WorldWideScience

Sample records for ab initio study

  1. Ab initio study of hot electrons in GaAs

    OpenAIRE

    Bernardi, Marco; Vigil-Fowler, Derek; Ong, Chin Shen; Neaton, Jeffrey B.; Louie, Steven G.

    2015-01-01

    Hot carrier dynamics critically impacts the performance of electronic, optoelectronic, photovoltaic, and plasmonic devices. Hot carriers lose energy over nanometer lengths and picosecond timescales and thus are challenging to study experimentally, whereas calculations of hot carrier dynamics are cumbersome and dominated by empirical approaches. In this work, we present ab initio calculations of hot electrons in gallium arsenide (GaAs) using density functional theory and many-body perturbation...

  2. 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

  3. Ab initio study of styrene isotopomers

    International Nuclear Information System (INIS)

    Zhang Jicheng; Tang Yongjian; Wu Weidong; Wang Hongyan; Zhu Zhenghe

    2002-01-01

    Using Gaussian98W program, the equilibrium geometry molecule structure of styrene has been optimized with HF/6-31G, MP2/6-31G and BLYP/6-31G methods. At same time, using BLYP/6-31G method, the harmonic frequency of styrene and its isotopomers, the bond energy of C-D bond (with ZPE correction), the intensity of IR spectrum are studied, and the modes of harmonic vibrational frequencies are simply discussed. At the same time, the effect of temperature and pressure on the thermodynamics parameter-entropy are studied. The results show that the calculated results are in good agreement with the experimental results

  4. Ab Initio Studies of Metal Hexaboride Materials

    Science.gov (United States)

    Schmidt, Kevin M.

    Metal hexaborides are refractory ceramics with several qualities relevant to materials design, such as low work functions, high hardness, low thermal expansion coefficients, and high melting points, among many other properties of interest for industrial applications. Thermal and mechanical stability is a common feature provided by the covalently-bonded network boron atoms, and electronic properties can vary significantly with the resident metal. While these materials are currently employed as electron emitters and abrasives, promising uses of these materials also include catalytic applications for chemical dissociation reactions of various molecules such as hydrogen, water and carbon monoxide, for example. However, these extensions require a thorough understanding of particular mechanical and electronic properties. This dissertation is a collection of studies focused on understanding the behavior of metal hexaboride materials using computational modeling methods to investigate materials properties of these from both classical and quantum mechanical points of view. Classical modeling is performed using molecular dynamics methods with interatomic potentials obtained from density functional theory (DFT) calculations. Atomic mean-square displacements from the quasi-harmonic approximation and lattice energetic data are produced with DFT for developing the potentials. A generalized method was also developed for the inversion of cohesive energy curves of crystalline materials; pairwise interatomic potentials are extracted using detailed geometrical descriptions of the atomic interactions and a list of atomic displacements and degeneracies. The surface structure of metal hexaborides is studied with DFT using several model geometries to describe the terminal cation layouts, and these provide a basis for further studies on metal hexaboride interactions with hydrogen. The surface electronic structure calculations show that segregated regions of metal and boron

  5. TiAl doping by vanadium: ab initio study

    International Nuclear Information System (INIS)

    Smirnova, E.A.; Isaev, Eh.I.; Vekilov, Yu.Kh.

    2004-01-01

    Tetragonality degree in TiAl and vanadium doping effect on it were studied using the methods of calculation based on approximation of coherent potential and ab initio pseudopotentials. It is shown that vanadium substitution for Ti sublattice atoms entails increase in tetragonality degree but with substitution of the atoms in aluminium sublattice the tetragonality of the TiAl:V alloy decreases and at the content of vanadium about 8 at. % the lattice becomes actually cubical. In its turn, it may result in increase in TiAl ductility, the alloy being brittle at low temperatures [ru

  6. 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.

  7. Early stage precipitation in aluminum alloys : An ab initio study

    NARCIS (Netherlands)

    Zhang, X.

    2017-01-01

    Multiscale computational materials science has reached a stage where many complicated phenomena or properties that are of great importance to manufacturing can be predicted or explained. The word “ab initio study” becomes commonplace as the development of density functional theory has enabled the

  8. Ab initio study of alanine polypeptide chain twisting

    DEFF Research Database (Denmark)

    Solov'yov, Ilia; Yakubovich, Alexander V.; Solov'yov, Andrey V.

    2006-01-01

    chains. These particular degrees of freedom are essential for the characterization of the proteins folding process. Calculations have been carried out within the ab initio theoretical framework based on the density functional theory and accounting for all the electrons in the system. We have determined...

  9. Ab initio study of phase equilibria in TiCx

    DEFF Research Database (Denmark)

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

    2002-01-01

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

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

    DEFF Research Database (Denmark)

    Marshall, Paul; Glarborg, Peter

    2015-01-01

    A detailed chemical kinetic model for oxidation of formic acid (HOCHO) in flames has been developed, based on theoretical work and data from literature. Ab initio calculations were used to obtain rate coefficients for reactions of HOCHO with H, O, and HO2. Modeling predictions with the mechanism...

  11. Ab initio study of isomerism in molecular ions Li2AB+ with 10 valence electrons

    International Nuclear Information System (INIS)

    Charkin, O.P.; Mak-Ki, M.L.; Shlojer, P.R.

    1997-01-01

    Ab initio calculations of surfaces of Li 2 AB + molecular ion potential energy with biatomic anions AB - with 10 valence electrons have been made in the framework of approximations MP2/6-31G 1 /HF/6-31G*+ZPE(HF/6-31G*) and MP4SDTQ/631G*//MP2/6-31G*+ZPE(MP2/6-31G*). Influence of electron correlation on the accuracy of calculations of their structural and vibrational characteristics is studied. The following most favourable structures have been found: linear for Li 2 BO + , Li 2 CN + , and bent one for Li 2 BS + , with cations coordinated at different anion atoms; onium one for AlOLi 2 + , AlSLi 2 + , SiNLi 2 + and SiPLi 2 + with both cations at electronegative atom of anion

  12. Domain Wall Formation in Ferromagnetic Layers: An Ab Initio Study

    Science.gov (United States)

    Herper, Heike C.

    Domain walls are an inherent feature of ferromagnetic (FM) films consisting of layers with different magnetic orientations. Since FM films are used in electrical devices the question of the influence of domain walls on, e.g., the magnetoresistance has attracted much interest. Besides discussing the resistance contribution of domain walls, it is appropriate to study different types of domain walls and their energy of formation. The behaviour of domain walls is usually discussed within model calculations. In the present paper it is done within an ab initio Green's function technique for layered systems, i.e., the fully relativistic, spin-polarized screened Korringa-Kohn Rostoker method. Results are presented for fcc Co layers covered by two semi-infinite fcc Pt(001) bulk systems or by bulk fcc Co(001), respectively. The resistance, which is caused by the different types of domain walls is discussed within a Kubo-Greenwood approach considering Co(001)/Co24/Co(001) as an example.

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

    KAUST Repository

    Tao, Kun

    2012-01-05

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

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

    KAUST Repository

    Tao, Kun; Stepanyuk, V. S.; Rungger, I.; Sanvito, S.

    2012-01-01

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

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

    KAUST Repository

    Zhang, Qianfan

    2010-09-08

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

  16. An ab initio study of plutonium oxides surfaces

    International Nuclear Information System (INIS)

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

    2007-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-10-12

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

  18. 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.

  19. Ab initio study of MgH2 formation

    International Nuclear Information System (INIS)

    Novakovic, Nikola; Matovic, Ljiljana; Novakovic, Jasmina Grbovic; Manasijevic, Miodrag; Ivanovic, Nenad

    2009-01-01

    Even if there is considerable literature dealing with structure and properties of MgH 2 compound there are still some uncertain details about nature of bonding governing its formation and decomposition. In order to better understand the processes essential for absorption and desorption of MgH 2 , ab initio DFT based calculations of rutile MgH 2 compound, elemental hcp-Mg, and three different hypothetical hcp-Mg-derived hydrides are performed. Our findings show that all structures are unstable, and that MgH (Wurtzite) is a closest possible candidate for intermediate phase between the hcp-Mg and MgH 2 at 1:1 stoichiometry. An alternative hydration pathway is suggested, including promotion of hcp-Mg to bcc-Mg and consecutive transformation to rutile MgH 2 by means of hydrogen incorporation into Mg matrix. Rutile MgH 2 calculations with various hydrogen vacancies concentration are performed. Calculation shows that at high hydrogen concentration close to 1:2, stable substoichiometric hydride is possible. Calculation also shows that high vacancy (low hydrogen) concentration favors bcc-Mg 2 H over rutile Mg 2 H structure.

  20. Ab initio study of point defects in magnesium oxide

    International Nuclear Information System (INIS)

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

    2007-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2007-07-01

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

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

    Science.gov (United States)

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

    2017-05-01

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

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

    Science.gov (United States)

    Saieswari, A.; Kumar, Sanjay

    2007-12-01

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

  4. Studies of urea geometry by means of ab initio methods and computer simulations of liquids

    OpenAIRE

    Cirino, José Jair Vianna; Bertran, Celso Aparecido

    2002-01-01

    A study was carried out on the urea geometries using ab initio calculation and Monte Carlo computational simulation of liquids. The ab initio calculated results showed that urea has a non-planar conformation in the gas phase in which the hydrogen atoms are out of the plane formed by the heavy atoms. Free energies associated to the rotation of the amino groups of urea in water were obtained using the Monte Carlo method in which the thermodynamic perturbation theory is implemented. The magnitud...

  5. The Influence of Square Planar Platinum Complexes on DNA Bases Pairing. An ab initio DFT Study

    Czech Academy of Sciences Publication Activity Database

    Burda, J. V.; Šponer, Jiří; Leszczynski, J.

    2001-01-01

    Roč. 3, č. 19 (2001), s. 4404-4411 ISSN 1463-9076 R&D Projects: GA MŠk LN00A032 Institutional research plan: CEZ:AV0Z4040901 Keywords : DNA base pairing * platinated base pairs * ab initio DFT study Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.787, year: 2001

  6. The Pu–U–Am system: An ab initio informed CALPHAD thermodynamic study

    International Nuclear Information System (INIS)

    Perron, A.; Turchi, P.E.A.; Landa, A.; Söderlind, P.; Ravat, B.; Oudot, B.; Delaunay, F.

    2015-01-01

    Highlights: • The ab initio informed CALPHAD assessment of the Am–U system has been realized. • A strong tendency toward phase separation across the whole composition range is predicted. • The ab initio informed Pu–U–Am thermodynamic database has been developed. • The solubility of Am and U in the liquid phase is improved by adding Pu. • The δ-Pu (fcc) phase is strongly stabilized by Am, on the contrary to the bcc phase. - Abstract: Phase diagram and thermodynamic properties of the Am–U system, that are experimentally unknown, are calculated using the CALPHAD method with input from ab initio electronic-structure calculations for the fcc and bcc phases. A strong tendency toward phase separation across the whole composition range is predicted. In addition, ab initio informed Pu–U and Am–Pu thermodynamic assessments are combined to build a Pu–U–Am thermodynamic database. Regarding the Pu-rich corner of the ternary system, predictions indicate that Am acts as a powerful δ-Pu (fcc) stabilizer. In the U-rich corner, similar predictions are made but to a lesser extent. In both cases, the bcc phase is destabilized and the fcc phase is enhanced. Finally, results and methodology are discussed and compared with previous assessments and guidelines are provided for further experimental studies

  7. The Pu–U–Am system: An ab initio informed CALPHAD thermodynamic study

    Energy Technology Data Exchange (ETDEWEB)

    Perron, A., E-mail: perron1@llnl.gov [Lawrence Livermore National Laboratory, Livermore, CA 94550 (United States); Turchi, P.E.A.; Landa, A.; Söderlind, P. [Lawrence Livermore National Laboratory, Livermore, CA 94550 (United States); Ravat, B.; Oudot, B.; Delaunay, F. [CEA-Centre de Valduc, 21120 Is sur Tille (France)

    2015-03-15

    Highlights: • The ab initio informed CALPHAD assessment of the Am–U system has been realized. • A strong tendency toward phase separation across the whole composition range is predicted. • The ab initio informed Pu–U–Am thermodynamic database has been developed. • The solubility of Am and U in the liquid phase is improved by adding Pu. • The δ-Pu (fcc) phase is strongly stabilized by Am, on the contrary to the bcc phase. - Abstract: Phase diagram and thermodynamic properties of the Am–U system, that are experimentally unknown, are calculated using the CALPHAD method with input from ab initio electronic-structure calculations for the fcc and bcc phases. A strong tendency toward phase separation across the whole composition range is predicted. In addition, ab initio informed Pu–U and Am–Pu thermodynamic assessments are combined to build a Pu–U–Am thermodynamic database. Regarding the Pu-rich corner of the ternary system, predictions indicate that Am acts as a powerful δ-Pu (fcc) stabilizer. In the U-rich corner, similar predictions are made but to a lesser extent. In both cases, the bcc phase is destabilized and the fcc phase is enhanced. Finally, results and methodology are discussed and compared with previous assessments and guidelines are provided for further experimental studies.

  8. 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.

  9. 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....

  10. 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...

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

    International Nuclear Information System (INIS)

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

    2016-01-01

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

  12. 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.

  13. Ab initio studies on [bmim][PF6]–CO2 mixture and CO2 clusters

    Indian Academy of Sciences (India)

    Wintec

    Ionic liquids; supercritical carbon dioxide; ab initio; molecular dynamics. 1. Introduction .... Several experi- mental and simulation studies have been carried out to .... from an analysis of its electronic polarizability (α), which is a measure of the ...

  14. Theoretical study of silicon carbide under irradiation at the nano scale: classical and ab initio modelling

    International Nuclear Information System (INIS)

    Lucas, G.

    2006-10-01

    The behaviour of silicon carbide under irradiation has been studied using classical and ab initio simulations, focusing on the nano scale elementary processes. First, we have been interested in the calculation of threshold displacement energies, which are difficult to determine both experimentally and theoretically, and also the associated Frenkel pairs. In the framework of this thesis, we have carried out simulations in classical and ab initio molecular dynamics. For the classical approach, two types of potentials have been used: the Tersoff potential, which led to non satisfactory results, and a new one which has been developed during this thesis. This potential allows a better modelling of SiC under irradiation than most of the empirical potentials available for SiC. It is based on the EDIP potential, initially developed to describe defects in silicon, that we have generalized to SiC. For the ab initio approach, the feasibility of the calculations has been validated and average energies of 19 eV for the C and 38 eV for the Si sublattices have been determined, close to the values empirically used in the fusion community. The results obtained with the new potential EDIP are globally in agreement with those values. Finally, the elementary processes involved in the crystal recovery have been studied by calculating the stability of the created Frenkel pairs and determining possible recombination mechanisms with the nudged elastic band method. (author)

  15. Ab Initio Studies of Shock-Induced Chemical Reactions of Inter-Metallics

    Science.gov (United States)

    Zaharieva, Roussislava; Hanagud, Sathya

    2009-06-01

    Shock-induced and shock assisted chemical reactions of intermetallic mixtures are studied by many researchers, using both experimental and theoretical techniques. The theoretical studies are primarily at continuum scales. The model frameworks include mixture theories and meso-scale models of grains of porous mixtures. The reaction models vary from equilibrium thermodynamic model to several non-equilibrium thermodynamic models. The shock-effects are primarily studied using appropriate conservation equations and numerical techniques to integrate the equations. All these models require material constants from experiments and estimates of transition states. Thus, the objective of this paper is to present studies based on ab initio techniques. The ab inito studies, to date, use ab inito molecular dynamics. This paper presents a study that uses shock pressures, and associated temperatures as starting variables. Then intermetallic mixtures are modeled as slabs. The required shock stresses are created by straining the lattice. Then, ab initio binding energy calculations are used to examine the stability of the reactions. Binding energies are obtained for different strain components super imposed on uniform compression and finite temperatures. Then, vibrational frequencies and nudge elastic band techniques are used to study reactivity and transition states. Examples include Ni and Al.

  16. 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...

  17. 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

  18. Time-resolved photoelectron spectroscopy and ab initio multiple spawning studies of hexamethylcyclopentadiene

    DEFF Research Database (Denmark)

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

    2014-01-01

    Time-resolved photoelectron spectroscopy and ab initio multiple spawning were applied to the ultrafast non-adiabatic dynamics of hexamethylcyclopentadiene. The high level of agreement between experiment and theory associates wavepacket motion with a distinct degree of freedom.......Time-resolved photoelectron spectroscopy and ab initio multiple spawning were applied to the ultrafast non-adiabatic dynamics of hexamethylcyclopentadiene. The high level of agreement between experiment and theory associates wavepacket motion with a distinct degree of freedom....

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

    KAUST Repository

    Zhang, Qianfan; Zhang, Wenxing; Wan, Wenhui; Cui, Yi; Wang, Enge

    2010-01-01

    The ultrahigh specific lithium ion storage capacity of Si nanowires (SiNWs) has been demonstrated recently and has opened up exciting opportunities for energy storage. However, a systematic theoretical study on lithium insertion in SiNWs remains a

  20. Ab initio study, investigation of NMR shielding tensors, NBO and ...

    African Journals Online (AJOL)

    The electrochemical oxidation of dopamine and 3,4-dihydroxymethamphetamine (HHMA) has been studied in the presence of GSH and cysteine as a nucleophile. In order to determine the optimized geometries, energies, dipole moments, atomic charges, thermochemical analysis and other properties, we performed ...

  1. THEORETICAL STUDY (AB INITIO AND DFT METHODS) ON ...

    African Journals Online (AJOL)

    ng reaction mechanisms that involve hydrogen atom transfer/proton-coupled. 5]. For these ... f theory have been extensively employed to the study of acidities and the compared with the .... evidence for the second deprotonation of XO. Also, as ...

  2. Defective pyrite (100) surface: An ab initio study

    International Nuclear Information System (INIS)

    Stirling, Andras; Bernasconi, Marco; Parrinello, Michele

    2007-01-01

    The structural and electronic properties of sulfur monomeric defects at the FeS 2 (100) surface have been studied by periodic density-functional calculations. We have shown that for a monomeric sulfur bound to an originally fivefold coordinated surface Fe site, the defect core features a triplet electronic ground state with unpaired spins localized on the exposed Fe-S unit. At this site, the iron and sulfur ions have oxidation states +4 and -2, respectively. This defect can be seen as produced via heterolytic bond breaking of the S-S sulfur dimer followed by a Fe-S redox reaction. The calculated sulfur 2p core-level shifts of the monomeric defects are in good agreement with experimental photoemission spectra, which allow a compelling assignment of the different spectroscopic features. The effect of water on the stability of the defective surface has also been studied, and it has been shown that the triplet state is stable against the wetting of the surface. The most important implications of the presence of the monomeric sulfur defect on the reactivity are also discussed

  3. Ab-initio study of surface segregation in aluminum alloys

    Energy Technology Data Exchange (ETDEWEB)

    Qin, Yifa, E-mail: yfqin10s@imr.ac.cn; Wang, Shaoqing

    2017-03-31

    Highlights: • A thorough study of surface segregation energies of 41 elements in Al is performed. • Segregation energies vary periodically with the atomic numbers of impurities. • 41 elements are classified into 3 groups according to the signs of segregation energies. • The results are validated by the surface/total concentration ratio in Al alloys. - Abstract: We have calculated surface segregation energies of 41 impurities by means of density functional theory calculations. An interesting periodical variation tendency was found for surface segregation energies derived. For the majority of main group elements, segregation energies are negative which means solute elements enrichment at Al surface is energetically more favorable than uniformly dissolution. Half of transition elements possess positive segregation energies and the energies are sensitive to surface crystallographic orientations. A strong correlation is found between the segregation energies at the Al surface and the surface energ of solute elements.

  4. Ab initio study of spin-dependent transport in carbon nanotubes with iron and vanadium adatoms

    DEFF Research Database (Denmark)

    Fürst, Joachim Alexander; Brandbyge, Mads; Jauho, Antti-Pekka

    2008-01-01

    (majority or minority) being scattered depends on the adsorbate and is explained in terms of d-state filling. We contrast the single-walled carbon nanotube results to the simpler case of the adsorbate on a flat graphene sheet with periodic boundary conditions and corresponding width in the zigzag direction......We present an ab initio study of spin-dependent transport in armchair carbon nanotubes with transition metal adsorbates: iron or vanadium. The method based on density functional theory and nonequilibrium Green's functions is used to compute the electronic structure and zero-bias conductance...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-01-15

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

  6. Ab initio simulations and neutron scattering studies of structure and dynamics in PdH

    International Nuclear Information System (INIS)

    Totolici, I.E.

    2001-07-01

    The work presented in this PhD thesis is concerned with the interpretation of the neutron scattering measurements from the palladium hydrogen system by means of ab initio electronic structure calculations. The motivation of performing such calculations was due to recent neutron scattering studies on this system that showed a strong directional dependence to the dynamical structure factor together with a complex dependence on energy. Here we attempt to describe the origin of these features by ab initio simulations of the dynamical structure factor. The method assumes an adiabatic separation of the motion of the proton and palladium atoms. The proton wave functions are calculated by a direct solution of the associated single-particle Schroedinger equation using a plane wave basis set method and a mapping of the adiabatic surface. The Fourier components of the adiabatic potential are obtained from LDA pseudopotential calculations. Using Fermi's golden rule within the Born approximation we were then able to calculate the dynamical structure factor, S(Q,ω), for exciting the proton from its ground state to various excited states as a function of the magnitude and direction of the scattering wave vector. The results are in agreement with the inelastic neutron scattering spectra and allow us to identify the origin of previous inexplicable features, in particular the strong directional dependence to the experimental data. The method was extended to investigate the expansion of the equilibrium lattice constant as a function of the H isotope when the zero-point energy of the proton/deuterium is explicitly taken into account in the relaxation process. The results we obtained predicted a bigger lattice constant for the hydride, as expected. Furthermore, other complex ab initio calculations were carried out in order to describe the origin of the large optic dispersion, seen previously in the coherent neutron scattering data. Our calculated dispersion proved to be in good

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

    International Nuclear Information System (INIS)

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

    1994-01-01

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

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

    Science.gov (United States)

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

    2013-01-01

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

  9. Vibrational inelastic and charge transfer processes in H++H2 system: An ab initio study

    Science.gov (United States)

    Amaran, Saieswari; Kumar, Sanjay

    2007-12-01

    State-resolved differential cross sections, total and integral cross sections, average vibrational energy transfer, and the relative probabilities are computed for the H++H2 system using the newly obtained ab initio potential energy surfaces at the full CI/cc-pVQZ level of accuracy which allow for both the direct vibrational inelastic and the charge transfer processes. The quantum dynamics is treated within the vibrational close-coupling infinite-order-sudden approximation approach using the two ab initio quasidiabatic potential energy surfaces. The computed collision attributes for both the processes are compared with the available state-to-state scattering experiments at Ec.m.=20eV. The results are in overall good agreement with most of the observed scattering features such as rainbow positions, integral cross sections, and relative vibrational energy transfers. A comparison with the earlier theoretical study carried out on the semiempirical surfaces (diatomics in molecules) is also made to illustrate the reliability of the potential energy surfaces used in the present work.

  10. Atomic carbon chains as spin-transmitters: An ab initio transport study

    DEFF Research Database (Denmark)

    Fürst, Joachim Alexander; Brandbyge, Mads; Jauho, Antti-Pekka

    2010-01-01

    An atomic carbon chain joining two graphene flakes was recently realized in a ground-breaking experiment by Jin et al. (Phys. Rev. Lett., 102 (2009) 205501). We present ab initio results for the electron transport properties of such chains and demonstrate complete spin-polarization of the transmi......An atomic carbon chain joining two graphene flakes was recently realized in a ground-breaking experiment by Jin et al. (Phys. Rev. Lett., 102 (2009) 205501). We present ab initio results for the electron transport properties of such chains and demonstrate complete spin...

  11. Structural investigation of water-acetonitrile mixtures: An ab initio, molecular dynamics and X-ray diffraction study

    International Nuclear Information System (INIS)

    Bako, Imre; Megyes, Tuende; Palinkas, Gabor

    2005-01-01

    In this work, we present a study on water-acetonitrile (AN) mixtures by molecular dynamics ab initio and X-ray diffraction techniques. Comparison of the experimental total G(r) functions of the mixtures with the results of molecular dynamics simulation shows an overall good agreement. The properties of hydrogen bonded clusters (water clusters, and water-AN clusters) in these mixtures have been determined. Two different types of AN-water dimers were identified by ab initio quantum chemical calculation. One of these structures proved to be a true H-bonded dimer and the other a dipole bound dimer

  12. Ab initio study of perovskite type oxide materials for solid oxide fuel cells

    Science.gov (United States)

    Lee, Yueh-Lin

    2011-12-01

    Perovskite type oxides form a family of materials of significant interest for cathodes and electrolytes of solid oxide fuel cells (SOFCs). These perovskites not only are active catalysts for surface oxygen reduction (OR) reactions but also allow incorporating the spilt oxygen monomers into their bulk, an unusual and poorly understood catalytic mechanism that couples surface and bulk properties. The OR mechanisms can be influenced strongly by defects in perovskite oxides, composition, and surface defect structures. This thesis work initiates a first step in developing a general strategy based on first-principles calculations for detailed control of oxygen vacancy content, transport rates of surface and bulk oxygen species, and surface/interfacial reaction kinetics. Ab initio density functional theory methods are used to model properties relevant for the OR reactions on SOFC cathodes. Three main research thrusts, which focus on bulk defect chemistry, surface defect structures and surface energetics, and surface catalytic properties, are carried to investigate different level of material chemistry for improved understanding of key physics/factors that govern SOFC cathode OR activity. In the study of bulk defect chemistry, an ab initio based defect model is developed for modeling defect chemistry of LaMnO 3 under SOFC conditions. The model suggests an important role for defect interactions, which are typically excluded in previous defect models. In the study of surface defect structures and surface energetics, it is shown that defect energies change dramatically (1˜2 eV lower) from bulk values near surfaces. Based on the existing bulk defect model with the calculated ab initio surface defect energetics, we predict the (001) MnO 2 surface oxygen vacancy concentration of (La0.9Sr0.1 )MnO3 is about 5˜6 order magnitude higher than that of the bulk under typical SOFC conditions. Finally, for surface catalytic properties, we show that area specific resistance, oxygen

  13. Ab initio study of Ni2MnGa under shear deformation

    Directory of Open Access Journals (Sweden)

    Zelený Martin

    2015-01-01

    Full Text Available The effect of shear deformation on Ni2MnGa magnetic shape memory alloy has been investigated using ab initio electronic structure calculations. We used the projector-augmented wave method for the calculations of total energies and stresses as functions of applied affine shear deformation. The studied nonmodulated martensite (NM phase exhibits a tetragonally distorted L21 structure with c/a > 1. A large strain corresponding to simple shears in {001}, {100} and {100} systems was applied to describe a full path between two equivalent NM lattices. We also studied {101} shear which is related to twining of NM phase. Twin reorientation in this system is possible, because applied positive shear results in path with significantly smaller energetic barrier than for negative shear and for shears in other studied systems. When the full relaxation of lattice parameters is allowed, the barriers further strongly decrease and the structures along the twinning path can be considered as orthorhombic.

  14. Ammonia-hydrogen bromide and ammonia-hydrogen iodide complexes: anion photoelectron and ab initio studies.

    Science.gov (United States)

    Eustis, S N; Whiteside, A; Wang, D; Gutowski, M; Bowen, K H

    2010-01-28

    The ammonia-hydrogen bromide and ammonia-hydrogen iodide, anionic heterodimers were studied by anion photoelectron spectroscopy. In complementary studies, these anions and their neutral counterparts were also investigated via ab initio theory at the coupled cluster level. In both systems, neutral NH(3)...HX dimers were predicted to be linear, hydrogen-bonded complexes, whereas their anionic dimers were found to be proton-transferred species of the form, (NH(4)(+)X(-))(-). Both experimentally measured and theoretically predicted vertical detachment energies (VDE) are in excellent agreement for both systems, with values for (NH(4)(+)Br(-))(-) being 0.65 and 0.67 eV, respectively, and values for (NH(4)(+)I(-))(-) being 0.77 and 0.81 eV, respectively. These systems are discussed in terms of our previous study of (NH(4)(+)Cl(-))(-).

  15. 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)

  16. Ab initio study of gas phase and water-assisted tautomerization of ...

    Indian Academy of Sciences (India)

    WINTEC

    Water-assisted tautomerization in maleimide and formamide showed that difference in energy barrier reduces to 2⋅83 kcal/mol from 10⋅41 kcal/mol (in gas phase) at B3LYP level, which resulted that maleimide readily undergoes tautomerization in water molecule. Keywords. Ab Initio calculations; maleimide; formamide; ...

  17. Ab initio study of antiphase boundaries and stacking faults in L12 and DO22 compounds

    DEFF Research Database (Denmark)

    Rosengaard, N. M.; Skriver, Hans Lomholt

    1994-01-01

    We have performed ab initio calculations of the energies of antiphase boundaries as well as complex and superlattice intrinsic stacking faults in nine intermetallic compounds observed in the face-centered-cubic L1(2) and DO22 structures. The calculations were performed by means of a Green...

  18. Ab initio study of the bcc-hcp transformation in iron

    Czech Academy of Sciences Publication Activity Database

    Friák, Martin; Šob, Mojmír

    2008-01-01

    Roč. 77, č. 17 (2008), 174117/1-174117/7 ISSN 1098-0121 R&D Projects: GA MŠk OC 147; GA AV ČR IAA1041302 Institutional research plan: CEZ:AV0Z20410507 Keywords : ab initio calculations * phase transformations * iron Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.322, year: 2008

  19. Water-mediated tautomerization of cytosine to the rare imino form: An ab initio dynamics study

    Energy Technology Data Exchange (ETDEWEB)

    Fogarasi, Geza [Institute of Chemistry, Eotvos University, H-1518 Budapest, Pf. 32. (Hungary)], E-mail: fg@chem.elte.hu

    2008-06-16

    Tautomerism in nucleotide bases is one of the possible mechanisms of mutation of DNA. In spite of numerous studies on the structure and energy of cytosine tautomers, little information is available on the process of proton transfer itself. We present here Born-Oppenheimer dynamics calculations, with the potential surface obtained 'on the fly' from ab initio quantum chemistry (QC) and the atoms moving classically. In search for water-mediated tautomerization the monohydrated complex was studied, running about 300 trajectories each of 3000-5000 points of 1 fs steps. One single trajectory has been found to lead to tautomerization. Although the QC method used in the simulations was inevitably modest (B3LYP/3-21G), higher-level test calculations along the same trajectory suggest that the simulation grasped the basic mechanism of proton transfer: a concerted, synchronous process characterized by strong coupling between the motions of the two participating hydrogen atoms.

  20. Ab initio molecular dynamics study of pressure-induced phase transition in ZnS

    International Nuclear Information System (INIS)

    Martinez, Israel; Durandurdu, Murat

    2006-01-01

    The pressure-induced phase transition in zinc sulfide is studied using a constant-pressure ab initio technique. The reversible phase transition from the zinc-blende structure to a rock-salt structure is successfully reproduced through the simulations. The transformation mechanism at the atomistic level is characterized and found to be due to a monoclinic modification of the simulation cell, similar to that obtained in SiC. This observation supports the universal transition state of high-pressure zinc-blende to rock-salt transition in semiconductor compounds. We also study the role of stress deviations on the transformation mechanism and find that the system follows the same transition pathway under nonhydrostatic compressions as well

  1. 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

  2. Formation Dynamics of Potassium-Based Graphite Intercalation Compounds: An Ab Initio Study

    Science.gov (United States)

    Jiang, Xiankai; Song, Bo; Tománek, David

    2018-04-01

    This paper is a contribution to the Physical Review Applied collection in memory of Mildred S. Dresselhaus. We use ab initio molecular dynamics simulations to study the microscopic dynamics of potassium intercalation in graphite. Upon adsorbing on graphite from the vapor phase, K atoms transfer their valence charge to the substrate. K atoms adsorbed on the surface diffuse rapidly along the graphene basal plane and eventually enter the interlayer region following a "U -turn" across the edge, gaining additional energy. This process is promoted at higher coverages associated with higher K pressure, leading to the formation of a stable intercalation compound. We find that the functionalization of graphene edges is an essential prerequisite for intercalation since bare edges reconstruct and reconnect, closing off the entry channels for the atoms.

  3. Carbon diffusion in molten uranium: an ab initio molecular dynamics study

    Science.gov (United States)

    Garrett, Kerry E.; Abrecht, David G.; Kessler, Sean H.; Henson, Neil J.; Devanathan, Ram; Schwantes, Jon M.; Reilly, Dallas D.

    2018-04-01

    In this work we used ab initio molecular dynamics within the framework of density functional theory and the projector-augmented wave method to study carbon diffusion in liquid uranium at temperatures above 1600 K. The electronic interactions of carbon and uranium were described using the local density approximation (LDA). The self-diffusion of uranium based on this approach is compared with literature computational and experimental results for liquid uranium. The temperature dependence of carbon and uranium diffusion in the melt was evaluated by fitting the resulting diffusion coefficients to an Arrhenius relationship. We found that the LDA calculated activation energy for carbon was nearly twice that of uranium: 0.55 ± 0.03 eV for carbon compared to 0.32 ± 0.04 eV for uranium. Structural analysis of the liquid uranium-carbon system is also discussed.

  4. Evolution of local atomic structure during solidification of Al2Au liquid: An ab initio study

    International Nuclear Information System (INIS)

    Xiong, L.H.; Lou, H.B.; Wang, X.D.; Debela, T.T.; Cao, Q.P.; Zhang, D.X.; Wang, S.Y.; Wang, C.Z.; Jiang, J.Z.

    2014-01-01

    The local atomic structure evolution in Al 2 Au alloy during solidification from 2000 K to 400 K was studied by ab initio molecular dynamics simulations and analyzed using the structure factor, pair correlation functions, bond angle distributions, the Honeycutt–Anderson (HA) index and Voronoi tessellation methods. It was found that the icosahedral-like clusters are negligible in the Al 2 Au stable liquid and supercooled liquid states, and the most abundant clusters are those having HA indices of 131 and 120 or Voronoi indices of 〈0, 4, 4, 0〉, 〈0, 3, 6, 0〉 and 〈0, 4, 4, 2〉 with coordination numbers of 8, 9 and 10, respectively. These clusters are similar to the local atomic structures in the CaF 2 -type Al 2 Au crystal, revealing the existence of structure heredity between liquid and crystalline phase in Al 2 Au alloy

  5. Ab initio study of M2AlN (M = Ti,V,Cr)

    International Nuclear Information System (INIS)

    Sun, Zhimei; Music, Denis; Ahuja, Rajeev; Schneider, Jochen M

    2005-01-01

    We have studied M 2 AlN phases, where M = Ti, V, and Cr, by means of ab initio total energy calculations. The bulk modulus of M 2 AlN increases as Ti is replaced with V and Cr by 19.0% and 26.5%, respectively, which can be understood on the basis of the increased number of valence electrons filling the p-d hybridized bonding states. The bulk modulus of M 2 AlN is generally higher than that of the corresponding M 2 AlC phase, which may be explained by an extra electron in the former phases contributing to stronger chemical bonding. This work is important for fundamental understanding of elastic properties of these ternary nitrides and may inspire future experimental research. (letter to the editor)

  6. Evolution of local atomic structure during solidification of Al2Au liquid: An ab initio study

    Energy Technology Data Exchange (ETDEWEB)

    Xiong, L H; Lou, H B; Wang, X D; Debela, T T; Cao, Q P; Zhang, D X; Wang, S Y; Wang, C Z; Jiang, J Z

    2014-04-01

    The local atomic structure evolution in Al2Au alloy during solidification from 2000 K to 400 K was studied by ab initio molecular dynamics simulations and analyzed using the structure factor, pair correlation functions, bond angle distributions, the Honeycutt-Anderson (HA) index and Voronoi tessellation methods. It was found that the icosahedral-like clusters are negligible in the Al2Au stable liquid and supercooled liquid states, and the most abundant clusters are those having HA indices of 131 and 120 or Voronoi indices of < 0,4,4,0 >, < 0,3, 6,0 > and < 0,4,4,2 > with coordination numbers of 8, 9 and 10, respectively. These clusters are similar to the local atomic structures in the CaF2-type Al2Au crystal, revealing the existence of structure heredity between liquid and crystalline phase in Al2Au alloy. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

  7. Structural properties of iron nitride on Cu(100): An ab-initio molecular dynamics study

    KAUST Repository

    Heryadi, Dodi

    2011-01-01

    Due to their potential applications in magnetic storage devices, iron nitrides have been a subject of numerous experimental and theoretical investigations. Thin films of iron nitride have been successfully grown on different substrates. To study the structural properties of a single monolayer film of FeN we have performed an ab-initio molecular dynamics simulation of its formation on a Cu(100) substrate. The iron nitride layer formed in our simulation shows a p4gm(2x2) reconstructed surface, in agreement with experimental results. In addition to its structural properties, we are also able to determine the magnetization of this thin film. Our results show that one monolayer of iron nitride on Cu(100) is ferromagnetic with a magnetic moment of 1.67 μ B. © 2011 Materials Research Society.

  8. Ab initio study of structural and mechanical property of solid molecular hydrogens

    Science.gov (United States)

    Ye, Yingting; Yang, Li; Yang, Tianle; Nie, Jinlan; Peng, Shuming; Long, Xinggui; Zu, Xiaotao; Du, Jincheng

    2015-06-01

    Ab initio calculations based on density functional theory (DFT) were performed to investigate the structural and the elastic properties of solid molecular hydrogens (H2). The influence of molecular axes of H2 on structural relative stabilities of hexagonal close-packed (hcp) and face-centered cubic (fcc) structured hydrogen molecular crystals were systematically investigated. Our results indicate that for hcp structures, disordered hydrogen molecule structure is more stable, while for fcc structures, Pa3 hydrogen molecular crystal is most stable. The cohesive energy of fcc H2 crystal was found to be lower than hcp. The mechanical properties of fcc and hcp hydrogen molecular crystals were obtained, with results consistent with previous theoretical calculations. In addition, the effects of zero point energy (ZPE) and van der Waals (vdW) correction on the cohesive energy and the stability of hydrogen molecular crystals were systematically studied and discussed.

  9. Ab initio studies on the reaction of O2 with Ban (n=2,5) clusters

    International Nuclear Information System (INIS)

    Li, S.F.; Xue Xinlian; Chen, G.; Yuan, D.W.; Jia Yu; Gong, X.G.

    2006-01-01

    Ab initio theoretical calculations have been performed to study the reaction of O 2 with Ba n (n=2,5) clusters. Our results show that O 2 can easily chemisorb and dissociate on small Ba n clusters and there is no obvious energy barrier in the process of the dissociation. The local magnetic moment contributed by oxygen must vanish during the intermediate states before the O 2 dissociation. Correspondingly, local magnetic moment only decreases from 2μ B to about 1μ B if O 2 molecularly adsorbs onto Ba 5 cluster. The electronic structure analysis indicates that the charge transfer from Ba n cluster to O 2 as well as the orbital hybridization between the cluster and the oxygen molecule may play a key role in O 2 dissociation

  10. Sensitivity of core-level spectroscopy to electrostatic environments of nitrile groups: An ab initio study

    Directory of Open Access Journals (Sweden)

    Abid Hussain

    2017-09-01

    Full Text Available Ab initio quantum chemistry calculations have been performed to probe the influence of hydrogen bonding on the electronic structure of hydrogen cyanide (HCN. Our calculations determine the origin of nitrogen-specific Raman spectral features from resonant inelastic X-ray scattering occurring in the presence of a water molecule and an electric dipole field. The similarity of the two interactions in altering the electronic structure of the nitrogen atom differs only in the covalent contributions from the water molecule. The CN stretching mode as a structural probe was also investigated to study the electronic origin of the anomalous frequency shift of the nitrile group when subjected to hydrogen bonding and an electrostatic dipole field. The major changes in the electronic structure of HCN are electrostatic in nature and originate from dipole-dipole interactions. The relative shifts of the CN stretching frequency are in good agreement with those experimentally observed.

  11. High multiplicity states in disordered carbon systems: Ab initio and semiempirical study

    International Nuclear Information System (INIS)

    Khavryuchenko, Volodymyr D.; Khavryuchenko, Oleksiy V.; Lisnyak, Vladyslav V.

    2010-01-01

    Stability of non-zero spin projection states for disordered carbon clusters of low symmetry were examined using semiempirical and ab initio methods. The study proves previous results of V.D. Khavryuchenko, Y.A. Tarasenko, V.V. Strelko, O.V. Khavryuchenko, V.V. Lisnyak, Int. J. Mod. Phys. B 21 (2007) 4507, obtained for the large polyaromatic hydrocarbons clusters and shows that the phenomenon is intrinsic for carbon-rich systems and independent of their symmetries. The electronic properties of the carbon clusters may alter from insulating to semiconducting upon change of C/H ratio and stabilization of non-zero spin projection states. A partial collectivization of the electrons is observed in deeply carbonized carbon clusters in higher S z states.

  12. Ab initio study of thermoelectric properties of doped SnO{sub 2} superlattices

    Energy Technology Data Exchange (ETDEWEB)

    Borges, P.D., E-mail: pdborges@gmail.com [Instituto de Ciências Exatas e Tecnológicas, Universidade Federal de Viçosa, 38810-000 Rio Paranaíba, MG (Brazil); Silva, D.E.S.; Castro, N.S.; Ferreira, C.R.; Pinto, F.G.; Tronto, J. [Instituto de Ciências Exatas e Tecnológicas, Universidade Federal de Viçosa, 38810-000 Rio Paranaíba, MG (Brazil); Scolfaro, L. [Department of Physics, Texas State University, 78666 San Marcos, TX (United States)

    2015-11-15

    Transparent conductive oxides, such as tin dioxide (SnO{sub 2}), have recently shown to be promising materials for thermoelectric applications. In this work we studied the thermoelectric properties of Fe-, Sb- and Zn-uniformly doping and co-doping SnO{sub 2}, as well as of Sb and Zn planar (or delta)-doped layers in SnO{sub 2} forming oxide superlattices (SLs). Based on the semiclassical Boltzmann transport equations (BTE) in conjunction with ab initio electronic structure calculations, the Seebeck coefficient (S) and figure of merit (ZT) are obtained for these systems, and are compared with available experimental data. The delta doping approach introduces a remarkable modification in the electronic structure of tin dioxide, when compared with the uniform doping, and colossal values for ZT are predicted for the delta-doped oxide SLs. This result is a consequence of the two-dimensional electronic confinement and the strong anisotropy introduced by the doped planes. In comparison with the uniformly doped systems, our predictions reveal a promising use of delta-doped SnO{sub 2} SLs for enhanced S and ZT, which emerge as potential candidates for thermoelectric applications. - Graphical abstract: Band structure and Figure of merit for SnO2:Sb superlattice along Z direction, P. D. Borges, D. E. S. Silva, N. S. Castro, C. R. Ferreira, F. G. Pinto, J. Tronto and L. Scolfaro, Ab initio study of thermoelectric properties of doped SnO2 superlattices. - Highlights: • Thermoelectric properties of SnO{sub 2}-based alloys and superlattices. • High figure of merit is predicted for planar-doped SnO{sub 2} superlattices. • Nanotechnology has an important role for the development of thermoelectric devices.

  13. Ab initio study of thermoelectric properties of doped SnO_2 superlattices

    International Nuclear Information System (INIS)

    Borges, P.D.; Silva, D.E.S.; Castro, N.S.; Ferreira, C.R.; Pinto, F.G.; Tronto, J.; Scolfaro, L.

    2015-01-01

    Transparent conductive oxides, such as tin dioxide (SnO_2), have recently shown to be promising materials for thermoelectric applications. In this work we studied the thermoelectric properties of Fe-, Sb- and Zn-uniformly doping and co-doping SnO_2, as well as of Sb and Zn planar (or delta)-doped layers in SnO_2 forming oxide superlattices (SLs). Based on the semiclassical Boltzmann transport equations (BTE) in conjunction with ab initio electronic structure calculations, the Seebeck coefficient (S) and figure of merit (ZT) are obtained for these systems, and are compared with available experimental data. The delta doping approach introduces a remarkable modification in the electronic structure of tin dioxide, when compared with the uniform doping, and colossal values for ZT are predicted for the delta-doped oxide SLs. This result is a consequence of the two-dimensional electronic confinement and the strong anisotropy introduced by the doped planes. In comparison with the uniformly doped systems, our predictions reveal a promising use of delta-doped SnO_2 SLs for enhanced S and ZT, which emerge as potential candidates for thermoelectric applications. - Graphical abstract: Band structure and Figure of merit for SnO2:Sb superlattice along Z direction, P. D. Borges, D. E. S. Silva, N. S. Castro, C. R. Ferreira, F. G. Pinto, J. Tronto and L. Scolfaro, Ab initio study of thermoelectric properties of doped SnO2 superlattices. - Highlights: • Thermoelectric properties of SnO_2-based alloys and superlattices. • High figure of merit is predicted for planar-doped SnO_2 superlattices. • Nanotechnology has an important role for the development of thermoelectric devices.

  14. Studies Of Urea Geometry By Means Of Ab Initio Methods And Computer Simulations Of Liquids [estudo Da Geometria Da Uréia Por Métodos Ab Initio E Simulaição Computacional De Líquidos

    OpenAIRE

    Cirino J.J.V.; Bertran C.A.

    2002-01-01

    A study was carried out on the urea geometries using ab initio calculation and Monte Carlo computational simulation of liquids. The ab initio calculated results showed that urea has a non-planar conformation in the gas phase in which the hydrogen atoms are out of the plane formed by the heavy atoms. Free energies associated to the rotation of the amino groups of urea in water were obtained using the Monte Carlo method in which the thermodynamic perturbation theory is implemented. The magnitud...

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

    DEFF Research Database (Denmark)

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

    2008-01-01

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

  16. Mechanistic Aspects of the Reversible Binding of SO2 on Arylplatinum Complexes: Experimental and ab Initio Studies

    NARCIS (Netherlands)

    Koten, G. van; Albrecht, M.A.; Gossage, R.A.; Frey, H.; Ehlers, A.W.; Baerends, E.J.; Merbach, A.E.

    2001-01-01

    The detailed mechanism of the reversible binding and fast exchange of SO2 on the organoplatinum(II) complex [PtI(NCN)], 1, has been studied experimentally in solution (C2F4Br2) using low-temperature NMR spectroscopy and theoretically by ab initio calculations. Direct bonding of SO2 and formation of

  17. An ab-initio study of mechanical, dynamical and electronic properties of MgEu intermetallic

    Science.gov (United States)

    Kumar, S. Ramesh; Jaiganesh, G.; Jayalakshmi, V.

    2018-04-01

    The theoretical investigation on the mechanical, dynamical and electronic properties of MgEu in CsCl-type structure has been carried out through the ab-initio calculations within the framework of the density functional theory and the density functional perturbation theory. For the purpose, Vienna Ab initio Simulation Package and Phonopy packages were used. Our calculated ground-state properties of MgEu are in good agreement with other available results. Our computed elastic constants and phonon spectrum results suggest that MgEu is mechanically and dynamically stable up to 5 GPa. The thermodynamic quantities as a function of temperatures are also reported and discussed. The band structure, density of states and charge density also calculated to understand the electronic properties of MgEu.

  18. Ab initio study of thermodynamic, electronic, magnetic, structural, and elastic properties of Ni4N allotropes

    Czech Academy of Sciences Publication Activity Database

    Hemzalová, P.; Friák, Martin; Šob, Mojmír; Ma, D.; Udyansky, A.; Raabe, D.; Neugebauer, J.

    2013-01-01

    Roč. 88, č. 17 (2013), Art. no. 174103 ISSN 1098-0121 R&D Projects: GA ČR(CZ) GAP108/12/0311; GA ČR GD106/09/H035; GA AV ČR IAA100100920 Institutional support: RVO:68081723 Keywords : nitrides * ab initio * thermodynamics * elasticity Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.664, year: 2013

  19. Ab initio study of Co and Ni under uniaxial and biaxial loading and in epitaxial overlayers

    Czech Academy of Sciences Publication Activity Database

    Zelený, Martin; Legut, Dominik; Šob, Mojmír

    2008-01-01

    Roč. 78, č. 22 (2008), 224105/1-224105/11 ISSN 1098-0121 R&D Projects: GA ČR GD106/05/H008; GA AV ČR IAA1041302; GA MŠk OC 147 Institutional research plan: CEZ:AV0Z20410507 Keywords : ab initio calculations * epitaxial overlayers * uniaxial and biaxial loading Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.322, year: 2008

  20. Ab initio and empirical studies on the asymmetry of molecular current-voltage characteristics

    International Nuclear Information System (INIS)

    Hoft, R C; Armstrong, N; Ford, M J; Cortie, M B

    2007-01-01

    We perform theoretical calculations of the tunnelling current through various small organic molecules sandwiched between gold electrodes by using both a tunnel barrier model and an ab initio transport code. The height of the tunnelling barrier is taken to be the work function of gold as modified by the adsorbed molecule and calculated from an ab initio electronic structure code. The current-voltage characteristics of these molecules are compared. Asymmetry is introduced into the system in two ways: an asymmetric molecule and a gap between the molecule and the right electrode. The latter is a realistic situation in scanning probe experiments. The asymmetry is also realized in the tunnel barrier model by two distinct work functions on the left and right electrodes. Significant asymmetry is observed in the ab initio i(V) curves. The tunnel barrier i(V) curves show much less pronounced asymmetry. The relative sizes of the currents through the molecules are compared. In addition, the performance of the WKB approximation is compared to the results obtained from the exact Schroedinger solution to the tunnelling barrier problem

  1. 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)

  2. High pressure behaviour of uranium dicarbide (UC{sub 2}): Ab-initio study

    Energy Technology Data Exchange (ETDEWEB)

    Sahoo, B. D., E-mail: bdsahoo@barc.gov.in; Mukherjee, D.; Joshi, K. D.; Kaushik, T. C. [Applied Physics Division, Bhabha Atomic Research Centre, Mumbai 400085 (India)

    2016-08-28

    The structural stability of uranium dicarbide has been examined under hydrostatic compression employing evolutionary structure search algorithm implemented in the universal structure predictor: evolutionary Xtallography (USPEX) code in conjunction with ab-initio electronic band structure calculation method. The ab-initio total energy calculations involved for this purpose have been carried out within both generalized gradient approximations (GGA) and GGA + U approximations. Our calculations under GGA approximation predict the high pressure structural sequence of tetragonal → monoclinic → orthorhombic for this material with transition pressures of ∼8 GPa and 42 GPa, respectively. The same transition sequence is predicted by calculations within GGA + U also with transition pressures placed at ∼24 GPa and ∼50 GPa, respectively. Further, on the basis of comparison of zero pressure equilibrium volume and equation of state with available experimental data, we find that GGA + U approximation with U = 2.5 eV describes this material better than the simple GGA approximation. The theoretically predicted high pressure structural phase transitions are in disagreement with the only high experimental study by Dancausse et al. [J. Alloys. Compd. 191, 309 (1993)] on this compound which reports a tetragonal to hexagonal phase transition at a pressure of ∼17.6 GPa. Interestingly, during lowest enthalpy structure search using USPEX, we do not see any hexagonal phase to be closer to the predicted monoclinic phase even within 0.2 eV/f. unit. More experiments with varying carbon contents in UC{sub 2} sample are required to resolve this discrepancy. The existence of these high pressure phases predicted by static lattice calculations has been further substantiated by analyzing the elastic and lattice dynamic stability of these structures in the pressure regimes of their structural stability. Additionally, various thermo-physical quantities such as

  3. Comparative classical and 'ab initio' molecular dynamics study of molten and glassy germanium dioxide

    International Nuclear Information System (INIS)

    Hawlitzky, M; Horbach, J; Binder, K; Ispas, S; Krack, M

    2008-01-01

    A molecular dynamics (MD) study of the static and dynamic properties of molten and glassy germanium dioxide is presented. The interactions between the atoms are modeled by the classical pair potential proposed by Oeffner and Elliott (OE) (1998 Phys. Rev. B 58 14791). We compare our results to experiments and previous simulations. In addition, an 'ab initio' method, the so-called Car-Parrinello molecular dynamics (CPMD), is applied to check the accuracy of the structural properties, as obtained by the classical MD simulations with the OE potential. As in a similar study for SiO 2 , the structure predicted by CPMD is only slightly softer than that resulting from the classical MD. In contrast to earlier simulations, both the static structure and dynamic properties are in very good agreement with pertinent experimental data. MD simulations with the OE potential are also used to study the relaxation dynamics. As previously found for SiO 2 , for high temperatures the dynamics of molten GeO 2 is compatible with a description in terms of mode coupling theory

  4. Conformational study of glyoxal bis(amidinohydrazone) by ab initio methods

    Science.gov (United States)

    Mannfors, B.; Koskinen, J. T.; Pietilä, L.-O.

