WorldWideScience

Sample records for initio mo calculations

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

    DEFF Research Database (Denmark)

    Bak, Börge; Jansen, Peter; Stafast, Herbert

    1975-01-01

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

  2. Study of carvedilol by combined Raman spectroscopy and ab initio MO calculations

    OpenAIRE

    Marques, M. P. M.; Oliveira, P. J.; Moreno, A. J. M.; Carvalho, L. A. E. Batista de

    2002-01-01

    The novel cardioprotective drug carvedilol was studied by both Raman spectroscopy and ab initio molecular orbital methods (using the density functional theory approach). The spectra, acquired both for the solid samples and DMSO solutions as a function of pH, were assigned in view of the calculated wavenumbers and intensities, and also based on the experimental data obtained for individual compounds which comprise the molecule, namely carbazole and 1,2-dimethoxybenzene. The pH dependence of th...

  3. Ab initio calculation of mechanical and thermal properties of U{sub 2}Mo intermetallic

    Energy Technology Data Exchange (ETDEWEB)

    Jaroszewicz, S., E-mail: jaroszew@tandar.cnea.gov.ar [Gerencia de Investigación y Aplicaciones, Comisión Nacional de Energía Atómica (Argentina); Losada, E.L.; Garcés, J.E. [DAEE, Centro Atómico Bariloche, Comisión Nacional de Energía Atómica (Argentina); Mosca, H.O. [Gerencia de Investigación y Aplicaciones, Comisión Nacional de Energía Atómica (Argentina)

    2013-10-15

    We present a study of structural, elastic and thermodynamic properties of tetragonal (C11{sub b}) U{sub 2}Mo by means of density-functional theory based calculations using full-potential linearized augmented plane wave method. In this approach the generalized gradient approximation were used for the exchange–correlation potential calculation. The optimized lattice parameters are in excellent agreement with the experimental data. Through the Debye–Grüneisen model the temperature and pressure dependence of equation of state, bulk modulus, thermal expansion and specific heat have been obtained and discussed in the range of pressure 0–20 GPa and the temperature 0–800 K.

  4. A program system for ab initio MO calculations on vector and parallel processing machines. Pt. 1

    International Nuclear Information System (INIS)

    Ernenwein, R.; Rohmer, M.M.; Benard, M.

    1990-01-01

    We present a program system for ab initio molecular orbital calculations on vector and parallel computers. The present article is devoted to the computation of one- and two-electron integrals over contracted Gaussian basis sets involving s-, p-, d- and f-type functions. The McMurchie and Davidson (MMD) algorithm has been implemented and parallelized by distributing over a limited number of logical tasks the calculation of the 55 relevant classes of integrals. All sections of the MMD algorithm have been efficiently vectorized, leading to a scalar/vector ratio of 5.8. Different algorithms are proposed and compared for an optimal vectorization of the contraction of the 'intermediate integrals' generated by the MMD formalism. Advantage is taken of the dynamic storage allocation for tuning the length of the vector loops (i.e. the size of the vectorization buffer) as a function of (i) the total memory available for the job, (ii) the number of logical tasks defined by the user (≤13), and (iii) the storage requested by each specific class of integrals. Test calculations carried out on a CRAY-2 computer show that the average number of finite integrals computed over a (s, p, d, f) CGTO basis set is about 1180000 per second and per processor. The combination of vectorization and parallelism on this 4-processor machine reduces the CPU time by a factor larger than 20 with respect to the scalar and sequential performance. (orig.)

  5. A program system for ab initio MO calculations on vector and parallel processing machines. Pt. 3

    International Nuclear Information System (INIS)

    Wiest, R.; Demuynck, J.; Benard, M.; Rohmer, M.M.; Ernenwein, R.

    1991-01-01

    This series of three papers presents a program system for ab initio molecular orbital calculations on vector and parallel computers. Part III is devoted to the four-index transformation on a molecular orbital basis of size NMO of the file of two-electorn integrals (pqparallelrs) generated by a contracted Gaussian set of size NATO (number of atomic orbitals). A fast Yoshimine algorithm first sorts the (pqparallelrs) integrals with respect to index pq only. This file of half-sorted integrals labelled by their rs-index can be processed without further modification to generate either the transformed integrals or the supermatrix elements. The large memory available on the CRAY-2 hase made possible to implement the transformation algorithm proposed by Bender in 1972, which requires a core-storage allocation varying as (NATO) 3 . Two versions of Bender's algorithm are included in the present program. The first version is an in-core version, where the complete file of accumulated contributions to transformed integrals in stored and updated in central memory. This version has been parallelized by distributing over a limited number of logical tasks the NATO steps corresponding to the scanning of the most external loop. The second version is an out-of-core version, in which twin files are alternatively used as input and output for the accumulated contributions to transformed integrals. This version is not parallel. The choice of one or another version and (for version 1) the determination of the number of tasks depends upon the balance between the available and the requested amounts of storage. The storage management and the choice of the proper version are carried out automatically using dynamic storage allocation. Both versions are vectorized and take advantage of the molecular symmetry. (orig.)

  6. Ab-initio ZORA calculations

    NARCIS (Netherlands)

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

    2000-01-01

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

  7. Ab initio valence calculations in chemistry

    CERN Document Server

    Cook, D B

    1974-01-01

    Ab Initio Valence Calculations in Chemistry describes the theory and practice of ab initio valence calculations in chemistry and applies the ideas to a specific example, linear BeH2. Topics covered include the Schrödinger equation and the orbital approximation to atomic orbitals; molecular orbital and valence bond methods; practical molecular wave functions; and molecular integrals. Open shell systems, molecular symmetry, and localized descriptions of electronic structure are also discussed. This book is comprised of 13 chapters and begins by introducing the reader to the use of the Schrödinge

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

    DEFF Research Database (Denmark)

    Shim, Irene; Gingerich, Karl A.

    1999-01-01

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

  9. Ab Initio Calculations of Oxosulfatovanadates

    DEFF Research Database (Denmark)

    Frøberg, Torben; Johansen, Helge

    1996-01-01

    Restricted Hartree-Fock and multi-configurational self-consistent-field calculations together with secondorder perturbation theory have been used to study the geometry, the electron density, and the electronicspectrum of (VO2SO4)-. A bidentate sulphate attachment to vanadium was found to be stabl...

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

    DEFF Research Database (Denmark)

    Berg, Rolf W.; Nørbygaard, Thomas; White, Peter C.

    2011-01-01

    For the first time, the differences between the spectra of amphetamine and amphetamine-H+ and between different conformers are thoroughly studied by ab initio model calculations, and Raman and surface-enhanced Raman spectroscopy (SERS) spectra are measured for different species of amphetamine....... The spectra of amphetamine and amphetamine-H+ sampleswere obtained and assigned according to a comparison of the experimental spectra and the ab initio MO calculations, performed using the Gaussian 03W program (Gaussian, Inc., Pittsburgh, PA). The analyses were based on complete geometry minimization...

  11. Electronic structure investigation of MoS2 and MoSe2 using angle-resolved photoemission spectroscopy and ab initio band structure studies.

    Science.gov (United States)

    Mahatha, S K; Patel, K D; Menon, Krishnakumar S R

    2012-11-28

    Angle-resolved photoemission spectroscopy (ARPES) and ab initio band structure calculations have been used to study the detailed valence band structure of molybdenite, MoS(2) and MoSe(2). The experimental band structure obtained from ARPES has been found to be in good agreement with the theoretical calculations performed using the linear augmented plane wave (LAPW) method. In going from MoS(2) to MoSe(2), the dispersion of the valence bands decreases along both k(parallel) and k(perpendicular), revealing the increased two-dimensional character which is attributed to the increasing interlayer distance or c/a ratio in these compounds. The width of the valence band and the band gap are also found to decrease, whereas the valence band maxima shift towards the higher binding energy from MoS(2) to MoSe(2).

  12. AB INITIO calculations of magneto-optical effects

    Czech Academy of Sciences Publication Activity Database

    Kuneš, Jan; Oppeneer, P. M.

    2002-01-01

    Roč. 2, - (2002), s. 141-146 ISSN 1346-7948 R&D Projects: GA AV ČR IAA1010214 Institutional research plan: CEZ:AV0Z1010914 Keywords : electronic structure * ab initio calculation * polar magneto-optical Kerr effect * transitiom metal * uranium intermetallics * CrO 2 Subject RIV: BM - Solid Matter Physics ; Magnetism

  13. Quantifying transition voltage spectroscopy of molecular junctions: Ab initio calculations

    DEFF Research Database (Denmark)

    Chen, Jingzhe; Markussen, Troels; Thygesen, Kristian Sommer

    2010-01-01

    Transition voltage spectroscopy (TVS) has recently been introduced as a spectroscopic tool for molecular junctions where it offers the possibility to probe molecular level energies at relatively low bias voltages. In this work we perform extensive ab initio calculations of the nonlinear current...

  14. Ab initio calculations of cross luminescence materials

    International Nuclear Information System (INIS)

    Kanchana, V.

    2016-01-01

    Abintio calculations have been performed to study the structural, electronic, and optical properties of ABX 3 (A=alkali, B=alkaline-earth, and X=halide) compounds. The ground state properties are calculated using the pseudopotential method with the inclusion of van der Waals interaction, which we find inevitable in reproducing the experimental structure properties in alkali iodides because of its layered structure. All calculations were performed using the Full-Potential Linearized Augmented Plane Wave method. The band structures are plotted with various functionals and we find the newly developed Tran and Blaha modified Becke-Johnson potential to improve the band gap significantly. The optical properties such as complex dielectric function, refractive index, and absorption spectra are calculated which clearly reveal the optically isotropic nature of these materials though being structurally anisotropic, which is the key requirement for ceramic scintillators. Cross luminescence materials are very interesting because of its fast decay. One of the major criteria for the cross luminescence to happen is the energy difference between valence band and next deeper core valence band being lesser when compared to energy gap of the compound, so that radiative electronic transition may occur between valence band and core valence band. We found this criteria to be satisfied in all the studied compounds leading to cross luminescence except for KSrI 3 , RbSrI 3 . The present study suggest that among the six compounds studied, CsSrI 3 , CsMgCl 3 , CsCaCl 3 , and CsSrCl 3 compounds are cross luminescence materials, which is well explained from the band structure, optical properties calculations. Chlorides are better scintillators that iodides and CsMgCl 3 is found to be promising one among the studied compounds. Apart from these materials we have also discussed electronic structure and optical properties of other scintillator compounds. (author)

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

    International Nuclear Information System (INIS)

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

    2007-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2007-02-01

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

  17. Ab Initio Calculations of Transport in Titanium and Aluminum Mixtures

    Science.gov (United States)

    Walker, Nicholas; Novak, Brian; Tam, Ka Ming; Moldovan, Dorel; Jarrell, Mark

    In classical molecular dynamics simulations, the self-diffusion and shear viscosity of titanium about the melting point have fallen within the ranges provided by experimental data. However, the experimental data is difficult to collect and has been rather scattered, making it of limited value for the validation of these calculations. By using ab initio molecular dynamics simulations within the density functional theory framework, the classical molecular dynamics data can be validated. The dynamical data from the ab initio molecular dynamics can also be used to calculate new potentials for use in classical molecular dynamics, allowing for more accurate classical dynamics simulations for the liquid phase. For metallic materials such as titanium and aluminum alloys, these calculations are very valuable due to an increasing demand for the knowledge of their thermophysical properties that drive the development of new materials. For example, alongside knowledge of the surface tension, viscosity is an important input for modeling the additive manufacturing process at the continuum level. We are developing calculations of the viscosity along with the self-diffusion for aluminum, titanium, and titanium-aluminum alloys with ab initio molecular dynamics. Supported by the National Science Foundation through cooperative agreement OIA-1541079 and the Louisiana Board of Regents.

  18. Stability, elastic properties and fracture toughness of Al0.75X0.75B14 (X=Sc, Ti, V, Cr, Y, Zr, Nb, Mo) investigated using ab initio calculations

    International Nuclear Information System (INIS)

    Emmerlich, Jens; Thieme, Niklas; To Baben, Moritz; Music, Denis; Schneider, Jochen M

    2013-01-01

    The effect of the transition metal valence electron concentration on the energy of formation, effective charge of B icosahedra, elastic properties, surface energy and fracture toughness was calculated using density functional theory for icosahedral transition metal borides of AlXB 14 (X=Sc, Ti, V, Cr, Y, Zr, Nb, Mo). Consistent with previous work on AlYB 14 (Kölpin et al 2009 J. Phys.: Condens. Matter 21 355006) it is shown that phase stability is generally dependent on the effective charge of the icosahedral transition metal borides. Also, ionization potential and electronegativity are identified as parameters affecting the effective charge of B icosahedra suitable for use in predicting the phase stability. Al 0.75 Y 0.75 B 14 , Al 0.75 Sc 0.75 B 14 and Al 0.75 Zr 0.75 B 14 have been identified as promising phases for application as protective coatings as they exhibit high phase stability and stiffness combined with a comparatively high fracture toughness. (paper)

  19. Ab initio theory and calculations of X-ray spectra

    International Nuclear Information System (INIS)

    Rehr, J.J.; Kas, J.J.; Prange, M.P.; Sorini, A.P.; Takimoto, Y.; Vila, F.

    2009-01-01

    There has been dramatic progress in recent years both in the calculation and interpretation of various x-ray spectroscopies. However, current theoretical calculations often use a number of simplified models to account for many-body effects, in lieu of first principles calculations. In an effort to overcome these limitations we describe in this article a number of recent advances in theory and in theoretical codes which offer the prospect of parameter free calculations that include the dominant many-body effects. These advances are based on ab initio calculations of the dielectric and vibrational response of a system. Calculations of the dielectric function over a broad spectrum yield system dependent self-energies and mean-free paths, as well as intrinsic losses due to multielectron excitations. Calculations of the dynamical matrix yield vibrational damping in terms of multiple-scattering Debye-Waller factors. Our ab initio methods for determining these many-body effects have led to new, improved, and broadly applicable x-ray and electron spectroscopy codes. (authors)

  20. Ab Initio Calculations Of Light-Ion Reactions

    International Nuclear Information System (INIS)

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

    2012-01-01

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

  1. Routine calculation of ab initio melting curves: application to aluminum

    OpenAIRE

    Robert, Grégory; Legrand, Philippe; Arnault, Philippe; Desbiens, Nicolas; Clérouin, Jean

    2014-01-01

    We present a simple, fast, and reliable method to compute the melting curves of materials with ab initio molecular dynamics. It is based on the two-phase thermodynamic model of [Lin et al., J. Chem. Phys. 119, 11792 (2003)] and its improved version given by [Desjarlais, Phys. Rev. E, 88, 062145 (2013)]. In this model, the velocity autocorrelation function is utilized to calculate the contribution of the nuclei motion to the entropy of the solid and liquid phases. It is then possible to find t...

  2. Ab initio calculation of tensile strength in iron

    Czech Academy of Sciences Publication Activity Database

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

    2003-01-01

    Roč. 83, 31-34 (2003), s. 3529-3537 ISSN 1478-6435. [Multiscale Materials Modelling: Working Theory for Industry /1./. London, 17.06.2002-20.06.2002] R&D Projects: GA AV ČR IAA1041302; GA ČR GA202/03/1351; GA MŠk OC 523.90 Institutional research plan: CEZ:AV0Z2041904 Keywords : ab initio calculations * electronic structure * theoretical tensile strength Subject RIV: BM - Solid Matter Physics ; Magnetism

  3. Ab initio molecular orbital calculations on the associated complexes of lithium cyanide with ammonia

    International Nuclear Information System (INIS)

    Mohandas, P.; Shivaglal, M.C.; Chandrasekhar, J.

    1995-01-01

    Ab initio molecular orbital (MO) calculations with the 3-21G and 6-31G basis sets are carried out on a series of complexes of NH 3 with Li + , C triple-bond N - , LiCN, and its isomer LiNC. The BSSE-corrected interaction energies, geometrical parameters, internal force constants, and harmonic vibrational frequencies are evaluated for 15 species. Complexes with trifurcated (C 3v ) structures are calculated to be saddle points on the potential energy surfaces and have one imaginary frequency each. Calculated energies, geometrical parameters, internal force constants, and harmonic vibrational frequencies of the various species considered are discussed in terms of the nature of association of LiCN with ammonia. The vibrational frequencies of the relevant complexed species are compared with the experimental frequencies reported earlier for solutions of lithium cyanide in liquid ammonia. 40 refs., 1 fig., 4 tabs

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

    Energy Technology Data Exchange (ETDEWEB)

    Ching, Wai-Yim

    2013-12-31

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

  5. H3+: Ab initio calculation of the vibration spectrum

    International Nuclear Information System (INIS)

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

    1976-01-01

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

  6. Ab-initio calculations for dilute magnetic semiconductors

    Energy Technology Data Exchange (ETDEWEB)

    Belhadji, Brahim

    2008-03-03

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

  7. Simple calculation of ab initio melting curves: Application to aluminum.

    Science.gov (United States)

    Robert, Grégory; Legrand, Philippe; Arnault, Philippe; Desbiens, Nicolas; Clérouin, Jean

    2015-03-01

    We present a simple, fast, and promising method to compute the melting curves of materials with ab initio molecular dynamics. It is based on the two-phase thermodynamic model of Lin et al [J. Chem. Phys. 119, 11792 (2003)] and its improved version given by Desjarlais [Phys. Rev. E 88, 062145 (2013)]. In this model, the velocity autocorrelation function is utilized to calculate the contribution of the nuclei motion to the entropy of the solid and liquid phases. It is then possible to find the thermodynamic conditions of equal Gibbs free energy between these phases, defining the melting curve. The first benchmark on the face-centered cubic melting curve of aluminum from 0 to 300 GPa demonstrates how to obtain an accuracy of 5%-10%, comparable to the most sophisticated methods, for a much lower computational cost.

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

    Science.gov (United States)

    You, Y.; Yan, M. F.

    2013-05-01

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

  9. Ab initio study of energetics and magnetism of sigma phase in Co–Mo and Fe–Mo systems

    Czech Academy of Sciences Publication Activity Database

    Pavlů, Jana; Vřešťál, Jan; Šob, Mojmír

    2016-01-01

    Roč. 24, č. 2 (2016), č. článku Art. Number 025009. ISSN 0965-0393 R&D Projects: GA ČR GA14-15576S Institutional support: RVO:68081723 Keywords : intermetallics * magnetic properties * phase stability * thermodynamic properties * site occupancy * ab-initio calculations Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.891, year: 2016

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

    International Nuclear Information System (INIS)

    Bergli, Elise; Hjorth-Jensen, Morten

    2011-01-01

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

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

    International Nuclear Information System (INIS)

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

    1995-01-01

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

  12. Atomic structure calculations of Mo XV-XL

    International Nuclear Information System (INIS)

    Kubo, Hirotaka; Sugie, Tatsuo; Shiho, Makoto; Suzuki, Yasuo; Ishii, Keishi; Maeda, Hikosuke.

    1986-06-01

    Energy levels and oscillator strengths were calculated for Mo XV - Mo XL. The computer program for atomic structure calculation, developed by Dr. Robert D. Cowan, Los Alamos National Laboratory, was used in the present work. The scaled energy parameters were empirically determined from the observed spectral data. We present wavelengths and transition probabilities of Mo XV-XL. Energy levels and spectral patterns are presented in figures that are useful for the identification of spectral lines. (author)

  13. Permanent and induced dipole requirements in ab initio calculations of electron affinities of polar molecules

    International Nuclear Information System (INIS)

    Garrett, W.R.

    1979-01-01

    Through the use of a molecular pseudopotential method, we determine the a approximate magnitudes of errors that result when electron affinity determinations of polar negative ions are made through ab initio calculations in which the use of a given basis set yields inappropriate values for permanent and induced dipole moments of the neutral molecule. These results should prove useful in assessing the adequacy of basis sets in ab initio calculations of molecular electron affinities for simple linear polar molecules

  14. Ab initio calculations and modelling of atomic cluster structure

    DEFF Research Database (Denmark)

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

    2004-01-01

    The optimized structure and electronic properties of small sodium and magnesium clusters have been investigated using it ab initio theoretical methods based on density-functional theory and post-Hartree-Fock many-body perturbation theory accounting for all electrons in the system. A new theoretical...

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

    Czech Academy of Sciences Publication Activity Database

    Pokluda, J.; Černý, Miroslav; Šob, Mojmír; Umeno, Y.

    2015-01-01

    Roč. 73, AUG (2015), s. 127-158 ISSN 0079-6425 R&D Projects: GA ČR(CZ) GAP108/12/0311 Institutional support: RVO:68081723 Keywords : Ab initio methods * Elastic moduli * Intrinsic hardness * Stability analysis * Theoretical strength * Intrinsic brittleness/ductility Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 31.083, year: 2015

  16. Ab Initio Calculation of Hyperfine Interaction Parameters: Recent Evolutions, Recent Examples

    International Nuclear Information System (INIS)

    Cottenier, Stefaan; Vanhoof, Veerle; Torumba, Doru; Bellini, Valerio; Cakmak, Mehmet; Rots, Michel

    2004-01-01

    For some years already, ab initio calculations based on Density Functional Theory (DFT) belong to the toolbox of the field of hyperfine interaction studies. In this paper, the standard ab initio approach is schematically sketched. New features, methods and possibilities that broke through during the past few years are listed, and their relation to the standard approach is explained. All this is illustrated by some highlights of recent ab initio work done by the Nuclear Condensed Matter Group at the K.U.Leuven.

  17. Equation of state of U2Mo up-to Mbar pressure range: Ab-initio study

    Science.gov (United States)

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

    2018-04-01

    Experimentally, U2Mo is known to exist in tetragonal structure at ambient conditions. In contrast to experimental reports, the past theoretical studies carried out in this material do not find this phase to be stable structure at zero pressure. In order to examine this discrepancy between experiment and theory, we have performed ab-initio electronic band structure calculations on this material. In our theoretical study, we have attempted to search for lowest enthalpy structure at ambient as well at high pressure up to 200 GPa, employing evolutionary structure search algorithm in conjunction with ab-inito method. Our investigations suggest that a hexagonal structure with space group symmetry P6/mmm is the lowest enthalpy structure not only at ambient pressure but also up to pressure range of ˜200 GPa. To further, substantiate the results of these static lattice calculations the elastic and lattice dynamical stability has also been analysed. The theoretical isotherm derived from these calculations has been utilized to determine the Hugoniot of this material. Various physical properties such as zero pressure equilibrium volume, bulk modulus and its pressure derivative has also been derived from theoretical isotherm.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-09-28

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

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

    International Nuclear Information System (INIS)

    Draayer, Jerry P.

    2014-01-01

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

  20. Ab-initio calculations of superconducting properties of YBa2Cu3O7

    International Nuclear Information System (INIS)

    Zhao, G.L.; Bagayoko, D.

    1999-01-01

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

  1. Ab initio calculations on hydrogen storage in porous carbons

    International Nuclear Information System (INIS)

    Maresca, O.; Marinelli, F.; Pellenq, R.J.M.; Duclaux, L.; Azais, Ph.; Conard, J.

    2005-01-01

    We have investigated through ab initio computations the possible ways to achieve efficient hydrogen storage on carbons. Firstly, we have considered how the curvature of a carbon surface could affect the chemisorption of atomic H 0 Secondly, we show that electron donor elements such as Li and K, used as dopants for the carbon substrate, strongly enhance the physi-sorption energy of H 2 , allowing in principle its storage in this type of material at room temperature under mild conditions of pressure. (authors)

  2. (4)He Thermophysical Properties: New Ab Initio Calculations.

    Science.gov (United States)

    Hurly, John J; Mehl, James B

    2007-01-01

    Since 2000, atomic physicists have reduced the uncertainty of the helium-helium "ab initio" potential; for example, from approximately 0.6 % to 0.1 % at 4 bohr, and from 0.8 % to 0.1 % at 5.6 bohr. These results led us to: (1) construct a new inter-atomic potential ϕ 07, (2) recalculate values of the second virial coefficient, the viscosity, and the thermal conductivity of (4)He from 1 K to 10,000 K, and (3), analyze the uncertainties of the thermophysical properties that propagate from the uncertainty of ϕ 07 and from the Born-Oppenheimer approximation of the electron-nucleon quantum mechanical system. We correct minor errors in a previous publication [J. J. Hurly and M. R. Moldover, J. Res. Nat. Inst. Standards Technol. 105, 667 (2000)] and compare our results with selected data published after 2000. The ab initio results tabulated here can serve as standards for the measurement of thermophysical properties.

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

    Energy Technology Data Exchange (ETDEWEB)

    Chernyshev, Vladimir, E-mail: Vladimir.Chernyshev@urfu.ru; Petrov, Vladislav; Nikiforov, Anatoliy; Zakiryanov, Dmitriy [Ural Federal University, Ekaterinburg (Russian Federation)

    2015-12-07

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

  4. MoS{sub 2} on an amorphous HfO{sub 2} surface: An ab initio investigation

    Energy Technology Data Exchange (ETDEWEB)

    Scopel, W. L., E-mail: wlscopel@if.uff.br [Departamento de Física, Universidade Federal do Espírito Santo, Vitória, Brazil and Departamento de Ciências Exatas, Universidade Federal Fluminense, Volta Redonda, Rio de Janerio (Brazil); Miwa, R. H., E-mail: hiroki@infis.ufu.br; Schmidt, T. M., E-mail: tome@infis.ufu.br [Instituto de Física, Universidade Federal de Uberlândia, Uberlândia, Minas Gerais (Brazil); Venezuela, P., E-mail: vene@if.uff.br [Instituto de Física, Universidade Federal Fluminense, Niterói, Rio de Janerio (Brazil)

    2015-05-21

    The energetic stability, electronic and structural properties of MoS{sub 2} adsorbed on an amorphous a-HfO{sub 2} surface (MoS{sub 2}/HfO{sub 2}) are examined through ab initio theoretical investigations. Our total energy results indicate that the formation of MoS{sub 2}/HfO{sub 2} is an exothermic process with an adsorption energy of 34 meV/Å{sup 2}, which means that it is more stable than similar systems like graphene/HfO{sub 2} and MoS{sub 2}/SiO{sub 2}. There are no chemical bonds at the MoS{sub 2}-HfO{sub 2} interface. Upon formation of MoS{sub 2}/HfO{sub 2}, the electronic charge distribution is mostly localized at the interface region with no net charge transfer between the adsorbed MoS{sub 2} sheet and –HfO{sub 2} surface. However, the MoS{sub 2} sheet becomes n-type doped when there are oxygen vacancies in the HfO{sub 2} surface. Further investigation of the electronic distribution reveals that there are no electron- and hole-rich regions (electron-hole puddles) on the MoS{sub 2} sheet, which makes this system promising for use in high-speed nanoelectronic devices.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1996-10-01

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

  6. An Efficient Method for Electron-Atom Scattering Using Ab-initio Calculations

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Yuan; Yang, Yonggang; Xiao, Liantuan; Jia, Suotang [Shanxi University, Taiyuan (China)

    2017-02-15

    We present an efficient method based on ab-initio calculations to investigate electron-atom scatterings. Those calculations profit from methods implemented in standard quantum chemistry programs. The new approach is applied to electron-helium scattering. The results are compared with experimental and other theoretical references to demonstrate the efficiency of our method.

  7. Inelastic neutron scattering an ab-initio calculation of negative thermal expansion in Ag2O

    International Nuclear Information System (INIS)

    Gupta, M.K.; Mittal, R.; Rols, S.; Chaplot, S.L.

    2012-01-01

    The compound Ag 2 O undergoes large and isotropic negative thermal expansion over 0-500 K. We report temperature dependent inelastic neutron scattering measurements and ab-initio calculations of the phonon spectrum. The temperature dependence of the experimental phonon spectrum shows strong anharmonic nature of phonon modes of energy around 2.4 meV. The ab-initio calculations reveal that the maximum negative Grüneisen parameter, which is a measure of the relevant anharmonicity, occurs for the transverse phonon modes that involve bending motions of the Ag 4 O tetrahedra. The thermal expansion is evaluated from the ab-initio calculation of the pressure dependence of the phonon modes, and found in good agreement with available experimental data.

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

    International Nuclear Information System (INIS)

    Navratil, Petr; Quaglioni, Sofia

    2012-01-01

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

  9. Stacking stability of MoS2 bilayer: An ab initio study

    International Nuclear Information System (INIS)

    Tao Peng; Guo Huai-Hong; Yang Teng; Zhang Zhi-Dong

    2014-01-01

    The study of the stacking stability of bilayer MoS 2 is essential since a bilayer has exhibited advantages over single layer MoS 2 in many aspects for nanoelectronic applications. We explored the relative stability, optimal sliding path between different stacking orders of bilayer MoS 2 , and (especially) the effect of inter-layer stress, by combining first-principles density functional total energy calculations and the climbing-image nudge-elastic-band (CI-NEB) method. Among five typical stacking orders, which can be categorized into two kinds (I: AA, AB and II: AA', AB', A'B), we found that stacking orders with Mo and S superposing from both layers, such as AA' and AB, is more stable than the others. With smaller computational efforts than potential energy profile searching, we can study the effect of inter-layer stress on the stacking stability. Under isobaric condition, the sliding barrier increases by a few eV/(ucGPa) from AA' to AB', compared to 0.1 eV/(ucGPa) from AB to [AB]. Moreover, we found that interlayer compressive stress can help enhance the transport properties of AA'. This study can help understand why inter-layer stress by dielectric gating materials can be an effective means to improving MoS 2 on nanoelectronic applications. (condensed matter: structural, mechanical, and thermal properties)

  10. Shear stiffness in nanolaminar Ti3SiC2 challenges ab initio calculations

    International Nuclear Information System (INIS)

    Kisi, E H; Zhang, J F; Kirstein, O; Riley, D P; Styles, M J; Paradowska, A M

    2010-01-01

    Nanolaminates such as the M n+1 AX n (MAX) phases are a material class with ab initio derived elasticity tensors published for over 250 compounds. We have for the first time experimentally determined the full elasticity tensor of the archetype MAX phase, Ti 3 SiC 2 , using polycrystalline samples and in situ neutron diffraction. The experimental elastic constants show extreme shear stiffness, with c 44 more than five times greater than expected for an isotropic material. Such shear stiffness is quite rare in hexagonal materials and strongly contradicts the predictions of all published MAX phase elastic constants derived from ab initio calculations. It is concluded that second order properties such as elastic moduli derived from ab initio calculations require careful experimental verification. The diffraction technique used currently provides the only method of verification for the elasticity tensor for the majority of new materials where single crystals are not available. (fast track communication)

  11. 4He Thermophysical Properties: New Ab Initio Calculations

    Science.gov (United States)

    Hurly, John J.; Mehl, James B.

    2007-01-01

    Since 2000, atomic physicists have reduced the uncertainty of the helium-helium “ab initio” potential; for example, from approximately 0.6 % to 0.1 % at 4 bohr, and from 0.8 % to 0.1 % at 5.6 bohr. These results led us to: (1) construct a new inter-atomic potential 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

  12. Unraveling the structure of the h-BN/Rh(111) nanomesh with ab initio calculations

    International Nuclear Information System (INIS)

    Laskowski, R; Blaha, P

    2008-01-01

    The properties of a single layer of h-BN on top of a Rh(111) surface are discussed in terms of an ab initio generated force field approach as well as by direct ab initio density-functional theory (DFT) calculations. A single-layer model for the h-BN/Rh(111) nanomesh, in contrast to a previously considered (incomplete) double-layer model of h-BN, can explain the experimental data. The main focus of this work is to compare a force field approach described earlier in (Laskowski et al 2007 Phys. Rev. Lett. 98 106802) with direct ab initio calculations. The calculated geometry of the h-BN layer is very similar to the structure predicted by the force field approach. The ab initio calculated density of states projected on N-p x,y of BN corresponding to 'low' and 'high' regions with respect to the Rh surface shows a 1 eV splitting and thus explains the observed σ-band splitting. Moreover, we find good agreement between calculated and experimental scanning tunneling microscope (STM) images of this system

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

    International Nuclear Information System (INIS)

    Ishibashi, Shoji; Kohyama, Masanori

    2000-01-01

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

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

    Czech Academy of Sciences Publication Activity Database

    Gazda, Daniel; Gal, A.

    2016-01-01

    Roč. 116, č. 12 (2016), s. 122501 ISSN 0031-9007 R&D Projects: GA ČR(CZ) GA15-04301S Institutional support: RVO:61389005 Keywords : ab initio * shell model * four-body calculations Subject RIV: BE - Theoretical Physics Impact factor: 8.462, year: 2016

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

    DEFF Research Database (Denmark)

    Berg, Rolf W.

    2007-01-01

    spectroscopy and ab-initio molecular orbital calculations. A discussion is given, based mainly on some recent FT-Raman spectroscopic results on the model ionic liquid system of 1-butyl-3-methylimidazolium ([C4mim][X]) salts. The rotational isomerism of the [C4mim]þ cation is described: the presence of anti...

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

    International Nuclear Information System (INIS)

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

    2007-01-01

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

  17. Ab-initio calculations of electric field gradient in Ru compounds and ...

    Indian Academy of Sciences (India)

    S N Mishra

    2017-07-11

    Jul 11, 2017 ... with calculated electric field gradient (EFG) for a large number of Ru-based compounds. The ab-initio ... zz assumed to stem from geometric arrangement of ... tant nuclear probes for the measurements of quadrupole ... with the unit cell including the nucleus and no restriction is put on ..... The effect of on-site ...

  18. Ab-initio electronic band structure calculations for beryllium chalcogenides

    International Nuclear Information System (INIS)

    Kalpana, G.; Pari, G.; Yousuf, Mohammad

    1997-01-01

    The first principle tight-binding linear muffin-tin orbital method within the local density approximation (LDA) has been used to calculate the ground state properties, structural phase transition and pressure dependence of band gap of BeS, BeSe and BeTe. We have calculated the energy-volume relations for these compounds in the B3 and B8 phases. The calculated lattice parameters, bulk modulus and the pressure-volume relation were found to be in good agreement with the recent experimental results. The calculated B3→B8 structural transition pressure for BeS, BeSe and BeTe agree well with the recent experimental results. Our calculations show that these compounds are indirect band gap (Γ-X) semiconductors at ambient conditions. The calculated band gap values are found to be underestimated by 20-30% which is due to the usage of LDA. After the structural transition to the B8 phase, BeS continues to be indirect band gap semiconductors and ultimately above 100 GPa it metallises, BeSe and BeTe are metallic at the B3→B8 structural transition. (author)

  19. Structural determination of stable MoOx monolayers on O/Cu3Au(1 0 0): DFT calculations

    International Nuclear Information System (INIS)

    Valadares, George C.S.; Mendes, F.M.T.; Dionízio Moreira, M.; Leitão, A.A.; Niehus, H.

    2012-01-01

    Highlights: ► Molybdenum oxide is widely used in catalysis in the chemical industry. ► Recently, ultra-thin (monolayer) films of MoO x have been produced on top of O-Cu 3 Au substrates. ► XPS measurements suggest an unusual +5 charge state of the Mo cation. ► Seeking for a low-energy structure with good match to the experimental STM and XPS. ► Bader charges indicate indeed an intermediate charge state as compared to the more common Mo +4 O 2 and Mo +6 O 3 bulk oxides. -- Abstract: Using ab initio calculations based on density functional theory (DFT), we propose a geometrical structure for MoO x monolayers recently grown on O/Cu 3 Au(1 0 0) substrates. The proposed structure reproduces the p(2 × 2) symmetry found by scanning tunneling microscopy (STM) and low-energy electron diffraction (LEED), as well as the intermediate oxidation state between Mo(IV) and Mo(VI) identified by X-ray photoelectron spectroscopy (XPS). Simulated STM images assign the bright spots in the experimental images to oxygen 2p states.

  20. Amino acids interacting with defected carbon nanotubes: ab initio calculations

    Directory of Open Access Journals (Sweden)

    M. Darvish Ganji

    2016-09-01

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

  1. Thermodynamic properties of titanium from ab initio calculations

    International Nuclear Information System (INIS)

    Argaman, Uri; Makov, Guy; Eidelstein, Eitan; Levy, Ohad

    2015-01-01

    The lattice parameters, lattice stability and phonon dispersion curves of five proposed phases of Ti: α, β, γ, δ and ω are investigated within density functional theory (DFT). It is found that the sequence of high pressure phases at zero temperature is α→ω→γ→δ→β with the δ and β phases becoming degenerate at high pressure. However, the γ phase may be unstable as is reflected by the existence of imaginary values in the phonon spectra. The results of the DFT calculations are employed to estimate the entropy and free energies of the α and ω phases. It is found that converged phonon calculations lead to an entropy difference which is much smaller than previous estimates, and a much steeper α−ω phase transition line. (paper)

  2. Ab initio calculation of hyperfine splitting constants of molecules

    Science.gov (United States)

    Ohta, K.; Nakatsuji, H.; Hirao, K.; Yonezawa, T.

    1980-08-01

    Hyperfine splitting (hfs) constants of molecules, methyl, ethyl, vinyl, allyl, cyclopropyl, formyl, O3-, NH2, NO2, and NF2 radicals have been calculated by the pseudo-orbital (PO) theory, the unrestricted HF (UHF), projected UHF (PUHF) and single excitation (SE) CI theories. The pseudo-orbital (PO) theory is based on the symmetry-adapted-cluster (SAC) expansion proposed previously. Several contractions of the Gaussian basis sets of double-zeta accuracy have been examined. The UHF results were consistently too large to compare with experiments and the PUHF results were too small. For molecules studied here, the PO theory and SECI theory gave relatively close results. They were in fair agreement with experiments. The first-order spin-polarization self-consistency effect, which was shown to be important for atoms, is relatively small for the molecules. The present result also shows an importance of eliminating orbital-transformation dependence from conventional first-order perturbation calculations. The present calculations have explained well several important variations in the experimental hfs constants.

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

    Institute of Scientific and Technical Information of China (English)

    XUE Xu-Yan; WANG Chun-Lei; ZHONG Wei-Lie

    2004-01-01

    @@ The ab initio method within the local density approximation is applied to calculate cubic BaTiO3 (001) surface relaxation and rumpling for two different terminations (BaO and TiO2). Our calculations demonstrate that cubic perovskite BaTiO3 crystals possess surface polarization, accompanied by the presence of the relevant electric field.We analyse their electronic structures (band structure, density of states and the electronic density redistribution with emphasis on the covalency effects). The results are also compared with that of the previous ab initio calculations. Considerable increases of Ti-O chemical bond covalency nearby the surface have been observed.The band gap reduces especially for the TiO2 termination.

  4. Ab initio calculation of electron excitation energies in solids

    International Nuclear Information System (INIS)

    Louie, S.G.

    1996-02-01

    Progress in the first-principles calculation of electron excitation energies in solids is discussed. Quasiparticle energies are computed by expanding the electron self energy to first order in the screened Coulomb interaction in the so-called GW approximation. The method was applied to explain and predict spectroscopic properties of a variety of systems. Several illustrative applications to semiconductors, materials under pressure, chemisorption, and point defects in solids are presented. A recent reformulation of the method employing mixed- space functions and imaginary time techniques is also discussed

  5. Ab initio and relativistic DFT study of spin–rotation and NMR shielding constants in XF{sub 6} molecules, X = S, Se, Te, Mo, and W

    Energy Technology Data Exchange (ETDEWEB)

    Ruud, Kenneth [Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromsø—The Arctic University of Norway, N-9037 Tromsø (Norway); Demissie, Taye B. [Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromsø—The Arctic University of Norway, N-9037 Tromsø (Norway); Institute of Physical Chemistry, Polish Academy of Sciences, 01-224 Warszawa, Kasprzaka 44 (Poland); Jaszuński, Michał, E-mail: michal.jaszunski@icho.edu.pl [Institute of Organic Chemistry, Polish Academy of Sciences, 01-224 Warszawa, Kasprzaka 44 (Poland)

    2014-05-21

    We present an analysis of the spin–rotation and absolute shielding constants of XF{sub 6} molecules (X = S, Se, Te, Mo, W) based on ab initio coupled cluster and four-component relativistic density-functional theory (DFT) calculations. The results show that the relativistic contributions to the spin–rotation and shielding constants are large both for the heavy elements as well as for the fluorine nuclei. In most cases, incorporating the computed relativistic corrections significantly improves the agreement between our results and the well-established experimental values for the isotropic spin–rotation constants and their anisotropic components. This suggests that also for the other molecules, for which accurate and reliable experimental data are not available, reliable values of spin–rotation and absolute shielding constants were determined combining ab initio and relativistic DFT calculations. For the heavy nuclei, the breakdown of the relationship between the spin–rotation constant and the paramagnetic contribution to the shielding constant, due to relativistic effects, causes a significant error in the total absolute shielding constants.

  6. Ab Initio Calculations Of Nuclear Reactions And Exotic Nuclei

    Energy Technology Data Exchange (ETDEWEB)

    Quaglioni, S. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2014-05-05

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

  7. Ab initio MCHF structural calculations of Mg-like cerium

    Science.gov (United States)

    Wajid, Abdul; Jabeen, S.; Husain, Abid

    2018-05-01

    Energy levels and emission line wavelengths of high-Z materials are useful for impurity diagnostics in the next generation fusion devices. For this here we have calculated E1, M2 transitions, oscillator strengths, and transition probabilities for transitions among the terms belonging to the 2p63s2, 2p63s3p, 2p63p2 and 2p63s3d for the Magnesium like cerium (Ce XLVII) using the GRASP2K package based on the fully relativistic multi-configuration Dirac-Fock method. The electron correlation effects, Breit interaction and quantum electrodynamics effects to the atomic state wave functions and the corresponding energies have been taken into account.

  8. Ab Initio Calculations of Transport Properties of Vanadium Oxides

    Science.gov (United States)

    Lamsal, Chiranjivi; Ravindra, N. M.

    2018-04-01

    The temperature-dependent transport properties of vanadium oxides have been studied near the Fermi energy using the Kohn-Sham band structure approach combined with Boltzmann transport equations. V2O5 exhibits significant thermoelectric properties, which can be attributed to its layered structure and stability. Highly anisotropic electrical conduction in V2O5 is clearly manifested in the calculations. Due to specific details of the band structure and anisotropic electron-phonon interactions, maxima and crossovers are also seen in the temperature-dependent Seebeck coefficient of V2O5. During the phase transition of VO2, the Seebeck coefficient changes by 18.9 µV/K, which is close to (within 10% of) the observed discontinuity of 17.3 µV/K.

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

    International Nuclear Information System (INIS)

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

    2012-01-01

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

  10. Geometry optimization of supersymmetrical molecules in quantum chemical ab-initio calculations

    International Nuclear Information System (INIS)

    Gruenbichler, H.

    1985-01-01

    One-dimensional geometry optimizations in ab-initio SCF-calculations are investigated. It is shown, that the well known standard algorithms are sometimes too expensive and can be replaced or accompanied by more recent algorithms. Two alternatives were realized in the molecule calculating program GAUSSIAN 80, basing on the Fibonacci algorithm and Kryachco potential adjustment. The algorithms were compared in terms of accuracy of results, CPU-time used and reliability of the method. The results are presented in various tables, showing the efficiency of the various methods. A survey of the usual model potentials is given and the compatibility with ab-initio data is evaluated. (Author, shortened and translated by A.N.)

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

    DEFF Research Database (Denmark)

    Berg, Rolf W.

    2009-01-01

    spectroscopy and ab-initio molecular orbital calculations. A discussion is given, based mainly on some recent FT- Raman spectroscopic results on the model ionic liquid system of 1-butyl-3-methyl-imidazolium ([C4C1Im]+X-) salts. The rotational isomerism of the [C4C1Im]+ cation is described: the presence of anti.......3 Brief introduction to ab-initio model calculations .... 312 12.4 Case study on Raman spectroscopy and structure of imidazolium-based ionic liquids ..... 312 12.5 Raman spectra and structure of [C4C1Im]+ liquids ..... 315 12.6 Normal mode analysis and rotational isomerism of the [C4C1Im]+ cation...

  12. Ab-initio study of electronic and magnetic properties of Co-doped Mo2C monolayer

    Science.gov (United States)

    Mehta, Veenu; Tankeshwar, K.; Saini, Hardev S.

    2018-05-01

    The spin polarized density functional theory (DFT) based calculations has been performed to investigate the electronic and magnetic properties of pristine and Co-doped Mo2C using VASP code. The calculated results show that the pristine Mo2C is found to be non-magnetic whereas the Co dopant at Mo-site in the Mo2C monolayer generates the ferromagnetism in the resultant compound. The total magnetic moment of the system has been found to be 1.2µB which increases to 2.03µB as the concentration of Co increase from 3% to 8%, respectively. The electronic structure calculations of the pristine and Co-doped Mo2C show its metallic behavior which may found its application in magnetic energy storage devices, magnetic tape etc.

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

    OpenAIRE

    Berg, Rolf W.

    2009-01-01

    A review of the recent developments in the study and understanding of room temperature ionic liquids are given. An intimate picture of how and why these liquids are not crystals at ambient conditions is attempted, based on evidence from crystallographical results combined with vibrational spectroscopy and ab-initio molecular orbital calculations. A discussion is given, based mainly on some recent FT- Raman spectroscopic results on the model ionic liquid system of 1-butyl-3-methyl-imidazolium ...

  14. Raman Spectroscopy and Ab-Initio Model Calculations on Ionic Liquids:Invited Review

    OpenAIRE

    Berg, Rolf W.

    2007-01-01

    A review of the recent developments in the study and understanding of room temperature ionic liquids are given. An intimate picture of how and why these liquids are not crystals at ambient conditions is attempted, based on evidence from crystallographical results combined with vibrational spectroscopy and ab-initio molecular orbital calculations. A discussion is given, based mainly on some recent FT-Raman spectroscopic results on the model ionic liquid system of 1-butyl-3-methylimidazolium ([...

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

    DEFF Research Database (Denmark)

    Abild-Pedersen, Frank; Nørskov, Jens Kehlet; Rostrup-Nielsen, Jens

    2006-01-01

    Mechanisms and energetics of graphene growth catalyzed by nickel nanoclusters were studied using ab initio density functional theory calculations. It is demonstrated that nickel step-edge sites act as the preferential growth centers for graphene layers on the nickel surface. Carbon is transported......, and it is argued how these processes may lead to different nanofiber structures. The proposed growth model is found to be in good agreement with previous findings....

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

    Czech Academy of Sciences Publication Activity Database

    Pluhařová, Eva; Jungwirth, Pavel

    2008-01-01

    Roč. 73, 6/7 (2008), s. 733-744 ISSN 0010-0765 R&D Projects: GA MŠk LC512; GA ČR GA203/07/1006 Institutional research plan: CEZ:AV0Z40550506 Keywords : ions * water cluster * methanol * ab initio calculations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.784, year: 2008

  17. Ab initio quantum chemical calculation as a tool of evaluating diamagnetic susceptibility of magnetically levitating substances

    Energy Technology Data Exchange (ETDEWEB)

    Fujiwara, Y [Department of Mathematical and Life Sciences, Graduate School of Science, Hiroshima University, Higashi-Hiroshima, Hiroshima 739-8526 (Japan); Tanimoto, Y [Faculty of Pharmacy, Osaka Ohtani University, Nishikiorikita, Tondabayashi 584-8540 (Japan)], E-mail: fuji0710@sci.hiroshima-u.ac.jp

    2009-03-01

    On magnetic force evaluation necessary for magnetically levitated diamagnetic substances, isotropic diamagnetic susceptibility estimation by the ab initio quantum chemical calculation using Gaussian03W was verified for more than 300 molecules in a viewpoint of the accuracy in the absolute value and the calculation level affording good cost performance. From comparison, the method of B3PW91 / 6-311+G(d,p) was found to give the adequate absolute value by the relation of (observed) = (1.03 {+-} 0.005) x (calculated) - (1.22 {+-} 0.60) x 10{sup -6} in a unit of cm{sup 3} mol{sup -1} and good cost performance.

  18. Ab initio quantum chemical calculation as a tool of evaluating diamagnetic susceptibility of magnetically levitating substances

    International Nuclear Information System (INIS)

    Fujiwara, Y; Tanimoto, Y

    2009-01-01

    On magnetic force evaluation necessary for magnetically levitated diamagnetic substances, isotropic diamagnetic susceptibility estimation by the ab initio quantum chemical calculation using Gaussian03W was verified for more than 300 molecules in a viewpoint of the accuracy in the absolute value and the calculation level affording good cost performance. From comparison, the method of B3PW91 / 6-311+G(d,p) was found to give the adequate absolute value by the relation of (observed) = (1.03 ± 0.005) x (calculated) - (1.22 ± 0.60) x 10 -6 in a unit of cm 3 mol -1 and good cost performance.

  19. Pulse radiolysis and ab initio SCF MO studies of hydroxyl radical reactions with 2,2'-bipyridine and its complexes with transition metal ions

    Energy Technology Data Exchange (ETDEWEB)

    Maliyachel, A C

    1984-01-01

    In the present study, reactions of hydroxyl radical with 2,2'-bipyridine (bpy) and complexes of iron(II) and cobalt(III) containing 2,2'-bipyridine and/or cyanide as ligands have been investigated by pulse radiolysis and also by ab initio self-consistent field, molecular orbital (SCF MO) theoretical techniques for 2,2'-bipyridine and pyridines. In the pulse radiolysis experiments, the nascent products of hydroxyl radical reactions with these compounds have been characterized through their spectral and kinetic properties. All these reactions occur at near diffusion controlled rates to give transient products having absorption in the ultraviolet, visible and, in some cases, near-IR region. The primary reactions of OH are considered to take place by addition mechanisms in the cases of 2,2'-bipyridine, (Fe(bpy)/sub 3/)/sup 2 +/, (Fe(DMbpy)/sub 3/)/sup 2 +/ and (Co(bpy)/sub 3/)/sup 3 +/. With (Fe(pby)/sub 2/(CN)/sub 2/) and (Fe(bpy)(CN)/sub 4/)/sup 2 -/, both addition and charge transfer processes occur. The present study indicates that hydroxyl radical reactions with 2,2'-bipyridine can be considerably altered by complexation with metal ions such as iron(II) and cobalt(III), and the factors associated with this are discussed. In the second part of this work, ab initio SCF MO calculations have been performed for the reactions of OH with pyridine, pyridinium ion and 2,2'-bipyridine. Based on the calculated total energies for the various hydroxy radical products, the relative stability of OH addition products are found to be for pyridine, meta-C > N >> para-C > ortho-C; for pyridinium ion, meta-C >> para-C > ortho-C > N, and for 2,2'- bipyridine, C/sub 5/ > C/sub 6/ > C/sub 3/ > C/sub 4/ > N.

  20. Interrelations between EOS parameters and cohesive energy of transition metals: Thermostatistical approach, ab initio calculations and analysis of ;universality; features

    Science.gov (United States)

    Bertoldi, Dalía S.; Ramos, Susana B.; Guillermet, Armando Fernández

    2017-08-01

    We present a theoretical analysis of the equation of state (EOS) of metals using a quasi-harmonic Einstein model with a dimensionless cohesive energy versus distance function (F(z)) involving the Wigner-Seitz radius and a material-dependent scaling length, as suggested in classical works by Rose, Ferrante, Smith and collaborators. Using this model, and "universal" values for the function and its first and second derivatives at the equilibrium distance (z=0), three general interrelations between EOS parameters and the cohesive energy are obtained. The first correlation involves the bulk modulus, and the second, the thermal expansion coefficient. In order to test these results an extensive database is developed, which involves available experimental data, and results of current ab initio density-functional-theory calculations using the VASP code. In particular, the 0 K values for volume, bulk modulus, its pressure derivative, and the cohesive energy of 27 elements belonging to the first (Sc, Ti, V, Cr, Fe, Co, Ni, Cu, Zn), second (Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd) and third (Hf, Ta, W, Re, Os, Ir, Pt, Au) transition row of the Periodic Table are calculated ab initio and used to test the present results. The third correlation obtained, allows an evaluation of the third derivative of F(z) at z=0 for the current elements. With this new information, a discussion is presented of the possibility of finding a "universal" F(z) versus z function able to account accurately for the pressure derivative of the bulk modulus of the transition elements.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-07-01

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

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

    International Nuclear Information System (INIS)

    Levesque, M.

    2010-11-01

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

  3. A Review of Solid-Solution Models of High-Entropy Alloys Based on Ab Initio Calculations

    Directory of Open Access Journals (Sweden)

    Fuyang Tian

    2017-11-01

    Full Text Available Similar to the importance of XRD in experiments, ab initio calculations, as a powerful tool, have been applied to predict the new potential materials and investigate the intrinsic properties of materials in theory. As a typical solid-solution material, the large degree of uncertainty of high-entropy alloys (HEAs results in the difficulty of ab initio calculations application to HEAs. The present review focuses on the available ab initio based solid-solution models (virtual lattice approximation, coherent potential approximation, special quasirandom structure, similar local atomic environment, maximum-entropy method, and hybrid Monte Carlo/molecular dynamics and their applications and limits in single phase HEAs.

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

    Energy Technology Data Exchange (ETDEWEB)

    Quaglioni, S; Navratil, P

    2008-12-17

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

  5. Ab initio theoretical calculations of the electronic excitation energies of small water clusters.

    Science.gov (United States)

    Tachikawa, Hiroto; Yabushita, Akihiro; Kawasaki, Masahiro

    2011-12-14

    A direct ab initio molecular dynamics method has been applied to a water monomer and water clusters (H(2)O)(n) (n = 1-3) to elucidate the effects of zero-point energy (ZPE) vibration on the absorption spectra of water clusters. Static ab initio calculations without ZPE showed that the first electronic transitions of (H(2)O)(n), (1)B(1)←(1)A(1), are blue-shifted as a function of cluster size (n): 7.38 eV (n = 1), 7.58 eV (n = 2) and 8.01 eV (n = 3). The inclusion of the ZPE vibration strongly affects the excitation energies of a water dimer, and a long red-tail appears in the range of 6.42-6.90 eV due to the structural flexibility of a water dimer. The ultraviolet photodissociation of water clusters and water ice surfaces is relevant to these results.

  6. Atomic defects in monolayer WSe2 tunneling FETs studied by systematic ab initio calculations

    Science.gov (United States)

    Wu, Jixuan; Fan, Zhiqiang; Chen, Jiezhi; Jiang, Xiangwei

    2018-05-01

    Atomic defects in monolayer WSe2 tunneling FETs (TFETs) are studied through systematic ab initio calculations aiming at performance predictions and enhancements. The effects of various defect positions and different passivation atoms are characterized in WSe2 TFETs by rigorous ab initio quantum transport simulations. It is suggested that the Se vacancy (VSe) defect located in the gate-controlled channel region tends to increase the OFF current (I off), whereas it can be well suppressed by oxygen passivation. It is demonstrated that chlorine (Cl) passivation at the source-side tunneling region can largely suppress I off, leading to an impressively improved on–off ratio (I on/I off) compared with that without any defect. However, it is also observed that randomly positioned atomic defects tend to induce significant fluctuation of the TFET output. Further discussions are made with focus on the performance-variability trade-off for robust circuit design.

  7. The role of ab initio electronic structure calculations in studies of the strength of materials

    International Nuclear Information System (INIS)

    Sob, M.; Friak, M.; Legut, D.; Fiala, J.; Vitek, V.

    2004-01-01

    In this paper we give an account of applications of quantum-mechanical (first-principles) electronic structure calculations to the problem of theoretical tensile strength in metals and intermetallics. First, we review previous as well as ongoing research on this subject. We then describe briefly the electronic structure calculational methods and simulation of the tensile test. This approach is then illustrated by calculations of theoretical tensile strength in iron and in the intermetallic compound Ni 3 Al. The anisotropy of calculated tensile strength is explained in terms of higher-symmetry structures encountered along the deformation paths studied. The table summarizing values of theoretical tensile strengths calculated up to now is presented and the role of ab initio electronic structure calculations in contemporary studies of the strength of material is discussed

  8. Benefits of Parallel I/O in Ab Initio Nuclear Physics Calculations

    International Nuclear Information System (INIS)

    Laghave, Nikhil; Sosonkina, Masha; Maris, Pieter; Vary, James P.

    2009-01-01

    Many modern scientific applications rely on highly parallel calculations, which scale to 10's of thousands processors. However, most applications do not concentrate on parallelizing input/output operations. In particular, sequential I/O has been identified as a bottleneck for the highly scalable MFDn (Many Fermion Dynamics for nuclear structure) code performing ab initio nuclear structure calculations. In this paper, we develop interfaces and parallel I/O procedures to use a well-known parallel I/O library in MFDn. As a result, we gain efficient input/output of large datasets along with their portability and ease of use in the downstream processing.

  9. Elasticity, electronic properties and hardness of MoC investigated by first principles calculations

    International Nuclear Information System (INIS)

    Liu, YangZhen; Jiang, YeHua; Feng, Jing; Zhou, Rong

    2013-01-01

    The crystal structure, cohesive energy, formation enthalpy, mechanical anisotropy, electronic properties and hardness of α−MoC, β−MoC and γ−MoC are investigated by the first-principles calculations. The elastic constants and the bulk moduli, shear moduli, Young's moduli are calculated. The Young's modulus values of α−MoC, β−MoC and γ−MoC are 395.6 GPa, 551.2 GPa and 399.5 GPa, respectively. The surface constructions of Young's moduli identify the mechanical anisotropy of molybdenum carbide, and the results show that anisotropy of α−MoC is stronger than others. The electronic structure indicates that the bonding behaviors of MoC are the combinations of covalent and metallic bonds. The hardness of β−MoC is obviously higher than those of α−MoC and γ−MoC

  10. Single-layer 1T‧-MoS2 under electron irradiation from ab initio molecular dynamics

    Science.gov (United States)

    Pizzochero, Michele; Yazyev, Oleg V.

    2018-04-01

    Irradiation with high-energy particles has recently emerged as an effective tool for tailoring the properties of two-dimensional transition metal dichalcogenides. In order to carry out an atomically-precise manipulation of the lattice, a detailed understanding of the beam-induced events occurring at the atomic scale is necessary. Here, we investigate the response of 1T' -MoS2 to the electron irradiation by ab initio molecular dynamics means. Our simulations suggest that an electron beam with energy smaller than 75 keV does not result in any knock-on damage. The displacement threshold energies are different for the two nonequivalent sulfur atoms in 1T' -MoS2 and strongly depend on whether the top or bottom chalcogen layer is considered. As a result, a careful tuning of the beam energy can promote the formation of ordered defects in the sample. We further discuss the effect of the electron irradiation in the neighborhood of a defective site, the mobility of the sulfur vacancies created and their tendency to aggregate. Overall, our work provides useful guidelines for the imaging and the defect engineering of 1T' -MoS2 using electron microscopy.

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Roemelt, Michael, E-mail: michael.roemelt@theochem.rub.de [Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, D-44780 Bochum, Germany and Max-Planck Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr (Germany)

    2015-07-28

    Spin Orbit Coupling (SOC) is introduced to molecular ab initio density matrix renormalization group (DMRG) calculations. In the presented scheme, one first approximates the electronic ground state and a number of excited states of the Born-Oppenheimer (BO) Hamiltonian with the aid of the DMRG algorithm. Owing to the spin-adaptation of the algorithm, the total spin S is a good quantum number for these states. After the non-relativistic DMRG calculation is finished, all magnetic sublevels of the calculated states are constructed explicitly, and the SOC operator is expanded in the resulting basis. To this end, spin orbit coupled energies and wavefunctions are obtained as eigenvalues and eigenfunctions of the full Hamiltonian matrix which is composed of the SOC operator matrix and the BO Hamiltonian matrix. This treatment corresponds to a quasi-degenerate perturbation theory approach and can be regarded as the molecular equivalent to atomic Russell-Saunders coupling. For the evaluation of SOC matrix elements, the full Breit-Pauli SOC Hamiltonian is approximated by the widely used spin-orbit mean field operator. This operator allows for an efficient use of the second quantized triplet replacement operators that are readily generated during the non-relativistic DMRG algorithm, together with the Wigner-Eckart theorem. With a set of spin-orbit coupled wavefunctions at hand, the molecular g-tensors are calculated following the scheme proposed by Gerloch and McMeeking. It interprets the effective molecular g-values as the slope of the energy difference between the lowest Kramers pair with respect to the strength of the applied magnetic field. Test calculations on a chemically relevant Mo complex demonstrate the capabilities of the presented method.

  13. Ionization energies of aqueous nucleic acids: Photoelectron spectroscopy of pyridine nucleosides and ab initio calculations

    Czech Academy of Sciences Publication Activity Database

    Slavíček, Petr; Winter, B.; Faubel, M.; Bradforth, S. E.; Jungwirth, Pavel

    2009-01-01

    Roč. 131, č. 18 (2009), s. 6460-6467 ISSN 0002-7863 R&D Projects: GA MŠk LC512; GA ČR GA203/08/0114 Grant - others:GA ČR(CZ) GP203/07/P449 Institutional research plan: CEZ:AV0Z40550506; CEZ:AV0Z40400503 Keywords : DNA bases * photoelectron spectroscopy * ab initio calculations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 8.580, year: 2009

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

    Science.gov (United States)

    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.

