be vertical bar{sup 7}Li+p>, <{sup 9}Li vertical bar{sup 8}Li+n>, and <{sup 13}C vertical bar{sup 12}C+n>, with all the nuclei described by multi-({Dirac_h}/2{pi}){omega} NCSM wave functions.

  6. Rate constant calculations of the GeH4 + OH/OD → GeH3 + H2O/HOD reactions using an ab initio based full-dimensional potential energy surface.

    PubMed

    Espinosa-Garcia, J; Rangel, C; Corchado, J C

    2016-06-22

    We report an analytical full-dimensional potential energy surface for the GeH4 + OH → GeH3 + H2O reaction based on ab initio calculations. It is a practically barrierless reaction with very high exothermicity and the presence of intermediate complexes in the entrance and exit channels, reproducing the experimental evidence. Using this surface, thermal rate constants for the GeH4 + OH/OD isotopic reactions were calculated using two approaches: variational transition state theory (VTST) and quasi-classical trajectory (QCT) calculations, in the temperature range 200-1000 K, and results were compared with the only experimental data at 298 K. Both methods showed similar values over the whole temperature range, with differences less than 30%; and the experimental data was reproduced at 298 K, with negative temperature dependence below 300 K, which is associated with the presence of an intermediate complex in the entrance channel. However, while the QCT approach reproduced the experimental kinetic isotope effect, the VTST approach underestimated it. We suggest that this difference is associated with the harmonic approximation used in the treatment of vibrational frequencies. PMID:27292879

  7. Synthesis, spectroscopy, electrochemistry and thermogravimetry of copper(II) tridentate Schiff base complexes, theoretical study of the structures of compounds and kinetic study of the tautomerism reactions by ab initio calculations

    NASA Astrophysics Data System (ADS)

    Kianfar, Ali Hossein; Ramazani, Shapour; Fath, Roghaye Hashemi; Roushani, Mahmoud

    2013-03-01

    Attempts to spectroscopic and structural study of copper complexes, some Cu(II) Schiff base complexes were synthesized and characterized by means of electronic, IR, 1HNMR spectra and elemental analysis. The thermal analyses of the complexes were investigated and the first order kinetic parameters were derived for them. The cyclic voltammetric studies in acetonitrile were proposed a monomeric structure for complexes. The structures of compounds were determined by ab initio calculations. In the solid state, the ligands exist as keto-amine/enol-imine tautomeric forms with an intramolecular hydrogen bond (Nsbnd H⋯O) between amine and carbonyl group. The kinetic studies of the tautomerism and equilibrium constant of the reactions were calculated using transition state theory. The optimized molecular geometry and atomic charges were calculated using MP2 method with 6-31G(d) basis set for H, C, N and O atoms and LANL2DZ for the Cu atom. The results suggested that, in the complexes, Cu(II) ion is in pseudo square-planar NO3 coordination geometry. Also the bond lengths and angles were studied and compared.

  8. Large scale ab initio calculations of extended defects in materials: screw dislocations in bcc metals

    NASA Astrophysics Data System (ADS)

    Dézerald, Lucile; Ventelon, Lisa; Willaime, François; Clouet, Emmanuel; Rodney, David

    2014-06-01

    Ab initio methods, based on the Density Functional Theory (DFT), have been extensively used to study point defects and defect clusters in materials. Present HPC resources and DFT codes now allow similar investigations to be performed on dislocations. The study of these extended defects requires not only larger simulation cells but also a higher accuracy because the energy differences, which are involved, are rather small, typically 50-to-100 meV for supercells containing 50-to-500 atoms. The topology of the Peierls potential of screw dislocations with 1/2 <111>Burgers vector, i.e. the 2D energy landscape seen by these dislocations, is being completely revisited by DFT calculations. From results obtained in all body-centered cubic (bcc) transition metals, except Cr (V, Nb, Ta, Mo, W and Fe), using the PWSCF code, which is part of the Quantum-Espresso package, we concluded that the 2D Peierls potentials have two common features: the single-hump shape of the barrier between two minima of the potential, and the presence of a maximum - and not a minimum as predicted by most empirical potentials - around the split core. In iron, the topology of the Peierls potential is reversed compared to the classical sinusoidal picture: the location of the saddle point and the maximum are indeed inverted with unexpected flat regions. The first results obtained within the framework of the PRACE project, DIMAIM (DIslocations in Metals using Ab Initio Methods), started at the beginning of 2013, will also be presented. In particular, in order to address the twinning-antitwinning asymmetry often observed in bcc metals and regarded as the major contribution to the breakdown of Schmid's law, we have determined the crystal orientation dependence of the Peierls stress, i.e. the critical stress required for dislocation motion. These computationally most expensive simulations were performed on the PRACE Tier-0 system at Barcelona Supercomputing Center (Marenostrum III). The scalability results

  9. Ab initio R-matrix calculations of e+-molecule scattering

    NASA Technical Reports Server (NTRS)

    Danby, Grahame; Tennyson, Jonathan

    1990-01-01

    The adaptation of the molecular R-matrix method, originally developed for electron-molecule collision studies, to positron scattering is discussed. Ab initio R-matrix calculations are presented for collisions of low energy positrons with a number of diatomic systems including H2, HF and N2. Differential elastic cross sections for positron-H2 show a minimum at about 45 deg for collision energies between 0.3 and 0.5 Ryd. The calculations predict a bound state of positronHF. Calculations on inelastic processes in N2 and O2 are also discussed.

  10. Ab initio calculations of the vibrational and dielectric properties of PbSnTe alloys

    NASA Astrophysics Data System (ADS)

    Scolfaro, Luisa; Rezende Neto, A. R.; Leite Alves, H. W.; Petersen, J. E.; Myers, T. H.; Borges, P. D.

    Thermoelectric devices have promise in dealing with the challenges of the growing demand for alternative clean energy and Te-based materials well-known candidates for them. Recently, we have shown that the high values for the dielectric constant, together with anharmonic LA-TO coupling, reduces the lattice thermal conductivity and enhances the electronic conductivity in PbTe. Also, it was shown that by alloying this material with Se, the electronic conductivity of the alloys is also enhanced. But, it is not clear if the same occurs when alloying with Sn. We show, in this work, our ab initio results for the vibrational and dielectric properties of Pb1-xSnxTe alloys. The calculations were carried out by using the Density Functional Theory, and the alloys were described by both the Virtual Crystal Approximation and Cluster Expansion Method. Our results show that the anharmonic LA-TO coupling enhances and reach its maximum for Sn concentration values of 0.75, corresponding to the maximum value for the dielectric constant, which is higher than that obtained for PbTe

  11. Ab initio calculations of self-interstitial interaction and migration with solute atoms in bcc Fe

    NASA Astrophysics Data System (ADS)

    Vincent, E.; Becquart, C. S.; Domain, C.

    2006-12-01

    The embrittlement of pressure vessel steels under radiation has been long ago correlated with the presence of solute Cu. Indeed the atom probe and the small angle neutron scattering, principally, have revealed the formation of Cu clusters under neutron flux in reactor pressure vessel (RPV) steels and dilute FeCu alloys. Other solutes such as Ni, Mn and Si which are also found within the clusters, are now suspected to contribute to the embrittlement. The interactions of these solutes with radiation induced point defects need thus to be characterized properly in order to understand the elementary mechanisms behind the formation of these clusters. We have investigated by ab initio calculations based on the density functional theory the interactions of self-interstitials with solute atoms in dilute FeX alloys (X = Cu, Mn, Ni or Si). Different possible configurations of solute-dumbbell complexes have been studied. Their binding energies are discussed, as well as their relative stability. The migration of dumbbells with a solute atom in their vicinity was also investigated. All these results are compared to some experimental ones obtained on dilute FeX model alloys. Our results indicate that for Mn solute atoms, diffusion via an interstitial mechanism is very likely.

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

    PubMed

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

    2010-09-14

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

  13. Ab initio pseudopotential calculation for TTF-TCNQ and TSeF-TCNQ

    NASA Astrophysics Data System (ADS)

    Ishibashi, Shoji; Kohyama, Masanori

    2000-09-01

    We have investigated the electronic structure of the quasi-one-dimensional organic conductor TTF-TCNQ [at room temperature (RT) and 100 K] and TSeF-TCNQ (RT), which have isomorphic crystal structure, by an ab initio plane-wave pseudopotential band calculation. To express the exchange and correlation energy for electrons, we used both the local density approximation and generalized gradient approximation for comparison. For each case, electronic band dispersions were calculated along several symmetric lines and tight-binding parameters were evaluated. The Fermi surface shape was also obtained. The six sets of results (for three structures and two approximations) were compared systematically.

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

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

    PubMed

    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

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

    PubMed

    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

  17. Carbon dioxide hydrate phase equilibrium and cage occupancy calculations using ab initio intermolecular potentials.

    PubMed

    Velaga, Srinath C; Anderson, Brian J

    2014-01-16

    Gas hydrate deposits are receiving increased attention as potential locations for CO2 sequestration, with CO2 replacing the methane that is recovered as an energy source. In this scenario, it is very important to correctly characterize the cage occupancies of CO2 to correctly assess the sequestration potential as well as the methane recoverability. In order to predict accurate cage occupancies, the guest–host interaction potential must be represented properly. Earlier, these potential parameters were obtained by fitting to experimental equilibrium data and these fitted parameters do not match with those obtained by second virial coefficient or gas viscosity data. Ab initio quantum mechanical calculations provide an independent means to directly obtain accurate intermolecular potentials. A potential energy surface (PES) between H2O and CO2 was computed at the MP2/aug-cc-pVTZ level and corrected for basis set superposition error (BSSE), an error caused due to the lower basis set, by using the half counterpoise method. Intermolecular potentials were obtained by fitting Exponential-6 and Lennard-Jones 6-12 models to the ab initio PES, correcting for many-body interactions. We denoted this model as the “VAS” model. Reference parameters for structure I carbon dioxide hydrate were calculated using the VAS model (site–site ab initio intermolecular potentials) as Δμ(w)(0) = 1206 ± 2 J/mol and ΔH(w)(0) = 1260 ± 12 J/mol. With these reference parameters and the VAS model, pure CO2 hydrate equilibrium pressure was predicted with an average absolute deviation of less than 3.2% from the experimental data. Predictions of the small cage occupancy ranged from 32 to 51%, and the large cage is more than 98% occupied. The intermolecular potentials were also tested by calculating the pure CO2 density and diffusion of CO2 in water using molecular dynamics simulations. PMID:24328234

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

    SciTech Connect

    Vary, J. P.; Maris, P.; Honkanen, H.; Li, J.; Shirokov, A. M.; Brodsky, S. J.; Harindranath, A.

    2009-12-17

    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.

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

    SciTech Connect

    Vary, J.P.; Maris, P.; Shirokov, A.M.; Honkanen, H.; li, J.; Brodsky, S.J.; Harindranath, A.; 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. Ab initio calculations of the electronic structure of silicon nanocrystals doped with shallow donors (Li, P)

    SciTech Connect

    Kurova, N. V. Burdov, V. A.

    2013-12-15

    The results of ab initio calculations of the electronic structure of Si nanocrystals doped with shallow donors (Li, P) are reported. It is shown that phosphorus introduces much more significant distortions into the electronic structure of the nanocrystal than lithium, which is due to the stronger central cell potential of the phosphorus ion. It is found that the Li-induced splitting of the ground state in the conduction band of the nanocrystal into the singlet, doublet, and triplet retains its inverse structure typical for bulk silicon.

  1. Peculiarities of geminal atom interaction in chloro-containing imidazoles using ab initio calculations

    NASA Astrophysics Data System (ADS)

    Feshin, V. P.; Feshina, E. V.

    2000-07-01

    The results of ab initio calculations at the RHF/6-31G ∗ level of 1-methyl-4-chloro- and -5-chloroimidazoles as well as of 1-methyl-4,5-dichloroimidazoles with total optimization of their geometry were presented. They were used for the interpretation of peculiarities of an influence of the "pyridine" and "pyrrole" N atoms on the electron distribution of the Cl atoms in these molecules and of their 35Cl NQR frequencies. These peculiarities are caused by the different space electron distribution of these N atoms that causes the different polarization of the geminal Cl atom p-electron shell.

  2. Ab Initio Calculations of Singlet and Triplet Excited States of Chlorine Nitrate and Nitric Acid

    NASA Technical Reports Server (NTRS)

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

    1994-01-01

    Ab initio calculations of vertical excitations to singlet and triplet excited states of chlorine nitrate and nitric acid are reported. The nature of the electronic transitions are examined by decomposing the difference density into the sum of detachment and attachment densities. Counterparts for the three lowest singlet excited states of nitric acid survive relatively unperturbed in chlorine nitrate, while other low-lying singlet states of chlorine nitrate appear to be directly dissociative in the ClO chromophore. These results suggest an assignment of the two main peaks in the experimental chlorine nitrate absorption spectrum. In addition, triplet vertical excitations and the lowest optimized triplet geometries of both molecules are studied.

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

    PubMed

    Shaughnessy, M C; Jones, R E

    2016-02-01

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

  4. Ab initio calculations of the equations of state for hydrogen, helium, and water and the relevance to the giant planets

    NASA Astrophysics Data System (ADS)

    French, Martin

    2010-11-01

    Since the interior structure of giant planets inside or outside our solar system cannot be probed directly by experiments, planetary models have been developed to gain further insight. Such models require accurate equations of state (EOS) for the major components (H, He, and heavier compounds like water) up to extreme thermodynamic conditions (pressures of several ten megabars and temperatures of more than ten thousand degrees Kelvin) [1]. Ab initio methods that combine finite temperature density functional theory (FT-DFT) for the electrons with classical molecular dynamics (MD) for the ions have proven to be a powerful tool to calculate such accurate EOS data. In addition, the FT-DFT-MD also generates structural information, transport and optical properties and, most important, information on phase diagrams and demixing regions. Based on our recently calculated ab initio data for H, He, and water, we derive interior models of Saturn and Jupiter and discuss the role of H-He demixing [2] and of the plasma phase transition in hydrogen on the planetary interiors. We also present new models for Uranus and Neptune which offer conditions to allow the formation of the exotic superionic phase of water [3]. The ab initio data can also be applied in planetary evolution scenarios and dynamo simulations of solar and extrasolar planets.[4pt] [1] J. J. Fortney, N. Nettelmann, Space Sci. Rev. 152, 423 (2010)[0pt] [2] W. Lorenzen, B. Holst, R. Redmer, Phys. Rev. Lett. 102, 115701 (2009)[0pt] [3] M. French, T. R. Mattsson, N. Nettelmann, R. Redmer, Phys. Rev. B 79, 054107 (2009)

  5. ParaDynamics: An Effective and Reliable Model for Ab Initio QM/MM Free Energy Calculations and Related Tasks

    PubMed Central

    Plotnikov, Nikolay; Kamerlin, Shina Caroline Lynn; Warshel, Arieh

    2011-01-01

    Recent years have seen tremendous effort in the development of approaches with which to obtain quantum mechanics/molecular mechanics (QM/MM) free energies for reactions in the condensed phase. Nevertheless, there remain significant challenges to address, particularly the high computational cost involved in performing proper configurational sampling and in particular in obtaining ab initio QM/MM (QM(ai)/MM) free energy surfaces. One increasingly popular approach that seems to offer an ideal way to progress in this direction is the elegant metadynamics (MTD) approach. However, in the current work we point out the subtle efficiency problems associated with this approach, and illustrate that we have at hand what is arguably a more powerful approach. More specifically, we demonstrate the effectiveness of an updated version of our original idea of using a classical reference potential for QM(ai)/MM calculations [J. Phys. Chem. B. 102 (1998), 2293)], which we refer to as “paradynamics” (PD). This approach is based on the use of an empirical valence bond (EVB) reference potential, which is already similar to the real ab initio potential. The reference potential is fitted to the ab initio potential by an iterative and, to a great degree, automated refinement procedure. The corresponding free energy profile is then constructed using the refined EVB potential, and the linear response approximation (LRA) is used to evaluate the QM(ai)/MM activation free energy barrier. The automated refinement of the EVB surface (and thus the reduction of the difference between the reference and ab initio potentials) is a key factor in accelerating the convergence of the LRA approach. We apply our PD approach to a test reaction, namely the SN2 reaction between chloride ion and methyl chloride, and demonstrate that, at present, this approach is far more powerful and cost effective than the metadynamics approach (at least in its current implementation). We also discuss the general features

  6. Fully ab initio finite-size corrections for charged-defect supercell calculations.

    PubMed

    Freysoldt, Christoph; Neugebauer, Jörg; Van de Walle, Chris G

    2009-01-01

    In ab initio theory, defects are routinely modeled by supercells with periodic boundary conditions. Unfortunately, the supercell approximation introduces artificial interactions between charged defects. Despite numerous attempts, a general scheme to correct for these is not yet available. We propose a new and computationally efficient method that overcomes limitations of previous schemes and is based on a rigorous analysis of electrostatics in dielectric media. Its reliability and rapid convergence with respect to cell size is demonstrated for charged vacancies in diamond and GaAs. PMID:19257218

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

    NASA Astrophysics Data System (ADS)

    Sano, Haruyuki; Mizutani, Goro

    2015-11-01

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

  8. Ab initio calculation of oxygen self-diffusion coefficient in uranium dioxide UO2

    NASA Astrophysics Data System (ADS)

    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).

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

    SciTech Connect

    Sano, Haruyuki; Mizutani, Goro

    2015-11-15

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

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

    NASA Astrophysics Data System (ADS)

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

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

  11. Synthesis, crystal structure and ab initio/DFT calculations of a derivative of dithiophosphonates

    NASA Astrophysics Data System (ADS)

    Karakus, M.; Solak, S.; Hökelek, T.; Dal, H.; Bayrakdar, A.; Özdemir Kart, S.; Karabacak, M.; Kart, H. H.

    2014-03-01

    The compound 2 has been synthesized from the reaction of 2,4-Bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulfide and (R)-1-[3,5-Bis(trifloromethyl)phenyl]ethanol in toluene. The obtained crude dithiophosphonic acid 1 has been treated with the excess of N(C2H5)3 to give rise to 2, [(+HN(C2H5)3][(O-CH3CH-C6H3(CF3)2)(CH3OC6H4)PS2-]. The compound 2 has been characterized by using the spectroscopic methods such as IR, 1H, 13C, 31P NMR and structural analysing method such as X-ray crystallography. It crystallizes in the orthorhombic system, whose space group is P212121. It consists of a dithiophosphonate bridged methoxyphenyl and bis(triflorophenylethyl) groups and a triethylammonium moiety linked by Nsbnd H⋯S and Csbnd H⋯F hydrogen bonds. In the crystal structure, the C17H14F6O2PS2 molecule is elongated along the b-axis and stacked along the a-axis. The triethylammonium, N(CH2CH3)3, molecule fill in the cavities between the C17H14F6O2PS2 molecule. Moreover, ab initio methods based on Hartree-Fock (HF) and Density Functional Theory (DFT) calculations with the basis set of 6-31G(d) are also carried out to determine the molecular structural properties and to calculate FT-IR and NMR spectrum of the compound 2. The experimental results and theoretical calculations have been compared, and they are found to be in good agreement.

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

    SciTech Connect

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

    2015-05-15

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

  13. Hydrogen Bonds in Crystalline Imidazoles Studied by 15N NMR and ab initio MO Calculations

    NASA Astrophysics Data System (ADS)

    Ueda, Takahiro; Nagatomo, Shigenori; Masui, Hirotsugu; Nakamura, Nobuo; Hayashi, Shigenobu

    1999-07-01

    Intermolecular hydrogen bonds of the type N-H...N in crystals of imidazole and its 4-substituted and 4,5-disubstituted derivatives were studied by 15N CP/MAS NMR and an ab initio molecular orbital (MO) calculation. In the 15N CP/MAS NMR spectrum of each of the imidazole derivatives, two peaks due to the two different functional groups, >NH and =N-, were observed. The value of the 15N isotropic chemical shift for each nitrogen atom depends on both the length of the intermolecular hydrogen bond and the kind of the substituent or substituents. It was found that the difference between the experimen-tal chemical shifts of >NH and =N-varies predominantly with the hydrogen bond length but does not show any systematic dependence on the kind of substituent. The ab initio MO calculations suggest that the hydrogen bond formation influences the 15N isotropic chemical shift predominantly, and that the difference between the 15N isotropic chemical shift of >NH and =N-varies linearly with the hydrogen bond length.

  14. Dynamics and Structure of Point Defects in Forsterite: ab initio calculations

    NASA Astrophysics Data System (ADS)

    Churakov, S.; Khisina, N.; Urusov, V.; Wirth, R.

    2001-12-01

    OH-bearing fluid inclusions in Fo92 forsterite samples from peridotite nodule 9206 (Udachnaja kimberlite pipe)[1] were documented recently based on TEM and IR studies. The Fourier transform of diffraction pattern from the inclusions exhibited a pattern, which is interpreted as ordered planar (2H)xMg defects. In this study the structure and dynamics of protons associated with Mg(1), Mg(2) vacancies and interstitial polyhedrons ordered in a (100) plane corresponding to double unite cell periodicity of the forsterite lattice has been investigated by ab initio quantum mechanic calculations. Static structure optimizations and ab-initio molecular dynamics (MD) simulations have been performed using the CPMD density functional code[2]. The calculations were accomplished with the BLYP-functional utilizing the generalized gradient approximation. Non-local Goedecker-type pseudopotentials[3] have been applied to account for core electrons. Valence electron orbitals were approximated by plane wave expansion up to 70 Ry energy cutoff. The energy of static structures was sampled on 2x2x2 Monkhorst-Pack mesh[4]. During the structure relaxation parameters of an orthorhombic 2x1x2 supercell contaning 116 atoms corresponding to Mg28Si16O64H8 hydrous olivine was fixed at experimental values of a=9.524Å b=10.225Å and c=11.988Å relative to the Pbnm space group. Series of NVT-MD calculations were performed at 1000 K on 2x1x1 supercell with 58 atoms using four chain Nose thermostat. Randomly disturbed optimized structures were used as initial configuration for MD runs. The 1ps system equilibration is followed by trajectory production over 5 ps interval. A point energy sampling was applied in all MD calculations. A series of geometry optimizations, starting with various initial position of protons in Mg(1), Mg(2) and interstitial sites were carried out to obtain a structure with the lowest lattice energy. It was found that structures with protons completely located within the M1

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  16. Equilibrium and Dynamics Properties of Poly(oxyethylene) Melts and Related Poly(alkylethers) from Simulations and Ab Initio Calculations

    NASA Technical Reports Server (NTRS)

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

    1994-01-01

    Molecular dynamics simulations of POE melts have been performed utilizing a potential force field parameterized to reproduce conformer energies and rotational energy barriers in dimethoxyethane as determined from ab initio electronic structure calculations. Chain conformations and dimensions of POE from the simulations were found to be in good agreement with predictions of a rotational isomeric state (RIS) model based upon the ab initio conformational. energies. The melt chains were found to be somewhat extended relative to chains at theta conditions. This effect will be discussed in light of neutron scattering experiments which indicate that POE chains are extended in the melt relative to theta solutions. The conformational characteristics of POE chains will also be compared with those of other poly (alkylethers), namely poly(oxymethylene), poly(oxytrimethylene) and poly(oxytetramethylene). Local conformational dynamics were found to be more rapid than in polymethylene. Calculated C-H vector correlation times were found to be in reasonable agreement with experimental values from C-13 NMR spin-lattice relaxation times. The influence of ionic salts on local conformations and dynamics will also be discussed.

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

    NASA Astrophysics Data System (ADS)

    Navratil, Petr; Quaglioni, Sofia; Roth, Robert

    2008-10-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  19. Probing the possibility of coexistence of martensite transition and half-metallicity in Ni and Co-based full-Heusler alloys: An ab initio calculation

    NASA Astrophysics Data System (ADS)

    Roy, Tufan; Pandey, Dhanshree; Chakrabarti, Aparna

    2016-05-01

    Using first-principles calculations based on density functional theory, we have studied the mechanical, electronic, and magnetic properties of Heusler alloys, namely, Ni2B C and Co2B C (B = Sc, Ti, V, Cr, and Mn as well as Y, Zr, Nb, Mo, and Tc; C = Ga and Sn). On the basis of electronic structure (density of states) and mechanical properties (tetragonal shear constant), as well as magnetic interactions (Heisenberg exchange coupling parameters), we probe the properties of these materials in detail. We calculate the formation energy of these alloys in the (face-centered) cubic austenite structure to probe the stability of all these materials. From the energetic point of view, we have studied the possibility of the electronically stable alloys having a tetragonal phase lower in energy compared to the respective cubic phase. A large number of the magnetic alloys is found to have the cubic phase as their ground state. On the other hand, for another class of alloys, the tetragonal phase has been found to have lower energy compared to the cubic phase. Further, we find that the values of tetragonal shear constant show a consistent trend: a high positive value for materials not prone to tetragonal transition and low or negative for others. In the literature, materials which have been seen to undergo the martensite transition are found to be metallic in nature. We probe here if there is any Heusler alloy which has a tendency to undergo a tetragonal transition and at the same time possesses a high spin polarization at the Fermi level. From our study, it is found that out of the four materials which exhibit a martensite phase as their ground state, three of these, namely, Ni2MnGa , Ni2MoGa , and Co2NbSn have a metallic nature; on the contrary, Co2MoGa exhibits a high spin polarization.

  20. Ab Initio Calculations of the Electronic Structures and Biological Functions of Protein Molecules

    NASA Astrophysics Data System (ADS)

    Zheng, Haoping

    The self-consistent cluster-embedding (SCCE) calculation method reduces the computational effort from M3 to about M1 (M is the number of atoms in the system) with precise calculations. Thus the ab initio, all-electron calculation of the electronic structure and biological function of protein molecule has become a reality, which will promote new proteomics considerably. The calculated results of two real protein molecules, the trypsin inhibitor from the seeds of squash Cucurbita maxima (CMTI-I, 436 atoms) and the ascaris trypsin inhibitor (912 atoms, two three-dimensional structures), will be presented in this paper. The reactive sites of the inhibitors are determined and explained. The accuracy of structure determination of the inhibitors are tested theoretically.

  1. Ab Initio Calculations of the Electronic Structures and Biological Functions of Protein Molecules

    NASA Astrophysics Data System (ADS)

    Zheng, Haoping

    2003-04-01

    The self-consistent cluster-embedding (SCCE) calculation method reduces the computational effort from M3 to about M1 (M is the number of atoms in the system) with unchanged calculation precision. So the ab initio, all-electron calculation of the electronic structure and biological function of protein molecule becomes a reality, which will promote new proteomics considerably. The calculated results of two real protein molecules, the trypsin inhibitor from the seeds of squash Cucurbita maxima (CMTI-I, 436 atoms) and the Ascaris trypsin inhibitor (912 atoms, two three-dimensional structures), are presented. The reactive sites of the inhibitors are determined and explained. The precision of structure determination of inhibitors are tested theoretically.

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

    NASA Astrophysics Data System (ADS)

    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. ).

  3. Ab-initio calculations and phase diagram assessments of An-Al systems (An = U, Np, Pu)

    NASA Astrophysics Data System (ADS)

    Sedmidubský, D.; Konings, R. J. M.; Souček, P.

    2010-02-01

    The enthalpies of formation of binary intermetallic compounds AnAl n(n=2,3,4, An=U,Np,Pu) were assessed from first principle calculations of total energies performed using full potential APW + lo technique within density functional theory ( WIEN2k). The substantial contribution to entropies, S298°, arising from lattice vibrations was calculated by direct method within harmonic crystal approximation ( Phonon software + VASP for obtaining Hellmann-Feynman forces). The electronic heat capacity and the corresponding contribution to entropy were estimated from the density of states at Fermi level obtained from electronic structure calculations. The phase diagrams of the relevant systems An-Al were calculated based on the thermodynamic data assessed from ab-initio calculations, known equilibrium and calorimetry data by employing the FactSage program.

  4. Experimental measurement of the elastic constants of GdScO3 via resonant ultrasound spectroscopy utilizing ab initio calculations

    NASA Astrophysics Data System (ADS)

    Pestka, K. A.; Maynard, J. D.; Soukiassian, A.; Xi, X. X.; Schlom, D. G.; Le Page, Y.; Bernhagen, M.; Reiche, P.; Uecker, R.

    2008-03-01

    The complete elastic tensor of single crystal GdScO3 was determined using resonant ultrasound spectroscopy (RUS) in combination with ab initio calculations. The experimental determination of all nine elastic constants also provides a method for probing the dynamic lattice properties for this recently developed orthorhombic material. The experimentally determined elastic constants differed from theoretical values on average by 10%, and all but three of the nine elastic constants varied by less than 10%. These results indicate that ab initio calculations are now sufficiently accurate for the precise determination of the elastic tensor using RUS as the sole experimental source.

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

    NASA Astrophysics Data System (ADS)

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

    2004-03-01

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

  6. Transport coefficients of helium-argon mixture based on ab initio potential

    NASA Astrophysics Data System (ADS)

    Sharipov, Felix; Benites, Victor J.

    2015-10-01

    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.

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

    SciTech Connect

    Ejembi, J. I.; Nwigboji, I. H.; Franklin, L.; Malozovsky, Y.; Zhao, G. L.; Bagayoko, D.

    2014-09-14

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

  8. Ab initio calculation of the ion feature in x-ray Thomson scattering.

    PubMed

    Plagemann, Kai-Uwe; Rüter, Hannes R; Bornath, Thomas; Shihab, Mohammed; Desjarlais, Michael P; Fortmann, Carsten; Glenzer, Siegfried H; Redmer, Ronald

    2015-07-01

    The spectrum of x-ray Thomson scattering is proportional to the dynamic structure factor. An important contribution is the ion feature which describes elastic scattering of x rays off electrons. We apply an ab initio method for the calculation of the form factor of bound electrons, the slope of the screening cloud of free electrons, and the ion-ion structure factor in warm dense beryllium. With the presented method we can calculate the ion feature from first principles. These results will facilitate a better understanding of x-ray scattering in warm dense matter and an accurate measurement of ion temperatures which would allow determining nonequilibrium conditions, e.g., along shock propagation. PMID:26274290

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  10. Infrared spectra, photochemistry, and ab initio calculations of matrix isolated methanethiol/sulfur dioxide complex

    NASA Astrophysics Data System (ADS)

    Li, S.; Kurtz, H.; Korambath, P.; Li, Y.-S.

    2000-09-01

    Intermolecular complexes of methanethiol with sulfur dioxide have been prepared by condensing the reagents diluted in argon and in nitrogen at 12-14 K. The 1:1 CH 3SH/SO 2 complexes were identified from the infrared spectra of the mixtures of methanethiol with sulfur dioxide in argon and nitrogen matrices. Perturbations to the vibrational energy spaces of some vibrational modes were identified and assigned. Ab initio calculations with the 6-311G ∗∗ basis set have been performed to get some information about the structure, binding energy, dipole moment, and potential function governing the internal rotation of SO 2 for the complex. The calculated results have suggested that the dipole/dipole interaction held the constituent species together to form the complex. Photochemical reactions were performed by exposing the matrix mixtures to UV irradiation. The appearance of new bands indicated the presence of more than one photochemical reaction product.

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

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

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

  12. A new method for distinguishing between Al 2X 6 (X=Cl, Br) conformers based on ab initio calculated nuclear quadrupole coupling constants

    NASA Astrophysics Data System (ADS)

    Hadipour, N. L.; Elmi, F.

    2003-03-01

    Nuclear quadrupole coupling constants ( χ) of 27Al, 35Cl and 81Br in AlX 3 monomers as well as Al 2X 6 (X=Cl, Br) dimers are calculated at the RHF/6-311G* and B 3LYP/6-311G* levels, using G AUSSIAN 98 package. Correlations are made between χ and dihedral angles θ, of Al 2X 6. These θs are produced through the ring puckering motions about the hinge line which joins the two bridge halogens (X b). Nuclear quadrupole coupling constants of 35Cl, 81Br and 27Al are used as probes for monitoring the departure of the symmetry of Al 2X 6 from a high symmetry point group D 2h to a lower one. The χs of chlorine nuclei of AlCl 3 differ significantly from those of Al 2Cl 6. These differences appear negligible for AlBr 3 in comparison to Al 2Br 6. This work demonstrates the considerable sensitivity of nuclear quadrupole resonance in distinguishing between Al 2X 6 conformers. This is in comparison to the usage of energy differences which is customarily employed.

  13. Correlation-induced metal-insulator transitions in d0 magnetic superlattices based on alkaline-earth monoxides: Insights from ab initio calculations

    NASA Astrophysics Data System (ADS)

    Lu, Yi-Lin; Dong, Shengjie; Zhou, Baozeng; Zhao, Hui; Wu, Ping

    2015-06-01

    Using first-principles density functional theory calculations, we have investigated the electronic structure and magnetic properties of four superlattices (MO)1/(MX)1 (001) (M=Ca and Sr; X=N and C). Our results show that compared with standard GGA approach, the GGA plus effective Ueff scheme can correct electronic structure and magnetic properties in some extent. With enhancing electronic correlation, for (CaO)1/(CaN)1, (SrO)1/(SrN)1, and (SrO)1/(SrC)1, the bands across Fermi level are divided into two parts and the shape of isotropic spherical spin atmosphere becomes anisotropic dumbbell-like with specific orientation, accompanying metal-insulator transitions. For (CaO)1/(CaC)1, the states just smearing with the Fermi level shift to lower energy region below Fermi level, indicating the transformation from a nearly half metal to an actual half metal occurs. The different behavior of (CaO)1/(CaC)1 compared with three other compounds may be caused by the larger ionization energy of calcium than that of strontium and the smaller electronegativity of carbon than that of nitrogen.

  14. Automated, ab initio calculations of X-ray spectra including many-body excitations and vibrational damping

    NASA Astrophysics Data System (ADS)

    Jorissen, Kevin; Story, Shauna; Rehr, John

    2014-03-01

    Accurate calculations of x-ray absorption spectra (XAS) often require linking several materials science codes. To reduce the complexity and support the hardware requirements of such calculations, we have virtualized XAS modeling workflows using a Cloud-based approach, with interfacing and configuration of codes handled by developers, and virtual HPC resources allocated on demand. When coupled to user-friendly GUIs this puts powerful multi-code simulations in the hands of general users. For instance, FEFF users can improve XAS interpretation and analysis using accurate ab initio Debye-Waller factors and self energy from the ABINIT DFT code, rather than semi-empirical models. Additionally, such workflows allow robust automation of large-scale calculation sets such as the Materials Project where our approach could enable a theoretical spectroscopy database of many thousands of structures for systematic study of materials. Supported by NSF-1216716.

  15. High-Level Ab-Initio Calculation on the NiO₂ System

    SciTech Connect

    Song, Jie; Apra, Edoardo; Khait, Yuri; Hoffmann, Mark R.; Kowalski, Karol

    2006-09-20

    Several high-level ab-initio methods were employed in studies of the narrow singlet-triplet separation of the cyclic dorm of the nickel dioxide (NiO?). It is shown that the complete visions of the locally renormalized couples cluster method with singles, doubles, and noniterative triples (LR-CCSD(T)) approach, in contrast to the standard CCSD(T) method, provides results in concert with predictions of the density functional theory (DFT) and internally contracted multi-reference configuration interaction method (IIC-MCRCI), which favor the triplet state to be the lowest one. Relevant discussion of several aspects related to underlying CCSD calculations, indicate that the dominate roll of singly excited amplitudes violates the paradigm about the leading role to two-body effect in description of the correlation energy. These results are compared with the results of the second order Generalized Van Vleck Perturbation Theory (GVVPPT2) approach which supports the CCSD(T) predictions.

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

    PubMed

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

    2003-01-01

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

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

    SciTech Connect

    Li, Xiaowei; Ke, Peiling; Wang, Aiying

    2015-01-15

    Structure and properties of Cu-doped diamond-like carbon films (DLC) were investigated using ab initio calculations. The effect of Cu concentrations (1.56∼7.81 at.%) on atomic bond structure was mainly analyzed to clarify the residual stress reduction mechanism. Results showed that with introducing Cu into DLC films, the residual compressive stress decreased firstly and then increased for each case with the obvious deterioration of mechanical properties, which was in agreement with the experimental results. Structural analysis revealed that the weak Cu-C bond and the relaxation of both the distorted bond angles and bond lengths accounted for the significant reduction of residual compressive stress, while at the higher Cu concentration the increase of residual stress attributed to the existence of distorted Cu-C structures and the increased fraction of distorted C-C bond lengths.

  18. Ab Initio Infrared Spectra and Electronic Response Calculations for the Insulating Phases of VO2

    NASA Astrophysics Data System (ADS)

    Hendriks, Christopher; Huffman, Tyler; Walter, Eric; Qazilbash, Mumtaz; Krakauer, Henry

    Previous studies have shown that, under doping or tensile strain and upon heating, the well-known vanadium dioxide (VO2) transition from an insulating monoclinic (M1) to a metallic rutile (R) phase progresses through a triclinic symmetry (T) phase and a magnetic monoclinic phase (M2), both of which are insulating. Structurally, this progression from M1 to R through T and M2 can be characterized by the progressive breaking of the V dimers. Investigation of the effect of these structural changes on the insulating phases of VO2 may help resolve questions surrounding the long-debated issue of the respective roles of electronic correlation and Peierls mechanisms in driving the MIT. We investigated electronic and vibrational properties of the insulating phases of VO2 in the framework of DFT+U. We will present ab initio calculations of infrared spectra and optical electronic responses for the insulating phases and compare these to available experimental measurements. Supported by ONR.

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

    NASA Astrophysics Data System (ADS)

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

    2011-02-01

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

  20. Ab initio calculations of the reaction pathways for methane decomposition over the Cu (111) surface

    NASA Astrophysics Data System (ADS)

    Gajewski, Grzegorz; Pao, Chun-Wei

    2011-08-01

    Growth of large-area, few-layer graphene has been reported recently through the catalytic decomposition of methane (CH4) over a Cu surface at high temperature. In this study, we used ab initio calculations to investigate the minimum energy pathways of successive dehydrogenation reactions of CH4 over the Cu (111) surface. The geometries and energies of all the reaction intermediates and transition states were identified using the climbing image nudged elastic band method. The activation barriers for CH4 decomposition over this Cu surface are much lower than those in the gas phase; furthermore, analysis of electron density differences revealed significant degrees of charge transfer between the adsorbates and the Cu atoms along the reaction path; these features reveal the role of Cu as the catalytic material for graphene growth. All the dehydrogenation reactions are endothermic, except for carbon dimer (C2) formation, which is, therefore, the most critical step for subsequent graphene growth, in particular, on Cu (111) surface.

  1. 3,5-Difluorobenzonitrile: ab initio calculations, FTIR and Raman spectra.

    PubMed

    Rastogi, V K; Alcolea Palafox, M; Tanwar, R P; Mittal, Lalit

    2002-07-01

    Geometry, vibrational wavenumbers and several thermodynamic parameters were calculated using ab initio quantum chemical methods for the 3,5-difluorobenzonitrile molecule. The results were compared with the experimental values. With the help of three specific scaling procedures, the observed vibrational wavenumbers in FTIR and Raman spectra were analysed and assigned to different normal modes of the molecule. Most of the modes have wavenumbers in the expected range and the error obtained was in general very low. Using PEDs the contributions were determined for the different modes to each wavenumber. From the PED, it is apparent that the frequency corresponding to C[triple bond]N stretching contains 87% contribution from the C[triple bond]N stretching force constant and it mixes with the C-CN stretching mode 13 to the extent of 12%. Other general conclusions were also deduced. PMID:12164497

  2. Scrutinizing negative thermal expansion in MOF-5 by scattering techniques and ab initio calculations.

    PubMed

    Lock, Nina; Christensen, Mogens; Wu, Yue; Peterson, Vanessa K; Thomsen, Maja K; Piltz, Ross O; Ramirez-Cuesta, Anibal J; McIntyre, Garry J; Norén, Katarina; Kutteh, Ramzi; Kepert, Cameron J; Kearley, Gordon J; Iversen, Bo B

    2013-02-14

    Complementary experimental techniques and ab initio calculations were used to determine the origin and nature of negative thermal expansion (NTE) in the archetype metal-organic framework MOF-5 (Zn(4)O(1,4-benzenedicarboxylate)(3)). The organic linker was probed by inelastic neutron scattering under vacuum and at a gas pressure of 175 bar to distinguish between the pressure and temperature responses of the framework motions, and the local structure of the metal centers was studied by X-ray absorption spectroscopy. Multi-temperature powder- and single-crystal X-ray and neutron diffraction was used to characterize the polymeric nature of the sample and to quantify NTE over the large temperature range 4-400 K. Ab initio calculations complement the experimental data with detailed information on vibrational motions in the framework and their correlations. A uniform and comprehensive picture of NTE in MOF-5 has been drawn, and we provide direct evidence that the main contributor to NTE is translational transverse motion of the aromatic ring, which can be dampened by applying a gas pressure to the sample. The linker motion is highly correlated rather than local in nature. The relative energies of different framework vibrations populated in MOF-5 are suggested by analysis of neutron diffraction data. We note that the lowest-energy motion is a librational motion of the aromatic ring which does not contribute to NTE. The libration is followed by transverse motion of the linker and the carboxylate group. These motions result in unit-cell contraction with increasing temperature. PMID:23044752

  3. Far infrared spectra, conformational equilibria, vibrational assignments, ab initio calculations and structural parameters for 2-bromoethanol

    NASA Astrophysics Data System (ADS)

    Durig, J. R.; Shen, S.; Guirgis, G. A.

    2001-01-01

    The far infrared spectrum from 370 to 50 cm -1 of gaseous 2-bromoethanol, BrCH 2CH 2OH, was recorded at a resolution of 0.10 cm -1. The fundamental O-H torsion of the more stable gauche ( Gg') conformer, where the capital G refers to internal rotation around the C-C bond and the lower case g to the internal rotation around the C-O bond, was observed as a series of Q-branch transitions beginning at 340 cm -1. The corresponding O-H torsional modes were observed for two of the other high energy conformers, Tg (285 cm -1) and Tt (234 cm -1). The heavy atom asymmetric torsion (rotation around C-C bond) for the Gg' conformer has been observed at 140 cm -1. Variable temperature (-63 to -100°C) studies of the infrared spectra (4000-400 cm -1) of the sample dissolved in liquid xenon have been recorded. From these data the enthalpy differences have been determined to be 411±40 cm -1 (4.92±0.48 kJ/mol) for the Gg'/ Tt and 315±40 cm -1 (3.76±0.48 kJ/mol) for the Gg'/ Tg, with the Gg' conformer the most stable form. Additionally, the infrared spectrum of the gas, and Raman spectrum of the liquid phase are reported. The structural parameters, conformational stabilities, barriers to internal rotation and fundamental frequencies have been obtained from ab initio calculations utilizing different basis sets at the restricted Hartree-Fock or with full electron correlation by the perturbation method to second order. The theoretical results are compared to the experimental results when appropriate. Combining the ab initio calculations with the microwave rotational constants, r0 adjusted parameters have been obtained for the three 2-haloethanols (F, Cl and Br) for the Gg' conformers.

  4. Analysis of Intermolecular Interactions Using Calculated Molecular Properties: AN AB Initio Quantum Chemical Study

    NASA Astrophysics Data System (ADS)

    Brinck, Nils Tore

    The objective of this study has been to investigate the use of computed molecular properties in predicting and interpreting intermolecular interactions. The molecular properties have been calculated rigorously from ab initio wave functions. We have found the electrostatic potential to be a good tool for the analysis of nonbonding intermolecular interactions. It is demonstrated that the calculated electrostatic potentials around carbon-halogen bonds can be used to explain the directional preferences of halogen interactions in crystals. We also show that the orientation of the molecules in weak gas phase complexes between dihalogens and Lewis bases can be rationalized from their electrostatic potentials. However an analysis of the bonding in boron trifluoride and boron trichloride and their complexes with ammonia indicates that the relative stabilities of these complexes are dictated by charge transfer rather than electrostatics. The higher binding affinity for boron trichloride compared to boron trifluoride is explained by the higher charge capacity of the former. This is contrary to the commonly accepted explanation, which is based on backbonding. A local charge separation index has been defined from surface electrostatic potentials. This provides a measure of local polarity, even for molecules with zero dipole moments. Average local ionization energies computed on molecular surfaces permit predictions of relative reactivities of various sites toward electrophilic attack. There is a very good relationship between {rm p}K_{a} and minima in |{I}({bf r}), designated as |{I}_{S,min }, for a series of azines and azoles. Excellent correlations have also been found between { rm p}K_{a} values for a variety of carbon, oxygen and nitrogen acids and the |{I}_{S,min} of their conjugate bases. A study of the electrostatic potentials and average local ionization energies of the V-VII hydrides of the first three rows of the periodic table and their anions demonstrates the

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

    DOE PAGESBeta

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

    2016-05-17

    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. Our 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. We review some of the recent accomplishments. We also present new results. The recently optimized chiral interaction NNLOmore » $${}_{{\\rm{sat}}}$$ is shown to provide an accurate description of both charge radii and binding energies in selected light- and medium-mass nuclei up to 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. Finally, the coupling to the continuum impacts the energies of the $${J}^{\\pi }=1/{2}^{-},3/{2}^{-},7/{2}^{-},3/{2}^{+}$$ states in $${}^{\\mathrm{17,23,25}}$$O, and—contrary to naive shell-model expectations—the level ordering of the $${J}^{\\pi }=3/{2}^{+},5/{2}^{+},9/{2}^{+}$$ states in $${}^{\\mathrm{53,55,61}}$$Ca.« less

  6. Ab initio calculations of structure and thermodynamic properties of tetragonal-TiH2 under high temperatures and pressures

    NASA Astrophysics Data System (ADS)

    Liu, X. K.; Tang, B.; Zhang, Y.

    2013-10-01

    The structural and thermodynamic properties of tetragonal-TiH2 under high temperatures and pressures are investigated by Ab initio calculations based on pseudo-potential plane-wave density functional theory method within using the generalized gradient approximation (GGA) and quasi-harmonic Debye model. Some ground state properties such as lattice constants, bulk modulus and elastic constants are good agreement with the available experimental results and other theoretical data. Through the quasiharmonic Debye model, in which the phononic effects are considered, the thermodynamic properties of tetragonal-TiH2 such as thermal expansion coefficient, Debye temperature, heat capacity and Grüneisen parameters dependence of temperature and pressure in the range of 0-1000 K and 0-10 GPa are also presented, respectively.

  7. Ab initio G W plus cumulant calculation for isolated band systems: Application to organic conductor (TMTSF) 2PF6 and transition-metal oxide SrVO3

    NASA Astrophysics Data System (ADS)

    Nakamura, Kazuma; Nohara, Yoshiro; Yosimoto, Yoshihide; Nomura, Yusuke

    2016-02-01

    We present ab initio G W plus cumulant-expansion calculations for an organic compound (TMTSF) 2PF6 and a transition-metal oxide SrVO3. These materials exhibit characteristic low-energy band structures around the Fermi level, which bring about interesting low-energy properties; the low-energy bands near the Fermi level are isolated from the other bands, and, in the isolated bands, unusually low-energy plasmon excitations occur. To study the effect of this low-energy-plasmon fluctuation on the electronic structure, we calculate spectral functions and photoemission spectra using the ab initio cumulant expansion of the Green's function based on the G W self-energy. We found that the low-energy plasmon fluctuation leads to an appreciable renormalization of the low-energy bands and a transfer of the spectral weight into the incoherent part, thus resulting in an agreement with experimental photoemission data.