    1997-08-01

    We report the first ab initio molecular orbital study on the ground state of the endiamine tautomer of glyoxal bis(amidinohydrazone) (or glyoxal bis(guanylhydrazone), GBG) free base. The calculations were performed at the following levels of theory: Hartree-Fock, second-order Møller-Plesset perturbation theory and density functional theory (B-LYP and B3-LYP) as implemented in the Gaussian 94 software. The standard basis set 6-31G(d) was found to be sufficient. The default fine grid of Gaussian 94 was used in the density functional calculations. Molecular properties, such as optimized structures, total energies and the electrostatic potential derived (CHELPG) atomic charges, were studied as functions of C-C and N-N conformations. The lowest energy conformation was found to be all- trans, in agreement with the experimental solid-state structure. The second conformer with respect to rotation around the central C-C bond was found to be the cis conformer with an MP2//HF energy of 4.67 kcal mol -1. For rotation around the N-N bond the energy increased monotonically from the trans conformation to the cis conformation, the cis energy being very high, 22.01 kcal mol -1 (MP2//HF). The atomic charges were shown to be conformation dependent, and the bond charge increments and especially the conformational changes of the bond charge increments were found to be easily transferable between structurally related systems.

  5. Elastic properties of amorphous boron suboxide based solids studied using ab initio molecular dynamics

    International Nuclear Information System (INIS)

    Music, Denis; Schneider, Jochen M

    2008-01-01

    We have studied the correlation between chemical composition, structure, chemical bonding and elastic properties of amorphous B 6 O based solids using ab initio molecular dynamics. These solids are of different chemical compositions, but the elasticity data appear to be a function of density. This is in agreement with previous experimental observations. As the density increases from 1.64 to 2.38 g cm -3 , the elastic modulus increases from 74 to 253 GPa. This may be understood by analyzing the cohesive energy and the chemical bonding of these compounds. The cohesive energy decreases from -7.051 to -7.584 eV/atom in the elastic modulus range studied. On the basis of the electron density distributions, Mulliken analysis and radial distribution functions, icosahedral bonding is the dominating bonding type. C and N promote cross-linking of icosahedra and thus increase the density, while H hinders the cross-linking by forming OH groups. The presence of icosahedral bonding is independent of the density

  6. Perpendicular magnetic anisotropy in Mn2VIn (001) films: An ab initio study

    Science.gov (United States)

    Zipporah, Muthui; Robinson, Musembi; Julius, Mwabora; Arti, Kashyap

    2018-05-01

    First principles study of the magnetic anisotropy of Mn2VIn (001) films show perpendicular magnetic anisotropy (PMA), which increases as a function of the thickness of the film. Density functional theory (DFT) as implemented in the Vienna Ab initio simulation package (VASP) is employed here to perform a comprehensive theoretical investigation of the structural, electronic and magnetic properties of the Mn2VIn(001) films of varying thickness. Our calculations were performed on fully relaxed structures, with five to seventeen mono layers (ML). The degree of spin polarization is higher in the (001) Mn2VIn thin films as compared to the bulk in contrast to what is usually the case and as in Mn2VAl, which is isoelectronic to Mn2VIn as well as inCo2VIn (001) films studied for comparison. Tetragonal distortions are found in all the systems after relaxation. The distortion in the Mn2VIn system persists even for the 17ML thin film, resulting in PMA in the Mn2VIn system. This significant finding has potential to contribute to spin transfer torque (STT) and magnetic random access memory MRAM applications, as materials with PMA derived from volume magnetocrystalline anisotropy are being proposed as ideal magnetic electrodes.

  7. Ab initio study of the EFG tensor at Cd impurities in Sc2O3 semiconductor

    International Nuclear Information System (INIS)

    Munoz, E.L.; Richard, D.; Errico, L.A.; Renteria, M.

    2009-01-01

    We present an ab initio study of diluted Cd impurities localized at both cation sites of the semiconductor Sc 2 O 3 . The electric-field-gradient (EFG) tensor at Cd impurities located at both cationic sites of the host structure was determined from the calculation of the electronic structure of the doped system. Calculations were performed with the full-potential augmented-plane wave plus local orbitals (APW+lo) method within the framework of the density functional theory. We studied the atomic structural relaxations and the perturbation of the electronic charge density induced by the impurities in the host system in a fully self-consistent way. We showed that the Cd impurity introduces an increase of 8% in the nearest oxygen neighbors bond-lengths, changing the EFG sign for probes located at the asymmetric cation site. The APW+lo predictions for the charged state of the Cd impurity were compared with EFG results existent in the literature, coming from time-differential γ-γ perturbed-angular-correlations experiments performed on 111 Cd-implanted Sc 2 O 3 powder samples. From the excellent agreement between theory and experiment, we can strongly suggest that the Cd acceptor impurities are ionized at room temperature. Finally, we showed that simple calculations like those performed within the point-charge model with antishielding factors do not correctly describe the problem of a Cd impurity in Sc 2 O 3 .

  8. Systematic ab initio study of half-Heusler materials for optoelectronic applications

    Energy Technology Data Exchange (ETDEWEB)

    Gruhn, Thomas; Felser, Claudia [Institute of Inorganic and Analytical Chemistry, Johannes Gutenberg University, Mainz (Germany)

    2010-07-01

    The development of new, optimized optoelectronic devices depends crucially on the availability of semiconductors with taylored electronic and structural properties. At the moment, the majority of applications is based on a rather small set of semiconducting materials, while many more semiconductors exist in the huge class of ternary compounds. Especially, the class of 8-electron half-Heusler materials comprises a large number semiconducters with various properties. With the help of ab initio density functional theory we have studied essentially all 8-electron half-Heusler compounds that are of technological relevance. For more than 650 compounds we have determined the optimum configuration by varying the lattice constant and permuting the elements over the sublattices. Within this exceptionally large data set we have studied the band structure and the lattice constants as a function of the electronegativities of the elements, the arrangement of the atoms, and the atomic radii. The results are used to select suitable materials for the buffer layer in thin-film solar cells with a Cu(In,Ga)Se{sub 2} (CIGS) absorber layer. Considering the bandgap and the geometrical matching with the CIGS film, we have obtained a set of 29 compounds that are promissing materials for cadmium-free CIGS buffer layer.

  9. Tunneling of electrons via rotor–stator molecular interfaces: Combined ab initio and model study

    Energy Technology Data Exchange (ETDEWEB)

    Petreska, Irina, E-mail: irina.petreska@pmf.ukim.mk [Institute of Physics, Faculty of Natural Sciences and Mathematics, Ss. Cyril and Methodius University, PO Box 162, 1000 Skopje, Former Yugolav Republic of Macedonia, The (Macedonia, The Former Yugoslav Republic of); Ohanesjan, Vladimir [Institute of Physics, Faculty of Natural Sciences and Mathematics, Ss. Cyril and Methodius University, PO Box 162, 1000 Skopje, Former Yugolav Republic of Macedonia, The (Macedonia, The Former Yugoslav Republic of); Pejov, Ljupčo [Institute of Chemistry, Department of Physical Chemistry, Ss. Cyril and Methodius University, Arhimedova 5, P.O. Box 162, 1000 Skopje, Former Yugolav Republic of Macedonia, The (Macedonia, The Former Yugoslav Republic of); Kocarev, Ljupčo [Macedonian Academy of Sciences and Arts, Krste Misirkov 2, PO Box 428, 1000 Skopje, Former Yugolav Republic of Macedonia, The (Macedonia, The Former Yugoslav Republic of); Faculty of Computer Science and Engineering, Ss. Cyril and Methodius University, Skopje, Former Yugolav Republic of Macedonia, The (Macedonia, The Former Yugoslav Republic of)

    2016-07-01

    Tunneling of electrons through rotor–stator anthracene aldehyde molecular interfaces is studied with a combined ab initio and model approach. Molecular electronic structure calculated from first principles is utilized to model different shapes of tunneling barriers. Together with a rectangular barrier, we also consider a sinusoidal shape that captures the effects of the molecular internal structure more realistically. Quasiclassical approach with the Simmons’ formula for current density is implemented. Special attention is paid on conformational dependence of the tunneling current. Our results confirm that the presence of the side aldehyde group enhances the interesting electronic properties of the pure anthracene molecule, making it a bistable system with geometry dependent transport properties. We also investigate the transition voltage and we show that conformation-dependent field emission could be observed in these molecular interfaces at realistically low voltages. The present study accompanies our previous work where we investigated the coherent transport via strongly coupled delocalized orbital by application of Non-equilibrium Green’s Function Formalism.

  10. Ab initio study of isomerism in molecular Li2AB+ ions with 12 and 14 valence electrons

    International Nuclear Information System (INIS)

    Charkin, O.P.; Klimenko, N.M.; Mak-Ki, M.L.; Shlojer, P.R.

    1997-01-01

    Ab initio calculations of potential energy surfaces (PES) of molecular ions Li 2 AB + with 12 and 14 valence electrons have been made in the framework of approximations MP2/6-31G*//HF/6-31G*+ZPE(HF/6-31G*) and MP4SDTQ/6-31*//MP2/6-31G*+ZPE(MP2/6-31G*). The following most favourable structures have been found: a double-terminal linear for LiNO + (a triplet); a plane bicyclic one for Li 2 OF + , Li 2 SCl + , Li 2 NO + (a singlet) and Li 2 PS + (a singlet), where both cations are coordinated to A-B bond; rectangular (T-shaped) for Li 2 OCl + and SFLi + , as well as for LiNS + and POLi 2 + ions in singlet and triplet states; in the form of a half-opened butterfly for Li 2 PS + (a triplet) and Li 2 SCl +

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-02-15

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

  12. AB INITIO molecular orbital studies of some high temperature metal halide complexes

    International Nuclear Information System (INIS)

    Curtiss, L.A.

    1978-01-01

    The use of ab initio molecular orbital calculations to aid in the characterization, i.e., structures and energies, of metal halide complexes present in high temperature salt vapors has been investigated. Standard LCAO-SCF methods were used and calculations were carried out using the minimal STO-3G basis set. The complexes included in this study were Al 2 F 6 , Al 2 Cl 6 , AlF 3 NH 3 , AlCl 3 NH 3 , and AlF 3 N 2 . The Al 2 X 6 complexes are found to have D/sub 2h/ symmetry in agreement with most experimental results. A planar form was found to be considerably higher in energy. The AlX 3 NH 3 complexes are found to have C/sub 3v/ symmetry with a small barrier to rotation about the Al-N axis. The AlF 3 N 2 complex is found to be weakly bound together with a binding energy of -8.2 kcal/mole at the STO-3G level

  13. Communication: A hydrogen-bonded difluorocarbene complex: Ab initio and matrix isolation study

    Science.gov (United States)

    Sosulin, Ilya S.; Shiryaeva, Ekaterina S.; Tyurin, Daniil A.; Feldman, Vladimir I.

    2017-10-01

    Structure and spectroscopic features of the CF2⋯HF complexes were studied by ab initio calculations at the CCSD(T) level and matrix isolation FTIR spectroscopy. The calculations predict three stable structures. The most energetically favorable structure corresponds to hydrogen bonding of HF to the lone pair of the C atom (the interaction energy of 3.58 kcal/mol), whereas two less stable structures are the H⋯F bonded complexes (the interaction energies of 0.30 and 0.24 kcal/mol). The former species was unambiguously characterized by the absorptions in the FTIR spectra observed after X-ray irradiation of fluoroform in a xenon matrix at 5 K. The corresponding features appear at 3471 (H-F stretching), 1270 (C-F symmetric stretching, shoulder), 1175 (antisymmetric C-F stretching), and 630 (libration) cm-1, in agreement with the computational predictions. To our knowledge, it is the first hydrogen-bonded complex of dihalocarbene. Possible weaker manifestations of the H⋯F bonded complexes were also found in the C-F stretching region; however, their assignment is tentative. The H⋯C bonded complex is protected from reaction yielding a fluoroform molecule by a remarkably high energy barrier (23.85 kcal/mol), so it may be involved in various chemical reactions.

  14. 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.

  15. Ab initio computational study of vincristine as a biological active compound: NMR and NBO analyses

    Directory of Open Access Journals (Sweden)

    Shiva Joohari

    2015-06-01

    Full Text Available Vincristine is a biological active alkaloid that has been used clinically against a variety of neoplasms. In the current study we have theoretically investigated the magnetic properties of titled compound to predict physical and chemical properties of vincristine as a biological inhibitor. Ab initio computation using HF and B3LYP with 3-21G(d and 6-31G(d level of theory have been performed and then magnetic shielding tensor (, ppm, shielding asymmetry (, magnetic shielding anisotropy (aniso, ppm, the skew of a tensor (K, chemical shift anisotropy ( and chemical shift ( were calculated to indicate the details of the interaction mechanism between microtubules and vincristine. Moreover, EHOMO, ELUMO and Ebg were evaluated. The maximum and minimum values of Ebg were found in HF/3-21g and B3LYP/3-21g respectively. It was also uggested that O24, O37, O49 and O55 with minimum values of iso, are active sites of titled compound. Furthermore the calculated chemical shifts were compared with experimental data in DMSO and CDCl3 solvents.

  16. An ab initio study of the polytypism in InP

    Science.gov (United States)

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

    2016-09-01

    The existence of polytypism in semiconductor nanostructures gives rise to the appearance of stacking faults which many times can be treated as quantum wells. In some cases, despite of a careful growth, the polytypism can be hardly avoided. In this work, we perform an ab initio study of zincblende stacking faults in a wurtzite InP system, using the supercell approach and taking the limit of low density of narrow stacking faults regions. Our results confirm the type II band alignment between the phases, producing a reliable qualitative description of the band gap evolution along the growth axis. These results show an spacial asymmetry in the zincblende quantum wells, that is expected due to the fact that the wurtzite stacking sequence (ABAB) is part of the zincblende one (ABCABC), but with an unexpected asymmetry between the valence and the conduction bands. We also present results for the complex dielectric function, clearly showing the influence of the stacking on the homostructure values and surprisingly proving that the correspondent bulk results can be used to reproduce the polytypism even in the limit we considered.

  17. Matrix Isolation and ab initio study of the noncovalent complexes between formamide and acetylene.

    Science.gov (United States)

    Mardyukov, Artur; Sánchez-García, Elsa; Sander, Wolfram

    2009-02-12

    Matrix isolation spectroscopy in combination with ab initio calculations is a powerful technique for the identification of weakly bound intermolecular complexes. Here, weak complexes between formamide and acetylene are studied, and three 1:1 complexes with binding energies of -2.96, -2.46, and -1.79 kcal/mol have been found at the MP2 level of theory (MP2/cc-pVTZ + ZPE + BSSE). The two most stable dimers A and B are identified in argon and nitrogen matrices by comparison between the experimental and calculated infrared frequencies. Both complexes are stabilized by the formamide C=O...HC acetylene and H...pi interactions. Large shifts have been observed experimentally for the C-H stretching vibrations of the acetylene molecule, in very good agreement with the calculated values. Eight 1:2 FMA-acetylene trimers (T-A to T-H) with binding energies between -5.44 and -2.62 kcal/mol (MP2/aug-cc-pVDZ + ZPE + BSSE) were calculated. The two most stable trimers T-A and T-B are very close in energy and have similar infrared spectra. Several weak bands that are in agreement with the calculated frequencies of the trimers T-A and T-B are observed under matrix isolation conditions. However, the differences are too small for a definitive assignment.

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

    International Nuclear Information System (INIS)

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

    2017-01-01

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

  19. Yttrium aluminium garnet under pressure: Structural, elastic, and vibrational properties from ab initio studies

    International Nuclear Information System (INIS)

    Monteseguro, V.; Rodríguez-Hernández, P.; Muñoz, A.

    2015-01-01

    The structural, elastic, and vibrational properties of yttrium aluminum garnet Y 3 Al 5 O 12 are studied under high pressure by ab initio calculations in the framework of the density functional theory. The calculated ground state properties are in good agreement with the available experimental data. Pressure dependences of bond length and bulk moduli of the constituent polyhedra are reported. The evolution of the elastic constants and the major elastic properties, Young and shear modulus, Poisson's ratios, and Zener anisotropy ratio, are described. The mechanical stability is analyzed, on the light of “Born generalized stability criteria,” showing that the garnet is mechanically unstable above 116 GPa. Symmetries, frequencies, and pressure coefficients of the Raman-active modes are discussed on the basis of the calculated total and partial phonon density of states, which reflect the dynamical contribution of each atom. The relations between the phonon modes of Y 3 Al 5 O 12 and the internal and external molecular modes of the different polyhedra are discussed. Infrared-active modes, as well as the silent modes, and their pressure dependence are also investigated. No dynamical instabilities were found below 116 GPa

  20. Characterization of Elastic Properties of Porous Graphene Using an Ab Initio Study

    Directory of Open Access Journals (Sweden)

    Reza Ansari

    2016-12-01

    Full Text Available Importance of covalent bonded two-dimensional monolayer nanostructures and also hydrocarbons is undeniably responsible for creation of new fascinating materials like polyphenylene polymer, a hydrocarbon super honeycomb network, so-called porous graphene. The mechanical properties of porous graphene such as its Young’s modulus, Poisson’s ratio and the bulk modulus as the determinative properties are calculated in this paper using ab initio calculations. To accomplish this aim, the density functional theory on the basis of generalized gradient approximation and the Perdew–Burke–Ernzerhof exchange correlation is employed. Density functional theory calculations are used to calculate strain energy of porous graphene with respect to applied strain. Selected numerical results are then presented to study the properties of porous graphene. Comparisons are made between the properties of porous graphene and those of other analogous nanostructures. The results demonstrated lower stiffness of porous graphene than those of graphene and graphyne, and higher stiffness than that of graphdyine and other graphyne families. Unlikely, Poisson’s ratio is observed to be more than that of graphene and also less than that of graphyne. It is further observed that the presence of porosity and also formation of C-H bond in the pore sites is responsible for these discrepancies. Porous graphene is found to behave as the isotropic material.

  1. Ab initio study of the O4H(+) novel species: spectroscopic fingerprints to aid its observation.

    Science.gov (United States)

    Xavier, F George D; Hernández-Lamoneda, Rámon

    2015-06-28

    A detailed ab initio characterization of the structural, energetic and spectroscopic properties of the novel O4H(+) species is presented. The equilibrium structures and relative energies of all multiplet states have been determined systematically by analyzing static and dynamical correlation effects. The two and three body dissociation processes have been studied and indicate the presence of conical intersections in various states including the ground state. Comparison with available thermochemical data is very good, supporting the applied methodology. The reaction, H3(+) + O4→ O4H(+) + H2, was found to be exothermic ΔH = -19.4 kcal mol(-1) and therefore, it is proposed that the product in the singlet state could be formed in the interstellar medium (ISM) via collision processes. To aid in its laboratory or radioastronomy detection in the interstellar medium we determined spectroscopic fingerprints. It is estimated for the most stable geometry of O4H(+) dipole allowed electronic transitions in the visible region at 429 nm and 666 nm, an intense band at 1745 cm(-1) in the infrared and signals at 40.6, 81.2 and 139.2 GHz in the microwave region at 10, 50 and 150 K respectively, relevant for detection in the ISM.

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

    Science.gov (United States)

    Esrafili, Mehdi D.; Mousavian, Parisasadat

    2017-12-01

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

  3. Ab Initio Study of the Dynamical Si–O Bond Breaking Event in α-Quartz

    International Nuclear Information System (INIS)

    Su Rui; Zhang Hong; Han Wei; Chen Jun

    2015-01-01

    The Si–O bond breaking event in the α-quartz at the first triplet (T_1) excitation state is studied by using ab initio molecular dynamics (AIMD) and nudged elastic band calculations. A meta-stable non-bridging oxygen hole center and E′ center (NBOHC-E′) is observed in the AIMD which consists of a broken Si–O bond with a Si–O distance of 2.54 Å. By disallowing the re-bonding of the Si and O atoms, another defect configuration (III-Si/V-Si) is obtained and validated to be stable at both ground and excitation states. The NBOHC-E′ is found to present on the minimal energy pathway of the initial to III-Si/V-Si transition, showing that the generating of the NBOHC-E′ is an important step of the excitation induced structure defect. The energy barriers to produce the NBOHC-E′ and III-Si/V-Si defects are calculated to be 1.19 and 1.28 eV, respectively. The electronic structures of the two defects are calculated by the self-consistent GW calculations and the results show a clear electron transition from the bonding orbital to the non-bonding orbital. (paper)

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

    International Nuclear Information System (INIS)

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

    2011-01-01

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

  5. Conformational composition of neutral leucine. Matrix isolation infrared and ab initio study

    International Nuclear Information System (INIS)

    Stepanian, Stepan G.; Ivanov, Alexander Yu.; Adamowicz, Ludwik

    2013-01-01

    Highlights: • FTIR spectra of leucine isolated in argon, neon and xenon matrices are obtained. • UV irradiation is used to separate bands of the leucine conformers. • Populations of the leucine conformers is determined. - Abstract: Low-temperature matrix-isolation FTIR spectroscopy and ab initio calculations are employed to determine conformational composition of neutral leucine. The presence of three leucine conformers in the matrices is revealed. This is in agreement with the results of a detailed study of the potential energy surface of leucine which demonstrates that only five out of 105 possible conformers should have populations in the matrices larger than 2% and only three conformers, which are the ones detected in the experiment, should have populations larger than 10%. UV irradiation of the matrix samples are used to separate bands of the different conformers. We also show that the populations of the leucine conformers in the gas phase at 440 K are significantly different from the ones in matrices. The population of the lowest energy conformer in the gas phase being approximately 23% in the gas phase increases to over 64% in matrices

  6. Ab initio pseudopotential studies of cubic BC2N under high pressure

    International Nuclear Information System (INIS)

    Pan Zicheng; Sun Hong; Chen Changfeng

    2005-01-01

    We present the results of a systematic study of the structural, electronic, and vibrational properties of various cubic BC 2 N phases under high pressure. Ab initio pseudopotential total-energy and phonon calculations have been carried out to examine the changes in the structural parameters, bonding behaviours, band structures, and dynamic instabilities caused by phonon softening in these phases. We find that an experimentally synthesized high-density phase of cubic BC 2 N exhibits outstanding stability in the structural and electronic properties up to very high pressures. On the other hand, another experimentally identified phase with lower density and lower symmetry undergoes a dramatic structural transformation with a volume and bond-length collapse and a concomitant semi-metal to semiconductor transition. A third phase is predicted to be favourable over the above-mentioned lower-density phase by the enthalpy calculations. However, the dynamic phonon calculations reveal that it develops imaginary phonon modes and, therefore, is unstable in the experimental pressure range. The calculations indicate that its synthesis may be achieved at reduced pressures. These results provide a comprehensive understanding for the high-pressure behaviour of the cubic BC 2 N phases and reveal their interesting properties that can be verified by experiments

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

    International Nuclear Information System (INIS)

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

    2009-01-01

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

  8. 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.

  9. Ab initio Hartree-Fock study on surface desorption process in tritium release

    International Nuclear Information System (INIS)

    Taniguchi, M.; Tanaka, S.

    1998-01-01

    Dissociative adsorption of hydrogen on Li 2 O (110) surface has been investigated with ab initio Hartree-Fock quantum chemical calculation technique. Heat of adsorption and surface potential energy for H 2 dissociative adsorption were evaluated by calculating the total energy of the system. The calculated results on adsorption heat indicated that H 2 adsorption is endothermic. However, when an oxygen vacancy exists adjacent to the adsorption site, the heat of adsorption became less endothermic and the activation energy required to dissociate the H-H bonding was smaller than that for the terrace site. This is considered to be caused by the excess charge localized near the defect. (orig.)

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

    Science.gov (United States)

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

    2004-04-01

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

  11. Charge carrier motion in disordered conjugated polymers: a multiscale ab-initio study

    Energy Technology Data Exchange (ETDEWEB)

    Vukmirovic, Nenad; Wang, Lin-Wang

    2009-11-10

    We developed an ab-initio multiscale method for simulation of carrier transport in large disordered systems, based on direct calculation of electronic states and electron-phonon coupling constants. It enabled us to obtain the never seen before rich microscopic details of carrier motion in conjugated polymers, which led us to question several assumptions of phenomenological models, widely used in such systems. The macroscopic mobility of disordered poly(3- hexylthiophene) (P3HT) polymer, extracted from our simulation, is in agreement with experimental results from the literature.

  12. Electronic structure and magnetism of titanium substituted Cd3P2: An ab-initio study

    Science.gov (United States)

    Jaiganesh, G.; Jaya, S. Mathi

    2018-05-01

    Using the ab-initio computations that are based on the density functional theory, we have investigated the magnetism and electronic properties of one and two Ti atom substituted Cd3P2 compound. The magnetic stability of the substituted compounds was obtained by analyzing the minimum total energies in nonmagnetic, ferromagnetic and antiferromagnetic phases. Our results indicated the formation of magnetic order in one and two Ti atom substituted Cd3P2 as well as metallic characteristics in these systems. A significant value of the magnetic moment of Ti atom is observed from our calculations. We further find that the neighboring Cd and P atoms too acquire a small magnetic moment.

  13. Ab-initio theoretical study of electronic excitations and optical properties in nanostructures

    OpenAIRE

    Marchesín, Federico

    2017-01-01

    218 p. La miniaturización de los dispositivos electrónicos para la transferencia de información y procesado de señales ha impulsado el estudio de las propiedades electrónicas y la dinámica de excitaciones electrónicas en nanoestructuras. En particular, los cálculos ab-initio de las repuestas ópticas y los modos plasmónicos colectivos de nanoestructuras metálicas y de grafeno, han permitido profundizar en el conocimiento de la física y así poder avanzar hacia aplicaciones industriales en mu...

  14. Experimental and ab initio study of the photofragmentation of DNA and RNA sugars

    Science.gov (United States)

    Ha, D. T.; Huels, M. A.; Huttula, M.; Urpelainen, S.; Kukk, E.

    2011-09-01

    The photoelectron-photoion-photoion coincidence method is used to measure the photodissociation of doubly charged D-ribose (C5H10O5), the RNA sugar molecules, and 2-deoxy-D-ribose (C5H10O4), the DNA sugar molecules, following normal Auger decay after initial C 1s and O 1s core ionizations. The fragment identification is facilitated by measuring isotopically labeled D-ribose, such as D-ribose deuterated at C(1), and with 13C at the C(5) position. Ab initio quantum chemistry calculations are used to gain further insight into the abundant appearance of the CHO+ fragment.

  15. Ab initio study of intrinsic profiles of liquid metals and their reflectivity

    Science.gov (United States)

    del Rio, B. G.; Souto, J.; Alemany, M. M. G.; González, L. E.

    2017-08-01

    The free surfaces of liquid metals are known to exhibit a stratified profile that, in favourable cases, shows up in experiments as a peak in the ratio between the reflectivity function and that of an ideal step-like profile. This peak is located at a wave-vector related to the distance between the layers of the profile. In fact the surface roughness produced by thermally induced capillary waves causes a depletion of the previous so called intrinsic reflectivity by a damping factor that may hinder the observation of the peak. The behaviour of the intrinsic reflectivity below the layering peak is however far from being universal, with systems as Ga or In where the reflectiviy falls uniformly towards the q → 0 value, others like Sn or Bi where a shoulder appears at intermediate wavevectors, and others like Hg which show a minimum. We have performed extensive ab initio simulations of the free liquid surfaces of Bi, Pb and Hg, that yield direct information on the structure of the profiles and found that the macroscopic capillary wave theory usually employed in order to remove the capillary wave components fails badly in some cases for the typical sample sizes affordable in ab initio simulations. However, a microscopic method for the determination of the intrinsic profile is shown to be succesful in obtaining meaningful intrinsic profiles and corresponding reflectivities which reproduce correctly the qualitative behaviour observed experimentally.

  16. Ab initio study of hydrogen adsorption on benzenoid linkers in metal-organic framework materials

    International Nuclear Information System (INIS)

    Gao Yi; Zeng, X C

    2007-01-01

    We have computed the energies of adsorption of molecular hydrogen on a number of molecular linkers in metal-organic framework solid materials using density functional theory (DFT) and ab initio molecular orbital methods. We find that the hybrid B3LYP (Becke three-parameter Lee-Yang-Parr) DFT method gives a qualitatively incorrect prediction of the hydrogen binding with benzenoid molecular linkers. Both local-density approximation (LDA) and generalized gradient approximation (GGA) DFT methods are inaccurate in predicting the values of hydrogen binding energies, but can give a qualitatively correct prediction of the hydrogen binding. When compared to the more accurate binding-energy results based on the ab initio Moeller-Plesset second-order perturbation (MP2) method, the LDA results may be viewed as an upper limit while the GGA results may be viewed as a lower limit. Since the MP2 calculation is impractical for realistic metal-organic framework systems, the combined LDA and GGA calculations provide a cost-effective way to assess the hydrogen binding capability of these systems

  17. Ab initio study on electron excitation and electron transfer in tryptophan-tyrosine system

    International Nuclear Information System (INIS)

    Tong Jing; Li Xiangyuan

    2002-01-01

    In this article, ab initio calculation has been performed to evaluate the transition energy of electronic excitation in tryptophan and tyrosine by using semiempirical molecular orbital method AM1 and complete active space self-consistent field method. The solvent effect has been considered by means of the conductor-like screening model. After geometric optimizations of isolated tryptophan and tyrosine, and their corresponding radicals and cations, reaction heat of these electron transfer reactions have been obtained by the means of complete active space self-consistent field method. The transition energies from the ground state, respectively, to the lowest excited state and to the lowest triplet state of these two amino acids are also calculated and compared with the experimentally observed values. The ionization potential and electron affinity are also calculated for tryptophan and tyrosine employing Koopmans' theorem and ab initio calculation. Compared with the experimental measurements, the theoretical results are found satisfactory. Theoretical results give good explanations on the experimental phenomena that N 3 · can preferably oxide the side chain of tryptophan residue and then the electron transfer from tyrosine residue to tryptophan residue follows in peptides involving tryptophan and tyrosine

  18. The Conformational Landscape of L-Threonine Matrix Isolation Infrared and {AB-INITIO Studies

    Science.gov (United States)

    Dubey, Pankaj; Mukhopadhyay, Anamika; Viswanathan, K. S.

    2017-06-01

    Amino acids, containing hydroxy side chains such as L-threonine and tyrosine play an important role in molecular recognition, such as in the docking of propofol, which is a commonly used anaesthetic. A rich conformational landscape of these amino acids makes them interesting candidates in the study of intra and intermolecular interactions. In this work, the conformational landscape of L-threonine was studied, as it can be expected to serve as a basis for understanding structure and functions of polypeptides and other biomolecules. The matrix isolation technique (MI) coupled with a high temperature effusive molecular beam (EMB) nozzle was used to trap conformers of amino acid, which were then characterized using FTIR spectroscopy. The usefulness of MI-EMB-FTIR spectroscopy is that it can trap structures corresponding to the local minima along with the global minimum and hence allows for a better exploration of the potential energy surface. A major challenge in conformational analysis of amino acids using matrix isolation FTIR arises from its non-volatile nature. A home built heating system which was mounted close to the cryotip, was used to evaporate the non-volatile amino acids. Our infrared spectra show that three conformations were trapped in the matrix. Experimental results were supported by {ab-initio calculations performed using the CCSD(T), MP2 and M06-2X methods together with 6-311++G(d,p) and aug/cc-pVDZ basis sets. The side chains of the amino acids appeared to have an influence on the preferential stabilisation of a particular backbone structure of amino acids. Factors such as entropy, anomeric effect and intramolecular H-bonding were also found to play an important role in determining conformal preferences, which will be discussed.

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

    Science.gov (United States)

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

    1996-09-01

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

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

    Science.gov (United States)

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

    2014-10-07

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

  1. A comparative ab initio study of Br2*- and Br2 water clusters.

    Science.gov (United States)

    Pathak, A K; Mukherjee, T; Maity, D K

    2006-01-14

    The work presents ab initio results on structure and electronic properties of Br2*-.nH2O(n=1-10) and Br2.nH2O(n=1-8) hydrated clusters to study the effects of an excess electron on the microhydration of the halide dimer. A nonlocal density functional, namely, Becke's half-and-half hybrid exchange-correlation functional is found to perform well on the present systems with a split valence 6-31++G(d,p) basis function. Geometry optimizations for all the clusters are carried out with several initial guess structures and without imposing any symmetry restriction. Br2*-.nH2O clusters prefer to have symmetrical double hydrogen-bonding structures. Results on Br2.nH2O(n>or=2) cluster show that the O atom of one H2O is oriented towards one Br atom and the H atom of another H2O is directed to other Br atom making Br2 to exist as Br+-Br- entity in the cluster. The binding and solvation energies are calculated for the Br2*-.nH2O and Br2.nH2O clusters. Calculations of the vibrational frequencies show that the formation of Br2*- and Br2 water clusters induces significant shifts from the normal modes of isolated water. Excited-state calculations are carried out on Br2*-.nH2O clusters following configuration interaction with single electron excitation procedure and UV-VIS absorption profiles are simulated. There is an excellent agreement between the present theoretical UV-VIS spectra of Br2*-.10H2O cluster and the reported transient optical spectra for Br2*- in aqueous solution.

  2. Reaction mechanisms and kinetics of the iminovinylidene radical with NO: Ab initio study

    Energy Technology Data Exchange (ETDEWEB)

    Hsiao, Ming-Kai; Chung, Yi-Hua; Hung, Yu-Ming; Chen, Hui-Lung, E-mail: chl3@faculty.pccu.edu.tw [Department of Chemistry and Institute of Applied Chemistry, Chinese Culture University, Taipei 111, Taiwan (China)

    2014-05-28

    The nitric oxide (NO) is a notorious compound for polluting environment. Recent year, removing nitric oxide from the atmosphere becomes a focus of the investigation. In our work, we study the iminovinylidene (HNCC) radical reacted with NO molecule. The mechanism and kinetic for reaction of the HNCC radical with the NO molecule is investigated via considering the possible channels of the N and O atoms of NO attacking the N and C atoms of the HNCC based on the high level ab initio molecular orbital calculations in conjunction with variational TST and RRKM calculations. The species involved have been optimized at the B3LYP/6-311++G(3df,2p) level and their single-point energies are refined by the CCSD(T)/aug-cc-PVQZ//B3LYP/6-311++G(3df,2p) method. The calculated potential energy surfaces indicated that energetically the most favorable channel for the HNCC + NO reaction was predicted to be the formation of HNC+CNO (P8) product via the addition reaction of the C atom of HNCC radical and the N atom of NO with the head to head orientation. To rationalize the scenario of the calculated results, we also employ the Fukui functions and HSAB theory to seek for a possible explanation. In addition, the reaction rate constants were calculated using VariFlex code, and the results show that the total rate coefficient, k{sub total}, at Ar pressure 760 Torr can be represented with an equation: k{sub total} = 6.433 × 10{sup −11} T {sup 0.100} exp(0.275 kcal mol{sup −1}/RT) at T = 298–3000 K, in units of cm{sup 3} molecule{sup −1} s{sup −1}.

  3. An Ab Initio MP2 Study of HCN-HX Hydrogen Bonded Complexes

    Directory of Open Access Journals (Sweden)

    Araújo Regiane C.M.U.

    1998-01-01

    Full Text Available An ab initio MP2/6-311++G** study has been performed to obtain geometries, binding energies and vibrational properties of HCN-HX H-bonded complexes with X = F, Cl, NC, CN and CCH. These MP2/6-311++G** results have revealed that: (i the calculated H-bond lengths are in very good agreement with the experimental ones; (ii the H-bond strength is associated with the intermolecular charge transfer and follows the order: HCN-HNC ~ HCN-HF > HCN-HCl ~ HCN-HCN > HCN-HCCH; (iii BSSE correction introduces an average reduction of 2.4 kJ/mol on the MP2/6-311++G** binding energies, i.e. 11% of the uncorrected binding energy; (iv the calculated zero-point energies reduce the stability of these complexes and show a good agreement with the available experimental values; (v the H-X stretching frequency is shifted downward upon H-bond formation. This displacement is associated with the H-bond length; (vi The more pronounced effect on the infrared intensities occurs with the H-X stretching intensity. It is much enhanced after complexation due to the charge-flux term; (vii the calculated intermolecular stretching frequencies are in very good agreement with the experimental ones; and, finally, (viii the results obtained for the HCN-HX complexes follow the same profile as those found for the acetylene-HX series but, in the latter case, the effects on the properties of the free molecules due to complexation are less pronounced than those in HCN-HX.

  4. Doping in silicon nanocrystals: An ab initio study of the structural, electronic and optical properties

    International Nuclear Information System (INIS)

    Iori, Federico; Degoli, Elena; Luppi, Eleonora; Magri, Rita; Marri, Ivan; Cantele, G.; Ninno, D.; Trani, F.; Ossicini, Stefano

    2006-01-01

    There are experimental evidences that doping control at the nanoscale can significantly modify the optical properties with respect to the pure systems. This is the case of silicon nanocrystals (Si-nc), for which it has been shown that the photoluminescence (PL) peak can be tuned also below the bulk Si band gap by properly controlling the impurities, for example by boron (B) and phosphorus (P) codoping. In this work, we report on an ab initio study of impurity states in Si-nc. We consider B and P substitutional impurities for Si-nc with a diameter up to 2.2 nm. Formation energies (FEs), electronic, optical and structural properties have been determined as a function of the cluster dimension. For both B-doped and P-doped Si-nc the FE increases on decreasing the dimension, showing that the substitutional doping gets progressively more difficult for the smaller nanocrystals. Moreover, subsurface impurity positions result to be the most stable ones. The codoping reduces the FE strongly favoring this process with respect to the simple n-doping or p-doping. Such an effect can be attributed to charge compensation between the donor and the acceptor atoms. Moreover, smaller structural deformations, with respect to n-doped and p-doped cases, localized only around the impurity sites are observed. The band gap and the optical threshold are largely reduced with respect to the undoped Si-nc showing the possibility of an impurity-based engineering of the Si-nc PL properties

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

    International Nuclear Information System (INIS)

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

    2008-01-01

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

  6. Study of the behaviour of cesium fission product in uranium dioxide by the ab initio method

    International Nuclear Information System (INIS)

    Gupta, Florence

    2008-01-01

    The knowledge of the behaviour of fission products in the nuclear fuel is very important for safety considerations and for understanding the evolution of the fuel properties under irradiation. In this work, we focussed mainly on the behaviour of caesium in UO 2 through ab initio studies of its solubility at point defects in the matrix, its diffusion and its contribution to the formation of solid phases in the fuel. The role of electronic correlation effects of the f electrons of uranium on these properties and on the description of the defect free crystal, is assessed. The formation energies of the main point defects are calculated and their concentration as a function of fuel stoichiometry and temperature is estimated. The migration barriers and migration paths for the self-diffusion of oxygen and uranium vacancies and oxygen interstitials in UO 2 are discussed. The solubility of Cs is found to be very low in UO 2 in agreement with experimental findings. The most favourable trapping sites are determined as a function of oxygen concentration in the fuel. Our results show that in the hyper-stoichiometric regime, the diffusion of Cs from its most favourable trapping site is limited by the uranium vacancy diffusion mechanism. We also considered the formation of the main solid phases of caesium resulting from its oxidation (Cs 2 O, Cs 2 O 2 , CsO 2 ) and from its interaction with the fuel (Cs 2 UO 4 ), with molybdenum (Cs 2 MoO 4 ) and with the zirconium of the clad (Cs 2 ZrO 3 ), since the formation of such phases, their solubility and their interdependence will affect the release of caesium. (author)

  7. 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.

  8. Initial Chemical Events in CL-20 Under Extreme Conditions: An Ab Initio Molecular Dynamics Study

    National Research Council Canada - National Science Library

    Isaev, Olexandr; Kholod, Yana; Gorb, Leonid; Qasim, Mohammad; Fredrickson, Herb; Leszczynski, Jerzy

    2006-01-01

    .... In the present study molecular structure, electrostatic potential, vibrational spectrum and dynamics of thermal decomposition of CL-20 have been investigated by static and dynamic methods of ab...

  9. Theoretical study of silicon carbide under irradiation at the nano scale: classical and ab initio modelling; Etude theorique a l'echelle nanometrique du carbure de silicium sous irradiation: modelisation classique et ab initio

    Energy Technology Data Exchange (ETDEWEB)

    Lucas, G

    2006-10-15

    The behaviour of silicon carbide under irradiation has been studied using classical and ab initio simulations, focusing on the nano scale elementary processes. First, we have been interested in the calculation of threshold displacement energies, which are difficult to determine both experimentally and theoretically, and also the associated Frenkel pairs. In the framework of this thesis, we have carried out simulations in classical and ab initio molecular dynamics. For the classical approach, two types of potentials have been used: the Tersoff potential, which led to non satisfactory results, and a new one which has been developed during this thesis. This potential allows a better modelling of SiC under irradiation than most of the empirical potentials available for SiC. It is based on the EDIP potential, initially developed to describe defects in silicon, that we have generalized to SiC. For the ab initio approach, the feasibility of the calculations has been validated and average energies of 19 eV for the C and 38 eV for the Si sublattices have been determined, close to the values empirically used in the fusion community. The results obtained with the new potential EDIP are globally in agreement with those values. Finally, the elementary processes involved in the crystal recovery have been studied by calculating the stability of the created Frenkel pairs and determining possible recombination mechanisms with the nudged elastic band method. (author)

  10. Structural, magnetic and electronic properties of FexCoyIrz (x + y + z = 5, 6) clusters: an ab initio study

    KAUST Repository

    Devi, Assa Aravindh Sasikala

    2014-01-01

    Investigations on freestanding binary and ternary clusters of Fe (x) Co (y) Ir (z) (x + y + z = 5, 6) are carried out using ab initio density functional theory techniques. The geometry, chemical order, binding energy, magnetic moment and electronic

  11. 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

  12. Ab initio study of charge transfer in B2+ low-energy collisions with atomic hydrogen

    Science.gov (United States)

    Turner, A. R.; Cooper, D. L.; Wang, J. G.; Stancil, P. C.

    2003-07-01

    Charge transfer processes due to collisions of ground state B2+(2s 2S) ions with atomic hydrogen are investigated using the quantum-mechanical molecular-orbital close-coupling (MOCC) method. The MOCC calculations utilize ab initio adiabatic potentials and nonadiabatic radial and rotational coupling matrix elements obtained with the spin-coupled valence-bond approach. Total and state-selective cross sections and rate coefficients are presented. Comparison with the existing experiments shows our results to be in good agreement. When EMOCC cross sections with and without rotational coupling are small (400 eV/u, inclusion of rotational coupling increases the total cross section by 50% 80%, improving the agreement between the current calculations and experiments. For state-selective cross sections, rotational coupling induces mixing between different symmetries; however, its effect, especially at low collision energies, is not as important as had been suggested in previous work.

  13. Ab initio study of charge transfer in B2+ low-energy collisions with atomic hydrogen

    International Nuclear Information System (INIS)

    Turner, A.R.; Cooper, D.L.; Wang, J.G.; Stancil, P.C.

    2003-01-01

    Charge transfer processes due to collisions of ground state B 2+ (2s 2 S) ions with atomic hydrogen are investigated using the quantum-mechanical molecular-orbital close-coupling (MOCC) method. The MOCC calculations utilize ab initio adiabatic potentials and nonadiabatic radial and rotational coupling matrix elements obtained with the spin-coupled valence-bond approach. Total and state-selective cross sections and rate coefficients are presented. Comparison with the existing experiments shows our results to be in good agreement. When E 400 eV/u, inclusion of rotational coupling increases the total cross section by 50%-80%, improving the agreement between the current calculations and experiments. For state-selective cross sections, rotational coupling induces mixing between different symmetries; however, its effect, especially at low collision energies, is not as important as had been suggested in previous work

  14. Ab initio study on the reaction between uranium and O2

    International Nuclear Information System (INIS)

    Shuai Maobing; Zhao Pengji; Tian Anmin

    2000-08-01

    Optimized geometries, total energies and electronic structures of some gaseous atoms and molecules of uranium-oxygen system are calculated with harmonic vibration analysis using ab initio method. The potential energy surfaces (PESs) of the uranium oxidation process are also constructed. The calculated optimized geometries, infrared vibrational frequencies and the first ionized potential energies are in well accordance with available experimental data. Although U6p, U7s and U6d valence orbital electrons take part in the formation of U - O bond, the U5f electrons play an dominant role in this process and because the energies of U5f, U6d, U7s and Uds atomic orbitals are close to each other, these orbitals may hybrid and interact with O2p orbital, simultaneously, to form molecular orbitals of uranium oxides. The PESs show that different reaction modes result in different product geometries

  15. Ab initio study on the dynamics of furfural at the liquid-solid interfaces

    Science.gov (United States)

    Dang, Hongli; Xue, Wenhua; Shields, Darwin; Liu, Yingdi; Jentoft, Friederike; Resasco, Daniel; Wang, Sanwu

    2013-03-01

    Catalytic biomass conversion sometimes occurs at the liquid-solid interfaces. We report ab initio molecular dynamics simulations at finite temperatures for the catalytic reactions involving furfural at the water-Pd and water-Cu interfaces. We found that, during the dynamic process, the furan ring of furfural prefers to be parallel to the Pd surface and the aldehyde group tends to be away from the Pd surface. On the other hand, at the water-Cu(111) interface, furfural prefers to be tilted to the Cu surface while the aldehyde group is bonded to the surface. In both cases, interaction of liquid water and furfural is identified. The difference of dynamic process of furfural at the two interfaces suggests different catalytic reaction mechanisms for the conversion of furfural, consistent with the experimental investigations. Supported by DOE (DE-SC0004600). Simulations and calculations were performed on XSED's and NERSC's supercomputers

  16. Ab initio study of low-energy electron collisions with ethylene

    International Nuclear Information System (INIS)

    Trevisan, C.S.; Orel, A.E.; Rescigno, T.N.

    2003-01-01

    We present the results of an investigation of elastic electron scattering by ethylene C 2 H 4 with incident electron energies ranging from 0.5 to 20 eV, using the complex Kohn variational method. These fully ab initio calculations accurately reproduce experimental angular differential cross sections at energies below 3 eV. Low-energy electron scattering by ethylene is sensitive to the inclusion of electronic correlation and target-distortion effects. We therefore report results that describe the dynamic polarization of the target by the incident electron and involve calculations over a range of different geometries, including the effects of nuclear motion in the resonant 2 B 2g symmetry with an adiabatic nuclei treatment of the C-C stretch mode. The inclusion of dynamic polarization and the effect of nuclear motion are equally critical in obtaining accurate results. The calculated cross sections are compared with recent experimental measurements

  17. Experimental and ab initio study of Ta-doped ZnO semiconductor

    Energy Technology Data Exchange (ETDEWEB)

    Munoz, E. L., E-mail: munoz@fisica.unlp.edu.ar; Richard, D., E-mail: richard@fisica.unlp.edu.ar [UNLP, Departamento de Fisica and Instituto de Fisica La Plata (IFLP, CCT La Plata, CONICET), Fac. de Ciencias Exactas (Argentina); Eversheim, P. D. [Universitaet Bonn, Helmholtz-Institut fuer Strahlen-und Kernphysik (H-ISKP) (Germany); Renteria, M., E-mail: renteria@fisica.unlp.edu.ar [UNLP, Departamento de Fisica and Instituto de Fisica La Plata (IFLP, CCT La Plata, CONICET), Fac. de Ciencias Exactas (Argentina)

    2010-04-15

    In this work, we present {gamma}-{gamma} Perturbed-Angular-Correlation results in polycrystalline ZnO semiconductor implanted with {sup 181}Hf({yields}{sup 181}Ta) probes. Calculations in Ta-doped ZnO were carried out using the Full-Potential Augmented Plane Wave plus local orbital method in a supercell and varying self-consistently the charge state of the impurity. Ta is a triple donor impurity with respect to Zn{sup 2 + } in ZnO and thus it can loose 1, 2 or 3 donor electrons under certain circumstances. As expected, the comparison between the experimental Electric-Field-Gradient tensor results and our ab initio predictions shows that the Ta impurity is in an ionized charge state at room temperature.

  18. Experimental and ab initio study of Ta-doped ZnO semiconductor

    International Nuclear Information System (INIS)

    Muñoz, E. L.; Richard, D.; Eversheim, P. D.; Rentería, M.

    2010-01-01

    In this work, we present γ–γ Perturbed-Angular-Correlation results in polycrystalline ZnO semiconductor implanted with 181 Hf(→ 181 Ta) probes. Calculations in Ta-doped ZnO were carried out using the Full-Potential Augmented Plane Wave plus local orbital method in a supercell and varying self-consistently the charge state of the impurity. Ta is a triple donor impurity with respect to Zn 2 +  in ZnO and thus it can loose 1, 2 or 3 donor electrons under certain circumstances. As expected, the comparison between the experimental Electric-Field-Gradient tensor results and our ab initio predictions shows that the Ta impurity is in an ionized charge state at room temperature.

  19. Isomerism of OBe3F3+ cation: an ab initio study

    International Nuclear Information System (INIS)

    Klimenko, N.M.; Rykova, E.A.; MakKi, M.L.; Senchenya, I.N.

    1999-01-01

    Ab initio MP2/6-31G*/HF/6-31G*+ZPE(HF/6-31G*) calculations of the potential energy surface in the vicinity of stationary points and the pathways of intramolecular rearrangements between low-lying structures of the OBe 3 F 3 + cation detected in the mass spectra of μ 4 -Be 4 O(CF 3 COO) 6 were carried out. Ten stable isomers with di- and tricoordinate oxygen atoms were localized. The relative energies of six structures lie in the range 0-8 kcal mol -1 and those of the rest four structures lie in the range 20-40 kcal mol -1 . two most favorable isomers are a planar C 2 , isomer and a pyramidal C 3 isomer [ru

  20. A direct ab initio molecular dynamics (MD) study on the benzophenone-water 1 : 1 complex.

    Science.gov (United States)

    Tachikawa, Hiroto; Iyama, Tetsuji; Kato, Kohichi

    2009-07-28

    Direct ab initio molecular dynamics (MD) method has been applied to a benzophenone-water 1 : 1 complex Bp(H(2)O) and free benzophenone (Bp) to elucidate the effects of zero-point energy (ZPE) vibration and temperature on the absorption spectra of Bp(H(2)O). The n-pi transition of free-Bp (S(1) state) was blue-shifted by the interaction with a water molecule, whereas three pi-pi transitions (S(2), S(3) and S(4)) were red-shifted. The effects of the ZPE vibration and temperature of Bp(H(2)O) increased the intensity of the n-pi transition of Bp(H(2)O) and caused broadening of the pi-pi transitions. In case of the temperature effect, the intensity of n-pi transition increases with increasing temperature. The electronic states of Bp(H(2)O) were discussed on the basis of the theoretical results.