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

    International Nuclear Information System (INIS)

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

    1988-06-01

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

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

    Science.gov (United States)

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

    2018-06-01

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

  17. Irradiation of diffusion couples U-Mo/Al. Thermal calculation

    International Nuclear Information System (INIS)

    Fortis, Ana M.; Mirandou, Monica; Denis, Alicia C.

    2004-01-01

    The development of new low enrichment fuel elements for research reactors has lead to obtaining a number of compounds and alloys where the decrease in the enrichment is compensated by a higher uranium density in the fuel material. This has been achieved in particular with the uranium silicides dispersed in an aluminum matrix, where uranium densities about 4.8 g/cm 3 have been reached. Among the diverse candidate alloys, those of U-Mo with molybdenum content in the range 6 to 10 w % can yield, upon dispersion, to uranium densities of about 8 g/cm 3 . The first irradiation experiments employing these alloys in fuel plates, either dispersed in Al or monolithic revealed certain phenomena which are worthy of further studies. Failures have been detected apparently due to the formation of reaction products between the fissile material and the aluminum matrix, which exhibit a poor irradiation behavior. An experiment was designed which final purpose is to irradiate diffusion couples U-Mo/Al in the RA-3 reactor and to analyze the interaction zone at the working temperatures of the fuel elements. A simple device was built consisting of two Al 6063 blocks which press the U-Mo sample in between, located in an Al capsule. The ensemble is placed in a tube, which can be filled with different gases and introduced in the reactor. For safety reasons temperature predictions are necessary before performing the experiment. To this end, the COSMOS code was used. As a preliminary step and in order to test to exactness of the numerical estimations, two irradiations were performed in the RA-1 reactor with He and N 2 as transference gases. The agreement between the measured and calculated temperatures was good, particularly in the case of He and, along with the numerical predictions for the RA-3 reactor, provides a reliable basis to proceed with the following steps. (author)

  18. Identifying stereoisomers by ab-initio calculation of secondary isotope shifts on NMR chemical shieldings.

    Science.gov (United States)

    Böhm, Karl-Heinz; Banert, Klaus; Auer, Alexander A

    2014-04-23

    We present ab-initio calculations of secondary isotope effects on NMR chemical shieldings. The change of the NMR chemical shift of a certain nucleus that is observed if another nucleus is replaced by a different isotope can be calculated by computing vibrational corrections on the NMR parameters using electronic structure methods. We demonstrate that the accuracy of the computational results is sufficient to even distinguish different conformers. For this purpose, benchmark calculations for fluoro(2-2H)ethane in gauche and antiperiplanar conformation are carried out at the HF, MP2 and CCSD(T) level of theory using basis sets ranging from double- to quadruple-zeta quality. The methodology is applied to the secondary isotope shifts for 2-fluoronorbornane in order to resolve an ambiguity in the literature on the assignment of endo- and exo-2-fluoronorbornanes with deuterium substituents in endo-3 and exo-3 positions, also yielding insight into mechanistic details of the corresponding synthesis.

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

    Directory of Open Access Journals (Sweden)

    Karl-Heinz Böhm

    2014-04-01

    Full Text Available We present ab-initio calculations of secondary isotope effects on NMR chemical shieldings. The change of the NMR chemical shift of a certain nucleus that is observed if another nucleus is replaced by a different isotope can be calculated by computing vibrational corrections on the NMR parameters using electronic structure methods. We demonstrate that the accuracy of the computational results is sufficient to even distinguish different conformers. For this purpose, benchmark calculations for fluoro(2-2Hethane in gauche and antiperiplanar conformation are carried out at the HF, MP2 and CCSD(T level of theory using basis sets ranging from double- to quadruple-zeta quality. The methodology is applied to the secondary isotope shifts for 2-fluoronorbornane in order to resolve an ambiguity in the literature on the assignment of endo- and exo-2-fluoronorbornanes with deuterium substituents in endo-3 and exo-3 positions, also yielding insight into mechanistic details of the corresponding synthesis.

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

    International Nuclear Information System (INIS)

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

    2012-01-01

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

  1. An ab initio LAPW study of the α and β phases of bulk molybdenum trioxide, MoO3

    International Nuclear Information System (INIS)

    Sayede, A.D.; Amriou, T.; Pernisek, M.; Khelifa, B.; Mathieu, C.

    2005-01-01

    Structure and electronic properties of the α and β-MoO 3 , have been studied with periodic LAPW calculations. The structure and electronic properties of the α-MoO 3 are in quite agreement with experimental and previous theoretical results. The oxide is partially ionic and the symmetrically bridging oxygens exhibit more ionic feature while the terminal oxygens are more covalent. The lattice scaling of the β-MoO 3 give results in excellent agreement with the reported experimental pseudo-cubic results. It has been found from density of states (DOS) that β-MoO 3 is not fully ionic system and some covalent contributions are still appreciable. These covalent contributions to the bonding appear derisory compared to the covalent contributions of the α phase. The β-MoO 3 → α-MoO 3 transformation is explained by metal off-center displacement toward O 1 (and a little less toward O 2 ) centers which is stabilized by an increase in covalency between the Mo and oxygen atoms

  2. Possible doping strategies for MoS 2 monolayers: An ab initio study

    KAUST Repository

    Dolui, Kapildeb; Rungger, Ivan; Das Pemmaraju, Chaitanya; Sanvito, Stefano

    2013-01-01

    Density functional theory is used to systematically study the electronic properties of doped MoS2 monolayers, where the dopants are incorporated both via S/Mo substitution or as adsorbates. Among the possible substitutional dopants at the Mo site, Nb is identified as suitable p-type dopant, while Re is the donor with the lowest activation energy. When dopants are simply adsorbed on a monolayer we find that alkali metals shift the Fermi energy into the MoS2 conduction band, making the system n type. Finally, the adsorption of charged molecules is considered, mimicking an ionic liquid environment. We find that molecules adsorption can lead to both n- and p-type conductivity, depending on the charge polarity of the adsorbed species. © 2013 American Physical Society.

  3. Possible doping strategies for MoS 2 monolayers: An ab initio study

    KAUST Repository

    Dolui, Kapildeb

    2013-08-14

    Density functional theory is used to systematically study the electronic properties of doped MoS2 monolayers, where the dopants are incorporated both via S/Mo substitution or as adsorbates. Among the possible substitutional dopants at the Mo site, Nb is identified as suitable p-type dopant, while Re is the donor with the lowest activation energy. When dopants are simply adsorbed on a monolayer we find that alkali metals shift the Fermi energy into the MoS2 conduction band, making the system n type. Finally, the adsorption of charged molecules is considered, mimicking an ionic liquid environment. We find that molecules adsorption can lead to both n- and p-type conductivity, depending on the charge polarity of the adsorbed species. © 2013 American Physical Society.

  4. An ab initio study of hydrotreating of thiirene and thiirane on MoS 3 ...

    African Journals Online (AJOL)

    The catalytic site used is based on molybdenum disulfide (MoS2), which is considered ... Two steps characterise the desulfurization process: the adsorption and the ... catalytic site and molecules obtained in previous works in the EHT method.

  5. Lattice structures and electronic properties of MO/MoSe2 interface from first-principles calculations

    Science.gov (United States)

    Zhang, Yu; Tang, Fu-Ling; Xue, Hong-Tao; Lu, Wen-Jiang; Liu, Jiang-Fei; Huang, Min

    2015-02-01

    Using first-principles plane-wave calculations within density functional theory, we theoretically studied the atomic structure, bonding energy and electronic properties of the perfect Mo (110)/MoSe2 (100) interface with a lattice mismatch less than 4.2%. Compared with the perfect structure, the interface is somewhat relaxed, and its atomic positions and bond lengths change slightly. The calculated interface bonding energy is about -1.2 J/m2, indicating that this interface is very stable. The MoSe2 layer on the interface has some interface states near the Fermi level, the interface states are mainly caused by Mo 4d orbitals, while the Se atom almost have no contribution. On the interface, Mo-5s and Se-4p orbitals hybridize at about -6.5 to -5.0 eV, and Mo-4d and Se-4p orbitals hybridize at about -5.0 to -1.0 eV. These hybridizations greatly improve the bonding ability of Mo and Se atom in the interface. By Bader charge analysis, we find electron redistribution near the interface which promotes the bonding of the Mo and MoSe2 layer.

  6. Ab initio effective core potentials for molecular calculations. Potentials for main group elements Na to Bi

    International Nuclear Information System (INIS)

    Wadt, W.R.; Hay, P.J.

    1985-01-01

    A consistent set of ab initio effective core potentials (ECP) has been generated for the main group elements from Na to Bi using the procedure originally developed by Kahn. The ECP's are derived from all-electron numerical Hartree--Fock atomic wave functions and fit to analytical representations for use in molecular calculations. For Rb to Bi the ECP's are generated from the relativistic Hartree--Fock atomic wave functions of Cowan which incorporate the Darwin and mass--velocity terms. Energy-optimized valence basis sets of (3s3p) primitive Gaussians are presented for use with the ECP's. Comparisons between all-electron and valence-electron ECP calculations are presented for NaF, NaCl, Cl 2 , Cl 2 - , Br 2 , Br 2 - , and Xe 2 + . The results show that the average errors introduced by the ECP's are generally only a few percent

  7. Magnetic properties of vanadium doped CdTe: Ab initio calculations

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-04-15

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

  8. Theoretical calculations of valence states in Fe-Mo compounds

    International Nuclear Information System (INIS)

    Estrada, F; Navarro, O; Noverola, H; Suárez, J R; Avignon, M

    2014-01-01

    The half-metallic ferromagnetic double perovskite compound Sr 2 FeMoO 6 is considered as an important material for spintronic applications. It appears to be fundamental to understand the role of electronic parameters controlling the half-metallic ground state. Fe-Mo double perovskites usually present some degree of Fe/Mo disorder which generally increases with doping. In this work, we study the valence states of Fe-Mo cations in the off-stoichiometric system Sr 2 Fe 1+x Mo 1−x O 6 (−1 ≤ x ≤ 1/3) with disorder. Our results for Fe and Mo valence states are obtained using the Green functions and the renormalization perturbation expansion method. The model is based on a correlated electron picture with localized Fe-spins and conduction Mo-electrons interacting with the local spins via a double-exchange-type mechanism

  9. High pressure stability of lithium metatitanate and metazirconate: Insight from experiments & ab-initio calculations

    Science.gov (United States)

    Chitnis, Abhishek; Chakraborty, B.; Tripathi, B. M.; Tyagi, A. K.; Garg, Nandini

    2018-02-01

    Lithium metatitanate (LTO) and lithium metazirconate (LZO) are lithium rich ceramics which can be used as tritium breeder materials for thermonuclear reactors. In-situ x-ray diffraction and ab-initio studies at high pressure show that LTO has a higher bulk modulus than that of LZO. In fact these studies indicate that they are the least compressible of the known lithium rich ceramics like Li2O or Li4SiO4, which are potential candidates for blanket materials. These studies show that the TiO6 octahedra are responsible for the higher bulk modulus of LTO when compared to that of LZO. It has also been shown that the compressibility and distortion of the softer LiO6 octahedra can be controlled by altering the stacking sequence of the more rigid covalently bonded octahedra. This knowledge can be used by chemists to design new lithium based ceramics with higher bulk modulus. It was observed that LTO was stable upto 34 GPa. Ab initio DFT calculations helped to understand the anisotropy in compressibility of both LZO and LTO. This study also shows, that even though the empirical potentials developed by Vijaykumar et al. successfully determine the ambient pressure structure of lithium metatitanate, they cannot be used at non ambient conditions like high pressure [1].

  10. X-ray diffraction analysis and MO calculations of 1H-tetrazole; 1H-tetorazoru no Xsen kessho kozo kaiseki to bunshi kido keisan

    Energy Technology Data Exchange (ETDEWEB)

    Ono, Yoshio.; Akutsu, Yoshiaki.; Arai, Mitsuru.; Tamura, Masamitsu. [The University of Tokyo, Tokyo (Japan). School of Engineering; Matsunaga, Takehiro. [National Institute of Materials and Chemical Research, Tsukuba (Japan)

    1999-02-28

    The X-ray diffraction analysis and the MO calculations of 1H-tetrazole were carried out, in order to explain its high stability. From the X-ray diffraction analysis, five bonds in the ring have intermediate lengths between single and double bond lengths. Therefore, 1H-tetrazole is quite stable because of its aromaticity. The N1-C5 distance of 1.315A is significantly short. The molecular structure which was calculated by the ab initio MO calculation of one 1H-tetrazole molecule at MP2/6-31G* level, showed a good agreement with our experimental one, except for the abnormal short N1-C5 distance. From the calculations of dimers and trimers, 1H-tetrazole is shown to be stabilized by a strong intermolecular electrostatic interaction between the protons and the delocalized electrons over the ring. (author)

  11. Ab initio electronic band structure calculation of InP in the wurtzite phase

    Science.gov (United States)

    Dacal, Luis C. O.; Cantarero, Andrés

    2011-05-01

    We present ab initio calculations of the InP band structure in the wurtzite phase and compare it with that of the zincblende phase. In both calculations, we use the full potential linearized augmented plane wave method as implemented in the WIEN2k code and the modified Becke-Johnson exchange potential, which provides an improved value of the bandgap. The structural optimization of the wurtizte InP gives a=0.4150 nm, c=0.6912 nm, and an internal parameter u=0.371, showing the existence of a spontaneous polarization along the growth axis. As compared to the ideal wurtzite structure (that with the lattice parameter derived from the zincblende structure calculations), the actual wurtzite structure is compressed (-1.3%) in plane and expanded (0.7%) along the c-direction. The value of the calculated band gaps agrees well with recent optical experiments. The calculations are also consistent with the optical transitions found using polarized light.

  12. Ab-initio study of superconducting state in intercalated MoSe2 and WSe2 bilayers

    Science.gov (United States)

    Szcześniak, R.; Durajski, A. P.; Jarosik, M. W.

    2018-05-01

    A two-dimensional systems have attracted significant interest due to their outstanding physical, chemical and optoelectronic properties. This paper focuses on the detailed investigations of the electronic, phononic and superconducting properties of transition-metal dichalcogenide bilayers MSe 2 (M = Mo, W) intercalated by calcium atoms. The first-principles calculations show that (MoSe2)2Ca and (WSe2)2Ca systems exhibit metallic behavior and weak phonon-mediated superconductivity with low critical temperature of 0.51 and 0.30 K, respectively. These results confirm other theoretical predictions and suggest that the investigated materials cannot be a good candidates for a nanoscale superconductors.

  13. Organic carbonates: experiment and ab initio calculations for prediction of thermochemical properties.

    Science.gov (United States)

    Verevkin, Sergey P; Emel'yanenko, Vladimir N; Kozlova, Svetlana A

    2008-10-23

    This work has been undertaken in order to obtain data on thermodynamic properties of organic carbonates and to revise the group-additivity values necessary for predicting their standard enthalpies of formation and enthalpies of vaporization. The standard molar enthalpies of formation of dibenzyl carbonate, tert-butyl phenyl carbonate, and diphenyl carbonate were measured using combustion calorimetry. Molar enthalpies of vaporization of these compounds were obtained from the temperature dependence of the vapor pressure measured by the transpiration method. Molar enthalpy of sublimation of diphenyl carbonate was measured in the same way. Ab initio calculations of molar enthalpies of formation of organic carbonates have been performed using the G3MP2 method, and results are in excellent agreement with the available experiment. Then the group-contribution method has been developed to predict values of the enthalpies of formation and enthalpies of vaporization of organic carbonates.

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

    Directory of Open Access Journals (Sweden)

    Xiaowei Li

    2015-01-01

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

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

    Institute of Scientific and Technical Information of China (English)

    WANG Yan-hua; CHEN Xue-song; ZOU Jian-wei; YU Qing-sen

    2007-01-01

    Ab initio calculations of complexes formed between N-bromosuccinimide and a series of electron-donating groups were performed at the level of MP2/Lanl2DZ* to gain a deeper insight into the nature of the N-Br halogen stronger halogen-bonding complex than the C-Br. A comparison of neutral hydrogen bond complex series reveals that the electron-donating capacities of the atoms decrease in the order, N>O>S; O(sp3)>O(sp2), which is adequate for the C-Br halogen bonding. Interaction energies, in conjunction with the geometrical parameters show that the affinitive capacity of trihalide anions X-3 with N-bromosuccinimide are markedly lower than that of the corresponding X- with N-bromosuccinimide, even lower than those of neutral molecules with N-bromosuccinimide. AIM analyses further confirmed the above results.

  16. Dielectric Response and Born Dynamic Charge of BN Nanotubes from Ab Initio Finite Electric Field Calculations

    Science.gov (United States)

    Guo, Guang-Yu; Ishibashi, Shoji; Tamura, Tomoyuki; Terakura, Kiyoyuki

    2007-03-01

    Since the discovery of carbon nanotubes (CNTs) in 1991 by Iijima, carbon and other nanotubes have attracted considerable interest worldwide because of their unusual properties and also great potentials for technological applications. Though CNTs continue to attract great interest, other nanotubes such as BN nanotubes (BN-NTs) may offer different opportunities that CNTs cannot provide. In this contribution, we present the results of our recent systematic ab initio calculations of the static dielectric constant, electric polarizability, Born dynamical charge, electrostriction coefficient and piezoelectric constant of BN-NTs using the latest crystalline finite electric field theory [1]. [1] I. Souza, J. Iniguez, and D. Vanderbilt, Phys. Rev. Lett. 89, 117602 (2002); P. Umari and A. Pasquarello, Phys. Rev. Lett. 89, 157602 (2002).

  17. Electronic, vibrational and related properties of group IV metal oxides by ab initio calculations

    International Nuclear Information System (INIS)

    Leite Alves, H.W.; Silva, C.C.; Lino, A.T.; Borges, P.D.; Scolfaro, L.M.R.; Silva, E.F. da

    2008-01-01

    We present our theoretical results for the structural, electronic, vibrational and optical properties of MO 2 (M = Sn, Zr, Hf and Ti) obtained by first-principles calculations. Relativistic effects are demonstrated to be important for a realistic description of the detailed structure of the electronic frequency-dependent dielectric function, as well as of the carrier effective masses. Based on our results, we found that the main contribution of the high values calculated for the oxides dielectric constants arises from the vibrational properties of these oxides, and the vibrational static dielectric constant values diminish with increasing pressure

  18. Magnetization, resistivity, specific heat and ab initio calculations of Gd5Sb3.

    Science.gov (United States)

    Samatham, S Shanmukharao; Patel, Akhilesh Kumar; Lukoyanov, Alexey V; Suresh, K G

    2018-06-07

    We report on the combined results of structural, magnetic, transport and calorimetric properties of Mn5Si3-type hexagonal Gd5Sb3, together with ab-initio calculations. It exhibits a ferromagnetic (FM)-like transition at 265 K, antiferromagnetic (AFM) Néel transition at 95.5 K followed by a spin-orientation transition at 62 K. The system is found to be in AFM state down to 2 K in a field of 70 kOe. The FM-AFM phase coexistence is not noticeable despite large positive Curie-Weiss temperature (θCW = 223.5 ± 0.2 K). Instead, low-temperature AFM and high-temperature FM-like phases are separated in large temperatures. Temperature-magnetic field (H-T) phase diagram reveals field-driven complex magnetic phases. Within the AFM phase, the system is observed to undergo field-driven spin-orientation transitions. Field-induced tricritical and quantum critical points appear to be absent due to strong AFM nature and by the intervention of FM-like state between paramagnetic and AFM states, respectively. The metallic behavior of the compound is inferred from resistivity along with large Sommerfeld parameter. However, no sign of strong electron-correlations is reasoned from the Kadowaki-Wood's ratio A2 ∼ 1.9×10-6 μΩ.cm.(mol.K)2(mJ)-2, despite heavy γ. Essentially, ab initio calculations accounting for electronic correlations confirm AFM nature of low-temperature magnetic state in Gd5Sb3 and attainable FM ordering in agreement with experimental data. © 2018 IOP Publishing Ltd.

  19. WatAA: Atlas of Protein Hydration. Exploring synergies between data mining and ab initio calculations.

    Science.gov (United States)

    Černý, Jiří; Schneider, Bohdan; Biedermannová, Lada

    2017-07-14

    Water molecules represent an integral part of proteins and a key determinant of protein structure, dynamics and function. WatAA is a newly developed, web-based atlas of amino-acid hydration in proteins. The atlas provides information about the ordered first hydration shell of the most populated amino-acid conformers in proteins. The data presented in the atlas are drawn from two sources: experimental data and ab initio quantum-mechanics calculations. The experimental part is based on a data-mining study of a large set of high-resolution protein crystal structures. The crystal-derived data include 3D maps of water distribution around amino-acids and probability of occurrence of each of the identified hydration sites. The quantum mechanics calculations validate and extend this primary description by optimizing the water position for each hydration site, by providing hydrogen atom positions and by quantifying the interaction energy that stabilizes the water molecule at the particular hydration site position. The calculations show that the majority of experimentally derived hydration sites are positioned near local energy minima for water, and the calculated interaction energies help to assess the preference of water for the individual hydration sites. We propose that the atlas can be used to validate water placement in electron density maps in crystallographic refinement, to locate water molecules mediating protein-ligand interactions in drug design, and to prepare and evaluate molecular dynamics simulations. WatAA: Atlas of Protein Hydration is freely available without login at .

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

    Science.gov (United States)

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

    2018-02-01

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

  1. Structural determination of stable MoO{sub x} monolayers on O/Cu{sub 3}Au(1 0 0): DFT calculations

    Energy Technology Data Exchange (ETDEWEB)

    Valadares, George C.S., E-mail: georgevaladares@if.ufrj.br [Instituto de Fisica, Universidade Federal do Rio de Janeiro, Caixa Postal 68528, Rio de Janeiro, RJ 21941-972 (Brazil); Mendes, F.M.T. [Divisao de Metrologia de Materiais (DIMAT), Instituto Nacional de Metrologia, Normalizacao e Qualidade Industrial (Inmetro), CEP 25250-020, Xerem, Duque de Caxias, RJ (Brazil); Instituto Nacional de Tecnologia, Av. Venezuela 82, Centro, Rio de Janeiro, RJ 20081-312 (Brazil); Dionizio Moreira, M. [Divisao de Metrologia de Materiais (DIMAT), Instituto Nacional de Metrologia, Normalizacao e Qualidade Industrial (Inmetro), CEP 25250-020, Xerem, Duque de Caxias, RJ (Brazil); Universidade Federal do Triangulo Mineiro, Instituto de Ciencias Exatas, Naturais e Educacao, Av. Getulio Guarita, 159, Bairro Abadia, CEP.: 38025-180, Uberaba, MG (Brazil); Leitao, A.A. [Departamento de Quimica, Universidade Federal de Juiz de Fora, Juiz de Fora, MG 36036-330 (Brazil); Niehus, H. [Divisao de Metrologia de Materiais (DIMAT), Instituto Nacional de Metrologia, Normalizacao e Qualidade Industrial (Inmetro), CEP 25250-020, Xerem, Duque de Caxias, RJ (Brazil); Institut fuer Physik, Humboldt Universitaet zu Berlin, Newtonstrasse 15, Berlin 12489 (Germany); and others

    2012-10-08

    Highlights: Black-Right-Pointing-Pointer Molybdenum oxide is widely used in catalysis in the chemical industry. Black-Right-Pointing-Pointer Recently, ultra-thin (monolayer) films of MoO{sub x} have been produced on top of O-Cu{sub 3}Au substrates. Black-Right-Pointing-Pointer XPS measurements suggest an unusual +5 charge state of the Mo cation. Black-Right-Pointing-Pointer Seeking for a low-energy structure with good match to the experimental STM and XPS. Black-Right-Pointing-Pointer Bader charges indicate indeed an intermediate charge state as compared to the more common Mo{sup +4}O{sub 2} and Mo{sup +6}O{sub 3} bulk oxides. -- Abstract: Using ab initio calculations based on density functional theory (DFT), we propose a geometrical structure for MoO{sub x} monolayers recently grown on O/Cu{sub 3}Au(1 0 0) substrates. The proposed structure reproduces the p(2 Multiplication-Sign 2) symmetry found by scanning tunneling microscopy (STM) and low-energy electron diffraction (LEED), as well as the intermediate oxidation state between Mo(IV) and Mo(VI) identified by X-ray photoelectron spectroscopy (XPS). Simulated STM images assign the bright spots in the experimental images to oxygen 2p states.

  2. In-medium no-core shell model for ab initio nuclear structure calculations

    International Nuclear Information System (INIS)

    Gebrerufael, Eskendr

    2017-01-01

    In this work, we merge two successful ab initio nuclear-structure methods, the no-core shell model (NCSM) and the multi-reference in-medium similarity renormalization group (IM-SRG), to define a novel many-body approach for the comprehensive description of ground and excited states of closed- and open-shell medium-mass nuclei. Building on the key advantages of the two methods - the decoupling of excitations at the many-body level in the IM-SRG, and the exact diagonalization in the NCSM applicable up to medium-light nuclei - their combination enables fully converged no-core calculations for an unprecedented range of nuclei and observables at moderate computational cost. The efficiency and rapid model-space convergence of the new approach make it ideally suited for ab initio studies of ground and low-lying excited states of nuclei up to the medium-mass regime. Interactions constructed within the framework of chiral effective field theory provide an excellent opportunity to describe properties of nuclei from first principles, i.e., rooted in quantum chromodynamics, they overcome the lack of predictive power of phenomenological potentials. The hard core of these interactions causes strong short-range correlations, which we soften by using the similarity-renormalization-group transformation that accelerates the model-space convergence of many-body calculations. Three-nucleon effects, which are mandatory for the correct description of bulk properties of nuclei, are included in our calculations by using the normal-ordered two-body approximation, which has been shown to be sufficient to capture the main effects of the three-nucleon interaction. Using these interactions, we analyze energies of ground and excited states in the carbon and oxygen isotopic chains, where conventional NCSM calculations are still feasible and provide an important benchmark. Furthermore, we study the Hoyle state in 12 C - a three-alpha cluster state that cannot be converged in standard NCSM

  3. Potential Energy and Free Energy Surfaces of the Formic Acid Dimer: Correlared ab initio Calculations and Molecular Dynamics Simulations

    Czech Academy of Sciences Publication Activity Database

    Chocholoušová, Jana; Vacek, Jaroslav; Hobza, Pavel

    2002-01-01

    Roč. 4, - (2002), s. 2119-2122 ISSN 1463-9076 R&D Projects: GA MŠk LN00A032 Institutional research plan: CEZ:AV0Z4040901 Keywords : formic acid dimer * ab initio calculations * molecular dynamics simulations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.838, year: 2002

  4. Ab initio calculations of the structure and conformations of 2,6-lutidine

    International Nuclear Information System (INIS)

    Porcinai, S.; Foggi, P.

    1997-01-01

    Ab initio molecular orbital calculations at the SCF level have been utilized to determine the structure and the electronic and vibrational properties of 2,6-lutidine (2,6-dimethyl-pyridine) in the ground electronic state. Comparative calculations have been performed on the parent molecule pyridine. Structure predictions of both molecules are in good agreement with experimental data. The most stable rotamer of 2,6-lutidine has C 2v symmetry with one of the C-H bonds of both the methyl groups lying in the plane of the aromatic ring and pointing in the opposite direction with respect to the nitrogen atom. This is the result of the minimization of competing forces deriving from steric hindrance and electronic stabilization. Vibrational frequencies and oscillator strengths of C-H stretching in the fundamental region have been calculated for both pyridine and the most stable rotamer of 2,6-lutidine and compared to IR data obtained in pure liquids. The potential energy profile of the C-H bond in and out of plane has been investigated up to five times the equilibrium distance. The trend of the potential curves confirms that the C-H bond lying in the plane has a higher dissociation energy than that of the in-plane bonds as observed in experiments on vibrational overtones

  5. Vibrational spectrum, ab initio calculations, conformational stabilities and assignment of fundamentals of 1,2-dibromopropane

    Science.gov (United States)

    LaPlante, Arthur J.; Stidham, Howard D.

    2009-10-01

    The mid and far infrared and the Raman spectrum of 1,2-dibromopropane is reported in solid, liquid and gas. Several bands reported by earlier workers are not present in the spectrum of the purified material. Ab initio calculations of optimized geometry, energy, dipole moment, molar volume, vibrational spectrum and normal coordinate calculation were performed using the density functional B3LYP/6-311++g(3df,2pd), and the results used to assist a complete assignment of the 81 fundamental modes of vibrations of the three conformers of 1,2-dibromopropane. Relative energies found conformer A the lowest with G and G' at 815.6 and 871.4 cm -1 higher. The temperature dependence of the Raman spectrum of the liquid was investigated in the CCC bending region and the relative energies determined. It was found that the G' and G conformers lie 236 ± 11 and 327 ±11 cm -1, respectively above the A conformer, leading to the room temperature composition of the liquid as A, 65 ± 1; G', 21 ± 1; G, 14 ± 1%. It is apparent that the calculated highest energy conformer G' is stabilized more than the G conformer in the liquid. The G' conformer has the lowest molar volume effectively changing the interaction distance between conformers in the liquid, and enhancing the effect of its dipole moment.

  6. Ab initio calculations of the electronic structure and bonding characteristics of LaB6

    International Nuclear Information System (INIS)

    Hossain, Faruque M.; Riley, Daniel P.; Murch, Graeme E.

    2005-01-01

    Lanthanum hexaboride (LaB 6 , NIST SRM-660a) is widely used as a standard reference material for calibrating the line position and line shape parameters of powder diffraction instruments. The accuracy of this calibration technique is highly dependent on how completely the reference material is characterized. Critical to x-ray diffraction, this understanding must include the valence of the La atomic position, which in turn will influence the x-ray form factor (f) and hence the diffracted intensities. The electronic structure and bonding properties of LaB 6 have been investigated using ab initio plane-wave pseudopotential total energy calculations. The electronic properties and atomic bonding characteristics were analyzed by estimating the energy band structure and the density of states around the Fermi energy level. The calculated energy band structure is consistent with previously reported experimental findings; de Haas-van Alphen and two-dimensional angular correlation of electron-positron annihilation radiation. In addition, the bond strengths and types of atomic bonds in the LaB 6 compound were estimated by analyzing the Mulliken charge density population. The calculated result revealed the coexistence of covalent, ionic, and metallic bonding in the LaB 6 system and partially explains its high efficiency as a thermionic emitter

  7. Ab initio calculations and experimental measurement of the deuterium quadrupole coupling constant in Na2PDO3

    International Nuclear Information System (INIS)

    Trudeau, J.D.; Schwartz, J.L.; Farrar, T.C.

    1991-01-01

    The deuterium quadrupole coupling constant, χ D , in the PDO 3 2- anion has been measured in solution by NMR spin-lattice (T 1 ) relaxation time measurements and it has been calculated via ab initio methods. The experimental value of 94.7 ± 0.5 kHz is in excellent agreement with the ab initio value of 95.0 kHz. The activation energy for the ion reorientation is 2.23 ± 0.01 kJ mol -1

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

    Science.gov (United States)

    Tossell, J. A.

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

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

    International Nuclear Information System (INIS)

    Navratil, Petr

    2004-01-01

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

  10. Au55, a stable glassy cluster: results of ab initio calculations

    Directory of Open Access Journals (Sweden)

    Dieter Vollath

    2017-10-01

    Full Text Available Structure and properties of small nanoparticles are still under discussion. Moreover, some thermodynamic properties and the structural behavior still remain partially unknown. One of the best investigated nanoparticles is the Au55 cluster, which has been analyzed experimentally and theoretically. However, up to now, the results of these studies are still inconsistent. Consequently, we have carried out the present ab initio study of the Au55 cluster, using up-to-date computational concepts, in order to clarify these issues. Our calculations have confirmed the experimental result that the thermodynamically most stable structure is not crystalline, but it is glassy. The non-crystalline structure of this cluster was validated by comparison of the coordination numbers with those of a crystalline cluster. It was found that, in contrast to bulk materials, glass formation is connected to an energy release that is close to the melting enthalpy of bulk gold. Additionally, the surface energy of this cluster was calculated using two different theoretical approaches resulting in values close to the surface energy for bulk gold. It shall be emphasized that it is now possible to give a confidence interval for the value of the surface energy.

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

    Science.gov (United States)

    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.

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

    International Nuclear Information System (INIS)

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

    2010-01-01

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

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

    International Nuclear Information System (INIS)

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

    2014-01-01

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

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

    Science.gov (United States)

    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.

  15. Ab-initio calculation of quasi-particle bandstructure, exciton binding energies and dielectric properties of polythiophene

    NARCIS (Netherlands)

    van der Horst, J.W.; Bobbert, P.A.; Bobbert, Peter A.; Michels, M.A.J.; Brocks, G.; Kelly, Paul J.

    1999-01-01

    We use the ab-initio many-body GW method to calculate the quasi-particle spectrum of polythiophene. For the isolated chain, we find a large increase of the gap compared to DFT-LDA calculations (1.2 eV). The result (4.1 eV) exceeds experimental values, due to the absence of long-range screening in

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

    Energy Technology Data Exchange (ETDEWEB)

    Borges, P. D., E-mail: pdborges@gmail.com, E-mail: lscolfaro@txstate.edu; Scolfaro, L., E-mail: pdborges@gmail.com, E-mail: lscolfaro@txstate.edu [Department of Physics, Texas State University, San Marcos, Texas 78666 (United States)

    2014-12-14

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

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

    Directory of Open Access Journals (Sweden)

    Hirokazu Takaki

    2014-01-01

    Full Text Available We present an efficient computation technique for ab-initio electron transport calculations based on density functional theory and the nonequilibrium Green’s function formalism for application to heterostructures with two-dimensional (2D interfaces. The computational load for constructing the Green’s functions, which depends not only on the energy but also on the 2D Bloch wave vector along the interfaces and is thus catastrophically heavy, is circumvented by parallel computational techniques with the message passing interface, which divides the calculations of the Green’s functions with respect to energy and wave vectors. To demonstrate the computational efficiency of the present code, we perform ab-initio electron transport calculations of Al(100-Si(100-Al(100 heterostructures, one of the most typical metal-semiconductor-metal systems, and show their transmission spectra, density of states (DOSs, and dependence on the thickness of the Si layers.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-06-09

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

  19. Electronic structure of polycrystalline cadmium dichloride studied by X-ray spectroscopies and ab initio calculations

    International Nuclear Information System (INIS)

    Demchenko, I.N.; Chernyshova, M.; Stolte, W.C.; Speaks, D.T.; Derkachova, A.

    2012-01-01

    The electronic structure of cadmium dichloride has been studied by X-ray absorption near edge structure (XANES) and, for the first time, by resonant inelastic X-ray scattering (RIXS) at the Cl K edge. Good agreement was obtained between the non-resonant X-ray emission (XES) along with XANES experimental spectra and the calculated Cl 3p local partial density of states (DOS). The calculations were performed using the full-potential linearized-augmented-plane-wave with the local orbitals (FP-(L)APW l o) method utilized in the WIEN2k code. It was shown that the position of the RIXS band in CdCl 2 follows a linear dispersion according to the Raman–Stokes law if the excitation energy is tuned below the absorption threshold. The situation changes for core excitation above the photoabsorption threshold where the dispersion relation is split into two branches. The position of the resonant contribution does not depend on the excitation energy, while the excitonic sideband follows the Raman–Stoke law. Combined XANES and RIXS measurements compared to calculated band structure allowed us to determine the direct band gap of CdCl 2 to be at 5.7 ± 0.05 eV. -- Highlights: ► XANES at the K edge of Cl and related emission KV band interpreted within the ab initio DFT formalism. ► Two dominant contributions observed in RIXS data: the resonant and the excitonic ones. ► The dispersion relation below the absorption threshold follows Raman–Stokes law. ► Dispersion above the threshold splits into two qualitatively different relations. ► Overlapping of XAS spectrum with RIXS one makes possible to estimate direct band gap value to be 5.7 eV.

  20. Tuning the Electronic Properties, Effective Mass and Carrier Mobility of MoS2 Monolayer by Strain Engineering: First-Principle Calculations

    Science.gov (United States)

    Phuc, Huynh V.; Hieu, Nguyen N.; Hoi, Bui D.; Hieu, Nguyen V.; Thu, Tran V.; Hung, Nguyen M.; Ilyasov, Victor V.; Poklonski, Nikolai A.; Nguyen, Chuong V.

    2018-01-01

    In this paper, we studied the electronic properties, effective masses, and carrier mobility of monolayer MoS_2 using density functional theory calculations. The carrier mobility was considered by means of ab initio calculations using the Boltzmann transport equation coupled with deformation potential theory. The effects of mechanical biaxial strain on the electronic properties, effective mass, and carrier mobility of monolayer MoS_2 were also investigated. It is demonstrated that the electronic properties, such as band structure and density of state, of monolayer MoS_2 are very sensitive to biaxial strain, leading to a direct-indirect transition in semiconductor monolayer MoS_2. Moreover, we found that the carrier mobility and effective mass can be enhanced significantly by biaxial strain and by lowering temperature. The electron mobility increases over 12 times with a biaxial strain of 10%, while the carrier mobility gradually decreases with increasing temperature. These results are very useful for the future nanotechnology, and they make monolayer MoS_2 a promising candidate for application in nanoelectronic and optoelectronic devices.

  1. Characterization of adsorbed water in MIL-53(Al) by FTIR spectroscopy and ab-initio calculations.

    Science.gov (United States)

    Salazar, J M; Weber, G; Simon, J M; Bezverkhyy, I; Bellat, J P

    2015-03-28

    Here, we report ab-initio calculations developed with a twofold purpose: understand how adsorbed water molecules alter the infrared spectrum of the metal-organic framework MIL-53(Al) and to investigate which are the associated physico-chemical processes. The analyzed structures are the two anhydrous narrow (np⊘) and large (lp⊘) pore forms and the hydrated narrow pore form (np-H2O) of the MIL-53(Al). For these structures, we determined their corresponding infrared spectra (FTIR) and we identified the vibrational modes associated to the dominant spectral lines. We show that wagging and scissoring modes of CO2 give flexibility to the structure for facilitating the lp⊘- np⊘ transition. In our studies, this transition is identified by eight vibrational modes including the δCH(18a) vibrational mode currently used to identify the mentioned transition. We report an exhaustive band identification of the infrared spectra associated to the analyzed structures. Moreover, the FTIR for the np-H2O structure allowed us to identify four types of water molecules linked to the host structure by one to three hydrogen bonds.

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

    DEFF Research Database (Denmark)

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

    2011-01-01

    The red dye Sudan I was investigated by Raman spectroscopy using different excitation wavelengths (1064, 532 and 244 nm). A calculation of the Raman spectrum based on quantum mechanical ab initio density functional theory (DFT) was made using the RB3LYP method with the 3-21G and 6-311+G(d,p) basis...... of the Sudan I molecule was involved in the majority of the vibrations through N N and C–N stretching and various bending modes. Low-intensity bands in the lower wavenumber range (at about 721, 616, 463 and 218 cm−1) were selectively enhanced by the resonance Raman effect when using the 532 nm excitation line....... Comparison was made with other azo dyes in the literature on natural, abundant plant pigments. The results show that there is a possibility in foodstuff analysis to distinguish Sudan I from other dyes by using Raman spectroscopy with more than one laser wavelength for resonance enhancement of the different...

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

    Directory of Open Access Journals (Sweden)

    Lei Li

    2015-01-01

    Full Text Available The ab initio calculations about the properties of the interstitials doping in the rutile TiO2 and their impact on the transport coefficients are reported. As the doping of the Zr or Ti interstitials in the TiO2, the lattice Ti4+ ions acquire the excess electrons so reduced to the Ti3+ or Ti2+ ions. However, the Cu interstitials could not lose enough electrons to reduce the lattice Ti4+ ions. Furthermore, the Ti or Cu interstitials in the ZrO2 also are unable to promote the lattice Zr4+ ions to form the lattice Zr3+ or Zr2+ ions. The high transport coefficients are observed in the defected TiO2 with the Ti or Zr interstitials as the high concentration of the Ti3+ or Ti2+ ions. So, the Zr interstitials are the favorable choice for the extra-doping to improve the transport properties in the TiO2-based resistive random access memory.

  4. Asymmetrical distorted structure, dynamics, and reactions of the silacyclohexane and related radical cations: ESR and ab-initio MO study

    International Nuclear Information System (INIS)

    Komaguchi, Kenji; Shiotani, Masaru; Ishikawa, Mitsuo

    1995-01-01

    The σ-type radical cations generated by one electron oxidation of the saturated hydrocarbon have been attracted much attention because of their fundamental importance as primary reactant species in radiation chemistry. Our studies on σ-type radical cations were recently extended to the silacyclohexane (cSiC5), silacyclopentane (cSiC4), and silacyclobutane (cSiC3) radical cations. Their electronic structure, dynamics, and reactions were investigated by means of low temperature matrix isolation ESR technique combined with ionizing radiation (γ-rays from 60 Co). In the preceding paper, the 1-methylsilacyclohexane (1-Me-cSiC5) radical cation has been found to take an asymmetrically distorted C 1 structure with one of two Si-C bonds elongated in which the unpaired electron mainly resides ( 2 A in C 1 ). This conclusion was based on the 4.2 K ESR spectra of radical cations of selectively deuteriated and/or methylsubstituted silacyclohexanes, i.e., cSiC5-2,2,6,6-d 4 + , 1-Me-cSiC5 + , 1-Me-cSiC5-2,2-d 2 + , 1-Me-cSiC5-2,2,6,6-d 4 + , 1,1-Me 2 -cSiC5 + , and 4,4-Me 2 -cSiC5 + , in a frozen CF 3 -cC 6 F 11 matrix. Here we report further experimental and theoretical results on 1-methylsilacyclohexane radical cation, especially on the ab initio MO results and matrix effects on the structural distortion, as well as thermal reactions of the radical cations. The results will make it clear that the distorted C 1 structure of the 1-Me-cSiC5 + is the intrinsic nature at the ground electronic state. (J.P.N.)

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

    International Nuclear Information System (INIS)

    Laghave, Nikhil

    2010-01-01

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

  6. Ab initio calculation of intermolecular potentials for dimer Cl_2-Cl_2 and prediction of second virial coefficients

    International Nuclear Information System (INIS)

    Nguyen Thanh Duoc; Nguyen Thi Ai Nhung; Tran Duong; Pham Van Tat

    2015-01-01

    The results presented in this paper are the ab initio intermolecular potentials and the second virial coefficient, B_2 (T) of the dimer Cl_2-Cl_2. These ab initio potentials were proposed by the quantum chemical calculations at high level of theory CCSD(T) with basis sets of Dunning valence correlation-consistent aug-cc-pVmZ (m = 2, 3); these results were extrapolated to complete basis set limit aug-cc-pV23Z. The ab initio energies of complete basis set limit aug-cc-pV23Z resulted from the exponential extrapolation were used to construct the 5-site pair potential functions. The second virial coefficients for this dimer were predicted from those with four-dimensional integration. The second virial coefficients were also corrected to first-order quantum effects. The results turn out to be in good agreement with experimental data, if available, or with those from empirical correlation. The quality of ab initio 5-site potentials proved the reliability for prediction of molecular thermodynamic properties. (author)

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

    Czech Academy of Sciences Publication Activity Database

    Čársky, Petr

    2010-01-01

    Roč. 43, č. 17 (2010), s. 175204 ISSN 0953-4075 R&D Projects: GA MŠk OC09079; GA MŠk(CZ) OC10046; GA ČR GA202/08/0631 Institutional research plan: CEZ:AV0Z40400503 Keywords : ab initio calculations * electron scattering * polyatomic molecules Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.902, year: 2010

  8. Application of Ab Initio Electronic Structure Calculations in Construction of Phase Diagrams of Metallic Systems with Complex Phases

    Czech Academy of Sciences Publication Activity Database

    Šob, Mojmír; Kroupa, Aleš; Pavlů, Jana; Vřešťál, Jan

    2009-01-01

    Roč. 150, č. 1 (2009), s. 1-28 ISSN 1012-0394 R&D Projects: GA MŠk OC 147; GA ČR GA106/07/1078 Institutional research plan: CEZ:AV0Z20410507 Keywords : Ab initio calculations * CALPHAD method * Laves phases * sigma phase * ternary systems * super-austenitic steels Subject RIV: BM - Solid Matter Physics ; Magnetism

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

    Czech Academy of Sciences Publication Activity Database

    Čurík, Roman; Šulc, M.

    2010-01-01

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

  10. Investigation on electronic and magnetic properties of Mn2NiAl by ab initio calculations and Monte Carlo simulations

    International Nuclear Information System (INIS)

    Masrour, R.; Jabar, A.; Hlil, E.K.; Hamedoun, M.; Benyoussef, A.; Hourmatallah, A.; Rezzouk, A.; Bouslykhane, K.; Benzakour, N.

    2017-01-01

    Self-consistent ab initio calculations, based on Density Functional Theory (DFT) approach and using Full potential Linear Augmented Plane Wave (FLAPW) method, are performed to investigate both electronic and magnetic properties of the Mn 2 NiAl. Magnetic moment considered to lie along (001) axes are computed. Obtained data from ab initio calculations are used as input for Monte Carlo simulations to compute other magnetic parameters. Also, the magnetic properties of Mn 2 NiAl are studied using the Monte Carlo simulations. The variation of magnetization and magnetic susceptibility with the reduced temperature of Mn 2 NiAl are investigated. The transition temperature of this system is deduced for different values exchange interaction and crystal field. The thermal total magnetization has been obtained, and the magnetic hysteresis cycle is established. The total magnetic moment is superior to those obtained by the other method and is mainly determined by the antiparallel aligned Mn I , Mn II and Ni spin moments. The superparamagnetic phase is found at the neighborhood of transition temperature. - Highlights: • Ab initio calculations are used to study magnetic and electronic properties of Mn 2 NiX. • The transition temperature of Mn 2 NiX is established. • The magnetic hysteresis cycle of M n2 NiX (X = Al, Ga, In, Sn) is deduced. • The magnetic coercive field of Mn 2 NiX (X = Al, Ga, In, Sn) is given.

  11. [Mo2(CN)11]:5- A detailed description of ligand-field spectra and magnetic properties by first-principles calculations.

    Science.gov (United States)

    Hendrickx, Marc F A; Clima, S; Chibotaru, L F; Ceulemans, A

    2005-10-06

    An ab initio multiconfigurational approach has been used to calculate the ligand-field spectrum and magnetic properties of the title cyano-bridged dinuclear molybdenum complex. The rather large magnetic coupling parameter J for a single cyano bridge, as derived experimentally for this complex by susceptibility measurements, is confirmed to a high degree of accuracy by our CASPT2 calculations. Its electronic structure is rationalized in terms of spin-spin coupling between the two constituent hexacyano-monomolybdate complexes. An in-depth analysis on the basis of Anderson's kinetic exchange theory provides a qualitative picture of the calculated CASSCF antiferromagnetic ground-state eigenvector in the Mo dimer. Dynamic electron correlations as incorporated into our first-principles calculations by means of the CASPT2 method are essential to obtain quantitative agreement between theory and experiment.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-05-21

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

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

    International Nuclear Information System (INIS)

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

    2015-01-01

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

  14. Force fields for silicas and aluminophosphates based on ab initio calculations

    NARCIS (Netherlands)

    Beest, van B.W.H.; Kramer, G.J.; Santen, van R.A.

    1990-01-01

    Authors address the problem of finding interat. force fields for silicas from ab initio calcns. on small clusters. The force field cannot be detd. from cluster data alone; incorporation of bulk-system information into the force field remains essential. Bearing this in mind, authors derive a force

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

    Czech Academy of Sciences Publication Activity Database

    Ma, D.; Friák, Martin; von Pezold, J.; Raabe, D.; Neugebauer, J.

    2015-01-01

    Roč. 85, FEB (2015), s. 53-66 ISSN 1359-6454 Institutional support: RVO:68081723 Keywords : Solid-solution strengthening * DFT * Peierls–Nabarro model * Ab initio * Al alloys Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 5.058, year: 2015

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

    DEFF Research Database (Denmark)

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

    2012-01-01

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

  17. The elastic and thermodynamic properties of ZrMo2 from first principles calculations

    International Nuclear Information System (INIS)

    Liu, Xian-Kun; Zhou, Wei; Zheng, Zhou; Peng, Shu-Ming

    2014-01-01

    Highlights: • Elastic and thermodynamic properties of ZrMo 2 under high temperature and pressure are calculated by first principles. • Mechanical stability is testified from elastic constants at zero pressure. • Phonon scattering of ZrMo 2 under different temperature are obtained. - Abstract: The elastic and thermodynamic properties of ZrMo 2 under high temperature and pressure are investigated by first-principles calculations based on pseudopotential plane-wave density functional theory (DFT) within the generalized gradient approximation (GGA) and quasi-harmonic Debye model. The calculated lattice parameters are in good agreement with the available experimental data. The calculated elastic constants of ZrMo 2 increase monotonically with increasing pressure, and the relationship between the elastic constants and pressure show that ZrMo 2 satisfies the mechanical stability criteria under applied pressure (0–65 GPa). The related mechanical properties such as bulk modulus (B), shear modulus (G), Young’s modulus (E), and Poisson’s ratio (v) are also studied for polycrystalline of ZrMo 2 . The calculated B/G value shows that ZrMo 2 behaves in a ductile manner, and higher pressure can significantly improve the ductility of ZrMo 2 . The pressure and temperature dependencies of the relative volume, the bulk modulus, the elastic constants, the heat capacity and the thermal expansion coefficient, as well as the Grüneisen parameters are obtained and discussed by the quasi-harmonic Debye model in the ranges of 0–1800 K and 0–65 GPa

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

    International Nuclear Information System (INIS)

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

    2009-01-01

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

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

    Czech Academy of Sciences Publication Activity Database

    Milko, Petr; Kalus, R.; Paidarová, Ivana; Hrušák, Jan; Gadéa, F. X.

    -, 23 June (2009), s. 25 ISSN 1432-2234 R&D Projects: GA AV ČR IAA100400501 Institutional research plan: CEZ:AV0Z40400503 Keywords : cluster modelling * rare gas ions * ab initio potential energie * evaporation energies Subject RIV: CF - Physical ; Theoretical Chemistry http://www.springerlink.com/content/100493/?Content+Status=Accepted&sort=p_OnlineDate&sortorder=desc&v=condensed&o=20

  20. Effect of Cu Alloying on S Poisoning of Ni Surfaces and Nanoparticle Morphologies Using Ab-Initio Thermodynamics Calculations.

    Science.gov (United States)

    Kim, Ji-Su; Kim, Byung-Kook; Kim, Yeong-Cheol

    2015-10-01

    We investigated the effect of Cu alloying on S poisoning of Ni surfaces and nanoparticle morphologies using ab-initio thermodynamics calculations. Based on the Cu segregation energy and the S adsorption energy, the surface energy and nanoparticle morphology of pure Ni, pure Cu, and NiCu alloys were evaluated as functions of the chemical potential of S and the surface orientations of (100), (110), and (111). The constructed nanoparticle morphology was varied as a function of chemical potential of S. We find that the Cu added to Ni for NiCu alloys is strongly segregated into the top surface, and increases the S tolerance of the NiCu nanoparticles.

  1. Elasticity and wave velocity in fcc iron (austenite) at elevated temperatures - Experimental verification of ab-initio calculations.

    Science.gov (United States)

    Hutchinson, Bevis; Malmström, Mikael; Lönnqvist, Johan; Bate, Pete; Ehteshami, Hossein; Korzhavyi, Pavel A

    2018-07-01

    High temperature crystal elasticity constants for face centred cubic austenite are important for interpreting the ultrasonic properties of iron and steels but cannot be determined by normal single crystal methods. Values of these constants have recently been calculated using an ab-initio approach and the present work was carried out to test their applicability using laser-ultrasonic measurements. Steel samples having a known texture were examined at temperatures between 800 °C and 1100 °C to measure the velocity of longitudinal P-waves which were found to be in good agreement with modelled values. Copyright © 2018 Elsevier B.V. All rights reserved.

  2. Role of interlayer coupling in ultra thin MoS2

    KAUST Repository

    Cheng, Yingchun; Zhu, Zhiyong; Schwingenschlö gl, Udo

    2012-01-01

    The effects of interlayer coupling on the vibrational and electronic properties of ultra thin MoS 2 were studied by ab initio calculations. For smaller slab thickness, the interlayer distance is significantly elongated because of reduced interlayer

  3. Ab initio CASSCF study of the electronic structure of the transition-metal alkylidene-like complexes Mo-M[prime]H[sub 2] (M[prime] = C, Si, Ge, and Sn)

    Energy Technology Data Exchange (ETDEWEB)

    Marquez, A.; Sanz, J.F. (Universidad de Sevilla (Spain))

    1992-12-02

    Experimental and theoretical research on the electronic and geometric structure of transition-metal-carbenes and -alkylidenes is an active area in chemistry nowadays due to their potential activity in catalysis and in organic and organometallic synthesis. A theoretical investigation of the electronic structure of the high-valent, transition-metal, alkylidene-like complexes MoM[prime]H[sub 2] (M[prime] = C, Si, Ge, and Sn) is reported. Based on ab initio calculations carried out at the complete active space multiconfiguration self-consistent field (CASSCF) level, the molecular structure of the ground state and some low-lying excited states have been determined. For M[prime] = C, Si, and Ge, the ground state has C[sub 2v] symmetry (state [sup 5]B[sub 1]) and corresponds to pairing each electron of the M[prime]H[sub 2] triplet [sup 3]B[sub 1] with an electron of Mo ([sup 7]S). In the case of MoSnH[sub 2], the lowest state is bent (C[sub s] symmetry, state [sup 7]A[prime]), the out-of-plane angle being 68[degrees], and dissociates into SnH[sub 2] ([sup 1]A[sub 1]) + Mo ([sup 7]S). Dissociation energies, potential energy profiles for the dissociation, harmonic force constants in terms of internal symmetry coordinates, and vibrational frequencies are reported. The comparison of these properties with those of their pentacarbonylated homologous (CO)[sub 5]M[double bond]M[prime]H[sub 2] shows that the carbene-like (Fischer) type of complexation is stronger than the alkylidene-like one (Schrock). 28 refs., 4 figs., 6 tabs.

  4. Ab initio effective core potentials for molecular calculations. Potentials for the transition metal atoms Sc to Hg

    International Nuclear Information System (INIS)

    Hay, P.J.; Wadt, W.R.

    1985-01-01

    Ab initio effective core potentials (ECP's) have been generated to replace the Coulomb, exchange, and core-orthogonality effects of the chemically inert core electron in the transition metal atoms Sc to Hg. For the second and third transition series relative ECP's have been generated which also incorporate the mass--velocity and Darwin relativistic effects into the potential. The ab initio ECP's should facilitate valence electron calculations on molecules containing transition-metal atoms with accuracies approaching all-electron calculations at a fraction of the computational cost. Analytic fits to the potentials are presented for use in multicenter integral evaluation. Gaussian orbital valence basis sets are developed for the (3d,4s,4p), (4d,5s,5p), and (5d,6s,6p) orbitals of the first, second, and third transition series atoms, respectively. All-electron and valence-electron atomic excitation energies are also compared for the low-lying states of Sc--Hg, and the valence-electron calculations are found to reproduce the all-electron excitation energies (typically within a few tenths of an eV)

  5. Semiempirical and ab initio calculations versus dynamic NMR on conformational analysis of cyclohexyl-N,N-dimethylcarbamate

    Directory of Open Access Journals (Sweden)

    Basso Ernani A.

    2001-01-01

    Full Text Available Axial-equatorial conformational proportions for cyclohexyl-N,N-dimethyl carbamate have been measured, for the first time, by the Eliel method, ¹H and 13C dynamic nuclear magnetic resonance (DNMR. The results were compared against those determined by theoretical calculations. By the Eliel method at least five experimentally independent measureables were used in CCl4, CDCl3 and CD3CN. The ¹H and 13C low temperature experiments were performed in CF2Br2/CD2Cl2 . Semiempirical methods MNDO, AM1 and PM3 and ab initio molecular orbital calculations at the HF/STO-3G and HF/6-31G(d,p levels have been performed on the axial and equatorial conformers populations. All applied methods correctly predict the equatorial conformer preference over the axial one. The resulting equatorial preferences determined by NMR data and theoretical calculations are in good agreement.

  6. Structure impact on the thermal and electronic properties of bismuth telluride by ab-initio and molecular dynamics calculations

    International Nuclear Information System (INIS)

    Termentzidis, K; Pokropivny, A; Xiong, S-Y; Chumakov, Y; Volz, S; Woda, M; Cortona, P

    2012-01-01

    We use molecular dynamics and ab-initio methods to predict the thermal and electronic properties of new materials with high figures of merit. The simulated systems are bulk bismuth tellurides with antisite and vacancy defects. Optimizations of the materials under investigation are performed by the SIESTA code for subsequent calculations of force constants, electronic properties, and Seebeck coefficients. The prediction of the thermal conductivity is made by Non-Equilibrium Molecular Dynamics (NEMD) using the LAMMPS code. The thermal conductivity of bulk bismuth telluride with different stoichiometry and with a number of substitution defects is calculated. We have found that the thermal conductivity can be decreased by 60% by introducing vacancy defects. The calculated thermal conductivities for the different structures are compared with the available experimental and theoretical results.

  7. Prediction of high-temperature point defect formation in TiO2 from combined ab initio and thermodynamic calculations

    International Nuclear Information System (INIS)

    He, J.; Behera, R.K.; Finnis, M.W.; Li, X.; Dickey, E.C.; Phillpot, S.R.; Sinnott, S.B.

    2007-01-01

    A computational approach that integrates ab initio electronic structure and thermodynamic calculations is used to determine point defect stability in rutile TiO 2 over a range of temperatures, oxygen partial pressures and stoichiometries. Both donors (titanium interstitials and oxygen vacancies) and acceptors (titanium vacancies) are predicted to have shallow defect transition levels in the electronic-structure calculations. The resulting defect formation energies for all possible charge states are then used in thermodynamic calculations to predict the influence of temperature and oxygen partial pressure on the relative stabilities of the point defects. Their ordering is found to be the same as temperature increases and oxygen partial pressure decreases: titanium vacancy → oxygen vacancy → titanium interstitial. The charges on these defects, however, are quite sensitive to the Fermi level. Finally, the combined formation energies of point defect complexes, including Schottky, Frenkel and anti-Frenkel defects, are predicted to limit the further formation of point defects

  8. Using Ab-Initio Calculations to Appraise Stm-Based - and Kink-Formation Energies

    Science.gov (United States)

    Feibelman, Peter J.

    2001-03-01

    Ab-initio total energies can and should be used to test the typically model-dependent results of interpreting STM morphologies. The benefits of such tests are illustrated here by ab-initio energies of step- and kink-formation on Pb and Pt(111) which show that the STM-based values of the kink energies must be revised. On Pt(111), the computed kink-energies for (100)- and (111)-microfacet steps are about 0.25 and 0.18 eV. These results imply a specific ratio of formation energies for the two step types, namely 1.14, in excellent agreement with experiment. If kink-formation actually cost the same energy on the two step types, an inference drawn from scanning probe observations of step wandering,(M. Giesen et al., Surf. Sci. 366, 229(1996).) this ratio ought to be 1. In the case of Pb(111), though computed energies to form (100)- and (111)-microfacet steps agree with measurement, the ab-initio kink-formation energies for the two step types, 41 and 60 meV, are 40-50% below experimental values drawn from STM images.(K. Arenhold et al., Surf. Sci. 424, 271(1999).) The discrepancy results from interpreting the images with a step-stiffness vs. kink-energy relation appropriate to (100) but not (111) surfaces. Good agreement is found when proper account of the trigonal symmetry of Pb(111) is taken in reinterpreting the step-stiffness data.

  9. Double ionization in Helium. Ab initio calculations beyond the one dimensional approximation

    International Nuclear Information System (INIS)

    Camilo Ruiz; Luis Plaja; Luis Roso; Andreas Becker

    2006-01-01

    Complete test of publication follows. We present ab-initio computations of the ionization of two-electron atoms by short pulses of coherent radiation beyond the one-dimensional approximation. In the model the electron correlation is included in its full dimensionality, while the center-of-mass motion is restricted along the polarization axis. We show some result for Non Sequential Double Ionization (NSDI) as well as for SDI for high intensity low IR frequency. Some recent applications for this correlated system is also presented.