  8. Ab initio no core configuration interaction calculations in the natural orbital basis

    NASA Astrophysics Data System (ADS)

    Constantinou, Chrysovalantis; Caprio, Mark A.; Vary, James P.; Maris, Pieter

    2015-10-01

    The natural orbital basis has been successfully used in the past in atomic and molecular structure calculations. The natural orbitals used in those calculations are calculated by diagonalizing the electron one-body density matrix. Here we develop natural orbitals for nuclear no-core configuration interaction (NCCI) calculations. A NCCI calculation using an initial single particle basis, such as the harmonic oscillator basis, must first be performed in order to obtain a one-body density matrix. The eigenvectors of the one-body density matrix are the natural orbitals, and the corresponding eigenvalues are the occupations of these natural orbitals in the nuclear wave function. According to these occupancies, the most important natural orbitals, in the sense of the most occupied, can then be selected and used in a NCCI calculation. We discuss ab initio nuclear NCCI calculations for light nuclei and assess their ability to provide faster convergence. Supported by the US DOE (under Grants DE-FG02-95ER-40934, DESC0008485 SciDAC/NUCLEI, and DE-FG02-87ER40371), and the US NSF (under Grant 0904782). Computational resources provided by NERSC (supported by US DOE Contract DE-AC02-05CH11231), and NDCRC.

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

    NASA Astrophysics Data System (ADS)

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

    2013-06-01

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

  10. Electronic structure of ScN determined using optical spectroscopy, photoemission, and ab initio calculations

    SciTech Connect

    Gall, D.; Sta''dele, M.; Ja''rrendahl, K.; Petrov, I.; Desjardins, P.; Haasch, R. T.; Lee, T.-Y.; Greene, J. E.

    2001-03-15

    Experimental and ab initio computational methods are employed to conclusively show that ScN is a semiconductor rather than a semimetal; i.e., there is a gap between the N 2p and the Sc 3d bands. Previous experimental investigators reported, in agreement with band structure calculations showing a band overlap of 0.2 eV, that ScN is a semimetal while others concluded that it is a semiconductor with a band gap larger than 2 eV. We have grown high quality, single crystalline ScN layers on MgO(001) and on TiN(001) buffer layers on MgO(001) by ultrahigh vacuum reactive magnetron sputter deposition. ScN optical properties were determined by transmission, reflection, and spectroscopic ellipsometry while in-situ x-ray and ultraviolet valence band photoelectron spectroscopy were used to determine the density of states (DOS) below the Fermi level. The measured DOS exhibits peaks at 3.8 and 5.2 eV stemming from the N 2p bands and at 15.3 eV due to the N 2s bands. The imaginary part of the measured dielectric function {epsilon}{sub 2} consists of two primary features due to direct X- and {Gamma}-point transitions at photon energies of 2.7 and 3.8 eV, respectively. For comparison, the ScN band structure was calculated using an ab initio Kohn--Sham approach which treats the exchange interactions exactly within density-functional theory. Calculated DOS and the complex dielectric function are in good agreement with our ScN valence-band photoelectron spectra and measured optical properties, respectively. We conclude, combining experimental and computational results, that ScN is a semiconductor with an indirect {Gamma}--X bandgap of 1.3{+-}0.3eV and a direct X-point gap of 2.4{+-}0.3eV.

  11. Engineering materials-design parameters of the Mg-Li Alloy System from ab initio calculations

    NASA Astrophysics Data System (ADS)

    Counts, William; Friak, Martin; Raabe, Dierk; Neugebauer, Jorg

    2008-03-01

    Ab initio calculations are becoming increasingly useful to engineers interested in designing new alloys because these calculations are able to accurately predict basic material properties only knowing the atomic composition of the material. Fundamental physical properties (like formation energy and elastic constants) of 11 bcc magnesium-lithium alloys were calculated using density-functional theory (DFT) and compared with available experimental data. These DFT determined properties were in turn used to calculate engineering parameters like the bulk modulus/shear modulus (B/G) and Young's modulus/density (E/ρ). From these engineering parameters, alloys with optimal mechanical properties need for a light weight structural material were identified. It was found that the stiffest bcc magnesium-lithium alloys contain about 70 at.% magnesium while the most ductile alloys have 0-20 at.% magnesium. In addition, the specific modulus for alloys with 70 at.% magnesium was found to be equal to that of aluminum-magnesium alloys and slightly lower than that of aluminum-lithium alloys.

  12. Precise Electromagnetic Tests of Ab Initio Calculations of Light Nuclei: States in {sup 10}Be

    SciTech Connect

    McCutchan, E. A.; Lister, C. J.; Wiringa, R. B.; Pieper, Steven C.; Seweryniak, D.; Greene, J. P.; Carpenter, M. P.; Janssens, R. V. F.; Khoo, T. L.; Lauritsen, T.; Zhu, S.; Chiara, C. J.; Stefanescu, I.

    2009-11-06

    In order to test ab initio calculations of light nuclei, we have remeasured lifetimes in {sup 10}Be using the Doppler shift attenuation method (DSAM) following the {sup 7}Li({sup 7}Li,alpha){sup 10}Be reaction at 8 and 10 MeV. The new experiments significantly reduce systematic uncertainties in the DSAM technique. The J{sup p}i=2{sub 1}{sup +} state at 3.37 MeV has tau=205+-(5){sub stat}+-(7){sub sys} fs corresponding to a B(E2arrow down) of 9.2(3)e{sup 2} fm{sup 4} in broad agreement with many calculations. The J{sup p}i=2{sub 2}{sup +} state at 5.96 MeV was found to have a B(E2arrow down) of 0.11(2)e{sup 2} fm{sup 4} and provides a more discriminating test of nuclear models. New Green's function Monte Carlo calculations for these states and transitions with a number of Hamiltonians are also reported and compared to experiment.

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

    NASA Astrophysics Data System (ADS)

    Akin-Ojo, Omololu; Szalewicz, Krzysztof

    2005-10-01

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

  14. Ab initio calculations of phonon properties and spectra in condensed matter

    NASA Astrophysics Data System (ADS)

    Story, Shauna M.

    Phonons, the quantization of atomic vibrations, are important in studying many solid state properties, ranging from Raman, infrared, and neutron scattering to thermal expansion, specific heat, and heat conductivity to electrical resistivity and superconductivity. Generally, modeling the interatomic forces and vibrational modes of a given system require costly computer simulations, though once calculated, they provide the means to a wide variety of phonon properties. Our goal is to enable easy access to these phonon properties and to do this, we have developed a framework for easily automating the workflows involved in interfacing a phonon mode calculation with the analysis tools for determining such physical properties. This was originally implemented with the AI2PS (ab initio to phonon spectra) tool, meant solely for the calculation of vibrational properties. It has since greatly expanded in scope and capabilities to a general scientific workflow tool called Corvus, which was started with the eventual goal of collecting all our various scientific workflow efforts---phonon properties, optical properties, and so on---into a single hub. We present here both the evolution of AI2PS into the Corvus project and the phonon properties simulated, including Debye--Waller factors, phonon contributions the electron self--energy and spectral function, vibrational free energy, thermal expansion, and heat capacity.

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

    NASA Astrophysics Data System (ADS)

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

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

  16. Ab initio calculations of cooperativity effects on clusters of methanol, ethanol, 1-propanol, and methanethiol

    SciTech Connect

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

    2000-02-17

    The results of ab initio calculations for cyclic clusters of methanol, ethanol, 1-propanol, and methanethiol are presented. Dimer, trimer, and tetramer clusters of all four compounds are studied, as are pentamer and hexamer clusters of methanol. From optimized clusters at HG/6--31G**, total energies and binding energies were calculated with both the HF and MP2 theories using the aug-cc-pVDZ basis set. Accurate binding energies were also calculated for the dimer and trimer of methanol using symmetry-adapted perturbation theory with the same basis set. Intermolecular and intramolecular distances, charge distribution of binding sites, binding energies, and equilibrium constants were computed to determine the hydrogen bond cooperativity effect for each species. The cooperativity effect, exclusive to hydrogen bonding systems, results form specific forces among the molecules, in particular charge-transfer processes and the greater importance of interactions between molecules not directly hydrogen bonded because of the longer range of the interactions. The ratios of equilibrium constants for forming multimer hydrogen bonds to that for dimer hydrogen bond formation increase rapidly with the cluster size, in contrast to the constant value commonly used in thermodynamic models for hydrogen bonding liquids.

  17. Ab initio calculations of magnetic properties of the interstitially doped YFe11Mo compound

    NASA Astrophysics Data System (ADS)

    Kokorina, E. E.; Medvedev, M. V.; Nekrasov, I. A.

    2016-02-01

    The recent increase in the number of studies of RFe11- x M x compounds is related to their promising application as permanent magnets. However, the insufficiently high value of the Curie temperature T C of these compounds is a barrier to their widespread use. The increase in the Curie temperature of these compounds is achieved by doping with the light nonmetallic atoms such as hydrogen, nitrogen, and carbon. In this paper, it is shown numerically that this doping leads to drastic changes of the electronic band dispersions in a wide energy region around the Fermi level. This in turn changes values of the magnetic moments of ions and Heisenberg exchange interaction parameters. The values of ab initio calculated magnetic moments and direct exchange interaction parameters make it possible to calculate the Curie temperatures for both parent and nitrogen-doped compounds within the mean-field approach to the Heisenberg model in the sample of YFe11Mo, a typical representative of the R(Fe,M)12L class. Theoretical values of T C obtained for YFe11Mo and YFe11MoN (514 and 723 K respectively) are consistent with experimental ones (472 and 664 K) with an accuracy of 10%. Also, the calculated increase in T C upon nitrogenization (about 200 K) is in good agreement with the experimental data.

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

    SciTech Connect

    Sharda, Anurag

    2008-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

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

  20. Ab-initio Calculations of Electronic Properties of InP and GaP

    NASA Astrophysics Data System (ADS)

    Malozovsky, Yuriy; Franklin, Lashounda; Ekuma, Chinedu; Zhao, Guang-Lin; Bagayoko, Diola

    2013-03-01

    We present results from ab-initio, self consistent local density approximation (LDA) calculations of electronic and related properties of zinc blende indium and gallium phosphides (InP & GaP) We employed a local density approximation (LDA) potential and implemented the linear combination of atomic orbitals (LCAO) formalism. This implementation followed the Bagayoko, Zhao, and Williams (BZW) method, as enhanced by Ekuma and Franklin (BZW-EF). This method searches for the optimal basis set that yields the minima of the occupied energies. This search entails methodically increasing the size of the basis set, up to the optimal one, and the accompanying enrichment of angular symmetry and of radial orbitals. Our calculated, direct band gap of 1.398 eV (1.40 eV) for InP, at the Γ point, is in excellent agreement with experimental values. We discuss our preliminary results for the indirect band gap, from Γ to X, of GaP. We also report calculated electron and hole effective masses for both InP and GaP and the total (DOS) and partial (pDOS) densities of states. This work was funded in part by the National Science Foundation and the Louisiana Board of Regents, through LASiGMA and LS-LAMP, [EPS-1003897, No. NSF (2010-15)-RII-SUBR, and HRD-1002541] and by the Louisiana Optical Network Initiative (LONI) at SUBR.

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

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1991-11-01

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

  3. Transport coefficients of helium-argon mixture based on ab initio potential.

    PubMed

    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

  4. An ab initio calculation of the rotational-vibrational energies in the electronic ground state of NH2

    NASA Astrophysics Data System (ADS)

    Jensen, Per; Buenker, Robert J.; Hirsch, Gerhard; Rai, Sachchida N.

    We have calculated ab initio the three-dimensional potential-energy surface of the NH2 molecule at 145 nuclear geometries spanning energy ranges of about 18 000 cm-1 for the NH stretch and 12 000 cm-1 for the bend. The ab initio configuration-interaction calculations were done using the multireference MRD-CI method. The calculated equilibrium configuration has NH bond length re = 1·0207 Å and bond angle α = 103·1°. The rotational-vibrational energies for 14NH2, 14NHD and 14ND2 were calculated variationally using the Morse-oscillator rigid-bender internal-dynamics Hamiltonian. For 14NH2 we calculate that υ1 = 3267 (3219) cm-1, υ2 = 1462 (1497) cm-1 and υ3 = 3283 (3301) cm-1, where experimental values are given in parentheses.

  5. Ab initio calculation of structural stability, electronic and optical properties of Ag{sub 2}Se

    SciTech Connect

    Rameshkumar, S.; Jayalakshmi, V.; Jaiganesh, G.; Palanivel, B.

    2015-06-24

    The structural stability, electronic and optical properties of Ag{sub 2}Se compound is studied using ab initio packages. Ag{sub 2}Se is found to crystallize in orthorhombic structure with two different space groups i.e. P2{sub 1}2{sub 1}2{sub 1} (No. 19) and P222{sub 1} (No. 17). For this compound in these two space groups, the total energy has been computed as a function of volume. Our calculated results suggest that the P2{sub 1}2{sub 1}2{sub 1}–phase is more stable than that of the P222{sub 1}–phase. The band structure calculation show that Ag{sub 2}Se is semimetallic with an overlap of about 0.014 eV in P2{sub 1}2{sub 1}2{sub 1}–phase whereas is metallic in nature in P222{sub 1}–phase. Moreover, the optical properties including the dielectric function, energy loss spectrum are obtained and analysed.

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

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

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

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

    SciTech Connect

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

    2014-04-28

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

  8. Ab initio calculations for dissociative hydrogen adsorption on lithium oxide surfaces

    SciTech Connect

    Sutjianto, A. |; Tam, S.W.; Curtiss, L.A.; Johnson, C.E.; Pandey, R.

    1994-12-01

    Lithium ceramics are one class of materials being considered as tritium breeders for fusion technology,and hydrogen is known to enhance the release of tritium from lithium ceramic materials. Dissociative hydrogen chemisorption on the Li{sub 2}O surfaces of the (100), (110), and (111) planes has been investigated with ab initio Hartree-Fock calculations. Calculations for unrelaxed crystal Li{sub 2}O structures indicated that except for the (100) surface, the (110) and (111) surfaces are stable. Results on the heterolytic sites of n-layer (110) (where n {ge} 2) slabs and three-layer (111) slabs suggest that dissociative hydrogen chemisorption is endothermic. For a one-layer (110) slab at 100% surface coverage, the dissociative hydrogen chemisorption is exothermic, forming OH{sup {minus}} and Li{sup +}H{sup {minus}}Li{sup +}. The results also indicate that the low coordination environment in surface step structures, such as kinks and ledges, may plan an important role in the hydrogen chemisorption process. On the homolytic sites of the (110) and (111) surfaces, there is no hydrogen chemisorption.

  9. Electronic structure of silicon nitride according to ab initio quantum-chemical calculations and experimental data

    SciTech Connect

    Nekrashevich, S. S. Gritsenko, V. A.; Klauser, R.; Gwo, S.

    2010-10-15

    Charge transfer {Delta}Q = 0.35e at the Si-N bond in silicon nitride is determined experimentally using photoelectron spectroscopy, and the ionic formula of silicon nitride Si{sub 3}{sup +1.4}N{sub 4}{sup -1.05} is derived. The electronic structure of {alpha}-Si{sub 3}N{sub 4} is studied ab initio using the density functional method. The results of calculations (partial density of states) are compared with experimental data on X-ray emission spectroscopy of amorphous Si{sub 3}N{sub 4}. The electronic structure of the valence band of amorphous Si{sub 3}N{sub 4} is studied using synchrotron radiation at different excitation energies. The electron and hole effective masses m{sub e}{sup *} {approx} m{sub h}{sup *} {approx} 0.5m{sub e} are estimated theoretically. The calculated values correspond to experimental results on injection of electrons and holes into silicon nitride.

  10. ``Phantom'' Modes in Ab Initio Tunneling Calculations: Implications for Theoretical Materials Optimization, Tunneling, and Transport

    NASA Astrophysics Data System (ADS)

    Barabash, Sergey V.; Pramanik, Dipankar

    2015-03-01

    Development of low-leakage dielectrics for semiconductor industry, together with many other areas of academic and industrial research, increasingly rely upon ab initio tunneling and transport calculations. Complex band structure (CBS) is a powerful formalism to establish the nature of tunneling modes, providing both a deeper understanding and a guided optimization of materials, with practical applications ranging from screening candidate dielectrics for lowest ``ultimate leakage'' to identifying charge-neutrality levels and Fermi level pinning. We demonstrate that CBS is prone to a particular type of spurious ``phantom'' solution, previously deemed true but irrelevant because of a very fast decay. We demonstrate that (i) in complex materials, phantom modes may exhibit very slow decay (appearing as leading tunneling terms implying qualitative and huge quantitative errors), (ii) the phantom modes are spurious, (iii) unlike the pseudopotential ``ghost'' states, phantoms are an apparently unavoidable artifact of large numerical basis sets, (iv) a presumed increase in computational accuracy increases the number of phantoms, effectively corrupting the CBS results despite the higher accuracy achieved in resolving the true CBS modes and the real band structure, and (v) the phantom modes cannot be easily separated from the true CBS modes. We discuss implications for direct transport calculations. The strategy for dealing with the phantom states is discussed in the context of optimizing high-quality high- κ dielectric materials for decreased tunneling leakage.

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

    SciTech Connect

    Li, Arvin Huang-Te; Chao, Sheng D.; Chang, Chien-Cheng

    2010-12-15

    Intermolecular interaction potentials of the silane dimer in 12 orientations have been calculated by using the Hartree-Fock (HF) self-consistent theory and the second-order Moeller-Plesset (MP2) perturbation theory. We employed basis sets from Pople's medium-size basis sets [up to 6-311++G(3df, 3pd)] and Dunning's correlation consistent basis sets (up to the triply augmented correlation-consistent polarized valence quadruple-zeta basis set). We found that the minimum energy orientations were the G and H conformers. We have suggested that the Si-H attractions, the central silicon atom size, and electronegativity play essential roles in weakly binding of a silane dimer. The calculated MP2 potential data were employed to parametrize a five-site force field for molecular simulations. The Si-Si, Si-H, and H-H interaction parameters in a pairwise-additive, site-site potential model for silane molecules were regressed from the ab initio energies.

  12. Raman spectroscopic features of the neutral vacancy in diamond from ab initio quantum-mechanical calculations.

    PubMed

    Baima, Jacopo; Zelferino, Alessandro; Olivero, Paolo; Erba, Alessandro; Dovesi, Roberto

    2016-01-21

    Quantum-mechanical ab initio calculations are performed to elucidate the vibrational spectroscopic features of a common irradiation-induced defect in diamond, i.e. the neutral vacancy. Raman spectra are computed analytically through a Coupled-Perturbed-Hartree-Fock/Kohn-Sham approach as a function of both different defect spin states and defect concentration. The experimental Raman features of defective diamond located in the 400-1300 cm(-1) spectral range, i.e. below the first-order line of pristine diamond at 1332 cm(-1), are well reproduced, thus corroborating the picture according to which, at low damage densities, this spectral region is mostly affected by non-graphitic sp(3) defects. No peaks above 1332 cm(-1) are found, thus ruling out previous tentative assignments of different spectral features (at 1450 and 1490 cm(-1)) to the neutral vacancy. The perturbation introduced by the vacancy to the thermal nuclear motion of carbon atoms in the defective lattice is discussed in terms of atomic anisotropic displacement parameters (ADPs), computed from converged lattice dynamics calculations. PMID:26686374

  13. Carbon and proton Overhauser DNP from MD simulations and ab initio calculations: TEMPOL in acetone.

    PubMed

    Küçük, Sami Emre; Biktagirov, Timur; Sezer, Deniz

    2015-10-14

    A computational analysis of the Overhauser effect is reported for the proton, methyl carbon, and carbonyl carbon nuclei of liquid acetone doped with the nitroxide radical TEMPOL. A practical methodology for calculating the dynamic nuclear polarization (DNP) coupling factors by accounting for both dipole-dipole and Fermi-contact interactions is presented. The contribution to the dipolar spectral density function of nuclear spins that are not too far from TEMPOL is computed through classical molecular dynamics (MD) simulations, whereas the contribution of distant spins is included analytically. Fermi contacts are obtained by subjecting a few molecules from every MD snapshot to ab initio quantum mechanical calculations. Scalar interaction is found to be an essential part of the (13)C Overhauser DNP. While mostly detrimental to the carbonyl carbon of acetone it is predicted to result in large enhancements of the methyl carbon signal at magnetic fields of 9 T and beyond. In contrast, scalar coupling is shown to be negligible for the protons of acetone. The additional influence of proton polarization on the carbon DNP (three-spin effect) is also analyzed computationally. Its effect, however, is concluded to be practically insignificant for liquid acetone. PMID:26343351

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

    PubMed

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

    2016-04-18

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

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

    NASA Astrophysics Data System (ADS)

    Gazda, Daniel; Gal, Avraham

    2016-03-01

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

  16. Ab initio calculations of the mechanical and electronic properties of strained Si nanowires

    NASA Astrophysics Data System (ADS)

    Leu, Paul W.; Svizhenko, Alexei; Cho, Kyeongjae

    2008-06-01

    This paper reports a systematic study of the mechanical and electronic properties of strained small diameter (0.7-2.6 nm) silicon nanowires (Si NWs) using ab initio density functional theory calculations. The values of Young’s modulus, Poisson ratio, band gap, effective mass, work function, and deformation potentials are calculated for ⟨110⟩ and ⟨111⟩ Si NWs. We find that quantum confinement in ⟨110⟩ Si NWs splits conduction band valleys and decreases transport effective mass compared to the bulk case. Consequently, additional tensile strain should not lead to further significant electron mobility improvement. An interesting finding we report in this paper is that under compressive strain, there is a dramatic decrease in deformation potentials of ⟨110⟩ Si NWs, which may result in a strong increase in electron mobilities, despite a concurrent increase in effective mass. We also observe a similar strain-induced counterplay of hole deformation potentials and effective masses for both ⟨110⟩ and ⟨111⟩ Si NWs. Finally, we do not see any significant effect of tensile or compressive strain on electron effective masses and deformation potentials in ⟨111⟩ Si NWs. The sudden changes in effective mass and deformation potentials are concurrent with a change in the conduction and valence band edge states. In ⟨110⟩ NWs, this change corresponds to a transition from direct-to-indirect band gap under strain.

  17. Ab initio calculations of scytonemin derivatives of relevance to extremophile characterization by Raman spectroscopy.

    PubMed

    Varnali, Tereza; Edwards, Howell G M

    2010-07-13

    The recognition that scytonemin, the radiation protectant pigment produced by extremophilic cyanobacterial colonies in stressed terrestrial environments, is a key biomarker for extinct or extant life preserved in geological scenarios is critically important for the detection of life signatures by remote analytical instrumentation on planetary surfaces and subsurfaces. The ExoMars mission to seek life signatures on Mars is just one experiment that will rely upon the detection of molecules such as scytonemin in the Martian regolith. Following a detailed structural analysis of the parent scytonemin, we report here for the first time a similar analysis of several of its methoxy derivatives that have recently been extracted from stressed cyanobacteria. Ab initio calculations have been carried out to determine the most stable molecular configurations, and the implications of the structural changes imposed by the methoxy group additions on the spectral characteristics of the parent molecule are discussed. The calculated electronic absorption bands of the derivative molecules reveal that their capability of removing UVA wavelengths is removed while preserving the ability to absorb the shorter wavelength UVB and UVC radiation, in contrast to scytonemin itself. This is indicative of a special role for these molecules in the protective strategy of the cyanobacterial extremophiles. PMID:20529954

  18. The T2 phase in the Nb-Si-B system studied by ab initio calculations and synchrotron X-ray diffraction

    SciTech Connect

    Joubert, J.-M.; Colinet, C.; Rodrigues, G.; Suzuki, P.A.; Nunes, C.A.; Coelho, G.C.; Tedenac, J.-C.

    2012-06-15

    The solid solution based on Nb{sub 5}Si{sub 3} (Cr{sub 5}B{sub 3} structure type, D8{sub l}, tI32, I4/mcm, No140, a=6.5767 A, c=11.8967 A) in the Nb-Si-B system was studied from the structural and thermodynamic point of view both experimentally and by ab initio calculations. Rietveld refinement of powder X-ray synchrotron data allowed to determine the boron to silicon substitution mechanism and the structural parameters. Ab initio calculations of different ordered compounds and selected disordered alloys allowed to obtain in addition to the enthalpy of formation of the solution, substitution mechanism and structural parameters which are in excellent agreement with the experimental data. The stability of the phase is discussed. - Graphial abstract: Valence-charge electron localization function in the z=0 plane of the D8{sub l} structure for the ordered compound Nb{sub 5}SiB{sub 2}. Highlights: Black-Right-Pointing-Pointer Coupling between ab initio data and experimental results from synchrotron powder diffraction. Black-Right-Pointing-Pointer Excellent agreement between the two techniques for the site occupancies and internal coordinates. Black-Right-Pointing-Pointer Explanation of the phase stability up to Nb{sub 5}SiB{sub 2}.

  19. Ab initio theory of iron-based superconductors

    NASA Astrophysics Data System (ADS)

    Essenberger, F.; Sanna, A.; Buczek, P.; Ernst, A.; Sandratskii, L.; Gross, E. K. U.

    2016-07-01

    We report a first-principles study of the superconducting critical temperature and other properties of Fe-based superconductors taking into account, on equal footing, phonon, charge, and spin-fluctuation mediated Cooper pairing. We show that in FeSe this leads to a modulated s ± gap symmetry and that the antiferromagnetic paramagnons are the leading mechanism for superconductivity in FeSe, overcoming the strong repulsive effect of both phonons and charge pairing.

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

    NASA Astrophysics Data System (ADS)

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

    2003-04-01

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

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

    PubMed

    Patil, Amol Baliram; Bhanage, Bhalchandra Mahadeo

    2016-06-21

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

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

    DOE PAGESBeta

    Hupin, Guillaume; Langhammer, Joachim; Navratil, Petr; Quaglioni, Sofia; Calci, Angelo; Roth, Robert

    2013-11-27

    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 elastic scattering using similarity-renormalization-group (SRG)-evolved nucleon-nucleon plus 3N 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 themore » 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. As a result, we find remarkably good agreement with measured differential cross sections at various energies below the d+3H threshold, while analyzing powers manifest larger deviations from experiment for certain energies and angles.« less

  3. Ab initio calculations of the reaction pathways for methane decomposition over the Cu (111) surface.

    PubMed

    Gajewski, Grzegorz; Pao, Chun-Wei

    2011-08-14

    Growth of large-area, few-layer graphene has been reported recently through the catalytic decomposition of methane (CH(4)) over a Cu surface at high temperature. In this study, we used ab initio calculations to investigate the minimum energy pathways of successive dehydrogenation reactions of CH(4) over the Cu (111) surface. The geometries and energies of all the reaction intermediates and transition states were identified using the climbing image nudged elastic band method. The activation barriers for CH(4) decomposition over this Cu surface are much lower than those in the gas phase; furthermore, analysis of electron density differences revealed significant degrees of charge transfer between the adsorbates and the Cu atoms along the reaction path; these features reveal the role of Cu as the catalytic material for graphene growth. All the dehydrogenation reactions are endothermic, except for carbon dimer (C(2)) formation, which is, therefore, the most critical step for subsequent graphene growth, in particular, on Cu (111) surface. PMID:21842949

  4. Regioselective synthesis and ab initio calculations of fused heterocycles thermally and under microwave irradiation

    NASA Astrophysics Data System (ADS)

    Salem, Mostafa E.; Ahmed, Ashour A.; Shaaban, Mohamed R.; Shibl, Mohamed F.; Farag, Ahmad M.

    2015-09-01

    Pyrazolo[1,5-a]pyrimidine, triazolo[1,5-a]pyrimidine, and pyrimido[1,2-a]benzimidazole, pyrido[1,2-a]benzimidazole ring systems incorporating phenylsulfonyl moiety were synthesized via the reaction of 3-(N,N-dimethylamino)-1-(thiophen-2-yl)-2-(phenylsulfonyl)prop-2-en-1-one derivatives with the appropriate aminoazoles as 1,3-binucleophiles and 1H-benzimidazol-2-ylacetonitrile using conventional methods as well as microwave irradiation. The regioselectivity of the cyclocondensation reactions was confirmed both experimentally by alternative synthesis of reaction products and theoretically using ab initio quantum chemical calculations namely the Density Functional Theory (DFT). The theoretical work was carried out using the Becke, three parameter, Lee-Yang-Parr hybrid functional (B3LYP) combined with the 6-311++G(d,p) basis set. It was found that the final cyclocondensation reaction product depends mainly on the initial addition to the activated double bond by the nitrogen atom of the 1,3-binucleophiles that has the higher electron density.

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

    PubMed

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

    2012-06-20

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

  6. Molecular spectroscopic studies and ab initio calculations of four alcohols derived from 2,2-dimethylpropane

    NASA Astrophysics Data System (ADS)

    Granzow, B.; Klaeboe, P.; Sablinskas, V.

    1995-04-01

    Four alcohols with the formulas C(CH 2OH) x(CH 3) 4- x (x=1,2,3,4) have been investigated by IR and Raman spectroscopy at different temperatures from the crystalline phases to the plastic phases and the melts. Solution spectra in different solvents have also been obtained. The alcohols with the highest vapour pressures, 2,2-dimethyl-1-propanol and 2,2-dimethyl-1,3-propanediol were studied in argon and nitrogen matrices at 4.5 K using the hot nozzle technique. As observed for the corresponding halogenated compounds, the alcohols are expected to have conformational equilibria due to restricted rotations around the C-C bonds in the plastic phases, the melts and in solution. Additional conformers from rotations around the C-O bonds cannot be excluded. The energies and frequencies of the expected conformations were determined by ab initio calculations using a 3-21 G∗ basis set and compared with the experimental values. The data reveal that the {G}/{G} ( C2) conformer is the most stable in 2,2-dimethyl-1,3-propanediol, while in 2-hydroxymethyl-2-methyl-1,3-propanediol the C1 conformer is more stable than both C3 and Cs with enthalpy differences of 2.9 and 3.7 kJ mol -1, respectively.

  7. Low-energy states of manganese-oxo corrole and corrolazine: multiconfiguration reference ab initio calculations.

    PubMed

    Zhao, Hailiang; Pierloot, Kristine; Langner, Ernie H G; Swarts, Jannie C; Conradie, Jeanet; Ghosh, Abhik

    2012-04-01

    Manganese(V)-oxo corrole and corrolazine have been studied with ab initio multiconfiguration reference methods (CASPT2 and RASPT2) and large atomic natural orbital (ANO) basis sets. The calculations confirm the expected singlet d(δ)(2) ground states for both complexes and rule out excited states within 0.5 eV of the ground states. The lowest excited states are a pair of Mn(V) triplet states with d(δ)(1)d(π)(1) configurations 0.5-0.75 eV above the ground state. Manganese(IV)-oxo macrocycle radical states are much higher in energy, ≥1.0 eV relative to the ground state. The macrocyclic ligands in the ground states of the complexes are thus unambiguously 'innocent'. The approximate similarity of the spin state energetics of the corrole and corrolazine complexes suggests that the latter macrocycle on its own does not afford any special stabilization for the Mn(V)O center. The remarkable stability of an Mn(V)O octaarylcorrolazine thus appears to be ascribable to the steric protection afforded by the β-aryl groups. PMID:22432719

  8. Structures and energies of D-galactose and galabiose conformers as calculated by ab initio and semiempirical methods.

    PubMed

    Rahal-Sekkal, Majda; Sekkal, Nezha; Kleb, Dirk C; Bleckmann, Paul

    2003-05-01

    Optimized geometries and total energies of some conformers of alpha- and beta-D-galactose have been calculated using the RHF/6-31G* ab initio method. Vibrational frequencies were computed at the 6-31G* level for the conformers that favor internal hydrogen bonding, in order to evaluate their enthalpies, entropies, Gibbs free energies, and then their structural stabilities. The semiempirical AM1, PM3, MNDO methods have also been performed on the conformers GG, GT, and TG of alpha- and beta-D-galactose. In order to test the reliability of each semiempirical method, the obtained structures and energies from the AM1, PM3, and MNDO methods have been compared to those achieved using the RHF/6-31G* ab initio method. The MNDO method has not been investigated further, because of the large deviation in the structural parameters compared with those obtained by the ab initio method for the galactose. The semiempirical method that has yielded the best results is AM1, and it has been chosen to perform structural and energy calculations on the galabiose molecule (the disaccharides constituted by two galactose units alpha 1,4 linked). The goal of such calculations is to draw the energy surface maps for this disaccharide. To realize each map, 144 different possible conformations resulting from the rotations of the two torsional angles psi and phi of the glycosidic linkage are considered. In each calculation, at each increment of psi and phi, using a step of 30 degrees from 0 to 330 degrees, the energy optimization is employed. In this article, we report also calculations concerning the galabiose molecule using different ab initio levels such as RHF/6-31G*, RHF/6-31G**, and B3Lyp/6-31G*. PMID:12692790

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

    SciTech Connect

    Kostadinova, O.; Chrissanthopoulos, A.; Petkova, T.; Petkov, P.; Yannopoulos, S.N.

    2011-02-15

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

  10. An hybrid computing approach to accelerating the multiple scattering theory based ab initio methods

    NASA Astrophysics Data System (ADS)

    Wang, Yang; Stocks, G. Malcolm

    2014-03-01

    The multiple scattering theory method, also known as the Korringa-Kohn-Rostoker (KKR) method, is considered an elegant approach to the ab initio electronic structure calculation for solids. Its convenience in accessing the one-electron Green function has led to the development of locally-self consistent multiple scattering (LSMS) method, a linear scaling ab initio method that allows for the electronic structure calculation for complex structures requiring tens of thousands of atoms in unit cell. It is one of the few applications that demonstrated petascale computing capability. In this presentation, we discuss our recent efforts in developing a hybrid computing approach for accelerating the full potential electronic structure calculation. Specifically, in the framework of our existing LSMS code in FORTRAN 90/95, we explore the many core resources on GPGPU accelerators by implementing the compute intensive functions (for the calculation of multiple scattering matrices and the single site solutions) in CUDA, and move the computational tasks to the GPGPUs if they are found available. We explain in details our approach to the CUDA programming and the code structure, and show the speed-up of the new hybrid code by comparing its performances on CPU/GPGPU and on CPU only. The work was supported in part by the Center for Defect Physics, a DOE-BES Energy Frontier Research Center.

  11. Ab Initio Molecular Dynamics Simulations and GIPAW NMR Calculations of a Lithium Borate Glass Melt.

    PubMed

    Ohkubo, Takahiro; Tsuchida, Eiji; Takahashi, Takafumi; Iwadate, Yasuhiko

    2016-04-14

    The atomic structure of a molten 0.3Li2O-0.7B2O3 glass at 1250 K was investigated using ab initio molecular dynamics (AIMD) simulations. The gauge including projector augmented wave (GIPAW) method was then employed for computing the chemical shift and quadrupolar coupling constant of (11)B, (17)O, and (7)Li from 764 AIMD derived structures. The chemical shift and quadrupolar coupling constant distributions were directly estimated from the dynamical structure of the molten glass. (11)B NMR parameters of well-known structural units such as the three-coordinated ring, nonring, and four-coordinated tetrahedron were found to be in good agreement with the experimental results. In this study, more detailed classification of B units was presented based on the number of O species bonded to the B atoms. This highlights the limitations of (11)B NMR sensitivity for resolving (11)B local environment using the experimentally obtained spectra only. The (17)O NMR parameter distributions can theoretically resolve the bridging and nonbridging O atoms with different structural units such as nonring, single boroxol ring, and double boroxol ring. Slight but clear differences in the number of bridging O atoms surrounding Li that have not been reported experimentally were observed in the theoretically obtained (7)Li NMR parameters. PMID:27010637

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

    NASA Astrophysics Data System (ADS)

    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.

  13. A coupled channel study of HN2 unimolecular decay based on a global ab initio potential surface

    NASA Technical Reports Server (NTRS)

    Koizumi, Hiroyasu; Schatz, George C.; Walch, Stephen P.

    1991-01-01

    The unimolecular decay lifetimes of several vibrational states of HN2 are determined on the basis of an accurate coupled channel dynamics study using a global analytical potential surface. The surface reproduces the ab initio points with an rms error of 0.08 kcal/mol for energies below 20 kcal/mol. Modifications to the potential that describe the effect of improving the basis set in the ab initio calculations are provided. Converged coupled channel calculations are performed for the ground rotational state of HN2 to determine the lifetimes of the lowest ten vibrational states. Only the ground vibrational state (000) and first excited bend (001) are found to have lifetimes longer than 1 ps. The lifetimes of these states are estimated at 3 x 10 to the -9th and 2 x 10 to the -10th s, respectively. Variation of these results with quality of the ab initio calculations is not more than a factor of 5.

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

    SciTech Connect

    Hegde, Ganesh Bowen, R. Chris

    2015-10-15

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

  15. Matrix-isolation study and ab initio calculations of the structure and spectra of hydroxyacetone.

    PubMed

    Sharma, Archna; Reva, Igor; Fausto, Rui

    2008-07-01

    The structure of hydroxyacetone (HA) isolated in an argon matrix (at 12 K) and in a neat solid phase (at 12-175 K) was characterized by using infrared (IR) spectroscopy. The interpretation of the experimental results was supported by high-level quantum chemical calculations, undertaken by using both ab initio (MP2) and density functional theory methods. A potential-energy surface scan, carried out at the MP2/6-311++G(d,p) level of theory, predicted four nonequivalent minima, Cc, Tt, Tg, and Ct, all of them doubly degenerate by symmetry. The energy barriers for conversion between most of the symmetrically related structures and also between some of the nonequivalent minima (e.g., Tg --> Tt and Ct --> Tt) are very small and stay below the zero-point vibrational level associated with the isomerization coordinate in the higher-energy form in each pair. Therefore, only Cc and Tt conformers have physical significance, with populations of 99 and 1%, respectively, in gas phase at room temperature. For the matrix-isolated compound, only the most stable Cc conformer was observed. On the other hand, the polarizable continuum model calculations indicated that in water solution, the population of Tt and Ct conformers might be high enough (ca. 6 and 11%, respectively) to enable their experimental detection, thus supporting the conclusions of a previous IR spectroscopy study [ Spectrochim. Acta A 2005, 61, 477] in which the presence of more than one HA conformer in aqueous solution was postulated. The signatures of these minor conformers, however, do not appear in the spectra of the neat HA crystal, and the crystal structure was rationalized in terms of centrosymmetric hydrogen-bonded dimers consisting of two Cc-like units. Finally, we calculated (1)H, (13)C, and (17)O NMR chemical shifts at different levels of theory and found them to agree with available experimental data. PMID:18537231

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

    PubMed

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

    2015-10-21

    The rotational spectrum of the van der Waals complex CH4-CO has been measured with the intracavity OROTRON jet spectrometer in the frequency range of 110-145 GHz. Newly observed and assigned transitions belong to the K = 2-1 subband correlating with the rotationless jCH4 = 0 ground state and the K = 2-1 and K = 0-1 subbands correlating with the jCH4 = 2 excited state of free methane. The (approximate) quantum number K is the projection of the total angular momentum J on the intermolecular axis. The new data were analyzed together with the known millimeter-wave and microwave transitions in order to determine the molecular parameters of the CH4-CO complex. Accompanying ab initio calculations of the intermolecular potential energy surface (PES) of CH4-CO have been carried out at the explicitly correlated coupled cluster level of theory with single, double, and perturbative triple excitations [CCSD(T)-F12a] and an augmented correlation-consistent triple zeta (aVTZ) basis set. The global minimum of the five-dimensional PES corresponds to an approximately T-shaped structure with the CH4 face closest to the CO subunit and binding energy De = 177.82 cm(-1). The bound rovibrational levels of the CH4-CO complex were calculated for total angular momentum J = 0-6 on this intermolecular potential surface and compared with the experimental results. The calculated dissociation energies D0 are 91.32, 94.46, and 104.21 cm(-1) for A (jCH4 = 0), F (jCH4 = 1), and E (jCH4 = 2) nuclear spin modifications of CH4-CO, respectively. PMID:26493903

  17. Structural stability and thermodynamics of CrN magnetic phases from ab initio calculations and experiment

    NASA Astrophysics Data System (ADS)

    Zhou, Liangcai; Körmann, Fritz; Holec, David; Bartosik, Matthias; Grabowski, Blazej; Neugebauer, Jörg; Mayrhofer, Paul H.

    2014-11-01

    The dynamical and thermodynamic phase stabilities of the stoichiometric compound CrN including different structural and magnetic configurations are comprehensively investigated using a first-principles density functional theory (DFT) plus U (DFT +U ) approach in conjunction with experimental measurements of the thermal expansion. Comparing DFT and DFT +U results with experimental data reveals that the treatment of electron correlations using methods beyond standard DFT is crucial. The nonmagnetic face-centered cubic B1-CrN phase is both elastically and dynamically unstable, even under high pressure, while CrN phases with nonzero local magnetic moments are predicted to be dynamically stable within the framework of the DFT +U scheme. Furthermore, the impact of different treatments for the exchange-correlation (xc)-functional is investigated by carrying out all computations employing the local density approximation and generalized gradient approximation. To address finite-temperature properties, both magnetic and vibrational contributions to the free energy have been computed employing our recently developed spin-space averaging method. The calculated phase transition temperature between low-temperature antiferromagnetic and high-temperature paramagnetic (PM) CrN variants is in excellent agreement with experimental values and reveals the strong impact of the choice of the xc-functional. The temperature-dependent linear thermal expansion coefficient of CrN is experimentally determined by the wafer curvature method from a reactive magnetron sputter deposited single-phase B1-CrN thin film with dense film morphology. A good agreement is found between experimental and ab initio calculated linear thermal expansion coefficients of PM B1-CrN. Other thermodynamic properties, such as the specific heat capacity, have been computed as well and compared to previous experimental data.

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

    SciTech Connect

    Laghave, Nikhil

    2010-01-01

    Many modern scientific applications rely on highly computation intensive calculations. However, most applications do not concentrate as much on the role that input/output operations can play for improved performance and portability. Parallelizing input/output operations of large files can significantly improve the performance of parallel applications where sequential I/O is a bottleneck. A proper choice of I/O library also offers a scope for making input/output operations portable across different architectures. Thus, use of parallel I/O libraries for organizing I/O of large data files offers great scope in improving performance and portability of applications. In particular, sequential I/O has been identified as a bottleneck for the highly scalable MFDn (Many Fermion Dynamics for nuclear structure) code performing ab-initio nuclear structure calculations. We develop interfaces and parallel I/O procedures to use a well-known parallel I/O library in MFDn. As a result, we gain efficient I/O of large datasets along with their portability and ease of use in the down-stream processing. Even situations where the amount of data to be written is not huge, proper use of input/output operations can boost the performance of scientific applications. Application checkpointing offers enormous performance improvement and flexibility by doing a negligible amount of I/O to disk. Checkpointing saves and resumes application state in such a manner that in most cases the application is unaware that there has been an interruption to its execution. This helps in saving large amount of work that has been previously done and continue application execution. This small amount of I/O provides substantial time saving by offering restart/resume capability to applications. The need for checkpointing in optimization code NEWUOA has been identified and checkpoint/restart capability has been implemented in NEWUOA by using simple file I/O.

  19. An accurate {ital ab initio} HOCl potential energy surface, vibrational and rotational calculations, and comparison with experiment

    SciTech Connect

    Skokov, S.; Peterson, K.A.; Bowman, J.M.

    1998-08-01

    Accurate {ital ab initio} multireference configuration interaction (CI) calculations with large correlation-consistent basis sets are performed for HOCl. After extrapolation to the complete basis set limit, the {ital ab initio} data are precisely fit to give a semiglobal three-dimensional potential energy surface to describe HOCl{r_arrow}Cl+OH from high overtone excitation of the OH-stretch. The average absolute deviation between the {ital ab initio} and fitted energies is 4.2thinspcm{sup {minus}1} for energies up to 60 kcal/mol relative to the HOCl minimum. Vibrational energies of HOCl including the six overtones of the OH-stretch are computed using a vibrational-Cl method on the fitted potential and also on a slightly adjusted potential. Near-spectroscopic accuracy is obtained using the adjusted potential; the average absolute deviation between theory and experiment for 19 experimentally reported states is 4.8thinspcm{sup {minus}1}. Very good agreement with experiment is also obtained for numerous rotational energies for the ground vibrational state, the ClO-stretch fundamental, and the fifth overtone of the OH-stretch. {copyright} {ital 1998 American Institute of Physics.}

  20. Microsolvation of LiBO2 in water: anion photoelectron spectroscopy and ab initio calculations.

    PubMed

    Zeng, Zhen; Hou, Gao-Lei; Song, Jian; Feng, Gang; Xu, Hong-Guang; Zheng, Wei-Jun

    2015-04-14

    The microsolvation of LiBO2 in water was investigated by conducting anion photoelectron spectroscopy and ab initio studies on the LiBO2(H2O)n(-) (n = 0-5) clusters. By comparing calculations with experiments, the structures of these clusters and their corresponding neutrals were assigned, and their structural evolutions were revealed. During the anionic structural evolution with n increasing to 5, hydroxyborate and metaborate channels were identified and the metaborate channel is more favorable. For the hydroxyborate structures, the anionic Li(+)-BO2(-) ion pair reacts with a water molecule to produce the LiBO(OH)2(-) moiety and three water molecules tend to dissolve this moiety. In the metaborate channel, two types of solvent-separated ion pair (SSIP) geometries were determined as the ring-type and linear-type. The transition from the contact ion pair (CIP) to the ring-type of SSIP starts at n = 3, while that to the linear-type of SSIP occurs at n = 4. In neutral LiBO2(H2O)n clusters, the first water molecule prefers to react with the Li(+)-BO2(-) ion pair to generate the LiBO(OH)2 moiety, analogous to the bulk crystal phase of α-LiBO2 with two O atoms substituted by two OH groups. The Li-O distance in the LiBO(OH)2 moiety increases with the increasing number of water molecules and elongates abruptly at n = 4. Our studies provide new insight into the initial dissolution of LiBO2 salt in water at the molecular level and may be correlated to the bulk state. PMID:25758204

  1. Nonadiabatic ab initio dynamics of a model protonated Schiff base of 9-cis retinal.

    PubMed

    Chung, Wilfredo Credo; Nanbu, Shinkoh; Ishida, Toshimasa

    2010-08-19

    The dynamics of the photoisomerization of a model protonated Schiff base of 9-cis retinal in isorhodopsin is investigated using nonadiabatic molecular dynamics simulation combined with ab initio quantum chemical calculations on-the-fly. The quantum chemical part is treated at the complete-active space self-consistent field level for six electrons in six active pi orbitals with the 6-31G basis set (CASSCF(6,6)/6-31G). The probabilities of nonadiabatic transitions between the S(1) ((1)pipi*) and S(0) states are estimated in light of the Zhu-Nakamura theory. The photoinduced cis-trans isomerization of 9-cis retinal proceeds slower than that of its 11-cis analogue and at a lower quantum yield, confirming experimental observations. An energetic barrier in the excited state impedes the elongation and twist of the C(9)=C(10) stretch and torsion coordinates, respectively, resulting in the trapping of trajectories before transition. Consequently, the isomerization takes longer time and the transition more often occurs at smaller twist angle of =C(8)-C(9)=C(10)-C(11)=, which leads to regeneration of the 9-cis reactant. Thus, neither the smaller twist observed in the X-ray crystal nor the slower movement of nuclei in the transition region would be the main reason for the longer reaction time and lower yield. A well-known space-saving asynchronous bicycle pedal or crankshaft photoisomerization mechanism is found to be operational in 9-cis retinal. The simulation in vacuo suggests that the excited-state barrier and the photoisomerization itself are intrinsic properties of the visual chromophore and not triggered mainly by the protein environment that surrounds the chromophore. PMID:20666503

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

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

    NASA Astrophysics Data System (ADS)

    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.

  4. Ab initio calculation of the elastic properties of Al1-xLix (x⩽0.20) random alloys

    NASA Astrophysics Data System (ADS)

    Taga, A.; Vitos, L.; Johansson, B.; Grimvall, G.