  1. Ab Initio Molecular Dynamics Studies of Pb m Sb n ( m + n ≤ 9) Alloy Clusters

    Science.gov (United States)

    Song, Bingyi; Xu, Baoqiang; Yang, Bin; Jiang, Wenlong; Chen, Xiumin; Xu, Na; Liu, Dachun; Dai, Yongnian

    2017-10-01

    Structure, stability, and dynamics of Pb m Sb n ( m + n ≤ 9) clusters were investigated using ab initio molecular dynamics. Size dependence of binding energies, the second-order energy difference of clusters, dissociation energy, HOMO-LUMO gaps, Mayer bond order, and the diffusion coefficient of Pb m Sb n clusters were discussed. Results suggest that Pb3Sb2, Pb4Sb2, and Pb5Sb4 ( n = 2 or 4) clusters have higher stability than other clusters, which is consistent with previous findings. In case of Pb-Sb alloy, the dynamics results show that Pb4Sb2 (Pb-22.71 wt pct Sb) can exist in gas phase at 1073 K (800 °C), which reasonably explains the azeotropic phenomenon, and the calculated values are in agreement with the experimental results (Pb-22 wt pct Sb).

  2. Ab-initio Hartree-Fock study of tritium desorption from Li{sub 2}O

    Energy Technology Data Exchange (ETDEWEB)

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

    1998-03-01

    Dissociative adsorption of hydrogen on Li{sub 2}O (110) surface has been investigated with ab-initio Hartree-Fock quantum chemical calculation technique. Heat of adsorption and potential energy surface for H{sub 2} dissociative adsorption was evaluated by calculating the total energy of the system. Calculation results on adsorption heat indicated that H{sub 2} adsorption is endothermic. However, when oxygen vacancy exists adjacent to the adsorption sites, heat of adsorption energy became less endothermic and the activation energy required to dissociate the H-H bonding was smaller than that for the terrace site. This is considered to be caused by the excess charge localized near the defect. (author)

  3. Conformations of Trimethyl Phosphite: a Matrix Isolation Infrared and AB Initio Study

    Science.gov (United States)

    Ramanathan, N.; Sundararajan, K.; Kar, Bishnu Prasad; Viswanathan, K. S.

    2011-06-01

    Hyperconjugative interactions have received considerable attention because of its importance in determining structure and reactivity in organic compounds. In all these molecules, our studies, as many others in the literature, indicated that the O-P-O and O-C-O segments played a crucial role in conformational preferences. In the case of the organic phosphates, in addition to the O-P-O segments, the P=O group was also found to influence the structures. To address this issue further, it was thought interesting to study the conformations of trimethylphosphite (TMPhite), which lacks a P=O group. A comparison of the conformations of trimethylphosphate (TMP) and TMPhite was expected to highlight the role of the P=O group in the conformational preference of organic phosphates, which is the motivation for the present work. The conformations of TMPhite were studied using matrix isolation infrared spectroscopy. TMPhite was trapped in a nitrogen matrix using an effusive source maintained at 298 K and 410 K and also a supersonic source. These experiments were designed to enable us to assign the infrared features of the higher energy conformer(s). As a result of these experiments, infrared spectra of the conformations of TMPhite were obtained. The experimental studies were supported by ab initio computations performed at the B3LYP/6-31++G** level. Computations indicated four minima corresponding to conformers with the following symmetries: C_1, C_s, C1a and C_3, given in order of increasing energy. This conformational picture was clearly different from that of TMP, in which the C_3 was the lowest energy structure, thereby clearly indicating the role of the P=O group in structural preferences in these systems. We also performed a photochemical insertion of oxygen in TMPhite to produce TMP in the matrix, in an effort to correlate the conformers of the two molecules. These experiments also gave rise to interesting side reactions, where in addition to TMP, we also observed the

  4. Origin of the Hadži ABC structure: An ab initio study

    Energy Technology Data Exchange (ETDEWEB)

    Van Hoozen, Brian L.; Petersen, Poul B. [Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853 (United States)

    2015-11-14

    Medium and strong hydrogen bonds are well known to give rise to broad features in the vibrational spectrum often spanning several hundred wavenumbers. In some cases, these features can span over 1000 cm{sup −1} and even contain multiple broad peaks. One class of strongly hydrogen-bonded dimers that includes many different phosphinic, phosphoric, sulfinic, and selenic acid homodimers exhibits a three-peaked structure over 1500 cm{sup −1} broad. This unusual feature is often referred to as the Hadži ABC structure. The origin of this feature has been debated since its discovery in the 1950s. Only a couple of theoretical studies have attempted to interpret the origin of this feature; however, no previous study has been able to reproduce this feature from first principles. Here, we present the first ab initio calculation of the Hadži ABC structure. Using a reduced dimensionality calculation that includes four vibrational modes, we are able to reproduce the three-peak structure and much of the broadness of the feature. Our results indicate that Fermi resonances of the in-plane bend, out-of-plane bend, and combination of these bends play significant roles in explaining this feature. Much of the broadness of the feature and the ability of the OH stretch mode to couple with many overtone bending modes are captured by including an adiabatically separated dimer stretch mode in the model. This mode modulates the distance between the monomer units and accordingly the strength of the hydrogen-bonds causing the OH stretch frequency to shift from 2000 to 3000 cm{sup −1}. Using this model, we were also able to reproduce the vibrational spectrum of the deuterated isotopologue which consists of a single 500 cm{sup −1} broad feature. Whereas previous empirical studies have asserted that Fermi resonances contribute very little to this feature, our study indicates that while not appearing as a separate peak, a Fermi resonance of the in-plane bend contributes substantially to

  5. Ab initio studies of vacancies in (8,0) and (8,8) single-walled carbon and boron nitride nanotubes

    CSIR Research Space (South Africa)

    Mashapa, MG

    2012-09-01

    Full Text Available -1 Journal of Nanoscience and Nanotechnology Vol. 12, 7030?7036, 2012 Ab Initio Studies of Vacancies in (8,0) and (8,8) Single-Walled Carbon and Boron Nitride NanotubesAb M. G. Mashapa 1, 2, *, N. Chetty 2, and S. Sinha Ray 1, 3 1 DST...

  6. 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

  7. Ab-initio study of hydrogen technology materials for hydrogen storage and proton conduction

    Energy Technology Data Exchange (ETDEWEB)

    Luduena, Guillermo Andres

    2011-07-01

    This dissertation deals with two specific aspects of a potential hydrogen-based energy economy, namely the problems of energy storage and energy conversion. In order to contribute to the solution of these problems, the structural and dynamical properties of two promising materials for hydrogen storage (lithium imide/amide) and proton conduction (poly[vinyl phosphonic acid]) are modeled on an atomistic scale by means of first principles molecular dynamics simulation methods. In the case of the hydrogen storage system lithium amide/imide (LiNH{sub 2}/Li{sub 2}NH), the focus was on the interplay of structural features and nuclear quantum effects. For these calculations, Path-Integral Molecular Dynamics (PIMD) simulations were used. The structures of these materials at room temperature were elucidated; in collaboration with an experimental group, a very good agreement between calculated and experimental solid-state {sup 1}H-NMR chemical shifts was observed. Specifically, the structure of Li{sub 2}NH features a disordered arrangement of the Li lattice, which was not reported in previous studies. In addition, a persistent precession of the NH bonds was observed in our simulations. We provide evidence that this precession is the consequence of a toroid-shaped effective potential, in which the protons in the material are immersed. This potential is essentially flat along the torus azimuthal angle, which might lead to important quantum delocalization effects of the protons over the torus. On the energy conversion side, the dynamics of protons in a proton conducting polymer (poly[vinyl phosphonic acid], PVPA) was studied by means of a steered ab-initio Molecular Dynamics approach applied on a simplified polymer model. The focus was put on understanding the microscopic proton transport mechanism in polymer membranes, and on characterizing the relevance of the local environment. This covers particularly the effect of water molecules, which participate in the hydrogen bonding

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

    Directory of Open Access Journals (Sweden)

    Stojanović Ljiljana

    2013-01-01

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

  9. Ab initio study of isomerism of Li2AB2 molecules and Li2AB2+ ions with 16 valent electrons

    International Nuclear Information System (INIS)

    Charkin, O.P.; Klimenko, N.M.; MakKi, M.L.

    2000-01-01

    In the framework of MP2(6-31*//HF/6-31G + ZPE(HF/6-31G*) and MP4SDTQ/6-31G*//MP2/6-31G* + ZPE(MP2/6-31G*) approximations ab initio calculations of surfaces of potential energy of molecules of lithium salts of Li 2 AB 2 (Li 2 BeO 2 , L 2 MgO 2 , Li 2 BeS 2 , Li 2 MgS 2 , Li 2 CN 2 , Li 2 SiN 2 , Li 2 CP 2 ) type and ions of Li 2 AB 2 + (Li 2 BO 2 + , Li 2 AlO 2 + , Li 2 BS 2 + , Li 2 AlS 2 + , Li 2 N 3 + , Li 2 PN 2 + , Li 2 P 3 + ) type with 16 valent electrons are done. For oxide and nitride systems global minimum corresponds to symmetric linear structure D ∞h and for their sulfide and phosphorus analogues curved plane or unplane (C 2 ) structure with bond angle φ(LBA)=90-110 Deg are preferable. Equilibrium geometric parameters, relative energies and energies of isomer decomposition, frequencies and IR-intensities of normal vibrations are determined [ru

  10. Ab Initio molecular dynamics with excited electrons

    NARCIS (Netherlands)

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

    1994-01-01

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

  11. 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 ...

  12. 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)

  13. Ab initio electronic stopping power in materials

    International Nuclear Information System (INIS)

    Shukri, Abdullah-Atef

    2015-01-01

    The average energy loss of an ion per unit path length when it is moving through the matter is named the stopping power. The knowledge of the stopping power is essential for a variety of contemporary applications which depend on the transport of ions in matter, especially ion beam analysis techniques and ion implantation. Most noticeably, the use of proton or heavier ion beams in radiotherapy requires the knowledge of the stopping power. Whereas experimental data are readily available for elemental solids, the data are much more scarce for compounds. The linear response dielectric formalism has been widely used in the past to study the electronic stopping power. In particular, the famous pioneering calculations due to Lindhard evaluate the electronic stopping power of a free electron gas. In this thesis, we develop a fully ab initio scheme based on linear response time-dependent density functional theory to predict the impact parameter averaged quantity named the random electronic stopping power (RESP) of materials without any empirical fitting. The purpose is to be capable of predicting the outcome of experiments without any knowledge of target material besides its crystallographic structure. Our developments have been done within the open source ab initio code named ABINIT, where two approximations are now available: the Random-Phase Approximation (RPA) and the Adiabatic Local Density Approximation (ALDA). Furthermore, a new method named 'extrapolation scheme' have been introduced to overcome the stringent convergence issues we have encountered. These convergence issues have prevented the previous studies in literature from offering a direct comparison to experiment. First of all, we demonstrate the importance of describing the realistic ab initio electronic structure by comparing with the historical Lindhard stopping power evaluation. Whereas the Lindhard stopping power provides a first order description that captures the general features of the

  14. Theoretical study (ab initio and DFT methods on acidic dissociation constant of xylenol orange in aqueous solution

    Directory of Open Access Journals (Sweden)

    F. Kiani

    2017-07-01

    Full Text Available Analytical measurement of materials requires exact knowledge of their acid dissociation constant (pKa values. In recent years, quantum mechanical calculations have been extensively used to study of acidities in the aqueous solutions and the results were compared with the experimental values. In this study, a theoretical study was carried out on xylenol orange (in water solution by ab initio method. We calculated the pKa values of xylenol orange in water, using high-level ab initio (PM3, DFT (HF, B3LYP/6-31+G(d and SCRF methods. The experimental determination of these values (pKa,s is a challenge because xylenol orange has a low solubility in water. We considered several ionization reactions and equilibriums in water that constitute the indispensable theoretical basis to calculate the pKa values of xylenol orange. The results show that the calculated pKa values have a comparable agreement with the experimentally determined pKa values. Therefore, this method can be used to predict such properties for indicators, drugs and other important molecules.

  15. Analytical modeling of electron energy loss spectroscopy of graphene: Ab initio study versus extended hydrodynamic model.

    Science.gov (United States)

    Djordjević, Tijana; Radović, Ivan; Despoja, Vito; Lyon, Keenan; Borka, Duško; Mišković, Zoran L

    2018-01-01

    We present an analytical modeling of the electron energy loss (EEL) spectroscopy data for free-standing graphene obtained by scanning transmission electron microscope. The probability density for energy loss of fast electrons traversing graphene under normal incidence is evaluated using an optical approximation based on the conductivity of graphene given in the local, i.e., frequency-dependent form derived by both a two-dimensional, two-fluid extended hydrodynamic (eHD) model and an ab initio method. We compare the results for the real and imaginary parts of the optical conductivity in graphene obtained by these two methods. The calculated probability density is directly compared with the EEL spectra from three independent experiments and we find very good agreement, especially in the case of the eHD model. Furthermore, we point out that the subtraction of the zero-loss peak from the experimental EEL spectra has a strong influence on the analytical model for the EEL spectroscopy data. Copyright © 2017 Elsevier B.V. All rights reserved.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-02-15

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

  17. Ab-initio study on electronic properties of rocksalt SnAs

    Science.gov (United States)

    Babariya, Bindiya; Vaghela, M. V.; Gajjar, P. N.

    2018-05-01

    Within the frame work of Local Density Approximation of Exchange and Correlation, ab-initio method of density functional theory with Abinit code is used to compute electronic energy band structure, density of States and charge density of SnAs in rocksalt phase. Our result after optimization for lattice constant agrees with experimental value within 0.59% deviation. The computed electronic energy bands in high symmetry directions Γ→K→X→Γ→L→X→W→L→U shown metallic nature. The lowest band in the electronic band structure is showing band-gap approximately 1.70 eV from next higher band and no crossing between lowest two bands are seen. The density of states revels p-p orbit hybridization between Sn and As atoms. The spherical contour around Sn and As in the charge density plot represent partly ionic and partly covalent bonding. Fermi surface topology is the resultant effect of the single band crossing along L direction at Ef.

  18. Ab initio study of the electron-phonon coupling at the Cr(001) surface

    Science.gov (United States)

    Peters, L.; Rudenko, A. N.; Katsnelson, M. I.

    2018-04-01

    It is experimentally well established that the Cr(001) surface exhibits a sharp resonance around the Fermi level. However, there is no consensus about its physical origin. It is proposed to be either due to a single particle dz2 surface state renormalized by electron-phonon coupling or the orbital Kondo effect involving the degenerate dx z/ dy z states. In this paper we examine the electron-phonon coupling of the Cr(001) surface by means of ab-initio calculations in the form of density functional perturbation theory. More precisely, the electron-phonon mass-enhancement factor of the surface layer is investigated for the 3d states. For the majority and minority spin dz2 surface states we find values of 0.19 and 0.16. We show that these calculated electron-phonon mass-enhancement factors are not in agreement with the experimental data even if we use realistic values for the temperature range and surface Debye frequency for the fit of the experimental data. More precisely, then experimentally an electron-phonon mass-enhancement factor of 0.70 ±0.10 is obtained, which is not in agreement with our calculated values of 0.19 and 0.16. Our findings suggest that the experimentally observed resonance at the Cr(001) surface is not due to electron-phonon effects but due to electron-electron correlation effects.

  19. Ab initio study of effects of substitutional additives on the phase stability of γ-alumina

    International Nuclear Information System (INIS)

    Jiang Kaiyun; Music, Denis; Sarakinos, Kostas; Schneider, Jochen M

    2010-01-01

    Using ab initio calculations, we have evaluated two structural descriptions of γ-Al 2 O 3 , spinel and tetragonal hausmannite, and explored the relative stability of γ-Al 2 O 3 with respect to α-Al 2 O 3 with 2.5 at.% of Si, Cr, Ti, Sc, and Y additives to identify alloying element induced electronic structure changes that impede the γ to α transition. The total energy calculations indicate that Si stabilizes γ-Al 2 O 3 , while Cr stabilizes α-Al 2 O 3 . As Si is added, a bond length increase in α-Al 2 O 3 is observed, while strong and short Si-O bonds are formed in γ-Al 2 O 3 , consequently stabilizing this phase. On the other hand, Cr additions induce a smaller bond length increase in α-Al 2 O 3 than in γ-Al 2 O 3 , therefore stabilizing the α-phase. The bulk moduli of γ-Al 2 O 3 with these additives show no significant changes. The phase stability and elastic property data discussed here underline the application potential of Si alloyed γ-Al 2 O 3 for applications at elevated temperatures. Furthermore it is evident that the tetragonal hausmannite structure is a suitable description for γ-Al 2 O 3 .

  20. Synthesis, FTIR, FT-Raman, UV-visible, ab initio and DFT studies on benzohydrazide.

    Science.gov (United States)

    Arjunan, V; Rani, T; Mythili, C V; Mohan, S

    2011-08-01

    A systematic vibrational spectroscopic assignment and analysis of benzohydrazide (BH) has been carried out by using FTIR and FT-Raman spectral data. The vibrational analysis were aided by electronic structure calculations--ab initio (RHF) and hybrid density functional methods (B3LYP and B3PW91) performed with 6-31G(d,p) and 6-311++G(d,p) basis sets. Molecular equilibrium geometries, electronic energies, IR intensities, harmonic vibrational frequencies, depolarization ratios and Raman activities have been computed. Potential energy distribution (PED) and normal mode analysis have also been performed. The assignments proposed based on the experimental IR and Raman spectra have been reviewed and complete assignment of the observed spectra have been proposed. UV-visible spectrum of the compound was also recorded and the electronic properties, such as HOMO and LUMO energies and λ(max) were determined by time-dependent DFT (TD-DFT) method. The geometrical, thermodynamical parameters and absorption wavelengths were compared with the experimental data. The interactions of carbonyl and hydrazide groups on the benzene ring skeletal modes were investigated. Copyright © 2011 Elsevier B.V. All rights reserved.

  1. Ab-initio study of the dielectric response of high-permittivity perovskites for energy storage

    International Nuclear Information System (INIS)

    Do-Amaral-De-Andrade-Sophia, Gustavo

    2014-01-01

    Many of materials based on transition metals have a wide range of applications, such as the storage of energy, due to their peculiar properties (high-dielectric constants, ferro-electricity,...). The knowledge of their bulk properties is essential in designing targeted devices with high performance. For instance, ABO 3 perovskites are peculiarly interesting for their atomic structural flexibility, allowing high number of atoms substitution and giving them specific chemical and electrical properties compared to the pure compounds. In this context, first principles calculations can be useful to understand the structural and electronic properties of these materials. The pressure-induced giant dielectric anomaly of ABO 3 perovskites has been investigated at the ab initio level. Its mechanism has been analyzed in terms of thermodynamic phase stability, structural and phonon contributions and Born effective charges. It is shown that the IR-active soft phonon is responsible for the anomaly. This mode always involves a displacement and a deformation of the oxygen octahedra, while the roles of A and B ions vary among the materials and between high- and low-pressure phase transitions. A sharp increase in the phonon amplitude near the phase transition gives rise to the dielectric anomaly. The use of hybrid functionals is required for agreement with experimental data. The calculations show that the dielectric anomaly in the pressure-induced phase transitions of these perovskites is a property of the bulk material. (author)

  2. Ab-initio and atomistic study of the ferroelectric properties of Cu doped potassium niobate

    Energy Technology Data Exchange (ETDEWEB)

    Koerbel, Sabine; Elsaesser, Christian [Fraunhofer-Institut fuer Werkstoffmechanik IWM, Woehlerstrasse 11, 79108 Freiburg (Germany)

    2011-07-01

    KNbO{sub 3} is one end member of the solid solution (K,Na)NbO{sub 3} (KNN), which has promising ferroelectric properties to become a future lead-free substitute for lead zirconate titanate Pb(Zr,Ti)O{sub 3} (PZT) in piezoelectric actors and sensors. Both KNN and PZT exhibit a phase transition with composition and a morphotropic phase boundary, at which enhanced piezoelectric coefficients are obtained. The material properties of PZT and KNN are commonly optimized by doping. E.g., CuO can be added when fabricating KNN as a sintering aid. Ab initio density functional theory and atomistic simulation using a classical shell model potential have been combined to investigate low Cu concentrations in the KNbO{sub 3}-CuNbO{sub 3} system. The atomistic model predicts a morphotropic phase boundary at a few percent Cu, analogous to the one found in the LiNbO{sub 3}-KNbO{sub 3} system.

  3. Nanolines of transition metals ruled by grain boundaries in graphene: An ab initio study

    Energy Technology Data Exchange (ETDEWEB)

    Lima, F.D.C. de, E-mail: felipe.lima@ufu.br; Miwa, R.H., E-mail: hiroki@infis.ufu.br

    2017-06-15

    We have performed an ab initio investigation of the energetic stability, and the electronic properties of transition metals (TMs = Mn, Fe, Co, and Ru) adsorbed on graphene, upon the presence of grain boundaries (GBs); where we found an energetic preference for the TMs lying on the GB sites (TM/GB). Further energy barrier calculations, of the transition metals in TM/GB, reveal that the GBs promote the formation of energetically favorable diffusion channels on graphene. By increasing the concentration of the TM adatoms, the energetic stability of the TM/GB systems has been strengthened; giving rise to TM nanolines (TM-NLs). The electronic properties of those TM-NLs were characterized through extensive electronic band structure calculations, where the energy bands of the TM/GB systems indicate the appearance of an anisotropic spin-polarized electronic current along the TM-NLs on graphene. - Highlights: • Formation of transition metal (TM) nanolines on graphene ruled by extended defects. • Those extended defects give rise to diffusion pipes of TMs on graphene. • The electronic band structure calculations indicate the formation of spin-polarized current upon the presence of TM nanolines. • The formation of those TM nanolines support the recent experimental findings.

  4. Ab initio study of properties of BaBiO3 at high pressure

    Science.gov (United States)

    Martoňák, Roman; Ceresoli, Davide; Kagayama, Tomoko; Tosatti, Erio

    BaBiO3 is a mixed-valence perovskite which escapes metallic state by creating a Bi-O bond disproportionation or CDW pattern, resulting in a Peierls semiconductor with gap of nearly 1 eV at zero pressure. Evolution of structural and electronic properties at high pressure is, however, largely unknown. Pressure, it might be natural to expect, could reduce the bond-disproportionation and bring the system closer to metalicity or even superconductivity. We address this question by ab initio DFT methods based on GGA and hybrid functionals in combination with crystal structure prediction techniques based on genetic algorithms. We analyze the pressure evolution of bond disproportionation as well as other order parameters related to octahedra rotation for various phases in connection with corresponding evolution of the electronic structure. Results indicate that BaBiO3 continues to resist metalization also under pressure, through structural phase transitions which sustain and in fact increase the diversity of length of Bi-O bonds for neighboring Bi ions, in agreement with preliminary high pressure resistivity data. R.M. Slovak Research and Development Agency Contract APVV-15-0496, VEGA project No. 1-0904-15; E.T. ERC MODPHYSFRICT Advanced Grant No. 320796.

  5. Erbium(III) in aqueous solution: an ab initio molecular dynamics study.

    Science.gov (United States)

    Canaval, Lorenz R; Sakwarathorn, Theerathad; Rode, Bernd M; Messner, Christoph B; Lutz, Oliver M D; Bonn, Günther K

    2013-12-05

    Structural and dynamical properties of the erbium(III) ion in water have been obtained by means of ab initio quantum mechanical charge field molecular dynamics (QMCF-MD) simulations for the ground state and an excited state. The quality of the simulations has been monitored by recording UV/vis and Raman spectra of dilute solutions of ErCl3 and Er(NO3)3 in water and by comparison with EXAFS data from literature. Slight deviations between these data can be mainly attributed to relativistic effects, which are not sufficiently considered by the methodological framework. In both simulations, a mixture of coordination numbers eight and nine and a ligand exchange on the picosecond range are observed. The strength of the Er-ligand bond is considerably lower than that of trivalent transition metal ions but higher than that for La(III) and Ce(III) in aqueous solution. The main difference between ground state and excited state is the ligand exchange rate of the first shell. The second hydration shell is stable in both cases but with significantly different properties.

  6. Effect of Au proximity on the LSMO surface: An ab initio study

    International Nuclear Information System (INIS)

    Petti, D.; Stroppa, A.; Picozzi, S.; Brivio, S.; Cantoni, M.; Bertacco, R.

    2012-01-01

    The effect of the proximity of Au on the electronic and magnetic properties of La 0.66 Sr 0.33 MnO 3 (LSMO) has been investigated by means of ab initio calculations within the density-functional theory. The calculations show an orbital reconstruction of the interfacial Mn, which is due more to the presence of a discontinuity rather than to a real chemical interaction with Au atoms. In fact, the same orbital reconstruction is found in the free LSMO surface. In both cases of Au/LSMO and LSMO surface, the Mn magnetic moments change very little with respect to the bulk case. In general, the calculations show a negligible influence of the Au atomic layer on LSMO at an ideal interface, with the LSMO surface magnetic and electronic properties essentially unchanged. - Highlights: ► Three structures considered: bulk LSMO, Au/LSMO and vacuum LSMO interfaces. ► At the two interfaces the formation of a discontinuity creates an orbital ordering. ► DFT calculations point toward an enhancement of the magnetization at the interface. ► Negligible chemical interaction with gold is seen for a 2D ideal interface. ► Crucial role of the 3D nature of Au on LSMO in depressing LSMO magnetic properties.

  7. Lithium ion diffusion in Li4+xTi5O12: From ab initio studies

    International Nuclear Information System (INIS)

    Chen, Y.C.; Ouyang, C.Y.; Song, L.J.; Sun, Z.L.

    2011-01-01

    Highlights: → Li diffusion pathways in Li 4 Ti 5 O 12 and Li 7 Ti 5 O 12 are obtained from ab initio calculations. → Cooperative Li migration in Li 7+δ Ti 5 O 12 with very low energy barrier is proposed. → Li diffusion is faster in lithiated state than in delithiated state is confirmed theoretically. - Abstract: Lithium ion dynamics in Li 4+x Ti 5 O 12 spinel are investigated from first principles calculations. The diffusion pathways are optimized and the energy barriers of lithium migration under four types of dilute defect extremes: Li 4+δ Ti 5 O 12 , Li 4-δ Ti 5 O 12 , Li 7+δ Ti 5 O 12 and Li 7-δ Ti 5 O 12 (δ << 1) are calculated with the nudged elastic band method. Results show that lithium diffusion in the charged state (energy barriers are 1.0 and 0.7 eV for interstitial Li and Li vacancy diffusion, respectively) is much slower than in the discharged state (energy barriers are 0.13 and 0.35 eV for interstitial Li and Li vacancy diffusion, respectively). The diffusion coefficients are evaluated based on lattice gas model and hopping mechanism. The obtained results are compared with available experimental data within a two-phase co-existence framework.

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

    International Nuclear Information System (INIS)

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

    2008-01-01

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

  9. Ab initio studies of the electronic structure of Be93, Be105, Be111, and Be123 clusters

    International Nuclear Information System (INIS)

    Ross, R.B.; Kern, C.W.; Pitzer, R.M.; Ermler, W.C.

    1995-01-01

    Ab initio self-consistent-field calculations are reported for electronic states of beryllium clusters comprised of 93, 105, 111, and 123 atoms. The respective clusters correspond to coordination shells 12-15 of a central Be atom with internuclear separations derived from the lattice constants of the bulk metal. Ab initio effective core potentials have been employed to replace the 1s electrons, thereby reducing the complexity of the calculations. In addition, use of the full D 3h point group symmetry or the clusters results in a substantial reduction of the numbers of two-electron integrals that must be computed and processed. Binding energies, orbital energies, electric field gradient, nuclear-electrostatic potential, diamagnetic shielding constant, second moments, and Mulliken populations are calculated for selected electronic states. Calculated binding energies when compared among the different clusters as well as to smaller and larger fragments from earlier studies provide evidence for the onset of convergence to the Hartree-Fock limit of the bulk. Lowest-state ionization potentials are consistently above and agree to within 14% of the experimental workfunction. The net charge on the central beryllium atom decreases toward zero. The variability of observed bulklike behavior is not sharp and depends on the quantity of interest. 24 refs., 8 figs., 13 tabs

  10. Systematic ab initio study of the electronic and magnetic properties of different pure and mixed iron systems

    International Nuclear Information System (INIS)

    Izquierdo, J.; Vega, A.; Balbas, L. C.; Sanchez-Portal, Daniel; Junquera, Javier; Artacho, Emilio; Soler, Jose M.; Ordejon, Pablo

    2000-01-01

    We present a theoretical study of the electronic and magnetic properties of iron systems in different environments: pure iron systems [dimer, bcc bulk, (100) surface, and free-standing iron monolayer], and low-dimensional iron systems deposited on Ag (100) surface (monoatomic linear wires, iron monolayer, planar, and three-dimensional clusters). Electronic and magnetic properties have been calculated using a recently developed total-energy first-principles method based on density-functional theory with numerical atomic orbitals as a basis set for the description of valence electrons and nonlocal pseudopotentials for the atomic core. The Kohn-Sham equations are solved self-consistently within the generalized gradient approximation for the exchange-correlation potential. Tests on the pseudopotential, the basis set, grid spacing, and k sampling are carefully performed. This technique, which has been proved to be very efficient for large nonmagnetic systems, is applied in this paper to calculate electronic and magnetic properties of different iron nanostructures. The results compare well with previous ab initio all-electron calculations and with experimental data. The method predicts the correct trends in the magnetic moments of Fe systems for a great variety of environments and requires a smaller computational effort than other ab initio methods. (c) 2000 The American Physical Society

  11. Systematic ab initio study of the electronic and magnetic properties of different pure and mixed iron systems

    Energy Technology Data Exchange (ETDEWEB)

    Izquierdo, J. [Departamento de Fisica Teorica, Universidad de Valladolid, E-47011 Valladolid, (Spain); Vega, A. [Departamento de Fisica Teorica, Universidad de Valladolid, E-47011 Valladolid, (Spain); Balbas, L. C. [Departamento de Fisica Teorica, Universidad de Valladolid, E-47011 Valladolid, (Spain); Sanchez-Portal, Daniel [Department of Physics and Materials Research Laboratory, University of Illinois, Urbana, Illinois 61801 (United States); Junquera, Javier [Departamento de Fisica de la Materia Condensada, C-III, and Institut Nicolas Cabrera, Universidad Autonoma de Madrid, 28049 Madrid, (Spain); Artacho, Emilio [Departamento de Fisica de la Materia Condensada, C-III, and Institut Nicolas Cabrera, Universidad Autonoma de Madrid, 28049 Madrid, (Spain); Soler, Jose M. [Department of Physics, Harvard University, Cambridge, Massachusetts 02138 (United States); Ordejon, Pablo [Institut de Ciencia de Materials de Barcelona (CSIC), Campus de la U.A.B., Bellaterra, E-08193 Barcelona, (Spain)

    2000-05-15

    We present a theoretical study of the electronic and magnetic properties of iron systems in different environments: pure iron systems [dimer, bcc bulk, (100) surface, and free-standing iron monolayer], and low-dimensional iron systems deposited on Ag (100) surface (monoatomic linear wires, iron monolayer, planar, and three-dimensional clusters). Electronic and magnetic properties have been calculated using a recently developed total-energy first-principles method based on density-functional theory with numerical atomic orbitals as a basis set for the description of valence electrons and nonlocal pseudopotentials for the atomic core. The Kohn-Sham equations are solved self-consistently within the generalized gradient approximation for the exchange-correlation potential. Tests on the pseudopotential, the basis set, grid spacing, and k sampling are carefully performed. This technique, which has been proved to be very efficient for large nonmagnetic systems, is applied in this paper to calculate electronic and magnetic properties of different iron nanostructures. The results compare well with previous ab initio all-electron calculations and with experimental data. The method predicts the correct trends in the magnetic moments of Fe systems for a great variety of environments and requires a smaller computational effort than other ab initio methods. (c) 2000 The American Physical Society.

  12. An ab initio chemical reaction model for the direct simulation Monte Carlo study of non-equilibrium nitrogen flows.

    Science.gov (United States)

    Mankodi, T K; Bhandarkar, U V; Puranik, B P

    2017-08-28

    A new ab initio based chemical model for a Direct Simulation Monte Carlo (DSMC) study suitable for simulating rarefied flows with a high degree of non-equilibrium is presented. To this end, Collision Induced Dissociation (CID) cross sections for N 2 +N 2 →N 2 +2N are calculated and published using a global complete active space self-consistent field-complete active space second order perturbation theory N 4 potential energy surface and quasi-classical trajectory algorithm for high energy collisions (up to 30 eV). CID cross sections are calculated for only a selected set of ro-vibrational combinations of the two nitrogen molecules, and a fitting scheme based on spectroscopic weights is presented to interpolate the CID cross section for all possible ro-vibrational combinations. The new chemical model is validated by calculating equilibrium reaction rate coefficients that can be compared well with existing shock tube and computational results. High-enthalpy hypersonic nitrogen flows around a cylinder in the transition flow regime are simulated using DSMC to compare the predictions of the current ab initio based chemical model with the prevailing phenomenological model (the total collision energy model). The differences in the predictions are discussed.

  13. Ab initio study of electron-ion structure factors in binary liquids with different types of chemical bonding

    International Nuclear Information System (INIS)

    Klevets, Ivan; Bryk, Taras

    2014-01-01

    Electron-ion structure factors, calculated in ab initio molecular dynamics simulations, are reported for several binary liquids with different kinds of chemical bonding: metallic liquid alloy Bi–Pb, molten salt RbF, and liquid water. We derive analytical expressions for the long-wavelength asymptotes of the partial electron-ion structure factors of binary systems and show that the analytical results are in good agreement with the ab initio simulation data. The long-wavelength behaviour of the total charge structure factors for the three binary liquids is discussed

  14. Towards hydrogen metallization: an Ab initio approach

    International Nuclear Information System (INIS)

    Bernard, St.

    1998-01-01

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

  15. Highly scalable Ab initio genomic motif identification

    KAUST Repository

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

    2011-01-01

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

  16. Ab initio simulation of dislocation cores in metals

    International Nuclear Information System (INIS)

    Ventelon, L.

    2008-01-01

    In the framework of the multi scale simulation of metals and alloys plasticity, the aim of this study is to develop a methodology of ab initio dislocations study and to apply it to the [111] screw dislocation in the bc iron. (A.L.B.)

  17. Ab initio study on stacking sequences, free energy, dynamical stability and potential energy surfaces of graphite structures

    International Nuclear Information System (INIS)

    Anees, P; Valsakumar, M C; Chandra, Sharat; Panigrahi, B K

    2014-01-01

    Ab initio simulations have been performed to study the structure, energetics and stability of several plausible stacking sequences in graphite. These calculations suggest that in addition to the standard structures, graphite can also exist in AA-simple hexagonal, AB-orthorhombic and ABC-hexagonal type stacking. The free energy difference between these structures is very small (∼1 meV/atom), and hence all the structures can coexist from purely energetic considerations. Calculated x-ray diffraction patterns are similar to those of the standard structures for 2θ ⩽ 70°. Shear elastic constant C 44 is negative in AA-simple hexagonal, AB-orthorhombic and ABC-hexagonal structures, suggesting that these structures are mechanically unstable. Phonon dispersions show that the frequencies of some modes along the Γ–A direction in the Brillouin zone are imaginary in all of the new structures, implying that these structures are dynamically unstable. Incorporation of zero point vibrational energy via the quasi-harmonic approximation does not result in the restoration of dynamical stability. Potential energy surfaces for the unstable normal modes are seen to have the topography of a potential hill for all the new structures, confirming that all of the new structures are inherently unstable. The fact that the potential energy surface is not in the form of a double well implies that the structures are linearly as well as globally unstable. (paper)

  18. Structural, dynamical, electronic, and bonding properties of laser-heated silicon: An ab initio molecular-dynamics study

    NARCIS (Netherlands)

    Silvestrelli, P.-L.; Alavi, A.; Parrinello, M.; Frenkel, D.

    1997-01-01

    The method of ab initio molecular dynamics, based on finite-temperature density-functional theory, is used to simulate laser heating of crystalline silicon. We found that a high concentration of excited electrons dramatically weakens the covalent bonding. As a result the system undergoes a melting

  19. Ab initio studies of the electronic structure of the quaternary system LiBC4N4

    International Nuclear Information System (INIS)

    Matar, S.F.; Betranhandy, E.; Nakhl, M.

    2007-01-01

    Starting from experimental data on the synthesis of solid LiBC 4 N 4 , an ab initio study has been carried out within the DFT-LDA framework of its structure and completed by accounting for other potential cubic arrangements. The consideration of stabilization energies confirms the experimental phase as the most stable one but predicts some other potential arrangements. The system is found very compressible with a bulk modulus close to that of gypsum (B 0 = 35 GPa). The electronic structure characteristics are provided allowing to confirm an ionic behavior involving complex anionic species (Li + [B(China) 4 ] - ). The control of the crystal cell size by a stoichiometry modification, such as by a CN group substitution is also studied. The proposition of LiBX 4 and LiBS 4 N 4 stoichiometries leads to predict new materials

  20. Plasmon Lifetime in K: A Case Study of Correlated Electrons in Solids Amenable to Ab Initio Theory

    International Nuclear Information System (INIS)

    Ku, W.; Eguiluz, A.G.

    1999-01-01

    We solve the puzzle posed by the anomalous dispersion of the plasmon linewidth in K via all-electron density-response calculations, performed within the framework of time-dependent density-functional theory. The key damping mechanism is shown to be decay into particle-hole pairs involving empty states of d symmetry. While the effect of many-particle correlations is small, the correlations built into the 'final-state' d bands play an important, and novel, role related to the phase-space complexity introduced by these flat bands. Our case study of plasmon lifetime in K illustrates the importance of ab initio paradigms for the study of excitations in correlated-electron systems. copyright 1999 The American Physical Society

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

    Science.gov (United States)

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

    1993-02-01

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

  2. Ab initio correlated study of the Al13H- anion: Isomers, their kinetic stability and vertical detachment energies

    Science.gov (United States)

    Moc, Jerzy

    2012-01-01

    We report correlated ab initio calculations for the Al13H- cluster anion isomers, their kinetic stability and vertical detachment energies (VDEs). Of the two most energetically favored anion structures involving H atom in terminal and threefold bridged sites of the icosahedral Al13-, the higher energy ‘threefold bridged' isomer is shown to be of low kinetic stability. Our results are consistent with the recent photoelectron spectroscopy (PE) study of Grubisic et al. who observed two distinct Al13H- isomers, one of them identified as ‘metastable'. The VDE energies computed at the CCSD(T)/aug-cc-pVTZ//MP2/aug-cc-pVDZ level for the ‘terminal' and ‘threefold bridged' Al13H- isomers of 3.21 and 2.32 eV are in good agreement with those determined in the PE study.

  3. X-ray magnetic scattering in SDW Cr - ab initio study

    International Nuclear Information System (INIS)

    Takahashi, M.; Igarashi, J.-I.; Hirai, K.

    2004-01-01

    Full text: Resonant x-ray scattering at the K-edge of transition metal atom has attracted much attention as a powerful tool for obtaining information on magnetic or orbital properties of 3d electrons. Recently Mannix et al. performed the x-ray magnetic scattering experiment in SDW Chromium and observed the finite scattering intensity with resonant enhancement at Cr K-edge on the SDW magnetic spot (0, 0, 1 ±δ). Applying ab-initio band structure calculation based on the local spin density approximation, we analyze the scattering spectra and elucidate the mechanism of the resonant enhancement in connection with the electronic structure. We assumed the bcc structure with the lattice constant a = 5.45a 0 and the SDW wavelength λ SDW = 20a, which are nearly equilibrium value at the spin-flip temperature T SF = 122K. The K-edge x-ray absorption and scattering spectra are calculated using Fermi's golden rule. We evaluate the non-resonant scattering amplitude within the spherical and dipolar approximations for spin and orbital moment contributions, respectively. The calculated absorption spectra are in good agreement with the experiment. This may assure the validity of the calculation. We obtained finite scattering amplitude with resonant enhancement at the K-edge. The calculated photon energy dependence of the scattering intensity shows good agreement with the experiment. The contribution of the 3d and 4p orbital moments to the non-resonant scattering amplitude is negligible in consequence of the smallness of their values, which are l max d ∼ 0.006ℎ and l max p ∼ 0.00007ℎ. On the other hand, although the 3d and 4p orbital moments are infinitesimal, they play important role on the resonant enhancement, which occurs through the 1s - 4p dipole transition and reflects the 4p orbital polarization. The 4p orbital polarization is caused by the on-site spin-orbit interaction in 4p orbital itself and the hybridization of the 4p orbital with the 3d orbital at neighboring

  4. Ab initio and density functional force field studies on the IR spectra and structure of diazonium dicyanomethylide (diazodicyanomethane)

    Science.gov (United States)

    Georgieva, Miglena K.

    2004-03-01

    The structure of diazonium dicyanomethylide (diazodicyanomethane) +N 2-C(CN) 2-↔N 2C(CN) 2 has been studied on the basis of ab initio HF, MP2 and DFT BLYP force field calculations, as well as of literature IR spectra and X-ray diffraction structural data. The results have been compared with those obtained for a series of chemical relatives of the title compound, i.e. molecules, push-pull molecules, anions and zwitterions, containing α-dicyano or diazo fragments, and especially substituted ammonium dicyanomethylides and diazomethane +N 2-CH 2-↔N 2CH 2. It has been found on the basis of spectral, bond length, bond order and electric charge analyses that the diazonium (or carbanionic, left) canonical form is much more important for the title zwitterion, than the corresponding one for diazomethane. So, the title compound can be named (and considered as) both diazonium dicyanomethylide and dicyanodiazomethane.

  5. An ab initio study of the structure and dynamics of bulk liquid Cd and its liquid-vapor interface

    International Nuclear Information System (INIS)

    Calderín, L; González, L E; González, D J

    2013-01-01

    Several static and dynamic properties of bulk liquid Cd at a thermodynamic state near its triple point have been calculated by means of ab initio molecular dynamics simulations. The calculated static structure shows a very good agreement with the available experimental data. The dynamical structure reveals collective density excitations with an associated dispersion relation which points to a small positive dispersion. Results are also reported for several transport coefficients. Additional simulations have also been performed at a slightly higher temperature in order to study the structure of the free liquid surface. The ionic density profile shows an oscillatory behavior with two different wavelengths, as the spacing between the outer and first inner layer is different from that between the other inner layers. The calculated reflectivity shows a marked maximum whose origin is related to the surface layering, along with a shoulder located at a much smaller wavevector transfer.

  6. Investigation of electronic structure and chemical bonding of intermetallic Pd2HfIn: An ab-initio study

    Science.gov (United States)

    Bano, Amreen; Gaur, N. K.

    2018-05-01

    Ab-initio calculations are carried out to study the electronic and chemical bonding properties of Intermetallic full Heusler compound Pd2HfIn which crystallizes in F-43m structure. All calculations are performed by using density functional theory (DFT) based code Quantum Espresso. Generalized gradient approximations (GGA) of Perdew- Burke- Ernzerhof (PBE) have been adopted for exchange-correlation potential. Calculated electronic band structure reveals the metallic character of the compound. From partial density of states (PDoS), we found the presence of relatively high intensity electronic states of 4d-Pd atom at Fermi level. We have found a pseudo-gap just abouve the Fermi level and N(E) at Fermi level is observed to be 0.8 states/eV, these finding indicates the existence of superconducting character in Pd2HfIn.

  7. Static structure, microscopic dynamics and electronic properties of the liquid Bi–Li alloy. An ab initio molecular dynamics study

    International Nuclear Information System (INIS)

    Souto, J; Alemany, M M G; Gallego, L J; González, L E; González, D J

    2013-01-01

    We report an ab initio molecular dynamics study of the static, dynamic and electronic properties of the liquid Bi x Li 1−x alloy, which is a complex binary system with a marked tendency to heterocoordination. The calculated total static structure factors are in good agreement with the available experimental data. The partial dynamic structure factors exhibit side peaks indicative of propagating density fluctuations, and for some concentrations we have found a density fluctuation mode with phase velocity greater than the hydrodynamic sound velocity. We have also evaluated other dynamical properties such as the diffusion coefficients, the shear viscosity and the adiabatic sound velocity. The electronic density of states show that the liquid Bi x Li 1−x alloy has a metallic character, although with strong deviations from the free-electron parabolic curve. The results reported improve the understanding of binary liquid alloys with both fast and slow propagating collective modes. (paper)

  8. Ab initio molecular dynamics study of the properties of cerium in liquid sodium at 1000 K temperature

    Energy Technology Data Exchange (ETDEWEB)

    Samin, Adib; Li, Xiang; Zhang, Jinsuo [Nuclear Engineering Program, Department of Mechanical and Aerospace Engineering, The Ohio State University, 201 W 19th Avenue, Columbus, Ohio 43210 (United States); Mariani, R. D. [Idaho National Laboratory, Materials and Fuels Complex, Idaho Falls, Idaho 83415 (United States); Unal, Cetin [Los Alamos National Laboratory, P.O. Box 1663, Los Alamos, New Mexico 87545 (United States)

    2015-12-21

    For liquid-sodium-cooled fast nuclear reactor systems, it is crucial to understand the behavior of lanthanides and other potential fission products in liquid sodium or other liquid metal solutions such as liquid cesium-sodium. In this study, we focus on lanthanide behavior in liquid sodium. Using ab initio molecular dynamics, we found that the solubility of cerium in liquid sodium at 1000 K was less than 0.78 at. %, and the diffusion coefficient of cerium in liquid sodium was calculated to be 5.57 × 10{sup −9} m{sup 2}/s. Furthermore, it was found that cerium in small amounts may significantly alter the heat capacity of the liquid sodium system. Our results are consistent with the experimental results for similar materials under similar conditions.

  9. Ab initio study of the diatomic fluorides FeF, CoF, NiF, and CuF.

    Science.gov (United States)

    Koukounas, Constantine; Mavridis, Aristides

    2008-11-06

    The late-3d transition-metal diatomic fluorides MF = FeF, CoF, NiF, and CuF have been studied using variational multireference (MRCI) and coupled-cluster [RCCSD(T)] methods, combined with large to very large basis sets. We examined a total of 35 (2S+1)|Lambda| states, constructing as well 29 full potential energy curves through the MRCI method. All examined states are ionic, diabatically correlating to M(+)+F(-)((1)S). Notwithstanding the "eccentric" character of the 3d transition metals and the difficulties to accurately be described with all-electron ab initio methods, our results are, in general, in very good agreement with available experimental numbers.

  10. Ab initio molecular orbital and infrared spectroscopic study of the conformation of secondary amides: derivatives of formanilide, acetanilide and benzylamides

    Science.gov (United States)

    Ilieva, S.; Hadjieva, B.; Galabov, B.

    1999-09-01

    Ab initio molecular orbital calculations at HF/4-31G level and infrared spectroscopic data for the frequencies are applied to analyse the grouping in a series model aromatic secondary amides: formanilide; acetanilide; o-methylacetanilide; 2,6-dimethylformanilide, 2,6-dimethylacetanilide; N-benzylacetamide and N-benzylformamide. The theoretical and experimental data obtained show that the conformational state of the molecules studied is determined by the fine balance of several intramolecular factors: resonance effect between the amide group and the aromatic ring, steric interaction between various substituents around the -NH-CO- grouping in the aromatic ring, conjugation between the carbonyl bond and the nitrogen lone pair as well as direct field influences inside the amide group.

  11. Density functional and ab initio study of the tautomeric forms of 3-acetyl tetronic and 3-acetyl tetramic acids

    International Nuclear Information System (INIS)

    Skylaris, Chris-Kriton; Igglessi-Markopoulou, Olga; Detsi, Anastasia; Markopoulos, John

    2003-01-01

    We propose all the accessible paths of interconversion between the tautomers of 3-acetyl tetronic and 3-acetyl tetramic acids by performing calculations with the density functional B3LYP method and the ab initio MP2 method. Our findings clarify at the atomic level the mechanisms of the equilibria between these tautomers, a topic so far only partially understood on the basis of studies by nuclear magnetic resonance (NMR) spectroscopy. We show that thermal effects via relative Gibbs free energies ΔG must be taken into account in order to reach good quantitative agreement with the available experimental information on the ratios of the most stable tautomers. The calculated 1 H and 13 C chemical shifts are in agreement with the experimental values from NMR spectroscopy

  12. Sexual attraction in the silkworm moth: nature of binding of bombykol in pheromone binding protein - an ab .I.initio study./I..

    Czech Academy of Sciences Publication Activity Database

    Klusák, Vojtěch; Havlas, Zdeněk; Rulíšek, Lubomír; Vondrášek, Jiří; Svatoš, Aleš

    2003-01-01

    Roč. 10, č. 4 (2003), s. 331-340 ISSN 1074-5521 R&D Projects: GA MŠk LN00A032 Institutional research plan: CEZ:AV0Z4055905 Keywords : .I.ab initio./I. study * hydrophobicity * bombykol Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 6.129, year: 2003

  13. Bicanonical ab Initio Molecular Dynamics for Open Systems.

    Science.gov (United States)

    Frenzel, Johannes; Meyer, Bernd; Marx, Dominik

    2017-08-08

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

  14. On the room-temperature phase diagram of high pressure hydrogen: An ab initio molecular dynamics perspective and a diffusion Monte Carlo study

    International Nuclear Information System (INIS)

    Chen, Ji; Ren, Xinguo; Li, Xin-Zheng; Alfè, Dario; Wang, Enge

    2014-01-01

    The finite-temperature phase diagram of hydrogen in the region of phase IV and its neighborhood was studied using the ab initio molecular dynamics (MD) and the ab initio path-integral molecular dynamics (PIMD). The electronic structures were analyzed using the density-functional theory (DFT), the random-phase approximation, and the diffusion Monte Carlo (DMC) methods. Taking the state-of-the-art DMC results as benchmark, comparisons of the energy differences between structures generated from the MD and PIMD simulations, with molecular and dissociated hydrogens, respectively, in the weak molecular layers of phase IV, indicate that standard functionals in DFT tend to underestimate the dissociation barrier of the weak molecular layers in this mixed phase. Because of this underestimation, inclusion of the quantum nuclear effects (QNEs) in PIMD using electronic structures generated with these functionals leads to artificially dissociated hydrogen layers in phase IV and an error compensation between the neglect of QNEs and the deficiencies of these functionals in standard ab initio MD simulations exists. This analysis partly rationalizes why earlier ab initio MD simulations complement so well the experimental observations. The temperature and pressure dependencies for the stability of phase IV were also studied in the end and compared with earlier results

  15. 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.

  16. 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...

  17. 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

  18. X-ray spectroscopy at the Mn K edge in LaMnO3 : An ab initio study

    NARCIS (Netherlands)

    Hozoi, L.; Vries, A.H. de; Broer, R.