  10. Oxide nanostructures on a Nb surface and related systems: experiments and ab initio calculations

    International Nuclear Information System (INIS)

    Kuznetsov, Mikhail V; Razinkin, A S; Ivanovskii, Alexander L

    2011-01-01

    This review discusses the state of the art in two related research areas: the surfaces of niobium and of its related group IV-VI transition metals, and surface (primarily oxide) nanostructures that form on niobium (and group IV-VI d-metals) due to gas adsorption or impurity diffusion from the bulk. Experimental (X-ray photoelectron spectroscopy, photoelectron diffraction, scanning tunneling microscopy) and theoretical (ab initio simulation) results on d-metal surfaces are summarized and reviewed. (reviews of topical problems)

  11. Introducing DInaMo: A Package for Calculating Protein Circular Dichroism Using Classical Electromagnetic Theory

    Directory of Open Access Journals (Sweden)

    Igor V. Uporov

    2015-09-01

    Full Text Available The dipole interaction model is a classical electromagnetic theory for calculating circular dichroism (CD resulting from the π-π* transitions of amides. The theoretical model, pioneered by J. Applequist, is assembled into a package, DInaMo, written in Fortran allowing for treatment of proteins. DInaMo reads Protein Data Bank formatted files of structures generated by molecular mechanics or reconstructed secondary structures. Crystal structures cannot be used directly with DInaMo; they either need to be rebuilt with idealized bond angles and lengths, or they need to be energy minimized to adjust bond lengths and bond angles because it is common for crystal structure geometries to have slightly short bond lengths, and DInaMo is sensitive to this. DInaMo reduces all the amide chromophores to points with anisotropic polarizability and all nonchromophoric aliphatic atoms including hydrogens to points with isotropic polarizability; all other atoms are ignored. By determining the interactions among the chromophoric and nonchromophoric parts of the molecule using empirically derived polarizabilities, the rotational and dipole strengths are determined leading to the calculation of CD. Furthermore, ignoring hydrogens bound to methyl groups is initially explored and proves to be a good approximation. Theoretical calculations on 24 proteins agree with experiment showing bands with similar morphology and maxima.

  12. Substituent Inductive Effects on the Electrochemical Oxidation of Flavonoids Studied by Square Wave Voltammetry and Ab Initio Calculations.

    Science.gov (United States)

    Arroyo-Currás, Netzahualcóyotl; Rosas-García, Víctor M; Videa, Marcelo

    2016-10-27

    Flavonoids are natural products commonly found in the human diet that show antioxidant, anti-inflammatory and anti-hepatotoxic activities. These nutraceutical properties may relate to the electrochemical activity of flavonoids. To increase the understanding of structure-electrochemical activity relations and the inductive effects that OH substituents have on the redox potential of flavonoids, we carried out square-wave voltammetry experiments and ab initio calculations of eight flavonoids selected following a systematic variation in the number of hydroxyl substituents and their location on the flavan backbone: three flavonols, three anthocyanidins, one anthocyanin and the flavonoid backbone flavone. We compared the effect that the number of -OH groups in the ring B of flavan has on the oxidation potential of the flavonoids considered, finding linear correlations for both flavonols and anthocyanidins ( R 2 = 0.98 ). We analyzed the effects that position and number of -OH substituents have on electron density distributions via ab initio quantum chemical calculations. We present direct correlations between structural features and oxidation potentials that provide a deeper insight into the redox chemistry of these molecules.

  13. Substrate Screening Effects in ab initio Many-body Green's Function Calculations of Doped Graphene on SiC

    Science.gov (United States)

    Vigil-Fowler, Derek; Lischner, Johannes; Louie, Steven

    2013-03-01

    Understanding many-electron interaction effects and the influence of the substrate in graphene-on-substrate systems is of great theoretical and practical interest. Thus far, both model Hamiltonian and ab initio GW calculations for the quasiparticle properties of such systems have employed crude models for the effect of the substrate, often approximating the complicated substrate dielectric matrix by a single constant. We develop a method in which the spatially-dependent dielectric matrix of the substrate (e.g., SiC) is incorporated into that of doped graphene to obtain an accurate total dielectric matrix. We present ab initio GW + cumulant expansion calculations, showing that both the cumulant expansion (to include higher-order electron correlations) and a proper account of the substrate screening are needed to achieve agreement with features seen in ARPES. We discuss how this methodology could be used in other systems. This work was supported by NSF Grant No. DMR10-1006184 and U.S. DOE Contract No. DE-AC02-05CH11231. Computational resources have been provided by the NERSC and NICS. D.V-F. acknowledges funding from the DOD's NDSEG fellowship.

  14. A computer calculation of the ternary Mo-Pd-Rh phase diagram

    International Nuclear Information System (INIS)

    Guerler, R.; Pratt, J.N.

    1993-01-01

    Thermodynamic coefficients for the phases in the binary Mo-Pd, Pd-Rh and Mo-Rh systems were derived by the assessment of the available experimental data using the binary Lukas optimization program. The resulting coefficients were first successfully utilised in reestablishing the binaries. The coefficients thus obtained in the binary computation were combined with ternary descriptions to compute ternary isothermal sections. Although no ternary interaction term was involved in the construction of the isotherms, the section calculated at 1373 K is found to be consistent with the experimentally established isothermal section at the same temperature. The location of three-phase field (bcc+hcp+fcc) and phase boundaries in both isotherms are matching reasonably well. Combining only binary coefficients of these phases, it is possible to construct reasonable isothermal sections at different temperatures. Following this conclusion, isothermal sections ranging from 1373 to 2673 K of the ternary Mo-Pd-Rh system were calculated. (orig.)

  15. Ab initio calculation of the shear viscosity of neon in the liquid and hypercritical state over a wide pressure and temperature range

    Science.gov (United States)

    Eggenberger, Rolf; Gerber, Stefan; Huber, Hanspeter; Searles, Debra; Welker, Marc

    1992-08-01

    The shear viscosity is calculated ab initio for the liquid and hypercritical state, i.e. a previously published potential for Ne 2, obtained from ab initio calculations including electron correlation, is used in classical equilibrium molecular dynamics simulations to obtain the shear viscosity from a Green-Kubo integral. The quality of the results is quite uniform over a large pressure range up to 1000 MPa and a wide temperature range from 26 to 600 K. In most cases the calculated shear viscosity deviates by less than 10% from the experimental value, in general the error being only a few percent.

  16. Electric field gradient in FeTiO3 by nuclear magnetic resonance and ab initio calculations.

    Science.gov (United States)

    Procházka, V; Stěpánková, H; Chlan, V; Tuček, J; Cuda, J; Kouřil, K; Filip, J; Zbořil, R

    2011-05-25

    Temperature dependence of nuclear magnetic resonance (NMR) spectra of (47)Ti and (49)Ti in polycrystalline ilmenite FeTiO(3) was measured in the range from 5 to 300 K under an external magnetic field of 9.401 T. NMR spectra collected between 300 and 77 K exhibit a resolved quadrupole splitting. The electric field gradient (EFG) tensor was evaluated for Ti nuclei and the ratio of (47)Ti and (49)Ti nuclear quadrupole moments was refined during the fitting procedure. Below 77 K, the fine structure of quadrupole splitting disappears due to the enormous increase of anisotropy. As a counterpart, ab initio calculations were performed using full potential augmented plane waves + local orbitals. The calculated EFG tensors for Ti and Fe were compared to the experimental ones evaluated from NMR and the Mössbauer spectroscopy experiments.

  17. All-electron ab initio calculations of YBa2Cu3O7 with self-consistence crystal field

    Institute of Scientific and Technical Information of China (English)

    刘洪霖; 陈念贻

    1995-01-01

    The quantum chemical calculations of cluster YBa2Cu3O7 considering all electrons have been per-formed by using the ab initio HF method with self-consistence crystal field.A Hartree-Fork surface potentialis proposed to make an asymmetric duster model possess a relatively symmetric potential field and to obtaina relatively symmetric electronic structure,electronic distributions,frontier orbitals,and bond order,etc.Thesuggestions that there exists a covalent bonding complex,[CuO2-O-CuO-O-Cu2]6,8-,in the cell unit ofthe crystal,and the cell units are connected with each other by ionic bonds along the c direction of the crys-tal lattice are offered based on the chemical bonding characteristics from the calculated results.The importantcontribution of the apical oxygen to superconductivities is emphasized as well.

  18. Ab initio calculations of dissociative excitation of water and methane molecules upon electron impact at low energies

    International Nuclear Information System (INIS)

    Gil, T.J.; McCurdy, C.W.; Rescigno, T.N.; Lengsfield, B.H. III

    1994-01-01

    The authors are reporting results of ab-initio calculations of electron-impact excitation of water and methane occurring at scattering energies up to 60 eV. The authors consider dissociative excited states of both systems since the understanding of their chemistry has considerable importance in plasma technology and atmospheric research. In the case of methane the authors are dealing with the promotion of a valence electron into Rydberg orbitals, while in water the excited states have one electron in an antibonding unoccupied valence orbital and support Feshbach resonances. The authors discuss issues related to convergence of the close-coupling expansion in the case of Rydberg excitation, where the authors have coupled up to 16 channels. The practical realization of the calculation within the framework of the complex Kohn variational principle represents merging of quantum chemistry and quantum scattering theory and is also discussed

  19. Ab-initio calculations of Co-based diluted magnetic semiconductors Cd 1-xCoxX (X=S, Se, Te)

    KAUST Repository

    Saeed, Yasir; Nazir, Safdar; Shaukat, Ali; Reshak, A. H.

    2010-01-01

    Ab-initio calculations are performed to investigate the structural, electronic and magnetic properties of spin-polarized diluted magnetic semiconductors composed of IIVI compounds Cd1-xCoxX (X=S, Se, Te) at x=0.25. From the calculated results

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

    International Nuclear Information System (INIS)

    Wimmer, E

    2008-01-01

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

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

    Science.gov (United States)

    Wimmer, E.

    2008-02-01

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

  2. Trends in magnetism of free Rh clusters via relativistic ab-initio calculations.

    Science.gov (United States)

    Šipr, O; Ebert, H; Minár, J

    2015-02-11

    A fully relativistic ab-initio study on free Rh clusters of 13-135 atoms is performed to identify general trends concerning their magnetism and to check whether concepts which proved to be useful in interpreting magnetism of 3d metals are applicable to magnetism of 4d systems. We found that there is no systematic relation between local magnetic moments and coordination numbers. On the other hand, the Stoner model appears well-suited both as a criterion for the onset of magnetism and as a guide for the dependence of local magnetic moments on the site-resolved density of states at the Fermi level. Large orbital magnetic moments antiparallel to spin magnetic moments were found for some sites. The intra-atomic magnetic dipole Tz term can be quite large at certain sites but as a whole it is unlikely to affect the interpretation of x-ray magnetic circular dichroism experiments based on the sum rules.

  3. Ab initio molecular dynamics, iterative methods and multiscale approaches in electronic structure calculations

    International Nuclear Information System (INIS)

    Bernholc, J.

    1998-01-01

    The field of computational materials physics has grown very quickly in the past decade, and it is now possible to simulate properties of complex materials completely from first principles. The presentation has mostly focused on first-principles dynamic simulations. Such simulations have been pioneered by Car and Parrinello, who introduced a method for performing realistic simulations within the context of density functional theory. The Car-Parrinello method and related plane wave approaches are reviewed in depth. The Car-Parrinello method was reviewed and illustrated with several applications: the dynamics of the C 60 solid, diffusion across Si steps, and computing free energy differences. Alternative ab initio simulation schemes, which use preconditioned conjugate gradient techniques for energy minimization and dynamics were also discussed

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

    Directory of Open Access Journals (Sweden)

    K. A. Pestka II

    2011-09-01

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

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

    International Nuclear Information System (INIS)

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

    2017-01-01

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

  6. Optical properties of Nb and Mo calculated from augmented-plane-wave band structures

    International Nuclear Information System (INIS)

    Pickett, W.E.; Allen, P.B.

    1975-01-01

    Nonrelativistic band calculations of Mattheiss for Nb and Petroff and Viswanathan for Mo are used to calculate the imaginary part epsilon 2 of the dielectric function for these metals. The structure resulting from interband transitions in the frequency range 0.1--0.5 Ry is found to give fairly good agreement with experiment. The calculation indicates that structure in epsilon 2 can arise from transitions away from symmetry points and lines in the Brillouin zone. The difficulty in distinguishing between the direct and indirect transition models for epsilon 2 is shown to arise from a lack of strong optical critical points. Predictions of the rigid-band model for the optical properties of Nb-Mo alloys are presented

  7. Mechanical Calculations on U-Mo Dispersion fuel plates with MAIA

    International Nuclear Information System (INIS)

    Marelle, V.; Huet, F.; Lemoine, P.

    2005-01-01

    CEA has developed a 2D thermo-mechanical code, called MAIA, for modelling the behaviour of U-Mo dispersion fuel. MAIA uses a finite element method for the resolution of the thermal and mechanical problems. Physical models, issued of the DOE-ANL code PLATE, evaluate the fission products swelling and the volume fraction of the interaction between U-Mo and Al. They allow establishing strains in the meat imposed as loading for the mechanical calculation. MAIA has been validated on the irradiations IRIS 1 and RERTR-3 and a rather good agreement is obtained with post irradiation examinations. MAIA is used to calculate the last irradiation of the French UMo group, IRIS 2. MAIA predicts a maximum temperature of 112 deg. C and meat swelling of 16%. Mechanical calculations are finally performed to evaluate the sensitivity to some mechanical hypotheses such as constitutive laws and the way the meat swelling is applied. (author)

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

    International Nuclear Information System (INIS)

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

    2008-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-06-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Orlando, Roberto, E-mail: roberto.orlando@unito.it; Erba, Alessandro; Dovesi, Roberto [Dipartimento di Chimica, Università di Torino and NIS, Nanostructured Interfaces and Surfaces, Centre of Excellence, Via P. Giuria 7, 10125 Torino (Italy); De La Pierre, Marco [Dipartimento di Chimica, Università di Torino and NIS, Nanostructured Interfaces and Surfaces, Centre of Excellence, Via P. Giuria 7, 10125 Torino (Italy); Nanochemistry Research Institute, Department of Chemistry, Curtin University, GPO Box U1987, Perth, WA 6845 (Australia); Zicovich-Wilson, Claudio M. [Facultad de Ciencias, Universidad Autónoma del Estado de Morelos, Av. Universidad, 1001, Col. Chamilpa, 62209 Cuernavaca (Morelos) (Mexico)

    2014-09-14

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

  11. Ab initio electronic structure calculations for Mn linear chains deposited on CuN/Cu(001) surfaces

    International Nuclear Information System (INIS)

    Barral, Maria Andrea; Weht, Ruben; Lozano, Gustavo; Maria Llois, Ana

    2007-01-01

    In a recent experiment, scanning tunneling microscopy has been used to obtain a direct probe of the magnetic interaction in linear manganese chains arranged by atomic manipulation on thin insulating copper nitride islands grown on Cu(001). The local spin excitation spectra of these chains have been measured with inelastic electron tunneling spectroscopy. Analyzing the spectroscopic results with a Heisenberg Hamiltonian the interatomic coupling strength within the chains has been obtained. It has been found that the coupling strength depends on the deposition sites of the Mn atoms on the islands. In this contribution, we perform ab initio calculations for different arrangements of infinite Mn chains on CuN in order to understand the influence of the environment on the value of the magnetic interactions

  12. Electronic Structure of Hydrogenated and Surface-Modified GaAs Nanocrystals: Ab Initio Calculations

    Directory of Open Access Journals (Sweden)

    Hamsa Naji Nasir

    2012-01-01

    Full Text Available Two methods are used to simulate electronic structure of gallium arsenide nanocrystals. The cluster full geometrical optimization procedure which is suitable for small nanocrystals and large unit cell that simulates specific parts of larger nanocrystals preferably core part as in the present work. Because of symmetry consideration, large unit cells can reach sizes that are beyond the capabilities of first method. The two methods use ab initio Hartree-Fock and density functional theory, respectively. The results show that both energy gap and lattice constant decrease in their value as the nanocrystals grow in size. The inclusion of surface part in the first method makes valence band width wider than in large unit cell method that simulates the core part only. This is attributed to the broken symmetry and surface passivating atoms that split surface degenerate states and adds new levels inside and around the valence band. Bond length and tetrahedral angle result from full geometrical optimization indicate good convergence to the ideal zincblende structure at the centre of hydrogenated nanocrystal. This convergence supports large unit cell methodology. Existence of oxygen atoms at nanocrystal surface melts down density of states and reduces energy gap.

  13. Electron ejection cross sections in electron and ion impact ionization: Ab initio and semiempirical calculations

    International Nuclear Information System (INIS)

    Manson, S.T.; Miller, J.H.; Pacific Northwest Lab., Richland, WA)

    1983-01-01

    Ionization cross sections for heavy ions and electrons incident on various atoms and molecules are required in the modeling of the interaction of radiation with matter. For each case, the energy distribution of secondary electrons (the single differential cross section, SDCS) is needed over a broad range of projectile and secondary electron (delta-ray) energies. In many cases the energy and angular distribution of secondary electrons (the double differential cross section, DDCS) is also necessary. Clearly, it would be desirable to have laboratory SDCS and DDCS measurements for all of the cases required. For a variety of reasons, this is not yet possible. Thus, one must turn elsewhere to obtain the needed cross sections. In this paper, we discuss cross sections obtained in two different ways; ab initio theory based on the first Born approximation, and a semi-empirical method based on the Bethe-Born Approximation. In both cases, results on helium will be presented since the largest amount of data is available in this case. Applications of both methods to other target species are given in the references. The accuracy of the methods and plans for the near future are also discussed. 23 references, 6 figures

  14. Efficacy of the semiempirical sparkle model as compared to ECP ab-initio calculations for the prediction of ligand field parameters of europium (III) complexes

    International Nuclear Information System (INIS)

    Freire, Ricardo O.; Rocha, Gerd B.; Albuquerque, Rodrigo Q.; Simas, Alfredo M.

    2005-01-01

    The second version of the sparkle model for the calculation of lanthanide complexes (SMLC II) as well as ab-initio calculations (HF/STO-3G and HF/3-21G) have been used to calculate the geometries of a series of europium (III) complexes with different coordination numbers (CN=7, 8 and 9), ligating atoms (O and N) and ligands (mono, bi and polydentate). The so-called ligand field parameters, Bqk's, have been calculated from both SMLC II and ab-initio optimized structures and compared to the ones calculated from crystallographic data. The results show that the SMLC II model represents a significant improvement over the previous version (SMLC) and has given good results when compared to ab-initio methods, which demand a much higher computational effort. Indeed, ab-initio methods take around a hundred times more computing time than SMLC. As such, our results indicate that our sparkle model can be a very useful and a fast tool when applied to the prediction of both ground state geometries and ligand field parameters of europium (III) complexes

  15. Ab initio calculation on the low-lying excited states of Si2+ cation including spin–orbit coupling

    International Nuclear Information System (INIS)

    Liu, Yanlei; Zhai, Hongsheng; Zhang, Xiaomei; Liu, Yufang

    2013-01-01

    Highlights: • 24 Λ–S states are correlated to the dissociation limit of Si( 3 P g ) + Si + ( 2 P u ) are first reported. • The dissociation energies of the calculated electronic states are predicted in our work. • It is first time that the entire 54 Ω states generated from the 24 Λ–S states have been studied. • PECs of Λ–S and Ω states are depicted with the aid of avoided crossing rule between the same symmetry. - Abstract: Ab initio all-electron relativistic calculations of the low-lying excited states of Si 2 + have been performed at MRCI+Q/AVQZ level. The calculated electronic states, including 12 doublet and 12 quartet Λ–S states, are correlated to the dissociation limit of Si( 3 P g ) + Si + ( 2 P u ). Spin–orbit interaction is taken into account via the state interaction approach with the full Breit-Pauli Hamiltonian, which causes the entire 24 Λ–S states to split into 54 Ω states. This is the first time that spin–orbit coupling (SOC) calculation has been performed on Si 2 + . The obtained potential energy curves (PECs) of Λ–S and Ω states are respectively depicted with the aid of the avoided crossing rule between the same symmetry. The spectroscopic constants of the bound Λ–S and Ω states are determined, and excellent agreements with the latest theoretical results are achieved

  16. Calculation of thermodynamic equilibrium between bcc disordered solid solutions U and Mo

    International Nuclear Information System (INIS)

    Alonso, Paula R.; Rubiolo, Gerardo H.

    2003-01-01

    There is actually an interest to develop a new fuel with higher density for research reactors. Fuel plates would be obtained by dispersion, a method that requires both a very dense fuel dispersant (>15.0 g U/cm 3 ) and a very high volume loading of the dispersant (>55%). Dispersants based in gamma (BCC) stabilized uranium alloys are being investigated, as they are able to reach uranium densities of 17.0 g U/cm 3 . Among them, we focus in U(Mo) bcc solid solutions with the addition of ternary elements to stabilize gamma phase. Transition metals, 4d and 5d, of groups VII and VIII are good candidates for the ternary alloy U - Mo - X. Their relative power to stabilize gamma phase seems to be in close relation with bonding energies between atoms in the alloy. A first approach to the calculation of these energies has been performed by the semi empiric method of Miedema where only bonds between pairs are considered, neglecting ternary and quaternary bonds. There is also a lack of information concerning solubilities of the ternary elements in the ternary cubic phase. In this work we aim to calculate bonding energies between atoms in the alloy using a cluster expansion of the formation energy (T=0 K) of a series of bcc ordered compounds in the systems U-Mo-X. Then the calculation of the equilibrium phase diagram by the Cluster Variation Method will be done (CVM). We show here the first part of the investigation devoted to calculation of phases equilibria in the U Mo system Formation energies of the ordered compounds were obtained by the first principles methods TB-LMTO-ASA and FP-LAPW. Another set of bonding energies was calculated in order to fit the known experimental diagram and new formation energies for the ordered compounds were derived from them. Discrepancies between both sets are discussed. (author)

  17. Ab initio determination of the novel perovskite-related structure of La7Mo7O30 from powder diffraction

    International Nuclear Information System (INIS)

    Goutenoire, F.; Retoux, R.; Lacorre, P.

    1999-01-01

    A new mixed valence molybdate, La 7 Mo 7 O 30 , first prepared by high energy ball milling, has been successfully synthesized by controlled hydrogen reduction of La 2 Mo 2 O 9 . Its original crystal structure was determined from X-ray and neutron powder diffraction (space group R 3 ; a = b = 17.0051(2) angstrom, c = 6.8607(1) angstrom; Z = 3; reliability factors: R p = 0.081, R wp = 0.091, χ 2 = 3.1, R Bragg = 0.049, R F = 0.033). It consists in the hexagonal stacking of individual cylinders of perovskite-type arrangement. These cylinders are built up from perovskite cages sharing corners in trans-position along their diagonal axis. Two different mixed-valence molybdenum sites coexist, with more (Mo +5.75 ) or less (Mo +4.5 ) distorted octahedral environments. Lanthanum atoms are located within the perovskite cages and around them, very close to their regular positions in the perovskite structure. Lanthanum and molybdenum atoms thus form two rows of almost perfect cubes, shifted from each other by c/2. An electron microscopy study revealed the defect-free cationic and octahedral arrangements in the (a,b) plane

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

    DEFF Research Database (Denmark)

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

    1986-01-01

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

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

    Czech Academy of Sciences Publication Activity Database

    Chalupský, Jakub; Rokob, Tibor András; Kurashige, Y.; Yanai, T.; Solomon, E. I.; Rulíšek, Lubomír; Srnec, Martin

    2014-01-01

    Roč. 136, č. 45 (2014), s. 15977-15991 ISSN 0002-7863 R&D Projects: GA ČR(CZ) GA14-31419S Institutional support: RVO:61388963 ; RVO:61388955 Keywords : DMRG-CASPT2 * ab initio calculations * reaction mechanisms Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 12.113, year: 2014

  20. Molecular Structure of 3,3-Diethylpenthane (Tetraethylmethane) in the Gas Phase As Determined by Electron Diffraction and ab Initio Calculations

    Czech Academy of Sciences Publication Activity Database

    Adler, R. W.; Allen, P. R.; Hnyk, Drahomír; Rankin, D. W. H.; Robertson, H. E.; Smart, B. A.; Gillespie, R. J.; Bytheway, I.

    1999-01-01

    Roč. 64, č. 12 (1999), s. 4226-4232 ISSN 0022-3263 Institutional research plan: CEZ:AV0Z4032918 Keywords : structure * initio calculations * 3,3-Diethylpentane Subject RIV: CC - Organic Chemistry Impact factor: 3.440, year: 1999

  1. Conformational and vibrational analysis of 5-hydroxy 2-nitrobenzaldehyde by AB initio hartree-fock, density functional theory calculations

    International Nuclear Information System (INIS)

    Cinakli, S.; Sert, Y.; Boeyuekata, M.; Ucun, F.

    2010-01-01

    The vibrational spectra of benzaldehyde and its derivatives have been studied earlier. The substitution of a functional group changes the spectra markedly. Recent spectroscopic studies of the benzaldehyde and their derivatives have been motivated because the vibrational spectra are very useful for understanding of specific biological process and in the analysis of relatively complex systems. The optimized molecular structure, vibrational frequencies and corresponding vibrational assignments, the total energy calculations, relative energies, the mean vibrational deviations of the two planar O-cis and O-trans roomers of 5-Hydroxy 2-nitrobenzaldehydes have been calculated using ab initio Hartree Fock (HF) and Density Functional Theory (B3LYP) with 6-311++G(d,p) basis set. All computations have been performed on personal computer using the Gaussian 03 program package. The calculations were adapted to Cs symmetries of all the molecules. The O-trans rotomers with lower energy of all the molecules have been found as preferential rotomers in the ground state.

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

    International Nuclear Information System (INIS)

    Saha, H.P.

    1993-01-01

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

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

    DEFF Research Database (Denmark)

    Åstrand, Per-Olof; Ramanujam, P.S.; Hvilsted, Søren

    2000-01-01

    Electronic excitation energies of 16 azobenzene dyes have been calculated by ab initio methods within the second-order polarization propagator approximation (SOPPA). Good agreement with expriment is found for the lowest singlet and triplet states for both the trans- and cis-azobenzene molecules......, the experimental singlet π → π* transitions are reproduced for a set of azobenzene dyes with different electron donor and acceptor groups and the correct shifts in excitation energy are obtained for the different substituents. It has also been demonstrated that ab initio methods can be used to determine suitable...

  4. Tunable redox potential of nonmetal doped monolayer MoS{sub 2}: First principle calculations

    Energy Technology Data Exchange (ETDEWEB)

    Lu, S. [Center for Coordination Bond Engineering, China Jiliang University (China); Li, C., E-mail: canli1983@gmail.com [Center for Coordination Bond Engineering, China Jiliang University (China); School of Materials Science and Engineering, China Jiliang University (China); Zhao, Y.F.; Gong, Y.Y.; Niu, L.Y.; Liu, X.J. [Center for Coordination Bond Engineering, China Jiliang University (China)

    2016-10-30

    Graphical abstract: Both E{sub CBM} and E{sub VBM} values are affected by the chemical valences of dopants, which also affect the redox potentials of specimens. Compared to the pristine monolayer MoS{sub 2}, the nonmetal ions with odd chemical valences [monovalent (H{sup +}, F{sup –}, Cl{sup –}, Br{sup –} and I{sup –}), trivalent (N{sup 3–}, P{sup 3–} and As{sup 3–}) and pentavalence (B{sup 5–})] enhance the oxidation potential and reduce the reduction potential of specimens, but the nonmetal ions with even chemical valences [divalent (O{sup 2–}, Se{sup 2–} and Te{sup 2–}) and quadravalent (C{sup 4–} and Si{sup 4–})] have the opposite effects on the redox potentials. Display Omitted - Highlights: • The newly formed chemical bonds affect the electronic distribution around the dopants and the nearby Mo atoms. • Compared to pristine monolayer MoS{sub 2}, the nonmetal ions with odd (even) chemical valences enhance (reduce) the oxidation potential and reduce (enhance) the reduction potential of specimens. • The lone pair electrons in nonmetal ions with odd chemical valences extra interact with the Mo ions which reduces the E{sub CBM} and E{sub VBM} values of specimens. - Abstract: Doping is an effective method to alter the electronic behavior of materials by forming new chemical bonds and bringing bond relaxation. With this aid of first principle calculations, the crystal configuration and electronic properties of monolayer MoS{sub 2} have been modulated by the nonmetal (NM) dopants (H, B, C, N, O, F, Si, P, Cl, As, Se, Br, Te and I), and the thermodynamic stability depending on the preparation conditions (Mo-rich and S-rich conditions) were discussed. Results shown that, the NM dopants substituted preferentially for S under Mo-rich condition, the electronic distribution around the dopants and the nearby Mo atoms are changed by the new formed Mo-NM bonds and bands relaxation. Compared to pristine monolayer MoS{sub 2}, the NM ions with odd

  5. Ab initio calculation of conformation and vibrational spectrum for the pyrosulfate ion

    DEFF Research Database (Denmark)

    Dyekjær, Jane Dannow; Berg, Rolf W.; Johansen, Helge

    2003-01-01

    Theoretical calculations have been performed and applied to determine the most likely geometry for the pyrosulfate ion. The main question was to determine as to whether the system has C-2 or C-2, conformation. The present study favors C-2 symmetry. Bond lengths and angles have been calculated for...

  6. Ab initio calculations on collisions of low energy electrons with polyatomic molecules

    International Nuclear Information System (INIS)

    Rescigno, T.N.

    1991-01-01

    The Kohn variational method is one of simplest, and oldest, techniques for performing scattering calculations. Nevertheless, a number of formal problems, as well as practical difficulties associated with the computation of certain required matrix elements, delayed its application to electron--molecule scattering problems for many years. This paper will describe the recent theoretical and computational developments that have made the ''complex'' Kohn variational method a practical tool for carrying out calculations of low energy electron--molecule scattering. Recent calculations on a number of target molecules will also be summarized. 41 refs., 7 figs

  7. Ab initio quantum chemical calculations of the interaction between radioactive elements and imidazolium based ionic liquids

    Science.gov (United States)

    Saravanan, A. V. Sai; Abishek, B.; Anantharaj, R.

    2018-04-01

    The fundamental natures of the molecular level interaction and charge transfer between specific radioactive elements and ionic liquids of 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide ([BMIM]+[NTf2]-), 1-Butyl-3-methylimidazolium ethylsulfate ([BMIM]+[ES]-) and 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]+[BF4]-) were investigated utilising HF theory and B3LYP hybrid DFT. The ambiguity in reaction mechanism of the interacting species dictates to employ Effective Core Potential (ECP) basis sets such as UGBS, SDD, and SDDAll to account for the relativistic effects of deep core electrons in the system involving potential, heavy and hazardous radioactive elements present in nuclear waste. The SCF energy convergence of each system validates the characterisation of the molecular orbitals as a linear combination of atomic orbitals utilising fixed MO coefficients and the optimized geometry of each system is visualised based on which Mulliken partial charge analysis is carried out to account for the polarising behaviour of the radioactive element and charge transfer between the IL phase by comparison with the bare IL species.

  8. Ab initio MO study on the thermal stability of 1-phenyl-1H-tetrazoles; Hikeikenteki bunshi kidoho ni yoru 1-Ph-1H tetorazoru yudotai no netsu anteisei hyoka ni kansuru kenkyu

    Energy Technology Data Exchange (ETDEWEB)

    Ono, Yoshio.; Akutsu, Yoshiaki.; Arai, Mitsuru.; Tamura, Masamitsu. [The University of Tokyo, Tokyo (Japan). School of Engineering; Matsunaga, Takehiro. [National Institute of Materials and Chemical Research, Tsukuba (Japan)

    1999-06-30

    Ab initio MO calculations of 1-phenyl-1H-tetrazoles were carried out, in order to explain a substituent effects on its high thermal stability and to estimate the thermal stability of the other tetrazoles. Similar to 1H-tetrazole, five bonds in the tetrazole ring have intermediate lengths between single and double bond lengths. Phenyl and tetrazole rings are not both on one plane showing no interaction. Three indexes addopted as a measure of thermal stability indicate that the more equal the bond lengths of the ring are and that the bigger the stabilization energy by ring formation is, the more thermally stable they are. It is found out that there is the relationship between the thermal stability and the ring charge. That is, the more negative the ring charge is, the more thrmally stable the tetrazole is. Also, there is a good relationship between the thermal stability and the energy level of orbital of which orbital is an anti bonding type with respect to the N3-N4 bond. The higher the energy level is, the more thermally stable the tetrazole is. (author)

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

    International Nuclear Information System (INIS)

    Kucharczyk, M.; Olszewski, S.

    1982-01-01

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

  10. Structural characterization of tellurite glasses doped with transition metal oxides using Raman spectra and ab initio calculations.

    Science.gov (United States)

    Mohamed, Tarek A; Shaltout, I; Al Yahyaei, K M

    2006-05-01

    Systems of iron tellurite glasses were prepared by melt quenching with compositions of [85%TeO2+5%Fe2O3+10%TMO], where transition metal oxides (TMO) are TiO2, V2O5, MnO, CoO, NiO and CuO. Furthermore, the main structural units of these samples have been characterized by means of Raman spectra (150-1200 cm(-1)) as well as wavenumber predictions by means of Gaussian 98 ab initio calculations for the proposed site symmetries of TeO4(4-) triagonal bipyramid (C2v) and Te2O7(6-) bridged tetrahedra (Cs and C1). Aided by normal coordinate analysis, calculated vibrational frequencies, Raman scattering activities, force constants in internal coordinates and potential energy distributions (PEDs), revised vibrational assignments for the fundamental modes have been proposed. The main structural features are correlated to the dominant units of triagonal bipyramid (tbp) or bridged tetrahedral (TeO3+1 binds to TeO3 through TeOTe bridge; corner sharing). Moreover, the Raman spectra of the investigated tellurites reflect a structural change from tbp (coordination number is four) to triagonal pyramidal (coordination number is three).

  11. Ab Initio Calculations of 31P NMR Chemical Shielding Anisotropy Tensors in Phosphates: Variations Due to Ring Formation

    Directory of Open Access Journals (Sweden)

    Todd M. Alam

    2002-08-01

    Full Text Available Abstract: Ring formation in phosphate systems is expected to influence both the magnitude and orientation of the phosphorus (31P nuclear magnetic resonance (NMR chemical shielding anisotropy (CSA tensor. Ab initio calculations of the 31P CSA tensor in both cyclic and acyclic phosphate clusters were performed as a function of the number of phosphate tetrahedral in the system. The calculation of the 31P CSA tensors employed the GAUSSIAN 98 implementation of the gauge-including atomic orbital (GIAO method at the Hartree-Fock (HF level. It is shown that both the 31P CSA tensor anisotropy, and the isotropic chemical shielding can be used for the identification of cyclic phosphates. The differences between the 31P CSA tensor in acyclic and cyclic phosphate systems become less pronounced with increasing number of phosphate groups within the ring. The orientation of the principal components for the 31P CSA tensor shows some variation due to cyclization, most notably with the smaller, highly strained ring systems.

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

    Science.gov (United States)

    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

  13. Ab Initio Calculation of XAFS Debye-Waller Factors for Crystalline Materials

    Science.gov (United States)

    Dimakis, Nicholas

    2007-02-01

    A direct an accurate technique for calculating the thermal X-ray absorption fine structure (XAFS) Debye-Waller factors (DWF) for materials of crystalline structure is presented. Using the Density Functional Theory (DFT) under the hybrid X3LYP functional, a library of MnO spin—optimized clusters are built and their phonon spectrum properties are calculated; these properties in the form of normal mode eigenfrequencies and eigenvectors are in turn used for calculation of the single and multiple scattering XAFS DWF. DWF obtained via this technique are temperature dependent expressions and can be used to substantially reduce the number of fitting parameters when experimental spectra are fitted with a hypothetical structure without any ad hoc assumptions. Due to the high computational demand a hybrid approach of mixing the DFT calculated DWF with the correlated Debye model for inner and outer shells respectively is presented. DFT obtained DWFs are compared with corresponding values from experimental XAFS spectra on manganosite. The cluster size effect and the spin parameter on the DFT calculated DWFs are discussed.

  14. Electronic structure and metallization of cubic GdH{sub 3} under pressure: Ab initio many-body GW calculations

    Energy Technology Data Exchange (ETDEWEB)

    Kong, Bo, E-mail: kong79@yeah.net, E-mail: yachao.zhang@pku.edu.cn [School of Physics and Electronic Sciences, Guizhou Education University, Guiyang 550018 (China); Guizhou Provincial Key Laboratory of Computational Nano-Material Science, Guizhou Education University, Guiyang 550018 (China); Zhang, Yachao, E-mail: kong79@yeah.net, E-mail: yachao.zhang@pku.edu.cn [Guizhou Provincial Key Laboratory of Computational Nano-Material Science, Guizhou Education University, Guiyang 550018 (China)

    2016-07-07

    The electronic structures of the cubic GdH{sub 3} are extensively investigated using the ab initio many-body GW calculations treating the Gd 4f electrons either in the core (4f-core) or in the valence states (4f-val). Different degrees of quasiparticle (QP) self-consistent calculations with the different starting points are used to correct the failures of the GGA/GGA + U/HSE03 calculations. In the 4f-core case, GGA + G{sub 0}W{sub 0} calculations give a fundamental band gap of 1.72 eV, while GGA+ GW{sub 0} or GGA + GW calculations present a larger band gap. In the 4f-val case, the nonlocal exchange-correlation (xc) functional HSE03 can account much better for the strong localization of the 4f states than the semilocal or Hubbard U corrected xc functional in the Kohn–Sham equation. We show that the fundamental gap of the antiferromagnetic (AFM) or ferromagnetic (FM) GdH{sub 3} can be opened up by solving the QP equation with improved starting point of eigenvalues and wave functions given by HSE03. The HSE03 + G{sub 0}W{sub 0} calculations present a fundamental band gap of 2.73 eV in the AFM configuration, and the results of the corresponding GW{sub 0} and GW calculations are 2.89 and 3.03 eV, respectively. In general, for the cubic structure, the fundamental gap from G{sub 0}W{sub 0} calculations in the 4f-core case is the closest to the real result. By G{sub 0}W{sub 0} calculations in the 4f-core case, we find that H or Gd defects can strongly affect the band structure, especially the H defects. We explain the mechanism in terms of the possible electron correlation on the hydrogen site. Under compression, the insulator-to-metal transition in the cubic GdH{sub 3} occurs around 40 GPa, which might be a satisfied prediction.

  15. RHFPPP, SCF-LCAO-MO Calculation for Closed Shell and Open Shell Organic Molecules

    International Nuclear Information System (INIS)

    Bieber, A.; Andre, J.J.

    1987-01-01

    1 - Nature of physical problem solved: Complete program performs SCF-LCAO-MO calculations for both closed and open-shell organic pi-molecules. The Pariser-Parr-People approximations are used with- in the framework of the restricted Hartree-Fock method. The SCF calculation is followed, if desired, by a variational configuration interaction (CI) calculation including singly excited configurations. 2 - Method of solution: A standard procedure is used; at each step a real symmetric matrix has to be diagonalized. The self-consistency is checked by comparing the eigenvectors between two consecutive steps. 3 - Restrictions on the complexity of the problem: i) The calculations are restricted to planar molecules. ii) In order to avoid accumulation of round-off errors, in the iterative procedure, double precision arithmetic is used. iii) The program is restricted to systems up to about 16 atoms; however the size of the systems can easily be modified if required

  16. Ab-initio calculation of ZnGeAs{sub 2} semiconductor

    Energy Technology Data Exchange (ETDEWEB)

    Tripathy, S. K., E-mail: susanta96@gmail.com; Kumar, V., E-mail: susanta96@gmail.com [Department of Electronics Engineering, Indian School of Mines, Dhanbad 826004 (India)

    2014-04-24

    The structural, electronic, optical and elastic properties of ZnGeAs{sub 2} semiconductor have been investigated using pseudopotential plane wave method within the density functional theory (DFT). The optimized lattice constants, energy gap and crystal field splitting parameter are calculated. The optical properties such as dielectric function, optical reflectivity,, extinction coefficient, absorption spectra, refractive index and electron energy loss spectrum have been studied. The values of bulk modulus (B), elastic constants (C{sub ij}), Young’s modulus (Y), Zener anisotropic factor (A), Poisson’s ratio (ν) and Debye temperature (Θ{sub D}) have been calculated. The calculated values of all these parameters are compared with the available experimental values and the values reported by different workers. A fairly good agreement has been found between them.

  17. Abs-initio, Predictive Calculations for Optoelectronic and Advanced Materials Research

    Science.gov (United States)

    Bagayoko, Diola

    2010-10-01

    Most density functional theory (DFT) calculations find band gaps that are 30-50 percent smaller than the experimental ones. Some explanations of this serious underestimation by theory include self-interaction and the derivative discontinuity of the exchange correlation energy. Several approaches have been developed in the search for a solution to this problem. Most of them entail some modification of DFT potentials. The Green function and screened Coulomb approximation (GWA) is a non-DFT formalism that has led to some improvements. Despite these efforts, the underestimation problem has mostly persisted in the literature. Using the Rayleigh theorem, we describe a basis set and variational effect inherently associated with calculations that employ a linear combination of atomic orbitals (LCAO) in a variational approach of the Rayleigh-Ritz type. This description concomitantly shows a source of large underestimation errors in calculated band gaps, i.e., an often dramatic lowering of some unoccupied energies on account of the Rayleigh theorem as opposed to a physical interaction. We present the Bagayoko, Zhao, and Williams (BZW) method [Phys. Rev. B 60, 1563 (1999); PRB 74, 245214 (2006); and J. Appl. Phys. 103, 096101 (2008)] that systematically avoids this effect and leads (a) to DFT and LDA calculated band gaps of semiconductors in agreement with experiment and (b) theoretical predictions of band gaps that are confirmed by experiment. Unlike most calculations, BZW computations solve, self-consistently, a system of two coupled equations. DFT-BZW calculated effective masses and optical properties (dielectric functions) also agree with measurements. We illustrate ten years of success of the BZW method with its results for GaN, C, Si, 3C-SIC, 4H-SiC, ZnO, AlAs, Ge, ZnSe, w-InN, c-InN, InAs, CdS, AlN and nanostructures. We conclude with potential applications of the BZW method in optoelectronic and advanced materials research.

  18. Voltage profile, structural prediction, and electronic calculations for MgxMo6S8

    CSIR Research Space (South Africa)

    Kganyago, KR

    2003-03-01

    Full Text Available the binary Mo6S8 and MgAMo6S8 ~see Table III!, the Mo-Mo distances decrease by (0.521)%. This decrease corresponds to an an- isotropic contraction of the Mo6 octahedron. The Mo cluster of the rhombohedral compounds forms an elongated octahe- dron of symmetry...

  19. Ab initio calculation of the bcc Fe-Al phase diagram including magnetic interactions

    International Nuclear Information System (INIS)

    Gonzales-Ormeno, Pablo Guillermo; Petrilli, Helena Maria; Schoen, Claudio Geraldo

    2006-01-01

    The metastable phase diagram of the body-centered cubic-based ordering equilibria in the Fe-Al system has been calculated by the cluster expansion method, through the combination of the full potential-linear augmented plane wave and cluster variation methods. The results are discussed with reference to the effect of including the spin polarizations of Fe in the thermodynamic model

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

    DEFF Research Database (Denmark)

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

    2011-01-01

    (D), in ammonium and amines decrease as a counterion or water molecule moves closer to the nitrogen. 1Δ15N(D) and 2Δ1H(D) of the NH3+ groups of lysine residues in the B1 domain of protein G have been calculated using truncated side chains and also determined experimentally by NMR. Comparisons show...

  1. Ab initio calculation of the sound velocity of dense hydrogen: implications for models of Jupiter

    NARCIS (Netherlands)

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

    1995-01-01

    First-principles molecular dynamics simulations were used to calculate the sound velocity of dense hydrogen, and the results were compared with extrapolations of experimental data that currently conflict with either astrophysical models or data obtained from recent global oscillation measurements of

  2. Ab-initio calculations of electric field gradient in Ru compounds and ...

    Indian Academy of Sciences (India)

    Home; Journals; Pramana – Journal of Physics; Volume 89; Issue 2. A b − i n i t i o calculations of electric field gradient in Ru compounds and their implication on the nuclear quadrupole moments of 99 Ru and 101 Ru. S N MISHRA. Research Article Volume 89 Issue 2 August 2017 Article ID 22 ...

  3. Ab initio calculations of fundamental properties of SrTe1−xOx alloys

    Indian Academy of Sciences (India)

    dielectric constant was studied by different models. On the other hand, the ... system in the framework of the density-functional theory. ∗ ... first principles calculations. Earlier ... by Vegard's law [19], but this is not the case of the band gap value.

  4. AB-INITIO CALCULATIONS OF ANHARMONIC VIBRATIONAL TRANSITION INTENSITIES OF TRANS-2,3-DIDEUTERIOOXIRANE

    DEFF Research Database (Denmark)

    Bludsky, O.; Bak, Keld L.; JORGENSEN, P

    1995-01-01

    The quartic force field and the cubic dipole moment surface are calculated for trans-2,3-dideuteriooxirane at the self-consistent field and the second order Moller-Plesset levels of theory using a triple zeta plus two polarization functions basis set. Contact transformation theory is used to dete...

  5. Ab initio calculations of partial molar properties in the single-site approximation

    DEFF Research Database (Denmark)

    Ruban, Andrei; Skriver, Hans Lomholt

    1997-01-01

    We discuss the application of the single-site approximation in calculations of partial molar quantities, e.g., impurity solution energy, segregation energy, and effective chemical potential, which are related to a variation of the composition of an alloy or its nonequivalent parts. We demonstrate...

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

    Science.gov (United States)

    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.

  7. Vibrational spectra of methyllithium and its aggregates: a new interpretation from ab initio anharmonic calculations

    International Nuclear Information System (INIS)

    Gohaud, Neil; Begue, Didier; Pouchan, Claude

    2005-01-01

    The complete quartic force field of methyllithium (CH 3 Li) is computed at the B3LYP/cc-pVTZ level of theory. The vibrational energy levels calculated from a perturbational and a variational procedure are in agreement with the observed spectra except for the C-Li stretching and the symmetric methyl deformation modes for which a disagreement with the experimental assignment given by Andrews is apparent. This discrepancy between experiment and theory is so large that questions are raised either about a correct characterization of, or correct calculations for the monomeric species CH 3 Li. Our theoretical study of methyllithium aggregates (CH 3 Li) n , with n = 2, 3, 4 and 6, gives a new interpretation of the experimental data

  8. Ab initio calculations of torsionally mediated hyperfine splittings in E states of acetaldehyde

    Science.gov (United States)

    Xu, Li-Hong; Reid, E. M.; Guislain, B.; Hougen, J. T.; Alekseev, E. A.; Krapivin, I.

    2017-12-01

    Quantum chemistry packages can be used to predict with reasonable accuracy spin-rotation hyperfine interaction constants for methanol, which contains one methyl-top internal rotor. In this work we use one of these packages to calculate components of the spin-rotation interaction tensor for acetaldehyde. We then use torsion-rotation wavefunctions obtained from a fit to the acetaldehyde torsion-rotation spectrum to calculate the expected magnitude of hyperfine splittings analogous to those observed at relatively high J values in the E symmetry states of methanol. We find that theory does indeed predict doublet splittings at moderate J values in the acetaldehyde torsion-rotation spectrum, which closely resemble those seen in methanol, but that the factor of three decrease in hyperfine spin-rotation constants compared to methanol puts the largest of the acetaldehyde splittings a factor of two below presently available Lamb-dip resolution.

  9. Ab initio calculations of the electronic and structural properties of beryllium-, magnesium- and calcium-nitrides

    Energy Technology Data Exchange (ETDEWEB)

    Mokhtari, A.; Akbarzadeh, H

    2003-09-01

    The electronic and structural properties of beryllium nitride (alpha and beta), magnesium- and calcium-nitrides were investigated using first principle full potential-linearized augmented plane wave method within density functional theory. We used Perdew and Wang-generalized gradient approximation, which is based on exchange correlation energy optimization, to calculate the total energy and the Engel-Vosko's GGA formalism, which optimize the corresponding potential, for band structure calculations. We also optimized internal parameters by relaxing the atomic positions in the force directions. Our results including lattice parameter, bulk modulus and it's pressure derivative, cohesive energy, band structure and density of states are compared with the experimental and other theoretical (Hartree-Fock approximation with a posteriori density functional correction) data.

  10. Ab initio calculations of the electronic and structural properties of beryllium-, magnesium- and calcium-nitrides

    International Nuclear Information System (INIS)

    Mokhtari, A.; Akbarzadeh, H.

    2003-01-01

    The electronic and structural properties of beryllium nitride (alpha and beta), magnesium- and calcium-nitrides were investigated using first principle full potential-linearized augmented plane wave method within density functional theory. We used Perdew and Wang-generalized gradient approximation, which is based on exchange correlation energy optimization, to calculate the total energy and the Engel-Vosko's GGA formalism, which optimize the corresponding potential, for band structure calculations. We also optimized internal parameters by relaxing the atomic positions in the force directions. Our results including lattice parameter, bulk modulus and it's pressure derivative, cohesive energy, band structure and density of states are compared with the experimental and other theoretical (Hartree-Fock approximation with a posteriori density functional correction) data

  11. Thermodynamic and mechanical properties of TiC from ab initio calculation

    International Nuclear Information System (INIS)

    Dang, D. Y.; Fan, J. L.; Gong, H. R.

    2014-01-01

    The temperature-dependent thermodynamic and mechanical properties of TiC are systematically investigated by means of a combination of density-functional theory, quasi-harmonic approximation, and thermal electronic excitation. It is found that the quasi-harmonic Debye model should be pertinent to reflect thermodynamic properties of TiC, and the elastic properties of TiC decease almost linearly with the increase of temperature. Calculations also reveal that TiC possesses a pronounced directional pseudogap across the Fermi level, mainly due to the strong hybridization of Ti 3d and C 2p states. Moreover, the strong covalent bonding of TiC would be enhanced (reduced) with the decrease (increase) of temperature, while the change of volume (temperature) should have negligible effect on density of states at the Fermi level. The calculated results agree well with experimental observations in the literature.

  12. Optical absorption spectra of semiconductors and insulators: ab initio calculation of many-body effects

    International Nuclear Information System (INIS)

    Albrecht, Stefan

    1999-01-01

    A method for the inclusion of self-energy and excitonic effects in first-principle calculations of absorption spectra, within the state-of-the-art plane wave pseudopotential approach, is presented. Starting from a ground state calculation, using density functional theory (DFT) in the local density approximation (LDA), we correct the exchange-correlation potential of DFT-LDA with the self-energy applying Hedin's GW approximation to obtain the physical quasiparticles states. The electron-hole interaction is treated solving an effective two-particle equation, which we derive from Hedin's coupled integral equations, leading to the fundamental Bethe-Salpeter equation in an intermediate step. The interaction kernel contains the screened electron-hole Coulomb interaction and the electron-hole exchange effects, which reflect the microscopic structure of the system and are thus also called local-field effects. We obtain the excitonic eigenstates through diagonalization. This allows us a detailed analysis of the optical properties. The application of symmetry properties enables us to reduce the size of the two-particle Hamiltonian matrix, thus minimizing the computational effort. We apply our method to silicon, diamond, lithium oxide and the sodium tetramer. Good agreement with experiment is obtained for the absorption spectra of Si and diamond, the static dielectric constant of diamond, and for the onset of optical absorption of Li 2 O due to discrete bound excitons. We discuss various approximations of our method and show the strong mixing of independent particle transitions to a bound excitonic state in the Na 4 cluster. The influence of ground state calculations on optical spectra is investigated under particular consideration of the pseudopotential generation and we discuss the use of different Brillouin zone point sampling schemes for spectral calculations. (author) [fr

  13. Numerical Exact Ab Initio Four-Nucleon Scattering Calculations: from Dream to Reality

    Science.gov (United States)

    Fonseca, A. C.; Deltuva, A.

    2017-03-01

    In the present manuscript we review the work of the last ten years on the pursuit to obtain numerical exact solutions of the four-nucleon scattering problem using the most advanced force models that fit two nucleon data up to pion production threshold with a χ ^2 per data point approximately one, together with the Coulomb interaction between protons; three- and four-nucleon forces are also included in the framework of a meson exchange potential model where NN couples to NΔ. Failure to describe the world data on four-nucleon scattering observables in the framework of a non relativistic scattering approach falls necessarily on the force models one uses. Four-nucleon observables pose very clear challenges, particular in the low energy region where there are a number of resonances whose position and width needs to be dynamically generated by the nucleon-nucleon (NN) interactions one uses. In addition, our calculations constitute the most advance piece of work where observables for all four-nucleon reactions involving isospin I=0, I=0 coupled to I=1 and isospin I=1 initial states are calculated at energies both below and above breakup threshold. We also present a very extensive comparison between calculated results and data for cross sections and spin observables. Therefore the present work reveals both the shortcomings and successes of some of the present NN force models in describing four-nucleon data and serve as a benchmark for future developments.

  14. Magnetic properties of polar ZnO surfaces from ab-initio calculations

    Energy Technology Data Exchange (ETDEWEB)

    Fischer, Guntram; Adeagbo, Waheed; Hergert, Wolfram [University Halle, Halle (Germany); Ernst, Arthur [Max-Planck-Institute of Microstructure Physics, Halle (Germany); Sanchez, Nadia; Mu noz, Carmen [Instituto de Ciencia de Materiales de Madrid, Madrid (Spain); Szotek, Zdzislawa; Temmerman, Walter [Daresbury Laboratory, Warrington (United Kingdom)

    2011-07-01

    We have investigated a magnetic moment formation of three oxygen-terminated polar ZnO surfaces. Specifically, these are the (000-1) surface, the (0001) surface with an oxygen atom on top of the Zn atom [(0001)-t], and the (0001) surface with an oxygen atom in a threefold hollow site [(0001)-h]. In this study we have used a multi-code approach allowing us to relax the surface structure and calculate the Heisenberg exchange parameters via a magnetic force theorem. Also, the influence of applying self-interaction corrections (SIC) to the oxygen p orbitals has been investigated. Our calculations show that all three surfaces are magnetic. In addition, we find that applying SIC is necessary to correctly describe the top oxygen atom of the (0001)-h and (0001)-t surfaces, for both of which we find Curie temperatures to be larger than room temperature. The latter have been derived from Monte Carlo simulations based on the calculated exchange parameters.

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

    International Nuclear Information System (INIS)

    Koehler, W.E.; Schaefer, J.

    1983-01-01

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

  16. Electronic structure and magnetic properties of Pr-Co intermetallics: ab initio FP-LAPW calculations and correlation with experiments

    Science.gov (United States)

    Bakkari, Karim; Fersi, Riadh; Kebir Hlil, El; Bessais, Lotfi; Thabet Mliki, Najeh

    2018-03-01

    First-principle calculations combining density functional theory and the full-potential linearized augmented plane wave (FP-LAPW) method are performed to investigate the electronic and magnetic structure of Pr2Co7 in its two polymorphic forms, (2:7 H) and (2:7 R), for the first time. This type of calculation was also performed for PrCo5 and PrCo2 intermetallics. We have computed the valence density of states separately for spin-up and spin-down states in order to investigate the electronic band structure. This is governed by the strong contribution of the partial DOS of 3d-Co bands compared to the partial DOS of the 4f-Pr bands. Such a high ferromagnetic state is discussed in terms of the strong spin polarization observed in the total DOS. The magnetic moments carried by the Co and Pr atoms located in several sites for all compounds are computed. These results mainly indicate that cobalt atoms make a dominant contribution to the magnetic moments. The notable difference in the atomic moments of Pr and Co atoms between different structural slabs is explained in terms of the magnetic characteristics of the PrCo2 and PrCo5 compounds and the local chemical environments of the Pr and Co atoms in different structural slabs of Pr2Co7. From spin-polarized calculations we have simulated the 3d and 4f band population to estimate the local magnetic moments. These results are in accordance with the magnetic moments calculated using the FP-LAPW method. In addition, the exchange interactions J ij are calculated and used as input for M(T) simulations. Involving the data obtained from the electronic structure calculations, the appropriate Padé Table is applied to simulate the magnetization M(T) and to estimate the mean-field Curie temperature. We report a fairly good agreement between the ab initio calculation of magnetization and Curie temperature with the experimental data.

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

    International Nuclear Information System (INIS)

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

    2015-01-01

    The rotational spectrum of the van der Waals complex CH 4 –CO has been measured with the intracavity OROTRON jet spectrometer in the frequency range of 110–145 GHz. Newly observed and assigned transitions belong to the K = 2–1 subband correlating with the rotationless j CH4 = 0 ground state and the K = 2–1 and K = 0–1 subbands correlating with the j CH4 = 2 excited state of free methane. The (approximate) quantum number K is the projection of the total angular momentum J on the intermolecular axis. The new data were analyzed together with the known millimeter-wave and microwave transitions in order to determine the molecular parameters of the CH 4 –CO complex. Accompanying ab initio calculations of the intermolecular potential energy surface (PES) of CH 4 –CO have been carried out at the explicitly correlated coupled cluster level of theory with single, double, and perturbative triple excitations [CCSD(T)-F12a] and an augmented correlation-consistent triple zeta (aVTZ) basis set. The global minimum of the five-dimensional PES corresponds to an approximately T-shaped structure with the CH 4 face closest to the CO subunit and binding energy D e = 177.82 cm −1 . The bound rovibrational levels of the CH 4 –CO complex were calculated for total angular momentum J = 0–6 on this intermolecular potential surface and compared with the experimental results. The calculated dissociation energies D 0 are 91.32, 94.46, and 104.21 cm −1 for A (j CH4 = 0), F (j CH4 = 1), and E (j CH4 = 2) nuclear spin modifications of CH 4 –CO, respectively

  18. Self-consistent ab initio Calculations for Photoionization and Electron-Ion Recombination Using the R-Matrix Method

    Science.gov (United States)

    Nahar, S. N.

    2003-01-01

    Most astrophysical plasmas entail a balance between ionization and recombination. We present new results from a unified method for self-consistent and ab initio calculations for the inverse processes of photoionization and (e + ion) recombination. The treatment for (e + ion) recombination subsumes the non-resonant radiative recombination and the resonant dielectronic recombination processes in a unified scheme (S.N. Nahar and A.K. Pradhan, Phys. Rev. A 49, 1816 (1994);H.L. Zhang, S.N. Nahar, and A.K. Pradhan, J.Phys.B, 32,1459 (1999)). Calculations are carried out using the R-matrix method in the close coupling approximation using an identical wavefunction expansion for both processes to ensure self-consistency. The results for photoionization and recombination cross sections may also be compared with state-of-the-art experiments on synchrotron radiation sources for photoionization, and on heavy ion storage rings for recombination. The new experiments display heretofore unprecedented detail in terms of resonances and background cross sections and thereby calibrate the theoretical data precisely. We find a level of agreement between theory and experiment at about 10% for not only the ground state but also the metastable states. The recent experiments therefore verify the estimated accuracy of the vast amount of photoionization data computed under the OP, IP and related works. features. Present work also reports photoionization cross sections including relativistic effects in the Breit-Pauli R-matrix (BPRM) approximation. Detailed features in the calculated cross sections exhibit the missing resonances due to fine structure. Self-consistent datasets for photoionization and recombination have so far been computed for approximately 45 atoms and ions. These are being reported in a continuing series of publications in Astrophysical J. Supplements (e.g. references below). These data will also be available from the electronic database TIPTOPBASE (http://heasarc.gsfc.nasa.gov)

  19. Calculation of electronic stopping power along glancing swift heavy ion tracks in perovskites using ab initio electron density data

    Energy Technology Data Exchange (ETDEWEB)

    Osmani, O; Duvenbeck, A; Akcoeltekin, E; Meyer, R; Schleberger, M [Department of Physics, University of Duisburg-Essen, D-47048 Duisburg (Germany); Lebius, H [CIMAP, blvd Henri Becquerel, 14070 Caen (France)], E-mail: marika.schleberger@uni-due.de

    2008-08-06

    In recent experiments the irradiation of insulators of perovskite type with swift (E{approx}100 MeV) heavy ions under glancing incidence has been shown to provide a unique means to generate periodically arranged nanodots at the surface. The physical origin of these patterns has been suggested as stemming from a highly anisotropic electron density distribution within the bulk. In order to show the relevance of the electron density distribution of the target we present a model calculation for the system Xe{sup 23+} {yields} SrTiO{sub 3} that is known to produce the aforementioned surface modifications. On the basis of the Lindhard model of electronic stopping, we employ highly-resolved ab initio electron density data to describe the conversion of kinetic energy into excitation energy along the ion track. The primary particle dynamics are obtained via integration of the Newtonian equations of motion that are governed by a space- and time-dependent frictional force originating from Lindhard stopping. The analysis of the local electronic stopping power along the ion track reveals a pronounced periodic structure. The periodicity length varies strongly with the particular choice of the polar angle of incidence and is directly correlated to the experimentally observed formation of periodic nanodots at insulator surfaces.

  20. Ab Initio Electronic Structure Calculation of [4Fe-3S] Cluster of Hydrogenase as Dihydrogen Dissociation/Production Catalyst

    Science.gov (United States)

    Kim, Jaehyun; Kang, Jiyoung; Nishigami, Hiroshi; Kino, Hiori; Tateno, Masaru

    2018-03-01

    Hydrogenases catalyze both the dissociation and production of dihydrogen (H2). Most hydrogenases are inactivated rapidly and reactivated slowly (in vitro), in the presence of dioxygen (O2) and H2, respectively. However, membrane-bound [NiFe] hydrogenases (MBHs) sustain their activity even together with O2, which is termed "O2 tolerance". In previous experimental analyses, an MBH was shown to include a hydroxyl ion (OH-) bound to an Fe of the super-oxidized [4Fe-3S]5+ cluster in the proximity of the [NiFe] catalytic cluster. In this study, the functional role of the OH- in the O2 tolerance was investigated by ab initio electronic structure calculation of the [4Fe-3S] proximal cluster. The analysis revealed that the OH- significantly altered the electronic structure, thereby inducing the delocalization of the lowest unoccupied molecular orbital (LUMO) toward the [NiFe] catalytic cluster, which may intermediate the electron transfer between the catalytic and proximal clusters. This can promote the O2-tolerant catalytic cycle in the hydrogenase reaction.