    2005-01-01

    Ab initio total energy calculations, based on the exact muffin-tin orbital (EMTO) theory, are used to determine the elastic properties of Al1-xLix random alloys (x⩽0.20) in the face-centered-cubic crystallographic phase. The compositional disorder is treated within the framework of the single-site coherent potential approximation (CPA). The effect of the local lattice relaxation on the elastic constants is estimated using a supercell technique. We study the effect of the single-site approximation by comparing the theoretical ground-state properties calculated using different corrections to the Madelung energy. We find that the calculated equilibrium volumes and alloy formation energies strongly depend on the approximations employed in the Poisson equation, in accordance with former observations. At the same time, the experimental trends of the elastic moduli of disordered Al-Li alloys are well reproduced by the EMTO-CPA method. Using these theoretical results we show that the nonlinear effect of Li addition on the elastic constants originates from the detailed band structure of Al near the Fermi level.

  5. Ab Initio Calculations and Experimental Properties of CuAl x Ga1- x Te2 for Photovoltaic Solar Cells

    NASA Astrophysics Data System (ADS)

    Benabdeslem, M.; Sehli, H.; Rahal, S.; Benslim, N.; Bechiri, L.; Djekoun, A.; Touam, T.; Boujnah, M.; El Kenz, A.; Benyoussef, A.; Portier, X.

    2016-02-01

    Nanostructured chalcopyrite CuAl x Ga1- x Te2 ( x = 0.25, 0.50, and 0.75) has been prepared by ball milling of Cu, Al, Ga, and Te precursors. Preliminary ab initio calculations of the main properties have been performed on the prototype chalcopyrite semiconductor CuAlGaTe2. The simulation method used is based on the density functional theory within the framework of pseudo-potentials and plane waves. Band Structure calculations suggest that CuAlGaTe2 is a direct bandgap semiconductor having a band gap = 1.35 eV. In the experimental part, x-ray diffraction analysis revealed the presence of (112), (220)/(204), (312)/(116), and (400) reflections for all the milled powders characteristic of the chalcopyrite structure. A shift in peaks towards a higher value of 2 θ is observed with the increase in Al composition. With increasing Al content, it is found that the average crystallite size decreases whereas the bandgap energy increases from 1.34 eV to 1.51 eV. Compared with experimental data, calculated results by GGA-mBJ functional quantitatively agree with experimental data.

  6. TOPICAL REVIEW: Recent advances in jointed quantum mechanics and molecular mechanics calculations of biological macromolecules: schemes and applications coupled to ab initio calculations

    NASA Astrophysics Data System (ADS)

    Hagiwara, Yohsuke; Tateno, Masaru

    2010-10-01

    We review the recent research on the functional mechanisms of biological macromolecules using theoretical methodologies coupled to ab initio quantum mechanical (QM) treatments of reaction centers in proteins and nucleic acids. Since in most cases such biological molecules are large, the computational costs of performing ab initio calculations for the entire structures are prohibitive. Instead, simulations that are jointed with molecular mechanics (MM) calculations are crucial to evaluate the long-range electrostatic interactions, which significantly affect the electronic structures of biological macromolecules. Thus, we focus our attention on the methodologies/schemes and applications of jointed QM/MM calculations, and discuss the critical issues to be elucidated in biological macromolecular systems.

  7. An AB Initio Relativistic Many-Body Calculation of Mercury 6

    NASA Astrophysics Data System (ADS)

    Cai, Ziyong

    1990-01-01

    In this work, the energy levels and widths of mercury 6p^2 resonance states are investigated, completing the second branch of our whole ab initio relativistic many-body calculation procedure. ^1 Relativistic zeroth-order wavefunctions are obtained by solving the multi-configurational Dirac -Fock (MCDF) equations.^2 The Breit effects are included. Relativistic configuration interaction (RCI) calculations are then carried out for the localized portion of the wavefunction^3 for which we included single and double excitations to account for both valence-shell correlations and the most important parts of the core-valence correlations, 5d-valence correlations. A total of 4 sets of virtual basis functions are used in the RCI calculations. Two virtual sets are used for valence shell correlations, both from vs_{1/2 } to vg_{9/2}. Another two sets are used for core-valence correlations, each ranging from vs_{1/2} to vf _{7/2}. To evaluate the continuum effects, relativistic continuum wavefunctions are calculated by using Perger's program^4 in the presence of a frozen core generated from Grant's program. ^5 Wavefunctions of the open channel discrete states are generated using Desclaux's program. ^2 The interactions between the resonances and the open channels are then calculated by using the method of the configuration interaction in continuum (CIC), ^6 for which a program, PVINT, ^7 is implemented to give both energy shifts and widths for the resonance states caused by the open channels. References. (1) D. R. Beck and Z. Cai, Phys. Rev. A 41, 301 (1990). (2) J. P. Desclaux, Comput. Phys. Commun 9, 31 (1975). (3) D. R. Beck, Program RELCOR, 1987, unpublished. (4) W. F. Perger and V. S. Karighattam, Program to generate continua and R^{k } integrals, 1990, Submitted to Comp. Phys. Commun. (5) I. P. Grant, B. J. McKenzie, P. H. Norrington, D. F. Mayers and N. C. Pyper, Comput. Phys. Commun. 21, 207 (1980). (6) U. Fano, Phys. Rev. 124, 1866 (1961). (7) Z. Cai, Program PVINT, 1990

  8. Conformational analysis from low-frequency vibrational data and ab initio calculations for 3-chloropropene

    NASA Astrophysics Data System (ADS)

    Durig, J. R.; Durig, D. T.; Jalilian, M. R.; Zhen, Mengzhang; Little, T. S.

    1989-03-01

    The asymmetric torsion of 3-chloropropene, CH 2CHCH 2Cl, has been investigated by far-infrared and Raman spectra of the gas and the low-frequency Raman spectrum of the liquid at various temperatures. Both the gauche and cis (halogen to double bond) conformers are present in the fluid phases at ambient temperature and the gauche isomer is the predominant form in the liquid. The asymmetric torsion of the cis rotamer is observed in the far-infrared spectrum of the gas at 147.28 cm -1 with four accompanying "hot bands" and the corresponding fundamental of the gauche conformer is observed at 101.97 cm -1 also with four "hot bands". From these data, a potential function governing the internal rotation of the asymmetric top has been determined with potential constants of: V1 = -47±19, V2 = 145±17, V3 = 862±8, V4 = 14±6, V6 = -50±4 cm -1. This potential function is consistent with the cis form being thermodynamically preferred by 81 cm -1 (0.23 kcal mol -1), and a torsional dihedral angle of 122° for the gauche conformer away from the cis form. The calculated cis to gauche, gauche to gauche, and gauche to cis barriers are 969 cm -1 (2.77 kcal mol -1), 734 cm -1 (2.10 kcal mol -1) and 888 cm -1 (2.54 kcal mol -1), respectively. From relative intensities of the Raman lines of the liquid at 245 ( cis) and 289 ( gauche) cm -1 as a function of temperature, the enthalpy difference was found to be 178±11 cm -1 (509±31 cal mol -1) with the gauche form being more stable. The normal vibrations for both the cis and gauche rotamers have been calculated by ab initio Hartree-Fock gradient calculations employing the 3-21G* basis set. The calculated frequencies and force constants are compared to those previously reported. Potential surface calculations and structural determinations have been carried out employing both the 3-21G* and 6-31G* basis sets and compared to those obtained experimentally. These results are compared to similar quantities in some related molecules.

  9. Different models for phosphate anion shielding in DNA duplexes: An elaboration with ab initio and molecular mechanics calculations

    NASA Astrophysics Data System (ADS)

    Buck, Henk

    In an effort to overcome a significant difference between high-level ab initio calculations and X-ray data of DNA duplexes, Fonseca Guerra et al. 9-11 studied a number of model systems for A-T and G-C basepairs at various levels of nonlocal Density Functional Theory. There was an excellent agreement with the gas-phase experimental bond enthalpies for the A-T and G-C basepairs. On the other hand the hydrogen bond lengths between the bases differ from the X-ray results. After introduction of a molecular environment as local water and Na+ ions, the agreement between theory and experiment was excellent. However, careful analysis shows that this picture is far from correct. In fact, the model was constructed as a backbone-modified DNA duplex in which the nonbonding oxygens of the phosphate linkages are completely shielded by proton addition. Experimental results with respect to backbone-modified DNAs clearly show that changes in the backbone focused on phosphate shielding result in DNA duplexes with a variety in conformational behavior. In addition to an analysis of the aforementioned contradiction, we also give molecular mechanics calculations which show that the A-T and G-C bond enthalpies are of the same order as the corresponding results of Fonseca Guerra et al. under the condition of complete anionic shielding of the nonbonded oxygens in the phosphate linkages.

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

    NASA Astrophysics Data System (ADS)

    Mozafari, E.; Shulumba, N.; Steneteg, P.; Alling, B.; Abrikosov, Igor A.

    2016-08-01

    We present a theoretical scheme to calculate the elastic constants of magnetic materials in the high-temperature paramagnetic state. Our approach is based on a combination of disordered local moments picture and ab initio molecular dynamics (DLM-MD). Moreover, we investigate a possibility to enhance the efficiency of the simulations of elastic properties using the recently introduced method: symmetry imposed force constant temperature-dependent effective potential (SIFC-TDEP). We have chosen cubic paramagnetic CrN as a model system. This is done due to its technological importance and its demonstrated strong coupling between magnetic and lattice degrees of freedom. We have studied the temperature-dependent single-crystal and polycrystalline elastic constants of paramagentic CrN up to 1200 K. The obtained results at T = 300 K agree well with the experimental values of polycrystalline elastic constants as well as the Poisson ratio at room temperature. We observe that the Young's modulus is strongly dependent on temperature, decreasing by ˜14 % from T = 300 K to 1200 K. In addition we have studied the elastic anisotropy of CrN as a function of temperature and we observe that CrN becomes substantially more isotropic as the temperature increases. We demonstrate that the use of Birch law may lead to substantial errors for calculations of temperature induced changes of elastic moduli. The proposed methodology can be used for accurate predictions of mechanical properties of magnetic materials at temperatures above their magnetic order-disorder phase transition.

  11. Ab initio-based fracture toughness estimates and transgranular traction-separation modelling of zirconium hydrides

    NASA Astrophysics Data System (ADS)

    Olsson, P. A. T.; Kese, K.; Kroon, M.; Alvarez Holston, A.-M.

    2015-06-01

    In this work we report the results of an ab initio study of the transgranular fracture toughness and cleavage of brittle zirconium hydrides. We use the Griffith-Irwin relation to assess the fracture toughness using calculated surface energy and estimated isotropic Voigt-Reuss-Hill averages of the elastic constants. The calculated fracture toughness values are found to concur well with experimental data, which implies that fracture is dominated by cleavage failure. To investigate the cleavage energetics, we model the decohesion process. To describe the interplanar interaction we adopt Rose’s universal binding energy relation, which is found to reproduce the behaviour accurately. The modelling shows that the work of fracture and ductility decreases with increasing hydrogen content.

  12. Ab initio based investigation of interstitial interactions and Snoek relaxation in Nb-O

    NASA Astrophysics Data System (ADS)

    Dmitriev, V. V.; Blanter, M. S.; Ruban, A. V.; Johansson, B.

    2012-02-01

    Chemical and strain-induced effective pair interactions of interstitial oxygen atoms in bcc Nb have been determined in supercell first-principles calculations using Vienna ab initio simulation package (VASP). The strain-induced interactions are in reasonable agreement with those obtained earlier within a phenomenological microscopic Krivoglaz-Kanzaki-Khachaturyan model (KKKM). At the same time, the chemical interactions, which have been considered to be small in earlier theoretical considerations, turned out to be dominating at the first several coordination shells. The obtained interactions have been used in calculations of the concentration- and temperature-dependence of the internal friction Snoek peak. The theoretical results are found to be in good agreement with the existing experimental data.

  13. Structure and Radiationless Transition of Pahs : Ultrahigh-Resolution Spectroscopy and AB Initio Calculation

    NASA Astrophysics Data System (ADS)

    Baba, Masaak

    2009-06-01

    Polycyclic aromatic hydrocarbons (PAHs) are fascinating objects of basic studies on molecular structure and excited-state dynamics. We have observed and analyzed rotationally resolved ultrahigh-resolution spectra of the S_1 ← S_0 transition of naphthalene, anthracene, pyrene and perylene (all D_{2h} symmetry) in collimated supersonic jets. We conclude that radiationless transitions are all slow in the S_1 zero-vibrational level of the isolated PAH molecule. Possible radiationless processes are intersystem crossing (ISC), internal conversion (IC), and predissociation. Predissociation does not take place because all of the bond energies are larger than the S_1 ← S_0 excitation energy. The observed radiationless process has been presumed to be ISC so far. However, it is inconsistent with El-Sayed's rule that spin-orbit interaction is very weak between the ^1ππ^* and ^3ππ^* states. We have observed Zeeman splitting of each rotational line and shown that the magnetic moment is very small in the S_1 state. Therefore, the main radiationless process is not ISC to the triplet state, but IC to the hot ground state. IC is caused by non-Born-Oppenheimer vibronic interaction, which is expected to be very weak if the molecular structure is identical for both electronic states. The experimentally determined rotational constants are almost identical for the S_0 and S_1 states. It is consistent with the observed long lifetime and high fluorescence quantum yield of PAHs. We carried out ab initio calculation, and the resultant values of rotational constants of the S_0 state are in extremely good coincidence with the experimental ones for naphthalene and anthracene. On the contrary, for the excited state, it is necessary to perform huge SAC-CI calculation to obtain satisfactory results. Fast IC has been found, for instance, in high vibrational levels of benzene (channel 3), which is due to unavoided potential crossing (conical intersection). However, it is not likely in large

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

    NASA Astrophysics Data System (ADS)

    Titantah, John T.; Karttunen, Mikko

    2016-05-01

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

  15. Magnetic and electronic properties of Cr- and Mn-doped SnO2: ab initio calculations

    NASA Astrophysics Data System (ADS)

    Ziat, Y.; Benyoussef, A.; El Kenz, A.

    2014-06-01

    The ab initio calculations, based on the Korringa-Kohn-Rostoker (KKR) approximation method combined with the coherent potential approximation (CPA), indicated as KKR-CPA, have been used to study the stability of ferromagnetic and ferrimagnetic states, for systems that are SnO2 doped and co-doped with two transition metals, that is, chromium and manganese. Our results indicate that the ferromagnetic state is more stable than the spin-glass state for the (Sn1-xCrxO2; x = 0.07, 0.09, 0.12 and 0.15)-doped system, while the spin-glass state is more stable than the ferromagnetic state for the (Sn1-xMnxO2; x = 0.02 and 0.05)-doped system. However, the ferromagnetic and/or the ferrimagnetic states are stable for the (Sn0.98-xMn0.02CrxO2; x = 0.05, 0.09 and 0.13)-doped system depending on the Cr concentration. Moreover, we estimated the Curie temperature (Tc) for the Cr-doped tin dioxide (SnO2), and we explained the origin of magnetic behaviour through the total density of states for different doped and co-doped SnO2 systems.

  16. Conformational stability, barriers to internal rotation, vibrational assignment, and ab initio calculations of chloroacetyl fluoride

    NASA Astrophysics Data System (ADS)

    Durig, J. R.; Zhao, Wenyun; Lewis, Durig; Little, T. S.

    1988-08-01

    The far infrared spectrum of gaseous chloroacetyl fluoride, CH2ClC(O)F, has been recorded at a resolution of 0.10 cm-1 in the 350 to 35 cm-1 region. The fundamental asymmetric torsional frequencies of the more stable trans (two halogen atoms oriented trans to one another) and high energy gauche (Cl-C-C=O torsional dihedral angle of 122°) have been observed at 86.5 and 48.8 cm-1, respectively, each with excited states falling to lower frequency. From these data the asymmetric torsional potential function governing internal rotation about the C-C bond has been determined. This potential function is consistent with torsional potential coefficients of: V1=350±12, V2=306±6, V3=420±1, V4=44±1, and V6=2±1 cm-1. The trans to gauche, gauche to gauche, and gauche to trans barriers have been determined to be 796, 245, and 271 cm-1, respectively, with an energy difference between the conformations of 525±24 cm-1 (1.50±0.07 kcal/mol). From studies of the Raman spectrum at variable temperatures the conformational energy difference has been determined to be 445±80 (1.27±0.2 kcal/mol) and 534±68 cm-1 (1.53±0.2 kcal/mol) for the gaseous and liquid phases, respectively. A complete assignment of the vibrational fundamentals observed from the infrared (3500 to 50 cm-1) spectra of the gaseous and solid states and Raman (3200 to 10 cm-1) spectra of the gaseous, liquid, and solid states is proposed. All of these data are compared to the corresponding quantities obtained from ab initio Hartree-Fock gradient calculations employing both the 3-21G* and 6-31G* basis sets. Additionally, complete equilibrium geometries have been determined for both rotamers. The results are discussed and compared with the corresponding quantities obtained for some similar molecules.

  17. Ab initio variational calculations of the vibrational properties of Li + 3, Li2Na + , LiNa + 2, and KLiNa +

    NASA Astrophysics Data System (ADS)

    Searles, D. J.; von Nagy-Felsobuki, E. I.

    1991-07-01

    A rovibrational Hamiltonian has been derived in terms of rectilinear displacement coordinates which is based on the Watson Hamiltonian. Moreover, it is a generalization of the Carney and Porter analysis for D3h triatomic systems [J. Chem. Phys. 65, 3547 (1976)] and Carney et al. analysis for C2v triatomic systems [J. Chem. Phys. 66, 3724 (1977)]. It is therefore the most general form of the Watson Hamiltonian which is applicable to a bent triatomic system. Ab initio variational calculations using this Hamiltonian are presented for vibrational properties of Li+3, Li2Na+, LiNa+2, and KLiNa+.

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

    SciTech Connect

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

    2014-10-07

    We perform an ab initio computational study of molecular complexes with the general formula CF{sub 3}X—B that involve one trifluorohalomethane CF{sub 3}X (X = Cl or Br) and one of a series of Lewis bases B in the gas phase. The Lewis bases are so chosen that they provide a range of electron-donating abilities for comparison. Based on the characteristics of their electron pairs, we consider the Lewis bases with a single n-pair (NH{sub 3} and PH{sub 3}), two n-pairs (H{sub 2}O and H{sub 2}S), two n-pairs with an unsaturated bond (H{sub 2}CO and H{sub 2}CS), and a single π-pair (C{sub 2}H{sub 4}) and two π-pairs (C{sub 2}H{sub 2}). The aim is to systematically investigate the influence of the electron pair characteristics and the central atom substitution effects on the geometries and energetics of the formed complexes. The counterpoise-corrected supermolecule MP2 and coupled-cluster single double with perturbative triple [CCSD(T)] levels of theory have been employed, together with a series of basis sets up to aug-cc-pVTZ. The angular and radial configurations, the binding energies, and the electrostatic potentials of the stable complexes have been compared and discussed as the Lewis base varies. For those complexes where halogen bonding plays a significant role, the calculated geometries and energetics are consistent with the σ-hole model. Upon formation of stable complexes, the C–X bond lengths shorten, while the C–X vibrational frequencies increase, thus rendering blueshifting halogen bonds. The central atom substitution usually enlarges the intermolecular bond distances while it reduces the net charge transfers, thus weakening the bond strengths. The analysis based on the σ-hole model is grossly reliable but requires suitable modifications incorporating the central atom substitution effects, in particular, when interaction components other than electrostatic contributions are involved.

  19. Hydroxyl-functionalized 1-(2-hydroxyethyl)-3-methyl imidazolium ionic liquids: thermodynamic and structural properties using molecular dynamics simulations and ab initio calculations.

    PubMed

    Fakhraee, Mostafa; Zandkarimi, Borna; Salari, Hadi; Gholami, Mohammad Reza

    2014-12-11

    The influences of hydroxyl functional group (-OH) on the thermodynamic and structural properties of ionic liquids (ILs) composed of 1-(2-Hydroxyethyl)-3-methyl imidazolium ([C2OHmim](+)) cation and the six different conventional anions, including [Cl](-), [NO3](-), [BF4](-), [PF6](-), [TfO](-), and [Tf2N](-) have been extensively investigated using classical molecular dynamics (MD) simulations combined with ab initio calculations over a wide range of temperature (298-550 K). The volumetric thermodynamic properties, enthalpy of vaporization, cohesive energy density, Hildebrand solubility parameter, and heat capacity at constant pressure were estimated at desired temperature. The simulated densities were in good agreement with the experimental data with a slight overestimation. The interionic interaction of selected ILs was also computed using both the MD simulations and ab initio calculations. It was found that the highest association of cation and anion is attributed to [C2OHmim][Cl] followed by [C2OHmim][NO3], and [C2OHmim][Tf2N] with the bulkiest anion has the weakest interionic interaction among chosen ILs. The similar trend of interactions energies was nearly observed from cohesive energy density results. Additional structural details were comprehensively yielded by calculating radial distribution functions (RDFs) and spatial distribution function (SDFs) at 358 K. The most stable configurations of isolated and dimer ion pairs of these ILs were in excellent consistency with RDFs and SDFs results. Significant changes in arrangement of anions around the [C2OHmim](+) cation in comparison with conventional imidazolium-based ILs can be inferred from the MD simulations and ab initio results. Also, microscopic structural properties disclosed that the most strong cation-cation interaction is ascribed to the hydroxyl-functionalized ILs composed of bulkier anions, whereas ILs incorporating [Cl](-) and [NO3](-) anions are mainly involved in cation-anion interactions. The

  20. AB INITIO Modeling of Thermomechanical Properties of Mo-Based Alloys for Fossil Energy Conversion

    SciTech Connect

    Ching, Wai-Yim

    2013-12-31

    In this final scientific/technical report covering the period of 3.5 years started on July 1, 2011, we report the accomplishments on the study of thermo-mechanical properties of Mo-based intermetallic compounds under NETL support. These include computational method development, physical properties investigation of Mo-based compounds and alloys. The main focus is on the mechanical and thermo mechanical properties at high temperature since these are the most crucial properties for their potential applications. In particular, recent development of applying ab initio molecular dynamic (AIMD) simulations to the T1 (Mo{sub 5}Si{sub 3}) and T2 (Mo{sub 5}SiB{sub 2}) phases are highlighted for alloy design in further improving their properties.

  1. Evolution of optical properties of tin film from solid to liquid studied by spectroscopic ellipsometry and ab initio calculation

    SciTech Connect

    Zhang, D X; Shen, B; Zheng, Y X; Wang, S Y; Zhang, J B; Yang, S D; Zhang, R J; Chen, L Y; Wang, C Z; Ho, K M

    2014-03-24

    The temperature dependent optical properties of tin film from solid to liquid were studied by spectroscopic ellipsometry and ab initio molecular dynamics simulations. The dielectric function of liquid Sn was different from solid, and an interband transition near 1.5 eV was easily observed in solid while it apparently disappeared upon melting. From the evolution of optical properties with temperature, an optical measurement to acquire the melting point by ellipsometry was presented. From first principles calculation, we show that the local structure difference in solid and liquid is responsible for this difference in the optical properties observed in experiment.

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

    PubMed

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

    2016-02-01

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

  3. Angular momentum conservation for coherently manipulated spin polarization in photoexcited NiO: an ab initio calculation.

    PubMed

    Lefkidis, Georgios; Zhang, G P; Hübner, W

    2009-11-20

    In an ultrafast laser-induced magnetization-dynamics scenario we demonstrate for the first time an exact microscopic spin-switch mechanism. Combining ab initio electronic many-body theory and quantum optics analysis we show in detail how the coherently induced material polarization for every elementary process leads to angular-momentum exchange between the light and the irradiated antiferromagnetic NiO. Thus we answer the long-standing question where the angular momentum goes. The calculation also predicts a dynamic Kerr effect, which provides a signature for monitoring spin dynamics, by simply measuring the transient rotation and ellipticity of the reflected light. PMID:20366066

  4. Ab Initio Protein Structure Assembly Using Continuous Structure Fragments and Optimized Knowledge-based Force Field

    PubMed Central

    Xu, Dong; Zhang, Yang

    2012-01-01

    Ab initio protein folding is one of the major unsolved problems in computational biology due to the difficulties in force field design and conformational search. We developed a novel program, QUARK, for template-free protein structure prediction. Query sequences are first broken into fragments of 1–20 residues where multiple fragment structures are retrieved at each position from unrelated experimental structures. Full-length structure models are then assembled from fragments using replica-exchange Monte Carlo simulations, which are guided by a composite knowledge-based force field. A number of novel energy terms and Monte Carlo movements are introduced and the particular contributions to enhancing the efficiency of both force field and search engine are analyzed in detail. QUARK prediction procedure is depicted and tested on the structure modeling of 145 non-homologous proteins. Although no global templates are used and all fragments from experimental structures with template modeling score (TM-score) >0.5 are excluded, QUARK can successfully construct 3D models of correct folds in 1/3 cases of short proteins up to 100 residues. In the ninth community-wide Critical Assessment of protein Structure Prediction (CASP9) experiment, QUARK server outperformed the second and third best servers by 18% and 47% based on the cumulative Z-score of global distance test-total (GDT-TS) scores in the free modeling (FM) category. Although ab initio protein folding remains a significant challenge, these data demonstrate new progress towards the solution of the most important problem in the field. PMID:22411565

  5. On the Construction of Diabatic and Adiabatic Potential Energy Surfaces Based on Ab Initio Valence Bond Theory‡

    PubMed Central

    Song, Lingchun; Gao, Jiali

    2009-01-01

    A theoretical model is presented for deriving effective diabatic states based on ab initio self-consistent field valence bond (VBSCF) theory by reducing the multi-configurational VB Hamiltonian into an effective two-state model. We describe two computational approaches for the optimization of the effective diabatic configurations, resulting in two ways of interpreting such effective diabatic states. In the variational diabatic configuration (VDC) method, the energies of the individual diabatic states are variationally minimized. In the consistent diabatic configuration (CDC) method, both the configuration coefficients and orbital coefficients are simultaneously optimized to minimize the adiabatic ground-state energy in VBSCF calculations. In addition, we describe a mixed molecular orbital and valence bond (MOVB) approach to construct the CDC diabatic and adiabatic states for a chemical reaction, whereas the VDC-MOVB method has been described previously. Employing the symmetric SN2 reaction between NH3 and CH3NH3+ as a test system, we found that the results from ab initio VBSCF and from MOVB calculations are in good agreement, suggesting that the computationally efficient MOVB method is a reasonable model for VB simulations of condensed phase reactions. The results indicate that CDC and VDC diabatic states converge, respectively, to covalent and ionic states as the molecular geometries are distorted from the minimum of the respective diabatic state along the reaction coordinate. Furthermore, the resonance energy that stabilizes the energy of crossing between the two diabatic states, resulting in the transition state of the adiabatic ground-state reaction, has a strong dependence on the overlap integral between the two diabatic states and is a function of both the exchange integral and the total diabatic ground-state energy. PMID:18828577

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

    NASA Astrophysics Data System (ADS)

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

    2013-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

  8. Ab Initio Potential Energy Surfaces and the Calculation of Accurate Vibrational Frequencies

    NASA Technical Reports Server (NTRS)

    Lee, Timothy J.; Dateo, Christopher E.; Martin, Jan M. L.; Taylor, Peter R.; Langhoff, Stephen R. (Technical Monitor)

    1995-01-01

    Due to advances in quantum mechanical methods over the last few years, it is now possible to determine ab initio potential energy surfaces in which fundamental vibrational frequencies are accurate to within plus or minus 8 cm(exp -1) on average, and molecular bond distances are accurate to within plus or minus 0.001-0.003 Angstroms, depending on the nature of the bond. That is, the potential energy surfaces have not been scaled or empirically adjusted in any way, showing that theoretical methods have progressed to the point of being useful in analyzing spectra that are not from a tightly controlled laboratory environment, such as vibrational spectra from the interstellar medium. Some recent examples demonstrating this accuracy will be presented and discussed. These include the HNO, CH4, C2H4, and ClCN molecules. The HNO molecule is interesting due to the very large H-N anharmonicity, while ClCN has a very large Fermi resonance. The ab initio studies for the CH4 and C2H4 molecules present the first accurate full quartic force fields of any kind (i.e., whether theoretical or empirical) for a five-atom and six-atom system, respectively.

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

    NASA Astrophysics Data System (ADS)

    Quaglioni, Sofia

    2008-10-01

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

  10. Validating a polarizable model for the glass-forming liquid Ca0.4K0.6(NO3)1.4 by ab initio calculations

    NASA Astrophysics Data System (ADS)

    Ribeiro, Mauro C. C.; Almeida, Luiz C. J.

    2000-09-01

    Ab initio calculations have been performed in order to investigate a recently proposed polarizable model [M. C. C. Ribeiro, Phys. Rev. B 61, 3297 (2000)] for molecular dynamics (MD) simulation of the molten salt Ca0.4K0.6(NO3)1.4. On the basis of the electronegativity equalization method, polarization effects in the MD simulations have been introduced by a fluctuating charge (FC) model for the nitrate ion. Partial charges in the nitrate ion are obtained by ab initio calculations at several levels of theory, and compared with previously proposed models for MD simulations of nitrate melts. Charge fluctuation is achieved in the ab initio calculations by using positive probe charges placed around a nitrate ion. The parameters of the FC model are corroborated by comparison of the ab initio partial charges with the ones obtained directly by the electronegativity equalization method. Simulated annealing of a cluster including two double-charged cations and two nitrate ions shows that very different structures are obtained depending on whether the FC model or its nonpolarizable counterpart is considered. Ab initio calculations show that the structure of this cluster is strongly dependent on polarization effects in the nitrate ions.

  11. Microwave spectra and conformational studies of ethylamine from temperature dependent Raman spectra of xenon solutions and ab initio calculations

    NASA Astrophysics Data System (ADS)

    Darkhalil, Ikhlas D.; Nagels, Nick; Herrebout, Wouter A.; van der Veken, Benjamin J.; Gurusinghe, Ranil M.; Tubergen, Michael J.; Durig, James R.

    2014-06-01

    FT-microwave spectroscopy was carried out where the trans conformer was identified to be the most stable conformer. Variable temperature (-60 to -100 °C) studies of the Raman spectra (4000-50 cm-1) of ethylamine, CH3CH2NH2 dissolved in liquefied xenon have been carried out. From these data both conformers have been identified and their relative stabilities obtained. The enthalpy difference has been determined to be 62 ± 6 cm-1 (0.746 ± 0.072 kJ mol-1) with the trans conformer the more stable form. The percentage of the gauche conformer is estimated to be 60% at ambient temperature. The conformational stabilities have been predicted from ab initio calculations with the Møller-Plesset perturbation method to the second order (MP2(full)) and the fourth order (MP4(SDTQ)) as well as with density functional theory by the B3LYP method by utilizing a variety of basis sets. Vibrational assignments have been made for the observed bands which have been predicted by MP2(full)/6-31G(d) ab initio calculations which includes harmonic force fields, frequencies, infrared intensities, Raman activities and depolarization ratios for both conformers. The results are discussed and compared to the corresponding properties of some similar molecule.

  12. Ab initio calculations on the excited states of Na3 cluster to explore beyond Born-Oppenheimer theories: adiabatic to diabatic potential energy surfaces and nuclear dynamics.

    PubMed

    Paul, Amit Kumar; Ray, Somrita; Mukhopadhyay, Debasis; Adhikari, Satrajit

    2011-07-21

    We perform ab initio calculation using quantum chemistry package (MOLPRO) on the excited states of Na(3) cluster and present the adiabatic PESs for the electronic states 2(2)E' and 1(2)A(1)', and the non-adiabatic coupling (NAC) terms among those states. Since the ab initio calculated NAC elements for the states 2(2)E' and 1(2)A(1)' demonstrate the numerical validity of so called "Curl Condition," such states closely form a sub-Hilbert space. For this subspace, we employ the NAC terms to solve the "adiabatic-diabatic transformation (ADT)" equations to obtain the functional form of the transformation angles and pave the way to construct the continuous and single valued diabatic potential energy surface matrix by exploiting the existing first principle based theoretical means on beyond Born-Oppenheimer treatment. Nuclear dynamics has been carried out on those diabatic surfaces to reproduce the experimental spectrum for system B of Na(3) cluster and thereby, to explore the numerical validity of the theoretical development on beyond Born-Oppenheimer approach for adiabatic to diabatic transformation. PMID:21786987

  13. Bonding Structure of Phenylacetylene on Hydrogen-Terminated Si(111) and Si(100): Surface Photoelectron Spectroscopy Analysis and Ab Initio Calculations

    SciTech Connect

    M Kondo; T Mates; D Fischer; F Wudl; E Kramer

    2011-12-31

    Interfaces between phenylacetylene (PA) monolayers and two silicon surfaces, Si(111) and Si(100), are probed by X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, and the results are analyzed using ab initio molecular orbital calculations. The monolayer systems are prepared via the surface hydrosilylation reaction between PA and hydrogen-terminated silicon surfaces. The following spectral features are obtained for both of the PA-Si(111) and PA-Si(100) systems: a broad {pi}-{pi}* shakeup peak at 292 eV (XPS), a broad first ionization peak at 3.8 eV (UPS), and a low-energy C 1s {yields} {pi}* resonance peak at 284.3 eV (NEXAFS). These findings are ascribed to a styrene-like {pi}-conjugated molecular structure at the PA-Si interface by comparing the experimental data with theoretical analysis results. A conclusion is drawn that the vinyl group can keep its {pi}-conjugation character on the hydrogen-terminated Si(100) [H:Si(100)] surface composed of the dihydride (SiH{sub 2}) groups as well as on hydrogen-terminated Si(111) having the monohydride (SiH) group. The formation mechanism of the PA-Si(100) interface is investigated within cluster ab initio calculations, and the possible structure of the H:Si(100) surface is discussed based on available data.

  14. Spectra and structure of small ring compounds. LI. Infrared and Raman spectra, vibrational assignment and ab initio calculations of 1,1-dicyanocyclobutane

    NASA Astrophysics Data System (ADS)

    Durig, J. R.; Zhao, Wenyun; Little, T. S.; Dakkouri, M.

    1988-12-01

    The infrared (3500 to 50 cm -1) and Raman (3500 to 20 cm -1) spectra of solid 1,1-dicyanocyclobutane have been recorded. Additionally, the Raman spectrum of the liquid has been recorded and qualitative depolarization values have been obtained. The spectral features observed at room temperature for the solid phase (m.p. 37 °C) are very similar to those obtained for the neat liquid at ≈ 60 °C but the spectral features observed at -120 °C were clearly those of an annealed solid. These spectra have been interpreted on the basis of C s molecular symmetry for 1,1-dicyanocyclobutane where the ring is puckered and the two cyano groups are "quasi-linear". The vibrational assignment is based on depolarization values, group frequencies, and in some cases the relative intensities of the observed bands. The potential function governing the ring puckering motion has been determined from optimized geometries obtained by ab initio Hartree-Fock gradient calculations at both the 3-21G and 4-31G basis set levels. The assignments of the fundamental vibrational frequencies are compared to those obtained from a force field obtained by ab initio calculations employing the 3-21G basis set. These results are discussed and compared to those obtained for some similar molecules.

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

    SciTech Connect

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

    2014-07-15

    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 ab initio calculation which is based on the quantum molecular dynamics, density functional theory, and the Kubo-Greenwood formula. Then the semiempirical approximation was constructed based on the results of our simulation. This approximation yields the dependences σ{sub 1{sub D{sub C}}}∝1/T{sub i}{sup 0.25} and K∝T{sub e}/T{sub i}{sup 0.25} for the static electrical conductivity and thermal conductivity, respectively, for liquid aluminum at ρ = 2.70 g/cm{sup 3}, 3 kK ≤ T{sub i} ≤ T{sub e} ≤ 20 kK. Our results are well described by the Drude model with the effective relaxation time τ∝T{sub i}{sup −0.25}. We have considered a number of other models for the static electrical and thermal conductivities of aluminum, they are all reduced in the low-temperature limit to the Drude model with different expressions for the relaxation time τ. Our results are not consistent with the models in which τ∝T{sub i}{sup −1} and support the models which use the expressions with the slower decrease of the relaxation time.

  16. Investigation of the liquid Pb/Si(001) interface from ab initio molecular-dynamics calculations

    NASA Astrophysics Data System (ADS)

    Gonzalez, D. J.; Souto, J.; Alemany, M. M. G.; Longo, R. C.; Gallego, L. J.; Gonzalez, L. E.

    2013-03-01

    The structure of liquid Pb on an ideal Si(001) surface was studied experimentally a decade ago by means of x-ray diffraction and the results were interpreted in terms of the presence of fivefold symmetry Pb structures captured transiently by the potential created by the unreconstructed Si(001) surface. We critically analyze this interpretation in the light of the results obtained in an extensive ab initio molecular dynamics study of a system comprising 314 Pb atoms and 175 Si atoms setup in 7 (001) ideal layers (a total number of 1956 valence electrons) in a slab geometry. The structure found for the first Pb layer is very different from that of bulk Pb, mostly consisting in one-dimensional lines. However, we do observe the possibility of forming transient structures, in particular icosahedral caps. Supported by FIS2008-02490/FIS, FIS2008-04894/FIS, GR120, INCITE09E2R206033ES and INCITE08PXIB206107PR.

  17. The constrained space orbital variation analysis for periodic ab initio calculations

    SciTech Connect

    Cruz Hernandez, N.; Zicovich-Wilson, Claudio Marcelo; Fdez Sanz, Javier

    2006-05-21

    The constrained space orbital variation (CSOV) method for the analysis of the interaction energy has been implemented in the periodic ab initio CRYSTAL03 code. The method allows for the partition of the energy of two interacting chemical entities, represented in turn by periodic models, into contributions which account for electrostatic effects, mutual polarization and charge transfer. The implementation permits one to carry out the analysis both at the Hartree-Fock and density functional theory levels, where in the latter the most popular exchange-correlation functionals can be used. As an illustrating example, the analysis of the interaction between CO and the MgO (001) surface has been considered. As expected by the almost fully ionic character of the support, our periodic CSOV results, in general agree with those previously obtained using the embedded cluster approach, showing the reliability of the present implementation.

  18. Ab initio calculations of mechanical, thermodynamic and electronic structure properties of mullite, iota-alumina and boron carbide

    NASA Astrophysics Data System (ADS)

    Aryal, Sita Ram

    The alumino-silicate solid solution series (Al 4+2xSi2-2 xO10-x) is an important class of ceramics. Except for the end member (x=0), Al2 SiO5 the crystal structures of the other phases, called mullite, have partially occupied sites. Stoichiometric supercell models for the four mullite phases 3Al2O 3 · 2SiO2 · 2Al 2O3 · SiO2, 4 Al2O3· SiO 2, 9Al2O3 · SiO2, and iota-Al2 O3 (iota-alumina) are constructed starting from experimentally reported crystal structures. A large number of models were built for each phase and relaxed using the Vienna ab initio simulation package (VASP) program. The model with the lowest total energy for a given x was chosen as the representative structure for that phase. Electronic structure and mechanical properties of mullite phases were studied via first-principles calculations. Of the various phases of transition alumina, iota-Al 2O3 is the least well known. In addition structural details have not, until now, been available. It is the end member of the aluminosilicate solid solution series with x=1. Based on a high alumina content mullite phase, a structural model for iota- Al2O3 is constructed. The simulated x-ray diffraction (XRD) pattern of this model agrees well with a measured XRD pattern. The iota-Al2 O3 is a highly disordered ultra-low-density phase of alumina with a theoretical density of 2854kg/m3. Using this theoretically constructed model, elastic, thermodynamic, electronic, and spectroscopic properties of iota-Al2 O3 have been calculated and compared it with those of alpha- Al2O3 and gamma- Al2O3. Boron carbide (B4C) undergoes an amorphization under high velocity impacts. The mechanism of amorphization is not clear. Ab initio methods are used to carry out large-scale uniaxial compression simulations on two polytypes of stoichiometric boron carbide (B4C), B 11C-CBC, and B12- CCC where B11C or B12 is the 12-atom icosahedron and CBC or CCC is the three-atom chain. The simulations were performed on large supercells of 180 atoms

  19. Full-dimensional vibrational calculations for H5O2+ using an ab initio potential energy surface

    NASA Astrophysics Data System (ADS)

    McCoy, Anne B.; Huang, Xinchuan; Carter, Stuart; Landeweer, Marc Y.; Bowman, Joel M.

    2005-02-01

    We report quantum diffusion Monte Carlo (DMC) and variational calculations in full dimensionality for selected vibrational states of H5O2+ using a new ab initio potential energy surface [X. Huang, B. Braams, and J. M. Bowman, J. Chem. Phys. 122, 044308 (2005)]. The energy and properties of the zero-point state are focused on in the rigorous DMC calculations. OH-stretch fundamentals are also calculated using "fixed-node" DMC calculations and variationally using two versions of the code MULTIMODE. These results are compared with infrared multiphoton dissociation measurements of Yeh et al. [L. I. Yeh, M. Okumura, J. D. Myers, J. M. Price, and Y. T. Lee, J. Chem. Phys. 91, 7319 (1989)]. Some preliminary results for the energies of several modes of the shared hydrogen are also reported.

  20. Direct molecular simulation of nitrogen dissociation based on an ab initio potential energy surface

    SciTech Connect

    Valentini, Paolo Schwartzentruber, Thomas E. Bender, Jason D. Nompelis, Ioannis Candler, Graham V.

    2015-08-15

    The direct molecular simulation (DMS) approach is used to predict the internal energy relaxation and dissociation dynamics of high-temperature nitrogen. An ab initio potential energy surface (PES) is used to calculate the dynamics of two interacting nitrogen molecules by providing forces between the four atoms. In the near-equilibrium limit, it is shown that DMS reproduces the results obtained from well-established quasiclassical trajectory (QCT) analysis, verifying the validity of the approach. DMS is used to predict the vibrational relaxation time constant for N{sub 2}–N{sub 2} collisions and its temperature dependence, which are in close agreement with existing experiments and theory. Using both QCT and DMS with the same PES, we find that dissociation significantly depletes the upper vibrational energy levels. As a result, across a wide temperature range, the dissociation rate is found to be approximately 4–5 times lower compared to the rates computed using QCT with Boltzmann energy distributions. DMS calculations predict a quasi-steady-state distribution of rotational and vibrational energies in which the rate of depletion of high-energy states due to dissociation is balanced by their rate of repopulation due to collisional processes. The DMS approach simulates the evolution of internal energy distributions and their coupling to dissociation without the need to precompute rates or cross sections for all possible energy transitions. These benchmark results could be used to develop new computational fluid dynamics models for high-enthalpy flow applications.

  1. Measurement of the elastic tensor of SmScO3 and NdScO3 using resonant ultrasound spectroscopy with ab initio calculations

    NASA Astrophysics Data System (ADS)

    Pestka, K. A.; Scott, E. S.; Le Page, Y.

    2011-09-01

    The complete elastic tensors of SmScO3 and NdScO3 were measured using resonant ultrasound spectroscopy (RUS) in combination with ab-initio calculations. Measurement of the elastic tensor of these recently synthesized single crystal RE scandates is essential for understanding dynamic lattice applications including phonon confinement, strain induced thin film growth and superlattice construction. On average, the experimental elastic constants differed by less than 5% of the theoretical values, further validating the accuracy of modern ab-initio calculations as a means of estimating the initial elastic constants used in RUS measurements.

  2. Symmetry-general least-squares extraction of elastic data for strained materials from ab initio calculations of stress

    NASA Astrophysics Data System (ADS)

    Le Page, Yvon; Saxe, Paul

    2002-03-01

    A symmetry-general approach for the least-squares, therefore precise, extraction of elastic coefficients for strained materials is reported. It analyzes stresses calculated ab initio for properly selected strains. The problem, its implementation, and its solution strategy all differ radically from a previous energy-strain approach that we published last year, but the normal equations turn out to be amenable to the same constrainment scheme that makes both approaches symmetry general. The symmetry considerations governing the automated selection of appropriately strained models and their Cartesian systems are detailed. The extension to materials under general stress is discussed and implemented. VASP was used for ab initio calculation of stresses. A comprehensive range of examples includes a triclinic material (kyanite) and simple materials with a range of symmetries at zero pressure, MgO under hydrostatic pressure, Ti4As3 under [001] uniaxial strain, and Si under [001] uniaxial stress. The MgO case agrees with recent experimental work including elastic coefficients as well as their first and second derivatives. The curves of elastic coefficients for Si show a gradual increase in the 33 compliance coefficient, leading to a collapse of the material at -11.7 GPa, compared with -12.0 GPa experimentally. Interpretation of results for Be using two approximations [local density (LDA), generalized gradient (GGA)], two approaches (stress strain and energy strain), two potential types (projector augmented wave and ultrasoft), and two quantum engines (VASP and ORESTES) expose the utmost importance of the cell data used for the elastic calculations and the lesser importance of the other factors. For stiffness at relaxed cell data, differences are shown to originate mostly in the considerable overestimation of the residual compressive stresses at x-ray cell data by LDA, resulting in a smaller relaxed cell, thus larger values for diagonal stiffness coefficients. The symmetry

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

    NASA Astrophysics Data System (ADS)

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

    2009-07-01

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

  4. Vibrational spectrum of p-fluoroanisole in the first excited state (S 1) and ab initio calculations

    NASA Astrophysics Data System (ADS)

    Xiao, Daoqing; Yu, Dan; Xu, Xiling; Yu, Zijun; Du, Yikui; Gao, Zhen; Zhu, Qihe; Zhang, Cunhao

    2008-06-01

    The vibronic structure of p-fluoroanisole in the first excited state (S 1) has been investigated with mass selected resonance-enhanced two photon ionization spectroscopy. The band origin of S 1 ← S 0 transition of p-fluoroanisole is measured to be 35149 cm -1, which is red-shifted by 1234 cm -1 with respect to that of anisole. Combining with the ab initio calculations, the measured frequencies 397, 487, 559, 840 and 1150 cm -1 in the S 1 state are assigned as the in-plane ring vibrational mode 9 b, 6 a, 6 b, 1 and 9 a, respectively. The optimized molecular geometries and vibrational frequencies of p-fluoroanisole in the ground state (S 0) and cation ground state (D 0) are also achieved from DFT calculations.

  5. Toluene Valence and Rydberg Excitations as Studied by ab initio Calculations and Vacuum Ultraviolet (VUV) Synchrotron Radiation.

    PubMed

    Serralheiro, C; Duflot, D; da Silva, F Ferreira; Hoffmann, S V; Jones, N C; Mason, N J; Mendes, B; Limão-Vieira, P

    2015-08-27

    The electronic spectroscopy of isolated toluene in the gas phase has been investigated using high-resolution photoabsorption spectroscopy in the 4.0-10.8 eV energy range, with absolute cross-section measurements derived. We present the first set of ab initio calculations (vertical energies and oscillator strengths), which we use in the assignment of valence and Rydberg transitions of the toluene molecule. The spectrum reveals several new features not previously reported in the literature, with particular relevance to 7.989 and 8.958 eV, which are here tentatively assigned to the π*(17a') ← σ(15a') and 1π*(10a″) ← 1π(14a') transitions, respectively. The measured absolute photoabsorption cross sections have been used to calculate the photolysis lifetime of toluene in the upper stratosphere (20-50 km). PMID:26244250

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

    SciTech Connect

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

    2015-12-07

    The influence of hydrostatic pressure on structure and dynamics of a crystal lattice of elpasolites Cs{sub 2}NaYbF{sub 6} and Cs{sub 2}NaYF{sub 6} (S.G. 225) within ab initio approach is investigated. Frequencies and irreducible representations (irreps) of phonon modes are determined. Elastic constants are calculated. The calculations are carried out within MO LCAO approach using DFT method with hybrid functionalities of B3LYP and PBE0 in CRYSTAL09 periodic code. For the description of rare earth ion the pseudopotential replacing internal orbitals including 4f orbitals was used. External 5s and 5p orbitals defining chemical bond were described by valence basis sets.

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

    The influence of hydrostatic pressure on structure and dynamics of a crystal lattice of elpasolites Cs2NaYbF6 and Cs2NaYF6 (S.G. 225) within ab initio approach is investigated. Frequencies and irreducible representations (irreps) of phonon modes are determined. Elastic constants are calculated. The calculations are carried out within MO LCAO approach using DFT method with hybrid functionalities of B3LYP and PBE0 in CRYSTAL09 periodic code. For the description of rare earth ion the pseudopotential replacing internal orbitals including 4f orbitals was used. External 5s and 5p orbitals defining chemical bond were described by valence basis sets.