    2001-01-01

    We present ab initio quantum chemical embedded cluster calculations of Mn core-valence and d-d transitions in LaMnO3. The results are also important for the analysis of recent x-ray absorption and x-ray scattering experiments at the Mn K edge in LaMnO3. We find that the first two peaks of the

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

    Science.gov (United States)

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

    2015-04-21

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

  20. Ab-initio study of pressure evolution of structural, mechanical and magnetic properties of cementite (Fe3C) phase

    Science.gov (United States)

    Gorai, S.; Ghosh, P. S.; Bhattacharya, C.; Arya, A.

    2018-04-01

    The pressure evolution of phase stability, structural and mechanical properties of Fe3C in ferro-magnetic (FM) and high pressure non magnetic (NM) phase is investigated from first principle calculations. The 2nd order FM to NM phase transition of Fe3C is identified around 60 GPa. Pressure (or density) variation of sound velocities from our ab-initio calculated single crystal elastic constants are determined to predict these parameters at Earth's outer core pressure.

  1. Quantum-chemical ab initio and B3LYP study of donor-acceptor complexes of gallium halides with pyridine

    International Nuclear Information System (INIS)

    Timoshkin, A.Yu.; Suvorov, A.V.; Shefer, G.F.

    1999-01-01

    By the ab initio and density functional methods the structural characteristics and vibrational spectra of gallium iodide donor-acceptor complexes with pyridine have been calculated. The standard thermodynamic characteristics of GaI 3 Py complex dissociation in gaseous phase have been calculated, as well. Short I-H intramolecular distances suggest that hydrogen iodide elimination with Ga-N chemical bond retention is the first stage of the complex pyrolysis [ru

  2. Ab initio lattice dynamics of metal surfaces

    International Nuclear Information System (INIS)

    Heid, R.; Bohnen, K.-P.

    2003-01-01

    Dynamical properties of atoms on surfaces depend sensitively on their bonding environment and thus provide valuable insight into the local geometry and chemical binding at the boundary of a solid. Density-functional theory provides a unified approach to the calculation of structural and dynamical properties from first principles. Its high accuracy and predictive power for lattice dynamical properties of semiconductor surfaces has been demonstrated in a previous article by Fritsch and Schroeder (Phys. Rep. 309 (1999) 209). In this report, we review the state-of-the-art of these ab initio approaches to surface dynamical properties of metal surfaces. We give a brief introduction to the conceptual framework with focus on recent advances in computational procedures for the ab initio linear-response approach, which have been a prerequisite for an efficient treatment of surface dynamics of noble and transition metals. The discussed applications to clean and adsorbate-covered surfaces demonstrate the high accuracy and reliability of this approach in predicting detailed microscopic properties of the phonon dynamics for a wide range of metallic surfaces

  3. Ab-initio study of magnetism behavior in TiO{sub 2} semiconductor with structural defects

    Energy Technology Data Exchange (ETDEWEB)

    Zarhri, Z., E-mail: z.zarhri@gmail.com; Houmad, M.; Ziat, Y.; El Rhazouani, O.; Slassi, A.; Benyoussef, A.; El Kenz, A.

    2016-05-15

    Magnetic, electronic and structural properties of titanium dioxide material with different structural defects are studied using the first-principles ab-initio calculations and the Korringa–Kohn–Rostoker method (KKR) combined with the coherent potential approximation (CPA) method in connection with the local density approximation (LDA). We investigated all structural defects in rutile TiO{sub 2} such as Titanium interstitial (Ti{sub i}), Titanium anti-sites (Ti{sub o}), Titanium vacancies (V{sub Ti}), Oxygen interstitial (O{sub i}), Oxygen anti-sites (O{sub Ti}) and oxygen vacancies (V{sub o}). Mechanisms of hybridization and interaction between magnetic atoms are investigated. The transition temperature is computed using the Mean Field Approximation (MFA).Magnetic stability energy of ferromagnetic and disordered local moment states is calculated to determine the most stable state. Titanium anti-sites have a half-metallic aspect. We also studied the change type caused by structural defects in this material. - Highlights: • Green function technique is used to study disordered systems. • We used DFT to study electronic structure of TiO{sub 2} perturbed by defects. • TiO{sub 2} with titanium antisite defect posesses a magnetic behavior. • The transition temperature is computed using the Mean Field Approximation.

  4. SFG experiment and ab initio study of the chemisorption of CN - on low-index platinum surfaces

    Science.gov (United States)

    Tadjeddine, M.; Flament, J.-P.; Le Rille, A.; Tadjeddine, A.

    2006-05-01

    A dual analysis is proposed in order to have a better understanding of the adsorption of the cyanide ions on a platinum electrode. The SFG (Sum Frequency Generation) spectroscopy allows the in situ vibrational study and the SFG spectra of the CN - species adsorbed on single crystal Pt electrode allow a systematic study of the low-index platinum surfaces. This experimental work is supported by ab initio calculations using density functional theory and cluster models. For each surface orientation and each geometry, a cluster model of 20-30 Pt atoms has been built in order to interpret the chemisorption of the CN - ions through four kinds of adsorption geometry: on-top or bridge site, bonding via C or N atoms. Geometries have been optimized and adsorption energies, electronic properties and vibrational frequencies have been computed. From the electronic properties, we can propose an analysis of the bonding mechanism for each studied kind of adsorption. The SFG spectra of the CN -/Pt(1 1 1) system present an unique resonance owing to the top C adsorption. It is mainly the same for the CN -/Pt(1 0 0) system. It is also the case for the SFG spectra of the CN -/Pt(1 1 0) system recorded at negative electrochemical voltage; at more positive voltage, a second resonance appears at a lower frequency, owing to the top N adsorption. Experimental and theoretical values of the C-N stretching frequencies are in excellent agreement.

  5. Ab initio study of the EFG tensor at Cd impurities in Sc{sub 2}O{sub 3} semiconductor

    Energy Technology Data Exchange (ETDEWEB)

    Munoz, E.L.; Richard, D. [Departamento de Fisica and IFLP (CONICET-UNLP), Facultad de Ciencias Exactas, Universidad Nacional de La Plata, CC 67, 1900 La Plata (Argentina); Errico, L.A. [Departamento de Fisica and IFLP (CONICET-UNLP), Facultad de Ciencias Exactas, Universidad Nacional de La Plata, CC 67, 1900 La Plata (Argentina); Universidad Nacional del Noroeste Bonaerense (UNNOBA), Monteagudo 2772, Pergamino, CP 2700 Buenos Aires (Argentina); Renteria, M., E-mail: renteria@fisica.unlp.edu.a [Departamento de Fisica and IFLP (CONICET-UNLP), Facultad de Ciencias Exactas, Universidad Nacional de La Plata, CC 67, 1900 La Plata (Argentina)

    2009-10-01

    We present an ab initio study of diluted Cd impurities localized at both cation sites of the semiconductor Sc{sub 2}O{sub 3}. The electric-field-gradient (EFG) tensor at Cd impurities located at both cationic sites of the host structure was determined from the calculation of the electronic structure of the doped system. Calculations were performed with the full-potential augmented-plane wave plus local orbitals (APW+lo) method within the framework of the density functional theory. We studied the atomic structural relaxations and the perturbation of the electronic charge density induced by the impurities in the host system in a fully self-consistent way. We showed that the Cd impurity introduces an increase of 8% in the nearest oxygen neighbors bond-lengths, changing the EFG sign for probes located at the asymmetric cation site. The APW+lo predictions for the charged state of the Cd impurity were compared with EFG results existent in the literature, coming from time-differential gamma-gamma perturbed-angular-correlations experiments performed on {sup 111}Cd-implanted Sc{sub 2}O{sub 3} powder samples. From the excellent agreement between theory and experiment, we can strongly suggest that the Cd acceptor impurities are ionized at room temperature. Finally, we showed that simple calculations like those performed within the point-charge model with antishielding factors do not correctly describe the problem of a Cd impurity in Sc{sub 2}O{sub 3}.

  6. 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

  7. 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.

  8. Vibrational lifetimes of hydrogen on lead films: An ab initio molecular dynamics with electronic friction (AIMDEF) study

    Energy Technology Data Exchange (ETDEWEB)

    Saalfrank, Peter [Institut für Chemie, Universität Potsdam, Karl-Liebknecht-Strasse 24-25, D-14476 Potsdam (Germany); Donostia International Physics Center (DIPC), Paseo Manuel de Lardizabal 4, 20018 Donostia-San Sebastián (Spain); Juaristi, J. I. [Donostia International Physics Center (DIPC), Paseo Manuel de Lardizabal 4, 20018 Donostia-San Sebastián (Spain); Centro de Física de Materiales CFM/MPC (CSIC-UPV/EHU), Paseo Manuel de Lardizabal 5, 20018 Donostia-San Sebastián (Spain); Departamento de Física de Materiales, Facultad de Químicas UPV/EHU, Apartado 1072, 20018 Donostia-San Sebastián (Spain); Alducin, M.; Muiño, R. Díez [Donostia International Physics Center (DIPC), Paseo Manuel de Lardizabal 4, 20018 Donostia-San Sebastián (Spain); Centro de Física de Materiales CFM/MPC (CSIC-UPV/EHU), Paseo Manuel de Lardizabal 5, 20018 Donostia-San Sebastián (Spain); Blanco-Rey, M. [Donostia International Physics Center (DIPC), Paseo Manuel de Lardizabal 4, 20018 Donostia-San Sebastián (Spain); Departamento de Física de Materiales, Facultad de Químicas UPV/EHU, Apartado 1072, 20018 Donostia-San Sebastián (Spain)

    2014-12-21

    Using density functional theory and Ab Initio Molecular Dynamics with Electronic Friction (AIMDEF), we study the adsorption and dissipative vibrational dynamics of hydrogen atoms chemisorbed on free-standing lead films of increasing thickness. Lead films are known for their oscillatory behaviour of certain properties with increasing thickness, e.g., energy and electron spillout change in discontinuous manner, due to quantum size effects [G. Materzanini, P. Saalfrank, and P. J. D. Lindan, Phys. Rev. B 63, 235405 (2001)]. Here, we demonstrate that oscillatory features arise also for hydrogen when chemisorbed on lead films. Besides stationary properties of the adsorbate, we concentrate on finite vibrational lifetimes of H-surface vibrations. As shown by AIMDEF, the damping via vibration-electron hole pair coupling dominates clearly over the vibration-phonon channel, in particular for high-frequency modes. Vibrational relaxation times are a characteristic function of layer thickness due to the oscillating behaviour of the embedding surface electronic density. Implications derived from AIMDEF for frictional many-atom dynamics, and physisorbed species will also be given.

  9. Ab initio study of single-crystalline and polycrystalline elastic properties of Mg-substituted calcite crystals.

    Science.gov (United States)

    Zhu, L-F; Friák, M; Lymperakis, L; Titrian, H; Aydin, U; Janus, A M; Fabritius, H-O; Ziegler, A; Nikolov, S; Hemzalová, P; Raabe, D; Neugebauer, J

    2013-04-01

    We employ ab initio calculations and investigate the single-crystalline elastic properties of (Ca,Mg)CO3 crystals covering the whole range of concentrations from pure calcite CaCO3 to pure magnesite MgCO3. Studying different distributions of Ca and Mg atoms within 30-atom supercells, our theoretical results show that the energetically most favorable configurations are characterized by elastic constants that nearly monotonously increase with the Mg content. Based on the first principles-derived single-crystalline elastic anisotropy, the integral elastic response of (Ca,Mg)CO3 polycrystals is determined employing a mean-field self-consistent homogenization method. As in case of single-crystalline elastic properties, the computed polycrystalline elastic parameters sensitively depend on the chemical composition and show a significant stiffening impact of Mg atoms on calcite crystals in agreement with the experimental findings. Our analysis also shows that it is not advantageous to use a higher-scale two-phase mix of stoichiometric calcite and magnesite instead of substituting Ca atoms by Mg ones on the atomic scale. Such two-phase composites are not significantly thermodynamically favorable and do not provide any strong additional stiffening effect. Copyright © 2013 Elsevier Ltd. All rights reserved.

  10. Ab initio study of He trapping, diffusion and clustering in Y{sub 2}O{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Lai, Wensheng, E-mail: wslai@tsinghua.edu.cn [Advanced Material Laboratory, School of Materials Science & Engineering, Tsinghua University, Beijing 100084 (China); Ou, Yidian; Lou, Xiaofeng [Advanced Material Laboratory, School of Materials Science & Engineering, Tsinghua University, Beijing 100084 (China); Wang, Fei [Advanced Material Laboratory, School of Materials Science & Engineering, Tsinghua University, Beijing 100084 (China); Xi’an High Technology Research Center, Xi’an 710025 (China)

    2017-02-15

    Ab initio calculations have been performed to study the formation and migration energies of helium atoms and the stability of helium-vacancy clusters in a Y{sub 2}O{sub 3} crystal. The calculated formation energies show that a helium atom is preferred to occupy an yttrium vacancy site with a large volume and low electron density. The migration energy of the helium atom by an interstitial mechanism is 0.31 eV. Calculations of the binding energies of an extra helium atom to the helium-vacancy clusters vary with the number of helium atoms in the clusters with a typical value of 0.4–0.7 eV. This turns negative when the He atoms reach saturation; that indicates that vacancy clusters can attract a limited number of helium atoms to form small stable helium-vacancy clusters. Our calculations suggest that the use of Y{sub 2}O{sub 3} in oxide dispersion strengthened ferritic steels may reduce He gas bubble formation as it may act as sink for trapping helium atoms.

  11. Chlorine Evolution Reaction on RuO2(110): Ab initio Atomistic Thermodynamics Study - Pourbaix Diagrams

    International Nuclear Information System (INIS)

    Exner, Kai S.; Anton, Josef; Jacob, Timo; Over, Herbert

    2014-01-01

    Graphical abstract: - Highlights: • Using the method Pourbaix diagram we identified the oxygen covered RuO 2 (110) surface as the catalytically active phase under chlorine evolution reaction (CER) conditions. This active phase is compared with the active phase in the Deacon process, the heterogeneous gas phase counterpart of the CER. - Abstract: Constrained ab initio thermodynamics in the form of a Pourbaix diagram can greatly assist kinetic modeling of a particular electrochemical reaction such as the chlorine evolution reaction (CER) over RuO 2 (110). Pourbaix diagrams reveal stable surface structures, as a function of pH and the potential. The present DFT study indicates that the Pourbaix diagram in the CER potential region above 1.36 V and pH values around zero is dominated by a stable surface structure in which all coordinatively undercoordinated Ru sites (Ru cus ) are capped by on-top oxygen (O ot ). This oxygen saturated RuO 2 (110) surface is considered to serve as the catalytically active phase in the CER, quite in contrast to the heterogeneously catalyzed HCl oxidation (Deacon process), for which the active RuO 2 (110) surface is mainly covered by on-top chlorine. The active sites in the CER are suggested to be Ru cus O ot surface complexes, while in the Deacon process both undercoordinated surface Ru and oxygen sites must be available for the activation of HCl molecules

  12. Infrared matrix isolation and ab initio studies on isothiocyanic acid HNCS and its complexes with nitrogen and xenon

    International Nuclear Information System (INIS)

    Wierzejewska, Maria; Wieczorek, Robert

    2003-01-01

    The isothiocyanic acid HNCS (DNCS) and its complexes with nitrogen and xenon have been studied experimentally by FTIR matrix isolation technique and computationally with the use of ab initio calculations at the MP2 level. The spectra show that HNCS (DNCS) interacts specifically with nitrogen forming 1:1 hydrogen bonded complex in argon matrix while non-hydrogen bonded structure is probably formed in solid xenon. Two stable minima were localized on the potential energy surface. One of them involves an almost linear hydrogen bond from NH group of the acid molecule to nitrogen molecule lone pair (structure I) and has an interaction energy ΔE CP equal to -6.85 kJ/mol. The second structure (II) where the nitrogen molecule interacts with the sulfur atom of the HNCS was found to be weaker bound and is characterized by ΔE CP =-1.99 kJ/mol. A low energetic barrier of 5.86 kJ/mol between the structures I and II was found. Both experimental and theoretical results obtained for the Xe···HNCS system point to a structure with the NH group interacting with the xenon atom. An interaction energy ΔE CP for this complex is equal to -3.64 kJ/mol

  13. Ab initio study of a TiO{sub 2}/LaAlO{sub 3} heterostructure

    Energy Technology Data Exchange (ETDEWEB)

    Weissmann, M; Ferrari, V, E-mail: weissman@cnea.gov.a, E-mail: ferrari@tandar.cnea.gov.a [Departamento de Fisica, Comision Nacional de EnergIa Atomica, Gral. Paz 1499, 1650 San Martin, Buenos Aires (Argentina)

    2009-05-01

    In this work we explore the origin of the ferromagnetism appearing when a TiO{sub 2} film is grown on another non-magnetic oxide as a substrate such as LaAlO{sub 3} (001), concentrating on the role played by the oxygen vacancies in this phenomenon. Using Density Functional Theory ab-initio methods, we study the free-standing anatase film as well as the interfaces with either the LaO or AlO{sub 2} planes of LaAlO{sub 3}. Our results show that the interface LaO/TiO{sub 2} is favored against the AlO{sub 2}/TiO{sub 2} one if no oxygen vacancies are present in the interface whereas the contrary happens when there are oxygen vacancies. In both cases, the cohesive energy is of the same order of magnitude but only at AlO{sub 2}/TiO{sub 2} we found a magnetic solution.

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

    Science.gov (United States)

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

    2018-05-01

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

  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. 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).

  17. 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).

  18. Energetic, electronic and optical properties of lanthanide doped TiO2: An ab initio LDA+U study

    CSIR Research Space (South Africa)

    Mulwa, WM

    2016-05-01

    Full Text Available potential, J. Chem. Phys. 118 (2003) 8207. doi:10.1063/1.1564060. [23] X. Ren, Beyond LDA and GGA - Tackling exact exchange , hybrid functional , MP2 , and RPA with numeric atom-centered orbitals The Fritz-Haber-Institute ab initio molecular simulations.... Calzolari, A. Ruini, A. Catellani, Anchor Group versus Conjugation: Toward the Gap-State Engineering of Functionalized ZnO (101̅0) Surface for Optoelectronic Applications, J. Am. Chem. Soc. 133 (2011) 5893–5899. [36] R. Gillen, S.J. Clark, J. Robertson...

  19. Ab initio study of the effects of thin CsI coatings on the work function of graphite cathodes

    Science.gov (United States)

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

    2007-10-01

    Cesium-iodide (CsI)-coated graphite cathodes are promising electron sources for high power microwave generators, but the mechanism driving the improved emission is not well understood. Therefore, an ab initio modeling investigation on the effects of thin CsI coatings on graphite has been carried out. It is demonstrated that the CsI coatings reduce the work function of the system significantly through a mechanism of induced dipoles. The results suggest that work function modification is a major contribution to the improved emission seen when CsI coatings are applied to C.

  20. Functionalization of silicon-doped single walled carbon nanotubes at the doping site: An ab initio study

    International Nuclear Information System (INIS)

    Song Chen; Xia Yueyuan; Zhao Mingwen; Liu Xiangdong; Li Feng; Huang Boda; Zhang Hongyu; Zhang Bingyun

    2006-01-01

    We performed ab initio calculations on the cytosine-functionalized silicon-doped single walled carbon nanotubes (SWNT). The results show that silicon substitutional doping to SWNT can dramatically change the atomic and electronic structures of the SWNT. And more importantly, it may provide an efficient pathway for further sidewall functionalization to synthesize more complicated SWNT based complex materials, for example, our previously proposed base-functionalized SWNTs, because the doping silicon atom can improve the reaction activity of the tube at the doping site due to its preference to form sp3 hybridization bonding

  1. Simple and accurate model for voltage-dependent resistance of metallic carbon nanotube interconnects: An ab initio study

    International Nuclear Information System (INIS)

    Yamacli, Serhan; Avci, Mutlu

    2009-01-01

    In this work, development of a voltage dependent resistance model for metallic carbon nanotubes is aimed. Firstly, the resistance of metallic carbon nanotube interconnects are obtained from ab initio simulations and then the voltage dependence of the resistance is modeled through regression. Self-consistent non-equilibrium Green's function formalism combined with density functional theory is used for calculating the voltage dependent resistance of metallic carbon nanotubes. It is shown that voltage dependent resistances of carbon nanotubes can be accurately modeled as a polynomial function which enables rapid integration of carbon nanotube interconnect models into electronic design automation tools.

  2. Orbital free ab initio molecular dynamics simulation study of some static and dynamic properties of liquid noble metals

    Directory of Open Access Journals (Sweden)

    G.M. Bhuiyan

    2012-10-01

    Full Text Available Several static and dynamic properties of liquid Cu, Ag and Au at thermodynamic states near their respective melting points, have been evaluated by means of the orbital free ab-initio molecular dynamics simulation method. The calculated static structure shows good agreement with the available X-ray and neutron diffraction data. As for the dynamic properties, the calculated dynamic structure factors point to the existence of collective density excitations along with a positive dispersion for l-Cu and l-Ag. Several transport coefficients have been obtained which show a reasonable agreement with the available experimental data.

  3. Study on the effects of fluorine and oxygen deficiency on YBa2Cu3O7 by ab initio method

    Institute of Scientific and Technical Information of China (English)

    刘洪霖; 曹晓卫; 瞿丽曼; 陈念贻

    1997-01-01

    The calculations of clusters modeling the fluorine-doping and oxygen deficiency of YBa2Cu3O2,have been performed by the method of all-electron ab initio Hartree-Fock with self-consistent crystal field Results show that in CuO planes electric charge significantly increases,the chemical valence of Cu decreases and the covalent bonding of Cu-O greatly weakens owing to oxygen deficiency,while the effect of F restores the local electronic structure of YBa2Cu3O7 The reported opinion that F occupied the oxygen vacancy in Cu-O chains seems disputable according to the calculated bonding characteristics.

  4. Magnetism of coherent Co and Ni thin films on Cu(111) and Au(111) substrates: An ab initio study

    Energy Technology Data Exchange (ETDEWEB)

    Zelený, Martin, E-mail: zeleny@fme.vutbr.cz; Dlouhý, Ivo

    2017-02-15

    We present an ab initio study of structural and magnetic properties of coherent Co and Ni thin films on Cu(111) and Au(111) substrates with thicknesses of up to 6 monolayers. All studied films on Cu(111) substrates prefer structures close their ground state (hcp for Co and fcc for Ni), whereas only the hcp stacking sequence has been found for both films on Au(111) substrates. All studied films exhibit instability of the first monolayer with respect to decomposition into 2-monolayer- or 3-monolayer-high islands, which is in agreement with experimental findings. All studied films are also ferromagnetic, nevertheless the Ni/Cu(111) films reduce their magnetic moments in the layer adjacent to the substrate due to a stronger Cu–Ni interaction at the interface. The magnetic anisotropy of a Co film does not depend on the film thickness: all the studied Co/Au(111) films exhibit a perpendicular magnetic anisotropy, whereas all the Co/Cu(111) films prefer in-plane magnetization. On the other hand, both Ni films change their preference for in-plane orientation of their easy axis to out-of-plane orientation at a critical thickness of 2 monolayers, however, the magnetic anisotropy energies for films thicker than 1 monolayer are smaller than 1 meV/Ni atom. These behaviors of magnetic anisotropy do not depend on the structure of the studied films. - Highlights: • All films exhibit instability of the first monolayer and prefer grow in islands. • The Cu–Ni interaction is responsible for reduced Ni magnetic moments in Ni/Cu(111) films. • The Co/Au(111) and Co/Cu(111) films show different orientations of magnetic anisotropy. • The Ni films exhibit in-plane magnetization only for single monolayer. • Behaviors of magnetic anisotropy do not depend on the structure of the studied films.

  5. 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 .

  6. Ab initio study of the isomerism of (LiAB)2 salt dimers with 24 valence electrons (AB- = NO-, PO-, NS-, PS-)

    International Nuclear Information System (INIS)

    Charkin, O.P.; Klimenko, N.M.; MakKi, M.L.

    2000-01-01

    The nonempiric calculations of the potential energies surfaces in the vicinity of the key structures of the loose dimer molecules of the (LiNO) 2 , (LiPO) 2 , (LiNS) 2 and (LiPS) 2 lithium salts with 24 valence electrons are accomplished within the frames of the MP2/6-31G * //HF/6-31g * + ZPE(HF/6-31G * and MP4SDTQ/6-31G * //MP2/6-31G * + ZPE(MP2/6-31G * ) approximation. The equilibrium geometrical parameters, relative energies and isomer decay energies, frequencies and IR-intensities of normal vibrations are determined. The geometrical deformations and shifts of vibrational frequencies of the cis- and trans-dianions under the effect of cations by different ways of their coordination as well as tendencies of the molecular properties behaviour in various series of dimers (LiAB) 2 are analyzed. The results obtained are compared with the data of previous calculations of the LiAB salts monomeric molecules, the Li 2 AB + ions with 12 valence electrons and the (LiAB) 2 dimers with 20 valence electrons [ru

  7. 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)

  8. Ab initio study of aspirin adsorption on single-walled carbon and carbon nitride nanotubes

    Science.gov (United States)

    Lee, Yongju; Kwon, Dae-Gyeon; Kim, Gunn; Kwon, Young-Kyun

    We use ab intio density functional theory to investigate the adsorption properties of acetylsalicylic acid or aspirin on a (10, 0) carbon nanotube (CNT) and a (8, 0) triazine-based graphitic carbon nitride nanotube (CNNT). It is found that an aspirin molecule binds stronger to the CNNT with its adsorption energy of 0.67 eV than to the CNT with 0.51 eV. The stronger adsorption energy on the CNNT is ascribed to the high reactivity of its N atoms with high electron affinity. The CNNT exhibits local electric dipole moments, which cause strong charge redistribution in the aspirin molecule adsorbed on the CNNT than on the CNT. We also explore the influence of an external electric field on the adsorption properties of aspirin on these nanotubes by examining the modifications in their electronic band structures, partial densities of states, and charge distributions. It is found that an electric field applied along a particular direction induces aspirin molecular states in the in-gap region of the CNNT implying a potential application of aspirin detection.

  9. 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.

  10. Ab-Initio Modelling Of Surface Site Reactivity And Fluid Transport In Clay Minerals Case Study: Pyrophyllite

    International Nuclear Information System (INIS)

    Churakov, S.V.

    2005-01-01

    Pyrophyllite, Al 2 [Si 4 O 10 ](OH) 2 , is the simplest structural prototype for 2:1 dioctahedral phyllosilicate. Because the net electric charge in pyrophyllite is zero, it is the best candidate for investigating the non electrostatic contribution to sorption and transport phenomena in clays. Using ab-initio simulations, we have investigated the reactivity and structure of the water-solid interface on the basal plane and edge sites of pyrophyllite. The calculations predict slightly hydrophobic behaviour of the basal plane. For the high water coverage (100), (110) and (-110), lateral facets have a lower energy than for the (010), (130) and (-130) surfaces. Analysis of the surface reactivity reveals that the =Al-OH groups are most easily protonated on the (010), (130) and (-130) facets. The =Al-O-Si= sites will be protonated on the (100), (130), (110), (-110) and (-130) surfaces. The =Al-OH 2 complexes are more easily de-protonated than the =Si-OH and =Al-OH sites. A spontaneous, reversible exchange of the protons between the solution and the edge sites has been observed in ab-initio molecular dynamics simulations at 300 K. Such near-surface proton diffusion may result in a significant contribution to the diffusion coefficients measured in neutron scattering experiments. (author)

  11. A theoretical-spectroscopy, ab initio-based study of the electronic ground state of 121SbH3

    International Nuclear Information System (INIS)

    Yurchenko, Sergei N.; Carvajal, Miguel; Yachmenev, Andrey; Thiel, Walter; Jensen, Per

    2010-01-01

    For the stibine isotopologue 121 SbH 3 , we report improved theoretical calculations of the vibrational energies below 8000 cm -1 and simulations of the rovibrational spectrum in the 0-8000 cm -1 region. The calculations are based on a refined ab initio potential energy surface and on a new dipole moment surface obtained at the coupled cluster CCSD(T) level. The theoretical results are compared with the available experimental data in order to validate the ab initio surfaces and the TROVE computational method [Yurchenko SN, Thiel W, Jensen P. J Mol Spectrosc 2007;245:126-40] for calculating rovibrational energies and simulating rovibrational spectra of arbitrary molecules in isolated electronic states. A number of predicted vibrational energies of 121 SbH 3 are provided in order to stimulate new experimental investigations of stibine. The local-mode character of the vibrations in stibine is demonstrated through an analysis of the results in terms of local-mode theory.

  12. Ab initio and shell model studies of structural, thermoelastic and vibrational properties of SnO2 under pressure

    Science.gov (United States)

    Casali, R. A.; Lasave, J.; Caravaca, M. A.; Koval, S.; Ponce, C. A.; Migoni, R. L.

    2013-04-01

    The pressure dependences of the structural, thermoelastic and vibrational properties of SnO2 in its rutile phase are studied, as well as the pressure-induced transition to a CaCl2-type phase. These studies have been performed by means of ab initio (AI) density functional theory calculations using the localized basis code SIESTA. The results are employed to develop a shell model (SM) for application in future studies of nanostructured SnO2. A good agreement of the SM results for the pressure dependences of the above properties with the ones obtained from present and previous AI calculations as well as from experiments is achieved. The transition is characterized by a rotation of the Sn-centered oxygen octahedra around the tetragonal axis through the Sn. This rotation breaks the tetragonal symmetry of the lattice and an orthorhombic distortion appears above the critical pressure Pc. A zone-center phonon of B1g symmetry in the rutile phase involves such rotation and softens on approaching Pc. It becomes an Ag mode which stabilizes with increasing pressure in the CaCl2 phase. This behavior, together with the softening of the shear modulus (C11-C12)/2 related to the orthorhombic distortion, allows a precise determination of a value for Pc. An additional determination is provided by the splitting of the basal plane lattice parameters. Both the AI and the experimentally observed softening of the B1g mode are incomplete, indicating a small discontinuity at the transition. However, all results show continuous changes in volume and lattice parameters, indicating a second-order transition. All these results indicate that there should be sufficient confidence for the future employment of the shell model.

  13. Ab initio and shell model studies of structural, thermoelastic and vibrational properties of SnO2 under pressure

    International Nuclear Information System (INIS)

    Casali, R A; Ponce, C A; Lasave, J; Koval, S; Migoni, R L; Caravaca, M A

    2013-01-01

    The pressure dependences of the structural, thermoelastic and vibrational properties of SnO 2 in its rutile phase are studied, as well as the pressure-induced transition to a CaCl 2 -type phase. These studies have been performed by means of ab initio (AI) density functional theory calculations using the localized basis code SIESTA. The results are employed to develop a shell model (SM) for application in future studies of nanostructured SnO 2 . A good agreement of the SM results for the pressure dependences of the above properties with the ones obtained from present and previous AI calculations as well as from experiments is achieved. The transition is characterized by a rotation of the Sn-centered oxygen octahedra around the tetragonal axis through the Sn. This rotation breaks the tetragonal symmetry of the lattice and an orthorhombic distortion appears above the critical pressure P c . A zone-center phonon of B 1g symmetry in the rutile phase involves such rotation and softens on approaching P c . It becomes an A g mode which stabilizes with increasing pressure in the CaCl 2 phase. This behavior, together with the softening of the shear modulus (C 11 −C 12 )/2 related to the orthorhombic distortion, allows a precise determination of a value for P c . An additional determination is provided by the splitting of the basal plane lattice parameters. Both the AI and the experimentally observed softening of the B 1g mode are incomplete, indicating a small discontinuity at the transition. However, all results show continuous changes in volume and lattice parameters, indicating a second-order transition. All these results indicate that there should be sufficient confidence for the future employment of the shell model. (paper)

  14. Ab initio study of structural, electronic, optical, and vibrational properties of ZnxSy (x + y = 2 to 5) nanoclusters

    International Nuclear Information System (INIS)

    Yadav, P. S.; Pandey, D. K.; Agrawal, S.; Agrawal, B. K.

    2010-01-01

    An ab initio study of the stability, structural, electronic. and optical properties has been performed for 46 zinc sulfide nanoclusters Zn x S y (x + y = n = 2 to 5). Five out of them are seen to be unstable as their vibrational frequencies are found to be imaginary. A B3LYP-DFT/6-311G(3df) method is employed to optimize the geometries and a TDDFT method is used for the study of the optical properties. The binding energies (BE), HOMO-LUMO gaps and the bond lengths have been obtained for all the clusters. For the ZnS 2 , ZnS 3 , and ZnS 4 nanoclusters, our stable structures are seen to be different from those obtained earlier by using the effective core potentials. We have also considered the zero point energy (ZPE) corrections ignored by the earlier workers. For a fixed value of n, we designate the most stable structure the one, which has maximum final binding energy per atom. The adiabatic and vertical ionization potentials (IP) and electron affinities (EA), charges on the atoms, dipole moments, optical properties, vibrational frequencies, infrared intensities, relative infrared intensities, and Raman scattering activities have been investigated for the most stable structures. The nanoclusters containing large number of S atoms for each n is found to be most stable. The HOMO-LUMO gap decreases from n = 2-3 and then increases above n = 3. The IP and EA both fluctuate with the cluster size n. The optical absorption is quite weak in visible region but strong in the ultraviolet region in most of the nanoclusters except a few. The optical absorption spectrum or electron energy loss spectrum (EELS) is unique for every nanocluster and may be used to characterize a specific nanocluster. The growth of most stable nanoclusters may be possible in the experiments.

  15. 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.

  16. Effect of alkaline metal cations on the ionic structure of cryolite melts: Ab-initio NpT MD study

    Science.gov (United States)

    Bučko, Tomáš; Šimko, František

    2018-02-01

    Ab initio molecular dynamics simulations in an NpT ensemble have been performed to study the role of alkaline metal cations (Me = Li, Na, K, Rb) on the structure and vibrational properties of melts of Me-cryolites (Me3AlF6) at T = 1300 K. In all melts examined in this work, the species AlF52 - has been found to be formed at the highest abundance [from 58% (Li) to 70% (Na)] among the Al-containing anionic clusters. The concentration of clusters AlF4- increases with the size of cations while that of anions AlF63 - follows the opposite trend and it becomes negligible in the melts of the K- and Rb-cryolites. The computed percentage of the Al atoms participating in the formation of dimers Al2Fm6 -m bridged via common F atoms is significant only in the case of Li- and Na-cryolites (16% and 10%, respectively) and the formation of even larger aggregates is found to be unlikely in all four melts. The percentage of the F atoms that are not bound to Al is ˜20% in all four melts and the ions formed by Me+ and F- are found to be only short-lived. Vibrational analysis has been performed using the velocity autocorrelation functions computed for the Cartesian and selected internal coordinates describing Raman-active symmetric stretching vibrations of different AlFn species. The results of vibrational analysis allowed us to identify trends in the variation of positions and shapes of peaks corresponding to the anionic fragments AlF4-, AlF52 -, and AlF63 - with the size of cations, and these trends are found to be consistent with those deduced from the available Raman spectroscopy experiments. Our findings represent a new insight into the properties of cryolite melts, which will be useful for the interpretation of experimental data.

  17. Ab initio molecular dynamics study of temperature and pressure-dependent infrared dielectric functions of liquid methanol

    Directory of Open Access Journals (Sweden)

    C. C. Wang

    2017-03-01

    Full Text Available The temperature and pressure-dependent dielectric functions of liquids are of great importance to the thermal radiation transfer and the diagnosis and control of fuel combustion. In this work, we apply the state-of-the-art ab initio molecular dynamics (AIMD method to calculate the infrared dielectric functions of liquid methanol at 183–573 K and 0.1–160 MPa in the spectral range 10−4000 cm−1, and study the temperature and pressure effects on the dielectric functions. The AIMD approach is validated by the Infrared Variable Angle Spectroscopic Ellipsometry (IR-VASE experimental measurements at 298 K and 0.1 MPa, and the proposed IR-VASE method is verified by comparison with paper data of distilled water. The results of the AIMD approach agrees well with the experimental values of IR-VASE. The experimental and theoretical analyses indicate that the temperature and pressure exert a noticeable influence on the infrared dielectric functions of liquid methanol. As temperature increases, the average molecular dipole moment decreases. The amplitudes of dominant absorption peaks reduce to almost one half as temperature increases from 183 to 333 K at 0.1 MPa and from 273 to 573 K at 160 MPa. The absorption peaks below 1500 cm–1 show a redshift, while those centered around 3200 cm–1 show a blueshift. Moreover, larger average dipole moments are observed as pressure increases. The amplitudes of dominant absorption peaks increase to almost two times as pressure increases from 1 to 160 MPa at 373 K.

  18. Ab initio study of 3C-SiC/M (M = Ti or Al) nano-hetero interfaces

    International Nuclear Information System (INIS)

    Tanaka, Shingo; Kohyama, Masanori

    2003-01-01

    Ab initio pseudopotential calculation of 3C-SiC(1 1 1)/Al nano-hetero interfaces have been performed and interface atom species dependence (IASD) and interface orientation dependence (IOD) of nano-hetero interfaces between 3C-SiC ((1 1 1) or (0 0 1) orientation) and metal (Ti or Al) have been studied systematically. Stable atomic configurations of the 3C-SiC(1 1 1)/Al interfaces are quite different from those of the 3C-SiC(1 1 1)/Ti interfaces. Two terminated, Si-terminated (Si-TERM) and C-terminated (C-TERM), 3C-SiC(1 1 1)/Al interfaces have covalent bonding nature. In 3C-SiC/M (M = Ti or Al) nano-hetero interfaces, the C-terminated interface has relative strong, covalent and ionic C-Ti or C-Al bonds as TiC or SiC while the Si-terminated interface has various type of bonding nature, relative weak Si-Ti or Si-Al bonds from metallic character at the (0 0 1) interface to covalent character at the (1 1 1) interface. Adhesive energy (AE) shows strong IASD and IOD. The AE of the C-terminated interface is larger than that of the Si-terminated one. In the C-terminated interface, the AE of the (1 1 1) interface is smaller than that of the (0 0 1) one while in the Si-terminated interface there exists opposite interrelation. Schottky barrier height (SBH) also shows strong IASD and IOD. The SBH of the C-terminated interface is smaller than that of the Si-terminated one. The C-terminated SiC/Al interfaces have extremely small SBHs. In comparison with some experimental SBH, the present result is reliable as the difference of SBH between the two terminated interfaces and qualitative properties

  19. 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.)

  20. Ab initio study of the binding of collagen amino acids to graphene and A-doped (A = H, Ca) graphene

    Energy Technology Data Exchange (ETDEWEB)

    Cazorla, Claudio, E-mail: c.silva@ucl.ac.u

    2010-09-30

    We present a theoretical study of the binding of collagen amino acids (AA, namely glycine, Gly; proline, Pro; and hydroxyproline, Hyp) to graphene (Gr), Ca-doped graphene and graphane (Gra) using density functional theory calculations and ab initio molecular dynamics (AIMD) simulations. It is found that binding of Gly, Pro and Hyp to Gr and Gra is thermodynamically favorable yet dependent on the amino acid orientation and always very weak (adsorption energies E{sub ads} range from -90 to -20 meV). AIMD simulations reveal that room-temperature thermal excitations are enough to induce detachment of Gly and Pro from Gr and of all three amino acids from Gra. Interestingly, we show that collagen AA binding to Gr is enhanced dramatically by doping the carbon surface with calcium atoms (corresponding E{sub ads} values decrease by practically two orders of magnitude with respect to the non-doped case). This effect is result of electronic charge transfers from the Ca impurity (donor) to Gr (acceptor) and the carboxyl group (COOH) of the amino acid (acceptor). The possibility of using Gr and Gra as nanoframes for sensing of collagen amino acids has also been investigated by performing electronic density of states analysis. It is found that, whether Gr is hardly sensitive, the electronic band gap of Gra can be modulated by attaching different number and species of AAs onto it. The results presented in this work provide fundamental insights on the quantum interactions of collagen protein components with carbon-based nanostructures and can be useful for developments in bio and nanotechnology fields.

  1. 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,.

  2. Ab Initio Predictions of Structures and Densities of Energetic Solids

    National Research Council Canada - National Science Library

    Rice, Betsy M; Sorescu, Dan C

    2004-01-01

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

  3. Ab Initio Atomistic Thermodynamics for Surfaces: A Primer

    National Research Council Canada - National Science Library

    Rogal, Jutta; Reuter, Karsten

    2006-01-01

    .... These techniques are referred to as first-principles (or in latin: ab initio) to indicate that they do not rely on empirical or fitted parameters, which then makes them applicable for a wide range of realistic conditions...

  4. Phonocatalysis. An ab initio simulation experiment

    Directory of Open Access Journals (Sweden)

    Kwangnam Kim

    2016-06-01

    Full Text Available Using simulations, we postulate and show that heterocatalysis on large-bandgap semiconductors can be controlled by substrate phonons, i.e., phonocatalysis. With ab initio calculations, including molecular dynamic simulations, the chemisorbed dissociation of XeF6 on h-BN surface leads to formation of XeF4 and two surface F/h-BN bonds. The reaction pathway and energies are evaluated, and the sorption and reaction emitted/absorbed phonons are identified through spectral analysis of the surface atomic motion. Due to large bandgap, the atomic vibration (phonon energy transfer channels dominate and among them is the match between the F/h-BN covalent bond stretching and the optical phonons. We show that the chemisorbed dissociation (the pathway activation ascent requires absorption of large-energy optical phonons. Then using progressively heavier isotopes of B and N atoms, we show that limiting these high-energy optical phonons inhibits the chemisorbed dissociation, i.e., controllable phonocatalysis.

  5. Structural properties of iron nitride on Cu(100): An ab-initio molecular dynamics study

    KAUST Repository

    Heryadi, Dodi; Schwingenschlö gl, Udo

    2011-01-01

    Due to their potential applications in magnetic storage devices, iron nitrides have been a subject of numerous experimental and theoretical investigations. Thin films of iron nitride have been successfully grown on different substrates. To study

  6. Ab initio study of native defects in SnO under strain

    KAUST Repository

    Bianchi Granato, Danilo; Albar, Arwa; Schwingenschlö gl, Udo

    2014-01-01

    Tin monoxide (SnO) has promising properties to be applied as a p-type semiconductor in transparent electronics. To this end, it is necessary to understand the behaviour of defects in order to control them. We use density functional theory to study

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

    International Nuclear Information System (INIS)

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

    2008-01-01

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

  8. Band-gap sensitive adsorption of fluorine molecules on sidewalls of carbon nanotubes: an ab initio study

    International Nuclear Information System (INIS)

    Choi, Woon Ih; Park, Sohee; Kim, Tae-Eun; Park, Noejung; Lee, Kwang-Ryeol; Lee, Young Hee; Ihm, Jisoon; Han, Seungwu

    2006-01-01

    We report from ab initio calculations that the band-gap sensitive side-wall functionalization of a carbon nanotube is feasible with the fluorine molecule (F 2 ), which can provide a route to the extraction of semiconducting nanotubes by etching away metallic ones. In the small diameter cases like (11, 0) and (12, 0), the nanotubes are easily functionalized with F 2 regardless of their electronic properties. As the diameter becomes larger, however, the fluorination is favoured on metallic CNTs with smaller activation barriers than those of semiconducting ones. Our results suggest that low-temperature exposure to F 2 molecules in the gas phase can make a dominant portion of fluorinated metallic nanotubes and unfluorinated semiconducting ones. This is consistent with recent experimental reports

  9. Ab initio study of the excited-state coupled electron-proton-transfer process in the 2-aminopyridine dimer

    International Nuclear Information System (INIS)

    Sobolewski, Andrzej L.; Domcke, Wolfgang

    2003-01-01

    The low-lying 1 ππ* excited states of the 2-aminopyridine dimer have been investigated with multi-reference ab initio methods (CASSCF and MRMP2). The 2-aminopyridine dimer can be considered as a mimetic model of Watson-Crick DNA base pairs. The reaction path and the energy profile for single proton transfer in the lowest 1 ππ* inter-monomer charge-transfer state have been obtained. A weakly avoided crossing of the 1 ππ* surface with the electronic ground-state surface has been found near the single-proton-transfer minimum of the 1 ππ* surface. From the splitting of the adiabatic surfaces at the avoided crossing, an internal-conversion lifetime of the excited state of <100 ps has been estimated. The potential relevance of these results for the rationalization of radiation-induced mutations and the photostability of the genetic code is briefly discussed

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

    International Nuclear Information System (INIS)

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

    2009-01-01

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

  11. Carbon monoxide adsorption on alkali and proton-exchanged chabazite: an ab-initio periodic study using the CRYSTAL code

    Science.gov (United States)

    Ugliengo, P.; Busco, C.; Civalleri, B.; Zicovich-Wilson, C. M.

    Ab initio periodic calculations based on local Gaussian basis sets as coded in the CRYSTAL program have been performed to investigate the structure, the binding energy and the vibrational features of carbon monoxide adsorbed on H+, Li+, Na+ and K+-exchanged chabazite (Si/Al = 11/1, i.e. one Al atom per unit cell). The hybrid B3LYP functional has been adopted for all calculations with a polarized double-zeta quality basis set. The B3LYP binding energies (BSSE corrected) are 16.0, 24.6, 20.4 and 5.1 kJ/mol for H+, Li+, Na+ and K+-exchanged chabazite, respectively. Corresponding CO hypsochromic stretching frequency shifts are 47, 68, 43 and 33 cm-1, respectively. Comparison with the case of CO interacting with bare alkali cations and the available experimental data on a variety of zeolites has also been addressed.

  12. Structural, magnetic and electronic properties of FexCoyIrz (x + y + z = 5, 6) clusters: an ab initio study

    KAUST Repository

    Devi, Assa Aravindh Sasikala

    2014-05-01

    Investigations on freestanding binary and ternary clusters of Fe (x) Co (y) Ir (z) (x + y + z = 5, 6) are carried out using ab initio density functional theory techniques. The geometry, chemical order, binding energy, magnetic moment and electronic structure of the clusters are analyzed for the entire range of composition. Composition dependent structural transition is observed in the five atom clusters, while octahedral geometry prevailed in clusters with six atoms. Both the clusters show increment in binding energy with the increase in number of heterogeneous bonds. Analysis based on the chemical order parameter indicates that clusters favor mixing rather than segregation. The clusters exhibit ferromagnetic ordering and the inter-dependence of optimal cluster geometry to the magnetic moments and electronic structure is observed.

  13. Structure, stability and mobility of point defects in hexagonal close packed zirconium: an ab initio study

    International Nuclear Information System (INIS)

    Verite, G.

    2007-09-01

    This research aims at determining, by means of DFT (density functional theory) electronic structure computations, the structure, the stability, and the mobility of isolated point defects, lack defects, auto-interstitial defects, or small aggregate defects in the compact hexagonal zirconium (hc Zr). After a literature survey on the studied materials and a review of computer simulation methods in material science, the author presents and comments the available results from experiments or simulations on point defects in hc Zr. He presents the growth phenomenon under radiation. Then, he briefly described the computing techniques used in this study, reports the determination of the network parameters and elastic constants of each material. He reports and comments the results obtained with the SIESTA code and with a Monte Carlo kinetic simulation. The different types of defects are investigated

  14. Ab-initio study of the relation between electric polarization and electric field gradients in ferroelectrics

    CERN Document Server

    Gonçalves, J N; Correia, J G; Butz, T; Picozzi, S; Fenta, A S; Amaral, V S

    2012-01-01

    The hyperfine interaction between the quadrupole moment of atomic nuclei and the electric field gradient (EFG) provides information on the electronic charge distribution close to a given atomic site. In ferroelectric materials, the loss of inversion symmetry of the electronic charge distribution is necessary for the appearance of the electric polarization. We present first-principles density functional theory calculations of ferroelectrics such as BaTiO$_{3}$, KNbO$_{3}$, PbTiO$_{3}$ and other oxides with perovskite structures, by focusing on both EFG tensors and polarization. We analyze the EFG tensor properties such as orientation and correlation between components and their relation with electric polarization. This work supports previous studies of ferroelectric materials where a relation between EFG tensors and polarization was observed, which may be exploited to study the ferroelectric order when standard techniques to measure polarization are not easily applied.

  15. Ab initio study of low-energy electrons interacting with HCN molecules

    International Nuclear Information System (INIS)

    Jain, A.; Norcross, D.W.

    1984-01-01

    Our earlier study of low-energy electron scattering with HCN molecules is further improved by treating exchange exactly (in a separable exchange approximation 2 ) in Σ, π and Δ symmetries: the 3.8 eV π resonance is shifted towards lower energy (2.56 eV, the experimental position is around 2.26 eV 3 ), while in Σ and the Δ symmetries the difference is within 15%. We also study possible negative ion states of HCN by calculating potential energy curves with respect to C-H and C-N stretches. For example, there is evidence of an avoiding crossing between a 1Σ + and a 2Σ + state (C-H stretch) of HCN -

  16. Ab initio study of dissociative attachment of low-energy electrons to F2

    International Nuclear Information System (INIS)

    Hazi, A.U.; Orel, A.E.; Rescigno, T.N.

    1981-01-01

    Adiabatic-nuclei resonance theory has been applied to the study of dissociative attachment of low-energy electrons to F 2 . Stieltjes moment theory was used to derive fixed-nuclei electronic resonance parameters from large scale configuration-interaction calculations on F 2 and F 2 - . Dissociative attachment cross sections are reported for the four lowest vibrational levels of F 2 and compared to available experimental data

  17. Ab initio study of adsorption and diffusion of lithium on transition metal dichalcogenide monolayers

    OpenAIRE

    Sun, Xiaoli; Wang, Zhiguo

    2017-01-01

    Using first principles calculations, we studied the stability and electronic properties of transition metal dichalcogenide monolayers of the type MX2 (M = Ti, Zr, Hf, V, Nb, Ta, Mo, Cr, W; X= S, Se, Te). The adsorption and diffusion of lithium on the stable MX2 phase was also investigated for potential application as an anode for lithium ion batteries. Some of these compounds were found to be stable in the 2H phase and some are in the 1T or 1T' phase, but only a few of them were stable in bot...

  18. Structural, dynamical, and electronic properties of amorphous silicon: An ab initio molecular dynamics study

    Energy Technology Data Exchange (ETDEWEB)

    Car, R.; Parrinello, M.

    1988-01-18

    An amorphous silicon structure is obtained with a computer simulation based on a new molecular-dynamics technique in which the interatomic potential is derived from a parameter-free quantum mechanical method. Our results for the atomic structure, the phonon spectrum, and the electronic properties are in excellent agreement with experiment. In addition we study details of the microscopic dynamics which are not directly accessible to experiment. We find in particular that structural defects are associated with weak bonds. These may give rise to low-frequency vibrational modes.

  19. Ab initio study of double perovskites Ba{sub 2}DySbO{sub 6}

    Energy Technology Data Exchange (ETDEWEB)

    Jha, Dhiraj Kumar; Mandal, Golak; Singh, B. K. [Department of Physics, T.M. Bhagalpur University, Bhagalpur, Bihar 812007 (India); Ray, Chandan [Department of Applied Physics & Ballistics, F. M. University, Balasore, Odisha, 756019 (India); Himanshu, A. K., E-mail: akh@vecc.gov.in [Nanostructured & Advanced Material Laboratory, Variable Energy Cyclotron Centre, 1/AF, Bidhannagar, Saltlake, Kolkata-700064 (India); Kumar, Uday [Department of Physical Sciences, IISER Kolkata, Mohanpur Campus, Mohanpur, West Bengal (India); Choudhary, B. K. [Department of Physics, Ranchi University, Jharkhand-834001 (India)

    2016-05-23

    First principle study of the electronic band structure of Ba2DySbO{sub 6} synthesied by the solid state reaction technique have been performed within the framework of density function theory using WIEN2K. It has been shown in the absence of electron-electron interaction (U=0), BaDySO{sub 6} behaves like a half-metal. Even in the presence of DFT+U, electron-electron interaction via the Hubbard term (from U = 0, 2.72e -7.02 eV), it still shows half metals.