  1. Accuracy and Transferability of Ab Initio Electronic Band Structure Calculations for Doped BiFeO3

    Science.gov (United States)

    Gebhardt, Julian; Rappe, Andrew M.

    2017-11-01

    BiFeO3 is a multiferroic material and, therefore, highly interesting with respect to future oxide electronics. In order to realize such devices, pn junctions need to be fabricated, which are currently impeded by the lack of successful p-type doping in this material. In order to guide the numerous research efforts in this field, we recently finished a comprehensive computational study, investigating the influence of many dopants onto the electronic structure of BiFeO3. In order to allow for this large scale ab initio study, the computational setup had to be accurate and efficient. Here we discuss the details of this assessment, showing that standard density-functional theory (DFT) yields good structural properties. The obtained electronic structure, however, suffers from well-known shortcomings. By comparing the conventional DFT results for alkali and alkaline-earth metal doping with more accurate hybrid-DFT calculations, we show that, in this case, the problems of standard DFT go beyond a simple systematic error. Conventional DFT shows bad transferability and the more reliable hybrid-DFT has to be chosen for a qualitatively correct prediction of doping induced changes in the electronic structure of BiFeO3.

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

    International Nuclear Information System (INIS)

    Olsson, Paer

    2004-04-01

    The efficiency of fast neutron reactors, such as for fusion, breeding and transmutation, depend strongly on the neutron radiation resistance of the materials used in the reactors. The binary Fe-Cr alloy, which has many attractive properties in this regard, is the base for the best steels of today which are, however, still not up to the required standards. Therefore, substantial effort has been devoted to finding new materials that can cope with the demands better. Experimental studies must be complemented with extensive theoretical modelling in order to understand the effects that different alloying elements has on the resistance properties of materials. To this end, the first steps of multi-scale modelling has been taken, starting out with ab initio calculations of the electronic structure of the complete concentration range range of the disordered binary Fe-C alloy. The mixing enthalpy of Fe-Cr has been quantitatively predicted and has, together with data from literature, been used in order to fit two sets of interatomic potentials for the purpose of simulating defect evolution with molecular dynamics and kinetic Monte-Carlo codes. These dedicated Fe-Cr alloy potentials are new and represent important additions to the pure element potentials that can be found in literature

  3. Relaxation of energetic S(1D) atoms in Xe gas: comparison of ab initio calculations with experimental data.

    Science.gov (United States)

    Bovino, S; Zhang, P; Kharchenko, V; Dalgarno, A

    2011-07-14

    In this paper, we report our investigation of the translational energy relaxation of fast S((1)D) atoms in a Xe thermal bath. The interaction potential of Xe-S was constructed using ab initio methods. Total and differential cross sections were then calculated. The latter have been incorporated into the construction of the kernel of the Boltzmann equation describing the energy relaxation process. The solution of the Boltzmann equation was obtained and results were compared with those reported in experiments [G. Nan, and P. L. Houston, J. Chem. Phys. 97, 7865 (1992)]. Good agreement with the measured time-dependent relative velocity of fast S((1)D) atoms was obtained except at long relaxation times. The discrepancy may be due to the error accumulation caused by the use of hard sphere approximation and the Monte Carlo analysis of the experimental data. Our accurate description of the energy relaxation process led to an increase in the number of collisions required to achieve equilibrium by an order of magnitude compared to the number given by the hard-sphere approximation.

  4. Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals

    International Nuclear Information System (INIS)

    Hay, P.J.; Wadt, W.R.

    1985-01-01

    Ab initio effective core potentials (ECP's) have been generated to replace the innermost core electron for third-row (K--Au), fourth-row (Rb--Ag), and fifth-row (Cs--Au) atoms. The outermost core orbitals: corresponding to the ns 2 np 6 configuration for the three rows here: are not replaced by the ECP but are treated on an equal footing with the nd, (n+1)s and (n+1)p valence orbitals. These ECP's have been derived for use in molecular calculations where these outer core orbitals need to be treated explicitly rather than to be replaced by an ECP. The ECP's for the forth and fifth rows also incorporate the mass--velocity and Darwin relativistic effects into the potentials. Analytic fits to the potentials are presented for use in multicenter integral evaluation. Gaussian orbital valence basis sets are developed for the (3s, 3p, 3d, 4s, 4p), (4s, 4p, 4d, 5s, 5p), and (5s, 5p, 5d, 6s, 6p) ortibals of the three respective rows

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

    Energy Technology Data Exchange (ETDEWEB)

    Olsson, Paer

    2004-04-01

    The efficiency of fast neutron reactors, such as for fusion, breeding and transmutation, depend strongly on the neutron radiation resistance of the materials used in the reactors. The binary Fe-Cr alloy, which has many attractive properties in this regard, is the base for the best steels of today which are, however, still not up to the required standards. Therefore, substantial effort has been devoted to finding new materials that can cope with the demands better. Experimental studies must be complemented with extensive theoretical modelling in order to understand the effects that different alloying elements has on the resistance properties of materials. To this end, the first steps of multi-scale modelling has been taken, starting out with ab initio calculations of the electronic structure of the complete concentration range range of the disordered binary Fe-C alloy. The mixing enthalpy of Fe-Cr has been quantitatively predicted and has, together with data from literature, been used in order to fit two sets of interatomic potentials for the purpose of simulating defect evolution with molecular dynamics and kinetic Monte-Carlo codes. These dedicated Fe-Cr alloy potentials are new and represent important additions to the pure element potentials that can be found in literature.

  6. Ab initio calculations of indium arsenide in the wurtzite phase: structural, electronic and optical properties

    International Nuclear Information System (INIS)

    Dacal, Luis C O; Cantarero, A

    2014-01-01

    Most III–V semiconductors, which acquire the zinc-blende phase as bulk materials, adopt the metastable wurtzite phase when grown in the form of nanowires. These are new semiconductors with new optical properties, in particular, a different electronic band gap when compared with that grown in the zinc-blende phase. The electronic gap of wurtzite InAs at the Γ–point of the Brillouin zone (E 0 gap) has been recently measured, E 0 =0.46 eV at low temperature. The electronic gap at the A–point of the Brillouin zone (equivalent to the L–point in the zinc-blende structure, E 1 ) has also been obtained recently based on a resonant Raman scattering experiment. In this work, we calculate the band structure of InAs in the zinc-blende and wurtzite phases, using the full potential linearized augmented plane wave method, including spin-orbit interaction. The electronic band gap has been improved through the modified Becke–Johnson exchange-correlation potential. Both the E 0 and E 1 gaps agree very well with the experiment. From the calculations, a crystal field splitting of 0.122 eV and a spin-orbit splitting of 0.312 eV (the experimental value in zinc-blende InAs is 0.4 eV) has been obtained. Finally, we calculate the dielectric function of InAs in both the zinc-blende and wurtzite phases and a comparative discussion is given. (paper)

  7. Ab initio calculations of indium arsenide in the wurtzite phase: structural, electronic and optical properties

    Science.gov (United States)

    Dacal, Luis C. O.; Cantarero, A.

    2014-03-01

    Most III-V semiconductors, which acquire the zinc-blende phase as bulk materials, adopt the metastable wurtzite phase when grown in the form of nanowires. These are new semiconductors with new optical properties, in particular, a different electronic band gap when compared with that grown in the zinc-blende phase. The electronic gap of wurtzite InAs at the \\Gamma -point of the Brillouin zone ({{E}_{0}} gap) has been recently measured, {{E}_{0}}=0.46 eV at low temperature. The electronic gap at the A-point of the Brillouin zone (equivalent to the L-point in the zinc-blende structure, {{E}_{1}}) has also been obtained recently based on a resonant Raman scattering experiment. In this work, we calculate the band structure of InAs in the zinc-blende and wurtzite phases, using the full potential linearized augmented plane wave method, including spin-orbit interaction. The electronic band gap has been improved through the modified Becke-Johnson exchange-correlation potential. Both the {{E}_{0}} and {{E}_{1}} gaps agree very well with the experiment. From the calculations, a crystal field splitting of 0.122 eV and a spin-orbit splitting of 0.312 eV (the experimental value in zinc-blende InAs is 0.4 eV) has been obtained. Finally, we calculate the dielectric function of InAs in both the zinc-blende and wurtzite phases and a comparative discussion is given.

  8. Optimizing porphyrins for dye sensitized solar cells using large-scale ab initio calculations

    DEFF Research Database (Denmark)

    Ørnsø, Kristian Baruël; Pedersen, Christian S.; García Lastra, Juan Maria

    2014-01-01

    different side and anchoring groups. Based on the calculated frontier orbital energies and optical gaps we quantify the energy level alignment with the TiO2 conduction band and different redox mediators. An analysis of the energy level-structure relationship reveals a significant structural diversity among...... the dyes with the highest level alignment quality, demonstrating the large degree of flexibility in porphyrin dye design. As a specific example of dye optimization, we show that the level alignment of the high efficiency record dye YD2-o-C8 [Yella et al., Science, 2011, 334, 629-634] can be significantly...

  9. Ab initio calculations of anharmonic vibrational circular dichroism intensities of trans-2,3-dideuteriooxirane

    DEFF Research Database (Denmark)

    Bak, KL; Bludsky, O.; Jorgensen, P

    1995-01-01

    A priori theory is derived for anharmonic calculations of vibrational circular dichroism (VCD). The anharmonic VCD expression is gauge origin independent and reduce to the magnetic field perturbation theory expression in the double-harmonic approximation. The theory has been implemented using...... for the atomic axial tensors and using second-order Moller-Plesset theory for the atomic polar tensors and the force fields, The changes of the vibrational rotatory strengths from anharmonicities are small, and do not explain the previously observed large discrepancies between the double-harmonic results...

  10. Ab initio calculation of the electronic and optical properties of solid pentacene

    International Nuclear Information System (INIS)

    Tiago, Murilo L.; Northrup, John E.; Louie, Steve G.

    2002-01-01

    The optical and electronic properties of crystalline pentacene are studied, using a first-principles Green's-function approach. The quasiparticle energies are calculated within the GW approximation and the electron-hole excitations are computed by solving the Bethe-Salpeter equation. We investigate the role of polymorphism on the electronic energy gap and linear optical spectrum by studying two different crystalline phases: the solution-phase structure and the vapor-phase structure. charge-transfer excitons are found to dominate the optical spectrum. Excitons with sizable binding energies are predicted for both phases

  11. Structural, electronic and optical properties of cubic SrTiO{sub 3} and KTaO{sub 3}: Ab initio and GW calculations

    Energy Technology Data Exchange (ETDEWEB)

    Benrekia, A.R., E-mail: benrekia.ahmed@yahoo.com [Faculty of Science and Technology, University of Medea (Algeria); Benkhettou, N. [Laboratoire des Materiaux Magnetiques, Faculte des Sciences, Universite Djillali Liabes de Sidi Bel Abbes (Algeria); Nassour, A. [Laboratoire de Cristallographie, Resonance Magnetique et Modelisations (CRM2, UMR CNRS 7036) Institut Jean Barriol, Nancy Universite BP 239, Boulevard des Aiguillettes, 54506 Vandoeuvre-les-Nancy (France); Driz, M. [Applied Material Laboratory (AML), Electronics Department, University of Sidi bel Abbes (DZ 22000) (Algeria); Sahnoun, M. [Laboratoire de Physique Quantique de la Matiere et Modelisations Mathematique (LPQ3M), Faculty of Science and Technology,University of Mascara (Algeria); Lebegue, S. [Laboratoire de Cristallographie, Resonance Magnetique et Modelisations (CRM2, UMR CNRS 7036) Institut Jean Barriol, Nancy Universite BP 239, Boulevard des Aiguillettes, 54506 Vandoeuvre-les-Nancy (France)

    2012-07-01

    We present first-principles VASP calculations of the structural, electronic, vibrational, and optical properties of paraelectric SrTiO{sub 3} and KTaO{sub 3}. The ab initio calculations are performed in the framework of density functional theory with different exchange-correlation potentials. Our calculated lattice parameters, elastic constants, and vibrational frequencies are found to be in good agreement with the available experimental values. Then, the bandstructures are calculated with the GW approximation, and the corresponding band gap is used to obtain the optical properties of SrTiO{sub 3} and KTaO{sub 3}.

  12. Ab initio calculation of transport properties between PbSe quantum dots facets with iodide ligands

    Science.gov (United States)

    Wang, B.; Patterson, R.; Chen, W.; Zhang, Z.; Yang, J.; Huang, S.; Shrestha, S.; Conibeer, G.

    2018-01-01

    The transport properties between Lead Selenide (PbSe) quantum dots decorated with iodide ligands has been studied using density functional theory (DFT). Quantum conductance at each selected energy levels has been calculated along with total density of states and projected density of states. The DFT calculation is carried on using a grid-based planar augmented wave (GPAW) code incorporated with the linear combination of atomic orbital (LCAO) mode and Perdew Burke Ernzerhof (PBE) exchange-correlation functional. Three iodide ligand attached low index facets including (001), (011), (111) are investigated in this work. P-orbital of iodide ligand majorly contributes to density of state (DOS) at near top valence band resulting a significant quantum conductance, whereas DOS of Pb p-orbital shows minor influence. Various values of quantum conductance observed along different planes are possibly reasoned from a combined effect electrical field over topmost surface and total distance between adjacent facets. Ligands attached to (001) and (011) planes possess similar bond length whereas it is significantly shortened in (111) plane, whereas transport between (011) has an overall low value due to newly formed electric field. On the other hand, (111) plane with a net surface dipole perpendicular to surface layers leading to stronger electron coupling suggests an apparent increase of transport probability. Apart from previously mentioned, the maximum transport energy levels located several eVs (1 2 eVs) from the edge of valence band top.

  13. Laser Spectroscopy and AB Initio Calculations on the TaF Molecule

    Science.gov (United States)

    Ng, Kiu Fung; Zou, Wenli; Liu, Wenjian; Cheung, Allan S. C.

    2016-06-01

    Electronic transition spectrum of the tantalum monoflouride (TaF) molecule in the spectral region between 448 and 520 nm has been studied using the technique of laser-ablation/reaction free jet expansion and laser induced fluorescence spectroscopy. TaF molecule was produced by reacting laser-ablated tantalum atoms with sulfur hexafluoride gas seeded in argon. Sixteen vibrational bands with resolved rotational structure have been recorded and analyzed, which were organized into six electronic transition systems and the ground state has been identified to be the X3Σ-(0+) state with bond length, ro, and equilibrium vibrational frequency, ωe, determined to be 1.8209 Å and 700.1 wn respectively. In addition, four vibrational bands belong to another transition system involving lower state with Ω = 2 component has also been analyzed. All observed transitions are with ΔΩ = 0. Least-squares fit of the measured line positions yielded molecular constants for the electronic states involved. The Λ-S and Ω states of TaF were calculated at the state-averaged complete active space self-consistent field (SA-CASSCF) and the subsequent internally contracted multi-reference configuration interaction with singles and doubles and Davidson's cluster correction (MRCISD+Q) levels of theory with the active space of 4 electrons in 6 orbitals, that is, the molecular orbitals corresponding to Ta 5d6s are active. The spin-orbit coupling (SOC) is calculated by the state-interaction approach at the SA-CASSCF level via the relativistic effective core potentials (RECPs) spin-orbit operator, where the diagonal elements of the spin-orbit matrix are replaced by the above MRCISD+Q energies. The spectroscopic properties of the ground and many low-lying electronic states of the TaF molecule will be reported. With respect to the observed electronic states in this work, the calculated results are in good agreement with our experimental determinations. This work represents the first experimental

  14. Determining the phase diagram of lithium via ab initio calculation and ramp compression

    Science.gov (United States)

    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.

  15. Phenomenological approach to spin fluctuations in itinerant magnets and superconductors from ab initio calculations

    Energy Technology Data Exchange (ETDEWEB)

    Ortenzi, Luciano

    2013-10-17

    In this thesis I study the interplay between magnetism and superconductivity in itinerant magnets and superconductors. I do this by applying a semiphenomenological method to four representative compounds. In particular I use the discrepancies (whenever present) between density functional theory (DFT) calculations and the experiments in order to construct phenomenological models which explain the magnetic, superconducting and optical properties of four representative systems. I focus my attention on the superconducting and normal state properties of the recently discovered APt3P superconductors, on superconducting hole-doped CuBiSO, on the optical properties of LaFePO and finally on the ferromagnetic-paramagnetic transition of Ni3Al under pressure. At the end I present a new method which aims to describe the effect of spin fluctuations in itinerant magnets and superconductors that can be used to monitor the evolution of the electronic structure from non magnetic to magnetic in systems close to a quantum critical point.

  16. Ab initio calculation of the thermodynamic properties of InSb under intense laser irradiation

    International Nuclear Information System (INIS)

    Feng, ShiQuan; Cheng, XinLu; Zhao, JianLing; Zhang, Hong

    2013-01-01

    In this paper, phonon spectra of InSb at different electronic temperatures are presented. Based on the phonon dispersion relationship, we further perform a theoretical investigation of the thermodynamic properties of InSb under intense laser irradiation. The phonon entropy, phonon heat capacity, and phonon contribution to Helmholtz free energy and internal energy of InSb are calculated as functions of temperature at different electronic temperatures. The abrupt change in the phonon entropy- temperature curve from T e = 0.75 to 1.0 eV provides an indication of InSb undergoing a phase transition from solid to liquid. It can be considered as a collateral evidence of non-thermal melting for InSb under intense electronic excitation effect

  17. Ab initio calculation of the thermodynamic properties of InSb under intense laser irradiation

    Science.gov (United States)

    Feng, ShiQuan; Zhao, JianLing; Cheng, XinLu; Zhang, Hong

    2013-07-01

    In this paper, phonon spectra of InSb at different electronic temperatures are presented. Based on the phonon dispersion relationship, we further perform a theoretical investigation of the thermodynamic properties of InSb under intense laser irradiation. The phonon entropy, phonon heat capacity, and phonon contribution to Helmholtz free energy and internal energy of InSb are calculated as functions of temperature at different electronic temperatures. The abrupt change in the phonon entropy- temperature curve from Te = 0.75 to 1.0 eV provides an indication of InSb undergoing a phase transition from solid to liquid. It can be considered as a collateral evidence of non-thermal melting for InSb under intense electronic excitation effect.

  18. Application of ab initio calculations and molecular dynamics to collagen and brome mosaic virus

    Science.gov (United States)

    Eifler, Jay Quinson

    In bio-related research, large proteins are of important interest. We study two such proteins. Collagen is one such protein which forms part of the structural matrix for animals, such as in their bones and teeth. 1JS9 is another protein that is a component of the protein shell of the brome mosaic virus (BMV). And BMV is important for drug delivery and imaging. To better understand the properties of these proteins, quantum mechanically (QM) based results are needed, however computationally feasible methods are also necessary. The Orthogonalized Linear Combination of Atomic Orbitals (OLCAO) method is well-suited for application to such large proteins. However, a new approach to reduce the computational cost is required and this extension to the method we call the Amino-Acid Based Method (AAPM) of OLCAO. The AAPM roughly calculates electronic, self-consistent field (scf) potentials for individual amino-acids with their neighboring amino-acids included as a boundary condition. This allows the costly scf part of the calculation to be skipped out. Additionally, the number of potentials used to describe the how protein i s also minimized. Results for effective charge and bond order are obtained and analyzed for Collagen and preliminary effective charge results are obtained for 1JS9. The effective charge results reproduce those already obtained with other QM based methods but without reduced cost and preserved accuracy that are characteristically different than the formal charges mostly still in use to describe the charge properties of proteins. The bond order results for Collagen nicely reproduce the observed experimentally-derived hydrogen bonding between the individual chains of the collagen triple-helix as well as the observed hydrogen bonding network.

  19. Ab initio calculations of non-stoichiometric copper nitride, pure and with palladium

    International Nuclear Information System (INIS)

    Moreno-Armenta, Maria G.; Soto, Gerardo; Takeuchi, Noboru

    2011-01-01

    Research highlights: → The most stable arrangement corresponds to the Cu 3 N-anti ReO 3 structure. → Formation energy of Cu 32 Vac 0 N 8 and Cu 24 Pd 8 Vac 0 N 8 are very similar. → The biggest volume in the compound is Cu 31 Pd 1 Vac 0 N 8/ . → Small amount introduction of extra metal atoms in copper nitride is possible. - Abstract: We present first principles calculations of copper nitride by using periodic density functional theory within a plane-wave ultrasoft pseudopotential scheme. The insertions of extra Cu and/or Pd atoms in the empty sites, vacancy reorganization, and substitution of Cu by Pd atoms were studied. We have used an equivalent reduced-symmetry 2 x 2 x 2 Cu 3 N-like cubic super-cell. Small Cu and/or Pd concentrations and vacancy rearrangements in the copper sub-lattice were conveniently calculated in these low-symmetry cells. We cover probable situations like: the occupation of the initially empty copper sites by (1) copper atoms, and by (2) palladium; (3) the relocation of vacancies in the copper sub-lattice; and (4) the substitution of small quantities of copper by palladium atoms in the copper sub-lattice. The equilibrium volumes and energies after relaxing the atomic positions are compared to those of intrinsic copper nitride. We found that the most stable arrangement corresponds to the ideal stoichiometric Cu 3 N. We also found that any deviation from this ideal configuration shift the semiconductor state to a metallic or semi-metallic one.

  20. Elastic and thermo-physical properties of TiC, TiN, and their intermediate composition alloys using ab initio calculations

    International Nuclear Information System (INIS)

    Kim, Jiwoong; Kang, Shinhoo

    2012-01-01

    Highlights: ► Elastic properties of TiC, TiN and their alloys were calculated by ab initio calculations. ► Debye temperature and Gruneisen constant of TiC, TiN and their alloys were calculated as a function of nitrogen content. ► Thermo-physical properties were calculated as a function of nitrogen content. ► Thermal expansion of the alloys was fitted in different temperature range. - Abstract: The equilibrium lattice parameters, elastic properties, material brittleness, heat capacities, and thermal expansion coefficients of TiC, TiN, and their intermediate composition alloys (Ti(C 1−x N x ), x = 0.25, 0.5, and 0.75) were calculated using ab initio density functional theory (DFT) methods. We employed the Debye–Gruneisen model to calculate a finite temperature heat capacity and thermal expansion coefficient. The calculated elastic moduli and thermal expansion coefficients agreed well with the experimental data and with other DFT calculations. Accurate heat capacities of TiC, TiN, and their intermediate composition alloys were obtained by calculating not only the phonon contributions but also the electron contributions to the heat capacity. Our calculations indicated that the heat capacity differences between each composition originated mainly from the electronic contributions.

  1. Energy gap of extended states in SiC-doped graphene nanoribbon: Ab initio calculations

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Xiaoshi; Wu, Yong [College of Science, University of Shanghai for Science and Technology, Shanghai 200093 (China); Shanghai Key Lab of Modern Optical System, Shanghai 200093 (China); Li, Zhongyao, E-mail: lizyusst@gmail.com [College of Science, University of Shanghai for Science and Technology, Shanghai 200093 (China); Shanghai Key Lab of Modern Optical System, Shanghai 200093 (China); Gao, Yong [School of Science, Shanghai Second Polytechnic University, Shanghai 201209 (China)

    2017-04-01

    Highlights: • The gap of isolated ribbon is inversely proportional to the width of ribbon. • The gap of doped ribbon cannot be modeled by effective width approximation. • The fitted energy gap can match the experimental observations. • The doping results in a spin-polarized metallic-like band structure. - Abstract: The energy gap of extended states in zigzag graphene nanoribbons (ZGNRs) was examined on the basis of density-functional theory. In isolated ZGNRs, the energy gap is inversely proportional to the width of ribbon. It agrees well with the results from the Dirac equation in spin-unpolarized ZGNRs, although the considered ZGNRs have spin-polarized edges. However, the energy gap in SiC-doped ZGNRs cannot be modeled by effective width approximation. The doping also lifts the spin-degenerate of edge states and results in a metallic-like band structure near the Fermi level in SiC-doped ZGNRs. Our calculations may be helpful for understanding the origin of the reported single-channel ballistic transport in epitaxial graphene nanoribbons.

  2. Chemical trend of exchange coupling in diluted magnetic II-VI semiconductors: Ab initio calculations

    Science.gov (United States)

    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.

  3. Attractive PHHP interactions revealed by state-of-the-art ab initio calculations.

    Science.gov (United States)

    Yourdkhani, Sirous; Jabłoński, Mirosław; Echeverría, Jorge

    2017-10-25

    We report in this work a combined structural and state-of-the-art computational study of homopolar P-HH-P intermolecular contacts. Database surveys have shown the abundance of such surprisingly unexplored contacts, which are usually accompanied by other weak interactions in the solid state. By means of a detailed theoretical study utilizing SAPT(DFT), MP2, SCS-MP2, MP2C and CCSD(T) methods and both aug-cc-pVXZ and aug-cc-pCVXZ (X = D, T, Q, 5) basis sets as well as extrapolation to the CBS limit, we have shown that P-HH-P contacts are indeed attractive and considerably strong. SAPT(DFT) calculations have revealed the dispersive nature of the P-HH-P interaction with only minor contribution of the inductive term, whereas the first-order electrostatic term is clearly overbalanced by the first-order exchange energy. In general the computed interaction energies follow the trend: E ≈ E < E < E. Our results have also shown that the aug-cc-pVDZ (or aug-cc-pCVDZ) basis set is not yet well balanced and that the second-order dispersion energy term is the slowest converging among all SAPT(DFT) energy components. Compared to aug-cc-pVXZ basis sets, their core-correlation counterparts have a modest influence on all supermolecular interaction energies and a negligible influence on both the SAPT(DFT) interaction energy and its components.

  4. Insights inot the atomic many-particle dynamics of scattering processes by ab-initio calculations

    International Nuclear Information System (INIS)

    Zapukhlyak, Myroslav

    2008-01-01

    The present thesis gives a theoretical contribution to the understanding of the many-particle dynamics in inelastic ion-atom collisions. Many-electron dynamics in ion-helium collisions and proton-sodium collisions was theoretically studied. The description is based on the semiclassical approximation with the straight orbit for the projectile motion. The ion-atom collision problem is by this reduced to a time-dependent many-electron problem and in the non-relativistic approximation described by the time-dependent Schroedinger equation. The solution of the many-electron problem pursues in the framework of the time-dependent density functional theory. The time-dependent Schroedinger equation for the interacting many-electron problem is transformed to the system of the time-dependent Kohn-Sham equations and solved by the two-center-basis generator method. The unknown time-dependent exchange-correlation one-particle potential forces different approximation int he time-dependent Kohn-Shan scheme. In this thesis the model of the independent electrons was applied as basis model, in which the electron-electron correlation is consistently neglected in all parts and in all steps. Differential cross sections for different one- and two-electron processes were calculated in the so-called eikonal approximation for the collisional systems p-He, He 2+ -He, and Ar q+ -He (q=15-18) [de

  5. Ab initio calculation of pentacene-PbSe hybrid interface for photovoltaic applications.

    Science.gov (United States)

    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.

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

    International Nuclear Information System (INIS)

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

    2001-01-01

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

  7. Structural Characterization of MAO and Related Aluminum Complexes. 1. Solid-State 27 Al NMR with Comparison to EFG Tensors from ab Initio Molecular Orbital Calculations

    Energy Technology Data Exchange (ETDEWEB)

    Bryant, Pamela L.; Harwell, Chris; Mrse, Anthony A.; Emery, Earl F.; Gan, Zhedong; Caldwell, Tod; Reyes, Arneil P.; Kuhns, Philip; Hoyt, David W.; Simeral, Larry S.; Hall, Randall W.; Butler, Leslie G.

    2001-11-07

    Aminato and propanolato aluminum clusters with 3-, 4-, and 6-coordinate aluminum sites are studied with three 27Al NMR techniques optimized for large 27Al Quadrupole coupling constants: field-swept, frequency-stepped, and high-field MAS NMR. The 27Al quadrupole coupling constants and asymmetry parameters of molecular species, both experimental and derived from ab initio molecular orbital calculations, are correlated with structure.

  8. Negative ions of p-nitroaniline: Photodetachment, collisions, and ab initio calculations

    Science.gov (United States)

    Smith, Byron H.; Buonaugurio, Angela; Chen, Jing; Collins, Evan; Bowen, Kit H.; Compton, Robert N.; Sommerfeld, Thomas

    2013-06-01

    The structures of parent anion, M-, and deprotonated molecule, [M-H]-, anions of the highly polar p-nitroaniline (pNA) molecule are studied experimentally and theoretically. Photoelectron spectroscopy (PES) of the parent anion is employed to estimate the adiabatic electron affinity (EAa = 0.75 ± 0.1 eV) and vertical detachment energy (VDE = 1.1 eV). These measured energies are in good agreement with computed values of 0.73 eV for the EAa and the range of 0.85 to 1.0 eV for the VDE at the EOM-CCSD/Aug-cc-pVTZ level. Collision induced dissociation (CID) of deprotonated pNA, [pNA - H]-, with argon yielded [pNA - H - NO]- (i.e., rearrangement to give loss of NO) with a threshold energy of 2.36 eV. Calculations of the energy difference between [pNA - H]- and [pNA - H - NO]- give 1.64 eV, allowing an estimate of a 0.72 eV activation barrier for the rearrangement reaction. Direct dissociation of [pNA - H]- yielding NO_2^ - occurs at a threshold energy of 3.80 eV, in good agreement with theory (between 3.39 eV and 4.30 eV). As a result of the exceedingly large dipole moment for pNA (6.2 Debye measured in acetone), we predict two dipole-bound states, one at ˜110 meV and an excited state at 2 meV. No dipole-bound states are observed in the photodetachment experiments due the pronounced mixing between states with dipole-bound and valence character similar to what has been observed in other nitro systems. For the same reason, dipole-bound states are expected to provide highly efficient "doorway states" for the formation of the pNA- valence anion, and these states should be observable as resonances in the reverse process, that is, in the photodetachment spectrum of pNA- near the photodetachment threshold.

  9. Ab initio molecular dynamics calculations on scattering of hyperthermal H atoms from Cu(111) and Au(111)

    Energy Technology Data Exchange (ETDEWEB)

    Kroes, Geert-Jan, E-mail: g.j.kroes@chem.leidenuniv.nl; Pavanello, Michele [Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA Leiden (Netherlands); Blanco-Rey, María [Departamento de Física de Materiales, Facultad de Químicas UPV/EHU, Apartado 1072, 20080 Donostia-San Sebastián (Spain); Donostia International Physics Center, Paseo Manuel de Lardizabal 4, 20018 Donostia-San Sebastián (Spain); Alducin, Maite [Donostia International Physics Center, Paseo Manuel de Lardizabal 4, 20018 Donostia-San Sebastián (Spain); Centro de Física de Materiales, Centro Mixto CSIC-UPV/EHU, Paseo Manuel de Lardizabal 5, 20018 Donostia-San Sebastián (Spain); Auerbach, Daniel J. [Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA Leiden (Netherlands); Max Planck Institute for Biophysical Chemistry, Göttingen (Germany); Institute for Physical Chemistry, Georg-August University of Göttingen, Göttingen (Germany)

    2014-08-07

    Energy loss from the translational motion of an atom or molecule impinging on a metal surface to the surface may determine whether the incident particle can trap on the surface, and whether it has enough energy left to react with another molecule present at the surface. Although this is relevant to heterogeneous catalysis, the relative extent to which energy loss of hot atoms takes place to phonons or electron-hole pair (ehp) excitation, and its dependence on the system's parameters, remain largely unknown. We address these questions for two systems that present an extreme case of the mass ratio of the incident atom to the surface atom, i.e., H + Cu(111) and H + Au(111), by presenting adiabatic ab initio molecular dynamics (AIMD) predictions of the energy loss and angular distributions for an incidence energy of 5 eV. The results are compared to the results of AIMDEFp calculations modeling energy loss to ehp excitation using an electronic friction (“EF”) model applied to the AIMD trajectories, so that the energy loss to the electrons is calculated “post” (“p”) the computation of the AIMD trajectory. The AIMD calculations predict average energy losses of 0.38 eV for Cu(111) and 0.13-0.14 eV for Au(111) for H-atoms that scatter from these surfaces without penetrating the surface. These energies closely correspond with energy losses predicted with Baule models, which is suggestive of structure scattering. The predicted adiabatic integral energy loss spectra (integrated over all final scattering angles) all display a lowest energy peak at an energy corresponding to approximately 80% of the average adiabatic energy loss for non-penetrative scattering. In the adiabatic limit, this suggests a way of determining the approximate average energy loss of non-penetratively scattered H-atoms from the integral energy loss spectrum of all scattered H-atoms. The AIMDEFp calculations predict that in each case the lowest energy loss peak should show additional energy

  10. Embedding Fragment ab Initio Model Potentials in CASSCF/CASPT2 Calculations of Doped Solids: Implementation and Applications.

    Science.gov (United States)

    Swerts, Ben; Chibotaru, Liviu F; Lindh, Roland; Seijo, Luis; Barandiaran, Zoila; Clima, Sergiu; Pierloot, Kristin; Hendrickx, Marc F A

    2008-04-01

    In this article, we present a fragment model potential approach for the description of the crystalline environment as an extension of the use of embedding ab initio model potentials (AIMPs). The biggest limitation of the embedding AIMP method is the spherical nature of its model potentials. This poses problems as soon as the method is applied to crystals containing strongly covalently bonded structures with highly nonspherical electron densities. The newly proposed method addresses this problem by keeping the full electron density as its model potential, thus allowing one to group sets of covalently bonded atoms into fragments. The implementation in the MOLCAS 7.0 quantum chemistry package of the new method, which we call the embedding fragment ab inito model potential method (embedding FAIMP), is reported here, together with results of CASSCF/CASPT2 calculations. The developed methodology is applied for two test problems: (i) the investigation of the lowest ligand field states (2)A1 and (2)B1 of the Cr(V) defect in the YVO4 crystal and (ii) the investigation of the lowest ligand field and ligand-metal charge transfer (LMCT) states at the Mn(II) substitutional impurity doped into CaCO3. Comparison with similar calculations involving AIMPs for all environmental atoms, including those from covalently bounded units, shows that the FAIMP treatment of the YVO4 units surrounding the CrO4(3-) cluster increases the excitation energy (2)B1 → (2)A1 by ca. 1000 cm(-1) at the CASSCF level of calculation. In the case of the Mn(CO3)6(10-) cluster, the FAIMP treatment of the CO3(2-) units of the environment give smaller corrections, of ca. 100 cm(-1), for the ligand-field excitation energies, which is explained by the larger ligands of this cluster. However, the correction for the energy of the lowest LMCT transition is found to be ca. 600 cm(-1) for the CASSCF and ca. 1300 cm(-1) for the CASPT2 calculation.

  11. Ab initio molecular dynamics calculations on scattering of hyperthermal H atoms from Cu(111) and Au(111).

    Science.gov (United States)

    Kroes, Geert-Jan; Pavanello, Michele; Blanco-Rey, María; Alducin, Maite; Auerbach, Daniel J

    2014-08-07

    Energy loss from the translational motion of an atom or molecule impinging on a metal surface to the surface may determine whether the incident particle can trap on the surface, and whether it has enough energy left to react with another molecule present at the surface. Although this is relevant to heterogeneous catalysis, the relative extent to which energy loss of hot atoms takes place to phonons or electron-hole pair (ehp) excitation, and its dependence on the system's parameters, remain largely unknown. We address these questions for two systems that present an extreme case of the mass ratio of the incident atom to the surface atom, i.e., H + Cu(111) and H + Au(111), by presenting adiabatic ab initio molecular dynamics (AIMD) predictions of the energy loss and angular distributions for an incidence energy of 5 eV. The results are compared to the results of AIMDEFp calculations modeling energy loss to ehp excitation using an electronic friction ("EF") model applied to the AIMD trajectories, so that the energy loss to the electrons is calculated "post" ("p") the computation of the AIMD trajectory. The AIMD calculations predict average energy losses of 0.38 eV for Cu(111) and 0.13-0.14 eV for Au(111) for H-atoms that scatter from these surfaces without penetrating the surface. These energies closely correspond with energy losses predicted with Baule models, which is suggestive of structure scattering. The predicted adiabatic integral energy loss spectra (integrated over all final scattering angles) all display a lowest energy peak at an energy corresponding to approximately 80% of the average adiabatic energy loss for non-penetrative scattering. In the adiabatic limit, this suggests a way of determining the approximate average energy loss of non-penetratively scattered H-atoms from the integral energy loss spectrum of all scattered H-atoms. The AIMDEFp calculations predict that in each case the lowest energy loss peak should show additional energy loss in the

  12. Integrated design of Nb-based superalloys: Ab initio calculations, computational thermodynamics and kinetics, and experimental results

    International Nuclear Information System (INIS)

    Ghosh, G.; Olson, G.B.

    2007-01-01

    An optimal integration of modern computational tools and efficient experimentation is presented for the accelerated design of Nb-based superalloys. Integrated within a systems engineering framework, we have used ab initio methods along with alloy theory tools to predict phase stability of solid solutions and intermetallics to accelerate assessment of thermodynamic and kinetic databases enabling comprehensive predictive design of multicomponent multiphase microstructures as dynamic systems. Such an approach is also applicable for the accelerated design and development of other high performance materials. Based on established principles underlying Ni-based superalloys, the central microstructural concept is a precipitation strengthened system in which coherent cubic aluminide phase(s) provide both creep strengthening and a source of Al for Al 2 O 3 passivation enabled by a Nb-based alloy matrix with required ductile-to-brittle transition temperature, atomic transport kinetics and oxygen solubility behaviors. Ultrasoft and PAW pseudopotentials, as implemented in VASP, are used to calculate total energy, density of states and bonding charge densities of aluminides with B2 and L2 1 structures relevant to this research. Characterization of prototype alloys by transmission and analytical electron microscopy demonstrates the precipitation of B2 or L2 1 aluminide in a (Nb) matrix. Employing Thermo-Calc and DICTRA software systems, thermodynamic and kinetic databases are developed for substitutional alloying elements and interstitial oxygen to enhance the diffusivity ratio of Al to O for promotion of Al 2 O 3 passivation. However, the oxidation study of a Nb-Hf-Al alloy, with enhanced solubility of Al in (Nb) than in binary Nb-Al alloys, at 1300 deg. C shows the presence of a mixed oxide layer of NbAlO 4 and HfO 2 exhibiting parabolic growth

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

    International Nuclear Information System (INIS)

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

    1980-01-01

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

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

    International Nuclear Information System (INIS)

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

    2012-01-01

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

  15. Investigation of the binding mode of a novel cruzain inhibitor by docking, molecular dynamics, ab initio and MM/PBSA calculations

    Science.gov (United States)

    Martins, Luan Carvalho; Torres, Pedro Henrique Monteiro; de Oliveira, Renata Barbosa; Pascutti, Pedro Geraldo; Cino, Elio A.; Ferreira, Rafaela Salgado

    2018-05-01

    Chagas disease remains a major health problem in South America, and throughout the world. The two drugs clinically available for its treatment have limited efficacy and cause serious adverse effects. Cruzain is an established therapeutic target of Trypanosoma cruzi, the protozoan that causes Chagas disease. Our group recently identified a competitive cruzain inhibitor (compound 1) with an IC50 = 15 µM that is also more synthetically accessible than the previously reported lead, compound 2. Prior studies, however, did not propose a binding mode for compound 1, hindering understanding of the structure-activity relationship and optimization. Here, the cruzain binding mode of compound 1 was investigated using docking, molecular dynamics (MD) simulations with ab initio derived parameters, ab initio calculations, and MM/PBSA. Two ligand protonation states and four binding poses were evaluated. A careful ligand parameterization method was employed to derive more physically meaningful parameters than those obtained by automated tools. The poses of unprotonated 1 were unstable in MD, showing large conformational changes and diffusing away from the binding site, whereas the protonated form showed higher stability and interaction with negatively charged residues Asp161 and Cys25. MM/PBSA also suggested that these two residues contribute favorably to binding of compound 1. By combining results from MD, ab initio calculations, and MM/PBSA, a binding mode of 1 is proposed. The results also provide insights for further optimization of 1, an interesting lead compound for the development of new cruzain inhibitors.

  16. The hydrogen abstraction reaction O(3P) + CH4: A new analytical potential energy surface based on fit to ab initio calculations

    International Nuclear Information System (INIS)

    González-Lavado, Eloisa; Corchado, Jose C.; Espinosa-Garcia, Joaquin

    2014-01-01

    Based exclusively on high-level ab initio calculations, a new full-dimensional analytical potential energy surface (PES-2014) for the gas-phase reaction of hydrogen abstraction from methane by an oxygen atom is developed. The ab initio information employed in the fit includes properties (equilibrium geometries, relative energies, and vibrational frequencies) of the reactants, products, saddle point, points on the reaction path, and points on the reaction swath, taking especial caution respecting the location and characterization of the intermediate complexes in the entrance and exit channels. By comparing with the reference results we show that the resulting PES-2014 reproduces reasonably well the whole set of ab initio data used in the fitting, obtained at the CCSD(T) = FULL/aug-cc-pVQZ//CCSD(T) = FC/cc-pVTZ single point level, which represents a severe test of the new surface. As a first application, on this analytical surface we perform an extensive dynamics study using quasi-classical trajectory calculations, comparing the results with recent experimental and theoretical data. The excitation function increases with energy (concave-up) reproducing experimental and theoretical information, although our values are somewhat larger. The OH rotovibrational distribution is cold in agreement with experiment. Finally, our results reproduce experimental backward scattering distribution, associated to a rebound mechanism. These results lend confidence to the accuracy of the new surface, which substantially improves the results obtained with our previous surface (PES-2000) for the same system

  17. Ab initio calculations of PbTiO{sub 3}/SrTiO{sub 3} (001) heterostructures

    Energy Technology Data Exchange (ETDEWEB)

    Eglitis, R.I.; Piskunov, S.; Zhukovskii, Yu.F. [Institute of Solid State Physics, University of Latvia, 8 Kengaraga Str., 1063 Riga (Latvia)

    2016-12-15

    We performed ab initio calculations for the PbTiO{sub 3}/SrTiO{sub 3} (001) heterostructures. For both PbO and TiO{sub 2}-terminations of the PbTiO{sub 3} (001) thin film, augmented on the SrTiO{sub 3} (001) substrate, the magnitudes of atomic relaxations Δz increases as a function of the number of augmented monolayers. For both terminations of the augmented PbTiO{sub 3} (001) nanothin film, all upper, third and fifth monolayers are displaced inwards (Δz is negative), whereas all second, fourth and sixth monolayers are displaced outwards (Δz is positive). The B3PW calculated PbTiO{sub 3}/SrTiO{sub 3} (001) heterostructure band gaps, independently from the number of augmented layers, are always smaller than the PbTiO{sub 3} and SrTiO{sub 3} bulk band gaps. For both PbO and TiO{sub 2}-terminated PbTiO{sub 3}/SrTiO{sub 3}(001) heterostructures, their band gaps are reduced due to the increased number of PbTiO{sub 3} (001) monolayers. The band gaps of PbO-terminated augmented PbTiO{sub 3} (001) films are always larger than those for TiO{sub 2}-terminated PbTiO{sub 3} (001) thin films. The only exception is the case of 7-layer PbO-terminated and 8-layer TiO{sub 2}-terminated augmented PbTiO{sub 3} (001) thin films, where their band gaps both are equal to 2.99 eV. For each monolayer of the SrTiO{sub 3} (001) substrate, charge magnitudes always are more than several times larger, than for each monolayer in the augmented PbTiO{sub 3} (001) thin film. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  18. Extended Fenske-Hall LCAO MO calculations of core-level shifts in solid P compounds

    Science.gov (United States)

    Franke, R.; Chassé, T.; Reinhold, J.; Streubel, P.; Szargan, R.

    1997-08-01

    Extended Fenske-Hall LCAO-MO ΔSCF calculations on solids modelled as H-pseudoatom saturated clusters are reported. The computational results verify the experimentally obtained initial-state (effective atomic charges, Madelung potential) and relaxation-energy contributions to the XPS phosphorus core-level binding energy shifts measured in Na 3PO 3S, Na 3PO 4, Na 2PO 3F and NH 4PF 6 in reference to red phosphorus. It is shown that the different initial-state contributions observed in the studied phosphates are determined by local and nonlocal terms while the relaxation-energy contributions are mainly dependent on the nature of the nearest neighbors of the phosphorus atom.

  19. Ab initio quasi-particle approximation bandgaps of silicon nanowires calculated at density functional theory/local density approximation computational effort

    Energy Technology Data Exchange (ETDEWEB)

    Ribeiro, M., E-mail: ribeiro.jr@oorbit.com.br [Office of Operational Research for Business Intelligence and Technology, Principal Office, Buffalo, Wyoming 82834 (United States)

    2015-06-21

    Ab initio calculations of hydrogen-passivated Si nanowires were performed using density functional theory within LDA-1/2, to account for the excited states properties. A range of diameters was calculated to draw conclusions about the ability of the method to correctly describe the main trends of bandgap, quantum confinement, and self-energy corrections versus the diameter of the nanowire. Bandgaps are predicted with excellent accuracy if compared with other theoretical results like GW, and with the experiment as well, but with a low computational cost.

  20. Ab initio calculations of the electron spectrum and density of states of TlFeS{sub 2} and TlFeSe{sub 2} crystals

    Energy Technology Data Exchange (ETDEWEB)

    Ismayilova, N. A., E-mail: ismayilova-narmin-84@mail.ru; Orudjev, H. S.; Jabarov, S. H. [Azerbaijan National Academy of Sciences, Institute of Physics (Azerbaijan)

    2017-04-15

    The results of ab initio calculations of the electron spectrum of TlFeS{sub 2} and TlFeSe{sub 2} crystals in the antiferromagnetic phase are reported. Calculations are carried out in the context of the density functional theory. The origin of the bands of s, p, and d electron states of Tl, Fe, S, and Se atoms is studied. It is established that, in the antiferromagnetic phase, the crystals possess semiconductor properties. The band gaps are found to be 0.05 and 0.34 eV for TlFeS{sub 2} and TlFeSe{sub 2} crystals, respectively.

  1. Elastic properties of fcc Fe–Mn–X (X = Cr, Co, Ni, Cu) alloys studied by the combinatorial thin film approach and ab initio calculations

    International Nuclear Information System (INIS)

    Reeh, S; Kasprzak, M; Klusmann, C D; Stalf, F; Music, D; Schneider, J M; Ekholm, M; Abrikosov, I A

    2013-01-01

    The elastic properties of fcc Fe–Mn–X (X = Cr, Co, Ni, Cu) alloys with additions of up to 8 at.% X were studied by combinatorial thin film growth and characterization and by ab initio calculations using the disordered local moments (DLM) approach. The lattice parameter and Young’s modulus values change only marginally with X. The calculations and experiments are in good agreement. We demonstrate that the elastic properties of transition metal alloyed Fe–Mn can be predicted by the DLM model. (paper)

  2. Elastic properties of fcc Fe-Mn-X (X = Cr, Co, Ni, Cu) alloys studied by the combinatorial thin film approach and ab initio calculations.

    Science.gov (United States)

    Reeh, S; Kasprzak, M; Klusmann, C D; Stalf, F; Music, D; Ekholm, M; Abrikosov, I A; Schneider, J M

    2013-06-19

    The elastic properties of fcc Fe-Mn-X (X = Cr, Co, Ni, Cu) alloys with additions of up to 8 at.% X were studied by combinatorial thin film growth and characterization and by ab initio calculations using the disordered local moments (DLM) approach. The lattice parameter and Young's modulus values change only marginally with X. The calculations and experiments are in good agreement. We demonstrate that the elastic properties of transition metal alloyed Fe-Mn can be predicted by the DLM model.

  3. Ab initio quasi-particle approximation bandgaps of silicon nanowires calculated at density functional theory/local density approximation computational effort

    International Nuclear Information System (INIS)

    Ribeiro, M.

    2015-01-01

    Ab initio calculations of hydrogen-passivated Si nanowires were performed using density functional theory within LDA-1/2, to account for the excited states properties. A range of diameters was calculated to draw conclusions about the ability of the method to correctly describe the main trends of bandgap, quantum confinement, and self-energy corrections versus the diameter of the nanowire. Bandgaps are predicted with excellent accuracy if compared with other theoretical results like GW, and with the experiment as well, but with a low computational cost

  4. Model calculations for a 600 A laser based on photopumping of Mo6+ by a spectral line of Mo11+

    International Nuclear Information System (INIS)

    Klapisch, M.; Cohen, M.; Goldstein, W.H.; Feldman, U.

    1990-01-01

    We assess aspects of the feasibility of a recent proposal to use the coincidence between a Mo 11+ , 136.499 A, line and a 4p 6 -(4p 5 ) 1/2 6s, J=1, transition of Mo 6+ , to obtain amplified spontaneous emission around 600 A. A collisional-radiative model for the Mo 6+ ion, including resonant photoexcitation of the 4p 5 1/2 6s level, was constructed using the HULLAC atomic physics package. The model included the 4s 2 4p 6 ; 4p 5 4d, 4f; 4p 5 5s, 5p, 5d; 4p 5 6s, 6p, 6d; 4s4p 6 4d, 4f; 4p 6 4d 2 and 4s 2 4p 4 4d 2 configurations, amounting to 193 levels. All configuration interactions and collisional mixing were taken into account. A gain of 3 cm -1 is obtained for the 4p 5 6s(J = 1)-4p 5 5p(J = 2) transition at 645 A with T e = 5 eV, n e = 10 18 cm -3 , and an effective radiation temperature of T rad > 40 eV for the pump transition. Other transitions exhibit lower gains. (orig.)

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

    Czech Academy of Sciences Publication Activity Database

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

    2016-01-01

    Roč. 207, OCT (2016), s. 202-210 ISSN 0010-4655 R&D Projects: GA ČR GA16-16772S Institutional support: RVO:61389005 Keywords : nuclear structure * Ab initio methods * Shell model * models based on group theory Subject RIV: BE - Theoretical Physics Impact factor: 3.936, year: 2016

  6. Ab initio calculation of the transition-state properties and addition rate constants for H + C2H2 and selected isotopic analogues

    International Nuclear Information System (INIS)

    Harding, L.B.; Wagner, A.F.; Bowman, J.M.; Schatz, G.C.; Christoffel, K.

    1982-01-01

    GVB-POL-CI ab initio calculations of the geometries, energetics, and normal mode frequencies of C 2 H 2 , C 2 H 3 , and the transition state for the addition reaction of H + C 2 H 2 are presented. In addition, normal mode frequencies for the isotopic variants D + C 2 D 2 , D + C 2 H 2 , and H + C 2 D 2 are preented. These results are compared to experimental values for C 2 H 2 and to ab initio values of Hagase and Kern, and semiempirical values of Keil, Lynch, Cowfer, and Michael. The results are also used to calculate the apparent bimolecular addition rate constant using conventional RRKM theory for chemical activation. The calculated rate constants and their isotopic variants are compared as a function of temperature and pressure to available experimental information. The agreement is little different from that obtained by Keil et al. with a similar calculation using semiempirical values for acetylene, transition-state, and vinyl radical properties. In particular, the calculated high-pressure limit of the rate constant appears to be at least 1 order of magnitude higher than the experimental limit. Several possible reasons for this discrepancy are discussed

  7. Quantum-Chemical ab initio Calculations on the Three Isomers of Diborabenzene (C4H4B2)

    Science.gov (United States)

    Singh, Jaswinder; Wang, Yuekui; Raabe, Gerhard

    2010-01-01

    Quantum-chemical ab initio calculations up to the ZPE+CCSD(T)/aug-cc-pVTZ//MP2/6- 311++G** level were performed on three possible structural isomers of diborabenzene (C4H4B2). All three molecules were found to be local minima on the C4H4B2 energy surface and to have closed shell singlet ground states. While the ground states of the 1,3- and 1,4-isomer are planar and of C2v and D2h symmetry, respectively, 1,2-diborabenzene is non-planar with a C2 axis passing through the center of the BB bond and the middle of the opposite carbon-carbon bond as the only symmetry element. The energetically most favourable 1,3-diborabenzene was found to be about 19 and 36 kcal/mol lower in energy than the 1,2- and the 1,4-isomer. Planar 1,3- and 1,4-diborabenzene have three doubly occupied π orbitals while non-planar 1,2-diborabenzene has also three doubly occupied orbitals which can be derived from the π orbitals of its 3.7 kcal/mol energetically less favourable planar form ("π-like" orbitals). The lowest unoccupied orbitals of all three isomers have σ symmetry with large coefficients at the two boron atoms. These orbitals are lower in energy than the lowest unoccupied molecular orbitals (LUMOs) of e. g. benzene and pyridine and might cause pronounced acceptor properties which could be one of the reasons for the elusiveness of the title compounds. The results of bond separation reactions show that cyclic conjugation stabilizes all three diborabenzenes relative to their isolated fragments. The most effective stabilization energy of about 24 kcal/mol was found for the energetically lowest 1,3-isomer. This value amounts to approximately one third of the experimental value for the bond separation energy of pyridine. In all cases the energetically lowest triplet states are significantly (16 - 24 kcal/mol) higher in energy than the singlet ground states. Also among the triplets the 1,3-isomer is the energetically most fabourable species.

  8. Photoabsorption spectra of (Mo/W)@Au12Si60 clusters from time-dependent DFT calculations

    KAUST Repository

    Mokkath, Junais Habeeb

    2013-11-14

    The electronic structure and photoabsorption spectrum of encapsulated (Mo/W)@Au12Si60 clusters are theoretically investigated via static and time-dependent density functional theory. The photoabsorption spectrum is calculated both at the scalar relativistic and spin-orbit coupling levels. The encapsulated (Mo/W)@Au12 clusters interact with the Si and thus stabilize the Si60 cage. The spin-orbit coupling strongly affects the optical properties of (Mo/W)@Au12 clusters as it leads to a splitting of spectral lines together with an intensity redistribution, whereas the spectra of (Mo/W)@Au12Si60 clusters show hardly any difference. The nanoscale properties thus can be tuned by choosing the endohedral metal atom, while keeping the optical properties unaffected. © 2013 American Chemical Society.

  9. Photoabsorption spectra of (Mo/W)@Au12Si60 clusters from time-dependent DFT calculations

    KAUST Repository

    Mokkath, Junais Habeeb; Schwingenschlö gl, Udo

    2013-01-01

    The electronic structure and photoabsorption spectrum of encapsulated (Mo/W)@Au12Si60 clusters are theoretically investigated via static and time-dependent density functional theory. The photoabsorption spectrum is calculated both at the scalar relativistic and spin-orbit coupling levels. The encapsulated (Mo/W)@Au12 clusters interact with the Si and thus stabilize the Si60 cage. The spin-orbit coupling strongly affects the optical properties of (Mo/W)@Au12 clusters as it leads to a splitting of spectral lines together with an intensity redistribution, whereas the spectra of (Mo/W)@Au12Si60 clusters show hardly any difference. The nanoscale properties thus can be tuned by choosing the endohedral metal atom, while keeping the optical properties unaffected. © 2013 American Chemical Society.

  10. Bandgap engineering in van der Waals heterostructures of blue phosphorene and MoS{sub 2}: A first principles calculation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Z.Y. [Key Laboratory for Magnetism and Magnetic Materials of the Ministry of Education, Lanzhou University, Lanzhou 730000 (China); Si, M.S., E-mail: sims@lzu.edu.cn [Key Laboratory for Magnetism and Magnetic Materials of the Ministry of Education, Lanzhou University, Lanzhou 730000 (China); Peng, S.L. [Key Laboratory for Magnetism and Magnetic Materials of the Ministry of Education, Lanzhou University, Lanzhou 730000 (China); Zhang, F. [Key Lab of Photovoltaic Materials of Henan Province, Henan University, Kaifeng 475001 (China); Wang, Y.H.; Xue, D.S. [Key Laboratory for Magnetism and Magnetic Materials of the Ministry of Education, Lanzhou University, Lanzhou 730000 (China)

    2015-11-15

    Blue phosphorene (BP) was theoretically predicted to be thermally stable recently. Considering its similar in-layer hexagonal lattice to MoS{sub 2}, MoS{sub 2} could be an appropriate substrate to grow BP in experiments. In this work, the van der Waals (vdW) heterostructures are constructed by stacking BP on top of MoS{sub 2}. The thermal stability and electronic structures are evaluated based on first principles calculations with vdW-corrected exchange-correlation functional. The formation of the heterostructures is demonstrated to be exothermic and the most stable stacking configuration is confirmed. The heterostructures BP/MoS{sub 2} preserve both the properties of BP and MoS{sub 2} but exhibit relatively narrower bandgaps due to the interlayer coupling effect. The band structures can be further engineered by applying external electric fields. An indirect–direct bandgap transition in bilayer BP/MoS{sub 2} is demonstrated to be controlled by the symmetry property of the built-in electric dipole fields. - Graphical abstract: An indirect-direct band gap transition occurs in van der Waals heterostructure of MoS{sub 2}/BP under external electric fields which is demonstrated to be controlled by the symmetry of the built-in electric dipole fields. - Highlights: • The stacking of heterostructures of BP/MoS{sub 2} is demonstrated to be exothermic. • This suggests that it is possible to grow BP using MoS{sub 2} as the substrate. • The band structures of the heterostructures are exploited. • It realizes an indirect–direct gap transition under external electric fields. • The symmetry of the built-in electric dipole fields controls such gap transition.

  11. Increasing the efficiency and accuracy of time-resolved electronic spectra calculations with on-the-fly ab initio quantum dynamics methods

    Science.gov (United States)

    Vanicek, Jiri

    2014-03-01

    Rigorous quantum-mechanical calculations of coherent ultrafast electronic spectra remain difficult. I will present several approaches developed in our group that increase the efficiency and accuracy of such calculations: First, we justified the feasibility of evaluating time-resolved spectra of large systems by proving that the number of trajectories needed for convergence of the semiclassical dephasing representation/phase averaging is independent of dimensionality. Recently, we further accelerated this approximation with a cellular scheme employing inverse Weierstrass transform and optimal scaling of the cell size. The accuracy of potential energy surfaces was increased by combining the dephasing representation with accurate on-the-fly ab initio electronic structure calculations, including nonadiabatic and spin-orbit couplings. Finally, the inherent semiclassical approximation was removed in the exact quantum Gaussian dephasing representation, in which semiclassical trajectories are replaced by communicating frozen Gaussian basis functions evolving classically with an average Hamiltonian. Among other examples I will present an on-the-fly ab initio semiclassical dynamics calculation of the dispersed time-resolved stimulated emission spectrum of the 54-dimensional azulene. This research was supported by EPFL and by the Swiss National Science Foundation NCCR MUST (Molecular Ultrafast Science and Technology) and Grant No. 200021124936/1.

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

    Science.gov (United States)

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

    2014-08-27

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

  13. Ab Initio Study of the Electronic Structure, Elastic Properties, Magnetic Feature and Thermodynamic Properties of the Ba2NiMoO6 Material

    Science.gov (United States)

    Deluque Toro, C. E.; Mosquera Polo, A. S.; Gil Rebaza, A. V.; Landínez Téllez, D. A.; Roa-Rojas, J.

    2018-04-01

    We report first-principles calculations of the elastic properties, electronic structure and magnetic behavior performed over the Ba2NiMoO6 double perovskite. Calculations are carried out through the full-potential linear augmented plane-wave method within the framework of the Density Functional Theory (DFT) with exchange and correlation effects in the Generalized Gradient and Local Density Approximations, including spin polarization. The elastic properties calculated are bulk modulus (B), the elastic constants (C 11, C 12 and C 44), the Zener anisotropy factor (A), the isotropic shear modulus (G), the Young modulus (Y) and the Poisson ratio (υ). Structural parameters, total energies and cohesive properties of the perovskite are studied by means of minimization of internal parameters with the Murnaghan equation, where the structural parameters are in good agreement with experimental data. Furthermore, we have explored different antiferromagnetic configurations in order to describe the magnetic ground state of this compound. The pressure and temperature dependence of specific heat, thermal expansion coefficient, Debye temperature and Grüneisen parameter were calculated by DFT from the state equation using the quasi-harmonic model of Debye. A specific heat behavior C V ≈ C P was found at temperatures below T = 400 K, with Dulong-Petit limit values, which is higher than those, reported for simple perovskites.