  8. Structures and stabilities of small silicon clusters: Ab initio molecular-orbital calculations of Si7-Si11

    NASA Astrophysics Data System (ADS)

    Zhu, Xiaolei; Zeng, X. C.

    2003-02-01

    Ab initio all-electron molecular-orbital calculations have been carried out to study the structure and relative stability of small silicon clusters (Sin, n=7-11). A number of low-energy geometric isomers are optimized at the second-order Møller-Plesset (MP2) MP2/6-31G(d) level. Harmonic vibrational analysis has been performed to assure that the optimized geometries are stable. The total energies of stable isomers are computed at the coupled-cluster single and double substitutions (including triple excitations) [CCSD(T)] CCSD(T)/6-31G(d) level. The calculated binding energies per atom at both the MP2/6-31G(d) and CCSD(T)/6-31G(d) levels agree with the experiments. For Si7, Si8, and Si10, the lowest-energy structures are the same as those predicted previously from the all-electron optimization at the Hartree-Fock (HF) HF/6-31G(d) level [Raghavachari and Rohlfing, J. Chem. Phys. 89, 2219 (1988)]. For Si9, the lowest-energy isomer is same as that predicted based on density-functional plane-wave pseudopotential method [Vasiliev, Ogut, and Chelikowsky, Phys. Rev. Lett. 78, 4805 (1997)]. Particular attention has been given to Si11 because several low-energy geometric isomers were found nearly isoenergetic. On the basis of MP2/6-311G(2d)//CCSD(T)/6-311G(2d) calculation, we identified that the C2v isomer, a tricapped trigonal prism with two additional caps on side trigonal faces, is most likely the global-minimum structure. However, another competitive geometric isomer for the global minimum is also found on basis of the MP2/6-311G(2d)//CCSD(T)/6-311G(2d) calculation. Additionally, calculations of the binding energy and the cluster polarizability offer more insights into relatively strong stability of two magic-number clusters Si6 and Si10.

  9. Revealing Missing Human Protein Isoforms Based on Ab Initio Prediction, RNA-seq and Proteomics

    PubMed Central

    Hu, Zhiqiang; Scott, Hamish S.; Qin, Guangrong; Zheng, Guangyong; Chu, Xixia; Xie, Lu; Adelson, David L.; Oftedal, Bergithe E.; Venugopal, Parvathy; Babic, Milena; Hahn, Christopher N.; Zhang, Bing; Wang, Xiaojing; Li, Nan; Wei, Chaochun

    2015-01-01

    Biological and biomedical research relies on comprehensive understanding of protein-coding transcripts. However, the total number of human proteins is still unknown due to the prevalence of alternative splicing. In this paper, we detected 31,566 novel transcripts with coding potential by filtering our ab initio predictions with 50 RNA-seq datasets from diverse tissues/cell lines. PCR followed by MiSeq sequencing showed that at least 84.1% of these predicted novel splice sites could be validated. In contrast to known transcripts, the expression of these novel transcripts were highly tissue-specific. Based on these novel transcripts, at least 36 novel proteins were detected from shotgun proteomics data of 41 breast samples. We also showed L1 retrotransposons have a more significant impact on the origin of new transcripts/genes than previously thought. Furthermore, we found that alternative splicing is extraordinarily widespread for genes involved in specific biological functions like protein binding, nucleoside binding, neuron projection, membrane organization and cell adhesion. In the end, the total number of human transcripts with protein-coding potential was estimated to be at least 204,950. PMID:26156868

  10. Ab initio infrared and Raman spectra

    NASA Astrophysics Data System (ADS)

    Fredkin, Donald R.; Komornicki, Andrew; White, Steven R.; Wilson, Kent R.

    1983-06-01

    We discuss several ways in which molecular absorption and scattering spectra can be computed ab initio, from the fundamental constants of nature. These methods can be divided into two general categories. In the first, or sequential, type of approach, one first solves the electronic part of the Schrödinger equation in the Born-Oppenheimer approximation, mapping out the potential energy, dipole moment vector (for infrared absorption) and polarizability tensor (for Raman scattering) as functions of nuclear coordinates. Having completed the electronic part of the calculation, one then solves the nuclear part of the problem either classically or quantum mechanically. As an example of the sequential ab initio approach, the infrared and Raman rotational and vibrational-rotational spectral band contours for the water molecule are computed in the simplest rigid rotor, normal mode approximation. Quantum techniques are used to calculate the necessary potential energy, dipole moment, and polarizability information at the equilibrium geometry. A new quick, accurate, and easy to program classical technique involving no reference to Euler angles or special functions is developed to compute the infrared and Raman band contours for any rigid rotor, including asymmetric tops. A second, or simultaneous, type of ab initio approach is suggested for large systems, particularly those for which normal mode analysis is inappropriate, such as liquids, clusters, or floppy molecules. Then the curse of dimensionality prevents mapping out in advance the complete potential, dipole moment, and polarizability functions over the whole space of nuclear positions of all atoms, and a solution in which the electronic and nuclear parts of the Born-Oppenheimer approximation are simultaneously solved is needed. A quantum force classical trajectory (QFCT) molecular dynamic method, based on linear response theory, is described, in which the forces, dipole moment, and polarizability are computed quantum

  11. Disulfuric acid dissociated by two water molecules: ab initio and density functional theory calculations.

    PubMed

    Kim, Seong Kyu; Lee, Han Myoung; Kim, Kwang S

    2015-11-21

    We have studied geometries, energies and vibrational spectra of disulfuric acid (H2S2O7) and its anion (HS2O7(-)) hydrated by a few water molecules, using density functional theory (M062X) and ab initio theory (SCS-MP2 and CCSD(T)). The most noteworthy result is found in H2S2O7(H2O)2 in which the lowest energy conformer shows deprotonated H2S2O7. Thus, H2S2O7 requires only two water molecules, the fewest number of water molecules for deprotonation among various hydrated monomeric acids reported so far. Even the second deprotonation of the first deprotonated species HS2O7(-) needs only four water molecules. The deprotonation is supported by vibration spectra, in which acid O-H stretching peaks disappear and specific three O-H stretching peaks for H3O(+) (eigen structure) appear. We have also kept track of variations in several geometrical parameters, atomic charges, and hybrid orbital characters upon addition of water. As the number of water molecules added increases, the S-O bond weakens in the case of H2S2O7, but strengthens in the case of HS2O7(-). It implies that the decomposition leading to H2SO4 and SO3 hardly occurs prior to the 2nd deprotonation at low temperatures. PMID:26400266

  12. Parametrization and Validation of Coarse Grained Force-Fields Derived from ab Initio Calculations.

    PubMed

    Prampolini, Giacomo

    2006-05-01

    A novel multisite interaction potential, suitable for computer simulations of complex materials as liquid crystals or polymers, is proposed and parametrized. Its validation is achieved through Monte Carlo numerical experiments at constant temperature and pressure, performed on the p-n-phenyls series and a typical mesogenic molecule (5CB). The model is constructed by connecting an array of anisotropic Gay-Berne sites and a collection of isotropic Lennard-Jones sites. The former mimics the rigid planar six-membered rings of the molecule, while the latter represents the flexible chain, if present. Such intermolecular potential, coupled with an intramolecular part to account for molecular flexibility, is parametrized from ab initio information only, obtained through the recently proposed Fragmentation-Reconstruction Method (FRM). Computer simulations are performed on all systems by exploring phase behavior at several temperatures and by comparing the resulting thermodynamic and structural properties with the relevant experimental data. Despite the simplicity of the present models, the good agreement with the experimental measures suggests the possibility of adopting such hybrid potentials for those systems with a large number of atoms, where high computational cost does not allow the use of more accurate atomistic potentials. PMID:26626663

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

    SciTech Connect

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

    2014-09-14

    Use of symmetry can dramatically reduce the computational cost (running time and memory allocation) of self-consistent-field ab initio calculations for molecular and crystalline systems. Crucial for running time is symmetry exploitation in the evaluation of one- and two-electron integrals, diagonalization of the Fock matrix at selected points in reciprocal space, reconstruction of the density matrix. As regards memory allocation, full square matrices (overlap, Fock, and density) in the Atomic Orbital (AO) basis are avoided and a direct transformation from the packed AO to the symmetry adapted crystalline orbital basis is performed, so that the largest matrix to be handled has the size of the largest sub-block in the latter basis. Quantitative examples, referring to the implementation in the CRYSTAL code, are given for high symmetry families of compounds such as carbon fullerenes and nanotubes.

  14. AB initio free energy calculations of the solubility of silica in metallic hydrogen and application to giant planet cores

    SciTech Connect

    González-Cataldo, F.; Wilson, Hugh F.; Militzer, B.

    2014-05-20

    By combining density functional molecular dynamics simulations with a thermodynamic integration technique, we determine the free energy of metallic hydrogen and silica, SiO{sub 2}, at megabar pressures and thousands of degrees Kelvin. Our ab initio solubility calculations show that silica dissolves into fluid hydrogen above 5000 K for pressures from 10 and 40 Mbars, which has implications for the evolution of rocky cores in giant gas planets like Jupiter, Saturn, and a substantial fraction of known extrasolar planets. Our findings underline the necessity of considering the erosion and redistribution of core materials in giant planet evolution models, but they also demonstrate that hot metallic hydrogen is a good solvent at megabar pressures, which has implications for high-pressure experiments.

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

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

    Use of symmetry can dramatically reduce the computational cost (running time and memory allocation) of self-consistent-field ab initio calculations for molecular and crystalline systems. Crucial for running time is symmetry exploitation in the evaluation of one- and two-electron integrals, diagonalization of the Fock matrix at selected points in reciprocal space, reconstruction of the density matrix. As regards memory allocation, full square matrices (overlap, Fock, and density) in the Atomic Orbital (AO) basis are avoided and a direct transformation from the packed AO to the symmetry adapted crystalline orbital basis is performed, so that the largest matrix to be handled has the size of the largest sub-block in the latter basis. Quantitative examples, referring to the implementation in the CRYSTAL code, are given for high symmetry families of compounds such as carbon fullerenes and nanotubes.

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

    SciTech Connect

    Yu, Xuegong; Chen, Peng; Chen, Xianzi; Liu, Yong; Yang, Deren

    2015-07-15

    Boron-oxygen (B-O) complex in crystalline silicon (c-Si) solar cells is responsible for the light-induced efficiency degradation of solar cell. However, the formation mechanism of B-O complex is not clear yet. By Ab-initio calculation, it is found that the stagger-type oxygen dimer (O{sub 2i}{sup st}) should be the component of B-O complex, whose movement occurs through its structure reconfiguration at low temperature, instead of its long-distance diffusion. The O{sub 2i}{sup st} can form two stable “latent centers” with the B{sub s}, which are recombination-inactive. The latent centers can be evolved into the metastable recombination centers via their structure transformation in the presence of excess carriers. These results can well explain the formation behaviors of B-O complexes in c-Si.

  17. Theoretical study of ionic liquids based on the cholinium cation. Ab initio simulations of their condensed phases.

    PubMed

    Campetella, Marco; Bodo, Enrico; Montagna, Maria; De Santis, Serena; Gontrani, Lorenzo

    2016-03-14

    We have explored by means of ab initio molecular dynamics the homologue series of 11 different ionic liquids based on the combination of the cholinium cation with deprotonated amino acid anions. We present a structural analysis of the liquid states of these compounds as revealed by accurate ab initio computations of the forces. We highlight the persistent structural motifs that see the ionic couple as the basic building block of the liquid whereby a strong hydrogen bonding network substantially determines the short range structural behavior of the bulk state. Other minor docking features of the interaction network are also discovered and described. Special cases along the series such as Cysteine and Phenylalanine are discussed in the view of their peculiar properties due to zwitterion formation and additional long-range structural organization. PMID:26979694

  18. Theoretical study of ionic liquids based on the cholinium cation. Ab initio simulations of their condensed phases

    NASA Astrophysics Data System (ADS)

    Campetella, Marco; Bodo, Enrico; Montagna, Maria; De Santis, Serena; Gontrani, Lorenzo

    2016-03-01

    We have explored by means of ab initio molecular dynamics the homologue series of 11 different ionic liquids based on the combination of the cholinium cation with deprotonated amino acid anions. We present a structural analysis of the liquid states of these compounds as revealed by accurate ab initio computations of the forces. We highlight the persistent structural motifs that see the ionic couple as the basic building block of the liquid whereby a strong hydrogen bonding network substantially determines the short range structural behavior of the bulk state. Other minor docking features of the interaction network are also discovered and described. Special cases along the series such as Cysteine and Phenylalanine are discussed in the view of their peculiar properties due to zwitterion formation and additional long-range structural organization.

  19. Ab initio Based Modeling of Radiation Effects in Multi-Component Alloys: Final Scientific/Technical Report

    SciTech Connect

    Dane Morgan

    2010-06-10

    The project began March 13, 2006, allocated for three years, and received a one year extension from March 13, 2009 to March 12, 2010. It has now completed 48 of 48 total months. The project was focused on using ab initio methods to gain insights into radiation induced segregation (RIS) in Ni-Fe-Cr alloys. The project had the following key accomplishments • Development of a large database of ab initio energetics that can be used by many researchers in the future for increased understanding of this system. For example, we have the first calculations showing a dramatic stabilization effect of Cr-Cr interstitial dumbbells in Ni. • Prediction of both vacancy and interstitial diffusion constants for Ni-Cr and Ni-Fe for dilute Cr and Fe. This work included generalization of widely used multifrequency models to make use of ab initio derived energetics and thermodynamics. • Prediction of qualitative trends of RIS from vacancy and interstitial mechanisms, suggesting the two types of defect fluxes drive Cr RIS in opposite directions. • Detailed kinetic Monte Carlo modeling of diffusion by vacancy mechanism in Ni-Cr as a function of Cr concentration. The results demonstrate that Cr content can have a significant effect on RIS. • Development of a quantitative RIS transport model, including models for thermodynamic factors and boundary conditions.

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

    PubMed

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

    2016-07-28

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

  1. Flexible nuclear screening approximation to the two-electron spin–orbit coupling based on ab initio parameterization

    SciTech Connect

    Chalupský, Jakub Yanai, Takeshi

    2013-11-28

    The derivation, implementation, and validation of a new approximation to the two-electron spin–orbit coupling (SOC) terms is reported. The approximation, referred to as flexible nuclear screening spin–orbit, is based on the effective one-electron spin–orbit operator and accounts for two-electron SOC effects by screening nuclear charges. A highly flexible scheme for the nuclear screening is developed, mainly using parameterization based on ab initio atomic SOC calculations. Tabulated screening parameters are provided for contracted and primitive Gaussian-type basis functions of the ANO-RCC basis set for elements from H to Cm. The strategy for their adaptation to any other Gaussian basis set is presented and validated. A model to correct for the effect of splitting of transition metal d orbitals on their SOC matrix elements is introduced. The method is applied to a representative set of molecules, and compared to exact treatment and other approximative approaches at the same level of relativistic theory. The calculated SOC matrix elements are in very good agreement with their “exact” values; deviation below 1% is observed on average. The presented approximation is considered to be generally applicable, simple to implement, highly efficient, and accurate.

  2. Flexible nuclear screening approximation to the two-electron spin-orbit coupling based on ab initio parameterization

    NASA Astrophysics Data System (ADS)

    Chalupský, Jakub; Yanai, Takeshi

    2013-11-01

    The derivation, implementation, and validation of a new approximation to the two-electron spin-orbit coupling (SOC) terms is reported. The approximation, referred to as flexible nuclear screening spin-orbit, is based on the effective one-electron spin-orbit operator and accounts for two-electron SOC effects by screening nuclear charges. A highly flexible scheme for the nuclear screening is developed, mainly using parameterization based on ab initio atomic SOC calculations. Tabulated screening parameters are provided for contracted and primitive Gaussian-type basis functions of the ANO-RCC basis set for elements from H to Cm. The strategy for their adaptation to any other Gaussian basis set is presented and validated. A model to correct for the effect of splitting of transition metal d orbitals on their SOC matrix elements is introduced. The method is applied to a representative set of molecules, and compared to exact treatment and other approximative approaches at the same level of relativistic theory. The calculated SOC matrix elements are in very good agreement with their "exact" values; deviation below 1% is observed on average. The presented approximation is considered to be generally applicable, simple to implement, highly efficient, and accurate.

  3. Developing ab initio quality force fields from condensed phase quantum-mechanics/molecular-mechanics calculations through the adaptive force matching method

    NASA Astrophysics Data System (ADS)

    Akin-Ojo, Omololu; Song, Yang; Wang, Feng

    2008-08-01

    A new method called adaptive force matching (AFM) has been developed that is capable of producing high quality force fields for condensed phase simulations. This procedure involves the parametrization of force fields to reproduce ab initio forces obtained from condensed phase quantum-mechanics/molecular-mechanics (QM/MM) calculations. During the procedure, the MM part of the QM/MM is iteratively improved so as to approach ab initio quality. In this work, the AFM method has been tested to parametrize force fields for liquid water so that the resulting force fields reproduce forces calculated using the ab initio MP2 and the Kohn-Sham density functional theory with the Becke-Lee-Yang-Parr (BLYP) and Becke three-parameter LYP (B3LYP) exchange correlation functionals. The AFM force fields generated in this work are very simple to evaluate and are supported by most molecular dynamics (MD) codes. At the same time, the quality of the forces predicted by the AFM force fields rivals that of very expensive ab initio calculations and are found to successfully reproduce many experimental properties. The site-site radial distribution functions (RDFs) obtained from MD simulations using the force field generated from the BLYP functional through AFM compare favorably with the previously published RDFs from Car-Parrinello MD simulations with the same functional. Technical aspects of AFM such as the optimal QM cluster size, optimal basis set, and optimal QM method to be used with the AFM procedure are discussed in this paper.

  4. Study of the thermodynamic properties of CeO{sub 2} from ab initio calculations: The effect of phonon-phonon interaction

    SciTech Connect

    Niu, Zhen-Wei; Zeng, Zhao-Yi; Hu, Cui-E; Cai, Ling-Cang; Chen, Xiang-Rong

    2015-01-07

    The thermodynamic properties of CeO{sub 2} have been reevaluated by a simple but accurate scheme. All our calculations are based on the self-consistent ab initio lattice dynamical (SCAILD) method that goes beyond the quasiharmonic approximation. Through this method, the effects of phonon-phonon interactions are included. The obtained thermodynamic properties and phonon dispersion relations are in good agreement with experimental data when considering the correction of phonon-phonon interaction. We find that the correction of phonon-phonon interaction is equally important and should not be neglected. At last, by comparing with quasiharmonic approximation, the present scheme based on SCAILD method is probably more suitable for high temperature systems.

  5. Ab initio molecular orbital-configuration interaction based quantum master equation (MOQME) approach to the dynamic first hyperpolarizabilities of asymmetric π-conjugated systems

    SciTech Connect

    Kishi, Ryohei; Fujii, Hiroaki; Minami, Takuya; Shigeta, Yasuteru; Nakano, Masayoshi

    2015-01-22

    In this study, we apply the ab initio molecular orbital - configuration interaction based quantum master equation (MOQME) approach to the calculation and analysis of the dynamic first hyperpolarizabilities (β) of asymmetric π-conjugated molecules. In this approach, we construct the excited state models by the ab initio configuration interaction singles method. Then, time evolutions of system reduced density matrix ρ(t) and system polarization p(t) are calculated by the QME approach. Dynamic β in the second harmonic generation is calculated based on the nonperturbative definition of nonlinear optical susceptibility, using the frequency domain system polarization p(ω). Spatial contributions of electrons to β are analyzed based on the dynamic hyperpolarizability density map, which visualizes the second-order response of charge density oscillating with a frequency of 2ω. We apply the present method to the calculation of the dynamic β of a series of donor/acceptor substituted polyene oligomers, and then discuss the applicability of the MOQME method to the calculation and analysis of dynamic NLO properties of molecular systems.

  6. Strong π-π interaction of porphyrins on (6,5) carbon nanotubes with full surface coverage: Ab-initio calculations

    NASA Astrophysics Data System (ADS)

    Orellana, Walter

    2014-07-01

    The stability, electronic, and optical properties of (6,5) single-walled carbon nanotubes (CNTs) functionalized with free-base tetraphenylporphyrin (TPP) molecules through π-stacking interactions are studied by ab-initio calculations. The stability and optical response of the CNT-TPP compounds for increasing CNT-surface coverage are investigated. Our results show that four TPP molecules forming a ring around the CNT is the most stable configuration, showing strong binding energies of about 2.5 eV/TPP. However, this binding energy can increase even more after additional molecules assemble side by side along the CNT, favoring the formation of a full single layer of TPP, as experimentally suggested. The strong π-π attractive forces induce molecular distortions that move the TPP higher-occupied molecular orbital levels inside the CNT bandgap, changing the optical response of the TPP molecules stacked on the CNT.

  7. Investigating crystalline-polarity-dependent electronic structures of GaN by hard x-ray photoemission and ab-initio calculations

    NASA Astrophysics Data System (ADS)

    Ohsawa, Takeo; Ueda, Shigenori; Suzuki, Motohiro; Tateyama, Yoshitaka; Williams, Jesse R.; Ohashi, Naoki

    2015-10-01

    Crystalline-polarity-dependent electronic structures of gallium nitride (GaN) were studied by photoemission spectroscopy (PES) using soft and hard x-rays with different linear polarizations. A peak located near the valence band (VB) maximum was enhanced for a (0001) surface compared with that for a ( 000 1 ¯ ) surface regardless of photon energy. Comparison of the VB density of states obtained by ab-initio calculations with the observed VB-PES spectra indicates that the crystalline-polarity dependence is associated with the Ga 4p and N 2p states. The most plausible origin of the crystalline-polarity-dependent VB feature is based on the photoemission phenomena of electrons in the pz-orbitals due to spontaneous electric polarization along the c-axis of GaN.

  8. An ab initio calculation of the zero-field splitting parameters of the 3A-double prime state of formaldehyde

    NASA Technical Reports Server (NTRS)

    Davidson, E. R.; Ellenbogen, J. C.; Langhoff, S. R.

    1980-01-01

    The spin dipole-dipole and spin-orbit contributions to the zero-field splitting of the 3A-double prime state of formaldehyde have been evaluated at the excited state experimental geometry. Ab initio CI wave functions were generated from a Dunning double zeta plus polarization bases set using 3A-double prime rhf orbitals. Twelve states of each symmetry were used to evaluate the second-order spin-orbit effect. The resulting values of D and E were 0.19 and 0.03 kayser with the principal magnetic axes rotated 36 deg from the CO bond. The values of alpha and beta relative to the inertial axes were calculated to be 0.03 and 0.01 kayser compared to the experimental values of 0.05 plus or minus 0.01 and 0.02 plus or minus 0.02 kayser.

  9. Strong π-π interaction of porphyrins on (6,5) carbon nanotubes with full surface coverage: Ab-initio calculations

    SciTech Connect

    Orellana, Walter

    2014-07-14

    The stability, electronic, and optical properties of (6,5) single-walled carbon nanotubes (CNTs) functionalized with free-base tetraphenylporphyrin (TPP) molecules through π-stacking interactions are studied by ab-initio calculations. The stability and optical response of the CNT-TPP compounds for increasing CNT-surface coverage are investigated. Our results show that four TPP molecules forming a ring around the CNT is the most stable configuration, showing strong binding energies of about 2.5 eV/TPP. However, this binding energy can increase even more after additional molecules assemble side by side along the CNT, favoring the formation of a full single layer of TPP, as experimentally suggested. The strong π-π attractive forces induce molecular distortions that move the TPP higher-occupied molecular orbital levels inside the CNT bandgap, changing the optical response of the TPP molecules stacked on the CNT.

  10. Analysis of the local structure around Cr3+ centers in perovskite KMgF3 using both ab initio (DFT) and semi-empirical (SPM) calculations

    NASA Astrophysics Data System (ADS)

    Emül, Y.; Erbahar, D.; Açıkgöz, M.

    2014-11-01

    The local structure around Cr3+ centers in perovskite KMgF3 crystal have been investigated through the applications of both an ab-initio, density functional theory (DFT), and a semi empirical, superposition model (SPM), analyses. A supercell approach is used for DFT calculations. All the tetragonal (Cr3+-VMg and Cr3+-Li+), trigonal (Cr3+-VK), and CrF5O cluster centers have been considered with various structural models based on the previously suggested experimental inferences. The significant structural changes around the Cr3+ centers induced by Mg2+ or K+ vacancies and the Li substitution at those vacancy sites have been determined and discussed by means of charge distribution. This study provides insight on both the roles of Mg2+ and K+ vacancies and Li+ ion in the local structural properties around Cr3+ centers in KMgF3.

  11. Ab Initio and Improved Empirical Potentials for the Calculation of the Anharmonic Vibrational States and Intramolecular Mode Coupling of N-Methylacetamide

    NASA Technical Reports Server (NTRS)

    Gregurick, Susan K.; Chaban, Galina M.; Gerber, R. Benny; Kwak, Dochou (Technical Monitor)

    2001-01-01

    The second-order Moller-Plesset ab initio electronic structure method is used to compute points for the anharmonic mode-coupled potential energy surface of N-methylacetamide (NMA) in the trans(sub ct) configuration, including all degrees of freedom. The vibrational states and the spectroscopy are directly computed from this potential surface using the Correlation Corrected Vibrational Self-Consistent Field (CC-VSCF) method. The results are compared with CC-VSCF calculations using both the standard and improved empirical Amber-like force fields and available low temperature experimental matrix data. Analysis of our calculated spectroscopic results show that: (1) The excellent agreement between the ab initio CC-VSCF calculated frequencies and the experimental data suggest that the computed anharmonic potentials for N-methylacetamide are of a very high quality; (2) For most transitions, the vibrational frequencies obtained from the ab initio CC-VSCF method are superior to those obtained using the empirical CC-VSCF methods, when compared with experimental data. However, the improved empirical force field yields better agreement with the experimental frequencies as compared with a standard AMBER-type force field; (3) The empirical force field in particular overestimates anharmonic couplings for the amide-2 mode, the methyl asymmetric bending modes, the out-of-plane methyl bending modes, and the methyl distortions; (4) Disagreement between the ab initio and empirical anharmonic couplings is greater than the disagreement between the frequencies, and thus the anharmonic part of the empirical potential seems to be less accurate than the harmonic contribution;and (5) Both the empirical and ab initio CC-VSCF calculations predict a negligible anharmonic coupling between the amide-1 and other internal modes. The implication of this is that the intramolecular energy flow between the amide-1 and the other internal modes may be smaller than anticipated. These results may have

  12. Conformational and isomerizational studies of 3- N, N-dimethylhydrazino-2-methylsulfonyl propenenitrile using NMR and vibrational spectra, X-ray analysis and ab initio calculations

    NASA Astrophysics Data System (ADS)

    Gróf, M.; Gatial, A.; Milata, V.; Prónayová, N.; Kožíšek, J.; Breza, M.; Matějka, P.

    2008-11-01

    The IR, Raman and NMR spectra of 3- N, N-dimethylhydrazino-2-methylsulfonyl propenenitrile (DMHSP) [(H 3C) 2N sbnd NH sbnd CH dbnd C(CN) (SO 2CH 3)] as a solid and in different solvents were measured. The spectra and X-ray analysis revealed that DMHSP was prepared as a pure E-isomer and E- syn conformer with the syn orientation of N, N-dimethylhydrazino group towards the C dbnd C double bond in the solid state. Due to the low barrier practically free isomerization process occurred in solutions at room temperature. DMHSP exists in more polar solvents as pure E-isomer in conformational equilibrium between E- syn and E- anti but in a less polar solvent the presence of Z-isomer was observed as well. From the IR and NMR temperature dependence spectra in polar solvents the energy difference between E- anti and E- syn of Δ H = 2.3 ± 0.9 kJ/mol and Δ H = 3.2 ± 0.4 kJ/mol, respectively, was estimated with the syn one being more stable. The geometries and relative energies of possible conformers of DMHSP were evaluated using ab initio MP2 and B3LYP density functional methods in 6-31G ∗∗ basis set and compared with the X-ray data. The interpretation of NMR spectra was supported by ab initio MP2 calculations. The influence of solvent polarity on the conformational equilibrium is discussed with respect to the SCRF solvent effect calculations using PCM model. In addition, the observed IR and Raman bands were compared also with harmonic vibrational frequencies, calculated on the same levels of theory, and assigned on the base of potential energy distribution.

  13. 42214 layered Fe-based superconductors: An ab initio study of their structural, magnetic, and electronic properties

    NASA Astrophysics Data System (ADS)

    Bucci, F.; Sanna, A.; Continenza, A.; Katrych, S.; Karpinski, J.; Gross, E. K. U.; Profeta, G.

    2016-01-01

    As a follow-up to the discovery of a new family of Fe-based superconductors, namely, the RE4Fe2As2Te1 -xO4 (42214) (RE = Pr, Sm, and Gd), we present a detailed ab initio study of these compounds highlighting the role of rare-earth (RE) atoms, external pressure, and Te content on their physical properties. Modifications of the structural, magnetic, and electronic properties of the pure (e.g., x =0.0 ) 42214 compounds and their possible correlations with the observed superconducting properties are calculated and discussed. The careful analysis of the results obtained shows that (i) changing the RE atoms allows one to tune the internal pressure acting on the As height with respect to the Fe planes; (ii) similarly to other Fe pnictides, the 42214 pure compounds show an antiferromagnetic-stripe magnetic ground state phase joined by an orthorhombic distortion (not experimentally found yet); (iii) smaller RE atoms increase the magnetic instability of the compounds possibly favoring the onset of the superconducting state; (iv) external pressure induces the vanishing of the magnetic order with a transition to the tetragonal phase and can be a possible experimental route towards higher superconducting critical temperature (Tc) ; and (v) Te vacancies act on the structural parameters, changing the As height and affecting the stability of the magnetic phase.

  14. C 1s and N 1s core excitation of aniline: Experiment by electron impact and ab initio calculations

    SciTech Connect

    Duflot, D.; Flament, J.-P.; Giuliani, A.; Heinesch, J.; Grogna, M.; Hubin-Franskin, M.-J.

    2007-05-15

    Core shell excitation spectra of aniline at the carbon and nitrogen 1s edges have been obtained by inner-shell electron energy-loss spectroscopy recorded under scattering conditions where electric dipolar conditions dominate, with higher resolution than in the previous studies. They are interpreted with the aid of ab initio configuration interaction calculations. The spectrum at the C 1s edge is dominated by an intense {pi}{sup *} band. The calculated chemical shift due to the different chemical environment at the carbon 1s edge calculated is in agreement with the experimental observations within a few tenths of an eV. The transition energies of the most intense bands in the C 1s excitation spectrum are discussed at different levels of calculations. In the nitrogen 1s excitation spectrum the most intense bands are due to Rydberg-valence transitions involving the {sigma}{sup *}-type molecular orbitals, in agreement with the experiment. This assignment is different from that of extended Hueckel molecular orbital calculations. The geometries of the core excited states have been calculated and compared to their equivalent core molecules and benzene.

  15. Pressure-induced phonon freezing in the ZnSeS II-VI mixed crystal: phonon-polaritons and ab initio calculations.

    PubMed

    Hajj Hussein, R; Pagès, O; Polian, A; Postnikov, A V; Dicko, H; Firszt, F; Strzałkowski, K; Paszkowicz, W; Broch, L; Ravy, S; Fertey, P

    2016-05-25

    Near-forward Raman scattering combined with ab initio phonon and bond length calculations is used to study the 'phonon-polariton' transverse optical modes (with mixed electrical-mechanical character) of the II-VI ZnSe1-x S x mixed crystal under pressure. The goal of the study is to determine the pressure dependence of the poorly-resolved percolation-type Zn-S Raman doublet of the three oscillator [1  ×  (Zn-Se), 2  ×  (Zn-S)] ZnSe0.68S0.32 mixed crystal, which exhibits a phase transition at approximately the same pressure as its two end compounds (~14 GPa, zincblende  →  rocksalt), as determined by high-pressure x-ray diffraction. We find that the intensity of the lower Zn-S sub-mode of ZnSe0.68S0.32, due to Zn-S bonds vibrating in their own (S-like) environment, decreases under pressure (Raman scattering), whereas its frequency progressively converges onto that of the upper Zn-S sub-mode, due to Zn-S vibrations in the foreign (Se-like) environment (ab initio calculations). Ultimately, only the latter sub-mode survives. A similar 'phonon freezing' was earlier evidenced with the well-resolved percolation-type Be-Se doublet of Zn1-x Be x Se (Pradhan et al 2010 Phys. Rev. B 81 115207), that exhibits a large contrast in the pressure-induced structural transitions of its end compounds. We deduce that the above collapse/convergence process is intrinsic to the percolation doublet of a short bond under pressure, at least in a ZnSe-based mixed crystal, and not due to any pressure-induced structural transition. PMID:27114448

  16. Pressure-induced phonon freezing in the ZnSeS II–VI mixed crystal: phonon–polaritons and ab initio calculations

    NASA Astrophysics Data System (ADS)

    Hajj Hussein, R.; Pagès, O.; Polian, A.; Postnikov, A. V.; Dicko, H.; Firszt, F.; Strzałkowski, K.; Paszkowicz, W.; Broch, L.; Ravy, S.; Fertey, P.

    2016-05-01

    Near-forward Raman scattering combined with ab initio phonon and bond length calculations is used to study the ‘phonon–polariton’ transverse optical modes (with mixed electrical–mechanical character) of the II–VI ZnSe1‑x S x mixed crystal under pressure. The goal of the study is to determine the pressure dependence of the poorly-resolved percolation-type Zn–S Raman doublet of the three oscillator [1  ×  (Zn–Se), 2  ×  (Zn–S)] ZnSe0.68S0.32 mixed crystal, which exhibits a phase transition at approximately the same pressure as its two end compounds (~14 GPa, zincblende  →  rocksalt), as determined by high-pressure x-ray diffraction. We find that the intensity of the lower Zn–S sub-mode of ZnSe0.68S0.32, due to Zn–S bonds vibrating in their own (S-like) environment, decreases under pressure (Raman scattering), whereas its frequency progressively converges onto that of the upper Zn–S sub-mode, due to Zn–S vibrations in the foreign (Se-like) environment (ab initio calculations). Ultimately, only the latter sub-mode survives. A similar ‘phonon freezing’ was earlier evidenced with the well-resolved percolation-type Be–Se doublet of Zn1‑x Be x Se (Pradhan et al 2010 Phys. Rev. B 81 115207), that exhibits a large contrast in the pressure-induced structural transitions of its end compounds. We deduce that the above collapse/convergence process is intrinsic to the percolation doublet of a short bond under pressure, at least in a ZnSe-based mixed crystal, and not due to any pressure-induced structural transition.

  17. Collective rotation from ab initio theory

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

    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.

  18. Improved ab initio calculation of surface second-harmonic generation from Si(111)(1 ×1 ):H

    NASA Astrophysics Data System (ADS)

    Anderson, Sean M.; Tancogne-Dejean, Nicolas; Mendoza, Bernardo S.; Véniard, Valérie

    2016-06-01

    We carry out an improved ab initio calculation of surface second-harmonic generation (SSHG) from the Si(111)(1 ×1 ):H surface. This calculation includes three new features in one formulation: (i) the scissors correction, (ii) the contribution of the nonlocal part of the pseudopotentials, and (iii) the inclusion of a cut function to extract the surface response, all within the independent particle approximation. We apply these improvements on the Si(111)(1 ×1 ):H surface and compare with various experimental spectra from several different sources. We also revisit the three-layer model for the SSHG yield and demonstrate that it provides more accurate results over several, more common, two-layer models. We demonstrate the importance of using properly relaxed coordinates for the theoretical calculations. We conclude that this approach to the calculation of the second-harmonic spectra is versatile and accurate within this level of approximation. This well-characterized surface offers an excellent platform for comparison with theory and allows us to offer this study as an efficient benchmark for this type of calculation.

  19. Ab initio molecular orbital calculations of DNA radical ions. 5. Scaling of calculated electron affinities and ionization potentials to experimental values

    SciTech Connect

    Sevilla, M.D.; Colson, A.O. ); Besler, B. )

    1995-01-19

    Ab initio molecular orbital calculations of the electron affinities (EAs) and ionization potentials (IPs) of the DNA bases are presented in this work. Comparisons of calculated and experimental values are made for a series of compounds of size and/or structure similar to the DNA bases. Excellent correlations between calculated and experimental values are found for both Koopmans EAs at the 6-31G[sup *] and D95v levels and calculated vertical EAs of the model compounds. Several basis sets are considered: 6-31G[sup *], 6-31+G(d), and D95v. Calculations at 6-31G[sup *] and 6-31+G(d) using both ROHF and ROMP2 theories show a consistent difference between calculated vertical and adiabatic EAs. This allows for a good estimate of DNA base adiabatic EAs. i.e., -0.7, -0.3, 0.2, 0.3, and 0.4 eV; from the vertical EAs -1.23, -0.74, -0.40, -0.32, and -0.19 eV for G, A, C, T, and U respectively. While EAs must be scaled, we find that Koopmans IPs calculated at the simple 3-21G level predict vertical IPs of the DNA bases with only a 0.15 eV average absolute deviation from the experimentally reported values and calculations at MP2/6-31+G(d)//6-31G[sup *] for the adiabatic ionization potentials of the DNA bases are all within 0.1 eV of experiment. 41 refs., 2 figs., 5 tabs.

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

    SciTech Connect

    Tohme, Samir N.; Korek, Mahmoud E-mail: fkorek@yahoo.com; Awad, Ramadan

    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.

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

    PubMed

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

    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, 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. PMID:25796254

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

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

  4. Global analytical potential energy surface for the electronic ground state of NH3 from high level ab initio calculations.

    PubMed

    Marquardt, Roberto; Sagui, Kenneth; Zheng, Jingjing; Thiel, Walter; Luckhaus, David; Yurchenko, Sergey; Mariotti, Fabio; Quack, Martin

    2013-08-15

    The analytical, full-dimensional, and global representation of the potential energy surface of NH(3) in the lowest adiabatic electronic state developed previously (Marquardt, R.; et al. J. Phys. Chem. B 2005, 109, 8439–8451) is improved by adjustment of parameters to an enlarged set of electronic energies from ab initio calculations using the coupled cluster method with single and double substitutions and a perturbative treatment of connected triple excitations (CCSD(T)) and the method of multireference configuration interaction (MRCI). CCSD(T) data were obtained from an extrapolation of aug-cc-pVXZ results to the basis set limit (CBS), as described in a previous work (Yurchenko, S.N.; et al. J. Chem. Phys 2005, 123, 134308); they cover the region around the NH3 equilibrium structures up to 20,000 hc cm(–1). MRCI energies were computed using the aug-cc-pVQZ basis to describe both low lying singlet dissociation channels. Adjustment was performed simultaneously to energies obtained from the different ab initio methods using a merging strategy that includes 10,000 geometries at the CCSD(T) level and 500 geometries at the MRCI level. Characteristic features of this improved representation are NH3 equilibrium geometry r(eq)(NH(3)) ≈ 101.28 pm, α(eq)(NH(3)) ≈ 107.03°, the inversion barrier at r(inv)(NH(3)) ≈ 99.88 pm and 1774 hc cm(–1) above the NH(3) minimum, and dissociation channel energies 41,051 hc cm(–1) (for NH(3) → ((2)B(2))NH(2) + ((2)S(1/2))H) and 38,450 hc cm(–1) (for NH(3) → ((3)Σ(–))NH +((1)Σ(g)(+))H(2)); the average agreement between calculated and experimental vibrational line positions is 11 cm(–1) for (14)N(1)H(3) in the spectral region up to 5000 cm(–1). A survey of our current knowledge on the vibrational spectroscopy of ammonia and its isotopomers is also given. PMID:23688044

  5. The isomers and conformers of some push pull enamines studied by vibrational and NMR spectroscopy and by ab initio calculations

    NASA Astrophysics Data System (ADS)

    Pigošová, J.; Gatial, A.; Milata, V.; Černuchová, P.; Prónayová, N.; Liptaj, T.; Matějka, P.

    2005-06-01

    The isomers and conformers of six push-pull enamines: 3-dimethylamino-, 3-methylamino- and 3-amino-2-acetyl propenenitrile [(H 3C) 2N-CH dbnd6 C(CN)(COCH 3), H 3C-NH-CH dbnd6 C(CN)(COCH 3) and H 2N-CH dbnd6 C(CN)(COCH 3)] and 3-dimethylamino-, 3-methylamino- and 3-amino-2-methylsulfonyl propenenitrile [(H 3C) 2N-CH dbnd6 C(CN)(SO 2CH 3), H 3C-NH-CH dbnd6 C(CN)(SO 2CH 3) and H 2N-CH dbnd6 C(CN)(SO 2CH 3)] have been studied experimentally by vibrational and NMR spectroscopy and theoretically by the ab initio calculations at MP2 level in 6-31G** basis set. The IR and Raman spectra of all compounds as a solid and solute in various solvents have been recorded in the region 4000-50 cm -1. The NMR spectra were obtained in chloroform and DMSO at room temperature. All six compounds have been prepared by the same way. NMR spectra revealed that both dimethylamino compounds were prepared as a pure E isomers whereas in the case of methylamino compounds the 3-methylamino-2-methylsulfonyl propenenitrile was prepared also as a pure E isomer but 3-methylamino-2-acetyl propenenitrile as a pure Z isomer. Also 3-amino-2-methylsulfonyl propenenitrile was obtained as a pure the E isomer, but 3-amino-2-acetyl propenenitrile as a mixture of both E and Z isomers. Confomational possibilities of studied compounds are given only by the rotation of the acetyl and methylamino groups. Vibrational spectra revealed existence of two conformers with Z and E orientation of acetyl group for 3-dimethylamino-2-acetyl propenenitrile. Two conformers with anti or syn orientation of methylamino group for 3-methylamino-2-methylsulfonyl propenenitrile have been confirmed by vibrational and NMR spectra, but only one conformer with anti orientation of methylamino group for 3-methylamino-2-acetyl propenenitrile in chloroform solution and in solid phase was found. For latter compound the additional isomer/conformer was detected in more polar solvents (acetonitrile/DMSO). These experimental findings have been

  6. Isomers and conformers of two push pull hydrazines studied by NMR and vibrational spectroscopy and by ab initio calculations

    NASA Astrophysics Data System (ADS)

    Gróf, M.; Polovková, J.; Gatial, A.; Milata, V.; Černuchová, P.; Prónayová, N.; Matějka, P.

    2007-05-01

    The isomers and conformers of two push-pull hydrazines: 3- N, N-dimethylhydrazino-2-acetyl propenenitrile [(H 3C) 2N sbnd NH sbnd CH dbnd C(CN)(COCH 3)] (DMHAP) and 3- N, N-dimethylhydrazino-2-methylsulfonyl propenenitrile [(H 3C) 2N sbnd NH sbnd CH dbnd C(CN)(SO 2CH 3)] (DMHSP) have been studied experimentally by NMR and vibrational spectroscopy and theoretically by the ab initio calculations at MP2 level in 6-31G** basis set. The IR and Raman spectra of both compounds as a solid and solute in various solvents have been recorded. The NMR spectra were obtained in chloroform and DMSO at room temperature. Both compounds have been prepared by the same way. NMR spectra revealed that DMHAP was prepared as a pure Z-isomer whereas in the case of DMHSP a pure E-isomer was obtained. Due to the low barrier for both compounds practically free isomerisation process occurred in the solutions but in opposite directions. Whereas DMHAP exists in the solid state and in the less polar solvent as Z-isomer, in more polar solvents the appearance of next two conformers of E-isomer was observed. On the contrary DMHSP exists in the solid state and in the more polar solvent as E-isomer only but in less polar solvent the presence of Z-isomer was observed as well. Conformational possibilities of both studied compounds are given by the rotation of dimethylhydrazino group with its anti- or syn-orientation towards the olefinic double bond. Moreover, by the rotation of the acetyl group with Z- and E-orientation of carbonyl bond towards olefinic double bond can occur in DMHAP. Vibrational and NMR spectra revealed the existence of single conformer with intramolecular hydrogen bond for Z-isomer in less polar solvent and next two conformers for E-isomer of DMHAP with Z-orientation of acetyl group and anti and syn orientation of dimethylhydrazine group in more polar solvents. For E-isomer of DMHSP two conformers with anti or syn orientations of dimethylhydrazino group have been also confirmed by NMR

  7. Precise electromagnetic tests of ab-initio calculations of light nucle i: states in {sup10}Be.

    SciTech Connect

    McCutchan, E. A.; Lister, C. J.; Wiringa, R. B.; Pieper, S. C.; Seweryniak, D.; Greene, J. P.; Carpenter, M. P.; Chiara, C. J.; Janssens, R. V. F.; Khoo, T. L.; Lauritsen, T.; Stefanescu, I.; Zhu, S.; Physics; Univ. of Maryland

    2009-01-01

    In order to test ab initio calculations of light nuclei, we have remeasured lifetimes in {sup 10}Be using the Doppler shift attenuation method (DSAM) following the {sup 7}Li({sup 7}Li,{alpha}){sup 10}Be reaction at 8 and 10 MeV. The new experiments significantly reduce systematic uncertainties in the DSAM technique. The J{sup TT} = 2{sub 1}{sup +} state at 3.37 MeV has T = 205 {+-} (5){sub stat}{+-}(7){sub sys} fs corresponding to a B(E2{down_arrow}) of 9.2(3)e{sup 2}fm{sup 4} in broad agreement with many calculations. The J{sup TT} = 2{sub 2}{sup +} state at 5.96 MeV was found to have a B(E2{down_arrow}) of 0.11(2)e{sup 2}fm{sup 4} and provides a more discriminating test of nuclear models. New Green's function Monte Carlo calculations for these states and transitions with a number of Hamiltonians are also reported and compared to experiment.

  8. Electronic State Spectroscopy of Halothane As Studied by ab Initio Calculations, Vacuum Ultraviolet Synchrotron Radiation, and Electron Scattering Methods.

    PubMed

    da Silva, F Ferreira; Duflot, D; Hoffmann, S V; Jones, N C; Rodrigues, F N; Ferreira-Rodrigues, A M; de Souza, G G B; Mason, N J; Eden, S; Limão-Vieira, P

    2015-08-01

    We present the first set of ab initio calculations (vertical energies and oscillator strengths) of the valence and Rydberg transitions of the anaesthetic compound halothane (CF3CHBrCl). These results are complemented by high-resolution vacuum ultraviolet photoabsorption measurements over the wavelength range 115-310 nm (10.8-4.0 eV). The spectrum reveals several new features that were not previously reported in the literature. Spin-orbit effects have been considered in the calculations for the lowest-lying states, allowing us to explain the broad nature of the 6.1 and 7.5 eV absorption bands assigned to σ*(C-Br) ← nBr and σ*(C-Cl) ← n(Cl) transitions. Novel absolute photoabsorption cross sections from electron scattering data were derived in the 4.0-40.0 eV range. The measured absolute photoabsorption cross sections have been used to calculate the photolysis lifetime of halothane in the upper stratosphere (20-50 km). PMID:26171941

  9. Crystal structure, ab initio calculations and fingerprint plots of a new polymorph of N‧,N″,N″‧-triphenylbiuret

    NASA Astrophysics Data System (ADS)

    Pereira Silva, Pedro S.; Ghalib, Raza Murad; Mehdi, Sayed Hasan; Hashim, Rokiah; Sulaiman, Othman; Silva, Manuela Ramos

    2011-05-01

    A new polymorph of N', N″, N″'-triphenylbiuret, C 20H 17N 3O 2 (form II), has been synthesized and the structure has been solved by X-ray diffraction. The crystals are monoclinic, space group P2 1/ c, with a = 7.6966 (3) Å, b = 12.5490 (4) Å, c = 18.5996 (6) Å, β = 107.632(2)°, Mr = 331.37, V = 1712.04 (10) Å 3, Z = 4 and R = 0.0454. The hydrogen bonding of this polymorph is considerably different from that of the previously known structure. The molecules are linked in infinite chains, via C-H⋯O hydrogen bonds and there is also an intramolecular N-H⋯O hydrogen bond. The intermolecular interactions present in this polymorph, and on the previously reported polymorph, were analysed by means of the fingerprint plots derived from the Hirshfeld surfaces. The fingerprint plots evidenced the different packing modes of the two structures. Quantum-mechanical ab initio calculations for the free molecule were performed using the Hartree-Fock and DFT/B3LYP methods with the 6-31G(d,p) basis set of wave functions. The solid-state conformations compared with those obtained theoretically from DFT calculations for the isolated molecules show significant differences. Some difficulties of using quantum-mechanical calculations for the determination of relative conformational energies are also discussed.