  20. Ab initio study of double perovskites Ba_2DySbO_6

    International Nuclear Information System (INIS)

    Jha, Dhiraj Kumar; Mandal, Golak; Singh, B. K.; Ray, Chandan; Himanshu, A. K.; Kumar, Uday; Choudhary, B. K.

    2016-01-01

    First principle study of the electronic band structure of Ba2DySbO_6 synthesied by the solid state reaction technique have been performed within the framework of density function theory using WIEN2K. It has been shown in the absence of electron-electron interaction (U=0), BaDySO_6 behaves like a half-metal. Even in the presence of DFT+U, electron-electron interaction via the Hubbard term (from U = 0, 2.72e -7.02 eV), it still shows half metals.

  1. Ab initio study of the trapping of polonium on noble metals

    Science.gov (United States)

    Rijpstra, Kim; Van Yperen-De Deyne, Andy; Maugeri, Emilio Andrea; Neuhausen, Jörg; Waroquier, Michel; Van Speybroeck, Veronique; Cottenier, Stefaan

    2016-04-01

    In the future MYRRHA reactor, lead bismuth eutectic (LBE) will be used both as coolant and as spallation target. Due to the high neutron flux a small fraction of the bismuth will transmute to radiotoxic 210Po. Part of this radiotoxic element will evaporate into the gas above the coolant. Extracting it from the gas phase is necessary to ensure a safe handling of the reactor. An issue in the development of suitable filters is the lack of accurate knowledge on the chemical interaction between a candidate filter material and either elemental polonium or polonium containing molecules. Experimental work on this topic is complicated by the high radiotoxicity of polonium. Therefore, we present in this paper a first-principles study on the adsorption of polonium on noble metals as filter materials. The adsorption of monoatomic Po is considered on the candidate filter materials palladium, platinum, silver and gold. The case of the gold filter is looked upon in more detail by examining how bismuth pollution affects its capability to capture polonium and by studying the adsorption of the heavy diatomic molecules Po2, PoBi and PoPb on this gold filter.

  2. Ab initio study of the trapping of polonium on noble metals

    Energy Technology Data Exchange (ETDEWEB)

    Rijpstra, Kim; Van Yperen-De Deyne, Andy [Center for Molecular Modeling (CMM), Ghent University, Technologiepark 903, 9052 Ghent (Belgium); Maugeri, Emilio Andrea; Neuhausen, Jörg [Laboratory for Radiochemistry, Paul Scherrer Institute (PSI), 5232 Villigen (Switzerland); Waroquier, Michel; Van Speybroeck, Veronique [Center for Molecular Modeling (CMM), Ghent University, Technologiepark 903, 9052 Ghent (Belgium); Cottenier, Stefaan, E-mail: stefaan.cottenier@ugent.be [Center for Molecular Modeling (CMM), Ghent University, Technologiepark 903, 9052 Ghent (Belgium); Department of Materials Science and Engineering, Ghent University, Technologiepark 903, 9052 Ghent (Belgium)

    2016-04-15

    In the future MYRRHA reactor, lead bismuth eutectic (LBE) will be used both as coolant and as spallation target. Due to the high neutron flux a small fraction of the bismuth will transmute to radiotoxic {sup 210}Po. Part of this radiotoxic element will evaporate into the gas above the coolant. Extracting it from the gas phase is necessary to ensure a safe handling of the reactor. An issue in the development of suitable filters is the lack of accurate knowledge on the chemical interaction between a candidate filter material and either elemental polonium or polonium containing molecules. Experimental work on this topic is complicated by the high radiotoxicity of polonium. Therefore, we present in this paper a first-principles study on the adsorption of polonium on noble metals as filter materials. The adsorption of monoatomic Po is considered on the candidate filter materials palladium, platinum, silver and gold. The case of the gold filter is looked upon in more detail by examining how bismuth pollution affects its capability to capture polonium and by studying the adsorption of the heavy diatomic molecules Po{sub 2}, PoBi and PoPb on this gold filter.

  3. Ab Initio Study of Electronic Excitation Effects on SrTiO3

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Shijun [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Zhang, Yanwen [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States); Weber, William J. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)

    2017-11-14

    Interaction of energetic ions or lasers with solids often induces electronic excitations that may modify material properties significantly. In this study, effects of electronic excitations on strontium titanate SrTiO3 (STO) are investigated based on first-principles calculations. The lattice structure, electronic properties, lattice vibrational frequencies, and dynamical stabilities are studied in detail. The results suggest that electronic excitation induces charge redistribution that is mainly observed in Ti–O bonds. The electronic band gap increases with increasing electronic excitation, as excitation mainly induces depopulation of Ti 3d states. Phonon analysis indicates that there is a large phonon band gap induced by electronic excitation because of the changes in the vibrational properties of Ti and O atoms. In addition, a new peak appears in the phonon density of states with imaginary frequencies, an indication of lattice instability. Further dynamics simulations confirm that STO undergoes transition to an amorphous structure under strong electronic excitations. In conclusion, the optical properties of STO under electronic excitation are consistent with the evolution of atomic and electronic structures, which suggests a possibility to probe the properties of STO in nonequilibrium state using optical measurement.

  4. Usage of cobalt oxide particles as precursor for FEBID: Ab initio study

    Energy Technology Data Exchange (ETDEWEB)

    Skachkova, Veranika [Belarusian State University of Informatics and Radioelectronics (Belarus); Tamuliene, Jelena, E-mail: Jelena.Tamuliene@tfai.vu.lt [Vilnius University, Institute of Theoretical Physics and Astronomy (Lithuania); Stempitsky, Viktor [Belarusian State University of Informatics and Radioelectronics (Belarus)

    2016-09-15

    The investigation of the fragmentation of Co{sub 18}O{sub n} (n = 0–17) particles is presented with the aim to demonstrate that the mentioned particles could be used as precursors for focused electron beam induced deposition (FEBID). The shape of Co{sub 18} and Co{sub 18}O{sub n} particles is confirmed. The study validates that oxygen atoms stabilize Co nanoparticles. The thermal and chemical stabilities, toxicity, hardness and softness of the particles under study are determined. It is found that the absorption of oxygen atoms could occur when the number of oxygen atoms is larger than the number of external Co atoms. A low volatility and high sticking on the surface probability of Co{sub 18}O{sub 17} particles are proposed referring to the obtained results. The results of the calculated susceptibility exhibit Co{sub 18}O{sub n} particles as paramagnetics with some exceptions. The value of magnetic susceptibility of Co{sub 18}O{sub 12} is the largest one among the particle under investigation. Referring to the obtained results several most effective reactions of fragmentation are proposed and their appearance energy is evaluated. The obtained results also evidenced that Co{sub 18}O{sub 17} nanoparticle shows great potential to be used as a precursor for FEBID.

  5. Electronic and magnetic properties of modified silicene/graphene hybrid: Ab initio study

    Energy Technology Data Exchange (ETDEWEB)

    Chowdhury, Suman; Jana, Debnarayan, E-mail: cujanad@yahoo.com

    2016-11-01

    Among other two-dimensional (2D) novel materials, graphene and silicene both have drawn intense research interest among the researchers because they possess some unique intriguing properties which can change the scenario of the current electronic industry. In this work we have studied the electronic and the magnetic properties of a new kind of materials which is the hybrid of these two materials. Density functional theory (DFT) has been employed to calculate the relevant electronic and magnetic properties of this hybrid material. The pristine structure is modified by substitutional doping or by creating vacancy (Y-X, where one Y atom (Si or C) has been replaced by one X atom (B, N, Al, P or void)). The calculations have revealed that void systems are unstable while Si-B and Si-N are most stable ones. It has been noticed that some of these doped structures are magnetic in nature having induced mid-gap states in the system. In particular, Si-void structure is unstable yet it possess the highest magnetic moment of the order of 4 μ{sub B} (μ{sub B} being the Bohr magneton). The estimated band gaps of modified silicene/graphene hybrid from spin polarized partial density of states (PDOS) vary between 1.43–2.38 eV and 1.58–2.50 eV for spin-up and spin-down channel respectively. The implication of midgap states has been critically analysed in the light of magnetic nature. This study may be useful to build hybrid spintronic devices with controllable gap for spin up and spin down states. - Graphical abstract: We have studied the electronic and magnetic properties of silicene/graphene hybrid by employing density functional theory (DFT). - Highlights: • Electronic and magnetic properties of two dimensional graphene/silicene hybrid have been explored. • There is no magnetism in the system for a single carbon atom vacancy. • A net magnetic moment of 4.0 Bohr magneton is observed for a single silicon atom vacancy. • Unpaired electrons introduce mid-gap states which

  6. AB INITIO STUDY OF ADVANCED METALLIC NUCLEAR FUELS FOR FAST BREEDER REACTORS

    Energy Technology Data Exchange (ETDEWEB)

    Landa, A; Soderlind, P; Grabowski, B; Turchi, P A; Ruban, A V; Vitos, L

    2012-04-23

    Density-functional formalism is applied to study the ground state properties of {gamma}-U-Zr and {gamma}-U-Mo solid solutions. Calculated heats of formation are compared with CALPHAD assessments. We discuss how the heat of formation in both alloys correlates with the charge transfer between the alloy components. The decomposition curves for {gamma}-based U-Zr and U-Mo solid solutions are derived from Ising-type Monte Carlo simulations. We explore the idea of stabilization of the {delta}-UZr{sub 2} compound against the {alpha}-Zr (hcp) structure due to increase of Zr d-band occupancy by the addition of U to Zr. We discuss how the specific behavior of the electronic density of states in the vicinity of the Fermi level promotes the stabilization of the U{sub 2}Mo compound. The mechanism of possible Am redistribution in the U-Zr and U-Mo fuels is also discussed.

  7. 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.

  8. Ab initio design of nanostructures for solar energy conversion: a case study on silicon nitride nanowire.

    Science.gov (United States)

    Pan, Hui

    2014-01-01

    Design of novel materials for efficient solar energy conversion is critical to the development of green energy technology. In this work, we present a first-principles study on the design of nanostructures for solar energy harvesting on the basis of the density functional theory. We show that the indirect band structure of bulk silicon nitride is transferred to direct bandgap in nanowire. We find that intermediate bands can be created by doping, leading to enhancement of sunlight absorption. We further show that codoping not only reduces the bandgap and introduces intermediate bands but also enhances the solubility of dopants in silicon nitride nanowires due to reduced formation energy of substitution. Importantly, the codoped nanowire is ferromagnetic, leading to the improvement of carrier mobility. The silicon nitride nanowires with direct bandgap, intermediate bands, and ferromagnetism may be applicable to solar energy harvesting.

  9. 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.

  10. Ab initio study of metastability of Eu{sup 3+} defect complexes in GaN

    Energy Technology Data Exchange (ETDEWEB)

    Ouma, Cecil N.M., E-mail: Cecil.Ouma@up.ac.za; Meyer, Walter E.

    2014-04-15

    Density functional theory (DFT) within the generalized gradient approximation (GGA) has been used to study the structural and electronic properties of Eu{sup 3+} defect complexes in GaN under Ga-rich conditions. Two distinct configurations of the Eu{sub Ga}V{sub N} defect complex, the axial and basal configuration, have been investigated. We report two forms of metastable defects namely; the Negative U defect in the lower half of the GaN band-gap and a metastable defect with two distinct configurations each with levels at E{sub C} −0.46 eV and −0.56 eV in the upper half of the GaN band-gap.

  11. Ab-initio study of thermodynamic properties of boron nanowire at atomic scale

    Science.gov (United States)

    Bhuyan, Prabal D.; Gupta, Sanjeev K.; Sonvane, Y.; Gajjar, P. N.

    2018-04-01

    In the present work, we have optimized ribbon like zigzag structure of boron (B) nanowire (NW) and investigated vibrational and thermodynamic properties using quasi-harmonic approximations (QHA). All positive phonon in the phonon dispersive curve have confirmed dynamical stability of ribbon B-NW. The thermodynamic properties, like Debye temperature, internal energy and specific heat, are calculated as a function of temperature. The variation of specific heat is proportional to T3 Debye law at lower temperature for B-NW, while it becomes constant above room temperature at 1200K; obeys Dulong-Petit's law. The high Debye temperature of 1120K is observed at ambient temperature, which can be attributed to high thermal conductivity. Our study shows that B-NW with high thermal conductivity could be the next generation electron connector for nanoscale electronic devices.

  12. Ab-initio study of double perovskite Ba2YSbO6

    Science.gov (United States)

    Mondal, Golak; Jha, D.; Himanshu, A. K.; Lahiri, J.; Singh, B. K.; Kumar, Uday; Ray, Rajyavardhan

    2018-04-01

    The density functional theory with generalized gradient approximation has been used to investigate the electronic structure of double perovskite oxide Ba2YSbO6 (BYS) synthesized in polycrystalline form by solid state reaction. Structural characterization of the compound was done through X-ray diffraction (XRD) followed by Riedvelt analysis of the XRD pattern. The crystal structure is cubic, space group being Fm-3m (No. 225) with the lattice parameter, a = 8.424 Å. Optical band-gap of this system has been calculated using UV-Vis Spectroscopy and Kubelka-Munk (KM) function, having the value 4.56eV. A detailed study of the electronic properties has also been carried out using the Full-Potential Linear Augmented Plane Wave (FPLAPW) as implemented in WIEN2k. BYS is found to be a large band-gap insulator with potential technological applications, such as dielectric resonators and filters in microwave applications.

  13. Ab initio electronic band structure study of III-VI layered semiconductors

    Science.gov (United States)

    Olguín, Daniel; Rubio-Ponce, Alberto; Cantarero, Andrés

    2013-08-01

    We present a total energy study of the electronic properties of the rhombohedral γ-InSe, hexagonal ɛ-GaSe, and monoclinic GaTe layered compounds. The calculations have been done using the full potential linear augmented plane wave method, including spin-orbit interaction. The calculated valence bands of the three compounds compare well with angle resolved photoemission measurements and a discussion of the small discrepancies found has been given. The present calculations are also compared with recent and previous band structure calculations available in the literature for the three compounds. Finally, in order to improve the calculated band gap value we have used the recently proposed modified Becke-Johnson correction for the exchange-correlation potential.

  14. Ab initio study of cubic complex Bi2CrCuO6 perovskite

    International Nuclear Information System (INIS)

    Fajardo, F.; Cardona, R.; Landinez Tellez, D.A.; Arbey Rodriguez M, J.; Roa-Rojas, J.

    2008-01-01

    We report a detailed calculation of the structural and electronic properties for the cubic complex Bi 2 CrCuO 6 perovskite material by density functional theory. The exchange-correlation potential was included through the generalized gradient approximation. From the adjusting of Murnaghan state equation to the energy as a function of volume data, we obtain an ideal lattice parameter of 7.763 A. The density of states study was carried out considering the two spin polarizations. Results reveal that this material behaves as a conductor to the spin-down polarization and evidence a semiconductor tendency to the spin-up configuration. This tendency to the half-metallicity character is corroborated by the integer number of magnetic moment (3.0 μ B ), which is attributed to the Cr-spin-up orbital contribution

  15. The ab initio study of the catalytic hydrogenation of the oxirene

    Directory of Open Access Journals (Sweden)

    J.B. Mensah

    2008-04-01

    Full Text Available The oxirene is an unsaturated heterocyclic molecule with one oxygen atom and two carbon atoms. Its hydrogenation has been performed on two catalytic site based on molybdenum disulfide (MoS2 and tungsten disulfide (WS2 of MoS3H3+ and WS3H3+ type, respectively. The calculations were carried out using the SCF and MP2 methods and B3LYP functional calculations. The results obtained showed that the hydrogenation of the oxirene is possible on these two kinds of catalytic sites on the one hand, and the reaction product is the acetaldehyde molecule, on the other hand. The reaction process study that led to the results showed that the catalytic hydrogenation of the oxirene is a dissociative process. On the basis of the variation of some parameters during the process, a mechanism of the reaction has been proposed.

  16. Ab-initio study of Mg-doped InN(0001 surface

    Directory of Open Access Journals (Sweden)

    A. Belabbes

    2013-01-01

    Full Text Available We study the incorporation of Mg atoms into the InN(0001 surface. Energies and atomic geometries are described within density functional theory, while the electronic structure is investigated by an approximate quasiparticle method that yields a gap value of 0.7 eV for bulk InN. The formation of substitutional Mg is energetically favored in the surface layer. The surface electronic structure is less influenced by Mg-derived states. The Fermi level is pinned by In-derived surface states. With increasing depth of Mg beneath the surface the Fermi-level position moves toward the valence band top, suggesting formation of holes and, hence, p-doping of Mg in bulk-like layers.

  17. Ab initio study of native defects in SnO under strain

    KAUST Repository

    Bianchi Granato, Danilo

    2014-04-01

    Tin monoxide (SnO) has promising properties to be applied as a p-type semiconductor in transparent electronics. To this end, it is necessary to understand the behaviour of defects in order to control them. We use density functional theory to study native defects of SnO under tensile and compressive strain. We show that Sn vacancies are less stable under tension and more stable under compression, irrespectively of the charge state. In contrast, O vacancies behave differently for different charge states. It turns out that the most stable defect under compression is the +1 charged O vacancy in an Sn-rich environment and the charge neutral O interstitial in an O-rich environment. Therefore, compression can be used to transform SnO from a p-type into either an n-type or an undoped semiconductor. Copyright © EPLA, 2014.

  18. Electronic transport properties of nano-scale Si films: an ab initio study

    Science.gov (United States)

    Maassen, Jesse; Ke, Youqi; Zahid, Ferdows; Guo, Hong

    2010-03-01

    Using a recently developed first principles transport package, we study the electronic transport properties of Si films contacted to heavily doped n-type Si leads. The quantum transport analysis is carried out using density functional theory (DFT) combined with nonequilibrium Green's functions (NEGF). This particular combination of NEGF-DFT allows the investigation of Si films with thicknesses in the range of a few nanometers and lengths up to tens of nanometers. We calculate the conductance, the momentum resolved transmission, the potential profile and the screening length as a function of length, thickness, orientation and surface structure. Moreover, we compare the properties of Si films with and without a top surface passivation by hydrogen.

  19. Ab Initio Study of Electronic, Structural, Thermal and Mechanical Characterization of Cadmium Chalcogenides

    Directory of Open Access Journals (Sweden)

    Devi Prasadh P.S.

    2017-06-01

    Full Text Available Based on Density Functional Theory, we have applied Full Potential Augmented Plane Wave plus local orbital method (FAPW+loto study the electronic, structural, optical, thermal and mechanical properties of some semiconducting materials. In this paper we discuss the Zinc blende, CdX (X = S, Se and Te compounds with the full-potential linear-augmented plane wave (FP-LAPW method within the framework of the density functional theory (DFT for electronic, structural, thermal and mechanical properties using the WIEN2k code. For the purpose of exchange-correlation energy (Exc determination in Kohn–Sham calculation, the standard local density approximation (LDA formalism is utilized. Murnaghan’s equation of state (EOS is used for volume optimization by minimizing the total energy with respect to the unit cell volume. The calculated lattice parameters and thermal parameters are in good agreement with other theoretical calculations as well as available experimental data.

  20. Structural and electronic properties of AlX (X = P, As, Sb) nanowires: Ab initio study

    International Nuclear Information System (INIS)

    Srivastava, Anurag; Tyagi, Neha

    2012-01-01

    Present paper discusses the structural stability and electronic properties of AlX (X = P, As and Sb) nanowires in its linear, zigzag, ladder, square and hexagonal type atomic configurations. The structural optimization has been performed in self consistence manner by using generalized gradient approximation with revised Perdew, Burke and Ernzerhof type parameterization. The study observes that in all the three nanowires, the square shaped atomic configuration is the most stable one. The calculated electronic band structures and density of states profile confirms the semiconducting behaviour of linear and zigzag shaped nanowires of AlP, whereas for AlAs and AlSb nanowires are metallic. The ground state properties have also been analysed in terms of bond length, bulk modulus and pressure derivative for all the nanowires along with their bulk counterpart. The lower bulk modulus of all the linear shaped geometries of AlX nanowires in comparison to its bulk counterpart indicates softening of the material at reduced dimension. -- Graphical abstract: Figure-Electronic band structure of zigzag shaped AlP nanowire. The present electronic band structures of zigzag and linear shaped AlP nanowires are showing a clear band gap at Γ point, however others (AlAs and AlSb) in zigzag as well as in linear shape show metallic behaviour. Highlights: ► Stability analysis of five geometries of AlX (X = P, As and Sb) nanowires studied. ► Square shaped geometry of AlX nanowires is most stable. ► Linear and zigzag shaped AlP nanowires are semiconducting. ► Bulk moduli of all the linear nanowires are lower than their bulk counterpart. ► Lower bulk moduli defends the softening of material.

  1. Ab initio study of the elastic properties of sodium chloride at high pressure

    International Nuclear Information System (INIS)

    Liu Lei; Bi Yan; Xu Jian; Chen Xiangrong

    2010-01-01

    The equation of state and elastic properties for B1- and B2-NaCl up to 160 GPa have been studied by using the density functional simulation within the generalized gradient approximation (GGA). The calculated lattice constants of NaCl agree well with experimental values in a precision of 0.1% over the pressure range studied. It is found that the cell volume decreases 5.5% at the phase transition point. All three independent elastic stiffness coefficients, c 11 , c 12 and c 44 for B1- and B2-NaCl are evaluated by a calculated stress tensor which was generated by forcing small strain to the optimized unit cell. The calculated zero-pressure elastic moduli, wave velocities, and their initial pressure dependences of B1-NaCl are in excellent agreement with experiments. Systematic investigation on the elasticity of NaCl has been done through four parameters, the Zener anisotropy ratio (A Z ), the acoustic anisotropy factor (A a ), the Cauchy deviation (δ), and the normalized elastic constants (c ij '). With the pressure, the Zener anisotropy ratio A Z decreases in the B1-phase, but increases in the B2-phase and reaches 1 at about 174 GPa, it suggests that NaCl would become elastic isotropic at this pressure range. The acoustic anisotropy factor A a shows the similar pressure behavior as A Z . The Cauchy deviation (δ)) increases with pressures, it demonstrates that in the interatomic interaction, the many-body contribution becomes more important at higher pressures. A discussion on the normalized elastic constants is also presented.

  2. Unique electron transport in ultrathin black phosphorene: Ab-initio study

    International Nuclear Information System (INIS)

    Srivastava, Anurag; Khan, Md. Shahzad; Gupta, Sanjeev Kumar; Pandey, Ravindra

    2015-01-01

    Graphical abstract: Charge transfer configuration for NH 3 and NO 2 adsorbed 2D black-phospherene. - Highlights: • Ultrathin black phosphorene has been investigated, in terms of its optical and ballistic quantum transport properties. • The device performance subtaintially increases in armchair direction of black phosphorene. • Maximum reflectivity (43%) is observed at 1.85 eV (670 nm) and the reflective spectrum dispersed in visible range. • At low bias semiconducting and higher bias ohmic nature pointing black phospherene a promising material for high perfomrance device applications. • For NO 2 gas, this quasi 2D-black phosphorene surface shows strong affinity followed with substantial charge tranfer. - Abstract: We present first principle structural, electronic, optical and transport analysis of black phosphorene a 2D layered material. The studied configuration shows semiconducting nature and the states around the Fermi energy are mainly contributed by the p-orbitals of atoms. In optical properties, the reflective spectrum is approximately dispersed in visible range suggesting that this 2D-nanostructure can be considered as shielding for visible region. Due to the anisotropy of the electronic structure of black phosphorene, the device performance is subtaintially preferable in armchair direction. Zero-bias transmission shows no conductance channel near Fermi level but in far region prominent spectra for the same is observed for black-phospherene. The studied configurations show non-linear current–voltage (I–V) characteristics. The sensitivity for NH 3 and NO 2 gas molecule is explored using electronic and current–voltage (I–V) characteristics. Investigations show that the black phosphorene has strong affinity for electron seeking NO 2 molecule, thus providing an opportunity for its sensor application.

  3. Unique electron transport in ultrathin black phosphorene: Ab-initio study

    Energy Technology Data Exchange (ETDEWEB)

    Srivastava, Anurag, E-mail: profanurag@gmail.com [Advanced Materials Research Group, Computational Nanoscience & Technology Lab, ABV-Indian Institute of Information Technology and Management, Gwalior (M.P.) 474010 India (India); Khan, Md. Shahzad [Advanced Materials Research Group, Computational Nanoscience & Technology Lab, ABV-Indian Institute of Information Technology and Management, Gwalior (M.P.) 474010 India (India); Gupta, Sanjeev Kumar [Department of Physics, St. Xavier' s College, Ahmedabad 380009 (India); Pandey, Ravindra [Michigan Technological University, 1400 Townsend Drive, Houghton, MI 49931 (United States)

    2015-11-30

    Graphical abstract: Charge transfer configuration for NH{sub 3} and NO{sub 2} adsorbed 2D black-phospherene. - Highlights: • Ultrathin black phosphorene has been investigated, in terms of its optical and ballistic quantum transport properties. • The device performance subtaintially increases in armchair direction of black phosphorene. • Maximum reflectivity (43%) is observed at 1.85 eV (670 nm) and the reflective spectrum dispersed in visible range. • At low bias semiconducting and higher bias ohmic nature pointing black phospherene a promising material for high perfomrance device applications. • For NO{sub 2} gas, this quasi 2D-black phosphorene surface shows strong affinity followed with substantial charge tranfer. - Abstract: We present first principle structural, electronic, optical and transport analysis of black phosphorene a 2D layered material. The studied configuration shows semiconducting nature and the states around the Fermi energy are mainly contributed by the p-orbitals of atoms. In optical properties, the reflective spectrum is approximately dispersed in visible range suggesting that this 2D-nanostructure can be considered as shielding for visible region. Due to the anisotropy of the electronic structure of black phosphorene, the device performance is subtaintially preferable in armchair direction. Zero-bias transmission shows no conductance channel near Fermi level but in far region prominent spectra for the same is observed for black-phospherene. The studied configurations show non-linear current–voltage (I–V) characteristics. The sensitivity for NH{sub 3} and NO{sub 2} gas molecule is explored using electronic and current–voltage (I–V) characteristics. Investigations show that the black phosphorene has strong affinity for electron seeking NO{sub 2} molecule, thus providing an opportunity for its sensor application.

  4. Ab initio study of adsorption and diffusion of lithium on transition metal dichalcogenide monolayers

    Directory of Open Access Journals (Sweden)

    Xiaoli Sun

    2017-12-01

    Full Text Available Using first principles calculations, we studied the stability and electronic properties of transition metal dichalcogenide monolayers of the type MX2 (M = Ti, Zr, Hf, V, Nb, Ta, Mo, Cr, W; X= S, Se, Te. The adsorption and diffusion of lithium on the stable MX2 phase was also investigated for potential application as an anode for lithium ion batteries. Some of these compounds were found to be stable in the 2H phase and some are in the 1T or 1T' phase, but only a few of them were stable in both 2H/1T or 2H/1T' phases. The results show that lithium is energetically favourable for adsorption on MX2 monolayers, which can be semiconductors with a narrow bandgap and metallic materials. Lithium cannot be adsorbed onto 2H-WS2 and 2H-WSe2, which have large bandgaps of 1.66 and 1.96 eV, respectively. The diffusion energy barrier is in the range between 0.17 and 0.64 eV for lithium on MX2 monolayers, while for most of the materials it was found to be around 0.25 eV. Therefore, this work illustrated that most of the MX2 monolayers explored in this work can be used as promising anode materials for lithium ion batteries.

  5. Ab initio study of adsorption and diffusion of lithium on transition metal dichalcogenide monolayers.

    Science.gov (United States)

    Sun, Xiaoli; Wang, Zhiguo

    2017-01-01

    Using first principles calculations, we studied the stability and electronic properties of transition metal dichalcogenide monolayers of the type MX 2 (M = Ti, Zr, Hf, V, Nb, Ta, Mo, Cr, W; X= S, Se, Te). The adsorption and diffusion of lithium on the stable MX 2 phase was also investigated for potential application as an anode for lithium ion batteries. Some of these compounds were found to be stable in the 2H phase and some are in the 1T or 1T' phase, but only a few of them were stable in both 2H/1T or 2H/1T' phases. The results show that lithium is energetically favourable for adsorption on MX 2 monolayers, which can be semiconductors with a narrow bandgap and metallic materials. Lithium cannot be adsorbed onto 2H-WS 2 and 2H-WSe 2 , which have large bandgaps of 1.66 and 1.96 eV, respectively. The diffusion energy barrier is in the range between 0.17 and 0.64 eV for lithium on MX 2 monolayers, while for most of the materials it was found to be around 0.25 eV. Therefore, this work illustrated that most of the MX 2 monolayers explored in this work can be used as promising anode materials for lithium ion batteries.

  6. Ab Initio Study of Hydration and Proton Dissociation in Ionomer Membranes

    International Nuclear Information System (INIS)

    Idupulapati, Nagesh B.; Devanathan, Ramaswami; Dupuis, Michel

    2010-01-01

    We present a comparative study of proton dissociation in various functional acidic units that are promising candidates as building blocks for polymeric electrolyte membranes. Minimum energy structures for four acidic moieties with clusters of 1-6 water molecules were determined using density functional theory at the B3LYP/6-311G** level starting from chemically rational initial configurations. The perfluoro sulfonyl imide acid group (CF3CF2SO2NHSO2CF3) was observed to be the strongest acid, due to the substantial electron withdrawing effect of both fluorocarbon groups. The hydrophilic functional group (CH3OC6H3OCH3C6H4SO3H) of sulfonated polyetherether ketone (SPEEK) membrane was found to be the strongest base with the acidic proton dissociation requiring the addition of six water molecules and the hydrated proton being more tightly bound to the conjugate base. Even though both perfluoro sulfonyl imides and sulfonic acids (hydrophilic functional groups for sulfonyl imide and Nafion ionomers respectively) required only three water molecules to exhibit spontaneous proton dissociation, the largest possible solvent-separated hydronium ion was attained only for the sulfonyl imide moiety. These results provide a scientific basis for understanding the improved conductivity of perfluorinated sulfonyl imide-based membranes relative to that of the widely-used Nafion membrane.

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

    International Nuclear Information System (INIS)

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

    2015-01-01

    New valence electron photoelectron spectra of iodobenzene obtained using synchrotron radiation have been recorded. Ionization energies (IEs) determined using multi-configuration SCF calculation (MCSCF) procedures confirmed the adiabatic IE order as: X 2 B 1 studies. The calculated Franck-Condon vibrational spectral envelopes, including hot band contributions, for the first four ionic states reproduce the observed peak positions and intensities with reasonable accuracy. In order to simulate the observed spectra, different bandwidths are required for different states. The increase in the required bandwidths for the A 2 A 2 and B 2 B 2 states is attributed to internal conversion to lower-lying states. The presence of relatively high intensity sequence bands leads to asymmetry of each of the X 2 B 1 state bands

  8. Ab initio study of F- and Cl-functionalized single wall carbon nanotubes

    International Nuclear Information System (INIS)

    Pan, H; Feng, Y P; Lin, J Y

    2006-01-01

    First-principles calculations were carried out to study the functionalization of single wall carbon nanotubes by the chemical absorption of F and Cl atoms. Our results confirmed that the band gap of semiconductor zigzag carbon nanotubes is reduced on addition of F or Cl atoms on the walls of the nanotubes. For metallic armchair nanotubes, the doubly degenerate states crossing the Fermi level were separated by the introduction of F or Cl atoms. An additional energy level emerged near the Fermi level, due to coupling between the carbon nanotube and the F or Cl atom. For zigzag nanotubes, charge transfers of 0.27e from the tube to the Cl atom and of 0.41e to the F atom took place, while for armchair nanotubes, the charge transfers from the nanotube to Cl and F are 0.25 and 0.42e, respectively. The Cl-C and F-C bond lengths were found to be 2.09 and 1.49 A, respectively. The systems show semiconducting behaviour when charged with one electron per halogen atom, but remain metallic under hole injection, regardless of the chirality of the carbon nanotubes

  9. Ab initio study on the electronic transport properties of carbon nanotube intramolecular junctions

    Energy Technology Data Exchange (ETDEWEB)

    Wang, R.N. [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031 (China); Graduate School of the Chinese Academy of Sciences, 19A Yu Quan Rd, Beijing 100049 (China); Zheng, X.H.; Zeng, Z. [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031 (China); Song, L.L. [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031 (China); Graduate School of the Chinese Academy of Sciences, 19A Yu Quan Rd, Beijing 100049 (China); School of Electronic Science and Applied Physics, Hefei University of Technology, Hefei 230009 (China)

    2011-12-15

    The effects of electron doping and molecule adsorption on the electronic transport properties of carbon nanotube (CNT) junctions CNT(3,3)/n-CNT(6,0)/CNT(3,3) (n = 1-5) are simulated by first-principles calculations combined with a non-equilibrium Green's function technique. The doping effects are investigated by N substitution for the carbon atom while the molecule adsorption effects are studied by adsorbing a H{sub 2}O molecule or an OH group on the top of one carbon atom, respectively. The transmission function around the Fermi level is highly dependent on the doping or adsorption site. The effects are negligible when the site is at the interface, while it always forms a scattering barrier which causes a valley of the transmission spectra around the Fermi level when the doping/adsorption site is inside the sandwiched CNT(6,0). The conductance of CNT intramolecular junctions is very sensitive to the environment, which may provide potential of application in future nanoelectronic devices and gas sensors. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  10. High-pressure polymorphs of TbVO4: A Raman and ab initio study

    International Nuclear Information System (INIS)

    Errandonea, D.; Manjón, F.J.; Muñoz, A.; Rodríguez-Hernández, P.; Panchal, V.; Achary, S.N.; Tyagi, A.K.

    2013-01-01

    Highlights: •Three phase transitions are induced in zircon-type TbVO4 at 6.7, 26.7, and 34.4 GPa. •The proposed structural sequence is zircon-scheelite-fergusonite-orthorhombic Cmca. •Scheelite phase is metaestable after decompression. •The equation of states for all phases is reported. •Compressibility is enhanced in the Cmca phase due to f-electron delocalization. -- Abstract: Raman measurements on TbVO 4 show the occurrence of three pressure-induced phase transitions. The first one, an irreversible transition from the zircon to the scheelite structure, occurs beyond 6.7 GPa. In addition, two reversible transformations take place at 26.7 and 34.4 GPa. The last transition was never reported before. The experimental findings are supported by structural and lattice-dynamics calculations that helped us to identify the post-scheelite phase as a monoclinic fergusonite structure. According to the calculations, the third transition involves a symmetry increase. An orthorhombic structure is proposed for the phase found above 34.4 GPa. The results have been compared with previous studies in TbVO 4 and discussed in comparison with related compounds. The calculated equations of state are reported for the different polymorphs of TbVO 4 . A compressibility increase is caused by the third transition. It is associated to a bond-strength decrease, which is related to a coordination increase and a delocalization of Tb f-electrons

  11. Electronic and optical properties of graphene-like InAs: An ab initio study

    Science.gov (United States)

    Sohrabi, Leila; Boochani, Arash; Ali Sebt, S.; Mohammad Elahi, S.

    2018-03-01

    The present work initially investigates structural, optical, and electronic properties of graphene-like InAs by using the full potential linear augmented plane wave method in the framework of density functional theory and is then compared with the bulk Indium Arsenide in the wurtzite phase. The lattice parameters are optimized with GGA-PBE and LDA approximations for both 2D- and 3D-InAs. In order to study the electronic properties of graphene-like InAs and bulk InAs in the wurtzite phase, the band gap is calculated by GGA-PBG and GGA-EV approximations. Moreover, optical parameters of graphene-like InAs and bulk InAs such as the real and imaginary parts of dielectric function, electron energy loss function, refractivity, extinction and absorption coefficients, and optical conductivity are investigated. Plasmonic frequencies of 2D- and 3D-InAs are also calculated by using maximum electron energy loss function and the roots of the real part of the dielectric function.

  12. Ab initio simulation study of defect assisted Zener tunneling in GaAs diode

    Science.gov (United States)

    Lu, Juan; Fan, Zhi-Qiang; Gong, Jian; Jiang, Xiang-Wei

    2017-06-01

    The band to band tunneling of defective GaAs nano-junction is studied by using the non-equilibrium Green's function formalism with density functional theory. Aiming at performance improvement, two types of defect-induced transport behaviors are reported in this work. By examining the partial density of states of the system, we find the substitutional defect OAs that locates in the middle of tunneling region will introduce band-gap states, which can be used as stepping stones to increase the tunneling current nearly 3 times higher at large bias voltage (Vb≥0.3V). Another type of defects SeAs and VGa (Ga vacancy) create donor and acceptor states at the edge of conduction band (CB) and valence band (VB)respectively, which can change the band bending of the junction as well as increase the tunneling field obtaining a 1.5 times higher ON current. This provides an effective defect engineering approach for next generation TFET device design.

  13. Flexibility of "polyunsaturated fatty acid chains" and peptide backbones: A comparative ab initio study.

    Science.gov (United States)

    Law, Jacqueline M S; Setiadi, David H; Chass, Gregory A; Csizmadia, Imre G; Viskolcz, Béla

    2005-01-27

    The conformational properties of omega-3 type of polyunsaturated fatty acid (PUFA) chains and their fragments were studied using Hartree-Fock (RHF/3-21G) and DFT (B3LYP/6-31G(d)) methods. Comparisons between a unit (U) fragment of the PUFA chain and a mono N-Ac-glycine-NHMe residue show that both structures have the same sequence of sp2-sp3-sp2 atoms. The flexibility of PUFA originates in the internal rotation about the above pairs of sigma bonds. Therefore, potential energy surfaces (PESs) were generated by a scan around the terminal dihedral angles (phi t1 and phi t2) as well as the phi 1 and psi 1 dihedrals of both 1U congeners (Me-CHCH-CH2-CHCHMe and MeCONH-CH2-CONHMe) at the RHF/3-21G level of theory. An interesting similarity was found in the flexibility between the cis allylic structure and the trans peptide models. A flat landscape can be seen in the cis 1U (hepta-2,5-diene) surface, implying that several conformations are expected to be found in this (PES). An exhaustive search carried out on the 1U and 2U models revealed that straight chain structures such as trans and cis beta (phi 1 approximately psi 1 approximately 120 degrees; phi 2 approximately psi 2 approximately -120 degrees) or trans and cis extended (phi 1 approximately psi 1 approximately phi 2 approximately psi 2 approximately 120 degrees) can be formed at the lowest energy of both isomers. However, forming helical structures, such as trans helix (phi 1 approximately -120 degrees, psi 1 approximately 12 degrees; phi 2 approximately -120 degrees, psi 2 approximately 12 degrees) or cis helix (phi 1 approximately -130 degrees, psi 1 approximately 90 degrees; phi 2 approximately -145 degrees, psi 2 approximately 90 degrees) will require more energy. These six conformations, found in 2U, were selected to construct longer chains such as 3U, 4U, 5U, and 6U to obtain the thermochemistry of secondary structures. The variation in the extension or compression of the chain length turned out to be a factor

  14. High-pressure polymorphs of TbVO{sub 4}: A Raman and ab initio study

    Energy Technology Data Exchange (ETDEWEB)

    Errandonea, D., E-mail: daniel.errandonea@uv.es [Departamento de Física Aplicada-ICMUV, Universidad de Valencia, MALTA Consolider Team, Edificio de Investigación, C/Dr. Moliner 50, Burjassot, 46100 Valencia (Spain); Manjón, F.J. [Instituto de Diseño para la Fabricación y Producción Automatizada, MALTA Consolider Team, Universidad Politécnica de Valencia, Camino de Vera s/n, 46022 Valencia (Spain); Muñoz, A.; Rodríguez-Hernández, P. [Departamento de Física Fundamental II, Instituto de Materiales y Nanotecnología, MALTA Consolider Team, Universidad de La Laguna, La Laguna 38205, Tenerife (Spain); Panchal, V. [Departamento de Física Aplicada-ICMUV, Universidad de Valencia, MALTA Consolider Team, Edificio de Investigación, C/Dr. Moliner 50, Burjassot, 46100 Valencia (Spain); Royal College of Arts, Science and Commerce, Mira Road, Mumbai 401 107 (India); Achary, S.N.; Tyagi, A.K. [Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085 (India)

    2013-11-15

    Highlights: •Three phase transitions are induced in zircon-type TbVO4 at 6.7, 26.7, and 34.4 GPa. •The proposed structural sequence is zircon-scheelite-fergusonite-orthorhombic Cmca. •Scheelite phase is metaestable after decompression. •The equation of states for all phases is reported. •Compressibility is enhanced in the Cmca phase due to f-electron delocalization. -- Abstract: Raman measurements on TbVO{sub 4} show the occurrence of three pressure-induced phase transitions. The first one, an irreversible transition from the zircon to the scheelite structure, occurs beyond 6.7 GPa. In addition, two reversible transformations take place at 26.7 and 34.4 GPa. The last transition was never reported before. The experimental findings are supported by structural and lattice-dynamics calculations that helped us to identify the post-scheelite phase as a monoclinic fergusonite structure. According to the calculations, the third transition involves a symmetry increase. An orthorhombic structure is proposed for the phase found above 34.4 GPa. The results have been compared with previous studies in TbVO{sub 4} and discussed in comparison with related compounds. The calculated equations of state are reported for the different polymorphs of TbVO{sub 4}. A compressibility increase is caused by the third transition. It is associated to a bond-strength decrease, which is related to a coordination increase and a delocalization of Tb f-electrons.

  15. Ab initio study of the lattice dynamics of CsNiF3

    International Nuclear Information System (INIS)

    Legut, Dominik; Wdowik, Urszula D

    2010-01-01

    Lattice dynamics of the quasi-one-dimensional ferromagnetic chain-like structure of CsNiF 3 has been studied using density functional theory and the direct method. Investigations were limited to the harmonic approximation. Antiferromagnetic and ferromagnetic spin orderings on Ni atoms were considered. It is found that phonons remain practically insensitive to the type of magnetic arrangement. The difference in the calculated Helmholtz free energies between antiferro- and ferromagnetic ordering is too small to provide sufficient information on the preference of the type of magnetic ordering in CsNiF 3 . Calculated acoustic phonons agree very well with the inelastic neutron scattering experiments, while the optical phonons remain in an acceptable agreement with Raman and infrared measurements. Comparison of the experimental heat capacity and the calculated lattice contribution to the heat capacity shows that the magnetic contribution is negligible above 20-30 K. Thermal motions of particular atoms in CsNiF 3 crystals are highly anisotropic with surprisingly high mean-squared vibrations of Cs ions which exceed thermal vibrations of very light F ions. Such a behavior could be explained by the difference of the force constants between the Cs and F sites which overcomes the effect associated with the difference between masses of Cs and F ions. Nickel cations reveal very high on-site force constants, i.e. very low amplitudes of thermal vibrations, as they form some kind of rigid rods in the CsNiF 3 lattice. Calculated elastic constants indicate CsNiF 3 to be rather a soft material.

  16. Characterization of Ag adsorption on TiC(001) substrate: an ab initio study

    International Nuclear Information System (INIS)

    Ma Shangyi; Wang Shaoqing

    2008-01-01

    Ag adsorptions at 0.25–3 monolayer (ML) coverage on a perfect TiC(001) surface and at 0.25 ML coverage on C vacancy are separately investigated by using the pseudopotential-based density functional theory. The preferential adsorption sites and the adsorption-induced modifications of electronic structures of both the substrate and adsorbate are analysed. Through the analyses of adsorption energy, ideal work of separation, interface distance, projected local density of states, and the difference electron density, the characteristic evolution of the adatom-surface bonding as a function of the amount of deposited silver is studied. The nature of the Ag/TiC bonding changes as the coverage increases from 0.25 to 3 MLs. Unlike physisorption in an Ag/MgO system, polar covalent component contributes to the Ag/TiC interfacial adhesion in most cases, however, for the case of 1–3 ML coverage, an additional electrostatic interaction between the absorption layer and the substrate should be taken into account. The value of ideal work of separation, 1.55 J/m 2 for a 3-ML-thick adlayer accords well with other calculations. The calculations predict that Ag does not wet TiC(001) surface and prefers a three-dimensional growth mode in the absence of kinetic factor. This work reports on a clear site and coverage dependence of the measurable physical parameters, which would benefit the understanding of Ag/TiC (001) interface and the analysis of experimental data. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  17. Conformers and non-covalent interactions studied by laser spectroscopies and ab initio calculations

    Energy Technology Data Exchange (ETDEWEB)

    Ullrich, Susanne

    2001-07-01

    The model peptides, formanilide and acetanilide, and their weakly bound complexes were studied in the gas-phase using resonance enhanced multi-photon ionisation (REMPI) and zero electron kinetic energy (ZEKE) photoelectron spectroscopy. Both, cis- and trans-isomers of formanilide, were observed under molecular beam conditions. Trans-formanilide displayed predominantly in-plane vibrational excitation indicative of a planar geometry with modest geometry changes upon excitation and ionisation. In cis-formanilide the side-chain is twisted compared to the phenyl plane in the S{sub 0} state, but planar in the S{sub 1} and D{sub 0} states, revealed in characteristic side-chain torsional and out-of-plane bending excitations. Additionally, the ZEKE spectra provide evidence that excess cationic charge is delocalised from the aromatic ring to the side chain. The work on trans-formanilide was extended to its van der Waals complex with Argon with the purpose of investigating the torsional potential of the side-chain and probing charge delocalisation. Complexation of amides with water is of considerable interest since water is not only present as a bulk solvent surrounding a peptide but also attached to specific binding sites in its interior. Evidence was found for the existence of a NH- and CO-bound isomer of trans-formanilide in the neutral, S{sub 0} and S{sub 1}, states, with the ZEKE spectrum of the cationic 'CO-bound' complex indicating a strong preference for the NH binding site. (author)

  18. Ab-initio study of C and O impurities in uranium nitride

    Energy Technology Data Exchange (ETDEWEB)

    Lopes, Denise Adorno; Claisse, Antoine; Olsson, Pär, E-mail: polsson@kth.se

    2016-09-15

    Uranium nitride (UN) has been considered a potential fuel for Generation IV (GEN-IV) nuclear reactors as well as a possible new fuel for Light Water Reactors (LWR), which would permit an extension of the fuel residence time in the reactor. Carbon and oxygen impurities play a key role in the UN microstructure, influencing important parameters such as creep, swelling, gas release under irradiation, compatibility with structural steel and coolants, and thermal stability. In this work, a systematic study of the electronic structure of UN containing C and O impurities using first-principles calculations by the Density Functional Theory (DFT) method is presented. In order to describe accurately the localized U 5f electrons, the DFT + U formalism was adopted. Moreover, to avoid convergence toward metastable states, the Occupation Matrix Control (OMC) methodology was applied. The incorporation of C and O in the N-vacancy is found to be energetically favorable. In addition, only for O, the incorporation in the interstitial position is energetically possible, showing some degree of solubility for this element in this site. The binding energies show that the pairs (C−N{sub vac}) and (O−N{sub vac}) interact much further than the other defects, which indicate the possible occurrence of vacancy drag phenomena and clustering of these impurities in grain boundaries, dislocations and free surfaces. The migration energy of an impurity by single N-vacancy show that C and O employ different paths during diffusion. Oxygen migration requires significantly lower energy than carbon. This fact is due to flexibility in the U−O chemical bonds, which bend during the diffusion forming a pseudo UO{sub 2} coordination. On the other hand, C and N have a directional and inflexible chemical bond with uranium; always requiring the octahedral coordination. These findings provide detailed insight into how these impurities behave in the UN matrix, and can be of great interest for assisting the

  19. Ab-initio study of C and O impurities in uranium nitride

    International Nuclear Information System (INIS)

    Lopes, Denise Adorno; Claisse, Antoine; Olsson, Pär

    2016-01-01

    Uranium nitride (UN) has been considered a potential fuel for Generation IV (GEN-IV) nuclear reactors as well as a possible new fuel for Light Water Reactors (LWR), which would permit an extension of the fuel residence time in the reactor. Carbon and oxygen impurities play a key role in the UN microstructure, influencing important parameters such as creep, swelling, gas release under irradiation, compatibility with structural steel and coolants, and thermal stability. In this work, a systematic study of the electronic structure of UN containing C and O impurities using first-principles calculations by the Density Functional Theory (DFT) method is presented. In order to describe accurately the localized U 5f electrons, the DFT + U formalism was adopted. Moreover, to avoid convergence toward metastable states, the Occupation Matrix Control (OMC) methodology was applied. The incorporation of C and O in the N-vacancy is found to be energetically favorable. In addition, only for O, the incorporation in the interstitial position is energetically possible, showing some degree of solubility for this element in this site. The binding energies show that the pairs (C−N_v_a_c) and (O−N_v_a_c) interact much further than the other defects, which indicate the possible occurrence of vacancy drag phenomena and clustering of these impurities in grain boundaries, dislocations and free surfaces. The migration energy of an impurity by single N-vacancy show that C and O employ different paths during diffusion. Oxygen migration requires significantly lower energy than carbon. This fact is due to flexibility in the U−O chemical bonds, which bend during the diffusion forming a pseudo UO_2 coordination. On the other hand, C and N have a directional and inflexible chemical bond with uranium; always requiring the octahedral coordination. These findings provide detailed insight into how these impurities behave in the UN matrix, and can be of great interest for assisting the development

  20. Structural, electronic and magnetic properties of small bimetallic zirconium–palladium clusters: Ab initio study

    International Nuclear Information System (INIS)

    Bezi Javan, Masoud

    2015-01-01

    Highlights: • Electronic and magnetic properties of small Zr n Pd m (n + m ⩽ 5) have been investigated. • Binding energies of the Zr n clusters are significantly higher than Pd n clusters. • Binding energy of the Pd n clusters increase with substituting one or more Zr atom. • HOMO–LUMO gap of the Zr n Pd m clusters increase in comparison with pure states. - Abstract: Structural, electronic and magnetic properties of small bimetallic zirconium–palladium clusters, Zr n Pd m (n + m ⩽ 5), have been investigated using density functional theory with considering generalized gradient approximation and PBE functional. We have determined the ground state conformations of the bimetallic zirconium–palladium clusters by substitution of Zr and Pd atoms in the optimized lowest energy structures of pure zirconium and palladium clusters. Results reveal that binding energies of the pure Zr n clusters are significantly higher than Pd n clusters with the same number of atoms. Also it is found that binding energy of the Zr n and Pd n clusters increase with growth of the number of consisting atoms in the clusters. Results indicate that, for both Zr n and Pd n clusters the binding energy of planar forms is lower than three-dimensional structures. We have also found that the binding energy of the Pd n clusters increase with substituting one or more Zr atoms in these clusters. We have also studied the HOMO–LUMO energy gap and magnetic moment of the pure and combined Zr and Pd clusters. The energy gap analysis of the pure and combined Pd and Zr clusters show that in generally the HOMO–LUMO gap of the bimetallic Zr n Pd m clusters increase in comparison with their corresponding pure clusters with the same number of atoms. According to the spin polarization DFT calculations all of the Zr n Pd m (n + m ⩽ 5) have net magnetic moments as instance the Zr 2 , Pd 2 and ZrPd clusters show a total magnetic moment value of 2 μ B . Some more discussions around charge population

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

    Science.gov (United States)

    Clerc, Daryl G

    2016-07-21

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

  2. Ab initio multiple spawning dynamics study of dimethylnitramine and dimethylnitramine-Fe complex to model their ultrafast nonadiabatic chemistry.