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

    International Nuclear Information System (INIS)

    Hellmann, Robert

    2009-01-01

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

  15. Investigation on electronic and magnetic properties of Mn{sub 2}NiAl by ab initio calculations and Monte Carlo simulations

    Energy Technology Data Exchange (ETDEWEB)

    Masrour, R., E-mail: rachidmasrour@hotmail.com [Laboratory of Materials, Processes, Environment and Quality, Cady Ayyed University, National School of Applied Sciences, PB 63 46000 Safi (Morocco); Jabar, A. [Laboratory of Materials, Processes, Environment and Quality, Cady Ayyed University, National School of Applied Sciences, PB 63 46000 Safi (Morocco); Hlil, E.K. [Institut Néel, CNRS, Université Grenoble Alpes, BP 166, F-38042 Grenoble cedex 9 (France); Hamedoun, M. [Institute of Nanomaterials and Nanotechnologies, MAScIR, Rabat (Morocco); Benyoussef, A. [Institute of Nanomaterials and Nanotechnologies, MAScIR, Rabat (Morocco); Hassan II Academy of Science and Technology, Rabat (Morocco); Hourmatallah, A. [Equipe de Physique du Solide, Laboratoire LIPI, Ecole Normale Supérieure, BP 5206, Bensouda, Fes (Morocco); Rezzouk, A.; Bouslykhane, K.; Benzakour, N. [Laboratoire de Physique du Solide, Université Sidi Mohammed Ben Abdellah, Faculté des sciences DharMahraz, BP 1796, Fes (Morocco)

    2017-04-15

    Self-consistent ab initio calculations, based on Density Functional Theory (DFT) approach and using Full potential Linear Augmented Plane Wave (FLAPW) method, are performed to investigate both electronic and magnetic properties of the Mn{sub 2}NiAl. Magnetic moment considered to lie along (001) axes are computed. Obtained data from ab initio calculations are used as input for Monte Carlo simulations to compute other magnetic parameters. Also, the magnetic properties of Mn{sub 2}NiAl are studied using the Monte Carlo simulations. The variation of magnetization and magnetic susceptibility with the reduced temperature of Mn{sub 2}NiAl are investigated. The transition temperature of this system is deduced for different values exchange interaction and crystal field. The thermal total magnetization has been obtained, and the magnetic hysteresis cycle is established. The total magnetic moment is superior to those obtained by the other method and is mainly determined by the antiparallel aligned Mn{sub I}, Mn{sub II} and Ni spin moments. The superparamagnetic phase is found at the neighborhood of transition temperature. - Highlights: • Ab initio calculations are used to study magnetic and electronic properties of Mn{sub 2}NiX. • The transition temperature of Mn{sub 2}NiX is established. • The magnetic hysteresis cycle of M{sub n2}NiX (X = Al, Ga, In, Sn) is deduced. • The magnetic coercive field of Mn{sub 2}NiX (X = Al, Ga, In, Sn) is given.

  16. Ground state hydrogen conformations and vibrational analysis of 1,2-dihdroxyanthraquinone (alizarin) molecule by AB initio Hartree-Fock and density functional theory calculations

    International Nuclear Information System (INIS)

    Delta, E.; Ucun, F.; Saglam, A.

    2010-01-01

    The ground state hydrogen conformations of 1,2-dihydroxyanthraquinone (alizarin) molecule have been investigated using ab initio Hartree-Fock (HF) and density functional theory (B3LYP) methods with 6-31G(d,p) basis set. The calculations indicate that the compound in the ground state exist with the doubly bonded O atom linked intra molecularly by the two hydrogen bonds. The vibrational analyses of the ground state conformation of the compound were also made and its optimized geometry parameters were given.

  17. Impact of arsenic/phosphorus substitution on the intrinsic conformational properties of the phosphodiester backbone of DNA investigated using ab initio quantum mechanical calculations.

    Science.gov (United States)

    Denning, Elizabeth J; Mackerell, Alexander D

    2011-04-20

    Deoxyribonucleic acid (DNA) is composed of five major elements carbon, hydrogen, nitrogen, oxygen, and phosphorus. The substitution of any of these elements in DNA would be anticipated to have major biological implications. However, recent studies have suggested that the substitution of arsenic into DNA (As-DNA) in bacteria may be possible. To help evaluate this possibility, ab initio quantum mechanical calculations are used to show that arsenodiester and phosphodiester linkages have similar geometric and conformational properties. Based on these results, it is suggested that the As-DNA will have similar conformational properties to phosphorus-based DNA, including the maintenance of base stacking.

  18. State-dependent electron delocalization dynamics at the solute-solvent interface: soft-x-ray absorption spectroscopy and ab initio calculations.

    Science.gov (United States)

    Bokarev, Sergey I; Dantz, Marcus; Suljoti, Edlira; Kühn, Oliver; Aziz, Emad F

    2013-08-23

    Nonradiative decay channels in the L-edge fluorescence yield spectra from transition-metal-aqueous solutions give rise to spectral distortions with respect to x-ray transmission spectra. Their origin is unraveled here using partial and inverse partial fluorescence yields on the microjet combined with multireference ab initio electronic structure calculations. Comparing Fe2+, Fe3+, and Co2+ systems we demonstrate and quantify unequivocally the state-dependent electron delocalization within the manifold of d orbitals as one origin of this observation.

  19. Full-Dimensional Quantum Calculations of Vibrational Levels of NH4(+) and Isotopomers on An Accurate Ab Initio Potential Energy Surface.

    Science.gov (United States)

    Yu, Hua-Gen; Han, Huixian; Guo, Hua

    2016-04-14

    Vibrational energy levels of the ammonium cation (NH4(+)) and its deuterated isotopomers are calculated using a numerically exact kinetic energy operator on a recently developed nine-dimensional permutation invariant semiglobal potential energy surface fitted to a large number of high-level ab initio points. Like CH4, the vibrational levels of NH4(+) and ND4(+) exhibit a polyad structure, characterized by a collective quantum number P = 2(v1 + v3) + v2 + v4. The low-lying vibrational levels of all isotopomers are assigned and the agreement with available experimental data is better than 1 cm(-1).

  20. Molecular structures and vibrational frequencies of xanthine and its methyl derivatives (caffeine and theobromine) by ab initio Hartree-Fock and density functional theory calculations

    Science.gov (United States)

    Ucun, Fatih; Sağlam, Adnan; Güçlü, Vesile

    2007-06-01

    The molecular structures, vibrational frequencies and corresponding vibrational assignments of xanthine and its methyl derivatives (caffeine and theobromine) have been calculated using ab initio Hartree-Fock (HF) and density functional theory (B3LYP) methods with 6-31G(d, p) basis set level. The calculations were utilized to the CS symmetries of the molecules. The obtained vibrational frequencies and optimised geometric parameters (bond lengths and bond angles) were seen to be well agreement with the experimental data. The used scale factors which have been obtained the ratio of the frequency values of the strongest peaks in the calculated and experimental spectra seem to cause the gained vibrations well corresponding to the experimental ones. Theoretical infrared intensities and Raman activities are also reported.

  1. Origin of the n -type and p -type conductivity of MoS 2 monolayers on a SiO 2 substrate

    KAUST Repository

    Dolui, Kapildeb; Rungger, Ivan; Sanvito, Stefano

    2013-01-01

    Ab initio density functional theory calculations are performed to study the electronic properties of a MoS2 monolayer deposited over a SiO 2 substrate in the presence of interface impurities and defects. When MoS2 is placed on a defect

  2. Physical properties of molybdenum monoboride: Ab-initio study

    Science.gov (United States)

    Rajpoot, Priyanka; Rastogi, Anugya; Verma, U. P.

    2018-02-01

    The Ab initio investigations on structural, electronic, optical and thermal properties of MoB have been reported using full potential linearised-augmented plane wave method within the framework of density functional theory. The exchange and correlation potentials were calculated using the Perdew-Burke-Ernzerhof-Sol generalised gradient approximation. The calculated equilibrium lattice constants and cell volume are in excellent agreement with the experimental results as compared to the available theoretical data. Electronic band structure shows that MoB is metallic in nature. From the partial densities of states of MoB it has been found that major contribution on the Fermi level is due to Mo-4d states. Among the reported optical parameters the large value of reflectivity at low energy shows that MoB can be used as a coating material in IR region. Maximum absorption in extreme UV region shows that it can be used in production of electricity through solar power in space vehicles. Various thermal properties have been calculated in a wide temperature range at high pressures. Change in thermal expansion coefficient with respect to temperature shows that anharmonic effect in MoB is very weak at high temperature. The optical and thermal properties of MoB are presented for the first time in this work.

  3. The QUANTUM I project: Parallel processing in a local area network work dedicated to ab initio calculation of potential hypersurfaces

    International Nuclear Information System (INIS)

    Lavenir, E.; Pic, J.M.; Alibran, P.; Leclercq, J.M.

    1987-01-01

    The QUANTUM I project is a three-stage device. The stages are respectively dedicated to particular steps of the ab initio determination of a point on the hypersurface. The first stage deals with the computation of the integrals between the basis functions, the second with the S.C.F. (or M.C.S.C.F.) process and the third with the C.I treatment. Each step is developed in terms of parallel mode (M.I.M.D.), the whole device working following a pipeline mode: the three stages works simultaneously for different points

  4. Ti, Al and N adatom adsorption and diffusion on rocksalt cubic AlN (001) and (011) surfaces: Ab initio calculations

    Science.gov (United States)

    Mastail, C.; David, M.; Nita, F.; Michel, A.; Abadias, G.

    2017-11-01

    We use ab initio calculations to determine the preferred nucleation sites and migration pathways of Ti, Al and N adatoms on cubic NaCl-structure (B1) AlN surfaces, primary inputs towards a further thin film growth modelling of the TiAlN alloy system. The potential energy landscape is mapped out for both metallic species and nitrogen adatoms for two different AlN surface orientations, (001) and (110), using density functional theory. For all species, the adsorption energies on AlN(011) surface are larger than on AlN(001) surface. Ti and Al adatom adsorption energy landscapes determined at 0 K by ab initio show similar features, with stable binding sites being located in, or near, epitaxial surface positions, with Ti showing a stronger binding compared to Al. In direct contrast, N adatoms (Nad) adsorb preferentially close to N surface atoms (Nsurf), thus forming strong N2-molecule-like bonds on both AlN(001) and (011). Similar to N2 desorption mechanisms reported for other cubic transition metal nitride surfaces, in the present work we investigate Nad/Nsurf desorption on AlN(011) using a drag calculation method. We show that this process leaves a Nsurf vacancy accompanied with a spontaneous surface reconstruction, highlighting faceting formation during growth.

  5. Exchange coupling and magnetic anisotropy in a family of bipyrimidyl radical-bridged dilanthanide complexes: density functional theory and ab initio calculations.

    Science.gov (United States)

    Zhang, Yi-Quan; Luo, Cheng-Lin; Zhang, Qiang

    2014-05-05

    The origin of the magnetic anisotropy energy barriers in a series of bpym(-) (bpym = 2,2'-bipyrimidine) radical-bridged dilanthanide complexes [(Cp*2Ln)2(μ-bpym)](+) [Cp* = pentamethylcyclopentadienyl; Ln = Gd(III) (1), Tb(III) (2), Dy(III) (3), Ho(III) (4), Er(III) (5)] has been explored using density functional theory (DFT) and ab initio methods. DFT calculations show that the exchange coupling between the two lanthanide ions for each complex is very weak, but the antiferromagnetic Ln-bpym(-) couplings are strong. Ab initio calculations show that the effective energy barrier of 2 or 3 mainly comes from the contribution of a single Tb(III) or Dy(III) fragment, which is only about one third of a single Ln energy barrier. For 4 or 5, however, both of the two Ho(III) or Er(III) fragments contribute to the total energy barrier. Thus, it is insufficient to only increase the magnetic anisotropy energy barrier of a single Ln ion, while enhancing the Ln-bpym(-) couplings is also very important. Copyright © 2014 Wiley Periodicals, Inc.

  6. Electronic properties of mixed molybdenum dichalcogenide MoTeSe: LCAO calculations and Compton spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Ahuja, Ushma [Department of Electrical Engineering, Veermata Jijabai Technological Institute, H. R. Mahajani Marg, Matunga (East), Mumbai 400019, Maharashtra (India); Kumar, Kishor; Joshi, Ritu [Department of Physics, University College of Science, M.L. Sukhadia University, Udaipur 313001, Rajasthan (India); Bhavsar, D.N. [Department of Physics, Bhavan' s Seth R.A. College of Science, Khanpur, Ahmedabad 380001, Gujarat (India); Heda, N.L., E-mail: nlheda@yahoo.co.in [Department of Pure and Applied Physics, University of Kota, Kota 324007, Rajasthan (India)

    2016-07-01

    We have employed linear combination of atomic orbitals (LCAO) method to compute the Mulliken’s population (MP), energy bands, density of states (DOS) and Compton profiles for hexagonal MoTeSe. The density functional theory (DFT) and hybridization of Hartree-Fock with DFT (B3LYP) have been used within the LCAO approximation. Performance of theoretical models has been tested by comparing the theoretical momentum densities with the experimental Compton profile of MoTeSe measured using {sup 137}Cs Compton spectrometer. It is seen that the B3LYP prescription gives a better agreement with the experimental data than other DFT based approximations. The energy bands and DOS depict an indirect band gap character in MoTeSe. In addition, a relative nature of bonding in MoTeSe and its isovalent MoTe{sub 2} is discussed in terms of equal-valence-electron-density (EVED) profiles. On the basis of EVED profiles it is seen that MoTeSe is more covalent than MoTe{sub 2}.

  7. Insights inot the atomic many-particle dynamics of scattering processes by ab-initio calculations; Einblicke in die atomare Vielteilchendynamik von Streuprozessen durch ab-initio-Rechnungen

    Energy Technology Data Exchange (ETDEWEB)

    Zapukhlyak, Myroslav

    2008-12-05

    The present thesis gives a theoretical contribution to the understanding of the many-particle dynamics in inelastic ion-atom collisions. Many-electron dynamics in ion-helium collisions and proton-sodium collisions was theoretically studied. The description is based on the semiclassical approximation with the straight orbit for the projectile motion. The ion-atom collision problem is by this reduced to a time-dependent many-electron problem and in the non-relativistic approximation described by the time-dependent Schroedinger equation. The solution of the many-electron problem pursues in the framework of the time-dependent density functional theory. The time-dependent Schroedinger equation for the interacting many-electron problem is transformed to the system of the time-dependent Kohn-Sham equations and solved by the two-center-basis generator method. The unknown time-dependent exchange-correlation one-particle potential forces different approximation in the time-dependent Kohn-Shan scheme. In this thesis the model of the independent electrons was applied as basis model, in which the electron-electron correlation is consistently neglected in all parts and in all steps. Differential cross sections for different one- and two-electron processes were calculated in the so-called eikonal approximation for the collisional systems p-He, He{sup 2+}-He, and Ar{sup q+}-He (q=15-18). [German] Die vorliegende Arbeit leistet einen theoretischen Beitrag zum Verstaendnis der Vielteilchendynamik in inelastischen Ion-Atom-Stoessen. Vielelektronendynamik in Ion-Helium-Stoessen und Proton-Natrium-Stoessen wurde theoretisch untersucht. Die Beschreibung basiert auf der semiklassischen Naeherung mit der geraden Bahn fuer die Projektilbewegung. Das Ion-Atom- Stossproblem wird damit auf ein zeitabhaengiges Vielelektronenproblem reduziert und in der nichtrelativistischen Naeherung mit der zeitabhaengigen Schroedinger-Gleichung beschrieben. Die Loesung des Vielelektronenproblems erfolgt im

  8. Clustering/anticlustering effects on the GeSi Raman spectra at moderate (Ge,Si) contents: Percolation scheme vs. ab initio calculations

    Science.gov (United States)

    Torres, V. J. B.; Hajj Hussein, R.; Pagès, O.; Rayson, M. J.

    2017-02-01

    We test a presumed ability behind the phenomenological percolation scheme used for the basic description of the multi-mode Raman spectra of mixed crystals at one dimension along the linear chain approximation, to determine, via the Raman intensities, the nature of the atom substitution, as to whether this is random or due to local clustering/anticlustering. For doing so, we focus on the model percolation-type GeySi1-y system characterized by six oscillators { 1 × ( G e - G e ) , 3 × ( G e - S i ) , 2 × ( S i - S i ) } and place the study around the critical compositions y ˜ (0.16, 0.71, and 0.84) corresponding to nearly matching of intensities between the like Raman modes from a given multiplet ( G e - S i triplet or S i - S i doublet). The interplay between the GeySi1-y Raman intensities predicted by the percolation scheme depending on a suitable order parameter κ of local clustering/anticlustering is found to be consistent with ab initio calculations of the GeySi1-y Raman spectra done with the Ab Initio Modeling PROgram code using large (64-, 216-, and 512-atoms) disordered cubic supercells matching the required ( y , κ ) values. The actual "percolation vs. ab initio" comparative insight at moderate/dilute-(Ge,Si) limits, with an emphasis on the κ -induced intra-bond transfer of oscillator strength, extends a pioneering one earlier achieved at an intermediate composition ( y ˜ 0.50) by using small (32-atom) supercells [O. Pagès et al., J. Appl. Phys. 114, 033513 (2013)], mainly concerned with the inter-bond transfer of oscillator strength, providing altogether a complete picture.

  9. Ab-initio calculation and experimental observation of room temperature ferromagnetism in 50 keV nitrogen implanted rutile TiO2

    Science.gov (United States)

    Luitel, Homnath; Chakrabarti, Mahuya; Sarkar, A.; Dechoudhury, S.; Bhowmick, D.; Naik, V.; Sanyal, D.

    2018-02-01

    Room temperature magnetic properties of 50 keV N4+ ion beam implanted rutile TiO2 have been theoretically and experimentally studied. Ab-initio calculation under the frame work of density functional theory has been carried out to study the magnetic properties of the different possible nitrogen related defects in TiO2. Spin polarized density of states calculation suggests that both Ninst and NO can induce ferromagnetic ordering in rutile TiO2. In both cases the 2p orbital electrons of nitrogen atom give rise to the magnetic moment in TiO2. The possibility of the formation of N2 molecule in TiO2 system is also studied but in this case no significant magnetic moment has been observed. The magnetic measurements, using SQUID magnetometer, results a ferromagnetic ordering even at room temperature for the 50 keV N4+ ion beam implanted rutile TiO2.

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

    Science.gov (United States)

    Partovi-Azar, Pouya; Kühne, Thomas D

    2015-11-05

    We present a novel computational method to accurately calculate Raman spectra from first principles. Together with an extension of the second-generation Car-Parrinello method of Kühne et al. (Phys. Rev. Lett. 2007, 98, 066401) to propagate maximally localized Wannier functions together with the nuclei, a speed-up of one order of magnitude can be observed. This scheme thus allows to routinely calculate finite-temperature Raman spectra "on-the-fly" by means of ab-initio molecular dynamics simulations. To demonstrate the predictive power of this approach we investigate the effect of hydrophobic and hydrophilic solutes in water solution on the infrared and Raman spectra. © 2015 Wiley Periodicals, Inc.

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

    DEFF Research Database (Denmark)

    Shim, Irene; Gingerich, K. A.

    1984-01-01

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

  12. The gaseous enthalpy of formation of the ionic liquid 1-butyl-3-methylimidazolium dicyanamide from combustion calorimetry, vapor pressure measurements, and ab initio calculations.

    Science.gov (United States)

    Emel'yanenko, Vladimir N; Verevkin, Sergey P; Heintz, Andreas

    2007-04-04

    Ionic liquids are attracting growing interest as alternatives to conventional molecular solvents. Experimental values of vapor pressure, enthalpy of vaporization, and enthalpy of formation of ionic liquids are the key thermodynamic quantities, which are required for the validation and development of the molecular modeling and ab initio methods toward this new class of solvents. In this work, the molar enthalpy of formation of the liquid 1-butyl-3-methylimidazolium dicyanamide, 206.2 +/- 2.5 kJ.mol-1, was measured by means of combustion calorimetry. The molar enthalpy of vaporization of 1-butyl-3-methylimidazolium dicyanamide, 157.2 +/- 1.1 kJ.mol-1, was obtained from the temperature dependence of the vapor pressure measured using the transpiration method. The latter method has been checked with measurements of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide, where data are available from the effusion technique. The first experimental determination of the gaseous enthalpy of formation of the ionic liquid 1-butyl-3-methylimidazolium dicyanamide, 363.4 +/- 2.7 kJ.mol-1, from thermochemical measurements (combustion and transpiration) is presented. Ab initio calculations of the enthalpy of formation in the gaseous phase have been performed for 1-butyl-3-methylimidazolium dicyanamide using the G3MP2 theory. Excellent agreement with experimental results has been observed. The method developed opens a new way to obtain thermodynamic properties of ionic liquids which have not been available so far.

  13. Prediction of folding preference of 10 kDa silk-like proteins using a Lego approach and ab initio calculations.

    Science.gov (United States)

    Pohl, Gábor; Beke, Tamás; Borbély, János; Perczel, András

    2006-11-15

    Because of their great flexibility and strength resistance, both spider silks and silkworm silks are of increasing scientific and commercial interest. Despite numerous spectroscopic and theoretical studies, several structural properties at the atomic level have yet to be identified. The present theoretical investigation focuses on these issues by studying three silk-like model peptides: (AG)(64), [(AG)(4)EG](16), and [(AG)(4)PEG](16), using a Lego-type approach to construct these polypeptides. On the basis of these examples it is shown that thermoneutral isodesmic reactions and ab initio calculations provide a capable method to investigate structural properties of repetitive polypeptides. The most probable overall fold schema of these molecules with respect to the type of embedded hairpin structures were determined at the ab initio level of theory (RHF/6-311++G(d,p)//RHF/3-21G). Further on, analysis is carried out on the possible hairpin and turn regions and on their effect on the global fold. In the case of the (AG)(64) model peptide, the optimal beta-sheet/turn ratio was also determined, which provided good support for experimental observations. In addition, lateral shearing of a hairpin "folding unit" was investigated at the quantum chemical level to explain the mechanical properties of spider silk. The unique mechanical characteristics of silk bio-compounds are now investigated at the atomic level.

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

    Science.gov (United States)

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

    2017-04-01

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

  15. Ab initio calculations and kinetic modeling of thermal conversion of methyl chloride: implications for gasification of biomass

    DEFF Research Database (Denmark)

    Singla, Mallika; Rasmussen, Morten Lund; Hashemi, Hamid

    2018-01-01

    . In the present work, the thermal conversion of CH3Cl under gasification conditions was investigated. A detailed chemical kinetic model for pyrolysis and oxidation of methyl chloride was developed and validated against selected experimental data from the literature. Key reactions of CH2Cl with O2 and C2H4......Limitations in current hot gas cleaning methods for chlorine species from biomass gasification may be a challenge for end use such as gas turbines, engines, and fuel cells, all requiring very low levels of chlorine. During devolatilization of biomass, chlorine is released partly as methyl chloride...... in low-temperature gasification. The present work illustrates how ab initio theory and chemical kinetic modeling can help to resolve emission issues for thermal processes in industrial scale....

  16. Calculation of intermolecular potentials for H2−H2 and H2−O2 dimers ab initio and prediction of second virial coefficients

    International Nuclear Information System (INIS)

    Pham Van, Tat; Deiters, Ulrich K.

    2015-01-01

    Highlights: • We construct the angular orientations of dimers H 2 −H 2 and H 2 −O 2 . • We calculate the ab initio intermolecular interaction energies for all built orientations. • Extrapolating the interaction energies to the complete basis set limit aug-cc-pV23Z. • We develop two 5-site ab initio intermolecular potentials of dimers H 2 −H 2 , H 2 −O 2 . • Calculating the virial coefficients of dimer H 2 −H 2 and H 2 −O 2 . - Abstract: The intermolecular interaction potentials of the dimers H 2 −H 2 and H 2 −O 2 were calculated from quantum mechanics, using coupled-cluster theory CCSD(T) and correlation-consistent basis sets aug-cc-pVmZ (m = 2, 3); the results were extrapolated to the basis set limit aug-cc-pV23Z. The interaction energies were corrected for the basis set superposition error with the counterpoise scheme. For comparison also Møller–Plesset perturbation theory (at levels 2–4) with the basis sets aug-cc-pVTZ were considered, but the results proved inferior. The quantum mechanical results were used to construct analytical pair potential functions. From these functions the second virial coefficients of hydrogen and the cross virial coefficients of the hydrogen–oxygen system were obtained by integration; in both cases corrections for quantum effects were included. The results agree well with experimental data, if available, or with empirical correlations

  17. Plasmons on the edge of MoS2 nanostructures

    DEFF Research Database (Denmark)

    Andersen, Kirsten; Jacobsen, Karsten Wedel; Thygesen, Kristian Sommer

    2014-01-01

    Using ab initio calculations we predict the existence of one-dimensional (1D), atomically confined plasmons at the edges of a zigzag MoS2 nanoribbon. The strongest plasmon originates from a metallic edge state localized on the sulfur dimers decorating the Mo edge of the ribbon. A detailed analysis...... of the dielectric function reveals that the observed deviations from the ideal 1D plasmon behavior result from single-particle transitions between the metallic edge state and the valence and conduction bands of the MoS2 sheet. The Mo and S edges of the ribbon are clearly distinguishable in calculated spatially...... resolved electron energy loss spectrum owing to the different plasmonic properties of the two edges. The edge plasmons could potentially be utilized for tuning the photocatalytic activity of MoS2 nanoparticles....

  18. Electronic excitation of furfural as probed by high-resolution vacuum ultraviolet spectroscopy, electron energy loss spectroscopy, and ab initio calculations

    Science.gov (United States)

    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.

  19. Electronic excitation of furfural as probed by high-resolution vacuum ultraviolet spectroscopy, electron energy loss spectroscopy, and ab initio calculations

    International Nuclear Information System (INIS)

    Ferreira da Silva, F.; Lange, E.; Limão-Vieira, P.; Jones, N. C.; Hoffmann, S. V.; Hubin-Franskin, M.-J.; Delwiche, J.; Brunger, M. J.

    2015-01-01

    The electronic spectroscopy of isolated furfural (2-furaldehyde) in the gas phase has been investigated using high-resolution photoabsorption spectroscopy in the 3.5–10.8 eV energy-range, with absolute cross section measurements derived. Electron energy loss spectra are also measured over a range of kinematical conditions. Those energy loss spectra are used to derive differential cross sections and in turn generalised oscillator strengths. These experiments are supported by ab initio calculations in order to assign the excited states of the neutral molecule. The good agreement between the theoretical results and the measurements allows us to provide the first quantitative assignment of the electronic state spectroscopy of furfural over an extended energy range

  20. Temperature dependence of the EFG at Cd-doped Lu2O3: How ab initio calculations can complement PAC experiments

    International Nuclear Information System (INIS)

    Errico, L.A.; Renteria, M.; Bibiloni, A.G.; Darriba, G.N.

    2005-01-01

    We report an ab initio study of the temperature dependence of the electric-field gradient (EFG) tensor at Cd impurities replacing cations in Lu 2 O 3 . Calculations were performed with the Full-Potential Linearized-Augmented Plane Wave method that allows us to treat the electronic structure and the processes induced by the impurity in the host-lattice without the use of external parameters. In this new insight, the EFG thermal dependence arises from the ionization of an impurity acceptor level introduced in the band-gap of Lu 2 O 3 by Cd impurities, in good agreement with a previously proposed two state model. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  1. Temperature dependence of the EFG at Cd-doped Lu{sub 2}O{sub 3}: How ab initio calculations can complement PAC experiments

    Energy Technology Data Exchange (ETDEWEB)

    Errico, L.A.; Renteria, M.; Bibiloni, A.G.; Darriba, G.N. [Departamento de Fisica, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, CC 67, 1900 La Plata (Argentina)

    2005-08-01

    We report an ab initio study of the temperature dependence of the electric-field gradient (EFG) tensor at Cd impurities replacing cations in Lu{sub 2}O{sub 3}. Calculations were performed with the Full-Potential Linearized-Augmented Plane Wave method that allows us to treat the electronic structure and the processes induced by the impurity in the host-lattice without the use of external parameters. In this new insight, the EFG thermal dependence arises from the ionization of an impurity acceptor level introduced in the band-gap of Lu{sub 2}O{sub 3} by Cd impurities, in good agreement with a previously proposed two state model. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  2. Oxygen-metal bonding in Ti-bearing compounds from O 1s spectra and ab initio full multiple-scattering calculations

    International Nuclear Information System (INIS)

    Ziyu Wu; Paris, E.; Langenhorst, F.; Seifert, F.

    2002-01-01

    The O K-edge spectra of a series of Ti-bearing compounds with Ti in diffrent structural and chemical environments have been measured using electron energy-loss spectroscopy and analyzed using ab initio full multiple-scattering (MS) calculations. The near-edge structures arise mainly from covalency by direct and/or indirect interaction between O and metal atoms and between O and Si atoms. The coordination number of the cation and the site symmetry also influence the spectral shape and structures. Using different size clusters around the excited atom in the full MS simulation, it is possible to interpret and assign the features present in the spectra of each compund to its specific atomic arrangement and electronic structure. (au)

  3. Electronic excitation of furfural as probed by high-resolution vacuum ultraviolet spectroscopy, electron energy loss spectroscopy, and ab initio calculations

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira da Silva, F.; Lange, E. [Laboratório de Colisões Atómicas e Moleculares, CEFITEC, Departamento de Física, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica (Portugal); Limão-Vieira, P., E-mail: plimaovieira@fct.unl.pt, E-mail: michael.brunger@flinders.edu.au, E-mail: maplima@ifi.unicamp.br [Laboratório de Colisões Atómicas e Moleculares, CEFITEC, Departamento de Física, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica (Portugal); School of Chemical and Physical Sciences, Flinders University, GPO Box 2100, Adelaide, South Australia 5001 (Australia); Jones, N. C.; Hoffmann, S. V. [ISA, Department of Physics and Astronomy, Aarhus University, Ny Munkegade, DK-8000 Århus C (Denmark); Hubin-Franskin, M.-J.; Delwiche, J. [Départment de Chimie, Institut de Chimie-Bât. B6C, Université de Liège, B-4000 Liège 1 (Belgium); Brunger, M. J., E-mail: plimaovieira@fct.unl.pt, E-mail: michael.brunger@flinders.edu.au, E-mail: maplima@ifi.unicamp.br [School of Chemical and Physical Sciences, Flinders University, GPO Box 2100, Adelaide, South Australia 5001 (Australia); Institute of Mathematical Sciences, University of Malaya, 50603 Kuala Lumpur (Malaysia); and others

    2015-10-14

    The electronic spectroscopy of isolated furfural (2-furaldehyde) in the gas phase has been investigated using high-resolution photoabsorption spectroscopy in the 3.5–10.8 eV energy-range, with absolute cross section measurements derived. Electron energy loss spectra are also measured over a range of kinematical conditions. Those energy loss spectra are used to derive differential cross sections and in turn generalised oscillator strengths. These experiments are supported by ab initio calculations in order to assign the excited states of the neutral molecule. The good agreement between the theoretical results and the measurements allows us to provide the first quantitative assignment of the electronic state spectroscopy of furfural over an extended energy range.

  4. Stability and mobility of self-interstitials and small interstitial clusters in α-iron: ab initio and empirical potential calculations

    International Nuclear Information System (INIS)

    Willaime, F.; Fu, C.C.; Marinica, M.C.; Dalla Torre, J.

    2005-01-01

    The stability and mobility of self-interstitials and small interstitial clusters, I n , in α-Fe is investigated by means of calculations performed in the framework of the density functional theory using the SIESTA code. The mono-, di- and tri-interstitials are shown to be made of (parallel) dumbbells and to migrate by nearest-neighbor translation-rotation jumps, according to Johnson's mechanism. The orientation of the dumbbells becomes energetically more favourable for I 5 and larger clusters. The performance of a semi-empirical potential recently developed for Fe, including ab initio self-interstitial data in the fitted properties, is evaluated over the present results. The superiority over previous semi-empirical potentials is confirmed. Finally the impact of the present results on the formation mechanism of loops, observed experimentally in α-Fe is discussed

  5. CARS spectroscopy of the NaH2 collision complex: The nature of the Na(3 2P)H2 exciplex - ab initio calculations and experimental results

    International Nuclear Information System (INIS)

    Vivie-Riedle, R. de; Hering, P.; Kompa, K.L.

    1990-01-01

    CARS has been used to analyze the rovibronic state distribution of H 2 after collision with Na(3 2 P). New lines, which do not correspond to H 2 lines are observed in the CARS spectrum. The experiments point to the formation of a complex of Na(3 2 P)H 2 in A 2 B 2 symmetry. Ab initio calculations of the A 2 B 2 potential were performed. On this surface the vibrational spectra of the exciplex is evaluated. The observed lines can be attributed to vibrational transitions in the complex, in which combinational modes are involved. The connection of experimental and theoretical results indicates that a collisionally stabilized exciplex molecule is formed during the quenching process. (orig.)

  6. Fluorine substitution and nonconventional OH...pi intramolecular bond: high-resolution UV spectroscopy and ab initio calculations of 2-(p-fluorophenyl)ethanol.

    Science.gov (United States)

    Karaminkov, Rosen; Chervenkov, Sotir; Neusser, Hans J

    2008-05-21

    The para-fluorinated flexible neurotransmitter analogue 2-phenylethanol has been investigated by highly resolved resonance-enhanced two-photon ionisation two-colour UV laser spectroscopy with mass resolution and ab initio structural optimisations and energy calculations. Two stable conformations, gauche and anti, separated by a high potential barrier have been identified in the cold molecular beam by rotational analysis of the vibronic band structures. The theoretically predicted higher-lying conformations most likely relax to these two structures during the adiabatic expansion. The lowest-energy gauche conformer is stabilised by an intramolecular nonconventional OH...pi-type hydrogen bond between the terminal OH group of the side chain and the pi electrons of the phenyl ring. The good agreement between the experimental and theoretical results demonstrates that even the substitution with a strongly electronegative atom of 2-phenylethanol at the para position has no noticeable effect on the strength and orientation of the OH...pi bond.

  7. Ab initio calculation of a global potential, vibrational energies, and wave functions for HCN/HNC, and a simulation of the (A-tilde)-(X-tilde) emission spectrum

    Science.gov (United States)

    Bowman, Joel M.; Gazdy, Bela; Bentley, Joseph A.; Lee, Timothy J.; Dateo, Christopher E.

    1993-01-01

    A potential energy surface for the HCN/HNC system which is a fit to extensive, high-quality ab initio, coupled-cluster calculations is presented. All HCN and HNC states with energies below the energy of the first delocalized state are reported and characterized. Vibrational transition energies are compared with all available experimental data on HCN and HNC, including high CH-overtone states up to 23,063/cm. A simulation of the (A-tilde)-(X-tilde) stimulated emission pumping (SEP) spectrum is also reported, and the results are compared to experiment. Franck-Condon factors are reported for odd bending states of HCN, with one quantum of vibrational angular momentum, in order to compare with the recent assignment by Jonas et al. (1992), on the basis of axis-switching arguments of a number of previously unassigned states in the SEP spectrum.

  8. Hydrogenation of ethene catalyzed by Ir atom deposited on γ-Al2O3(001) surface: From ab initio calculations

    International Nuclear Information System (INIS)

    Chen, Yongchang; Sun, Zhaolin; Song, Lijuan; Li, Qiang; Xu, Ming

    2012-01-01

    Ethene hydrogenation reaction, catalyzed by an iridium atom adsorbed on γ-Al 2 O 3 (001) surface, is studied via ab initio calculations based on density functional theory (DFT). The catalyzed reaction process and activation energy are compared with the counterparts of a reaction occurs in vacuum condition. It is found that the activation energy barrier is substantially lowered by the adsorbed Ir atom on the γ-Al 2 O 3 (001). The catalyzed reaction is modeled in two steps: (1) Hydrogen molecular dissolution and then bonded with C 2 H 4 molecular. (2) Desorption of the C 2 H 6 molecular from the surface. -- Highlights: ► The ethene hydrogenation reaction is simulated with nudged elastic band methods. ► The catalytic effect of the Ir atom on γ-Al 2 O 3 (001) surface is modeled. ► Details of the catalytic reaction are exhibited.

  9. Ab initio atomistic thermodynamics calculations of the initial deposition of epitaxial MgO film on GaAs(001)-{beta}2(2 Multiplication-Sign 4)

    Energy Technology Data Exchange (ETDEWEB)

    Tamarany, Rizcky; Lee, Seung-Cheol [Korea Institute of Science and Technology, Seoul 136-791 (Korea, Republic of); Department of Nanomaterials Science and Engineering, University of Science and Technology, Daejeon 305-350 (Korea, Republic of); Kim, Hyung-Jun; Choi, Jung-Hae [Korea Institute of Science and Technology, Seoul 136-791 (Korea, Republic of)

    2013-02-07

    Ab initio calculations were performed to investigate the initial deposition of epitaxial MgO on GaAs(001)-{beta}2(2 Multiplication-Sign 4). The differences between the chemical bonding of Mg-As and O-As were characterized by the adsorption energies of atomic O and Mg at several symmetrically distinct sites, and O bonding was substantially stronger than that of Mg. Thermodynamics were analyzed through the introduction of environmental chemical potentials simulating in situ growth conditions by the sputtering of a stoichiometric MgO target. A surface phase diagram was generated under Mg and O environments with constrained equilibrium, and the results explained the initial formation of an epitaxial MgO phase on GaAs(001)-{beta}2(2 Multiplication-Sign 4).

  10. Ab initio atomistic thermodynamics calculations of the initial deposition of epitaxial MgO film on GaAs(001)-β2(2 × 4)

    International Nuclear Information System (INIS)

    Tamarany, Rizcky; Lee, Seung-Cheol; Kim, Hyung-Jun; Choi, Jung-Hae

    2013-01-01

    Ab initio calculations were performed to investigate the initial deposition of epitaxial MgO on GaAs(001)-β2(2 × 4). The differences between the chemical bonding of Mg-As and O-As were characterized by the adsorption energies of atomic O and Mg at several symmetrically distinct sites, and O bonding was substantially stronger than that of Mg. Thermodynamics were analyzed through the introduction of environmental chemical potentials simulating in situ growth conditions by the sputtering of a stoichiometric MgO target. A surface phase diagram was generated under Mg and O environments with constrained equilibrium, and the results explained the initial formation of an epitaxial MgO phase on GaAs(001)-β2(2 × 4).

  11. Local coordination structure and electronic structure of the large electron mobility amorphous oxide semiconductor In-Ga-Zn-O: Experiment and ab initio calculations

    International Nuclear Information System (INIS)

    Nomura, Kenji; Ohta, Hiromichi; Hirano, Masahiro; Kamiya, Toshio; Uruga, Tomoya; Hosono, Hideo

    2007-01-01

    Ionic amorphous oxide semiconductors (IAOSs) are new materials for flexible thin film transistors that exhibit field-effect mobilities of ∼10 cm 2 V -1 s -1 [K. Nomura et al., Nature 488, 432 (2004)]. The local coordination structure in an IAOS, In-Ga-Zn-O (a-IGZO), was examined using extended x-ray absorption fine structure analysis combined with ab initio calculations. The short-range ordering and coordination structures in a-IGZO are similar to those in the corresponding crystalline phase, InGaZnO 4 , and edge-sharing structures consisting of In-O polyhedra remain in the amorphous structure. The In 3+ 5s orbitals form an extended state with a band effective mass of ∼0.2m e at the conduction band bottom

  12. CNDO/2-SCF and PCILO (MO) calculations on the 1-butene/NA/and (charge-transfer) complex

    Energy Technology Data Exchange (ETDEWEB)

    Lochmann, R; Meiler, W

    1977-01-01

    CNDO/2-SCF and PCILO (MO) calculations on the 1-Butene/Na/sup +/ (charge-transfer) complex involving the olefinic m electrons were made in connection with butene adsorption in zeolites, including the effect of the cation on the conformation of the butene in the zeolite cavity. Calculations were made of rotational energy barriers, preferred cation arrangements with respect to the butene molecule, and charge distributions by both methods. Taking into account systematic errors with the two methods, it is concluded that the PCILO method, which predicts a stabilization of the skew over the cis conformation by the cation, gives closer agreement with experiment. Graph, tables, diagrams, and 19 references.

  13. Ab initio calculation of transition state normal mode properties and rate constants for the H(T)+CH4(CD4) abstraction and exchange reactions

    International Nuclear Information System (INIS)

    Schatz, G.C.; Walch, S.P.; Wagner, A.F.

    1980-01-01

    We present ab initio (GVB--POL--CI) calculations for enough of the region about the abstraction and exchange saddle points for H(T)+CH 4 (CD 4 ) to perform a full normal mode analysis of the transition states. The resulting normal mode frequencies are compared to four other published surfaces: an ab initio UHF--SCF calculation by Carsky and Zahradnik, a semiempirical surface by Raff, and two semiempirical surfaces by Kurylo, Hollinden, and Timmons. Significant quantitative and qualitative differences exist between the POL--CI results and those of the other surfaces. Transition state theory rate constants and vibrationally adiabatic reaction threshold energies were computed for all surfaces and compared to available experimental values. For abstraction, the POL--CI rates are in good agreement with experimental rates and in better agreement than are the rates of any of the other surfaces. For exchange, uncertainties in the experimental values and in the importance of vibrationally nonadiabatic effects cloud the comparison of theory to experiment. Tentative conclusions are that the POL--CI barrier is too low by several kcal. Unless vibrationaly nonadiabatic effects are severe, the POL--CI surface is still in better agreement with experiment than are the other surfaces. The rates for a simple 3-atom transition state theory model (where CH 3 is treated as an atom) are compared to the rates for the full 6-atom model. The kinetic energy coupling of reaction coordinate modes to methyl group modes is identified as being of primary importance in determining the accuracy of the 3-atom model for this system. Substantial coupling in abstraction, but not exchange, causes the model to fail for abstraction but succeed for exchange

  14. Extended Fenske-Hall LCAO MO Calculations for Mixed Methylene Dihalides

    Science.gov (United States)

    Ziemann, Hartmut; Paulun, Manfred

    1988-10-01

    The electronic structure of mixed methylene dihalides CH2XY (X, Y = F, Cl, Br. I) has been studied using extended Fenske-Hall LCAO MO method. The comparison with available photoelec­tron spectra confirmes previous assignments of all bands with binding energies <100 eV. The electronic structure changes occurring upon varying the halogen substituents are discussed.

  15. Ab-initio calculations of semiconductor MgGeP{sub 2} and MgGeAs{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Kocak, B.; Ciftci, Y.O., E-mail: yasemin@gazi.edu.tr

    2016-05-15

    Highlights: • MgGeP{sub 2} and MgGeAs{sub 2} are semiconductor compounds. • MgGeP{sub 2} and MgGeAs{sub 2} are energetically, mechanically and dynamically stable. • The electronic charge density contour plot shows that the nature of bonding is a mixture of ionic-covalent. - Abstract: In this study, we focus on structural, electronic, elastic, lattice dynamic and optic properties of MgGeP{sub 2} and MgGeAs{sub 2} using ab-initio density-functional theory (DFT) within Armiento-Mattson 2005 (AM05) scheme of the generalized gradient approximation (GGA) for the exchange-correlation potential. Our computed structural results are in reasonable agreement with the literature. The band gap of these compounds is predicted to be direct. Our elastic results prove that these compounds are mechanically stable. The obtained phonon spectra of MgGeP{sub 2} and MgGeAs{sub 2} do not exhibit any significant imaginary branches using GGA-AM05 for the exchange-correlation approximation. Further analysis of the optical response of the dielectric functions, optical reflectivity, refractive index, extinction coefficient and electron energy loss delves into for the energy range of 0–22.5 eV. It motivated that there exists an optical polarization anisotropy of these compounds for optoelectronic device applications.

  16. Accurate orbital-dependent correlation and exchange-correlation potentials from non-iterative ab initio dft calculations

    Science.gov (United States)

    Grabowski, Ireneusz; Lotrich, Victor

    2005-08-01

    A new approximate non-iterative procedure to obtain accurate correlation and exchange-correlation potentials of Kohn-Sham (KS) density functional theory (DFT) is presented. By carrying out only one step of the correlated optimized effective potential (OEP) iterations following the standard iterative exchange-only OEP, one can recover accurate correlation potentials corresponding to the orbital-dependent second-order many-body perturbation theory [MBPT(2)] energy functional that are hardly discernible from those obtained by the more expensive, fully iterative procedure. This new 'one-step' OEP-MBPT(2) algorithm reflects the non-iterative, perturbative algorithm of standard, canonical MBPT(2) of ab initio wave function theory, while it allows the correlation potentials to readjust and include the majority of the MBPT(2) correlation effect. It is also flexible in the treatment of exchange and the Hartree-Fock orbitals may be used in lieu of the exchange-only OEP orbitals, when the correlation or exchange-correlation potential is of interest.

  17. Ab-initio study on the absorption spectrum of color change sapphire based on first-principles calculations with considering lattice relaxation-effect

    Science.gov (United States)

    Novita, Mega; Nagoshi, Hikari; Sudo, Akiho; Ogasawara, Kazuyoshi

    2018-01-01

    In this study, we performed an investigation on α-Al2O3: V3+ material, or the so-called color change sapphire, based on first-principles calculations without referring to any experimental parameter. The molecular orbital (MO) structure was estimated by the one-electron MO calculations using the discrete variational-Xα (DV-Xα) method. Next, the absorption spectra were estimated by the many-electron calculations using the discrete variational multi-electron (DVME) method. The effect of lattice relaxation on the crystal structures was estimated based on the first-principles band structure calculations. We performed geometry optimizations on the pure α-Al2O3 and with the impurity V3+ ion using Cambridge Serial Total Energy Package (CASTEP) code. The effect of energy corrections such as configuration dependence correction and correlation correction was also investigated in detail. The results revealed that the structural change on the α-Al2O3: V3+ resulted from the geometry optimization improved the calculated absorption spectra. By a combination of both the lattice relaxation-effect and the energy correction-effect improve the agreement to the experiment fact.

  18. Electronic, magnetic properties and phase diagrams of system with Fe4N compound: An ab initio calculations and Monte Carlo study

    Science.gov (United States)

    Masrour, R.; Jabar, A.; Hlil, E. K.

    2018-05-01

    Self-consistent ab initio calculations, based on Density Functional Theory (DFT) approach and using Full potential Linear Augmented Plane Wave (FLAPW) method, are performed to investigate the electronic and magnetic properties of the Fe4N compound. Polarized spin and spin-orbit coupling are included in calculations within the framework of the ferromagnetic state between Fe(I) and Fe(II) in Fe4N compound. We have used the obtained data from abinitio calculations as an input in Monte Carlo simulation to calculate the magnetic properties of this compounds such as the ground state phase diagrams, total and partial magnetization of Fe(I) and Fe(II) as well as the transition temperatures are computed. The variation of magnetization with the crystal field are also studied. The magnetic hysteresis cycle of the same Fe4N compound are determined for different values of temperatures and crystal field values. The two-step hysteresis loop are evidenced, which is typical for Fe4N structure. The ferromagnetic and superparamagnetic phase is observed as well.

  19. Effective representation of amide III, II, I, and A modes on local vibrational modes: Analysis of ab initio quantum calculation results.

    Science.gov (United States)

    Hahn, Seungsoo

    2016-10-28

    The Hamiltonian matrix for the first excited vibrational states of a protein can be effectively represented by local vibrational modes constituting amide III, II, I, and A modes to simulate various vibrational spectra. Methods for obtaining the Hamiltonian matrix from ab initio quantum calculation results are discussed, where the methods consist of three steps: selection of local vibrational mode coordinates, calculation of a reduced Hessian matrix, and extraction of the Hamiltonian matrix from the Hessian matrix. We introduce several methods for each step. The methods were assessed based on the density functional theory calculation results of 24 oligopeptides with four different peptide lengths and six different secondary structures. The completeness of a Hamiltonian matrix represented in the reduced local mode space is improved by adopting a specific atom group for each amide mode and reducing the effect of ignored local modes. The calculation results are also compared to previous models using C=O stretching vibration and transition dipole couplings. We found that local electric transition dipole moments of the amide modes are mainly bound on the local peptide planes. Their direction and magnitude are well conserved except amide A modes, which show large variation. Contrary to amide I modes, the vibrational coupling constants of amide III, II, and A modes obtained by analysis of a dipeptide are not transferable to oligopeptides with the same secondary conformation because coupling constants are affected by the surrounding atomic environment.

  20. Ab-initio calculations of Co-based diluted magnetic semiconductors Cd 1-xCoxX (X=S, Se, Te)

    KAUST Repository

    Saeed, Yasir

    2010-10-01

    Ab-initio calculations are performed to investigate the structural, electronic and magnetic properties of spin-polarized diluted magnetic semiconductors composed of IIVI compounds Cd1-xCoxX (X=S, Se, Te) at x=0.25. From the calculated results of band structure and density of states, the half-metallic character and stability of ferromagnetic state for Cd1-xCoxS, Cd1-xCoxSe and Cd 1-xCoxTe alloys are determined. It is found that the tetrahedral crystal field gives rise to triple degeneracy t2g and double degeneracy eg. Furthermore, we predict the values of spin-exchange splitting energies Δx(d) and Δ x(p-d) and exchange constants N0α and N 0β produced by the Co 3d states. Calculated total magnetic moments and the robustness of half-metallicity of Cd1-xCo xX (X=S, Se, Te) with respect to the variation in lattice parameters are also discussed. We also extend our calculations to x=0.50, 0.75 for S compounds in order to observe the change due to increase in Co. © 2010 Elsevier B.V.

  1. Synthesis, characterization and DFT calculations of electronic and optical properties of CaMoO{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Bouzidi, Chaker, E-mail: bouzidtc@yahoo.fr [Laboratoire de Physico-chimie des Matériaux Minéraux et leurs Applications, Centre National des Recherches en Sciences des Matériaux, BP No.73, 8027 Soliman (Tunisia); Horchani-Naifer, Karima; Khadraoui, Zied [Laboratoire de Physico-chimie des Matériaux Minéraux et leurs Applications, Centre National des Recherches en Sciences des Matériaux, BP No.73, 8027 Soliman (Tunisia); Elhouichet, Habib [Laboratoire de Physico-chimie des Matériaux Minéraux et leurs Applications, Centre National des Recherches en Sciences des Matériaux, BP No.73, 8027 Soliman (Tunisia); Département de Physique, Faculté des Sciences de Tunis, Université de Tunis-ElManar ElManar, 2092 Tunis (Tunisia); Ferid, Mokhtar [Laboratoire de Physico-chimie des Matériaux Minéraux et leurs Applications, Centre National des Recherches en Sciences des Matériaux, BP No.73, 8027 Soliman (Tunisia)

    2016-09-15

    The electronic and optical properties of calcium molybdate (CaMoO{sub 4}) have been determined by X-ray diffraction, spectroscopic measurements and calculations of energy-band structures, density of states, and optical response functions by density functional theory. The chemical bonding analysis indicates that Mo–O bonds exhibit more covalent character than the Ca–O bond. The linear photon-energy-dependent dielectric functions, conductivity, refractive index, reflectivity and extinction coefficients were investigated and analyzed. The results are in agreement with previous theoretical works and the experimental data. Reflectivity spectra revealed that the CaMoO{sub 4} promises as good coating materials in the energy region of 9.3–11.6 eV with reflectivity larger than 75%.

  2. Electronic, elastic, thermodynamic properties and structure disorder of {gamma}-AlON solid solution from ab initio calculations

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yuezhong, E-mail: wyzphysics@163.com [Department of Physics and Key Laboratory for Radiation Physics and Technology of Ministry of Education, Sichuan University, Chengdu 610064 (China); Tianjin Jinhang Institute of Technical Physics, Tianjin 300192 (China); Lu, Tiecheng, E-mail: lutiecheng@scu.edu.cn [Department of Physics and Key Laboratory for Radiation Physics and Technology of Ministry of Education, Sichuan University, Chengdu 610064 (China); International Center for Material Physics, Chinese Academy of Sciences, Shenyang 110015 (China); Zhang, Rongshi [Tianjin Jinhang Institute of Technical Physics, Tianjin 300192 (China); Jiang, Shengli; Qi, Jianqi; Wang, Ying [Department of Physics and Key Laboratory for Radiation Physics and Technology of Ministry of Education, Sichuan University, Chengdu 610064 (China); Chen, Qingyun [Department of Physics and Key Laboratory for Radiation Physics and Technology of Ministry of Education, Sichuan University, Chengdu 610064 (China); National Defense Key Discipline Laboratory of Nuclear Waste and Environmental Safety, Southwest University of Science and Technology, Mianyang 621010 (China); Miao, Naihua [Physique Theorique des Materiaux, Universite de Liege, Sart Tilman B-4000 (Belgium); He, Duanwei [Institute of Atomic and Molecular Physics, Sichuan University, Chengdu 610064 (China)

    2013-01-25

    Highlights: Black-Right-Pointing-Pointer We reassess the chemical bonding character of {gamma}-AlON which shows strong ionicity. Black-Right-Pointing-Pointer {gamma}-AlON single-crystals exhibit highly elastic anisotropy. Black-Right-Pointing-Pointer The thermodynamic properties are investigated in a wider temperature/pressure range. Black-Right-Pointing-Pointer {gamma}-AlON is an O/N partially disordered structure. - Abstract: Spinel aluminium oxynitride ({gamma}-AlON), as a kind of transparent ceramic material expectable, is studied using the ab initio density functional method, in terms of electronic, elastic, thermodynamic properties and structure disorder. The results show that {gamma}-AlON exhibits strong ionicity, as quantitatively expressed by (Al{sub O}{sup 2.43+}){sub 15}(Al{sub T}{sup 2.41+}){sub 8}(O{sup 1.64-}){sub 27}(N{sup 2.27-}){sub 5} from our reassessment of the ionic character. We summarize and speculate that the considered oxynitride single-crystals exhibit highly elastic anisotropy. The interpretation of the thermodynamic properties of {gamma}-AlON according to quasi-harmonic Debye model confirm the available experiments and are extended to a wider temperature/pressure range. This material holds high elastic strength under extreme environments, where dB/dT absolute value is less than 0.03 GPa/K, independent of the pressure. Finally, we study the O/N structure disorder character of {gamma}-AlON solid solution by investigating nine possible crystal structures. It is found that {gamma}-AlON should be partially disordered, and in fact, the O/N ordering has a significant effect on the properties.

  3. Electronic, elastic, thermodynamic properties and structure disorder of γ-AlON solid solution from ab initio calculations

    International Nuclear Information System (INIS)

    Wang, Yuezhong; Lu, Tiecheng; Zhang, Rongshi; Jiang, Shengli; Qi, Jianqi; Wang, Ying; Chen, Qingyun; Miao, Naihua; He, Duanwei

    2013-01-01

    Highlights: ► We reassess the chemical bonding character of γ-AlON which shows strong ionicity. ► γ-AlON single-crystals exhibit highly elastic anisotropy. ► The thermodynamic properties are investigated in a wider temperature/pressure range. ► γ-AlON is an O/N partially disordered structure. - Abstract: Spinel aluminium oxynitride (γ-AlON), as a kind of transparent ceramic material expectable, is studied using the ab initio density functional method, in terms of electronic, elastic, thermodynamic properties and structure disorder. The results show that γ-AlON exhibits strong ionicity, as quantitatively expressed by (Al O 2.43+ ) 15 (Al T 2.41+ ) 8 (O 1.64- ) 27 (N 2.27- ) 5 from our reassessment of the ionic character. We summarize and speculate that the considered oxynitride single-crystals exhibit highly elastic anisotropy. The interpretation of the thermodynamic properties of γ-AlON according to quasi-harmonic Debye model confirm the available experiments and are extended to a wider temperature/pressure range. This material holds high elastic strength under extreme environments, where dB/dT absolute value is less than 0.03 GPa/K, independent of the pressure. Finally, we study the O/N structure disorder character of γ-AlON solid solution by investigating nine possible crystal structures. It is found that γ-AlON should be partially disordered, and in fact, the O/N ordering has a significant effect on the properties.

  4. A study of the atmospherically important reactions between dimethyl selenide (DMSe) and molecular halogens (X2 = Cl2, Br2, and I2) with ab initio calculations.

    Science.gov (United States)

    Rhyman, Lydia; Armata, Nerina; Ramasami, Ponnadurai; Dyke, John M

    2012-06-14

    The atmospherically relevant reactions between dimethyl selenide (DMSe) and the molecular halogens (X(2) = Cl(2), Br(2), and I(2)) have been studied with ab initio calculations at the MP2/aug-cc-pVDZ level of theory. Geometry optimization calculations showed that the reactions proceed from the reagents to the products (CH(3)SeCH(2)X + HX) via three minima, a van der Waals adduct (DMSe:X(2)), a covalently bound intermediate (DMSeX(2)), and a product-like complex (CH(3)SeCH(2)X:HX). The computed potential energy surfaces are used to predict what molecular species are likely to be observed in spectroscopic experiments such as gas-phase photoelectron spectroscopy and infrared matrix isolation spectroscopy. It is concluded that, for the reactions of DMSe with Cl(2) and Br(2), the covalent intermediate should be seen in spectroscopic experiments, whereas, in the DMSe + I(2) reaction, the van der Waals adduct DMSe:I(2) should be observed. Comparison is made with previous related calculations and experiments on dimethyl sulfide (DMS) with molecular halogens. The relevance of the results to atmospheric chemistry is discussed. The DMSeX(2) and DMSe:X(2) intermediates are likely to be reservoirs of molecular halogens in the atmosphere which will lead on photolysis to ozone depletion.

  5. Ab initio study of the positronation of the CaO and SrO molecules including calculation of annihilation rates.

    Science.gov (United States)

    Buenker, Robert J; Liebermann, Heinz-Peter

    2012-07-15

    Ab initio multireference single- and double-excitation configuration interaction calculations have been performed to compute potential curves for ground and excited states of the CaO and SrO molecules and their positronic complexes, e(+)CaO, and e(+)SrO. The adiabatic dissociation limit for the (2)Σ(+) lowest states of the latter systems consists of the positive metal ion ground state (M(+)) and the OPs complex (e(+)O(-)), although the lowest energy limit is thought to be e(+)M + O. Good agreement is found between the calculated and experimental spectroscopic constants for the neutral diatomics wherever available. The positron affinity of the closed-shell X (1)Σ(+) ground states of both systems is found to lie in the 0.16-0.19 eV range, less than half the corresponding values for the lighter members of the alkaline earth monoxide series, BeO and MgO. Annihilation rates (ARs) have been calculated for all four positronated systems for the first time. The variation with bond distance is generally similar to what has been found earlier for the alkali monoxide series of positronic complexes, falling off gradually from the OPs AR value at their respective dissociation limits. The e(+)SrO system shows some exceptional behavior, however, with its AR value reaching a minimum at a relatively large bond distance and then rising to more than twice the OPs value close to its equilibrium distance. Copyright © 2012 Wiley Periodicals, Inc.

  6. Ab initio supercell calculations of the (0001) α-Cr2O3 surface with a partially or totally Al-substituted external layer

    International Nuclear Information System (INIS)

    Sun Jizhong; Stirner, Thomas

    2009-01-01

    Ab initio supercell calculations employing the periodic Hartree-Fock formalism are presented of the (0001) α-Cr 2 O 3 surface with a partially or totally Al-substituted external layer. In the simulations a fraction of the Cr atoms at the surface of the chromia slab are replaced by Al atoms, and the Al surface coverage is varied between zero (pure chromia) and 100% (Al-terminated chromia). The surface Al atoms are found to relax inwards considerably, with the magnitude of the relaxation decreasing with increasing Al surface coverage. The calculations also reveal that the surface energy of the slab decreases with increasing Al coverage. Finally, the electronic properties at the surface of the Al-substituted (0001) α-Cr 2 O 3 slabs are investigated. Here the calculations show that the substitution of Cr by Al gives rise to an increase in the covalency of the Al-O bonds compared to slabs of pure alumina. In contrast, the influence of the surface Al atoms on the electrostatic potential in the (0001) plane of metal ions is relatively small. These findings support the utilisation of α-chromia substrates for the templated growth of α-alumina, which is consistent with recent experiments.

  7. Communication: A new ab initio potential energy surface for HCl-H2O, diffusion Monte Carlo calculations of D0 and a delocalized zero-point wavefunction.

    Science.gov (United States)

    Mancini, John S; Bowman, Joel M

    2013-03-28

    We report a global, full-dimensional, ab initio potential energy surface describing the HCl-H2O dimer. The potential is constructed from a permutationally invariant fit, using Morse-like variables, to over 44,000 CCSD(T)-F12b∕aug-cc-pVTZ energies. The surface describes the complex and dissociated monomers with a total RMS fitting error of 24 cm(-1). The normal modes of the minima, low-energy saddle point and separated monomers, the double minimum isomerization pathway and electronic dissociation energy are accurately described by the surface. Rigorous quantum mechanical diffusion Monte Carlo (DMC) calculations are performed to determine the zero-point energy and wavefunction of the complex and the separated fragments. The calculated zero-point energies together with a De value calculated from CCSD(T) with a complete basis set extrapolation gives a D0 value of 1348 ± 3 cm(-1), in good agreement with the recent experimentally reported value of 1334 ± 10 cm(-1) [B. E. Casterline, A. K. Mollner, L. C. Ch'ng, and H. Reisler, J. Phys. Chem. A 114, 9774 (2010)]. Examination of the DMC wavefunction allows for confident characterization of the zero-point geometry to be dominant at the C(2v) double-well saddle point and not the C(s) global minimum. Additional support for the delocalized zero-point geometry is given by numerical solutions to the 1D Schrödinger equation along the imaginary-frequency out-of-plane bending mode, where the zero-point energy is calculated to be 52 cm(-1) above the isomerization barrier. The D0 of the fully deuterated isotopologue is calculated to be 1476 ± 3 cm(-1), which we hope will stand as a benchmark for future experimental work.