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

    NASA Technical Reports Server (NTRS)

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

    1974-01-01

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

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

    SciTech Connect

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

    2006-01-27

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

  12. Chemical Bonding in Si52- and NaSi5- via Photoelectron Spectroscopy and Ab Initio Calculations

    SciTech Connect

    Yu, Dmitry; Boldyrev, Zubarev; Boldyrev, Alexander I.; Li, Xi; Cui, Lifeng; Wang, Lai S.

    2005-12-22

    Photoelectron spectroscopy and ab initio calculations are used to investigate the electronic structure and chemical bonding of Si5 - and Si5 2- in NaSi5 -. Photoelectron spectra of Si5 - and NaSi5 - are obtained at several photon energies and are compared with theoretical calculations at four different levels of theory, TD-B3LYP, R(U)OVGF, UCCSD(T), and EOM-CCSD(T), all with 6-311+G(2df) basis sets. Excellent agreement is observed between experiment and theory, confirming the obtained ground-state structures for Si5 - and Si5 2-, which are both found to be trigonal bipyramid with D3h symmetry at several levels of theory. Chemical bonding in Si5, Si5 -, and Si5 2- is analyzed using NPA, molecular orbitals, ELF, and NICS indices. The bonding in Si5 2- is compared with that in the isoelectronic and isostructural B5H5 2- species, but they are found to differ due to the involvement of electron densities, which are supposed to be lone pairs in the skeletal bonding in Si5 2-.

  13. Ab initio calculation of Hubbard parameters for Rydberg-dressed atoms in a one-dimensional optical lattice

    NASA Astrophysics Data System (ADS)

    Chougale, Yashwant; Nath, Rejish

    2016-07-01

    We obtain ab initio the Hubbard parameters for Rydberg-dressed atoms in a one-dimensional (1D) sinusoidal optical lattice on the basis of maximally-localized Wannier states. Finite range, soft-core interatomic interactions become the trait of Rydberg admixed atoms, which can be extended over many neighboring lattice sites. In contrast to dipolar gases, where the interactions follow an inverse cubic law, the key feature of Rydberg-dressed interactions is the possibility of making neighboring couplings to the same magnitude as that of the onsite ones. The maximally-localized Wannier functions (MLWFs) are typically calculated via a spread-minimization procedure (Marzari N and Vanderbilt D 1997 Phys. Rev. B 56 12847) and are always found to be real functions apart from a trivial global phase when an isolated set of Bloch bands are considered. For an isolated single Bloch band, the above procedure reduces to a simple quasi-momentum-dependent unitary phase transformation. Here, instead of minimizing the spread, we employ a diagonal phase transformation which eliminates the imaginary part of the Wannier functions. The resulting Wannier states are found to be maximally localized and in exact agreement with those obtained via a spread-minimization procedure. Using these findings, we calculate the Hubbard couplings from the Rydberg admixed interactions, including dominant density-assisted tunneling (DAT) coefficients. Finally, we provide realistic lattice parameters for the state-of-the-art experimental Rydberg-dressed rubidium setup.

  14. Ab initio molecular dynamics with noisy and cheap quantum Monte Carlo forces: accurate calculation of vibrational frequencies

    NASA Astrophysics Data System (ADS)

    Luo, Ye; Sorella, Sandro

    2014-03-01

    We introduce a general and efficient method for the calculation of vibrational frequencies of electronic systems, ranging from molecules to solids. By performing damped molecular dynamics with ab initio forces, we show that quantum vibrational frequencies can be evaluated by diagonalizing the time averaged position-position or force-force correlation matrices, although the ionic motion is treated on the classical level within the Born-Oppenheimer approximation. The novelty of our approach is to evaluate atomic forces with QMC by means of a highly accurate and correlated variational wave function which is optimized simultaneously during the dynamics. QMC is an accurate and promising many-body technique for electronic structure calculation thanks to massively parallel computers. However, since infinite statistics is not feasible, property evaluation may be affected by large noise that is difficult to harness. Our approach controls the QMC stochastic bias systematically and gives very accurate results with moderate computational effort, namely even with noisy forces. We prove the accuracy and efficiency of our method on the water monomer[A. Zen et al., JCTC 9 (2013) 4332] and dimer. We are currently working on the challenging problem of simulating liquid water at ambient conditions.

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

    PubMed Central

    Gorenstein, D G; Taira, K

    1984-01-01

    Ab initio molecular orbital calculations have been performed on the reaction profile for the addition/elimination reaction between ammonia and formic acid, proceeding via a tetrahedral intermediate: NH3 + HCO2H----H2NCH(OH)2----NH2CHO + H2O. Calculated transition state energies for the first addition step of the reaction revealed that a lone pair on the oxygen of the OH group, which is antiperiplanar to the attacking nitrogen, stabilized the transition state by 3.9 kcal/mol, thus supporting the hypothesis of stereoelectronic control for this reaction. In addition, a secondary, counterbalancing stereoelectronic effect stabilizes the second step, water elimination, transition state by 3.1 kcal/mol if the lone pair on the leaving water oxygen is not antiperiplanar to the C-N bond. The best conformation for the transition states was thus one with a lone pair antiperiplanar to the adjacent scissile bond and also one without a lone-pair orbital on the scissile bond oxygen or nitrogen antiperiplanar to the adjacent polar bond. The significance of these stereoelectronic effects for the mechanism of action of serine proteases is discussed. PMID:6394065

  16. Prebiotic Atmospheric Chemistry on Titan: Formation Kinetics via Ab Initio Calculations for Potential Energy Surface (PES) Mapping

    NASA Astrophysics Data System (ADS)

    Gonzalez, Dayana; Mebel, Alexander

    2016-03-01

    It has been recently shown that Titan provides a unique perspective in our solar system: its atmosphere is comparable to a model of prebiotic Earth's. Provided the organic cationic and anionic molecular species identified by the Cassini spacecraft, this research characterizes reaction pathways for the reactions of methyl derivatives of the cyclopropenyl cation, the methyl cation with methyl- and dimethyl-acetylene, and reactions of resonance structures of protonated acrylonitrile with CH2NH. Isomerization and dissociation reactions involving methyl-cyclopropenyl cations, the perinaphthenyl cation and anion, and cations of pyrimidine and purine precursors of nucleobases will be examined to locate reaction pathways, intermediates, transition states, and products of the reactions. Gaussian '09 software is used for ab initio calculations to map out the PES. Geometry optimizations and vibrational frequency computations are preformed via the double-hybrid density functional B2PLYP-D3. Single-point energies are refined by use of the explicitly-correlated coupled-cluster CCSD(T)-F12 method. Rate constants are calculated using microcanonical RRKM theory, and pressure effects evaluated used the Master Equation approach; these allow for prediction of absolute rate constants and product branching ratios at different pressures and temperatures.

  17. The conversion of phenylpropanedinitrile (phenylmalononitrile) into the carbanion, followed by IR spectra, ab initio and DFT force field calculations

    NASA Astrophysics Data System (ADS)

    Binev, Yuri I.; Georgieva, Miglena K.; Novkova, Snezhana I.

    2003-11-01

    The spectral and structural changes, caused by the conversion of phenylpropanedinitrile (phenylmalononitrile) into the carbanion, have been followed by IR spectra, ab initio HF, MP2 and DFT BLYP force field calculations. In agreement between theory and experiment, the conversion is accompanied with strong frequency decreases (with 114 cm -1, mean value) of the cyano stretching bands νCN, dramatic increases in the corresponding integrated intensities (136-fold, total value), strong enhancement of the νCN vibrational coupling and other essential spectral changes. According to the calculations, the strongest structural changes take place at the carbanionic center: (i) shortenings of the CPh and CCN bonds with 0.064-0.092 Å, and increases in the corresponding bond orders with 0.14-0.21 U; (ii) simultaneous enlargements of the bond angles at the same carbon atom with 7.6°-9.7°, as from tetrahedral its configuration becomes trigonal. The carbanionic charge is distributed between the two cyano groups (0.44-0.52 e -), phenyl ring (0.31-0.34 e -) and carbanionic center (0.14-0.25 e -). The formation of moderately strong (CH 3) 2SO⋯HC(CN) 2C 6H 5 hydrogen bonds has been found experimentally.

  18. Structural characterization of tellurite glasses doped with transition metal oxides using Raman spectra and ab initio calculations

    NASA Astrophysics Data System (ADS)

    Mohamed, Tarek A.; Shaltout, I.; Al Yahyaei, K. M.

    2006-05-01

    Systems of iron tellurite glasses were prepared by melt quenching with compositions of [85%TeO 2 + 5%Fe 2O 3 + 10%TMO], where transition metal oxides (TMO) are TiO 2, V 2O 5, MnO, CoO, NiO and CuO. Furthermore, the main structural units of these samples have been characterized by means of Raman spectra (150-1200 cm -1) as well as wavenumber predictions by means of Gaussian 98 ab initio calculations for the proposed site symmetries of TeO 44- triagonal bipyramid ( C2v) and Te 2O 76- bridged tetrahedra ( Cs and C1). Aided by normal coordinate analysis, calculated vibrational frequencies, Raman scattering activities, force constants in internal coordinates and potential energy distributions (PEDs), revised vibrational assignments for the fundamental modes have been proposed. The main structural features are correlated to the dominant units of triagonal bipyramid (tbp) or bridged tetrahedral (TeO 3+1 binds to TeO 3 through TeOTe bridge; corner sharing). Moreover, the Raman spectra of the investigated tellurites reflect a structural change from tbp (coordination number is four) to triagonal pyramidal (coordination number is three).

  19. Conformational studies of 3-aminomethylene-2,4-pentanedione using vibrational and NMR spectra, and ab initio calculations

    NASA Astrophysics Data System (ADS)

    Gróf, M.; Gatial, A.; Milata, V.; Prónayová, N.; Sümmchen, L.; Salzer, R.

    2007-10-01

    The IR, Raman and NMR spectra of 3-aminomethylene-2,4-pentanedione (AMP) H 2N sbnd CH dbnd C(COCH 3) 2 were measured. According to the NMR spectra in chloroform and more polar DMSO at room temperature, the sample exists as single entity. On the other hand vibrational spectra revealed that in less polar solutions AMP exists as two conformers with EZ or ZZ orientation of acetyl groups whereas in more polar solvent only one EZ conformer is observed. Such interpretation was confirmed also by the temperature-dependent measurements of IR spectra in chloroform. The observed IR and Raman bands were compared with harmonic vibrational frequencies, calculated using ab initio MP2 and B3LYP density functional methods in 6-31G ∗∗ basis set, and assigned on the basis of potential energy distribution. In addition, the geometries and relative energies of possible conformers of AMP were also evaluated at the same levels of theory and compared with the data from X-ray analysis which revealed that AMP exists in solid state as EZ conformer. The influence of environment polarity on this conformational equilibrium is discussed with respect to the SCRF solvent effect calculations using PCM, IPCM and ONSAGER models.

  20. Point defect properties in hcp and bcc Zr with trace solute Nb revealed by ab initio calculations

    NASA Astrophysics Data System (ADS)

    Xin, X. K.; Lai, W. S.; Liu, B. X.

    2009-08-01

    The properties of simple point defect (i.e. vacancy, self and foreign interstitial atoms) in the hcp (alpha) and bcc (beta) Zr with trace solute Nb have been studied by ab initio calculations with VASP codes. The calculations indicate that the formation energies of vacancy and substitutional Nb atom are 1.94 eV and 0.68 eV in alpha Zr and 0.36 eV and 0.07 eV in beta Zr, respectively, while the binding energies of the nearest neighbor vacancy-substitutional Nb pair and the nearest neighbor substitutional Nb-Nb pair are 0.09 eV and 0.03 eV in alpha Zr and 2.78 eV and 0.72 eV in beta Zr, respectively. These results suggest that the Nb atoms are more likely to agglomerate and form precipitates in the beta Zr than in the alpha Zr. Thus, the α-Zr-β-Zr-β-Nb transition mechanism through in situ α to β transformation of Zr and the vacancy-assisted Nb diffusion for Nb conglomeration in beta Zr under irradiation is proposed to explain the existence of beta Nb and Zr precipitate mixtures observed in the experiments for the Zr-Nb alloy. In addition, the defect formation energies in bcc Nb are also presented.

  1. Ab Initio Calculation of the Zn Isotope Effect in Phosphates, Citrates, and Malates and Applications to Plants and Soil

    PubMed Central

    Fujii, Toshiyuki; Albarède, Francis

    2012-01-01

    Stable Zn isotopes are fractionated in roots and leaves of plants. Analyses demonstrate that the heavy Zn isotopes are enriched in the root system of plants with respect to shoots and leaves as well as the host soil, but the fractionation mechanisms remain unclear. Here we show that the origin of this isotope fractionation is due to a chemical isotope effect upon complexation by Zn malates and citrates in the aerial parts and by phosphates in the roots. We calculated the Zn isotope effect in aqueous citrates, malates, and phosphates by ab initio methods. For pH<5, the Zn isotopic compositions of the various parts of the plants are expected to be similar to those of groundwater. In the neutral to alkaline region, the calculations correctly predict that 66Zn is enriched over 64Zn in roots, which concentrate phosphates, with respect to leaves, which concentrate malates and citrates, by about one permil. It is proposed that Zn isotope fractionation represents a useful tracer of Zn availability and mobility in soils. PMID:22363478

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

    NASA Astrophysics Data System (ADS)

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

    2004-03-01

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

  3. Collisional excitation of CH(X²Π) by He: new ab initio potential energy surfaces and scattering calculations.

    PubMed

    Marinakis, Sarantos; Dean, Indigo Lily; Kłos, Jacek; Lique, François

    2015-09-01

    We present a new set of potential energy surfaces (PESs) for the CH(X(2)Π)-He van der Waals system. Ab initio calculations of the CH-He PES were carried out using the open-shell single- and double-excitation coupled cluster approach with non-iterative perturbational treatment of triple excitations [RCCSD(T)]. The augmented correlation-consistent polarized valence quadruple-zeta (aug-cc-pVQZ) basis set was employed augmented by mid-bond functions. Integral cross sections for the rotational excitation in CH-He collisions were calculated using the new PES and compared with available experimental results. The newly constructed PES reproduces the available experimental results for CH(X(2)Π, v = 0)-He collisions better than any previously available PES. Differential cross sections (DCS) are presented for the first time for this system and discussed within the context of rotational rainbows. Finally, our work provides the first rate thermal coefficients for this system that are crucially needed for astrochemical modelling and future anticipated experiments in CH(X(2)Π)-He collisions. PMID:26220835

  4. TRIQS/DFTTools: A TRIQS application for ab initio calculations of correlated materials

    NASA Astrophysics Data System (ADS)

    Aichhorn, Markus; Pourovskii, Leonid; Seth, Priyanka; Vildosola, Veronica; Zingl, Manuel; Peil, Oleg E.; Deng, Xiaoyu; Mravlje, Jernej; Kraberger, Gernot J.; Martins, Cyril; Ferrero, Michel; Parcollet, Olivier

    2016-07-01

    We present the TRIQS/DFTTools package, an application based on the TRIQS library that connects this toolbox to realistic materials calculations based on density functional theory (DFT). In particular, TRIQS/DFTTools together with TRIQS allows an efficient implementation of DFT plus dynamical mean-field theory (DMFT) calculations. It supplies tools and methods to construct Wannier functions and to perform the DMFT self-consistency cycle in this basis set. Post-processing tools, such as band-structure plotting or the calculation of transport properties are also implemented. The package comes with a fully charge self-consistent interface to the Wien2k band structure code, as well as a generic interface that allows to use TRIQS/DFTTools together with a large variety of DFT codes. It is distributed under the GNU General Public License (GPLv3).

  5. Ab initio calculation of mechanical and thermal properties of U2Mo intermetallic

    NASA Astrophysics Data System (ADS)

    Jaroszewicz, S.; Losada, E. L.; Garcés, J. E.; Mosca, H. O.

    2013-10-01

    We present a study of structural, elastic and thermodynamic properties of tetragonal (C11b) U2Mo by means of density-functional theory based calculations using full-potential linearized augmented plane wave method. In this approach the generalized gradient approximation were used for the exchange-correlation potential calculation. The optimized lattice parameters are in excellent agreement with the experimental data. Through the Debye-Grüneisen model the temperature and pressure dependence of equation of state, bulk modulus, thermal expansion and specific heat have been obtained and discussed in the range of pressure 0-20 GPa and the temperature 0-800 K.

  6. Obtaining model parameters for real materials from ab-initio calculations: Heisenberg exchange

    NASA Astrophysics Data System (ADS)

    Korotin, Dmitry; Mazurenko, Vladimir; Anisimov, Vladimir; Streltsov, Sergey

    An approach to compute exchange parameters of the Heisenberg model in plane-wave based methods is presented. This calculation scheme is based on the Green's function method and Wannier function projection technique. It was implemented in the framework of the pseudopotential method and tested on such materials as NiO, FeO, Li2MnO3, and KCuF3. The obtained exchange constants are in a good agreement with both the total energy calculations and experimental estimations for NiO and KCuF3. In the case of FeO our calculations explain the pressure dependence of the Néel temperature. Li2MnO3 turns out to be a Slater insulator with antiferromagnetic nearest neighbor exchange defined by the spin splitting. The proposed approach provides a unique way to analyze magnetic interactions, since it allows one to calculate orbital contributions to the total exchange coupling and study the mechanism of the exchange coupling. The work was supported by a grant from the Russian Scientific Foundation (Project No. 14-22-00004).

  7. Ab Initio Calculation of Nuclear Magnetic Resonance Chemical Shift Anisotropy Tensors 1. Influence of Basis Set on the Calculation of 31P Chemical Shifts

    SciTech Connect

    Alam, T.M.

    1998-09-01

    The influence of changes in the contracted Gaussian basis set used for ab initio calculations of nuclear magnetic resonance (NMR) phosphorous chemical shift anisotropy (CSA) tensors was investigated. The isotropic chemical shitl and chemical shift anisotropy were found to converge with increasing complexity of the basis set at the Hartree-Fock @IF) level. The addition of d polarization function on the phosphorous nucIei was found to have a major impact of the calculated chemical shi~ but diminished with increasing number of polarization fimctions. At least 2 d polarization fimctions are required for accurate calculations of the isotropic phosphorous chemical shift. The introduction of density fictional theory (DFT) techniques through tie use of hybrid B3LYP methods for the calculation of the phosphorous chemical shift tensor resulted in a poorer estimation of the NMR values, even though DFT techniques result in improved energy and force constant calculations. The convergence of the W parametem with increasing basis set complexity was also observed for the DFT calculations, but produced results with consistent large deviations from experiment. The use of a HF 6-31 l++G(242p) basis set represents a good compromise between accuracy of the simulation and the complexity of the calculation for future ab initio calculations of 31P NMR parameters in larger complexes.

  8. Feature Article: Thermodynamic properties from ab-initio calculations: New theoretical developments, and applications to various materials systems

    NASA Astrophysics Data System (ADS)

    Fähnle, Manfred; Drautz, Ralf; Lechermann, Frank; Singer, Reinhard; Diaz-Ortiz, Alejandro; Dosch, Helmut

    2005-05-01

    The cover picture from the Feature Article [1] depicts the calculated landscape of lowest formation energies for the ternary compound system Ni-Fe-Al. The figure shows for each composition the difference in the formation energy (in meV/atom) for the respective homogeneous configuration with lowest energy on the bcc and the fcc parent lattice. The phases on the fcc lattice dominate the Ni- and Al-rich regions of the Gibbs triangle.The first author Manfred Fähnle is Professor at the University of Stuttgart and member of the theory group of the department of Prof. Schütz at the Max-Planck-Institut für Metallforschung in Stuttgart. In 1980 he was awarded with the Otto-Hahn medal of the Max-Planck Society and in 1985 he received the Academy Award for Physics of the University of Göttingen. His present research interests are the static and dynamic properties of bulk and nanostructured magnetic systems, as well as the ab-initio statistical mechanics of alloys.

  9. EPR and ab initio calculation study on the EI4 center in 4H- and 6H-SiC

    SciTech Connect

    Carlsson, P.; Son, N. T.; Janzen, E.; Gali, A.; Isoya, J.; Morishita, N.; Ohshima, T.; Magnusson, B.

    2010-12-15

    We present results from electron paramagnetic resonance (EPR) studies of the EI4 EPR center in 4H- and 6H-SiC. The EPR signal of the EI4 center was found to be drastically enhanced in electron-irradiated high-purity semi-insulating materials after annealing at 700-750 deg. C. Strong EPR signals of the EI4 center with minimal interferences from other radiation-induced defects in irradiated high-purity semi-insulating materials allowed our more detailed study of the hyperfine (hf) structures. An additional large-splitting {sup 29}Si hf structure and {sup 13}C hf lines of the EI4 defect were observed. Comparing the data on the hf interactions and the annealing behavior obtained from EPR experiments and from ab initio supercell calculations of different carbon-vacancy-related complexes, we suggest a complex between a carbon vacancy-carbon antisite and a carbon vacancy at the third-neighbor site of the antisite in the neutral charge state, (V{sub C}-C{sub Si}V{sub C}){sup 0}, as a new defect model for the EI4 center.

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

    NASA Astrophysics Data System (ADS)

    Ogitsu, Tadashi; Gygi, Francois; Galli, Giulia

    2004-03-01

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

  11. Photoelectron Spectroscopy and Ab Initio Calculations of CS3(-) Isomers: Carbon Trisulfide and Carbon Disulfide S-Sulfide Anions.

    PubMed

    Nakanishi, Ryuzo; Kato, Shugo; Matsuyama, Yasushi; Nagata, Takashi

    2016-09-01

    Carbon sulfides are known as a class of binary compounds that can exist in various isomeric and/or polymeric forms. As for a sulfur-rich compound with the composition formula CS3, two possible constitutional isomers have been proposed experimentally or theoretically for the neutral species and its corresponding radical cation and anion. Although the previous studies claim that one isomer has a carbon trisulfide (CS3) C-centered configuration and the other has a carbon disulfide S-sulfide (SCSS) chain configuration, they have not yet been fully identified by a spectroscopic method. In this study, we have prepared the anions of those isomers in the gas phase by employing two types of reactions: dissociative electron attachment to 1,3-dithiole-2-thione for CS3(-) formation and the S(-) + CS2 ion-molecule reaction for SCSS(-). Photoelectron spectroscopic measurements reveal that the reactions result in the production of two anionic species that can be well distinguished by their vertical detachment energy. With the aid of ab initio calculations, they are identified distinctively as the anions of carbon trisulfide and carbon disulfide S-sulfide. PMID:27533492

  12. Electroabsorption measurements and ab initio calculations of the dipolar properties of 2-(2'-hydroxyphenyl)-benzothiazole and -benzoxazole: two photostabilizers that undergo excited-state proton transfer

    NASA Astrophysics Data System (ADS)

    Premvardhan, Lavanya; Peteanu, Linda

    1998-11-01

    Electroabsorption is used to determine the difference dipole moment, ∣Δ μ∣, and the difference polarizability, Δ α, of HBT and HBO, two molecules that undergo excited-state intramolecular proton transfer (ESIPT). These measurements are compared to ab initio (6-31G ∗) and semi-empirical (INDO1/s) calculations. Good agreement is obtained between ab initio and experimental ∣Δ μ∣ values. However, the negative Δ α values obtained experimentally for both molecules are in disagreement with the calculated Δ α values which are positive. The absorption maxima, measured as a function of solvent polarity, support the electroabsorption results. Agreement between the observed and calulated shift requires that Δ α for both molecules be negative.

  13. Accurate ab initio-based DMBE potential energy surface for HLi2(X 2A') via scaling of the external correlation

    NASA Astrophysics Data System (ADS)

    Song, Yu-Zhi; Li, Yong-Qing; Gao, Shou-Bao; Meng, Qing-Tian

    2014-01-01

    A globally accurate potential energy surface is reported for the electronic ground-state HLi2 by fitting ab initio energies to double many-body expansion formalism. The total 3726 ab initio energies used to map the HLi2 potential energy surface are calculated using the multi-reference configuration interaction method, with their dynamical correlation being semiempirically corrected by the double many-body expansion-scaled external correlation method. The current potential energy surface generates an excellent fit of the ab initio energies, showing a small root-mean squared derivation of 0.636 kcal mol-1. The topographical features of the HLi2 potential energy surface are examined in detail, which concludes that the H + Li2(X 1Σg) → Li + LiH(X 1Σ) reaction is essentially barrierless and the exothermicity is calculated to be 33.668 kcal mol-1, thus corroborates the available experimental and theoretical results.

  14. Ab initio nuclear many-body perturbation calculations in the Hartree-Fock basis

    NASA Astrophysics Data System (ADS)

    Hu, B. S.; Xu, F. R.; Sun, Z. H.; Vary, J. P.; Li, T.

    2016-07-01

    Starting from realistic nuclear forces, the chiral N3LO and JISP16, we have applied many-body perturbation theory (MBPT) to the structure of closed-shell nuclei, 4He and 16O. The two-body N3LO 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 antisymmetrized 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 probabilities of single-particle orbits as found in other treatments. We compare our results with other methods where available and find good agreement. This supports the conclusion that our methods produce reasonably converged results with these interactions. We also compare our results with experimental data.

  15. Ab initio molecular dynamics with noisy forces: Validating the quantum Monte Carlo approach with benchmark calculations of molecular vibrational properties

    SciTech Connect

    Luo, Ye Sorella, Sandro; Zen, Andrea

    2014-11-21

    We present a systematic study of a recently developed ab initio simulation scheme based on molecular dynamics and quantum Monte Carlo. In this approach, a damped Langevin molecular dynamics is employed by using a statistical evaluation of the forces acting on each atom by means of quantum Monte Carlo. This allows the use of an highly correlated wave function parametrized by several variational parameters and describing quite accurately the Born-Oppenheimer energy surface, as long as these parameters are determined at the minimum energy condition. However, in a statistical method both the minimization method and the evaluation of the atomic forces are affected by the statistical noise. In this work, we study systematically the accuracy and reliability of this scheme by targeting the vibrational frequencies of simple molecules such as the water monomer, hydrogen sulfide, sulfur dioxide, ammonia, and phosphine. We show that all sources of systematic errors can be controlled and reliable frequencies can be obtained with a reasonable computational effort. This work provides convincing evidence that this molecular dynamics scheme can be safely applied also to realistic systems containing several atoms.

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

    SciTech Connect

    Roemelt, Michael

    2015-07-28

    Spin Orbit Coupling (SOC) is introduced to molecular ab initio density matrix renormalization group (DMRG) calculations. In the presented scheme, one first approximates the electronic ground state and a number of excited states of the Born-Oppenheimer (BO) Hamiltonian with the aid of the DMRG algorithm. Owing to the spin-adaptation of the algorithm, the total spin S is a good quantum number for these states. After the non-relativistic DMRG calculation is finished, all magnetic sublevels of the calculated states are constructed explicitly, and the SOC operator is expanded in the resulting basis. To this end, spin orbit coupled energies and wavefunctions are obtained as eigenvalues and eigenfunctions of the full Hamiltonian matrix which is composed of the SOC operator matrix and the BO Hamiltonian matrix. This treatment corresponds to a quasi-degenerate perturbation theory approach and can be regarded as the molecular equivalent to atomic Russell-Saunders coupling. For the evaluation of SOC matrix elements, the full Breit-Pauli SOC Hamiltonian is approximated by the widely used spin-orbit mean field operator. This operator allows for an efficient use of the second quantized triplet replacement operators that are readily generated during the non-relativistic DMRG algorithm, together with the Wigner-Eckart theorem. With a set of spin-orbit coupled wavefunctions at hand, the molecular g-tensors are calculated following the scheme proposed by Gerloch and McMeeking. It interprets the effective molecular g-values as the slope of the energy difference between the lowest Kramers pair with respect to the strength of the applied magnetic field. Test calculations on a chemically relevant Mo complex demonstrate the capabilities of the presented method.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    Roemelt, Michael

    2015-07-28

    Spin Orbit Coupling (SOC) is introduced to molecular ab initio density matrix renormalization group (DMRG) calculations. In the presented scheme, one first approximates the electronic ground state and a number of excited states of the Born-Oppenheimer (BO) Hamiltonian with the aid of the DMRG algorithm. Owing to the spin-adaptation of the algorithm, the total spin S is a good quantum number for these states. After the non-relativistic DMRG calculation is finished, all magnetic sublevels of the calculated states are constructed explicitly, and the SOC operator is expanded in the resulting basis. To this end, spin orbit coupled energies and wavefunctions are obtained as eigenvalues and eigenfunctions of the full Hamiltonian matrix which is composed of the SOC operator matrix and the BO Hamiltonian matrix. This treatment corresponds to a quasi-degenerate perturbation theory approach and can be regarded as the molecular equivalent to atomic Russell-Saunders coupling. For the evaluation of SOC matrix elements, the full Breit-Pauli SOC Hamiltonian is approximated by the widely used spin-orbit mean field operator. This operator allows for an efficient use of the second quantized triplet replacement operators that are readily generated during the non-relativistic DMRG algorithm, together with the Wigner-Eckart theorem. With a set of spin-orbit coupled wavefunctions at hand, the molecular g-tensors are calculated following the scheme proposed by Gerloch and McMeeking. It interprets the effective molecular g-values as the slope of the energy difference between the lowest Kramers pair with respect to the strength of the applied magnetic field. Test calculations on a chemically relevant Mo complex demonstrate the capabilities of the presented method. PMID:26233112

  19. Structure of 1-naphthol-water clusters in the S1 state studied by UV-IR fluorescence dip spectroscopy and ab initio molecular orbital calculations

    NASA Astrophysics Data System (ADS)

    Shimizu, Toshihiko; Yoshino, Ruriko; Ishiuchi, Shun-ichi; Hashimoto, Kenro; Miyazaki, Mitsuhiko; Fujii, Masaaki

    2013-02-01

    IR spectra of trans-1-naphthol-(H2O)n (n = 0-3) clusters in the S1 state were measured by UV-IR fluorescence dip spectroscopy. The observed dip spectra were compared with theoretical ones of various stable conformations predicted by ab initio MO calculations. From the comparison, linear (n = 1) and cyclic hydrogen-bond structures (n = 2 and 3) were concluded. The relation between the structures and photochemical reactivity was discussed.

  20. Ab-Initio Description and Prediction of Properties of Carbon-Based and Other Non-Metallic Materials

    NASA Technical Reports Server (NTRS)

    Bagayoko, D.; Zhao, G. L.; Hasan, S.

    2001-01-01

    We have resolved the long-standing problem consisting of 30%-50% theoretical underestimates of the band gaps of non-metallic materials. We describe the Bagayoko, Zhao, and Williams (BZW) method that rigorously circumvents the basis-set and variational effect presumed to be a cause of these underestimates. We present ab-initio, computational results that are in agreement with experiment for diamond (C), silicon (Si), silicon carbides (3C-SiC and 4H-SiC), and other semiconductors (GaN, BaTiO3, AlN, ZnSe, ZnO). We illustrate the predictive capability of the BZW method in the case of the newly discovered cubic phase of silicon nitride (c-Si3N4) and of selected carbon nanotabes [(10,0), and (8,4)]. Our conclusion underscores the inescapable need for the BZW method in ab-initio calculations that employ a basis set in a variational approach. Current nanoscale trends amplify this need. We estimate that the potential impact of applications of the BZW method in advancing our understanding of nonmetallic materials, in informing experiment, and particularly in guiding device design and fabrication is simply priceless.

  1. Ab initio calculations of optical constants from ultraviolet to X-rays

    NASA Astrophysics Data System (ADS)

    Rivas, Gildardo

    We present a theory of x-ray absorption based on the real space Green's function formalism implemented in the FEFF x-ray spectroscopy code, and test it from UV to the hard x-ray limits. The one-electron theory includes self-consistent scattering potentials, core-hole and self-energy effects, and full or high order multiple scattering. From it we derive the total photo-absorption cross section summed over all edges. In contrast to standard atomic tables, the calculations include important solid-state corrections, e.g., the x-ray absorption fine structure, inelastic losses, lifetime broadening, etc. We further show that the same theory can be used to calculate the imaginary part of the complex dielectric function, from which other optical constants can be derived, e.g., the real part of the dielectric function, the complex index of refraction, and energy loss spectra. Typical results for elemental solids are presented and compared with standard theoretical tables and with experiment.

  2. Ab initio calculation of thermodynamic potentials and entropies for superionic water

    DOE PAGESBeta

    French, Martin; Desjarlais, Michael P.; Redmer, Ronald

    2016-02-25

    We construct thermodynamic potentials for two superionic phases of water [with body-centered cubic (bcc) and face-centered cubic (fcc) oxygen lattice] using a combination of density functional theory (DFT) and molecular dynamics simulations (MD). For this purpose, a generic expression for the free energy of warm dense matter is developed and parametrized with equation of state data from the DFT-MD simulations. A second central aspect is the accurate determination of the entropy, which is done using an approximate two-phase method based on the frequency spectra of the nuclear motion. The boundary between the bcc superionic phase and the ices VII andmore » X calculated with thermodynamic potentials from DFT-MD is consistent with that directly derived from the simulations. As a result, differences in the physical properties of the bcc and fcc superionic phases and their impact on interior modeling of water-rich giant planets are discussed.« less

  3. Ab initio calculation of thermodynamic potentials and entropies for superionic water

    NASA Astrophysics Data System (ADS)

    French, Martin; Desjarlais, Michael P.; Redmer, Ronald

    2016-02-01

    We construct thermodynamic potentials for two superionic phases of water [with body-centered cubic (bcc) and face-centered cubic (fcc) oxygen lattice] using a combination of density functional theory (DFT) and molecular dynamics simulations (MD). For this purpose, a generic expression for the free energy of warm dense matter is developed and parametrized with equation of state data from the DFT-MD simulations. A second central aspect is the accurate determination of the entropy, which is done using an approximate two-phase method based on the frequency spectra of the nuclear motion. The boundary between the bcc superionic phase and the ices VII and X calculated with thermodynamic potentials from DFT-MD is consistent with that directly derived from the simulations. Differences in the physical properties of the bcc and fcc superionic phases and their impact on interior modeling of water-rich giant planets are discussed.

  4. Ab initio calculation of thermodynamic potentials and entropies for superionic water.

    PubMed

    French, Martin; Desjarlais, Michael P; Redmer, Ronald

    2016-02-01

    We construct thermodynamic potentials for two superionic phases of water [with body-centered cubic (bcc) and face-centered cubic (fcc) oxygen lattice] using a combination of density functional theory (DFT) and molecular dynamics simulations (MD). For this purpose, a generic expression for the free energy of warm dense matter is developed and parametrized with equation of state data from the DFT-MD simulations. A second central aspect is the accurate determination of the entropy, which is done using an approximate two-phase method based on the frequency spectra of the nuclear motion. The boundary between the bcc superionic phase and the ices VII and X calculated with thermodynamic potentials from DFT-MD is consistent with that directly derived from the simulations. Differences in the physical properties of the bcc and fcc superionic phases and their impact on interior modeling of water-rich giant planets are discussed. PMID:26986321

  5. Ab initio calculation of the thermodynamic properties of InSb under intense laser irradiation

    SciTech Connect

    Feng, ShiQuan; Cheng, XinLu; Key Laboratory of High Energy Density Physics and Technology of Ministry of Education, Sichuan University, Chengdu, 610064 ; Zhao, JianLing; Zhang, Hong

    2013-07-28

    In this paper, phonon spectra of InSb at different electronic temperatures are presented. Based on the phonon dispersion relationship, we further perform a theoretical investigation of the thermodynamic properties of InSb under intense laser irradiation. The phonon entropy, phonon heat capacity, and phonon contribution to Helmholtz free energy and internal energy of InSb are calculated as functions of temperature at different electronic temperatures. The abrupt change in the phonon entropy- temperature curve from T{sub e} = 0.75 to 1.0 eV provides an indication of InSb undergoing a phase transition from solid to liquid. It can be considered as a collateral evidence of non-thermal melting for InSb under intense electronic excitation effect.

  6. Comparative study of tight-binding and ab initio electronic structure calculations focused on magnetic anisotropy in ordered CoPt alloy

    NASA Astrophysics Data System (ADS)

    Zemen, J.; Mašek, J.; Kučera, J.; Mol, J. A.; Motloch, P.; Jungwirth, T.

    2014-04-01

    An empirical multiorbital (spd) tight binding (TB) model including magnetism and spin-orbit coupling is applied to calculations of magnetic anisotropy energy (MAE) in CoPt L10 structure. A realistic Slater-Koster parametrisation for single-element transition metals is adapted for the ordered binary alloy. Spin magnetic moment and density of states are calculated using a full-potential linearised augmented plane-wave (LAPW) ab initio method and our TB code with different variants of the interatomic parameters. Detailed mutual comparison of this data allows for determination of a subset of the compound TB parameters tuning of which improves the agreement of the TB and LAPW results. MAE calculated as a function of band filling using the refined parameters is in broad agreement with ab initio data for all valence states and in quantitative agreement with ab initio and experimental data for the natural band filling. Our work provides a practical basis for further studies of relativistic magnetotransport anisotropies by means of local Green's function formalism which is directly compatible with our TB approach.

  7. HOSO/sub 2/ and HOSO/sub 4/ radicals studied by ab initio calculation and matrix isolation technique

    SciTech Connect

    Nagase, S.; Hashimoto, S.; Akimoto, H.

    1988-02-11

    Sulfo (HOSO/sub 2/) and sulfodioxy (HOSO/sub 4/) radicals have been characterized by use of ab initio calculations at the HF/3-21G(*) level, and the results were compared with the infrared spectral data from low-temperature-matrix experiments. The calculated vibrational frequencies and the isotope shift as well as a supplemental experimental result supported the assignment of the observed infrared absorption bands in the Ar matrix at 3539.9 (3528.6), 1309.2 (1308.7), 1097.3 (1096.0), and 759.5 (735.1) cm/sup -1/ to the O--H st, S(=O)/sub 2/ asym st, S(=O)/sub 2/ sym st, and S-OH st modes of the H/sup 16/OS/sup 16/O/sub 2/ (H/sup 18/OS/sup 16/O/sub 2/) radical, respectively. The HOSO/sub 4/ radical was found to be located as a minimum on the potential surface, and the fully optimized geometry and vibrational frequencies were obtained, although the detection of the radical in the O/sub 2/ matrix was unsuccessful. Enthalpy changes for the reactions HOSO/sub 2/ + O/sub 2/ ..-->.. HO/sub 2/ + SO/sub 3/ (2) and HOSO/sub 2/ + O/sub 2/ ..-->.. HOSO/sub 4/ (3) were calculated at the MP4(SDTQ)/6031G**//3-21G(*) and MP3/6-31G**//3-21G(*) levels, respectively, and the results were discussed in comparison with the experimental evidence

  8. Rotational study of the CH{sub 4}–CO complex: Millimeter-wave measurements and ab initio calculations

    SciTech Connect

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

    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.

  9. An Isolated Complex of Ethyne and Gold Iodide Characterized by Broadband Rotational Spectroscopy and Ab initio Calculations.

    PubMed

    Mullaney, John C; Stephens, Susanna L; Zaleski, Daniel P; Sprawling, Matthew J; Tew, David P; Walker, Nicholas R; Legon, Anthony C

    2015-09-17

    A molecular complex of C2H2 and AuI has been generated and isolated in the gas phase through laser ablation of a gold surface in the presence of an expanding sample containing small percentages of C2H2 and CF3I in a buffer gas of argon. Rotational, B0, centrifugal distortion, ΔJ and ΔJK, and nuclear quadrupole coupling constants, χaa(Au), χbb(Au) - χcc(Au), χaa(I), and χbb(I) - χcc(I), are measured for three isotopologues of C2H2···AuI through broadband rotational spectroscopy. The complex is C2v and T-shaped with C2H2 coordinating to the gold atom via donation of electrons from the π-orbitals of ethyne. On formation of the complex, the C≡C bond of ethyne extends by 0.032(4) Å relative to r(C≡C) in isolated ethyne when the respective r0 geometries are compared. The geometry of ethyne distorts such that ∠(*-C-H) (where * indicates the midpoint of the C≡C bond) is 194.7(12)° in the r0 geometry of C2H2···AuI. Ab initio calculations at the CCSD(T)(F12*)/AVTZ level are consistent with the experimentally determined geometry and further allow calculation of the dissociation energy (De) as 136 kJ mol(-1). The χaa(Au) and χaa(I) nuclear quadrupole coupling constants of AuI and also the Au-I bond length change significantly on formation of the complex consistent with the strong interaction calculated to occur between C2H2 and AuI. PMID:26305995

  10. Molecular structure and vibrational spectra of dithionite ion by ab initio calculations

    NASA Astrophysics Data System (ADS)

    Leszczynski, Jerzy; Zerner, Michael C.

    1989-07-01

    The structure of the dithionite ion, S 2O 42-, is examined using quantum chemical calculations. These studies strongly suggest that only the C 2h (trans) isomer is stable in solution. The C 2v (cis) form reported in Na 2S 2O 4·2H 2O is stabilized by crystal forces. The calculated vibrational spectrum of the C 2h form is in excellent agreement with that observed in aqueous solution. Taking into account the negative frequency calculated for the C 2v structure yields a calculated spectrum in good agreement with that observed for the crystal.

  11. Chemical trend of exchange coupling in diluted magnetic II-VI semiconductors: Ab initio calculations

    NASA Astrophysics Data System (ADS)

    Chanier, T.; Virot, F.; Hayn, R.

    2009-05-01

    We have calculated the chemical trend of magnetic exchange parameters ( Jdd , Nα , and Nβ ) of Zn-based II-VI semiconductors ZnA ( A=O , S, Se, and Te) doped with Co or Mn. We show that a proper treatment of electron correlations by the local spin-density approximation (LSDA)+U method leads to good agreement between experimental and theoretical values of the nearest-neighbor exchange coupling Jdd between localized 3d spins in contrast to the LSDA method. The exchange couplings between localized spins and doped electrons in the conduction band Nα are in good agreement with experiment as well. But the values for Nβ (coupling to doped holes in the valence band) indicate a crossover from weak coupling (for A=Te and Se) to strong coupling (for A=O ) and a localized hole state in ZnO:Mn. This hole localization explains the apparent discrepancy between photoemission and magneto-optical data for ZnO:Mn.

  12. Electronic and Magnetic Properties of Al Adsorption on α-Uranium(001) Surface: Ab Initio Calculations

    SciTech Connect

    Nie, JL; Xiao, Haiyan J.; Gao, Fei; Zu, Xiaotao T.

    2009-05-12

    First-principles calculations based on density functional theory with the generalized gradient approximation have been performed to study the aluminum (Al) adsorption on the (001) surface of α-uranium (α-U). The geometric, electronic and magnetic properties have been investigated at coverages of 0.25 and 0.5 monolayer. The results show that the quasi-trigonal sites are preferred at both coverages. The bonding of Al with U is found to be metallic, which mainly arises from the mixing of Al 3sp and U 5f states. A ferromagnetic phase is determined for the bare α-U(001) surface, while the adsorption of Al on the surface significantly perturbs the spin arrangement pattern and reduces the local magnetic moment, leading to a ferrimagnetic phase on the α-U(001) surface at the coverage of 0.5 monolayer. However, the Al overlayer is paramagnetic. Generally, the spin polarization has negligible effects on the geometric and electronic properties of Al atoms on the α-U(001) surface.

  13. Magnetic properties in Pd doped ZnS from ab initio calculations

    NASA Astrophysics Data System (ADS)

    Dong, Xinlong; Li, Qiuhang; Xu, Mingxiang

    2013-11-01

    First-principles calculations based on density functional theory within the general gradient approximation (GGA) are performed to study the electronic structure and magnetic properties of Pd doped ZnS. It is found that an isolated Pd atom doped 2 × 2 × 2 ZnS supercell shows half-metallic ferromagnetic character with a total magnetic moment of 2.0 μ B per supercell, which is significantly enhanced compared with the pure ZnS supercell. The strong ferromagnetic coupling of the local magnetic moments can be explained in terms of strong hybridisation between Pd-4 d and S-3 p states. The hybridisation between Pd and the neighbouring S atoms leads to a strong coupling chain Pd(4 d)-S(3 p)-Zn(3 d)-S(3 p)-Pd(4 d), which induces strong indirect long range FM coupling between Pd dopants. The results of several doping configurations demonstrate that ferromagnetic coupling exists between the two doped palladium atoms. These results suggest that Pd doped ZnS can also be considered as suitable candidates for exploring new half-metallic ferromagnetism in semiconductors.

  14. Mechanical and dynamical stability of TiAsTe compound from ab initio calculations

    NASA Astrophysics Data System (ADS)

    Deligoz, E.; Ozisik, H.

    2015-07-01

    The first-principles calculations are employed to provide a fundamental understanding of the structural features and relative thermodynamical, mechanical and phonon stability of TiAsTe compound. The calculated lattice parameters are in good agreement with available experimental results. We have computed elastic constants, its derived moduli and ratios that characterize mechanical properties for the first time. The calculated elastic constants indicate that these materials are mechanically stable at ambient condition. The minimum thermal conductivities of TiAsTe are calculated using both Clarke's model and Cahill's model. Furthermore, the elastic anisotropy has been visualized in detail by plotting the directional dependence of compressibility, Young's modulus and shear modulus. Our results suggest strong elastic anisotropy for this compound. Additionally, the phonon spectra and phonon density of states are also obtained and discussed. The full phonon dispersion calculations confirm the dynamic stability of TiAsTe.

  15. Ab initio calculations on collisions of low energy electrons with polyatomic molecules

    SciTech Connect

    Rescigno, T.N.

    1991-08-01

    The Kohn variational method is one of simplest, and oldest, techniques for performing scattering calculations. Nevertheless, a number of formal problems, as well as practical difficulties associated with the computation of certain required matrix elements, delayed its application to electron--molecule scattering problems for many years. This paper will describe the recent theoretical and computational developments that have made the complex'' Kohn variational method a practical tool for carrying out calculations of low energy electron--molecule scattering. Recent calculations on a number of target molecules will also be summarized. 41 refs., 7 figs.

  16. Investigation of the structure and interaction of cellulose triacetate I crystal using ab initio calculations.

    PubMed

    Kobayashi, Takanori; Hayakawa, Daichi; Khishigjargal, Tegshjargal; Ueda, Kazuyoshi

    2014-03-31

    The crystal structure of cellulose triacetate I (CTA I) was investigated using first-principles density functional theory (DFT) calculations. The results are in good agreement with the experimental structure obtained by Sikorski et al. when performing the calculation with inclusion of the dispersion correction. However, the cell parameters calculated with inclusion of the dispersion correction are slightly smaller than those experimentally obtained, especially along the a-axis. This smaller cell parameter could be reasonably explained by considering thermal expansion effects, since optimization with the density functional calculation gives the structure without inclusion of thermal effects. The atoms-in-molecules (AIM) theory is also employed to identify and characterize interatomic interactions in the CTA I crystal. CH/O interactions sites are shown to exist in the crystal structure of CTA I. Moreover, CH/O interactions are considered the main interactions in operation to maintain the crystal structure of CTA I. PMID:24614690

  17. A compilation of ab-initio calculations of embrittling potencies in binary metallic alloys.

    PubMed

    Gibson, Michael A; Schuh, Christopher A

    2016-03-01

    Segregation-induced changes in interfacial cohesion often control the mechanical properties of metals. The change in the work of separation of an interface upon segregation of a solute to the interface, termed the embrittling potency, is an atomic-level quantity used to predict and understand embrittlement phenomena. We present a compilation of calculations of embrittling potencies, along with references for these calculations. A discussion of this data is made in a separate article (Gibson and Schuh, 2016 [1]). PMID:26858979

  18. A compilation of ab-initio calculations of embrittling potencies in binary metallic alloys

    PubMed Central

    Gibson, Michael A.; Schuh, Christopher A.