    Science.gov (United States)

    Bera, Anupam; Ghosh, Jayanta; Bhattacharya, Atanu

    2017-07-28

    Conical intersections are now firmly established to be the key features in the excited electronic state processes of polyatomic energetic molecules. In the present work, we have explored conical intersection-mediated nonadiabatic chemical dynamics of a simple analogue nitramine molecule, dimethylnitramine (DMNA, containing one N-NO 2 energetic group), and its complex with an iron atom (DMNA-Fe). For this task, we have used the ab initio multiple spawning (AIMS) dynamics simulation at the state averaged-complete active space self-consistent field(8,5)/6-31G(d) level of theory. We have found that DMNA relaxes back to the ground (S 0 ) state following electronic excitation to the S 1 excited state [which is an (n,π*) excited state] with a time constant of approximately 40 fs. This AIMS result is in very good agreement with the previous surface hopping-result and femtosecond laser spectroscopy result. DMNA does not dissociate during this fast internal conversion from the S 1 to the S 0 state. DMNA-Fe also undergoes extremely fast relaxation from the upper S 1 state to the S 0 state; however, this relaxation pathway is dissociative in nature. DMNA-Fe undergoes initial Fe-O, N-O, and N-N bond dissociations during relaxation from the upper S 1 state to the ground S 0 state through the respective conical intersection. The AIMS simulation reveals the branching ratio of these three channels as N-N:Fe-O:N-O = 6:3:1 (based on 100 independent simulations). Furthermore, the AIMS simulation reveals that the Fe-O bond dissociation channel exhibits the fastest (time constant 24 fs) relaxation, while the N-N bond dissociation pathway features the slowest (time constant 128 fs) relaxation. An intermediate time constant (30 fs) is found for the N-O bond dissociation channel. This is the first nonadiabatic chemical dynamics study of metal-contained energetic molecules through conical intersections.

  3. Ab initio multiple spawning dynamics study of dimethylnitramine and dimethylnitramine-Fe complex to model their ultrafast nonadiabatic chemistry

    Science.gov (United States)

    Bera, Anupam; Ghosh, Jayanta; Bhattacharya, Atanu

    2017-07-01

    Conical intersections are now firmly established to be the key features in the excited electronic state processes of polyatomic energetic molecules. In the present work, we have explored conical intersection-mediated nonadiabatic chemical dynamics of a simple analogue nitramine molecule, dimethylnitramine (DMNA, containing one N-NO2 energetic group), and its complex with an iron atom (DMNA-Fe). For this task, we have used the ab initio multiple spawning (AIMS) dynamics simulation at the state averaged-complete active space self-consistent field(8,5)/6-31G(d) level of theory. We have found that DMNA relaxes back to the ground (S0) state following electronic excitation to the S1 excited state [which is an (n,π*) excited state] with a time constant of approximately 40 fs. This AIMS result is in very good agreement with the previous surface hopping-result and femtosecond laser spectroscopy result. DMNA does not dissociate during this fast internal conversion from the S1 to the S0 state. DMNA-Fe also undergoes extremely fast relaxation from the upper S1 state to the S0 state; however, this relaxation pathway is dissociative in nature. DMNA-Fe undergoes initial Fe-O, N-O, and N-N bond dissociations during relaxation from the upper S1 state to the ground S0 state through the respective conical intersection. The AIMS simulation reveals the branching ratio of these three channels as N-N:Fe-O:N-O = 6:3:1 (based on 100 independent simulations). Furthermore, the AIMS simulation reveals that the Fe-O bond dissociation channel exhibits the fastest (time constant 24 fs) relaxation, while the N-N bond dissociation pathway features the slowest (time constant 128 fs) relaxation. An intermediate time constant (30 fs) is found for the N-O bond dissociation channel. This is the first nonadiabatic chemical dynamics study of metal-contained energetic molecules through conical intersections.

  4. Electronic, optical and transport properties of {alpha}-, {beta}- and {gamma}-phases of spinel indium sulphide: An ab initio study

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Yamini, E-mail: sharma.yamini62@gmail.com [Department of Physics, Feroze Gandhi College, Rae Bareli 229001, U.P. (India); Srivastava, Pankaj [Department of Physics, Feroze Gandhi College, Rae Bareli 229001, U.P. (India)

    2012-08-15

    Spinel indium sulphide exists in three phases. The tetragonal {beta}-phase transforms to the cubic {alpha}-phase at 420 Degree-Sign C which further transforms to the trigonal {gamma}-phase at 754 Degree-Sign C. Due to wide energy bandgap, the phases of indium sulphide have possibilities of applications in photo-electrochemical solar cell devices as a replacement of toxic CdS. The electronic, optical and transport properties of the three phases have therefore been investigated using full potential linear augmented plane wave (FP-LAPW) + local orbitals (lo) scheme, in the framework of density functional theory (DFT) with generalized gradient approximation (GGA) for the purpose of exchange-correlation energy functional. We present the structure, energy bands and density of states (DOS) for {alpha}-, {beta}- and {gamma}-phases. The partial density of states (PDOS) of {beta}-In{sub 2}S{sub 3} is in good agreement with experiment and earlier ab initio calculations. To obtain the fundamental characteristics of these phases we have analysed their linear optical properties such as the dynamic dielectric function in the energy range of 0-15 eV. From the dynamic dielectric function it is seen that there is no directional anisotropy for {alpha}-phase since the longitudinal and transverse components are almost identical, however the {beta} and {gamma}-phases show birefringence. The optical absorption profiles clearly indicate that {beta}-phase has possibility of greater multiple direct and indirect interband transitions in the visible regions compared to the other phases. To study the existence of interesting thermoelectric properties, transport properties like electrical and thermal conductivities, Seebeck and Hall coefficients etc. are also calculated. Good agreements are found with the available experimental results. -- Highlights: Black-Right-Pointing-Pointer The electronic properties of phases of In{sub 2}S{sub 3} have been investigated. Black-Right-Pointing-Pointer The

  5. A review on ab initio studies of static, transport, and optical properties of polystyrene under extreme conditions for inertial confinement fusion applications

    Science.gov (United States)

    Hu, S. X.; Collins, L. A.; Boehly, T. R.; Ding, Y. H.; Radha, P. B.; Goncharov, V. N.; Karasiev, V. V.; Collins, G. W.; Regan, S. P.; Campbell, E. M.

    2018-05-01

    Polystyrene (CH), commonly known as "plastic," has been one of the widely used ablator materials for capsule designs in inertial confinement fusion (ICF). Knowing its precise properties under high-energy-density conditions is crucial to understanding and designing ICF implosions through radiation-hydrodynamic simulations. For this purpose, systematic ab initio studies on the static, transport, and optical properties of CH, in a wide range of density and temperature conditions (ρ = 0.1 to 100 g/cm3 and T = 103 to 4 × 106 K), have been conducted using quantum molecular dynamics (QMD) simulations based on the density functional theory. We have built several wide-ranging, self-consistent material-properties tables for CH, such as the first-principles equation of state, the QMD-based thermal conductivity (κQMD) and ionization, and the first-principles opacity table. This paper is devoted to providing a review on (1) what results were obtained from these systematic ab initio studies; (2) how these self-consistent results were compared with both traditional plasma-physics models and available experiments; and (3) how these first-principles-based properties of polystyrene affect the predictions of ICF target performance, through both 1-D and 2-D radiation-hydrodynamic simulations. In the warm dense regime, our ab initio results, which can significantly differ from predictions of traditional plasma-physics models, compared favorably with experiments. When incorporated into hydrocodes for ICF simulations, these first-principles material properties of CH have produced significant differences over traditional models in predicting 1-D/2-D target performance of ICF implosions on OMEGA and direct-drive-ignition designs for the National Ignition Facility. Finally, we will discuss the implications of these studies on the current small-margin ICF target designs using a CH ablator.

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

    International Nuclear Information System (INIS)

    Bankura, Arindam; Chandra, Amalendu

    2012-01-01

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

  7. Ab-initio study of the electronic structure of sup 1 sup 9 F implanted in GaAs and GaN crystals

    CERN Document Server

    Park, J H; Cho, H S; Shin, Y N

    1998-01-01

    We have studied the nuclear quadrupole interaction of a fluorine atom implanted in gallium arsenide and gallium nitride cluster models using the ab-initio Hartree-Fock theory. For the three possible fluorine sites in GaAs and GaN, we have determined the location of the implanted fluorine atom by using a self-consistent calculation, the electric field gradient at the implanted atom, and the electronic structure. Good agreement is found with experimental data wherever they are available. Predictions are made for the implanted fluorine site associated with the total energy and the electric field gradient which are expected to be measurable by a variety of experimental techniques.

  8. 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.

  9. Properties of the In{sub 2}O{sub 3}-Si interface: An ab initio study of a model geometry

    Energy Technology Data Exchange (ETDEWEB)

    Höffling, Benjamin; Bechstedt, Friedhelm [Institut für Festkörpertheorie und -optik, Friedrich-Schiller-Universität and European Theoretical Spectroscopy Facility (ETSF), Max-Wien-Platz 1, 07743 Jena (Germany)

    2014-05-15

    The In{sub 2}O{sub 3}(001)-Si(001) heterojunction is studied by means of the ab initio density functional theory, quasiparticle corrections, and the supercell method. We construct a model interface based on the idea of a coincidence lattice, only Si-O interface bonds and biaxially strained In{sub 2}O{sub 3}. The properties of the interface and their consequences for the junction are mainly described in terms of electronic band levels and charge redistribution. The results indicate a type II heterostructure caused by interface dipole alteration due to electron rearrangements.

  10. 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)

  11. 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.

  12. Sites and reactivity of sulfides in hydro-treatment catalysis: theoretical ab-initio study; Sites et reactivite des sulfures en catalyse d`hydrotraitement: etude theorique ab-initio

    Energy Technology Data Exchange (ETDEWEB)

    Raybaud, P.

    1998-10-28

    Ab-initio calculations within the DFT and GGA have been carried out in an attempt to understand better which property sets the activity of transition metal sulfides (TMS) in the hydro-desulfurization reaction (HDS), a most important step in the refining of crude oil. A systematic study of the structural cohesive and electronic properties of more than thirty bulk TMS has allowed us to find a new simple relationship between the experimental catalytic activities known in HDS, and the properly defined sulfur-metal (S-M) bond energy. On this volcano curve reminiscent of the Sabatier principles, ionic metallic sulfides (as Ni{sub 3}S{sub 2}, Ci{sub 9}S{sub 8}) exhibit the weakest bonds whereas ion-covalent semi-conductors (as MoS{sub 2}) exhibit the strongest bonds: the highest activities correspond to intermediate bond strengths (RuS{sub 2}). Our study of the electronic structure of the MoS{sub 2} edge surfaces has revealed acceptor surface states localized on Coordinatively Unsaturated Mo ions and the significance of those states for the activation of hetero-aromatic molecules like thiophene. On such surfaces, the energetic profiles we establish for the thiophene HDS reaction point out the surface anionic vacancy regeneration steps as rate determining. We have calculated the optimal positions of Co (Ni) in decoration on the MoS{sub 2} edge planes, in excellent agreement with available EXAFS data on real catalysts. Introducing the promoter Co (Ni) induces a lower optimal sulfur coverage and a lower surface S-M bond strength in proportion of the Co (Ni) coverage, and lower for Ni than for Co. Simplified energy profiles for the thiophene HDS reactions on promoted (101-bar 0) surfaces show that the C-S scission step is likely to become rate determining. Our results show altogether that bulk and surface S-M strengths in TMS systems show similar trends, insofar as they are primarily determined by the local electronic structure. (author)

  13. Dynamics of ligand exchange mechanism at Cu(II) in water: An ab initio quantum mechanical charge field molecular dynamics study with extended quantum mechanical region

    International Nuclear Information System (INIS)

    Moin, Syed Tarique; Hofer, Thomas S.; Weiss, Alexander K. H.; Rode, Bernd M.

    2013-01-01

    Ab initio quantum mechanical charge field molecular dynamics (QMCF-MD) were successfully applied to Cu(II) embedded in water to elucidate structure and to understand dynamics of ligand exchange mechanism. From the simulation studies, it was found that using an extended large quantum mechanical region including two shells of hydration is required for a better description of the dynamics of exchanging water molecules. The structural features characterized by radial distribution function, angular distribution function and other analytical parameters were consistent with experimental data. The major outcome of this study was the dynamics of exchange mechanism and reactions in the first hydration shell that could not be studied so far. The dynamical data such as mean residence time of the first shell water molecules and other relevant data from the simulations are close to the results determined experimentally. Another major characteristic of hydrated Cu(II) is the Jahn-Teller distortion which was also successfully reproduced, leading to the final conclusion that the dominating aqua complex is a 6-coordinated species. The ab initio QMCF-MD formalism proved again its capabilities of unraveling even ambiguous properties of hydrated species that are far difficult to explore by any conventional quantum mechanics/molecular mechanics (QM/MM) approach or experiment

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

    Science.gov (United States)

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

    2013-06-01

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

  15. Dynamics of ligand exchange mechanism at Cu(II) in water: an ab initio quantum mechanical charge field molecular dynamics study with extended quantum mechanical region.

    Science.gov (United States)

    Moin, Syed Tarique; Hofer, Thomas S; Weiss, Alexander K H; Rode, Bernd M

    2013-07-07

    Ab initio quantum mechanical charge field molecular dynamics (QMCF-MD) were successfully applied to Cu(II) embedded in water to elucidate structure and to understand dynamics of ligand exchange mechanism. From the simulation studies, it was found that using an extended large quantum mechanical region including two shells of hydration is required for a better description of the dynamics of exchanging water molecules. The structural features characterized by radial distribution function, angular distribution function and other analytical parameters were consistent with experimental data. The major outcome of this study was the dynamics of exchange mechanism and reactions in the first hydration shell that could not be studied so far. The dynamical data such as mean residence time of the first shell water molecules and other relevant data from the simulations are close to the results determined experimentally. Another major characteristic of hydrated Cu(II) is the Jahn-Teller distortion which was also successfully reproduced, leading to the final conclusion that the dominating aqua complex is a 6-coordinated species. The ab initio QMCF-MD formalism proved again its capabilities of unraveling even ambiguous properties of hydrated species that are far difficult to explore by any conventional quantum mechanics/molecular mechanics (QM/MM) approach or experiment.

  16. A computational ab initio study of surface diffusion of sulfur on the CdTe (111) surface

    Energy Technology Data Exchange (ETDEWEB)

    Naderi, Ebadollah, E-mail: enaderi42@gmail.com [Department of Physics, Savitribai Phule Pune University (SPPU), Pune-411007 (India); Ghaisas, S. V. [Department of Electronic Science, Savitribai Phule Pune University (SPPU), Pune-411007 (India)

    2016-08-15

    In order to discern the formation of epitaxial growth of CdS shell over CdTe nanocrystals, kinetics related to the initial stages of the growth of CdS on CdTe is investigated using ab-initio methods. We report diffusion of sulfur adatom on the CdTe (111) A-type (Cd-terminated) and B-type (Te-terminated) surfaces within the density functional theory (DFT). The barriers are computed by applying the climbing Nudge Elastic Band (c-NEB) method. From the results surface hopping emerges as the major mode of diffusion. In addition, there is a distinct contribution from kick-out type diffusion in which a CdTe surface atom is kicked out from its position and is replaced by the diffusing sulfur atom. Also, surface vacancy substitution contributes to the concomitant dynamics. There are sites on the B- type surface that are competitively close in terms of the binding energy to the lowest energy site of epitaxy on the surface. The kick-out process is more likely for B-type surface where a Te atom of the surface is displaced by a sulfur adatom. Further, on the B-type surface, subsurface migration of sulfur is indicated. Furthermore, the binding energies of S on CdTe reveal that on the A-type surface, epitaxial sites provide relatively higher binding energies and barriers than on B-type.

  17. Ab initio molecular dynamics study of thermite reaction at Al and CuO nano-interfaces at different temperatures

    Science.gov (United States)

    Tang, Cui-Ming; Chen, Xiao-Xu; Cheng, Xin-Lu; Zhang, Chao-Yang; Lu, Zhi-Peng

    2018-05-01

    The thermite reaction at Al/CuO nano-interfaces is investigated with ab initio molecular dynamics calculations in canonical ensemble at 500 K, 800 K, 1200 K and 1500 K, respectively. The reaction process and reaction products are analyzed in terms of chemical bonds, average charge, time constants and total potential energy. The activity of the reactants enhances with increasing temperature, which induces a faster thermite reaction. The alloy reaction obviously expands outward at Cu-rich interface of Al/CuO system, and the reaction between Al and O atoms obviously expands outward at O-rich interface as temperature increases. Different reaction products are found at the outermost layer of different interfaces in the Al/CuO system. In generally, the average charge of the outer layer aluminum atoms (i.e., Al1, Al2, Al5 and Al6) increases with temperature. The potential energy of Al/CuO system decreases significantly, which indicates that drastic exothermic reaction occurs at the Al/CuO system. This research enhances fundamental understanding in temperature effect on the thermite reaction at atomic level, which can potentially open new possibilities for its industrial application.

  18. A computational ab initio study of surface diffusion of sulfur on the CdTe (111) surface

    Science.gov (United States)

    Naderi, Ebadollah; Ghaisas, S. V.

    2016-08-01

    In order to discern the formation of epitaxial growth of CdS shell over CdTe nanocrystals, kinetics related to the initial stages of the growth of CdS on CdTe is investigated using ab-initio methods. We report diffusion of sulfur adatom on the CdTe (111) A-type (Cd-terminated) and B-type (Te-terminated) surfaces within the density functional theory (DFT). The barriers are computed by applying the climbing Nudge Elastic Band (c-NEB) method. From the results surface hopping emerges as the major mode of diffusion. In addition, there is a distinct contribution from kick-out type diffusion in which a CdTe surface atom is kicked out from its position and is replaced by the diffusing sulfur atom. Also, surface vacancy substitution contributes to the concomitant dynamics. There are sites on the B- type surface that are competitively close in terms of the binding energy to the lowest energy site of epitaxy on the surface. The kick-out process is more likely for B-type surface where a Te atom of the surface is displaced by a sulfur adatom. Further, on the B-type surface, subsurface migration of sulfur is indicated. Furthermore, the binding energies of S on CdTe reveal that on the A-type surface, epitaxial sites provide relatively higher binding energies and barriers than on B-type.

  19. Ab-initio study of structural and electronic properties of WS2/h-BN van der Waals heterostructure

    Science.gov (United States)

    Ghasemi majd, Zahra; Amiri, Peiman; Taghizadeh, Seyed Fardin

    2018-06-01

    First-principle calculations with different exchange-correlation functionals, including LDA, GGA, semi-empirical and ab-initio van der Waals in the forms of vdW-DF2B86R and vdW-DF2 were performed to evaluate the performance of different functionals in describing the bonding mechanism, adsorption energy and interlayer distance of WS2 monolayer on and between h-BN layers. The finding was that the vdW-DF2B86R seems to be the approach best lending itself to this purpose. In order to include the van der Waals (vdW) interactions in our calculations, we used the DFT-D2 and vdW methods, which gave rise to a physical adsorption with no net charge transfer between the WS2 layer and the corresponding substrates. In addition, we investigated the electronic and structural properties of WS2 and h-BN heterolayers, using vdW-DF2B86R functional. Based on density functional theory calculations, WS2 on and between h-BN layers showed a direct band gap at the K-point, which was experimentally observed.

  20. Static, dynamic and electronic properties of expanded fluid mercury in the metal-nonmetal transition range. An ab initio study

    International Nuclear Information System (INIS)

    CalderIn, L; Gonzalez, L E; Gonzalez, D J

    2011-01-01

    Fluid Hg undergoes a metal-nonmetal (M-NM) transition when expanded toward a density of around 9 g cm -3 . We have performed ab initio molecular dynamics simulations for several thermodynamic states around the M-NM transition range and the associated static, dynamic and electronic properties have been analyzed. The calculated static structure shows a good agreement with the available experimental data. It is found that the volume expansion decreases the number of nearest neighbors from 10 (near the triple point) to around 8 at the M-NM transition region. Moreover, these neighbors are arranged into two subshells and the decrease in the number of neighbors occurs in the inner subshell. The calculated dynamic structure factors agree fairly well with their experimental counterparts obtained by inelastic x-ray scattering experiments, which display inelastic side peaks. The derived dispersion relation exhibits some positive dispersion for all the states, although its value around the M-NM transition region is not as marked as suggested by the experiment. We have also calculated the electronic density of states, which shows the appearance of a gap at a density of around 8.3 g cm -3 . (paper)

  1. Mechanical and magneto-opto-electronic investigation of transition metal based fluoro-perovskites: An ab-initio DFT study

    Science.gov (United States)

    Erum, Nazia; Azhar Iqbal, Muhammad

    2017-09-01

    Detailed ab-initio calculations are performed to investigate structural, elastic, mechanical, magneto-electronic and optical properties of the KXF3 (X = V, Fe, Co, Ni) fluoro-perovskites using Full Potential Linearized Augmented Plane Wave (FP-LAPW) method within the framework of density functional theory (DFT). The calculated structural parameters by DFT and analytical methods are found consistent with the experimental results. From the elastic and mechanical properties, it can be inferred that these compounds are elastically stable and anisotropic while KCoF3 is harder than rest of the compounds. Furthermore, thermal behavior of these compounds is analyzed by calculating Debye temperature (θD). The calculated spin dependent magneto-electronic properties in these compounds reveal that exchange splitting is dominated by N-3d orbital. The stable magnetic phase optimizations verify the experimental observations at low temperature. Type of chemical bonding is analyzed with the help of variations in electron density difference distribution that is induced due to changes of the second cation. The linear optical properties are also discussed in terms of optical spectra. The present methodology represents an influential approach to calculate the whole set of mechanical and magneto-opto-electronic parameters, which would support to understand various physical phenomena and empower device engineers for implementing these materials in spintronic applications.

  2. Thermal decomposition of 1,3,3-trinitroazetidine (TNAZ): A density functional theory and ab initio study

    International Nuclear Information System (INIS)

    Veals, Jeffrey D.; Thompson, Donald L.

    2014-01-01

    Density functional theory and ab initio methods are employed to investigate decomposition pathways of 1,3,3-trinitroazetidine initiated by unimolecular loss of NO 2 or HONO. Geometry optimizations are performed using M06/cc-pVTZ and coupled-cluster (CC) theory with single, double, and perturbative triple excitations, CCSD(T), is used to calculate accurate single-point energies for those geometries. The CCSD(T)/cc-pVTZ energies for NO 2 elimination by N–N and C–N bond fission are, including zero-point energy (ZPE) corrections, 43.21 kcal/mol and 50.46 kcal/mol, respectively. The decomposition initiated by trans-HONO elimination can occur by a concerted H-atom and nitramine NO 2 group elimination or by a concerted H-atom and nitroalkyl NO 2 group elimination via barriers (at the CCSD(T)/cc-pVTZ level with ZPE corrections) of 47.00 kcal/mol and 48.27 kcal/mol, respectively. Thus, at the CCSD(T)/cc-pVTZ level, the ordering of these four decomposition steps from energetically most favored to least favored is: NO 2 elimination by N–N bond fission, HONO elimination involving the nitramine NO 2 group, HONO elimination involving a nitroalkyl NO 2 group, and finally NO 2 elimination by C–N bond fission

  3. The Raman Spectrum of the Squarate (C4O4-2 Anion: An Ab Initio Basis Set Dependence Study

    Directory of Open Access Journals (Sweden)

    Miranda Sandro G. de

    2002-01-01

    Full Text Available The Raman excitation profile of the squarate anion, C4O4-2 , was calculated using ab initio methods at the Hartree-Fock using Linear Response Theory (LRT for six excitation frequencies: 632.5, 514.5, 488.0, 457.9, 363.8 and 337.1 nm. Five basis set functions (6-31G*, 6-31+G*, cc-pVDZ, aug-cc-pVDZ and Sadlej's polarizability basis set were investigated aiming to evaluate the performance of the 6-31G* set for numerical convergence and computational cost in relation to the larger basis sets. All basis sets reproduce the main spectroscopic features of the Raman spectrum of this anion for the excitation interval investigated. The 6-31G* basis set presented, on average, the same accuracy of numerical results as the larger sets but at a fraction of the computational cost showing that it is suitable for the theoretical investigation of the squarate dianion and its complexes and derivatives.

  4. 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

  5. Thermal decomposition of 1,3,3-trinitroazetidine (TNAZ): A density functional theory and ab initio study

    Energy Technology Data Exchange (ETDEWEB)

    Veals, Jeffrey D.; Thompson, Donald L. [Department of Chemistry, University of Missouri-Columbia, Columbia, Missouri 65211 (United States)

    2014-04-21

    Density functional theory and ab initio methods are employed to investigate decomposition pathways of 1,3,3-trinitroazetidine initiated by unimolecular loss of NO{sub 2} or HONO. Geometry optimizations are performed using M06/cc-pVTZ and coupled-cluster (CC) theory with single, double, and perturbative triple excitations, CCSD(T), is used to calculate accurate single-point energies for those geometries. The CCSD(T)/cc-pVTZ energies for NO{sub 2} elimination by N–N and C–N bond fission are, including zero-point energy (ZPE) corrections, 43.21 kcal/mol and 50.46 kcal/mol, respectively. The decomposition initiated by trans-HONO elimination can occur by a concerted H-atom and nitramine NO{sub 2} group elimination or by a concerted H-atom and nitroalkyl NO{sub 2} group elimination via barriers (at the CCSD(T)/cc-pVTZ level with ZPE corrections) of 47.00 kcal/mol and 48.27 kcal/mol, respectively. Thus, at the CCSD(T)/cc-pVTZ level, the ordering of these four decomposition steps from energetically most favored to least favored is: NO{sub 2} elimination by N–N bond fission, HONO elimination involving the nitramine NO{sub 2} group, HONO elimination involving a nitroalkyl NO{sub 2} group, and finally NO{sub 2} elimination by C–N bond fission.

  6. Thermal decomposition of 1,3,3-trinitroazetidine (TNAZ): A density functional theory and ab initio study

    Science.gov (United States)

    Veals, Jeffrey D.; Thompson, Donald L.

    2014-04-01

    Density functional theory and ab initio methods are employed to investigate decomposition pathways of 1,3,3-trinitroazetidine initiated by unimolecular loss of NO2 or HONO. Geometry optimizations are performed using M06/cc-pVTZ and coupled-cluster (CC) theory with single, double, and perturbative triple excitations, CCSD(T), is used to calculate accurate single-point energies for those geometries. The CCSD(T)/cc-pVTZ energies for NO2 elimination by N-N and C-N bond fission are, including zero-point energy (ZPE) corrections, 43.21 kcal/mol and 50.46 kcal/mol, respectively. The decomposition initiated by trans-HONO elimination can occur by a concerted H-atom and nitramine NO2 group elimination or by a concerted H-atom and nitroalkyl NO2 group elimination via barriers (at the CCSD(T)/cc-pVTZ level with ZPE corrections) of 47.00 kcal/mol and 48.27 kcal/mol, respectively. Thus, at the CCSD(T)/cc-pVTZ level, the ordering of these four decomposition steps from energetically most favored to least favored is: NO2 elimination by N-N bond fission, HONO elimination involving the nitramine NO2 group, HONO elimination involving a nitroalkyl NO2 group, and finally NO2 elimination by C-N bond fission.

  7. Ab initio theoretical study of dipole-bound anions of molecular complexes: (HF)3- and (HF)4- anions

    Science.gov (United States)

    Ramaekers, Riet; Smith, Dayle M. A.; Smets, Johan; Adamowicz, Ludwik

    1997-12-01

    Ab initio calculations have been performed to determine structures and vertical electron detachment energy (VDE) of the hydrogen fluoride trimer and tetramer anions, (HF)3- and (HF)4-. In these systems the excess electron is bound by the dipole field of the complex. It was determined that, unlike the neutral complexes which prefer the cyclic structures, the equilibrium geometries of the anions have "zig-zag" shapes. For both complexes the predicted VDEs are positive [210 meV and 363 meV for (HF)3- and (HF)4-, respectively], indicating that the anions are stable systems with respect to the vertical electron detachment. These results were obtained at the coupled-cluster level of theory with single, double and triple excitations [CCSD(T) method; the triple-excitation contribution in this method is calculated approximately using the perturbation approach] with the anion geometries obtained using the second-order Møller-Plesset perturbation theory (MP2) method. The same approach was also used to determine the adiabatic electron affinities (AEA) of (HF)3 and (HF)4. In addition to the electronic contribution, we also calculated the contributions (using the harmonic approximation) resulting from different zero-point vibration energies of the neutral and anionic clusters. The calculations predicted that while the AEA of (HF)3 is positive (44 meV), the AEA for (HF)4 is marginally negative (-16 meV). This suggests that the (HF)3- anion should be a stable system, while the (HF)4- is probably metastable.

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

    Science.gov (United States)

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

    2016-02-01

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

  9. Study on Exploration of Azeotropic Point of Pb-Sb Alloys by Vacuum Distillation and Ab Initio Molecular Dynamic Simulation

    Science.gov (United States)

    Song, Bingyi; Jiang, Wenlong; Yang, Bin; Chen, Xiumin; Xu, Baoqiang; Kong, Lingxin; Liu, Dachun; Dai, Yongnian

    2016-10-01

    The possibility of the separation of Pb-Sb alloys by vacuum distillation was investigated theoretically. The results show that Pb and Sb can be separated by vacuum distillation. However, the experimental results show that vacuum distillation technique does not provide clear separation. According to the literature, Pb-Sb alloys belong to azeotropic compounds under some certain temperature; the experiment and computer simulation were carried out based on the exceptional condition so as to analyze the reason from the experiment and microstructure of Pb-Sb alloys perspective. The separation of Pb-Sb alloys by vacuum distillation was experimentally carried out to probe the azeotropic point. Also, the functions, such as partial radial distributions functions, the structure factor, mean square displacement, and the density of state, were calculated by ab-initio molecular dynamics for the representation of the structure and properties of Pb-Sb alloys with different composition of Sb. The experimental results indicate that there exists common volatilization for Pb-Sb alloys when Sb content is 16.5 wt pct. On the other hand, the calculation results show that there is an intense interaction between Pb and Sb when Sb content is 22 wt pct, which supports the experimental results although Sb content is slightly deviation.

  10. A computational ab initio study of surface diffusion of sulfur on the CdTe (111) surface

    International Nuclear Information System (INIS)

    Naderi, Ebadollah; Ghaisas, S. V.

    2016-01-01

    In order to discern the formation of epitaxial growth of CdS shell over CdTe nanocrystals, kinetics related to the initial stages of the growth of CdS on CdTe is investigated using ab-initio methods. We report diffusion of sulfur adatom on the CdTe (111) A-type (Cd-terminated) and B-type (Te-terminated) surfaces within the density functional theory (DFT). The barriers are computed by applying the climbing Nudge Elastic Band (c-NEB) method. From the results surface hopping emerges as the major mode of diffusion. In addition, there is a distinct contribution from kick-out type diffusion in which a CdTe surface atom is kicked out from its position and is replaced by the diffusing sulfur atom. Also, surface vacancy substitution contributes to the concomitant dynamics. There are sites on the B- type surface that are competitively close in terms of the binding energy to the lowest energy site of epitaxy on the surface. The kick-out process is more likely for B-type surface where a Te atom of the surface is displaced by a sulfur adatom. Further, on the B-type surface, subsurface migration of sulfur is indicated. Furthermore, the binding energies of S on CdTe reveal that on the A-type surface, epitaxial sites provide relatively higher binding energies and barriers than on B-type.

  11. Ab initio molecular dynamics study of lithium diffusion in tetragonal Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12}

    Energy Technology Data Exchange (ETDEWEB)

    Andriyevsky, B., E-mail: bohdan.andriyevskyy@tu.koszalin.pl [Faculty of Electronics and Computer Sciences, Koszalin University of Technology, 2 Śniadeckich Str., PL-75-453, Koszalin (Poland); Institute of Electrochemistry, Ulm University, Albert-Einstein-Allee 47, D-89069, Ulm (Germany); Doll, K. [Institute of Electrochemistry, Ulm University, Albert-Einstein-Allee 47, D-89069, Ulm (Germany); Institute of Theoretical Chemistry, Pfaffenwaldring 55, D-70569, Stuttgart (Germany); Jacob, T. [Institute of Electrochemistry, Ulm University, Albert-Einstein-Allee 47, D-89069, Ulm (Germany); Helmholtz Institute Ulm (HIU) for Electrochemical Energy Storage, Albert-Einstein-Allee 11, D-89081, Ulm (Germany)

    2017-01-01

    Using ab initio density functional theory the thermally-stimulated migration of lithium ions in the garnet-type material Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12} is investigated. The methods of ab initio molecular dynamics have been applied to calculate the lithium ion self-diffusion coefficient and the diffusion barriers as function of lithium ion concentration. The concentration of lithium in the initial Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12} crystal unit cell is varied from 53 to 59 atoms, where 56 lithium atoms represent the stoichiometric concentration. Almost monotonous dependencies of the main characteristics on the number of lithium atoms N{sup (Li)} have been found, except for a non-monotonous peculiarity of the stoichiometric compound (N{sup (Li)} = 56). Finally, the influence of the unit cell volume change on lithium ion diffusion parameters as well as lithium ion hopping rates has been studied. - Highlights: • Partial lithium atoms subtraction from LLZO increases diffusion coefficient D{sup (Li)}. • Partial subtraction of lithium atoms from LLZO decreases activation energy E{sub a}{sup (Li)}. • Activation energy E{sub a}{sup (Li)} is the smallest for tetrahedral oxygen surrounding. • Compression of LLZO leads to a decrease of lithium ion diffusion coefficient D{sup (Li)}.

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

    Science.gov (United States)

    Gopi, R; Ramanathan, N; Sundararajan, K

    2014-07-24

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

  13. Study of hydrogen-molecule guests in type II clathrate hydrates using a force-matched potential model parameterised from ab initio molecular dynamics

    Science.gov (United States)

    Burnham, Christian J.; Futera, Zdenek; English, Niall J.

    2018-03-01

    The force-matching method has been applied to parameterise an empirical potential model for water-water and water-hydrogen intermolecular interactions for use in clathrate-hydrate simulations containing hydrogen guest molecules. The underlying reference simulations constituted ab initio molecular dynamics (AIMD) of clathrate hydrates with various occupations of hydrogen-molecule guests. It is shown that the resultant model is able to reproduce AIMD-derived free-energy curves for the movement of a tagged hydrogen molecule between the water cages that make up the clathrate, thus giving us confidence in the model. Furthermore, with the aid of an umbrella-sampling algorithm, we calculate barrier heights for the force-matched model, yielding the free-energy barrier for a tagged molecule to move between cages. The barrier heights are reasonably large, being on the order of 30 kJ/mol, and are consistent with our previous studies with empirical models [C. J. Burnham and N. J. English, J. Phys. Chem. C 120, 16561 (2016) and C. J. Burnham et al., Phys. Chem. Chem. Phys. 19, 717 (2017)]. Our results are in opposition to the literature, which claims that this system may have very low barrier heights. We also compare results to that using the more ad hoc empirical model of Alavi et al. [J. Chem. Phys. 123, 024507 (2005)] and find that this model does very well when judged against the force-matched and ab initio simulation data.

  14. Use of ab initio quantum chemical methods in battery technology

    Energy Technology Data Exchange (ETDEWEB)

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

    1997-06-01

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

  15. 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.

  16. 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

  17. N2O + CO reaction over Si- and Se-doped graphenes: An ab initio DFT study

    International Nuclear Information System (INIS)

    Gholizadeh, Reza; Yu, Yang-Xin

    2015-01-01

    Graphical abstract: Si-doped graphene can be one of efficient green catalysts for conversion of the airborne pollutants. - Highlights: • N 2 O can be efficiently reduced by CO over Si-doped graphenes. • Enough charge transferred from Si to N 2 O makes the N 2 –O bond break easily. • Si-doped graphene is efficient green catalysts for conversion of the airborne pollutants. • vdW interaction and ZPE energy significantly influence the predictions of activation energies. - Abstract: Catalytic conversion of non-CO 2 green house gases and other harmful gases is a promising way to protect the atmospheric environment. Non-metal atom-doped graphene is attractive for use as a catalyst in the conversion due to its unique electronic properties, relatively low price and leaving no burden to the environment. To make an attempt on the development of green catalysts for the conversion, ab initio density functional theory is used to investigate the mechanisms of N 2 O reduction by CO on Si- and Se-doped graphenes. We have calculated the geometries and adsorption energies of reaction species (N 2 O, CO, N 2 and CO 2 ) as well as energy profiles along the reaction pathways. The activation energies of N 2 O decomposition and CO oxidation on both Si- and Se-doped graphenes have been obtained. Our calculated results indicate that the catalytic activity of Si-doped graphene is better than the Fe + in gas phase and comparable to the single Fe atom embedded on graphene. In the calculations, we found that van der Waals interactions and zero-point energy are two non-negligible factors for the predictions of the activation energies. Further discussion shows that Si-doped graphene can be one of efficient green catalysts for conversion of the airborne pollutants and Se-doped graphene can be a candidate for oxidizing CO by atomic oxygen.

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

    Science.gov (United States)

    Varadwaj, Pradeep Risikrishna

    2010-05-01

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

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

    Science.gov (United States)

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

    2016-02-28

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

  20. Evidence for phosphorus bonding in phosphorus trichloride-methanol adduct: a matrix isolation infrared and ab initio computational study.

    Science.gov (United States)

    Joshi, Prasad Ramesh; Ramanathan, N; Sundararajan, K; Sankaran, K

    2015-04-09

    The weak interaction between PCl3 and CH3OH was investigated using matrix isolation infrared spectroscopy and ab initio computations. In a nitrogen matrix at low temperature, the noncovalent adduct was generated and characterized using Fourier transform infrared spectroscopy. Computations were performed at B3LYP/6-311++G(d,p), B3LYP/aug-cc-pVDZ, and MP2/6-311++G(d,p) levels of theory to optimize the possible geometries of PCl3-CH3OH adducts. Computations revealed two minima on the potential energy surface, of which, the global minimum is stabilized by a noncovalent P···O interaction, known as a pnictogen bonding (phosphorus bonding or P-bonding). The local minimum corresponded to a cyclic adduct, stabilized by the conventional hydrogen bonding (Cl···H-O and Cl···H-C interactions). Experimentally, 1:1 P-bonded PCl3-CH3OH adduct in nitrogen matrix was identified, where shifts in the P-Cl modes of PCl3, O-C, and O-H modes of CH3OH submolecules were observed. The observed vibrational frequencies of the P-bonded adduct in a nitrogen matrix agreed well with the computed frequencies. Furthermore, computations also predicted that the P-bonded adduct is stronger than H-bonded adduct by ∼1.56 kcal/mol. Atoms in molecules and natural bond orbital analyses were performed to understand the nature of interactions and effect of charge transfer interaction on the stability of the adducts.

  1. Ab initio localized basis set study of structural parameters and elastic properties of HfO2 polymorphs

    International Nuclear Information System (INIS)

    Caravaca, M A; Casali, R A

    2005-01-01

    The SIESTA approach based on pseudopotentials and a localized basis set is used to calculate the electronic, elastic and equilibrium properties of P 2 1 /c, Pbca, Pnma, Fm3m, P4 2 nmc and Pa3 phases of HfO 2 . Using separable Troullier-Martins norm-conserving pseudopotentials which include partial core corrections for Hf, we tested important physical properties as a function of the basis set size, grid size and cut-off ratio of the pseudo-atomic orbitals (PAOs). We found that calculations in this oxide with the LDA approach and using a minimal basis set (simple zeta, SZ) improve calculated phase transition pressures with respect to the double-zeta basis set and LDA (DZ-LDA), and show similar accuracy to that determined with the PPPW and GGA approach. Still, the equilibrium volumes and structural properties calculated with SZ-LDA compare better with experiments than the GGA approach. The bandgaps and elastic and structural properties calculated with DZ-LDA are accurate in agreement with previous state of the art ab initio calculations and experimental evidence and cannot be improved with a polarized basis set. These calculated properties show low sensitivity to the PAO localization parameter range between 40 and 100 meV. However, this is not true for the relative energy, which improves upon decrease of the mentioned parameter. We found a non-linear behaviour in the lattice parameters with pressure in the P 2 1 /c phase, showing a discontinuity of the derivative of the a lattice parameter with respect to external pressure, as found in experiments. The common enthalpy values calculated with the minimal basis set give pressure transitions of 3.3 and 10.8?GPa for P2 1 /c → Pbca and Pbca → Pnma, respectively, in accordance with different high pressure experimental values

  2. Ab initio localized basis set study of structural parameters and elastic properties of HfO{sub 2} polymorphs

    Energy Technology Data Exchange (ETDEWEB)

    Caravaca, M A [Facultad de Ingenieria, Universidad Nacional del Nordeste, Avenida Las Heras 727, 3500-Resistencia (Argentina); Casali, R A [Facultad de Ciencias Exactas y Naturales y Agrimensura, Universidad Nacional del Nordeste, Avenida Libertad, 5600-Corrientes (Argentina)

    2005-09-21

    The SIESTA approach based on pseudopotentials and a localized basis set is used to calculate the electronic, elastic and equilibrium properties of P 2{sub 1}/c, Pbca, Pnma, Fm3m, P4{sub 2}nmc and Pa3 phases of HfO{sub 2}. Using separable Troullier-Martins norm-conserving pseudopotentials which include partial core corrections for Hf, we tested important physical properties as a function of the basis set size, grid size and cut-off ratio of the pseudo-atomic orbitals (PAOs). We found that calculations in this oxide with the LDA approach and using a minimal basis set (simple zeta, SZ) improve calculated phase transition pressures with respect to the double-zeta basis set and LDA (DZ-LDA), and show similar accuracy to that determined with the PPPW and GGA approach. Still, the equilibrium volumes and structural properties calculated with SZ-LDA compare better with experiments than the GGA approach. The bandgaps and elastic and structural properties calculated with DZ-LDA are accurate in agreement with previous state of the art ab initio calculations and experimental evidence and cannot be improved with a polarized basis set. These calculated properties show low sensitivity to the PAO localization parameter range between 40 and 100 meV. However, this is not true for the relative energy, which improves upon decrease of the mentioned parameter. We found a non-linear behaviour in the lattice parameters with pressure in the P 2{sub 1}/c phase, showing a discontinuity of the derivative of the a lattice parameter with respect to external pressure, as found in experiments. The common enthalpy values calculated with the minimal basis set give pressure transitions of 3.3 and 10.8?GPa for P2{sub 1}/c {yields} Pbca and Pbca {yields} Pnma, respectively, in accordance with different high pressure experimental values.

  3. 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

  4. Ab initio molecular dynamics simulation of laser melting of silicon

    NARCIS (Netherlands)

    Silvestrelli, P.-L.; Alavi, A.; Parrinello, M.; Frenkel, D.

    1996-01-01

    The method of ab initio molecular dynamics, based on finite temperature density functional theory, is used to simulate laser heating of crystal silicon. We have found that a high concentration of excited electrons dramatically weakens the covalent bond. As a result, the system undergoes a melting

  5. Multiple time step integrators in ab initio molecular dynamics

    International Nuclear Information System (INIS)

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

    2014-01-01

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

  6. 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...

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

    NARCIS (Netherlands)

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

    1997-01-01

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

  8. Ab initio electronic properties of dual phosphorus monolayers in silicon

    DEFF Research Database (Denmark)

    Drumm, Daniel W.; Per, Manolo C.; Budi, Akin

    2014-01-01

    In the midst of the epitaxial circuitry revolution in silicon technology, we look ahead to the next paradigm shift: effective use of the third dimension - in particular, its combination with epitaxial technology. We perform ab initio calculations of atomically thin epitaxial bilayers in silicon...

  9. 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...

  10. 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...

  11. 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

  12. The Properties of Some Simple Covalent Hydrides: An Ab Initio ...

    African Journals Online (AJOL)

    Some properties of the monomeric binary hydrides of the elements of the first two rows of the periodic table have been determined using ab initio molecular orbital theory. The properties in question are the energetic, structural, electronic, topological and vibrational characteristics. In general, a gradual convergence towards ...

  13. Hydrogen Bond Dynamics in Aqueous Solutions: Ab initio Molecular ...

    Indian Academy of Sciences (India)

    Rate equation for the decay of CHB(t) · Definition of Hydrogen Bonds · Results of Molecular Dynamics · Dynamics of anion-water and water-water hydrogen bonds · Structural relaxation of anion-water & water-water H-bonds · Ab initio Molecular Dynamics : · Slide 14 · Dynamics of hydrogen bonds : CPMD results · Slide 16.

  14. Ab initio transport across bismuth selenide surface barriers

    KAUST Repository

    Narayan, Awadhesh; Rungger, Ivan; Droghetti, Andrea; Sanvito, Stefano

    2014-01-01

    © 2014 American Physical Society. We investigate the effect of potential barriers in the form of step edges on the scattering properties of Bi2Se3(111) topological surface states by means of large-scale ab initio transport simulations. Our results

  15. Perspective: Ab initio force field methods derived from quantum mechanics

    Science.gov (United States)

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

    2018-03-01

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

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

    Directory of Open Access Journals (Sweden)

    Mingyuan Xu

    2018-05-01

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

  17. Ab initio Eliashberg Theory: Making Genuine Predictions of Superconducting Features

    Science.gov (United States)

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

    2018-04-01

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

  18. Ab initio benchmark study for the oxidative addition of CH4 to Pd: importance of basis-set flexibility and polarization

    NARCIS (Netherlands)

    de Jong, G.T.; Sola, M.; Visscher, L.; Bickelhaupt, F.M.

    2004-01-01

    To obtain a state-of-the-art benchmark potential energy surface (PES) for the archetypal oxidative addition of the methane C-H bond to the palladium atom, we have explored this PES using a hierarchical series of ab initio methods (Hartree-Fock, second-order Møller-Plesset perturbation theory,

  19. 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.

  20. 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

  1. Ab-initio study of the magneto-optical properties of the ultrathin films of Fe{sub n}/Au(001)

    Energy Technology Data Exchange (ETDEWEB)

    Boukelkoul, Mebarek, E-mail: boukelkoul_mebarek@yahoo.fr [Laboratoire de Physique Quantique et Systèmes Dynamiques, Faculté des sciences, Université Sétif1, Sétif, 19000 Algeria (Algeria); Haroun, Mohamed Fahim [Laboratoire de Physique Quantique et Systèmes Dynamiques, Faculté des sciences, Université Sétif1, Sétif, 19000 Algeria (Algeria); Haroun, Abdelhalim [Laboratoire de Physique Quantique et Systèmes Dynamiques, Faculté des sciences, Université Sétif1, Sétif, 19000 Algeria (Algeria); IPCMS, UMR 7504 CNRS-UNISTRA, 23 Rue du Loess, Strasbourg, 67034 France (France)

    2016-12-15

    With the aim of understand the microscopic origin of the magneto-optical response in the Fe ultrathin films, we used the first principle full-relativistic Spin-Polarized Relativistic Linear Muffin-Tin Orbitals with Atomic Sphere Approximation. We performed an ab-initio study of the structural, magnetic and magneto-optical properties of Fe deposited on semi-infinite Au(001). The structure and growth of the film leads to a pseudomorphic body centered tetragonal structure with tetragonality ratio c/a=1.62, and the pseudomorphic growth is found to be larger than 3 monolayers. The magnetic study revealed a ferromagnetic phase with a large magnetic moment compared to the bulk one. The magneto-optical response is calculated via the polar magneto-optical Kerr effect over a photon energy range up to 10 eV. The most important features of the Kerr rotation spectra are interpreted trough the interband transitions between localized states.

  2. A comparison of hydrogen-bonded and van der Waals isomers of phenolṡṡnitrogen and phenolṡṡcarbon monoxide: An ab initio study

    Science.gov (United States)

    Chapman, Darren M.; Müller-Dethlefs, Klaus; Peel, J. Barrie

    1999-08-01

    The hydrogen-bonded and van der Waals isomers of phenolṡṡnitrogen and phenolṡṡcarbon monoxide in their neutral electronic (S0) and cation ground state (D0) were studied using ab initio HF/6-31G*, MP2/6-31G*, and B3LYP/6-31G* methods. The hydrogen-bonded isomers have the ligand bound via the hydroxyl group of the phenol ring, while the van der Waals isomers studied have the ligand located above the aromatic ring. For both complexes, the hydrogen-bonded isomer was found to be the most stable form for both the S0 and the D0 states. For phenolṡṡcarbon monoxide, twice as many isomers as compared to phenolṡṡnitrogen were found. The hydrogen-bonded isomer with the carbon end bonded to the hydroxyl group was the most stable structure for both the S0 and the D0 states.

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

    International Nuclear Information System (INIS)

    Nakayama, Akira; Taketsugu, Tetsuya; Shiga, Motoyuki

    2009-01-01

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

  4. N{sub 2}O + CO reaction over Si- and Se-doped graphenes: An ab initio DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Gholizadeh, Reza [Laboratory of Chemical Engineering Thermodynamics, Department of Chemical Engineering, Tsinghua University, Beijing 100084 (China); Yu, Yang-Xin, E-mail: yangxyu@mail.tsinghua.edu.cn [Laboratory of Chemical Engineering Thermodynamics, Department of Chemical Engineering, Tsinghua University, Beijing 100084 (China); State Key Laboratory of Chemical Engineering, Tsinghua University, Beijing 100084 (China)

    2015-12-01

    Graphical abstract: Si-doped graphene can be one of efficient green catalysts for conversion of the airborne pollutants. - Highlights: • N{sub 2}O can be efficiently reduced by CO over Si-doped graphenes. • Enough charge transferred from Si to N{sub 2}O makes the N{sub 2}–O bond break easily. • Si-doped graphene is efficient green catalysts for conversion of the airborne pollutants. • vdW interaction and ZPE energy significantly influence the predictions of activation energies. - Abstract: Catalytic conversion of non-CO{sub 2} green house gases and other harmful gases is a promising way to protect the atmospheric environment. Non-metal atom-doped graphene is attractive for use as a catalyst in the conversion due to its unique electronic properties, relatively low price and leaving no burden to the environment. To make an attempt on the development of green catalysts for the conversion, ab initio density functional theory is used to investigate the mechanisms of N{sub 2}O reduction by CO on Si- and Se-doped graphenes. We have calculated the geometries and adsorption energies of reaction species (N{sub 2}O, CO, N{sub 2} and CO{sub 2}) as well as energy profiles along the reaction pathways. The activation energies of N{sub 2}O decomposition and CO oxidation on both Si- and Se-doped graphenes have been obtained. Our calculated results indicate that the catalytic activity of Si-doped graphene is better than the Fe{sup +} in gas phase and comparable to the single Fe atom embedded on graphene. In the calculations, we found that van der Waals interactions and zero-point energy are two non-negligible factors for the predictions of the activation energies. Further discussion shows that Si-doped graphene can be one of efficient green catalysts for conversion of the airborne pollutants and Se-doped graphene can be a candidate for oxidizing CO by atomic oxygen.