  8. Determination of nuclear quadrupole moments – An example of the synergy of ab initio calculations and microwave spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Kellö, Vladimir [Department of Physical Chemistry, Comenius University, SK-842 15 Bratislava (Slovakia)

    2015-01-22

    Highly correlated scalar relativistic calculations of electric field gradients at nuclei in diatomic molecules in combination with accurate nuclear quadrupole coupling constants obtained from microwave spectroscopy are used for determination of nuclear quadrupole moments.

  9. Molecular dynamics simulation, ab initio calculation, and size-selected anion photoelectron spectroscopy study of initial hydration processes of calcium chloride.

    Science.gov (United States)

    He, Zhili; Feng, Gang; Yang, Bin; Yang, Lijiang; Liu, Cheng-Wen; Xu, Hong-Guang; Xu, Xi-Ling; Zheng, Wei-Jun; Gao, Yi Qin

    2018-06-14

    To understand the initial hydration processes of CaCl 2 , we performed molecular simulations employing the force field based on the theory of electronic continuum correction with rescaling. Integrated tempering sampling molecular dynamics were combined with ab initio calculations to overcome the sampling challenge in cluster structure search and refinement. The calculated vertical detachment energies of CaCl 2 (H 2 O) n - (n = 0-8) were compared with the values obtained from photoelectron spectra, and consistency was found between the experiment and computation. Separation of the Cl-Ca ion pair is investigated in CaCl 2 (H 2 O) n - anions, where the first Ca-Cl ionic bond required 4 water molecules, and both Ca-Cl bonds are broken when the number of water molecules is larger than 7. For neutral CaCl 2 (H 2 O) n clusters, breaking of the first Ca-Cl bond starts at n = 5, and 8 water molecules are not enough to separate the two ion pairs. Comparing with the observations on magnesium chloride, it shows that separating one ion pair in CaCl 2 (H 2 O) n requires fewer water molecules than those for MgCl 2 (H 2 O) n . Coincidentally, the solubility of calcium chloride is higher than that of magnesium chloride in bulk solutions.

  10. A theoretical study on 2-chloro-5-(2-hydroxyethyl-4-methoxy-6-methylpyrimidine by DFT/ab initio calculations

    Directory of Open Access Journals (Sweden)

    Gümüs Hacer Pir

    2015-06-01

    Full Text Available Quantum chemical calculations have been performed to study the molecular geometry, 1H and 13C NMR chemical shifts, conformational, natural bond orbital (NBO and nonlinear optical (NLO properties of the 2-chloro-5-(2-hydroxyethyl-4- methoxy-6-methylpyrimidine molecule in the ground state using DFT and HF methods with 6-311++G(d,p basis set. The optimized geometric parameters and 1H and 13C NMR chemical shifts have been compared with the experimental values of the title molecule. The results of the calculations show excellent agreement between the experimental and calculated frequencies at B3LYP/6-311++G(d,p level. In order to provide a full understanding of the properties of the title molecule in the context of molecular orbital picture, the highest occupied molecular energy level (EHOMO, the lowest unoccupied molecular energy level (ELUMO, the energy difference (DE between EHOMO and ELUMO, electronegativity (χ, hardness (η and softness (S have been calculated using B3LYP/6-311++G(d,p and HF/6-311++G(d,p levels. The calculated HOMO and LUMO energies show that the charge transfer occurs within the title molecule.

  11. Ab-initio calculations of the Ruddlesden-Popper phases CaMnO3, CaO(CaMnO3) and CaO(CaMnO3)2

    International Nuclear Information System (INIS)

    Cardoso, C; Borges, R P; Gasche, T; Godinho, M

    2008-01-01

    The present work reports ab-initio density functional theory calculations for the Ruddlesden-Popper phase CaO(CaMnO 3 ) n compounds. In order to study the evolution of the properties with the number of perovskite layers, a detailed analysis of the densities of states calculated for each compound and for several magnetic configurations was performed. The effect of distortions of the crystal structure on the magnetic ground state is also analysed and the exchange constants and transition temperatures are calculated for the three compounds using a mean field model. The calculated magnetic ground state structures and magnetic moments are in good agreement with experimental results and previous calculations

  12. Changes in the geometries of C₂H₂ and C₂H₄ on coordination to CuCl revealed by broadband rotational spectroscopy and ab-initio calculations.

    Science.gov (United States)

    Stephens, Susanna L; Bittner, Dror M; Mikhailov, Victor A; Mizukami, Wataru; Tew, David P; Walker, Nicholas R; Legon, Anthony C

    2014-10-06

    The molecular geometries of isolated complexes in which a single molecule of C2H4 or C2H2 is bound to CuCl have been determined through pure rotational spectroscopy and ab-initio calculations. The C2H2···CuCl and C2H4···CuCl complexes are generated through laser vaporization of a copper rod in the presence of a gas sample undergoing supersonic expansion and containing C2H2 (or C2H4), CCl4, and Ar. Results are presented for five isotopologues of C2H2···CuCl and six isotopologues of C2H4···CuCl. Both of these complexes adopt C(2v), T-shaped geometries in which the hydrocarbon binds to the copper atom through its π electrons such that the metal is equidistant from all H atoms. The linear and planar geometries of free C2H2 and C2H4, respectively, are observed to distort significantly on attachment to the CuCl unit, and the various changes are quantified. The ∠(*-C-H) parameter in C2H2 (where * indicates the midpoint of the C≡C bond) is measured to be 192.4(7)° in the r0 geometry of the complex representing a significant change from the linear geometry of the free molecule. This distortion of the linear geometry of C2H2 involves the hydrogen atoms moving away from the copper atom within the complex. Ab-initio calculations at the CCSD(T)(F12*)/AVTZ level predict a dihedral ∠(HCCCu) angle of 96.05° in C2H4···CuCl, and the experimental results are consistent with such a distortion from planarity. The bonds connecting the carbon atoms within each of C2H2 and C2H4, respectively, extend by 0.027 and 0.029 Å relative to the bond lengths in the isolated molecules. Force constants, k(σ), and nuclear quadrupole coupling constants, χ(aa)(Cu), [χ(bb)(Cu) - χ(cc)(Cu)], χ(aa)(Cl), and [χ(bb)(Cl) - χ(cc)(Cl)], are independently determined for all isotopologues of C2H2···CuCl studied and for four isotopologues of C2H4···CuCl.

  13. Ab initio calculation of the electronic structure and spectroscopic properties of spinel γ-Sn3N4

    International Nuclear Information System (INIS)

    Ching, W. Y.; Rulis, Paul

    2006-01-01

    The electronic structure and physical properties of γ-Sn 3 N 4 in the spinel structure are investigated by first-principles calculations. The calculated band structure, electronic bonding, and optical properties are compared with two well-studied spinel nitrides γ-Si 3 N 4 and γ-Ge 3 N 4 . γ-Sn 3 N 4 is a semiconductor with a direct band gap of 1.40 eV and an attractive small electron effective mass of 0.17. Its optical properties are different from that of γ-Si 3 N 4 and γ-Ge 3 N 4 because of the difference in the conduction band minimum. The Sn K, Sn L 3 , Sn M 5 , and N K edges of the x-ray-absorption near-edge structure spectra in γ-Sn 3 N 4 are calculated using a supercell approach and are found to be rich in structures. These spectra are discussed in the context of the electronic structure of the unoccupied conduction band in the presence of the electron core-hole interaction. These calculated spectra can be used for the characterization of this novel compound

  14. The structural and electronic properties of cubic AgMO{sub 3} (M=Nb, Ta) by first principles calculations

    Energy Technology Data Exchange (ETDEWEB)

    Prasad, K. Ganga; Niranjan, Manish K.; Asthana, Saket [Department of Physics, Indian Institute of Technology Hyderabad, India, 502205 (India)

    2016-05-06

    We report the electronic structure of the AgMO{sub 3}(M=Nb, Ta) within the frame work of density functional theory and calculations are performed within the generalized gradient approximation (GGA) by using ultrasoft pseudopotentials. The calculated equilibrium lattice parameters and volumes are extracted from fitting of Birch third order equation of state and which are reasonable agreement with the available experimental results. The density of states,band structure of Ag(Nb,Ta)O{sub 3} reveals that the valance bands mostly occupied with O-2p and O-2s states and whereas conduction band occupied with Nb (Ta) 4d(5d) states including less contribution from Ag 5s states.

  15. Phase composition of Al-Ti-Nb-Mo γ alloys in the heat-treatment temperature range: Calculation and experiment

    Science.gov (United States)

    Belov, N. A.; Dashkevich, N. I.; Bel'tyukova, S. O.

    2015-07-01

    The phase composition of TNM-type Al-Ti-Nb-Mo γ alloys at heat-treatment temperatures is quantitatively studied using the Thermo-Calc program package and experimental methods. Isothermal cross sections are calculated and the joint influence of two alloying elements on the phase composition of the alloy is determined at the mean concentration of a third component. Based on the calculations of vertical cross sections, the boundaries of the four-phase eutectoid reaction α → α2 + β + γ are found. The temperature is shown to significantly influence the phase compositions of the γ alloys, among them the mass fractions of various phases (α, β, γ,α2) and the element concentration in them.

  16. A study of the valence shell electronic states of s-triazine by photoabsorption spectroscopy and ab initio calculations

    Energy Technology Data Exchange (ETDEWEB)

    Holland, D.M.P., E-mail: david.holland@stfc.ac.uk [Daresbury Laboratory, Daresbury, Warrington, Cheshire WA4 4AD (United Kingdom); Shaw, D.A. [Daresbury Laboratory, Daresbury, Warrington, Cheshire WA4 4AD (United Kingdom); Stener, M.; Decleva, P. [Dipartimento di Scienze Chimiche e Farmaceutiche, Università degli Studi di Trieste, Via L. Giorgieri, I-34127 Trieste (Italy); Consorzio Interuniversitario Nazionale per la Scienze e Tecnologia dei Materiali, INSTM, Unità di Trieste (Italy); CNR-IOM, Trieste (Italy); Coriani, S. [Dipartimento di Scienze Chimiche e Farmaceutiche, Università degli Studi di Trieste, Via L. Giorgieri, I-34127 Trieste (Italy); Consorzio Interuniversitario Nazionale per la Scienze e Tecnologia dei Materiali, INSTM, Unità di Trieste (Italy); Aarhus Institute of Advanced Studies, Aarhus University, 8000 Aarhus C (Denmark)

    2016-09-30

    Highlights: • The valence shell photoabsorption spectrum of s-triazine has been measured. • Electronic structure calculated with TDDFT and coupled cluster approaches. • Assignments proposed for Rydberg and valence states. • Mixing between Rydberg and valence states important. - Abstract: The absolute photoabsorption cross section of s-triazine has been measured between 4 and 40 eV, and is dominated by bands associated with valence states. Structure due to Rydberg excitations is both weak and irregular. Jahn-Teller interactions affect the vibronic structure observed in the Rydberg absorption bands due to excitation from the 1e″ or 6e′ orbitals. The interpretation of the experimental spectrum has been guided by transition energies and oscillator strengths, for Rydberg and valence states, calculated with the time-dependent version of density functional theory and with the coupled cluster linear response approach. The theoretical studies indicate that Rydberg/Rydberg and Rydberg/valence mixing is important.

  17. Local versus global electronic properties of chalcopyrite alloys: X-ray absorption spectroscopy and ab initio calculations

    Energy Technology Data Exchange (ETDEWEB)

    Sarmiento-Pérez, Rafael; Botti, Silvana, E-mail: silvana.botti@univ-lyon1.fr [Institut Lumière Matière and ETSF, UMR5306 Université Lyon 1-CNRS, Université de Lyon, F-69622 Villeurbanne Cedex (France); Schnohr, Claudia S., E-mail: c.schnohr@uni-jena.de [Institut für Festkörperphysik, Friedrich-Schiller-Universität Jena, Max-Wien-Platz 1, 07743 Jena (Germany); Lauermann, Iver [Helmholtz-Zentrum Berlin für Materialien und Energie, Hahn-Meitner Platz 1, 14109 Berlin (Germany); Rubio, Angel [Nano-Bio Spectroscopy Group and ETSF Scientific Development Centre, Departamento de Física de Materiales, Centro de Física de Materiales CSIC-MPC and DIPC, Universidad del País Vasco UPV/EHU, Avenida de Tolosa 72, E-20018 San Sebastián (Spain); Fritz Haber Institute, Max Planck Society, Faradayweg 4-6, 14195 Berlin (Germany); Johnson, Benjamin, E-mail: benjamin.johnson@alumni.tu-berlin.de [Fritz Haber Institute, Max Planck Society, Faradayweg 4-6, 14195 Berlin (Germany)

    2014-09-07

    Element-specific unoccupied electronic states of Cu(In, Ga)S{sub 2} were studied as a function of the In/Ga ratio by combining X-ray absorption spectroscopy with density functional theory calculations. The S absorption edge shifts with changing In/Ga ratio as expected from the variation of the band gap. In contrast, the cation edge positions are largely independent of composition despite the changing band gap. This unexpected behavior is well reproduced by our calculations and originates from the dependence of the electronic states on the local atomic environment. The changing band gap arises from a changing spatial average of these localized states with changing alloy composition.

  18. Ab initio calculations of the magnetic properties of TM (Ti, V)-doped zinc-blende ZnO

    Science.gov (United States)

    Goumrhar, F.; Bahmad, L.; Mounkachi, O.; Benyoussef, A.

    2018-01-01

    In order to promote suitable material to be used in spintronics devices, this study purposes to evaluate the magnetic properties of the titanium and vanadium-doped zinc-blende ZnO from first-principles. The calculations of these properties are based on the Korringa-Kohn-Rostoker (KKR) method combined with the coherent potential approximation (CPA), using the local density approximation (LDA). We have calculated and discussed the density of states (DOSs) in the energy phase diagrams for different concentration values, of the dopants. We have also investigated the magnetic and half-metallic properties of this doped compound. Additionally, we showed the mechanism of the exchange coupling interaction. Finally, we estimated and studied the Curie temperature for different concentrations.

  19. A study of the valence shell electronic states of s-triazine by photoabsorption spectroscopy and ab initio calculations

    DEFF Research Database (Denmark)

    Holland, D.M.P.; Shaw, D.A.; Stener, Mauro

    2016-01-01

    absorption bands due to excitation from the 1e00 or 6e0 orbitals. The interpretation of the experimental spectrum has been guided by transition energies and oscillator strengths, for Rydberg and valence states, calculated with the time-dependent version of density functional theory and with the coupled...... cluster linear response approach. The theoretical studies indicate that Rydberg/Rydberg and Rydberg/valence mixing is important....

  20. Calculating solution redox free energies with ab initio quantum mechanical/molecular mechanical minimum free energy path method

    International Nuclear Information System (INIS)

    Zeng Xiancheng; Hu Hao; Hu Xiangqian; Yang Weitao

    2009-01-01

    A quantum mechanical/molecular mechanical minimum free energy path (QM/MM-MFEP) method was developed to calculate the redox free energies of large systems in solution with greatly enhanced efficiency for conformation sampling. The QM/MM-MFEP method describes the thermodynamics of a system on the potential of mean force surface of the solute degrees of freedom. The molecular dynamics (MD) sampling is only carried out with the QM subsystem fixed. It thus avoids 'on-the-fly' QM calculations and thus overcomes the high computational cost in the direct QM/MM MD sampling. In the applications to two metal complexes in aqueous solution, the new QM/MM-MFEP method yielded redox free energies in good agreement with those calculated from the direct QM/MM MD method. Two larger biologically important redox molecules, lumichrome and riboflavin, were further investigated to demonstrate the efficiency of the method. The enhanced efficiency and uncompromised accuracy are especially significant for biochemical systems. The QM/MM-MFEP method thus provides an efficient approach to free energy simulation of complex electron transfer reactions.

  1. Computational study of the hydrolysis of carbonyl sulphide: Thermodynamics and kinetic constants estimation using ab initio calculations

    International Nuclear Information System (INIS)

    Vidal-Vidal, Á.; Pérez-Rodríguez, M.; Piñeiro, M.M.

    2017-01-01

    Highlights: • OCS hydrolysis equilibrium constants were calculated using QM composite methods. • CBS-QB3 was found to be the most adequate method for OCS thermodynamic calculations. • Calculated hydrolysis yields decrease when temperature increases. • The isotopic effect is less significant than temperature or initial concentration dependences. - Abstract: Carbonyl sulphide is the predominant sulphur compound in the atmosphere, contributing to the formation of aerosol particles affecting global climate. Human activity has significantly increased its total amount since the beginning of the Industrial Revolution due to its presence in petroleum and coal, reason why it is necessary to understand and control its emissions. On the other hand, carbonyl sulphide is an undesired substance for catalysis in important industrial processes. Hydrolysis is the most promising among the different strategies to reduce its presence, giving as products carbon dioxide and hydrogen sulphide. In the present work, the mechanism of reaction of carbonyl sulphide hydrolysis process in gas phase was studied from 400 K to 1500 K, equilibrium constants were obtained and reaction yields were estimated, by means of composite quantum-computational methods. Good agreement with literature experimental results confirms the suitability of the chosen methods, specially CBS-QB3, in supporting the reaction mechanism, giving accurate equilibrium constant values, and obtaining realistic yields. The effect of isotopic substitution in OCS was also studied, from 300 K to 1500 K, being much less significant than temperature dependence.

  2. Electronic structure investigations of 4-aminophthal hydrazide by UV-visible, NMR spectral studies and HOMO-LUMO analysis by ab initio and DFT calculations.

    Science.gov (United States)

    Sambathkumar, K; Jeyavijayan, S; Arivazhagan, M

    2015-08-05

    Combined experimental and theoretical studies were conducted on the molecular structure and vibrational spectra of 4-AminoPhthalhydrazide (APH). The FT-IR and FT-Raman spectra of APH were recorded in the solid phase. The molecular geometry and vibrational frequencies of APH in the ground state have been calculated by using the ab initio HF (Hartree-Fock) and density functional methods (B3LYP) invoking 6-311+G(d,p) basis set. The optimized geometric bond lengths and bond angles obtained by HF and B3LYP method show best agreement with the experimental values. Comparison of the observed fundamental vibrational frequencies of APH with calculated results by HF and density functional methods indicates that B3LYP is superior to the scaled Hartree-Fock approach for molecular vibrational problems. The difference between the observed and scaled wave number values of most of the fundamentals is very small. A detailed interpretation of the NMR spectra of APH was also reported. The theoretical spectrograms for infrared and Raman spectra of the title molecule have been constructed. UV-vis spectrum of the compound was recorded and the electronic properties, such as HOMO and LUMO energies, were performed by time dependent density functional theory (TD-DFT) approach. Finally the calculations results were applied to simulated infrared and Raman spectra of the title compound which show good agreement with observed spectra. And the temperature dependence of the thermodynamic properties of constant pressure (Cp), entropy (S) and enthalpy change (ΔH0→T) for APH were also determined. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Structural characterization of MAO and related aluminum complexes. 1. Solid-state (27)Al NMR with comparison to EFG tensors from ab initio molecular orbital calculations.

    Science.gov (United States)

    Bryant, P L; Harwell, C R; Mrse, A A; Emery, E F; Gan, Z; Caldwell, T; Reyes, A P; Kuhns, P; Hoyt, D W; Simeral, L S; Hall, R W; Butler, L G

    2001-12-05

    Experimental and ab initio molecular orbital techniques are developed for study of aluminum species with large quadrupole coupling constants to test structural models for methylaluminoxanes (MAO). The techniques are applied to nitrogen- and oxygen-containing complexes of aluminum and to solid MAO isolated from active commercial MAO preparations. (Aminato)- and (propanolato)aluminum clusters with 3-, 4-, and 6-coordinate aluminum sites are studied with three (27)Al NMR techniques optimized for large (27)Al quadrupole coupling constants: field-swept, frequency-stepped, and high-field MAS NMR. Four-membered (aminato)aluminum complexes with AlN(4) coordination yield slightly smaller C(q) values than similar AlN(2)C(2) sites: 12.2 vs 15.8 MHz. Planar 3-coordinate AlN(2)C sites have the largest C(q) values, 37 MHz. In all cases, molecular orbital calculations of the electric field gradient tensors yields C(q) and eta values that match with experiment, even for a large hexameric (aminato)aluminum cage. A D(3d) symmetry hexaaluminum oxane cluster, postulated as a model for MAO, yields a calculated C(q) of -23.7 MHz, eta = 0.7474, and predicts a spectrum that is too broad to match the field-swept NMR of methylaluminoxane, which shows at least three sites, all with C(q) values greater than 15 MHz but less than 21 MHz. Thus, the proposed hexaaluminum cluster, with its strained four-membered rings, is not a major component of MAO. However, calculations for dimers of the cage complex, either edge-bridged or face-bridged, show a much closer match to experiment. Also, MAO preparations differ, with a gel form of MAO having significantly larger (27)Al C(q) values than a nongel form, a conclusion reached on the basis of (27)Al NMR line widths in field-swept NMR spectra acquired from 13 to 24 T.

  4. Ab initio calculations of the Fe(II) and Fe(III) isotopic effects in citrates, nicotianamine, and phytosiderophore, and new Fe isotopic measurements in higher plants

    Science.gov (United States)

    Moynier, Frédéric; Fujii, Toshiyuki; Wang, Kun; Foriel, Julien

    2013-05-01

    Iron is one of the most abundant transition metal in higher plants and variations in its isotopic compositions can be used to trace its utilization. In order to better understand the effect of plant-induced isotopic fractionation on the global Fe cycling, we have estimated by quantum chemical calculations the magnitude of the isotopic fractionation between different Fe species relevant to the transport and storage of Fe in higher plants: Fe(II)-citrate, Fe(III)-citrate, Fe(II)-nicotianamine, and Fe(III)-phytosiderophore. The ab initio calculations show firstly, that Fe(II)-nicotianamine is ˜3‰ (56Fe/54Fe) isotopically lighter than Fe(III)-phytosiderophore; secondly, even in the absence of redox changes of Fe, change in the speciation alone can create up to ˜1.5‰ isotopic fractionation. For example, Fe(III)-phytosiderophore is up to 1.5‰ heavier than Fe(III)-citrate2 and Fe(II)-nicotianamine is up to 1‰ heavier than Fe(II)-citrate. In addition, in order to better understand the Fe isotopic fractionation between different plant components, we have analyzed the iron isotopic composition of different organs (roots, seeds, germinated seeds, leaves and stems) from six species of higher plants: the dicot lentil (Lens culinaris), and the graminaceous monocots Virginia wild rye (Elymus virginicus), Johnsongrass (Sorghum halepense), Kentucky bluegrass (Poa pratensis), river oat (Uniola latifolia), and Indian goosegrass (Eleusine indica). The calculations may explain that the roots of strategy-II plants (Fe(III)-phytosiderophore) are isotopically heavier (by about 1‰ for the δ56Fe) than the upper parts of the plants (Fe transported as Fe(III)-citrate in the xylem or Fe(II)-nicotianamine in the phloem). In addition, we suggest that the isotopic variations observed between younger and older leaves could be explained by mixing of Fe received from the xylem and the phloem.

  5. Atomic-scale investigation of ε and θ precipitates in bainite in 100Cr6 bearing steel by atom probe tomography and ab initio calculations

    International Nuclear Information System (INIS)

    Song, W.; Appen, J. von; Choi, P.; Dronskowski, R.; Raabe, D.; Bleck, W.

    2013-01-01

    Carbide precipitation during upper and lower bainite formation in high-carbon bearing steel 100Cr6 is characterized using transmission electron microscopy and atom probe tomography. The results reveal that both ε and θ carbides precipitate in lower bainite isothermally held at 260 °C and only θ precipitates form in upper bainite isothermally held at 500 °C. ε and θ precipitate under paraequilibrium condition at 260 °C in lower bainite and θ precipitates under negligible partitioning local equilibrium condition in upper bainite at 500 °C. In order to theoretically study ε and θ precipitation and the ε → θ transition in bainite, thermodynamic calculations have been carried out using ab initio techniques. We find that ε and θ carbides in ferrite have almost identical thermodynamic stability, and hence have similar formation probability. In austenite, however, cementite formation is clearly preferred: it is favored by 5 kJ mol −1 at room temperature and still by 4 kJ mol −1 at 500 °C. Hence, the thermodynamic predictions agree well with the atom probe tomography results

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-04-15

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

  7. Mechanistic Insights into Radical-Mediated Oxidation of Tryptophan from ab Initio Quantum Chemistry Calculations and QM/MM Molecular Dynamics Simulations.

    Science.gov (United States)

    Wood, Geoffrey P F; Sreedhara, Alavattam; Moore, Jamie M; Wang, John; Trout, Bernhardt L

    2016-05-12

    An assessment of the mechanisms of (•)OH and (•)OOH radical-mediated oxidation of tryptophan was performed using density functional theory calculations and ab initio plane-wave Quantum Mechanics/Molecular Mechanics (QM/MM) molecular dynamics simulations. For the (•)OH reactions, addition to the pyrrole ring at position 2 is the most favored site with a barrierless reaction in the gas phase. The subsequent degradation of this adduct through a H atom transfer to water was intermittently observed in aqueous-phase molecular dynamics simulations. For the (•)OOH reactions, addition to the pyrrole ring at position 2 is the most favored pathway, in contrast to the situation in the model system ethylene, where concerted addition to the double bond is preferred. From the (•)OOH position 2 adduct QM/MM simulations show that formation of oxy-3-indolanaline occurs readily in an aqueous environment. The observed transformation starts from an initial rupture of the O-O bond followed by a H atom transfer with the accompanying loss of an (•)OH radical to solution. Finally, classical molecular dynamics simulations were performed to equate observed differential oxidation rates of various tryptophan residues in monoclonal antibody fragments. It was found that simple parameters derived from simulation correlate well with the experimental data.

  8. Unveiling the chemical and morphological features of Sb:SnO2 nanocrystals by the combined use of HRTEM and Ab Initio surface energy calculations

    International Nuclear Information System (INIS)

    Stroppa, Daniel G.; Montoro, Luciano A.; Ramirez, Antonio J.; Beltran, Armando; Andres, Juan; Conti, Tiago G.; Silva, Rafael O. da; Longo, Elson; Leite, Edson R.

    2009-01-01

    Modeling of nanocrystals supported by advanced morphological and chemical characterization is a unique tool for the development of reliable nanostructured devices, which depends on the ability to synthesize and characterize material on the atomic scale. Among the most significant challenges in nanostructural characterization is the evaluation of crystal growth mechanisms and their dependence on the shape of nanoparticles and the distribution of doping elements. This work presents a new strategy to characterize nanocrystals, applied here to antimony-doped tin oxide (Sb-SnO 2 ) (ATO) by the combined use of experimental and simulated high-resolution transmission electron microscopy (HRTEM) images and surface energy ab initio calculations. The results show that the Wulff construction can not only describe the shape of nanocrystals as a function of surface energy distribution but also retrieve quantitative information on dopant distribution by the dimensional analysis of nanoparticle shapes. In addition, a novel three-dimensional evaluation of an oriented attachment growth mechanism is provided in the proposed methodology. This procedure is a useful approach for faceted nanocrystal shape modeling and indirect quantitative evaluation of dopant spatial distribution, which are difficult to evaluate by other techniques. (author)

  9. Lattice dynamics at high pressure: application of inelastic X-ray scattering and ab-initio calculations -MgO at 35 GPa

    International Nuclear Information System (INIS)

    Ghose, Subrata

    2006-01-01

    Full text: Until recently, inelastic neutron scattering (INS) has been extensively used to study the phonon dispersion throughout the Brillouin zone and phonon density of states in crystalline materials. The weak interaction of neutrons with matter and the typical size of the neutron beams require the use of cm-size single crystals that puts an upper limit to the measurement of phonon dispersion at high pressure to about 10-15 Gpa by INS. Inelastic X-ray scattering (IXS) using third generation synchrotron sources now makes it possible to measure the phonon dispersion at high pressures up to 50 GP A in crystals tens of microns in size mounted in a diamond-anvil cell, usually using He as the pressure transmitting medium. We have used this technique to measure the longitudinal acoustic and optic phonon branches of MgO along the Γ-X direction at 35 Gpa. The experimentally observed phonon-branches are in remarkable agreement with ab-initio quantum mechanical calculations using the density-functional perturbation theory. The derived thermodynamic properties, such as specific heat and the entropy are in very good agreement with values obtained from a thermodynamically assessed data set

  10. Investigation of 3C-SiC/SiO2 interfacial point defects from ab initio g-tensor calculations and electron paramagnetic resonance measurements

    Science.gov (United States)

    Nugraha, T. A.; Rohrmueller, M.; Gerstmann, U.; Greulich-Weber, S.; Stellhorn, A.; Cantin, J. L.; von Bardeleben, J.; Schmidt, W. G.; Wippermann, S.

    SiC is widely used in high-power, high-frequency electronic devices. Recently, it has also been employed as a building block in nanocomposites used as light absorbers in solar energy conversion devices. Analogous to Si, SiC features SiO2 as native oxide that can be used for passivation and insulating layers. However, a significant number of defect states are reported to form at SiC/SiO2 interfaces, limiting mobility and increasing recombination of free charge carriers. We investigated the growth of oxide on different 3C-SiC surfaces from first principles. Carbon antisite Csi defects are found to be strongly stabilized in particular at the interface, because carbon changes its hybridization from sp3 in the SiC-bulk to sp2 at the interface, creating a dangling bond inside a porous region of the SiO2 passivating layer. Combining ab initio g-tensor calculations and electron paramagnetic resonance (EPR) measurements, we show that Csi defects explain the measured EPR signatures, while the hyperfine structure allows to obtain local structural information of the oxide layer. Financial support from BMBF NanoMatFutur Grant 13N12972 and DFG priority program SPP-1601 is gratefully acknowledged.

  11. Signatures of attosecond electronic–nuclear dynamics in the one-photon ionization of molecular hydrogen: analytical model versus ab initio calculations

    International Nuclear Information System (INIS)

    Medišauskas, Lukas; Ivanov, Misha Yu; Morales, Felipe; Plimak, Lev; Smirnova, Olga; Palacios, Alicia; González-Castrillo, Alberto; Martín, Fernando

    2015-01-01

    We present an analytical model based on the time-dependent WKB approximation to reproduce the photoionization spectra of an H 2 molecule in the autoionization region. We explore the nondissociative channel, which is the major contribution after one-photon absorption, and we focus on the features arising in the energy differential spectra due to the interference between the direct and the autoionization pathways. These features depend on both the timescale of the electronic decay of the autoionizing state and the time evolution of the vibrational wavepacket created in this state. With full ab initio calculations and with a one-dimensional approach that only takes into account the nuclear wavepacket associated to the few relevant electronic states we compare the ground state, the autoionizing state, and the background continuum electronic states. Finally, we illustrate how these features transform from molecular-like to atomic-like by increasing the mass of the system, thus making the electronic decay time shorter than the nuclear wavepacket motion associated with the resonant state. In other words, autoionization then occurs faster than the molecular dissociation into neutrals. (paper)

  12. Measurement of the Spectroscopic Quadrupole Moment for the 2+1 State in 10Be:. Testing AB Initio Calculations

    Science.gov (United States)

    Orce, J. N.; Djongolov, M.; Navratil, P.; Ball, G.; Garnsworthy, A. B.; Hackman, G.; Lassen, J.; Meissner, J.; Pearson, C. J.; Li, R.; Milovanovic, L.; Sjue, S. K. L.; Teigelhoefer, A.; Triambak, S.; Williams, S. J.; Falou, H. Al; Drake, T. E.; Andreoiu, C.; Cross, D.; Kshetri, R.; Finlay, P.; Garrett, P. E.; Leach, K. G.; Rand, E. T.; Sumithrarachchi, C. S.; Svensson, C. E.; Tardiff, E. R.; Wong, J.; Forssen, C.; Hayes, A. B.; Sarazin, F.; Stoyer, M. A.; Wu, C. Y.

    2013-03-01

    The highly efficient and segmented TIGRESS HPGe γ-ray array at TRIUMF has been used to perform a reorientation effect Coulomb excitation study of the 2+1 state at 3.368 MeV in 10Be. This is the first Coulomb excitation measurement that provides information on diagonal matrix elements for such a high lying first excited state from μ-ray data. With the availability of accurate lifetime data, a restriction on the diagonal matrix element is determined. This result is compared to a no core shell model calculation with the CD-Bonn 2000 two nucleon potential.

  13. Ab-initio calculation of the valence-band offset at strained GaAs/InAs (001) heterojunction

    International Nuclear Information System (INIS)

    Tit, N.; Peressi, M.

    1993-06-01

    We present a self consistent pseudopotential calculation of the valence band offset (VBO) at GaAs/InAs (001) strained heterojunction, which is chose as an example of the isovalent polar with common-anion lattice mismatched heterojunctions. The effects of strain are studied by looking at the variation of the VBO versus the in plane lattice constant, which is imposed by the substrate. Our results show that the VBO can be tuned by about 0.17 eV going from GaAs to InAs substrates. Comparison of our work with the available experimental and theoretical results is also discussed. (author). 25 refs, 3 figs, 5 tabs

  14. Orbital energies and structural non-rigidity of complex hydrides according to data on ab initio calculations

    Energy Technology Data Exchange (ETDEWEB)

    Boldyrev, A I; Sukhanov, L P; Charkin, O P [AN SSSR, Moscow. Inst. Novykh Khimicheskikh Problem

    1982-01-01

    In approximation by the Hartree-Fock-Routine method using several Gauss type bases ionization potentials of complex hydrides LiBeH/sub 3/, NaBeH/sub 3/, LiMgH/sub 3/, LiBH/sub 4/, NaBH/sub 4/ and LiAlH/sub 4/ have been calculated. A problem of the show of structural non-rigidity of complex molecules L(MX/sub 4/) with tetrahedral anions (MX/sub 4/)/sup -/ in photoelectron spectra is considered.

  15. Standard Gibbs energies of formation and equilibrium constants from ab-initio calculations: Covalent dimerization of NO2 and synthesis of NH3

    International Nuclear Information System (INIS)

    Awasthi, Neha; Ritschel, Thomas; Lipowsky, Reinhard; Knecht, Volker

    2013-01-01

    Highlights: • ΔG and K eq for NO 2 dimerization and NH 3 synthesis calculated via ab-initio methods. • Vis-á-vis experiments, W1 and CCSD(T) are accurate and G3B3 also does quite well. • CBS-APNO most accurate for NH 3 reaction but shows limitations in modeling NO 2 . • Temperature dependence of ΔG and K eq is calculated for the NH 3 reaction. • Good agreement of calculated K eq with experiments and the van’t Hoff approximation. -- Abstract: Standard quantum chemical methods are used for accurate calculation of thermochemical properties such as enthalpies of formation, entropies and Gibbs energies of formation. Equilibrium reactions are widely investigated and experimental measurements often lead to a range of reaction Gibbs energies and equilibrium constants. It is useful to calculate these equilibrium properties from quantum chemical methods in order to address the experimental differences. Furthermore, most standard calculation methods differ in accuracy and feasibility of the system size. Hence, a systematic comparison of equilibrium properties calculated with different numerical algorithms would provide a useful reference. We select two well-known gas phase equilibrium reactions with small molecules: covalent dimer formation of NO 2 (2NO 2 ⇌ N 2 O 4 ) and the synthesis of NH 3 (N 2 + 3 H 2 ⇌ 2NH 3 ). We test four quantum chemical methods denoted by G3B3, CBS-APNO, W1 and CCSD(T) with aug-cc-pVXZ basis sets (X = 2, 3, and 4), to obtain thermochemical data for NO 2 , N 2 O 4 , and NH 3 . The calculated standard formation Gibbs energies Δ f G° are used to calculate standard reaction Gibbs energies Δ r G° and standard equilibrium constants K eq for the two reactions. Standard formation enthalpies Δ f H° are calculated in a more reliable way using high-level methods such as W1 and CCSD(T). Standard entropies S° for the molecules are calculated well within the range of experiments for all methods, however, the values of standard formation

  16. A VUV photoionization measurement and ab-initio calculation of the ionization energy of gas phase SiO2

    Energy Technology Data Exchange (ETDEWEB)

    Kostko, Oleg; Ahmed, Musahid; Metz, Ricardo B.

    2008-12-05

    In this work we report on the detection and vacuum-ultraviolet (VUV) photoionization of gas phase SiO2 generated in situ via laser ablation of silicon in a CO2 molecular beam. The resulting species are investigated by single photon ionization with tunable VUV synchrotron radiation and mass analyzed using reflectron mass spectrometry. Photoionization efficiency (PIE) curves are recorded for SiO and SiO2 and ionization energy estimates are revealed from such measurements. A state-to-state ionizationenergy of 12.60 (+-0.05) eV is recorded by fitting two prominent peaks in the PIE curve for the following process: 1SUM O-Si-O --> 2PRODg [O-Si-O]+. Electronic structure calculations aid in the interpretation of the photoionization process and allow for identification of the symmetric stretch of 2PRODg [O-Si-O]+ which is observed in the PIE spectrum to be 0.11 eV (890 cm-1) above the ground state of the cation and agrees with the 892 cm-1 symmetric stretch frequency calculated at the CCSD(T)/aug-cc-pVTZ level.

  17. Hydrogen insertion effects on the electronic structure of equiatomic MgNi traced by ab initio calculations

    Energy Technology Data Exchange (ETDEWEB)

    Matar, Samir F. [CNRS, ICMCB, UPR 9048, Pessac (France); Bordeaux Univ., Pessac (France). ICMCB, UPR 9048; Al Alam, Adel F.; Ouaini, Naim [Univ. Saint Esprit de Kaslik (USEK), Jounieh (Lebanon). URA GREVE, CSR-USEK

    2013-01-15

    For equiatomic MgNi which can be hydrogenated up to the composition MgNiH{sub 1.6} at an absorption/desorption temperature of 200 C, the effects of hydrogen absorption are approached with the model structures MgNiH, MgNiH{sub 2} and MgNiH{sub 3}. From full geometry optimization and calculated cohesive energies obtained within DFT, the MgNiH{sub 2} composition close to the experimental limit is identified as most stable. Charge density analysis shows an increasingly covalent character of hydrogen: MgNiH(H{sup -0.67}) {yields} MgNiH{sub 2}(H{sup -0.63}) {yields} MgNiH{sub 3}(H{sup -0.55}). While Mg-Ni bonding prevails in MgNi and hydrogenated model phases, extra itinerant low-energy Ni states appear when hydrogen is introduced signaling Ni-H bonding which prevails over Mg-H as evidenced from total energy calculations and chemical bonding analyses. (orig.)

  18. Adsorption of metal-phthalocyanine molecules onto the Si(111) surface passivated by δ doping: Ab initio calculations

    Science.gov (United States)

    Veiga, R. G. A.; Miwa, R. H.; McLean, A. B.

    2016-03-01

    We report first-principles calculations of the energetic stability and electronic properties of metal-phthalocyanine (MPc) molecules (M = Cr, Mn, Fe, Co, Ni, Cu, and Zn) adsorbed on the δ -doped Si(111)-B (√{3 }×√{3 }) reconstructed surface. (i) It can be seen that CrPc, MnPc, FePc, and CoPc are chemically anchored to the topmost Si atom. (ii) Contrastingly, the binding of the NiPc, CuPc, and ZnPc molecules to the Si (111 ) -B (√{3 }×√{3 }) surface is exclusively ruled by van der Waals interactions, the main implication being that these molecules may diffuse and rearrange to form clusters and/or self-organized structures on this surface. The electronic structure calculations reveal that in point (i), owing to the formation of the metal-Si covalent bond, the net magnetic moment of the molecule is quenched by 1 μB , remaining unchanged in point (ii). In particular, the magnetic moment of CuPc (1 μB ) is preserved after adsorption. Finally, we verify that the formation of ZnPc, CuPc, and NiPc molecular (self-assembled) arrangements on the Si(111)-B (√{3 }×√{3 } ) surface is energetically favorable, in good agreement with recent experimental findings.

  19. High-pressure structural behaviour of HoVO4: combined XRD experiments and ab initio calculations

    International Nuclear Information System (INIS)

    Garg, Alka B; Errandonea, D; Rodríguez-Hernández, P; Muñoz, A; López-Moreno, S; Popescu, C

    2014-01-01

    We report a high-pressure experimental and theoretical investigation of the structural properties of zircon-type HoVO 4 . Angle-dispersive x-ray diffraction measurements were carried out under quasi-hydrostatic and partial non-hydrostatic conditions up to 28 and 23.7 GPa, respectively. In the first case, an irreversible phase transition is found at 8.2 GPa. In the second case, the onset of the transition is detected at 4.5 GPa, a second (reversible) transition is found at 20.4 GPa, and a partial decomposition of HoVO 4 was observed. The structures of the different phases have been assigned and their equations of state (EOS) determined. Experimental results have also been compared to theoretical calculations which fully agree with quasi-hydrostatic experiments. Theory also suggests the possibility of another phase transition at 32 GPa; i.e. beyond the pressure limit covered by present experiments. Furthermore, calculations show that deviatoric stresses could trigger the transition found at 20.4 GPa under non-hydrostatic conditions. The reliability of the present experimental and theoretical results is supported by the consistency between the values yielded for transition pressures and EOS parameters by the two methods. (paper)

  20. Polarized Raman and Infrared Spectroscopy and ab Initio Calculation of Palmitic and Stearic Acids in the Bm and C Forms.

    Science.gov (United States)

    L da Silva, L F; Andrade-Filho, T; Freire, P T C; Filho, J Mendes; da Silva Filho, J G; Saraiva, G D; Moreira, S G C; de Sousa, F F

    2017-06-29

    A complete experimental study on the vibrational properties of palmitic and stearic acids crystallized in the B m and C forms, both belonging to the monoclinic system with the P2 1 /a (C 2h 5 ) space group, through polarized Raman and infrared spectroscopy, is reported in this paper. Density functional theory calculations were also performed to assign the normal modes and to help in the interpretation of the experimental data. The different polarizations were compared and their influence on the spectral profiles, in both the lattice and the internal mode regions, was discussed. In general, the Raman and infrared spectra exhibit accentuated differences among the polymorphic forms, which are associated with the different molecular modifications, defined as gauche and all-trans conformations. Insights about interaction among different groups are also furnished.

  1. Ab-initio calculations of structural, electronic, and optical properties of Zn3(VO4)2

    Science.gov (United States)

    Ahmed, Nisar; Mukhtar, S.; Gao, Wei; Zafar Ilyas, Syed

    2018-03-01

    The structural, electronic, and optical properties of Zn3(VO4)2 are investigated using full potential linearized augmented plane wave (FP-LAPW) method within the framework of density functional theory (DFT). Various approaches are adopted to treat the exchange and correlation potential energy such as generalized gradient approximation (GGA), GGA+U, and the Tran–Blaha modified Becke–Johnson (TB-mBJ) potential. The calculated band gap of 3.424 eV by TB-mBJ is found to be close to the experimental result (3.3 eV). The optical anisotropy is analyzed through optical constants, such as dielectric function and absorption coefficient along parallel and perpendicular crystal orientations. The absorption coefficient reveals high absorption (1.5× {10}6 {cm}}-1) of photons in the ultraviolet region.

  2. Valence-band splitting energies in wurtzite InP nanowires: Photoluminescence spectroscopy and ab initio calculations

    Science.gov (United States)

    Gadret, E. G.; Dias, G. O.; Dacal, L. C. O.; de Lima, M. M., Jr.; Ruffo, C. V. R. S.; Iikawa, F.; Brasil, M. J. S. P.; Chiaramonte, T.; Cotta, M. A.; Tizei, L. H. G.; Ugarte, D.; Cantarero, A.

    2010-09-01

    We investigated experimentally and theoretically the valence-band structure of wurtzite InP nanowires. The wurtzite phase, which usually is not stable for III-V phosphide compounds, has been observed in InP nanowires. We present results on the electronic properties of these nanowires using the photoluminescence excitation technique. Spectra from an ensemble of nanowires show three clear absorption edges separated by 44 meV and 143 meV, respectively. The band edges are attributed to excitonic absorptions involving three distinct valence-bands labeled: A, B, and C. Theoretical results based on “ab initio” calculation gives corresponding valence-band energy separations of 50 meV and 200 meV, respectively, which are in good agreement with the experimental results.

  3. Scheme for ab initio calculation of the Green function in large disordered systems with application to transport properties

    Science.gov (United States)

    Tanaka, Hiroshi

    1998-01-01

    A real-space scheme is developed to calculate matrix elements of the Green function from first principles for large disordered systems. The scheme is an extension of the particle source method, combined with the tight-binding linear muffin-tin orbitals and has the following advantages: (i) It is possible to evaluate both the diagonal and off-diagonal parts of the Green function and also their products with other quantum operators, (ii) it allows for an explicit control of the numerical accuracy and clear-cut physical interpretations of the results on the basis of the definition of the Green function, and (iii) the scheme is suitable for both vector and parallel processing and requires CPU time and memory size proportional only to the system size. The method is applied to the densities of states of bcc and amorphous Fe. The dc conductivity is also evaluated for the latter from the Kubo-Greenwood formula.

  4. Lithium formate ion clusters formation during electrospray ionization: Evidence of magic number clusters by mass spectrometry and ab initio calculations

    International Nuclear Information System (INIS)

    Shukla, Anil; Bogdanov, Bogdan

    2015-01-01

    Small cationic and anionic clusters of lithium formate were generated by electrospray ionization and their fragmentations were studied by tandem mass spectrometry (collision-induced dissociation with N 2 ). Singly as well as multiply charged clusters were formed in both positive and negative ion modes with the general formulae, (HCOOLi) n Li + , (HCOOLi) n Li m m+ , (HCOOLi) n HCOO − , and (HCOOLi) n (HCOO) m m− . Several magic number cluster (MNC) ions were observed in both the positive and negative ion modes although more predominant in the positive ion mode with (HCOOLi) 3 Li + being the most abundant and stable cluster ion. Fragmentations of singly charged positive clusters proceed first by the loss of a dimer unit ((HCOOLi) 2 ) followed by the loss of monomer units (HCOOLi) although the former remains the dominant dissociation process. In the case of positive cluster ions, all fragmentations lead to the magic cluster (HCOOLi) 3 Li + as the most abundant fragment ion at higher collision energies which then fragments further to dimer and monomer ions at lower abundances. In the negative ion mode, however, singly charged clusters dissociated via sequential loss of monomer units. Multiply charged clusters in both positive and negative ion modes dissociated mainly via Coulomb repulsion. Quantum chemical calculations performed for smaller cluster ions showed that the trimer ion has a closed ring structure similar to the phenalenylium structure with three closed rings connected to the central lithium ion. Further additions of monomer units result in similar symmetric structures for hexamer and nonamer cluster ions. Thermochemical calculations show that trimer cluster ion is relatively more stable than neighboring cluster ions, supporting the experimental observation of a magic number cluster with enhanced stability

  5. Ab initio calculations of ideal strength and lattice instability in W-Ta and W-Re alloys

    Science.gov (United States)

    Yang, Chaoming; Qi, Liang

    2018-01-01

    An important theoretical criterion to evaluate the ductility of metals with a body-centered cubic (bcc) lattice is the mechanical failure mode of their perfect crystals under tension along ; directions. When the tensile stress reaches the ideal tensile strength, the pure W crystal fails by a cleavage fracture along the {100 } plane so that it is intrinsically brittle. To discover the strategy to improve its ductility, we performed density functional theory and density functional perturbation theory calculations to study the ideal tensile strength and the lattice instability under tension for both W-Ta and W-Re alloys. Anisotropic linear elastic fracture mechanics (LEFM) theory and Rice's criterion were also applied to analyze the mechanical instability at the crack tip under tension based on the competition between cleavage propagation and dislocation emission. The results show that the intrinsic ductility can be achieved in both W-Ta and W-Re, however, by different mechanisms. Even though W-Ta alloys with low Ta concentrations are still intrinsically brittle, the intrinsic ductility of W-Ta alloys with high Ta concentrations is promoted by elastic shear instability before the cleavage failure. The intrinsic ductility of W-Re alloys is produced by unstable transverse phonon waves before the cleavage failure, and the corresponding phonon mode is related to the generation of 1/2 {2 ¯11 } dislocation in bcc crystals. The ideal tensile calculations, phonon analyses, and anisotropic LEFM examinations are mutually consistent in the evaluation of intrinsic ductility. These results bring us physical insights on the ductility-brittle mechanisms of W alloys under extreme stress conditions.

  6. Phonon spectra in the parent superconducting iron-tuned telluride F e1 +xTe from inelastic neutron scattering and ab initio calculations

    Science.gov (United States)

    Zbiri, Mohamed; Viennois, Romain

    2017-10-01

    We report inelastic neutron scattering measurements of phonon spectra in the parent superconductor iron-tuned chalcogenide F e1 +xTe for two different x contents (x ≤0.11 ) using neutron time-of-flight technique. Thermal neutron spectroscopy allowed the collection of the low-temperature Stokes spectra over an extended Q range at 2, 40, and 120 K, hence covering both the magnetic monoclinic and the paramagnetic tetragonal phases, whereas cold neutrons allowed the measurement of high-resolution anti-Stokes spectra at 140, 220, and 300 K, thus covering the tetragonal phase. Our results evidence a spin-phonon coupling behavior towards the observed noticeable temperature-dependent change of the Stokes spectra across the transition temperatures. On the other hand, the anti-Stokes spectra reveal a pronounced hardening of the low-energy, acoustic region of the phonon spectrum upon heating, indicating a strong anharmonicity and a subtle dependence of phonons on structural evolution within the tetragonal phase. Experimental results are accompanied by ab initio calculations of phonon spectra of the tetragonal stoichiometric phase for a comparison with the high-resolution anti-Stokes spectra. Calculations included different density functional methods. Spin polarization and van der Waals interaction were either considered or neglected, individually or concomitantly, in order to study their respective effect on lattice dynamics description. Our results suggest that including van der Waals interaction has only a slight effect on phonon dynamics; however, phonon spectra are better described when spin polarization is included in a cooperative way with van der Waals interactions.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-08-15

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

  8. Ab initio calculations of half-metallic ferromagnetism in Cr-doped MgSe and MgTe semiconductors

    Energy Technology Data Exchange (ETDEWEB)

    Noor, N.A. [Department of Physics, University of the Punjab, Quaid-e-Azam Campus, 54590 Lahore (Pakistan); Alay-e-Abbas, S.M. [Department of Physics, University of Sargodha, Sargodha 40100 (Pakistan); Department of Physics, GC University Faisalabad, Allama Iqbal Road, Faisalabad 38000 (Pakistan); Sohaib, M.U. [Lahore Development Authority, 54590 Lahore (Pakistan); Ghulam Abbas, S.M. [Department of Chemistry, University of Agriculture, Faisalabad 38040 (Pakistan); Shaukat, A., E-mail: schaukat@gmail.com [Department of Physics, University of Sargodha, Sargodha 40100 (Pakistan)

    2015-01-15

    The full-potential linear-augmented-plane-waves plus local-orbitals (FP-LAPW+lo) method has been employed for investigation of half-metallic ferromagnetism in Cr-doped ordered zinc-blende MgSe and MgTe semiconductors. Calculations of exchange and correlation (XC) effects have been carried out using generalized gradient approximation (GGA) and orbital independent modified Becke–Johnson potential coupled with local (spin) density approximation (mBJLDA). The thermodynamic stability of the compounds and their preferred magnetic orders have been analyzed in terms of the heat of formation and minimum total energy difference in ferromagnetic (FM) and anti-ferromagnetic (AFM) ordering, respectively. Calculated electronic properties reveal that the Cr-doping induces ferromagnetism in MgSe and MgTe which gives rise to a half-metallic (HM) gap at Fermi level (E{sub F}). Further, the electronic band structure is discussed in terms of s (p)–d exchange constants that are consistent with typical magneto-optical experiment and the behavior of charge spin densities is presented for understanding the bonding nature. Our results demonstrate that the higher effective potential for the spin-down case is responsible for p–d exchange splitting. Total magnetic moment (mainly due to Cr-d states) of these compounds is 4µ{sub B}. Importantly, the electronic properties and HM gap obtained using mBJLDA show remarkable improvement as compared to the results obtained using standard GGA functional. - Highlights: • Spin effect theoretical study on Cr-doped MgSe and MgTe is performed. • Half-metallic ferromagnetism in Cr{sub x}Mg{sub 1−x}Se and Cr{sub x}Mg{sub 1−x}Te is established. • Results of WC-GGA and mBJLDA are compared for performance. • HM gaps for Cr{sub x}Mg{sub 1−x}Se and Cr{sub x}Mg{sub 1−x}Te show nonlinear variation with x. • Important values of exchange splitting/constants and moments are reported.

  9. Ab initio calculations of mechanical properties of bcc W-Re-Os random alloys: effects of transmutation of W.

    Science.gov (United States)

    Li, Xiaojie; Schönecker, Stephan; Li, Ruihuan; Li, Xiaoqing; Wang, Yuanyuan; Zhao, Jijun; Johansson, Börje; Vitos, Levente

    2016-06-03

    To examine the effect of neutron transmutation on tungsten as the first wall material of fusion reactors, the elastic properties of W 1-x-y  Re x  Os y (0  ⩽  x, y  ⩽  6%) random alloys in body centered cubic (bcc) structure are investigated systematically using the all-electron exact muffin-tin orbitals (EMTO) method in combination with the coherent-potential approximation (CPA). The calculated lattice constant and elastic properties of pure W are consistent with available experiments. Both Os and Re additions reduce the lattice constant and increase the bulk modulus of W, with Os having the stronger effect. The polycrystalline shear modulus, Young's modulus and the Debye temperature increase (decrease) with the addition of Re (Os). Except for C 11 , the other elastic parameters including C 12 , C 44 , Cauchy pressure, Poisson ratio, B/G, increase as a function of Re and Os concentration. The variations of the latter three parameters and the trend in the ratio of cleavage energy to shear modulus for the most dominant slip system indicate that the ductility of the alloy enhances with increasing Re and Os content. The calculated elastic anisotropy of bcc W slightly increases with the concentration of both alloying elements. The estimated melting temperatures of the W-Re-Os alloy suggest that Re or Os addition will reduce the melting temperature of pure W solid. The classical Labusch-Nabarro model for solid-solution hardening predicts larger strengthening effects in W 1-y  Os y than in W 1-x  Re x . A strong correlation between C' and the fcc-bcc structural energy difference for W 1-x-y  Re x  Os y is revealed demonstrating that canonical band structure dictates the alloying effect on C'. The structural energy difference is exploited to estimate the alloying effect on the ideal tensile strength in the [0 0 1] direction.

  10. Ab initio calculation of the migration free energy of oxygen diffusion in pure and samarium-doped ceria

    Science.gov (United States)

    Koettgen, Julius; Schmidt, Peter C.; Bučko, Tomáš; Martin, Manfred

    2018-01-01

    We have studied the free energy migration barriers Δ F‡ for oxygen diffusion in pure ceria and Sm-doped ceria for the temperatures 300, 700, and 1000 K. We used the density functional theory in the generalized gradient approximation and an additional Hubbard U parameter for the Ce 4 f electronic states. We compare the results for the free energy deduced from three different methods. First, a static harmonic approach is applied in which the temperature dependent vibrational contributions to energy and entropy are deduced from the phonon frequencies of supercells with a fixed volume. Second, a static quasiharmonic approach is used in which a part of the anharmonicity effect is introduced via an implicit dependence of the harmonic frequencies on the thermally expanding cell volume. Third, the free energy barriers are calculated using metadynamics and molecular dynamics in which anharmonicity effects are naturally taken into account. The three methods examined in this study lead to distinctly different results. According to the harmonic approximation, the migration free energy difference Δ F‡ increases with increasing temperature due to an increasing entropic contribution. According to the quasiharmonic approximation, the migration free energy is independent of temperature. Finally, molecular dynamics predicts a thermally induced increase in the migration free energy. We conclude that temperature dependent experimental lattice constants cancel out the increasing entropic contribution with increasing temperature in the static quasiharmonic approach. The full consideration of anharmonicity effects in the metadynamics method again leads to a temperature dependent migration free energy.

  11. Electronic couplings for molecular charge transfer: Benchmarking CDFT, FODFT, and FODFTB against high-level ab initio calculations

    Energy Technology Data Exchange (ETDEWEB)

    Kubas, Adam; Blumberger, Jochen, E-mail: j.blumberger@ucl.ac.uk [Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT (United Kingdom); Hoffmann, Felix [Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT (United Kingdom); Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, Universitätsstr. 150, 44801 Bochum (Germany); Heck, Alexander; Elstner, Marcus [Institute of Physical Chemistry, Karlsruhe Institute of Technology, Fritz-Haber-Weg 6, 76131 Karlsruhe (Germany); Oberhofer, Harald [Department of Chemistry, Technical University of Munich, Lichtenbergstr. 4, 85747 Garching (Germany)

    2014-03-14

    We introduce a database (HAB11) of electronic coupling matrix elements (H{sub ab}) for electron transfer in 11 π-conjugated organic homo-dimer cations. High-level ab inito calculations at the multireference configuration interaction MRCI+Q level of theory, n-electron valence state perturbation theory NEVPT2, and (spin-component scaled) approximate coupled cluster model (SCS)-CC2 are reported for this database to assess the performance of three DFT methods of decreasing computational cost, including constrained density functional theory (CDFT), fragment-orbital DFT (FODFT), and self-consistent charge density functional tight-binding (FODFTB). We find that the CDFT approach in combination with a modified PBE functional containing 50% Hartree-Fock exchange gives best results for absolute H{sub ab} values (mean relative unsigned error = 5.3%) and exponential distance decay constants β (4.3%). CDFT in combination with pure PBE overestimates couplings by 38.7% due to a too diffuse excess charge distribution, whereas the economic FODFT and highly cost-effective FODFTB methods underestimate couplings by 37.6% and 42.4%, respectively, due to neglect of interaction between donor and acceptor. The errors are systematic, however, and can be significantly reduced by applying a uniform scaling factor for each method. Applications to dimers outside the database, specifically rotated thiophene dimers and larger acenes up to pentacene, suggests that the same scaling procedure significantly improves the FODFT and FODFTB results for larger π-conjugated systems relevant to organic semiconductors and DNA.

  12. Investigation of sputtered Mo2BC hard coatings : correlation of nanostructure and mechanical properties

    OpenAIRE

    Gleich, Stephan

    2017-01-01

    This thesis is dedicated to the study of Mo2BC coatings on silicon substrates. According to reported ab initio calculations in literature, which predicted a high stiffness and a moderate ductile behavior for the material, Mo2BC is a predestinated candidate to act as hard coating layer. The focus in this thesis is set on the nanostructure of Mo2BC hard coatings explored by transmission electron microscopy as a function of the used substrate temperature, applied during the deposition process us...

  13. Realization of prediction of materials properties by ab initio ...

    Indian Academy of Sciences (India)

    Unknown

    alization of the results of ab initio molecular dynamics simulation on atom insertion process to C60 and to carbon nanotube ... micro-clusters to estimate absolute highest occupied mo- .... To analyse the observed properties theoretically,.

  14. Conformational Change in the Mechanism of Inclusion of Ketoprofen in β-Cyclodextrin: NMR Spectroscopy, Ab Initio Calculations, Molecular Dynamics Simulations, and Photoreactivity.

    Science.gov (United States)

    Guzzo, T; Mandaliti, W; Nepravishta, R; Aramini, A; Bodo, E; Daidone, I; Allegretti, M; Topai, A; Paci, M

    2016-10-11

    Inclusion of drugs in cyclodextrins (CDs) is a recognized tool for modifying several properties such as solubility, stability, bioavailability, and so on. The photoreactive behavior of the β-CD/ketoprofen (KP) complex upon UV exposure showed a significant increase in photodecarboxylation, whereas the secondary degradation products by hydroxylation of the benzophenone moiety were inhibited. The results may account for an improvement of KP photophysical properties upon inclusion, thus better fostering its topical use. To correlate the structural details of the inclusion with these results, an NMR spectroscopic study of KP upon inclusion in β-CD was performed. Effects of the magnetically anisotropic centers of KP, changing their orientations upon inclusion and giving chemical shift variations, were specifically correlated with the results of the molecular dynamic simulations and ab initio calculations. In the large variety of papers focusing on the structural analysis of β-CD complexes, this work represents one of the few examples in which a detailed analysis of these simultaneous upfield-downfield NMR shifts of the same aromatic molecule upon inclusion is reported. Interestingly, the results demonstrate that the observed upfield and downfield shifts upon inclusion are not related to any direct magnetic role of β-CD. The conformational change of KP upon the inclusion process consists of a slight reduction in the angle between the two phenyl rings and in a remarkable reduction in the mobility of the carboxyl group, the latter being one of the main contributions to the NMR resonance shifts. These structural details help in understanding the features of the inclusion complex and, eventually, the driving force for its formation.

  15. Influence of thermal history on the photostructural changes in glassy As15S85 studied by Raman scattering and ab initio calculations

    International Nuclear Information System (INIS)

    Kolar, J.; Strizik, L.; Kohoutek, T.; Wagner, T.; Voyiatzis, G. A.; Chrissanthopoulos, A.; Yannopoulos, S. N.