    2015-01-01

    Segregation-induced changes in interfacial cohesion often control the mechanical properties of metals. The change in the work of separation of an interface upon segregation of a solute to the interface, termed the embrittling potency, is an atomic-level quantity used to predict and understand embrittlement phenomena. We present a compilation of calculations of embrittling potencies, along with references for these calculations. A discussion of this data is made in a separate article (Gibson and Schuh, 2016 [1]). PMID:26858979

  19. Ab initio MO based lattice energy for molecular crystals: packing structure of electron donor-acceptor (EDA) complex H 3N-BF 3

    NASA Astrophysics Data System (ADS)

    Ikeda, Tohru; Nagayoshi, Kanade; Kitaura, Kazuo

    2003-03-01

    A computational procedure is proposed for calculating the lattice energy of molecular crystals using the ab initio MO method. Our method does not require any adjustable parameters and provides a general description for various molecular crystals including electron donor-acceptor (EDA) complexes. Using the method, the packing structure of H 3N-BF 3 crystal was optimized at the HF/3-21 + G level and the lattice energy was calculated at the MP2/6-311 + G * level. The calculation reproduced the experimental lattice constants with reasonable accuracy. Moreover, the structural feature of the H 3N-BF 3 crystal was discussed based on the molecular interactions in the crystal.

  20. Structural determination of the Bi(110) semimetal surface by LEED analysis and ab initio calculations

    SciTech Connect

    Sun, J.; Pohl, K.; Mikkelsen, A.; Fuglsang Jensen, M.; Hofmann, Ph.; Koroteev, Y. M.; Bihlmayer, G.; Chulkov, E. V.

    2006-12-15

    The surface structure of Bi(110) has been investigated by low-energy electron diffraction intensity analysis and by first-principles calculations. Diffraction patterns at a sample temperature of 110 K and normal incidence reveal a bulk truncated (1x1) surface without indication of any structural reconstruction despite the presence of dangling bonds on the surface layer. Good agreement is obtained between the calculated and measured diffraction intensities for this surface containing only one mirror-plane symmetry element and a buckled bilayer structure. No significant interlayer spacing relaxations are found. The Debye temperature for the surface layer is found to be lower than in the bulk, which is indicative of larger atomic vibrational amplitudes at the surface. Meanwhile, the second layer shows a Debye temperature close to the bulk value. The experimental results for the relaxations agree well with those of our first-principles calculation.

  1. Configuration-averaged 4f orbitals in ab initio calculations of low-lying crystal field levels in lanthanide(iii) complexes.

    PubMed

    Van den Heuvel, Willem; Calvello, Simone; Soncini, Alessandro

    2016-06-21

    A successful and commonly used ab initio method for the calculation of crystal field levels and magnetic anisotropy of lanthanide complexes consists of spin-adapted state-averaged CASSCF calculations followed by state interaction with spin-orbit coupling (SI-SO). Based on two observations valid for Ln(iii) complexes, namely: (i) CASSCF 4f orbitals are expected to change very little when optimized for different states belonging to the 4f electronic configuration, (ii) due to strong spin-orbit coupling the total spin is not a good quantum number, we show here via a straightforward analysis and direct calculation that the CASSCF/SI-SO method can be simplified to a single configuration-averaged HF calculation and one complete active space CI diagonalization, including spin-orbit coupling, on determinant basis. Besides its conceptual simplicity, this approach has the advantage that all spin states of the 4f(n) configuration are automatically included in the SO coupling, thereby overcoming one of the computational limitations of the existing CASSCF/SI-SO approach. As an example, we consider three isostructural complexes [Ln(acac)3(H2O)2], Ln = Dy(3+), Ho(3+), Er(3+), and find that the proposed simplified method yields crystal field levels and magnetic g-tensors that are in very good agreement with those obtained with CASSCF/SI-SO. PMID:27231024

  2. Ab initio spur size calculation in liquid water at room temperature

    NASA Astrophysics Data System (ADS)

    Muroya, Yusa; Mozumder, Asokendu

    2016-07-01

    An attempt was made to calculate the spur size in liquid water at room temperature from fundamental interactions. Electron trapping, elastic scattering, and positive-ion back attraction undergone in sub-excitation and sub-vibrational stages in the 100 fs time scale for thermalization were considered and included in the model. Overall diffusional broadening was estimated to be 41.2 Å, attended by the positive-ion pull back of 24.0 Å, resulting in a calculated spur size of 17.2 Å. Electron trapping is seen in competition with thermalization in the ultimate stage, which results in the trapped electron position distribution as a sum of Gaussians.

  3. Highly localized quasiatomic minimal basis orbitals for Mo from ab initio calculations

    NASA Astrophysics Data System (ADS)

    Chan, T.-L.; Yao, Y. X.; Wang, C. Z.; Lu, W. C.; Li, J.; Qian, X. F.; Yip, S.; Ho, K. M.

    2007-11-01

    A minimal basis set of localized quasiatomic orbitals for Mo is constructed using the fully converged eigenstates from first-principles calculations with a large basis set. The orbitals, although similar in shape to those of a free atom, are slightly deformed such that it can reproduce all the occupied-state electronic properties of the system. They are very useful for analyzing chemical bonding by calculating the Mulliken overlap population and bond order index between atoms. In addition, the transferability of tight-binding parametrizations can be evaluated, for example, the effect of the two-center approximation.

  4. {ital Ab Initio} Calculation of Crystalline Electric Fields and Kondo Temperatures in Ce Compounds

    SciTech Connect

    Han, J.; Alouani, M.; Cox, D.; Han, J.; Cox, D.; Alouani, M.

    1997-02-01

    We have calculated the band-f hybridizations for Ce{sub x}La{sub 1-x}M{sub 3} compounds (x=1 and x{r_arrow}0; M=Pb,In,Sn,Pd) within the local density approximation and fed this into a noncrossing approximation for the Anderson impurity model applied to both dilute and concentrated limits. Our calculations produce crystalline electric field splittings and Kondo temperatures with trends in good agreement with experiment and demonstrate the need for detailed electronic structure information on hybridization to describe the diverse behaviors of these Ce compounds. {copyright} {ital 1997} {ital The American Physical Society}

  5. Ab initio nuclear structure theory

    NASA Astrophysics Data System (ADS)

    Negoita, Gianina Alina

    Ab initio no core methods have become major tools for understanding the properties of light nuclei based on realistic nucleon-nucleon (NN) and three-nucleon (NNN) interactions. A brief description is provided for the inter-nucleon interactions that fit two-body scattering and bound state data, as well as NNN interactions. Major new progress, including the goal of applying these interactions to solve for properties of nuclei, is limited by convergence issues. That is, with the goal of obtaining high precision solutions of the nuclear many-body Hamiltonian with no core methods (all nucleons treated on the same footing), one needs to proceed to very large basis spaces to achieve a convergence pattern suitable for extrapolation to the exact result. This thesis investigates (1) the similarity renormalization group (SRG) approach to soften the interaction, while preserving its phase shift properties, and (2) adoption of a realistic basis space using Woods-Saxon (WS) single-particle wavefunctions. Both have their advantages and limitations, discussed here. For (1), SRG was demonstrated by applying it to a realistic NN interaction, JISP16, in a harmonic oscillator (HO) representation. The degree of interaction softening achieved through a regulator parameter is examined. For (2), new results are obtained with the realistic JISP16 NN interaction in ab initio calculations of light nuclei 4He, 6He and 12C, using a WS basis optimized to minimize the ground-state energy within the truncated no core shell model. These are numerically-intensive many-body calculations. Finally, to gain insight into the potential for no core investigations of heavier nuclei, an initial investigation was obtained for the odd mass A = 47 - 49 region nuclei straddling 48Ca. The motivation for selecting these nuclei stems from the aim of preparing for nuclear double beta-decay studies of 48Ca. In these heavier systems, phenomenological additions to the realistic NN interaction determined by previous

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

    NASA Astrophysics Data System (ADS)

    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.

  7. Ab initio calculation of the thermodynamic properties and phase diagram of gallium nitride

    NASA Astrophysics Data System (ADS)

    Zhou, Ying; Wang, Shaofeng; Wang, Rui; Jiang, Na

    2013-12-01

    The thermodynamic properties of gallium nitride (GaN) with wurtzite (WZ) and rocksalt (RS) phases have been investigated by carrying out the first principles-calculations, in which the density-functional theory (DFT) and density-functional perturbation theory (DFPT) have been employed. The quasiharmonic approximation (QHA) has been utilized to estimate the free energies. The phonon dispersion, thermal expansion coefficients, bulk modulus, and heat capacities are presented and provided good agreement with the previous calculation and experimental data. Furthermore, the pressure-temperature (P-T) diagram of WZ-RS phase transition of GaN is predicted and the values of transition pressure range from 32.2 GPa at 0 K to about 21 GPa at 2480 K.

  8. Spectral line shape of the P(2) transition in CO-Ar: Uncorrelated ab initio calculation

    SciTech Connect

    Wehr, R.; Vitcu, A.; Drummond, J.R.; May, A.D.; Ciurylo, R.

    2002-12-01

    We calculate the spectral line shape of an isolated line from first principles, assuming that the translational motion is not statistically correlated with the evolution of the optical coherence, i.e., with the broadening. We use the known, realistic potentials for the influence of collisions on the translational motion and on the internal motion. We show that the calculated profiles do not agree, particularly at low pressures, with very precise experimental profiles of the P(2) line of CO in a bath of Ar. We establish that the source of the disagreement lies in the assumption of uncorrelated effects of collisions on the translational motion and the optical coherence associated with the internal degrees of freedom.

  9. Pressure Induced Structural Phase Transition in Actinide Monophospides: Ab Initio Calculations

    NASA Astrophysics Data System (ADS)

    Makode, Chandrabhan; Sanyal, Sankar P.

    2011-07-01

    The structural and electronic properties of monophospides of Thorium, Uranium and Neptunium have been investigated using tight binding linear muffin-in-orbital (TB-LMTO) method within the local density approximation (LDA). From present study with the help of total energy calculations it is found that ThP, UP and NpP are stable in NaCl- type structure under ambient pressure. The structure stability of ThP, UP and NpP changes under the application of pressure. We predict a structural phase transition from NaCl-type (B1-phase) structure to CsCl-type (B2-phase) structure for these phospides in the pressure range of 37.0-24.0 GPa (ThP to NpP). The calculated equilibrium lattice parameters and bulk modulus are in good agreement with experimental and theoretical work.

  10. Pressure induced structural phase transition in actinide mono-bismuthides: Ab initio calculations

    NASA Astrophysics Data System (ADS)

    Pataiya, J.; Makode, C.; Aynyas, M.; Sanyal, Sankar P.

    2013-06-01

    The structural and electronic properties of mono-bismuthides of Plutonium and Americium have been investigated using tight binding linear muffin-tin-orbital (TB-LMTO) method within the local density approximation (LDA). From present study with the help of total energy calculations it is found that PuBi and AmBi are stable in NaCl - type structure under ambient pressure. The structure stability of PuBi and AmBi changes under the application of pressure. We predict a structural phase transition from NaCl-type (B1-phase) structure to CsCl-type (B2-phase) structure for these phospides in the pressure range of 45 - 4.5 GPa for PuBi and AmBi respectively. The calculated equilibrium lattice parameters and bulk modulus are in good agreement with experimental and theoretical work.

  11. Thermodynamic and mechanical properties of TiC from ab initio calculation

    SciTech Connect

    Dang, D. Y.; Fan, J. L.; Gong, H. R.

    2014-07-21

    The temperature-dependent thermodynamic and mechanical properties of TiC are systematically investigated by means of a combination of density-functional theory, quasi-harmonic approximation, and thermal electronic excitation. It is found that the quasi-harmonic Debye model should be pertinent to reflect thermodynamic properties of TiC, and the elastic properties of TiC decease almost linearly with the increase of temperature. Calculations also reveal that TiC possesses a pronounced directional pseudogap across the Fermi level, mainly due to the strong hybridization of Ti 3d and C 2p states. Moreover, the strong covalent bonding of TiC would be enhanced (reduced) with the decrease (increase) of temperature, while the change of volume (temperature) should have negligible effect on density of states at the Fermi level. The calculated results agree well with experimental observations in the literature.

  12. Emergence of rotational bands in ab initio no-core configuration interaction calculations of light nuclei

    NASA Astrophysics Data System (ADS)

    Caprio, Mark A.; Maris, Pieter; Vary, James P.

    2014-03-01

    The emergence of rotational bands has recently been observed in no-core configuration interaction (NCCI) calculations for p-shell nuclei, as evidenced by rotational patterns for excitation energies, electromagnetic moments, and electromagnetic transitions. Yrast and low-lying excited bands are found. The results demonstrate the possibility of well-developed rotational structure in NCCI calculations, using realistic nucleon-nucleon interactions, and within finite, computationally-accessible configuration spaces. This talk will focus on results for rotation in both the even-mass and odd-mass Be isotopes (7 <= A <= 12). Supported by US DOE (DE-FG02-95ER-40934, DESC0008485 SciDAC/NUCLEI, DE-FG02-87ER40371), US NSF (0904782), and Research Corporation for Science Advancement (Cottrell Scholar Award). Computational resources provided by NERSC (US DOE DE-AC02-05CH11231).

  13. Ab initio calculation of the magnetism in GdFe 12

    NASA Astrophysics Data System (ADS)

    Trygg, Joakim; Johansson, Börje; Brooks, M. S. S.

    1992-02-01

    Electronic structure calculations by means of the LMTO-ASA method have been performed for the hypothetical rare earth-transition metal compound GdFe 12 with the ThMn 12 structure. The R-4f magnetic moments were obtained from the standard Russel-Saunders scheme but the radial 4f spin density was otherwise part of the self-consistent band calculation. The influence of localized 4f magnetism upon the conduction band magnetism is found to give noticeable changes in the local moments of the iron. The presence of the 4f spin moment is found to induce a redistribution of the conduction electron spin moment between the rare earth and iron sites while the total conduction moment remains practically constant.

  14. Reactive Inorganic Membranes for CO2/N2 separations: Ab-initio Density Functional Theory Calculations

    NASA Astrophysics Data System (ADS)

    Ostwal, M.; Way, J. D.; Lusk, M.

    2009-10-01

    The selectivity (CO2/N2) of mesoporous silica membranes can be enhanced by surface modification using APTS (3-aminopropyl-triethoxy silane). The hypothesized transport mechanism in such materialsis the reaction of CO2 with surface amine groups to form a carbamate species and subsequent surface ``hopping'' of CO2. DFT calculations were performed in order to elucidate the mechanism of CO2 transport in APTS modified membranes, to compute the CO2 diffusivity through the membrane, and to calculate its binding energy on an amine strand. The computed binding energy for docking one CO2 molecule to an amine was calculated to be 15.5 kcal/mol (0.67 eV). The activation/barrier energy for a CO2 molecule to hop from one amine strand (in form of carbamate) to another computed using Transition State Theory (TST) was 7.2 kcal/mol (0.31 eV) and compares well with our experimental data (˜ 8kcal/mol; 0.35 eV). In the configuration studied, CO2 hops from one strand to another in a zigzag fashion due to thermal motion of the strands; a strand with the CO2 molecule undulates and eventually moves so that the CO2 can be attracted by an adjacent strand. The CO2 diffusivity calculated using the computed activation energy ranged from 1.1 X 10-11m^2/sec (@ 25 C) to 5.7 X 10-10m^2/sec (@100 C).

  15. Equilibrium 2H/ 1H fractionations in organic molecules: I. Experimental calibration of ab initio calculations

    NASA Astrophysics Data System (ADS)

    Wang, Ying; Sessions, Alex L.; Nielsen, Robert J.; Goddard, William A., III

    2009-12-01

    Carbon-bound hydrogen in sedimentary organic matter can undergo exchange over geologic timescales, altering its isotopic composition. Studies investigating the natural abundance distribution of 1H and 2H in such molecules must account for this exchange, which in turn requires quantitative knowledge regarding the endpoint of exchange, i.e., the equilibrium isotopic fractionation factor ( α eq). To date, relevant data have been lacking for molecules larger than methane. Here we describe an experimental method to measure α eq for C-bound H positions adjacent to carbonyl group (H α) in ketones. H at these positions equilibrates on a timescale of days as a result of keto-enol tautomerism, allowing equilibrium 2H/ 1H distributions to be indirectly measured. Molecular vibrations for the same ketone molecules are then computed using Density Functional Theory at the B3LYP/6-311G∗∗ level and used to calculate α eq values for H α. Comparison of experimental and computational results for six different straight and branched ketones yields a temperature-dependent linear calibration curve with slope = 1.081-0.00376 T and intercept = 8.404-0.387 T, where T is temperature in degrees Celsius. Since the dominant systematic error in the calculation (omission of anharmonicity) is of the same size for ketones and C-bound H in most other linear compounds, we propose that this calibration can be applied to analogous calculations for a wide variety of organic molecules with linear carbon skeletons for temperatures below 100 °C. In a companion paper ( Wang et al., 2009) we use this new calibration dataset to calculate the temperature-dependent equilibrium isotopic fractionation factors for a range of linear hydrocarbons, alcohols, ethers, ketones, esters and acids.

  16. Study of interatomic potentials in ZnS -- Crystal-GRID experiments versus ab initio calculations

    SciTech Connect

    Koch, T.; Heinig, K.H.; Jentschel, M.; Boerner, H.G.

    2000-02-01

    Crystal-GRID measurements have been performed with ZnS single crystals. For the first time, an asymmetric Crystal-GRID line shape could be observed. The preliminary data evaluation indicates that the reported lifetime of the 3221 keV level in {sup 33}S is too short. A value of about 60 fs has been found. Due to this long lifetime the line shape is much less structured than calculated with the reported lifetime.

  17. Chemisorption of a Molecular Oxygen On the UN(0 0 1) Surface: Ab Initio Calculations

    SciTech Connect

    Zhukovskii, Yuri F.; Bocharov, Dmitry; Kotomin, Eugene Alexej

    2009-09-15

    The results of DFT GGA calculations on oxygen molecules adsorbed upon the (0 0 1) surface of uranium mononitride (UN) are presented and discussed. We demonstrate that O2 molecules oriented parallel to the substrate can dissociate either (i) spontaneously when the molecular center lies above the surface hollow site or atop N ion, (ii) with the activation barrier when a molecule sits atop the surface U ion. This explains fast UN oxidation in air.

  18. Ab-initio Calculations of Electronic Properties of Calcium Fluoride (CaF2)

    NASA Astrophysics Data System (ADS)

    Bohara, Bir; Franklin, Lashounda; Malozovsky, Yuriy; Bagayoko, Diola

    We have performed first principle, local density approximation (LDA) calculations of electronic and related properties of cubic calcium fluorite (CaF2) . Our non-relativistic computations employed the Ceperley and Alder LDA potential and the linear combination of atomic orbitals (LCAO) formalism. The implementation of the LCAO formalism followed the Bagayoko, Zhao, and Williams (BZW) method, as enhanced by Ekuma and Franklin (BZW-EF). We discuss the electronic energy bands, including the large band gap, total and partial density of states, electron and hole effective masses, and the bulk modulus. Our calculated, indirect (X- Γ) band gap is 12.98 eV; it is 1 eV above an experimental value of 11.8 eV. The calculated bulk modulus (82.89 GPA) is excellent agreement with the experimental result of 82.0 +/-0.7. Our predicted equilibrium lattice constant is 5.42Å. Acknowledgments: This work is funded in part by the National Science Foundation (NSF) and the Louisiana Board of Regents, through LASiGMA [Award Nos. EPS- 1003897, NSF (2010-15)-RII-SUBR], and NSF HRD-1002541, the US Department of Energy, National, Nuclear Security Administration (NNSA) (Award No. DE-NA-0002630), LaSPACE, and LONI-SUBR.

  19. Quantum mechanical ab initio calculations of the structural, electronic and optical properties of bulk gold nitrides

    NASA Astrophysics Data System (ADS)

    Suleiman, Mohammed S. H.; Joubert, Daniel P.

    2015-11-01

    In the present work, the atomic and the electronic structures of Au3N, AuN and AuN2 are investigated using first-principles density-functional theory (DFT). We studied cohesive energy vs. volume data for a wide range of possible structures of these nitrides. Obtained data were fitted to a Birch-Murnaghan third-order equation of state (EOS) so as to identify the most likely candidates for the true crystal structure in this subset of the infinite parameter space, and to determine their equilibrium structural parameters. The analysis of the electronic properties was achieved by the calculations of the band structure and the total and partial density of states (DOS). Some possible pressure-induced structural phase transitions have been pointed out. Further, we carried out GW0 calculations within the random-phase approximation (RPA) to the dielectric tensor to investigate the optical spectra of the experimentally suggested modification: Au3N(D09). Obtained results are compared with experiment and with some available previous calculations.

  20. Pressure induced structural phase transition and electronic properties of actinide monophospides: Ab-initio calculations

    NASA Astrophysics Data System (ADS)

    Makode, Chandrabhan; Sanyal, Sankar P.

    2011-09-01

    We have investigated the structural and electronic properties of monophospides of thorium, uranium and neptunium. The total energy as a function of volume is obtained by means of the self-consistent tight binding linear muffin-tin-orbital (TB-LMTO) method within the local density approximation (LDA). From the present study with the help of total energy calculations it is found that ThP, UP and NpP are stable in NaCl-type structure at ambient pressure. The structural stability of ThP, UP and NpP changes under the application of pressure. We predict a structural phase transition from NaCl-type (B 1-phase) structure to CsCl-type (B 2-phase) structure for these phospides in the pressure range of 37.0-24.0 GPa (ThP-NpP). We also calculate lattice parameter ( a0), bulk modulus ( B0), band structure and density of states. From energy band diagram it is observed that ThP, UP and NpP exhibit metallic behavior. The calculated equilibrium lattice parameters and bulk modulus are in good agreement with experimental and theoretical work.

  1. Efficient yet accurate approximations for ab initio calculations of alcohol cluster thermochemistry

    NASA Astrophysics Data System (ADS)

    Umer, Muhammad; Kopp, Wassja A.; Leonhard, Kai

    2015-12-01

    We have calculated the binding enthalpies and entropies of gas phase alcohol clusters from ethanol to 1-decanol. In addition to the monomers, we have investigated dimers, tetramers, and pentamers. Geometries have been obtained at the B3LYP/TZVP level and single point energy calculations have been performed with the Resolution of the Identity-MP2 (RIMP2) method and basis set limit extrapolation using aug-cc-pVTZ and aug-cc-pVQZ basis sets. Thermochemistry is calculated with decoupled hindered rotor treatment for large amplitude motions. The results show three points: First, it is more accurate to transfer the rigid-rotor harmonic oscillator entropies from propanol to longer alcohols than to compute them with an ultra-fine grid and tight geometry convergence criteria. Second, the computational effort can be reduced considerably by using dimerization energies of longer alcohols at density functional theory (B3LYP) level plus a RIMP2 correction obtained from 1-propanol. This approximation yields results almost with the same accuracy as RIMP2 — both methods differ for 1-decanol only 0.4 kJ/mol. Third, the entropy of dimerization including the hindered rotation contribution is converged at 1-propanol with respect to chain length. This allows for a transfer of hindered rotation contributions from smaller alcohols to longer ones which reduces the required computational and man power considerably.

  2. DFT Ab initio Calculation of Vibrational Frequencies in AsSe glass

    NASA Astrophysics Data System (ADS)

    Shrivastava, Keshav; Kassim, Hasan; Nazrul Rosli, Ahmad

    2008-03-01

    By using DFT double zeta wave functions, we calculated the structure, bond length (picometer, pm), frequencies(intensities)[degeneracy] for various clusters of arsenic selenide. Our results are as follows. (i) AsSe(diatomic) bond length 216pm, 244.0(1/cm). (ii) As2Se(linear) bond length 228.5 pm, frequencies 27.6(1.9) and 387.6(4.3). (iii) As2Se(triangular) As-Se 243.4 pm, As-As 223.3 pm, frequencies 237.3(2.4) and 332.4(0.05)(1/cm). (iv) As3Se (triangular) bond length 238.4 pm, frequencies 107.5 and 296(weak)(1/cm). (v) As4Se (square) bond length 250.2 pm, 58.5(0.04), 241.3(5.9)(1/cm). (vi) AsSe3 (triangular), bond length 231.2 pm, 75.9(0.003), 103.5(1.26)[2], 350.9(33.2)[2]. From this study we identify that linear As-Se-As for which the calculated frequency is 27.6(1/cm) is in agreement with the data of Nemanich, Phys. Rev. B 16, 1655(1977), J. C. Phillips et al Phys. Rev B 21, 5724(1980). We have successfully calculated several vibrational frequencies accurately which agree with the Raman data. *V. R. Devi et al J. Non-Cryst. Solids 351, 489(2005);353,111(2007)

  3. Efficient yet accurate approximations for ab initio calculations of alcohol cluster thermochemistry.

    PubMed

    Umer, Muhammad; Kopp, Wassja A; Leonhard, Kai

    2015-12-01

    We have calculated the binding enthalpies and entropies of gas phase alcohol clusters from ethanol to 1-decanol. In addition to the monomers, we have investigated dimers, tetramers, and pentamers. Geometries have been obtained at the B3LYP/TZVP level and single point energy calculations have been performed with the Resolution of the Identity-MP2 (RIMP2) method and basis set limit extrapolation using aug-cc-pVTZ and aug-cc-pVQZ basis sets. Thermochemistry is calculated with decoupled hindered rotor treatment for large amplitude motions. The results show three points: First, it is more accurate to transfer the rigid-rotor harmonic oscillator entropies from propanol to longer alcohols than to compute them with an ultra-fine grid and tight geometry convergence criteria. Second, the computational effort can be reduced considerably by using dimerization energies of longer alcohols at density functional theory (B3LYP) level plus a RIMP2 correction obtained from 1-propanol. This approximation yields results almost with the same accuracy as RIMP2 - both methods differ for 1-decanol only 0.4 kJ/mol. Third, the entropy of dimerization including the hindered rotation contribution is converged at 1-propanol with respect to chain length. This allows for a transfer of hindered rotation contributions from smaller alcohols to longer ones which reduces the required computational and man power considerably. PMID:26646881

  4. Methods and Strategies for the Ab Initio Design of Novel Manganese Oxide- Based Water Splitting Photocatalyst Materials

    NASA Astrophysics Data System (ADS)

    Kanan, Dalal K.

    Photoelectrochemical cells (PECs) use sunlight to drive endoergic reactions such as carbon dioxide reduction to fuels or water-splitting for renewable hydrogen production. However, materials that combine both the efficiency and low cost needed to make solar-powered catalysis a practical reality have yet to be discovered. This thesis presents methods and new design strategies for developing novel, efficient, robust, and inexpensive photocatalysts based on transition metal oxides (TMOs). Quantum mechanics methodologies are developed and tested for their ability to predict the properties of known materials and then used to predict how altering the composition by alloying and doping with abundant elements affects optical, electronic, transport, and catalytic properties. The first material considered for photocatalysis is MnO, the bio-inspired solid state analogue of the photosystem II active site. GW theory with input from hybrid DFT and ab initio DFT+U capably predicts the photoemission/inverse photoemission (PE/IPE) band gap and dielectric properties. An ab initio value of U-J = 3.5 eV for Mn2+ was determined using unrestricted Hartree-Fock theory on cluster-size-converged electrostatically embedded clusters. The lowest-lying excitations in MnO, studied using ECW theory, are found to be single Mn d → d ligand field excitations (~2.5 eV, ~108 s lifetime), followed by double d → d excitations (~5.2 eV, ~106 s lifetime), Mn 3d-4s excitations (~6.3 eV, ~10-3 s lifetime), and higher-lying O 2p → Mn 3d ligand-to-metal charge-transfer (LMCT) excitations (~10.1 eV, ~10-4 s lifetime). The longer-lived transitions should exhibit better electron-hole pair separation and enhance photoconductivity depending on ease of carrier transport. While MnO possesses suitable band edge energies, its band gap is too large for efficient sunlight absorption. We predict alloying MnO with ZnO in varying amounts reduces the PE/IPE band gap (to 2.6 eV for the 1:1 alloy) while preserving

  5. Intrinsic Defect Properties in GaN Calculated By Ab Initio and Empirical Potential Methods

    SciTech Connect

    Gao, Fei; Bylaska, Eric J.; Weber, William J.

    2004-12-13

    Density functional theory (DFT) has been used to investigate the formation, properties, and atomic configurations of vacancies, antisite defects and interstitials in GaN, and the DFT results are compared with those calculated by molecular dynamics (MD) simulations using two representative potentials. The DFT calculations reveal that the relaxation of vacancies is generally small, but the relaxation around antisite defects is large, especially for the Ga antisite that is not stable and converts to a N+-N<0001> split interstitial plus a Ga vacancy at the original site. The N interstitials, starting from all possible sites, eventually relax into a N+-N<11-20> split interstitial. In the case of Ga interstitials, the most stable configuration is a Ga octahedral interstitial, but the energy difference among all the interstitials is small. The Ga+-Ga<11-20> split interstitial can bridge the gap between non-bonded Ga atoms, thereby leading to a chain of four Ga atoms along the <11-20> direction in GaN. The formation energies of vacancies and antisite defects obtained using the Stillinger-Weber potential (SW) are in reasonable agreement with those obtained by DFT calculations, whereas the Tersoff-Brenner (TB) potential better describes the behavior of N interstitials. In the case of Ga interstitials, the most stable configuration predicted by the TB-model is a Ga+-N<11-20> split interstitial; while for the SW-model the Ga tetrahedral configuration is more stable, which is in contrast to DFT results.

  6. Ab initio calculation of the electronic and optical properties of solid pentacene

    SciTech Connect

    Tiago, Murilo L.; Northrup, John E.; Louie, Steve G.

    2002-11-01

    The optical and electronic properties of crystalline pentacene are studied, using a first-principles Green's-function approach. The quasiparticle energies are calculated within the GW approximation and the electron-hole excitations are computed by solving the Bethe-Salpeter equation. We investigate the role of polymorphism on the electronic energy gap and linear optical spectrum by studying two different crystalline phases: the solution-phase structure and the vapor-phase structure. charge-transfer excitons are found to dominate the optical spectrum. Excitons with sizable binding energies are predicted for both phases.

  7. Ab initio calculation of relative permittivity of La-doped HfO2

    NASA Astrophysics Data System (ADS)

    Ong, T. M.; Xu, S.

    2014-12-01

    First principles calculations of HfO2 and La-doped HfO2 structures were carried out to investigate the effect of La doping on the relative permittivity of HfO2 films. In this study 6.25% of La was incorporated into HfO2. Upon examination, we found out that La addition increased the value of the relative permittivity from 19 to 26 and this was because the La-induced distortion increased the range of frequencies that contribute to the IR-active modes.

  8. Ab initio calculations of one-electron-scattering properties of ethyne (acetylene) and ethylene molecules

    SciTech Connect

    Tripathi, A.N.; Smith, V.H. Jr. K7L3N6); Kaijser, P.; Siemens, A.G. ); Diercksen, G.H.F. )

    1990-03-01

    Isotropic scattering functions and Compton profiles together with their directional components for several directions relevant to the molecular structure of C{sub 2}H{sub 2} and C{sub 2}H{sub 4} have been evaluated for {ital ab} {ital initio} self-consistent field and configuration-interaction wave functions. The internally folded density (reciprocal form factor) {ital B}({ital r}) is calculated and discussed as are various momentum expectation values. Comparison is made with available experimental and other theoretical results.

  9. Pressure dependence of the isomer shifts in Gd2Fe17: An ab initio calculation

    NASA Astrophysics Data System (ADS)

    Komelj, M.; Grotheer, O.; Fähnle, M.

    1999-05-01

    The geometrical and chemical effects of interstitial doping on the average isomer shifts in the systems Gd2Fe17C3 and Gd2Fe17N3 are studied within the framework of the local density approximation using the linear-muffin-tin-orbital method in the atomic-sphere approximation. The sensitivity of the results on the details of the calculation is discussed. It is shown that it is not possible to extract reliable information on the geometrical effect of volume expansion upon interstitial doping of such system on the average isomer shifts by experiments on non-doped samples under compression.

  10. Statistical error propagation in ab initio no-core full configuration calculations of light nuclei

    NASA Astrophysics Data System (ADS)

    Navarro Pérez, R.; Amaro, J. E.; Ruiz Arriola, E.; Maris, P.; Vary, J. P.

    2015-12-01

    We propagate the statistical uncertainty of experimental N N scattering data into the binding energy of 3H and 4He. We also study the sensitivity of the magnetic moment and proton radius of the 3H to changes in the N N interaction. The calculations are made with the no-core full configuration method in a sufficiently large harmonic oscillator basis. For those light nuclei we obtain Δ Estat(3H) =0.015 MeV and Δ Estat(4He) =0.055 MeV .

  11. Multiple time step integrators in ab initio molecular dynamics

    SciTech Connect

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

    2014-02-28

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

  12. Ab initio calculation of the $$np \\to d ³$$ radiative capture process

    DOE PAGESBeta

    Beane, Silas R.; Chang, Emmanuel; Detmold, William; Orginos, Kostas; Parreño, Assumpta; Savage, Martin J.; Tiburzi, Brian C.

    2015-09-24

    In this study, lattice QCD calculations of two-nucleon systems are used to isolate the short-distance two-body electromagnetic contributions to the radiative capture processmore » $$np \\to d\\gamma$$, and the photo-disintegration processes $$\\gamma^{(\\ast)} d \\to np$$. In nuclear potential models, such contributions are described by phenomenological meson-exchange currents, while in the present work, they are determined directly from the quark and gluon interactions of QCD. Calculations of neutron-proton energy levels in multiple background magnetic fields are performed at two values of the quark masses, corresponding to pion masses of $$m_\\pi \\sim 450$$ and 806 MeV, and are combined with pionless nuclear effective field theory to determine these low-energy inelastic processes. Extrapolating to the physical pion mass, a cross section of $$\\sigma^{lqcd}(np\\to d\\gamma)=332.4({\\tiny \\begin{array}{l}+5.4 \\\\ - 4.7\\end{array}})\\ mb$$ is obtained at an incident neutron speed of $$v=2,200\\ m/s$$, consistent with the experimental value of $$\\sigma^{expt}(np \\to d\\gamma) = 334.2(0.5)\\ mb$$.« less

  13. Ab initio calculation of the $np \\to d ³$ radiative capture process

    SciTech Connect

    Beane, Silas R.; Chang, Emmanuel; Detmold, William; Orginos, Kostas; Parreño, Assumpta; Savage, Martin J.; Tiburzi, Brian C.

    2015-09-24

    In this study, lattice QCD calculations of two-nucleon systems are used to isolate the short-distance two-body electromagnetic contributions to the radiative capture process $np \\to d\\gamma$, and the photo-disintegration processes $\\gamma^{(\\ast)} d \\to np$. In nuclear potential models, such contributions are described by phenomenological meson-exchange currents, while in the present work, they are determined directly from the quark and gluon interactions of QCD. Calculations of neutron-proton energy levels in multiple background magnetic fields are performed at two values of the quark masses, corresponding to pion masses of $m_\\pi \\sim 450$ and 806 MeV, and are combined with pionless nuclear effective field theory to determine these low-energy inelastic processes. Extrapolating to the physical pion mass, a cross section of $\\sigma^{lqcd}(np\\to d\\gamma)=332.4({\\tiny \\begin{array}{l}+5.4 \\\\ - 4.7\\end{array}})\\ mb$ is obtained at an incident neutron speed of $v=2,200\\ m/s$, consistent with the experimental value of $\\sigma^{expt}(np \\to d\\gamma) = 334.2(0.5)\\ mb$.

  14. Traveling Wave Ion Mobility Mass Spectrometry and Ab Initio Calculations of Phosphoric Acid Clusters

    NASA Astrophysics Data System (ADS)

    Lavanant, Hélène; Tognetti, Vincent; Afonso, Carlos

    2014-04-01

    Positive and negative ion electrospray mass spectra obtained from 50 mM phosphoric acid solutions presented a large number of phosphoric acid clusters: [(H3PO4)n + zH] z+ or [(H3PO4)n - zH] z- , with n up to 200 and z up to 4 for positively charged clusters, and n up to 270 and z up to 7 for negatively charged cluster ions. Ion mobility experiments allowed very explicit separation of the different charge states. Because of the increased pressures involved in ion mobility experiments, dissociation to smaller clusters was observed both in the trap and transfer areas. Voltages along the ion path could be optimized so as to minimize this effect, which can be directly associated with the cleavage of hydrogen bonds. Having excluded the ion mobility times that resulted from dissociated ions, each cluster ion appeared at a single drift time. These drift times showed a linear progression with the number of phosphoric atoms for cluster ions of the same charge state. Cross section calculations were carried out with MOBCAL on DFT optimized geometries with different hydrogen locations and with three types of atomic charges. DFT geometry optimizations yielded roughly spherical structures. Our results for nitrogen gas interaction cross sections showed that values were dependent on the atomic charges definition used in the MOBCAL calculation. This pinpointed the necessity to define a clear theoretical framework before any comparative interpretations can be attempted with uncharacterized compounds.

  15. Ab initio calculations of dissociative attachment and dissociative recombination of electrons and polyatomic species

    NASA Astrophysics Data System (ADS)

    Haxton, Daniel

    2009-05-01

    Interactions of free electrons with neutral and positively charged molecular species play a role in various physical systems. In interstellar space, reactions such as dissociative recombination determine the balance of various charged and neutral species. In a laboratory equipped with an apparatus like a COLTRIMS device, the dissociative attachment process can be used as a microscope to study polyatomic molecular dynamics. We discuss the theoretical and numerical methods used to calculate dissociative attachment and dissociative recombination of electrons with larger molecules from first principles. Studies using these methods are complimentary to other methods that yield more approximate reaction rates at greatly lesser numerical cost; they may yield precise information about the dissociation dynamics, product distribution, and differential cross section that approximate methods cannot. We discuss calculations performed to date on the target species H2O, NO2, and LiH2^+. We discuss the scaling of our numerical methods with the number of atoms, and the prospects of applying them to tetra-atomics.

  16. Ab initio Calculation of the np→dγ Radiative Capture Process.

    PubMed

    Beane, Silas R; Chang, Emmanuel; Detmold, William; Orginos, Kostas; Parreño, Assumpta; Savage, Martin J; Tiburzi, Brian C

    2015-09-25

    Lattice QCD calculations of two-nucleon systems are used to isolate the short-distance two-body electromagnetic contributions to the radiative capture process np→dγ, and the photo-disintegration processes γ^{(*)}d→np. In nuclear potential models, such contributions are described by phenomenological meson-exchange currents, while in the present work, they are determined directly from the quark and gluon interactions of QCD. Calculations of neutron-proton energy levels in multiple background magnetic fields are performed at two values of the quark masses, corresponding to pion masses of m_{π}~450 and 806 MeV, and are combined with pionless nuclear effective field theory to determine the amplitudes for these low-energy inelastic processes. At m_{π}~806 MeV, using only lattice QCD inputs, a cross section σ^{806 MeV}~17 mb is found at an incident neutron speed of v=2,200 m/s. Extrapolating the short-distance contribution to the physical pion mass and combining the result with phenomenological scattering information and one-body couplings, a cross section of σ^{lqcd}(np→dγ)=334.9(+5.2-5.4) mb is obtained at the same incident neutron speed, consistent with the experimental value of σ^{expt}(np→dγ)=334.2(0.5) mb. PMID:26451545

  17. Prediction of vibrational frequencies of possible intermediates and side products of the methanol synthesis on ZnO(0001) by ab initio calculations.

    PubMed

    Kossmann, Jörg; Rossmüller, Guido; Hättig, Christof

    2012-01-21

    We used ab initio density functional theory in combination with an embedded cluster approach to calculate vibrational spectra and formation enthalpies of possible intermediates and side products (spectator species) in the synthesis of methanol out of syngas on the ZnO(0001) surface. Our investigations are based upon our previous work on possible reaction pathways and activation barriers for this reaction at oxygen vacancies on ZnO(0001). We present and discuss calculated vibrational frequencies of short-living formyl, hydroxymethylene, formaldehyde, acetale, and hydroxymethyl intermediates and compare the calculated frequencies of formate and methoxy species as well as CO and CO(2) species, at the defect free surface and at oxygen vacancies, with recent experimental findings. All investigated species show characteristic features in their spectra. Therefore, the analysis of their vibrational frequencies is a suitable mean to distinguish them and gain new insights in this reaction which is of recent experimental interest. We are able to identify the structure and characteristics of different surface species, such as monodentate and polydentate carbonate and formate species, in agreement with experimental results. PMID:22280776

  18. Ab initio calculation of hyperfine and superhyperfine interactions for shallow donors in semiconductors.

    PubMed

    Overhof, Harald; Gerstmann, Uwe

    2004-02-27

    For the shallow group V donors in Si we show that the hyperfine interaction for the donor nucleus and the superhyperfine interactions for the first five shells of Si ligands can be quite accurately calculated using the local spin-density approximation of the density-functional theory. We treat the impurity problem in a Green's function approach. Since we have to truncate the long-ranged part of the defect potential, we do not obtain a localized gap state. Instead we identify the resonance above the conduction band with the paramagnetic defect state. We show that the hf and shf interactions thus obtained are at least as accurate as those obtained from one-electron theories with fitting parameters. Application of this first principles method to other shallow donors could be an essential help in defect identification. PMID:14995814

  19. Ab-initio calculation of n-doped single-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Margine, Elena R.; Crespi, Vincent H.

    2004-03-01

    We study charge-induced changes in shape and electronic structure for n-doped single-walled carbon nanotubes within density functional theory. A certain nearly free electron state is downshifted in the presence of extra electrons. A similar effect has been seen in potassium-doped carbon nanotubes [1], where the downshift was attributed to the hybridization of the nearly free electron state with the K 4s state. In the present calculation the negative charge is neutralized by a uniform positive background, so the downshift must arise from a different effect. The state crosses the Fermi level at a charge per carbon atom of 0.04 for all the tubes studied. Connections are made to recent experiments in the group of P. Eklund.[1]Yoshiyuki Miyamoto, Angel Rubio, X. Blase, Marvin L. Cohen, and Steven G. Louie PRL 74, 2993 (1995)

  20. Ab initio calculations on the compensation mechanisms in InP

    NASA Astrophysics Data System (ADS)

    Schmidt, T. M.; Miwa, R. H.; Fazzio, A.; Mota, R.

    2001-01-01

    Compensation mechanisms which become semi-insulating InP from intrinsic n-type materials are investigated by first principles total energy calculations. Associated to the possible mechanisms two intrinsic defects are shown to play an important role in the transition, induced by annealing, from the n-type to the semi-insulating character. The single defect V In3- results from the In-vacancy-H-complex, which, before the annealing, was identified by infra-red spectra as responsible for the n-type conductivity, and the P In+V P complex defect comes from the diffusion of the neutral In vacancy. Both defects are shown to present localized levels inside the band gap which compensate for the free electron.

  1. Determining the phase diagram of lithium via ab initio calculation and ramp compression

    NASA Astrophysics Data System (ADS)

    Shulenburger, Luke; Seagle, Chris; Haill, Thomas; Harding, Eric

    2015-06-01

    Diamond anvil cell experiments have shown elemental lithium to have an extraordinarily complex phase diagram under pressure exhibiting numerous solid phases at pressures below 1 Mbar, as well as a complicated melting behavior. We explore this phase diagram utilizing a combination of quantum mechanical calculations and ramp compression experiments performed on Sandia National Laboratories' Z-machine. We aim to extend our knowledge of the high pressure behavior to moderate temperatures at pressures above 50 GPa with a specific focus on the melt line above 70 GPa. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Company, for the US Dept of Energy's Natl. Nuclear Security Administration under Contract DE-AC04-94AL85000.

  2. Millimetre-wave spectroscopy and ab initio calculations for fluorophosphaethyne (FCP)

    NASA Astrophysics Data System (ADS)

    Bizzocchi, L.; Degli Esposti, C.; Puzzarini, C.

    The semistable FCP molecule has been produced in the gas phase by a high temperature reaction between phosphine and trichlorofluoromethane. Its rotational spectrum has been observed in the millimetre- and submillimetre-wave regions, from 80 to 650 GHz, for the ground and various vibrationally excited states of F12CP, and for the ground state of F13CP. All the excited states that lie below 1200 cm-1, which are 1000, 0110, 0200, 0220, 0310, 0330, and 1110, have been investigated for the most abundant isotopologue. The analysis of the spectra has been performed taking simultaneously into account the strong Fermi resonance that couples the states v1, v2, v3 with v1 - 1, v2 + 2, v3, and l-type resonances between different sublevels of a given bending state, in order to obtain directly deperturbed rotational parameters. CCSD(T) calculations with a series of correlation consistent basis sets have been also performed, which provided a reliable estimate of the quartic force field of fluorophosphaethyne. Effects due to truncation of the basis and to core correlation have been accounted for. The theoretical force field has been partly refined by a least-squares fit to the available vibrational and rotational experimental data. A mixed experimental-theoretical equilibrium structure has been finally calculated combining experimental ground-state rotational constants of F12CP and F13CP with computed zero-point contributions. The best estimate of the equilibrium structure of fluorophosphaethyne can be established as re (F-C) = 1.2759 ± 0.0004 Å and re (C-P) = 1.5445 ± 0.0002 Å.

  3. Hydrogen spillover mechanism on covalent organic frameworks as investigated by ab initio density functional calculation.

    PubMed

    Guo, Jing-hua; Zhang, Hong; Tang, Yongjian; Cheng, Xinlu

    2013-02-28

    The hydrogen spillover mechanism, including the H chemisorption, diffusion, and H(2) associative desorption on the surface of COFs and H atoms migration from metal catalyst to COFs, have been studied via density functional theory (DFT) calculation. The results described herein show that each sp(2) C atom on COFs' surface can adsorb one H atom with the bond length d(C-H) between 1.11 and 1.14 Å, and the up-down arrangement of the adsorbed H atoms is the most stable configuration. By counting the chemisorption binding sites for these COFs, we can predict the saturation storage densities. High hydrogen storage densities show that the gravimetric uptakes of COFs are in the range of 5.13-6.06 wt%. The CI-NEB calculations reveal that one H atom diffusing along the C-C path on HHTP surface should overcome the 1.41-2.16 eV energy barrier. We chose tetrahedral Pt(4) cluster and HHTP as the representative catalyst and substrate, respectively, to study the H migration from metal cluster to COFs. At most, two H atoms can migrate from Pt(4) cluster to HHTP substrate. The migration reaction is an endothermic process, undergoing an activation barrier of 1.87 eV and 0.57 eV for the first and second H migration process, respectively. Three types of H(2) associative desorption from hydrogenated COFs were studied: (I) the two H adatoms recombining to one H(2) molecule with a recombination barrier of 4.28 eV, (II) the abstraction of adsorbed H atoms by gas-phase hydrogen atoms through ER type recombination reactions with a recombination barrier of 1.05 eV, (III) the H(2) desorption through the reverse spillover mechanism with an energy barrier of 2.90 eV. PMID:23338125

  4. Accurate ab initio calculations which demonstrate a 3 Pi u ground state for Al2

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Partridge, Harry; Langhoff, Stephen R.; Taylor, Peter R.; Walch, Stephen P.