  5. Ab initio molecular dynamics studies on effect of Zr on oxidation resistance of TiAlN coatings

    Energy Technology Data Exchange (ETDEWEB)

    Pi, Jingwu [State Key Lab of Powder Metallurgy, Central South University, Changsha,Hunan 410083 (China); Kong, Yi, E-mail: yikong@csu.edu.cn [State Key Lab of Powder Metallurgy, Central South University, Changsha,Hunan 410083 (China); Chen, Li [State Key Lab of Powder Metallurgy, Central South University, Changsha,Hunan 410083 (China); Zhuzhou Cemented Carbide Cutting Tools Co., Ltd., Zhuzhou, Hunan 412007 (China); Du, Yong [State Key Lab of Powder Metallurgy, Central South University, Changsha,Hunan 410083 (China)

    2016-08-15

    Highlights: • The lowest bonding energy sequence for dimers in the vacuum: Zr−O < Ti−O < Al−O. • The lowest bonding energy sequence for oxygen above the surface: Ti−O < Zr−O < Al−O. • At 300 K, the addition of Zr benefitting the formation of vacancy and TiO{sub 2}. • At 1123 K, the addition of Zr leading to a more stable surface. • Our findings explain that the oxidation resistance of TiAlZrN superior to TiAlN at 1123 K as well as TiAlZrN at 300 K. - Abstract: It was demonstrated experimentally that doping Zr into TiAlN coatings at room temperature will detriment its oxidation resistance. On the other hand, there are evidences that doping Zr into TiAlN at high temperature will improve coating's oxidation resistance. In the present work, we address the effect of Zr on the oxidation resistance of TiAlN by means of ab initio molecular dynamics simulations. The TiAlN and TiAlZrN (1 Zr atom replacing 1 Ti atom) surfaces covered with 4 oxygen atoms at 300 K and 1123 K were simulated. Based on the analysis of the atomic motion, bond formation after relaxation, and the charge density difference maps we find that at 300 K, the addition of Zr induces escape of Ti atoms from the surface, resulting in formation of surface vacancies and subsequently TiO{sub 2}. Comparison of metal-oxygen dimers in the vacuum and above the TiAlZrN surface further shows that the addition of Zr in the TiAlN surface will change the lowest bonding energy sequence from Zr−O < Ti−O < Al−O in the vacuum to Ti−O < Zr−O < Al−O above the TiAlZrN surface. From Molecular Dynamics simulations at 1123 K, it is find that no Ti vacancies were generated in the surface. Moreover, less charge is transferred from metal to N atoms and the bond lengths between Ti and O atoms become shorter at 1123 K as compared with 300 K, suggesting that the addition of Zr atom promotes the interaction of Ti and O at TiAlZrN surface at 1123 K, leading to a more stable surface. Our simulation

  6. Origin of the reverse optical-contrast change of Ga-Sb phase-change materials—An ab initio molecular-dynamics study

    Energy Technology Data Exchange (ETDEWEB)

    Dixon, J. A.; Elliott, S. R., E-mail: sre1@cam.ac.uk [Department of Chemistry, University of Cambridge, Cambridge CB2 1EW (United Kingdom)

    2014-04-07

    A large number of phase-change materials (PCMs) have been developed experimentally; however, only Ge{sub 2}Sb{sub 2}Te{sub 5}-based PCMs have been significantly explored using ab initio molecular-dynamics (AIMD) simulations. We present an AIMD study of the full melt/quench/anneal PC cycle for Ga-Sb materials, namely, the stoichiometric composition, GaSb, and the near-eutectic alloy, Ga{sub 16}Sb{sub 84}. The calculated electronic densities of states and optical reflectivities are compared between the amorphous and crystalline phases for both compositions, and it is shown that the contrasting opto-electronic properties of each crystalline material can be attributed to different structural transformations of Ga and Sb on crystallization from the amorphous state.

  7. Experimental and ab initio study of the hyperfine parameters of ZnFe {sub 2}O{sub 4} with defects

    Energy Technology Data Exchange (ETDEWEB)

    Quintero, J. Melo; Salcedo Rodríguez, K. L.; Pasquevich, G. A.; Zélis, P. Mendoza; Stewart, S. J., E-mail: stewart@fisica.unlp.edu.ar; Rodríguez Torres, C. E.; Errico, L. A. [Universidad Nacional de La Plata, IFLP-CCT- La Plata-CONICET and Departamento de Física, Facultad de Ciencias Exactas, C. C. 67 (Argentina)

    2016-12-15

    We present a combined Mössbauer and ab initio study on the influence of oxygen-vacancies on the hyperfine and magnetic properties of the ZnFe {sub 2}O{sub 4} spinel ferrite. Samples with different degree of oxygen-vacancies were obtained from zinc ferrite powder that was thermally treated at different temperatures up to 650 {sup ∘}C under vacuum.Theoretical calculations of the hyperfine parameters, magnetic moments and magnetic alignment have been carried out considering different defects such as oxygen vacancies and cation inversion. We show how theoretical and experimental approaches are complementary to characterize the local structure around Fe atoms and interpret the observed changes in the hyperfine parameters as the level of defects increases.

  8. Are trinuclear superhalogens promising candidates for building blocks of novel magnetic materials? A theoretical prospect from combined broken-symmetry density functional theory and ab initio study.

    Science.gov (United States)

    Yu, Yang; Li, Chen; Yin, Bing; Li, Jian-Li; Huang, Yuan-He; Wen, Zhen-Yi; Jiang, Zhen-Yi

    2013-08-07

    The structures, relative stabilities, vertical electron detachment energies, and magnetic properties of a series of trinuclear clusters are explored via combined broken-symmetry density functional theory and ab initio study. Several exchange-correlation functionals are utilized to investigate the effects of different halogen elements and central atoms on the properties of the clusters. These clusters are shown to possess stronger superhalogen properties than previously reported dinuclear superhalogens. The calculated exchange coupling constants indicate the antiferromagnetic coupling between the transition metal ions. Spin density analysis demonstrates the importance of spin delocalization in determining the strengths of various couplings. Spin frustration is shown to occur in some of the trinuclear superhalogens. The coexistence of strong superhalogen properties and spin frustration implies the possibility of trinuclear superhalogens working as the building block of new materials of novel magnetic properties.

  9. 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).

  10. Energetics of the lithium-magnesium imide-magnesium amide and lithium hydride reaction for hydrogen storage: An ab initio study

    International Nuclear Information System (INIS)

    Velikokhatnyi, Oleg I.; Kumta, Prashant N.

    2007-01-01

    An ab initio study within the density functional theory of the recently described reversible hydrogen storage reaction Mg(NH 2 ) 2 + 2LiH ↔ Li 2 Mg(NH) 2 + 2H 2 has been conducted. The electronic structure, structural parameters, vibrational spectra, and enthalpies of formation of all the reactants and products as well as the heat of the overall reaction at zero and finite temperature have been calculated in the generalized gradient approximation (GGA) to the exchange correlation potential. The heat of the overall reaction is calculated to be 53.4 kJ/mol H 2 in contrast to the experimentally obtained overall heat of reaction of ∼44.1 kJ/mol H 2 . The difference of ∼20% between the experimental and calculated values is discussed

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

    Science.gov (United States)

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

    2003-01-01

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

  12. 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.

  13. The electronic states of 1,2,4-triazoles: A study of 1H- and1-methyl-1,2,4-triazole by vacuum ultraviolet photoabsorption and ultraviolet photoelectron spectroscopy and a comparison with ab initio configuration interaction computations

    DEFF Research Database (Denmark)

    Palmer, Michael H.; Camp, Philip J.; Hoffmann, Søren Vrønning

    2012-01-01

    The first vacuum ultraviolet absorption spectrum of a 1,2,4-triazole has been obtained and analyzed in detail, with assistance from both an enhanced UV photoelectron spectroscopic study and ab initio multi-reference multi-root configuration interaction procedures. For both 1H- and 1-methyl-1,2...

  14. 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...

  15. Computational methods for ab initio detection of microRNAs

    Directory of Open Access Journals (Sweden)

    Malik eYousef

    2012-10-01

    Full Text Available MicroRNAs are small RNA sequences of 18-24 nucleotides in length, which serve as templates to drive post transcriptional gene silencing. The canonical microRNA pathway starts with transcription from DNA and is followed by processing via the Microprocessor complex, yielding a hairpin structure. Which is then exported into the cytosol where it is processed by Dicer and then incorporated into the RNA induced silencing complex. All of these biogenesis steps add to the overall specificity of miRNA production and effect. Unfortunately, their modes of action are just beginning to be elucidated and therefore computational prediction algorithms cannot model the process but are usually forced to employ machine learning approaches. This work focuses on ab initio prediction methods throughout; and therefore homology-based miRNA detection methods are not discussed. Current ab initio prediction algorithms, their ties to data mining, and their prediction accuracy are detailed.

  16. 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.

  17. GAUSSIAN 76: an ab initio molecular orbital program

    International Nuclear Information System (INIS)

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

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-07-01

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

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

    International Nuclear Information System (INIS)

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

    2009-01-01

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

  20. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Makhov, Dmitry V.; Shalashilin, Dmitrii V. [Department of Chemistry, University of Leeds, Leeds LS2 9JT (United Kingdom); Glover, William J.; Martinez, Todd J. [Department of Chemistry and The PULSE Institute, Stanford University, Stanford, California 94305, USA and SLAC National Accelerator Laboratory, Menlo Park, California 94025 (United States)

    2014-08-07

    We present a new algorithm for ab initio quantum nonadiabatic molecular dynamics that combines the best features of ab initio Multiple Spawning (AIMS) and Multiconfigurational Ehrenfest (MCE) methods. In this new method, ab initio multiple cloning (AIMC), the individual trajectory basis functions (TBFs) follow Ehrenfest equations of motion (as in MCE). However, the basis set is expanded (as in AIMS) when these TBFs become sufficiently mixed, preventing prolonged evolution on an averaged potential energy surface. We refer to the expansion of the basis set as “cloning,” in analogy to the “spawning” procedure in AIMS. This synthesis of AIMS and MCE allows us to leverage the benefits of mean-field evolution during periods of strong nonadiabatic coupling while simultaneously avoiding mean-field artifacts in Ehrenfest dynamics. We explore the use of time-displaced basis sets, “trains,” as a means of expanding the basis set for little cost. We also introduce a new bra-ket averaged Taylor expansion (BAT) to approximate the necessary potential energy and nonadiabatic coupling matrix elements. The BAT approximation avoids the necessity of computing electronic structure information at intermediate points between TBFs, as is usually done in saddle-point approximations used in AIMS. The efficiency of AIMC is demonstrated on the nonradiative decay of the first excited state of ethylene. The AIMC method has been implemented within the AIMS-MOLPRO package, which was extended to include Ehrenfest basis functions.

  2. The Pariser-Parr-Pople model for trans-polyenes. I. Ab initio and semiempirical study of the bond alternation in trans-butadiene

    Science.gov (United States)

    Förner, Wolfgang

    1992-03-01

    Ab initio investigations of the bond alternation in butadiene are presented. The atomic basis sets applied range from minimal to split valence plus polarization quality. With the latter one the Hartree-Fock limit for the bond alternation is reached. Correlation is considered on Møller-Plesset many-body perturbation theory of second order (MP2), linear coupled cluster doubles (L-CCD) and coupled cluster doubles (CCD) level. For the smaller basis sets it is shown that for the bond alternation π-π correlations are essential while the effects of σ-σ and σ-π correlations are, though large, nearly independent of bond alternation. On MP2 level the variation of σ-π correlation with bond alternation is surprisingly large. This is discussed as an artefact of MP2. Comparative Su-Schrieffer-Heeger (SSH) and Pariser-Parr-Pople (PPP) calculations show that these models in their usual parametrizations cannot reproduce the ab initio results.

  3. Surface Solvation of Halogen Anions in Water Clusters: An ab initio Molecular Dynamics Study of the Cl-(H.sub.2./sub.O).sub.6./sub. Complex

    Czech Academy of Sciences Publication Activity Database

    Tobias, D. J.; Jungwirth, Pavel; Parrinello, M.

    2001-01-01

    Roč. 114, č. 16 (2001), s. 7036-7044 ISSN 0021-9606 R&D Projects: GA MŠk LN00A032 Grant - others:NATO Science Program(XE) CLG-974459 Institutional research plan: CEZ:AV0Z4040901 Keywords : cluster * ab initio molecular dynamics * anionic solvation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.147, year: 2001

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

    Energy Technology Data Exchange (ETDEWEB)

    Bernard, St

    1999-12-31

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Bernard, St

    1998-12-31

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

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

    DEFF Research Database (Denmark)

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

    2009-01-01

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

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

    DEFF Research Database (Denmark)

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

    2003-01-01

    Liquid hydrogen fluoride is a simple but interesting system for studies of the influence of hydrogen bonds on physical properties. We have performed ab initio molecular dynamics simulations of HF at several thermodynamic states, where we examine the microscopic structure of the liquid as well...

  8. One Size Fits All? Learning Conditions and Working Memory Capacity in "Ab Initio" Language Development

    Science.gov (United States)

    Sanz, Cristina; Lin, Hui-Ju; Lado, Beatriz; Stafford, Catherine A.; Bowden, Harriet W.

    2016-01-01

    The article summarizes results from two experimental studies (N = 23, N = 21) investigating the extent to which working memory capacity (WMC) intervenes in "ab initio" language development under two pedagogical conditions [± grammar lesson + input-based practice + explicit feedback]. The linguistic target is the use of morphosyntax to…

  9. Ab initio study of friction of graphene flake on graphene/graphite or SiC surface

    Science.gov (United States)

    Gulseren, Oguz; Tayran, Ceren; Sayin, Ceren Sibel

    Recently, the rich dynamics of graphene flake on graphite or SiC surfaces are revealed from atomic force microcopy experiments. The studies toward to the understanding of microscopic origin of friction are getting a lot of attention. Despite the several studies of these systems using molecular dynamics methods, density functional theory based investigations are limited because of the huge system sizes. In this study, we investigated the frictional force on graphene flake on graphite or SiC surfaces from pseudopotential planewave calculations based on density functional theory. In both cases, graphene flake (24 C) on graphite or SiC surface, bilayer flake is introduced by freezing the top layer as well as the bottom layer of the surface slab. After fixing the load with these frozen layers, we checked the relative motion of the flake over the surface. A minimum energy is reached when the flake is moved on graphene to attain AB stacking. We also conclude that edge reconstruction because of the finite size of the flake is very critical for frictional properties of the flake; therefore the saturation of dangling bonds with hydrogen is also addressed. Not only the symmetric configurations remaining parameter space is extensively studied. Supported by TUBITAK Project No: 114F162. This work is supported by TUBITAK Project No: 114F162.

  10. Ab initio molecular crystal structures, spectra, and phase diagrams.

    Science.gov (United States)

    Hirata, So; Gilliard, Kandis; He, Xiao; Li, Jinjin; Sode, Olaseni

    2014-09-16

    Conspectus Molecular crystals are chemists' solids in the sense that their structures and properties can be understood in terms of those of the constituent molecules merely perturbed by a crystalline environment. They form a large and important class of solids including ices of atmospheric species, drugs, explosives, and even some organic optoelectronic materials and supramolecular assemblies. Recently, surprisingly simple yet extremely efficient, versatile, easily implemented, and systematically accurate electronic structure methods for molecular crystals have been developed. The methods, collectively referred to as the embedded-fragment scheme, divide a crystal into monomers and overlapping dimers and apply modern molecular electronic structure methods and software to these fragments of the crystal that are embedded in a self-consistently determined crystalline electrostatic field. They enable facile applications of accurate but otherwise prohibitively expensive ab initio molecular orbital theories such as Møller-Plesset perturbation and coupled-cluster theories to a broad range of properties of solids such as internal energies, enthalpies, structures, equation of state, phonon dispersion curves and density of states, infrared and Raman spectra (including band intensities and sometimes anharmonic effects), inelastic neutron scattering spectra, heat capacities, Gibbs energies, and phase diagrams, while accounting for many-body electrostatic (namely, induction or polarization) effects as well as two-body exchange and dispersion interactions from first principles. They can fundamentally alter the role of computing in the studies of molecular crystals in the same way ab initio molecular orbital theories have transformed research practices in gas-phase physical chemistry and synthetic chemistry in the last half century. In this Account, after a brief summary of formalisms and algorithms, we discuss applications of these methods performed in our group as compelling

  11. Zirconium - ab initio modelling of point defects diffusion

    International Nuclear Information System (INIS)

    Gasca, Petrica

    2010-01-01

    Zirconium is the main element of the cladding found in pressurized water reactors, under an alloy form. Under irradiation, the cladding elongate significantly, phenomena attributed to the vacancy dislocation loops growth in the basal planes of the hexagonal compact structure. The understanding of the atomic scale mechanisms originating this process motivated this work. Using the ab initio atomic modeling technique we studied the structure and mobility of point defects in Zirconium. This led us to find four interstitial point defects with formation energies in an interval of 0.11 eV. The migration paths study allowed the discovery of activation energies, used as entry parameters for a kinetic Monte Carlo code. This code was developed for calculating the diffusion coefficient of the interstitial point defect. Our results suggest a migration parallel to the basal plane twice as fast as one parallel to the c direction, with an activation energy of 0.08 eV, independent of the direction. The vacancy diffusion coefficient, estimated with a two-jump model, is also anisotropic, with a faster process in the basal planes than perpendicular to them. Hydrogen influence on the vacancy dislocation loops nucleation was also studied, due to recent experimental observations of cladding growth acceleration in the presence of this element [fr

  12. In search of the X{sub 2}BO and X{sub 2}BS (X = H, F) free radicals: Ab initio studies of their spectroscopic signatures

    Energy Technology Data Exchange (ETDEWEB)

    Clouthier, Dennis J., E-mail: dclaser@uky.edu [Department of Chemistry, University of Kentucky, Lexington, Kentucky 40506-0055 (United States)

    2014-12-28

    The F{sub 2}BO free radical is a known, although little studied, species but similar X{sub 2}BY (X = H, D, F; Y = O, S) molecules are largely unknown. High level ab initio methods have been used to predict the molecular structures, vibrational frequencies (in cm{sup −1}), and relative energies of the ground and first two excited electronic states of these free radicals, as an aid to their eventual spectroscopic identification. The chosen theoretical methods and basis sets were tested on F{sub 2}BO and found to give good agreement with the known experimental quantities. In particular, complete basis set extrapolations of coupled-cluster single and doubles with perturbative triple excitations/aug-cc-pVXZ (X = 3, 4, 5) energies gave excellent electronic term values, due to small changes in geometry between states and the lack of significant multireference character in the wavefunctions. The radicals are found to have planar C{sub 2v} geometries in the X{sup ~2}B{sub 2} ground state, the low-lying A{sup ~2}B{sub 1} first excited state, and the higher B{sup ~2}A{sub 1} state. Some of these radicals have very small ground state dipole moments hindering microwave measurements. Infrared studies in matrices or in the gas phase may be possible although the fundamentals of H{sub 2}BO and H{sub 2}BS are quite weak. The most promising method of identifying these species in the gas phase appears to be absorption or laser-induced fluorescence spectroscopy through the allowed B{sup ~}-X{sup ~} transitions which occur in the visible-near UV region of the electromagnetic spectrum. The ab initio results have been used to calculate the Franck-Condon profiles of the absorption and emission spectra, and the rotational structure of the B{sup ~}-X{sup ~}0{sub 0}{sup 0} bands has been simulated. The calculated single vibronic level emission spectra provide a unique, readily recognizable fingerprint of each particular radical, facilitating the experimental identification of new X{sub 2}BY

  13. An experimental and ab initio study of the electronic spectrum of the jet-cooled F{sub 2}BO free radical

    Energy Technology Data Exchange (ETDEWEB)

    Grimminger, Robert; Clouthier, Dennis J., E-mail: dclaser@uky.edu [Department of Chemistry, University of Kentucky, Lexington, Kentucky 40506-0055 (United States); Sheridan, Phillip M. [Department of Chemistry and Biochemistry, Canisius College, Buffalo, New York 14208 (United States)

    2014-04-28

    We have studied the B{sup ~} {sup 2}A{sub 1}–X{sup ~} {sup 2}B{sub 2} laser-induced fluorescence (LIF) spectrum of the jet-cooled F{sub 2}BO radical for the first time. The transition consists of a strong 0{sub 0}{sup 0} band at 446.5 nm and eight weak sequence bands to shorter wavelengths. Single vibronic level emission spectra obtained by laser excitation of individual levels of the B{sup ~} state exhibit two electronic transitions: a very weak, sparse B{sup ~}–X{sup ~} band system in the 450–500 nm region and a stronger, more extensive set of B{sup ~} {sup 2}A{sub 1}–A{sup ~} {sup 2}B{sub 1} bands in the 580–650 nm region. We have also performed a series of high level ab initio calculations to predict the electronic energies, molecular structures, vibrational frequencies, and rotational and spin-rotation constants in the X{sup ~} {sup 2}B{sub 2}, A{sup ~2}B{sub 1} and B{sup ~} {sup 2}A{sub 1} electronic states as an aid to the analysis of the experimental data. The theoretical results have been used as input for simulations of the rotationally resolved B{sup ~} {sup 2}A{sub 1}–X{sup ~} {sup 2}B{sub 2} 0{sub 0}{sup 0} LIF band and Franck-Condon profiles of the LIF and single vibronic level emission spectra. The agreement between the simulations obtained with purely ab initio parameters and the experimental spectra validates the geometries calculated for the ground and excited states and the conclusion that the radical has C{sub 2v} symmetry in the X{sup ~}, A{sup ~}, and B{sup ~} states. The spectra provide considerable new information about the vibrational energy levels of the X{sup ~} and A{sup ~} states, but very little for the B{sup ~} state, due to the very restrictive Franck-Condon factors in the LIF spectra.

  14. Thermal, spectroscopic, and ab initio structural characterization of carprofen polymorphs.

    Science.gov (United States)

    Bruni, Giovanna; Gozzo, Fabia; Capsoni, Doretta; Bini, Marcella; Macchi, Piero; Simoncic, Petra; Berbenni, Vittorio; Milanese, Chiara; Girella, Alessandro; Ferrari, Stefania; Marini, Amedeo

    2011-06-01

    Commercial and recrystallized polycrystalline samples of carprofen, a nonsteroidal anti-inflammatory drug, were studied by thermal, spectroscopic, and structural techniques. Our investigations demonstrated that recrystallized sample, stable at room temperature (RT), is a single polymorphic form of carprofen (polymorph I) that undergoes an isostructural polymorphic transformation by heating (polymorph II). Polymorph II remains then metastable at ambient conditions. Commercial sample is instead a mixture of polymorphs I and II. The thermodynamic relationships between the two polymorphs were determined through the construction of an energy/temperature diagram. The ab initio structural determination performed on synchrotron X-Ray powder diffraction patterns recorded at RT on both polymorphs allowed us to elucidate, for the first time, their crystal structure. Both crystallize in the monoclinic space group type P2(1) /c, and the unit cell similarity index and the volumetric isostructurality index indicate that the temperature-induced polymorphic transformation I → II is isostructural. Polymorphs I and II are conformational polymorphs, sharing a very similar hydrogen bond network, but with different conformation of the propanoic skeleton, which produces two different packing. The small conformational change agrees with the low value of transition enthalpy obtained by differential scanning calorimetry measurements and the small internal energy computed with density functional methods. Copyright © 2011 Wiley-Liss, Inc.

  15. Ab initio modelling of transition metals in diamond

    International Nuclear Information System (INIS)

    Watkins, M; Mainwood, A

    2003-01-01

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

  16. Modelling of nuclear glasses by classical and ab initio molecular dynamics; Modelisation de verres intervenant dans le conditionnement des dechets radioactifs par dynamiques moleculaires classique et ab initio

    Energy Technology Data Exchange (ETDEWEB)

    Ganster, P

    2004-10-15

    A calcium aluminosilicate glass of molar composition 67 % SiO{sub 2} - 12 % Al{sub 2}O{sub 3} - 21 % CaO was modelled by classical and ab initio molecular dynamics. The size effect study in classical MD shows that the systems of 100 atoms are more ordered than the larger ones. These effects are mainly due to the 3-body terms in the empirical potentials. Nevertheless, these effects are small and the structures generated are in agreement with experimental data. In such kind of glass, we denote an aluminium avoidance and an excess of non bridging oxygens which can be compensated by tri coordinated oxygens. When the dynamics of systems of 100 and 200 atoms is followed by ab initio MD, some local arrangements occurs (bond length, angular distributions). Thus, more realistic vibrational properties are obtained in ab initio MD. The modelling of thin films shows that aluminium atoms extend to the most external part of the surface and they are all tri-coordinated. Calcium atoms are set in the sub layer part of the surface and they produce a depolymerization of the network. In classical MD, tri-coordinated aluminium atoms produce an important electric field above the surface. With non bridging oxygens, they constitute attractive sites for single water molecules. (author)

  17. Effect of solute atoms on glass-forming ability for Fe–Y–B alloy: An ab initio molecular dynamics study

    International Nuclear Information System (INIS)

    Han, J.J.; Wang, W.Y.; Liu, X.J.; Wang, C.P.; Hui, X.D.; Liu, Z.K.

    2014-01-01

    The glass-forming abilities of Fe 78 B 22 , Fe 70 Y 6 B 24 , Fe 72 Y 6 B 22 and Fe 72.5 Y 3.5 B 24 alloys were characterized comprehensively using ab initio molecular dynamics simulations. The calculated results were correlated with the properties and atomic structures. It was found that the Fe 72 Y 6 B 22 alloy consists of both the most stable and the least deformed body centered cubic atomic packing structures in the supercooled liquid and glassy states. It was observed that the local compositions in the Fe 72 Y 6 B 22 alloy significantly deviate from the compositions of stable crystalline phases, indicating that the Fe 72 Y 6 B 22 alloy has the best glass-forming ability among the alloys studied. However, Fe 72 Y 6 B 22 alloy has two flaws in terms of glass-forming ability, i.e. relatively large atomic diffusivity and insufficiently close atomic packing. The best performance in these two aspects is observed in the Fe 72.5 Y 3.5 B 24 alloy. Thus, the theoretical study predicts that the best glass former for the Fe–Y–B system is within the compositional range of 22–24 at.% B and 3.5–6 at.% Y

  18. Mode specificity in the OH + CHD3 reaction: Reduced-dimensional quantum and quasi-classical studies on an ab initio based full-dimensional potential energy surface

    International Nuclear Information System (INIS)

    Song, Hongwei; Yang, Minghui; Lu, Yunpeng; Li, Jun; Guo, Hua

    2016-01-01

    An initial state selected time-dependent wave packet method is applied to study the dynamics of the OH + CHD 3 reaction with a six-dimensional model on a newly developed full-dimensional ab initio potential energy surface (PES). This quantum dynamical (QD) study is complemented by full-dimensional quasi-classical trajectory (QCT) calculations on the same PES. The QD results indicate that both translational energy and the excitation of the CH stretching mode significantly promote the reaction while the excitation of the umbrella mode has a negligible effect on the reactivity. For this early barrier reaction, interestingly, the CH stretching mode is more effective than translational energy in promoting the reaction except at very low collision energies. These QD observations are supported by QCT results. The higher efficacy of the CH stretching model in promoting this early barrier reaction is inconsistent with the prediction of the naively extended Polanyi’s rules, but can be rationalized by the recently proposed sudden vector projection model.

  19. 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.

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

    Science.gov (United States)

    Sadlej-Sosnowska, N

    2014-08-28

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

  1. The half-metallic ferromagnetism character in Be1−xVxY (Y=Se and Te) alloys: An ab-initio study

    International Nuclear Information System (INIS)

    Sajjad, M.; Manzoor, Sadia; Zhang, H.X.; Noor, N.A.; Alay-e-Abbas, S.M.; Shaukat, A.; Khenata, R.

    2015-01-01

    Ab-initio calculations for V-doped BeSe and BeTe semiconductors are performed by means of all-electrons full-potential linearized augmented plane wave plus local orbital (FP-LAPW+lo) method. The structural properties are optimized using the Wu-Cohen generalized gradient approximation functional, whereas modified Becke and Jhonson local density approximation functional has been employed for evaluating the spin-polarized electronic and magnetic properties. Magnetic stability at various doping concentrations in ferromagnetic (FM) and anti-ferromagnetic (AFM) ordering is investigated by comparing the minimum total energies and enthalpies of formation (ΔH). Studied band structures, density of states, total energy, exchange interactions and magnetic moments manifest both alloys with half-metallic ferromagnetic behavior. Moreover, their valance bands are found to be paired ferromagnetically with V atoms. Furthermore, it was observed that the magnetic moment of vanadium atom reduces from free space charge value due to p–d hybridization which yields small magnetic moments on the Be, Se and Te sites. - Highlights: • Density functional calculations for V-doped BeSe and BeTe are performed. • V-doped BeSe and BeTe are found to be stable half-metallic ferromagnetism. • Improved electronic properties are achieved using mBJLDA which confirm HMF. • The half-metallic gaps show non-linear variation with increasing dopant concentration

  2. The half-metallic ferromagnetism character in Be1-xVxY (Y=Se and Te) alloys: An ab-initio study

    Science.gov (United States)

    Sajjad, M.; Manzoor, Sadia; Zhang, H. X.; Noor, N. A.; Alay-e-Abbas, S. M.; Shaukat, A.; Khenata, R.

    2015-04-01

    Ab-initio calculations for V-doped BeSe and BeTe semiconductors are performed by means of all-electrons full-potential linearized augmented plane wave plus local orbital (FP-LAPW+lo) method. The structural properties are optimized using the Wu-Cohen generalized gradient approximation functional, whereas modified Becke and Jhonson local density approximation functional has been employed for evaluating the spin-polarized electronic and magnetic properties. Magnetic stability at various doping concentrations in ferromagnetic (FM) and anti-ferromagnetic (AFM) ordering is investigated by comparing the minimum total energies and enthalpies of formation (ΔH). Studied band structures, density of states, total energy, exchange interactions and magnetic moments manifest both alloys with half-metallic ferromagnetic behavior. Moreover, their valance bands are found to be paired ferromagnetically with V atoms. Furthermore, it was observed that the magnetic moment of vanadium atom reduces from free space charge value due to p-d hybridization which yields small magnetic moments on the Be, Se and Te sites.

  3. 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.

  4. Relative stability of major types of beta-turns as a function of amino acid composition: a study based on Ab initio energetic and natural abundance data.

    Science.gov (United States)

    Perczel, András; Jákli, Imre; McAllister, Michael A; Csizmadia, Imre G

    2003-06-06

    Folding properties of small globular proteins are determined by their amino acid sequence (primary structure). This holds both for local (secondary structure) and for global conformational features of linear polypeptides and proteins composed from natural amino acid derivatives. It thus provides the rational basis of structure prediction algorithms. The shortest secondary structure element, the beta-turn, most typically adopts either a type I or a type II form, depending on the amino acid composition. Herein we investigate the sequence-dependent folding stability of both major types of beta-turns using simple dipeptide models (-Xxx-Yyy-). Gas-phase ab initio properties of 16 carefully selected and suitably protected dipeptide models (for example Val-Ser, Ala-Gly, Ser-Ser) were studied. For each backbone fold most probable side-chain conformers were considered. Fully optimized 321G RHF molecular structures were employed in medium level [B3LYP/6-311++G(d,p)//RHF/3-21G] energy calculations to estimate relative populations of the different backbone conformers. Our results show that the preference for beta-turn forms as calculated by quantum mechanics and observed in Xray determined proteins correlates significantly.

  5. 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.

  6. Ab initio Study of Alkyl-oxonium Cations CnH2n+1OH2+, n=1,2,3,4

    Directory of Open Access Journals (Sweden)

    Francis F. Muguet

    2004-08-01

    Full Text Available ABSTRACT: Within the framework of the itinerant radical model, the solvated electron in liquid alcohols is understood as an itinerant alkyl-oxonium ROH2. radical. As a first step in the investigation of those radicals, this study deals with the optimization of related ROH2+ alky-oxonium cations: CnH2n+1OH2+,n=1,2,3,4. The structures were optimized at the MP2/6-31G**++ level with the help of the GAMESS ab initio package. Optimized structures are reported for the following cations: MethylOxonium; EthylOxonium; 1-PropylOxonium, 2-PropylOxonium and 1-ButylOxonium, 2-ButylOxonium, IsoButylOxonium, TertButylOxonium. Optimized geometries are displayed with the help of the ChemApp Java applet. Vibrational frequencies and ZPEs have been computed, and visual depictions of expected experimental IR spectra have been simulated with the help of Lorentzian functions.

  7. Effect of Si on the oxidation reaction of α-Ti(0 0 0 1) surface: ab initio molecular dynamics study.

    Science.gov (United States)

    Bhattacharya, Somesh Kr; Sahara, Ryoji; Ueda, Kyosuke; Narushima, Takayuki

    2017-01-01

    We present our ab initio molecular dynamics (MD) study of the effect of Si on the oxidation of α-Ti(0   0   0   1) surfaces. We varied the Si concentration in the first layer of the surface from 0 to 25 at.% and the oxygen coverage ( θ ) on the surface was varied up to 1 monolayer (ML). The MD was performed at 300, 600 and 973 K. For θ  = 0.5 ML, oxygen penetration into the slab was not observed after 16 ps of MD at 973 K while for θ  > 0.5 ML, oxygen penetration into the Ti slab was observed even at 300 K. From Bader charge analysis, we confirmed the formation of the oxide layer on the surface of the Ti slab. At higher temperatures, the Si atoms diffused from the first layer to the interior of the slab, while the Ti atoms moved from second layer to the first layer. The pair correlation function shows the formation of a disordered Ti-O network during the initial stage of oxidation. Si was found to have a strong influence on the penetration of oxygen in the Ti slab at high temperatures.

  8. Are polynuclear superhalogens without halogen atoms probable? A high-level ab initio case study on triple-bridged binuclear anions with cyanide ligands

    Science.gov (United States)

    Yin, Bing; Li, Teng; Li, Jin-Feng; Yu, Yang; Li, Jian-Li; Wen, Zhen-Yi; Jiang, Zhen-Yi

    2014-03-01

    The first theoretical exploration of superhalogen properties of polynuclear structures based on pseudohalogen ligand is reported here via a case study on eight triply-bridged [Mg2(CN)5]- clusters. From our high-level ab initio results, all these clusters are superhalogens due to their high vertical electron detachment energies (VDE), of which the largest value is 8.67 eV at coupled-cluster single double triple (CCSD(T)) level. Although outer valence Green's function results are consistent with CCSD(T) in most cases, it overestimates the VDEs of three anions dramatically by more than 1 eV. Therefore, the combined usage of several theoretical methods is important for the accuracy of purely theoretical prediction of superhalogen properties of new structures. Spatial distribution of the extra electron of high-VDE anions here indicates two features: remarkable aggregation on bridging CN units and non-negligible distribution on every CN unit. These two features lower the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to detachment of CN-1 were also investigated for these anions. The collection of these results indicates that polynuclear structures based on pseudohalogen ligand are promising candidates for new superhalogens with enhanced properties.

  9. Are polynuclear superhalogens without halogen atoms probable? A high-level ab initio case study on triple-bridged binuclear anions with cyanide ligands

    International Nuclear Information System (INIS)

    Yin, Bing; Wen, Zhen-Yi; Li, Teng; Li, Jin-Feng; Yu, Yang; Li, Jian-Li; Jiang, Zhen-Yi

    2014-01-01

    The first theoretical exploration of superhalogen properties of polynuclear structures based on pseudohalogen ligand is reported here via a case study on eight triply-bridged [Mg 2 (CN) 5 ] − clusters. From our high-level ab initio results, all these clusters are superhalogens due to their high vertical electron detachment energies (VDE), of which the largest value is 8.67 eV at coupled-cluster single double triple (CCSD(T)) level. Although outer valence Green's function results are consistent with CCSD(T) in most cases, it overestimates the VDEs of three anions dramatically by more than 1 eV. Therefore, the combined usage of several theoretical methods is important for the accuracy of purely theoretical prediction of superhalogen properties of new structures. Spatial distribution of the extra electron of high-VDE anions here indicates two features: remarkable aggregation on bridging CN units and non-negligible distribution on every CN unit. These two features lower the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to detachment of CN −1 were also investigated for these anions. The collection of these results indicates that polynuclear structures based on pseudohalogen ligand are promising candidates for new superhalogens with enhanced properties

  10. Ab-initio study of the interfacial properties in ultrathin MgO films on O-rich FeO/Fe(001) surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Jeon, Junjin; Yu, Byungdeok [University of Seoul, Seoul (Korea, Republic of)

    2014-09-15

    Using ab-initio simulations based on density functional theory, we systematically studied the interfacial properties of MgO films on O-rich FeO/Fe(001) surfaces with increasing number of MgO layers from one to three monolayers (MLs). The structural and the adhesion properties of the MgO/FeO/Fe(001) system were assessed and compared with those of simple MgO/Fe(001) interfaces. Our calculated results showed that the adhesion energy for MgO/FeO/Fe(001) was smaller than that for simple MgO/Fe(001). An analysis of the electronic structures and the charge rearrangements of the MgO/FeO/Fe(001) interfaces was also performed. The work functions of the MgO/FeO/Fe(001) systems upon the deposition of MgO films exhibited smaller decreases (0.45 - 0.67 eV) than those (1.43 - 1.74 eV) of the MgO/Fe(001) systems. In addition, the obtained work functions (3.77 - 3.99 eV) for MgO/FeO/Fe(001) were much larger than those (2.12 - 2.43 eV) for MgO/Fe(001).

  11. Ab initio configuration interaction study on the energetics and electronic structure of the 1-52Σ+ and 1-32Π states of CS+

    International Nuclear Information System (INIS)

    Honjou, Nobumitsu

    2006-01-01

    The energetics and electronic structure of the 1-5 2 Σ + and 1-3 2 Π states of CS + at and around the equilibrium internuclear distance R e for the CS X 1 Σ + state are studied by carrying out ab initio configuration interaction (CI) calculations. The spectroscopic constants of T e , ω e , and R e for the 1-4 2 Σ + , 1 2 Π, and 3 2 Π states are evaluated from the CI potential energy curves (PECs). The avoided crossing between the 2-3 2 Σ + PECs causes the 3 2 Σ + minimum and explains the observed high intensities for the photoionization from the CS X 1 Σ + state to both the 2-3 2 Σ + states. The avoided crossing between the 3-4 2 Σ + PECs produces the 3 2 Σ + maximum and 4 2 Σ + well minimum. The avoided crossing between the 2-3 2 Π PECs results in the 3 2 Π minimum and a small minimum spacing (0.14 eV) between the PECs

  12. Ab initio study of spectroscopic properties of bimetallic molecules MeB (where Me=Li, Na, K, Br, Cs, Fr) using CCSD(T) and MRCI methods

    International Nuclear Information System (INIS)

    Cukovicova, M.; Cernusak, I.

    2010-01-01

    For our study we have chosen a series of diatomic molecules MeB (where Me = Li, Na, K, Rb, Cs, Fr). These molecules present experimentally unknown species, hence we were motivated to predict theoretically potential energy curves, equilibrium bond lengths, harmonic frequencies, constants of anharmonicity, dipole moments and dissociation energies for the ground and low-lying excited states using high level ab initio techniques. Based on previous state averaged MRCI calculations in ANO-S basis set of NaB and KB molecules, we have focused on four lowest-lying electronic states, ground state 3Π and excited states 1Σ+, 1Π and 3Σ+. All four states dissociate to the atoms in ground states 2P1/2(B) and 2S1/2(Me). 3Π, 1Σ+, 1Π and 3Σ+ electronic states we investigated employing CCSD(T) method using relativistic ANO-RCC basis set. Our calculations include scalar relativistic effects via the second order one-component (spin-free) Douglas-Kroll-Hess Hamiltonian. Relativistic effects become remarkable in the case of heavy atoms, hence properties of CsB and FrB molecules may differ from trend of properties in row from LiB to FrB. Spectroscopic properties of particular state were obtained from the analysis of the potential energy curves using VIBROT and DUNHAM programs.

  13. Ab initio study of structural, elastic, and vibrational properties of transition-metal disilicides NbSi2 and TaSi2 in hexagonal C40 structure

    Science.gov (United States)

    Ertürk, Esra; Gürel, Tanju

    2018-05-01

    We present an ab initio study of structural, elastic and vibrational properties of transition-metal disilicides NbSi2 and TaSi2. The calculations have been carried out within the density-functional theory and linear-response formalism using norm-conserving pseudopotentials and a plane-wave basis. The calculated lattice parameters, bulk moduli, and elastic constants agree well with previous theoretical and experimental results. The calculated phonon frequencies at the Brillouin zone center are in good agreement with the reported Raman spectra and provide reference values for the future infrared and neutron phonon measurements. Phonon dispersion relations, mode Grüneisen parameters, and total and partial phonon density of states are also discussed. Mode Grüneisen parameters of NbSi2 and TaSi2 at Brillouin zone center show similar trends and all values are found to be positive. From phonon dispersion relations and phonon density of states, we have found a gap around 200 cm-1 for TaSi2, where the frequencies below this gap mainly belong to Ta vibrations and frequencies above the gap is mainly related with Si vibrations. In the case of NbSi2, there is no such gap and both Nb and Si atoms contribute to the phonon density of states in an energy range of 150-270 cm-1.

  14. Are polynuclear superhalogens without halogen atoms probable? A high-level ab initio case study on triple-bridged binuclear anions with cyanide ligands

    Energy Technology Data Exchange (ETDEWEB)

    Yin, Bing, E-mail: rayinyin@gmail.com; Wen, Zhen-Yi [MOE Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry and Materials Science, Northwest University, Xi' an 710069 (China); Institute of Modern Physics, Northwest University, Xi' an 710069 (China); Li, Teng; Li, Jin-Feng; Yu, Yang; Li, Jian-Li [MOE Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry and Materials Science, Northwest University, Xi' an 710069 (China); Jiang, Zhen-Yi [Institute of Modern Physics, Northwest University, Xi' an 710069 (China)

    2014-03-07

    The first theoretical exploration of superhalogen properties of polynuclear structures based on pseudohalogen ligand is reported here via a case study on eight triply-bridged [Mg{sub 2}(CN){sub 5}]{sup −} clusters. From our high-level ab initio results, all these clusters are superhalogens due to their high vertical electron detachment energies (VDE), of which the largest value is 8.67 eV at coupled-cluster single double triple (CCSD(T)) level. Although outer valence Green's function results are consistent with CCSD(T) in most cases, it overestimates the VDEs of three anions dramatically by more than 1 eV. Therefore, the combined usage of several theoretical methods is important for the accuracy of purely theoretical prediction of superhalogen properties of new structures. Spatial distribution of the extra electron of high-VDE anions here indicates two features: remarkable aggregation on bridging CN units and non-negligible distribution on every CN unit. These two features lower the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to detachment of CN{sup −1} were also investigated for these anions. The collection of these results indicates that polynuclear structures based on pseudohalogen ligand are promising candidates for new superhalogens with enhanced properties.

  15. Emergence of Metallic Properties at LiFePO4 Surfaces and LiFePO4/Li2S Interfaces: An Ab Initio Study.

    Science.gov (United States)

    Timoshevskii, Vladimir; Feng, Zimin; Bevan, Kirk H; Zaghib, Karim

    2015-08-26

    The atomic and electronic structures of the LiFePO4 (LFP) surface, both bare and reconstructed upon possible oxygenation, are theoretically studied by ab initio methods. On the basis of total energy calculations, the atomic structure of the oxygenated surface is proposed, and the effect of surface reconstruction on the electronic properties of the surface is clarified. While bare LFP(010) surface is insulating, adsorption of oxygen leads to the emergence of semimetallic behavior by inducing the conducting states in the band gap of the system. The physical origin of these conducting states is investigated. We further demonstrate that deposition of Li2S layers on top of oxygenated LFP(010) surface leads to the formation of additional conducting hole states in the first layer of Li2S surface because of the charge transfer from sulfur p-states to the gap states of LFP surface. This demonstrates that oxygenated LFP surface not only provides conducting layers itself, but also induces conducting channels in the top layer of Li2S. These results help to achieve further understanding of potential role of LFP particles in improving the performance of Li-S batteries through emergent interface conductivity.

  16. Tunneling Splittings in Vibronic Structure of CH_3F^+ ( X^2E): Studied by High Resolution Photoelectron Spectra and AB Initio Theoretical Method

    Science.gov (United States)

    Mo, Yuxiang; Gao, Shuming; Dai, Zuyang; Li, Hua

    2013-06-01

    We report a combined experimental and theoretical study on the vibronic structure of CH_3F^+. The results show that the tunneling splittings of vibrational energy levels occur in CH_3F^+ due to the Jahn-Teller effect. Experimentally, we have measured a high resolution ZEKE spectrum of CH_3F up to 3500 cm^-^1 above the ground state. Theoretically, we performed an ab initio calculation based on the diabatic model. The adiabatic potential energy surfaces (APES) of CH_3F^+ have been calculated at the MRCI/CAS/avq(t)z level and expressed by Taylor expansions with normal coordinates as variables. The energy gradients for the lower and upper APES, the derivative couplings between them and also the energies of the APES have been used to determine the coefficients in the Taylor expansion. The spin-vibronic energy levels have been calculated by accounting all six vibrational modes and their couplings. The experimental ZEKE spectra were assigned based on the theoretical calculations. W. Domcke, D. R. Yarkony, and H. Köpple (Eds.), Conical Intersections: Eletronic Structure, Dynamics and Spectroscopy (World Scientific, Singapore, 2004). M. S. Schuurman, D. E. Weinberg, and D. R. Yarkony, J. Chem. Phys. 127, 104309 (2007).

  17. An ab initio molecular dynamics study of thermal decomposition of 3,6-di(azido)-1,2,4,5-tetrazine.

    Science.gov (United States)

    Wu, Qiong; Zhu, Weihua; Xiao, Heming

    2014-10-21

    Ab initio molecular dynamics simulations were performed to study the thermal decomposition of isolated and crystal 3,6-di(azido)-1,2,4,5-tetrazine (DiAT). During unimolecular decomposition, the three different initiation mechanisms were observed to be N-N2 cleavage, ring opening, and isomerization, respectively. The preferential initial decomposition step is the homolysis of the N-N2 bond in the azido group. The release mechanisms of nitrogen gas are found to be very different in the early and later decomposition stages of crystal DiAT. In the early decomposition, DiAT decomposes very fast and drastically without forming any stable long-chains or heterocyclic clusters, and most of the nitrogen gases are released through rapid rupture of nitrogen-nitrogen and carbon-nitrogen bonds. But in the later decomposition stage, the release of nitrogen gas is inhibited due to low mobility, long distance from each other, and strong carbon-nitrogen bonds. To overcome the obstacles, the nitrogen gases are released through slow formation and disintegration of polycyclic networks. Our simulations suggest a new decomposition mechanism for the organic polyazido initial explosive at the atomistic level.

  18. Ab initio lattice dynamics of complex structures

    DEFF Research Database (Denmark)

    Voss, Johannes

    2008-01-01

    In this thesis, density functional theory is applied in a study of thermodynamic properties of so-called complex metal hydrides, which are promising materials for hydrogen storage applications. Since the unit cells of these crystals can be relatively large with many symmetrically inequivalent ato...

  19. 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)

  20. Cooperative effects in spherical spasers: Ab initio analytical model

    Science.gov (United States)

    Bordo, V. G.

    2017-06-01

    A fully analytical semiclassical theory of cooperative optical processes which occur in an ensemble of molecules embedded in a spherical core-shell nanoparticle is developed from first principles. Both the plasmonic Dicke effect and spaser generation are investigated for the designs in which a shell/core contains an arbitrarily large number of active molecules in the vicinity of a metallic core/shell. An essential aspect of the theory is an ab initio account of the feedback from the core/shell boundaries which significantly modifies the molecular dynamics. The theory provides rigorous, albeit simple and physically transparent, criteria for both plasmonic superradiance and surface plasmon generation.

  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. 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...

  3. 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

  4. Ab initio molecular dynamics in a finite homogeneous electric field.

    Science.gov (United States)

    Umari, P; Pasquarello, Alfredo

    2002-10-07

    We treat homogeneous electric fields within density functional calculations with periodic boundary conditions. A nonlocal energy functional depending on the applied field is used within an ab initio molecular dynamics scheme. The reliability of the method is demonstrated in the case of bulk MgO for the Born effective charges, and the high- and low-frequency dielectric constants. We evaluate the static dielectric constant by performing a damped molecular dynamics in an electric field and avoiding the calculation of the dynamical matrix. Application of this method to vitreous silica shows good agreement with experiment and illustrates its potential for systems of large size.

  5. Ab initio study of {sup 2}H(d,{gamma}){sup 4}He, {sup 2}H(d,p){sup 3}H, and {sup 2}H(d,n){sup 4}He reactions and the tensor force

    Energy Technology Data Exchange (ETDEWEB)

    Arai, K.; Aoyama, S.; Suzuki, Y.; Descouvemont, P.; Baye, D. [Division of General Education, Nagaoka National College of Technology, 888 Nishikatakai, Nagaoka, Niigata, 940-8532 (Japan); Center for Academic Information Service, Niigata University, Niigata 950-2181 (Japan); Department of Physics, Niigata University, Niigata 950-2181, Japan and RIKEN Nishina Center, Wako 351-0198 (Japan); Physique Nucleaire Theorique et Physique Mathematique, C.P.229, Universite Libre de Bruxelles, B 1050 Brussels (Belgium); Physique Quantique, CP165/82, Universite Libre de Bruxelles, B-1050 Brussels (Belgium)

    2012-11-12

    The {sup 2}H(d,p){sup 3}H, {sup 2}H(d,n){sup 3}He, and {sup 2}H(d,{gamma}){sup 4}He reactions at low energies are studied with realistic nucleon-nucleon interactions in an ab initio approach. The obtained astrophysical S-factors are all in very good agreement with experiment. The most important channels for both transfer and radiative capture are all found to dominate thanks to the tensor force.

  6. Electronic and magnetic properties of magnetoelectric compound Ca2CoSi2O7: An ab initio study

    Science.gov (United States)

    Chakraborty, Jayita

    2018-05-01

    The detailed first principle density functional theory calculations are carried out to investigate the electronic and magnetic properties of magnetoelectric compound Ca2CoSi2O7. The magnetic properties of this system are analyzed by calculating various hopping integrals as well as exchange interactions and deriving the relevant spin Hamiltonian. The dominant exchange path is visualized with Wannier functions plotting. Only intra planer nearest neighbor exchange interaction is strong in this system. The magnetocrystalline anisotropy is calculated for this system, and the results of the calculation reveal that the spin quantization axis lies in the ab plane.

  7. The electronic states of 1,2,3-triazole studied by vacuum ultraviolet photoabsorption and ultraviolet photoelectron spectroscopy, and a comparison with ab initio configuration interaction methods

    DEFF Research Database (Denmark)

    Palmer, Michael H.; Hoffmann, Søren Vrønning; Jones, Nykola C.

    2011-01-01

    The Rydberg states in the vacuum ultraviolet photoabsorption spectrum of 1,2,3-triazole have been measured and analyzed with the aid of comparison to the UV valence photoelectron ionizations and the results of ab initio configuration interaction (CI) calculations. Calculated electronic ionization...... and excitation energies for singlet, triplet valence, and Rydberg states were obtained using multireference multiroot CI procedures with an aug-cc-pVTZ [5s3p3d1f] basis set and a set of Rydberg [4s3p3d3f] functions. Adiabatic excitation energies obtained for several electronic states using coupled...... are the excitations consistent with an f-series....

  8. Free energy landscape of electrocatalytic CO2 reduction to CO on aqueous FeN4 center embedded graphene studied by ab initio molecular dynamics simulations

    Science.gov (United States)

    Sheng, Tian; Sun, Shi-Gang

    2017-11-01

    Experiments have found that the porphyrin-like FeN4 site in Fe-N-C materials is highly efficient for the electrochemical reduction of CO2 into CO. In this work, we investigated the reduction mechanisms on FeN4 embedded graphene layer catalyst with some explicit water molecules by combining the constrained ab initio molecular dynamics simulations and thermodynamic integrations. The reaction free energy and electron transfer in each elementary step were identified. The initial CO2 activation was identified to go through the first electron transfer to form adsorbed CO2- anion and the CO desorption was the rate limiting step in the overall catalytic cycle.