    2013-01-01

    Photostructural changes—the hallmark of non-crystalline chalcogenides—are in essence the basis of a number of photoinduced effects, i.e., changes of their physical properties, which are exploited in a variety of applications, especially in photonics and optoelectronics. Despite the vast number of investigations of photostructural changes, there is currently lack of systematic studies on how the thermal history, which affects glass structure, modifies the extent of photostructural changes. In this article, we study the role of thermal history on photostructural changes in glassy As 15 S 85 . This particular sulfur-rich composition has been chosen based on the colossal photostructural response it exhibits under near-band gap light irradiation, which inherently originates from its nanoscale phase-separated nature. To control the thermal history, the glass was quenched to various temperatures and each of these quenched products was annealed under four different conditions. Off-resonant Raman scattering was used to study the equilibrium study of each product. Structural changes of interest involve changes of the sulfur atoms participating into S 8 rings and S n chains. Their ratio was found to depend on quenching/annealing conditions. Near-band gap light was used to perturb the rings-to-chain ratio and at the same time to record these changes through Raman scattering, revealing an intricate behavior of photostructural changes. Ab initio calculations were employed to determine the stability of various sulfur clusters/molecules thus aiding the correlation of the particular photo-response of glassy As 15 S 85 with its structural constituents

  16. Dataset on the structure and thermodynamic and dynamic stability of Mo2ScAlC2 from experiments and first-principles calculations

    Directory of Open Access Journals (Sweden)

    Martin Dahlqvist

    2017-02-01

    Full Text Available The data presented in this paper are related to the research article entitled “Theoretical stability and materials synthesis of a chemically ordered MAX phase, Mo2ScAlC2, and its two-dimensional derivate Mo2ScC” (Meshkian et al. 2017 [1]. This paper describes theoretical phase stability calculations of the MAX phase alloy MoxSc3-xAlC2 (x=0, 1, 2, 3, including chemical disorder and out-of-plane order of Mo and Sc along with related phonon dispersion and Bader charges, and Rietveld refinement of Mo2ScAlC2. The data is made publicly available to enable critical or extended analyzes.

  17. Ab initio vel ex eventu

    Science.gov (United States)

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

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

  18. Ab initio potential for solids

    DEFF Research Database (Denmark)

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

    1992-01-01

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

  19. Electron transport in all-Heusler Co2CrSi/Cu2CrAl/Co2CrSi device, based on ab-initio NEGF calculations

    Science.gov (United States)

    Mikaeilzadeh, L.; Pirgholi, M.; Tavana, A.

    2018-05-01

    Based on the ab-initio non-equilibrium Green's function (NEGF) formalism based on the density functional theory (DFT), we have studied the electron transport in the all-Heusler device Co2CrSi/Cu2CrAl/Co2CrSi. Results show that the calculated transmission spectra is very sensitive to the structural parameters and the interface. Also, we obtain a range for the thickness of the spacer layer for which the MR effect is optimum. Calculations also show a perfect GMR effect in this device.

  20. An imitative calculation of W/C, Mo/Si articifial multilayered films' structures and properties as X-ray monochromators

    International Nuclear Information System (INIS)

    Liu Wen; Liu Wenhan; Wu Ziqin

    1989-01-01

    An imitative calculation on W/C and Mo/Si artificial multilayered films have been made. The influences of total period numbers and deviation of period thickness on X-ray diffraction peak were given. Two difference diviations, random fluctuation and system linear deviation have been imitated, their influences on X-ray energy distinguish power have been compared

  1. How dielectric screening in two-dimensional crystals affects the convergence of excited-state calculations: Monolayer MoS2

    DEFF Research Database (Denmark)

    Hüser, Falco; Olsen, Thomas; Thygesen, Kristian Sommer

    2013-01-01

    We present first-principles many-body calculations of the dielectric constant, quasiparticle band structure, and optical absorption spectrum of monolayer MoS2 using a supercell approach. As the separation between the periodically repeated layers is increased, the dielectric function of the layer...

  2. Quantum-chemical ab initio calculations on the three isomers of diborabenzene (C{sub 4}H{sub 4}B{sub 2})

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Jaswinder; Raabe, Gerhard [Inst. fuer Organische Chemie, RWTH Aachen Univ. (Germany); Wang Yuekui [Key Lab. of Chemical Biology and Molecular Engineering of the Education Ministry, Inst. of Molecular Science, Shanxi Univ., Taiyuan, SH (China)

    2010-01-15

    Quantum-chemical ab initio calculations up to the ZPE+CCSD(T)/aug-cc-pVTZ/MP2/6-311++G** level were performed on three possible structural isomers of diborabenzene (C{sub 4}H{sub 4}B{sub 2}). All three molecules were found to be local minima on the C{sub 4}H{sub 4}B{sub 2} energy surface and to have closed shell singlet ground states. While the ground states of the 1,3- and 1,4-isomer are planar and of C{sub 2v} and D{sub 2h} symmetry, respectively, 1,2-diborabenzene is non-planar with a C{sub 2} axis passing through the center of the BB bond and the middle of the opposite carbon-carbon bond as the only symmetry element. The energetically most favourable 1,3-diborabenzene was found to be about 19 and 36 kcal/mol lower in energy than the 1,2- and the 1,4-isomer. Planar 1,3- and 1,4-diborabenzene have three doubly occupied {pi} orbitals while non-planar 1,2-diborabenzene has also three doubly occupied orbitals which can be derived from the {pi} orbitals of its 3.7 kcal/mol energetically less favourable planar form (''{pi}=like'' orbitals). The lowest unoccupied orbitals of all three isomers have {sigma} symmetry with large coefficients at the two boron atoms. These orbitals are lower in energy than the lowest unoccupied molecular orbitals (LUMOs) of e. g. benzene and pyridine and might cause pronounced acceptor properties which could be one of the reasons for the elusiveness of the title compounds. The results of bond separation reactions show that cyclic conjugation stabilizes all three diborabenzenes relative to their isolated fragments. The most effective stabilization energy of about 24 kcal/mol was found for the energetically lowest 1,3-isomer. This value amounts to approximately one third of the experimental value for the bond separation energy of pyridine. In all cases the energetically lowest triplet states are significantly (16 - 24 kcal/mol) higher in energy than the singlet ground states. Also among the triplets the 1,3-isomer is the

  3. Ab-initio electronic structure calculations and properties of [Si{sub x}Sn{sub 1−x}]{sub 3}N{sub 4} ternary nitrides

    Energy Technology Data Exchange (ETDEWEB)

    Pavloudis, Th. [Department of Physics, Aristotle University of Thessaloniki, GR-54124 Thessaloniki (Greece); Zervos, M. [Nanostructured Materials and Devices Laboratory, Department of Mechanical and Manufacturing Engineering, PO Box 20537, Nicosia 1678 (Cyprus); Komninou, Ph. [Department of Physics, Aristotle University of Thessaloniki, GR-54124 Thessaloniki (Greece); Kioseoglou, J., E-mail: sifisl@auth.gr [Department of Physics, Aristotle University of Thessaloniki, GR-54124 Thessaloniki (Greece)

    2016-08-31

    We carry out ab initio electronic structure calculations of (Si{sub x}Sn{sub 1−x}){sub 3}N{sub 4} using density functional theory with projector augmented-wave potentials under the generalized gradient approximation. We find that the energetically favorable structure of Sn{sub 3}N{sub 4} is the face-centered cubic spinel structure, followed by the hexagonal structure which has energy band gaps of 1.85 eV and 1.44 eV respectively. The (Si{sub x}Sn{sub 1−x}){sub 3}N{sub 4} ternary compound can exhibit both cubic and hexagonal crystal structures over the full range of x. However, the cubic structure is found to be energetically favorable for x < 0.3 above which the hexagonal structure of (Si{sub x}Sn{sub 1−x}){sub 3}N{sub 4} dominates. The energy band gap can be tuned continuously from 1.44 eV up to 5.8 eV in the case of the hexagonal crystal structure of (Si{sub x}Sn{sub 1−x}){sub 3}N{sub 4} and from 1.85 eV to 4.82 eV in the case of cubic (Si{sub x}Sn{sub 1−x}){sub 3}N{sub 4}. Nevertheless the energy gap of (Si{sub x}Sn{sub 1−x}){sub 3}N{sub 4} is direct only for x < 0.3 when it is cubic and for x < 0.5 when hexagonal. - Highlights: • (Si{sub x}Sn{sub 1−x}){sub 3}N{sub 4} exhibits both cubic and hexagonal crystal structures. • The cubic structure is favorable for x < 0.3 and the hexagonal structure for x > 0.3. • The bandgap of hexagonal (Si{sub x}Sn{sub 1−x}){sub 3}N{sub 4} may be tuned from 1.44 eV up to 5.8 eV. • The bandgap may be tuned from 1.85 eV to 4.82 eV for the cubic (Si{sub x}Sn{sub 1−x}){sub 3}N{sub 4}. • Bandgaps are direct for x < 0.3 (cubic) and for x < 0.5 3 (hexagonal (Si{sub x}Sn{sub 1−x}){sub 3}N{sub 4}).

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

    Science.gov (United States)

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

    2012-10-30

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

  5. First-principles comparison of the cubic and tetragonal phases of Mo3Sb7

    KAUST Repository

    Nazir, Safdar; Auluck, Sushil V.; Pulikkotil, Jiji Thomas Joseph; Singh, Nirpendra; Schwingenschlö gl, Udo

    2011-01-01

    Using ab initio density functional based methods, we study the normal metal state properties of the ∼3 K Mo3Sb7 superconductor, in its high temperature cubic and low temperature tetragonal structures. Although the density of states at the Fermi energy is reasonably high in both structures, our calculations unequivocally show that there exists no long range magnetic ordering in this system. We also address the optical properties of the compound. The magnetism in Mo3Sb7 is studied by fixed spin moment calculations, which yield a shallow non-magnetic minimum, thus inferring propensity to a magnetic instability. © 2011 Elsevier B.V. All rights reserved.

  6. First-principles comparison of the cubic and tetragonal phases of Mo3Sb7

    KAUST Repository

    Nazir, Safdar

    2011-03-01

    Using ab initio density functional based methods, we study the normal metal state properties of the ∼3 K Mo3Sb7 superconductor, in its high temperature cubic and low temperature tetragonal structures. Although the density of states at the Fermi energy is reasonably high in both structures, our calculations unequivocally show that there exists no long range magnetic ordering in this system. We also address the optical properties of the compound. The magnetism in Mo3Sb7 is studied by fixed spin moment calculations, which yield a shallow non-magnetic minimum, thus inferring propensity to a magnetic instability. © 2011 Elsevier B.V. All rights reserved.

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

    Energy Technology Data Exchange (ETDEWEB)

    Hellmann, Robert

    2009-06-16

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

  8. Theoretical calculations of spin-Hamiltonian parameters for the rhombic-like Mo5+ centers in KTiOPO4 crystal

    International Nuclear Information System (INIS)

    Yang, Mei; Wen-Chen, Zheng; Hong-Gang, Liu

    2013-01-01

    The spin-Hamiltonian parameters (g factors g i and hyperfine structure constants A i , were i=x, y and z) for Mo 5+ ion occupying the Ti(1) site with approximately rhombic symmetry in KTiOPO 4 crystal are calculated from the high-order perturbation formulas based on the two-mechanism model. In the model, not only the contribution due to the conventional crystal-field (CF) mechanism, but also those due to the charge-transfer (CT) mechanism are included. The six calculated spin-Hamiltonian parameters with four adjustable parameters are in reasonable agreement with the experimental values. The calculations show that for more accurate calculations of spin-Hamiltonian parameters of the high valence d n ions (e.g., Mo 5+ considered here) in crystals, the contribution from CT mechanism, which is ignored in the conventional crystal field theory, should be taken into account. The reasonable crystal field energy levels of Mo 5+ in KTiOPO 4 are also predicted from calculations

  9. Interaction of Al with O2 exposed Mo2BC

    International Nuclear Information System (INIS)

    Bolvardi, Hamid; Music, Denis; Schneider, Jochen M.

    2015-01-01

    Highlights: • Al adheres to many surfaces. • Solid–solid interactions challenging for real (oxidized) surfaces. • Dissociative O 2 adsorption on Mo 2 BC(0 4 0). • Al nonamer is disrupted on oxidized Mo 2 BC(0 4 0). • Adhesion of a residual Al on the native oxide. - Abstract: A Mo 2 BC(0 4 0) surface was exposed to O 2 . The gas interaction was investigated using ab initio molecular dynamics and X-ray photoelectron spectroscopy (XPS) of air exposed surfaces. The calculations suggest that the most dominating physical mechanism is dissociative O 2 adsorption whereby Mo−O, O−Mo−O and Mo 2 −C−O bond formation is observed. To validate these results, Mo 2 BC thin films were synthesized utilizing high power pulsed magnetron sputtering and air exposed surfaces were probed by XPS. MoO 2 and MoO 3 bond formation is observed and is consistent with here obtained ab initio data. Additionally, the interfacial interactions of O 2 exposed Mo 2 BC(0 4 0) surface with an Al nonamer is studied with ab initio molecular dynamics to describe on the atomic scale the interaction between this surface and Al to mimic the interface present during cold forming processes of Al based alloys. The Al nonamer was disrupted and Al forms chemical bonds with oxygen contained in the O 2 exposed Mo 2 BC(0 4 0) surface. Based on the comparison of here calculated adsorption energy with literature data, Al−Al bonds are shown to be significantly weaker than the Al−O bonds formed across the interface. Hence, Al−Al bond rupture is expected for a mechanically loaded interface. Therefore the adhesion of a residual Al on the native oxide layer is predicted. This is consistent with experimental observations. The data presented here may also be relevant for other oxygen containing surfaces in a contact with Al or Al based alloys for example during forming operations

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

    Science.gov (United States)

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

    2017-04-01

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

  11. Collective rotation from ab initio theory

    International Nuclear Information System (INIS)

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

    2015-01-01

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

  12. Large theoretical thermoelectric power factor of suspended single-layer MoS{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Babaei, Hasan, E-mail: babaei@illinois.edu, E-mail: babaei@auburn.edu [Mechanical Science and Engineering Department, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801-2906 (United States); Mechanical Engineering Department, Auburn University, Auburn, Alabama 36849-5341 (United States); Khodadadi, J. M. [Mechanical Engineering Department, Auburn University, Auburn, Alabama 36849-5341 (United States); Sinha, Sanjiv [Mechanical Science and Engineering Department, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801-2906 (United States)

    2014-11-10

    We have calculated the semi-classical thermoelectric power factor of suspended single-layer (SL)- MoS{sub 2} utilizing electron relaxation times derived from ab initio calculations. Measurements of the thermoelectric power factor of SL-MoS{sub 2} on substrates reveal poor power factors. In contrast, we find the thermoelectric power factor of suspended SL-MoS{sub 2} to peak at ∼2.8 × 10{sup 4} μW/m K{sup 2} at 300 K, at an electron concentration of 10{sup 12} cm{sup −2}. This figure is higher than that in bulk Bi{sub 2}Te{sub 3}, for example. Given its relatively high thermal conductivity, suspended SL-MoS{sub 2} may hold promise for in-plane thin-film Peltier coolers, provided reasonable mobilities can be realized.

  13. Large theoretical thermoelectric power factor of suspended single-layer MoS2

    International Nuclear Information System (INIS)

    Babaei, Hasan; Khodadadi, J. M.; Sinha, Sanjiv

    2014-01-01

    We have calculated the semi-classical thermoelectric power factor of suspended single-layer (SL)- MoS 2 utilizing electron relaxation times derived from ab initio calculations. Measurements of the thermoelectric power factor of SL-MoS 2 on substrates reveal poor power factors. In contrast, we find the thermoelectric power factor of suspended SL-MoS 2 to peak at ∼2.8 × 10 4 μW/m K 2 at 300 K, at an electron concentration of 10 12 cm −2 . This figure is higher than that in bulk Bi 2 Te 3 , for example. Given its relatively high thermal conductivity, suspended SL-MoS 2 may hold promise for in-plane thin-film Peltier coolers, provided reasonable mobilities can be realized

  14. Dimethyl methylphosphonate adsorption and decomposition on MoO2 as studied by ambient pressure x-ray photoelectron spectroscopy and DFT calculations

    Science.gov (United States)

    Head, Ashley R.; Tsyshevsky, Roman; Trotochaud, Lena; Yu, Yi; Karslıoǧlu, Osman; Eichhorn, Bryan; Kuklja, Maija M.; Bluhm, Hendrik

    2018-04-01

    Organophosphonates range in their toxicity and are used as pesticides, herbicides, and chemical warfare agents (CWAs). Few laboratories are equipped to handle the most toxic molecules, thus simulants such as dimethyl methylphosphonate (DMMP), are used as a first step in studying adsorption and reactivity on materials. Benchmarked by combined experimental and theoretical studies of simulants, calculations offer an opportunity to understand how molecular interactions with a surface changes upon using a CWA. However, most calculations of DMMP and CWAs on surfaces are limited to adsorption studies on clusters of atoms, which may differ markedly from the behavior on bulk solid-state materials with extended surfaces. We have benchmarked our solid-state periodic calculations of DMMP adsorption and reactivity on MoO2 with ambient pressure x-ray photoelectron spectroscopy studies (APXPS). DMMP is found to interact strongly with a MoO2 film, a model system for the MoO x component in the ASZM-TEDA© gas filtration material. Density functional theory modeling of several adsorption and decomposition mechanisms assist the assignment of APXPS peaks. Our results show that some of the adsorbed DMMP decomposes, with all the products remaining on the surface. The rigorous calculations benchmarked with experiments pave a path to reliable and predictive theoretical studies of CWA interactions with surfaces.

  15. Ab Initio factorized LCAO calculations of the electronic band structure of ZnSe, ZnS, and the (ZnSe)1(ZnS)1 strained-layer superlattice

    International Nuclear Information System (INIS)

    Marshall, T.S.; Wilson, T.M.

    1992-01-01

    The authors report on the results of electronic band structure calculations of bulk ZnSe, bulk ZnS and the (ZnSe) 1 (ZnS) 1 , strained-layer superlattice (SLS) using the ab initio factorized linear combination of atomic orbitals method. The bulk calculations were done using the standard primitive nonrectangular 2-atom zinc blende unit cell, while the SLS calculation was done using a primitive tetragonal 4-atom unit cell modeled from the CuAu I structure. The analytic fit to the SLS crystalline potential was determined by using the nonlinear coefficients from the bulk fits. The CPU time saved by factorizing the energy matrix integrals and using a rectangular unit cell is discussed

  16. Ab Initio Density Functional Calculations and Infra-Red Study of CO Interaction with Pd Atoms on θ-Al2O3 (010) Surface.

    Science.gov (United States)

    Narula, Chaitanya K; Allard, Lawrence F; Wu, Zili

    2017-07-24

    The ab initio density functional theoretical studies show that energetics favor CO oxidation on single Pd atoms supported on θ-alumina. The diffuse reflectance infra-red spectroscopy (DRIFTS) results show that carbonates are formed as intermediates when single supported Pd atoms are exposed to a gaseous mixture of CO + O 2 . The rapid agglomeration of Pd atoms under CO oxidation conditions even at 6 °C leads to the presence of Pd particles along with single atoms during CO oxidation experiments. Thus, the observed CO oxidation has contributions from both single Pd atoms and Pd particles.

  17. Deformation behavior of Re alloyed Mo thin films on flexible substrates: In situ fragmentation analysis supported by first-principles calculations.

    Science.gov (United States)

    Jörg, Tanja; Music, Denis; Hauser, Filipe; Cordill, Megan J; Franz, Robert; Köstenbauer, Harald; Winkler, Jörg; Schneider, Jochen M; Mitterer, Christian

    2017-08-07

    A major obstacle in the utilization of Mo thin films in flexible electronics is their brittle fracture behavior. Within this study, alloying with Re is explored as a potential strategy to improve the resistance to fracture. The sputter-deposited Mo 1-x Re x films (with 0 ≤ x ≤ 0.31) were characterized in terms of structural and mechanical properties, residual stresses as well as electrical resistivity. Their deformation behavior was assessed by straining 50 nm thin films on polyimide substrates in uniaxial tension, while monitoring crack initiation and propagation in situ by optical microscopy and electrical resistance measurements. A significant toughness enhancement occurs with increasing Re content for all body-centered cubic solid solution films (x ≤ 0.23). However, at higher Re concentrations (x > 0.23) the positive effect of Re is inhibited due to the formation of dual-phase films with the additional close packed A15 Mo 3 Re phase. The mechanisms responsible for the observed toughness behavior are discussed based on experimental observations and electronic structure calculations. Re gives rise to both increased plasticity and bond strengthening in these Mo-Re solid solutions.

  18. Role of interlayer coupling in ultra thin MoS2

    KAUST Repository

    Cheng, Yingchun

    2012-01-01

    The effects of interlayer coupling on the vibrational and electronic properties of ultra thin MoS 2 were studied by ab initio calculations. For smaller slab thickness, the interlayer distance is significantly elongated because of reduced interlayer coupling. This explains the anomalous thickness dependence of the lattice vibrations observed by Lee et al. (ACS Nano, 2010, 4, 2695). The absence of interlayer coupling in mono-layer MoS 2 induces a transition from direct to indirect band gap behaviour. Our results demonstrate a strong interplay between the intralayer chemical bonding and the interlayer van-der-Waals interaction. This journal is © 2012 The Royal Society of Chemistry.

  19. Ab initio calculations of scattering cross sections of the three-body system (p ¯,e+,e- ) between the e-+H ¯(n =2 ) and e-+H ¯(n =3 ) thresholds

    Science.gov (United States)

    Valdes, Mateo; Dufour, Marianne; Lazauskas, Rimantas; Hervieux, Paul-Antoine

    2018-01-01

    The ab initio method based on the Faddeev-Merkuriev equations is used to calculate cross sections involving the (p ¯,e+,e-) three-body system, with an emphasis on antihydrogen formation (H ¯) via antiproton (p ¯) scattering on positronium. This system is studied in the energy range between the e-+H ¯(n =2 ) and the e-+H ¯(n =3 ) thresholds, where precisely calculated cross sections can be useful for future experiments (GBAR, AEGIS, etc.) aiming to produce antihydrogen atoms. A special treatment is developed to take into account the long-range charge-dipole interaction effect on the wave function. Emphasis is placed on the impact of Feshbach resonances and Gailitis-Damburg oscillations appearing in the vicinity of the p ¯+Ps (n =2 ) threshold.

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

    Science.gov (United States)

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

    2016-05-01

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

  1. Theoretical study of hydration in Y2Mo3O12: Effects on structure and negative thermal expansion

    Directory of Open Access Journals (Sweden)

    Ming-Yi Wu

    2015-02-01

    Full Text Available We report ab-initio calculations of water absorption in Y2Mo3O12. The absorption geometry of H2O in Y2Mo3O12 and the binding property between H2O and Y2Mo3O12 have been first identified. Our calculated results show that water is chemisorbed in Y2Mo3O12 with O of the water binding to the Y3+ cation, which is further strengthened by hydrogen bonding between each of the hydrogen atoms of H2O and the bridge O in Y2Mo3O12, shared by polyhedrons YO6 and MoO4. The absorption of water leads to a reduced angle of Y-O-Mo and shortened Y-Mo distance, and consequently volume contraction of the material, almost linearly with the increasing number of water molecules per unit cell, up to eight in total. In addition, our phonon calculation show that the transverse vibration of Y-O-Mo is restricted due to water absorption, which in turn hinders the NTE, as it is mainly originated from this vibrational mode. Our results clarify further the fundamental mechanisms of the large volume shrinkage and the lost NTE of the framework oxide due to water absorption.

  2. Half-metallic ferromagnetism prediction in MoS2-based two-dimensional superlattice from first-principles

    Science.gov (United States)

    Wen, Yan-Ni; Gao, Peng-Fei; Xia, Ming-Gang; Zhang, Sheng-Li

    2018-03-01

    Half-metallic ferromagnetism (HMFM) has great potential application in spin filter. However, it is extremely rare, especially in two-dimensional (2D) materials. At present, 2D materials have drawn international interest in spintronic devices. Here, we use ab initio density functional theory (DFT) calculations to study the structural stability and electrical and magnetic properties of the MoS2-based 2D superlattice formed by inserting graphene hexagonal ring in 6 × 6 × 1 MoS2 supercell. Two kinds of structures with hexagonal carbon ring were predicted with structural stability and were shown HMFM. The two structures combine the spin transport capacity of graphene with the magnetism of the defective 2D MoS2. And they have strong covalent bonding between the C and S or Mo atoms near the interface. This work is very useful to help us to design reasonable MoS2-based spin filter.

  3. An ab initio potential energy surface for the formic acid dimer: zero-point energy, selected anharmonic fundamental energies, and ground-state tunneling splitting calculated in relaxed 1-4-mode subspaces.

    Science.gov (United States)

    Qu, Chen; Bowman, Joel M

    2016-09-14

    We report a full-dimensional, permutationally invariant potential energy surface (PES) for the cyclic formic acid dimer. This PES is a least-squares fit to 13475 CCSD(T)-F12a/haTZ (VTZ for H and aVTZ for C and O) energies. The energy-weighted, root-mean-square fitting error is 11 cm -1 and the barrier for the double-proton transfer on the PES is 2848 cm -1 , in good agreement with the directly-calculated ab initio value of 2853 cm -1 . The zero-point vibrational energy of 15 337 ± 7 cm -1 is obtained from diffusion Monte Carlo calculations. Energies of fundamentals of fifteen modes are calculated using the vibrational self-consistent field and virtual-state configuration interaction method. The ground-state tunneling splitting is computed using a reduced-dimensional Hamiltonian with relaxed potentials. The highest-level, four-mode coupled calculation gives a tunneling splitting of 0.037 cm -1 , which is roughly twice the experimental value. The tunneling splittings of (DCOOH) 2 and (DCOOD) 2 from one to three mode calculations are, as expected, smaller than that for (HCOOH) 2 and consistent with experiment.

  4. Modelling the local atomic structure of molybdenum in nuclear waste glasses with ab initio molecular dynamics simulations.

    Science.gov (United States)

    Konstantinou, Konstantinos; Sushko, Peter V; Duffy, Dorothy M

    2016-09-21

    The nature of chemical bonding of molybdenum in high level nuclear waste glasses has been elucidated by ab initio molecular dynamics simulations. Two compositions, (SiO 2 ) 57.5 -(B 2 O 3 ) 10 -(Na 2 O) 15 -(CaO) 15 -(MoO 3 ) 2.5 and (SiO 2 ) 57.3 -(B 2 O 3 ) 20 -(Na 2 O) 6.8 -(Li 2 O) 13.4 -(MoO 3 ) 2.5 , were considered in order to investigate the effect of ionic and covalent components on the glass structure and the formation of the crystallisation precursors (Na 2 MoO 4 and CaMoO 4 ). The coordination environments of Mo cations and the corresponding bond lengths calculated from our model are in excellent agreement with experimental observations. The analysis of the first coordination shell reveals two different types of molybdenum host matrix bonds in the lithium sodium borosilicate glass. Based on the structural data and the bond valence model, we demonstrate that the Mo cation can be found in a redox state and the molybdate tetrahedron can be connected with the borosilicate network in a way that inhibits the formation of crystalline molybdates. These results significantly extend our understanding of bonding in Mo-containing nuclear waste glasses and demonstrate that tailoring the glass composition to specific heavy metal constituents can facilitate incorporation of heavy metals at high concentrations.

  5. Study of interfacial strain at the α-Al2O3/monolayer MoS2 interface by first principle calculations

    Science.gov (United States)

    Yu, Sheng; Ran, Shunjie; Zhu, Hao; Eshun, Kwesi; Shi, Chen; Jiang, Kai; Gu, Kunming; Seo, Felix Jaetae; Li, Qiliang

    2018-01-01

    With the advances in two-dimensional (2D) transition metal dichalcogenides (TMDCs) based metal-oxide-semiconductor field-effect transistor (MOSFET), the interface between the semiconductor channel and gate dielectrics has received considerable attention due to its significant impacts on the morphology and charge transport of the devices. In this study, first principle calculations were utilized to investigate the strain effect induced by the interface between crystalline α-Al2O3 (0001)/h-MoS2 monolayer. The results indicate that the 1.3 nm Al2O3 can induce a 0.3% tensile strain on the MoS2 monolayer. The strain monotonically increases with thicker dielectric layers, inducing more significant impact on the properties of MoS2. In addition, the study on temperature effect indicates that the increasing temperature induces monotonic lattice expansion. This study clearly indicates that the dielectric engineering can effectively tune the properties of 2D TMDCs, which is very attractive for nanoelectronics.

  6. Synthesis, spectroscopic studies, DFT calculations, electrochemical evaluation, BSA binding and molecular docking of an aroylhydrazone -based cis-dioxido Mo(VI) complex

    Science.gov (United States)

    Mohamadi, Maryam; Faghih-Mirzaei, Ehsan; Ebrahimipour, S. Yousef; Sheikhshoaie, Iran; Haase, Wolfgang; Foro, Sabine

    2017-07-01

    A cis-dioxido Mo(VI) complex, [MoO2(L)(MeOH)], [L2-: (3-methoxy-2-oxidobenzylidene) benzohydrazonate], has been synthesized and characterized using physicochemical and spectroscopic techniques including elemental analysis, FT-IR, 1HNMR, UV-Vis spectroscopy, molar conductivity and single crystal X-ray diffraction. DFT calculations in the ground state of the complex were carried out using hybrid functional B3LYP with DGDZVP as basis set. Non-linear optical properties including electric dipole moment (μ), polarizability (α) and molecular first hyperpolarizability (β) of the compound were also computed. The values of linear polarizability and first hyperpolarizability obtained for the studied molecule indicated that the compound could be a good candidate of nonlinear optical materials. TD-DFT calculation and molecular electrostatic potential (MEP) were also performed. The thermodynamic properties (heat capacity, entropy, and enthalpy) of the complex at different temperatures have been calculated. The interaction of a synthesized complex, with bovine serum albumin was also thoroughly investigated using experimental and theoretical studies. UV-Vis absorption and fluorescence quenching techniques were used to determine the binding parameters as well as the mechanism of the interaction. The values of binding constants were in the range of 104-105 M-1 demonstrating a moderate interaction between the synthesized complex and BSA making the protein suitable for transportation and delivery of the compound. Thermodynamic parameters were also indicating a binding through van der Waals force or hydrogen bond of [MoO2(L)(MeOH)] to BSA. The results obtained from docking studies were consistent to those obtained from experimental studies.

  7. On the isotropic Raman spectrum of Ar2 and how to benchmark ab initio calculations of small atomic clusters: Paradox lost.

    Science.gov (United States)

    Chrysos, Michael; Dixneuf, Sophie; Rachet, Florent

    2015-07-14

    This is the long-overdue answer to the discrepancies observed between theory and experiment in Ar2 regarding both the isotropic Raman spectrum and the second refractivity virial coefficient, BR [Gaye et al., Phys. Rev. A 55, 3484 (1997)]. At the origin of this progress is the advent (posterior to 1997) of advanced computational methods for weakly interconnected neutral species at close separations. Here, we report agreement between the previously taken Raman measurements and quantum lineshapes now computed with the employ of large-scale CCSD or smartly constructed MP2 induced-polarizability data. By using these measurements as a benchmark tool, we assess the degree of performance of various other ab initio computed data for the mean polarizability α, and we show that an excellent agreement with the most recently measured value of BR is reached. We propose an even more refined model for α, which is solution of the inverse-scattering problem and whose lineshape matches exactly the measured spectrum over the entire frequency-shift range probed.

  8. On the isotropic Raman spectrum of Ar{sub 2} and how to benchmark ab initio calculations of small atomic clusters: Paradox lost

    Energy Technology Data Exchange (ETDEWEB)

    Chrysos, Michael, E-mail: michel.chrysos@univ-angers.fr; Rachet, Florent [LUNAM Université, Université d’Angers, CNRS UMR 6200, Laboratoire MOLTECH-Anjou, 2 Bd Lavoisier, 49045 Angers (France); Dixneuf, Sophie [Centre du Commissariat à l’Énergie Atomique de Grenoble, Laboratoire CEA-bioMérieux, Bât 40.20, 17 rue des Martyrs, 38054 Grenoble (France)

    2015-07-14

    This is the long-overdue answer to the discrepancies observed between theory and experiment in Ar{sub 2} regarding both the isotropic Raman spectrum and the second refractivity virial coefficient, B{sub R} [Gaye et al., Phys. Rev. A 55, 3484 (1997)]. At the origin of this progress is the advent (posterior to 1997) of advanced computational methods for weakly interconnected neutral species at close separations. Here, we report agreement between the previously taken Raman measurements and quantum lineshapes now computed with the employ of large-scale CCSD or smartly constructed MP2 induced-polarizability data. By using these measurements as a benchmark tool, we assess the degree of performance of various other ab initio computed data for the mean polarizability α, and we show that an excellent agreement with the most recently measured value of B{sub R} is reached. We propose an even more refined model for α, which is solution of the inverse-scattering problem and whose lineshape matches exactly the measured spectrum over the entire frequency-shift range probed.

  9. Probing the Properties of Polynuclear Superhalogens without Halogen Ligand via ab Initio Calculations: A Case Study on Double-Bridged [Mg2 (CN)5 ](-1) Anions.

    Science.gov (United States)

    Li, Jin-Feng; Li, Miao-Miao; Bai, Hongcun; Sun, Yin-Yin; Li, Jian-Li; Yin, Bing

    2015-12-01

    An ab initio study of the superhalogen properties of eighteen binuclear double-bridged [Mg2 (CN)5 ](-1) clusters is reported herein by using various theoretical methods. High-level CCSD(T) results indicate that all the clusters possess strong superhalogen properties owing to their high vertical electron detachment energies (VDEs), which exceed 6.8 eV (highest: 8.15 eV). The outer valence Green's function method provides inaccurate relative VDE values; hence, this method is not suitable for this kind of polynuclear superhalogens. Both the HF and MP2 results are generally consistent with the CCSD(T) level regarding the relative VDE values and-especially interesting-the average values of the HF and MP2 VDEs are extremely close to the CCSD(T) results. The distributions of the extra electrons of the anions are mainly aggregated into the terminal CN units. These distributions are apparently different from those of previously reported triple-bridged isomers and may be the reason for the decreased VDE values of the clusters. In addition, comparisons of the VDEs of binuclear and mononuclear superhalogens as well as studies of the thermodynamic stabilities with respect to the detachment of various CN(-1) ligands are also performed. These results confirm that polynuclear structures with pseudohalogen ligands can be considered as probable new superhalogens with enhanced properties. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Structural, electronic and magnetic properties of LaCr2Si2C: Ab initio calculation, mean field approximation and Monte-Carlo simulation

    Science.gov (United States)

    Endichi, A.; Zaari, H.; Benyoussef, A.; El Kenz, A.

    2018-06-01

    The magnetic behavior of LaCr2Si2C compound is investigated in this work, using first principle methods, Monte Carlo simulation (MCS) and mean field approximation (MFA). The structural, electronic and magnetic properties are described using ab initio method in the framework of the Generalized Gradient Approximation (GGA), and the Full Potential-Linearized Augmented Plane Wave (FP-LAPW) method implemented in the WIEN2K packages. We have also computed the coupling terms between magnetic atoms which are used in Hamiltonian model. A theoretical study realized by mean field approximation and Monte Carlo Simulation within the Ising model is used to more understand the magnetic properties of this compound. Thereby, our results showed a ferromagnetic ordering of the Cr magnetic moments below the Curie temperature of 30 K (Tc magnetization, the energy, the specific heat and the susceptibility. This material shows the small sign of supra-conductivity; and future researches could be focused to enhance the transport and magnetic properties of this system.

  11. MCNP calculation of the critical H_3BO_3 concentrations for the first fuel loading into the reactor core of NPP MO-3-4 units

    International Nuclear Information System (INIS)

    Vrban, B.; Lueley, J.; Farkas, G.; Hascik, J.; Hinca, R.; Petriska, M.; Slugen, V.

    2012-01-01

    The purpose of the analysis was the determination of critical H_3BO_3 concentrations for the first fuel loading into the reactor core of MO34 units using 2"n"d generation fuel during the first start-up of new unit using calculation code MCNP 1.60. H_3BO_3 concentrations were computed for the given temperature of the primary circuit and position of the 6"t"h safety control rod group. Because of the very first start-up of these units, detailed analyses of active-core parameters are required by National Regulatory Authority and needed for safe operation of nuclear facility. (authors)

  12. Ab initio pseudopotential theory

    International Nuclear Information System (INIS)

    Yin, M.T.; Cohen, M.L.

    1982-01-01

    The ab initio norm-conserving pseudopotential is generated from a reference atomic configuration in which the pseudoatomic eigenvalues and wave functions outside the core region agree with the corresponding ab initio all-electron results within the density-functional formalism. This paper explains why such pseudopotentials accurately reproduce the all-electron results in both atoms and in multiatomic systems. In particular, a theorem is derived to demonstrate the energy- and perturbation-independent properties of ab initio pseudopotentials

  13. Spin transport properties of partially edge-hydrogenated MoS2 nanoribbon heterostructure

    International Nuclear Information System (INIS)

    Peng, Li; Yao, Kailun; Zhu, Sicong; Ni, Yun; Zu, Fengxia; Wang, Shuling; Guo, Bin; Tian, Yong

    2014-01-01

    We report ab initio calculations of electronic transport properties of heterostructure based on MoS 2 nanoribbons. The heterostructure consists of edge hydrogen-passivated and non-passivated zigzag MoS 2 nanoribbons (ZMoS 2 NR-H/ZMoS 2 NR). Our calculations show that the heterostructure has half-metallic behavior which is independent of the nanoribbon width. The opening of spin channels of the heterostructure depends on the matching of particular electronic orbitals in the Mo-dominated edges of ZMoS 2 NR-H and ZMoS 2 NR. Perfect spin filter effect appears at small bias voltages, and large negative differential resistance and rectifying effects are also observed in the heterostructure.

  14. Thermodynamic calculation and an experimental study of the combustion synthesis of (Mo{sub 1−x}Nb{sub x})Si{sub 2} (0 ⩽ x ⩽ 1)

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiaohong, E-mail: matinbow@163.com; Lu, Qiong; Wu, Guangzhi; Shi, Jialing; Sun, Zhi

    2015-08-25

    Highlights: • (Mo{sub 1−x}Nb{sub x})Si{sub 2} alloys were synthesized by a simple and energy-saving process of SHS. • Theoretical adiabatic temperature of (Mo{sub 1−x}Nb{sub x})Si{sub 2} was calculated for the first time. • The variation of the actual temperature is consistent with theoretical temperature. - Abstract: The theoretical adiabatic temperature of (Mo{sub 1−x}Nb{sub x})Si{sub 2} (0 ⩽ x ⩽ 1) is calculated. The results indicate that the theoretical adiabatic temperature of (Mo{sub 1−x}Nb{sub x})Si{sub 2} increases with an increasing Nb content when (Mo{sub 1−x}Nb{sub x})Si{sub 2} is of a single-phase structure, but decreases with an increasing Nb content when (Mo{sub 1−x}Nb{sub x})Si{sub 2} is of a double-phase structure. All of the temperatures are higher than 1800 K, indicating that (Mo{sub 1−x}Nb{sub x})Si{sub 2} (0 ⩽ x ⩽ 1) can be prepared by the combustion synthesis method. In this work, (Mo{sub 1−x}Nb{sub x})Si{sub 2} (0 ⩽ x ⩽ 1) alloys are successfully synthesized by the combustion synthesis process from elemental powders of Mo, Nb, and Si. The highest combustion temperature and combustion product structure are studied. The results confirm that the variation of the experimental maximum combustion temperature of (Mo{sub 1−x}Nb{sub x})Si{sub 2} is consistent with that of the theoretical adiabatic temperature. The combustion products are non-equilibrium species, and a supersaturated solid solution of C11{sub b} type (Mo{sub 1−x}Nb{sub x})Si{sub 2} forms during combustion synthesis.

  15. Rate coefficients of the CF3CHFCF3 + H → CF3CFCF3 + H2 reaction at different temperatures calculated by transition state theory with ab initio and DFT reaction paths.

    Science.gov (United States)

    Ng, Maggie; Mok, Daniel K W; Lee, Edmond P F; Dyke, John M

    2013-03-15

    The minimum energy path (MEP) of the reaction, CF(3)CHFCF(3) + H → transition state (TS) → CF(3)CFCF(3) + H(2), has been computed at different ab initio levels and with density functional theory (DFT) using different functionals. The computed B3LYP/6-31++G**, BH&HLYP/cc-pVDZ, BMK/6-31++G**, M05/6-31+G**, M05-2X/6-31+G**, UMP2/6-31++G**, PUMP2/6-31++G**//UMP2/6-31++G**, RCCSD(T)/aug-cc-pVDZ//UMP2/6-31++G**, RCCSD(T)/aug-cc-pVTZ(spd,sp)//UMP2//6-31++G**, RCCSD(T)/CBS//M05/6-31+G**, and RCCSD(T)/CBS//UMP2/6-31++G** MEPs, and associated gradients and Hessians, were used in reaction rate coefficient calculations based on the transition state theory (TST). Reaction rate coefficients were computed between 300 and 1500 K at various levels of TST, which include conventional TST, canonical variational TST (CVT) and improved CVT (ICVT), and with different tunneling corrections, namely, Wigner, zero-curvature, and small-curvature (SCT). The computed rate coefficients obtained at different ab initio, DFT and TST levels are compared with experimental values available in the 1000-1200 K temperature range. Based on the rate coefficients computed at the ICVT/SCT level, the highest TST level used in this study, the BH&HLYP functional performs best among all the functionals used, while the RCCSD(T)/CBS//MP2/6-31++G** level is the best among all the ab initio levels used. Comparing computed reaction rate coefficients obtained at different levels of theory shows that, the computed barrier height has the strongest effect on the computed reaction rate coefficients as expected. Variational effects on the computed rate coefficients are found to be negligibly small. Although tunneling effects are relatively small at high temperatures (~1500 K), SCT corrections are significant at low temperatures (~300 K), and both barrier heights and the magnitudes of the imaginary frequencies affect SCT corrections. Copyright © 2012 Wiley Periodicals, Inc.

  16. Ab initio calculation of the cross sections for electron impact vibrational excitation of CO via the {sup 2}Π shape resonance

    Energy Technology Data Exchange (ETDEWEB)

    Falcetta, Michael F., E-mail: mffalcetta@gcc.edu; Fair, Mark C.; Tharnish, Emily M.; Williams, Lorna M.; Hayes, Nathan J. [Department of Chemistry, Grove City College, Grove City, Pennsylvania 16127 (United States); Jordan, Kenneth D. [Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260 (United States)

    2016-03-14

    The stabilization method is used to calculate the complex potential energy curve of the {sup 2}Π state of CO{sup −} as a function of bond length, with the refinement that separate potentials are determined for p-wave and d-wave attachment and detachment of the excess electron. Using the resulting complex potentials, absolute vibrational excitation cross sections are calculated as a function of electron energy and scattering angle. The calculated cross sections agree well with experiment.

  17. Magneto-structural correlations in a family of Fe(II)Re(IV)(CN)2 single-chain magnets: density functional theory and ab initio calculations.

    Science.gov (United States)

    Zhang, Yi-Quan; Luo, Cheng-Lin; Wu, Xin-Bao; Wang, Bing-Wu; Gao, Song

    2014-04-07

    Until now, the expressions of the anisotropic energy barriers Δξ and ΔA, using the uniaxial magnetic anisotropy D, the intrachain coupling strength J, and the high-spin ground state S for single-chain magnets (SCMs) in the intermediate region between the Ising and the Heisenberg limits, were unknown. To explore this relationship, we used density functional theory and ab initio methods to obtain expressions of Δξ and ΔA in terms of D, J, and S of six R4Fe(II)-Re(IV)Cl4(CN)2 (R = diethylformamide (1), dibutylformamide (2), dimethylformamide (3), dimethylbutyramide (4), dimethylpropionamide (5), and diethylacetamide (6)) SCMs in the intermediate region. The ΔA value for compounds 1-3 was very similar to the magnetic anisotropic energy of a single Fe(II), while the value of Δξ was predicted using the exchange interaction of Fe(II) with the neighboring Re(IV), which could be expressed as 2JSReSFe. Similar to compounds 1-3, the anisotropy energy barrier ΔA of compounds 4 and 5 was also equal to (Di - Ei)SFe(2), but the correlation energy Δξ was closely equal to 2JSReSFe(cos 98.4 - cos 180) due to the reversal of the spins on the opposite Fe(II). For compound 6, one unit cell of Re(IV)Fe(II) was regarded as a domain wall since it had two different Re(IV)-Fe(II) couplings. Thus, the Δξ of compound 6 was expressed as 4J″SRe1Fe1SRe2Fe2, where J″ was the coupling constant of the neighboring unit cells of Re1Fe1 and Re2Fe2, and ΔA was equal to the anisotropic energy barrier of one domain wall given by DRe1Fe1(S(2)Re1Fe1 - 1/4).

  18. The effects of Na on high pressure phases of CuIn0.5Ga0.5Se2 from ab initio calculation

    International Nuclear Information System (INIS)

    Pluengphon, P; Bovornratanaraks, T; Pinsook, U; Vannarat, S

    2012-01-01

    The effects of Na atoms on high pressure structural phase transitions of CuIn 0.5 Ga 0.5 Se 2 (CIGS) were studied by an ab initio method using density functional theory. At ambient pressure, CIGS is known to have chalcopyrite (I 4-bar 2 d) structure. The high pressure phase transitions of CIGS were proposed to be the same as the order in the CuInSe 2 phase transitions which are I 4-bar 2 d→F m 3-bar m→C m c m structures. By using the mixture atoms method, the Na concentration in CIGS was studied at 0.1, 1.0 and 6.25%. The positive mixing enthalpy of Na at In/Ga sites (Na InGa ) is higher than that of Na at Cu sites (Na Cu ). It confirmed previous studies that Na preferably substitutes on the Cu sites more than the (In, Ga) sites. From the energy-volume curves, we found that the effect of the Na substitutes is to reduce the hardness of CIGS under high pressure. The most significant effects occur at 6.25% Na. We also found that the electronic density of states of CIGS near the valence band maximum is increased noticeably in the chalcopyrite phase. The band gap is close in the cubic and orthorhombic phases. Also, the Na Cu -Se bond length in the chalcopyrite phase is significantly reduced at 6.25% Na, compared with the pure Cu-Se bond length. Consequently, the energy band gap in this phase is wider than in pure CIGS, and the gap increased at the rate of 31 meV GPa -1 under pressure. The Na has a small effect on the transition pressure. The path of transformation from the cubic to orthorhombic phase was derived. The Cu-Se plane in the cubic phase displaced relatively parallel to the (In, Ga)-Se plane by 18% in order to transform to the Cmcm phase. The enthalpy barrier is 0.020 eV/atom, which is equivalent to a thermal energy of 248 K. We predicted that F m 3-bar m and Cmcm can coexist in some pressure range. (paper)

  19. Structural comparison of 1{beta}-Methylcarbapenem, Carbapenem and Penem: NMR studies and theoretical calculations

    Energy Technology Data Exchange (ETDEWEB)

    Sunagawa, M.; Sasaki, A.; Igarashi, J.-E.; Nishimura, T. [Research Center, Sumitomo Pharmaceuticals Co., Ltd., 3-1-98 Kasugadenaka, Konohanaku, Osaka (Japan)

    1998-04-01

    Structural comparisons of meropenem (1), desmethyl meropenem (2) and the penem analogue (3) which contain the same side chains at both C-2 and C-6 were performed using {sup 1}H NMR measurements together with 3-21G* level of ab initio MO and molecular mechanics calculations. The ab initio MO calculations reproduced the skeletons of these strained {beta}-lactam rings in good agreement with the crystallographic data. {sup 1}H NMR measurements in aqueous solution together with molecular modeling studies indicated that there were conformational differences of the C-2 and C-6 side chains in this series of compounds. These observations suggested that the conformational differences could affect their biological activities. (Copyright (c) 1998 Elsevier Science B.V., Amsterdam. All rights reserved.)

  20. Structural comparison of 1β-Methylcarbapenem, Carbapenem and Penem: NMR studies and theoretical calculations

    International Nuclear Information System (INIS)

    Sunagawa, M.; Sasaki, A.; Igarashi, J.-E.; Nishimura, T.

    1998-01-01

    Structural comparisons of meropenem (1), desmethyl meropenem (2) and the penem analogue (3) which contain the same side chains at both C-2 and C-6 were performed using 1 H NMR measurements together with 3-21G* level of ab initio MO and molecular mechanics calculations. The ab initio MO calculations reproduced the skeletons of these strained β-lactam rings in good agreement with the crystallographic data. 1 H NMR measurements in aqueous solution together with molecular modeling studies indicated that there were conformational differences of the C-2 and C-6 side chains in this series of compounds. These observations suggested that the conformational differences could affect their biological activities. (Copyright (c) 1998 Elsevier Science B.V., Amsterdam. All rights reserved.)

  1. MO-D-213-07: RadShield: Semi- Automated Calculation of Air Kerma Rate and Barrier Thickness

    International Nuclear Information System (INIS)

    DeLorenzo, M; Wu, D; Rutel, I; Yang, K

    2015-01-01

    Purpose: To develop the first Java-based semi-automated calculation program intended to aid professional radiation shielding design. Air-kerma rate and barrier thickness calculations are performed by implementing NCRP Report 147 formalism into a Graphical User Interface (GUI). The ultimate aim of this newly created software package is to reduce errors and improve radiographic and fluoroscopic room designs over manual approaches. Methods: Floor plans are first imported as images into the RadShield software program. These plans serve as templates for drawing barriers, occupied regions and x-ray tube locations. We have implemented sub-GUIs that allow the specification in regions and equipment for occupancy factors, design goals, number of patients, primary beam directions, source-to-patient distances and workload distributions. Once the user enters the above parameters, the program automatically calculates air-kerma rate at sampled points beyond all barriers. For each sample point, a corresponding minimum barrier thickness is calculated to meet the design goal. RadShield allows control over preshielding, sample point location and material types. Results: A functional GUI package was developed and tested. Examination of sample walls and source distributions yields a maximum percent difference of less than 0.1% between hand-calculated air-kerma rates and RadShield. Conclusion: The initial results demonstrated that RadShield calculates air-kerma rates and required barrier thicknesses with reliable accuracy and can be used to make radiation shielding design more efficient and accurate. This newly developed approach differs from conventional calculation methods in that it finds air-kerma rates and thickness requirements for many points outside the barriers, stores the information and selects the largest value needed to comply with NCRP Report 147 design goals. Floor plans, parameters, designs and reports can be saved and accessed later for modification and recalculation

  2. MO-D-213-07: RadShield: Semi- Automated Calculation of Air Kerma Rate and Barrier Thickness

    Energy Technology Data Exchange (ETDEWEB)

    DeLorenzo, M [Oklahoma University Health Sciences Center, Oklahoma City, OK (United States); Wu, D [University of Oklahoma Health Sciences Center, Oklahoma City, Ok (United States); Rutel, I [University of Oklahoma Health Science Center, Oklahoma City, OK (United States); Yang, K [Massachusetts General Hospital, Boston, MA (United States)

    2015-06-15

    Purpose: To develop the first Java-based semi-automated calculation program intended to aid professional radiation shielding design. Air-kerma rate and barrier thickness calculations are performed by implementing NCRP Report 147 formalism into a Graphical User Interface (GUI). The ultimate aim of this newly created software package is to reduce errors and improve radiographic and fluoroscopic room designs over manual approaches. Methods: Floor plans are first imported as images into the RadShield software program. These plans serve as templates for drawing barriers, occupied regions and x-ray tube locations. We have implemented sub-GUIs that allow the specification in regions and equipment for occupancy factors, design goals, number of patients, primary beam directions, source-to-patient distances and workload distributions. Once the user enters the above parameters, the program automatically calculates air-kerma rate at sampled points beyond all barriers. For each sample point, a corresponding minimum barrier thickness is calculated to meet the design goal. RadShield allows control over preshielding, sample point location and material types. Results: A functional GUI package was developed and tested. Examination of sample walls and source distributions yields a maximum percent difference of less than 0.1% between hand-calculated air-kerma rates and RadShield. Conclusion: The initial results demonstrated that RadShield calculates air-kerma rates and required barrier thicknesses with reliable accuracy and can be used to make radiation shielding design more efficient and accurate. This newly developed approach differs from conventional calculation methods in that it finds air-kerma rates and thickness requirements for many points outside the barriers, stores the information and selects the largest value needed to comply with NCRP Report 147 design goals. Floor plans, parameters, designs and reports can be saved and accessed later for modification and recalculation

  3. On the energy scale involved in the metal to insulator transition of quadruple perovskite EuCu3Fe4O12: infrared spectroscopy and ab-initio calculations.

    Science.gov (United States)

    Brière, B; Kalinko, A; Yamada, I; Roy, P; Brubach, J B; Sopracase, R; Zaghrioui, M; Phuoc, V Ta

    2016-06-27

    Optical measurements were carried out by infrared spectroscopy on AA'3B4O12 A-site ordered quadruple perovskite EuCu3Fe4O12 (microscopic sample) as function of temperature. At 240 K (=TMI), EuCu3Fe4O12 undergoes a very abrupt metal to insulator transition, a paramagnetic to antiferromagnetic transition and an isostructural transformation with an abrupt large volume expansion. Above TMI, optical conductivity reveals a bad metal behavior and below TMI, an insulating phase with an optical gap of 125 meV is observed. As temperature is decreased, a large and abrupt spectral weight transfer toward an energy scale larger than 1 eV is detected. Concurrently, electronic structure calculations for both high and low temperature phases were compared to the optical conductivity results giving a precise pattern of the transition. Density of states and computed optical conductivity analysis identified Cu3dxy, Fe3d and O2p orbitals as principal actors of the spectral weight transfer. The present work constitutes a first step to shed light on EuCu3Fe4O12 electronic properties with optical measurements and ab-initio calculations.

  4. Full-dimensional quantum calculations of the dissociation energy, zero-point, and 10 K properties of H7+/D7+ clusters using an ab initio potential energy surface.

    Science.gov (United States)

    Barragán, Patricia; Pérez de Tudela, Ricardo; Qu, Chen; Prosmiti, Rita; Bowman, Joel M

    2013-07-14

    Diffusion Monte Carlo (DMC) and path-integral Monte Carlo computations of the vibrational ground state and 10 K equilibrium state properties of the H7 (+)/D7 (+) cations are presented, using an ab initio full-dimensional potential energy surface. The DMC zero-point energies of dissociated fragments H5 (+)(D5 (+))+H2(D2) are also calculated and from these results and the electronic dissociation energy, dissociation energies, D0, of 752 ± 15 and 980 ± 14 cm(-1) are reported for H7 (+) and D7 (+), respectively. Due to the known error in the electronic dissociation energy of the potential surface, these quantities are underestimated by roughly 65 cm(-1). These values are rigorously determined for first time, and compared with previous theoretical estimates from electronic structure calculations using standard harmonic analysis, and available experimental measurements. Probability density distributions are also computed for the ground vibrational and 10 K state of H7 (+) and D7 (+). These are qualitatively described as a central H3 (+)/D3 (+) core surrounded by "solvent" H2/D2 molecules that nearly freely rotate.

  5. Interaction of Al with O{sub 2} exposed Mo{sub 2}BC

    Energy Technology Data Exchange (ETDEWEB)

    Bolvardi, Hamid; Music, Denis, E-mail: music@mch.rwth-aachen.de; Schneider, Jochen M.

    2015-03-30

    Highlights: • Al adheres to many surfaces. • Solid–solid interactions challenging for real (oxidized) surfaces. • Dissociative O{sub 2} adsorption on Mo{sub 2}BC(0 4 0). • Al nonamer is disrupted on oxidized Mo{sub 2}BC(0 4 0). • Adhesion of a residual Al on the native oxide. - Abstract: A Mo{sub 2}BC(0 4 0) surface was exposed to O{sub 2}. The gas interaction was investigated using ab initio molecular dynamics and X-ray photoelectron spectroscopy (XPS) of air exposed surfaces. The calculations suggest that the most dominating physical mechanism is dissociative O{sub 2} adsorption whereby Mo−O, O−Mo−O and Mo{sub 2}−C−O bond formation is observed. To validate these results, Mo{sub 2}BC thin films were synthesized utilizing high power pulsed magnetron sputtering and air exposed surfaces were probed by XPS. MoO{sub 2} and MoO{sub 3} bond formation is observed and is consistent with here obtained ab initio data. Additionally, the interfacial interactions of O{sub 2} exposed Mo{sub 2}BC(0 4 0) surface with an Al nonamer is studied with ab initio molecular dynamics to describe on the atomic scale the interaction between this surface and Al to mimic the interface present during cold forming processes of Al based alloys. The Al nonamer was disrupted and Al forms chemical bonds with oxygen contained in the O{sub 2} exposed Mo{sub 2}BC(0 4 0) surface. Based on the comparison of here calculated adsorption energy with literature data, Al−Al bonds are shown to be significantly weaker than the Al−O bonds formed across the interface. Hence, Al−Al bond rupture is expected for a mechanically loaded interface. Therefore the adhesion of a residual Al on the native oxide layer is predicted. This is consistent with experimental observations. The data presented here may also be relevant for other oxygen containing surfaces in a contact with Al or Al based alloys for example during forming operations.

  6. Half-metallic behavior and electronic structure of Sr2CrMoO6 magnetic system

    International Nuclear Information System (INIS)

    Bonilla, C.M.; Landinez Tellez, D.A.; Arbey Rodriguez, J.; Vera Lopez, E.; Roa-Rojas, J.

    2007-01-01

    Complex perovskite materials with the A 2 BB'O 6 formula have been recently studied because of their peculiar magnetic and electronic properties. The origin of magnetism in the double perovskite Sr 2 FeMoO 6 brought these properties again into discussion. Recently, a new interaction mechanism was proposed for cases in which the hybridization of 3d and 2p levels of Mo with the 3d Fe levels is responsible for the half-metallic behavior in the Sr 2 FeMoO 6 material. We report on LAPW ab initio calculations within the generalized gradient approximation (GGA) to density functional theory (DFT) for another double perovskite, namely, Sr 2 CrMoO 6 . Our results show that this is also a half-metallic system. We correlate our results with an extension of the recent model proposed by Sarma to explain the conduction mechanism in this compound

  7. Spectra and structure of silicon containing compounds. XXXII. Raman and infrared spectra, conformational stability, vibrational assignment and ab initio calculations of n-propylsilane-d0 and Si-d3.