    1986-01-01

    The spectroscopic parameters and separations between the three low-lying X 3 Pi u, A 3 Sigma g -, and a 1 Sigma g + states of Al2 are studied as a function of both the one-particle and n-particle basis set. Approximate correlation treatments are calibrated against full Cl calculations correlating the six valence electrons in a double-zeta plus two d-function basis set. Since the CASSCF/MRCI 3 Pi u to 3 Sigma g - separation is in excellent agreement wtih the FCI value, the MRCI calculations were carried out in an extended (20s13p6d4f)/(6s5p3d2f) gaussian basis. Including a small correction for relativistic effects, the best estimate is that 3 Sigma g - state lies 174/cm above the 3 Pi u ground state. The 1 Sigma g + state lies at least 2000/cm higher in energy. At the CPF level, inclusion of 2s and 2p correlation has little effect on D sub e, reduces T sub e by only 26/cm, and shortens the bond lengths by about 0.02 a sub o. Further strong support for a 3 Pi u ground state comes from the experimental absorption spectra, since both observed transitions can be convincingly assigned as 3 Pi u yields 3 Pi g. The (2) 3 Pi g state is observed to be sensitive to the level of correlation treatment, and to have its minimum shifted to shorter rho values, such that the strongest experimental absorption peak probably corresponds to the 0 yields 2 transition.

  5. Ab initio calculations on elastic properties in L12 structure Al3X and X3Al-type (X=transition or main group metal) intermetallic compounds

    NASA Astrophysics Data System (ADS)

    Tian, T.; Wang, X. F.; Li, W.

    2013-03-01

    As high-temperature structural materials, L12 intermetallic compounds have attracted the strong interest from both fundamental and industrial aspects. Understanding of elastic property is a basis for the complete investigations of mechanical behavior of L12 alloys. In an effort to explore the electronic origin of elastic properties of L12 intermetallics, we have performed a systematic study on elastic constants for single crystals, and Young's modulus, shear modulus, bulk modulus and Poisson's ratio for poly-crystals of 22 known Al3X and X3Al-type (X=transition or main group metal) intermetallics using the ab initio calculations. Based on the calculations of elastic constants and extreme (both positive and negative) Poisson's ratios, we found a pronounced correlation between the extreme Poisson's ratio and the elastic anisotropy, i.e., approximate 40% of the investigated L12 intermetallics exhibit intrinsic auxetic behavior. Furthermore, based on the distribution of bonding charge densities, we revealed that the ductility and extreme Poisson's ratios were attributable to the directionality of bonds of these alloys. Our findings provide a new method to predict mechanical behavior of intermetallics.

  6. Ab Initio Calculations of Structural, Electronic, and Mechanical Stability Properties of Magnesium Sulfide

    NASA Astrophysics Data System (ADS)

    Wu, Hai-Ying; Chen, Ya-Hong; Zhou, Ping; Han, Xiang-Yu; Liu, Zi-Jiang

    2014-09-01

    The structural, electronic, and mechanical stability properties of magnesium sulfide in different phases are presented using the plane wave pseudopotential method within the generalized gradient approximation. Eight different phases such as rocksalt (B1), zincblende (B3), wurtzite (B4), nickel arsenide (B8), cesium chloride (B2), PH4I-type (B11), FeSi-type (B28), and MnP-type (B31) are considered in great detail. The calculated ground-state properties of these phases are consistent with available experimental and theoretical data. It is found that MgS in the B1 and B8 phases are indirect band gap materials, the B3, B4, B11, B28, and B31 phases are all direct gap materials, while the B2 phase displays the metallic character. The B1, B3, B4, B8, B28, and B31 phases are mechanically stable at ambient conditions, but the B2 and B11 phases are mechanically unstable under zero pressure and zero temperature

  7. Ab initio calculations on the defect structure of β-Ga2O3

    NASA Astrophysics Data System (ADS)

    Zacherle, T.; Schmidt, P. C.; Martin, M.

    2013-06-01

    The intrinsic point defects of β-Ga2O3 are investigated using density functional theory. We have chosen two different exchange-correlation potentials: the generalized gradient approximation (GGA) and a hybrid potential (HSE06). Defect formation energies were determined taking into account finite-size effects. Schottky, anti-Frenkel, and Frenkel energies have been extracted for T=0 K. We calculate formation entropies for an oxygen and a gallium vacancy and determine the Gibbs energy of Schottky disorder. Furthermore, we investigate the defect concentrations as a function of the oxygen partial pressure. The obtained purely intrinsic defect concentrations for charged defects are very small and result in a pO2 dependence of the electron concentration of [e']˜ pO2-1/6, whereas experimentally [e']˜ pO2-1/4 is found. So we assume that, experimentally, a small unintentional donor doping is unavoidable. A small extrinsic donor concentration [D·] = 1018 cm-3 (10 ppm) changes the electron concentration to [e']˜ pO2-1/4 and gives an activation energy of the conductivity σ of 1.7 eV in good agreement to experimental values. So we propose as majority disorder 3[VGa'''] = [D·] with electrons being minority defects.

  8. Long-range dispersion forces between molecules subject to attosecond pulses from ab initio calculations

    NASA Astrophysics Data System (ADS)

    Oliveira, Micael; Komarova-Vladimirova, Ksenia; Remacle, Francoise; Vertraete, Matthieu

    The London-van der Waals dispersion forces arising from instantaneously induced dipoles in molecules are a key ingredient in a wide range of phenomena in physics, chemistry, and biology. Therefore, the ability to control and manipulate dispersion forces between atoms and molecules is of great importance. Because those dispersion interactions depend crucially on the electronic properties of the molecular systems, a simple route to achieve this would consist in manipulating their electronic states. The recent development of ultra-short optical pulses has given researchers unprecedented control over the electronic degrees of freedom. These pulses, tailored in their frequency and envelope, allow the generation of a strongly out of equilibrium population of electronic states. In this talk we show how the Hamacker constants characterizing the London-van der Waals interaction between two molecules subject to an optical pulse can be calculated using time-dependent density functional theory (TD-DFT) or standard quantum chemistry methods and present several test cases of molecules subjected to IR and UV attosecond pulses.

  9. Microsolvation of sodium acetate in water: Anion photoelectron spectroscopy and ab initio calculations

    SciTech Connect

    Zhang, Wen-Jing; Hou, Gao-Lei; Wang, Peng; Xu, Hong-Guang; Feng, Gang; Xu, Xi-Ling; Zheng, Wei-Jun

    2015-08-07

    To understand the microsolvation of sodium acetate (CH{sub 3}COONa, NaOAc) in water, we studied NaOAc(H{sub 2}O){sub n}{sup −} (n = 0–3) clusters by photoelectron spectroscopy. We also investigated the structures of NaOAc(H{sub 2}O){sub n}{sup −} (n = 0–5) anions and NaOAc(H{sub 2}O){sub n} (n = 0–7) neutrals by quantum chemistry calculations. By comparing the theoretical results with the photoelectron experiment, the most probable structures of NaOAc(H{sub 2}O){sub n}{sup −/0} (n = 0–3) were determined. The study also shows that, with increasing n, the solvent-separated ion pair (SSIP) structures of NaOAc(H{sub 2}O){sub n}{sup −} anions become nearly energetically degenerate with the contact ion pair (CIP) structures at n = 5, while the SSIP structures of the neutral NaOAc(H{sub 2}O){sub n} clusters appear at n = 6 and become dominant at n = 7.

  10. Comparative Study of Defect Properties in GaN: Ab initio and Empirical Potential Calculations

    SciTech Connect

    Gao, Fei; Bylaska, Eric J.; El-Azab, Anter; Weber, William J.; LM Wang, R Fromknecht, LL Snead, DF Downey and H Takahashi

    2004-04-05

    Density functional theory (DFT) is used to study the formation, properties and atomic configurations of monovacancies, antisite defects and possible interstitials in GaN. The relaxation around a vacancy is generally small, but the relaxation around antisite defects is large, particularly for a Ga antisite defect, which is not stable and converts to an N-N<0001> split interstitial. All N interstitials, starting from any possible sites, eventually transfer into the N-N split interstitials, forming N molecules. In the case of Ga interstitials, the most favorable configuration is the Ga octahedral interstitial. However, it is found that the Ga-Ga<> split interstitial can bridge the gap between non-bonded Ga atoms along the <11-2> direction, which leads to the formation of Ga atomic wires in GaN, with bond distance close to those noted in bulk Ga. In addition, two representative potentials, namely Stillinger-Weber and Tersoff-Brenner potentials, have been employed to deter mine the formation of defects using molecular dynamics (MD) method in GaN. The MD results are discussed and compared to DFT calculations. The present DFT and MD results provide guidelines for evaluating the quality and fit of empirical potentials for large-scale simulations of ion-solid interaction and thermal annealing of defects in GaN.

  11. Stacking fault energetics of α - and γ -cerium investigated with ab initio calculations

    NASA Astrophysics Data System (ADS)

    Östlin, A.; Di Marco, I.; Locht, I. L. M.; Lashley, J. C.; Vitos, L.

    2016-03-01

    At ambient pressure the element cerium shows a metastable (t1 /2˜40 years) double-hexagonal close-packed β phase that is positioned between two cubic phases, γ and α . With modest pressure the β phase can be suppressed, and a volume contraction (17%) occurs between the γ and the α phases as the temperature is varied. This phenomenon has been linked to subtle alterations in the 4 f band. In order to rationalize the presence of the metastable β phase, and its position in the phase diagram, we have computed the stacking fault formation energies of the cubic phases of cerium using an axial interaction model. This model links the total energy differences between hexagonal closed-packed stacking sequences and stacking fault energetics. Total energies are calculated by density functional theory and by dynamical mean-field theory merged with density functional theory. It is found that there is a large difference in the stacking fault energies between the α and the γ phase. The β -phase energy is nearly degenerate with the γ phase, consistent with previous third-law calorimetry results, and dislocation dynamics explain the pressure and temperature hysteretic effects.

  12. Ab-Initio Calculations of the Electronic Properties of Boron Nitride

    NASA Astrophysics Data System (ADS)

    Stewart, Anthony; Khamala, Bethuel; Hart, Daniel; Bagayoko, Diola

    2014-03-01

    The potential of Boron Nitride (BN) in nanotechnology is tremendous. BN in its bulk form has a wide band gap with excellent thermal and chemical stability. BN structures can be tailored using various techniques in order to obtain desired materials properties. The State-of-the-art Proton Exchange Membrane Fuel Cell (PEMFCs) technology exploits graphitized carbon as a support for platinum-type catalysts. However, some forms of carbon are susceptible to long-term durability issues such as corrosion which is a detriment to fuel cell performance and viability. Novel non-carbon supports such as BN may provide a pathway for addressing the durability and performance issues associated with carbon support materials. We present preliminary theoretical studies, using an linear combination of atomic orbital (LCAO) quantum chemistry package from Ames Laboratory, of the electronic properties of this potentially important material. Our calculated band gap of 6.48 eV for the cubic structure, obtained with an LDA potential and the BZW-EF method, is in agreement with experiment. LASIGMA/ NNSA_MSIP.

  13. Properties of Silicate Melts at High Pressure and Temperature from Ab Initio Calculations

    NASA Astrophysics Data System (ADS)

    Seclaman, A. C.; Caracas, R.

    2014-12-01

    The evolution of planetary interiors is intrinsically connected to the behavior and properties of silicate melts at high pressures and temperatures. Our work comes as a complement to existing data expanding the pressure, temperature, and compositional ranges. We used the V.A.S.P. code to perform NVT Molecular Dynamics simulations on two basic compositions: Mg2SiO4 and MgSiO3. All calculations are done within augmented planar wave formalism of the Density Functional Theory. Supercells of 160 atoms clino-enstatite and 112 atoms forsterite were melted at 5000K and then cooled and thermalized, using the Nose-Hoover thermostat, at temperatures more representative of Earth's interior (3000 and 4000K). The pressure range of our investigations spans from 0 to approximately 160GPa. Since important properties, density and magnetism, are dependent on the presence of iron we also created (Fex-1,Mgx)SiO3 and (Fex-1,Mgx)2SiO4melts from the thermalized pure compositions by replacing the desired amount of magnesium atoms with iron. Because other transitional elements present similar behavior as iron, and nickel is an important element in the core, compositions containing different amounts of nickel were also created by adding extra Ni atoms in the system. We analyze in detail the behavior with pressure of the density, clustering and coordination, total magnetization, and thermodynamical parameters of the melts. Our results indicate that changes in the structure and magnetic moment of the Forsterite melt begin at relatively low pressure. As an application of our data to the Earth's present deep interior we analyzed in great detail various possible mixtures of Fe bearing melt and solid mantle in an attempt to fit the density estimated for the Ultra Low Velocity Zones.

  14. Ab-initio calculation of C and CO adsorption on the Co (110) surface

    NASA Astrophysics Data System (ADS)

    Chin, Shin-Liang; Ionescu, Adrian; Reeve, Robert M.; Cheng, Jun; Barnes, Crispin H. W.

    2013-02-01

    The adsorption energies, structural, electrical and magnetic properties of adsorption of C and CO on the fcc Co (110) surface have been investigated using density functional theory. The preferential adsorption site for the fcc Co (110) has been calculated. For the case of C adsorption, the preferential adsorption site is the long-bridge for both the 0.5 and 1.0 monolayers (ML) coverages. Whilst for the CO case, the preferential adsorption sites are at the atop and short-bridge site for 0.5 and 1.0 ML coverages respectively. Structurally, the first two layers of the bare Co (110) surface expand whereas the second and third layers contract. Upon adsorption of either C or CO, however, the degree of expansion and compression reduces. Magnetically, the adsorbates were found to couple ferrimagnetically to the surface and suppress the magnetic moment of the Co layers beneath them. The C adsorbate has a much stronger suppression effect as compared to the CO adsorbate. At 0.5 ML coverage, the C adatom suppresses up to 47% of the magnetic moment in the surface layer compared to a clean Co (110), whereas the CO adsorbate only suppresses up to 16%. For the 1.0 ML coverage case, both the C and CO adsorbates suppress almost equivalently well at 68% and 63% respectively. We also report on a correlation between the amount of charge transfer and the degree of suppression of the surface magnetic moment. Finally, we observe that the electronic charge is shared in the [001] direction for the C adsorbate and in the [11¯0] direction for the CO adsorbate. This anisotropy of surface bonding, in conjunction with the ligand field theory, explains the mechanism behind the spin reorientation transition that occurs uniquely on the CO/Co(110) system.

  15. Ab initio calculation of pentacene-PbSe hybrid interface for photovoltaic applications.

    PubMed

    Roy, P; Nguyen, Thao P

    2016-07-21

    We perform density functional theory (DFT) quantum chemical calculations for the pentacene-PbSe hybrid interface at both molecular and crystal levels. At the interface, the parallel orientation of pentacene on the PbSe surface is found to be the most favorable, analogous to a pentacene-gold interface. The molecule-surface distance and the value of charge transfer from one pentacene molecule to the PbSe surface are estimated at around 4.15 Å and 0.12 e(-) respectively. We found that, standard-LDA/GGA-PBE/hybrid/meta-GGA xc-functionals incorrectly determine the band gaps of both pentacene and PbSe and leads to a failed prediction of the energy alignment in this system. So, we use a relativistic G0W0 functional and accurately model the electronic properties of pentacene and PbSe in both bulk material and near the interface. An energy shift of 0.23 eV, due to the difference in work function at the interface was supplemented after a detailed analysis of the electrostatic potential. The highest occupied molecular orbital level of pentacene is 0.01 eV above PbSe while the lowest unoccupied molecular orbital of pentacene lies 1.70 eV above PbSe, allowing both electrons and holes to transfer along the donor-acceptor junction. Our results provide additional insights into the electronic structure properties of the pentacene-PbSe heterojunction and establish it as a promising and efficient candidate for photovoltaic applications. PMID:27332630

  16. Interaction between single vacancies in graphene sheet: An ab initio calculation

    NASA Astrophysics Data System (ADS)

    Scopel, W. L.; Paz, Wendel S.; Freitas, Jair C. C.

    2016-08-01

    In order to investigate the interaction between single vacancies in a graphene sheet, we have used spin-polarized density functional theory (DFT). Two distinct configurations were considered, either with the two vacancies located in the same sublattice or in different sublattices, and the effect of changing the separation between the vacancies was also studied. Our results show that the ground state of the system is indeed magnetic, but the presence of the vacancies in the same sublattice or in different sublattices and the possible topological configurations can lead to different contributions from the π and σ orbitals to magnetism. On the other hand, our findings reveal that the net magnetic moment of the system with the two vacancies in the same sublattice move towards the value of the magnetic moment per isolated vacancy with the increase of the distance between the vacancies, which is ascribed to the different contributions due to π electrons. Moreover, it is also found that the local magnetic moments for vacancies in the same sublattice are in parallel configuration, while they have different orientations when the vacancies are created in different sublattices. So, our findings have clearly evidenced how difficult it would be to observe experimentally the emergence of magnetic order in graphene-based systems containing randomly created atomic vacancies, since the energy difference between cases of antiferromagnetic and ferromagnetic order decreases quickly with the increase in the distance separating each vacancy pair.

  17. Structures and optical absorptions of PbSe clusters from ab initio calculations

    NASA Astrophysics Data System (ADS)

    Zeng, Qun; Shi, Jing; Jiang, Gang; Yang, Mingli; Wang, Fan; Chen, Jun

    2013-09-01

    Based on the low-lying structures of (PbSe)n (n = 1-10) clusters identified with a first-principles molecular dynamics approach, two growth patterns with distinct structure and energy evolutions were predicted for the even-n and odd-n clusters, respectively. Moreover, the clusters favor a simple cubic and bulk-like growth pattern, unlike the extensively studied II-VI clusters whose structural diversity has been well established. The overlap between 6p of Pb and 4p of Se makes not only the ordered and bulk-like structures but also a stable building block of (PbSe)4. The high stability of (PbSe)4 is recognized in terms of its binding energy, HOMO-LUMO gap, appearance in the structures of larger-size clusters, as well as its appearance in the fragmentation products of PbSe clusters. The geometrical and electronic structures of the PbSe clusters were further studied within the density functional theory framework including spin-orbital (SO) coupling. We found that SO coupling does not change the relative stability of the clusters but reduces their binding energy significantly. Particularly, the SO effect has a great impact on the UV-vis spectra of the clusters, which were simulated with time-dependent density functional theory at SO level of zeroth-order regular approximation.

  18. A comparative study of Cr7C3, Fe3C and Fe2B in cast iron both from ab initio calculations and experiments

    NASA Astrophysics Data System (ADS)

    Xiao, B.; Xing, J. D.; Feng, J.; Zhou, C. T.; Li, Y. F.; Su, W.; Xie, X. J.; Cheng, Y. H.

    2009-06-01

    The ground state properties of three compounds, Cr7C3, Fe3C and Fe2B, are investigated using ab initio calculations based on density functional theory. Formation enthalpy values indicate that Cr7C3 is the most stable crystal among the three compounds. Fe3C is metastable which has a positive heat of formation value. The calculated bulk modulus, shear modulus and Young's modulus value of Cr7C3 are 311 GPa, 143.8 GPa and 374 GPa, respectively. The bulk modulus values of Fe2B and Fe3C are 194 GPa and 258 GPa. We also find that both the hardness and the stiffness of the Cr7C3 type carbides can be improved by doping with B, W, Mo, etc. The bulk modulus of transition metal doped Fe2B is considerably higher than pure Fe2B. The electronic structures of Fe2B and Fe3C are ferromagnetic and the evaluated average magnetic moment of Fe is 2.09μB/atom for Fe3C and 2.02μB/atom for Fe2B, respectively. Micro-indentation test results indicate that Cr7C3 is the hardest phase among the three phases and shows excellent wear resistance performance under three-body abrasive experiments. The experimental results are in agreement with the theoretical prediction that Cr7C3 is the best both in stability and mechanical performance.

  19. An ab initioCalculation of the Dipole Moment Surfaces and the Vibrational Transition Moments of the H 2Te Molecule

    NASA Astrophysics Data System (ADS)

    Kozin, Igor N.; Jensen, Per; Li, Yan; Buenker, Robert J.; Hirsch, Gerhard; Klee, Stefan

    1997-01-01

    The present work reports an ab initioMRD-CI calculation of the dipole moment surfaces for the electronic ground state of the H 2Te molecule. Using the ab initioresults, we calculate the vibrational transition moments, and we simulate the far-infrared spectrum of H 2Te by means of the MORBID program system. We obtain the equilibrium value of the dipole moment from the ab initiocalculation as 0.377 Debye based on our initial theoretical treatment which was employed over a wide range of molecular geometries. However, the use of an improved AO basis at the equilibrium geometry of H 2Te lowers this result to 0.298 Debye. The comparison of our simulated far-infrared spectrum with the experimental spectrum suggests that this value is too large, and that the correct value is certainly larger than 0.19 Debye and very probably smaller than 0.26 Debye. From the ab initiodata, we predict many vibrational transition moments for H 2Te, D 2Te, and HDTe. We hope that these results will be of assistance in the interpretation of the rotation-vibration spectrum of these molecules.

  20. Ab initio molecular dynamics calculations on scattering of hyperthermal H atoms from Cu(111) and Au(111)

    SciTech Connect

    Kroes, Geert-Jan Pavanello, Michele; Blanco-Rey, María; Alducin, Maite

    2014-08-07

    Energy loss from the translational motion of an atom or molecule impinging on a metal surface to the surface may determine whether the incident particle can trap on the surface, and whether it has enough energy left to react with another molecule present at the surface. Although this is relevant to heterogeneous catalysis, the relative extent to which energy loss of hot atoms takes place to phonons or electron-hole pair (ehp) excitation, and its dependence on the system's parameters, remain largely unknown. We address these questions for two systems that present an extreme case of the mass ratio of the incident atom to the surface atom, i.e., H + Cu(111) and H + Au(111), by presenting adiabatic ab initio molecular dynamics (AIMD) predictions of the energy loss and angular distributions for an incidence energy of 5 eV. The results are compared to the results of AIMDEFp calculations modeling energy loss to ehp excitation using an electronic friction (“EF”) model applied to the AIMD trajectories, so that the energy loss to the electrons is calculated “post” (“p”) the computation of the AIMD trajectory. The AIMD calculations predict average energy losses of 0.38 eV for Cu(111) and 0.13-0.14 eV for Au(111) for H-atoms that scatter from these surfaces without penetrating the surface. These energies closely correspond with energy losses predicted with Baule models, which is suggestive of structure scattering. The predicted adiabatic integral energy loss spectra (integrated over all final scattering angles) all display a lowest energy peak at an energy corresponding to approximately 80% of the average adiabatic energy loss for non-penetrative scattering. In the adiabatic limit, this suggests a way of determining the approximate average energy loss of non-penetratively scattered H-atoms from the integral energy loss spectrum of all scattered H-atoms. The AIMDEFp calculations predict that in each case the lowest energy loss peak should show additional energy loss

  1. Correlations between 29Si, 17O and 1H NMR properties and local structures in silicates: an ab initio calculation

    NASA Astrophysics Data System (ADS)

    Xue, X.; Kanzaki, M.

    In order to gain insight into the correlations between 29Si, 17O and 1H NMR properties (chemical shift and quadrupolar coupling parameters) and local structures in silicates, ab initio self-consistent field Hartree-Fock molecular orbital calculations have been carried out on silicate clusters of various polymerizations and intertetrahedral (Si-O-Si) angles. These include Si(OH)4 monomers (isolated as well as interacting), Si2O(OH)6 dimers (C2 symmetry) with the Si-O-Si angle fixed at 5° intervals from 120° to 180°, Si3O2(OH)8 linear trimers (C2 symmetry) with varying Si-O-Si angles, Si3O3(OH)6 three-membered rings (D3 and C1 symmetries), Si4O4(OH)8 four-membered ring (C4 symmetry) and Si8O12(OH)8 octamer (D4 symmetry). The calculated 29Si, 17O and 1H isotropic chemical shifts (δiSi, δiO and δiH) for these clusters are all close to experimental NMR data for similar local structures in crystalline silicates. The calculated 17O quadrupolar coupling constants (QCC) of the bridging oxygens (Si-O-Si) are also in good agreement with experimental data. The calculated 17O QCC of silanols (Si-O-H) are much larger than those of the bridging oxygens, but unfortunately there are no experimental data for similar groups in well-characterized crystalline phases for comparison. There is a good correlation between δiSi and the mean Si-O-Si angle for both Q1 and Q2, where Qn denotes Si with n other tetrahedral Si next-nearest neighbors. Both the δiO and the 17O electric field gradient asymmetry parameter, η of the bridging oxygens have been found to depend strongly on the O site symmetry, in addition to the Si-O-Si angle. On the other hand, the 17O QCC seems to be influenced little by structural parameters other than the Si-O-Si angle, and is thus expected to be the most reliable 17O NMR parameter that can be used to decipher Si-O-Si angle distribution information. Both the 17O QCC and the 2H QCC of silanols decrease with decreasing length of hydrogen bond to a second O atom

  2. Ab initio molecular dynamics calculations on scattering of hyperthermal H atoms from Cu(111) and Au(111)

    NASA Astrophysics Data System (ADS)

    Kroes, Geert-Jan; Pavanello, Michele; Blanco-Rey, María; Alducin, Maite; Auerbach, Daniel J.

    2014-08-01

    Energy loss from the translational motion of an atom or molecule impinging on a metal surface to the surface may determine whether the incident particle can trap on the surface, and whether it has enough energy left to react with another molecule present at the surface. Although this is relevant to heterogeneous catalysis, the relative extent to which energy loss of hot atoms takes place to phonons or electron-hole pair (ehp) excitation, and its dependence on the system's parameters, remain largely unknown. We address these questions for two systems that present an extreme case of the mass ratio of the incident atom to the surface atom, i.e., H + Cu(111) and H + Au(111), by presenting adiabatic ab initio molecular dynamics (AIMD) predictions of the energy loss and angular distributions for an incidence energy of 5 eV. The results are compared to the results of AIMDEFp calculations modeling energy loss to ehp excitation using an electronic friction ("EF") model applied to the AIMD trajectories, so that the energy loss to the electrons is calculated "post" ("p") the computation of the AIMD trajectory. The AIMD calculations predict average energy losses of 0.38 eV for Cu(111) and 0.13-0.14 eV for Au(111) for H-atoms that scatter from these surfaces without penetrating the surface. These energies closely correspond with energy losses predicted with Baule models, which is suggestive of structure scattering. The predicted adiabatic integral energy loss spectra (integrated over all final scattering angles) all display a lowest energy peak at an energy corresponding to approximately 80% of the average adiabatic energy loss for non-penetrative scattering. In the adiabatic limit, this suggests a way of determining the approximate average energy loss of non-penetratively scattered H-atoms from the integral energy loss spectrum of all scattered H-atoms. The AIMDEFp calculations predict that in each case the lowest energy loss peak should show additional energy loss in the

  3. Thermal properties of molecular crystals through dispersion-corrected quasi-harmonic ab initio calculations: the case of urea.

    PubMed

    Erba, Alessandro; Maul, Jefferson; Civalleri, Bartolomeo

    2016-01-31

    An ab initio quantum-mechanical theoretical framework is presented to compute the thermal properties of molecular crystals. The present strategy combines dispersion-corrected density-functional-theory (DFT-D), harmonic phonon dispersion, quasi-harmonic approximation to the lattice dynamics for thermal expansion and thermodynamic functions, and quasi-static approximation for anisotropic thermo-elasticity. The proposed scheme is shown to reliably describe thermal properties of the urea molecular crystal by a thorough comparison with experimental data. PMID:26670006

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

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

  6. Rotational study of the NH{sub 3}–CO complex: Millimeter-wave measurements and ab initio calculations

    SciTech Connect

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

    2015-03-21

    The rotational spectrum of the van der Waals complex NH{sub 3}–CO has been measured with the intracavity OROTRON jet spectrometer in the frequency range of 112–139 GHz. Newly observed and assigned transitions belong to the K = 0–0, K = 1–1, K = 1–0, and K = 2–1 subbands correlating with the rotationless (j{sub k}){sub NH3} = 0{sub 0} ground state of free ortho-NH{sub 3} and the K = 0–1 and K = 2–1 subbands correlating with the (j{sub k}){sub NH3} = 1{sub 1} ground state of free para-NH{sub 3}. The (approximate) quantum number K is the projection of the total angular momentum J on the intermolecular axis. Some of these transitions are continuations to higher J values of transition series observed previously [C. Xia et al., Mol. Phys. 99, 643 (2001)], the other transitions constitute newly detected subbands. The new data were analyzed together with the known millimeter-wave and microwave transitions in order to determine the molecular parameters of the ortho-NH{sub 3}–CO and para-NH{sub 3}–CO complexes. Accompanying ab initio calculations of the intermolecular potential energy surface (PES) of NH{sub 3}–CO has been carried out at the explicitly correlated coupled cluster level of theory with single, double, and perturbative triple excitations and an augmented correlation-consistent triple zeta basis set. The global minimum of the five-dimensional PES corresponds to an approximately T-shaped structure with the N atom closest to the CO subunit and binding energy D{sub e} = 359.21 cm{sup −1}. The bound rovibrational levels of the NH{sub 3}–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 210.43 and 218.66 cm{sup −1} for ortho-NH{sub 3}–CO and para-NH{sub 3}–CO, respectively.

  7. Atomic kinetic Monte Carlo model based on ab initio data: Simulation of microstructural evolution under irradiation of dilute Fe CuNiMnSi alloys

    NASA Astrophysics Data System (ADS)

    Vincent, E.; Becquart, C. S.; Domain, C.

    2007-02-01

    The embrittlement of pressure vessel steels under radiation has been long ago correlated with the presence of Cu solutes. Other solutes such as Ni, Mn and Si are now suspected to contribute also to the embrittlement. The interactions of these solutes with radiation induced point defects thus need to be characterized properly in order to understand the elementary mechanisms behind the formation of the clusters formed upon radiation. Ab initio calculations based on the density functional theory have been performed to determine the interactions of point defects with solute atoms in dilute FeX alloys (X = Cu, Mn, Ni or Si) in order to build a database used to parameterise an atomic kinetic Monte Carlo model. Some results of irradiation damage in dilute Fe-CuNiMnSi alloys obtained with this model are presented.

  8. Optimized energy landscape exploration using the ab initio based activation-relaxation technique.

    PubMed

    Machado-Charry, Eduardo; Béland, Laurent Karim; Caliste, Damien; Genovese, Luigi; Deutsch, Thierry; Mousseau, Normand; Pochet, Pascal

    2011-07-21

    Unbiased open-ended methods for finding transition states are powerful tools to understand diffusion and relaxation mechanisms associated with defect diffusion, growth processes, and catalysis. They have been little used, however, in conjunction with ab initio packages as these algorithms demanded large computational effort to generate even a single event. Here, we revisit the activation-relaxation technique (ART nouveau) and introduce a two-step convergence to the saddle point, combining the previously used Lanczós algorithm with the direct inversion in interactive subspace scheme. This combination makes it possible to generate events (from an initial minimum through a saddle point up to a final minimum) in a systematic fashion with a net 300-700 force evaluations per successful event. ART nouveau is coupled with BigDFT, a Kohn-Sham density functional theory (DFT) electronic structure code using a wavelet basis set with excellent efficiency on parallel computation, and applied to study the potential energy surface of C(20) clusters, vacancy diffusion in bulk silicon, and reconstruction of the 4H-SiC surface. PMID:21786982

  9. Role of charge in destabilizing AlH4 and BH4 complex anions for hydrogen storage applications: Ab initio density functional calculations

    NASA Astrophysics Data System (ADS)

    Du, A. J.; Smith, Sean C.; Lu, G. Q.

    2006-11-01

    NaAlH4 and LiBH4 are potential candidate materials for mobile hydrogen storage applications, yet they have the drawback of being highly stable and desorbing hydrogen only at elevated temperatures. In this letter, ab initio density functional theory calculations reveal how the stabilities of the AlH4 and BH4 complex anions will be affected by reducing net anionic charge. Tetrahedral AlH4 and BH4 complexes are found to be distorted with the decrease of negative charge. One H-H distance becomes smaller and the charge density will overlap between them at a small anion charge. The activation energies to release of H2 from AlH4 and BH4 complexes are thus greatly decreased. We demonstrate that point defects such as neutral Na vacancies or substitution of a Na atom with Ti on the NaAlH4(001) surface can potentially cause strong distortion of neighboring AlH4 complexes and even induce spontaneous dehydrogenation. Our results help to rationalize the conjecture that the suppression of charge transfer to AlH4 and BH4 anion as a consequence of surface defects should be very effective for improving the recycling performance of H2 in NaAlH4 and LiBH4 . The understanding gained here will aid in the rational design and development of hydrogen storage materials based on these two systems.

  10. Construction of diabatic Hamiltonian matrix from ab initio calculated molecular symmetry adapted nonadiabatic coupling terms and nuclear dynamics for the excited states of Na3 cluster.

    PubMed

    Mukherjee, Saikat; Bandyopadhyay, Sudip; Paul, Amit Kumar; Adhikari, Satrajit

    2013-04-25

    We present the molecular symmetry (MS) adapted treatment of nonadiabatic coupling terms (NACTs) for the excited electronic states (2(2)E' and 1(2)A1') of Na3 cluster, where the adiabatic potential energy surfaces (PESs) and the NACTs are calculated at the MRCI level by using an ab initio quantum chemistry package (MOLPRO). The signs of the NACTs at each point of the configuration space (CS) are determined by employing appropriate irreducible representations (IREPs) arising due to MS group, and such terms are incorporated into the adiabatic to diabatic transformation (ADT) equations to obtain the ADT angles. Since those sign corrected NACTs and the corresponding ADT angles demonstrate the validity of curl condition for the existence of three-state (2(2)E' and 1(2)A1') sub-Hilbert space, it becomes possible to construct the continuous, single-valued, symmetric, and smooth 3 × 3 diabatic Hamiltonian matrix. Finally, nuclear dynamics has been carried out on such diabatic surfaces to explore whether our MS-based treatment of diabatization can reproduce the pattern of the experimental spectrum for system B of Na3 cluster. PMID:23521047

  11. Formation and temperature stability of G-quadruplex structures studied by electronic and vibrational circular dichroism spectroscopy combined with ab initio calculations.

    PubMed

    Nový, Jakub; Böhm, Stanislav; Králová, Jarmila; Král, Vladimír; Urbanová, Marie

    2008-02-01

    Variations in the structure of d(GGGA)(5) oligonucleotide in the presence of Li(+), Na(+), and K(+) ions and its temperature stability were studied using electronic and vibrational circular dichroism, IR absorption, and ab initio calculations with the Becke 3-Lee-Yang-Parr functional at the 6-31G** level. The samples were characterized by nondenaturing gel electrophoresis. Oligonucleotide d(GGGA)(5) in the presence of Li(+) forms a nonplanar single tetramer, with angles of 102 degrees and 171 degrees between neighboring guanine bases. This tetramer changes its geometry at temperatures >50 degrees C, but does not form a quadruplex structure. In the presence of Na(+), the d(GGGA)(5) structure was optimized to almost planar tetramers with an angle of 177 degrees between neighboring guanines. The spectral results suggest that it stacks into a quadruplex helical structure. This quadruplex structure decayed to a single tetramer at temperatures >60 degrees C. The Hartree-Fock energies imply that d(GGGA)(5) prefers to form complexes with Na(+) rather than Li(+). The d(GGGA)(5) structure in the presence of monovalent ions is stabilized against thermal denaturation in the order Li(+) < Na(+) < K(+). PMID:17960602

  12. Ab initio quasi-particle approximation bandgaps of silicon nanowires calculated at density functional theory/local density approximation computational effort

    SciTech Connect

    Ribeiro, M.

    2015-06-21

    Ab initio calculations of hydrogen-passivated Si nanowires were performed using density functional theory within LDA-1/2, to account for the excited states properties. A range of diameters was calculated to draw conclusions about the ability of the method to correctly describe the main trends of bandgap, quantum confinement, and self-energy corrections versus the diameter of the nanowire. Bandgaps are predicted with excellent accuracy if compared with other theoretical results like GW, and with the experiment as well, but with a low computational cost.

  13. Helium Nanodroplet Isolation Spectroscopy and AB Initio Calculations of HO_3-(O_2)_N Clusters (N=0-4)

    NASA Astrophysics Data System (ADS)

    Liang, T.; Raston, P.; Douberly, G. E.

    2013-06-01

    The HOOO hydridotrioxygen radical and its deuterated analog (DOOO) have been isolated in helium nanodroplets following the in-situ association reaction between OH and O_2. The infrared spectrum in the 3500-3700 cm^{-1} region reveals bands that are assigned to the ν_1 (OH stretch) fundamental and ν_1+ν_6 (OH stretch plus torsion) combination band of the trans-HOOO isomer. The helium droplet spectrum is assigned on the basis of a detailed comparison to the infrared spectrum of HOOO produced in the gas phase [E. L. Derro, T. D. Sechler, C. Murray, and M. I. Lester, J. Chem. Phys. 128, 244313 (2008)]. Despite the characteristic low temperature and rapid cooling of helium nanodroplets, there is no evidence for the formation of a weakly bound OH-O_2 van der Waals complex, which implies the absence of a kinetically significant barrier in the entrance channel of the reaction. There is also no spectroscopic evidence for the formation of cis-HOOO, which is predicted by theory to be nearly isoenergetic to the trans isomer. Stark spectroscopy of the trans-HOOO species provides vibrationally averaged dipole moment components that qualitatively disagree with predictions obtained from CCSD(T) computations at the equilibrium, planar geometry, indicating a floppy complex undergoing large-amplitude motion about the torsional coordinate. Under conditions that favor the introduction of multiple O_2 molecules to the droplets, bands associated with larger H/DOOO-(O_2)_n clusters are observed shifted 1-10 cm^{-1} to the red of the trans-H/DOOO ν_1 bands. Detailed ab initio calculations are carried out for multiple isomers of cis- and trans-HO_3-O_2, corresponding to either hydrogen or oxygen bonded van der Waals complexes. Comparisons to theory suggest that the structure of the HO_3-O_2 complex formed in helium droplets is a hydrogen-bonded ^4A' species consisting of a trans-HO_3 core. The computed binding energy of the complex is approximately 240 cm^{-1}. Despite the weak

  14. Ab initio calculations of vibrational frequencies and infrared intensities for global warning potential of CFC substitutes. CF{sub 3}CH{sub 2}F (HFC-134a)

    SciTech Connect

    Papasavva, S.; Tai, S.; Esslinger, A.; Illinger, K.H.; Kenny, J.E.

    1995-03-16

    We have investigated the feasibility of using ab initio molecular orbital methods for predicting the global warming potential of the proposed chlorofluorocarbon (CFC) substitute CF{sub 3}CH{sub 2}F, HFC-134a. Various levels of theory and basis sets were used to optimize geometry and calculate harmonic vibrational frequencies and infrared intensities for the molecule using the GAUSSIAN 92 software package. In attempting to assess the quality of the computations, we found it necessary to reconsider the vibrational assignments available in the literature. On the basis of the current assignment, we find that for the highest level calculation, MP2/6-31G{sup **}, the calculated harmonic frequencies agree extremely well with the experimentally observed ones at frequencies below 800 cm{sup {minus}1}, with a systematic error toward higher calculated frequencies becoming apparent above 800 cm{sup {minus}1}. At lower levels of theory, the systematic error is apparent at all frequencies. The regularity of the deviation between calculated and observed frequencies makes ab initio calculations of vibrational frequencies much more useful than semiempirical calculations, which tend to show random deviations, as demonstrated with a PM3-UHF calculation in this work. The calculated absolute intensities are in good agreement with the limited experimental measurements previously reported. 23 refs., 3 figs., 5 tabs.

  15. Cation diffusion and hybridization effects at the Mn-GaSe(0001) reacted interface: Ab initio calculations and soft x-ray electron spectroscopy studies

    NASA Astrophysics Data System (ADS)

    Dash, S.; Joshi, N.; Drera, G.; Ghosh, P.; Magnano, E.; Bondino, F.; Galinetto, P.; Mozzati, M. C.; Salvinelli, G.; Aguekian, V.; Sangaletti, L.

    2016-03-01

    The electronic properties of the Mn:GaSe interface, produced by evaporating Mn at room temperature on a ɛ -GaSe(0001) single-crystal surface, have been studied by soft x-ray spectroscopies, and the experimental results are discussed at the light of ab initio DFT+U calculations of a model Ga1 -xMnxSe (x =0.055 ) surface alloy. Consistently with these calculations that also predict a high magnetic moment for the Mn ions (4.73 -4.83 μB), XAS measurements at the Mn L edge indicate that Mn diffuses into the lattice as a Mn2 + cation with negligible crystal-field effects. Ab initio calculations also show that the most energetically favorable lattice sites for Mn diffusion are those where Mn substitutes Ga cations in the Ga layers of the topmost Se-Ga-Ga-Se sandwich. Mn s and p states are found to strongly hybridize with Se and Ga p states, while weaker hybridization is predicted for Mn d states with Se s and p orbitals. Furthermore, unlike other Mn-doped semiconductors, there is strong interaction between the Ga -s and Mn -dz2 states. The effects of hybridization of Mn 3 d electrons with neighboring atoms are still clearly detectable from the characteristic charge-transfer satellites observed in the photoemission spectra. The Mn 3 d spectral weight in the valence band is probed by resonant photoemission spectroscopy at the Mn L edge, which also allowed an estimation of the charge transfer (Δ =2.95 eV) and Mott-Hubbard (U =6.4 eV) energies on the basis of impurity-cluster configuration-interaction model of the photoemission process. The Mott-Hubbard correlation energy U is consistent with the Ueff on-site Coulomb repulsion parameter (5.84 eV) determined for the ab initio calculations.

  16. Full-dimensional quantum calculations of vibrational levels of NH4+ and isotopomers on an accurate ab initio potential energy surface

    DOE PAGESBeta

    Hua -Gen Yu; Han, Huixian; Guo, Hua

    2016-03-29

    Vibrational energy levels of the ammonium cation (NH4+) and its deuterated isotopomers are calculated using a numerically exact kinetic energy operator on a recently developed nine-dimensional permutation invariant semiglobal potential energy surface fitted to a large number of high-level ab initio points. Like CH4, the vibrational levels of NH4+ and ND4+ exhibit a polyad structure, characterized by a collective quantum number P = 2(v1 + v3) + v2 + v4. As a result, the low-lying vibrational levels of all isotopomers are assigned and the agreement with available experimental data is better than 1 cm–1.

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

    SciTech Connect

    Nicolaides, Cleanthes A.; Mercouris, Theodoros; Komninos, Yannis

    2007-11-29

    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.

  18. Towards Accurate Ab Initio Predictions of the Spectrum of Methane

    NASA Technical Reports Server (NTRS)

    Schwenke, David W.; Kwak, Dochan (Technical Monitor)

    2001-01-01

    We have carried out extensive ab initio calculations of the electronic structure of methane, and these results are used to compute vibrational energy levels. We include basis set extrapolations, core-valence correlation, relativistic effects, and Born- Oppenheimer breakdown terms in our calculations. Our ab initio predictions of the lowest lying levels are superb.

  19. Electronic structure and mechanical properties of ternary ZrTaN alloys studied by ab initio calculations and thin-film growth experiments

    NASA Astrophysics Data System (ADS)

    Abadias, G.; Kanoun, M. B.; Goumri-Said, S.; Koutsokeras, L.; Dub, S. N.; Djemia, Ph.

    2014-10-01

    The structure, phase stability, and mechanical properties of ternary alloys of the Zr-Ta-N system are investigated by combining thin-film growth and ab initio calculations. Zr1-xTaxN films with 0≤x≤1 were deposited by reactive magnetron cosputtering in Ar +N2 plasma discharge and their structural properties characterized by x-ray diffraction. We considered both ordered and disordered alloys, using supercells and special quasirandom structure approaches, to account for different possible metal atom distributions on the cation sublattice. Density functional theory within the generalized gradient approximation was employed to calculate the electronic structure as well as predict the evolution of the lattice parameter and key mechanical properties, including single-crystal elastic constants and polycrystalline elastic moduli, of ternary Zr1-xTaxN compounds with cubic rocksalt structure. These calculated values are compared with experimental data from thin-film measurements using Brillouin light scattering and nanoindentation tests. We also study the validity of Vegard's empirical rule and the effect of growth-dependent stresses on the lattice parameter. The thermal stability of these Zr1-xTaxN films is also studied, based on their structural and mechanical response upon vacuum annealing at 850 °C for 3 h. Our findings demonstrate that Zr1-xTaxN alloys with Ta fraction 0.51⩽x⩽0.78 exhibit enhanced toughness, while retaining high hardness ˜30 GPa, as a result of increased valence electron concentration and phase stability tuning. Calculations performed for disordered or ordered structures both lead to the same conclusion regarding the mechanical behavior of these nitride alloys, in agreement with recent literature findings [H. Kindlund, D. G. Sangiovanni, L. Martinez-de-Olcoz, J. Lu, J. Jensen, J. Birch, I. Petrov, J. E. Greene, V. Chirita, and L. Hultman, APL Materials 1, 042104 (2013), 10.1063/1.4822440].

  20. A monomeric complex of ammonia and cuprous chloride: H3N⋯CuCl isolated and characterised by rotational spectroscopy and ab initio calculations.

    PubMed

    Bittner, Dror M; Zaleski, Daniel P; Stephens, Susanna L; Tew, David P; Walker, Nicholas R; Legon, Anthony C

    2015-04-14

    The H3N⋯CuCl monomer has been generated and isolated in the gas phase through laser vaporisation of a copper sample in the presence of low concentrations of NH3 and CCl4 in argon. The resulting complex cools to a rotational temperature approaching 2 K during supersonic expansion of the gas sample and is characterised by broadband rotational spectroscopy between 7 and 18.5 GHz. The spectra of six isotopologues are measured and analysed to determine rotational, B0; centrifugal distortion, DJ, DJK; and nuclear quadrupole coupling constants of Cu, Cl, and (14)N nuclei, χaa (X). The geometry of the complex is C3v with the N, Cu, and Cl atoms located on the a inertial axis. Bond distances and the ∠(H -N⋯Cu) bond angle within the complex are precisely evaluated through fitting of geometrical parameters to the experimentally determined moments of inertia and through ab initio calculations at the CCSD(T)(F12*)/AVQZ level. The r(Cu -Cl), r(Cu -N), and ∠(H -N⋯Cu) parameters are, respectively, evaluated to be 2.0614(7) Å, 1.9182(13) Å, and 111.40(6)° in the r0 geometry, in good agreement with the ab initio calculations. Geometrical parameters evaluated for the isolated complex are compared with those established crystallographically for a solid-state sample of [Cu(NH3)Cl]. PMID:25877573

  1. Titanium atoms dimerization phenomenon and magnetic properties of titanium-antisite (TiO) and chromium doped rutile TiO2, ab-initio calculation

    NASA Astrophysics Data System (ADS)

    Zarhri, Z.; Ziat, Y.; El Rhazouani, O.; Benyoussef, A.; Elkenz, A.

    2016-07-01

    The ab-initio calculations based on the Korringa Kohn Rostoker approximation approach combined with coherent potential approximation (KKR-CPA), were used to study the magnetic properties of the titanium anti-site (TiO) and chromium (Cr) doped TiO2. In the considered systems, we used different concentrations for TiO defect and Cr doping. In TiO2(0.98)(TiO)0.02, the obtained results indicate that TiO is a donor having half-metal behavior. TiO[3d] band is located at the Fermi level, although isn't 100% polarized, the ferromagnetic (FM) state is verified as being more stable than disordered local moment (DLM) state. For Ti0.98Cr0.02O2 the Cr doping introduced new states which give the material half-metallic feature. The majority spin of Cr impurities are located at the Fermi level and the conduction electrons around the Fermi level are 100% spin polarized. This indicates the stability of (FM) state. Moreover, in Ti0.98Cr0.02O2(0.98)(TiO)0.02, the top of the valence band is shifted to lower energy compared to pure TiO2, and the n-type of TiO2 is verified. The majority spin of Cr[3d] are located at 0.025 Ry close to the Fermi level. The predicted Curie temperatures (Tc) were calculated using the mean field approximation (MFA) and we predicted that TiO defect in Cr doped TiO2 makes Tc higher. This kind of defect makes the material useful for spinotronics's applications and devices.