  9. Molecular determinants for drug-receptor interactions. Part 2. An ab initio molecular orbital and dipole moment study of the novel nootropic agent piracetam (2-oxopyrrolidin-1-ylacetamide)

    Science.gov (United States)

    Lumbroso, H.; Liégeois, C.; Pappalardo, G. C.; Grassi, A.

    From the ab initio molecular energies of the possible conformers and from a classical dipole moment analysis of 2-oxopyrrolidin-l-ylacetamide (μ = 4.02 D in dioxan at 30.0°C), the preferred conformation in solution of this novel nootropic agent has been determined. The exocyclic N-CH 2 bond is rotated in one sense by 90° and the exocyclic CH 2-C bond rotated in the same sense by 120° from the "planar" ( OO)- cis conformation. The structures of the two enantiomers in solution differ from that of the crystalline molecule.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2005-07-01

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

  11. 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)

  12. (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.

  13. Ab initio thermodynamic model for magnesium carbonates and hydrates.

    Science.gov (United States)

    Chaka, Anne M; Felmy, Andrew R

    2014-09-04

    An ab initio thermodynamic framework for predicting properties of hydrated magnesium carbonate minerals has been developed using density-functional theory linked to macroscopic thermodynamics through the experimental chemical potentials for MgO, water, and CO2. Including semiempirical dispersion via the Grimme method and small corrections to the generalized gradient approximation of Perdew, Burke, and Ernzerhof for the heat of formation yields a model with quantitative agreement for the benchmark minerals brucite, magnesite, nesquehonite, and hydromagnesite. The model shows how small differences in experimental conditions determine whether nesquehonite, hydromagnesite, or magnesite is the result of laboratory synthesis from carbonation of brucite, and what transformations are expected to occur on geological time scales. Because of the reliance on parameter-free first-principles methods, the model is reliably extensible to experimental conditions not readily accessible to experiment and to any mineral composition for which the structure is known or can be hypothesized, including structures containing defects, substitutions, or transitional structures during solid state transformations induced by temperature changes or processes such as water, CO2, or O2 diffusion. Demonstrated applications of the ab initio thermodynamic framework include an independent means to evaluate differences in thermodynamic data for lansfordite, predicting the properties of Mg analogues of Ca-based hydrated carbonates monohydrocalcite and ikaite, which have not been observed in nature, and an estimation of the thermodynamics of barringtonite from the stoichiometry and a single experimental observation.

  14. AN AB INITIO MODEL FOR COSMIC-RAY MODULATION

    Energy Technology Data Exchange (ETDEWEB)

    Engelbrecht, N. E.; Burger, R. A. [Center for Space Research, North-West University, Potchefstroom 2520 (South Africa)

    2013-07-20

    A proper understanding of the effects of turbulence on the diffusion and drift of cosmic rays (CRs) is of vital importance for a better understanding of CR modulation in the heliosphere. This study presents an ab initio model for CR modulation, incorporating for the first time the results yielded by a two-component turbulence transport model. This model is solved for solar minimum heliospheric conditions, utilizing boundary values chosen so that model results are in reasonable agreement with spacecraft observations of turbulence quantities in the solar ecliptic plane and along the out-of-ecliptic trajectory of the Ulysses spacecraft. These results are employed as inputs for modeled slab and two-dimensional (2D) turbulence energy spectra. The modeled 2D spectrum is chosen based on physical considerations, with a drop-off at the very lowest wavenumbers. There currently exist no models or observations for the wavenumber where this drop-off occurs, and it is considered to be the only free parameter in this study. The modeled spectra are used as inputs for parallel mean free path expressions based on those derived from quasi-linear theory and perpendicular mean free paths from extended nonlinear guiding center theory. Furthermore, the effects of turbulence on CR drifts are modeled in a self-consistent way, also employing a recently developed model for wavy current sheet drift. The resulting diffusion and drift coefficients are applied to the study of galactic CR protons and antiprotons using a 3D, steady-state CR modulation code, and sample solutions in fair to good agreement with multiple spacecraft observations are presented.

  15. Cosmic-ray modulation: an ab initio approach

    Energy Technology Data Exchange (ETDEWEB)

    Engelbrecht, N.E.; Burger, R.A., E-mail: 12580996@nwu.ac.za [Center for Space Research, North-West University, Potchefstroom (South Africa)

    2014-07-01

    A better understanding of cosmic-ray modulation in the heliosphere can only be gained through a proper understanding of the effects of turbulence on the diffusion and drift of cosmic rays. We present an ab initio model for cosmic-ray modulation, incorporating for the first time the results yielded by a two-component turbulence transport model. This model is solved for periods of minimum solar activity, utilizing boundary values chosen so that model results are in fair to good agreement with spacecraft observations of turbulence quantities, not only in the solar ecliptic plane but also along the out-of-ecliptic trajectory of the Ulysses spacecraft. These results are employed as inputs for modelled slab and 2D turbulence energy spectra. The latter spectrum is chosen based on physical considerations, with a drop-off at the very lowest wavenumbers commencing at the 2D outerscale. There currently exist no models or observations for this quantity, and it is the only free parameter in this study. The modelled turbulence spectra are used as inputs for parallel mean free path expressions based on those derived from quasi-linear theory and perpendicular mean free paths from extended nonlinear guiding center theory. Furthermore, the effects of turbulence on cosmic-ray drifts are modelled in a self-consistent way, employing a recently developed model for drift along the wavy current sheet. The resulting diffusion coefficients and drift expressions are applied to the study of galactic cosmic-ray protons and antiprotons using a three dimensional, steady-state cosmic-ray modulation code, and sample solutions in fair agreement with multiple spacecraft observations are presented. (author)

  16. Cosmic-ray modulation: an ab initio approach

    International Nuclear Information System (INIS)

    Engelbrecht, N.E.; Burger, R.A.

    2014-01-01

    A better understanding of cosmic-ray modulation in the heliosphere can only be gained through a proper understanding of the effects of turbulence on the diffusion and drift of cosmic rays. We present an ab initio model for cosmic-ray modulation, incorporating for the first time the results yielded by a two-component turbulence transport model. This model is solved for periods of minimum solar activity, utilizing boundary values chosen so that model results are in fair to good agreement with spacecraft observations of turbulence quantities, not only in the solar ecliptic plane but also along the out-of-ecliptic trajectory of the Ulysses spacecraft. These results are employed as inputs for modelled slab and 2D turbulence energy spectra. The latter spectrum is chosen based on physical considerations, with a drop-off at the very lowest wavenumbers commencing at the 2D outerscale. There currently exist no models or observations for this quantity, and it is the only free parameter in this study. The modelled turbulence spectra are used as inputs for parallel mean free path expressions based on those derived from quasi-linear theory and perpendicular mean free paths from extended nonlinear guiding center theory. Furthermore, the effects of turbulence on cosmic-ray drifts are modelled in a self-consistent way, employing a recently developed model for drift along the wavy current sheet. The resulting diffusion coefficients and drift expressions are applied to the study of galactic cosmic-ray protons and antiprotons using a three dimensional, steady-state cosmic-ray modulation code, and sample solutions in fair agreement with multiple spacecraft observations are presented. (author)

  17. 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

  18. 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

  19. 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

  20. Embedded atom approach for gold–silicon system from ab initio

    Indian Academy of Sciences (India)

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

  1. 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.

  2. Structural and vibrational study of 2-MethoxyEthylAmmonium Nitrate (2-OMeEAN): Interpretation of experimental results with ab initio molecular dynamics

    International Nuclear Information System (INIS)

    Campetella, M.; Caminiti, R.; Bencivenni, L.; Gontrani, L.; Bovi, D.; Guidoni, L.

    2016-01-01

    In this work we report an analysis of the bulk phase of 2-methoxyethylammonium nitrate based on ab initio molecular dynamics. The structural and dynamical features of the ionic liquid have been characterized and the computational findings have been compared with the experimental X-ray diffraction patterns, with infrared spectroscopy data, and with the results obtained from molecular dynamics simulations. The experimental infrared spectrum was interpreted with the support of calculated vibrational density of states as well as harmonic frequency calculations of selected gas phase clusters. Particular attention was addressed to the high frequency region of the cation (ω > 2000 cm −1 ), where the vibrational motions involve the NH 3 + group responsible for hydrogen bond formation, and to the frequency range 1200-1400 cm −1 where the antisymmetric stretching mode (ν 3 ) of nitrate is found. Its multiple absorption lines in the liquid arise from the removal of the degeneracy present in the D 3h symmetry of the isolated ion. Our ab initio molecular dynamics leads to a rationalization of the frequency shifts and splittings, which are inextricably related to the structural modifications induced by a hydrogen bonding environment. The DFT calculations lead to an inhomogeneous environment.

  3. An ab initio CASSCF study of zero field splitting fluctuations in the octet ground state of aqueous [Gd(iii)(HPDO3A)(H2O)

    Science.gov (United States)

    Khan, Shehryar; Pollet, Rodolphe; Vuilleumier, Rodolphe; Kowalewski, Jozef; Odelius, Michael

    2017-12-01

    In this work, we present ab initio calculations of the zero-field splitting (ZFS) of a gadolinium complex [Gd(iii)(HPDO3A)(H2O)] sampled from an ab initio molecular dynamics (AIMD) simulation. We perform both post-Hartree-Fock (complete active space self-consistent field—CASSCF) and density functional theory (DFT) calculations of the ZFS and compare and contrast the methods with experimental data. Two different density functional approximations (TPSS and LC-BLYP) were investigated. The magnitude of the ZFS from the CASSCF calculations is in good agreement with experiment, whereas the DFT results in varying degrees overestimate the magnitude of the ZFS for both functionals and exhibit a strong functional dependence. It was found in the sampling over the AIMD trajectory that the fluctuations in the transient ZFS tensor derived from DFT are not correlated with those of CASSCF nor does the magnitude of the ZFS from CASSCF and DFT correlate. From the fluctuations in the ZFS tensor, we extract a correlation time of the transient ZFS which is on the sub-picosecond time scale, showing a faster decay than experimental estimates.

  4. Structural and vibrational study of 2-MethoxyEthylAmmonium Nitrate (2-OMeEAN): Interpretation of experimental results with ab initio molecular dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Campetella, M.; Caminiti, R.; Bencivenni, L.; Gontrani, L., E-mail: lorenzo.gontrani@uniroma1.it [Dipartimento di Chimica, Università di Roma, “La Sapienza,” P. le Aldo Moro 5, I-00185 Roma (Italy); Bovi, D. [Dipartimento di Fisica, Università di Roma, “La Sapienza,” P. le Aldo Moro 5, I-00185 Roma (Italy); Guidoni, L. [Dipartimento di Scienze Fisiche e Chimiche, Università degli Studi dell’Aquila, Via Vetoio, Coppito, I-67100 L’Aquila (Italy)

    2016-07-14

    In this work we report an analysis of the bulk phase of 2-methoxyethylammonium nitrate based on ab initio molecular dynamics. The structural and dynamical features of the ionic liquid have been characterized and the computational findings have been compared with the experimental X-ray diffraction patterns, with infrared spectroscopy data, and with the results obtained from molecular dynamics simulations. The experimental infrared spectrum was interpreted with the support of calculated vibrational density of states as well as harmonic frequency calculations of selected gas phase clusters. Particular attention was addressed to the high frequency region of the cation (ω > 2000 cm{sup −1}), where the vibrational motions involve the NH{sub 3}+ group responsible for hydrogen bond formation, and to the frequency range 1200-1400 cm{sup −1} where the antisymmetric stretching mode (ν{sub 3}) of nitrate is found. Its multiple absorption lines in the liquid arise from the removal of the degeneracy present in the D{sub 3h} symmetry of the isolated ion. Our ab initio molecular dynamics leads to a rationalization of the frequency shifts and splittings, which are inextricably related to the structural modifications induced by a hydrogen bonding environment. The DFT calculations lead to an inhomogeneous environment.

  5. Potentiometric and ab initio studies of acid-base interactions of substituted 4-halo(Cl, Br)pyridine N-oxide systems

    International Nuclear Information System (INIS)

    Gurzynski, Lukasz; Puszko, Aniela; Makowski, Mariusz; Makowska, Joanna; Chmurzynski, Lech

    2006-01-01

    By using the potentiometric method, acidity constants have been determined in systems of tri- and tetra-substituted pyridine N-oxides. The potentiometric measurements in systems of four 4-chloropyridine N-oxide derivatives containing the chlorine atom at position 4 to the NO 2 group and four bromine counterparts were carried out in polar non-aqueous solvents, viz. amphiprotic methanol (MeOH) and aprotic protophilic dimethyl sulfoxide (DMSO). It was found that in all the systems studied the pK a values were readily determinable (as indicated by small standard deviations) in MeOH, whereas in DMSO large standard deviations were obtained making the pK a values either hardly determinable or indeterminable from potentiometric measurements. Furthermore, it was demonstrated that the acidity constants of protonated N-oxides studied in MeOH changed according to the sequence of their acidity constants in water. It was also found that in the polar solvents studied, i.e. in the amphiprotic methanol and the highly basic aprotic dimethyl sulfoxide, the cationic homo-conjugation equlibrium constants could not be determined using potentiometric method. Also, by using ab initio methods at the RHF and MP2 levels and the PCM model, utilizing the Gaussian 6-31++G** basis set, energies and Gibbs free energies of the protonation reactions of the N-oxides have been determined. The energy parameters have been compared with acidity constants of the protonated N-oxides determined by potentiometric titration in methanol to establish a correlation between these approaches

  6. Potentiometric and ab initio studies of acid-base interactions of substituted 4-halo(Cl, Br)pyridine N-oxide systems

    Energy Technology Data Exchange (ETDEWEB)

    Gurzynski, Lukasz [Department of General Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland); Puszko, Aniela [Department of Organic Chemistry, School of Economics, Wroclaw (Poland); Makowski, Mariusz [Department of General Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland); Makowska, Joanna [Department of General Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland); Chmurzynski, Lech [Department of General Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland)]. E-mail: lech@chem.univ.gda.pl

    2006-12-15

    By using the potentiometric method, acidity constants have been determined in systems of tri- and tetra-substituted pyridine N-oxides. The potentiometric measurements in systems of four 4-chloropyridine N-oxide derivatives containing the chlorine atom at position 4 to the NO{sub 2} group and four bromine counterparts were carried out in polar non-aqueous solvents, viz. amphiprotic methanol (MeOH) and aprotic protophilic dimethyl sulfoxide (DMSO). It was found that in all the systems studied the pK {sub a} values were readily determinable (as indicated by small standard deviations) in MeOH, whereas in DMSO large standard deviations were obtained making the pK {sub a} values either hardly determinable or indeterminable from potentiometric measurements. Furthermore, it was demonstrated that the acidity constants of protonated N-oxides studied in MeOH changed according to the sequence of their acidity constants in water. It was also found that in the polar solvents studied, i.e. in the amphiprotic methanol and the highly basic aprotic dimethyl sulfoxide, the cationic homo-conjugation equlibrium constants could not be determined using potentiometric method. Also, by using ab initio methods at the RHF and MP2 levels and the PCM model, utilizing the Gaussian 6-31++G** basis set, energies and Gibbs free energies of the protonation reactions of the N-oxides have been determined. The energy parameters have been compared with acidity constants of the protonated N-oxides determined by potentiometric titration in methanol to establish a correlation between these approaches.

  7. Ab initio study of structural, electronic, optical, and vibrational properties of Zn{sub x}S{sub y} (x + y = 2 to 5) nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Yadav, P. S.; Pandey, D. K., E-mail: pdhiraj2000@gmail.com; Agrawal, S.; Agrawal, B. K. [Allahabad University, Department of Physics (India)

    2010-03-15

    An ab initio study of the stability, structural, electronic. and optical properties has been performed for 46 zinc sulfide nanoclusters Zn{sub x}S{sub y} (x + y = n = 2 to 5). Five out of them are seen to be unstable as their vibrational frequencies are found to be imaginary. A B3LYP-DFT/6-311G(3df) method is employed to optimize the geometries and a TDDFT method is used for the study of the optical properties. The binding energies (BE), HOMO-LUMO gaps and the bond lengths have been obtained for all the clusters. For the ZnS{sub 2}, ZnS{sub 3}, and ZnS{sub 4} nanoclusters, our stable structures are seen to be different from those obtained earlier by using the effective core potentials. We have also considered the zero point energy (ZPE) corrections ignored by the earlier workers. For a fixed value of n, we designate the most stable structure the one, which has maximum final binding energy per atom. The adiabatic and vertical ionization potentials (IP) and electron affinities (EA), charges on the atoms, dipole moments, optical properties, vibrational frequencies, infrared intensities, relative infrared intensities, and Raman scattering activities have been investigated for the most stable structures. The nanoclusters containing large number of S atoms for each n is found to be most stable. The HOMO-LUMO gap decreases from n = 2-3 and then increases above n = 3. The IP and EA both fluctuate with the cluster size n. The optical absorption is quite weak in visible region but strong in the ultraviolet region in most of the nanoclusters except a few. The optical absorption spectrum or electron energy loss spectrum (EELS) is unique for every nanocluster and may be used to characterize a specific nanocluster. The growth of most stable nanoclusters may be possible in the experiments.

  8. Ab initio study of structural, electronic, optical, and vibrational properties of Zn x S y ( x + y = 2 to 5) nanoclusters

    Science.gov (United States)

    Yadav, P. S.; Pandey, D. K.; Agrawal, S.; Agrawal, B. K.

    2010-03-01

    An ab initio study of the stability, structural, electronic. and optical properties has been performed for 46 zinc sulfide nanoclusters Zn x S y ( x + y = n = 2 to 5). Five out of them are seen to be unstable as their vibrational frequencies are found to be imaginary. A B3LYP-DFT/6-311G(3df) method is employed to optimize the geometries and a TDDFT method is used for the study of the optical properties. The binding energies (BE), HOMO-LUMO gaps and the bond lengths have been obtained for all the clusters. For the ZnS2, ZnS3, and ZnS4 nanoclusters, our stable structures are seen to be different from those obtained earlier by using the effective core potentials. We have also considered the zero point energy (ZPE) corrections ignored by the earlier workers. For a fixed value of n, we designate the most stable structure the one, which has maximum final binding energy per atom. The adiabatic and vertical ionization potentials (IP) and electron affinities (EA), charges on the atoms, dipole moments, optical properties, vibrational frequencies, infrared intensities, relative infrared intensities, and Raman scattering activities have been investigated for the most stable structures. The nanoclusters containing large number of S atoms for each n is found to be most stable. The HOMO-LUMO gap decreases from n = 2-3 and then increases above n = 3. The IP and EA both fluctuate with the cluster size n. The optical absorption is quite weak in visible region but strong in the ultraviolet region in most of the nanoclusters except a few. The optical absorption spectrum or electron energy loss spectrum (EELS) is unique for every nanocluster and may be used to characterize a specific nanocluster. The growth of most stable nanoclusters may be possible in the experiments.

  9. 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.

  10. 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.

  11. Ab initio studies of structural, electronic, optical, elastic and thermal properties of silver gallium dichalcogenides (AgGaX2: X = S, Se, Te)

    International Nuclear Information System (INIS)

    Sharma, Sheetal; Verma, A.S.; Jindal, V.K.

    2014-01-01

    Graphical abstract: - Highlights: • FP-LAPW method has been used to compute the solid state properties of AgGaX 2 (X = S, Se, Te). • Electronic and optical properties reported with recently developed mBJ potential. • Thermal expansion, heat capacity, Debye temperature, entropy and Grüneisen parameter were evaluated. • Hardness was calculated for the first time at different temperature and pressure. - Abstract: We have performed ab initio calculations for the structural, electronic, optical, elastic and thermal properties of the silver gallium dichalcogenides (AgGaX 2 : X = S, Se, Te). In this study, we have used the accurate full potential linearized augmented plane wave (FP-LAPW) method to find the equilibrium structural parameters and to compute the six elastic constants (C 11 , C 12 , C 13 , C 33 , C 44 and C 66 ). We have reported electronic and optical properties with the recently developed density functional theory of Tran and Blaha, and this theory is used along with the Wu-Cohen generalized gradient approximation (WC-GGA) for the exchange-correlation potential. Furthermore, optical features such as dielectric functions, refractive indices, extinction coefficient, optical reflectivity, absorption coefficients and optical conductivities were calculated for photon energies up to 40 eV. The thermodynamical properties such as thermal expansion, heat capacity, debye temperature, entropy, Grüneisen parameter and bulk modulus were calculated employing the quasi-harmonic Debye model at different temperatures (0–900 K) and pressures (0–8 GPa) and the silent results were interpreted. Hardness of the materials was calculated for the first time at different temperatures and pressures

  12. Ab initio computational study of –N-C and –O-C bonding formation : functional group modification reaction based chitosan

    Science.gov (United States)

    Siahaan, P.; Salimah, S. N. M.; Sipangkar, M. J.; Hudiyanti, D.; Djunaidi, M. C.; Laksitorini, M. D.

    2018-04-01

    Chitosan application in pharmaceutics and cosmeceutics industries is limited by its solubility issue. Modification of -NH2 and -OH fuctional groups of chitosan by adding carboxyl group has been shown to improve its solubility and application. Attempt to synthesize carboxymethyl chitosan (CMC) from monocloroacetic acid (MCAA) has been done prior this report. However no information is available wether –OH (-O-C bonding formation) or -NH2 (-N-C bonding formation) is the preference for - CH2COOH to attach. In the current study, the reaction mechanism between chitosan and MCAA reactants into carboxymethyl chitosan (CMC) was examined by computational approach. Dimer from of chitosan used as a molecular model in calculation All the molecular structure involved in the reaction mechanism was optimized by ab initio computational on the theory and basis set HF/6-31G(d,p). The results showed that the - N-C bonding formation via SN2 than the -O-C bonding formation via SN2 which have activation energy 469.437 kJ/mol and 533.219 kJ/mol respectively. However, the -O-C bonding formation more spontaneous than the -N-C bonding formation because ΔG the formation of O-CMC-2 reaction is more negative than ΔG of formation N-CMC-2 reaction is -4.353 kJ/mol and -1.095 kJ/mol respectively. The synthesis of N,O-CMC first forms -O-CH2COOH, then continues to form -NH-CH2COOH. This information is valuable to further optimize the reaction codition for CMC synthesis.

  13. Proton transfer in a short hydrogen bond caused by solvation shell fluctuations: an ab initio MD and NMR/UV study of an (OHO)(-) bonded system.

    Science.gov (United States)

    Pylaeva, Svetlana; Allolio, Christoph; Koeppe, Benjamin; Denisov, Gleb S; Limbach, Hans-Heinrich; Sebastiani, Daniel; Tolstoy, Peter M

    2015-02-14

    We present a joint experimental and quantum chemical study on the influence of solvent dynamics on the protonation equilibrium in a strongly hydrogen bonded phenol-acetate complex in CD2Cl2. Particular attention is given to the correlation of the proton position distribution with the internal conformation of the complex itself and with fluctuations of the aprotic solvent. Specifically, we have focused on a complex formed by 4-nitrophenol and tetraalkylammonium-acetate in CD2Cl2. Experimentally we have used combined low-temperature (1)H and (13)C NMR and UV-vis spectroscopy and showed that a very strong OHO hydrogen bond is formed with proton tautomerism (PhOH···(-)OAc and PhO(-)···HOAc forms, both strongly hydrogen bonded). Computationally, we have employed ab initio molecular dynamics (70 and 71 solvent molecules, with and without the presence of a counter-cation, respectively). We demonstrate that the relative motion of the counter-cation and the "free" carbonyl group of the acid plays the major role in the OHO bond geometry and causes proton "jumps", i.e. interconversion of PhOH···(-)OAc and PhO(-)···HOAc tautomers. Weak H-bonds between CH(CD) groups of the solvent and the oxygen atom of carbonyl stabilize the PhOH···(-)OAc type of structures. Breaking of CH···O bonds shifts the equilibrium towards PhO(-)···HOAc form.

  14. Ab initio study of ortho-meta-isomerism of Li4AB3+ ions of nitrite and phosphite oxo- and thiosalts (A=N, P; B=O, S)

    International Nuclear Information System (INIS)

    Charkin, O.D.; MakKi, M.L.; Charkin, O.P.

    2000-01-01

    In the framework of MP2(6-31*//HF/6-31G + ZPE(HF/6-31G*) and MP4SDTQ/6-31G*//MP2/6-31G* + ZPE(MP2/6-31G*) approximations ab initio calculations of surfaces of potential energy of Li 4 NO 3 + , Li 4 PO 3 + , Li 4 NS 3 + , LiPS 3 + ions and Li 3 NO 3 , Li 3 PO 3 , Li 3 NS 3 , Li 3 PS 3 molecules of lithium oxo-and thiosalts with 26 valent electrons. Several low-level energy local minimums are determined for each of these ions including (Li + ) 4 ·AB 3 3- ortho-structure of C 3V symmetry with pyramidal three-charge AB 3 3- anion and totality of meta-structures of L + ·AB 2 - ·BL 3 + ion type and AB 2 - ·BL 4 2+ ion pair of C 2V and C s symmetry with onium OLi 3 + , OLi 4 2+ cations or their thio-analogues. Equilibrium geometric parameters and relative energy of isomers, energy of different channels of decomposition, frequencies and IR-intensities of normal vibrations, characteristics of electron density distribution are determined [ru

  15. 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 ...

  16. 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 ([...

  17. Pair potentials for alumina from ab initio results on the Al2O3 molecule

    International Nuclear Information System (INIS)

    Akdeniz, Z.; Cicek, Z.; Tosi, M.P.

    2000-08-01

    We use results from an ab initio investigation by Chang et al. on energetically low-lying stationary points of the Al 2 O 3 molecule to determine interionic potentials for the Al-O, O-O and Al-Al pairs. Our results are discussed in the perspective of previous studies of the condensed phases of alumina, with special regard to the structure of its molten state. (author)

  18. Molecular structure determination of cyclootane by ab initio and electron diffraction methods in the gas phase

    OpenAIRE

    De Almeida, Wagner B.

    2000-01-01

    The determination of the molecular structure of molecules is of fundamental importance in chemistry. X-rays and electron diffraction methods constitute in important tools for the elucidation of the molecular structure of systems in the solid state and gas phase, respectively. The use of quantum mechanical molecular orbital ab initio methods offer an alternative for conformational analysis studies. Comparison between theoretical results and those obtained experimentally in the gas phase can ma...

  19. 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...

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

    Science.gov (United States)

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

    2009-10-29

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

  1. 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.

  2. A hydronitrogen solid: high pressure ab initio evolutionary structure searches

    International Nuclear Information System (INIS)

    Hu Anguang; Zhang Fan

    2011-01-01

    High pressure ab initio evolutionary structure searches resulted in a hydronitrogen solid with a composition of (NH) 4 . The structure searches also provided two molecular isomers, ammonium azide (AA) and trans-tetrazene (TTZ) which were previously discovered experimentally and can be taken as molecular precursors for high pressure synthesis of the hydronitrogen solid. The computed pressure versus enthalpy diagram showed that the transformation pressure to the hydronitrogen solid is 36 GPa from AA and 75 GPa from TTZ. Its metastability was analyzed by the phonon dispersion spectrum and room-temperature vibrational density of state together with the transformation energy barrier back to molecular phases at 298 K. The predicted energy barrier of 0.21 eV/atom means that the proposed hydronitrogen solid should be very stable at ambient conditions. (fast track communication)

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

    Science.gov (United States)

    Wu, Henry; Mayeshiba, Tam; Morgan, Dane

    2016-07-19

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

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

    Science.gov (United States)

    Olivares-Amaya, Roberto; Hu, Weifeng; Nakatani, Naoki; Sharma, Sandeep; Yang, Jun; Chan, Garnet Kin-Lic

    2015-01-21

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-01-21

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

  6. Quantitative verification of ab initio self-consistent laser theory.

    Science.gov (United States)

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

    2008-10-13

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

  7. Ab initio elastic properties and tensile strength of crystalline hydroxyapatite.

    Science.gov (United States)

    Ching, W Y; Rulis, Paul; Misra, A

    2009-10-01

    We report elastic constant calculation and a "theoretical" tensile experiment on stoichiometric hydroxyapatite (HAP) crystal using an ab initio technique. These results compare favorably with a variety of measured data. Theoretical tensile experiments are performed on the orthorhombic cell of HAP for both uniaxial and biaxial loading. The results show considerable anisotropy in the stress-strain behavior. It is shown that the failure behavior of the perfect HAP crystal is brittle for tension along the z-axis with a maximum stress of 9.6 GPa at 10% strain. Biaxial failure envelopes from six "theoretical" loading tests show a highly anisotropic pattern. Structural analysis of the crystal under various stages of tensile strain reveals that the deformation behavior manifests itself mainly in the rotation of the PO(4) tetrahedron with concomitant movements of both the columnar and axial Ca ions. These results are discussed in the context of mechanical properties of bioceramic composites relevant to mineralized tissues.

  8. Ab initio methods for electron-molecule collisions

    International Nuclear Information System (INIS)

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

    1987-01-01

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

  9. Ab Initio Symmetry-Adapted No-Core Shell Model

    International Nuclear Information System (INIS)

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

    2011-01-01

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

  10. Ab Initio Analysis of Auger-Assisted Electron Transfer.

    Science.gov (United States)

    Hyeon-Deuk, Kim; Kim, Joonghan; Prezhdo, Oleg V

    2015-01-15

    Quantum confinement in nanoscale materials allows Auger-type electron-hole energy exchange. We show by direct time-domain atomistic simulation and analytic theory that Auger processes give rise to a new mechanism of charge transfer (CT) on the nanoscale. Auger-assisted CT eliminates the renown Marcus inverted regime, rationalizing recent experiments on CT from quantum dots to molecular adsorbates. The ab initio simulation reveals a complex interplay of the electron-hole and charge-phonon channels of energy exchange, demonstrating a variety of CT scenarios. The developed Marcus rate theory for Auger-assisted CT describes, without adjustable parameters, the experimental plateau of the CT rate in the region of large donor-acceptor energy gap. The analytic theory and atomistic insights apply broadly to charge and energy transfer in nanoscale systems.

  11. Relaxation of structural parameters and potential coefficients of nonrigid molecules. General symmetry properties and application to ab initio study of 1,2-difluoroethane

    Science.gov (United States)

    Ha, T.-K.; Günthard, H. H.

    1989-07-01

    Structural parameters like bond length, bond angles, etc. and harmonic and anharmonic potential coefficients of molecules with internal rotation, inversion or puckering modes are generally assumed to vary with the large amplitude internal coordinates in a concerted manner (relaxation). Taking the coordinate vectors of the nuclear configuration of semirigid molecules with relaxation (SRMRs) as functions of relaxing structural parameters and finite amplitude internal coordinate, the isometric group of SRMRs is discussed and the irreducible representations of the latter are shown to classify into engendered and nonengendered ones. On this basis a concept of equivalent sets of nuclei SRMRs is introduced and an analytical expression is derived which defines the most general functional form of relaxation increments of all common types of structural parameters compatible with isometric symmetry. This formula is shown to be a close analog of an analytical expression defining the transformations induced by the isometric group of infinitesimal internal coordinates associated with typical structural parameters. Furthermore analogous formulae are given for the most general form of the relaxation of harmonic potential coefficients as a function of finite internal coordinates. The general relations are illustrated by ab initio calculations for 1,2-difluoroethane at the MP4/DZP//HF/4-31G* level for twelve values of the dihedral angle including complete structure optimization. The potential to internal rotation is found to be in essential agreement with experimentally derived data. For a complete set of ab initio structural parameters the associated relaxation increments are represented as Fourier series, which are shown to confirm the form predicted by the general formula and the isometric group of 1,2-difluoroethane. Depending on type of the structural parameters (bond length, bond angles, etc.), the associated relaxation increments appear to follow some simple rules. Similarly

  12. Dispersion and Solvation Effects on the Structure and Dynamics of N719 Adsorbed to Anatase Titania (101) Surfaces in Room-Temperature Ionic Liquids: An ab Initio Molecular Simulation Study

    KAUST Repository

    Byrne, Aaron; English, Niall J.; Schwingenschlö gl, Udo; Coker, David F.

    2015-01-01

    Ab initio, density functional theory (DFT)-based molecular dynamics (MD) has been carried out to investigate the effect of explicit solvation on the dynamical and structural properties of a [bmim][NTf2] room-temperature ionic liquid (RTIL

  13. 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

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

    Science.gov (United States)

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

    2018-01-18

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

  15. Ab-initio study of (Ga,Cr)N and (Ga,Mn)N DMSs: under hydrostatic pressure

    Science.gov (United States)

    Rani, Anita; Kumar, Ranjan

    2018-03-01

    The influence of hydrostatic pressure between 0-100 GPa on structural, electronic and magnetic properties of CrxGa1-xN and MnxGa1-xN (x = 0.25) diluted magnetic semiconductors has been studied. The calculations have been performed using DFT as implemented in code SIESTA. LDA + U as exchange-correlation (XC) potential have been used to study the parameters. Under external pressure, shifting in both valence band and conduction band energy levels from their actual positions has been observed, which lead to modification of electronic properties. Also, N0 α, s-d exchange constant and p-d exchange constants, N0 β have been calculated at different pressures. Both the compounds show half metallic nature at studied pressure range.

  16. Valence isomerization of 2-phospha-4-silabicyclo[1.1.0]butane: a high-level ab initio study

    NARCIS (Netherlands)

    Slootweg, J.C.; Ehlers, A.W.; Lammertsma, K.

    2006-01-01

    The rearrangements for 2-phospha-4-silabicyclo[1.1.0]butane, analogous to the valence isomerization of the hydrocarbons bicyclobutane, 1,3-butadiene, and cyclobutene, were studied at the (U)QCISD(T)/ 6-311+G**//(U)QCISD/6-31G* level of theory. The monocyclic 1,2-dihydro-1,2-phosphasiletes are shown

  17. Magneto-electronic properties and spin-resolved I-V curves of a Co/GeSe heterojunction diode: an ab initio study

    Science.gov (United States)

    Makinistian, Leonardo; Albanesi, Eduardo A.

    2013-06-01

    We present ab initio calculations of magnetoelectronic and transport properties of the interface of hcp Cobalt (001) and the intrinsic narrow-gap semiconductor germanium selenide (GeSe). Using a norm-conserving pseudopotentials scheme within DFT, we first model the interface with a supercell approach and focus on the spin-resolved densities of states and the magnetic moment (spin and orbital components) at the different atomic layers that form the device. We also report a series of cuts (perpendicular to the plane of the heterojunction) of the electronic and spin densities showing a slight magnetization of the first layers of the semiconductor. Finally, we model the device with a different scheme: using semiinfinite electrodes connected to the heterojunction. These latter calculations are based upon a nonequilibrium Green's function approach that allows us to explore the spin-resolved electronic transport under a bias voltage (spin-resolved I-V curves), revealing features of potential applicability in spintronics.

  18. Experimental and ab initio study of the nuclear quadrupole interaction of 181Ta-probes in an α-Fe2O3 single crystal

    International Nuclear Information System (INIS)

    Darriba, G. N.; Muñoz, E. L.; Eversheim, P. D.; Rentería, M.

    2010-01-01

    We report perturbed-angular-correlation (PAC) experiments on 181 Hf (→ 181 Ta)-implanted corundum α-Fe 2 O 3 single crystal in order to determine the magnitude, symmetry and orientation of the electric-field-gradient (EFG) tensor at Ta donor impurity sites of this semiconductor. These results are analyzed in the framework of ab initio full-potential augmented-plane wave plus local orbital (FP-APW+lo) calculations. This combined analysis enables us to quantify the magnitude of the lattice relaxations induced by the presence of the impurity and to determine the charge state of the impurity donor level introduced by Ta in the band gap of the semiconductor.

  19. An Insight into the Environmental Effects of the Pocket of the Active Site of the Enzyme. Ab initio ONIOM-Molecular Dynamics (MD) Study on Cytosine Deaminase

    International Nuclear Information System (INIS)

    Matsubara, Toshiaki; Dupuis, Michel; Aida, Misako

    2008-01-01

    We applied the ONIOM-molecular dynamics (MD) method to cytosine deaminase to examine the environmental effects of the amino acid residues in the pocket of the active site on the substrate taking account of their thermal motion. The ab initio ONIOM-MD simulations show that the substrate uracil is strongly perturbed by the amino acid residue Ile33, which sandwiches the uracil with His62, through the steric contact due to the thermal motion. As a result, the magnitude of the thermal oscillation of the potential energy and structure of the substrate uracil significantly increases. TM and MA were partly supported by grants from the Ministry of Education, Culture, Sports, Science and Technology of Japan.MD was supported by the Division of Chemical Sciences, Office of Basic Energy Sciences, and by the Office of Biological and Environmental Research of the U.S. Department of Energy DOE. Battelle operates Pacific Northwest National Laboratory for DOE

  20. Ab initio multiple spawning on laser-dressed states: a study of 1,3-cyclohexadiene photoisomerization via light-induced conical intersections

    Science.gov (United States)

    Kim, Jaehee; Tao, Hongli; Martinez, Todd J.; Bucksbaum, Phil

    2015-08-01

    We extend the ab initio multiple spawning method to include both field-free and field-induced nonadiabatic transitions. We apply this method to describe ultrafast pump-probe experiments of the photoinduced ring-opening of gas phase 1,3-cyclohexadiene. In the absence of a control field, nonadiabatic transitions mediated by a conical intersection (CoIn) lead to rapid ground state recovery with both 1,3-cyclohexadiene and ring-opened hexatriene products. However, application of a control field within the first 200 fs after photoexcitation results in suppression of the hexatriene product. We demonstrate that this is a consequence of population dumping prior to reaching the CoIn and further interpret this in terms of light-induced CoIns created by the control field.

  1. Pressure induced magnetic phase transition in RhFe{sub 3}N and IrFe{sub 3}N: An ab-initio study

    Energy Technology Data Exchange (ETDEWEB)

    Puvaneswari, S. [Department of physics, E.M.G.Yadava women’s college, Madurai, Tamilnadu-625014 (India); Manikandan, M. [Department of physics, N.M.S.S.V.N college, Madurai, Tamilnadu-625019 (India); Rajeswarapalanichamy, R., E-mail: rrpalanichamy@gmail.com

    2016-05-06

    The structural, electronic, elastic and magnetic properties of RhFe{sub 3}N and IrFe{sub 3}N are investigated using ab-initio calculations based on density functional theory as implemented in VASP code within the gradient generalized approximation. The non-spin polarized and spin polarized calculations are performed for these nitrides at normal and high pressures. It is found that these ternary nitrides are stable in ferromagnetic state at normal pressure. The lattice constant and bulk modulus values are calculated. The electronic structure reveals that these nitrides are metallic at normal pressure. The calculated elastic constants indicate that they are mechanically stable at ambient pressure. Ferromagnetic to nonmagnetic phase transition is observed in RhFe{sub 3}N and IrFe{sub 3}N at high pressure. Ferromagnetism is quenched in these nitrides at high pressure.

  2. Ab initio study of mechanical and thermo-acoustic properties of tough ceramics: applications to HfO2 in its cubic and orthorhombic phase

    International Nuclear Information System (INIS)

    Ponce, C A; Casali, R A; Caravaca, M A

    2008-01-01

    By means of the ab initio all-electron new full-potential linear-muffin-tin orbitals method, calculations were made for elastic constants C 11 , C 12 and C 44 for Si, ZrO 2 and HfO 2 in their cubic phase, and constants C 11 , C 22 , C 33 , C 12 , C 13 , C 23 , C 44 , C 55 and C 66 for HfO 2 in its orthorhombic phase. Using the Voigt and Reuss theory, estimations were made for polycrystals of their bulk, shear and Young moduli, and Poisson coefficients. The speed of elastic wave propagations and Debye temperatures were estimated for polycrystals built from Si and the above mentioned compounds. The semicore 4f 14 electrons should be included in the valence set of Hf atom in this all-electron approach if accurate results for elastic properties under pressures are looked for

  3. Static electric polarizabilities and first hyperpolarizabilities of molecular ions RgH + (Rg = He, Ne, Ar, Kr, Xe): ab initio study

    Science.gov (United States)

    Cukras, Janusz; Antušek, Andrej; Holka, Filip; Sadlej, Joanna

    2009-06-01

    Extensive ab initio calculations of static electric properties of molecular ions of general formula RgH + (Rg = He, Ne, Ar, Kr, Xe) involving the finite field method and coupled cluster CCSD(T) approach have been done. The relativistic effects were taken into account by Douglas-Kroll-Hess approximation. The numerical stability and reliability of calculated values have been tested using the systematic sequence of Dunning's cc-pVXZ-DK and ANO-RCC-VQZP basis sets. The influence of ZPE and pure vibrational contribution has been discussed. The component αzz has increasing trend in RgH + while the relativistic effect on αzz leads to a small increase of this molecular parameter.

  4. Ab initio study of the CO-N2 complex: a new highly accurate intermolecular potential energy surface and rovibrational spectrum

    DEFF Research Database (Denmark)

    Cybulski, Hubert; Henriksen, Christian; Dawes, Richard

    2018-01-01

    A new, highly accurate ab initio ground-state intermolecular potential-energy surface (IPES) for the CO-N2 complex is presented. Thousands of interaction energies calculated with the CCSD(T) method and Dunning's aug-cc-pVQZ basis set extended with midbond functions were fitted to an analytical...... function. The global minimum of the potential is characterized by an almost T-shaped structure and has an energy of -118.2 cm-1. The symmetry-adapted Lanczos algorithm was used to compute rovibrational energies (up to J = 20) on the new IPES. The RMSE with respect to experiment was found to be on the order...... of 0.038 cm-1 which confirms the very high accuracy of the potential. This level of agreement is among the best reported in the literature for weakly bound systems and considerably improves on those of previously published potentials....

  5. 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.)

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

    International Nuclear Information System (INIS)

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

    1990-01-01

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

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

    International Nuclear Information System (INIS)

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

    2015-01-01

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

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

    Science.gov (United States)

    Yang, Lina; Minnich, Austin J

    2017-03-14

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

  9. Modeling of nuclear glasses by classical and ab initio molecular dynamics

    International Nuclear Information System (INIS)

    Ganster, P.

    2004-01-01

    A calcium aluminosilicate glass of molar composition 67 % SiO 2 - 12 % Al 2 O 3 - 21 % CaO was modelled by classical and ab initio molecular dynamics. The size effect study in classical MD shows that the systems of 100 atoms are more ordered than the larger ones. These effects are mainly due to the 3-body terms in the empirical potentials. Nevertheless, these effects are small and the structures generated are in agreement with experimental data. In such kind of glass, we denote an aluminium avoidance and an excess of non bridging oxygens which can be compensated by tri-coordinated oxygens. When the dynamics of systems of 100 and 200 atoms is followed by ab initio MD, some local arrangements occurs (bond length, angular distributions). Thus, more realistic vibrational properties are obtained in ab initio MD. The modelling of thin films shows that aluminum atoms extend to the most external part of the surface and they are all tri-coordinated. Calcium atoms are set in the sub layer part of the surface and they produce a depolymerization of the network. In classical MD, tri-coordinated aluminium atoms produce an important electric field above the surface. With non bridging oxygens, they constitute attractive sites for single water molecules. (author) [fr

  10. Modelling of nuclear glasses by classical and ab initio molecular dynamics

    International Nuclear Information System (INIS)

    Ganster, P.

    2004-10-01

    A calcium aluminosilicate glass of molar composition 67 % SiO 2 - 12 % Al 2 O 3 - 21 % CaO was modelled by classical and ab initio molecular dynamics. The size effect study in classical MD shows that the systems of 100 atoms are more ordered than the larger ones. These effects are mainly due to the 3-body terms in the empirical potentials. Nevertheless, these effects are small and the structures generated are in agreement with experimental data. In such kind of glass, we denote an aluminium avoidance and an excess of non bridging oxygens which can be compensated by tri coordinated oxygens. When the dynamics of systems of 100 and 200 atoms is followed by ab initio MD, some local arrangements occurs (bond length, angular distributions). Thus, more realistic vibrational properties are obtained in ab initio MD. The modelling of thin films shows that aluminium atoms extend to the most external part of the surface and they are all tri-coordinated. Calcium atoms are set in the sub layer part of the surface and they produce a depolymerization of the network. In classical MD, tri-coordinated aluminium atoms produce an important electric field above the surface. With non bridging oxygens, they constitute attractive sites for single water molecules. (author)

  11. On the Importance of Nonbonding Donor-Acceptor Interactions Involving PO2. Radicals: An ab Initio Study.

    Science.gov (United States)

    Bauzá, Antonio; Frontera, Antonio

    2017-08-18

    In this study, several σ-type and π-hole bonding complexes between PO 2 . radicals and electron-rich entities have been optimized at the RI-MP2/aug-cc-pVQZ level of theory. We have used Cl - , Br - , I - anions, and ethene, ethyne, HCN, HF, and H 2 O as Lewis bases. In addition, we have performed natural bond orbital (NBO) and Mulliken spin density analyses, highlighting the donor-acceptor nature of the interaction. Moreover, an interesting retro-donation from the single electron lone pair of the PO 2 . radical to the Lewis base also contributes to the stabilization of the complexes studied herein. Finally, the Bader's atoms-in-molecules (AIM) analysis of several complexes has been performed to further characterize the interactions discussed herein. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Effect of chemical substitutions on photo-switching properties of 3-hydroxy-picolinic acid studied by ab initio methods

    International Nuclear Information System (INIS)

    Rode, Michał F.; Sobolewski, Andrzej L.

    2014-01-01

    Effect of chemical substitutions to the molecular structure of 3-hydroxy-picolinic acid on photo-switching properties of the system operating on excited-state intramolecular double proton transfer (d-ESIPT) process [M. F. Rode and A. L. Sobolewski, Chem. Phys. 409, 41 (2012)] was studied with the aid of electronic structure theory methods. It was shown that simultaneous application of electron-donating and electron-withdrawing substitutions at certain positions of the molecular frame increases the height of the S 0 -state tautomerization barrier (ensuring thermal stability of isomers) and facilitates a barrierless access to the S 1 /S 0 conical intersection from the Franck-Condon region of the S 1 potential-energy surface. Results of study point to the conclusion that the most challenging issue for practical design of a fast molecular photoswitch based on d-ESIPT phenomenon are to ensure a selectivity of optical excitation of a given tautomeric form of the system

  13. Effect of chemical substitutions on photo-switching properties of 3-hydroxy-picolinic acid studied by ab initio methods

    Science.gov (United States)

    Rode, Michał F.; Sobolewski, Andrzej L.

    2014-02-01

    Effect of chemical substitutions to the molecular structure of 3-hydroxy-picolinic acid on photo-switching properties of the system operating on excited-state intramolecular double proton transfer (d-ESIPT) process [M. F. Rode and A. L. Sobolewski, Chem. Phys. 409, 41 (2012)] was studied with the aid of electronic structure theory methods. It was shown that simultaneous application of electron-donating and electron-withdrawing substitutions at certain positions of the molecular frame increases the height of the S0-state tautomerization barrier (ensuring thermal stability of isomers) and facilitates a barrierless access to the S1/S0 conical intersection from the Franck-Condon region of the S1 potential-energy surface. Results of study point to the conclusion that the most challenging issue for practical design of a fast molecular photoswitch based on d-ESIPT phenomenon are to ensure a selectivity of optical excitation of a given tautomeric form of the system.

  14. 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....

  15. Recent progress in ab-initio studies of nuclear reactions of astrophysical interest with A ≤ 3

    Science.gov (United States)

    Marcucci, Laura E.

    2018-03-01

    We review the most recent theoretical studies of nuclear reactions of astrophysical interest involving few-nucleon systems. In particular, we focus on the consequences for the solar neutrino fluxes of the recent determination for the astrophysical S-factor of the proton weak capture by proton, and on the radiative capture of protons by deuterons in the energy range of interest for Big Bang Nucleosynthesis.

  16. Covalent Linking Greatly Enhances Photoinduced Electron Transfer in Fullerene-Quantum Dot Nanocomposites: Time-Domain Ab Initio Study

    DEFF Research Database (Denmark)

    Chaban, Vitaly V.; Prezhdo, Victor; Prezhdo, Oleg

    2013-01-01

    , it leads to a notably weaker QD-C-60 interaction than a lengthy molecular bridge. We show that the ET rate in a nonbonded mixture of QDs and C-60 can be enhanced by doping. The photoinduced ET is promoted primarily by mid- and low-frequency vibrations. The study establishes the basic design principles...... for enhancing photoinduced charge separation in nanoscale light harvesting materials....

  17. Recent Progresses in Ab-Initio Studies of Low-Energy Few-Nucleon Reactions of Astrophysical Interest

    Science.gov (United States)

    Marcucci, Laura E.

    2017-03-01

    We review the most recent theoretical studies of nuclear reactions of astrophysical interest involving few-nucleon systems. In particular, we focus on the radiative capture of protons by deuterons in the energy range of interest for Big Bang Nucleosynthesis. Related to this, we will discuss also the most recent calculation of tritium β -decay. Two frameworks will be considered, the conventional and the chiral effective field theory approach.

  18. Low-energy electron scattering from CO. 2: Ab-initio study using the frame-transformation theory

    Science.gov (United States)

    Chandra, N.

    1976-01-01

    The Wigner-Eisenbud R matrix method has been combined with the frame transformation theory to study electron scattering from molecular systems. The R matrix, calculated at the boundary point of the molecular core radius, has been transformed to the space frame in order to continue the solution of the scattering equations in the outer region where rotational motion of the nuclei is taken into account. This procedure has been applied to a model calculation of thermal energy electron scattering from CO.

  19. 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

  20. Does borazine–water behave like benzene-water? A matrix isolation infrared and ab initio study

    Energy Technology Data Exchange (ETDEWEB)

    Mishra, P. [Department of Chemistry, Indian Institute of Science Education and Research, Sector 81, Mohali, Punjab 140306 (India); Purdue University, West Lafayette, Indiana 47907 (United States); Verma, K.; Bawari, D.; Viswanathan, K. S., E-mail: vish@iisermohali.ac.in [Department of Chemistry, Indian Institute of Science Education and Research, Sector 81, Mohali, Punjab 140306 (India)

    2016-06-21

    Borazine is isoelectronic with benzene and is popularly referred to as inorganic benzene. The study of non-covalent interactions with borazine and comparison with its organic counterpart promises to show interesting similarities and differences. The motivation of the present study of the borazine-water interaction, for the first time, stems from such interesting possibilities. Hydrogen-bonded complexes of borazine and water were studied using matrix isolation infrared spectroscopy and quantum chemical calculations. Computations were performed at M06-2X and MP2 levels of theory using 6-311++G(d,p) and aug-cc-pVDZ basis sets. At both the levels of theory, the complex involving an N–H⋯O interaction, where the N–H of borazine serves as the proton donor to the oxygen of water was found to be the global minimum, in contrast to the benzene-water system, which showed an H–π interaction. The experimentally observed infrared spectra of the complexes corroborated well with our computations for the complex corresponding to the global minimum. In addition to the global minimum, our computations also located two local minima on the borazine-water potential energy surface. Of the two local minima, one corresponded to a structure where the water was the proton donor to the nitrogen of borazine, approaching the borazine ring from above the plane of the ring; a structure that resembled the global minimum in the benzene-water H–π complex. The second local minimum corresponded to an interaction of the oxygen of water with the boron of borazine, which can be termed as the boron bond. Clearly the borazine-water system presents a richer landscape than the benzene-water system.