    Science.gov (United States)

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

    2003-03-15

    The infrared (3100-40 cm(-1)) and Raman (3100-20 cm(-1)) spectra of gaseous and solid n-propylsilane, CH(3)CH(2)CH(2)SiH(3) and the Si-d(3) isotopomer, CH(3)CH(2)CH(2)SiD(3), have been recorded. Additionally, the Raman spectra of the liquids have been recorded and qualitative depolarization values obtained. Both the anti and gauche conformers have been identified in the fluid phases but only the anti conformer remains in the solid. Variable temperature (-105 to -150 degrees C) studies of the infrared spectra of n-propylsilane dissolved in liquid krypton have been recorded and the enthalpy difference has been determined to be 220+/-22 cm(-1) (2.63+/-0.26 kJ mol(-1)) with the anti conformer the more stable form. A similar value of 234+/-23 cm(-1) (2.80+/-0.28 kJ mol(-1)) was obtained for deltaH for the Si-d(3) isotopomer. At ambient temperature it is estimated that there is 30+/-2% of the gauche conformer present. The potential function governing the conformation interchange has been estimated from the far infrared spectral data, the enthalpy difference, and the dihedral angle of the gauche conformer, which is compared to the one predicted from ab initio MP2/6-31G(d) calculations. The barriers to conformational interchange are: 942, 970 and 716 cm(-1) for the anti to gauche, gauche to gauche, and gauche to anti conformers, respectively. Relatively complete vibrational assignments are proposed for both the n-propylsilane-d(0) and Si-d(3) molecules based on the relative infrared and Raman spectral intensities, infrared band contours, depolarization ratios, and normal coordinate calculations. The geometrical parameters, harmonic force constants, vibrational frequencies, infrared intensities, Raman activities and depolarization ratios, and energy differences have been obtained for the anti and gauche conformers from ab initio MP2/6-31G(d) calculations. Structural parameters and energy differences have also been obtained utilizing the larger 6-311 + G(d,p) and 6-311 + G(2

  8. Spectra and structure of silicon containing compounds. XXXII. Raman and infrared spectra, conformational stability, vibrational assignment and ab initio calculations of n-propylsilane-d 0 and Si-d 3

    Science.gov (United States)

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

    2003-03-01

    The infrared (3100-40 cm -1) and Raman (3100-20 cm -1) spectra of gaseous and solid n-propylsilane, CH 3CH 2CH 2SiH 3 and the Si-d 3 isotopomer, CH 3CH 2CH 2SiD 3, have been recorded. Additionally, the Raman spectra of the liquids have been recorded and qualitative depolarization values obtained. Both the anti and gauche conformers have been identified in the fluid phases but only the anti conformer remains in the solid. Variable temperature (-105 to -150 °C) studies of the infrared spectra of n-propylsilane dissolved in liquid krypton have been recorded and the enthalpy difference has been determined to be 220±22 cm -1 (2.63±0.26 kJ mol -1) with the anti conformer the more stable form. A similar value of 234±23 cm -1 (2.80±0.28 kJ mol -1) was obtained for Δ H for the Si-d 3 isotopomer. At ambient temperature it is estimated that there is 30±2% of the gauche conformer present. The potential function governing the conformation interchange has been estimated from the far infrared spectral data, the enthalpy difference, and the dihedral angle of the gauche conformer, which is compared to the one predicted from ab initio MP2/6-31G(d) calculations. The barriers to conformational interchange are: 942, 970 and 716 cm -1 for the anti to gauche, gauche to gauche, and gauche to anti conformers, respectively. Relatively complete vibrational assignments are proposed for both the n-propylsilane-d 0 and Si-d 3 molecules based on the relative infrared and Raman spectral intensities, infrared band contours, depolarization ratios, and normal coordinate calculations. The geometrical parameters, harmonic force constants, vibrational frequencies, infrared intensities, Raman activities and depolarization ratios, and energy differences have been obtained for the anti and gauche conformers from ab initio MP2/6-31G(d) calculations. Structural parameters and energy differences have also been obtained utilizing the larger 6-311+G(d,p) and 6-311+G(2d,2p) basis sets. From the isolated

  9. MO-F-CAMPUS-I-01: A System for Automatically Calculating Organ and Effective Dose for Fluoroscopically-Guided Procedures

    Energy Technology Data Exchange (ETDEWEB)

    Xiong, Z; Vijayan, S; Rana, V; Rudin, S; Bednarek, D [Toshiba Stroke and Vascular Research Center, University at Buffalo, Buffalo, NY (United States)

    2015-06-15

    Purpose: A system was developed that automatically calculates the organ and effective dose for individual fluoroscopically-guided procedures using a log of the clinical exposure parameters. Methods: We have previously developed a dose tracking system (DTS) to provide a real-time color-coded 3D- mapping of skin dose. This software produces a log file of all geometry and exposure parameters for every x-ray pulse during a procedure. The data in the log files is input into PCXMC, a Monte Carlo program that calculates organ and effective dose for projections and exposure parameters set by the user. We developed a MATLAB program to read data from the log files produced by the DTS and to automatically generate the definition files in the format used by PCXMC. The processing is done at the end of a procedure after all exposures are completed. Since there are thousands of exposure pulses with various parameters for fluoroscopy, DA and DSA and at various projections, the data for exposures with similar parameters is grouped prior to entry into PCXMC to reduce the number of Monte Carlo calculations that need to be performed. Results: The software developed automatically transfers data from the DTS log file to PCXMC and runs the program for each grouping of exposure pulses. When the dose from all exposure events are calculated, the doses for each organ and all effective doses are summed to obtain procedure totals. For a complicated interventional procedure, the calculations can be completed on a PC without manual intervention in less than 30 minutes depending on the level of data grouping. Conclusion: This system allows organ dose to be calculated for individual procedures for every patient without tedious calculations or data entry so that estimates of stochastic risk can be obtained in addition to the deterministic risk estimate provided by the DTS. Partial support from NIH grant R01EB002873 and Toshiba Medical Systems Corp.

  10. Structural, electronic, magnetic and thermodynamic properties of Ni1-xTixO alloys an ab initio calculation and Monte Carlo study

    Science.gov (United States)

    Klaa, K.; Labidi, S.; Masrour, R.; Jabar, A.; Labidi, M.; Amara, A.; Drici, A.; Hlil, E. K.; Ellouze, M.

    2018-06-01

    Structural, electronic, magnetic and thermodynamic main features for Ni1-xTixO ternary alloys in rock-salt structure with Ti content in the range ? were studied using the full potential Linearized augmented plane wave (FP-LAPW) method within density functional theory. The exchange-correlation potential was calculated by the generalized gradient approximation. The analysis of the electronic density of states curves allowed the computation of the magnetic moments which are considered to lie along (010) axes. The thermodynamic stability of this alloy was investigated by calculating the excess enthalpy of mixing ? as well as the phase diagram. In addition, the Monte Carlo simulations have been exploited to calculate the transition temperature and magnetic coercive field in the alloy.

  11. Investigations of mechanical, electronic, and magnetic properties of non-magnetic MgTe and ferro-magnetic Mg0.75TM0.25Te (TM = Fe, Co, Ni): An ab-initio calculation

    International Nuclear Information System (INIS)

    Mahmood, Q; Alay-e-Abbas, S M; Mahmood, I; Noor, N A; Asif, Mahmood

    2016-01-01

    The mechanical, electronic and magnetic properties of non-magnetic MgTe and ferro-magnetic (FM) Mg 0.75 TM 0.25 Te (TM = Fe, Co, Ni) in the zinc-blende phase are studied by ab-initio calculations for the first time. We use the generalized gradient approximation functional for computing the structural stability, and mechanical properties, while the modified Becke and Johnson local (spin) density approximation (mBJLDA) is utilized for determining the electronic and magnetic properties. By comparing the energies of non-magnetic and FM calculations, we find that the compounds are stable in the FM phase, which is confirmed by their structural stabilities in terms of enthalpy of formation. Detailed descriptions of elastic properties of Mg 0.75 TM 0.25 Te alloys in the FM phase are also presented. For electronic properties, the spin-polarized electronic band structures and density of states are computed, showing that these compounds are direct bandgap materials with strong hybridizations of TM 3d states and Te p states. Further, the ferromagnetism is discussed in terms of the Zener free electron model, RKKY model and double exchange model. The charge density contours in the (110) plane are calculated to study bonding properties. The spin exchange splitting and crystal field splitting energies are also calculated. The distribution of electron spin density is employed in computing the magnetic moments appearing at the magnetic sites (Fe, Co, Ni), as well as at the non-magnetic sites (Mg, Te). It is found that the p–d hybridization causes not only magnetic moments on the magnetic sites but also induces negligibly small magnetic moments at the non-magnetic sites. (paper)

  12. Consensus structures of the Mo(v) sites of sulfite-oxidizing enzymes derived from variable frequency pulsed EPR spectroscopy, isotopic labelling and DFT calculations.

    Science.gov (United States)

    Enemark, John H

    2017-10-10

    Sulfite-oxidizing enzymes from eukaryotes and prokaryotes have five-coordinate distorted square-pyramidal coordination about the molybdenum atom. The paramagnetic Mo(v) state is easily generated, and over the years four distinct CW EPR spectra have been identified, depending upon enzyme source and the reaction conditions, namely high and low pH (hpH and lpH), phosphate inhibited (P i ) and sulfite (or blocked). Extensive studies of these paramagnetic forms of sulfite-oxidizing enzymes using variable frequency pulsed electron spin echo (ESE) spectroscopy, isotopic labeling and density functional theory (DFT) calculations have led to the consensus structures that are described here. Errors in some of the previously proposed structures are corrected.

  13. Efficient spin injection and giant magnetoresistance in Fe / MoS 2 / Fe junctions

    KAUST Repository

    Dolui, Kapildeb

    2014-07-02

    We demonstrate giant magnetoresistance in Fe/MoS2/Fe junctions by means of ab initio transport calculations. We show that junctions incorporating either a monolayer or a bilayer of MoS2 are metallic and that Fe acts as an efficient spin injector into MoS2 with an efficiency of about 45%. This is the result of the strong coupling between the Fe and S atoms at the interface. For junctions of greater thickness, a maximum magnetoresistance of ∼300% is obtained, which remains robust with the applied bias as long as transport is in the tunneling limit. A general recipe for improving the magnetoresistance in spin valves incorporating layered transition metal dichalcogenides is proposed. © 2014 American Physical Society.

  14. Electronic structure and transport properties of zigzag MoS2 nanoribbons

    Science.gov (United States)

    Sharma, Uma Shankar; Shah, Rashmi; Mishra, Pankaj Kumar

    2018-05-01

    In present study, electronic and transport properties of the 8zigzag MoS2 nanoribbons (8ZMoS2NRs) are investigated using ab-initio density functional theory [DFT]. The calculations were performed using nonequilibrium Green's function (NEGF) formalism based on DFT as implemented in the TranSiesta code. Results show that the defect can introduces few extra states into the energy gap, which lead nanoribbons to reveal a metallic characteristic. The voltage-current (VI) graph of 8ZMoS2NRs show a threshold current increases after introducing Mo defect in the devices. when introducing a Mo vacancy under low biases, the current will be suppressed—whereas under high biases, the current through the defected 8ZMoS2NRs will increases rapidly, due to the other channel being opened, that make possibility of 8ZMoS2NRs application in electronic devices such as voltage regulation.

  15. Ab-initio calculation of EuO doped with 5% of (Ti, V, Cr and Fe): GGA and SIC approximation

    Science.gov (United States)

    Rouchdi, M.; Salmani, E.; Bekkioui, N.; Ez-Zahraouy, H.; Hassanain, N.; Benyoussef, A.; Mzerd, A.

    2017-12-01

    In this research, a simple theoretical method is proposed to investigate the electronic, magnetic and optical properties of Europium oxide (EuO) doped with 5% of (Ti, V, Cr and Fe). For a basic understanding of these properties, we employed Density-Functional Theory (DFT) based calculations with the Korringa-Kohn-Rostoker code (KKR) combined with the Coherent Potential Approximation (CPA). Also we investigated the half-metallic ferromagnetic behavior of EuO doped with 5% of (Ti, V, Cr and Fe) within the self-interaction-corrected Generalized Gradient Approximation (GGA-SIC). Our calculated results revealed that the Eu0.95TM0.05O is ferromagnetic with a high transition temperature. Moreover, the optical absorption spectra revealed that the half metallicity has been also predicted.

  16. Ab initio calculation of the electronic structures of the 7∑+ ground and A 7Π and a 5∑+ excited states of MnH

    Science.gov (United States)

    Tomonari, Mutsumi; Nagashima, Umpei; Hirano, Tsuneo

    2009-04-01

    Electronic structures and molecular constants of the ground ∑7+ and low-lying A 7Π and a ∑5+ electronic excited states of the MnH molecule were studied by multireference single and double excitation configuration interaction (MR-SDCI) with Davidson's correction (+Q) calculations under exact C∞v symmetry using Slater-type basis sets. To correctly describe the ∑7+ electronic ground state, X ∑7+, at the MR-SDCI+Q calculation, we employed a large number of reference configurations in terms of the state-averaged complete active space self-consistent field (CASSCF) orbitals, taking into account the contribution from the B ∑7+ excited state. The A 7Π and a ∑5+ states can well be described by the MR-SDCI wave functions based on the CASSCF orbitals obtained for the lowest state only. In the MR-SDCI+Q, calculations of the X ∑7+, A 7Π, and a ∑5+ states required 16, 7, and 17 reference configurations, respectively. Molecular constants, i.e., re and ωe of these states and excitation energy from the X ∑7+ state, obtained at the MR-SDCI+Q level, showed a good agreement with experimental values. The small remaining differences may be accounted for by taking relativistic effects into account.

  17. Ab initio calculation of the electronic structures of the (7)Sigma+ ground and A (7)Pi and a (5)Sigma+ excited states of MnH.

    Science.gov (United States)

    Tomonari, Mutsumi; Nagashima, Umpei; Hirano, Tsuneo

    2009-04-21

    Electronic structures and molecular constants of the ground (7)Sigma(+) and low-lying A (7)Pi and a (5)Sigma(+) electronic excited states of the MnH molecule were studied by multireference single and double excitation configuration interaction (MR-SDCI) with Davidson's correction (+Q) calculations under exact C(infinity v) symmetry using Slater-type basis sets. To correctly describe the (7)Sigma(+) electronic ground state, X (7)Sigma(+), at the MR-SDCI+Q calculation, we employed a large number of reference configurations in terms of the state-averaged complete active space self-consistent field (CASSCF) orbitals, taking into account the contribution from the B (7)Sigma(+) excited state. The A (7)Pi and a (5)Sigma(+) states can well be described by the MR-SDCI wave functions based on the CASSCF orbitals obtained for the lowest state only. In the MR-SDCI+Q, calculations of the X (7)Sigma(+), A (7)Pi, and a (5)Sigma(+) states required 16, 7, and 17 reference configurations, respectively. Molecular constants, i.e., r(e) and omega(e) of these states and excitation energy from the X (7)Sigma(+) state, obtained at the MR-SDCI+Q level, showed a good agreement with experimental values. The small remaining differences may be accounted for by taking relativistic effects into account.

  18. Correlated ab initio calculations of spectroscopic parameters of SnO within the framework of the higher-order generalized Douglas-Kroll transformation.

    Science.gov (United States)

    Wolf, Alexander; Reiher, Markus; Hess, Bernd Artur

    2004-05-08

    The first molecular calculations with the generalized Douglas-Kroll method up to fifth order in the external potential (DKH5) are presented. We study the spectroscopic parameters and electron affinity of the tin oxide molecule SnO and its anion SnO(-) applying nonrelativistic as well as relativistic calculations with higher orders of the DK approximation. In order to guarantee highly accurate results close to the basis set limit, an all-electron basis for Sn of at least quintuple-zeta quality has been constructed and optimized. All-electron CCSD(T) calculations of the potential energy curves of both SnO and SnO(-) reproduce the experimental values very well. Relative energies and valence properties are already well described with the established standard second-order approximation DKH2 and the higher-order corrections DKH3-DKH5 hardly affect these quantities. However, an accurate description of total energies and inner-shell properties requires superior relativistic schemes up to DKH5. (c) 2004 American Institute of Physics.

  19. An ab initio molecular

    Indian Academy of Sciences (India)

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

  20. Molecular structure and vibrational spectra of MHal3 (M = Sc, Y, La, Lu; Hal = F, Cl, Br, I): ab initio calculations by the CISD+Q method

    International Nuclear Information System (INIS)

    Solomonik, V.G.; Marochko, O.Yu.

    2000-01-01

    Structure and vibrational spectra of MHal 3 molecules (M = Sc, Y, La, Lu; Hal = F, Cl, Br, I) are studied by the CISD+Q method. It is ascertained that equilibrium configuration of nuclei in all the molecules, except LaF 3 , is plane (D 3h symmetry), while that of LaF 3 molecule - pyramidal (C 3c symmetry). Results of the calculations are compared with previously published experimental data. Band reference in IR spectra of ScBr 3 , YF 3 and YCl 3 molecules has been corrected [ru

  1. Calculation of radiation field integrals for higher-order basis functions in conical thin wire MoM formulation

    CSIR Research Space (South Africa)

    Lysko, AA

    2008-07-01

    Full Text Available stream_source_info LyskoA_2008.pdf.txt stream_content_type text/plain stream_size 24096 Content-Encoding UTF-8 stream_name LyskoA_2008.pdf.txt Content-Type text/plain; charset=UTF-8 On Calculation of Radiation Field... recursive manner. The speed performance of a Matlab implementation indicates that the presented method is favorable compared to the commercial software “WIPL-D” used as a reference. Key-Words: - antenna radiation patterns, moment methods, numerical...

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

    Science.gov (United States)

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

    2011-06-01

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

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

    International Nuclear Information System (INIS)

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

    2011-01-01

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

  4. Relative solvation free energies calculated using an ab initio QM/MM-based free energy perturbation method: dependence of results on simulation length.

    Science.gov (United States)

    Reddy, M Rami; Erion, Mark D

    2009-12-01

    Molecular dynamics (MD) simulations in conjunction with thermodynamic perturbation approach was used to calculate relative solvation free energies of five pairs of small molecules, namely; (1) methanol to ethane, (2) acetone to acetamide, (3) phenol to benzene, (4) 1,1,1 trichloroethane to ethane, and (5) phenylalanine to isoleucine. Two studies were performed to evaluate the dependence of the convergence of these calculations on MD simulation length and starting configuration. In the first study, each transformation started from the same well-equilibrated configuration and the simulation length was varied from 230 to 2,540 ps. The results indicated that for transformations involving small structural changes, a simulation length of 860 ps is sufficient to obtain satisfactory convergence. In contrast, transformations involving relatively large structural changes, such as phenylalanine to isoleucine, require a significantly longer simulation length (>2,540 ps) to obtain satisfactory convergence. In the second study, the transformation was completed starting from three different configurations and using in each case 860 ps of MD simulation. The results from this study suggest that performing one long simulation may be better than averaging results from three different simulations using a shorter simulation length and three different starting configurations.

  5. Monte Carlo and Ab-initio calculation of TM (Ti, V, Cr, Mn, Fe, Co, Ni) doped MgH{sub 2} hydride: GGA and SIC approximation

    Energy Technology Data Exchange (ETDEWEB)

    Salmani, E., E-mail: elmehdisalmani@gmail.com [LMPHE (URAC12), Faculty of Sciences, Mohammed V University in Rabat (Morocco); Laghrissi, A.; Lamouri, R. [LMPHE (URAC12), Faculty of Sciences, Mohammed V University in Rabat (Morocco); Benchafia, E. [Department of Materials Science and Engineering, New Jersey Institute of Technology, Newark, NJ 07102 (United States); Ez-Zahraouy, H. [LMPHE (URAC12), Faculty of Sciences, Mohammed V University in Rabat (Morocco); Benyoussef, A. [Institute for Nanomaterials and Nanotechnologies, MAScIR, Rabat (Morocco)

    2017-02-15

    MgH{sub 2}: TM (TM: V, Cr, Mn, Fe, Co, Ni) based dilute magnetic semiconductors (DMS) are investigated using first principle calculations. Our results show that the ferromagnetic state is stable when TM introduces magnetic moments as well as intrinsic carriers in TM: Co, V, Cr, Ti; Mg{sub 0.95}TM{sub 0.05}H{sub 2}. Some of the DMS Ferro magnets under study exhibit a half-metallic behavior, which make them suitable for spintronic applications. The double exchange is shown to be the underlying mechanism responsible for the magnetism of such materials. The exchange interactions obtained from first principle calculations and used in a classical Ising model by a Monte Carlo approach resulted in ferromagnetic states with Curie temperatures within the ambient conditions. - Highlights: • The half-metallic aspect was proven to take place for Ti, Cr, Co and Ni. • The TM impurities are shown to introduce the magnetic moment that makes MgH{sub 2} good candidates for spintronic applications.

  6. Charge-transfer energy in the water-hydrogen molecular aggregate revealed by molecular-beam scattering experiments, charge displacement analysis, and ab initio calculations.

    Science.gov (United States)

    Belpassi, Leonardo; Reca, Michael L; Tarantelli, Francesco; Roncaratti, Luiz F; Pirani, Fernando; Cappelletti, David; Faure, Alexandre; Scribano, Yohann

    2010-09-22

    Integral cross-section measurements for the system water-H(2) in molecular-beam scattering experiments are reported. Their analysis demonstrates that the average attractive component of the water-H(2) intermolecular potential in the well region is about 30% stronger than dispersion and induction forces would imply. An extensive and detailed theoretical analysis of the electron charge displacement accompanying the interaction, over several crucial sections of the potential energy surface (PES), shows that water-H(2) interaction is accompanied by charge transfer (CT) and that the observed stabilization energy correlates quantitatively with CT magnitude at all distances. Based on the experimentally determined potential and the calculated CT, a general theoretical model is devised which reproduces very accurately PES sections obtained at the CCSD(T) level with large basis sets. The energy stabilization associated with CT is calculated to be 2.5 eV per electron transferred. Thus, CT is shown to be a significant, strongly stereospecific component of the interaction, with water functioning as electron donor or acceptor in different orientations. The general relevance of these findings for water's chemistry is discussed.

  7. Ab initio calculation of reaction energies. III. Basis set dependence of relative energies on the FH2 and H2CO potential energy surfaces

    International Nuclear Information System (INIS)

    Frisch, M.J.; Binkley, J.S.; Schaefer, H.F. III

    1984-01-01

    The relative energies of the stationary points on the FH 2 and H 2 CO nuclear potential energy surfaces relevant to the hydrogen atom abstraction, H 2 elimination and 1,2-hydrogen shift reactions have been examined using fourth-order Moller--Plesset perturbation theory and a variety of basis sets. The theoretical absolute zero activation energy for the F+H 2 →FH+H reaction is in better agreement with experiment than previous theoretical studies, and part of the disagreement between earlier theoretical calculations and experiment is found to result from the use of assumed rather than calculated zero-point vibrational energies. The fourth-order reaction energy for the elimination of hydrogen from formaldehyde is within 2 kcal mol -1 of the experimental value using the largest basis set considered. The qualitative features of the H 2 CO surface are unchanged by expansion of the basis set beyond the polarized triple-zeta level, but diffuse functions and several sets of polarization functions are found to be necessary for quantitative accuracy in predicted reaction and activation energies. Basis sets and levels of perturbation theory which represent good compromises between computational efficiency and accuracy are recommended

  8. Anharmonic rovibrational calculations of singlet cyclic C{sub 4} using a new ab initio potential and a quartic force field

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiaohong; Bowman, Joel M., E-mail: jmbowma@emory.edu [Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, Georgia 30322 (United States); Huang, Xinchuan [SETI Institute, 189 Bernardo Ave, Suite 100, Mountain View, California 94043 (United States); Lee, Timothy J., E-mail: Timothy.J.Lee@nasa.gov [MS 245-1, NASA Ames Research Center, Mofffett Field, California 94035 (United States)

    2013-12-14

    We report a CCSD(T)/cc-pCV5Z quartic force field (QFF) and a semi-global CCSD(T)-F12b/aug-cc-pVTZ potential energy surface (PES) for singlet, cyclic C{sub 4}. Vibrational fundamentals, combinations, and overtones are obtained using vibrational second-order perturbation theory (VPT2) and the vibrational configuration-interaction (VCI) approach. Agreement is within 10 cm{sup −1} between the VCI calculated fundamentals on the QFF and PES using the MULTIMODE (MM) program, and VPT2 and VCI results agree for the fundamentals. The agreement between VPT2-QFF and MM-QFF results is also good for the C{sub 4} combinations and overtones. The J = 1 and J = 2 rovibrational energies are reported from both VCI (MM) on the PES and VPT2 on the QFF calculations. The spectroscopic constants of {sup 12}C{sub 4} and two C{sub 2v}-symmetry, single {sup 13}C-substituted isotopologues are presented, which may help identification of cyclic C{sub 4} in future experimental analyses or astronomical observations.

  9. A study of van der Waals complexes of 1,2-dichloroethane in paraffin oil by FTIR spectroscopy and ab initio calculations.

    Science.gov (United States)

    Fishman, A I; Noskov, A I; Aminova, R M; Skochilov, R A

    2015-02-05

    Weak molecular interactions of 1,2-dichloroethane dissolved in paraffin oil were investigated by FTIR spectroscopy. Occurrence of isosbestic points in the spectra along with the factor analysis showed that DCE⋯DCE dimers are formed in solutions at DCE concentrations between 7 and 15 vol.%. It was found that both trans and gauche conformers are involved in the complexation, forming a tg-dimer. From the spectra collected at 200-222 K, the complexation enthalpy was determined: -4.2±0.4 kcal mol(-1). The equilibrium geometry of tg-dimer and the vibrational frequencies were determined from the density functional calculations performed at B3LYP/6-311++G(d,p) and 6-31G(d,p) levels. The C-C bonds of the two molecules involved in tg-dimers were found to be oriented nearly perpendicular to each other. The complexation energy calculated using 6-31G(d,p) and 6-311++G(d,p) basis sets was found to be -1.59 and -1.52 kcal mol(-1), respectively. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. An ab initio and TD DFT

    Indian Academy of Sciences (India)

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

  11. Self-consistent mapping of the ab initio calculations to the multi-orbital p- d model: Magnetism in α-FeSi2 films as the effect of the local environment

    Science.gov (United States)

    Zhandun, V.; Zamkova, N.; Ovchinnikov, S.; Sandalov, I.

    2017-11-01

    To accurately translate the results obtained within density functional theory (DFT) to the language of many-body theory we suggest and test the following approach: the parameters of the formulated model are to be found from the requirement that the model self-consistent electron density and density of electron states are as close as possible to the ones found from the DFT-based calculations. The investigation of the phase diagram of the model allows us to find the critical regions in magnetic properties. Then the behavior of the real system in these regions is checked by the ab initio calculations. As an example, we studied the physics of magnetic moment (MM) formation due to substitutions of Si by Fe-atoms or vice versa in the otherwise non-magnetic alloy α-FeSi2. We find that the MM formation is essentially controlled by the interaction of Fe atoms with its next nearest atoms (NNN) and by their particular arrangement. The latter may result in different magnetic states at the same concentrations of constituents. Moreover, one of arrangements produces the counterintuitive result: a ferromagnetism arises due to an increase in Si concentration in Fe1-xSi2+ x ordered alloy. The existing phenomenological models associate the destruction of magnetic moment only with the number of Fe-Si nearest neighbors. The presented results show that the crucial role in MM formation is played by the particular local NNN environment of the metal atom in the transition metal-metalloid alloy.

  12. Ab initio derivation of model energy density functionals

    International Nuclear Information System (INIS)

    Dobaczewski, Jacek

    2016-01-01

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

  13. Ab initio model of porous periclase

    International Nuclear Information System (INIS)

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

    2004-01-01

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

  14. Reactivity of 12-tungstophosphoric acid and its inhibitor potency toward Na+/K+-ATPase: A combined 31P NMR study, ab initio calculations and crystallographic analysis.

    Science.gov (United States)

    Bošnjaković-Pavlović, Nada; Bajuk-Bogdanović, Danica; Zakrzewska, Joanna; Yan, Zeyin; Holclajtner-Antunović, Ivanka; Gillet, Jean-Michel; Spasojević-de Biré, Anne

    2017-11-01

    Influence of 12-tungstophosphoric acid (WPA) on conversion of adenosine triphosphate (ATP) to adenosine diphosphate (ADP) in the presence of Na + /K + -ATPase was monitored by 31 P NMR spectroscopy. It was shown that WPA exhibits inhibitory effect on Na + /K + -ATPase activity. In order to study WPA reactivity and intermolecular interactions between WPA oxygen atoms and different proton donor types (D=O, N, C), we have considered data for WPA based compounds from the Cambridge Structural Database (CSD), the Crystallographic Open Database (COD) and the Inorganic Crystal Structure Database (ICSD). Binding properties of Keggin's anion in biological systems are illustrated using Protein Data Bank (PDB). This work constitutes the first determination of theoretical Bader charges on polyoxotungstate compound via the Atom In Molecule theory. An analysis of electrostatic potential maps at the molecular surface and charge of WPA, resulting from DFT calculations, suggests that the preferred protonation site corresponds to WPA bridging oxygen. These results enlightened WPA chemical reactivity and its potential biological applications such as the inhibition of the ATPase activity. Copyright © 2017 Elsevier Inc. All rights reserved.

  15. First-principles study of MoS2 and MoSe2 nanoclusters in the framework of evolutionary algorithm and density functional theory

    Science.gov (United States)

    Hashemi, Zohreh; Rafiezadeh, Shohreh; Hafizi, Roohollah; Hashemifar, S. Javad; Akbarzadeh, Hadi

    2018-04-01

    Evolutionary algorithm is combined with full-potential ab initio calculations to investigate conformational space of (MoS2)n and (MoSe2)n (n = 1-10) nanoclusters and to identify the lowest energy structural isomers of these systems. It is argued that within both BLYP and PBE functionals, these nanoclusters favor sandwiched planar configurations, similar to their ideal planar sheets. The second order difference in total energy (Δ2 E) of the lowest energy isomers is computed to estimate the abundance of the clusters at different sizes and to determine the magic sizes of (MoS2)n and (MoSe2)n nanoclusters. In order to investigate the electronic properties of nanoclusters, their energy gap is calculated by several methods, including hybrid functionals (B3LYP and PBE0), GW approach, and Δ scf method. At the end, the vibrational modes of the lowest lying isomers are calculated by using the force constants method and the IR active modes of the systems are identified. The vibrational spectra are used to calculate the Helmholtz free energy of the systems and then to investigate abundance of the nanoclusters at finite temperatures.

  16. Acid-base interactions and secondary structures of poly-L-lysine probed by 15N and 13C solid state NMR and Ab initio model calculations.

    Science.gov (United States)

    Dos, Alexandra; Schimming, Volkmar; Tosoni, Sergio; Limbach, Hans-Heinrich

    2008-12-11

    The interactions of the 15N-labeled amino groups of dry solid poly-L-lysine (PLL) with various halogen and oxygen acids HX and the relation to the secondary structure have been studied using solid-state 15N and 13C CPMAS NMR spectroscopy (CP = cross polarization and MAS = magic angle spinning). For comparison, 15N NMR spectra of an aqueous solution of PLL were measured as a function of pH. In order to understand the effects of protonation and hydration on the 15N chemical shifts of the amino groups, DFT and chemical shielding calculations were performed on isolated methylamine-acid complexes and on periodic halide clusters of the type (CH3NH3(+)X(-))n. The combined experimental and computational results reveal low-field shifts of the amino nitrogens upon interaction with the oxygen acids HX = HF, H2SO4, CH3COOH, (CH3)2POOH, H3PO4, HNO3, and internal carbamic acid formed by reaction of the amino groups with gaseous CO2. Evidence is obtained that only hydrogen-bonded species of the type (Lys-NH2***H-X)n are formed in the absence of water. 15N chemical shifts are maximum when H is located in the hydrogen bond center and then decrease again upon full protonation, as found for aqueous solution at low pH. By contrast, halogen acids interact in a different way. They form internal salts of the type (Lys-NH3(+)X(-))n via the interaction of many acid-base pairs. This salt formation is possible only in the beta-sheet conformation. By contrast, the formation of hydrogen-bonded complexes can occur both in beta-sheet domains as well as in alpha-helical domains. The 15N chemical shifts of the protonated ammonium groups increase when the size of the interacting halogen anions is increased from chloride to iodide and when the number of the interacting anions is increased. Thus, the observed high-field 15N shift of ammonium groups upon hydration is the consequence of replacing interacting halogen atoms by oxygen atoms.

  17. Magneto-Structural Correlations in Pseudotetrahedral Forms of the [Co(SPh)4]2- Complex Probed by Magnetometry, MCD Spectroscopy, Advanced EPR Techniques, and ab Initio Electronic Structure Calculations.

    Science.gov (United States)

    Suturina, Elizaveta A; Nehrkorn, Joscha; Zadrozny, Joseph M; Liu, Junjie; Atanasov, Mihail; Weyhermüller, Thomas; Maganas, Dimitrios; Hill, Stephen; Schnegg, Alexander; Bill, Eckhard; Long, Jeffrey R; Neese, Frank

    2017-03-06

    The magnetic properties of pseudotetrahedral Co(II) complexes spawned intense interest after (PPh 4 ) 2 [Co(SPh) 4 ] was shown to be the first mononuclear transition-metal complex displaying slow relaxation of the magnetization in the absence of a direct current magnetic field. However, there are differing reports on its fundamental magnetic spin Hamiltonian (SH) parameters, which arise from inherent experimental challenges in detecting large zero-field splittings. There are also remarkable changes in the SH parameters of [Co(SPh) 4 ] 2- upon structural variations, depending on the counterion and crystallization conditions. In this work, four complementary experimental techniques are utilized to unambiguously determine the SH parameters for two different salts of [Co(SPh) 4 ] 2- : (PPh 4 ) 2 [Co(SPh) 4 ] (1) and (NEt 4 ) 2 [Co(SPh) 4 ] (2). The characterization methods employed include multifield SQUID magnetometry, high-field/high-frequency electron paramagnetic resonance (HF-EPR), variable-field variable-temperature magnetic circular dichroism (VTVH-MCD), and frequency domain Fourier transform THz-EPR (FD-FT THz-EPR). Notably, the paramagnetic Co(II) complex [Co(SPh) 4 ] 2- shows strong axial magnetic anisotropy in 1, with D = -55(1) cm -1 and E/D = 0.00(3), but rhombic anisotropy is seen for 2, with D = +11(1) cm -1 and E/D = 0.18(3). Multireference ab initio CASSCF/NEVPT2 calculations enable interpretation of the remarkable variation of D and its dependence on the electronic structure and geometry.

  18. On the violation of the exponential decay law in atomic physics: ab initio calculation of the time-dependence of the He-1s2p24P non-stationary state

    International Nuclear Information System (INIS)

    Nicolaides, C.A.; Mercouris, T.

    1996-01-01

    The detailed time dependence of the decay of a three-electron autoionizing state close to threshold has been obtained ab initio by solving the time-dependent Schrodinger equation (TDSE). The theory allows the definition and computation of energy-dependent matrix elements in terms of the appropriate N-electron wavefunctions, representing the localized initial state, Ψ O , the stationary scattering states of the continuous spectrum, U( e psilon ) , and the localized excited states, Ψ n , of the effective Hamiltonian QHQ, where Q ''ident to'' |Ψ O > O |. The time-dependent wavefunction is expanded over these states and the resulting coupled equations with time-dependent coefficients (in the thousands) are solved to all orders by a Taylor series expansion technique. The robustness of the method was verified by using a model interaction in analytic form and comparing the results from two different methods for integrating the TDSE (appendix B). For the physically relevant application, the chosen state was the He - 1s2p 24 P shape resonance, about which very accurate theoretical and experimental relevant information exists. Calculations using accurate wavefunctions and an energy grid of 20.000 points in the range 0.0-21.77 eV show that the effective interaction depends on energy in a state-specific manner, thereby leading to state-specific characteristics of non-exponential decay over about 6 x 10 4 au of time, from which a width of Γ = 5.2 meV and a lifetime of 1.26 x 10 -13 s is deduced. The results suggest that either in this state or in other autoionizing states close to threshold, NED may have sufficient presence to make the violation of the law of exponential decay observable. (Author)

  19. Improved assignments of the vibrational fundamental modes of ortho -, meta -, and para -xylene using gas- and liquid-phase infrared and Raman spectra combined with ab initio calculations: Quantitative gas-phase infrared spectra for detection

    Energy Technology Data Exchange (ETDEWEB)

    Lindenmaier, Rodica; Scharko, Nicole K.; Tonkyn, Russell G.; Nguyen, Kiet T.; Williams, Stephen D.; Johnson, Timothy J.

    2017-07-25

    Xylenes contain a blend of the ortho-, meta-, and para- isomers, and all are abundant contaminants in the ground, surface waters, and air. To better characterize xylene and to better enable its detection, we report high quality quantitative vapor-phase infrared spectra of all three isomers over the 540-6500 cm-1 range. All fundamental vibrational modes are assigned based on these vapor-phase infrared spectra, liquid-phase infrared and Raman spectra, along with density functional theory (DFT), ab initio MP2 and high energy-accuracy compound theoretical model (W1BD) calculations. Both MP2 and DFT predict a single conformer with C2v symmetry for ortho-xylene, and two conformers each for meta- and para-xylene, depending on the preferred orientations of the methyl groups. For meta-xylene the two conformers have Cs and C2 symmetry, and for para-xylene these conformers have C2v or C2h symmetry. Since the relative population of the two conformers is approximately 50% for both isomers and predicted frequencies and intensities are very similar for each conformer, we made an arbitrary choice to discuss the Cs conformer for meta-xylene and the C2v conformer for para-xylene. We report integrated band intensities for all isomers. Using the quantitative infrared data, we determine the global warming potential values of each isomer and discuss potential bands for atmospheric monitoring.

  20. Magnetic interactions in equi-atomic rare-earth intermetallic alloys RScGe (R = Ce, Pr, Nd and Gd) studied by time differential perturbed angular correlation spectroscopy and ab initio calculations.

    Science.gov (United States)

    Mishra, S N

    2009-03-18

    Applying the time differential perturbed angular correlation (TDPAC) technique we have measured electric and magnetic hyperfine fields of the (111)Cd impurity in equi-atomic rare-earth intermetallic alloys RScGe (R = Ce, Pr and Gd) showing antiferro- and ferromagnetism with unusually high ordering temperatures. The Cd nuclei occupying the Sc site show high magnetic hyperfine fields with saturation values B(hf)(0) = 21 kG, 45 kG and 189 kG in CeScGe, PrScGe and GdScGe, respectively. By comparing the results with the hyperfine field data of Cd in rare-earth metals and estimations from the RKKY model, we find evidence for the presence of additional spin density at the probe nucleus, possibly due to spin polarization of Sc d band electrons. The principal electric field gradient component V(zz) in CeScGe, PrScGe and GdScGe has been determined to be 5.3 × 10(21) V m(-2), 5.5 × 10(21) V m(-2) and 5.6 × 10(21) V m(-2), respectively. Supplementing the experimental measurements, we have carried out ab initio calculations for pure and Cd-doped RScGe compounds with R = Ce, Pr, Nd and Gd using the full potential linearized augmented plane wave (FLAPW) method based on density functional theory (DFT). From the total energies calculated with and without spin polarization we find ferrimagnetic ground states for CeScGe and PrScGe while NdScGe and GdScGe are ferromagnetic. In addition, we find a sizable magnetic moment at the Sc site, increasing from ≈0.10 μ(B) in CeScGe to ≈0.3 μ(B) in GdScGe, confirming the spin polarization of Sc d band electrons. The calculated electric field gradient and magnetic hyperfine fields of the Cd impurity closely agree with the experimental values. We believe spin polarization of Sc 3d band electrons, strongly hybridized with spin polarized 5d band electrons of the rare-earth, enables a long range Ruderman-Kittel-Kasuya-Yosida (RKKY) interaction between RE 4f moments which in turn leads to high magnetic ordering temperatures in

  1. The application of rational approximation in the calculation of a temperature field with a non-linear surface heat-transfer coefficient during quenching for 42CrMo steel cylinder

    Science.gov (United States)

    Cheng, Heming; Huang, Xieqing; Fan, Jiang; Wang, Honggang

    1999-10-01

    The calculation of a temperature field has a great influence upon the analysis of thermal stresses and stains during quenching. In this paper, a 42CrMo steel cylinder was used an example for investigation. From the TTT diagram of the 42CrMo steel, the CCT diagram was simulated by mathematical transformation, and the volume fraction of phase constituents was calculated. The thermal physical properties were treated as functions of temperature and the volume fraction of phase constituents. The rational approximation was applied to the finite element method. The temperature field with phase transformation and non-linear surface heat-transfer coefficients was calculated using this technique, which can effectively avoid oscillationin the numerical solution for a small time step. The experimental results of the temperature field calculation coincide with the numerical solutions.

  2. Ab initio hybrid DFT calculations of BaTiO{sub 3}, PbTiO{sub 3}, SrZrO{sub 3} and PbZrO{sub 3} (111) surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Eglitis, Roberts I., E-mail: rieglitis@gmail.com

    2015-12-15

    Highlights: • Surface energies for AO{sub 3}-term (111) surfaces are larger than for Ti (Zr)-term surfaces. • A increase of Ti−O (Zr−O) bond covalency near the ABO{sub 3} (111) surface relative to the bulk is observed. • The ABO{sub 3} (111) surface energy is larger than the earlier calculated (001) surface energy. • Band gap for PbTiO{sub 3}, SrZrO{sub 3} and PbZrO{sub 3} (111) surfaces becomes smaller, but for BaTiO{sub 3} (111) larger with respect to the bulk . - Abstract: The results of ab initio calculations for polar BaTiO{sub 3}, PbTiO{sub 3}, SrZrO{sub 3} and PbZrO{sub 3} (111) surfaces using the CRYSTAL code are presented. By means of the hybrid B3LYP approach, the surface relaxation has been calculated for two possible B (B = Ti or Zr) or AO{sub 3} (A = Ba, Pb or Sr) BaTiO{sub 3}, PbTiO{sub 3}, SrZrO{sub 3} and PbZrO{sub 3} (111) surface terminations. According to performed B3LYP calculations, all atoms of the first surface layer, for both terminations, relax inwards. The only exception is a small outward relaxation of the PbO{sub 3}-terminated PbTiO{sub 3} (111) surface upper layer Pb atom. B3LYP calculated surface energies for BaO{sub 3}, PbO{sub 3}, SrO{sub 3} and PbO{sub 3}-terminated BaTiO{sub 3}, PbTiO{sub 3}, SrZrO{sub 3} and PbZrO{sub 3} (111) surfaces are considerably larger than the surface energies for Ti (Zr)-terminated (111) surfaces. Performed B3LYP calculations indicate a considerable increase of Ti−O (Zr−O) chemical bond covalency near the BaTiO{sub 3}, PbTiO{sub 3}, SrZrO{sub 3} and PbZrO{sub 3} (111) surface relative to the BaTiO{sub 3}, PbTiO{sub 3}, SrZrO{sub 3} and PbZrO{sub 3} bulk. Calculated band gaps at the Γ-point near the PbTiO{sub 3}, SrZrO{sub 3} and PbZrO{sub 3} (111) surfaces are reduced, but near BaTiO{sub 3} (111) surfaces increased, with respect to the BaTiO{sub 3}, PbTiO{sub 3}, SrZrO{sub 3} and PbZrO{sub 3} bulk band gap at the Γ-point values.

  3. 3d-4p transitions in the soft X-ray spectra of Mo XIV and of isoelectronic Y to Ag ions from a low-inductance vacuum spark

    International Nuclear Information System (INIS)

    Klapisch, M.; Mandelbaum, P.; Schwob, J.L.; Bar-Shalom, A.; Schweitzer, N.

    1981-04-01

    Eight lines of 3d 10 4s - 3d 9 4s4p and 3d 10 4p-3d 9 4p 2 transitions of CuI-like Y XI to Ag XIX ions are identified in the 30-80 A range of spectra emitted from a low-inductance vacuum spark. Identification is based on isoelectronic analysis and comparison with ab-initio relativistic calculations. In the present paper is analyzed the spectra of Mo XIV

  4. Synthesis, characterization, ab initio calculations, thermal behaviour ...

    Indian Academy of Sciences (India)

    Administrator

    ticular, the starting temperature of decomposition of these complexes depends on the equatorial ligand. ... Vanadium oxide (vanadyl) ... red, mass and electronic spectral techniques. ... washed with 1 : 1 ethanol–water mixture and dried in.

  5. Sampling the potential energy surface of a DNA duplex damaged by a food carcinogen: Force field parameterization by ab initio quantum calculations and conformational searching using molecular mechanics computations

    Science.gov (United States)

    Wu, Xiangyang

    1999-07-01

    The heterocyclic amine 2-amino-3-methylimidazo (4, 5-f) quinoline (IQ) is one of a number of carcinogens found in barbecued meat and fish. It induces tumors in mammals and is probably involved in human carcinogenesis, because of great exposure to such food carcinogens. IQ is biochemically activated to a derivative which reacts with DNA to form a covalent adduct. This adduct may deform the DNA and consequently cause a mutation. which may initiate carcinogenesis. To understand this cancer initiating event, it is necessary to obtain atomic resolution structures of the damaged DNA. No such structures are available experimentally due to synthesis difficulties. Therefore, we employ extensive molecular mechanics and dynamics calculations for this purpose. The major IQ-DNA adduct in the specific DNA sequence d(5'G1G2C G3CCA3') - d(5'TGGCGCC3') with IQ modified at G3 is studied. The d(5'G1G2C G3CC3') sequence has recently been shown to be a hot-spot for mutations when IQ modification is at G3. Although this sequence is prone to -2 deletions via a ``slippage mechanism'' even when unmodified, a key question is why IQ increases the mutation frequency of the unmodified DNA by about 104 fold. Is there a structural feature imposed by IQ that is responsible? The molecular mechanics and dynamics program AMBER for nucleic acids with the latest force field was chosen for this work. This force field has been demonstrated to reproduce well the B-DNA structure. However, some parameters, the partial charges, bond lengths and angles, dihedral parameters of the modified residue, are not available in the AMBER database. We parameterized the force field using high level ab initio quantum calculations. We created 800 starting conformations which uniformly sampled in combination at 18° intervals three torsion angles that govern the IQ-DNA orientations, and energy minimized them. The most important structures are abnormal; the IQ damaged guanine is rotated out of its standard B

  6. Consistent force field modeling of matrix isolated molecules. V. Minimum energy path potential to the conformer conversion of 1,2-difluoroethane: Ar 364, ab initio calculation of electric multipole moments and electric polarization contribution to the conversion barrier

    Science.gov (United States)

    Gunde, R.; Ha, T.-K.; Günthard, H. H.

    1990-08-01

    In this paper results of consistent force field modeling (CFF) of the potential function to conversion of the gauche (g) to the trans (t) conformer of 1,2-difluoroethane (DFE) isolated in an argon matrix will be reported. Starting point are locally stable configurations gDFE:Ar 364 (defect GH1) and tDFE:Ar 364 (TH1) obtained in previous work from CFF modeling of a cube shaped Ar 364 fragment containing one DFE molecule in its center. Using the dihedral angle of DFE as an independent parameter the minimum energy path of the conversion process gDFE:Ar 364→tDFE:Ar 364 will be determined by CFF energy minimization. Determination of the minimum energy path is found to require large numbers of energy minimization steps and to lead to a rather complicated motion of the molecule with respect to the crystal fragment. Surprisingly the molecule-matrix interactions lead to a reduction of the g-t barrier by ≈500 cal/mol and to a stabilization of the trans species by ≈500 cal/mol. This finding is a consequence of a delicate interplay of matrix-molecule and matrix-matrix interactions. Calculation of the electric polarization energy (induced dipole-first-order polarization approximation) is based on extended ab initio calculations of dipole and quadrupole moments and a bond polarizability estimate of the first-order polarizability of DFE as a function of the internal rotation angle, on Fourier expansion of multipole components and use of symmetry for reduction of the order of the linear system defining the (self-consistent) induced dipole moments of all Ar atoms. Electric polarization is found to alter the potential function of the conversion process in a profound way: the g-t barrier and the t-g energy difference are increased to ≈3000 cal/mol and to ≈1500 cal/mol respectively (≈2500 and ≈530 cal/mol respectively for free DFE). Further applications of the technique developed in this work to related problems of matrix isolated molecules, e.g., vibrational matrix

  7. The effect of lithium adsorption on the formation of 1T-MoS2 phase based on first-principles calculation

    International Nuclear Information System (INIS)

    Zheng, Yuanliao; Huang, Yan; Shu, Haibo; Zhou, Xiaohao; Ding, Jiayi; Chen, Xiaoshuang; Lu, Wei

    2016-01-01

    The effect of lithium adsorption on the phase transition from 1H-MoS 2 to 1T-MoS 2 is studied by first-principles computations. The results indicate the possibilities of the phase transition for the lithium adsorption. Based on the results of charge density difference and charge-transfer of molybdenum disulfide with lithium adsorption, we elucidated that the mechanism of the changes of electronic property accompanying the phase transition is attributed to the electron transfer of different atoms. According to the result of transition state, it can be found that the phase-transition barrier is related to the coverage of lithium atoms on MoS 2 surface. It may be helpful to obtaining experimentally the stable 1T-MoS 2 structure. - Highlights: • The transformation of MoS 2 from semiconducting to metallic phases is elucidated on the essence of the electron transfer. • The relationship between Li coverage and phase transition barrier is obtained. • The decomposing of Lithiated 1T-MoS 2 at a high concentration of Li adsorption is explained. • The results can be helpful to obtaining experimentally the stable 1T-MoS 2 structure.

  8. A calorimetric and thermodynamic investigation of A2[(UO2)2(MoO4)O2] compounds with A = K and Rb and calculated phase relations in the system (K2MoO4 + UO3 + H2O)

    International Nuclear Information System (INIS)

    Lelet, Maxim I.; Suleimanov, Evgeny V.; Golubev, Aleksey V.; Geiger, Charles A.; Bosbach, Dirk; Alekseev, Evgeny V.

    2015-01-01

    Highlights: • We determined the low temperature heat capacity of A 2 [(UO 2 ) 2 (MoO 4 )O 2 ] compounds with A = K and Rb. • We determined enthalpy of formation of K 2 [(UO 2 ) 2 (MoO 4 )O 2 ] by HF solution calorimetry. • We calculated Δ f G° (T = 298 K) of all phases from studied series. • Using obtained data we performed a thermodynamic modelling in the system (K 2 MoO 4 + UO 3 + H 2 O). - Abstract: A calorimetric and thermodynamic investigation of two alkali-metal uranyl molybdates with general composition A 2 [(UO 2 ) 2 (MoO 4 )O 2 ], where A = K and Rb, was performed. Both phases were synthesized by solid-state sintering of a mixture of potassium or rubidium nitrate, molybdenum (VI) oxide and gamma-uranium (VI) oxide at high temperatures. The synthetic products were characterised by X-ray powder diffraction and X-ray fluorescence methods. The enthalpy of formation of K 2 [(UO 2 ) 2 (MoO 4 )O 2 ] was determined using HF-solution calorimetry giving Δ f H° (T = 298 K, K 2 [(UO 2 ) 2 (MoO 4 )O 2 ], cr) = −(4018 ± 8) kJ · mol −1 . The low-temperature heat capacity, C p °, was measured using adiabatic calorimetry from T = (7 to 335) K for K 2 [(UO 2 ) 2 (MoO 4 )O 2 ] and from T = (7 to 326) K for Rb 2 [(UO 2 ) 2 (MoO 4 )O 2 ]. Using these C p ° values, the third law entropy at T = 298.15 K, S°, is calculated as (374 ± 1) J · K −1 · mol −1 for K 2 [(UO 2 ) 2 (MoO 4 )O 2 ] and (390 ± 1) J · K −1 · mol −1 for Rb 2 [(UO 2 ) 2 (MoO 4 )O 2 ]. These new experimental results, together with literature data, are used to calculate the Gibbs energy of formation, Δ f G°, for both phases giving: Δ f G° (T = 298 K, K 2 [(UO 2 ) 2 (MoO 4 )O 2 ], cr) = (−3747 ± 8) kJ · mol −1 and Δ f G° (T = 298 K, Rb 2 [(UO 2 ) 2 (MoO 4 )], cr) = −3736 ± 5 kJ · mol −1 . Smoothed C p °(T) values between 0 K and 320 K are presented, along with values for S° and the functions [H°(T) − H°(0)] and [G°(T) − H°(0)], for both phases. The

  9. Oxygen Passivation Mediated Tunability of Trion and Excitons in MoS2

    KAUST Repository

    Gogoi, Pranjal Kumar

    2017-08-17

    Using wide spectral range in situ spectroscopic ellipsometry with systematic ultrahigh vacuum annealing and in situ exposure to oxygen, we report the complex dielectric function of MoS2 isolating the environmental effects and revealing the crucial role of unpassivated and passivated sulphur vacancies. The spectral weights of the A (1.92 eV) and B (2.02 eV) exciton peaks in the dielectric function reduce significantly upon annealing, accompanied by spectral weight transfer in a broad energy range. Interestingly, the original spectral weights are recovered upon controlled oxygen exposure. This tunability of the excitonic effects is likely due to passivation and reemergence of the gap states in the band structure during oxygen adsorption and desorption, respectively, as indicated by ab initio density functional theory calculation results. This Letter unravels and emphasizes the important role of adsorbed oxygen in the optical spectra and many-body interactions of MoS2.

  10. Oxygen Passivation Mediated Tunability of Trion and Excitons in MoS2

    KAUST Repository

    Gogoi, Pranjal Kumar; Hu, Zhenliang; Wang, Qixing; Carvalho, Alexandra; Schmidt, Daniel; Yin, Xinmao; Chang, Yung-Huang; Li, Lain-Jong; Sow, Chorng Haur; Neto, A.  H. Castro; Breese, Mark B.  H.; Rusydi, Andrivo; Wee, Andrew T.  S.

    2017-01-01

    Using wide spectral range in situ spectroscopic ellipsometry with systematic ultrahigh vacuum annealing and in situ exposure to oxygen, we report the complex dielectric function of MoS2 isolating the environmental effects and revealing the crucial role of unpassivated and passivated sulphur vacancies. The spectral weights of the A (1.92 eV) and B (2.02 eV) exciton peaks in the dielectric function reduce significantly upon annealing, accompanied by spectral weight transfer in a broad energy range. Interestingly, the original spectral weights are recovered upon controlled oxygen exposure. This tunability of the excitonic effects is likely due to passivation and reemergence of the gap states in the band structure during oxygen adsorption and desorption, respectively, as indicated by ab initio density functional theory calculation results. This Letter unravels and emphasizes the important role of adsorbed oxygen in the optical spectra and many-body interactions of MoS2.

  11. Oxygen Passivation Mediated Tunability of Trion and Excitons in MoS2

    Science.gov (United States)

    Gogoi, Pranjal Kumar; Hu, Zhenliang; Wang, Qixing; Carvalho, Alexandra; Schmidt, Daniel; Yin, Xinmao; Chang, Yung-Huang; Li, Lain-Jong; Sow, Chorng Haur; Neto, A. H. Castro; Breese, Mark B. H.; Rusydi, Andrivo; Wee, Andrew T. S.

    2017-08-01

    Using wide spectral range in situ spectroscopic ellipsometry with systematic ultrahigh vacuum annealing and in situ exposure to oxygen, we report the complex dielectric function of MoS2 isolating the environmental effects and revealing the crucial role of unpassivated and passivated sulphur vacancies. The spectral weights of the A (1.92 eV) and B (2.02 eV) exciton peaks in the dielectric function reduce significantly upon annealing, accompanied by spectral weight transfer in a broad energy range. Interestingly, the original spectral weights are recovered upon controlled oxygen exposure. This tunability of the excitonic effects is likely due to passivation and reemergence of the gap states in the band structure during oxygen adsorption and desorption, respectively, as indicated by ab initio density functional theory calculation results. This Letter unravels and emphasizes the important role of adsorbed oxygen in the optical spectra and many-body interactions of MoS2 .

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

    Directory of Open Access Journals (Sweden)

    Pavlu J.

    2012-01-01

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

  13. First-principles calculations on strain and electric field induced band modulation and phase transition of bilayer WSe2sbnd MoS2 heterostructure

    Science.gov (United States)

    Lei, Xiang; Yu, Ke

    2018-04-01

    A purposeful modulation of physical properties of material via change external conditions has long captured people's interest and can provide many opportunities to improve the specific performance of electronic devices. In this work, a comprehensive first-principles survey was performed to elucidate that the bandgap and electronic properties of WSe2sbnd MoS2 heterostructure exhibited unusual response to exterior strain and electric field in comparison with pristine structures. It demonstrates that the WSe2sbnd MoS2 is a typical type-II heterostructure, and thus the electron-hole pairs can be effectively spatially separated. The external effects can trigger the electronic phase transition from semiconducting to metallic state, which originates from the internal electric evolution induced energy-level shift. Interestingly, the applied strain shows no direction-depended character for the modulation of bandgap of WSe2sbnd MoS2 heterostructure, while it exists in the electric field tuning processes and strongly depends on the direction of the electric field. Our findings elucidate the tunable electronic property of bilayer WSe2sbnd MoS2 heterostructure, and would provide a valuable reference to design the electronic nanodevices.

  14. Theoretical study of hydration in Y{sub 2}Mo{sub 3}O{sub 12}: Effects on structure and negative thermal expansion

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Ming-Yi; Wang, Lei; Jia, Yu; Sun, Qiang, E-mail: qsun@zzu.edu.cn [International Laboratory for Quantum Functional Materials of Henan, and School of Physics and Engineering, Zhengzhou University, Zhengzhou, 450001 (China); Guo, Zheng-Xiao [Department of Chemistry, University College London, London WC1H 0AJ (United Kingdom)

    2015-02-15

    We report ab-initio calculations of water absorption in Y{sub 2}Mo{sub 3}O{sub 12}. The absorption geometry of H{sub 2}O in Y{sub 2}Mo{sub 3}O{sub 12} and the binding property between H{sub 2}O and Y{sub 2}Mo{sub 3}O{sub 12} have been first identified. Our calculated results show that water is chemisorbed in Y{sub 2}Mo{sub 3}O{sub 12} with O of the water binding to the Y{sup 3+} cation, which is further strengthened by hydrogen bonding between each of the hydrogen atoms of H{sub 2}O and the bridge O in Y{sub 2}Mo{sub 3}O{sub 12}, shared by polyhedrons YO{sub 6} and MoO{sub 4}. The absorption of water leads to a reduced angle of Y-O-Mo and shortened Y-Mo distance, and consequently volume contraction of the material, almost linearly with the increasing number of water molecules per unit cell, up to eight in total. In addition, our phonon calculation show that the transverse vibration of Y-O-Mo is restricted due to water absorption, which in turn hinders the NTE, as it is mainly originated from this vibrational mode. Our results clarify further the fundamental mechanisms of the large volume shrinkage and the lost NTE of the framework oxide due to water absorption.

  15. Origin of the n -type and p -type conductivity of MoS 2 monolayers on a SiO 2 substrate

    KAUST Repository

    Dolui, Kapildeb

    2013-04-02

    Ab initio density functional theory calculations are performed to study the electronic properties of a MoS2 monolayer deposited over a SiO 2 substrate in the presence of interface impurities and defects. When MoS2 is placed on a defect-free substrate, the oxide plays an insignificant role since the conduction band top and the valence band minimum of MoS2 are located approximately in the middle of the SiO2 band gap. However, if Na impurities and O dangling bonds are introduced at the SiO2 surface, these lead to localized states, which modulate the conductivity of the MoS2 monolayer from n- to p-type. Our results show that the conductive properties of MoS2 deposited on SiO 2 are mainly determined by the detailed structure of the MoS 2/SiO2 interface, and suggest that doping the substrate can represent a viable strategy for engineering MoS2-based devices. © 2013 American Physical Society.

  16. A proposal for an unusually stiff and moderately ductile hard coating material: Mo2BC

    International Nuclear Information System (INIS)

    Emmerlich, J; Music, D; Braun, M; Fayek, P; Schneider, J M; Munnik, F

    2009-01-01

    The elastic properties of Mo 2 BC were studied using ab initio calculations. The calculated bulk modulus of 324 GPa is 45% larger than that of Ti 0.25 Al 0.75 N and 14% smaller than that of c-BN, indicating a highly stiff material. The bulk modulus (B) to shear modulus (G) ratio is 1.72 at the transition from brittle to ductile behaviour. This, in combination with a positive Cauchy pressure (c 12 - c 44 ), suggests moderate ductility. When compared with a typical hard protective coating such as Ti 0.25 Al 0.75 N (B = 178 GPa; B/G = 1.44; negative Cauchy pressure), Mo 2 BC displays considerable potential as protective coating for metal cutting applications. In order to test this proposal, Mo 2 BC thin films were synthesized using dc magnetron sputtering from three plasma sources on Al 2 O 3 (0 0 0 1) at a substrate temperature of ∼900 0 C. The calculated lattice parameters are in good agreement with values determined from x-ray diffraction. The measured Young's modulus values of ∼460 ± 21 GPa are in excellent agreement with the 470 GPa value obtained by calculations. Scanning probe microscopy imaging of the residual indent revealed no evidence for crack formation as well as significant pile-up, which is consistent with the moderate plasticity predicted. The apparent contradiction between moderate ductility on the one hand and indentation hardness values of 29 GPa can be understood by considering the electronic structure particularly the extreme anisotropy. The presence of stiff Mo-C and Mo-B layers with metallic interlayer bonding enables this intriguing and unexpected property combination.

  17. Modeling Disordered Materials with a High Throughput ab-initio Approach

    Science.gov (United States)

    2015-11-13

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

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

    Science.gov (United States)

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

    2015-12-14

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

  19. Molecular orbital calculations using chemical graph theory

    CERN Document Server

    Dias, Jerry Ray

    1993-01-01

    Professor John D. Roberts published a highly readable book on Molecular Orbital Calculations directed toward chemists in 1962. That timely book is the model for this book. The audience this book is directed toward are senior undergraduate and beginning graduate students as well as practicing bench chemists who have a desire to develop conceptual tools for understanding chemical phenomena. Although, ab initio and more advanced semi-empirical MO methods are regarded as being more reliable than HMO in an absolute sense, there is good evidence that HMO provides reliable relative answers particularly when comparing related molecular species. Thus, HMO can be used to rationalize electronic structure in 1t-systems, aromaticity, and the shape use HMO to gain insight of simple molecular orbitals. Experimentalists still into subtle electronic interactions for interpretation of UV and photoelectron spectra. Herein, it will be shown that one can use graph theory to streamline their HMO computational efforts and to arrive...

  20. Molybdenum(VI) Oxosulfato Complexes in MoO3–K2S2O7–K2SO4 Molten Mixtures: Stoichiometry, Vibrational Properties, and Molecular Structures

    DEFF Research Database (Denmark)

    Kalampounias, Angelos G.; Tsilomelekis, George; Berg, Rolf W.

    2012-01-01

    effects were explored in the XMoO30 = 0–0.5 range. MoO3 undergoes a dissolution reaction in molten K2S2O7, and the Raman spectra point to the formation of molybdenum(VI) oxosulfato complexes. The MoO stretching region of the Raman spectrum provides sound evidence for the occurrence of a dioxo Mo(O)2...... configuration as a core. The stoichiometry of the dissolution reaction MoO3 + nS2O72– → C2n– was inferred by exploiting the Raman band intensities, and it was found that n = 1. Therefore, depending on the MoO3 content, monomeric MoO2(SO4)22– and/or associated [MoO2(SO4)2]m2m– complexes are formed in the binary...... with ab initio quantum chemical calculations carried out on [MoO2(SO4)3]4– and [{MoO2}2(SO4)4(μ-SO4)2]8– ions, in assumed isolated gaseous free states, at the DFT/B3LYP (HF) level and with the 3-21G basis set. The calculations included determination of vibrational infrared and Raman spectra, by use...