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

    NASA Astrophysics Data System (ADS)

    Muñoz, Emiliano L.; Mercurio, Marcio E.; Cordeiro, Moacir R.; Pereira, Luciano F. D.; Carbonari, Artur W.; Rentería, Mario

    2012-08-01

    In this work, we present results of Time-Differential γ-γ Perturbed-Angular-Correlations (PAC) experiments performed in 111Cd-doped ZnO semiconductor. The PAC technique has been applied in order to characterize the electric-field-gradient (EFG) tensor at (111In (EC)→) 111Cd nuclei located, as was later demonstrated, at defect-free cation sites of the ZnO host structure. The PAC experiments were performed in the temperature range of 77-1075 K. At first glance, the unexpected presence of low-intensity dynamic hyperfine interactions was observed, which were analyzed with a perturbation factor based on the Bäverstam and Othaz model. The experimental EFG results were compared with ab initio calculations performed with the Full-Potential Augmented Plane Wave plus local orbital (FP-APW+lo) method, in the framework of the Density Functional Theory (DFT), using the Wien2K code. The presence of the dynamic hyperfine interactions has been analyzed enlightened by the FP-APW+lo calculations of the EFG performed as a function of the charge state of the cell. We could correlate the large strength of the dynamic hyperfine interaction with the strong variation of the EFG due to changes in the electronic charge distribution in the Cd vicinity during the time-window of the PAC measurement. It was also revealed that the Cd impurity decays to a final stable neutral charge state (Cd2+) fast enough (in few ns) to produce the nearly undamped observed PAC spectra.

  3. Atomistic Texture of Amorphous Manganese Oxides for Electrochemical Water Splitting Revealed by Ab Initio Calculations Combined with X-ray Spectroscopy.

    PubMed

    Mattioli, Giuseppe; Zaharieva, Ivelina; Dau, Holger; Guidoni, Leonardo

    2015-08-19

    Amorphous transition-metal (hydr)oxides are considered as the most promising catalysts that promote the oxidation of water to molecular oxygen, protons, and "energized" electrons, and, in turn, as fundamental parts of "artificial leaves" that can be exploited for large scale generation of chemical fuels (e.g., hydrogen) directly from sunlight. We present here a joint theoretical-experimental investigation of electrodeposited amorphous manganese oxides with different catalytic activities toward water oxidation (MnCats). Combining the information content of X-ray absorption fine structure (XAFS) measurements with the predictive power of ab initio calculations based on density functional theory, we have been able to identify the essential structural and electronic properties of MnCats. We have elucidated (i) the localization and structural connection of Mn(II), Mn(III), and Mn(IV) ions in such amorphous oxides and (ii) the distribution of protons at the MnCat/water interface. Our calculations result in realistic 3D models of the MnCat atomistic texture, formed by the interconnection of small planar Mn-oxo sheets cross-linked through different kinds of defective Mn atoms, isolated or arranged in closed cubane-like units. Essential for the catalytic activity is the presence of undercoordinated Mn(III)O5 units located at the boundary of the amorphous network, where they are ready to act as hole traps that trigger the oxidation of neighboring water molecules when the catalyst is exposed to an external positive potential. The present validation of a sound 3D model of MnCat improves the accuracy of XAFS fits and opens the way for the development of mechanistic schemes of its functioning beyond a speculative level. PMID:26226190

  4. Close shell interactions in 3-ethoxycarbonyl-4-hydroxy-6-methoxymethyleneoxy-1-methyl-2-quinolone: 100 K single crystal neutron diffraction study and ab initio calculations

    NASA Astrophysics Data System (ADS)

    Pozzi, C. G.; Fantoni, A. C.; Goeta, A. E.; Wilson, C. C.; Autino, J. C.; Punte, G.

    2005-10-01

    The molecular and crystal structures of the title compound have been determined from a single crystal neutron diffraction experiment at 100 K. A comparison between the main geometrical features and related properties of the in-crystal and the ab initio optimized free molecule structures has shown that crystal packing induces a significant distortion in the molecular geometry. Packing instead would only have a moderate effect on the observed intramolecular resonance assisted hydrogen bond. Supermolecular ab initio molecular orbital calculations have been performed on the six different dimers one molecule forms with its nine nearest neighbours. The obtained results clearly show that dispersion contributions dominate in the most strongly interacting dimers, in good qualitative accord with the predictions made by using different empirical potentials. A qualitative description of the most prominent inductive effects determined from the electron density deformation upon dimer formation is presented. Topological analyses of the dimers charge densities have been performed in the framework of the Bader's AIM theory and all the intermolecular bond critical points have been identified. An attempt to determine some of the interaction energies only from topological quantities made evident the practical limitations of such an approach.

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

    NASA Astrophysics Data System (ADS)

    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.

  6. Exploring complex chemical reactions by ab-initio simulation

    NASA Astrophysics Data System (ADS)

    Parrinello, Michele

    1998-03-01

    Recent progress in the ab-initio molecular dynamics method and the power of parallel computing, allow the detailed study of complex chemical reaction of great industrial relevance. We illustrate this unprecedented capability by investigating the second generation Ziegler-Natta catalytic process. In this inhomogeneous catalyst, a polymerization reaction is induced by TiCl4 molecules deposited on an MgCl2 solid support. A density functional based ab-initio molecular dynamics calculation conducted with a minimum of initial assumption allows to understand the nature of the catalytic center and to determine the reaction path with the associated free energy barrier. Furthermore our calculation can explain in a nontrivial way the stereo-selectivity of the process.

  7. Half-metallic behaviour in doped TiO2 (rutile) with double impurities: ab initio calculation

    NASA Astrophysics Data System (ADS)

    Fakhim Lamrani, A.; Belaiche, M.; Benyoussef, A.; El Kenz, A.

    2013-12-01

    Dilute magnetic oxides are without doubt among the most interesting classes of magnetic materials. However, the nature of their electronic structure and magnetic exchange is far from understood. Here, we apply the ab initio augmented spherical wave (ASW) method, with corrected generalised gradient approximation to study the electronic structure and magnetic properties of doped TiO2 rutile with double impurities. The study reveals a half-metallic ferromagnetic behaviour for Ti1-2x Cr x Mo x O2, and the local magnetic moments of the impurities and their oxidation states agree with the charge transfer between Cr and Mo, which would lead to the ferromagnetic state through the double-exchange mechanism in transition metal oxides.

  8. Influence of thermal history on the photostructural changes in glassy As15S85 studied by Raman scattering and ab initio calculations

    NASA Astrophysics Data System (ADS)

    Kolar, J.; Strizik, L.; Kohoutek, T.; Wagner, T.; Voyiatzis, G. A.; Chrissanthopoulos, A.; Yannopoulos, S. N.

    2013-11-01

    Photostructural changes—the hallmark of non-crystalline chalcogenides—are in essence the basis of a number of photoinduced effects, i.e., changes of their physical properties, which are exploited in a variety of applications, especially in photonics and optoelectronics. Despite the vast number of investigations of photostructural changes, there is currently lack of systematic studies on how the thermal history, which affects glass structure, modifies the extent of photostructural changes. In this article, we study the role of thermal history on photostructural changes in glassy As15S85. This particular sulfur-rich composition has been chosen based on the colossal photostructural response it exhibits under near-band gap light irradiation, which inherently originates from its nanoscale phase-separated nature. To control the thermal history, the glass was quenched to various temperatures and each of these quenched products was annealed under four different conditions. Off-resonant Raman scattering was used to study the equilibrium study of each product. Structural changes of interest involve changes of the sulfur atoms participating into S8 rings and Sn chains. Their ratio was found to depend on quenching/annealing conditions. Near-band gap light was used to perturb the rings-to-chain ratio and at the same time to record these changes through Raman scattering, revealing an intricate behavior of photostructural changes. Ab initio calculations were employed to determine the stability of various sulfur clusters/molecules thus aiding the correlation of the particular photo-response of glassy As15S85 with its structural constituents.

  9. Influence of thermal history on the photostructural changes in glassy As{sub 15}S{sub 85} studied by Raman scattering and ab initio calculations

    SciTech Connect

    Kolar, J. E-mail: sny@iceht.forth.gr; Strizik, L.; Kohoutek, T.; Wagner, T.; Voyiatzis, G. A.; Chrissanthopoulos, A.; Yannopoulos, S. N. E-mail: sny@iceht.forth.gr

    2013-11-28

    Photostructural changes—the hallmark of non-crystalline chalcogenides—are in essence the basis of a number of photoinduced effects, i.e., changes of their physical properties, which are exploited in a variety of applications, especially in photonics and optoelectronics. Despite the vast number of investigations of photostructural changes, there is currently lack of systematic studies on how the thermal history, which affects glass structure, modifies the extent of photostructural changes. In this article, we study the role of thermal history on photostructural changes in glassy As{sub 15}S{sub 85}. This particular sulfur-rich composition has been chosen based on the colossal photostructural response it exhibits under near-band gap light irradiation, which inherently originates from its nanoscale phase-separated nature. To control the thermal history, the glass was quenched to various temperatures and each of these quenched products was annealed under four different conditions. Off-resonant Raman scattering was used to study the equilibrium study of each product. Structural changes of interest involve changes of the sulfur atoms participating into S{sub 8} rings and S{sub n} chains. Their ratio was found to depend on quenching/annealing conditions. Near-band gap light was used to perturb the rings-to-chain ratio and at the same time to record these changes through Raman scattering, revealing an intricate behavior of photostructural changes. Ab initio calculations were employed to determine the stability of various sulfur clusters/molecules thus aiding the correlation of the particular photo-response of glassy As{sub 15}S{sub 85} with its structural constituents.

  10. Melting of α-Al2O3 and vitrification of the undercooled alumina liquid: ab initio vibrational calculations and their thermodynamic implications.

    PubMed

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

    2013-02-14

    We present the results of a computational investigation of the structure-energy and vibrational properties of alumina under various aggregation states (crystalline, glassy, and liquid) with ab initio procedures. IV-fold, V-fold, and VI-fold oxygen-coordinated aluminum monomeric forms in a dielectric continuum with dielectric constant ε = 4.575 were investigated through DFT/B3LYP gas-phase calculations coupled with a Polarized Continuum Model approach and those of the periodical structure D(6)(3d) (R-3c) which leads to the α-Al(2)O(3) polymorph of alumina, when subjected to symmetry operations, were investigated with the same functional within the LCAO approximation and in the framework of Bloch's theorem. Based on the computed energies and vibrational features, an aggregate of the D(6)(3d) positively charged cluster [Al(12)O(11)](14+) contoured by [AlO(4)](5-) units in an approximate 1:3 proportion to achieve neutrality satisfactorily reproduce the heat capacity of the liquid within experimental uncertainty. The glass is seen as a wrong accretionary form induced by fast cooling rates and subjected to steric forces that locally modify the coordination state of the central atom. Cessation of rotational and translational movements, only partly counterbalanced by acoustic sine-wave-dispersed and excess phonons, gives rise to the huge heat-capacity gap observed at the glass transition (~5.3R). When cooling rates are sufficiently slow, the accretion around the D(6)(3d) seeds follows the structural constraints and the heat capacity of α-alumina is almost perfectly reproduced by the 27 Einstein oscillators coupled with the 3 acoustic terms and the anharmonic corrections. PMID:23425479

  11. Melting of α-Al2O3 and vitrification of the undercooled alumina liquid: Ab initio vibrational calculations and their thermodynamic implications

    NASA Astrophysics Data System (ADS)

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

    2013-02-01

    We present the results of a computational investigation of the structure-energy and vibrational properties of alumina under various aggregation states (crystalline, glassy, and liquid) with ab initio procedures. IV-fold, V-fold, and VI-fold oxygen-coordinated aluminum monomeric forms in a dielectric continuum with dielectric constant ɛ = 4.575 were investigated through DFT/B3LYP gas-phase calculations coupled with a Polarized Continuum Model approach and those of the periodical structure D63d (R-3c) which leads to the α-Al2O3 polymorph of alumina, when subjected to symmetry operations, were investigated with the same functional within the LCAO approximation and in the framework of Bloch's theorem. Based on the computed energies and vibrational features, an aggregate of the D63d positively charged cluster [Al12O11]14+ contoured by [AlO4]5- units in an approximate 1:3 proportion to achieve neutrality satisfactorily reproduce the heat capacity of the liquid within experimental uncertainty. The glass is seen as a wrong accretionary form induced by fast cooling rates and subjected to steric forces that locally modify the coordination state of the central atom. Cessation of rotational and translational movements, only partly counterbalanced by acoustic sine-wave-dispersed and excess phonons, gives rise to the huge heat-capacity gap observed at the glass transition (˜5.3R). When cooling rates are sufficiently slow, the accretion around the D63d seeds follows the structural constraints and the heat capacity of α-alumina is almost perfectly reproduced by the 27 Einstein oscillators coupled with the 3 acoustic terms and the anharmonic corrections.

  12. Ab initio calculations on the structure and nature of the hydrogen bonded complex H2S ṡṡṡ HF

    NASA Astrophysics Data System (ADS)

    Singh, U. Chandra; Kollman, Peter A.

    1984-01-01

    Ab initio calculations employing an extended basis set and correlation energy estimates at the MP2 (second order Möller-Plesset) level have been used to estimate the binding energy, minimum energy S ...F distance, and minimum energy bisector angle θ (angle between the twofold axis of H2S and the S ...F line) for the hydrogen bonded complex H2S ... HF. The calculated distance and bisector angle θ are in reasonable agreement with experiment; the calculated binding energy can be used to provide a good estimate of the (as yet unknown) experimental value. Morokuma component analyses and simple electrostatic (molecular mechanics) calculations have been carried out on the complex as a function of bisector angle and they demonstrated that, despite suggestions to the contrary, the H2S ... HF bisector angle is predominantly determined by the electrostatic energy.

  13. Ab Initio Study of Defect Properties in YPO4

    SciTech Connect

    Gao, Fei; Xiao, Haiyan Y.; Zhou, Yungang; Devanathan, Ramaswami; Hu, Shenyang Y.; Li, Yulan; Sun, Xin; Khaleel, Mohammad A.

    2012-03-01

    Ab initio methods based on density functional theory have been used to calculate the formation energies of intrinsic defects, including vacancies, interstitials, antisites and Frenkel pairs in YPO4 under the O-rich and Y2O3-rich, and the O-rich and Y-rich conditions. The larger size of the yttrium atom may give rise to higher formation energy of the phosphorus antisite defect. In general, the formation energies of anion interstitials are much smaller than those of cation interstitials for both conditions considered. It is of greatly interest to find that the relative stabilities among the same types of interstitials are independent of the reference states. The most stable configuration for oxygen interstitials is an O-O split interstitial near the Ta site, while the most stable configuration for cation interstitials is a tetrahedral interstitial near the Ta site. The cation split interstitials are unfavorable in YPO4, with much higher formation energies. Furthermore, the properties of Frenkel pairs are compared with those calculated using empirical potentials. The results reveal that both ab initio and empirical potential calculations show a similar trend in the formation energies of Frenkel pairs, but the formation energies obtained by empirical potentials are much larger than those calculated by ab initio method.

  14. Ab Initio and Phenomenological Modeling of the Phonon Spectrum of Superhard cp-BC2N

    NASA Astrophysics Data System (ADS)

    Basalaev, Yu. M.; Kopytov, A. V.; Pavlova, T. Yu.; Poplavnoi, A. S.

    2015-11-01

    The phonon spectrum of hypothetical superhard cp-BC2N is calculated based on ab initio method of density functional in the center of the Brillouin zone and interpolated over the entire Brillouin zone using the Keating phenomenological model. The interaction parameters are determined by optimization of the IR- and Ramanactive frequencies for a phenomenological model by their comparison with the results of ab initio calculations. Numerical values of short-range interaction constants and charges are in agreement with the characteristics of the chemical bond calculated ab initio. These parameters have transparent physical meaning and chemical nature and can further be used for both qualitative estimations of any physical and physico-chemical quantities and quantitative calculations of the phonon spectra of a number of isostructural compounds. The Keating phenomenological model is used to study the genesis of the phonon spectrum from the spectra of sublattices.

  15. A 'bottom up', ab initio computational approach to understanding fundamental photophysical processes in nitrogen containing heterocycles, DNA bases and base pairs.

    PubMed

    Marchetti, Barbara; Karsili, Tolga N V; Ashfold, Michael N R; Domcke, Wolfgang

    2016-07-27

    The availability of non-radiative decay mechanisms by which photoexcited molecules can revert to their ground electronic state, without experiencing potentially deleterious chemical transformation, is fundamental to molecular photostability. This Perspective Article combines results of new ab initio electronic structure calculations and prior experimental data in an effort to systematise trends in the non-radiative decay following UV excitation of selected families of heterocyclic molecules. We start with the prototypical uni- and bicyclic molecules phenol and indole, and explore the structural and photophysical consequences of incorporating progressively more nitrogen atoms within the respective ring structures en route to the DNA bases thymine, cytosine, adenine and guanine. For each of the latter, we identify low energy non-radiative decay pathways via conical intersections with the ground state potential energy surface accessed by out-of-plane ring deformations. This is followed by summary descriptions and illustrations of selected rival (electron driven H atom transfer) non-radiative excited state decay processes that demand consideration once the nucleobases are merely components in larger biomolecular systems like nucleosides, and both individual and stacked base-pairs. PMID:26980149

  16. Electronic state spectroscopy by high-resolution vacuum ultraviolet photoabsorption, He(I) photoelectron spectroscopy and ab initio calculations of ethyl acetate

    NASA Astrophysics Data System (ADS)

    Śmialek, Malgorzata A.; Łabuda, Marta; Guthmuller, Julien; Hubin-Franskin, Marie-Jeanne; Delwiche, Jacques; Hoffmann, Søren Vrønning; Jones, Nykola C.; Mason, Nigel J.; Limão-Vieira, Paulo

    2016-06-01

    The high-resolution vacuum ultraviolet photoabsorption spectrum of ethyl acetate, C4H8O2, is presented over the energy range 4.5-10.7 eV (275.5-116.0 nm). Valence and Rydberg transitions and their associated vibronic series observed in the photoabsorption spectrum, have been assigned in accordance with new ab initio calculations of the vertical excitation energies and oscillator strengths. Also, the photoabsorption cross sections have been used to calculate the photolysis lifetime of this ester in the upper stratosphere (20-50 km). Calculations have also been carried out to determine the ionisation energies and fine structure of the lowest ionic state of ethyl acetate and are compared with a newly recorded photoelectron spectrum (from 9.5 to 16.7 eV). Vibrational structure is observed in the first photoelectron band of this molecule for the first time.

  17. Ab initio many-body calculations of the (3)H(d,n)(4)He and (3)He(d,p)(4)He fusion reactions.

    PubMed

    Navrátil, Petr; Quaglioni, Sofia

    2012-01-27

    We apply the ab initio no-core shell model combined with the resonating-group method approach to calculate the cross sections of the (3)H(d,n)(4)He and (3)He(d,p)(4)He fusion reactions. These are important reactions for the big bang nucleosynthesis and the future of energy generation on Earth. Starting from a selected similarity-transformed chiral nucleon-nucleon interaction that accurately describes two-nucleon data, we performed many-body calculations that predict the S factor of both reactions. Virtual three-body breakup effects are obtained by including excited pseudostates of the deuteron in the calculation. Our results are in satisfactory agreement with experimental data and pave the way for microscopic investigations of polarization and electron-screening effects, of the (3)H(d,γn)(4)He bremsstrahlung and other reactions relevant to fusion research. PMID:22400830

  18. Conformational distribution of baclofen analogues by 1H and 13C NMR analysis and ab initio HF MO STO-3G or STO-3G* calculations

    NASA Astrophysics Data System (ADS)

    Vaccher, Claude; Berthelot, Pascal; Debaert, Michel; Vermeersch, Gaston; Guyon, René; Pirard, Bernard; Vercauteren, Daniel P.; Dory, Magdalena; Evrard, Guy; Durant, François

    1993-12-01

    The conformations of 3-(substituted furan-2-yl) and 3-(substituted thien-2-yl)-γ-aminobutyric acid 1-9 in solution (D 2O) are estimated from high-resolution (300 MHz) 1H NMR coupling data. Conformations and populations of conformers are calculated by means of a modified Karplus-like relationship for the vicinal coupling constants. The results are compared with X-ray crystallographic investigations (torsion angles) and ab initio HF MO ST-3G or STO-3G* calculations. 1H NMR spectral analysis shows how 1-9 in solution retain the preferred g- conformation around the C3C4 bond, as found in the solid state, while a partial rotation is set up around the C2C3 bond: the conformations about C2C3 are all highly populated in solution. The 13C spin-lattice relaxation times are also discussed.

  19. A package for the ab-initio calculation of one- and two-photon cross sections of two-electron atoms, using a CI B-splines method

    NASA Astrophysics Data System (ADS)

    Nikolopoulos, L. A. A.

    2003-02-01

    A package is presented for the fully ab-initio calculation of one- and two-photon ionization cross sections for two-electron atomic systems (H -, He, Mg, Ca, …) under strong laser fields, within lowest-order perturbation theory (LOPT) and in the dipole approximation. The atomic structure is obtained through configuration interaction (CI) of antisymmetrized two-electron states expanded in a B-spline finite basis. The formulation of the theory and the relevant codes presented here represent the accumulation of work over the last ten years [1-11,13-15]. Extensions to more than two-photon ionization is straightforward. Calculation is possible for both the length and velocity form of the laser-atom interaction operator. The package is mainly, written in standard FORTRAN language and uses the publicly available libraries SLATEC, LAPACK and BLAS.

  20. Ab initio quantum mechanical calculation of the reaction probability for the Cl-+PH2Cl→ClPH2+Cl- reaction

    NASA Astrophysics Data System (ADS)

    Farahani, Pooria; Lundberg, Marcus; Karlsson, Hans O.

    2013-11-01

    The SN2 substitution reactions at phosphorus play a key role in organic and biological processes. Quantum molecular dynamics simulations have been performed to study the prototype reaction Cl-+PH2Cl→ClPH2+Cl-, using one and two-dimensional models. A potential energy surface, showing an energy well for a transition complex, was generated using ab initio electronic structure calculations. The one-dimensional model is essentially reflection free, whereas the more realistic two-dimensional model displays involved resonance structures in the reaction probability. The reaction rate is almost two orders of magnitude smaller for the two-dimensional compared to the one-dimensional model. Energetic errors in the potential energy surface is estimated to affect the rate by only a factor of two. This shows that for these types of reactions it is more important to increase the dimensionality of the modeling than to increase the accuracy of the electronic structure calculation.

  1. Ab Initio Calculated Thermodynamic Properties of Mo5SiB2 Phase and Nb5SiB2 Phase

    NASA Astrophysics Data System (ADS)

    Kim, Sungtae; Park, J. S.

    2013-11-01

    Due to their attractive high-temperature properties, multiphase Mo-Si-B alloys in the Mo-rich Mo-Si-B ternary system have been identified for high-temperature applications. The ternary intermetallic T2 (Mo5SiB2) phase is a central feature of the phase equilibria within this ternary system. Experimental stability analyses of the T2 phase shows its broad homogeneous composition ranges that can yield a constitutional defect structure such as vacancies for Mo-rich compositions and antisite defects for Mo-lean compositions. Previous thermodynamic model did not conform to the defect structures as reported in experiments, and thus subsequently a new sublattice thermodynamic model for the T2 phase is initiated in this study. To support the new sublattice thermodynamic model, ab initio calculations were implemented to compute formation energy data. The calculated formation energy data explain a source for broad compositional homogeneity range of T2 structure.

  2. Phase Transformation in Sm{sub 2}O{sub 3} at High Pressure: in Situ Synchrotron X-Ray Diffraction Study And Ab Initio DFT Calculation

    SciTech Connect

    Guo, Q.X.; Zhao, Y.S.; Jiang, C.; Mao, W.L.; Wang, Z.W.; /Cornell U., CHESS

    2009-06-09

    Sm{sub 2}O{sub 3} was compressed at room temperature up to 44.0 GPa and then decompressed back to ambient pressure. In situ X-ray diffraction was used to monitor the structural changes in the sample. A cubic to hexagonal phase transformation was observed in Sm{sub 2}O{sub 3} for the first time. After decompression back to ambient pressure, the hexagonal phase was not quenchable and transformed to a monoclinic phase. Ab initio Density-Functional-Theory (DFT) calculations were performed to obtain theoretical data for comparison with the experimental results and elucidation of the transformation mechanism. A possible phase transformation mechanism that is consistent with the experimental results and theoretical calculations is proposed.

  3. Molecular structure, vibrational spectra and HOMO, LUMO analysis of yohimbine hydrochloride by density functional theory and ab initio Hartree-Fock calculations

    NASA Astrophysics Data System (ADS)

    Joshi, Bhawani Datt; Srivastava, Anubha; Tandon, Poonam; Jain, Sudha

    2011-11-01

    Yohimbine hydrochloride (YHCl) is an aphrodisiac and promoted for erectile dysfunction, weight loss and depression. The optimized geometry, total energy, potential energy surface and vibrational wavenumbers of yohimbine hydrochloride have been determined using ab initio, Hartree-Fock (HF) and density functional theory (DFT/B3LYP) method with 6-311++G(d,p) basis set. A complete vibrational assignment is provided for the observed Raman and IR spectra of YHCl. The UV absorption spectrum was examined in ethanol solvent and compared with the calculated one in gas phase as well as in solvent environment (polarizable continuum model, PCM) using TD-DFT/6-31G basis set. These methods are proposed as a tool to be applied in the structural characterization of YHCl. The calculated highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) with frontier orbital gap are presented.

  4. Surfactant design for the 1,1,1,2-tetrafluoroethane-water interface: ab initio calculations and in situ high-pressure tensiometry.

    PubMed

    Selvam, Parthiban; Peguin, Robson P S; Chokshi, Udayan; da Rocha, Sandro R P

    2006-10-10

    In situ high-pressure tensiometry and ab initio calculations were used to rationally design surfactants for the 1,1,1,2-tetrafluoroethane-water (HFA134a|W) interface. Nonbonded pair interaction (binding) energies (E(b)) of the complexes between HFA134a and candidate surfactant tails were used to quantify the HFA-philicity of selected moieties. The interaction between HFA134a and an ether-based tail was shown to be predominantly electrostatic in nature and much more favorable than that between HFA134a and a methyl-based fragment. The interfacial activity of (i) amphiphiles typically found in FDA-approved pressurized metered-dose inhaler (pMDI) formulations, (ii) a series of nonionic surfactants with methylene-based tails, and (iii) a series of nonionic surfactants with ether-based tails was investigated at the HFA134a|W interface using in situ tensiometry. This is the first time that the tension of the surfactant-modified HFA134a|W interface has been reported in the literature. The ether-based surfactants were shown to be very interfacially active, with tension decreasing by as much as 27 mN.m(-)(1). However, the methyl-based surfactants, including those from FDA-approved formulations, did not exhibit high activity at the HFA134a|W interface. These results are in direct agreement with the E(b) calculations. Significant differences in interfacial activity are noted for surfactants at the 2H,3H-perfluoropentane (HPFP)|water and HFA134a|W interfaces. Care should be taken, therefore, when results from the mimicking solvent (HPFP) are extrapolated to HFA134a-based systems. The results shown here are of relevance in the selection of surfactants capable of forming and stabilizing reverse aqueous aggregates in HFA-based pMDIs, which are promising formulations for the systemic delivery of biomolecules to and through the lungs. PMID:17014104

  5. Ab initio study on (CO2)n clusters via electrostatics- and molecular tailoring-based algorithm

    NASA Astrophysics Data System (ADS)

    Jovan Jose, K. V.; Gadre, Shridhar R.

    An algorithm based on molecular electrostatic potential (MESP) and molecular tailoring approach (MTA) for building energetically favorable molecular clusters is presented. This algorithm is tested on prototype (CO2)n clusters with n = 13, 20, and 25 to explore their structure, energetics, and properties. The most stable clusters in this series are seen to show more number of triangular motifs. Many-body energy decomposition analysis performed on the most stable clusters reveals that the 2-body is the major contributor (>96%) to the total interaction energy. Vibrational frequencies and molecular electrostatic potentials are also evaluated for these large clusters through MTA. The MTA-based MESPs of these clusters show a remarkably good agreement with the corresponding actual ones. The most intense MTA-based normal mode frequencies are in fair agreement with the actual ones for smaller clusters. These calculated asymmetric stretching frequencies are blue-shifted with reference to the CO2 monomer.

  6. Ab initio MO Calculations on the Structure and Raman and Infrared Spectra of [Al4O2Cl10]2- Oxide in Chloroaluminate Melts

    NASA Astrophysics Data System (ADS)

    Berg, Rolf W.

    2007-04-01

    The oxide complexation chemistry in molten tetrachloroaluminate salts and ionic liquids is discussed with respect to what possible structures may be formed in addition to [AlCl4]-: [Al2OCl6]2-, [Al3OCl8]-, [Al2O2Cl4]2-, [Al3O2Cl6]- and [Al4O2Cl10]2-. Ab initio molecular orbital calculations are carried out on these various aluminium chloride and oxochloride ions, in assumed isolated gaseous free ionic state, by use of the Gaussian 03W program at the restricted Hartree-Fock (HF) level and with the 6-31+G(d,p) basis set.Without any pre-assumed symmetries and with tight optimization convergence criteria and by using the modified GDIIS algorithm, the model calculations generally converge. The structures and their binding energies are presented. The expected geometries are supported, with one exception perhaps being the [Al2OCl6]2- ion, that gave a linear Al-O-Al bonding system of staggered AlCl3-groups (approximate D3d symmetry), in analogy to the linear Al-O-Al geometry of the analogous [Al2OF6]2- ion, found previously. The calculations include determination of the vibrational harmonic normal modes and the infrared and Raman spectra (vibrational band wavenumbers and intensities), without any empiric adjustments of the harmonic force constants, using constants directly predicted from the Gaussian 03W program. Previously obtained IR absorption and Raman scattering spectra of melts are assigned, by comparing to the ab initio quantum mechanical vibrational analysis results. It is concluded that the small oxide content commonly found in basic and neutral tetrachloroaluminate melts, most probably consists of [Al4O2Cl10]2- ions, and the vibrational spectra are given.

  7. Ensemble v-representable ab initio density-functional calculation of energy and spin in atoms: A test of exchange-correlation approximations

    SciTech Connect

    Kraisler, Eli; Makov, Guy; Kelson, Itzhak

    2010-10-15

    The total energies and the spin states for atoms and their first ions with Z=1-86 are calculated within the the local spin-density approximation (LSDA) and the generalized-gradient approximation (GGA) to the exchange-correlation (xc) energy in density-functional theory. Atoms and ions for which the ground-state density is not pure-state v-representable are treated as ensemble v-representable with fractional occupations of the Kohn-Sham system. A recently developed algorithm which searches over ensemble v-representable densities [E. Kraisler et al., Phys. Rev. A 80, 032115 (2009)] is employed in calculations. It is found that for many atoms, the ionization energies obtained with the GGA are only modestly improved with respect to experimental data, as compared to the LSDA. However, even in those groups of atoms where the improvement is systematic, there remains a non-negligible difference with respect to the experiment. The ab initio electronic configuration in the Kohn-Sham reference system does not always equal the configuration obtained from the spectroscopic term within the independent-electron approximation. It was shown that use of the latter configuration can prevent the energy-minimization process from converging to the global minimum, e.g., in lanthanides. The spin values calculated ab initio fit the experiment for most atoms and are almost unaffected by the choice of the xc functional. Among the systems with incorrectly obtained spin, there exist some cases (e.g., V, Pt) for which the result is found to be stable with respect to small variations in the xc approximation. These findings suggest a necessity for a significant modification of the exchange-correlation functional, probably of a nonlocal nature, to accurately describe such systems.

  8. Specific interactions between lactose repressor protein and DNA affected by ligand binding: ab initio molecular orbital calculations.

    PubMed

    Ohyama, Tatsuya; Hayakawa, Masato; Nishikawa, Shin; Kurita, Noriyuki

    2011-06-01

    Transcription mechanisms of gene information from DNA to mRNA are essentially controlled by regulatory proteins such as a lactose repressor (LacR) protein and ligand molecules. Biochemical experiments elucidated that a ligand binding to LacR drastically changes the mechanism controlled by LacR, although the effect of ligand binding has not been clarified at atomic and electronic levels. We here investigated the effect of ligand binding on the specific interactions between LacR and operator DNA by the molecular simulations combined with classical molecular mechanics and ab initio fragment molecular orbital methods. The results indicate that the binding of anti-inducer ligand strengthens the interaction between LacR and DNA, which is consistent with the fact that the binding of anti-inducer enhances the repression of gene transcription by LacR. It was also elucidated that hydrating water molecules existing between LacR and DNA contribute to the specific interactions between LacR and DNA. PMID:21328406

  9. Dzyaloshinskii-Moriya interaction and chiral magnetism in 3d-5d zigzag chains: Tight-binding model and ab initio calculations

    NASA Astrophysics Data System (ADS)

    Kashid, Vikas; Schena, Timo; Zimmermann, Bernd; Mokrousov, Yuriy; Blügel, Stefan; Shah, Vaishali; Salunke, H. G.

    2014-08-01

    We investigate the chiral magnetic order in freestanding planar 3d-5d biatomic metallic chains (3d: Fe, Co; 5d: Ir, Pt, Au) using first-principles calculations based on density functional theory. We find that the antisymmetric exchange interaction, commonly known as the Dzyaloshinskii-Moriya interaction (DMI), contributes significantly to the energetics of the magnetic structure. For the Fe-Pt and Co-Pt chains, the DMI can compete with the isotropic Heisenberg-type exchange interaction and the magnetocrystalline anisotropy energy, and for both cases a homogeneous left-rotating cycloidal chiral spin-spiral with a wavelength of 51 Å and 36 Å, respectively, was found. The sign of the DMI, which determines the handedness of the magnetic structure, changes in the sequence of the 5d atoms Ir(+), Pt(-), Au(+). We use the full-potential linearized augmented plane wave method and perform self-consistent calculations of homogeneous spin spirals, calculating the DMI by treating the effect of spin-orbit interaction in the basis of the spin-spiral states in first-order perturbation theory. To gain insight into the DMI results of our ab initio calculations, we develop a minimal tight-binding model of three atoms and four orbitals that contains all essential features: the spin canting between the magnetic 3d atoms, the spin-orbit interaction at the 5d atoms, and the structure inversion asymmetry facilitated by the triangular geometry. We find that spin canting can lead to spin-orbit active eigenstates that split in energy due to the spin-orbit interaction at the 5d atom. We show that the sign and strength of the hybridization, the bonding or antibonding character between d orbitals of the magnetic and nonmagnetic sites, the bandwidth, and the energy difference between occupied and unoccupied states of different spin projection determine the sign and strength of the DMI. The key features observed in the trimer model are also found in the first-principles results.

  10. Ab initio investigation on hydrogen adsorption capability in Zn and Cu-based metal organic frameworks

    NASA Astrophysics Data System (ADS)

    Tanuwijaya, V. V.; Hidayat, N. N.; Agusta, M. K.; Dipojono, H. K.

    2015-09-01

    One of the biggest challenge in material technology for hydrogen storage application is to increase hydrogen uptake in room temperature and pressure. As a class of highly porous material, Metal-Organic Frameworks (MOF) holds great potential with its tunable structure. However, little is known about the effect of metal cluster to its hydrogen storage capability. Investigation on this matter has been carried out carefully on small cluster of Zn and Cu-based MOF using first principles method. The calculation of two distinct building units of MOFs, namely octahedral and paddle-wheel models, have been done with B3LYP density functional method using 6-31G(d,p) and LANL2DZ basis sets. From geometry optimization of Zn-based MOF linked by benzene-dicarboxylate (MOF-5), it is found that hydrogen tends to keep distance from metal cluster group and stays above benzene ring. In the other hand, hydrogen molecule prefers to stay atop of the exposed Cu atom in Cu-based MOF system linked by the same linker group (Cu-bdc). Calculated hydrogen binding enthalpies for Zn and Cu octahedral cages at ZnO3 sites are 1.64kJ/mol and 2.73kJ/mol respectively, while hydrogen binding enthalpies for Zn and Cu paddle-wheel cages calculated on top of metal atoms are found to be at 6.05kJ/mol and 6.10kJ/mol respectively. Major difference between Zn-MOF-5 and Cu-bdc hydrogen uptake performance might be caused by unsaturated metal sites present in Cu-bdc system and the influence of their geometric structures, although a small difference on binding energy in the type of transition metal used is also observed. The comparison between Zn and Cu-based MOF may contribute to a comprehensive understanding of metal clusters and the importance of selecting best transition metal for design and synthesis of metal-organic frameworks.

  11. Ab initio investigation on hydrogen adsorption capability in Zn and Cu-based metal organic frameworks

    SciTech Connect

    Tanuwijaya, V. V.; Hidayat, N. N. Agusta, M. K. Dipojono, H. K.

    2015-09-30

    One of the biggest challenge in material technology for hydrogen storage application is to increase hydrogen uptake in room temperature and pressure. As a class of highly porous material, Metal-Organic Frameworks (MOF) holds great potential with its tunable structure. However, little is known about the effect of metal cluster to its hydrogen storage capability. Investigation on this matter has been carried out carefully on small cluster of Zn and Cu-based MOF using first principles method. The calculation of two distinct building units of MOFs, namely octahedral and paddle-wheel models, have been done with B3LYP density functional method using 6-31G(d,p) and LANL2DZ basis sets. From geometry optimization of Zn-based MOF linked by benzene-dicarboxylate (MOF-5), it is found that hydrogen tends to keep distance from metal cluster group and stays above benzene ring. In the other hand, hydrogen molecule prefers to stay atop of the exposed Cu atom in Cu-based MOF system linked by the same linker group (Cu-bdc). Calculated hydrogen binding enthalpies for Zn and Cu octahedral cages at ZnO{sub 3} sites are 1.64kJ/mol and 2.73kJ/mol respectively, while hydrogen binding enthalpies for Zn and Cu paddle-wheel cages calculated on top of metal atoms are found to be at 6.05kJ/mol and 6.10kJ/mol respectively. Major difference between Zn-MOF-5 and Cu-bdc hydrogen uptake performance might be caused by unsaturated metal sites present in Cu-bdc system and the influence of their geometric structures, although a small difference on binding energy in the type of transition metal used is also observed. The comparison between Zn and Cu-based MOF may contribute to a comprehensive understanding of metal clusters and the importance of selecting best transition metal for design and synthesis of metal-organic frameworks.

  12. Ab initio optical absorption spectra of size-expanded xDNA base assemblies.

    PubMed

    Varsano, Daniele; Garbesi, Anna; Di Felice, Rosa

    2007-12-20

    We present the results of time-dependent density functional theory calculations of the optical absorption spectra of synthetic nucleobases and of their hydrogen-bonded and stacked base pairs. We focus on size-expanded analogues of the natural nucleobases obtained through the insertion of a benzene ring bonded to the planar heterocycles (x-bases), according to the protocol designed and realized by the group of Eric Kool (e.g., see: Gao, J.; Liu, H.; Kool, E.T. Angew. Chem., Int. Ed. 2005, 44, 3118, and references therein). We find that the modifications of the frontier electron orbitals with respect to natural bases, which are induced by the presence of the aromatic ring, also affect the optical response. In particular, the absorption onset is pinned by the benzene component of the HOMO of each x-base (xA, xG, xT, xC). In addition, the main trait of the H-bonding interbase coupling is a conspicuous red shift of spectral peaks in the low-energy range. Finally, the hypochromicity, a well-known fingerprint of stacking, is more pronounced in stacked xG-C and xA-T pairs than that in stacked G-C and A-T pairs, an index of enhanced stacking. PMID:18034470

  13. Quadratic scaling of intrinsic Gilbert damping with spin-orbital coupling in L10 FePdPt films: experiments and Ab initio calculations.

    PubMed

    He, P; Ma, X; Zhang, J W; Zhao, H B; Lüpke, G; Shi, Z; Zhou, S M

    2013-02-15

    The dependence of the intrinsic Gilbert damping parameter α(0) on the spin-orbital coupling strength ξ is investigated in L1(0) ordered FePd(1-x) Pt(x) films by time-resolved magneto-optical Kerr effect measurements and spin-dependent ab initio calculations. Continuous tuning of α(0) over more than one order of magnitude is realized by changing the Pt/Pd concentration ratio showing that α(0) is proportional to ξ(2) as changes of other leading parameters are found to be negligible. The perpendicular magnetic anisotropy is shown to have a similar variation trend with x. The present results may facilitate the design and fabrication of new magnetic alloys with large perpendicular magnetic anisotropy and tailored damping properties. PMID:25166400

  14. Dynamic lattice distortions in Sr2RuO4: microscopic studies by perturbed angular correlation spectroscopy and ab initio calculations

    NASA Astrophysics Data System (ADS)

    Mishra, S. N.; Rots, M.; Cottenier, S.

    2010-09-01

    Applying time differential perturbed angular correlation (TDPAC) spectroscopy and ab initio calculations, we have investigated possible lattice instabilities in Sr2RuO4 by studying the electric quadrupole interaction of a 111Cd probe at the Ru site. We find evidence for a dynamic lattice distortion, revealed from the observations of: (i) a rapidly fluctuating electric-field gradient (EFG) tensor showing non-Arrhenius relaxation, (ii) an anomalous temperature dependence of the quadrupole interaction frequency, and (iii) a monotonic increase of the EFG asymmetry (η) below 300 K. We argue that the observed dynamic lattice distortion is caused by strong spin fluctuations associated with the inherent magnetic instability in Sr2RuO4.

  15. Dynamic lattice distortions in Sr2RuO4: microscopic studies by perturbed angular correlation spectroscopy and ab initio calculations.

    PubMed

    Mishra, S N; Rots, M; Cottenier, S

    2010-09-29

    Applying time differential perturbed angular correlation (TDPAC) spectroscopy and ab initio calculations, we have investigated possible lattice instabilities in Sr(2)RuO(4) by studying the electric quadrupole interaction of a (111)Cd probe at the Ru site. We find evidence for a dynamic lattice distortion, revealed from the observations of: (i) a rapidly fluctuating electric-field gradient (EFG) tensor showing non-Arrhenius relaxation, (ii) an anomalous temperature dependence of the quadrupole interaction frequency, and (iii) a monotonic increase of the EFG asymmetry (η) below 300 K. We argue that the observed dynamic lattice distortion is caused by strong spin fluctuations associated with the inherent magnetic instability in Sr(2)RuO(4). PMID:21386555

  16. Electronic excitation of furfural as probed by high-resolution vacuum ultraviolet spectroscopy, electron energy loss spectroscopy, and ab initio calculations

    NASA Astrophysics Data System (ADS)

    Ferreira da Silva, F.; Lange, E.; Limão-Vieira, P.; Jones, N. C.; Hoffmann, S. V.; Hubin-Franskin, M.-J.; Delwiche, J.; Brunger, M. J.; Neves, R. F. C.; Lopes, M. C. A.; de Oliveira, E. M.; da Costa, R. F.; Varella, M. T. do N.; Bettega, M. H. F.; Blanco, F.; García, G.; Lima, M. A. P.; Jones, D. B.

    2015-10-01

    The electronic spectroscopy of isolated furfural (2-furaldehyde) in the gas phase has been investigated using high-resolution photoabsorption spectroscopy in the 3.5-10.8 eV energy-range, with absolute cross section measurements derived. Electron energy loss spectra are also measured over a range of kinematical conditions. Those energy loss spectra are used to derive differential cross sections and in turn generalised oscillator strengths. These experiments are supported by ab initio calculations in order to assign the excited states of the neutral molecule. The good agreement between the theoretical results and the measurements allows us to provide the first quantitative assignment of the electronic state spectroscopy of furfural over an extended energy range.

  17. Hyperfine structure of the (5d+6s)3 configuration of 139 i: New measurements and ab initio multiconfigurational Dirac-Fock calculations

    NASA Astrophysics Data System (ADS)

    Childs, W. J.; Nielsen, U.

    1988-01-01

    The atomic-beam laser-rf double-resonance method has been used to measure precisely the dipole and quadrupole hyperfine structure (hfs) of 11 levels of the 5d26s configuration and four levels of the 5d3 configuration of 139La i. The results, together with earlier results for lower-lying levels, are compared in detail with new multiconfiguration Dirac-Fock (MCDF) ab initio calculations. The agreement is good to fair overall, but is poor in some areas. The comparison yields new insights and suggests areas in which the theoretical approach must be improved. In particular, the theory underestimates the importance of contact hfs in the 5d26s configuration by 25-40 %. In addition, there is at present no self-consistent way in the MCDF approach to take account of the large core polarization observed in the 5d3 4F term.

  18. Overcoming the existent computational challenges in the ab initio calculations of the two-photon circular dichroism spectra of large molecules using a fragment-recombination approach

    NASA Astrophysics Data System (ADS)

    Diaz, Carlos; Echevarria, Lorenzo; Hernández, Florencio E.

    2013-05-01

    Herein we report on the development of a fragment-recombination approach (FRA) that allows overcoming the computational limitations found in the ab initio calculation of the two-photon circular dichroism (TPCD) spectra of large optically active molecules. Through the comparative analysis of the corresponding theoretical TPCD spectra of the fragments and that of the entire molecule, we prove that TPCD is an additive property. We also demonstrate that the same property apply to two-photon absorption (TPA). TPCD-FRA is expected to find great applications in the structural-analysis of large catalysts and polypeptides due to its reduced computational complexity, cost and time, and to reveal fingerprints in the obscure spectral region between the near and far UV.

  19. Electronic excitation of furfural as probed by high-resolution vacuum ultraviolet spectroscopy, electron energy loss spectroscopy, and ab initio calculations.

    PubMed

    Ferreira da Silva, F; Lange, E; Limão-Vieira, P; Jones, N C; Hoffmann, S V; Hubin-Franskin, M-J; Delwiche, J; Brunger, M J; Neves, R F C; Lopes, M C A; de Oliveira, E M; da Costa, R F; Varella, M T do N; Bettega, M H F; Blanco, F; García, G; Lima, M A P; Jones, D B

    2015-10-14

    The electronic spectroscopy of isolated furfural (2-furaldehyde) in the gas phase has been investigated using high-resolution photoabsorption spectroscopy in the 3.5-10.8 eV energy-range, with absolute cross section measurements derived. Electron energy loss spectra are also measured over a range of kinematical conditions. Those energy loss spectra are used to derive differential cross sections and in turn generalised oscillator strengths. These experiments are supported by ab initio calculations in order to assign the excited states of the neutral molecule. The good agreement between the theoretical results and the measurements allows us to provide the first quantitative assignment of the electronic state spectroscopy of furfural over an extended energy range. PMID:26472380

  20. Electronic excitation of furfural as probed by high-resolution vacuum ultraviolet spectroscopy, electron energy loss spectroscopy, and ab initio calculations

    SciTech Connect

    Ferreira da Silva, F.; Lange, E.; Limão-Vieira, P. E-mail: michael.brunger@flinders.edu.au; Jones, N. C.; Hoffmann, S. V.; Hubin-Franskin, M.-J.; Delwiche, J.; Brunger, M. J. E-mail: michael.brunger@flinders.edu.au; and others

    2015-10-14

    The electronic spectroscopy of isolated furfural (2-furaldehyde) in the gas phase has been investigated using high-resolution photoabsorption spectroscopy in the 3.5–10.8 eV energy-range, with absolute cross section measurements derived. Electron energy loss spectra are also measured over a range of kinematical conditions. Those energy loss spectra are used to derive differential cross sections and in turn generalised oscillator strengths. These experiments are supported by ab initio calculations in order to assign the excited states of the neutral molecule. The good agreement between the theoretical results and the measurements allows us to provide the first quantitative assignment of the electronic state spectroscopy of furfural over an extended energy range.